JPH01172425A - Preparation of modified polyester - Google Patents

Abstract

PURPOSE:To obtain a high degree of polymn. and a melt viscosity suitable for melt spinning and to improve color tone etc., by adding kinds two specified of salts at an arbitrary stage and heating and reacting a dibasic carboxylic, acid and an alkylene glycol. CONSTITUTION:Dibasic carboxylic acids (A) (or its ester-forming deriv.) consisting of terephthalic acid and, if necessary, other dibasic carboxylic acid and one or more alkylene glycols (B) (e.g., ethylene glycol) are reacted together by adding 0.5-10mol.% in total, based on the component A, 0.4-10mol.% metal sulfonate (a) of formula I (wherein Z1 is an arom. group or an aliph. group; A1 is an ester-forming functional group; A2 is H or A1; M is a metal; m is a positive integer) based on the component A and 0.1-10mol.% quat. phosphonium salt of sulfonic acid of formula II (wherein Z2 is Z1; A3 is A1; A4 is A2; R1-4 are each an alkyl or an aryl; n is m) based on the component A in an arbitrary stage of reaction before the reaction is completed.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a modified polyester, which has a sufficient degree of polymerization, a melt viscosity suitable for melt molding, particularly melt spinning, and a method for producing a modified polyester. The present invention relates to a method for producing a modified polyester that has extremely high white skin and excellent one-color tone, and therefore exhibits exceptionally excellent vivid dyeability when dyed with a cationic dye.

<Prior art> Polyester has many excellent properties and is widely used as fibers and films, but it has poor dyeability and
'Difficult to dye with dyes other than P1 disperse dye. Various proposals have been made to improve this dyeability. One of these is isophthalic acid components, which traditionally contain sulfonic acid metal bases.

For example, a method is known in which a 5-sodium sulfoinphthalic acid component is copolymerized with polyester to make it dyeable with a cationic dye (I!!! Publication No. 34-104
(See Publication No. 97).

However, in this method, when the isophthalic acid component containing the sulfonic acid metal base is copolymerized in the necessary amount to raise the dyeability to a satisfactory level, the thickening effect of the inphthalic acid component containing the sulfonic acid metal salt is suppressed. Therefore, the melt viscosity of the polymerization reaction product increases significantly, making it difficult to sufficiently increase the degree of polymerization.

JIK was also in trouble when it came to spinning. Therefore, the melt viscosity of the modified polyester copolymerized with an isophthalic acid component containing such an amount of sulfonic acid metal base is to be within a range where polymerization is easy and spinning is possible.

It is necessary to lower the degree of polymerization of the modified polyester.

As a result, the yarn strength is reduced, which significantly limits the uses of the resulting cationic dye-dyeable polyester fibers.

On the other hand, a method is known in which an inphthalic acid component having a quaternary sulfonic acid phosphonium base is used as a cationic dye dye-enabling agent (see % Publication No. 47-22334 and US Pat. No. 3,732,183). According to this method, the thickening effect during the polymerization reaction is small, so even if the degree of polymerization of the modified polyester is increased, the melt viscosity can be kept within the range that allows normal spinning. For this reason, high-strength cationic dye machizomeya polyester fibers can now be easily obtained.
In addition to the advantages of cationic dyes such as bright color development and non-transferability, the high tenacity of threads can be utilized to expand the application to the field of sportswear, for example.

However, in this method, the isophthalic acid component having a quaternary phosphonium sulfonic acid base used has poor heat resistance, and may self-decompose under high heat conditions such as the polymerization reaction process or melt molding process of the modified polyester. This method has the serious disadvantage of accelerating the decomposition of the polymer, causing the resulting polyester and spun yarn to become yellowish brown in color, and furthermore, this coloring causes the color tone to change when dyed. For this reason, this method has never been industrially adopted.

<While the invention is intended to solve this problem, the present inventors have found that in the case of a modified polyester copolymerized with an inphthalate component containing the above-mentioned sulfonic acid metal base, the thickening effect of the inphthalate component is the cause of the problem. As a result of intensive studies to overcome the drawback of not being able to sufficiently increase the degree of monopolymerization, surprisingly, it was found that by using the sulfonic acid metal salt compound and the sulfonic acid quaternary phosphonium salt compound in combination, the modification could be achieved. It has been found that the increase in melt viscosity of high quality polyester can be suppressed and the degree of monopolymerization can be increased. Moreover, K has the serious drawback that when a sulfonic acid quaternary phosphonium salt compound is copolymerized alone, the modified polyester produced is colored yellowish brown.
A modified polyester using a combination of a sulfonic acid metal salt compound and a sulfo/acid quaternary phosphonium salt compound has a higher white carbon content than a modified polyester obtained by copolymerizing only a sulfonic acid metal salt and has an excellent single color tone. I came to find out that it can be done.

The present invention was completed as a result of further studies based on this knowledge.

<Configuration of the Invention> Namely, 1. The present invention provides a method for producing a polyester by subjecting a difunctional carboxylic acid, mainly terephthalic acid, or an ester-forming derivative thereof and at least one alkylene glycol to a heating reaction, when the reaction is completed. 0.4 to 10 for the difunctional carboxylic acid component at any previous stage.
The amount of the following general formula + 11 (80, M) m (wherein, zl is an aromatic group or aliphatic group, At is an ester-forming functional group, and A is the same or different ester-forming functional group as A1. 1M of groups or hydrogen atoms is a positive integer. (In the formula, 2. is an aromatic group or an aliphatic group, A is an ester-forming functional group t, A4 is an ester-forming functional group or a hydrogen atom f that is the same as or different from A, R11Rst R1
and R4 are the same or different groups selected from the group consisting of a furkyl group and an aryl group, and n represents a positive integer. ), the total amount of the sulfonic acid metal salt and the sulfonic acid quaternary phosphonium salt is more than 0.5 mole and 10 mole or less relative to the bifunctional carboxylic acid component. This is a method for producing a modified polyester, which is characterized in that the modified polyester is added in a certain amount and reacted.

The polyester referred to in the present invention has terephthalic acid as the main acid component [1. The main material used is polyester whose main glycol component is at least one alkylene glycol selected from ethylene glycol, trimethylene glycol, and tetramethylene glycol.

It may also be a polyester in which part of the terephthalic acid component is replaced with another difunctional carboxylic acid component, and/
Alternatively, it may be a polyester in which a part of the Glyfur component is replaced with the main component.

Examples of difunctional carboxylic acids other than terephthalic acid used here include inphthalic acid, naphthalene dicarboxylic acid, and diphenyl dicarboxylic acid.

Aromatic, aliphatic, and alicyclic difunctional carboxylic acids such as diphenoxyethanedicarboxylic acid, β-hydroxyethoxybenzoic acid, p-oxybenzoic acid, adipic acid, sebacic acid, and 1,4-cyclohexanedicarboxylic acid. I can give it to you.

Further, examples of diol compounds other than the above-mentioned Glyfur include cyclohexane-1,4-dimetatool, neopentyl glycol, and bisphenol A.

Examples include aliphatic, alicyclic, and aromatic diol compounds such as bisphenol S, and polyoxyalkylene glycols.

Furthermore, polycarboxylic acids such as trimellitic acid, pyromellitic acid, and polyols such as glycerin, trimethyp-propane, and pentaerythritol can be used as long as the polyester is substantially linear.

Such polyesters can be synthesized by any method.

For example, in the case of polyethylene terephthalate, usually terephthalic acid and ethylene glycol are directly esterified, a lower alkyl ester of terephthalic acid such as dimethyl terephthalate is transesterified with ethylene glycol, or terephthalic acid and ethylene glycol are transesterified. The first stage reaction is to react with terephthalic acid to produce a glycol ester and/or its low polymer, and the first stage reaction product is heated under reduced pressure until the desired degree of polymerization is achieved. It is produced by a second step of polycondensation reaction.

Any catalyst can be used in these reactions as necessary. Among these, when employing the transesterification method, calcium compounds, manganese compounds, magnesium compounds, zinc compounds, cobalt compounds, etc. are preferred as transesterification catalysts, and these may be used alone or in combination of two or more. The amount used is 0.00% relative to the difunctional carboxylic acid component used as the polyester raw material. O1 to 0.1 mol% is preferred.

In addition, a heptimony compound is used as a polycondensation catalyst.

Titanium compounds and germanium compounds are preferred.

%, a reaction product obtained by reacting an organic titanium compound, especially titanium tetraalfoxyte, and trimellitic anhydride in ethylene glycol is preferred. Incidentally, the titanium compound can be obtained by the method described in JP-A-53-453i. These polycondensation catalysts may also be used alone or in combination of two or more, and the amount used is preferably 0.003 to 0.1 molar based on the bifunctional carboxylic acid component.

The sulfonic acid metal salt used as a copolymerization component in the method of the present invention is represented by the following -Momona+11(So,M)m. In the formula, z represents an aromatic group or an aliphatic group, and among them, an aromatic group is preferable. A represents an ester-forming functional group; specific examples include +CHt+aOH, -0
+CH, dO(CHI)t, -), O)f.

(However, S R' is a lower furkyl group or a phenyl group, & and d are an integer of 1 or more, and b is an integer of 2 or more.). A represents an ester-forming functional group or a hydrogen atom that is the same as or different from A.

Among these, ester-forming functional groups are preferred.

M represents a metal atom, especially Na, Li, and K.

Ti, Ca + Zn + M11 + Mnt are preferred. m is a positive integer.

Among the sulfonic acid metal salts represented by the above-mentioned hole t1+, preferred are 5-sodium dimethyl sulfoisophthalate + 5-lithium dimethyl sulfoisophthalate, 5-
These include sodium sulfoisophthalate bis(p-hydroxyethyl) ester and 5-lithium sulfoisophthalate bis(p-hydroxyethyl) ester. Especially, 5
- Sodium sulfoiphthalate bis(p-hydroxyethyl) ester.

The sulfonic acid metal salt is preferably copolymerized with 0.4 to 10 moles, particularly preferably 1.0 to 10 moles, with respect to the difunctional carboxylic acid component that is the raw material of the polyester.
It is 6.0 molti.

If the sulfonic acid metal salt is less than 0.4 molty, the resulting modified polyester will have insufficient dyeability with cationic dyes, and if it exceeds 10 molty, the cationic dyeability will no longer show any significant improvement, and will instead become more characteristic of the polyester. The excellent properties of this material will be impaired, making it difficult to achieve the object of the present invention.

K for copolymerizing the sulfonic acid metal salt into a polyester may be added at any stage before the synthesis of the polyester described above is completed, preferably at any stage before the first stage reaction is completed.

In the present invention, a sulfonic acid quaternary phosphonium salt is used in combination with the above-mentioned sulfonic acid metal salt. This sulfonic acid quaternary phosphonium salt is represented by the following Misaki general formula (...).

In the formula, 2. represents an aromatic group or an aliphatic group, and among them, an aromatic group is preferable. A indicates an ester-forming functional group, and a specific example is 0.0.0 + mountain +, OH, -0÷ mountain + 0 (CHt)B 9,30
Examples include H--CGo (CH,) b-)dOH 1, where R/ is a lower fulkyl group or a phenyl group, & and d are an integer of 5 or more, and b is an integer of 2 or more. A4 represents an ester-forming functional group or a hydrogen atom that is the same as or different from A, and is preferably an ester-forming functional group. Rs t Rs
*Rs and R4 represent the same or different groups selected from alkyl groups and aryl groups. n is a positive integer.

Such quaternary phosphonium sulfonic acid salts can generally be easily synthesized by reacting the corresponding sulfonic acid with phosphines or by reacting the corresponding metal sulfonic acid salt with quaternary phosphonium halides.

Preferred specific examples of the quaternary phosphonium sulfonic acid salt include 3,5-dicarboxybenzenesulfonic acid (te)
butylphosphonium salt, ethyltributylphosphonium 3,5-dicarboxybenzenesulfonate tJ[*
3t5-dicarboxybenzenesulfonic acid benzyltributylphosphonium salt.

3,5-dicarboxybenzenesulfonic acid phenyltributylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid tetraphenylphosphonium salt! [+315
-Dicarboxybenzenesulfonic acid ethyltriphenylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid phthyltriphenylphosphonium salt s3+5-dicarboxybenzenesulfonic acid penzyltriphenylphosphoequum Mli * 3t5-dicarpomethoxybenzenesulfonic acid Tetrabutylphosphonium salt, 3.5-dicarpomethoxybenzenesulfonic acid ethyltriptylphosphonicum salt, 3,5-dicarbomethoxybenzenesulfonic acid benzyltributylphosphonium salt, 3.5-
Dicarpomethoxybenzenesulfonic acid phenyltributylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid tetraphenylphosphonium salt.

3.5-dicarbomethoxybenzenesulfonic acid ethyltriphenylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid butyltriphenylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid penzyltriphenylphosphonicum salt , 3-carboxybenzenesulfonic acid tetrabutylphosphonium salt t3-carboxybenzenesulfonic acid tetraphenylphosphonicum salt P3-carbomethoxybenzenesulfonic acid tetrabutylphosphonicum salt, 3-carbomethoxybenzenesulfonic acid tetraphenylphosphonicum salt, 3 ,5-di(β-b
3,5-di(β-human-oxyethoxycarbonyl)benzenesulfonic acid tetraphenylphosphonium salt, 3-(β-hyfa-oxyethoxycarbonyl)benzenesulfonic acid Tetrabutylphosphonium salt, 3-(β-HF'Roxyethoxycarbonyl)benzenesulfonic acid tetraphenylphosphonium salt, 4-hydroxyethoxybenzenesulfonic acid tetrazylphosphonium salt, 2,6-dicarpoxynaphthalene-4-sulfone Examples include acid tetrabutylphosphonium salt, α-tetrabutylphosphonium sulfosuccinic acid, and the like. The above quaternary phosphonium sulfonic acid salts may be used alone or in combination of two or more.

In order to copolymerize the quaternary phosphonium sulfonic acid salt into a polyester, it may be added at any stage before the synthesis of the polyester described above is completed. In this case, the relationship with the addition timing of the metal sulfonate may be arbitrary, and both may be added separately or may be mixed in advance and added simultaneously.

The amount of the sulfonic acid quaternary phosphonium salt used is 0.00% relative to the difunctional carboxylic acid component that is the raw material for polyester. The amount is 5 to 10 molt, and the special K O, 3 to 2
．． A range of 0 mol is preferred. If the amount is less than 0.1 molar, the thickening effect of the polyester copolymerized with the sulfonic acid metal salt compound cannot be suppressed, and therefore it is difficult to obtain a polyester with a high degree of polymerization. Furthermore, it is difficult to obtain polyester with high white skin and excellent color tone. on the other hand,
If the amount exceeds 10 molty, the color tone improving effect will be rather reduced, and the moldability and physical properties of the polyester will be deteriorated.

In the present invention, the total amount of the sulfonic acid metal salt and the sulfonic acid quaternary phosphonium salt exceeds 0.5 mol/1 based on the difunctional carboxylic acid component that is the raw material of the polyester.
It is necessary to reduce the amount to 0 molt or less. 0.5
If it is less than 10 moles, the resulting modified polyester will have insufficient dyeability with cationic dyes, and if it exceeds 10 moles, the cationic dyeability will no longer show any significant improvement, and on the contrary, the excellent properties unique to polyester will be impaired. Become.

As mentioned above, high whiteness and
It is possible to obtain a high-strength cationically dyeable polyester, but it is also possible to further improve the color tone of the produced polyester by adding the following compounds to improve the heat resistance of the modified polyester. becomes.

Specific compounds of this color tone improver include tetramethylammonium hydroxide, tetramethylammonium chloride, tetraethyl7mmonium hydroxide, and tetraethylammonium chloride+A? ) Laethylammonium, tetraethyl 7mmonicum iodide, tetrapropylammonium hydroxide, tetrapropylammonium chloride, tetranebutylammonium hydroxide, tetraisopropylammonium chloride, tetrabutylammonium hydroxide, tetrabutylammonium chloride, tetraphenyl hydroxide Quaternary ammonium salt compounds such as ammonium and tetraphenylammonium chloride.

Examples include alkali metal compounds and/or amine compounds such as sodium acetate, lithium fnnate, triethanolamine, triethylamine, and the like.

The amount of these compounds used is 0.010 to 0.50 based on the difunctional carboxylic acid component as a raw material for polyester.
A suitable range is 0.050 to 0.0 molar.
A range of 30 mol% is preferred.

The compound may be blended at any stage until the melt molding of the modified polyester is completed; for example, even if Km is added to the polyester raw material, from the end of the first stage reaction to the start of the second stage reaction. It may be added during the second stage reaction or during the second stage reaction.

<Effects of the Invention> According to the method of the present invention, it is possible to industrially obtain cationic dye-dyable polyester with high whiteness and high degree of polymerization, and molded products thereof. When dyed with dyes, high-strength cationic dyeable yarns are obtained that exhibit significantly improved vivid colors.

The modified polyester obtained in this way has the following advantages compared to conventional polyester modified by copolymerization with metal sulfonic acid or polyester modified by copolymerization with quaternary phosphonium salt of sulfonic acid. .

(1) Since it does not produce the thickening effect inherent to sulfonic acid metal salts, it is possible to develop modified polyesters with high polymerization degrees, and their melt spinning can be performed using the normal spinning method RTC.
Therefore, it is easy to carry out, and a high-strength cationic dye-dyeable polyester molded product can be easily obtained.

(2) Modified polyester copolymerized with quaternary phosphonium sulfonic acid salt has a serious drawback that it has poor heat resistance and colors the produced modified polyester and anti-breathing yarn yellowish brown, but the present invention improves the color tone. It is possible to obtain a modified polyester with excellent properties and high white discoloration.

(3) Since a cationic dye-dyeable polyester with high whiteness is obtained, when dyed with caron dye, it becomes a cationic dyeable yarn exhibiting significantly excellent clarity. Therefore, compared to conventional modified polyesters copolymerized with metal sulfonic acid salts or modified polyesters copolymerized with quaternary phosphonium sulfonic acids, the same level of cationic dyeability can be obtained with a smaller amount of dye.

(4) Because the dyeing clarity is improved, even if the amount of copolymerization of metal sulfonate or quaternary phosphonium sulfonate is reduced, it is possible to reduce the amount of copolymerization of metal sulfonate or quaternary phosphonium salt of sulfonate. It becomes possible to obtain cationic dyeability comparable to that of polymerized modified polyester.

(5) Regarding (1) K above, the modified polynisdel obtained by the method of the present invention has excellent spinnability Km, and the take-up speed is 3 ooom/min or more, especially 5 ooom/min.
Spinning is possible even at ultra high speeds of minutes or more. Also, 1
It is possible to spin ultrafine fibers of denier or less, and even 0.5 denier or less.

(6) Furthermore, the fibers obtained from the modified polyester of the present invention can be subjected to false twisting at high temperatures.

It is possible to provide excellent processed yarn without causing problems of strength reduction or fusion.

(7) Contrary to the fact that modified polyesters copolymerized with sulfonic acid metal salts are extremely prone to generating static electricity, the modified polyesters of the present invention exhibit excellent antistatic properties.

(8) Furthermore, since the modified polyester of the present invention contains a quaternary phosphonium salt, it has excellent twist resistance and antibacterial properties.

Note that the modified polyester of the present invention may contain optional additives, such as Catalyst 1 and color inhibitor, if necessary.

Heat resistant agent, retardant, antioxidant, matting agent 9 coloring agent.

Inorganic fine particles such as T101 may also be included.

<Example> Examples will be given below for further explanation. Parts and parts in the examples indicate parts by weight and % by weight, respectively.

The intrinsic viscosity (■) of the polymer was determined from the value measured in an orne chlorophenol solution at 35°C, and the softening point (sp) was determined by the penetration method. The hue of the polymer was indicated by the L value and b value determined by a Hunter color difference meter.

As for the L value, a larger value indicates good white skin, and b
The higher the value is on the + side, the stronger the yellowness is.

Examples 1 to 5 and Comparative Examples 1 to 4 100 parts of dimethyl terephthalate + ethylene glycol: l-
60 parts of sulfonic acid metal salt in the amounts listed in Table 1, 0.03 part of manganese acetate tetrahydrate (0.024 mole relative to dimethyl terephthalate), and 4 parts of cobalt acetate as a coloring agent.
0.009 parts of hydrate (0.00 parts per dimethyl terephthalate)
007 mol %) was charged into a transesterification tank, and the temperature was raised from 140° C. to 220° C. over 3 hours under a nitrogen gas atmosphere, and a transesterification reaction was carried out while the methanol produced was distilled out of the system. Subsequently, a 20% heated ethylene glycol solution of quaternary phosphonium salt of sulfonic acid in the amount shown in Table 1 was added to the obtained product, and after stirring at 220°C for 20 minutes, 56% of orthophosphoric acid was added as a stabilizer. % aqueous solution 0.03 part (
0.033 mol % based on dimethyl terephthalate) was added, and at the same time, expulsion of excess ethylene glyfur was started at elevated temperature. After 10 minutes, 0.7 timony dioxide was added as a polycondensation catalyst.
．． 0.04 parts (0.027 mol % based on dimethyl terephthalate) were added. When the internal temperature reached 240°C, expulsion of ethylene glycol was completed, and the reaction product was transferred to a polymerization vessel. Next, without raising the temperature, the reaction was carried out at normal pressure until the internal temperature reached 260°C, and then the reaction was carried out at 760 m11 over 1 hour.
The pressure was reduced from 9 to LmH9, and at the same time, the internal temperature was raised to 2801:1 over 1 hour and 30 minutes. The polymerization reaction was terminated after further polymerization for 2 hours at a polymerization temperature of 280'C under a reduced pressure of 111Hg or less. Table 1 shows the ω+SPt hue of the obtained polymer.

These polymers are melt-spun using conventional methods.

The fibers obtained by stretching the vines are dyed with cationic dye Cathilon C.
D-FRLH/Cathilon Blue CD
-FBLH=l/1 (manufactured by Hodogaya Chemical) 2
Dye bath containing %owf (31/l of Glauber's salt as auxiliaries, 0 acetic acid)
．． 3 g/l) for 60 minutes at 120°C. The clarity of the dyed fabric is not shown in Table 1.

Claims (1)

[Claims] (1) When producing a polyester by heating and reacting a difunctional carboxylic acid, mainly terephthalic acid, or its ester-forming derivative, and at least one alkylene glycol, at any stage before the completion of the reaction, The following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼・・・・・・(I) (In the formula, Z_1 is Aromatic group or aliphatic group, A_1 is an ester-forming functional group, A_2 is the same or different ester-forming functional group or hydrogen atom as A_1, M is a metal, and m is a positive integer). The following general formula (II) in an amount of 0.1 to 10 mol% based on the metal salt and the difunctional carboxylic acid component ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II) ( In the formula, Z_2 is an aromatic group or an aliphatic group, A_3 is an ester-forming functional group, A_4 is an ester-forming functional group or a hydrogen atom that is the same as or different from A_3, R_1, R_2
, R_3 and R_4 are the same or different groups selected from the group consisting of alkyl groups and aryl groups, and n represents a positive integer. ) A quaternary phosphonium sulfonic acid salt represented by
The total amount of the sulfonic acid metal salt and the sulfonic acid quaternary phosphonium salt is 0.5 with respect to the bifunctional carboxylic acid component.
A method for producing a modified polyester, which comprises adding the modified polyester in an amount exceeding 10 mol% and causing a reaction.