JPS62235324A - Production of polyester-polyether copolymer having high polymerization degree - Google Patents

Abstract

PURPOSE:To obtain the titled copolymer having good transparency and uniformity, by polymerizing an aromatic dicarboxylic acid, etc., 1,4-butanediol, etc., and polyalkylene glycol in the presence of a specific glycol and a catalyst of an organotitanium compound and lithium compound. CONSTITUTION:A dicarboxylic acid consisting essentially of an aromatic dicarboxylic acid, a glycol consisting essentially of 1,4-butanediol and a polyalkylene glycol having 400-6,000mol.wt. are polycondensed in the presence of at least one diol expressed by formula I (R1 and R2 are H or hydrocarbon or either one of R1 and R2 is hydrocarbon), formula II or III (R3 and R4 are H or hydrocarbon) and formula IV (R5 and R6 are H or hydrocarbon) and an organotitanium compound and lithium compound as a reaction catalyst to afford the aimed copolymer having good transparency and high polymerization degree.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for producing a highly polymerized polyester-polyether copolymer, particularly a dicarboxylic acid mainly containing an aromatic dicarboxylic acid, 1,4-butane Molten state made from glycols mainly containing diols and polyalkylene glycols with a molecular weight of 400 to 6,000.

and r! of a highly polymerized polyester-polyether copolymer with good transparency in a solution state. Regarding the A construction method.

[Prior Art] As a method for producing a polyester-polyether copolymer having aromatic polynisder as a hard segment and polyalkylene glycol as soft segments 1 to 1, dicarboxylic acid, glycol, and polyalkylene glycol are first subjected to an esterification reaction u. tightening, then polycondensation μ tightening,
The so-called direct polymerization method and the transesterification polymerization method in which dicarboxylic acid diesters, glycols, and polyalkylene glycols are first subjected to transesterification reaction and then polycondensation reaction are known, but these methods are disadvantageous in terms of raw material cost and by-product tetrahydrofuran. The former direct polymerization method is advantageous in terms of direct polymerization because it is easy to recover and reuse.

By the way, this direct polymerization method generally involves an esterification reaction ↑
1 and tetrahydrofuran (hereinafter, T
Various reaction catalysts have been investigated due to the large amount of by-products (called I-IF), and for example, n-type titanium compounds are known to be effective as Nisder conversion catalysts (14 Monsho). 52-18753, etc.).

When the esterification reaction of the polyester-polyether copolymer is carried out in the presence of a titanium compound as described above, the esterification reaction is accelerated and the amount of THF by-produced is reduced.

However, if an amount of the organic titanium compound is used in the esterification reaction in an amount sufficient to have a sufficient catalytic effect, turbidity due to the organic titanium compound will occur in the resulting polymer, making it opaque in the molten state or solution state. . Therefore, in order to eliminate the disadvantages of overcasting, for example 1? J Kaisho 5
In Publications No. 7-38817@ and JP-A No. 57-38819, when specific diols or polyhydric alcohols are used together with an organic titanium compound as an esterification catalyst, the esterification reactivity based on the organic titanium compound can be improved. - At 7f゛μ, the molten state of the produced polymer.

Alternatively, although it has been described that the opacity in a solution state is certainly improved, the polycondensation reactivity cannot be said to be sufficiently satisfactory.

In other words, the polyester-polyneedle copolymer has
Because the polyether component is included, the reactivity is essentially inferior to that of ordinary aromatic polyester polycondensation, and on the other hand, the mechanical properties of polyester-polyether copolymer molded products, 14 Breaking strength, tensile strength, abrasion resistance, etc. are mainly controlled by the degree of polymerization of the polymer, so in order to obtain a high quality polyester-polyneedle copolymer, it is essential to increase the degree of polymerization of the same polymer. .

In this way, the small condensation reaction of a polyester-polyether copolymer is only possible if the reaction rates are close, and even if reaction 11.1 is simply prolonged to compensate for the polycondensation, the polyether component It is extremely difficult to increase the degree of polymerization of polyester-polyether copolymers because they are susceptible to thermal decomposition.Therefore, in the production of polynisder-polyneedle copolymers by the direct polymerization method, it is difficult to increase the Nisderization reactivity using a reaction catalyst. The improvement in 'b', as well as the transparency of the produced polymer in the molten state, probably in the solution state, is a problem in the !P period in this technical field.How to prevent the small condensation reaction t'[ This was seen as an issue that needed to be solved.

[Problems to be Solved by the Invention] The purpose of the present invention is to solve the above-mentioned drawbacks of the prior art, and to improve the esterification reactivity and melting of the produced polymer in the production of polyester-polyether copolymers by direct polymerization. The objective is to improve the polycondensation reactivity as well as to improve the transparency in the state or solution state. Another objective is to improve the quality of the polyester-polyether copolymer by increasing the degree of polymerization.

[Means for Solving the Problems] The above-mentioned object of the present invention is to obtain dicarboxylic acids mainly including aromatic dicarboxylic acids, glycols mainly including 1,4-butanediol, and polycarbonyl 1-
When producing a polyester-polyether copolymer from lengelicol, the following general formula (I>, (I),
This can be achieved by using an organic titanium compound and a lithium compound as reaction catalysts in the presence of at least one of the diols represented by (1) and (IV). .

R1 (I> 1-100th 2-C-CH20f-(1
R2 R1R4R2 (However, R1, R2, R3, R4, R5.

and R6 is hydrogen or a hydrocarbon group, and R
At least one of 1 and R2 is a hydrocarbon group. ) The structure of the present invention will be explained below. First, in producing a polyester-polyether co-polymer by the direct polymerization method in J3 of the present invention, a reaction catalyst is added in the presence of a specific diol compound as a clarifying agent for the produced polymer. We will discuss the combined use of an organic titanium compound and a lithium compound.

In this case, the diol compounds used as the clarifying agent include the general formulas (I>, (II), and (1)).

A diol compound represented by (II), specifically neopentyl glycol, 2-methyl-1-rimedylene glycol, 2-methyl-2-ethyl-1-rimedylene glycol, and propylene glycol.

2,3-butanediol, 1,2-cyclobeki1nanediol, 1,3-butanediol, 2,3-butanediol.

3-methyl 2,4-bentanediol, 2-ethyl 1,
Among these, examples include 3-hexanediol.

In particular, neopentyl glycol, 1,3-butanediol, 2,3-butanediol, 3-methyl 2,4-pentanediol, and 2-ethyl 1,3-hexanediol are preferably used.

The amount of the diol compound added is 5.0 to 1 Kyoko of titanium of the organic titanium compound used as a reaction catalyst.
70 moles, especially 20 to 50' Tyl mole, is preferred. If this is less than 5.0 times by mole, the transparency improvement effect is insufficient, and if it is more than 70 times by mole, the transparency effect is saturated, and the diol compound is copolymerized, resulting in a decrease in the polymer melting point. This is undesirable as it causes hair loss, hair loss, etc.

The above diol compound is usually added to the reaction system in a form mixed with the reaction catalyst, but is not particularly limited thereto.

In addition, as an organic titanium compound used as a reaction catalyst for esterification reaction or polycondensation reaction, (R10) n
T i (OR2) 4-n [where R1 and R2 are aliphatic, alicyclic, or aromatic hydrocarbons having 1 to 10 carbon atoms, and n is 1
to 3 (including decimals). ] It is a titanic acid ester represented by the following, specifically methyl ester of titanic acid, tetra-n-propylnisal,
Tel~lysob mouth pill ester, de1~ra! 1-butyl ester, tert-butyl ester, tert-butyl ester, Schiff 1]hexyl ester, phenylconistyl, benzyl ester, I-lyl ester, or alkyl mixed ester thereof, d3
and reaction products of these with alkylene glycols. Among these, especially de1-ra n-propyl ester, tetra-n-propyl ester, tetra-n-
Butyl esters are preferably used.

Such an organic titanium compound usually has a titanium atomic weight of 0.001 to 0.04 2 degrees, based on the produced polymer.
Preferably, the organic titanium compound is added in a range of 0.003 to 0.03% before or at the beginning of the Nisdellization reaction, but the organic titanium compound is not only added to the Nisdellization reaction but also for the polycondensation reaction. Since it has a strong catalytic effect, it is preferable to add it at the latter stage of the Nisdell formation reaction or the early stage of the polycondensation reaction.

At this time, the amount of the organic titanium compound added is 0°0011
When ff is less than 1%, the effect as a catalyst for esterification reaction or polycondensation reaction is insufficient, the Nisdell reaction time for IS is prolonged, and the amount of by-product of 1 to 1 F increases. On the other hand, if the amount added is 0.04% by weight or more, the catalytic effect is saturated, the required amount of the transparency improver increases, and the color tone and heat resistance of the polymer deteriorate, which is not preferable.

In addition, T l-1F, which is produced as a by-product by increasing Nisderization reactivity,
In order to suppress the deactivation of the organotitanium compound and obtain a polymer with good transparency, in addition to the above organotitanium compound, a monoalkyltin compound, a monoaryltin compound, a sialgyltin compound, a diaryltin compound, trialkyltin compounds, triaryltin compounds,
An organic tin compound such as a detraalkyltin compound can be used within a range of 0.05 to 2.0 as the ratio of tin atoms to titanium atoms in the organic titanium compound.

As the lithium compound to be used with the Tul titanium compound 91, those soluble in the reaction system are preferably used, such as cuticum acetate, lithium sulfate, sodium citrate, and dizoic acid. lithium.

Weak acid salts of lithium such as lithium rA oxide, lithium sulfate, lithium borate, lithium phosphate, inorganic acid salts such as lithium chloride 1, and lithium hydroxide.

Lithium Alcola-1~, Lithium Phenocou 1~
There are 29 examples. Of these, weak acid salts of lithium are particularly preferred.

Such a lithium compound may coexist with the organic titanium compound particularly in the condensation reaction system, and therefore, the lithium compound should be used in an amount of 0.0002 to 0.3% by weight based on the resulting polymer.
, preferably O,OO'l to 0.2% by weight, and more preferably 0.2% by weight of lithium to the titanium atoms of the organic titanium compound present in the polycondensation system. The IE compound or more may be appropriately added together with the organic titanium compound or separately from before the esterification reaction to the early stage of the polycondensation reaction.

At this time, if the amount of the lithium compound added is below the lower limit of the above range, the desired improvement in polycondensation reactivity cannot be expected, whereas if it is added above the upper limit, the polymer will warp and thermal decomposition of the polymer will be accelerated, which is not preferable.

Next, the configuration of the present invention other than the above will be described.
The dicarboxylic acid according to the present invention is a dicarboxylic acid containing at least 50 mol% of aromatic dicarboxylic acid, and the aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid M, 1 ．．
5-naphthalene dicarboxylic M, 1,2-bis(phenoxy)ethane p, p'-dicarboxylic acid, Schifnyl p,
p-dicarboxylic acid and the like are preferably used. Among these aromatic dicarboxylic acids, terephthalic acid and isophthalic acid are preferably used, and the terephthalic acid is not only a so-called high-purity prephthalic acid, but also contains acetic acid impurities (approximately 0.0 .3 wt. Aliphatic dicarboxylic acids.

Alternatively, an alicyclic dicarboxylic acid can be used in an amount of less than 50 mol%.

Further, the glycol is a glycol containing at least 70 mol% of 1,4-butanediol, such as conidylene glycol, 1,3-propanediol, 1,6-butanediol, etc.
-to421nanediol, dielene glycol, 1~
Less than 30 mol % of glycols having a molecular size of ♀300 or less, such as litylene glycol and 1,4-cyclohexanedimethanol, may be used in combination.

Furthermore, polyalkylene glycols having a molecular weight of 400 to 6,000 include polyethylene glycol, poly[I pyrene glycol, bolide 1-ramethylene glycol 1-ol, J3
J: and copolymers thereof, and polyalkylene glycol copolymers containing polytetramethylene glycol and tetramebrene A oxide units as main components are particularly preferably used.

If the molecular weight of the polyalkylene glycol is less than 400, the pro-roughness of the polyester-polyether copolymer will decrease, resulting in undesirable effects such as a decrease in the polymer melting point, and the molecular weight of the polyalkylene glycol
If it is more than 000, the resulting polymer tends to become opaque, which is not preferable. A small amount of trifunctional or higher polyvalent carboxylic acids such as p-(β-hydroxyetho:1;shi)benzoic acid, p-oxymedylbenzoic acid, 1-limellitic acid, trimesic acid, pyromellitic acid, etc. It can also be used.

A dicarboxylic acid mainly consisting of such an aromatic dicarboxylic acid, 1
, 4-butanediol, J3, and polyalkylene glycol having a molecular weight of 400 to 6,000.

It is desirable that the molar ratio of glycol to dicarboxylic acid (glycol/dicarboxylic acid) used in reaction initiation 11.1 is 2°2 or less, preferably 1.2 to 2.0.If necessary, start the esterification reaction. A more desirable embodiment is to further add glycol at any stage after the reaction to maintain the glycol m (glycol/dicarboxylic acid 1 molar ratio) in the reaction system within the range of 1.2 to 1.8. At this time, if the molar ratio of the amount of glycol is less than 1.2, the esterification reaction is difficult to complete, and if it exceeds 2.2, the reaction itself is completed, but the T I-I of the 1,4-butanediol component Conversion to F is significant, and performance in producing a polyester-polyether copolymer is disadvantageous.

Also, the usage ratio of polyalkylene glycol to dicarboxylic acid (polyalkylene glycol/dicarboxylic acid;
(parts by weight) is preferably 0.1 to 5.0 times, and according to the rule 131 of addition, it is added at any stage from before the start of the esterification reaction to the start of the small condensation reaction.

Next, the esterification reaction humidity is 150-245°C.
It is best within the range of 245°C, especially above 245°C.

The decomposition of 1,4-butanediol becomes more intense and T I-
This is not preferable because the amount of by-product of IF increases.

The esterification reaction is usually carried out under normal pressure, but it can also be carried out under reduced pressure.

The esterification reaction product obtained in this way is subsequently subjected to a polycondensation reaction, but the conditions for the small condensation reaction are not particularly limited, and may be the reaction conditions used for the production of ordinary polyester-polyether copolymers. It can be used as it is, for example, the reaction temperature is 230 to 255
C., preferably 235-250.degree. C. conditions are employed.

In addition, various additives such as glossing agents, optical brighteners, stabilizers, ultraviolet absorbers, flame retardants, antistatic agents, A crystal nucleating agent or the like may be added as appropriate.

[Effects of the Invention] As described above, in the invention, in the production of a polyester-polyneedle copolymer, an organic titanium compound and a lithium compound are used as a reaction catalyst in the presence of a specific diol compound. If this is followed, the resulting polymer will have little turbidity when melted, will have excellent transparency in the melted state or solution state, and will have a high degree of polymerization.

Such high-degree polymerization polymers with excellent transparency do not contain insoluble foreign substances, so they have fewer defects in the polymer and less variation in mechanical properties.In addition, lowering of the melting point of the polymer is a practical problem. The effects brought about by the present invention are obvious, such as to the extent that there is no problem.

Note that the improvement in polycondensation reactivity of J in the present invention is achieved in a reaction system in which the deactivation of the organic titanium compound by the diol compound is suppressed as much as possible, and the catalytic effect of the polycondensation reaction of the lithium compound is expected. It is determined that 11F is the result of more than Il1.

The present invention will be specifically described below with reference to Examples.

The polymer properties in this example were measured by the following method.

(1) Relative viscosity 1 polymer ε3. g was dissolved in 100rnl of orthochlorophenol (dissolution conditions: 100°C, about 1135 minutes), allowed to cool, and measured at 25°C using Oss 1 to Wald viscosity h1.

(2) Solution Haze Poly 75.49 was dissolved in 40 mN of phenol/tetrachloroethane mixed solvent (mixing ratio 6:4) (dissolution conditions: 100°C,
After cooling for about 1 hour), the mixture was cooled using an integrating sphere turbidity colorimeter (Nippon Seimitsu Kogaku, type S13P-1-1-2).
'Measured using a 10mm glass rail. Solution haze (%)
The total C↑ can be calculated from the following formula.

Solution haze (%) = (diffuse transmitted light/untransmitted light) (3) A polymer layer heat-treated at a softening point of 70°C for 3 hours was measured using a Pennel-D meter (thickness was measured at a heating rate of 10°C/min). 3mm
The softening point is defined as the temperature at which the chip deforms by 0.1 mm).

(4) Note that the term ``part'' refers to an extended part.

Example 1-〇, Comparative Examples 1-5 Terephthal 154.2 parts, 1,4-butanediol 50
．． 0 parts, polytetramethylene glycol with molecule rj:z 1000, 31.0 parts, tetrabutylditanate (the amount added is listed in Table 1), J: and the diol (clarifying agent) from Table 1. The mixture was charged into an esterification reaction vessel equipped with a rectification column and a TI stirrer, and the esterification reaction was carried out while gradually warming from 160°C to 230°C, and the produced water and TIIF were distilled off through the rectification column. .

The time required until the esterification reaction was completed and undissolved terephthalic acid ceased to exist was between 3.5 and 4°.

After the esterification reaction was completed, 1 to 0.06 parts of tetrabutyl rapeseed as a polycondensation catalyst was dissolved in 1,4-butanediol and added, and the lithium compounds shown in Table 1,
and "I RGANOX" 1010 (manufactured by Ciba-Geigy) >0.01 part was suspended in a small amount of 1.4-butanediol and added.

Next, the esterification reaction product was transferred to a polycondensation reactor, and the pressure was gradually reduced from normal pressure to 1.0 mm and 11 g or less over a period of 1114 hours.
45°C, 'l, Qmml 1g or less, 3.51. '
Polycondensation between J was carried out. Table 1 shows the degree of polymerization level (relative viscosity) and transparency (solution haze) of the resulting polymer when the polycondensation time was kept constant. It is observed that only in systems in which , and a lithium compound coexist, the resulting polymer has a high degree of polymerization and has good transparency.

Examples 7-11, Comparative Examples 6-8 38.7 parts of prephthalic acid, 12.9 parts of isophthalic acid, 1
, 50.4 parts of 4-butanediol, 34.8 parts of polytetramethylene glycol with a molecular weight of 1000, 0.06 part of tetrabutylditanate (mo of titanium atoms relative to the resulting polymer, 0085 WT%), 7-n- 0.03 parts of butyl-monohydroxytin oxide, J3 and the diols of Table 2 (clarifiers).

The Lidzum compound was subjected to an esterification reaction in the same manner as in Example 1. The time required until the esterification reaction was completed and undissolved terephthal KiJ3 and isophthalic acid ceased to exist was 3.5 hours.

After completion of the esterification reaction, a small amount of 0.05 part of tetrabutyl titanate 1", the lithium compound shown in Table 2, and "I RGANOX" 1010 (manufactured by Ziba-Geigy Co., Ltd.) as a polycondensation catalyst. Suspend in 1,4-butanediol and add.

Next, the Nisderization reaction product was transferred to a polycondensation reactor, and the pressure was gradually reduced from normal to 1 g to 1 g, Qmml, and heated to 245°C in 11.1. Polycondensation was carried out for 3.5 hours at 0 mm 1 l (l) or less. Polymerization degree level (relative viscosity) and transparency (solution haze) of the produced polymer of 1!:1 with constant polymerization time ) are shown in Table 2.

Claims (1)

[Claims] Dicarboxylic acids, mainly aromatic dicarboxylic acids, 1,4-
Glycol mainly composed of butanediol, and molecular weight 4
When producing a polyester-polyether copolymer from a polyalkylene glycol of 00 to 6000, the presence of at least one diol represented by the following general formulas (I), (II), (III), and (IV) Below, a method for producing a highly polymerized polyester-polyether copolymer with good transparency, characterized in that an organic titanium compound and a lithium compound are used as reaction catalysts. (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. Yes▼ (However, R_1, R_2, R_3, R_4, R_5,
and R_6 is hydrogen or a hydrocarbon group, and at least one of R_1 and R_2 is a hydrocarbon group. )