JPS62109823A - Production of thermoplastic polyester - Google Patents

Abstract

PURPOSE:To obtain the titled polymer having high rigidity, improved heat resistance, smooth film surface and good running property without trouble in yarn breakage as fibers, by adding inert inorganic particles to a specific dicarboxylic acid and glycol and poplycondensing the mixture. CONSTITUTION:(A) A dicarboxylic acid expressed by the formula (R1 and R2 are 1-4C alkyl), e.g. dimethyl 1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate, and (B) a glycol, e.g. ethylene glycol, are charged into, e.g. a reactor, and ester interchange reaction is carried out. Before completing the reaction, (C) inert inorganic particles, e.g. mica, having <=5mum average primary particle diameter in water, etc., as a medium is added to continue the reaction and polycondensation is carried out to afford the aimed polyester.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a method for producing a highly polymerized thermoplastic polyester containing inert 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 as 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 field of textiles, fibers with high elastic modulus are required, for example, 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(2-10 fluorene/)ethane-4,4' dicarboxylate, which is a polyester that is relatively suitable for the above-mentioned required properties, is
This is proposed in Publication No. 9-1795. however,
When an all-polyester film produced by the method disclosed in the above-mentioned publication was 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 projection forming agent during film formation of the polyester was proposed in JP-A-59-38031. However, although the method of the above-mentioned publication improves the runnability of the film obtained, it is still not sufficient for applications that require a film surface that requires highly uniform protrusions, such as metal tapes and vapor deposition tapes. Ta.

As a result of intensive study on these problems, the inventors discovered that the above problems could be significantly improved by adding inert inorganic particles under specific conditions in the polyester manufacturing process. Reached.

[Purpose of the invention]

The object of the present invention is to provide polyester-1,2-Hys(-) with improved dispersibility of inert inorganic particles.

The object of the present invention is to provide a method for producing ethane-4,4-)carboxylate.

In addition, when the polyester is used in a film, the surface of the film is smooth and running properties are improved, and when used in fibers, troubles such as yarn breakage are less likely to occur, and the polyester has high rigidity and excellent heat resistance. be.

[Structure of the invention]

The object of the present invention is to produce a polyester from a compound having the following structural formula [I] as a main dicarboxylic acid component and glycol, and to prepare an inert inorganic material having an average primary particle size of 5 μm or less before the transesterification reaction is completed. This can be achieved by a method for producing thermoplastic polyester characterized by adding particles.

l Examples of the glycol used in the present invention include lower alkylev glycol, cyclohexanedimethanol, and cyclohexanedimethanol.

Among them, ethylene glycol and butanediol are preferred.

The alkyl ester of dicarboxylic acid used in the present invention is a compound represented by the following structural formula (1), and among them,
．． 2-bis(2-chlorophenoxy/)ethane-4,4'
-methyl dicarboxylate and diethyl 1,2-bis(2-10rufenoquine)ethane-4,4'-dicarboxylate are preferred.

Furthermore, in the present invention, in addition to the aforementioned alkyl ester of dicarboxylic acid and the aforementioned ethylene glycol, a small proportion of other compounds having ester-forming ability can also be copolymerized. For example, succinic acid, adipic acid, sepanonic acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-)phenylenecarboxylic acid, hexahydroxy/terephthalic acid, 1,2-bis(phenoxy ) Ethane-4,4'-dicarboxylic acid, 1,2-bis(2
,6-dichlorophenoxy)ethane-4,4'-dicarboxylic acid, +-,(2-chlorophenoxy/)-2-(phenoquine)ethane-4,4'-dicarboxylic acid and their esters. Forming derivatives and polyethylene/glycol, polypropylene glycol, hexamethylene glycol, 1.4-7 chlorohexanedimethanol, diethylenoglycol, neopentyl glycol, bis(β-hydroxy/ethyne)bisphenol A
Dioquino compounds such as 1-(2
-chlorophenoki/)-2-(phenoki/)ethane-4
, 4'-dicarboxylic acid and its ester-forming derivatives.

Inert inorganic particles used in the present invention include carbonates, sulfates, oxides, hydroxides, and natural minerals. More specifically, 5i02.5i02 AJ20s, A
/? 203, Tie, TiO2, CaCO2, Ca5
n4. BaCO3, BaSO4, ca, 5 (PO4)
2, CaHPO4, Ba3(PO4)2, B a HP
Oa, MgO*ZrOiZPO2, kaolinite, carbo/plaque, mica, etc., and two or more of these may be used in combination.

The average primary particle diameter of such inert inorganic particles needs to be 5 μm or less. Preferably it is 1μ or less. If it exceeds 5μ, the surface flatness of the film and fiber will be impaired, causing dropouts when made into a film and thread breakage when made into fibers, which is undesirable.

In addition, it is difficult to obtain a polymer with a uniform degree of polymerization due to the agglomeration of particles in the polymer and the increase in viscosity during the polycondensation process, and when used as a film, the film surface has small irregularities and has sufficient slipperiness. Therefore, the average diameter of the -deficient particles is preferably 2 mμ or more, more preferably 5 mμ or more.

A slurry is preferable as the form of addition of inert inorganic particles to the reaction system, and water, methanol,
Examples include ethylene glycol, 1,4-butanediol, neopentyl glycol, propylene glycol, diethylene glycol, etc., but it is preferable to use glycols used as polyester raw materials and copolymerization components.

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 inert 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.

The timing of addition of inert inorganic particles, which is a feature of the present invention, is at the beginning of charging 1,2-his(chlorophenoxy/)ethane-4,4'-dicarboxylic acid ester and glycol, which are the starting materials for polyester, into the reactor. It is to be added after the reaction is completed until the transesterification reaction is completed, and more preferably, it is added before the transesterification reaction rate reaches 40%. The polyester obtained by the method of the present invention has the added inorganic particles uniformly dispersed, and exhibits excellent surface properties when used for films, fibers, etc.

When such a slurry is added after the transesterification reaction or during the subsequent polycondensation step, the inert inorganic particles will aggregate,
This is undesirable as it causes coarse protrusions on the film and foreign matter on the fibers.

As the transesterification reaction catalyst, known catalysts such as ordinary glycol-compatible metal salts, such as acetates, oxalates, logogenides, hydroxides, aliphatic carboxylates, alcoholades, etc. can be used. It can be charged at the same time as the raw materials or after the addition of the inert inorganic particle slurry.

In addition, after the end of the transesterification reaction, phosphoric acid, phosphorous acid,
Known phosphorus compounds such as phosphonic acids and their lower alkyl esters and phenyl esters may be added.

The reaction product thus obtained is heated to 220 to 60
The polycondensation reaction can be carried out at 0°C.

〔Effect of the invention〕

The polyester obtained by the production method of the present invention has the following effects.

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

(2) When molded into a film, it has high rigidity even in a thin film compared to polyethylene terephthalate film, etc.
Moreover, it has flatness and easy sliding properties.

When such films are used for magnetic tapes such as metal tapes and vapor-deposited tapes, base films for magnetic disks, or base films for capacitors, they are extremely effective in miniaturizing equipment and improving performance, and are also useful in the film processing process. Process passability in the process is also improved.

(3) Also, when the polyester is molded into fiber,
Fibers with a high modulus of elasticity can be obtained and can be effectively used in a variety of applications including industrial materials. Furthermore, troubles such as yarn breakage can be prevented, and high-speed spinning is possible.

The present invention will be explained in detail below using Examples.

In addition, the part in an Example is all M, and the measuring method of each characteristic is as follows.

(1) Dispersion state of particles The particles were observed using a transmission electron microscope at a magnification of 30,000 times, and the monodisperse state was evaluated according to the following criteria.

Note that the monodisperse state here indicates how many of the total number of particles are dispersed in the form of primary particles, expressed as a percentage. In addition, A and B were defined as passing lines.

Rank: Monodisperse state A: 90 or more ...interval value).

(3) Polymer viscosity using a high-speed flow tester at 290°C and a sliding speed of 200.
The melt viscosity at S was measured.

(4) Softening point Measured with a venetrometer.

(5) Young's modulus A, measured at 25°C using an Inostron type tensile tester according to the method specified in STM-D-882.
, measured at 65 RH.

Example 1 1.2-bis(2-chlorophenoxy)ethane-4,4
After charging 100 parts of dicarboxylic acid, 42 parts of ethylene glycol, and 0.05 part of magnesium acetate/ram into a reactor equipped with a rectification column and a stirring device, when the reaction rate reached 2 parts, 20 parts of BG slurry containing 5 parts by weight of wet phosphoric acid having an average primary particle diameter of 45 mμ was added, and the temperature was gradually raised from 190° C. to 245° 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. The transesterification reaction rate was 99.5%.

After subsequently adding 0.01 part of chitrimethyl phosphate and 0.301 part of antimony dioxide, the mixture was transferred to a polycondensation reactor, and a polycondensation reaction was carried out under reduced pressure for 3 hours. The final temperature is 29
The temperature was 5° C. and the degree of vacuum was Q, Jl) (g).The obtained polymer had a viscosity of 3000 pO1se and was monodispersed with a coefficient of 95.

Examples 2 to 5, Comparative Examples 1 to 3 Polycondensation reactions were carried out in the same manner as in Example 1, except that the type, amount, and timing of addition of inert inorganic particles were changed to obtain the polymers shown in Table 1. Ta.

According to the method of the present invention, the dispersibility of the added inert inorganic particles in the polymer is good. On the other hand, when the addition timing was outside the range of the present invention, many aggregates of the added inorganic particles were observed.

Example 6 10 parts of the polymer obtained in Example 1 were blended with 90 parts of a polymer free of inert inorganic particles, and the polyester was then fed into a melt extruder at 300°C and cast into an unstretched film using a casting drum. I got it.

Next, the film was biaxially stretched by 6.5 times in both the longitudinal and width directions and immediately subjected to heat treatment to obtain a film with a thickness of 7 am. The Young's modulus of this film in the longitudinal direction is 750 kg/-,
The film had a high overall modulus of elasticity.

The film also had good surface flatness and excellent running properties.

Comparative Example 4 Using the polymer obtained in Comparative Example 1, a 7 μm thick film was obtained in the same manner as in Example 6.

This film had a Young's modulus in the longitudinal direction of 720 kg/wi and had a high elastic modulus, but there were many coarse protrusions on the surface and the flatness was impaired.

Claims (1)

[Claims] When producing polyester from a compound having the following structural formula [I] as a main dicarboxylic acid component and glycol, inert inorganic particles having an average primary particle size of 5 μm or less are produced before the transesterification reaction is completed. A method for producing thermoplastic polyester, characterized by adding. ▲There are mathematical formulas, chemical formulas, tables, etc.▼……[I] (However, in the formula, R_1 and R_2 represent an alkyl group having 1 to 4 carbon atoms.)