CN101029126B

CN101029126B - Polyester catalyst for polymerization, polyester and method thereby

Info

Publication number: CN101029126B
Application number: CN200610095882A
Authority: CN
Inventors: 中嶋孝宏; 塚本健一; 形舞祥一; 森山畅夫; 桑田光启; 松井义直; 林清秀; 伊藤胜也; 松田全央
Original assignee: Toyo Textile Co Ltd
Current assignee: Toyo Textile Co Ltd
Priority date: 2001-02-23
Filing date: 2001-02-23
Publication date: 2012-08-29
Anticipated expiration: 2021-02-23
Also published as: CN101029126A

Abstract

A polyester condensed catalyst and production of polyester are disclosed. The catalyst consists of aluminum compound and phosphor compound and the final product is thin-film fibrous hollow formed substance.

Description

Catalyst for polymerization of polyester, utilize the method for manufacture of its polyester that makes and polyester

Technical field

The present invention relates to catalyst for polymerization of polyester, utilize the method for manufacture of its polyester that makes and polyester; In more detail, relate to not germanium, antimony compounds as the catalyzer staple and the novel catalyst for polymerization of polyester that uses, the method for manufacture of utilizing its polyester that makes and polyester.

Background technology

With the polyester as representative such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), PEN (PEN); Its mechanical characteristics and chemical property are good; And, can in the wide spectrums such as shaping thing of the shell of various films that fiber, packaging or tape that dress material or industry resource are used are used etc. or hollow forming article such as thin slice, bottle, electric/electronic apparatus, other engineering plastics etc., use according to the characteristic of each polyester.

With aromatic dicarboxylic acid and alkylene glycol typical polyester as the main composition composition; Polyethylene terephthalate (PET) for example; Be through by two (2-hydroxyethyl) terephthalate of the esterification between terephthalic acid or DMT. Dimethyl p-benzenedicarboxylate and the terepthaloyl moietie or transesterify preparation in the industry, under high-temperature vacuum, utilizing catalyzer to make the condensation method etc. of its polycondensation then and obtain.

All the time, used catalyst for polymerization of polyester when carrying out described polycondensation of polyester, ANTIMONY TRIOXIDE SB 203 99.8 PCT is widely used.ANTIMONY TRIOXIDE SB 203 99.8 PCT is a kind of cheapness and catalyzer with superior catalytic activity; If but it is used as staple; If promptly the usage quantity to it is to have given play to the degree of practical polymerization velocity; Then Antimony Metal 99.65& 99.96 is separated out when polycondensation, so exist in the part of generation blackout in the polyester or the problem of impurity.In this case, people expectation does not contain antimony or fully as the not stibiated polyester of catalyzer principal constituent.

In addition, the said impurity in the polyester for example causes following variety of issue.

(1) in the polyester that film is used, the separating out of Antimony Metal 99.65& 99.96, as the impurity in the polyester, the tube head when not only polluting melt extruded also becomes the reason of the surface imperfection of film.In addition, as the raw material of hollow forming article etc. the time, be difficult to obtain the good hollow forming article of the transparency.

(2) impurity in the polyester used of fiber can make intensity reduce in fiber, and the lid when causing throwing pollutes.In the manufacturing of trevira, mainly from the viewpoint of operability, expectation has the catalyst for polymerization of polyester that does not produce impurity.

As solution to the problems described above, use ANTIMONY TRIOXIDE SB 203 99.8 PCT as catalyzer, carried out the trial that suppresses the PET blackout or produce impurity.For example, in No. the 2666502nd, special permission,,, suppressed in PET, to produce black impurity through using ANTIMONY TRIOXIDE SB 203 99.8 PCT and selenium compound as polycondensation catalyst.In addition, open in flat 9-291141 number the spy and to disclose,,, then can suppress separating out of Antimony Metal 99.65& 99.96 if use the ANTIMONY TRIOXIDE SB 203 99.8 PCT of the oxide compound that contains sodium and iron as polycondensation catalyst.But using these polycondensation catalysts is to reach the purpose that reduces the antimony content in the polyester.

The method of the problem that antimony catalyst exists when being used for the purposes of requirement such as the PET bottle transparency as solution is for example opened the spy and is disclosed a kind of amount ratio through regulation antimony compounds and phosphorus compound in the flat 6-279579 communique and improve transparent method.But the transparency of the hollow forming article of being processed by the polyester that obtains through this method can't be said so enough abundant.

Open in the flat 10-36495 communique the spy, proposed use ANTIMONY TRIOXIDE SB 203 99.8 PCT, phosphoric acid and carboxylic acid cpd, make the method for manufacture of the excellent polyester of the transparency continuously.But, the problem that exists the acetaldehyde of the hollow forming article of poor heat stability, gained to uprise in the polyester that obtains according to this method.

Also carrying out at present research and discussion to the polycondensation catalyst that can substitute antimony class catalyzer such as ANTIMONY TRIOXIDE SB 203 99.8 PCT; And to have proposed with four titan-alkoxide acid esters be the titanium compound and the tin compound of representative; But the polyester that uses these catalyzer to make; Be easy to generate thermal ageing when existing in melt-shaping, and polyester is significantly by painted problem.

As the trial that overcomes the described problem that titanium compound is occurred when the polycondensation catalyst, for example, open in clear 55-116722 number the spy, the method that four titan-alkoxide acid esters and cobalt salt and calcium salt are used has simultaneously been proposed.In addition, open flat 8-73581 number, proposed four titan-alkoxide acid esters and cobalt cpd to be used simultaneously, and use the method for white dyes as polycondensation catalyst according to the spy.But, in these technology, though can reduce painted with the PET of four titan-alkoxide acid esters when the polycondensation catalyst,, can not suppress the thermolysis of PET effectively.

As other method that suppresses titanium compound is carried out as catalyzer the thermal degradation when that the polymeric polyester exists when the melt-shaping; For example open in flat 10-259296 number the spy; Proposed with titanium compound to add the method for Phosphorus compound as after the polymerization catalyst polyester.But, say technically to be difficult to be blended into additive effectively in the polymkeric substance after the polymerization, and cost also rises, so can't realize practicability at present.

Aluminum compound generally is known as the bad catalyzer of catalytic activity.Someone has reported in aluminum compound; The inner complex of aluminium is compared with the compound of other aluminium, as polycondensation catalyst high catalytic activity is arranged, but compares with above-mentioned antimony compounds or titanium compound; Not talkative have enough catalytic activitys; And, as catalyzer and through long-time polymeric polyester, there is the bad problem of thermostability in aluminum compound.

People are also known to be added alkali metal cpd and makes the technology of the catalyst for polymerization of polyester with abundant catalytic activity in aluminum compound; Can obtain the polyester of excellent heat stability when using well-known catalysts, but when using this catalyzer of also having used alkali metal cpd, if will obtain practical catalytic activity; Must add a large amount of alkali metal cpds; Its result is because the alkali metal cpd in the gained polyester polymers will cause following any problem at least.

1) insoluble impurity increases, and when using as fiber, the rerum natura of throwing property or silk worsens, and when in film, using in addition, the rerum natura of film worsens.

2) hydrolytic resistance of polyester polymers descends, and because impurity, the transparency descends.

3) produce the colour-difference of polyester polymers, polymkeric substance promptly takes place be painted to and be the xanchromatic phenomenon, when being used for film or hollow bottle etc., will produce the problem of the colour-difference of molding.

4), when making molding,, productivity is descended because the obstruction of impurity makes the rising of strainer pressure with the polyester fusion.

Except that antimony compounds, as having excellent catalytic activity and the catalyzer of the polyester that does not have said problem being provided, ge cpd is practicability; But this catalyzer; Have the very high problem of price, or since its in polymerization process, outwards distillate from reactive system easily, so exist the catalyst concn of reactive system to change and to the unmanageable problem of polymerization; In addition, when using, also have problems as the catalyzer principal constituent.

In addition, the method for the thermal ageing during as the melt-shaping that suppresses polyester also can be enumerated the method for from polyester, removing catalyzer.As the method for from polyester, removing catalyzer, for example open in the flat 10-251394 communique and disclose the spy, in the presence of acidic substance, make vibrin and as the contacted method of the extraction agent of supercutical fluid.But, the method for this use supercutical fluid, and since difficult technically, and bring the cost of goods to raise, so be not preferred.

In above-mentioned this present situation, people expect to occur with the polymerizing catalyst of the metal ingredient beyond antimony and the germanium as the major metal composition of catalyzer, that is, catalytic activity is good and the polymerizing catalyst of the polyester that does not have above-described problem can be provided.

Summary of the invention

It is a kind of that the present invention provides, and uses the metal ingredient beyond antimony and the germanium as the novel catalyst for polymerization of polyester of the major metal composition of catalyzer, the method for using the polyester of this catalyzer manufacturing and using this catalyzer manufacturing polyester.

In addition; It is a kind of that the present invention provides; As catalyzer principal constituent not antimony containing compounds and ge cpd, and with aluminium as the good novel catalyst for polymerization of polyester of the catalytic performance of main metal ingredient, use the polyester of this catalyzer manufacturing and use this catalyzer to make the method for polyester.

Another object of the present invention is to provide a kind of; As the principal constituent of catalyzer not antimony containing compounds or ge cpd but with aluminium as main metal ingredient; Catalytic activity is good; And the thermal ageing when catalyzer does not have inactivation or do not carry out suppressing melt-shaping effectively under the prerequisite of removing of catalyzer and provide good heat stability, the few transparency of impurity excellent, and then the catalyst for polymerization of polyester of the also good polyester of color.

In addition; Even even the present invention also provides thermostability, the generation of impurity when using said catalyzer melt-shaping that be made, that carry out hollow forming article, fiber and engineering plastics etc. such as film and bottle, productivity improves and use new resin or when being shaped the bits of generation utilize the polyester that also can obtain superior in quality goods again, and the method for manufacture of using the polyester of said catalyst for polymerization of polyester.

Another object of the present invention is to provide a kind of, can make the excellent polyester of catalyst for polymerization of polyester, thermo-oxidative stability and the hydrolytic resistance of the excellent polyester of thermo-oxidative stability and hydrolytic resistance and use said catalyst for polymerization of polyester to make the method for polyester.

Another purpose of the present invention is to provide a kind of, the molding of the fiber that the polyester that is made by the said catalyzer of use constitutes, film, bottle etc.

Contrivers etc. are for solving above-mentioned problem; Carried out research with great concentration; The result finds, though the poor catalytic activity of aluminum compound itself, through together using aluminum compound and phosphorus compound with ad hoc structure; Can access sufficient activity, thereby accomplish the present invention as polymerizing catalyst.If use polycondensation catalyst of the present invention, then can access the superior in quality polyester that does not use antimony compounds, ge cpd.

That is, as the method that solves above-mentioned problem, the present invention provides the catalyst for polymerization of polyester that is made up of aluminum compound and the phosphorus compound with ad hoc structure, the polyester that uses this catalyzer manufacturing and the method for manufacture of polyester.

The present invention provides the novel polycondensation catalyst beyond a kind of antimony compounds, the polyester that utilizes this catalyzer manufacturing and the method for manufacture of polyester.Polycondensation catalyst of the present invention is the catalyst for polymerization of polyester that is made up of aluminum compound and the phosphorus compound with ad hoc structure.In addition, the present invention is to use the polyester of this catalyst for polymerization of polyester manufacturing and the method for manufacture of polyester.In addition, the present invention is fiber, film and the hollow forming article that are made up of this polyester.

Embodiment

Aluminium or aluminum compound as constituting polycondensation catalyst of the present invention except metallic aluminium, can use known any aluminum compound.

As aluminum compound, specifically can give an example carboxylate salts such as aluminum formate, aluminum acetate, plumbous subacetate propionic acid aluminium, oxalic acid aluminium, vinylformic acid aluminium, Aluminum trilaurate, StAl, TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M. aluminium, trichoroacetic acid(TCA) aluminium, Aluctyl, Tiorco 677, salumin; The inorganic acid salt of aluminum chloride, white lake, hydroxide chlorination aluminium, aluminium carbonate, phosphagel phosphaljel, phosphonic acids aluminium etc.; The aluminum alkoxide of aluminum methylate, aluminum ethylate, three positive propoxy aluminium, aluminium isopropoxide, three n-butoxy aluminium, three tert.-butoxy aluminium etc.; The aluminum chelate of aluminium acetylacetonate, etheric acid aluminium, methyl aceto acetate aluminium, methyl aceto acetate aluminium diiso propoxide etc.; Organo-aluminium compound such as trimethylaluminium, triethyl aluminum and their partial hydrolysate; Aluminum oxide etc.Wherein, optimization acid's salt, inorganic acid salt and inner complex, preferred especially aluminum acetate, aluminum chloride, white lake, hydroxide chlorination aluminium and aluminium acetylacetonate.

As the usage quantity of aluminium of the present invention or aluminum compound, preferably the entire infrastructure unit with respect to the carboxylic acid composition of the dicarboxylicacid of resulting polyester or polycarboxylic acid etc. is 0.001～0.05 mole of %, more preferably 0.005～0.02 mole of %.If usage quantity is less than 0.001 mole of %; Then can not give play to catalytic activity fully sometimes; If opposite usage quantity, then causes the decline of thermostability or thermo-oxidative stability sometimes more than 0.05%, because the problem of impurity that aluminium causes or painted increase.Like this, the key character of polymerizing catalyst of the present invention is, has also given play to sufficient catalytic activity even the addition of aluminium component is few.Its result, thermostability or thermo-oxidative stability are excellent, and because impurity that aluminium causes or painted minimizing.

As at least a kind of phosphorus compound that constitutes phosphorus compound polymerizing catalyst of the present invention, that have ad hoc structure, be meant in a group that the metal salt compound that is selected from by phosphorus constitutes; Or be selected from least a kind of phosphorus compound in a group that constitutes by the phosphorus compound that has 1 P-OH key at least; Or be selected from least a kind of phosphorus compound in a group that constitutes by phospho acid based compound, phosphine oxide based compound, phosphonous acid based compound, inferior phospho acid based compound, phosphine based compound; Or be selected from least a kind of phosphorus compound in a group that constitutes by compound with following general formula (22) expression; Or be selected from least a kind of phosphorus compound in a group that constitutes by compound with following general formula (30) expression.Wherein, if use at least a kind of phosphorus compound in a group that metal salt compound by phosphorus constitutes; Or be selected from least a kind of phosphorus compound in a group that constitutes by the phosphorus compound that has 1 P-OH key at least; Or at least 1 section's phosphorus compound in constitute by the compound of following general formula (22) expression a group; Or be selected from least a kind of phosphorus compound in a group that compound by following general formula (30) expression constitutes.

Constitute the metal salt compound of the phosphorus of polymerizing catalyst of the present invention, so long as the metal-salt of phosphorus compound just has no particular limits, but if use the metal-salt of phosphonic acids based compound, then the raising effect of catalyst activity is remarkable, so be ideal.As the metal-salt of phosphorus compound, comprise monometallic salt, two metal-salts, three metal-salts etc.

In addition, in the above-mentioned phosphorus compound, be the phosphorus compound that is selected from the metal among Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, the Zn if use the metal section and part of metal-salt, then the raising effect of catalyst activity is remarkable, so be ideal.Wherein, it is desirable to Li, Na, Mg especially.

As the metal salt compound of the phosphorus that constitutes polymerizing catalyst of the present invention, if use from the compound with following general formula (15) expression, select at least a, then the raising effect of catalyst activity is remarkable, so be ideal.

(in the formula (15): R ¹The alkyl of expression hydrogen, carbon number 1～50, contain the alkyl of hydroxyl or halogen atom or alkoxyl group or amino carbon number 1～50.R ²The alkyl of expression hydrogen, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group.R ³The alkyl of expression hydrogen, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group or carbonyl.L representes the integer more than 1, and m representes the integer more than 0 or 1, and l+m is below 4.M representes the metallic cation of (l+m) valency.N representes the integer more than 1.Alkyl can contain the alicyclic structure of cyclohexyl etc. or the aromatic ring structure of branched structure or phenyl, naphthyl etc.)

As above-mentioned R ¹, for example can enumerate phenyl, 1-naphthyl, 2-naphthyl, 9-and fear base, 4-xenyl, 2-xenyl etc.As above-mentioned R ², for example can enumerate hydrogen, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec.-butyl, the tertiary butyl, long-chain fat family base, phenyl, naphthyl, substituted phenyl or naphthyl, usefulness-CH ₂CH ₂The substituting group that OH representes etc.As R ³O ^-, for example can enumerate hydroxide ion, alkoxide ion, acetate ions or methyl ethyl diketone ion etc.

In the compound shown in the said general formula (15), the preferred use is selected from least a in the compound shown in the formula (16).

(in the formula (16): R ¹The alkyl of expression hydrogen, carbon number 1～50, contain the alkyl of hydroxyl or halogen atom or alkoxyl group or amino carbon number 1～50.R ³The alkyl of expression hydrogen, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group or carbonyl.L representes the integer more than 1, and m representes the integer more than 0 or 1, and l+m is below 4.M representes the metallic cation of (l+m) valency.Alkyl can contain the alicyclic structure of cyclohexyl etc. or the aromatic ring structure of branched structure or phenyl, naphthyl etc.)

R as above-mentioned general formula (16) ¹, for example can enumerate phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-xenyl, 2-xenyl etc.As R ³O ^-, for example can enumerate hydroxide ion, alkoxide ion, acetate ions or methyl ethyl diketone ion etc.

In said phosphorus compound, if use compound, then because the raising effect of catalytic activity is remarkable, so be preferred with aromatic ring structure.

In said general formula (16), if use is selected from the metal among Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, the Zn as M, then the raising effect of catalytic activity is remarkable, so be preferred.Wherein preferred especially Li, Na, Mg.

As the metallic compound of phosphorus of the present invention, can enumerate lithium [(1-naphthyl) methyl-phosphorous acid ethyl ester], sodium [(1-naphthyl) methyl-phosphorous acid ethyl ester], magnesium two [(1-naphthyl) methyl-phosphorous acid ethyl ester], potassium [(2-naphthyl) methyl-phosphorous acid ethyl ester], magnesium two [(2-naphthyl) methyl-phosphorous acid ethyl ester], lithiums [benzylphosphonic acid ethyl ester], sodium [benzylphosphonic acid ethyl ester], magnesium two [benzylphosphonic acid ethyl ester], beryllium two [benzylphosphonic acid ethyl ester], strontium two [benzylphosphonic acid ethyl ester], manganese two [benzylphosphonic acid ethyl ester], benzylphosphonic acid sodium, magnesium two [benzylphosphonic acid], sodium [(9-anthryl) methyl-phosphorous acid ethyl ester], magnesium two [(9-anthryl) methyl-phosphorous acid ethyl ester], sodium [4-hydroxybenzyl phosphinic acid ethyl ester], magnesium two [4-hydroxybenzyl phosphinic acid ethyl ester], sodium [4-benzyl chloride base phosphonic acids phenyl ester], magnesium two [4-benzyl chloride base phosphinic acid ethyl ester], sodium [4-aminobenzyl phosphinic acid ethyl ester], magnesium two [4-aminobenzyl phosphinic acid ethyl ester], phenyl-phosphonic acid sodium, magnesium two [phenyl-phosphonic acid ethyl ester], zinc two [phenyl-phosphonic acid ethyl ester] etc.In these, special preferred, lithium [(1-naphthyl) methyl-phosphorous acid ethyl ester], sodium [(1-naphthyl) methyl-phosphorous acid ethyl ester], magnesium two [(1-naphthyl) methyl-phosphorous acid ethyl ester], lithiums [benzylphosphonic acid ethyl ester], sodium [benzylphosphonic acid ethyl ester], magnesium two [benzylphosphonic acid ethyl ester], benzylphosphonic acid sodium, magnesium two [benzylphosphonic acid].

The metal salt compound that constitutes another phosphorus of polymerizing catalyst of the present invention is, by the compound of at least a formation of from the compound with following general formula (17) expression, selecting.

(in the formula (17): R ¹, R ²The alkyl of independent separately expression hydrogen, carbon number 1～30.R ³The alkyl of expression hydrogen, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group.R ⁴The alkyl of expression hydrogen, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group or carbonyl.As R ⁴O ^-, for example can enumerate hydroxide ion, alkoxide ion, acetate ions or methyl ethyl diketone ion etc.L representes the integer more than 1, and m representes the integer more than 0 or 1, and l+m is below 4.M representes the metallic cation of (l+m) valency.N representes the integer more than 1.Alkyl can contain the alicyclic structure of cyclohexyl etc. or the aromatic ring structure of branched structure or phenyl, naphthyl etc.)

Wherein, the preferred use is selected from least a in the compound shown in the formula (18).

(M in the formula (18) ^N+The metallic cation of expression n valency.N representes 1,2,3 or 4.)

In above-mentioned formula (17) or (18), if use is selected from the metal among Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, the Zn as M, the raising effect of catalytic activity is remarkable, so be preferred.Wherein preferred especially Li, Na, Mg.

As the metal salt compound of specific phosphorus of the present invention, can enumerate lithium [3,5-di-tert-butyl-4-hydroxyl benzyl phosphinic acid ethyl ester], sodium [3; 5-di-tert-butyl-4-hydroxyl benzyl phosphinic acid ethyl ester], sodium [3; 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids], potassium [3,5-di-tert-butyl-4-hydroxyl benzyl phosphinic acid ethyl ester], magnesium two [3,5-di-tert-butyl-4-hydroxyl benzyl phosphinic acid ethyl ester], magnesium two [3; 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids], beryllium two [3; 5-di-tert-butyl-4-hydroxyl benzyl phosphinic acid ethyl ester], strontium two [3,5-di-tert-butyl-4-hydroxyl benzyl phosphinic acid ethyl ester], barium two [3,5-di-tert-butyl-4-hydroxyl benzyl phosphinic acid ethyl ester], manganese two [3; 5-di-tert-butyl-4-hydroxyl benzyl phosphinic acid ethyl ester], nickel two [3; 5-di-tert-butyl-4-hydroxyl benzyl phosphinic acid ethyl ester], copper two [3,5-di-tert-butyl-4-hydroxyl benzyl phosphinic acid ethyl ester], zinc two [3,5-di-tert-butyl-4-hydroxyl benzyl phosphinic acid ethyl ester] etc.Special preferred, lithium [3,5-di-tert-butyl-4-hydroxyl benzyl phosphinic acid ethyl ester], sodium [3,5-di-tert-butyl-4-hydroxyl benzyl phosphinic acid ethyl ester], magnesium two [3,5-di-tert-butyl-4-hydroxyl benzyl phosphinic acid ethyl ester] in these.

The so-called phosphorus compound that has a P-OH key at least that constitutes polymerizing catalyst of the present invention so long as intramolecularly has the phosphorus compound of a P-OH key at least, does not just have particular restriction.In these phosphorus compounds, if use the phosphonic acids based compound that has a P-OH key at least, then because the raising effect of catalytic activity is remarkable, so be preferred.

As the phosphorus compound that has a P-OH key at least that constitutes polymerizing catalyst of the present invention, if use at least a in the compound that is selected from formula (19) expression, then the raising effect of catalytic activity is remarkable, so be preferred.

(in the formula (19): R ¹The alkyl of expression hydrogen, carbon number 1～50, contain the alkyl of hydroxyl or halogen atom or alkoxyl group or amino carbon number 1～50.R ²The alkyl of expression hydrogen, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group.N representes the integer more than 1.Alkyl can contain the alicyclic structure of cyclohexyl etc. or the aromatic nucleus structure of branched structure or phenyl, naphthyl etc.)

R as above-mentioned general formula (19) ¹, for example can enumerate phenyl, 1-naphthyl, 2-naphthyl, 9-and fear base, 4-xenyl, 2-xenyl etc.As above-mentioned R ², for example can enumerate hydrogen, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec.-butyl, the tertiary butyl, long-chain fat family base, phenyl, naphthyl, substituted phenyl or naphthyl, usefulness-CH ₂CH ₂The substituting group that OH representes etc.

In above-mentioned phosphorus compound, if use the compound with aromatic ring structure, then the raising effect of catalytic activity is remarkable, so be ideal.

As other phosphorus compound that has a P-OH key at least of the present invention, can enumerate (1-naphthyl) methyl-phosphorous acid ethyl ester, (1-naphthyl) methyl-phosphorous acid, (2-naphthyl) methyl-phosphorous acid ethyl ester, benzylphosphonic acid ethyl ester, benzylphosphonic acid, (9-fears base) methyl-phosphorous acid ethyl ester, 4-hydroxybenzyl phosphinic acid ethyl ester, 2-methyl-benzyl phosphinic acid ethyl ester, 4-benzyl chloride base phosphonic acids phenyl ester, 4-aminobenzyl methyl-phosphonate, 4-methoxy-benzyl phosphinic acid ethyl ester etc.Wherein preferred especially (1-naphthyl) methyl-phosphorous acid ethyl ester, benzylphosphonic acid ethyl ester.

In addition, as other phosphorus compound that constitutes polymerizing catalyst of the present invention, can give an example out has the specific phosphorus compound of 1 P-OH key at least.The so-called specific phosphorus compound that has a P-OH key at least is meant, is selected from at least a compound in the compound of following general formula (20) expression.

(in the general formula (20): R ¹, R ²The alkyl of independent separately expression hydrogen, carbon number 1～30.R ³The alkyl of expression hydrogen, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group.N representes the integer more than 1, and alkyl can contain the alicyclic structure of cyclohexyl etc. or the aromatic ring structure of branched structure or phenyl, naphthyl etc.)

That wherein, preferably from the compound of available formula (21) expression, selects is at least a.

(in the general formula (21): R ³The alkyl of expression hydrogen, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group.Alkyl can contain the alicyclic structure of cyclohexyl etc. or the aromatic ring structure of branched structure or phenyl, naphthyl etc.)

R as above-mentioned general formula (21) ³, for example can enumerate hydrogen, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec.-butyl, the tertiary butyl, long-chain fat family base, phenyl, naphthyl, substituted phenyl or naphthyl, usefulness-CH ₂CH ₂The substituting group that OH representes etc.

As the specific phosphorus compound that has 1 P-OH key at least of the present invention; Can give an example 3,5-di-tert-butyl-4-hydroxyl benzyl phosphinic acid ethyl ester, 3,5-di-tert-butyl-4-hydroxyl benzyl methyl-phosphonate, 3; 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids isopropyl ester, 3; 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids phenyl ester, 3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids octadecyl ester, 3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids etc.Wherein preferred especially 3,5-di-tert-butyl-4-hydroxyl benzyl phosphinic acid ethyl ester, 3,5-di-tert-butyl-4-hydroxyl benzyl methyl-phosphonate.

The phosphorus compound that constitutes another polymerizing catalyst of the present invention is, with the phosphorus compound of following general formula (22) expression.

R ¹-P(＝O)(OR ²)(OR ³) (22)

(in general formula (22), R ¹The alkyl of expression carbon number 1～50, contain the alkyl of hydroxyl or halogen atom or alkoxyl group or amino carbon number 1～50, R ², R ³The alkyl of independent separately expression hydrogen, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group.Wherein alkyl can contain alicyclic structure or branched structure or aromatic ring structure.)

Wherein, the preferred phosphorus compound that uses with following general formula (23) expression.

R ¹-CH ₂-P(＝O)(OR ²)(OR ³) (23)

(in the general formula (23), R ¹Represent the alkyl of carbon number 1～49 or contain hydroxyl or the alkyl of the carbon number 1～49 of halogen atom or alkoxyl group or amino, R ², R ³The alkyl of independent separately expression hydrogen, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group.Wherein alkyl can contain alicyclic structure or branched structure or aromatic ring structure.)

In addition, even more ideal is, in general formula (23), and R ¹, R ², R ³In at least one be the compound that contains aromatic ring structure.

As phosphorus compound, specifically can give an example with the phosphorus compound of following formula (24)～(29) expression and on the aromatic nucleus of these phosphorus compounds, have methyl, chlorine atom, or the compound of amino with above-mentioned general formula (23) expression.

In addition, in the present invention, the phosphorus compound that uses as polycondensation catalyst is because its molecular weight is difficult to distillated when polymerization when big, so excellent catalytic effect is an ideal.

The phosphorus compound that constitutes polymerizing catalyst of the present invention is to be selected from at least a phosphorus compound in the represented compound of following general formula (30).

(in the above-mentioned general formula (30), R ¹, R ²The alkyl of independent separately expression hydrogen, carbon number 1～30.R ³, R ⁴Represent independently of one another hydrogen, carbon number 1～50 alkyl, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group.N representes the integer more than 1, and alkyl can contain the alicyclic structure of cyclohexyl etc. or the aromatic ring structure of branched structure or phenyl, naphthyl etc.)

In above-mentioned general formula (30), if use is selected at least a from the compound with following general formula (31) expression, then the raising effect of catalytic activity is remarkable, so desirable.

(in above-mentioned general formula (31), R ³, R ⁴The alkyl of independent separately expression hydrogen, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group.Wherein alkyl can contain the alicyclic structure of cyclohexyl etc. or the aromatic ring structure of branched structure or phenyl, naphthyl etc.)

R as above-mentioned general formula (31) ³, R ⁴, the short-chain fat family that for example can enumerate hydrogen, methyl, butyl etc. is basic; The fatty group of long-chains such as octadecyl; The aromatic series base of phenyl, naphthyl, substituted phenyl or naphthyl etc.; Usefulness-CH ₂CH ₂The substituting group that OH representes etc.

Compound as specific phosphorus of the present invention; Can enumerate 3; 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids isopropyl ester, 3; The positive butyl ester of 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids, 3, two stearyl of 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids, 3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acid diphenyl ester etc.Wherein preferred especially 3, two stearyl of 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids, 3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acid diphenyl ester.

The phosphorus compound that constitutes other polymerizing catalyst of the present invention is to be selected from least a kind of phosphorus compound in phospho acid based compound, phosphine oxygen based compound, phosphonous acid based compound, inferior phospho acid based compound, the phosphine based compound.

Said phosphonic acids based compound, phospho acid based compound, phosphine oxygen based compound, phosphonous acid based compound, inferior phospho acid based compound, phosphine based compound among the present invention are meant the compound that has in order to the structure of following formula (32)～(37) expression respectively.

In phospho acid based compound, phosphine oxygen based compound, phosphonous acid based compound, inferior phospho acid based compound, phosphine based compound, as phosphorus compound of the present invention, the compound of preferably representing with following formula (38)～(43).

[(CH ₃)(CH ₂) ₇] ₃P (43)

In described phosphorus compound, if use compound, then because the raising effect of catalytic activity is remarkable, so be preferred with aromatic ring structure.

In addition; The phosphorus compound that has above ad hoc structure through use; Can access as the catalyzer principal constituent not antimony containing compounds or ge cpd and with aluminium as the major metal composition of catalyzer, catalytic activity thermal ageing excellent, when under the precursor of removing operation of inactivation that does not have catalyzer or catalyzer, melt-shaping being provided effectively is inhibited and good heat stability, and the also catalyst for polymerization of polyester of excellent polyester of thermo-oxidative stability or hydrolytic resistance.

With phosphorus compound,, also can access the catalyzer of having given play to sufficient catalytic effect through also even the addition of the aluminium in catalyst for polymerization of polyester is under a spot of situation with above-mentioned ad hoc structure.

As the usage quantity of phosphorus compound of the present invention, with respect to the unitary mole number of total formation of the poly carboxylic acid composition in the polyester of polymerization gained, preferably 0.0001～0.1 mole of % scope, more preferably in the scope of 0.005～0.05 mole of %.The addition of phosphorus compound when being lower than 0.0001 mole of %, can not have been given play to additive effect sometimes, if add to surpass 0.1 mole of %, on the contrary, reduces sometimes as the catalytic activity of catalyst for polymerization of polyester, and its reduction degree depends on the usage quantity of aluminium etc.

As not using phosphorus compound but with the technology of aluminum compound, the usage quantity of reduction aluminum compound is arranged, and then add cobalt cpd as main catalyzer staple; And when preventing with aluminum compound as main catalyzer because the painted technology that the reduction of thermostability causes, still, if when interpolation has the cobalt cpd of abundant catalytic activity level; Thermostability still reduces; Therefore, in this technology, be difficult to make both to satisfy simultaneously.

According to the present invention; The phosphorus compound that has described ad hoc structure through use; Even can not cause problem such as thermostability reduces, the generation of impurity and contain as metal under the addition condition seldom of aluminium of composition; Also can obtain having the polymerizing catalyst of abundant catalytic activity, through using this polymerizing catalyst, the thermostability the during melt-shaping of hollow forming article, fiber or the engineering plastics etc. of polyester film, bottle etc. is improved.Replace in the phosphorus compound of the present invention,, also do not find additive effect, so impracticable even add the SULPHOSUCCINIC ACID ESTER of phosphoric acid or trimethylammonium phosphoric acid etc.In addition; Even in addition scope of the present invention the catalyst for polymerization of polyester combination that phosphorus compound of the present invention and in the past antimony compounds, titanium compound, tin compound, ge cpd etc. contain metal is used, can not be found to promote the effect of melt polymerization.

Another embodiment of the present invention is to it is characterized in that containing at least a catalyst for polymerization of polyester in the aluminium salt that is selected from phosphorus compound.Also can the aluminium salt and the combinations such as aluminum compound or phosphorus compound of phosphorus compound be used.

As the aluminium salt of phosphorus compound of the present invention, so long as have the phosphorus compound of aluminum portions, just there is not particular restriction, if use the aluminium salt of phosphonic acids based compound, because the raising effect of catalytic activity is remarkable, so be preferred.As the aluminium salt of phosphorus compound, comprise single aluminium salt, two aluminium salt, three aluminium salt etc.

In the aluminium salt of said phosphorus compound, if use compound, then because the raising effect of catalytic activity is remarkable, so be preferred with aromatic ring structure.

As the aluminium salt of the phosphorus compound that constitutes polymerizing catalyst of the present invention, be selected from least a with in the compound of formula (44) expression if use, then because catalytic activity raising effect is remarkable, so be preferred.

(in the formula (44): R ¹The alkyl of expression hydrogen, carbon number 1～50, contain the alkyl of hydroxyl or halogen atom or alkoxyl group or amino carbon number 1～50.R ²The alkyl of expression hydrogen, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group.R ³The alkyl of expression hydrogen, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group or carbonyl.L representes the integer more than 1, and m representes the integer more than 0 or 1, and l+m is 3.N representes the integer more than 1.Alkyl can contain the alicyclic structure of cyclohexyl etc. or the aromatic ring structure of branched structure or phenyl, naphthyl etc.)

R as above-mentioned general formula (44) ¹, for example can enumerate phenyl, 1-naphthyl, 2-naphthyl, 9-and fear base, 4-xenyl, 2-xenyl etc.R as above-mentioned general formula (44) ², for example can enumerate hydrogen, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec.-butyl, the tertiary butyl, long-chain fat family base, phenyl, naphthyl, substituted phenyl or naphthyl, usefulness-CH ₂CH ₂The substituting group that OH representes etc.As R ³O ^-, for example can enumerate hydroxide ion, alkoxide ion, ethylene glycol bisthioglycolate oxyacetic acid ion, acetato-or methyl ethyl diketone ion etc.

As the aluminium salt of phosphorus compound of the present invention, can enumerate the aluminium salt of (1-naphthyl) methyl-phosphorous acid ethyl ester, the aluminium salt of (1-naphthyl) methyl-phosphorous acid, the aluminium salt of (2-naphthyl) methyl-phosphorous acid ethyl ester, the aluminium salt of benzylphosphonic acid ethyl ester, the aluminium salt of benzylphosphonic acid, the aluminium salt of (9-anthryl) methyl-phosphorous acid ethyl ester, the aluminium salt of 4-hydroxybenzyl phosphinic acid ethyl ester, the aluminium salt of 2-methyl-benzyl phosphinic acid ethyl ester, the aluminium salt of 4-benzyl chloride base phosphonic acids phenyl ester, the aluminium salt of 4-aminobenzyl methyl-phosphonate, the aluminium salt of 4-methoxy-benzyl phosphinic acid ethyl ester, the aluminium salt of phenyl-phosphonic acid ethyl ester etc.Wherein the aluminium salt of preferred especially (1-naphthyl) methyl-phosphorous acid ethyl ester, the aluminium salt of benzylphosphonic acid ethyl ester.

Another embodiment of the present invention is, by the catalyst for polymerization of polyester of selected at least a formation from the aluminium salt of the specific phosphorus compound shown in the following general formula (45).Also can the aluminium salt and the combinations such as other aluminum compound or phosphorus compound of phosphorus compound be used.

Constitute the aluminium salt of the specific phosphorus compound of polymerizing catalyst of the present invention, be meant by the aluminium salt that is selected from least a formation in the compound shown in the formula (45).

(in the general formula (45): R ¹, R ²The alkyl of representing hydrogen, carbon number 1～30 independently of one another.R ³The alkyl of expression hydrogen, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group.R ⁴The alkyl of expression hydrogen, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group or carbonyl.L representes the integer more than 1, and m representes the integer more than 0 or 1, and l+m is 3.N representes the integer more than 1.Alkyl can contain the alicyclic structure of cyclohexyl etc. or the aromatic ring structure of branched structure or phenyl, naphthyl etc.)

Wherein, the preferred use is selected from least a in the compound of representing with formula (46).

(in the formula (46): R ³The alkyl of expression hydrogen, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group.R ⁴The alkyl of expression hydrogen, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group or carbonyl.L representes the integer more than 1, and m representes the integer more than 0 or 1, and l+m is 3.Alkyl can contain the alicyclic structure of cyclohexyl etc. or the aromatic ring structure of branched structure or phenyl, naphthyl etc.)

R as above-mentioned general formula (46) ³, for example can enumerate hydrogen, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec.-butyl, the tertiary butyl, long-chain fat family base, phenyl, naphthyl, substituted phenyl or naphthyl, usefulness-CH ₂CH ₂The substituting group that OH representes etc.As R ⁴O ^-, for example can enumerate hydroxide ion, alkoxide ion, ethylene glycol bisthioglycolate oxyacetic acid ion, acetato-or methyl ethyl diketone ion etc.

Aluminium salt as specific phosphorus compound of the present invention; Can enumerate 3; The aluminium salt, 3 of 5-di-tert-butyl-4-hydroxyl benzyl phosphinic acid ethyl ester, the aluminium salt, 3 of 5-di-tert-butyl-4-hydroxyl benzyl methyl-phosphonate, the aluminium salt, 3 of 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids isopropyl ester; The aluminium salt, 3 of 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids phenyl ester, 5-di-tert-butyl-4-hydroxyl benzyl phosphonic aluminium salt etc.Wherein especially preferred 3, the aluminium salt, 3 of 5-di-tert-butyl-4-hydroxyl benzyl phosphinic acid ethyl ester, the aluminium salt of 5-di-tert-butyl-4-hydroxyl benzyl methyl-phosphonate.

Through using the aluminium salt of above phosphorus compound, can access as the catalyzer principal constituent not antimony containing compounds or ge cpd, catalytic activity is excellent and thermal ageing when under the precursor of removing operation of inactivation that does not have catalyzer or catalyzer, melt-shaping being provided effectively is inhibited and the also catalyst for polymerization of polyester of excellent polyester of good heat stability and thermo-oxidative stability or hydrolytic resistance.

The aluminium salt of the phosphorus compound of the application of the invention even the addition of the aluminium in catalyst for polymerization of polyester is under a spot of situation, also can access the catalyzer of having given play to sufficient catalytic effect.

As the usage quantity of phosphorus compound of the present invention, with respect to the unitary mole number of total formation of the poly carboxylic acid composition in the polyester of polymerization gained, preferably 0.0001～0.1 mole of % scope, more preferably in the scope of 0.005～0.05 mole of %.The addition of the aluminium salt of phosphorus compound when being lower than 0.0001 mole of %, can not have been given play to additive effect sometimes; Surpass 0.1 mole of % if add; On the contrary, the thermostability or the thermo-oxidative stability that the gained polyester can occur descend, and produce the problem of impurity or painted increase.Like this, even the addition of aluminium component also demonstrates sufficient catalytic activity less, this maximum characteristic that polymerizing catalyst of the present invention had just.Its result, thermostability or thermo-oxidative stability are excellent, impurity or painted reduction.

The aluminium salt of the phosphorus compound of the application of the invention; Can do not caused that thermostability reduces, the problems such as generation of impurity; Even and the polymerizing catalyst that also has abundant catalytic activity under the addition of the aluminium condition seldom; Through using this polymerizing catalyst, the thermostability the during melt-shaping of hollow forming article, fiber or the engineering plastics etc. of polyester film, bottle etc. is improved.

As catalyst for polymerization of polyester of the present invention, it is desirable to, use this catalyst for polymerization of polyester polymerization and the thermostability parameter (TS) of polyethylene terephthalate (PET) satisfy following mathematical expression (1).

(1)TS＜0.30

Wherein, TS representes by with intrinsicviscosity ([IV] _i) for the PET1g of 0.65dl/g packs in the glass test tube, after 12 hours, keeping 2 hours intrinsicviscosities ([IV] after the molten state under 300 ℃ under the atmosphere of non-negotiable nitrogen 130 ℃ of following vacuum-dryings _f), the numerical value that obtains according to computes.

The what is called nitrogen atmosphere that do not circulate is meant the nitrogen atmosphere that does not circulate, and for example, the glass test tube that resin flake is housed is connected on the valve tube, and after the decompression and nitrogen-sealed that repeat more than 5 times, inclosure nitrogen makes the tube sealing state into 100Toor.

TS＝0.245{[IV] _f ^-1.47-[IV] _i ^-1.47}。

Through using the catalyzer of this formation, can obtain the melting heat excellent in stability when making molding such as film, bottle, fiber and carry out heating and melting, and offer the polyester of the few molding of the generation etc. of painted or impurity.

TS is more preferably below 0.25, particularly preferably in below 0.20.

In addition, catalyst for polymerization of polyester of the present invention, its reactivity parameter (AP) preferably satisfies following mathematical expression (2).

(2) AP (branch)＜2T (branch)

Wherein, the AP catalyzer of representing to utilize specified rate polymerization intrinsicviscosity under 275 ℃, the decompression degree of 0.1Torr is the needed time of the polyethylene terephthalate of 0.65dl/g (branch).T is with respect to the sour composition in the polyethylene terephthalate that is generated, and adds the AP when reaching the ANTIMONY TRIOXIDE SB 203 99.8 PCT catalyzer of 0.05mol% in its content of antimony atoms.

In addition, in the present invention, as the ANTIMONY TRIOXIDE SB 203 99.8 PCT that is used for comparison, having used purity is the ANTIMONY TRIOXIDE SB 203 99.8 PCT more than 99%.For example, to be to use purity be 99.999% for the Antimony of ALDRICH system (III) oxide.

The measuring method of AP, specific as follows.

1) (BHET preparation section) uses the terepthaloyl moietie of terephthalic acid and its 2 times of amounts, two (2-hydroxyethyl) terephthalate (BHET) of preparation esterification yield 95% and the mixture of oligopolymer (below be called the BHET mixture).

2) (the interpolation operation of catalyzer) added a certain amount of catalyzer in said BHET mixture; Normal pressure stirred 10 minutes for 245 ℃ under nitrogen atmosphere, then, used to be heated to 275 ℃ in 50 minutes; The pressure of the reactive system of the mixture of slow simultaneously reduction oligopolymer, making pressure is 0.1Torr.

3) (polycondensation step) carries out polycondensation under 275 ℃, 0.1Torr, and the intrinsicviscosity (IV) that is aggregated to polyethylene terephthalate is 0.65dl/g.

4) polycondensation step is the required time is made as AP (branch).

These operations can use the intermittent reaction device to carry out.

1) preparation of the BHET mixture in (BHET preparation section) is carried out according to known method.For example, the terepthaloyl moietie of terephthalic acid and its 2 times of amounts is joined in the batch autoclave that has stirrer, depress, 245 ℃ of bottoms water is distilled to the system outside and carries out esterification and prepare in adding of 0.25MPa.

Through reactivity parameter AP is set in the said scope, can improve speed of response, the time for preparing polyester through polycondensation shortens.AP is preferably below the 1.5T, more preferably below 1.3T, below 1.0T.

2) what is called " catalyzer of specified rate " in (catalyzer interpolation operation) is meant the usage quantity of the catalyzer that changes according to catalytic activity, and active high catalyzer uses less amount, and active low catalyzer uses more amount.The usage quantity of catalyzer is with respect to the mole number of terephthalic acid, to be 0.1 mole of % to the maximum in aluminum compound.If consumption surpasses this value, then the catalyst residue quantitative change in polyester is many, thereby can not become practical catalyzer.

Catalyst for polymerization of polyester of the present invention preferably utilizes the thermo-oxidative stability parameter (TOS) of the polyethylene terephthalate (PET) of this polymerization catalyst to satisfy following formula (3).

(3)TOS＜0.10

In the above-mentioned formula; TOS is to be that the PET resin flake of 0.65dl/g carries out freezing and pulverizing by the IV with melt polymerization, is made as the powder below 20 orders, and in 12 hours powder 0.3g of 130 ℃ of following vacuum-drying packs glass test tube into; Under 70 ℃, carry out 12 hours vacuum-drying; Under with the air behind the silica dehydrator,, utilize computes to obtain afterwards at 230 ℃ of heating IV after 15 minutes.

TOS＝0.245{[IV] _f1 ^-1.47-[IV] _i ^-1.47}

[IV] _i[IV] _F1Represent before the heat test respectively and the IV (dl/g) after the heat test.

As the method for heating under with the air behind the silica dehydrator, for example, can example go out the top that the drying tube that adds silica gel is connected glass test tube, the method that under the exsiccant air, heats.

Through using the catalyst for polymerization of polyester of said formation, can obtain the good polyester of heat-resistant aging of molding such as film or PET bottle.

TOS is more preferably below 0.09, and then preferably below 0.08.

In addition, for catalyst for polymerization of polyester of the present invention, use the hydrolytic resistance parameter (HS) of the PET that this polymerization catalyst obtains preferably to satisfy following mathematical expression (4).

(4)HS＜0.10

(HS is that the intrinsicviscosity that gets by carrying out melt polymerization is about 0.65dl/g (before the test: [IV] _I) PET thin slice freezing and pulverizing; Be made as the powder below 20 orders; And 130 ℃ of following vacuum-dryings after 12 hours; Dried powder 1g that obtains and pure water 100ml are together joined in the beaker, and the intrinsicviscosity IV after under tightness system is heated to 130 ℃ and the condition of pressurizeing, stirring 6 hours] _F2The numerical value that utilizes computes to obtain.

HS＝0.245{[IV] _f2 ^-1.47-[IV] _i ^-1.47})

Be used to measure the beaker of HS, use acid or alkali can not dissolve the beaker of separating out.Concrete preferred stainless steel beaker, the quartz beaker of using.

Through using the catalyzer of said composition, can access the polyester polymers that can produce the excellent molding of hydrolytic resistance.

HS is more preferably below 0.09, particularly preferably in below 0.085.

As catalyst for polymerization of polyester of the present invention, it is desirable to, use the color Δ b value parameter (Δ b) of the PET of this polymerization catalyst to satisfy following mathematical expression (5).

(5)Δb＜4.0

In following formula; Δ b be expression use utilize given catalyzer melt polymerization, intrinsicviscosity is about polyethylene terephthalate (PET) resin flake of 0.65dl/g, from the special b value of the Chinese that utilizes colour-difference meter to record, deducts the value that obtains after the b value when using ANTIMONY TRIOXIDE SB 203 99.8 PCT to be used as catalyzer.Wherein, the add-on of ANTIMONY TRIOXIDE SB 203 99.8 PCT is with respect to the composition of the acid in the polyethylene terephthalate that is generated, to count 0.05 mole of % with antimony atoms.The ANTIMONY TRIOXIDE SB 203 99.8 PCT that is used to make comparisons, using purity is the ANTIMONY TRIOXIDE SB 203 99.8 PCT more than 99%.For example using Antimony (III) oxide, the purity of ALDRICH system is 99.999%.

According to described formation, catalyzer of the present invention can become the catalyzer of the better polyester of color that the melt-shaping article can be provided.Δ b value is more preferably below 3.0, further preferably below 2.5.

In the present invention,, use through said 1 as the PET resin flake that uses in order to measure TS, TOS)～3) after the operation, through the resin of making from the molten state chilling.As the shape of the resin flake that is used for these mensuration, for example can use the resin flake of the cylindrical shape that is about 3mm, the about 2mm of diameter.In addition, be used to measure the resin flake of color, use through said 1)～3) after the operation through make from the molten state chilling, be actually unbodied thin slice.As the method that obtains unbodied in fact thin slice; For example can enumerate; When reaction system is taken out polymkeric substance, after the relief outlet of reaction system is discharged polymkeric substance, use the cold water cool quickly at once behind the melt polymerization; In cold water, keep adequate time then, blocking at last becomes laminar method etc.Can't see in appearance because the whiting that crystallization causes according to the resin flake of such method gained.The resin flake that obtains like this is in room temperature, after air-dry about diel, be used to measure tone on filter paper etc.Also can't see in appearance because the whiting that crystallization causes is still transparent after such operation even carry out.In addition, in measuring the resin flake that tone uses, do not use titanium oxide etc. that outward appearance is brought the additive of influence.As shape, for example use the resin flake of the cylindrical shape of the about 3mm of length, the about 2mm of diameter as the resin flake of measuring tone.

In addition, catalyst for polymerization of polyester of the present invention preferably satisfy simultaneously in above-mentioned mathematical expression (1)～(5) more than 2.

Catalyst for polymerization of polyester of the present invention does not preferably contain the catalyzer of the compound of basic metal, alkaline-earth metal or these metals.

On the other hand, among the present invention,, together add and a spot ofly be selected from least a in basic metal, alkaline-earth metal and their compound to contain composition as the 2nd metal be an ideal mode except aluminium or its compound.Add described the 2nd metal when containing composition to catalyst system,, therefore, can obtain the higher catalyst component of speed of response, thereby boost productivity effectively except can effectively suppressing to improve catalytic activity the generation of glycol ether.

The technology of in aluminum compound, adding alkali metal cpd or alkali earth metallic compound and preparing the catalyzer with abundant catalytic activity is a technique known.If use this known catalyzer, then can obtain the polyester of good heat stability, but share the well-known catalysts of alkali metal cpd or alkali earth metallic compound; Obtain the catalytic activity of practicality; Their addition must be a lot, and when using alkali metal cpd, the impurity quantitative change that causes thus is many; When in fiber, using; Throwing property or silk rerum natura worsen, and when in film, using, deteriorations such as film rerum natura, the transparency, thermostability, thermo-oxidative stability, hydrolytic resistance.And then the tone of the melt-shaping article of fiber or film etc. worsens.In addition, when share alkali earth metallic compound, obtain the activity of practicality, then the thermostability of gained polyester, thermo-oxidative stability reduce, because the painted change that heating causes is big, it is many that the generation of impurity also becomes.

Among the present invention, when adding basic metal, alkaline-earth metal and compound thereof as polymerizing catalyst, its usage quantity M (mole %) is with respect to the unitary mole number of whole poly carboxylic acid that constitutes polyester, preferably 1 * 10 ^-6More than and be lower than 0.1 mole of %, more preferably 5 * 10 ^-6～0.05 mole of %, further preferred 1 * 10 ^-5～0.03 mole of %, preferred especially 1 * 10 ^-5～0.01 mole of %.Because the addition of basic metal, alkaline-earth metal seldom,, can improve speed of response so do not produce that thermostability reduces, the generation of impurity, problem such as painted.In addition, do not produce problems such as hydrolytic resistance reduction, can improve speed of response.If the usage quantity M of basic metal, alkaline-earth metal and compound thereof is at 0.1 mole more than the %, produces sometimes that thermostability reduces, the problem in the generation of impurity or the goods processing such as painted increase, hydrolytic resistance reduction.M is if be lower than 1 * 10 ^-6Mole is during %, even it is also not obvious to add its effect.

In the present invention; As constitute preferably join the 2nd metal that uses in aluminium or its compound contain composition metal, alkaline-earth metal; Be preferably selected from least a among Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, the Ba, more preferably use basic metal or its compound.When using basic metal or its compound, especially preferably use Li, Na, K.As the compound of basic metal or alkaline-earth metal, for example can enumerate the representative examples of saturated aliphatic carboxylic salt of the formic acid, acetate, propionic acid, butyric acid, oxalic acid etc. of these metals; The unsaturated aliphatic carboxylate salt of vinylformic acid, methylacrylic acid etc.; The aromatic carboxylic acid salt of TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M. etc.; The Halogen carboxylate salt of trichoroacetic acid(TCA) etc.; The hydroxycarboxylate of lactic acid, Hydrocerol A, Whitfield's ointment etc.; The inorganic acid salt of carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acids, hydrogen-carbonate, phosphoric acid hydrogen, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, Hydrogen bromide, chloric acid, bromic acid etc.; The organic sulfonate of 1-propanesulfonic acid, 1-penta sulfonic acid, naphthene sulfonic acid etc.; The organic sulfate of lauryl sulfate etc.; The alkoxide of methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, tert.-butoxy etc.; The inner complex of methyl ethyl diketone complex salt etc.; Hydrogenate; Oxide compound; Oxyhydroxide etc.

In these basic metal, alkaline-earth metal or their compound; When using the alkaline strong salt of oxyhydroxide etc.; These salt owing to have are difficult to be dissolved in the tendency in the organic solvent of glycol or the ethanol of terepthaloyl moietie etc. etc.; So must in paradigmatic system, add with the mode of the aqueous solution, this becomes the problem on the polymerization process sometimes.And then, when using the strong material of alkalescence such as oxyhydroxide, when polymerization, side reactions such as polyester hydrolysis take place easily, the polymeric polyester has the tendency of easy colorizing simultaneously, the tendency that also has hydrolytic resistance to reduce.Therefore, as the preferred basic metal of the present invention or their compound or alkaline-earth metal or their compound, be the representative examples of saturated aliphatic carboxylic salt of basic metal or alkaline-earth metal; The unsaturated aliphatic carboxylate salt; The aromatic carboxylic acid salt; The Halogen carboxylate salt; The hydroxycarboxylate; Be selected from the inorganic acid salt in sulfuric acid, nitric acid, phosphoric acid, phosphonic acids, phosphoric acid hydrogen, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, Hydrogen bromide, chloric acid, the bromic acid; Organic sulfonate, organic sulfate, inner complex and oxide compound.Wherein, the viewpoint of calm easy to operate or easy acquisition is preferably used representative examples of saturated aliphatic carboxylic salt, the especially acetate of basic metal or alkaline-earth metal.

In catalyst for polymerization of polyester of the present invention, also add with respect to polyester, be ideal in its content of cobalt atom less than the cobalt cpd of the amount of 10ppm.Even more ideal is less than 5ppm, so even more ideal be 3ppm.

Known cobalt cpd itself has certain catalytic activity, if add the degree that can give full play to catalytic activity to, then the transparency of the polyester polymers of gained or thermostability reduce.The polyester that obtains according to the present invention, its color harmony good thermal stability, and through adding the little cobalt compound like above-mentioned amount, it is not very remarkable making catalytic effect, thereby can not cause the reduction of the transparency of gained polyester, can further remove painted effectively.In addition, the cobalt cpd among the present invention its objective is to be used to remove painted that the time of interpolation can be arbitrary stage of polymeric, can be after polyreaction finishes, and also can be to finish any stage of back during till be shaped from polyreaction.

Do not have particular restriction as cobalt cpd, specifically, for example can enumerate cobaltous acetate, Xiao Suangu, NSC 51149, acetylacetone cobalt, cobalt naphthenate and their hydrate etc.Wherein, preferred especially cobaltous acetate four water salt.

The preparation of polyester of the present invention has in the past the method for known operation and carries out except using as catalyzer the catalyst for polymerization of polyester of the present invention, can using.For example, in preparation during PET, can use, distillate water, after the esterification, under reduced pressure carry out the direct esterification method of polycondensation with terephthalic acid and terepthaloyl moietie and as required also with other copolymer composition direct reaction; Also can use DMT. Dimethyl p-benzenedicarboxylate and terepthaloyl moietie and also add other copolymer composition as required and react, distillate methyl alcohol, carry out transesterify after, the ester exchange method that under reduced pressure carries out polycondensation.In addition, as required, in order to increase limiting viscosity, and reduce acetaldehyde etc. and can carry out solid state polymerization.In order to promote the crystallization before the solid state polymerization, heat crystallization after can making the moisture absorption of melt polymerization polyester earlier, perhaps can directly blow water vapour to polyester sheet, add thermal crystallization.

Said melt phase polycondensation device can be the intermittent reaction device, also can be continuous reaction apparatus.In described any mode, esterification or transesterification reaction can be carried out a stage, perhaps can divide a plurality of stages to carry out.Equally, melt polycondensation reaction also can be to carry out a stage, perhaps can divide a plurality of stages to carry out.Solid-phase polymerization and melt polycondensation reaction are same, can carry out with intermittent reaction device or continuous reaction apparatus.Melt phase polycondensation and solid state polymerization can carry out continuously, also can separately carry out.

Below, be example with the polyethylene terephthalate, an ideal continuous mode method of manufacture is described.

At first the situation of low-grade polymer is made in explanation through esterification.

Preparation contains 1.02～1.5 moles with respect to 1 mole in the verivate of terephthalic acid or its ester, is preferably the slurry of 1.03～1.4 moles of terepthaloyl moietie, and supplies with this slurry continuously in the esterification operation.

Esterification is to use the multi-stage type device that 1～3 esterifier is connected in series, and under the condition that terepthaloyl moietie refluxes, remove by rectifying tower water that is generated in the reaction or alcohol on the limit outside system, and react on the limit.First section esterification reaction temperature is 240～270 ℃, is preferably 245～265 ℃, and pressure is 0.2～3kg/cm ²G, be preferably 0.5～2kg/cm ²G.Normally 250～290 ℃ of the esterification reaction temperatures of back segment are preferably 255～275 ℃, and pressure is 0～1.5kg/cm normally ²G, be preferably 0～1.3kg/cm ²G.When dividing 3 to carry out more than the stage, the reaction conditions of the esterification in intermediate stage is the condition between the reaction conditions of said first section reaction conditions and final stage.The raising of the reactivity of these esterifications it is desirable to, and on each stage, improves sleekly.Last esterification rate reaches more than 90%, preferably reaches more than 93%.Through these esterifications, can obtain molecular weight and be about 500～5000 low polycondensate.

Above-mentioned esterification is when using terephthalic acid as raw material, and the catalyst action of the acid through terephthalic acid even also can not react under the condition of catalyzer having, but also can react under the condition that together exists of polycondensation catalyst.

In addition, if add tertiary amines such as a spot of triethylamine, tri-n-butylamine, benzyldimethylamine; Hydroxide quaternary amines such as tetraethylamine hydroxide, hydroxide four n-Butyl Amine 99s, hydroxide trimethyl benzyl amine; React with basic cpds such as Quilonum Retard, yellow soda ash, salt of wormwood, sodium acetates; Then the unitary ratio of dihydric para-phthalic acid's glycol ester composition in the polyethylene terephthalate main chain can be remained on lower level (is 5 moles below the % with respect to whole diol components), so be ideal.

Then, when making oligopolymer through transesterification reaction, chopping phase contains 1.1～1.6 moles for 1 mole of terephthalic acid, is preferably the solution of 1.2～1.5 moles of terepthaloyl moietie, and supplies with this solution continuously in the transesterification reaction operation.

Esterification is to use the device that 1～2 esterifier is connected in series, and under the condition that terepthaloyl moietie refluxes, remove by rectifying tower the methyl alcohol that is generated in the reaction on the limit outside system, and react on the limit.First section esterification reaction temperature is 180～250 ℃; Be preferably 200～240 ℃; Normally 230～270 ℃ of the esterification reaction temperatures of back segment; Be preferably 240～265 ℃, as transesterification catalyst, soap, carbonate or the Pb of use Zn, Cd, Mg, Mn, Co, Ca, Ba etc., Zn, Sb, Ge oxide compound etc.Through such transesterification reaction, obtain molecular weight and be about 200～500 low polycondensate.

Then, supply with the low polycondensate that obtains in the multistage liquid polycondensation operation.The polycondensation condition is, first section polycondensation temperature is 250～290 ℃, is preferably 260～280 ℃, and pressure is 500～20Torr, be preferably 200～30Torr.Normally 265～300 ℃ of the polycondensation temperature of final stage are preferably 275～295 ℃, and pressure is 10～0.1Torr, be preferably 5～0.5Torr.When dividing 3 to carry out more than the stage, the reaction conditions of the esterification in intermediate stage is the condition between the reaction conditions of said first section reaction conditions and final stage.The raising of the reactivity of these esterifications it is desirable to, and on each stage, improves sleekly.The limiting viscosity that on the different steps of these polycondensation operations, is reached is to rise sleekly.

In addition, require low acetaldehyde content with heat-resisting hollow forming body etc. or hang down under the situation of cyclic trimer content at low flavor beverage or mineral water, the polyester that is melted polycondensation that obtains like this is once again by solid state polymerization.According to the described polyester of known method solid state polymerization in the past.At first, with the said polyester of supplying with solid state polymerization, at rare gas element or under reduced pressure or containing under the inert gas atmosphere of water vapor, 100～210 ℃ temperature heating 1～5 hour, with its preparatory crystallization.Then, at inert gas atmosphere or in decompression, and under 190～230 ℃ temperature, carried out solid state polymerization 1～30 hour.

Catalyzer of the present invention is not only for polyreaction, and esterification and transesterification reaction are also had catalytic activity.For example; By the transesterification reaction of glycol such as the alkyl ester of dicarboxylicacid such as DMT. Dimethyl p-benzenedicarboxylate and terepthaloyl moietie and the polymerization that produces; Normally in the presence of the transesterification catalyst of titanium compound or zn cpds etc., carry out; But can substitute these catalyzer, or together use catalyzer of the present invention with these catalyzer.And catalyzer of the present invention is not only to melt polymerization, and solid state polymerization or solution polymerization are also had catalytic activity, can make polyester according to any one method wherein.

Polymerizing catalyst of the present invention can add in reactive system in any stage of polyreaction.For example, any stage that can be before the beginning of esterification or transesterification reaction and in reaction process or just begun any stage preceding or in reaction process in polycondensation and in reactive system, add.For aluminium or its compound, preferably just to begin preceding interpolation in polycondensation.

The addition means of polymerizing catalyst of the present invention both can be Powdered or needle-like, also can be the pasty state or the solution shape of the solvent of terepthaloyl moietie etc., did not have particular restriction.In addition, can add in advance, also can they be added respectively the mixed mixture of the constituent of polymerizing catalyst of the present invention.In addition, the constituent of polymerizing catalyst of the present invention can be in the same period in paradigmatic system, added, also each composition can be added respectively in each period.

In addition; For polyester catalyst of the present invention; When making other polymerizing catalyst and its coexistence of antimony compounds, titanium compound, ge cpd, tin compound etc. in the addition scope that in goods such as the characteristic of described polyester, processibility, tone, does not have problems; Because the polymeric time shortens, and can boost productivity effectively, so be preferred.

Wherein, with respect to the polyester of polymerization gained, can add the antimony compounds of the amount below the 50ppm of counting with antimony atoms.Be more preferably the amount of adding below the 30ppm.If the addition of antimony surpasses 50ppm, the phenomenon of separating out of Antimony Metal 99.65& 99.96 then occurs, and in polyester blackout or the polyester impurity is arranged, so undesirable.

With respect to the polymkeric substance of polymerization gained, can add the titanium compound of the following scope amount of 10ppm.Be more preferably the amount of adding below the 5ppm, further it is desirable to add the amount below the 2ppm.If the addition of titanium surpasses 10ppm, then the thermostability of gained resin will significantly descend.

With respect to the polymkeric substance of polymerization gained, can add the ge cpd of the amount below the 20ppm of counting with germanium atom.Be more preferably the amount of adding below the 10ppm.If the addition of germanium surpasses 20ppm, and is then unfavorable on cost, so undesirable.

When using polymerizing catalyst polymeric polyester of the present invention, can use in antimony compounds, titanium compound, ge cpd, the tin compound more than a kind or 2 kinds.

The antimony compounds, titanium compound, ge cpd, the tin compound that are used for the present invention do not have special qualification.

Particularly,, can enumerate ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide, antimony acetate, antimony glycol etc., wherein preferably use ANTIMONY TRIOXIDE SB 203 99.8 PCT as antimony compounds.

In addition, can enumerate metatitanic acid four n-propyls, titanium isopropylate, tetra-n-butyl titanate, metatitanic acid four isobutylates, metatitanic acid four tert-butyl esters, Fourth Ring hexyl titanic acid ester, tetraphenyl titanic acid ester, titanous oxalate etc., wherein preferred metatitanic acid four positive fourth oxygen esters as titanium compound.

In addition,, can enumerate germanium dioxide, germanium tetrachloride etc., wherein preferably use germanium dioxide as ge cpd.

In addition; As tin compound; Can enumerate dibutyl tin oxide, aminomethyl phenyl tin-oxide, tin tetraethyl, Hexaethyl tin-oxide, triethyltin oxyhydroxide, monobutyl hydroxyl tin-oxide, triisobutyl tin acetate, phenylbenzene moon silicic acid tin, Monobutyltin trichloride, dibutyl tin sulfide, dibutyl hydroxyl tin-oxide, the acid of methyl first stannane, the acid of ethyl first stannane etc., especially preferably use monobutyl hydroxyl tin-oxide.

Polyester described in the present invention; Be meant by be selected from the polycarboxylic acid that contains dicarboxylicacid and their the ester formation property verivate one or more and be selected from the polyvalent alcohol that contains glycol one or more and constitute; Perhaps constitute, perhaps constitute by cyclic ester by hydroxycarboxylic acid and their ester formation property verivate.

As dicarboxylicacid; Can enumerate oxalic acid, propanedioic acid, succsinic acid, normal pyrotartaric acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, decane dicarboxylic acid, dodecanedicarboxylic acid, tetradecane dicarboxylic acid, hexadecane dicarboxylic acid, 1; 3-CBDCA, 1; 3-pentamethylene dicarboxylicacid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1; 4-cyclohexane dicarboxylic acid, 2, the saturated aliphatic dicarboxylic acids of 5-norbornane dicarboxylicacid, dipolymer acid etc. or their ester formation property verivate; The unsaturated aliphatic dicarboxylicacid of fumaric acid, toxilic acid, methylene-succinic acid etc. or their ester formation property verivate; Phthalic acid, m-phthalic acid, terephthalate, 5-(basic metal) sulfoisophthalic acid, the peaceful acid of biphenyl, 1,3-naphthalene dicarboxylic acids, 1,4-naphthalene dicarboxylic acids, 1; 5-naphthalene dicarboxylic acids, 2,6-naphthalene dicarboxylic acids, 2,7-naphthalene dicarboxylic acids, 4; 4 '-diphenyl dicarboxylic acid, 4,4 '-biphenyl sulphur dicarboxylicacid, 4,4 '-biphenyl ether dicarboxylicacid, 1; Two (phenoxy) ethane-P of 2-, P '-dicarboxylicacid, Pamoic acid, the aromatic dicarboxylic acid or their ester of fearing dicarboxylicacid etc. form the property verivate.

In these dicarboxylicacid, from the viewpoint of the rerum natura of gained polyester etc., preferred terephthalic acid and naphthalene dicarboxylic acids, preferred especially 2, the 6-naphthalene dicarboxylic acids as required can also be with other dicarboxylicacid as moity.

As the polycarboxylic acid beyond these dicarboxylicacid, can enumerate ethane tricarboxylic acid, tricarballylic acid, BTCA, Pyromellitic Acid, trimellitic acid, trimesic acid, 3,4,3 ', 4 '-biphenyltetracarboxyacid acid and their ester formation property verivate etc.

As glycol, can enumerate terepthaloyl moietie, 1,2-Ucar 35,1, ammediol, glycol ether, triglycol, 1; 2-butyleneglycol, 1,3 butylene glycol, 2,3-butyleneglycol, 1,4-butyleneglycol, 1; 5-pentanediol, NSC 6366,1,6-pinakon, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1; 4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1; 4-hexamethylene di-alcohol, decamethylene-glycol, 1, gather three methylene glycols, gather the aliphatic diol of tetramethyl glycol etc. 12-dodecanediol, polyoxyethylene glycol; Resorcinol, 4; 4 '-dihydroxyl bis-phenol, 1; Two (beta-hydroxy oxyethyl group) benzene, 1 of 4-; Two (beta-hydroxy ethoxyl phenenyl) sulfones of 4-, two (p-hydroxybenzene) ether, two (p-hydroxybenzene) sulfone, two (p-hydroxybenzene) methane, 1, two (p-hydroxybenzene) ethane of 2-, dihydroxyphenyl propane, bisphenol-c, 2,5-naphthalene glycol, the aromatic series terepthaloyl moietie such as glycol behind addition of ethylene oxide on these glycol.

Preferred terepthaloyl moietie, 1 in these glycol, ammediol, 1,4-butyleneglycol, 1,4 cyclohexane dimethanol.

As the polyvalent alcohol beyond these glycol, can enumerate Pehanorm, trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane, glycerine, hexanetriol etc.

As hydroxycarboxylic acid, can enumerate lactic acid, Hydrocerol A, oxysuccinic acid, tartrate, oxyacetic acid, 3-hydroxybutyric acid, to Para Hydroxy Benzoic Acid, (2-hydroxyl-oxethyl) TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M., 4-hydroxyl hexahydrobenzoic acid or their ester are formed property verivate etc.

As cyclic ester, can enumerate 6-caprolactone, beta-propiolactone, Beta-methyl-beta-propiolactone, δ-Wu Neizhi, glycollide, lactide etc.

Form the property verivate as the ester of polycarboxylic acid or hydroxycarboxylic acid, can enumerate their alkyl ester, acyl chlorides, acid anhydrides etc.

Used polyester among the present invention is that main sour composition is that terephthalic acid or its ester form the polyester that property verivate or naphthalene dicarboxylic acids or its ester form the property verivate, and preferred main diol component is the polyester of alkylene glycol.

As main sour composition is the polyester of terephthalic acid or its ester formation property verivate or naphthalene dicarboxylic acids or its ester formation property verivate; Preferably with respect to all acid composition; Contain terephthalic acid or its ester form property verivate and naphthalene dicarboxylic acids or its ester form the property verivate altogether 70 moles of % above, more preferably contain the above polyester of 80 moles of %, further be preferably the polyester that contains more than 90 moles of %.

Polyester as main pure composition is the alkane glycol preferably becomes subtotaling to contain 70 moles of polyester more than the % of alkylene glycol with respect to whole alcohol, more preferably contains the above polyester of 80 moles of %, especially preferably contains the above polyester of 90 moles of %.Alkylene glycol described here can contain substituting group or alicyclic structure in molecular chain.

As naphthalene dicarboxylic acids used among the present invention or its ester formation property verivate, be preferably 1,3-naphthalene dicarboxylic acids, 1,4-naphthalene dicarboxylic acids, 1,5-naphthalene dicarboxylic acids, 2,6-naphthalene dicarboxylic acids, 2,7-naphthalene dicarboxylic acids or their ester formation property verivate.

As alkylene glycol used among the present invention, can enumerate terepthaloyl moietie, 1,2-Ucar 35,1, ammediol, 1,2-butyleneglycol, 1; 3-butyleneglycol, 2,3-butyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol, NSC 6366,1,6-pinakon, 1; 2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1; The 4-cyclohexanedimethanol, 1,4-hexamethylene di-alcohol, 1,10-decane glycol, 1,12-dodecanediol etc.These can use two or more simultaneously.

As polyester of the present invention; Preferred polyethylene terephthalate, polybutylene terephthalate, PTT, gather (1; 4-cyclohexanedimethyleterephthalate terephthalate), PEN, PBN, gather naphthalic acid propylene glycol ester and their multipolymers; In these, its preferred polyethylene terephthalate and multipolymer thereof especially.

A desirable example that is used for the present invention's polyester is; The polyester that main repeating unit is made up of ethylene glycol terephthalate; Better is to contain the above linear polyester of the 70 moles of % in ethylene glycol terephthalate unit; Further it is desirable to contain the above linear polyester of the 80 moles of % in ethylene glycol terephthalate unit, it is desirable to contain the above linear polyester of the 90 moles of % in ethylene glycol terephthalate unit especially.

Another the desirable example that is used for the present invention's polyester is, main repeating unit is by 2, the polyester that the 6-(ethylene naphthalate) constitutes; Better is to contain 2; The linear polyester that 70 moles of % of 6-(ethylene naphthalate) are above further it is desirable to contain 2, the linear polyester that 80 moles of % of 6-(ethylene naphthalate) are above; It is desirable to contain 2 especially, the linear polyester that 90 moles of % of 6-(ethylene naphthalate) are above.

Another the desirable example that is used for the present invention's polyester is; Contain the above linear polyester of the 70 moles of % in propylene glycol ester terephthalate unit, contain the above linear polyester of the 70 moles of % in naphthalic acid propylene glycol ester unit, contain 1, the above linear polyester of 70 moles of % of 4-hexanaphthene terephthalic acid diformazan diol ester, contain the above linear polyester of the 70 moles of % in naphthalic acid butanediol ester unit or contain the above linear polyester of the 70 moles of % in mutual-phenenyl two acid bromide two alcohol ester unit.

In addition, in polyester of the present invention, can be used as copolymer composition and add known phosphorus compound.As Phosphorus compound, the preferred Phosphorus compound of difunctionality.For example (2-carboxy ethyl) methyl phospho acid, (2-carboxy ethyl) phenyl phosphinic acid, 9,10-dihydro-10-oxo-(2,3-carboxyl propyl group)-10-oxidation phospho hetero phenanthrene etc.Through with these phosphorus series compounds as copolymer composition, can make the raisings such as flame retardant resistance of the polyester of gained.

In order to improve the dyeability of polyester when the fiber, as the constituent of polyester of the present invention, the poly carboxylic acid that preferably will have azochlorosulfonate acid alkali metal base is as copolymer composition.

As the compound that contains the metal sulfamate alkali as polymer monomers; Do not have special qualification, for example can enumerate 5-sulfoisophthalic acid sodium, 2 sulfotere phthalic acid sodium, 5-sulfoisophthalic acid lithium, 2 sulfotere phthalic acid lithium, 5-sulfoisophthalic acid potassium, 2 sulfotere phthalic acid potassium or their low alkyl group ester derivative etc.In the present invention, especially preferably use 5-sulfoisophthalic acid sodium or its ester formation property verivate.

The copolymerization amount that contains the compound of metal sulfamate alkali, the sour composition with respect to constituting polyester is preferably 0.3～10.0 mole of %, more preferably 0.80～5.0 mole of %.If polymerization amount is very few, the basic dyestuff dyeability reduces, if too much, and when making fiber, the deterioration of not only throwing property, and also because the thickening phenomenon can not obtain enough intensity as fiber.In addition, if copolymerization contains 2.0 moles of the compounds of metal sulfamate alkali more than the %, then can make the modified polyester fiber of gained obtain the normal pressure dyeability.In addition, through selecting suitable chromatophilia monomer, the usage quantity of the compound that contains the metal sulfamate alkali is suitably reduced.As the chromatophilia monomer, there is not particular restriction, can enumerate with polyoxyethylene glycol, gather long chain diol compound that the tetramethyl glycol is representative or be the aliphatic dicarboxylic acid of representative with hexanodioic acid, sebacic acid, nonane diacid.

According to the method for the invention, after carrying out polyester,, make catalyst deactivation, can further improve the thermostability of polyester through from this polyester, removing catalyzer or adding phosphorus series compound etc.

In polyester of the present invention; Can contain toner and the white dyes of organic system, inorganic system and organo-metallic system etc.; And, can suppress the problem that polyester is coloured to yellow etc. further, and make the inhibition degree reach excellent level through containing in them one or more.And, can also contain other polymkeric substance or static inhibitor, skimmer, dyeability modifying agent, dyestuff, pigment, matting agent, white dyes, stablizer, inhibitor and other additive arbitrarily.As inhibitor, can use inhibitors such as aromatic amine system, phenol system, as stablizer, can use the phosphorus system of phosphoric acid or SULPHOSUCCINIC ACID ESTER system etc.; Sulphur system; The stablizer of amine system etc.

These additives, can be when the polymerization of polyester, after the polymerization or any stage the during shaping of polyester add, which stage to add the desired properties of relatively good characteristic or polyester formed body according to compound and different separately in.

Use catalyst for polymerization of polyester polymeric polyester of the present invention, can utilize conventional melt spinning method to make fiber, can adopt method that the spinning and 2 steps of branch that stretch are carried out and the method for carrying out with 1 step.Also have, can be suitable for all known fibre manufactures such as method of manufacture or filamentary method of manufacture of the staple fibre that possesses wrinkle (crimping), thermal-setting or cut off operation.

And the fiber that obtains can have the various fibrous textures of special crosssection silk, hollow section silk, conjugated fibre, dyed in the mass silk etc., in yarn processing, also can adopt the technique known of blend fiber, blending etc.

In addition, above-mentioned trevira can be used as the fiber construct of woven fabric or non-woven fabrics etc. and uses.

Above-mentioned polyester for example can be as use fiber, curtain, carpet, bed clothes cotton, fiber etc. to use fiber as the indoor bedroom dress of representative with dress material; With the anti-tension line of tire cord, rope etc., civil construction material, vehicles such as lining tire use material etc. to use fiber as the Industrial materials of representative; The various fibers of various fabrics, various cloth, reticulattion, staple fiber nonwoven fabric, nonwoven fabric of long fibers etc.

Vibrin of the present invention is suitable as the hollow forming body.

Can give an example mineral water, juice, wine or whiskey beverage container as the hollow forming body; Feeding bottle, tinned pre-container; The haircut container of material or makeup etc.; Dwelling house and tableware are with washing container etc.

Wherein, as the effective wholesomeness that polyester had and intensity, the pressure vessel of solvent resistance, heat-resistant pressure vessel, anti-pure container of having utilized, be especially suitable for use as various beverage-containers.

The manufacturing of hollow forming body is; At first utilize the polyester sheet that will obtain through melt polymerization or solid state polymerization; After the boulton process drying; Utilize method that forming mills such as extrusion moulding machine or injection machine form or the molten mass behind the melt polymerization is introduced directly into the direct forming method that forming mill forms under molten state, make the preform at the end.Then, utilize the blow-moulding process of draw blow molding, directly blow molding, extrusion blowing etc., get hollow forming body to the end by said preform.Certainly, also can be the molding that utilizes forming mill gained such as above-mentioned extrusion moulding machine or injection machine as last hollow container.

When making above-mentioned hollow forming body, can mix use to waste resin that produces in the manufacturing process and the polyester that reclaims from market.Even under such situation that reclaims resin again, vibrin of the present invention is deterioration seldom, can obtain high-quality hollow forming article.

In addition, such container can be employed in the multilayered structure that the middle layer is provided with gas shield property resin layer, opacifying property resin layer or the recycle polyester layer of penylene n n dimetylaniline between Z 150PH or poly hexamethylene adipamide (polymetaxylylene diamine adipate) etc.And, also can utilize the method for vapor deposition or CVD (chemical vapor thermolysis) etc., inside and outside the layer covering container of the metal of aluminium etc. or diamond-like-carbon.

Also have,, can add with the Vilaterm inorganic nucleating agent of other resin or the talcum etc. that are representative for the crystallinity of the spigot that improves the hollow forming body etc.

In addition, vibrin of the present invention can become thin slice from extrusion machine with laminar extruding.Such thin slice; Through vacuum forming or press the processing of empty shapings, compacting etc., the carry strap (carrier tapes) of support of using as food or groceries or container, cup, blister packaging, electronic unit, electronic unit dispensing are with coiling (trays) etc.And thin slice can be used as various flap utilizations.Under the situation of this thin slice, also can be employed in the multilayered structure that the middle layer is provided with gas shield property resin layer, opacifying property resin layer or recycle polyester layer.

In addition, can mix equally and reclaim resin again.And, in order to make crystalline heat resistance container, can add inorganic nucleating agent, to improve crystallinity with other resin headed by the Vilaterm or talcum etc.

Use catalyst for polymerization of polyester polymeric polyester of the present invention can be used as film.Its method is, with the polyester melt extruded, utilize T-mold overflow mould on cooling rotation roller with laminar shaping, process the thin slice that do not stretch.At this moment, through being suitable for the technology of being put down in writing in for example special fair 6-39521 communique, the special fair 6-45175 communique, can make the high speed film-forming properties become possibility.And, can use a plurality of extrusion machines, make sandwich layer, epidermal area share various functions, utilize the co-extrusion platen press to make laminated film.

Use catalyst for polymerization of polyester polymeric polyester of the present invention can be used as oriented polyester films.Oriented polyester films is to use known method, more than the second-order transition temperature of polyester and under the condition less than crystallized temperature, obtains 1.1～6 times of single shaft direction stretchings at least.

For example, when making biaxially oriented polyester film, can adopt earlier vertical or horizontal carry out uniaxial extension after, then in the biaxial stretch-formed one by one method of perpendicular direction tensile; In tensile twin shaft while vertical and horizontal while tensile method; Driving method when stretching simultaneously as twin shaft, the method for use linear motor; Horizontal vertical vertical stretching method, vertical stretching method, vertical vertically and horizontally stretching method etc. are carried out tensile multistage drawing process several times on same direction in length and breadth.

In addition, after stretch finishing,, it is desirable to,, be preferably 10 seconds with interior to implement 0.5～10% vertical relaxation processes, horizontal relaxation processes etc. in (fusing point～50 ℃)～carry out heat setting less than the TR of fusing point to handle 30 seconds in order to reduce the percent thermal shrinkage of film.

The thickness of the oriented polyester films of gained it is desirable to below the above 1000 μ m of 1 μ m, and even more ideal is below the above 500 μ m of 5 μ m, further it is desirable to below the above 200 μ m of 10 μ m.If below 1 μ m, then there is not stiffness, operational difficulty.But if surpass 1000 μ m, thereby operational difficulty then really up to the mark.

In addition, in order to give various functions such as cementability, release property, static resistance, ultraviolet-absorbing, bacterinertness, scuff resistance, can on the surface of oriented polyester films, utilize coating lining macromolecule resin.In addition, also can only on coating, contain inorganic and/or organic filler, as being prone to sliding high transparent polyester film.And, inorganic vapor deposition layer also can be set, and give various barrier functions oxygen, water, oligopolymer etc., perhaps conductive layer is set and gives electroconductibility with sputtering method etc.

Also have,, can in the polymerization process of polyester, add inorganic and/or thermotolerance macromolecule resin particulate, and on film surface, form concavo-convex for the sliding property that improves oriented polyester films, the controllable characteristics of walking tropism, wearability, crimp tendency etc.

Oriented polyester films of the present invention is preferably used as anti-charging property film; The easy-adhesion film; Card is used; Slack tank is used; Agricultural is used; Building materials are used; Finishing material is used; Wallpaper is used; The OHP film is used; Printing is used; Ink-vapor recording is used; Usefulness is transcribed in distillation; The laser beam hard copy is used; The electrophotography record is used; Hot tranfer is employed; Heat-sensitive transfer recording is used; The printed base plate distribution is used; Thin film switch is used; Plasma shows to be used; Touch pad is used; Sheltering film uses; Photo plate-making is used; Roentgen's film is used; Plate is used; Phase-contrast film is used; Polarizing film is used; Light polarizing film protection (TAC) is used; Protective film is used; The photoresist film is used; The film of broadening one's vision is used; The diffusion thin slice is used; Reflective film is used; Reflection prevents film usefulness; Conductive membrane is used; Barrier film is used; Ultraviolet ray prevents to use; Back grindtapes uses etc.

As anti-charging property film, for example can use special permission No. 2952677 communique, spy and open the technology of being put down in writing in the flat 6-184337 communique.As the easy-adhesion film; For example can use the fair 07-108563 of spy, spy and open flat 10-235820, the spy opens the technology of being put down in writing in the flat 11-323271 communique, as card with for example can the spy be opened flat 10-171956, the spy opens the technology of being put down in writing in the flat 11-010815 communique and is applied in the film of the present invention.As slack tank usefulness, for example alternative spy opens the lamellar cylindrical shell of being put down in writing in the flat 10-101103 communique, can use the object of behind printed patterns on the film of the present invention, making tubular, half tubular again.As building materials with, building materials with decorating version, decorating and use material, for example can film of the present invention be opened and puts down the transparent thin board of being put down in writing in the 07-314630 communique as open the base material thin plate, the spy that are put down in writing in the flat 05-200927 communique the spy., can film of the present invention be opened transparent resin thin plate, the spy that flat 06-297831 communique put down in writing and opens the transparent polymer synthetic resin film of being put down in writing in the flat 08-305065 communique as special with (overhead projector with) as OHP.As ink-vapor recording usefulness, can be with film of the present invention as for example opening the transparent substrate of being put down in writing in the flat 05-032037 communique the spy.As sublimation transfer record usefulness, for example can be with film of the present invention as opening the transparent film of being put down in writing in the 2000-025349 communique the spy.As laser beam printing usefulness, electrophotographic recording usefulness, for example can be with film of the present invention as open the plastics film of being put down in writing in the flat 05-088400 communique the spy.Employ as hot tranfer; For example can use film of the present invention according to open the method for being put down in writing in the flat 07-032754 communique the spy; As thermal photography usefulness, can use film of the present invention according to open the method for being put down in writing in the flat 11-034503 communique the spy.As printed base plate usefulness, as using film of the present invention as for example opening the polyester film of being put down in writing in the flat 06-326453 communique the spy.As thin film switch, for example use film of the present invention according to open the method for being put down in writing in the flat 05-234459 communique the spy.As optics filter (hot line filter, plasma demonstration are used), for example use film of the present invention according to open the method for being put down in writing in the flat 11-231126 communique the spy.As transparent conducting film, touch pad usefulness, for example can use film of the present invention according to open the method for being put down in writing in the flat 11-224539 communique the spy.As sheltering film usefulness, for example can use film of the present invention according to open the method for being put down in writing in the flat 05-273737 communique the spy.As photoengraving usefulness, for example can use film of the present invention according to open the method for being put down in writing in the flat 05-057844 communique the spy.Use backsheet film as taking a picture, film of the present invention is used as the spy opens the pet film of being put down in writing in 0123 section that puts down the 06-167768 communique.As phase-contrast film, for example can be film of the present invention as opening the film of being put down in writing in the 2000-162419 communique the spy.As barrier film usefulness, can be film of the present invention as the film described in 0012 paragraph of opening flat 11-209711 communique the spy.Prevent usefulness as ultraviolet ray, can be with film of the present invention as open the polyester film of being put down in writing in the flat 10-329291 communique the spy.Use film as agricultural, for example, can be suitable for film of the present invention for open the pet film of being put down in writing in the flat 10-166534 communique the spy.As bonding thin plate,, be suitable for oriented polyester films of the present invention and obtain for example through for open the pet film of being put down in writing in the flat 06-122856 communique the spy.

Embodiment

Below through embodiment the present invention is described, but the present invention is not limited to these embodiment.Evaluation method used in each embodiment and comparative example is as follows.

[evaluation method]

(1) intrinsicviscosity (IV)

The weight ratio of using phenol/sym.-tetrachloroethane is 6/4 mixed solvent dissolved polyester, under 30 ℃ of temperature, measures.

(2) acid value

With polyester 0.1g, add benzylalcohol 10ml, heating for dissolving.The solution of methyl alcohol/benzylalcohol=1/9 of the NaOH of use 0.1N carries out titration, calculates acid value.

(3) glycol ether content (DGE)

In the methyl alcohol of 2ml, 250 ℃ with polyester 0.1g thermal degradation after, carry out quantitatively determined through vapor-phase chromatography.

(4) differential scanning calorimetric analysis (DSC)

Utilize the system DSC 2920 of TA instrument society to measure.Polyester 10.0mg packed into, and the heat-up rate with 50 ℃/minute is heated to 280 ℃ in the aluminum pot, after reaching 280 ℃, keeps 1 minute, in liquid nitrogen, carries out chilling then at once rapidly.Afterwards, be heated to 300 ℃ from room temperature, calculate crystallized temperature Tc1 and fusing point Tm when heating up with 20 ℃/minute heat-up rates.After reaching 300 ℃, kept 2 minutes, lower the temperature with 10 ℃/minute again, crystallized temperature Tc2 when calculating cooling.Tc1, Tm, Tc2 conduct be the temperature of the largest portion at peak separately.

(5) tone

In melt polymerization, reach the moment of given stirring torque, introduce nitrogen, get back to normal pressure and stopped polycondensation to autoclave.Then, depress, carry out chilling with tow shape ejection polymkeric substance, keep in cold water afterwards that the back cuts off in about 20 seconds, obtained the resin flake cylindraceous of the about 3mm of length, the about 2mm of diameter to cold water in little adding.With the resin flake that obtains like this, in room temperature, on filter paper, after air-dry about diel, be used to measure color.Color measurenent is, uses and carries out the PET resin flake that Iv that melt polymerization obtains is about 0.65dl/g, utilizes colour-difference meter (Tokyo electricity look (strain) system MODEL TC-1500MC-88) to measure L value, a value, the b value of Hunter.

(6) thermostability parameter (TS)

With the IV behind the melt polymerization is that 0.65dl/g is (before the fusion test; [IV] _i) PET resin flake 1g pack in the glass test tube of the about 14mm of internal diameter,, after 12 hours glass test tube is connected with valve tube 130 ℃ of following vacuum-dryings, after 5 decompressions were enclosed with nitrogen repeatedly, it was 100mmHg, tube sealing then that inclosure nitrogen makes vacuum tightness.This test tube is immersed in 300 ℃ the salt bath, keep 2 hours molten states after, take out sample, carry out freezing and pulverizing, after the vacuum-drying, measure IV (after the fusion test; [IV] _F2).Utilize following calculating formula by this [IV] _fObtain TS.Formula is quoted existing newspaper (go up a hill etc.: Japan rubber association will the 63rd volume No. 8 497 pages of nineteen nineties).

TS＝0.245{[IV] _f2 ^-1.47-[IV] _i ^-1.47}

(7) thermo-oxidative stability parameter (TOS)

PET resin flake freezing and pulverizing behind the melt polymerization, that IV is about 0.65dl/g is become the powder below 20 orders.Under 130 ℃ with this powder vacuum-drying 12 hours; With dry thing 300mg pack into the about 8mm of internal diameter, be about in the glass test tube of 140mm, after 12 hours, the drying tube of the silica gel of will packing into is connected test tube top 70 ℃ of following vacuum-dryings; Under the exsiccant air, be immersed in 230 ℃ the salt bath; Measure the IV of heating after 15 minutes, identical with above-mentioned TS then, utilize following calculating formula to calculate.Wherein [IV] _iAnd [IV] _F1Represent before the heat test respectively and the IV (dl/g) after the heat test.Freezing and pulverizing is to utilize cooling kibbler (U.S. specs society system 6750 types) to pulverize.In special container, pack into behind resin flake and the special-purpose knocker of about 2g; Container is set on the device; In device, fill liquid nitrogen and kept about 10 minutes, afterwards, pulverized 5 minutes through RATE10 (impactor approximately carried out about 20 times in 1 second).

TOS＝0.245{[IV] _f1 ^-1.47-[IV] _i ^-1.47}

(8) hydrolytic resistance parameter (HS)

With obtain behind the melt polymerization, intrinsicviscosity is about 0.65dl/g (before the test; [IV] _I) the PET resin flake, with above-mentioned (7) likewise freezing and pulverizing become the powder below 20 orders.Under 130 ℃ with this powder vacuum-drying 12 hours.Hydrolysis experiment is to use minicolour device ((strain) Texam skill development TypeMC12.ELB) to carry out.Above-mentioned powder 1g and pure water 100ml are together added in the stainless steel beaker, and be equipped with special-purpose stirring rake, make enclosed system, be set on the minicolour device, under 130 ℃ of heating and pressurized conditions, stirred 6 hours.Use glass filter, filter the PET after obtaining testing, measure IV ([IV] after the vacuum-drying _F2), obtain hydrolytic resistance parameter (HS) according to following formula then.

HS＝0.245{[IV] _f2 ^-1.47-[IV] _i ^-1.47}

(9) synthetic compound ¹H-NMR measures

With compound dissolution at CDCl ₃Or among the DMSO-d6, at room temperature utilize Varian GEMINI-200 to measure.

(10) fusing point test of synthetic compound

Compound is placed on the deckglass, utilizes Yanaco MICRO MELTING POINTAPPARATUS to measure with 1 ℃/minute heat-up rate.

(11) ultimate analysis of synthetic compound

The analysis of phosphorus is, PET resin flake wet type is decomposed after, carry out according to molybdenum blue colorimetric method.Other metal dissolves the back, utilizes high frequency plasma luminescence analysis and atomic absorption analysis to carry out through ashing/acid.

(12) the system film (except the embodiment 30～32) of film

In each embodiment and comparative example, with the PET resin flake of fusion test 135 ℃ of following vacuum-dryings 6 hours.Afterwards, supply with extrusion machine, in 280 ℃ of following melt extruded slabbings and taking-up, chilling solidifies on the metallic roll that keeps 20 ℃ of surface temperatures, obtains the cast film of thickness 1400 μ m.

Then, this cast film is heated to 100 ℃ with roller group and infrared heater after heating, afterwards,, carries out 3.5 times of stretchings in the longitudinal direction, obtain uniaxial orientation PET film having on the roller group of speed discrepancy.Then; Stretch 4.0 times to width under 120 ℃ with tenter machine,, heated for 0.5 second at 260 ℃ through ultraviolet well heater with the wide long fixed state of film; And then under 200 ℃, carry out 23 seconds 3% relaxation processes, obtain the diaxial orientation PET film of thickness 100 μ m.

(13) preparation of recovery disk (pellet)

To block rectangularity through the PET film of aforesaid method gained, and after the vacuum-drying, drop in the extrusion machine, with 280 ℃ of design temperatures, be after the nozzle of 5mm is extruded, to use water cooling with molten resin from bore, obtains reclaiming disk through blocking.

(14) prepare film by reclaiming disk

PET resin flake before the fusion test and described recovery disk are mixed with 50: 50 weight ratio, 135 ℃ of following vacuum-dryings 6 hours.Afterwards, supply with extrusion machine, in 280 ℃ of following melt extruded slabbings and taking-up, chilling solidifies on the metal roller that keeps 20 ℃ of surface temperatures, obtains the cast film of thickness 1400 μ m.

Then, this cast film is heated to 100 ℃ on cylinder group after the heating and infrared heater, afterwards, has on the cylinder group of speed discrepancy, carry out 3.5 times of stretchings in the longitudinal direction, obtain uniaxial orientation PET film.Then, under 120 ℃, stretch 4.0 times, obtain the twin shaft orientation PET film of thickness 100 μ m to width with tenter machine.

(15) thermostability of film

The appearance of films that detects by an unaided eye and obtain, and classify.

◎ does not have painted

Zero: have painted slightly

△: have painted

*: painted remarkable.

(16) heat-resistant aging of film

The film of method gained that will be through said (12) is cut into the test film of long 10cm, wide 5cm; Utilize the driven type hot air dryer with test film 200 ℃ handle 100 hours after; Film after handling is alongst stretched, estimate the film heat-resistant aging according to the disconnection difficulty or ease of this moment.

Zero: intensity is very high, is difficult to break off

△: intensity descends a little, breaks off a little easily

*: strength degradation, break off easily

(17) water tolerance of film

Will be in the method for above-mentioned (12) film of gained to cut into length be that 8cm, width are the test film of 4cm, and test film was boiled in boiling water 5 days.When the film after will boiling stretches along its length, classify according to the difficulty or ease of breaking off.

Zero: intensity is very high, is difficult to break off

△: intensity descends a little, breaks off a little easily

*: strength degradation, break off easily

(18) turbidity (turbidity %)

Middle portion (the about 0.45mm of thickness) by the hollow forming body of the molding (thickness 5mm) of following (19) and (20) cuts sample, measures with Japanese electric look (strain) system turbidimeter, modelNDH2000.

(19) shaping of staged forming board

Utilize name mechanism to make the M-150C of institute (DM) injection machine,, utilize water-cooled staged flat plate mold (surface temperature is about 22 ℃) shaping exsiccant polyester with 10 ℃ 290 ℃ of cylinder temperature.The staged forming board that obtains is to have steppedly that thickness is 2,3,4,5,6,7,8,9,10, the staged forming board of about 3cm * tetragonal plate of about 5cm of 11mm, and the weight of each plate is about 146g.The plate that 5mm is thick is used to measure turbidity (turbidity %).

(20) shaping of hollow forming body

Through the dry polyester of the drying machine that uses dehumidification nitrogen, and utilize name mechanism to make made M-150C (DM) injection machine, preformed articles is shaped under 295 ℃ of resin temperatures, 20 ℃ die temperature.With this preformed articles, utilize the LB-01E drawing blow molding machine of corpoplast society system, with 20kg/cm ²Blowing be pressed in 20 ℃ of moulds and carry out biaxial stretch blow molding, obtained the hollow forming body (pars intermedia is for circular) of 2000cc.

(21) thermotolerance the during shaping of hollow forming body

A) make to pulverize recovery article by the hollow forming system

The preformed articles that pulverizing obtains in above-mentioned (20) has obtained removing fines pulverizing recovery article afterwards.

B) sneaked into the shaping of the hollow forming body of recovery article

Mix by PET resin flake that obtains in the polycondensation step and described pulverizing recovery article with 80: 20 weight ratios; Then in the drying machine that uses dehumidification nitrogen, carry out drying at 150 ℃; And utilize name mechanism to make made M-150C (DM) injection machine, be configured as preformed articles in 295 ℃ of resin temperatures, 20 ℃ die temperature.Then with this preformed articles, use a) operation to carry out pulverization process once more, with 80: 20 weight ratios with mix by the PET resin flake that obtains in the polycondensation step, preformed articles likewise has been shaped.With aforesaid operations 5 times repeatedly.

C) thermotolerance evaluation

According at b) in the conservation rate of intrinsicviscosity (IV) of the thin plate that obtains estimate with the coloring degree that observes with the naked eye.

Conservation rate according to the computes intrinsicviscosity.

Conservation rate={ carry out IV/ polycondensation thin slice IV} * 100 afterwards of the shaping preformed articles afterwards of 5 times said (6b) repeatedly

(22) thermotolerance the during shaping of thin plate

A) make recovery article by thin plate

Utilize to use the drying machine of dehumidification nitrogen, dry polyester sheet is utilized the melted extrusion forming machine of Φ 40mm then, and 295 ℃ of resin temperature fusions, by the extruding of T mould, having obtained thickness is the not tensile thin plate of 0.5mm.This thin plate is cut off with sheet, obtained recovery article.

B) sneaked into the extrusion molding of the thin plate of recovery article

Mix by resin flake that obtains in the polycondensation step and described recovery article with 70: 30 weight ratios; Then in the drying machine that uses dehumidification nitrogen, carry out drying about 150 ℃; Utilize described melt extruded machine,, obtained and above-mentioned same thin plate 295 ℃ of resin temperature fusions.

Use a) operation that this thin plate is cut off processing once more, and with 70: 30 weight ratio with mix by the resin flake that obtains in the polycondensation step, likewise extrusion molding is a thin plate.Should operate altogether and carry out repeatedly 5 times.

C) thermotolerance evaluation

Conservation rate according to the computes intrinsicviscosity.

Conservation rate={ carry out IV/ polycondensation thin slice IV} * 100 afterwards of the shaping thin plate afterwards of 5 times said (7b) repeatedly

(embodiment 1)

(the synthetic example of phosphorus compound)

Synthesizing of phosphorus compound (NMPA) shown in the above-mentioned formula (25)

1.O-ethyl (1-naphthyl) methylphosphonate (NMPA) is synthetic

Under nitrogen atmosphere,, under 200 ℃ (outside temperature), do not produce gas (C with the mixture of triethyl-phosphite 8.31g (50mmol) and 1 chloromethyl naphthalene 8.83g (50mmol) ₂H ₅Cl) heating is about 30 minutes till.Be cooled to after the room temperature, obtained NPMA10.38g (thick yield 75%) as colourless oil liquid.

¹H-NMRCDCl ₃，δ)：1.151(6H，t)，3.641(2H，d)，3.948(4H，m)，7.381-7.579(4H，m)，7.749-7.867(2H，m)，8.088-8.133(1H，m)

(polyester example)

Autoclave to the circulating 2 liters of stainless steels of the thermal medium that has whisking appliance; The terepthaloyl moietie that adds high purity terephthalic acid and its 2 times of molar weights; Adding is the triethylamine of 0.3mol% with respect to sour composition, and adds the ethylene glycol solution of 50g/l of counting the above-mentioned NMPA of 0.03mol% with respect to sour composition with NMPA, depresses in adding of 0.25Mpa then; At 245 ℃; The limit is dephlegmate outside system, esterification was carried out 130 minutes in the limit, has obtained esterification yield and be the mixture (below be called the BHET mixture) of 95% two (2-hydroxyethyl) terephthalate (BHET) and oligopolymer.To this BHET mixture, with respect to the branch that is counted as in the polyester, add the ethylene glycol solution of 2.5g/l of counting the acetyl acetone aluminium of 0.015mol% with the aluminium atom, then under nitrogen atmosphere, stirred 10 minutes at 245 ℃ under the normal pressure.Be warming up to 275 ℃ with 50 minutes then, reduce simultaneously slowly the pressure of reactive system, make system pressure reach 0.1Torr, further carry out polycondensation at 275 ℃, 0.1Torr.The IV that in table 1, expresses polyethylene terephthalate reaches 0.65dlg ^-1Needed polymerization time (AP).

In addition, utilize conventional method, the IV that will in above-mentioned polycondensation, obtain is 0.65dlg ^-1Polyethylene terephthalate carry out sheet.Utilize this PET resin flake, measure its various rerum naturas and make an experiment.In table 1 and table 2, represented the result.

Utilization has been carried out the preparation of film, the preparation of reclaiming the particulate making and utilizing recovery particulate film by the PET resin flake that above-mentioned melt polymerization obtains.In table 3, express thermostability, heat-resistant aging and the water-proof evaluation result of film.

The catalytic activity of this catalyzer is high and use TS, TOS and the HS of the PET that this catalyzer obtains excellent, can access the excellent film of thermostability, heat-resistant aging and water tolerance.

(embodiment 2)

Carry out 1 identical operations, obtained the BHET mixture with embodiment.To this BHET mixture; Adding count with the aluminium atom with respect to the sour composition in the polyester 0.015mol% acetyl acetone aluminium 2.5g/l ethylene glycol solution and count the ethylene glycol solution of 50g/l of the magnesium acetate 4 hydrate of 0.01mol% with magnesium atom with respect to sour composition; Then under nitrogen atmosphere, stirred 10 minutes at 245 ℃ under the normal pressure.Be warming up to 275 ℃ with 50 minutes then, reduce simultaneously slowly the pressure of reactive system, make system pressure reach 0.1Torr, further carry out polycondensation at 275 ℃, 0.1Torr.The IV that in table 1, expresses polyethylene terephthalate reaches 0.65dlg ^-1Needed polymerization time (AP).

(embodiment 3)

Except the ethylene glycol solution that does not add NMPA, do with embodiment 1 identically, obtained the BHET mixture.To this BHET mixture add with respect to the sour composition in the polyester count with the aluminium atom 0.015mol% acetyl acetone aluminium 2.5g/l ethylene glycol solution, count ethylene glycol solution and the ethylene glycol solution of 50g/l of counting the lithium acetate duohydrate of 0.01mol% with respect to sour composition with lithium atom of 50g/l of the above-mentioned NMPA of 0.02mol% with NMPA with respect to sour composition; Then under nitrogen atmosphere, stirred 10 minutes at 245 ℃ under the normal pressure.Be warming up to 275 ℃ with 50 minutes then, reduce simultaneously slowly the pressure of reactive system, make system pressure reach 0.1Torr, further carry out polycondensation at 275 ℃, 0.1Torr.The IV that in table 1, expresses polyethylene terephthalate reaches 0.65dlg ^-1Needed polymerization time (AP).

The catalytic activity of this catalyzer is higher and use TS, TOS and the HS of the PET that this catalyzer obtains excellent, can access thermostability, the excellent film of heat-resistant aging.Use the HS of the PET that this catalyzer obtains relatively poor, the water tolerance of film is also poor slightly, but can obtain the practical unchallenged film of.

(embodiment 4)

Added except the ethylene glycol solution that do not add NMPA with respect to sour composition count with BPADE the BPADE (Tokyo changes into industry (strain) system, purity more than 98%) that above-mentioned (24) formula of usefulness of 0.03mol% representes 10g/l ethylene glycol solution and count with magnesium atom with respect to sour composition the ethylene glycol solution of 50g/l of magnesium acetate 4 hydrate of 0.01mol%; Do with embodiment 1 identically, obtained the BHET mixture.To this BHET mixture, add the ethylene glycol solution of 2.5g/l of counting the acetyl acetone aluminium of 0.015mol% with the aluminium atom, then under nitrogen atmosphere, stirred 10 minutes at 245 ℃ under the normal pressure.Be warming up to 275 ℃ with 50 minutes then, reduce simultaneously slowly the pressure of reactive system, make system pressure reach 0.1Torr, further carry out polycondensation at 275 ℃, 0.1Torr.The IV that in table 1, expresses polyethylene terephthalate reaches 0.65dlg ^-1Needed polymerization time (AP).

The catalytic activity of this catalyzer is poor a little but use the TS of the PET that this catalyzer obtains and HS excellent, can access the excellent film of thermostability and water tolerance.Use the TOS of the PET that this catalyzer obtains poor slightly, but can obtain the practical unchallenged film of.

(comparative example 1)

Except the ethylene glycol solution that does not add NMPA, do with embodiment 1 identically, obtained the BHET mixture.Add the ethylene glycol solution of 2.5g/l of counting the acetyl acetone aluminium of 0.015mol% with respect to the sour composition in the polyester with the aluminium atom to this BHET mixture, then under nitrogen atmosphere, stirred 10 minutes at 245 ℃ under the normal pressure.Be warming up to 275 ℃ with 50 minutes then, reduce simultaneously slowly the pressure of reactive system, make system pressure reach 0.1Torr, further carry out polycondensation at 275 ℃, 0.1Torr.Even the polycondensation time is 180 minutes more than the kind, but IV does not reach 0.65dlg yet ^-1

(comparative example 2)

Except the ethylene glycol solution that does not add NMPA, do with embodiment 1 identically, obtained the BHET mixture.Add ethylene glycol solution and the ethylene glycol solution of 20g/l of counting cobaltous acetate (II) tetrahydrate of 0.005mol% with respect to sour composition with cobalt atom of 2.5g/l of counting the acetyl acetone aluminium of 0.015mol% with respect to the sour composition in the polyester with the aluminium atom to this BHET mixture; Then under nitrogen atmosphere, normal pressure stirred 10 minutes for following 245 ℃.Be warming up to 275 ℃ with 50 minutes then, reduce simultaneously slowly the pressure of reactive system, make system pressure reach 0.1Torr, further carry out polycondensation at 275 ℃, 0.1Torr.The IV that in table 1, expresses polyethylene terephthalate reaches 0.65dlg ^-1Needed polymerization time (AP).

The catalytic activity of this catalyzer is poor a little and use TS and the HS of the PET that this catalyzer obtains all big, can only obtain the film of poor heat stability, poor water resistance.

By knowing in the above embodiments and the comparative example; The catalytic activity of catalyst for polymerization of polyester of the present invention is excellent; And by the film that the polyester that uses this catalyzer manufacturing constitutes, its thermostability, heat-resistant aging and water tolerance are excellent, and the quality of film is also excellent; The quality of the product film of utilizing film fragments more simultaneously and obtaining is also excellent, and carries out hot blast for a long time and handle the perhaps long-time phenomenon that also rare intensity reduces that contacts with water.On the other hand, when also not using phosphorus compound of the present invention, poor catalytic activity is even carry out the polyester that long polymerization can not obtain having enough polymerization degree.

(reference example 1)

Except the ethylene glycol solution that does not add NMPA, do with embodiment 1 identically, obtained the BHET mixture.Add with respect to the sour composition in the polyester to this BHET mixture and to count the ethylene glycol solution of the ANTIMONY TRIOXIDE SB 203 99.8 PCT of 0.05mol% with antimony atoms, then under nitrogen atmosphere, normal pressure stirred 10 minutes for following 245 ℃.Be warming up to 275 ℃ with 50 minutes then, reduce simultaneously slowly the pressure of reactive system, make system pressure reach 0.1Torr, further carry out polycondensation at 275 ℃, 0.1Torr.The IV that in table 1, expresses polyethylene terephthalate reaches 0.65dlg ^-1Needed polymerization time (AP).As ANTIMONY TRIOXIDE SB 203 99.8 PCT, used commercially available Antimony (III) oxide (ALDRICHCHEMICAL society system, purity 99.999%).ANTIMONY TRIOXIDE SB 203 99.8 PCT has used, and ANTIMONY TRIOXIDE SB 203 99.8 PCT is joined in the ethylene glycol solution, and stir 1 hour approximately with its dissolving, so that last ANTIMONY TRIOXIDE SB 203 99.8 PCT concentration is the solution of 10g/l at 150 ℃.

(embodiment 5)

(the synthetic example of phosphorus compound)

Synthetic with the phosphorus compound (phosphorus compound A) of following formula (47) expression

Synthesizing of (O-ethyl 3,5-two-tertiary butyl-4-acrinyl phosphonic acid ester) sodium (phosphide C)

In the mixing solutions of 50% aqueous sodium hydroxide solution 6.5g (84mmol) and methyl alcohol 6.1ml, add diethylammonium (3; 5-two-tertiary butyl-4-acrinyl) the methanol solution 6.1ml of phosphonic acid ester (Irganox1222 (CibaSpecialty Chemicals society system)) 5g (14mmol), reflux is 24 hours under nitrogen atmosphere.After the reaction, concentrated hydrochloric acid 7.33g (70mmol) is added on reaction mixture limit, limit, and the leaching precipitate cleans with Virahol, underpressure distillation filtrating.Residue obtained being dissolved in the hot Virahol, the leaching insolubles, after Virahol was removed in underpressure distillation, with the washed with heptane residue of heat, drying obtained (O-ethyl 3,5-two-tertiary butyl-4-acrinyl phosphonic acid ester) sodium 3.4g (69%).

Shape: white powder

Fusing point: 294-302 ℃ (decomposition)

¹H-NMR(DMSO-d6，δ)：1.078(3H，t，J＝7Hz)，1.354(18H，s)，2.711(2H，d)，3.724(2H，m，J＝7Hz)，6.626(1H，s)，6.9665(2H，s)

Ultimate analysis (in the bracket is theoretical value): Na6.36% (6.56%), P9.18% (8.84%)

O-ethyl 3,5-two-tertiary butyl-4-acrinyl phosphonic acids (phosphorus compound A) synthetic

At room temperature, in the aqueous solution 20ml of the 1g of phosphorus compound C (2.8mmol), under agitation add concentrated hydrochloric acid 1.5g, stirred 1 hour.In reaction mixture, add entry 150ml, the crystallization that leaching is separated out, washing, drying obtains O-ethyl 3,5-two-tertiary butyl-4-acrinyl phosphonic acids 826mg (88%).

Shape: plate crystal

Fusing point: 126-127 ℃

¹H-NMR(CDCl ₃，δ)：1.207(3H，t，J＝7Hz)，1.436(18H，s)，3.013(2H，d)，3.888(2H，m，J＝7Hz.)，7.088(2H，s)，7.679-8.275(1H，br)

(polyester example)

The terepthaloyl moietie that adds highly purified terephthalic acid and its 2 times of amounts to the autoclave of the circulating 2 liters of stainless steels of the thermal medium that has whisking appliance; Adding is the triethylamine of 0.3mol% with respect to sour composition; Depress in adding of 0.25MPa; At 245 ℃ of limit dephlegmates outside system, esterification was carried out 120 minutes in the limit, had obtained esterification yield and be the mixture (below be called the BHET mixture) of 95% two (2-hydroxyethyl) terephthalate (BHET) and oligopolymer.To this BHET mixture; The ethylene glycol solution of 2.5g/l of the acetyl acetone aluminium of 0.015mol% is counted in adding with the aluminium atom with respect to the sour composition in the polyester; And with respect to the sour composition in the polyester; The ethylene glycol solution of 10g/l of the above-mentioned phosphorus compound A of 0.04mol% is counted in adding with phosphorus compound A, then under nitrogen atmosphere, stirred 10 minutes at 245 ℃ under the normal pressure.Be warming up to 275 ℃ with 50 minutes then, reduce simultaneously slowly the pressure of reactive system, make system pressure reach 0.1Torr, further carry out polycondensation at 275 ℃, 0.1Torr.The IV that in table 4, expresses polyethylene terephthalate reaches 0.65dlg ^-1Needed polymerization time (AP).

In addition, utilize conventional method, the IV that will in above-mentioned polycondensation, obtain is 0.65dlg ^-1Polyethylene terephthalate carry out sheet.Utilize this PET resin flake, measure its various rerum naturas.In table 4 and table 5, represented the result.

Utilization is by the PET resin flake that above-mentioned melt polymerization obtains, carried out film preparation, reclaim particulate and make and utilize the preparation of reclaiming the film that particle carries out.In table 6, express thermostability, heat-resistant aging and the water-proof evaluation result of film.

(embodiment 6)

To the BHET mixture that obtains with embodiment 5 identical works; Adding count with the aluminium atom with respect to the sour composition in the polyester 0.015mol% acetyl acetone aluminium 2.5g/l ethylene glycol solution, add ethylene glycol solution and the ethylene glycol solution of 50g/l of counting the magnesium acetate 4 hydrate of 0.01mol% with magnesium atom of 10g/l of counting the above-mentioned phosphorus compound A of 0.03mol% with respect to the sour composition in the polyester with phosphorus compound A; Then under nitrogen atmosphere, stirred 10 minutes at 245 ℃ under the normal pressure.Be warming up to 275 ℃ with 50 minutes then, reduce simultaneously slowly the pressure of reactive system, make system pressure reach 0.1Torr, further carry out polycondensation at 275 ℃, 0.1Torr.The IV that in table 4, expresses polyethylene terephthalate reaches 0.65dlg ^-1Needed polymerization time (AP).

Utilization has been carried out the preparation of film, the preparation of reclaiming the particulate making and utilizing recovery particulate film by the PET resin flake that above-mentioned melt polymerization obtains.In table 6, express thermostability, heat-resistant aging and the water-proof evaluation result of film.

(comparative example 3)

Except not adding phosphorus compound A, carry out 5 identical operations with embodiment, polymerization PET.Though polymerization time is more than 200 minutes, IV does not reach 0.651g ^-1

(reference example 2)

The BHET mixture that obtains to do identically with embodiment 5, add with respect to the sour composition in the polyester with antimony atoms count 0.05mol%, as the ethylene glycol solution of the ANTIMONY TRIOXIDE SB 203 99.8 PCT of catalyzer, under nitrogen atmosphere, normal pressure stirred 10 minutes for following 245 ℃.Be warming up to 275 ℃ with 50 minutes then, reduce simultaneously slowly the pressure of reactive system, make system pressure reach 0.1Torr, further carry out polycondensation at 275 ℃, 0.1Torr.The IV that in table 1, expresses polyethylene terephthalate reaches 0.65dlg ^-1Needed polymerization time (AP).As ANTIMONY TRIOXIDE SB 203 99.8 PCT, used commercially available Antimony (III) oxide (ALDRICH CHEMICAL society system, purity 99.999%).Used as ANTIMONY TRIOXIDE SB 203 99.8 PCT, ANTIMONY TRIOXIDE SB 203 99.8 PCT has been joined in the ethylene glycol solution, and stirred 1 hour approximately with its dissolving, so that last ANTIMONY TRIOXIDE SB 203 99.8 PCT concentration is the solution of 10g/l at 150 ℃.In addition, utilize conventional method, the IV that will in above-mentioned polycondensation, obtain is 0.65dlg ^-1Polyethylene terephthalate carry out sheet.Utilize this PET resin flake, measure its various rerum naturas.In table 4 and table 5, represented the result.

(evaluation result)

Result by table 4～6 can know that if utilize catalyzer of the present invention, then intrinsicviscosity reaches practical value 0.65dlg ^-1Till the polycondensation time short, therefore, its catalytic activity of catalyzer of the present invention is high; And the polyester that obtains; Its tone is good, and low, the excellent heat stability of TS, thermo-oxidative stability and hydrolytic resistance are also excellent; And the thermostability of the film that is got by the gained polyester, heat-resistant aging and water tolerance are excellent; Membrane quality is excellent, utilizes film fragments more simultaneously and the quality of the product film that obtains is also excellent, and carries out for a long time that hot blast is handled or the long-time phenomenon that contacts also rare intensity reduction with water.

On the other hand, polymerization activity is low under the situation of not using phosphorus compound of the present invention, though then polymerization activity is high if use ANTIMONY TRIOXIDE SB 203 99.8 PCT, can not avoid the problem of aforesaid generation impurity.

(embodiment 7)

(the synthetic example of phosphorus compound)

Synthetic with the magnesium salts (phosphorus compound B) of the phosphorus compound of following formula (48) expression

1. synthesizing of two (O-ethyl 3,5-two-tertiary butyl-4-acrinyl phosphonic acid ester) magnesium (phosphorus compound B)

Under stirring at room, in the aqueous solution 4ml of (O-ethyl 3,5-two-tertiary butyl-4-acrinyl phosphonic acid ester) sodium (above-mentioned phosphorus compound C) 500mg (1.4mmol), splash into the aqueous solution 1ml of magnesium nitrate hexahydrate 192mg (0.75 mmol).After stirring 1 hour, the leaching insolubles, washing, drying obtain two (O-ethyl 3,5-two-tertiary butyl-4-acrinyl phosphonic acid ester) magnesium 359mg (74%).

Shape: white powder

Fusing point:＞300 ℃

¹H-NMR(DMSO-d6，δ)：1.0820(6H，t，J＝7Hz)，1.3558(36H，s)，2.8338(4H，d)，3.8102(4H，m，J＝7Hz)，6.6328(2H，s)，6.9917(4H，s)

(the polymerization example of polyester)

The terepthaloyl moietie that adds highly purified terephthalic acid and its 2 times of amounts to the autoclave of the circulating 2 liters of stainless steels of the thermal medium that has whisking appliance; Adding is the triethylamine of 0.3mol% with respect to sour composition; Depress in adding of 0.25MPa; At 245 ℃ of limit dephlegmates outside system, esterification was carried out 120 minutes in the limit, had obtained esterification yield and be the mixture (below be called the BHET mixture) of 95% two (2-hydroxyethyl) terephthalate (BHET) and oligopolymer.To this BHET mixture; The ethylene glycol solution of 2.5g/l of the acetyl acetone aluminium of 0.015mol% is counted in adding with the aluminium atom with respect to the sour composition in the polyester; And adding with respect to the sour composition in the polyester is the above-mentioned phosphorus compound B of 0.02mol%; Then under nitrogen atmosphere, stirred 10 minutes at 245 ℃ under the normal pressure.Be warming up to 275 ℃ with 50 minutes then, reduce simultaneously slowly the pressure of reactive system, make system pressure reach 0.1Torr, further carry out polycondensation at 275 ℃, 0.1Torr.The IV that in table 7, expresses polyethylene terephthalate reaches 0.65dlg ^-1Needed polymerization time (AP).

In addition, utilize conventional method, the IV that will in above-mentioned polycondensation, obtain is 0.65dlg ^-1Polyethylene terephthalate carry out sheet.Utilize this PET resin flake, measure its various rerum naturas.In table 7 and table 8, represented the result.

Utilization is by the PET resin flake that above-mentioned melt polymerization obtains, carried out film preparation, reclaim particulate and make and utilize the preparation of reclaiming the film that particle carries out.In table 9, express thermostability, heat-resistant aging and the water-proof evaluation result of film.

(comparative example 4)

Except not adding phosphorus compound B, carry out 7 identical operations with embodiment, polymerization PET.Though polymerization time is more than 120 minutes, IV does not reach 0.651g ^-1

(reference example 3)

The BHET mixture that obtains to do identically with embodiment 7, add with respect to the sour composition in the polyester with antimony atoms count 0.05mol%, as the ethylene glycol solution of the ANTIMONY TRIOXIDE SB 203 99.8 PCT of catalyzer, under nitrogen atmosphere, normal pressure stirred 10 minutes for following 245 ℃.Be warming up to 275 ℃ with 50 minutes then, reduce simultaneously slowly the pressure of reactive system, make system pressure reach 0.1Torr, further carry out polycondensation at 275 ℃, 0.1Torr.The IV that in table 7, expresses polyethylene terephthalate reaches 0.65dlg ^-1Needed polymerization time (AP).As ANTIMONY TRIOXIDE SB 203 99.8 PCT, used commercially available Antimony (III) oxide (ALDRICH CHEMICAL society system, purity 99.999%).Used as ANTIMONY TRIOXIDE SB 203 99.8 PCT, ANTIMONY TRIOXIDE SB 203 99.8 PCT has been joined in the ethylene glycol solution, and stirred 1 hour approximately with its dissolving, so that last ANTIMONY TRIOXIDE SB 203 99.8 PCT concentration is the solution of 10g/l at 150 ℃.In addition, utilize conventional method, the IV that will in above-mentioned polycondensation, obtain is 0.65dlg ^-1Polyethylene terephthalate carry out sheet.Utilize this PET resin flake, measure its various rerum naturas.In table 7 and table 8, represented the result.

(evaluation result)

Result by table 7～9 can know that if utilize catalyzer of the present invention, then intrinsicviscosity reaches practical value 0.65dlg ^-1Till the polycondensation time short, therefore, its catalytic activity of catalyzer of the present invention is high; And the polyester that obtains; Its tone is good, and low, the excellent heat stability of TS, thermo-oxidative stability and hydrolytic resistance are also excellent; And the thermostability of the film that is got by the gained polyester, heat-resistant aging and water tolerance are excellent; Membrane quality is excellent, utilizes film fragments more simultaneously and the quality of the product film that obtains is also excellent, and carries out for a long time that hot blast is handled or the long-time phenomenon that contacts also rare intensity reduction with water.

(embodiment 8)

In the mixture of two (2-hydroxyethyl) terephthalate processed by highly purified terephthalic acid and terepthaloyl moietie through conventional method and oligopolymer; Adding is counted 2.5g/l ethylene glycol solution 0.014mol%, acetyl acetone aluminium with respect to the sour composition in the polyester with the aluminium atom as catalyzer; Then, splashing into respect to the sour composition in the polyester is the above-mentioned phosphorus compound C of 0.01mol%.Stirred 10 minutes normal pressure, 245 ℃.Be warming up to 275 ℃ with 50 minutes then, slowly reduce the pressure of reactive system simultaneously, make system pressure reach 0.1mmHg, further carried out polycondensation 3 hours with depressing in equality of temperature.The IV of the polymkeric substance that obtains is 0.53.

(embodiment 9)

(the synthetic example of phosphorus compound)

Synthesizing of two (O-ethyl 3,5-two-tertiary butyl-4-acrinyl phosphonic acid ester) strontium (phosphorus compound D)

Under room temperature, stirring, in the aqueous solution 7.5ml of (O-ethyl 3,5-two-tertiary butyl-4-acrinyl phosphonic acid ester) sodium (above-mentioned phosphorus compound C) 1g (2.85mmol), splash into the aqueous solution 1ml of strontium nitrate 317mg (1.5mmol).After stirring 1 hour, the leaching insolubles, washing, drying obtain two (O-ethyl 3,5-two-tertiary butyl-4-acrinyl phosphonic acid ester) strontium 513mg (48%).

Shape: white powder

¹H-NMR(DMSO-d6，δ)：1.72(6H，t，J＝7Hz)，1.36(36H，s)，2.81(4H，d)，3.78(4H，m，J＝7Hz)，6.63(2H，s)，6.94(4H，s)

(the polymerization example of polyester)

Except replacing phosphorus compound C, adding with respect to the sour composition in the polyester is beyond the above-mentioned phosphorus compound D of 0.02mol%, carries out 8 identical operations with embodiment.The IV of the polymkeric substance that obtains is 0.57.

(embodiment 10)

(the synthetic example of phosphorus compound)

Synthesizing of two (O-ethyl 3,5-two-tertiary butyl-4-acrinyl phosphonic acid ester) barium (phosphorus compound E)

Under room temperature, stirring, in the aqueous solution 7.5ml of (O-ethyl 3,5-two-tertiary butyl-4-acrinyl phosphonic acid ester) sodium (above-mentioned phosphorus compound C) 1g (2.85mmol), splash into the aqueous solution 5ml of nitrate of baryta 392mg (1.5mmol).After stirring 1 hour, the leaching insolubles, washing, drying obtain two (O-ethyl 3,5-two-tertiary butyl-4-acrinyl phosphonic acid ester) barium 508mg (45%).

Shape: white powder

¹H-NMR(DMSO-d6，δ)：0.88-1.09(6H，br)，1.31(36H，s)，2.69-3.05(4H，br)，3.54-3.89(4H，br)，6.55(2H，s)，6.87-7.09(4H，br)

(the polymerization example of polyester)

Except replacing phosphorus compound C, adding with respect to the sour composition in the polyester is beyond the above-mentioned phosphorus compound E of 0.02mol%, carries out 8 identical operations with embodiment.The IV of the polymkeric substance that obtains is 0.55.

(comparative example 5)

Except not using phosphorus compound C, do with embodiment 8 identically, obtained polyester.The IV of the polymkeric substance that obtains is 0.33.

Can know that by the above embodiments and comparative example polymerization activity is poor when using aluminum compound as catalyzer separately, but through and use phosphorus compound of the present invention, improve polymerization activity significantly.

(embodiment 11)

(the synthetic example of phosphorus compound)

Synthetic with the magnesium salts (phosphorus compound F) of the phosphorus compound of following formula (49) expression

1. [O-ethyl (1-naphthyl) methylphosphonate] sodium (phosphorus compound G) is synthetic

In the mixing solutions of 50% aqueous sodium hydroxide solution 6.5g (84mmol) and methyl alcohol 6.1ml, add the methanol solution 6.1ml of O-ethyl (1-naphthyl) methylphosphonate (above-mentioned NMPA) 5g (18mmol), reflux is 24 hours under nitrogen atmosphere.After the reaction, concentrated hydrochloric acid 6.59g (63mmol) is added on reaction mixture limit, limit, and the leaching precipitate cleans with Virahol, underpressure distillation filtrating.Residue obtained being dissolved in the hot Virahol, the leaching insolubles, Virahol is removed in underpressure distillation.Normal heptane with heat cleans residue, uses the Virahol recrystallization, and drying obtains [O-ethyl (1-naphthyl) methylphosphonate] sodium 3.8g (78%).

Shape: needle crystal

Fusing point: 277-281 ℃ (decomposition)

¹H-NMR(DMSO-d6，δ)：0.961(3H，t，J＝7Hz)，3.223(2H，d)，3.589(2H，m).7.365-7.468(4H，m，J＝7Hz)，7.651-8.314(3H，m)

Synthesizing of O-ethyl (1-naphthyl) methyl-phosphorous acid (phosphorus compound F)

At room temperature, in the aqueous solution 10ml of [O-ethyl (1-naphthyl) methylphosphonate] sodium (above-mentioned phosphorus compound G) 1g (3.7mmol), under agitation add concentrated hydrochloric acid 1.9g, stirred 1 hour.Use the extracted in toluene reaction mixture, the washing toluene mutually after, underpressure distillation is removed toluene and is obtained O-ethyl (1-naphthyl) methyl-phosphorous acid 497mg (54%).

Shape: colourless oil liquid

¹H-NMR(CDCl ₃，δ)：1.085(3H，t，J＝7Hz)，3.450(2H，d)，3.719(2H，m，7Hz)，

7.369-7.532(4H，m)，7.727-8.043(3H，m)，10.939(1H，s)

(the polymerization example of polyester)

Autoclave to the circulating 2 liters of stainless steels of the thermal medium that has whisking appliance; The terepthaloyl moietie that adds highly purified terephthalic acid and its 2 times of amounts; Adding is the triethylamine of 0.3mol% with respect to sour composition, depresses in adding of 0.25MPa, at 245 ℃ of limit dephlegmates outside system; Esterification was carried out 120 minutes in the limit, had obtained esterification yield and be the mixture (below be called the BHET mixture) of 95% two (2-hydroxyethyl) terephthalate (BHET) and oligopolymer.To this BHET mixture; The ethylene glycol solution of 2.5g/l of the acetyl acetone aluminium of 0.015mol% is counted in adding with the aluminium atom with respect to the sour composition in the polyester; And adding with respect to the sour composition in the polyester is the 10g/l ethylene glycol solution of the above-mentioned phosphorus compound F of 0.03mol%; Then under nitrogen atmosphere, stirred 10 minutes at 245 ℃ under the normal pressure.Be warming up to 275 ℃ with 50 minutes then, reduce simultaneously slowly the pressure of reactive system, make system pressure reach 0.1Torr, further carry out polycondensation at 275 ℃, 0.1Torr.The IV that in table 10, expresses polyethylene terephthalate reaches 0.65dlg ^-1Needed polymerization time (AP).

In addition, utilize conventional method, the IV that will in above-mentioned polycondensation, obtain is 0.65dlg ^-1Polyethylene terephthalate carry out sheet.Utilize this PET resin flake, measure its various rerum naturas.In table 10 and table 11, represented the result.

Utilization is by the PET resin flake that above-mentioned melt polymerization obtains, carried out film preparation, reclaim particulate and make and utilize the preparation of reclaiming the film that particle carries out.In table 12, express thermostability, heat-resistant aging and the water-proof evaluation result of film.

(embodiment 12)

To make the BHET mixture that obtains identically with embodiment 11; Adding with respect to the sour composition in the polyester with the aluminium atom count 2.5g/l 0.015mol%, acetyl acetone aluminium ethylene glycol solution, and add ethylene glycol solution and the ethylene glycol solution of 50g/l of counting the magnesium acetate 4 hydrate of 0.01mol% with magnesium atom of 10g/l of counting the above-mentioned phosphorus compound F of 0.03mol% with respect to the sour composition in the polyester with phosphorus compound F; Then under nitrogen atmosphere, stirred 10 minutes at 245 ℃ under the normal pressure.Be warming up to 275 ℃ with 50 minutes then, reduce simultaneously slowly the pressure of reactive system, make system pressure reach 0.1Torr, further carry out polycondensation at 275 ℃, 0.1Torr.The IV that in table 10, expresses polyethylene terephthalate reaches 0.65dlg ^-1Needed polymerization time (AP).

(comparative example 6)

Except not adding phosphorus compound F, carry out 11 identical operations with embodiment, polymerization PET tries.Though polymerization time is more than 120 minutes, IV does not reach 0.651g ^-1

(reference example 4)

The BHET mixture that obtains to do identically with embodiment 11, add with respect to the sour composition in the polyester with antimony atoms count 0.05mol%, as the ethylene glycol solution of the ANTIMONY TRIOXIDE SB 203 99.8 PCT of catalyzer, under nitrogen atmosphere, normal pressure stirred 10 minutes for following 245 ℃.Be warming up to 275 ℃ with 50 minutes then, reduce simultaneously slowly the pressure of reactive system, make system pressure reach 0.1Torr, further carry out polycondensation at 275 ℃, 0.1Torr.The IV that in table 10, expresses polyethylene terephthalate reaches 0.65dlg ^-1Needed polymerization time (AP).As ANTIMONY TRIOXIDE SB 203 99.8 PCT, used commercially available Antimony (III) oxide (ALDRICH CHEMICAL society system, purity 99.999%).ANTIMONY TRIOXIDE SB 203 99.8 PCT has used, and ANTIMONY TRIOXIDE SB 203 99.8 PCT is joined in the ethylene glycol solution, and stir 1 hour approximately with its dissolving, so that last ANTIMONY TRIOXIDE SB 203 99.8 PCT concentration is the solution of 10g/l at 150 ℃.In addition, utilize conventional method, the IV that will in above-mentioned polycondensation, obtain is 0.65dlg ^-1Polyethylene terephthalate carry out sheet.Utilize this PET resin flake, measure its various rerum naturas.In table 10 and table 11, represented the result.

(evaluation result)

Result by table 10～12 can know that if utilize catalyzer of the present invention, then intrinsicviscosity reaches practical value 0.65dlg ^-1Till the polycondensation time short, therefore, its catalytic activity of catalyzer of the present invention is high; And the polyester that obtains; Its tone is good, and low, the excellent heat stability of TS, thermo-oxidative stability and hydrolytic resistance are also excellent; And the thermostability of the film that is got by the gained polyester, heat-resistant aging and water tolerance are excellent; Membrane quality is excellent, utilizes film fragments more simultaneously and the quality of the product film that obtains is also excellent, and carries out for a long time that hot blast is handled or the long-time phenomenon that contacts also rare intensity reduction with water.

(embodiment 13)

In the mixture of two (2-hydroxyethyl) terephthalate processed by highly purified terephthalic acid and terepthaloyl moietie through conventional method and oligopolymer; Adding is counted 2.5g/l ethylene glycol solution 0.014mol%, acetyl acetone aluminium with respect to the sour composition in the polyester with the aluminium atom as catalyzer; Then, splashing into respect to the sour composition in the polyester is the above-mentioned phosphorus compound G of 0.01mol%.Stirred 10 minutes for 245 ℃ at normal pressure.Be warming up to 275 ℃ with 50 minutes then, slowly reduce the pressure of reactive system simultaneously, make system pressure reach 0.1mmHg, further carried out polycondensation 3 hours with depressing in equality of temperature.The IV of the polymkeric substance that obtains is 0.54.

(comparative example 7)

Except not using phosphorus compound C, do with embodiment 1 identically, obtained polyester.The IV of the polymkeric substance that obtains is 0.33.

(embodiment 14)

(the synthetic example of the aluminium salt of phosphorus compound)

O-ethyl 3, the aluminium salt of 5-two-tertiary butyl-4-acrinyl phosphonic acid ester (aluminium salt A) synthetic

Under room temperature, stirring, in the aqueous solution 7.5ml of (O-ethyl 3,5-two-tertiary butyl-4-acrinyl phosphonic acid ester) sodium (above-mentioned phosphorus compound C) 1g (2.8mmol), splash into the aqueous solution 5ml of aluminum nitrate 9 hydrate 364mg (0.97mmol).After stirring 3 hours, the leaching insolubles, washing, drying obtains O-ethyl 3,5-two-tertiary butyl-4-acrinyl phosphonic acid ester aluminium salt 860mg.

Shape: white powder

Fusing point: 183～192 ℃

(the polymerization example of polyester)

Autoclave to the circulating 2 liters of stainless steels of the thermal medium that has whisking appliance; The terepthaloyl moietie that adds highly purified terephthalic acid and its 2 times of amounts; Also adding with respect to sour composition is the triethylamine of 0.3mol%, depresses in adding of 0.25MPa then, at 245 ℃ of limit dephlegmates outside system; Esterification was carried out 120 minutes in the limit, had obtained esterification yield and be the mixture (below be called the BHET mixture) of 95% two (2-hydroxyethyl) terephthalate (BHET) and oligopolymer.To this BHET mixture, add with respect to the sour composition in the polyester and count the above-mentioned aluminium salt A of 0.015mol% with the aluminium atom, under nitrogen atmosphere, stirred 10 minutes at 245 ℃ under the normal pressure.Be warming up to 275 ℃ with 50 minutes then, reduce simultaneously slowly the pressure of reactive system, make system pressure reach 0.1Torr, further carry out polycondensation at 275 ℃, 0.1Torr.The IV that in table 13, expresses polyethylene terephthalate reaches 0.65dlg ^-1Needed polymerization time (AP).

In addition, utilize conventional method, the IV that will in above-mentioned polycondensation, obtain is 0.65dlg ^-1Polyethylene terephthalate carry out sheet.Utilize this PET resin flake, measure its various rerum naturas.In table 13 and table 14, represented the result.

Utilization is by the PET resin flake that above-mentioned melt polymerization obtains, carried out film preparation, reclaim particulate and make and utilize the preparation of reclaiming the film that particle carries out.In table 15, express thermostability, heat-resistant aging and the water-proof evaluation result of film.

(comparative example 8)

To the BHET mixture that obtains with embodiment 14 identical methods, add and count 2.5g/l ethylene glycol solution 0.02mol%, triacetylacetonate alumium with the aluminium atom with respect to the sour composition in the polyester, under nitrogen atmosphere, normal pressure stirred 10 minutes for following 245 ℃.Be warming up to 275 ℃ with 50 minutes then, reduce simultaneously slowly the pressure of reactive system, make system pressure reach 0.1Torr, further carry out polycondensation at 275 ℃, 0.1Torr.Even polyreaction was carried out more than 200 hours, IV does not reach 0.65dlg yet ^-1

(reference example 5)

To the BHET mixture that obtains with embodiment 14 identical methods, add with respect to sour composition with antimony atoms count 0.05mol%, as the ethylene glycol solution of the ANTIMONY TRIOXIDE SB 203 99.8 PCT of catalyzer, under nitrogen atmosphere, normal pressure stirred 10 minutes for following 245 ℃.Be warming up to 275 ℃ with 50 minutes then, reduce simultaneously slowly the pressure of reactive system, make system pressure reach 0.1Torr, further carry out polycondensation at 275 ℃, 0.1Torr.The IV that in table 13, expresses polyethylene terephthalate reaches 0.65dlg ^-1Needed polymerization time (AP).As ANTIMONY TRIOXIDE SB 203 99.8 PCT, used commercially available Antimony (III) oxide (ALDRICH CHEMICAL society system, purity 99.999%).ANTIMONY TRIOXIDE SB 203 99.8 PCT has used, and ANTIMONY TRIOXIDE SB 203 99.8 PCT is joined in the ethylene glycol solution, and stir 1 hour approximately with its dissolving, so that last ANTIMONY TRIOXIDE SB 203 99.8 PCT concentration is the solution of 10g/l at 150 ℃.In addition, utilize conventional method, the IV that will in above-mentioned polycondensation, obtain is 0.65dlg ^-1Polyethylene terephthalate carry out sheet.Utilize this PET resin flake, measure its various rerum naturas.In table 14 and table 15, represented the result.

(evaluation result)

Result by table 13～15 can know, when using aluminum compound catalyzer of the present invention, intrinsicviscosity reaches practical value 0.65dlg ^-1Till the polycondensation time short, therefore, its catalytic activity of catalyzer of the present invention is high; And the polyester that obtains; Its tone is good, and low, the excellent heat stability of TS, thermo-oxidative stability and hydrolytic resistance are also excellent; And the thermostability of the film that is got by the gained polyester, heat-resistant aging and water tolerance are excellent; Membrane quality is excellent, utilizes film fragments more simultaneously and the quality of the product film that obtains is also excellent, and carries out for a long time that hot blast is handled or the long-time phenomenon that contacts also rare intensity reduction with water.

(embodiment 15)

(the synthetic example of the aluminium salt of phosphorus compound)

Synthesizing of the aluminium salt (aluminium salt B) of O-ethyl (1-naphthyl) methylphosphonate

Under room temperature, stirring, in the aqueous solution 10ml of [O-ethyl (1-naphthyl) methylphosphonate] sodium (above-mentioned phosphorus compound G) 500mg (1.8mmol), splash into the aqueous solution 5ml of aluminum nitrate 9 hydrate 236mg (0.63mmol).After stirring 1 hour, the leaching insolubles, washing, drying obtain the aluminium salt 420mg of [O-ethyl (1-naphthyl) methylphosphonate] sodium.

Shape: white powder

Fusing point:＞300 ℃

(the polymerization example of polyester)

Autoclave to the circulating 2 liters of stainless steels of the thermal medium that has whisking appliance; The terepthaloyl moietie that adds highly purified terephthalic acid and its 2 times of amounts; Also adding with respect to sour composition is the triethylamine of 0.3mol%, depresses in adding of 0.25MPa then, at 245 ℃ of limit dephlegmates outside system; Esterification was carried out 120 minutes in the limit, had obtained esterification yield and be the mixture (below be called the BHET mixture) of 95% two (2-hydroxyethyl) terephthalate (BHET) and oligopolymer.To this BHET mixture, add with respect to the sour composition in the polyester and count the above-mentioned aluminium salt B of 0.015mol% with the aluminium atom, under nitrogen atmosphere, stirred 10 minutes at 245 ℃ under the normal pressure.Be warming up to 275 ℃ with 50 minutes then, reduce simultaneously slowly the pressure of reactive system, make system pressure reach 0.1Torr, further carry out polycondensation at 275 ℃, 0.1Torr.The IV that in table 13, expresses polyethylene terephthalate reaches 0.65dlg ^-1Needed polymerization time (AP).

In addition, utilize conventional method, the IV that will in above-mentioned polycondensation, obtain is 0.65dlg ^-1Polyethylene terephthalate carry out sheet.Utilize this PET resin flake, measure its various rerum naturas.In table 16 and table 17, represented the result.

Utilization is by the PET resin flake that above-mentioned melt polymerization obtains, carried out film preparation, reclaim particulate and make and utilize the preparation of reclaiming the film that particle carries out.In table 18, express thermostability, heat-resistant aging and the water-proof evaluation result of film.

(comparative example 9)

To the BHET mixture of processing with embodiment 15 identical methods; Adding is counted 2.5g/l ethylene glycol solution 0.015mol%, triacetylacetonate alumium with respect to the sour composition in the polyester with the aluminium atom as catalyzer; Under nitrogen atmosphere, normal pressure stirred 10 minutes for following 245 ℃.Be warming up to 275 ℃ with 50 minutes then, reduce simultaneously slowly the pressure of reactive system, make system pressure reach 0.1Torr, further carry out polycondensation at 275 ℃, 0.1Torr.Even polyreaction was carried out more than 200 hours, IV does not reach 0.65dlg yet ^-1

(reference example 6)

To the BHET mixture that obtains with embodiment 15 identical methods, add with respect to sour composition as catalyzer and to count the ethylene glycol solution of the ANTIMONY TRIOXIDE SB 203 99.8 PCT of 0.05mol% with antimony atoms, under nitrogen atmosphere, normal pressure stirred 10 minutes for following 245 ℃.Be warming up to 275 ℃ with 50 minutes then, reduce simultaneously slowly the pressure of reactive system, make system pressure reach 0.1Torr, further carry out polycondensation at 275 ℃, 0.1Torr.The IV that in table 16, expresses polyethylene terephthalate reaches 0.65dlg ^-1Needed polymerization time (AP).As ANTIMONY TRIOXIDE SB 203 99.8 PCT, used commercially available Antimony (III) oxide (ALDRICH CHEMICAL society system, purity 99.999%).Used as ANTIMONY TRIOXIDE SB 203 99.8 PCT, ANTIMONY TRIOXIDE SB 203 99.8 PCT has been joined in the ethylene glycol solution, and stirred 1 hour approximately with its dissolving, so that last ANTIMONY TRIOXIDE SB 203 99.8 PCT concentration is the solution of 10g/l at 150 ℃.In addition, utilize conventional method, the IV that will in above-mentioned polycondensation, obtain is 0.65dlg ^-1Polyethylene terephthalate carry out sheet.Utilize this PET resin flake, measure its various rerum naturas.In table 16 and table 17, represented the result.

(evaluation result)

Result by table 16～18 can know, when using aluminum compound catalyzer of the present invention, intrinsicviscosity reaches practical value 0.65dlg ^-1Till the polycondensation time very short, therefore, its catalytic activity of catalyzer of the present invention is high; And the polyester that obtains; Its tone is good, and TS is low, excellent heat stability, and thermo-oxidative stability and hydrolytic resistance are also excellent; And the thermostability of the film that is got by the gained polyester, heat-resistant aging and water tolerance are excellent; Membrane quality is excellent, utilizes film fragments more simultaneously and the quality of the product film that obtains is also excellent, and carries out for a long time that hot blast is handled or the long-time phenomenon that contacts also rare intensity reduction with water.

(embodiment 16)

In the mixture of two (2-hydroxyethyl) terephthalate processed by highly purified terephthalic acid and terepthaloyl moietie through conventional method and oligopolymer; Adding is counted 10g/l ethylene glycol solution 0.03mol%, acetyl acetone aluminium with respect to the sour composition in the polyester with the aluminium atom as catalyzer; Then; Adding is the compound with following formula (50) expression of 0.05mol% with respect to the sour composition in the polyester, stirs 10 minutes for 245 ℃ at normal pressure.Be warming up to 275 ℃ with 50 minutes then, slowly reduce the pressure of reactive system simultaneously, make system pressure reach 0.1mmHg, further carried out polycondensation 3 hours with depressing in equality of temperature.The IV of the polymkeric substance that obtains is 0.55.

(comparative example 10)

Except not using compound with following formula (50) expression, do with embodiment 16 identically, obtained polyester.The IV of the polymkeric substance that obtains is 0.37.

(embodiment 17)

Autoclave to the circulating 2 liters of stainless steels of the thermal medium that has whisking appliance; The terepthaloyl moietie that adds highly purified terephthalic acid and its 2 times of amounts; Also adding with respect to sour composition is the triethylamine of 0.3mol%, depresses in adding of 0.25MPa then, at 245 ℃ of limit dephlegmates outside system; Esterification was carried out 120 minutes in the limit, had obtained esterification yield and be the mixture (below be called the BHET mixture) of 95% two (2-hydroxyethyl) terephthalate (BHET) and oligopolymer.To this BHET mixture; Add the 2.5g/l ethylene glycol solution of counting the acetyl acetone aluminium of 0.015mol% with respect to the sour composition in the polyester with the aluminium atom as polymerizing catalyst; Also add with respect to the sour composition in the polyester is the phosphorus compound with following formula (38) expression of 0.02mol%; Also add with respect to sour composition and count the 50g/l ethylene glycol solution of the lithium acetate duohydrate of 0.01mol%, under nitrogen atmosphere, stirred 10 minutes at 245 ℃ under the normal pressure with lithium atom.Be warming up to 275 ℃ with 50 minutes then, reduce simultaneously slowly the pressure of reactive system, make system pressure reach 0.1Torr, further carry out polycondensation at 275 ℃, 0.1Torr.The IV of polyethylene terephthalate reaches 0.65dlg ^-1Needed polymerization time is 61 minutes.

(embodiment 18)

Except add with respect to sour composition be 0.02mol%, with the phosphorus compound of following formula (39) expression with the phosphorus compound of representing for alternative type (38), carried out 17 identical operations with embodiment.The IV of polyethylene terephthalate reaches 0.65dlg ^-1Needed polymerization time is 59 minutes.

(embodiment 19)

Except add with respect to sour composition be 0.02mol%, with the phosphorus compound of following formula (40) expression with the phosphorus compound of representing for alternative type (38), carried out 17 identical operations with embodiment.The IV of polyethylene terephthalate reaches 0.65dlg ^-1Needed polymerization time is 62 minutes.

(embodiment 20)

Except add with respect to sour composition be 0.02mol%, with the phosphorus compound of following formula (41) expression with the phosphorus compound of representing for alternative type (38), carried out 17 identical operations with embodiment.The IV of polyethylene terephthalate reaches 0.65dlg ^-1Needed polymerization time is 81 minutes.

(embodiment 21)

Except add with respect to sour composition be 0.02mol%, with the phosphorus compound of following formula (42) expression with the phosphorus compound of representing for alternative type (38), carried out 17 identical operations with embodiment.The IV of polyethylene terephthalate reaches 0.65dlg ^-1Needed polymerization time is 75 minutes.

(embodiment 22)

Except add with respect to sour composition be 0.02mol%, with the phosphorus compound of following formula (43) expression with the phosphorus compound of representing for alternative type (38), carried out 17 identical operations with embodiment.The IV of polyethylene terephthalate reaches 0.65dlg ^-1Needed polymerization time is 78 minutes.

(comparative example 11)

Except as polymerizing catalyst, only added beyond the 2.5g/l ethylene glycol solution of acetyl acetone aluminium, carry out 17 identical operations with embodiment.Acetyl acetone aluminium is with respect to the sour composition in the polyester, has added 0.015mol% in the aluminium atom.Even carried out the polymerization more than 180 minutes, but the IV of polyethylene terephthalate does not reach 0.65dlg ^-1

(reference example 7)

Except as polymerizing catalyst, only added beyond the ethylene glycol solution of ANTIMONY TRIOXIDE SB 203 99.8 PCT, carry out 17 identical operations with embodiment.ANTIMONY TRIOXIDE SB 203 99.8 PCT is to have added 0.05mol% with respect to sour composition in antimony atoms.As ANTIMONY TRIOXIDE SB 203 99.8 PCT, used commercially available Antimony (III) oxide (ALDRICHCHEMICAL society system, purity 99.999%).ANTIMONY TRIOXIDE SB 203 99.8 PCT has used, and ANTIMONY TRIOXIDE SB 203 99.8 PCT is joined in the ethylene glycol solution, and stir 1 hour approximately with its dissolving, so that last ANTIMONY TRIOXIDE SB 203 99.8 PCT concentration is the solution of 10g/l at 150 ℃.The IV of polyethylene terephthalate reaches 0.65dlg ^-1Needed polymerization time is 55 minutes.

Can know that by the above embodiments and comparative example polymerization activity is poor when using aluminum compound as catalyzer separately, but through and use phosphorus compound of the present invention, improve polymerization activity significantly.But the catalyzer of knowledge capital invention has the catalytic activity that is equal to mutually with antimony catalyst.

(embodiment 23)

(the spinning example of polyester)

In order to carry out evaluation, carry out the polymerization of the polyester identical repeatedly, until the resin that obtains necessary amount with the above embodiments 5 to spinning; After the PET resin flake drying with gained; Supply with the melt extruded machine, under 290 ℃, from having the spinning nozzle ejection that 108 apertures are 0.14mm φ sieve aperture; Cool off through conventional method, divide taking-up with 1720m/ after the oiling.Under 150 ℃ of 80 ℃ of preheat rolls, design temperature, stretch 2.127 times then, obtain the drawn polyester yarn of 47 dtexs, 108 monofilament (filament).Operability in spinning and drawing process is very good, and there is not any problem when making above-mentioned tPolyester Filament be used on the dress material purposes in the mechanical characteristic of the silk that obtains yet.

(embodiment 24)

(the spinning example of polyester)

In order to carry out evaluation, carry out the polymerization of the polyester identical repeatedly, until the resin that obtains necessary amount with the above embodiments 7 to spinning; After the PET resin flake drying with gained; Supply with the melt extruded machine, under 290 ℃, from having the spinning nozzle ejection that 108 apertures are 0.14mm φ sieve aperture; Cool off through conventional method, divide taking-up with 1720m/ after the oiling.Under 150 ℃ of 80 ℃ of preheat rolls, design temperature, stretch 2.127 times then, obtain the drawn polyester yarn of 47 dtexs, 108 monofilament.Operability in spinning and drawing process is very good, and there is not any problem when making above-mentioned tPolyester Filament be used on the dress material purposes in the mechanical characteristic of the silk that obtains yet.

(embodiment 25)

(the spinning example of polyester)

In order to carry out evaluation, carry out the polymerization of the polyester identical repeatedly, until the resin that obtains necessary amount with the above embodiments 14 to spinning; After the PET resin flake drying with gained; Supply with the melt extruded machine, under 290 ℃, from having the spinning nozzle ejection that 108 apertures are 0.14mm φ sieve aperture; Cool off through conventional method, divide taking-up with 1720m/ after the oiling.Under 150 ℃ of 80 ℃ of preheat rolls, design temperature, stretch 2.127 times then, obtain the drawn polyester yarn of 47 dtexs, 108 monofilament.Operability in spinning and drawing process is very good, and there is not any problem when making above-mentioned tPolyester Filament be used on the dress material purposes in the mechanical characteristic of the silk that obtains yet.

(comparative example 12)

In order to carry out evaluation to spinning; Carry out the polymerization of the polyester identical repeatedly with above-mentioned reference example 2; Until the resin that obtains necessary amount, when resulting polyester was carried out melt-spinning with embodiment 23 identically, the outage when broken string and stretching was poorer than each embodiment.

(embodiment 26)

(the shaping example of hollow forming body)

The PET resin flake that will in the polymerization that embodiment 5 is put down in writing, obtain; 160 ℃ with the resin flake surface crystallizationization after; Under static solid-state polymerization tower, stream of nitrogen gas, after about 160～170 ℃ of dryings, carry out solid state polymerization at 205 ℃, having obtained IV is the PET of 0.82dl/g.

Then, according to the method for being put down in writing in above-mentioned (19) and (20), staged forming board and stretching hollow forming body have been obtained.Forming board and stretching hollow forming body that the PET that utilization is obtained by polycondensation catalyst of the present invention is shaped, and measure the turbidity of said forming board and stretching hollow forming body, its result is out of question.

The transparency of the hollow forming body that the PET that use is obtained by polycondensation catalyst of the present invention is shaped is excellent.

(embodiment 27)

(the shaping example of hollow forming body)

The PET resin flake that will in the polymerization that embodiment 7 is put down in writing, obtain; 160 ℃ with the resin flake surface crystallizationization after; Under static solid-state polymerization tower, stream of nitrogen gas, after about 160～170 ℃ of dryings, carry out solid state polymerization at 205 ℃, having obtained IV is the PET of 0.82dl/g.

(embodiment 28)

(the shaping example of hollow forming body)

The PET resin flake that will in the polymerization that embodiment 14 is put down in writing, obtain; 160 ℃ with the resin flake surface crystallizationization after; Under static solid-state polymerization tower, stream of nitrogen gas, after about 160～170 ℃ of dryings, carry out solid state polymerization at 205 ℃, having obtained IV is the PET of 0.82dl/g.

Then, according to the method for being put down in writing in above-mentioned (19) and (20), staged forming board and stretching hollow forming body have been obtained.The PET that utilization is obtained by polycondensation catalyst of the present invention, shaping forming board and stretching hollow forming body, and measure the turbidity of said forming board and stretching hollow forming body, its result is out of question.

(embodiment 29)

(the shaping example of thin plate)

The polyester of the solid state polymerization that use obtains in embodiment 26 has carried out the evaluation of (22), the phase result, and the coloring degree that observes with the naked eye is painted identical with the thin plate of being made by original resin that do not stretch, does not become any problem.

(comparative example 13)

The method polymeric PET resin flake that use is put down in writing according to reference example 2 carries out 26 identical operations with embodiment, and having obtained IV is the PET of 0.82dl/g.Then, according to the method that above-mentioned (19) and (20) are put down in writing, staged forming board and stretching hollow forming body have been obtained.The transparency of forming board that obtains and stretching hollow forming body is poor.

(comparative example 14)

Except having used as catalyzer; With respect to the sour composition in the polyester in titanium atom; Its addition is beyond the tetrabutyl titanate ester of 0.0015mol%, has carried out the polymerization identical with reference example 2, has obtained the PET resin flake; Further carry out 26 identical operations with embodiment, having obtained IV is the PET of 0.82dl/g.Then, according to the method that above-mentioned (19) and (20) are put down in writing, staged forming board and stretching hollow forming body have been obtained.Observe with the naked eye very yellow coloring degree, so there is not commodity value.

(embodiment 30)

(the manufacturing example of film)

The PET resin flake that will in embodiment 5, obtain was 135 ℃ of following vacuum-dryings 10 hours.Afterwards; To the said PET resin flake of double-shafted extruder weight feed and with respect to PET be that the median size of 0.2 total amount % is that 1.0 μ m, particle diameter plastisied dispersion are 20%, the area shape coefficient is 80% silicon dioxide granule; In 280 ℃ of following melt extruded slabbings and taking-up; Chilling solidifies on the metallic roll that keeps 20 ℃ of surface temperatures, obtains the cast film of thickness 1400 μ m.

Then, this cast film is heated to 100 ℃ with roller group and infrared heater after heating, afterwards,, carries out 3.5 times of stretchings in the longitudinal direction, obtain uniaxial orientation PET film having on the roller group of speed discrepancy.Then; Stretch 4.0 times to width under 120 ℃ with tenter machine,, heated for 0.5 second at 260 ℃ through ultraviolet well heater with the wide long fixed state of film; And then under 200 ℃, carry out 23 seconds 3% relaxation processes, obtain the diaxial orientation PET film of thickness 100 μ m.The film that obtains, its turbidity, thermostability, traveling property, wear resistant are all excellent.

(embodiment 31)

The PET resin flake that use obtains in embodiment 7 is likewise done with embodiment 30, has obtained diaxial orientation PET film.The film that obtains, its turbidity, thermostability, traveling property, wear resistant are all excellent.

(embodiment 32)

The PET resin flake that use obtains in embodiment 14 is likewise done with embodiment 30, has obtained diaxial orientation PET film.The film that obtains, its turbidity, thermostability, traveling property, wear resistant are all excellent.

According to the present invention, the novel polycondensation catalyst beyond a kind of antimony compounds is provided and utilizes the polyester of this catalyzer manufacturing and the method for manufacture of polyester.Polyester of the present invention for example can be applied to use fiber, curtain, carpet, bed clothes cotton etc. to use fiber as the indoor bedroom dress of representative with dress material; With tire cord, rope etc. is that the industry resource of representative is used fiber; The fiber of various fabrics, various cloth, staple fiber nonwoven fabric, nonwoven fabric of long fibers etc.; Packaging film, industrial film, film for optical use, tape with film, take a picture with the film of film, jar laminated film, capacitor membrane, Shrink Film, gas barrier film, white film, frangible membrane will etc.; The hollow forming body of nonrefractory oriented bottle, directblow bottle, gas barrier bottle, pressure bottle, heat-resisting pressure bottle etc.; With the thin slice of A-PET or C-PET etc., glass fiber-reinforced polyester, elastomerics etc. the various shaping things of the engineering plastics etc. of representative; And coating or caking agent etc.

Claims

1. catalyst for polymerization of polyester; Contain a kind of in aluminum formate, aluminum acetate, plumbous subacetate, propionic acid aluminium, oxalic acid aluminium, vinylformic acid aluminium, Aluminum trilaurate, StAl, TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M. aluminium, trichoroacetic acid(TCA) aluminium, Aluctyl, Tiorco 677, salumin, aluminium acetylacetonate, etheric acid aluminium, methyl aceto acetate aluminium, the methyl aceto acetate aluminium diiso propoxide, and contain and be selected from least a in the following phosphorus compound:

The usage quantity of phosphorus compound is 0.0001～0.1 mole of % with respect to the unitary mole number of total formation of the poly carboxylic acid composition in the resulting polyester;

The usage quantity of aluminium is 0.001～0.05 mole of % with respect to the carboxylic acid composition's of resulting polyester the unitary mole number of entire infrastructure.

2. catalyst for polymerization of polyester according to claim 1 is characterized in that being selected from one or more metals and/or metallic compound coexistence in the group of being made up of basic metal and compound thereof and alkaline-earth metal and compound thereof.

3. method of producing polyester, it comprises and uses any one described Catalyst Production polyester among the claim 1-2.

4. according to the method for the production polyester of claim 3, wherein add the antimony compounds of 50ppm or less amount with respect to polyester in antimony atoms.

5. according to the method for the production polyester of claim 3, wherein add the ge cpd of 20ppm or less amount with respect to polyester in germanium atom.