WO2001023456A1

WO2001023456A1 - Polymerization catalyst for polyester, polyester produced with the same, and process for producing polyester

Info

Publication number: WO2001023456A1
Application number: PCT/JP2000/006865
Authority: WO
Inventors: Takahiro Nakajima; Ken-Ichi Tsukamoto; Shoichi Gyobu
Original assignee: Toyo Boseki Kabushiki Kaisha
Priority date: 1999-09-30
Filing date: 2000-10-02
Publication date: 2001-04-05
Also published as: AU7453200A

Abstract

A novel polymerization catalyst for polyesters which contains no antimony compounds. The catalyst comprises an aluminum compound and a phosphorus compound having a phenol moiety in the same molecule, and is used as a polymerization catalyst in producing a polyester. The polyester is applicable to clothing fibers, fibers for industrial materials, various films and sheets, various moldings such as bottles and engineering plastics, coating materials, adhesives, etc.

Description

Description: Polyester polymerization catalyst, polyester produced using the same, and method for producing polyester

Technical field

The present invention relates to a polyester polymerization catalyst, a polyester produced using the same, and a method for producing a polyester.More specifically, the present invention relates to a novel polyester polymerization catalyst not using an antimony compound, and a production method using the same. The present invention relates to a polyester produced and a method for producing the polyester.

Background art

Polyester, especially polyethylene terephthalate (hereinafter abbreviated as PET), has excellent mechanical and chemical properties and can be used for many purposes, such as textiles for clothing and industrial materials, packaging and other materials. It has been applied to various film sheets such as magnetic tapes, and molded products such as bottles and engineering plastics.

PET industrially produces bis (2-hydroxyxethyl) terephthalate by esterification or transesterification of terephthalic acid or dimethyl terephthalate with ethylenic alcohol, which is produced under high temperature and vacuum. It is obtained by polycondensation using a catalyst. Antimony trioxide is widely used as a catalyst for polycondensation. Antimony trioxide is a catalyst that is inexpensive and has excellent catalytic activity, but has the problem that blackening and foreign matter are generated in PET because metal antimony precipitates during polycondensation. Recently, environmental issues have been pointed out regarding the safety of antimony. Under such circumstances, polyesters containing no or only a very small amount of antimony have been desired.

Attempts have been made to use antimony trioxide as a polycondensation catalyst and to suppress the occurrence of darkening and foreign matter in PET. For example, Patent No. 2666502 , The use of antimony trioxide, a compound of bismuth and selenium as a polycondensation catalyst suppresses the formation of black foreign substances in PET. JP-A-9-291141 also states that the use of antimony trioxide containing sodium and iron oxides as a polycondensation catalyst suppresses the deposition of antimony metal. I have. However, these polycondensation catalysts cannot achieve the purpose of an antimony-free polyester after all.

Studies have been made on polycondensation catalysts that can replace antimony trioxide. In particular, titanium compounds typified by tetraalkoxy titanates have already been proposed, but the PET produced using these compounds has problems that they are significantly colored and that thermal decomposition easily occurs.

As an attempt to overcome such problems when using a tetraalkoxy titanate as a polycondensation catalyst, for example, Japanese Patent Application Laid-Open No. 55-116722 discloses that A method that is used simultaneously with salt has been proposed. Japanese Patent Application Laid-Open No. 8-73581 proposes a method in which tetraalkoxy titanate is used simultaneously with a cobalt compound as a polycondensation catalyst, and a fluorescent whitening agent is used. However, in these proposals, although the coloring of PET is reduced when tetraalkoxy titanate is used as a polycondensation catalyst, it has been achieved that the thermal decomposition of PET is effectively suppressed. Absent.

Germanium compounds have been put into practical use as polycondensation catalysts that can replace antimony trioxide and that overcome problems such as the use of tetraalkoxy titanate. There are problems that it is expensive and that the catalyst concentration in the reaction system changes due to distilling out of the reaction system during polymerization, making it difficult to control the polymerization.

It is known that aluminum compounds generally have poor catalytic activity. Among aluminum compounds, aluminum chelate compounds are other aluminum compounds. It has been reported that it has higher catalytic activity as a polycondensation catalyst than minium compounds, but it cannot be said that it has sufficient catalytic activity compared to the above-mentioned antimony compounds and titanium compounds, and aluminum compounds Polyester polymerized over a long period of time using as a catalyst has a problem of poor thermal stability.

Generally, a phenolic compound or a phosphorus compound having a phenol moiety in the same molecule is well known as an antioxidant, and is known to be capable of suppressing the thermal decomposition of a polyester. Phosphorus compounds having a phenol moiety in the same molecule can suppress thermal decomposition in this way, but these compounds greatly accelerate the polymerization reaction without substantially changing the melting point of the polyester. Is not known. In practice, when an ester is polymerized using an antimony compound, a titanium compound, or a germanium compound, which is a typical catalyst for polyester polymerization, as a polymerization catalyst, a phosphorus compound having a phenol moiety in the same molecule is added. However, it is not found that the polymerization is promoted to a substantially useful level. The present invention provides a novel polycondensation catalyst other than an antimony compound, a polyester produced using the same, and a method for producing a polyester.

Disclosure of the invention

The authors of the present invention examined the effect of adding various antioxidants at the time of polymerization for the purpose of improving the thermal stability of polyester polymerized using an aluminum compound as a catalyst. By combining a phosphorus compound having a moiety in the same molecule, the thermal stability of the polyester is improved, and the aluminum compound, which originally has poor catalytic activity, has sufficient activity as a polycondensation catalyst This has led to the present invention. By using the polycondensation catalyst of the present invention, it is possible to obtain a polyester having excellent quality without using an antimony compound.

That is, the present invention provides an aluminum compound as a solution to the above problem. A polyester polymerization catalyst comprising a phosphorus compound having a phenol part in the same molecule and a method for producing a polyester and a polyester produced by using the same are provided as follows.

(1) A polyester polymerization catalyst consisting of an aluminum compound and a phosphorus compound having a phenol moiety in the same molecule.

(2) Phosphoric acid-based compounds, phosphinic acid-based compounds, phosphinoxide-based compounds, phosphonous acid-based compounds, and phosphonous acid-based compounds are those phosphorus compounds having a phenol moiety in the same molecule. The polyester polymerization catalyst according to [1], which is one or more compounds selected from the group consisting of phosphine compounds.

(3) The polyester polymerization catalyst according to (2), wherein the phosphorus compound having a phenol moiety in the same molecule is one or more phosphonic acid compounds.

リ A phosphorus compound having a phenol moiety in the same molecule is represented by the following general formula (1)

(1) The polyester polymerization catalyst according to (1), which is one or more selected from the group consisting of the compounds represented by (3).

P (= 〇) R ¹ (OR ² ) (OR ³ ) (1)

P (= 〇) R ¹ ^ ⁴ (OR ² ) (2)

P (= 〇) R ¹ R ⁵ R ⁶ (3)

(In the formulas (1) to (3), R ¹ is a hydrocarbon group having 1 to 50 carbon atoms including a phenol part, a hydroxyl group or a halogen group, an alkoxyl group or an amino group, and a carbon number including a phenol part.) 1 represents a 50 hydrocarbon group. containing R ^4, R ^5, hydrogen R ⁶ are each independently a hydrocarbon group, a hydroxyl group or a c port plasminogen group, an alkoxyl group, or an § Mi amino group of 1 to 50 carbon atoms Represents a hydrocarbon group having 1 to 50 carbon atoms, and R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a hydrocarbon group having 1 to 50 carbon atoms including an alkoxyl group. However, the hydrocarbon group may have a branched structure, an alicyclic structure or an aromatic ring structure, and the terminal of R ⁴ may be bonded to each other.)

⑤Alkali metals and their compounds and alkaline earth metals and their (1) The polyester polymerization catalyst according to any one of (1) to (4), wherein one or more members selected from the group consisting of the compounds are present.

A polyester produced using the catalyst according to any one of the above items 1 to 3.

(4) A method for producing a polyester, comprising using the catalyst described in any of (1) to (4) above when producing the polyester.

[5] The method for producing a polyester according to [1], wherein, when producing the polyester, the antimony compound is added as an antimony atom in an amount of 50 ppm or less to the polyester.

{The method for producing a polyester according to {}, wherein, when producing the polyester, a germanium compound is added as a germanium atom in an amount of 20 ppm or less to the polyester.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention provides a novel polycondensation catalyst other than an antimony compound, a polyester produced using the same, and a method for producing a polyester. The polycondensation catalyst of the present invention is a polyester polymerization catalyst comprising an aluminum compound and a phosphorus compound having a phenol moiety in the same molecule.

The aluminum compound constituting the polycondensation catalyst of the present invention is not particularly limited. Examples thereof include aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, and lauric acid. Aluminum, aluminum stearate, aluminum benzoate, trichloroaluminum acetate, aluminum lactate, aluminum citrate, aluminum salicylate, etc.Rubonate, aluminum chloride, hydroxide Inorganic acid salts such as aluminum, aluminum hydroxide chloride, aluminum carbonate, aluminum phosphate, aluminum phosphonate, aluminum methoxide, aluminum ethoxide, aluminum n-propoxide, aluminum i so- Propoxide, aluminum n-butoxide, aluminum t-butoxide Aluminum chelate compounds such as aluminum alkoxide, aluminum acetyl acetate, aluminum acetyl acetate, aluminum ethyl acetate acetate, aluminum ethyl acetate acetate, etc. Organic aluminum compounds such as methylaluminum and triethylaluminum, and partial hydrolysates thereof, aluminum oxide, metallic aluminum, and the like. Of these, carboxylate, inorganic acid salt and chelate compound are preferred, and among these, aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetyl acetate are particularly preferred. preferable.

The amount of aluminum compound of the invention, the entire configuration Interview force carboxylic acid component such as di-force carboxylic acid or polycarboxylic acid of the resulting polyester Le two Tsu bets against moles 5 x 1 (Γ ⁷ It is preferably from 0.01 to 0.01 mol, more preferably from 1 × 10 to ^{6 to} 0.005 mol.

The phosphorus compound having a phenol moiety in the same molecule constituting the polycondensation catalyst of the present invention is not particularly limited as long as it is a phosphorus compound having a phenol structure. Selected from the group consisting of phosphonic acid compounds, phosphinic acid compounds, phosphinic oxide compounds, phosphinous acid compounds, phosphinous acid compounds, and phosphinic compounds When one or more compounds are used, the effect of improving the catalytic activity is greatly increased, which is preferable. Among these, the use of a phosphonic acid-based compound having one or more phenol moieties in the same molecule is particularly preferable because the effect of improving the catalytic activity is particularly large.

The phosphonic acid compound, phosphinic acid compound, phosphinoxide compound, phosphonous acid compound, phosphinous acid compound and phosphine compound referred to in the present invention are represented by the following formula ( 4) A compound having a structure represented by any one of (9) to (9).

o

II

-p—o- (5)

-o- p- o- (7)

-p― o- (8)

“(9) Examples of the phosphonic acid-based compound having a phenol moiety in the same molecule as the present invention include, for example, p-hydroxyphenylphosphonic acid, p-dimethylhydroxyphenylphosphonate, p-hydroxyphenylphosphonic acid jet And phenyl p-hydroxyphenylphosphonate, etc. Examples of the phosphinate compound having a phenol moiety in the same molecule include bis (p-hydroxyphenyl) phosphine. Acid, bis (p-hydroxyphenyl) phosphinic acid methyl, bis (p-hydroxyphenyl) phosphinic acid phenyl, p-hydroxyphenylphenylphosphinic acid, p-hydroxyphenylphenylphosphinic acid Methyl phosphate, p-hydroxyphenylphenylphosphinate Sulfonyl, p - human Dorokishifu Eniruhosufu fin acid, p - human Dorokishifu Eniruhosufu fin methyl, p Phenylhydroxyphenyl phosphinate; and compounds represented by the following formulas (10) to (13). Examples of the phosphinoxide compound having a phenol moiety in the same molecule of the present invention include bis (p-hydroxyphenyl) phosphine oxide, tris (p-hydroxyphenyl) phosphine oxide, and bis (p-hydroxyphenyl) phosphine oxide. (P-hydroxyphenyl) methyl phosphinoxide and the like.

Further, when a compound represented by the following general formulas (1) to (3) is used as the phosphorus compound having a phenol moiety in the same molecule constituting the polycondensation catalyst of the present invention, the catalytic activity is particularly improved. Therefore, it is preferable.

P (= 〇) R ¹ (OR ² ) (OR ³ ) (1)

P (= 0) FTR ⁴ (OR ² ) (2)

P (= 0) R ¹ R ⁵ R ⁶ (3)

(In the formulas (1) to (3), R ¹ includes a substituent such as a hydrocarbon group having 1 to 50 carbon atoms including a phenol part, a hydroxyl group, a halogen group, an alkoxyl group or an amino group, and a phenol part. Represents a hydrocarbon group having 1 to 50 carbon atoms R ^4, R ⁵ and R ⁶ are each independently hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group or an amino group; Represents a hydrocarbon group having 1 to 50 carbon atoms including a substituent, and R ² and R ³ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 50 carbon atoms, a carbon number including a substituent such as a hydroxyl group or an alkoxyl group. 1 represents a 5 0 hydrocarbon group. However, the hydrocarbon group and alicyclic structure Ya off cycloalkenyl or aromatic ring structure naphthyl may contain. R ² of hexyl, etc., to the branch structure Ya consequent opening R The ends of ⁴ may be bonded.)

Examples of the phosphorus compounds of the present invention having a phenol moiety in the same molecule include, for example, p-hydroxyphenylphosphonic acid, dimethyl p-hydroxyphenylphosphonate, getyl p-hydroxyphenylphosphonate, and p-hydroxyphenylphosphonate. Diphenylphosphonate, bis (p-hydroxyphenyl) phosphinic acid, bis (p-hydroxyphenyl) phosphinic acid Tyl, bis (p-hydroxyphenyl) phosphinic acid phenyl, p-hydroxyphenylphenylphosphinic acid, p-methylhydroxyphenylphenylphosphinic acid, p-hydroxyphenylphenylphosphinic acid phenyl , P—hydroxyphenylphosphinic acid, p—methyl hydroxyphenylphosphinate, p—hydroxyphenylphenylphosphonate, bis (p—hydroxyphenyl) phosphine oxide, tris (p — Hydroxyphenyl) phosphine oxide, bis (p-hydroxyphenyl) methylphosphinoxide, and the following formula (10)

And the compound represented by (13). Among these, the compound represented by the following formula (12) and dimethyl ρ-hydro □ xyphenylphosphonate are particularly preferred.

As the compound represented by the above formula (12), SANK0-220 (manufactured by Sanko Co., Ltd.) is available.

By adding a phosphorus compound having such a phenol moiety in the same molecule during the polymerization of the polyester, the catalytic activity of the aluminum compound is improved and the thermal stability of the polymerized polyester is also improved.

The amount of the phosphorus compound having a phenol moiety in the same molecule of the present invention is 5 × 5 mol per mol of all constituent units of the carboxylic acid component such as dicarboxylic acid or polycarboxylic acid of the obtained polyester. 10 ⁷ to 0.01 mol, more preferably an IX 10 ⁶ to 0.005 mol.

In addition to the aluminum compound and the phosphorus compound having a phenol moiety in the same molecule as the polycondensation catalyst of the present invention, the polycondensation catalyst comprises an alkali metal and a compound thereof, and an alkaline earth metal and a compound thereof. The coexistence of one or more metals or metal compounds selected from the group is preferable because the catalytic activity can be further improved.

Alkali metals and their compounds and alkaline earth metals and their compounds according to the present invention include, in addition to alkaline metals and alkaline earth metals, Li, Na, K, Rb, Cs, Be , Mg, Ca, Sr, and Ba are not particularly limited as long as they are one or more compounds selected from the group consisting of, for example, saturated aliphatic aliphatic acids such as formic acid, acetic acid, propionic acid, butyric acid, and oxalic acid. Carboxylic acid salts, unsaturated aliphatic carboxylic acid salts such as acrylic acid and methacrylic acid, aromatic carboxylic acid salts such as benzoic acid, halogen-containing carboxylic acid salts such as trichloroacetic acid, lactic acid, citric acid, Hydroxycarboxylic acid salts such as salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen carbonate, hydrogen phosphate, hydrogen sulfate, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid, bromine Inorganic acid salts such as acids, Organic sulfonates such as lopansulfonic acid, 1-pentanesulfonic acid, and naphthalenesulfonic acid; organic sulfates such as lauryl sulfate; methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy , Tert-alkoxides such as butoxy, chelating compounds such as acetyl acetate, Examples include hydrides, oxides, and hydroxides. Among these alkali metals, their compounds and alkaline earth metals and their compounds, when those having strong alkaline properties such as hydroxides are used, they may be diols such as ethylene glycol or the like. Since it tends to be difficult to dissolve in organic solvents such as alcohols, it must be added to the polymerization system in an aqueous solution, which is a problem in the polymerization process. Furthermore, when a highly alkaline substance such as a hydroxide is used, the polyester is liable to undergo side reactions such as hydrolysis during the polymerization, and the polymerized polyester tends to be easily colored. Also tend to decline. Accordingly, the alkali metals and compounds thereof of the present invention, and alkaline earth metals and compounds thereof, which are suitable as the alkaline metals and alkaline earth metal saturated aliphatic carboxylate, Unsaturated aliphatic carboxylate, aromatic carboxylate, halogen-containing carboxylate, hydroxycarboxylate, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen phosphate, hydrogen sulfate, sulfurous acid, thiosulfate, An inorganic acid salt, an organic sulfonate, an organic sulfate, a chelate compound, and an oxide selected from hydrochloric acid, hydrobromic acid, chloric acid, and bromic acid. Among these, from the viewpoints of ease of handling and availability, etc., the saturated aliphatic lithium carbonates of alkali metals and alkaline earth metals, especially those of alkaline metals and alkaline earth metals, Acetate is preferred.

The amounts of these alkali metals and their compounds, and the alkali earth metals and their compounds, are determined based on the total composition units of the dicarboxylic acid and polyvalent rubonic acid components of the resulting polyester. IX 10 "is preferably in the range of ⁶ to 0.1 mol with respect to the number of moles, and more preferably IX 10".

5 is that x 1 0- ⁶ is in the range of ~ 0.05 mol.

The production of the polyester according to the present invention can be carried out by a conventionally known method. For example, when manufacturing PET, terephthalic acid and ethylene glycol

-Polyesterification followed by polycondensation, or the reaction of an alkyl ester of terephthalic acid such as dimethyl terephthalate with ethylene glycol After the transesterification reaction, any of the polycondensation methods can be used. The polymerization apparatus may be a batch type or a continuous type.

The catalyst of the present invention has catalytic activity not only in polycondensation reaction but also in esterification reaction and ester exchange reaction. The transesterification reaction of an alkyl ester of dicarbonic acid such as dimethyl terephthalate with a glycol such as ethylen glycol is usually carried out in the presence of a transesterification catalyst such as zinc. The catalyst of the present invention can be used together with the catalyst. Further, the catalyst of the present invention has catalytic activity not only in melt polymerization but also in solid phase polymerization and solution polymerization.

The time for adding the polycondensation catalyst of the present invention is preferably immediately before the start of the polycondensation reaction, but it can also be added to the reaction system before the start of the esterification reaction or the transesterification reaction and at any stage during the reaction. In particular, the aluminum compound is preferably added immediately before the start of the polycondensation reaction.

The method of adding the polycondensation catalyst of the present invention may be in the form of powder or neat, may be in the form of a slurry or a solution of a solvent such as ethylene glycol, and is not particularly limited. Alternatively, a mixture of an aluminum compound and a phosphorus compound having a phenol portion in the same molecule in a solvent such as neat or ethylene glycol may be added. They may be added separately. In addition, the aluminum compound and the phosphorus compound having a phenol L moiety in the same molecule may be added at the same addition time, or they may be added at different addition times. In addition, an aluminum compound and a phosphorus compound having a phenol moiety in the same molecule, and an alkali metal, or a compound thereof, or an alkaline earth metal or a mixture thereof are added in advance. Or these may be added separately. Further, they may be added at the same addition time, or they may be added at different addition times.

When polymerizing a polyester using the polymerization catalyst of the present invention, an antimony And a germanium compound. However, it is preferable to add the antimony compound in an amount of 50 ppm or less as an antimony atom to the polyester obtained by polymerization. More preferably, it is added in an amount of 30 ppDi or less. If the amount of antimony is set to 50 ppm or more, precipitation of metallic antimony occurs, and darkening or foreign matter is generated in polyester, which is not preferable. The germanium compound is preferably added to a polyester obtained by polymerization in an amount of 20 ppm or less as germanium atoms. More preferably, it is added in an amount of 10 ppm or less. It is not preferable to add germanium in an amount of 20 ppm or more because it is disadvantageous in terms of cost.

Examples of the antimony compound used in the present invention include antimony trioxide, antimony pentoxide, antimony acetate, antimony glycoxide, and the like. Of these, antimony trioxide is preferable. Examples of the germanium compound include germanium dioxide and germanium tetrachloride, among which germanium dioxide is preferable.

Further, the polymerization catalyst of the present invention can coexist with other polymerization catalysts such as a titanium compound, a tin compound, and a cobalt compound within a range that does not impair the thermal stability and color tone of the polyester.

The polyester referred to in the present invention is composed of one or more selected from polycarboxylic acids containing dicarboxylic acids and their ester-forming derivatives, and one or more selected from polyhydric alcohols containing glycol. Or those composed of hydroxycarboxylic acids and their ester-forming derivatives, or those composed of cyclic esters.

Examples of dicarboxylic acids include oxalic acid, malonic acid, succinic acid, daltaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, and tetradecanedicarboxylic acid. Acid, hexadecanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, Saturated aliphatic dicarboxylic acids exemplified by 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer acid and the like, and ester-forming derivatives thereof, and fumaric acid Acids, maleic acid, itaconic acid, etc., unsaturated aliphatic dicarboxylic acids or their ester-forming derivatives, orthophthalic acid, isophthalic acid, terephthalic acid, 5- (alkali metal) sulfoisophthalic acid , Diphenic acid, 1.3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4 , 4'-biphenyldicarboxylic acid, 4,4'-biphenylsulfonedicarboxylic acid, 4,4'-biphenylethyldicarboxylic acid, 1,2 —Bis (phenoxy) ethane—p, p ′ —Aromatic dicarboxylic acids exemplified by dicarboxylic acid, pamoic acid, anthracene dicarboxylic acid and the like or ester-forming derivatives thereof, among these dicarboxylic acids Terephthalic acid and naphthalenedicarboxylic acid are preferred, especially 2.6-naphthalenedicarboxylic acid.

Polycarboxylic acids other than these dicarboxylic acids include ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3, 4 , 3 ', 4'-biphenyltetracarboxylic acid, and ester-forming derivatives thereof.

Glycols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol Cole, 2, 3-butylene glycol, 1, 4-butylene glycol,

1,5-pentanediol, neopentylglycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexane Diol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexane Aliphatic exemplified by dimethylethanol, 1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, polyethylene dalichol, polytrimethylene glycol, polytetramethylene glycol, etc. Glycol, hydroxyquinone, 4,4'-dihydroxybisphenol, 1,4-bis () 3-hydroxyethoxy) benzene, 1,4-bis () 3-hydroxyethoxyphenyl ) Sulfone, bis (p-hydroxyphenyl) ether, bis (p-hydroxyphenyl) sulfone, bis (p-hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) ethane, bisphenol A, Bisphenol C, 2,5-naphthalenediol, these glycols with ethylene oxide Dali call that, it includes aromatic Dali calls illustrated in such as ethylene glycol Of these glycol and 1.4 Buchiren glycol are preferred.

Examples of polyhydric alcohols other than these glycols include trimethylol methane, trimethylol monolethane, trimethylolpropane, pentaerythritol, glycerol, and hexane triol.

Examples of hydroxycarponic acid include lactic acid, cunic acid, lingic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, 4- Hydroxycyclohexane carboxylic acid, or an ester-forming derivative thereof, and the like can be given. Cyclic esters include £ -caprolactone, (3-propiolactone, | 3-methyl-i3-propiolactone, δ-norrelactone, glycolide, and lactide.

In addition, the polyester of the present invention can contain a known phosphorus compound as a copolymer component. As the phosphorus compound, a bifunctional phosphorus compound is preferable, for example, dimethyl phenylphosphonate, diphenyl phenylphosphonate, (2-carboxyl) methylphosphinic acid, (2-carboxylethyl) phenylphosphinic acid , (2-methoxycarboxyl) Methyl phenylphosphinate, (4-methoxycarbonylphenyl) methylphenylphosphinate, ethylene glycol ester of [2- (| 3-hydroxyethoxycarbonyl) ethyl] methylphosphinic acid, (1,2 -Dicarboxyl) dimethylphosphinoxide, 9,10-dihydro-10-oxa- (2,3-carboxypropyl) -10-phosphaphenanthrene-10-oxide. By containing these phosphorus compounds as copolymer components, it is possible to improve the flame retardancy and the like of the obtained polyester. Examples of the ester-forming derivative of a polycarboxylic acid or a hydroxycarboxylic acid include these alkyl esters, acid chlorides, and acid anhydrides.

The polyester used in the present invention is a polyester whose main acid component is terephthalic acid or its ester-forming derivative or naphthylenedicarboxylic acid or its ester-forming derivative, and whose main glycol component is an alkylene glycol. I like it. Polyester whose main acid component is terephthalic acid or its ester-forming derivative or naphthalenedicarboxylic acid or its ester-forming derivative is defined as terephthalic acid or its ester-forming derivative and naphtha- It is preferable that the polyester contains a total of 70 mol% or more of range carboxylic acid or an ester-forming derivative thereof, more preferably a polyester containing 80 mol% or more, and further preferably 90 mol%. It is a polyester contained above. The polyester in which the main component is alkylene glycol is preferably a polyester containing alkylene glycol in a total amount of at least 70 mol%, more preferably at least 80 mol%, based on all the glycol components. Polyester, more preferably 90% by mole or more. The alkylene glycol referred to herein may have a substituent or an alicyclic structure in the molecular chain. Examples of the naphthalenedicarboxylic acid or its ester-forming derivative used in the present invention include 1,3-naphthalenedicarboxylic acid and 1,4-naphthalenedicarboxylic acid Preferred are dicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and ester-forming derivatives thereof.

The alkylene glycols used in the present invention include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3 — Butylene glycol, 1,4-butylene glycol, 1,5-pentaneddiol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol 1,4-cyclohexane dimethanol, 1,2-cyclohexane dimethanol, 1,3-cyclohexane dimethanol, 1,4-cyclohexane dimethanol, 1,

4-cyclohexanediethanol, 1,10-decamethylenedalicol, 1,12-dodecanediol and the like. Two or more of these may be used at the same time.

The polyester of the present invention contains oxalic acid, malonic acid, succinic acid, daltaric acid, adipic acid, pime acid as an acid component other than terephthalic acid or its ester-forming derivative, naphthalenedicarboxylic acid or its ester-forming derivative. Phosphoric acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadenic dicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,3-cyclohexane Bentanedicarboxylic acid, 1.2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,

Saturated aliphatic dicarboxylic acids exemplified by 5-norbornanedicarboxylic acid, dimeric acid and the like, and ester-forming derivatives thereof, unsaturated aliphatic dicarboxylic acids exemplified by fumaric acid, maleic acid, itaconic acid, etc. Or their ester-forming derivatives, orthophthalic acid, isophthalic acid,

(Alkali metal) sulfoisophtalic acid, diphenic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-biphenylsulfondicarboxylic acid, 4, 4'-biphenyletherdicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-Dicarboxylic acid, pamoic acid, anthracenedicarboxylic acid, etc. or aromatic dicarboxylic acids or esters thereof. Sex derivatives, ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromelitic acid, trimellitic acid, trimesic acid, 3, 4, 3 ', 4'-biphenyltetracarboxylic acid, etc. Polycarboxylic acids and ester-forming derivatives thereof exemplified above can be contained as copolymer components. Also, lactic acid, cunic acid, lingic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, 4-hydroxycyclohexane Hydroxycarboxylic acids exemplified by carboxylic acids or ester-forming derivatives thereof can also be included. It also contains cyclic esters such as £ -proprolactone,) 3-propiolactone, / 3-methyl-3-propiolactone, ό-norrelactone, glycolide and lactide. Can also.

The polyester of the present invention includes, as glycol components other than alkylene glycol, aliphatic glycols exemplified by diethylene glycol, triethylene glycol, polyethylene glycol, polyethylene glycol, polyethylene glycol, polytetramethylene glycol, and the like. Hydroquinone, 4,4'-dihydroxybisphenol, 1,4-bis (3-hydroxyethoxy) benzene, 1,4-bis (i3-hydroxyethoxyphenyl) sulfone, bis (p-hydroxyphenyl) ether, Bis (p-hydroxyphenyl) sulfone, bis (p-hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) ethane, bisphenol A, bisphenol (, 2,5-naphthalenediol, Ethylene is added to these glycols. Oxidized glycols, such as aromatic glycols, trimethylolmethane, trimethylol monolethane, trimethylolpropane, pentaerythritol, glycerol, hexanetriol, etc. A polyhydric alcohol or the like can be contained as a copolymer component. In addition, the polyester of the present invention can contain a known phosphorus compound as a copolymer component. As the phosphorus compound, a bifunctional phosphorus compound is preferred, and examples thereof include dimethyl phenylphosphonate, diphenyl phenylphosphonate, (2-carboxyl) methylphosphinic acid, (2-carboxyethyl) phenylphosphinic acid, -Methoxycarboxyethyl) methyl phenylphosphinate, Methyl (4-methoxycarbonylphenyl) phenylphosphinate, Ethylene of [2-(/ 3-hydroxyethoxycarbonyl) ethyl] methylphosphinic acid Glycol ester, (1,2-dicarboxyl) dimethylphosphinoxide, 9,10-dihydro-10-oxa- (2.3-carboxypropyl) -10-phosphaphenanthrene-10-oxo And the like. By including these phosphorus compounds as copolymer components, it is possible to improve the flame retardancy and the like of the obtained polyester. Examples of the polyester of the present invention include polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, poly (1,4-cyclohexanedimethylene terephthalate), polyethylene naphthate, and polybutylene naphthalate. And polypropylene naphthalate and their copolymers are preferred, and among them polyethylene terephthalate and this copolymer are particularly preferred.

The polyester of the present invention may contain phosphorus-based, sulfur-based, amine-based stabilizers or phenol-based or aromatic amine-based antioxidants, and these may be used alone or in combination. By containing more than one kind, the thermal stability of the polyester can be enhanced.

Phosphorus stabilizers include phosphoric acid esters such as phosphoric acid and trimethyl phosphate, phosphorous acid, triphenyl phosphite, and tris (2,4-di-tert. Phosphite, Tetrakis (2,4-di-tert-butylphenyl) 4,4'-Biphenyl Phenyl phosphite, etc. Distearyl pentaerythritol diphosphite Phosphonic acid esters such as iron, phosphonic acids such as methylphosphonic acid, phenylphosphonic acid, etc. And mono- or di-alkyl esters of phosphonic acid.

Examples of phenolic antioxidants include tetrakis- [methyl-3- (3 ', 5'-di-tert-butyl-4-hydroxyphenyl) propionate] methane and 4,4'-butylidenebis- (3- Methyl-6-tert-butylphenyl), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, thiomethylene And monobis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate].

The polyester of the present invention may contain a bluing agent such as a cobalt compound, an organic, inorganic, or organometallic toner, and a fluorescent whitening agent. By containing the above, coloring such as yellowing of the polyester can be suppressed.

The polyester of the present invention contains other optional polymers, stabilizers, antioxidants, antistatic agents, antifoaming agents, dyeing improvers, dyes, pigments, anti-glazing agents, and other additives. You may.

Example

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. In each of the examples and comparative examples, the intrinsic viscosity (IV) of the polyester was measured as follows. The measurement was performed at a temperature of 30 ° C using a 6/4 mixed solvent (weight ratio) of phenol I 1,1,2,2-tetrachloroethane.

(Example 1)

As a catalyst for bis (2-hydroxyxethyl) terephthalate, a 3 g / l ethylene glycol solution of aluminum chloride is used as a catalyst for the acid component in the polyester 0.015 mol% as aluminum Then, the compound represented by the formula (12) (compound A) was added in an amount of 0.01 mol% to the acid component in the polyester, and the mixture was stirred at normal pressure at 245 ° C for 10 minutes. Then, over 50 minutes, the temperature of the reaction system was gradually decreased while the temperature was raised to 275 ° C to 0.1 mmHg, and the polycondensation reaction was further performed at the same temperature and pressure for 3 hours. Physical properties of the obtained polymer The values are shown in Table 1. Compound A used SANK0-220 manufactured by Sanko Co., Ltd.

(Examples 2-7 and Comparative Examples 1-2)

A polyester was polymerized in exactly the same manner as in Example 1 except that the catalyst was changed. Table 1 shows the physical property values of the obtained polymer. In the table, the compound A indicates the compound represented by the above formula (12), and the compound B indicates dimethyl p-hydroxyphenylphosphonate. Compound A used SANKO-220 manufactured by Sanko Co., Ltd. The amount of metal catalyst added is the amount added as metal atoms.

(Comparative Example 3)

As a catalyst, antimony trioxide was added as an antimony atom in an amount of 0.05 mol% to the acid component in the polyester, and the polyester was polymerized in the same manner as in Example 1. Table 1 shows the physical property values of the obtained polymer.

(Comparative Example 4)

As a catalyst, 0.05 mol% of antimony trioxide is added as an antimony atom to the acid component in the polyester, and then the compound represented by the above formula (12) (compound A) is added to the acid in the polyester. A polyester was polymerized in the same manner as in Example 1, except that 0.01 mol ° / _{o was} added to the components. Table 1 shows the physical properties of the obtained polymer. Compound A used was SAM0-220 manufactured by Sanko Co., Ltd.

When the phosphorus compound of the present invention having a phenol moiety in the same molecule is used together with an antimony compound, the catalytic activity of the antimony compound is not affected, but the phosphorus compound having the phenol moiety in the same molecule is not affected. When the compound is used in combination with the aluminum compound of the present invention, the catalytic activity of the aluminum compound, which originally had poor catalytic activity, is greatly improved, and the catalytic activity becomes equivalent to that of the antimony compound. . table 1

Industrial applications

According to the present invention, a novel polycondensation catalyst other than an antimony compound, a polyester produced using the same, and a method for producing a polyester are provided. The polyester of the present invention can be applied to textiles for clothing, textiles for industrial materials, various films, sheets, molded products such as bottles and engineering plastics, and paints and adhesives. It is.

Claims

The scope of the claims

1. A polyester polymerization catalyst comprising an aluminum compound and a phosphorus compound having a phenol moiety in the same molecule.

2. Phosphoric acid compounds, phosphinic acid compounds, phosphinic oxide compounds, phosphonous acid compounds, and phosphinous acid compounds 2. The polyester polymerization catalyst according to claim 1, which is one or two or more compounds selected from the group consisting of phosphine compounds.

3. The polyester polymerization catalyst according to claim 1, wherein the phosphorus compound having a phenol moiety in the same molecule is one or more phosphonic acid compounds.

4. The polyester polymerization according to claim 1, wherein the phosphorus compound having a phenol moiety in the same molecule is one or more selected from the group consisting of compounds represented by the following general formulas (1) to (3). catalyst.

P (= 〇) R ¹ (OR ² ) (OR ³ ) (1)

P (= 〇) R ¹ R ⁴ (OR ² ) (2)

P (= 0) R ¹ R ⁵ R ⁶ (3)

(In the formulas (1) to (3), R ¹ is a hydrocarbon group having 1 to 50 carbon atoms including a phenol part, a hydroxyl group or a halogen group, an alkoxyl group or an amino group, and a carbon number including a phenol part. Represents a hydrocarbon group of 1 to 50. R ⁴ , R ⁵ , and R ⁶ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group; Represents a hydrocarbon group of numbers 1 to 50. R ² and R ³ each independently represent hydrogen, a hydrocarbon group of 1 to 50 carbon atoms, a hydrocarbon group of 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. However, the hydrocarbon group may have a branched structure, an alicyclic structure, or an aromatic ring structure. The terminals of R ² and R ⁴ may be bonded to each other.)

5. Al metal and their compounds, and earth metal and metal 5. The polyester polymerization catalyst according to claim 1, wherein one or more selected from the group consisting of these compounds coexist.

6. A polyester produced using the catalyst according to any one of claims 1 to 5.

7. A method for producing a polyester, comprising using the catalyst according to any one of claims 1 to 5 when producing the polyester.

8. BH characterized in that an antimony compound is added as an antimony atom in an amount of 50 ppm or less to the polyester when producing the polyester.

8. The method for producing a polyester according to claim 7.

9. The method for producing a polyester according to claim 7, wherein, when producing the polyester, a germanium compound is added as a germanium atom in an amount of 20 ppm or less based on the polyester.