JPS59135223A - Production of modified polyester - Google Patents

Abstract

PURPOSE:To obtain a basic dye-dyeable modified polyester, by adding a solution containing a bishydroxyethyl ester of a 5-metalosulfoisophthalic acid and a bishydroxyethyl ester of a dicarboxylic acid to ethylene terephthalate and polycondensing the mixture. CONSTITUTION:The purpose modified polyester is obtained by mixing (A) an esterification product obtained by esterifying terephthalic acid with ethylene glycol (EG) at an esterification degree of above 90% and EG/terephthalic acid molar ratio of 1.07-1.4 with (B) an EG solution of 0.5-5mol of a reaction product obtaned by transesterifying a dimethyl 5-metalosulfoisophthalate with EG at a transesterification degree of above 95%, and (C) a bishydroxyethyl ester of a discarboxylic acid in amounts which can satisfy the inequalities (wherein mol- BHET is the number of moles of component C, and mol-SEIS is the number of moles of component B) and polycondensing the mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a basic dye using a polynisdel fractional surface esterification method.

In more detail, the method for producing modified and straight polyester has a small amount of noethylene glycol (IJEG) in the polymer and a small rise in nozzle pressure during the spinning process.

Conventional basic dyes dyed polyesters are dyed with 5-metal sulfoisophthalate (Jits) at the beginning of the transesterification reaction, i.e., the reaction between methyl terephthalate (D) and ethylene glycol (EG). 3.
However, this transesterification method requires a high cost for the raw material Dfs4'J?, and also requires a large amount of EG used in the reaction. Since the cost of recovering the added h2G is high, the cost of the produced polymer is high.On the other hand, recently, the direct Nisdellization method, which has a low production cost, has been developed. However, since there are still various difficulties in producing modified polyester, it is currently produced by the transesterification method.

The main reasons why modified polynisdel is not produced industrially by the direct esterification method are (1) die→)-i'+
- component his-hydroxyethyl ester of 5-metal sulfoisophthalic acid (DEIS, ) and y-:).

Poor compatibility with chilled products (2) Even if 818 with good compatibility and low reaction rate is added, it takes a long time to carry out the transesterification reaction. By producing DEG components,
(3) The unreacted 5-metal sulfoisophthalate (1'MV)
If (S) is left in the polymer, the nozzle pressure increases significantly during spinning, making it impossible to perform spinning for a long time.

On the other hand, as an example of a method for producing modified poly(Nistyl) using the secondary vehicle method, when the esterification rate of terephucuric acid-poor ethylene glycol is 80 to 98.5%, the metal sulfoisophthalate [sialyl ester of p] 'IO method (Unexamined Patent Publication, @5], -4179,5)
- A method of adding 20 to 90 mol % of lower alkyl ester of isophthalic acid containing sulfone-1 groups to hydroxyethyl ester (Japanese Patent Publication No. 56-99
37) and addition of two 2-human and j-tocinic c-full esters of isophthalic acid having a sulfone group with a reaction percentage of 40 to 74% to an oligomer with an average degree of polymerization of 240 to 9.0 by the direct method. -method of
922) and g have been proposed. In all of these methods, the dispersion of the modifier is improved by directly adding a mixture of dialkyl nitride or nitride of metal sulfoisophthalic acid to the nitride compound. In this case, the dialkylnisdale of metal sulfoinphthalic acid is directly transesterified in the sprued product after polymerization.However, the esterified product EG/
When the molar ratio of TPA is low (+91J, for example, 1.20 times the mole or less), the transesterification reaction rate is low, so that unreacted dialkyl ester of metal sulfoisophthalic acid remains in the polymer, causing an increase in nostle pressure during spinning. The result is a large polymer.Also, a reaction time of 1 hour is required to complete the reaction. A large amount of A:me, ■tan]G is produced as a by-product, resulting in a polymer with poor heat resistance and weather resistance. When is the problem?

If the molar ratio of EG/TPA of the esterified product is high, for example, 12 times or more, the ester father reaction will be more rapid than the previous one, but the reaction will still be completed. In order to do this, [this decreases over a long period of time, and the molar ratio increases and the rate of D hy O production also increases, so 1) EG becomes larger. Therefore, what is the method for adding a large amount of the dialkyl ester of a metal sulfoisophthal into an esterified product? 1. F magic 0 muni) TP
The reaction rate of A and gG is 75 to 90, and the reaction rate of 5-metal sulfoisophthalate to the esterified product with an EG/TPA molar ratio of 1.1 to 16 or less is 75 to 90, and the concentration is 25 to 90.
45φ, pi-15, fl) to 7.5 or less, a method has been proposed (Special Enclosure Sho 52-47098).In this case, 5-metal sulfoisophthalic acid The residual amount of dimethyl is relatively small, and the ``-Sdell exchange reaction time may be short.

This polymer has poor compatibility with stellated products and causes a significantly large increase in nozzle pressure during spinning. Furthermore, EG/T
Because the PA mosole ratio is large (G), there is a problem that the amount of D1 G darkness 11 is increased.

Therefore, the present inventors (to reduce the DEC content in the polymer,
The present invention was arrived at as a result of extensive research into a method for producing a high-quality modified polyester with excellent dispersibility of the modifier and a small increase in nozzle pressure during the spinning process using a direct polymerization method.

Part 1, the present invention uses ethylene terephthalate as the king constituent unit, and the 5-metal sulfoisofucric acid component as 0.5 to 5.0.
When producing a modified polyester that has been subjected to molar copolymerization by a direct polymerization method, terephthalate and ethylene glycol are directly used as raw materials for the Nisdell reaction to achieve a Nisdell reaction rate of 90 or more. Le component/Terephthalis component Q) - Esterified product HvD with an Ele ratio of 2107 to 1.40 is combined with 5-metal sulfoinfucurate dimenal♂ ethylene glycol with a transesterification reaction rate of 95% or more. Metal Survivor ζ Isophthal's hiss
The bishydroxyethyl ester of at least one dicarboxylic acid selected from terephthalic acid, isophthalic acid, and aliphatic carboxylic acid, which is an ethylene glycol solution of This is a method for producing a modified polyester characterized by polycondensation after adding an r-ethylene glycol solution mixed so as to satisfy (1).

10≦(mol-13)iE'l"1 mol-pt>I
S)≦50 (1) Here, mol-B1-JET is the total number of moles of his-hydroxyethyl ester of terephthalic acid, isophthalic acid, and aliphatic dicarboxylic acid; D E I S (
Well, it is the number of moles of bishydroxyethyl ester of 5-metal sulfinophthalic acid.

In the present invention, when a modifier is added directly to the ester, the reaction rate is preferably 90% or more, more preferably 95 to 99%. Also, 1゛; U/ '1
'l) The A molar ratio is preferably 1.07 to 1.40, more preferably 1.09 to 125. When the esterification reaction rate is 90% and the ratio of 1>GlTPA is 107, the polycondensation time is undesirably longer. Also, EG
/TPA molar ratio exceeds 140, free 1>(
Since there are a lot of ``,'', )E('' are produced in large quantities as by-products, which is not preferable.

On the other hand, in order to produce a polymer with a small increase in nozzle pressure during spinning, it is safe to add ethylene glycol ester of 5-metal sulfoisophthalic acid to the ester to form a random copolymer; 1 of the reaction rate with inphthalene or ethylene glycol
In the method of adding ethylene glycol bath solution of DEIS, the compatibility with the esterified product appears to be improved, but unreacted 1. ) +VS remains in the polymer, resulting in a polymer with a significantly large increase in nozzle pressure during spinning. The present inventors have arrived at the present invention by noting that the modified polyester produced by simultaneously adding D f14 S, D MT and jDG in the transesterification method has an extremely small increase in nozzle pressure. That is, it has a reaction rate of 95% or more with the bishydroxy ester of at least one type of dicarboxylic acid that is excluded from the group consisting of terephthalic acid, isophthalic acid, and aliphatic dicarboxylic acids.
Adding a modifier mixed with an ethylene glycol solution of S to the esterification reaction product. Made of quality polyester.

A mixed EG solution of bishydroxyethyl esters of terephthalic acid, inphthalic acid, and aliphatic dicarboxylic acids, and bishydroxyethyl esters of 5-metal sulfoisophthalates, which are added to the esterified product, can be mixed with alkyl esters of these dicarboxylic acids (e.g., dicarboxylic acid). (dimenal acid, dimesal isophthalate, dimethyl adipate, dimethyl sebacate, etc.) and methyl 5-metal sulfoisophthalate.

Sterol (for example, 5-sulfoisophthalate dimethyl sulfoisophthalate, 5-potassium dimethyl sulfoisophthalate, etc.), ethylene glycol, and ethyl exchange reaction catalyst ((crie is manganese acetate, 150-200''
It is better to react separately for 2 to 6 hours at C for 2 to 6 hours. I (J' of hishydroquine-L-nal ester of 5-metal sulfoiphthalic acid with a reaction rate of 95% or more with G bath enemy)
l (J solution 1 night after preparing each, mix and mix EG
It may be dissolved. However, in this case, it is preferable to stir well beforehand and heat the mixture at 100'C or higher, preferably (
It is best to stir and mix using a 150-200'C1 iron for 2 to 3 hours.

Modified 1 adhesion agent that has been A'A according to the present invention - ethylene cleaner 1
- When directly adding the esterified product to the molten liquid,
The E G / T 1' A molar ratio of the Nisder compound at the time of addition is 1.・Even if the modifier is less than 1, a uniform 7↓ Jζ′- can be obtained because the modifier is quickly dispersed in the ester 11-material. - If you get it, then add this modifier 1!
The content of the unreacted modifier 5-metal sulfoisophthalate is small, and the modifier is
Since there is no indispensability for carrying out the I-product ζ(NiU\7Jli)-extracted Viconis hole exchange reaction, a polymer with a small content of L)+]0 can be obtained. The amount of l)L to JS remaining in the poly-7 is small, resulting in a polymer with a small increase in nosule E force.

When adding the b2G molten modifier, the temperature of the Nisdell compound was set at 250' (
``+'' It is preferable to keep it at a temperature of 0.
Also, metal forming catalysts (for example, antimony dioxide, germanium dioxide, titanium butoxide, etc.) and other additives (
・If you cut it, TlO2, kaolin, 5in2. CaCU3
etc.) may be added up to the start of the 1st cup, but it is preferably added after the 19G melt of the modifier is added.

The polycondensation reaction may be carried out by a known method, and after adding the modifier EG solution a to the esterified product, the polymerization medium and Ti
After adding 02 etc., temperature increase and pressure reduction were started, and the reaction was 6 degrees 2.
80~290'O, degree of vacuum 005~05'L'orr
The polybutylation reaction can be carried out for 15 to 3 hours under these conditions.

The present invention will be explained below using Examples, but these Examples are not intended to limit the scope of the present invention.

In addition, the valley measurement was performed as follows.

The viscosity of the polymer is 0.2.9 of the crushed polymer 207
After dissolving it in M-Fresol, it was measured using a Uherote viscometer (trowel).

The amount of BHO in the polymer was measured using a gas flow (71) after the polymer was mixed with powdered bamboo using a human run.

The reaction rate of the esterified product is calculated from the 1st grade and the saponification value. Acid, 1 piece (or esterification, benzylic acid: I
After heating and dissolving it in a liquid, the NaOHi-Ct concentration was determined.

The laan compound was determined by preparing the 1-stellate compound (excessive after cutting off the 11\KO1-i ehnol and saponifying it by heating) with a normal solution of sulfur. , Determined with a 1 millimeter sharp color difference a ten (manufactured by 8 pieces '4 Yomi Koso Co., Ltd.) f:.

Examples] -111 Preparation of modifier 5-Putoliur\sulfoisophthalene dimethyl 290
・11 Dimenal terephthalate 194a, p, Dimenal isophthalate 582u, y, Ethylene glycol 3i
The 0000000000000000000000000000000000000000000000000000000000 reactor was charged into an ester reactor equipped with a 57n, 3's atomization tower and heated to 150'O. Sl・riumo, 2.4 is! and gradually increase to 7
The methanol produced as a by-product was removed from the thread. The reaction time was 5 hours, and the temperature was gradually raised to 95□C.
The by-produced methanol (312q) was collected, cooled to 100'0, the amount at which the C1 reaction was completed, and stored.

1- +21 Modified polymer - made by Shinshin I varnish (2-
[Nido-t-noxyenal)delenomere-1 and its low-abundance aggregates are present in the ester 1f, terephthalic acid, J-ethylene glycol old)E()7/''fPA molar ratio of 1.20 slurry~ A series of 5
Reaction pressure (+, 6.% G, inversely 1.isd degree 260゛ C1 residence time 2.3 hours mJ (here, the reaction rate is 92% ester δ, after that, the reaction pressure is normally used, inversely 1; i temperature 260
``C''-Methyl 1 mL (1 mL during retention)
jl OG/'IIJ'A cell ratio 1.0 in 1.8 hours
9. Continuously convert the esterified product with a reaction rate of 968% to 0.
5) Transfer 1832, 1! of (-) to a polymerization pot, and add the modifier 92511 prepared in 11) for 30 minutes to form a "Nisdel". Of course, the temperature is 250'C!I added it at a low temperature so that it does not exceed 250'C!○
Attachment 7 JDrβ winter ff barley self
After adding □ and 7q of acid 1hinatan to 071 of antimony dioxide and ethylene glycol slurry 14 +-, heating and decreasing If were started. Reaction mass production 280C, true
? -K O-I Tor "' Trowel J Time:1 habit
71 5) j anti-1. After drying, the polymer was stranded, held at 1 liter, cooled for 1 liter, and cut into chips with a cutter.

The obtained polymer contained 5-trifluoride/, 2.3 mol % of Zulpo Inonotal a, and 6 Innotal j1.
It is a copolymer of 9-Cru candy, and has an ηrel of 1.5.
16, L) EG 1,63 wt %, l, j [74,
2, a IMK-1,9, t] value 25, melting point 234°C
and i) A high quality polymer with a low E a content was obtained.

This polymer was grown in a rotary vacuum tank], 30'Q
,, Q, ] After vacuuming with 1 Torr trowel for 7 hours, use LOmm stainless steel vinegar net filter (325 mesh x 1 piece, 600 mesh x 1 piece, 60 mesh x 1 piece)
A polymer discharge amount of 31.2. ¥/””, Sp
An IT yarn/thread pressure rise skin speed test was carried out at 2ss°C, and the result was 1.8 grains/hr, which was good.

<Example 2> Implementation/Iri 11. In the same manner as L, 5-su[-dimenal sulfoisophthalate, 1) IS4T, isophthalic dimenal (1) + ~ 41), γ-dipine dimethyl (1)
After preparing a modifier by varying the amount of IVLA) added, an esterified product was added to carry out a polymerization reaction. In both cases, polymers with a small amount of D t t,:r and a small increase in nozzle pressure were obtained.

Example: 3- Preparation of il+ modifier Isophthalic acid 498 Tsugo ethylene glycol 714, f
/ were mixed and the esterification reaction was carried out for 4 hours at a reaction temperature of 200 - (2tt) (T, distilled water). 1) Umusulhoisonotal Dimenal 444Q Toethylene Glycol 930
A transesterification reaction was carried out by adding 04.5 liters of methanol and 04.5 liters of mankan and 922 g of methanol to the reaction mixture while keeping the temperature up to 50-195°C. UB). Next, reaction ti, A prepared in advance and reaction solution B i were mixed and heated at 170°C for 3 hours.
The mixture was further stirred and mixed for a period of time to prepare a modifier (3-1).

:3- (2+ Production of modified polymer Same as Example 1 (Esterification reaction rate 968, EG/'l)
Poly-7- was produced by adding 420 g of the modifier (3-1) to 1,920 g of the esterified product with a PA molar ratio of 1.09. The results are shown below.

Polymer ηrel 1.495 DEG 1
．． 47wt% Melting point 243"0 1. Value 782 a value -
A high quality polymer with a 2,1b value of 2.1 was obtained. In addition, the spinning nozzle pressure car 1-increase test was performed at 1.2~/hr.
In Example 1, dimethyl 5-sodium sulfoinphthalate and ethylene glycol were reacted without adding dimethyl terephthalate and dimenal ionofucrate. , ll; EG solution of ethylene glycol ester of 5-natoIJumsulfoiphthalic acid at a rate of 95% (
L) IIIS) was prepared. Next, in the same manner as in Example 1, 5-sodium sulvoinphenol was added to the oEIsB esterification reaction product ζ in an amount of 23 molar based on the total acid components in the polymer to produce -C polymer. did.

The results are shown below.O Poly? -ηrel 1.512 1) EQ 2,0
6 wt% melting point 246°CL1 direct 77.2 a
Although the appearance was good, i-2, Obli 2,5, the spinning nozzle pressure rise test I-6,0%/hr was extremely large, indicating that the modifier was not uniformly dispersed in the polymer. It turns out there isn't.

Claims (1)

[Claims] In producing a modified polyester by copolymerizing 0.5 to 5.0 mole of 5-metal sulvoinophthalate with ethylene delphucrate as the main structural unit by direct molding method. , a reaction rate of 90 to upper stell I was obtained by direct esterification reaction of terephthalic acid and ethylene glycol as raw materials.
% or more, the molar ratio r of enalene glycol component/'Te1/fucric acid component, 4-1.07 ~], 5-gold 4-sulfoiisonomel L-wave methyl and 5-metal sulfinophthalic acid bishydrinophthalic acid with ethylene 5"liny]-/shi ξ-1 to sprue father reaction rate 95φ-1- At least one bishydroxyethyl ester of carboxylic acid selected from the group consisting of -Cte1/phthalic acid, i'tsunotalic acid and J''+i rib group dicarboxylic acids in a manner satisfying the following conditions: A method for producing modified polynisdel, which involves stepwise polycondensation with the addition of an ethylene glycol solution mixed with ethylene glycol. ]0≦(mol−81month・〕〕T1mol−1IDIs)≦
50... (1) Where, mole B) 4ET is the total number of moles of hishydroxy ethyl ester of terephthalic acid, infuculoids, and carbonyl esters; mole D is the 5-metal Mole drink of hishydroxyethyl ester from Surpoinovkul city.