JPS61197627A - Production of thermoplastic polyester - Google Patents

Abstract

PURPOSE:To improve the rigidity, etc., of a polyester, by adding specified particles, a metallic compound and a phosphorus compound to the reaction system in the production of the polyester from 1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylic acid and a glycol. CONSTITUTION:A polyester is produced by reacting 1,2-bis(2-chlorophenoxy) ethane-4,4'-dicarboxylic acid (alkyl ester) with 1.5-10mol, per mol of the acid component, of a glycol. At this time, 0.005-5wt%, based on the obtained polyester, inorganic particles containing an element of Group II, III or IV of the periodic table of the elements (e.g., alumina or calcium carbonate) are added to the reaction system. By adding a glycol-soluble metal compound M (e.g., magnesium acetate) and a phosphorus compound P (e.g., phosphoric acid or trimethyl phosphate) at a molar ratio of 0.3<=M/P<=10 to the reaction system, the purpose thermoplastic polyester can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a method for producing a high degree of polymerization thermoplastic polyester containing inorganic particles and having high rigidity and excellent heat resistance.

[Prior art and its problems]

Polyethylene terephthalate has excellent mechanical properties, heat resistance, weather resistance, and electrical insulation resistance, so it is widely used in films, fibers, and other molded products. However, in recent years, in the field of film, there has been a trend toward smaller and lighter equipment in fields such as magnetic recording media such as magnetic tapes and magnetic disks, and capacitors. The need for film is becoming stronger. Furthermore, in the textile field, fibers with high elastic modulus are required for industrial material applications. In order to meet these demands, various attempts have been made to improve the modulus of elasticity by modifying polyethylene terephthalate, but no satisfactory results have been obtained.

On the other hand, polyethylene 1,2-bis(2-chlorophenoxy/)ethane-4,4'-dicarboxylate is a polyester material that relatively meets the above-mentioned required properties.
This is proposed in Publication No. 9-1795. However, when polyester was produced by the method disclosed in the above publication and used for magnetic tapes and capacitors, the running properties of the film were insufficient. Therefore, for the purpose of improving running properties, a method of adding a surface protrusion forming agent during film formation of the polyester was proposed in JP-A-59-38031. However, although the method disclosed in the above-mentioned publication improves the runnability of the resulting film, it has the disadvantage of producing relatively coarse protrusions on the film surface.

As a result of intensive studies on these drawbacks, the present inventors have discovered that the above drawbacks can be significantly improved by adding inorganic particles under specific conditions in the polyester manufacturing process, and have arrived at the present invention. .

[Object of the Invention] The object of the present invention is to provide a method for producing polyethylene-1,2-bis(2-chlorophenoquine)ethane-4,4'-dicarboxylic acid with improved dispersibility of inorganic particles. Our goal is to provide the following.

Another object of the present invention is to provide a polyester with high rigidity and excellent heat resistance, which has a smooth surface and improved runnability when used in films, and is less prone to troubles such as yarn breakage when used in fibers. .

[Structure of the invention]

The object of the present invention is to produce a polyester from glycol and at least one of 1,2-bis(2-chlorophenoxy)ethane-4,47-dicarboxylic acid and hysonoalkyl ester, Inorganic particles containing at least one element from Groups ■, ■, and ■ of the Periodic Table of the Elements in a reaction system in which 1.5 to 10 times the mole of glycol (referred to as glycol molar ratio) to the alkyl ester is present. is added in an amount of 0.005 to 5% by weight to the resulting polyester, and the molar ratio C-p of the glycol-soluble metal compound to the phosphorus compound is set to 0.3≦
This can be achieved by a method for producing thermoplastic polyester characterized by adding i≦10. Here, M represents the number of moles of the glycol-soluble metal compound per 1062 polyester, and P represents the number of moles of the phosphorus compound per 1062 polyester.

Glycols used in the present invention include lower alkylene glycol, cyclohexanedimethanol xylylene glycol, etc. Among them, ethylene glycol,
Butanediol is preferred.

Furthermore, in addition to the above-mentioned dicarboxylic acid or its ester and the above-mentioned ethylene glycol in the present invention, a small proportion of other compounds having ester-forming ability can also be copolymerized. For example, succinic acid, adipic acid, succinic acid, terephthalic acid, inphthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, hexahydroterephthalic acid, 1,2-bis(phenoquine)
Ethane-4,4'-dicarboxylic acid, 1,2-bis(2,
Dicarboxylic acids such as 6-cyclophenoquine)ethane-4,4'-dicarboxylic acid, 1-(chlorophenoxy)-2(phenoxy)ethane-4,4'-dicarboxylic acid, and their ester-forming derivatives and polyethylene Glycol, polypropylene glycol, hexamethylene glycol, 1,4-cyclohexane-dimetatool,
Dioxy compounds such as diethylene glycol, neopentyl glycol, bis(β-hydroxyethoxy)bisphenol A, oxycarboxylic acids such as p-(β-oxyethoxy7)benzoic acid, and their ester-forming derivatives are used, but in particular Preferred are 1-(2-chlorphenoquine)-2(phenoquino)ethane-4,4'-dicarboxylic acid and ester-forming derivatives thereof.

The inorganic particles used in the present invention are particles containing at least one element of groups ①, ②, and ② of the periodic table, and specifically, carbonates, sulfates, phosphates, and oxides of group n. ,■
, group Ⅰ oxides, and the like.

More specifically, CaCOx, MgO0g, C! aso
a, BaSO4, Bag(PO4)z, Ca(H2PO
4) 2, CaHPOa, Ca3(PO4)2, MgO1
A120sx SiO2* Ti02tzro2
, kaolinite, and two or more of these may be used in combination. The average diameter of the primary particles of such a compound is 2
-5000mμ is preferable, more preferably 5-10
00 ncμ.

If the average diameter of the secondary particles is less than 2 mμ, the particles in the polymer tend to aggregate, and the viscosity increases in the polycondensation step, making it difficult to obtain a polymer with a uniform degree of polymerization. In addition, when used as a film, the surface unevenness of the film is small, making it difficult to obtain sufficient slipperiness4. On the other hand, if the average diameter of the secondary particles exceeds 5000 mμ, the surface flatness of the film and fibers will deteriorate. become scarce.

Further, the amount of inorganic particles added needs to be from o, oos to 5% by weight based on the polyester obtained.

The thus obtained polyester to which inorganic particles have been added can be used as a so-called master polymer, which is blended with polyester that does not substantially contain inorganic particles, or it can be used as a so-called homogeneous polymer, in which only the polyester to which inorganic particles have been added is used alone. You can also use

When yarn spinning or film forming is performed as a homogeneous polymer, the content of inorganic particles is preferably 0.05 to 1% by weight based on the resulting polyester. If the content of inorganic particles is less than 5% by weight of OO, the resulting film and fibers will not have sufficient slipperiness, and if it exceeds 1% by weight, the flatness of the resulting films and fibers will be impaired.

On the other hand, when used as a master polymer for fiber or film production, the amount of inorganic particles added is 0.000000000000000 with respect to the resulting polyester.
1 to 5% by weight is preferred. Addition amount of inorganic particles is 5% by weight
If it exceeds this amount, the added inorganic particles tend to aggregate, making it difficult to obtain a polymer with uniform dispersibility.

Further, it is preferable that the content of inorganic particles in the film or fiber obtained by blending the master polymer is from o, o o s to over 1 weight.

As the form of addition of the above-mentioned inorganic compound to the reaction system, slurry is preferably used as the slurry medium, such as water, methanol,
Examples include ethylene glycol/L/, 1,4-butanediol, neopentyl glycol, propylene glycol, diethylene glycol, etc., but it is preferable to use the same glycol as used as a polyester raw material and copolymerization component.

Further, the slurry may contain a polyester catalyst, a heat stabilizer, an oxidative deterioration inhibitor, an ultraviolet absorber, a wax, and the like.

It is more preferable to add these inorganic particle slurries to the reaction system after pretreatment such as mechanical dispersion using ultrasonic waves or high-speed stirring, and chemical dispersion using an ammonium compound or an alkali metal compound. Although there is no restriction on the timing of addition of the inorganic particles of the present invention, it is desirable to add them from before the start of the esterification reaction and transesterification reaction to the early stage of polycondensation of the polyester low polymer after the reaction.

Glycol component of the reaction system to which inorganic particle slurry is also added,! =1.2-bis(2-chlorophenoxy)ethane-
The molar ratio of glycol to 4,4'-dicarboxylic acid and its alkyl ester is 1.5 to 10, more preferably 2 to 8, even more preferably 3 to 6, including the glycol component entrained as m-particle slurry. be. When the glycol molar ratio is less than 15, the added inorganic particles aggregate,
On the other hand, if the glycol molar ratio exceeds 10, diethylene glycol will be produced as a by-product during the polymerization process, lowering the softening point of the resulting polymer and further increasing the load on the rectification column, which is undesirable.

As the glycol-soluble metal compound used in the present invention,
Examples include acetates, oxalates, etc. of magnesium, manganese, calcium, lithium, sodium, potassium, etc., rogens, hydroxides, aliphatic carboxylates, alcoholades, and the like.

More specifically, magnesium acetate, manga/acetate, cal/rum acetate, lithium acetate, potassium acetate, sodium acetate, magnesium/um oxalate, manganese oxalate, 7
Carunium oxalate, /Lithium oxalate, /Potassium oxalate, Sodium oxalate, Magnesium chloride, Calcium chloride, Manganese chloride, Lithium chloride, Potassium chloride,
Sodium bromide, magnesium hydroxide, cal/rum hydroxide, manganese hydroxide, lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium propionate, lithium propionate, sodium ethylate, potassium glycolate, etc. may be mentioned. Although two or more of these may be used in combination, magnesium compounds and manganese compounds are particularly preferred.

The amount of the glycol-soluble metal compound used in the present invention is preferably 0.1≦M≦50, more preferably O,5≦M≦40, and further preferably 1≦M≦30.

In the formula, M is a glycol-soluble metal compound polyester 1
When M is within the above range, the added inorganic particles have good dispersibility, the polymer has good thermal stability, and is evenly distributed.

Furthermore, since delay in reaction time can be prevented, productivity is also good.

There is no particular restriction on the timing of addition of the above-mentioned metal compounds, but before the start of esterification and transesterification reactions,
It is desirable to add the low polymer after the reaction at an early stage of polycondensation.

As the phosphorus compound used in the present invention, one or more selected from phosphoric acid, phosphorous acid, phosphonic acid, lower alkyl esters and phenyl esters thereof can be used. Specifically, phosphoric acid, trimethyl phosphate,
Phosphate esters such as triethyl phosphate, triphenyl phosphate, acidic methyl phosphate, phosphorous acid, phosphorous acid esters such as trimethyl sulfite, triethyl phosphite, methylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid Acids, phosphonic acid esters such as methylphosphonic acid methyl ester, phenylphosphonic acid methyl ester, phenylphosphonic acid ethyl ester, and benzylphosphonic acid phenyl ester can be mentioned.

The molar ratio (M) of the metal compound and phosphorus compound used is a,
It is necessary to set 3 × M × 1n, and more preferably P- is a, 5<M<7, and even more preferably 0.8≦M≦5.

If -P-, Py exceeds 10, the obtained polymer may be colored, the viscosity may decrease during melt extrusion for spinning or film-forming, or even coarse particles may be formed due to catalyst residue. This produces defects on the surface of films and fibers obtained by processing the polyester. On the other hand, if y is less than 065, the added inorganic particles will become coarse, resulting in an increase in furnace pressure and loss of smoothness when made into threads and membranes.

These phosphorus compounds may be added at the same time as the metal compound or may be added first.

The reaction product thus obtained is heated to 220 to 30
The polycondensation reaction can be carried out at 0°C.

〔Effect of the invention〕

The method for producing polyester of the present invention provides the following effects.

(1) A highly rigid polyester with good particle dispersibility can be obtained.

(2) Since the increase in viscosity during polycondensation due to the surface activity of inorganic particles is moderated, it is possible to obtain highly rigid polyester with low viscosity and graininess with good reproducibility.

(3) The film made of polyester obtained according to the present invention has high rigidity even in a thin film, as well as flatness and slipperiness, compared to polyethylene terephthalate film and the like.

When used in magnetic tapes such as metal tapes and vapor-deposited tapes, base films for magnetic disks, and base films for capacitors, films like Kono are extremely effective in making equipment more compact and improving their performance. Process passability in the process is also improved.

(4) Furthermore, when polyester is molded into fibers, fibers with a high modulus of elasticity can be obtained and can be effectively used for various purposes including industrial materials. Further, troubles such as yarn breakage can be prevented, and high-speed spinning is possible.

The present invention will be described in detail in the following examples.

In addition, parts in Examples are parts by weight, and the measurement method of each characteristic is as follows.

(Put 10 μ of dispersed chips of 11 particles between two cover glasses,
Prepared preparations were prepared by melt pressing at °C, and were evaluated by microscopic observation based on the number of coarse agglomerated particles present according to the following criteria.

Note that the term "coarse agglomerated particles" as used herein means coarse particles of 5 microns or more that are composed of a plurality of particles. Also, A
, B is the passing rank.

Rank Number of coarse agglomerated particles A Less than 10 pieces/- B 10 to 30 pieces/111 0 31 to 50 pieces/- D 51 to 100 pieces/+*j (2) Polymer color tone continuous color difference meter (Suga Test Instruments Co., Ltd.) It was measured in the form of a chip, and expressed as b value ()/inter value).

(3) Using a polymer viscosity high-speed 70-tester, at 290°C and at a sliding speed of 200
The melt viscosity in "sec" was measured.

(4) Softening point Measured with a venetrometer.

(5) Young's modulus measured at 25°C and 65°C using an Instron type tensile tester according to the method specified in ASTM-D-882.
Measured in %R,H.

Example 1 1,2-His(2-10 lphenoxy)ethane was charged into a reactor equipped with a rectification column and a stirring device, and the total M ratio was 3.2.
) and the temperature was gradually raised from 185°C to 240°C over 4 hours while stirring. The distilled methanol was continuously extracted from the rectification column to the outside of the system to complete the reaction, and the reaction rate was 99.0%.

This was followed by 0.04 m of trimethylphosphate (M=
1.6) After adding 0.02 parts of antimony trioxide, the low polymer was transferred to a polycondensation reactor, and a polycondensation reaction was carried out under reduced pressure for 3 hours.

The final temperature was 295°C, the degree of vacuum was 0.2 mmHg, and the stirring torque was 5 kq/crI.

The viscosity of this polymer was 2800 voids, and the added inorganic particles had good dispersibility.

Examples 2 to 5, Comparative Example 1 Stirring torque was 5 kg/ctil using the same method as Example 17 except that the type and amount of added inorganic particles were changed.
Polycondensation reaction was carried out until /C was obtained to obtain the polymers shown in Table 1. According to the method of the present invention, polymers with good dispersibility of the added inorganic particles are obtained.On the other hand, the amount added is within the range of the present invention. If it exceeds 100%, the resulting polymer has a low melt viscosity due to thickening during polycondensation, and many aggregates of the added inorganic particles are observed.

Examples 6 to 8 and Comparative Examples 2 to 3 Polycondensation reactions were carried out in the same manner as in Example 1, except that the amount of the metal compound added was changed, and the polymers shown in Table 2 were obtained. When Tk was smaller than 0.3, the polycondensation reaction was slow and the dispersibility of the added inorganic particles was also insufficient. On the other hand, when p exceeds 10, the polymer becomes colored and contains many coarse aggregates.

The following margins Examples 9 to 11, Comparative Examples 4 to 5 1.2-bis(2-chlorophenoxy7)ethane-4,4
A polymer was obtained in the same manner as in Example 1, except that the amount of ethylene glycol added at the same time as dimethyl '-dicarboxylate was changed. The results are shown in Table 3. When the glycol molar ratio is less than the range of the present invention, the added inorganic particles aggregate, while when the glycol molar ratio exceeds the range of the present invention, ethylene glycol is distilled out from the rectification column, which prevents the reaction at low temperatures. As a result, the transesterification reaction time was significantly delayed. Furthermore, although the dispersibility of inorganic particles in the obtained polymer was improved, the polymer had a low softening point.

Example 12 10 parts of the polymer obtained in Example 1 were blended with 90 parts of boria containing no inorganic particles. After that, the polyester was
The mixture was supplied to a melt extruder at 0° C., and an unstretched film was obtained using a casting drum.

Next, the film was axially stretched by 2λ1η by 3.5 times in both the longitudinal and width directions, and then immediately heat treated to obtain a 5-film. The Young's modulus of this film in the longitudinal direction was 700 kf//-, indicating a high elastic modulus.

This film had good surface flatness and excellent running properties.

Example 13 A film was obtained. The longitudinal direction of this film
was 710 kg/-, and the film had a high elastic modulus.

This film had good surface flatness and smooth running properties.

Patent application Daitoshi Co., Ltd.

Claims (1)

[Claims] 1,2-bis(2-chlorophenoxy)ethane-4,4
When producing polyester from glycol and at least one type of '-dicarboxylic acid and its alkyl ester, elements are 0.005 to 5% by weight is added to the polyester from which inorganic particles containing at least one element of groups II, III, and IV of the periodic table are obtained, and the molar ratio of the glycol-soluble metal compound to the phosphorus compound (M /P) to 0.
A method for producing thermoplastic polyester, characterized in that 5≦M/P≦10 is added. (M is the number of moles of glycol-soluble metal compound per 10^6 g of polyester, P is the number of moles of phosphorus compound per 10^6 g of polyester.)