KR810000654B1 - Catalysts for production of polyesters - Google Patents

Abstract

Polyester films and fibers are prepd. by polycondensation of dicarboxylic acids or derivs. with aliph. glycols using silicon compds. (I, II, III, IV) as catalysts. Thus, di-Me terephthalate 39.1g, ethylene glycol 32.8g, Zn(OAc)2 .2H2O 0.0176g and [2-(diethoxyphosphoryl)ethyl diethoxymethylsilane 0.0202 g were heated 3hrs at 168-200≰C, 1h at 218-230≰C and 2hrs at 273-284≰C to give a polyester.

Description

Method for producing polyester using a catalyst

The preparation of polyesters and copolyesters of dicarboxylic acids and aliphatic glycols has been carried out commercially for decades. The first description relating to this technology is described in US Pat. No. 2,465,319, issued March 22, 1949. Since then, many changes have been made in the process and many catalysts have been discovered and patented.

US Patent No. 3,546,179, issued December 8, 1970, relates to the use of compounds containing both silicon and phosphorus in the molecule as a catalyst.

It has been found that certain silicone compounds as defined below are excellent polyester catalysts for the production of polyesters and copolyesters useful for making films and other moldings. In the preparation of polyesters and copolyesters the reaction is generally considered to be a double or two stage reaction. Esterification or transesterification takes place in the first stage and polycondensation takes place in the second stage.

The present invention relates to a new polyesterification method.

In the process of the invention, the polyesterification catalyst used is the particular silicone compounds which will be defined more fully later. The use of these catalysts further shortens the reaction time and is highly polycondensed polyester and copolyester characterized by high melting point, high elongation at rupture point, good tensile strength, high whiteness, and good heat and light stability. Is prepared.

The first stage esterification or transesterification reaction is carried out in a conventional manner by heating the mixture of reactants at a temperature between about 150 ° -about 270 ° C, suitably about 175 ° -about 250 ° C. Any known esterification or transesterification catalysts may be used during this step, for example zinc acetate, manganese acetate, cobalt acetate, zinc succinate, zinc borate, magnesium methoxide, sodium methoxide, cadmium formate, etc. Can be raised. It is convenient that the concentration is about 0.001-4% by weight based on the weight of the filled dicarboxylic acid compound. Suitably 0.005-0.5% by weight and more suitably 0.01-0.02% by weight.

In the second stage, that is, the polycondensation stage, a silicon catalyst defined thereafter is used. The silicone catalyst is used at a concentration of about 0.01-1% by weight, suitably about 0.02-0.1% by weight, based on the weight of the charged dicarboxylic acid compound. Even catalytically effective concentrations may be employed. The term “dicarboxylic acid compound” as used in the present application means both free dicarboxylic acid and esters thereof.

Dicarboxylic acid compounds used for the production of polyesters and copolyesters are known, for example terephthalic acid, isoterephthal, P, P'-acid diphenylcarboxylic acid, P, P'-dicarboxydiphenyl ethane , P, P'-dicarboxydiphenyl hexane, P, P'-dicarboxydiphenyl ether, P, P'-dicarboxyphenoxy ethane, and the like, and also contain 1-5 carbon atoms in the alkyl group. These polyalkyl esters are mentioned.

Aliphatic glycols suitable for the preparation of polyesters and copolyesters are non-dilutable and aliphatic ring aliphatic glycols containing 2-10 carbon atoms, in particular represented by the general formula HO (CH ₂ ) pOH (wherein P is an integer of 2-10), For example, ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, decamethylene glycol, etc. are mentioned. Examples of other known suitable aliphatic glycols include 1,4-cyclohexanedimethanol, 3-ethyl-1,5-pentanediol, 1,4-xylene glycol, 2,2,4,4-tetramethyl-1,3- Cyclobutanediol and the like. Also mentioned are 4-hydroxybenzoic acid, 4-ethoxyhydroxybenzoic acid, or any other hydroxylcarboxylic compounds known to be useful in the art.

Mixtures of the foregoing dicarboxylic acid compounds or aliphatic glycols may also be used, and generally, small amounts of up to about 10 mole percent of the dicarboxylic acid compound are other such as adipic acid, succinic acid, sebacic acid, or esters thereof. It is known that they may be replaced by acids or modifiers or as modifiers that impart improved dyeability to the polymer. In addition thereto, pigments, matting, processing agents or optical brightening agents may be included in known methods and amounts.

The polycondensation reaction is generally carried out under reduced pressure and under an inert gas at a temperature between about 225-about 325 ° C, suitably about 250-290 ° C. These reaction conditions are well known in the art.

Silicon compounds used as catalysts in the present invention are represented by the following general formula.

In the above formula, W is CH ₂ = CX ^- or (R ^* O) ₂

X is hydrogen or methyl and when m is 1 methyl; R ^* is alkyl or haloalkyl having 1-4 carbon atoms; R ^** is methyl, ethyl, butyl, acetoxy, methoxy, ethoxy or butoxy, R is methyl, ethyl, butyl or trimethylsiloxy; R 'is methyl, methoxy, ethoxy butoxy or trimethylsiloxy; R 'is methoxy, ethoxy, butoxy, trimethylsiloxy or vinyl dimethylsiloxy; R '' is methyl, ethyl, butyl or trimethylsilyl; Me is methyl; Z is methyl or W; Q is NH ₂ CH _2- , NH ₂ CH ₂ CH ₂ NHCH _2- , NC-, HS- or HSCH ₂ CH ₂ S-group; n is an integer of 2-5; m is an integer of 0 or 1; x is an integer from 1-100; y is an integer from 1-100; There are compounds belonging to (I) represented by the following general formula:

There are compounds belonging to (II) represented by the following general formula:

Examples of suitable silicon compounds include the following; Beta-cyanoethyl triethoxysilane, gamma-mercaptopropyl triethoxysilane, gamma-aminopropyl triethoxysilane, diethoxyphosphorylethyl methyl diexysilane, vinyl triethoxysilane, vinyl trimethoxy Silane, vinyl triacetoxysilane, gamma-methacryloxypropyl trimethoxysilane, diethoxyphosphorylethyl heptamethyl cyclotetrasiloxane, beta-cyanoethyltrimethylsilane, N-gamma- (2-aminoethyl)- Aminopropyl triethoxysilane, S-beta (2-mercaptoethyl) mercaptoethyltriethoxysilane, beta-mercaptoethyl triethoxysilane, vinylmethyl diethoxysilane, vinyl methyl di (trimethylsiloxy) silane , Tetramethyl divinyl disiloxane, heptamethyl vinyl cyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl cyclotetrasiloxane, diethoxyphosphorylethyl methyldie Methoxysilane, diethoxyphosphoryl iso Lofil triethoxysilane, diethoxyphosphoryl ethyl methyl di (trimethylsiloxy) silane, heptamethyl diethoxyphosphorylethyl cyclotetrasiloxane, 1,3,5,7-tetramethyl 1,3,5,7-tetra (Diethoxyphosphorylethyl) cyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-di (diethoxyphosphorylethyl) disiloxane.

In a typical reaction, a prescribed amount of dicarboxylic acid compound, diol, modifier and catalyst is charged to the reactor.

The reaction mixture is then heated in an inert gas at a temperature between 180-210 ° C. to affect the initial esterification or transesterification.

Thereafter, any excess glycol is removed and transesterification is completed by heating the reaction mixture under reduced pressure and under an inert gas to a temperature between about 225 ° -235 ° C. The second stage polycondensation is then carried out by heating the reaction mixture to a temperature of about 225 ° -325 ° C. under a reduced pressure of about 0.1-20 mmHg, suitably about 0.1 mmHg. The use of the catalyst complex or mixture of the present invention often shortens the overall reaction time and in many cases reduces the formation of glycol dimers.

The invention is further illustrated by the embodiments described below.

Example 1

A mixture of 39.1 g of dimethyl terephthalate, 32.3 g of ethylene glycol, 0.01 g of zinc acetate dihydrate, and 0.172 g of 2-cyamyethyl triethoxysilane as a polycondensation catalyst as a transderder catalyst was found to be between 168 ° and 200 ° C. Heated in the presence of argon gas for 3 hours at temperature. During this first stage transesterification reaction, methanol was distilled from the reactor. The temperature was then raised to 218 ° -230 ° C. and maintained for about 1 hour to finish transesterification.

Thereafter, the temperature was raised, while the pressure was slowly reduced to below 1 mm Hg, and the temperature was maintained at 218 ° -284 ° C. for 2 hours to complete the second stage polycondensation reaction. A clean, white polyester was produced having excellent tensile and fiber properties.

Example 2

Following a method similar to that described in Example 1, using 39.1 g of dimethyl terephthalate, 32.8 g of ethylene glycol, 0.0176 g of zinc acetate dihydrate and 0.0202 g of beta-diethoxyphosphide ethyl methyl diethoxysilane as polycondensation catalysts Polyester was prepared.

The polyester was white, had good cold tensile properties, and had an intrinsic viscosity of 0.60.

Example 3

Following a method similar to that described in Example 1, polyesters were prepared using 39.6 g of dimethyl terephthalate, 32.4 g of ethylene glycol, 0.0165 g of zinc acetate dihydrate and 0.0158 g of 3-aminopropyl triethoxysilane as polycondensation catalysts. Prepared. The polyester appeared bright copper yellow and had an intrinsic viscosity of 0.60.

It has good cooling toughness and strength.

Example 4

Following a method similar to that described in Example 1, as a polycondensation catalyst, 736.9 g of dimethyl terephthalate, 536.4 g of ethylene glycol, 0.2716 g of zinc acetate dihydrate and 0.2674 g of 2-cyanoethyl triethoxysilane were reacted to be very thin. 544 g of yellow polyester were prepared.

Transesterification was initially carried out in the presence of argon gas for 3.5 hours at temperatures between 180 ° -185 ° C and for 1.25 hours at temperatures between 230 ° -235 ° C and polycondensation reactions between 277 ° -285 ° C. It was carried out at the temperature for 3.5 hours.

White fiber, 139 denier, had excellent cooling tensile strength and strength.

A portion of this polyester was vacuum dried and 5% by weight of the dyeable modifier poly [isopropylaminobis (trimethylene) prepared as described in US Pat. No. 3,886,230 (E. Marucs, May 27, 1975). ) -Succinate] in the extruder. The mixture was spun through a radiation exposure machine with 30 holes each 0.02 inches in diameter at a winding speed of 550 feet per minute.

The tow was stretched by heating over hot shoe and heated fins at 95 ° C. The draw ratio was about 4.5: 1. Pale yellow fiber, 104 denier had excellent cooling tensile strength and strength.

Claims (1)

In a known method for producing a fibrous polyester and a copolyester of a solid of a dicarboxylic acid compound and an aliphatic glycol in the presence of a catalyst, a dicar characterized by using a silicone compound selected from the group below as a polycondensation catalyst. A process for producing polyesters and copolyesters of acidic compounds and aliphatic glycols;

or

Where W is CH ₂ CX- or (R ^* O) ₂

; X is hydrogen or methyl and methyl when m is 1; R ^* is alkyl or haloalkyl having 1-4 carbon atoms; R ^** is methyl, ethyl, butyl, acetoxy, methoxy, ethoxy or butoxy; R is methyl, ethyl, butyl or trimethyl siloxy; R 'is methyl, methoxy, ethoxy, butoxy or trimethylsiloxy; R 'is methoxy, ethoxy, butoxy, trimethylsiloxy or vinyldimethylsiloxy; R '' is methyl, ethyl, butyl or trimethylsilyl; Me is methyl; Z is methyl or W; Q is NH ₂ CH _2- , NH ₂ CH ₂ CH ₂ NHCH _2- , NC-, HS- or HSCH ₂ CH ₂ S-group; n is an integer of 2-5; m is an integer of 0 or 1; x is an integer from 1-100; y is an integer from 1-100.