KR810000371B1 - Coordination complexes as catalysts for preparing polyester - Google Patents

Abstract

A process for the manufacture of solid fiber-forming polyesters of copolyesters of dicarboxylic acid compounds and aliphatic glycols in the presence of catalysts is disclosed, wherein the improvement comprises a coordination complex of a metal halide and a silicone compounds as polyesterification catalyst.

Description

Polyester manufacturing method using coordination complex catalyst

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

U.S. Patent No. 3,546,170, issued December 8, 1970, relates to the use of compounds containing both silicon and phosphorus atoms in a molecule as a catalyst.

Coordination complexes of metal halides and silicone compounds have been found to be good polyester catalysis complexes for producing polyesters and copolyesters useful for making films, fibers, and other shaped articles.

In the preparation of polyesters and copolyesters, the reaction is generally considered to be a double or two stage reaction. Esterification or trans esterification takes place in the first stage and polycondensation takes place in the second stage.

The present invention relates to a new polyesterification catalyst composition and a process for producing the polyester.

The new catalyst composition of the present invention is a coordination compound of (A) metal halide and (B) silicon compound as more fully defined below.

The use of the catalyst complex or composition according to the present invention further reduces reaction time, highly polycondensation characterized by high melting point, high elongation at break, excellent tensile strength, high whiteness and good heat and light stability. Resulting polyesters and copolyesters.

The first stage esterification or trans esterification reaction is carried out in a conventional manner by heating the mixture at a temperature between about 150-270 ° C., suitably between about 175-about 250 ° C. Any known esterification or transesterification catalyst 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. I can lift it. These concentrations are usually used at about 0.001-1% by weight based on the weight of the charged dicarboxylic acid compound. Suitably about 0.005-0.5 weight percent, more suitably about 0.01-0.2 weight percent.

The novel coordination compound catalyst of the present invention in the second stage, or polycondensation stage, is useful. These new coordination catalysts consist of two essential components. The first component is a metal halide, and the second component is one or more silicon compounds, defined later.

Metal halide compounds used to prepare coordination compounds useful as catalysts are halides of titanium, zirconium, zinc, germanium, tin, lead, antimony and bismuth metals. Examples of suitable metal halides include di-, tri and tetra-bromide, chloride, fluoride and iodide of titanium and zirconium: dibromide, chloride, fluoride and iodide of tin: mixed bromide of tin Di- and tetra-bromide, chlorides, fluorides and iodides of germanium, tin and lead, including chloride, bromide, iodide and chloride-iodide: tri- and penta-bromide-chloride, fluoride of antimony And tri- and tetra-bromide, chloride, fluoride and iodide of iodide and bismuth. These metal halides are well known to those with ordinary chemical knowledge, and their specific orders are listed in detail in the chemical handbook so that experts in the art do not need to know the chemical names of specific metal halides. See Handbook of Chemistry and Physics by Chemical Rubber Publishing Co.

In preparing coordination compounds useful as catalysts, the molar ratio of metalhalogen to silicon compound in the coordination compound is about 1: 0.5 to 1:10, suitably about 1: 1 to about 1: 7, and most preferably 1: 1. To a ratio of about 1: 2.

In the polycondensation reaction, the coordination catalyst compound is used at a concentration of 0.01-0.2% by weight, or more, suitably 0.02-0.06% by weight based on the weight of the charged dicarboxylic acid compound.

Any concentration may be adopted as long as it is catalytically useful. The term “dicarboxylic acid compound” as used herein refers to both free dicarboxylic acid and its esters.

Dicarboxylic acid compounds used in the manufacture of polyesters and copolyesters are well known to those skilled in the art, for example terephthalic acid, isoterephthalic acid, P, P'-diphenylcarboxylic acid, P, P ' Dicarboxylic diphenyl ethane, P, P'-dicarboxy diphenyl hexane, P, P'- dicarboxoxy diphenyl ether, P, P'-dicarboxyphenoxy ethane, etc. And dialkyl esters thereof containing a ruler.

Aliphatic glycols suitable for the production of polyesters and copolyesters include non-dilute and aliphatic ring aliphatic glycols having 2-10 carbon atoms, in particular the general formula HO (CH 2) pOH (where P is 2). And ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, decamethylene glycol, and the like, for example.

Other known suitable aliphatic glycols include 1,4-cyclohexanedimethanol, 3-ethyl-1,5-pentanediol, 1,4-xylene glycol, 2,2,4,4-tetramethyl-tetramethyl-1, 3-cyclobutanediol, and the like. Also mentioned are hydroxyl carboxyl compounds such as 4-hydroxybenzoic acid, 4-hydroxyethoxyethoxybenzoic acid or any other hydroxylcarboxyl compounds known 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 component are other acids or modifiers such as adipic acid, sebacic acid or It can be replaced as a modifier to impart improved dyeability to the esters or polymers. It may also be added to it by known methods and in known amounts to include pigments, optical brighteners, degreasers.

The polycondensation reaction is generally carried out under reduced pressure and at temperatures between about 225 ° C.-325 ° C., suitably about 250-290 ° C., under inert gas. These conventional reaction conditions are known.

The silicon compounds used together with the metal halides to prepare the coordination complex catalyst of the present invention are represented by the following general formula.

이고,Where W is CH2 = CX- or (R * O) ₂

ego,

X is hydrogen or methyl, methyl only when m is 1,

R ^* is alkyl or haloalkyl having 1-4 carbon atoms,

R ^** is methyl, ethyl, butyl, acetoxy, methoxy or butoxy,

R is methyl, ethyl, butyl, methoxy, ethoxy, butoxy or trimethylsiloxy,

R 'is methyl, methoxy, ethoxy, butoxy or trimethylsiloxy,

R 'is methoxy, ethoxy, butoxy, trimethylsiloxy or vinyldimethyl siloxy,

R 'is methyl, ethyl, butyl or trimethylsilyl,

Me is methyl,

Z is methyl or W,

Q is NC ₂ CH _2- , NH ₂ CH ₂ CH ₂ NHCH _2- , NC-, HS- or HSCH ₂ CH ₂ S-group,

n is an integer with a number from 2-5,

m is an integer with a value of 0 or 1,

X is an integer with a number from 1-100,

y is an integer with a value from 1-100.

Examples of the compound belonging to (I) include compounds having the following structural formulas.

Examples of the compound belonging to (II) include those represented by the following general formula.

Examples of suitable silicon compounds include the following.

Beta-cyanoethyl triethoxysilane, gamma-mercaptopropyl triethoxysilane, gamma-aminopropyl triethoxysilane, diethoxyphosphorylethylmethyl diethoxysilane, vinyl triethoxysilane, vinyl trimethoxysilane , Vinyltrimethoxysilane, vinyltriacetoxysilane, gamma-methacryloxypropyl trimethoxysilane, diethoxyphosphorylethyl heptamethyl cyclotetrasiloxane, trimethyl silyl having dimethylsiloxy and methylvinylsiloxy units in the molecule Terminated copolymer, beta-cyanoethyl trimethylsilane, gamma- (2-aminopropyl) triethoxysilane, S-beta (2-mercapto ethyl) mercapto ethyl triethoxysilane, beta-mercapto ethyl tree Ethoxysilane, vinyl methyldiethoxysilane, vinylmethyl di (trimethylsiloxy) silane, tetramethyl divinyl disiloxane, heptamethylvinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5 , 7-te Ravinyl cyclotetrasiloxane, diethoxyphosphorylethyl methyl diethoxysilane, diethoxyphosphoryl isopropyl triethoxysilane, diethoxyphosphorylethyl methyl di (trimethylsiloxy (silane, heptamethyl diethoxyphosphorylethyl cyclotetra Siloxane, 1,3,5,7-tetramethyl 1,3,5,7-tetra (diethoxy phosphoethylethyl) cyclotetra siloxane, 1,1,3,3-tetramethyl-1,3-die (die Oxyphosphorylethyl) disiloxane.

In a representative reaction, a prescribed amount of dicarboxylic acid compound, diol, modulator and catalyst was charged to the reactor. Then, the reaction mixture was heated to a temperature of 180 ° C. to 210 ° C. in an inert gas to perform initial esterification or transesterification.

Thereafter, excess glycool was removed and the reaction mixture was heated at a temperature of about 225-about 235 ° C. to complete transesterification.

The reaction mixture was then heated to a temperature between about 225-325 ° C. under reduced pressure of about 0.1-about 200 mmHg, preferably about 1 mmHg or less, to effect a second stage polycondensation reaction. The use of the catalyst complexes or mixtures of the present invention often shortens the overall reaction time and reduces the formation of glycol dimers, ie diethylene glycol.

The invention will be described in more detail by the following examples.

[Production of Coordination Compound]

Example 1

The coordination compound was prepared by dissolving 19 g of titanium tetrachloride in 60 ml of dry benzene in a reaction flask, and adding 29.8 g of diethoxyphosphorylethyl methyl diethoxysilane to the flask over 30 minutes. The reaction was exothermic and the temperature reached up to 60 ° C.

The mixture was stirred for 1 hour without adjusting the temperature, and then benzene was distilled off in vacuo. A 1: 1 molar coordination compound was an oily liquid, and its weight was 48.8 g. Microanalysis without further purification revealed 28.08% Cl and 5.98% P.

Example 2

A solution of 4.75 g of titanium tetrachloride dissolved in 60 ml of dry benzene was prepared in a reactor. 10.85 g of cyano ethyltriethoxysilane was added thereto over 30 minutes with stirring at 25 ° C.

The reaction was exothermic. After further stirring at 25 ° C. for 1 hour, benzene was distilled off in vacuo. The 1: 2 molar ratio coordination compound was a yellow oily liquid, and the weight was 15.6 g. Microanalysis without further purification revealed 21.20% Cl, 9.11% Si, 4.27% N and 8.77% Ti.

Example 3

A mixture of 4.56 g of antimony trichloride and 36 g of dry benzene was prepared in a reactor. To this mixture was added 41.8 g of diethoxyphosphorylethyl methyl diethoxysilane at 25 ° C. for at least 30 minutes.

The reaction was exothermic. After further stirring for 1 hour, benzene was removed in vacuo. The coordination compound of 1: 7 molar ratio was an oily liquid, and the weight was 46.4g.

Example 4

A solution of 6.5 g of titanium tetrachloride dissolved in 30 ml of dry benzene was slowly added to a stirring solution of 9.7 g of diethoxyphosphorylethyl methyl diethoxysilane dissolved in 30 ml of dry benzene. An exothermic reaction occurred and after being left to stand for 1 hour, the mixture was extracted in vacuo at 30 ° C. The 1: 1 molar ratio coordination compound was recovered to 16.2 g of a red oil residue. 1.4 minutes of this complex was added to ethylene glycol 1.8 at room temperature, and the mixture was stirred until a uniform solution was obtained.

Example 5

A solution of 10.7 g of germanium tetrachloride dissolved in 25 ml of dry benzene was added to 22.1 g of gamma-aminopropyl triethoxysilane for at least 30 minutes. An exothermic reaction was observed. After stirring for an hour without adjusting the temperature, benzene was distilled off in vacuo.

The 1: 2 molar ratio complex was a white crystalline material and the weight was 33.2 g.

Example 6

A suspension of 11.66 g of zirconium tetrachloride suspended in 30 ml of dry benzene was added to a solution of 32.8 g of diethoxyphosphorylethyl triethoxysilane dissolved in 50 ml of dry benzene. An exothermic reaction was observed. After the addition was completed, the mixture was stirred for 1 hour without further controlling the temperature, filtered, and then extracted in vacuo. As a residual product, colorless and odorless oily phase 1: 2 molar ratio coordination compound was obtained, and the weight thereof was 43.9 g.

Example 7

A solution of 13 g of tetrachloride stock dissolved in 30 ml of anhydrous benzene was slowly added to a solution of 14.99 g of diethoxyphosphorylethyl methyl diethoxysilane dissolved in 30 m of dry benzene. An exothermic reaction was observed. After standing at room temperature for 20 hours, benzene was distilled off in vacuo. A 1: 1 molar ratio coordination compound was obtained as a yellow oil, and the weight thereof was 28 g.

Example 8

A solution of titanium tetrachloride 9.5 dissolved in 30 ml of dry benzene was slowly added to a solution of 22.4 g of beta-mercapto ethyl triethoxysilane dissolved in 50 ml of dry benzene. An exothermic reaction was observed.

After standing for 30 minutes, benzene was streamed in vacuo. The coordination compound with a 1: 2 molar ratio was 32.1 g in weight and was recovered as an orange oily residue.

In a similar manner, coordination compounds can be prepared using zinc chloride, lead chloride or bismuth chloride in place of titanium tetrachloride.

Example 9

(A) A mixture of 39.8 g of dimethyl terephthalate, 34.1 g of ethylene glycol, and 0.0167 g of a 1: 1 molar coordination compound catalyst prepared in Example 4 without addition of ethylene glycol, and 0.0192 g of zinc acetate dihydrate were prepared in argon. Heated in the presence at 178-186 ° C. for 3 hours. Methanol was removed from the reactor during this first stage trans esterification. The temperature was raised to about 230 ° C. and maintained for 1 hour to complete transesterification. Thereafter, this temperature was raised to about 280 ° C. On the other hand, the pressure was reduced to 1 mmHg or less and the second stage polycondensation reaction was performed. During polycondensation, a sample of polyester was raised several times to measure the intrinsic viscosity.

The reaction is terminated when the intrinsic viscosity reaches 0.57, which is a representative value of commercial polyester, and the required time is recorded as the polycondensation time (the time at which 1 mmHg pressure is reached when the polyester has an intrinsic viscosity of 0.5). did.

In this example, the polycondensation time was 40 minutes.

The intrinsic viscosity measurement reported in this application was to dissolve 0.5% by weight of polyester in 0-chlorophenol and measure its viscosity at 25 ° C. with an Ubbelohde Viscometer.

(B) For comparison purposes, polyesters were prepared using 39.4 g of dimethyl terephthalate and 32.2 g of ethylene glycol under the same temperature and pressure conditions as described in section A above. However, the catalyst used was a conventional catalyst, i.e., 0.0179 g of zinc acetate dihydrate as the transesterification catalyst, and 0.003 g of antimony oxide as the polymerization catalyst. In this example, the polycondensation period was 75 minutes.

(C) Under another reaction with the same reaction conditions as described in section B but with different catalyst concentrations, polyesters were prepared using zinc acetate, 0.0172 g dihydrate and 0.0186 g antimony oxide. In this example, the polycondensation time was 60 minutes.

Example 10

One of the undesirable side reactions of the polyesterification reaction is the formation of diethylene glycol. This is undesirable for at least two reasons. This is because it cannot be recycled and is a byproduct of copolymerization. In addition, when the excess diethylene glycol is reacted in the condensation reaction, a polyester having a melting point below the required value is produced. In this example, it was found that when the coordination compound of the present invention was used as a condensation catalyst, a smaller amount of diethylene glycol was formed.

(A) A mixture of 44.9 g of dimethyl terephthalate, 35.3 g of ethylene glycol, and 0.0177 g of a 1: 1 molar coordination compound catalyst of Example 1 was reacted for 3 hours at a temperature of 174-190 ° C in the presence of argon. It was made to react at 1 degreeC for transesterification. Thereafter, polycondensation was carried out for 40 minutes at a pressure of 1 mmHg or less and a temperature of 276-288 ° C. The polyester was white and had an intrinsic viscosity of 0.57.

A portion of the polyester was hydrolyzed and the amount of diethylene glycol in the polyester was measured by gas chromatography analysis.

The analysis showed that 0.8% by weight of ethylene glycol, dimerized with diethylene glycol, was polycondensed.

(B) In the same manner as described in the above section (A), using polyacrylamide for 75 minutes after condensation using 0.0186 g of zinc acetate dihydrate and 0.02 g of antimony oxide, 39.5 g of dimethyl terephthalate and ethylene glycol 32.8 g were initially charged to obtain a polyester having the same viscosity.

Analysis of a portion of the polyester obtained in (B) found that the polyester contained 1.81% by weight of diethylene glycol, which was 2.25 times the amount present in paragraph A above.

Example 11

The effect of yarn dye modulators on fiber liquor was tested in the course of polymerization using the novel coordination compounds of the present invention and conventional catalysts.

(A) A mixture of 735.8 g of dimethyl terephthalate, 534.2 g of ethylene glycol, diacetate, 0.2663 g of dihydrate and 0.2622 g of coordination compound catalyst of Example 3: 1: 3 in Example 3 was carried out according to the method described in Example 9. Was reacted to prepare 605 g of polyester having an intrinsic viscosity of 0.5. Unmodulated polyethylene terephthalate was very pale yellow.

(B) A portion of the polyester of Part A was modulated using 5% by weight of poly [isopropyl iminobis- (trimethylene) succinate] as a dye modulator. This modulator was added to the melt in the compressor in the spinneret at 280 ° C. The modulated polyester did not show any color change until 30 minutes at the temperature of the compressor.

(C) White unmodified polyester 541 g was prepared by the method of the A part using 736.4 g of dimethyl terephthalate, 533.2 g of ethylene glycol, 0.2711 g of zinc acetate dihydrate, and 0.2726 g of antimony dioxide.

(D) The B part method was repeated using the C part polyester. The modulated polyester turned gray.

The spinning process used to prepare the fibers from the four mixtures of A to D is described in the examples below.

The difference between A and C and B and D is due to the rate of addition of a dye modulator to B and D as shown in B.

The polyester was triturated into powder and vacuum dried for 24 hours before spinning. The molten polyester resin was forced through a sand-bed filter at 290 ° C. to remove gel particles, followed by 30 pieces each having a diameter of 0.02 inches at a winding speed of 550 feet per minute. Compressed through a spinner with holes. The tow was stretched by heating on a hot shoe and a hot plate at 95 ° C. The draw ratio was about 4.5: 1. In B and D, dye modifiers were added as shown.

This fiber had the following properties.

Partial Color Denier Rupture Elongation,% Shoulder Cord g / d

(A) white 116 9.4 49

(B) white 127 17.0 3.5

(C) white 111 8.0 4.3

(D) gray 120 14.0 3.6

This data shows that the modulated polyester (B) prepared as the metal coordination compound catalyst of the present invention was of better quality and stability than the modulated polyester (D) prepared using the conventional catalyst system, white to gray.

Example 12

In a similar manner to that described in Example 9, a mixture of 50.1 g of dimethyl terephthalate, 42.7 g of ethylene glycol, zinc acetate dihydrate and 0.0163 g and 0.048 g of the catalyst solution prepared in Example 4 was reacted. The polycondensation time required to produce white polyester with an inherent viscosity of 0.57 was only 24 minutes.

In Part A of Example 9 using the coordination complex catalyst of Example 1, the same viscosity was achieved after 40 minutes of polymerization.

The coordination compound of Example 1 was not previously treated with ethylene glycol as part of the coordination compound of Example 4. This data indicates that pretreatment increases activity and requires only 60% (24 minutes) of the time required in Example 12 to produce polyesters having the same viscosity.

In the part (C) of Example 9 using a conventional zinc acetate-antimony oxide catalyst, the same viscosity was obtained after polycondensation for 60 minutes. This data indicates that the ethylene glycol pretreatment catalytically active liquid of Example 4 increases the activity and only requires 40% (24 minutes) of time required to produce polyesters of the same viscosity.

Example 13

In a similar manner as described in Example 9, a mixture of 939.7 g of dimethyl terephthalate, 32.5 g of ethylene glycol, 0.0181 g of zinc acetate dihydrate and 0.0195 g of the coordination compound catalyst of Example 5 was reacted. The polycondensation time required to prepare the white polyester with an intrinsic viscosity of 0.57 was 30 minutes.

In the same manner, a larger batch was used with 736 g of dimethyl terephthalate, 542 g of ethyleneglycool, 0.303 g of germanium coordination compound and 542 g of ethylene glycol, equivalent to 0.2747 g of zinc acetate dihydrate. The polyester was extruded in fiber-form as described in Example 11. This fiber exhibited 126 deniers, rupture elongation of 16.1% and adenoids of 3.99 g / d.

Example 14

In the method of Example 9, 736 g of dimethyl terephthalate, 542.9 g of ethylene glycol, 0,27 g of zinc acetate dihydrate, and 0.23 g of the coordination compound complex of Example 7 were reacted.

The polyester was white and exhibited an intrinsic viscosity of 0.55. Fibers were prepared in the same manner as described in Example 11. This fiber had a denier of 101, a rupture elongation of 9.7%, and a canon of 4.8 g / d.

Example 15

By the method of Example 9, a mixture of 38.8 g of dimethyl terephthalate, 31.2 g of ethylene glycol, 0.012 g of zinc acetate and 0.02 g of the coordination compound of Example 6 was reacted and polycondensed for about 90 minutes, followed by an average of about 12,500. Polyesters having a molecular weight were prepared.

Claims (1)

Coordination compound catalyst characterized in that the following coordination compounds of (A) and (B) are used as polyesterification catalysts in the preparation of solid fiber-forming polyesters or copolyesters of dicarboxylic acid compounds and aliphatic glycols. Polyester manufacturing method using. From here : (A) is a metal halide of a metal selected from the group consisting of titanium, zirconium, zinc, germanium, tin, lead, antimony and bismuth, (B) is a silicon compound selected from the following groups,

or

(V) diethoxyphosphorylethyl methyl diethoxysilane (VI) 3-aminopropyl triethoxysilane (Iii) 2-cyanoethyl triethoxysilane (iii) 2-mercap ethyltriethoxysilane In the above formula, W is CH ₂ = CX- or

ego, X is hydrogen or methyl, methyl only when m is 1, R ^* is alkyl or haloalkyl having 1-4 carbon atoms, R ^** is methyl, ethyl, butyl, acetoxy, methoxy or butoxy, R is methyl, ethyl, butyl, methoxy, ethoxy, butoxy or trimethylsiloxy, R 'is methyl, methoxy, ethoxy, butoxy or trimethylsiloxy, R 'is methoxy, ethoxy, butoxy, trimethylsiloxy or vinyldimethyl siloxy, R 'is methyl, ethyl, butyl or trimethylsilyl, Me is methyl, Z is methyl or W, Q is an NC-, HS- or HSCH2CH2S- group, n is an integer with a number from 2-5, m is an integer with a value of 0 or 1, X is an integer with a number from 1-100, y is an integer with a value from 1-100. The molar ratio of AB in the above-mentioned coordination complex is 1: 1-1: 7.