CN1954012A - Methods of making titanium-catalyzed polyethylene terephthalate resins - Google Patents

Abstract

The present invention relates to methods of making titanium-catalyzed polyethylene terephthalate resins having reduced comonomer substitution, as well as preforms, bottles, and films made from these resins.

Description

The manufacture method of the catalytic pet resin of titanium

Cross reference to the application of common transfer

The application is the part continuation application of the patent application of following common transfer: the U.S. Patent Application Serial 10/850,269 that on May 20th, 2004 submitted to, " manufacture method of titanium catalyst, polyester resin "; With the U.S. Patent Application Serial of submitting on May 21st, 2,004 10/850,918, " slow-crystallizing polyester resins ".In these co-pending applications each is intactly introduced for reference at this.U.S. Patent Application Serial 10/850,269 and 10/850,918 requires the U.S. Provisional Patent Application series number 60/472,309 of submission on May 21st, 2003, the right of priority the earliest of " the catalytic vibrin of titanium, preform and bottle ", this temporary patent application is equally intactly introduced for reference.

The application further requires the rights and interests of the following common temporary patent application of transferring the possession of: the US temporary patent application sequence number 60/559,983 that on April 6th, 2004 submitted to, " the catalytic vibrin of titanium, preform and bottle "; And the US temporary patent application sequence number 60/573,024 of submission on May 20th, 2004, " slow-crystallizing polyester resins and polyester preform " with improved reheat performance.It is for reference that the application intactly introduces these provisional application.

It is for reference that the application further intactly introduces the patent and the patent application of following common transfer: the sequence number 09/738 that on December 15th, 2000 submitted to, 150, " injecting method after the polymerization during polyethylene terephthalate is produced continuously ", existing US patent No.6,599,596; The sequence number 09/932,150 that submit to August 17 calendar year 2001, " extruding-injection method after the polymerization in the polyethylene terephthalate production ", existing US patent No.6,569,991; The sequence number 10/017,612 that submit to December 14 calendar year 2001, " injecting method after the polymerization in the condensation polymer production ", existing US patent No.6,573,359; The sequence number 10/017,400 that submit to December 14 calendar year 2001, " extruding-injection method after the polymerization in the condensation polymer production ", existing US patent No.6,590,069; The sequence number 10/628,077 that on July 25th, 2003 submitted to, " being used for the additive delay is incorporated into the method for polyethylene terephthalate "; The sequence number 09/738 that on December 15th, 2000 submitted to, 619, " copolyester bottle resin and preparation method thereof " with frictional behaviour of attenuating, existing US patent No.6,500, the sequence number 10/176 that on June 21st, 890 and 2002 submitted to, 737, " having the fluoropolymer resin that lowers frictional behaviour ", existing US patent No.6,727,306.

Background of the present invention

Because its intensity, thermotolerance and chemical-resistant, so the moiety in many consumer's goods that polyester container, film and fiber are the whole world to be made.In this respect, the polyester that commercial value is arranged most that is used for polyester container, film and fiber is a polyethylene terephthalate polyester.

Vibrin, especially polyethylene terephthalate and copolyesters thereof also are widely used for producing hard packing, for example 2 liters of soft drink containers.The polyester packages of producing by the stretch blow method of forming has outstanding intensity and splitting resistance, and has excellent gas-barrier and organoleptic properties.Therefore, this light weight plastics have substituted glass basically in the packing of many consumer's goods (for example carbonated soft drink, fruit juice and peanut butter).

In the usual way of preparation bottle resins, the modification pet resin is polymerized to the limiting viscosity of about 0.6 deciliter/gram (dl/g) in mutually at melt, after this it further solid mutually in polymerization, obtain to promote better the limiting viscosity of bottle moulding.After this, polyethylene terephthalate can be injection molded into preform, the latter and then can be blow molded into bottle.

Regrettably, under ordinary production speed, most of vibrin can not be shaped to effectively is suitable for preform and the bottle that heat is filled application.Most of high-clarity polyester bottles do not possess in about 180 to 205 , the necessary sized stability under the temperature of especially about 195 to 205  the hot filling product.Especially, under this high temperature, the conventional polyester bottle has shown unacceptable contraction and turbidity.

Therefore, for be suitable for preparing can be under the temperature of about 180 to 205  the high-clarity, the polyethylene terephthalate of hot filling bottle of filling product exist demand.

Summary of the invention

Therefore, the effective formation method that the purpose of this invention is to provide the catalytic pet resin of titanium, preform, bottle and film.

Another object of the present invention provides the high-clarity polyester bottles, and it keeps acceptable dimensional stability filling the back with product in about 195  heat under the temperature of 205 .

Another purpose of the present invention provides and can be shaped to the high-clarity preform that heat is filled polyester bottles effectively.

Another purpose of the present invention provides the polyethylene terephthalate that can be shaped to high-clarity, heat filling polyester preform and bottle effectively.

Another purpose of the present invention provides the polyethylene terephthalate that can be shaped to the high-clarity polyester bottles that is suitable for carbonated soft drink effectively.

Also purpose of the present invention provides the polyethylene terephthalate that can be used for preparing fiber, yarn and fabric.

Above other purpose and advantage and realization mode of the present invention of reaching of the present invention further illustrated in following detailed description and accompanying drawing thereof.

Description of drawings

Fig. 1-2 for example understands limiting viscosity with 0.78dl/g and the dsc heat analysis carried out with the catalytic pet resin of titanium of 1.6mol% glycol ether and 1.5mol% isophthalate modified.

Fig. 3-4 for example understands limiting viscosity with 0.78dl/g and the dsc heat analysis carried out with the catalytic pet resin of antimony of 1.6mol% glycol ether and 1.5mol% isophthalate modified.

Fig. 5-6 for example understands limiting viscosity with 0.78dl/g and the dsc heat analysis carried out with the catalytic pet resin of titanium of 1.6mol% glycol ether and 2.4mol% isophthalate modified.

Fig. 7-8 for example understands limiting viscosity with 0.78dl/g and the dsc heat analysis carried out with the catalytic pet resin of antimony of 1.6mol% glycol ether and 2.4mol% isophthalate modified.

Fig. 9 for example understands the turbidity of ladder parison (step parison) mensuration of titanium catalysis and the catalytic pet resin of antimony and the graphic representation of preform thickness.

Figure 10 for example understands under various molecular weight the theory loss of limiting viscosity of the polyethylene terephthalate of the limiting viscosity with 0.63dl/g that the concentration with reactive carrier becomes.

Figure 11 for example understands under various molecular weight the theory loss of limiting viscosity of the polyethylene terephthalate of the limiting viscosity with 0.45dl/g that the concentration with reactive carrier becomes.

Figure 12-13 for example understands by not using the absorption (cm of the representative polyethylene terephthalate of heating rate additive enhanced ^-1).

Describe in detail

The present invention is slow crystallization pet resin.Have those obvious higher heating crystalline exotherm peak temperature (T at pet resin of the present invention disclosed herein than the catalytic pet resin of common antimony _CH).To have postponed crystalline initial for the thermal crystalline exothermic temperature that adds of this rising.Therefore, pet resin of the present invention especially can be used for making the hot filling bottle with outstanding transparency and shrinkage.

In one aspect, the present invention has about 140 ℃ heating crystalline exotherm peak temperature (T of surpassing _CH), about at least 0.18cm under the wavelength of 1100nm or 1280nm ^-1Specific absorption (A), and as the pet resin that surpasses about 70 L* value of in the CIE L*a*b* color space, classifying.

In yet another aspect, the present invention comprises at least hundred 2/10000ths (ppm)-preferred, is less than the 50ppm-element titanium and is lower than the pet resin of about 6mol% comonomer substitution rate.The catalytic pet resin of this titanium especially can be used for container, film and packing, but also can be used for fiber, yarn and fabric.

In yet another aspect, the present invention is the polyethylene terephthalate preform that can be used for enhanced thermal-setting bottle.This polyethylene terephthalate preform has about 140 ℃ heating crystalline exotherm peak temperature (T of surpassing _CH), about at least 0.18cm under the wavelength of 1100nm or 1280nm ^-1Specific absorption (A), and as the pet resin that surpasses about 70 L* value of in the CIE L*a*b* color space, classifying.

In yet another aspect, the present invention is the polyester preform that can be shaped to the high-clarity bottle with excellent low-shrinkage energy.This preform comprises and is lower than about 6mol% comonomer substitution rate, and has the limiting viscosity that is lower than about 0.86dl/g.At a related aspect, the present invention is high-clarity, the hot filling bottle that is formed by preform.

In yet another aspect, the present invention is the polyester preform that can be shaped to the high-clarity bottle with excellent hot expansibility.This preform comprises and is lower than about 6mol% comonomer substitution rate and has about 0.78 to the limiting viscosity of 0.86dl/g.At a related aspect, the present invention is high-clarity, the carbonated Sofe drink bottle that is formed by this preform.Carbonated Sofe drink bottle can tolerate the internal pressure of about 60psig.

In yet another aspect, the present invention is the Ti-base catalyst system that promotes that the melt phase of pet resin closes.

In yet another aspect, the present invention promotes the I family of the solid state polymerization (SSP) of pet resin and the catalyst system of II family metal.The SSP catalyst system preferably includes basic metal (that is, I family metal), alkaline-earth metal (that is, II family metal), or the two.

In yet another aspect, the present invention includes the method for this vibrin of preparation, preform and bottle, in this respect, this method generally comprises and allows terephthalic acid component and diol component (promptly, terephthalic acid structure division and diol structure part) in the presence of titanium catalyst, react, thereby form the polyethylene terephthalate precursor, come polymerization via the polycondensation of melt phase then, form the polymkeric substance of the polyethylene terephthalate of desired molecule amount.By in the catalyzer enhanced polycondensation process, remove ethylene glycol continuously, usually to produce favourable reaction kinetics.

Those of ordinary skill in the art is clear, and most of industrial polyethylene terephthalate polymers in fact are the modification polyethylene terephthalate polyesters.In fact, preferably modification is poly-to dioctyl phthalate glycol ester polyester for pet resin as herein described.In this respect, the properties-correcting agent in terephthalic acid component and the diol component is random alternative in the gained polymer blend usually.

As mentioned above, the catalytic pet resin of titanium has the low comonomer substitution rate.Polyethylene terephthalate generally comprises and is lower than about 6mol% comonomer substitution rate.Polyethylene terephthalate generally comprises and is lower than 5mol% comonomer substitution rate or surpasses 2mol% comonomer substitution rate, or both of these case.

Though higher comonomer substitution rate has destroyed crystallization, thereby has improved transparency, thermal-setting strengthens under than the low comonomer substitution rate.Therefore, for the resin that is used for preparing hot filling bottle, polyethylene terephthalate preferably includes about 3 to 4mol% comonomer substitution rate.For example, in such embodiment, the modification polyethylene terephthalate is made up of the diol component of the ethylene glycol of the diacid component of the terephthalic acid of (1) the 2.4mol% m-phthalic acid of about 1: 1 mol ratio and remainder and (2) 1.6mol% glycol ether and remainder.

As used herein term " diol component " mainly is meant ethylene glycol, though can also use other glycol (for example glycol ether).

Term " terephthalic acid component " broadly refers to can be used in the diacid and the diester of preparation polyethylene terephthalate.Especially, the dioctyl phthalate component is mainly comprised terephthalic acid or dimethyl terephthalate (DMT), but can also comprise diacid and diester comonomer.In other words, " terephthalic acid component " is " diacid component " or " diester component ".

Term " diacid component " more specifically is meant and can be used in the diacid (for example, terephthalic acid) for preparing polyethylene terephthalate via direct esterification.Yet term " diacid component " intention comprises the diester comonomer (for example, mainly terephthalic acid and one or more diacid properties-correcting agent have some diester properties-correcting agent but also choose wantonly) of relatively small amount.

Similarly, term " diester component " more specifically is meant and can be used in the diester (for example dimethyl terephthalate (DMT)) for preparing polyethylene terephthalate via transesterify.Yet term " diester component " intention comprises the diacid comonomers (for example, mainly dimethyl terephthalate (DMT) and one or more diester properties-correcting agent also have some diacid properties-correcting agent but choose wantonly) of relatively small amount.

And term as used herein " comonomer " intention comprises monomer modified dose and oligomeric properties-correcting agent (for example, polyoxyethylene glycol).

Diol component can comprise other glycol (for example, glycol ether, the polyoxyethylene glycol except ethylene glycol, 1, ammediol, 1, the 4-butyleneglycol, 1,4 cyclohexane dimethanol, neopentyl glycol, and Isosorbide), or except terephthalic acid or its dialkyl (that is dimethyl terephthalate (DMT)) in addition, terephthalic acid component can comprise properties-correcting agent, m-phthalic acid or its dialkyl (that is, dimethyl isophthalate) 2 for example, 6-naphthalene dicarboxylic acids or its dialkyl are (promptly, 2,6-naphthalene dicarboxylic acids dimethyl ester), hexanodioic acid or its dialkyl (that is dimethyl adipate), Succinic Acid, its dialkyl (that is, dimethyl succinate), or its acid anhydrides is (promptly, or the functional derivative of one or more terephthalic acids Succinic anhydried).

For polyethylene terephthalate bottle resins according to the present invention, m-phthalic acid and glycol ether are preferred modifiers.Those of ordinary skill in the art knows that as properties-correcting agent, cyclohexanedimethanol has suppressed the polymer crystallization degree effectively, but has inferior oxygen permeability.

For pet fiber resin according to the present invention, it is necessary that no comonomer substitutes, but under situation about using, preferably includes glycol ether or polyoxyethylene glycol.

It should be understood that when terephthalic acid component mainly is terephthalic acid (that is diacid component), should use diacid comonomers, and when terephthalic acid component mainly is dimethyl terephthalate (DMT) (that is, the diester component), should use the diester comonomer.

Those of ordinary skill in the art should further be appreciated that the diol component and the terephthalic acid component of molar excess reacts (that is, diol component exists with the amount that surpasses stoichiometric ratio) in order to obtain polymer blend of the present invention.

In the reaction of diacid component and diol component via the direct esterification reaction, normally about 1.0: 1.0 to 1.0: 1.6 of the mol ratio of diacid component and diol component.Perhaps, in the reaction via transesterification reaction, the mol ratio of diester component and diol component was usually above about 1.0: 2.0 in diester component and diol component.

Diol component has formed the most of terminal of polymer chain usually, so be present in the gained polymer blend with high slightly deal.Here it is so-called phrase " terephthalic acid component of about 1: 1 mol ratio and diol component ", " diacid component of about 1: 1 mol ratio and diol component ", " the diester component and the diol component of about 1: 1 mol ratio ", they can be used for describing polymer blend of the present invention separately.

The catalytic pet resin of titanium preferably is made up of the diacid component and the diol component of about 1: 1 mol ratio.Diacid component comprises that 94mol% terephthalic acid (for example, terephthalic acid and m-phthalic acid) and diol component comprise 94mol% ethylene glycol (for example, ethylene glycol and glycol ether) at least at least.

The catalytic pet resin of titanium according to the present invention generally has the limiting viscosity that is lower than about 0.86dl/g.Yet those of ordinary skill in the art will understand that in the injection operation process, vibrin often loses limiting viscosity (for example, from the fragment to the preform, approximately the limiting viscosity of 0.02-0.06dl/g is lost).

For the polyester preform that can form according to high-clarity of the present invention, hot filling bottle, polyethylene terephthalate generally has the limiting viscosity that is lower than about 0.86dl/g, for example about 0.72 to 0.84dl/g limiting viscosity.More generally, polyethylene terephthalate has the limiting viscosity that surpasses about 0.68dl/g or be lower than about 0.80dl/g, perhaps both of these case (that is, about 0.68dl/g is to 0.80dl/g).Polyethylene terephthalate preferably has the limiting viscosity that surpasses about 0.72dl/g or be lower than 0.78dl/g, or both of these case (that is, about 0.72dl/g is to 0.78dl/g).Most preferably, polyethylene terephthalate also has the limiting viscosity (that is, about 0.75dl/g is to 0.78dl/g) that surpasses about 0.75dl/g.For the preform that is used for preparing hot filling bottle, the thermal-setting performance reduces under the high inherent viscosity level, and mechanical property (for example, stress crack, drop impact, and creep) reduces down in low limiting viscosity level (for example being lower than 0.6dl/g).

For the polyester preform that can form according to high-clarity of the present invention, carbonated Sofe drink bottle, polyethylene terephthalate generally has the limiting viscosity that surpasses about 0.72dl/g or be lower than about 0.84dl/g, or both of these case (that is, about 0.72dl/g is to 0.84dl/g).This polyethylene terephthalate preferably has the limiting viscosity that surpasses about 0.78dl/g, most preferably, and about 0.80 to 0.84dl/g limiting viscosity.

For trevira according to the present invention, polyethylene terephthalate generally has the limiting viscosity of about 0.50dl/g to 0.70dl/g, and preferably approximately 0.60dl/g to the limiting viscosity of 0.65dl/g (for example, 0.62dl/g).This pet resin generally only melt mutually in polymerization (that is, fibre resin does not carry out solid-state polymerization usually).

As used herein term " limiting viscosity " is the ratio of the concentration of the specific viscosity of polymers soln of concentration known and solute, is extrapolated to 0 concentration.The limiting viscosity that is considered to the standard criterion of polymer property widely is directly proportional with average polymer molecule weight.For example referring to Dictionary of Fiber and Textile Technology, Hoechst CelaneseCorporation (1990); Tortora﹠amp; Merkel, Fairchild ' s Dictionary ofTextiles (the 7th edition, 1996).

Those of ordinary skill in the art can too much test with regard to energy measurement and measure limiting viscosity.For inherent viscosity as herein described, limiting viscosity is by being dissolved in copolyesters ortho chloro phenol (OCP), adopt Schott Autoviscometer (AVS Schott and AVS500Viscosystem) to measure the relative viscosity of solution, determine according to relative viscosity estimated performance viscosity then.For example, referring to Dictionary of Fiber and Textile Technology (" limiting viscosity ").

Especially, under about 105 ℃ temperature with the 0.6g sample (+/-0.005g) dry polymer sample is dissolved in the ortho chloro phenol of about 50ml (61.0-63.5g).Usually fiber and yarn samples are cut into small shreds, grind chip samples again.After cool to room temperature, under the constant temperature (for example about 20 to 25 ℃) of control, solution is added in the viscometer, measure relative viscosity again.As mentioned above, by relative viscosity estimated performance viscosity.

As mentioned above, the catalytic pet resin of titanium generally comprises the element titanium of about 2ppm to 50ppm.Preferably, this resin comprises the element titanium (for example about 2 to 20ppm) that is lower than 25ppm.More preferably, this resin comprises at least the element titanium of about 5ppm or is lower than the element titanium of about 15ppm, perhaps both of these case (that is, about 5 to 15ppm, about 10ppm for example).Titanium catalyst is titanic acid ester normally, such as two (Acetyl Acetone) diisopropanol titanium or tetrabutyl titanate.

Those of ordinary skill in the art knows that germanium is excellent polyethylene terephthalate catalyzer.Yet, germanium cost an arm and a leg to such an extent that make us not daring to inquire, so in the production of industrial polyester, be out of favour.

Therefore, this resin is lower than the elements germanium of about 20ppm by introducing, is usually less than the elements germanium of about 15ppm, more generally is lower than the elements germanium of about 10ppm and reduces the cost.Preferably, the catalytic pet resin of titanium comprises the elements germanium that is lower than 5ppm and more preferably less than the elements germanium of about 2ppm.In many cases, the catalytic pet resin of titanium is substantially free of elements germanium.Yet in other cases, the catalytic pet resin of titanium comprises at least approximately elements germanium of 2ppm.

Those of ordinary skill in the art will further know, compares with the catalytic vibrin of common antimony, and the catalytic vibrin of titanium has lower crystallization rate.The catalytic pet resin of titanium of the present invention has than the lower degree of crystallinity of the catalytic pet resin of other identical antimony.Be not subjected to the restriction of particular theory, it is believed that with antimony and compare, titanium is bad nucleator.Therefore, the catalytic pet resin of titanium of the present invention has the crystallization rate that is lower than the catalytic polyester of antimony.As those of ordinary skill in the art will understand that, this makes can be blow molded into the high-clarity bottle according to preform of the present invention.

Therefore, resin of the present invention comprises the element antimony that is lower than about 100ppm, is usually less than the element antimony of about 75ppm, more generally is lower than the element antimony of about 50ppm.Preferably, the catalytic pet resin of titanium comprises the element antimony that is lower than 25ppm, more preferably less than the element antimony of about 10ppm.In many cases, the catalytic pet resin of titanium is substantially free of element antimony.Not stibiated pet resin may be an ideal, because antimony is considered to heavy metal.Yet in other cases, the catalytic pet resin of titanium comprises at least approximately element antimony of 10ppm.

It is that the titanium catalysis of about 0.78dl/g and dsc (DSC) that the catalytic vibrin of antimony carries out heat are analyzed that Fig. 1-8 has described limiting viscosity.Fig. 1-4 has compared titanium catalysis and the catalytic pet resin of antimony with about 3mol% comonomer substitution rate.Fig. 5-8 has compared titanium catalysis and the catalytic pet resin of antimony with about 4mol% comonomer substitution rate.

Dsc keeps modification polyethylene terephthalate sample 1 minute down at 30 ℃ by (1); (2) with 10 ℃/minute speed sample is heated to 280 ℃ from 30 ℃; (3) sample was kept 2 minutes down at 280 ℃; (4) with 10 ℃/minute speed sample being cooled to 30 ℃ from 280 ℃ carries out.Fig. 1,3,5 and 7 heating corresponding to amorphous polymer, and Fig. 2,4,6 with 8 corresponding to same polymer from the mutually initial cooling of melt.

Fig. 1-2 shows that under about 3% comonomer substitution rate (that is, 1.6mol% glycol ether and 1.5mol% m-phthalic acid substitution rate), the catalytic polyethylene terephthalate polyester of titanium has 144.2 ℃ heating crystalline exotherm peak temperature (T _CH), 253.2 ℃ crystallization melting peak temperature (T _M), and 186.8 ℃ crystallisation by cooling exothermic peak temperature (T _CC).

Fig. 3-4 shows that under about 3% comonomer substitution rate (that is, 1.6mol% glycol ether and 1.5mol% m-phthalic acid substitution rate), the catalytic polyethylene terephthalate polyester of antimony has 130.6 ℃ heating crystalline exotherm peak temperature (T _CH), 251.5 ℃ crystallization melting peak temperature (T _M), and 191.0 ℃ crystallisation by cooling exothermic peak temperature (T _CC).

Fig. 5-6 shows that under about 4% comonomer substitution rate (that is, 1.6mol% glycol ether and 2.4mol% m-phthalic acid substitution rate), the catalytic polyethylene terephthalate polyester of titanium has 146.3 ℃ heating crystalline exotherm peak temperature (T _CH), 250.0 ℃ crystallization melting peak temperature (T _M), and 181.3 ℃ crystallisation by cooling exothermic peak temperature (T _CC).

Fig. 7-8 shows that under about 4% comonomer substitution rate (that is, 1.6mol% glycol ether and 2.4mol% m-phthalic acid substitution rate), the catalytic polyethylene terephthalate polyester of antimony has 131.5 ℃ heating crystalline exotherm peak temperature (T _CH), 250.9 ℃ crystallization melting peak temperature (T _M), and 187.8 ℃ crystallisation by cooling exothermic peak temperature (T _CC).

Illustrated as Fig. 1-8, to compare with the catalytic polyethylene terephthalate of antimony, the catalytic pet resin of titanium of the present invention has obviously higher heating crystalline exotherm peak temperature (T _CH).Those of ordinary skill in the art will know that the thermal crystalline exothermic temperature that adds that this is higher is special ideal in blow molding operation, initial because it has postponed crystalline, thereby helps the formation of high-clarity bottle.

Therefore, passing through under 10 ℃/minute the rate of heating of determine with dsc method, pet resin has above about 140 ℃ and the preferred heating crystalline exotherm peak temperature (T that surpasses about 142 ℃ (for example 143 ℃ to 153 ℃) _CH).In fact, pet resin can have 〉=155 ℃ crystalline exotherm peak temperature (T _CH).Those of ordinary skill in the art will appreciate that, noncrystalline pet resin is measured heating crystalline exotherm peak temperature (T _CH).

Pet resin also has about at least 240 ℃, and about at least usually 245 ℃, more generally about at least 250 ℃ crystallization melting peak temperature (T _M).Those ordinarily skilled in the art are understood, and fusing point largely depends on co-monomer content.

And by under 10 ℃/minute the rate of cooling of determine with dsc method, pet resin has and is lower than about 190 ℃ and be usually less than about 185 ℃ crystallisation by cooling exothermic peak temperature (T _CC).In some cases, pet resin has and is lower than about 180 ℃ crystallisation by cooling exothermic peak temperature (T _CC).

The catalytic pet resin of titanium of the present invention has than the high transparency of the catalytic pet resin of other identical antimony.In this respect, Fig. 9 has described to the limiting viscosity with about 0.78dl/g and 3mol% comonomer substitution rate (promptly, 1.6mol% glycol ether and 1.5mol% m-phthalic acid substitution rate) or the turbidity percentage measured of the ladder parison (step parison) of the titanium catalysis of 4mol% comonomer substitution rate (that is, 1.6mol% glycol ether and 2.4mol% m-phthalic acid substitution rate) and the catalytic pet resin of antimony and the relation curve of preform thickness.Fig. 9 explanation, under set comonomer substitution rate, the catalytic pet resin of titanium has the significantly lower turbidity of the catalytic pet resin of antimony corresponding with it.Those of ordinary skill in the art will know that usually, higher comonomer substitution rate has destroyed the polymer crystallization degree, thereby lowers preform and bottle turbidity.

As the ladder parison is measured, polyethylene terephthalate of the present invention is lower than about 20% turbidity-preferably be lower than about 15% turbidity surpassing generally to have under the thickness of about 6mm, and surpassing under the thickness of about 4mm, be lower than about 5% turbidity.And, as the ladder parison is measured, polyethylene terephthalate is surpassing under the thickness of about 4.5mm, is being lower than about 10% turbidity (for example, being lower than about 10% turbidity under the thickness at 4.5-6.0mm) above preferably having under the thickness of 5.5mm sometimes.In some formulation, as the ladder parison was measured, polyethylene terephthalate had under the thickness of 5.5-6.5mm and is lower than about 20% turbidity.As depicted in figure 9, polyethylene terephthalate is being lower than about 50% turbidity above having under the thickness of about 7mm.

Those of ordinary skill in the art understands, and polyethylene terephthalate preform and bottle must have excellent color (that is not too jaundice).In this respect, the titanium catalyst of excessive level can make the pet resin jaundice.

Aberration is classified according to the L*a*b* color space of the Commission Internationale 1 ' Eclairage (CIE) usually.Three kinds of components of this system are by the L* that describes brightness by the yardstick of 0-100 (promptly 0 is that black 100 is white), red-green a* has been described (promptly, on the occasion of being red and negative value is green), and b* (that is, on the occasion of be that yellow and negative value the are bluenesss) composition of having described Huang-indigo plant axle.In order to characterize vibrin, L* and b* have special interests.

In this respect, preferably after polymerization, under solid phase, measure the color of polyester.After solid-state polymerization, pet resin of the present invention has as surpassing of classifying in the CIE L*a*b* color space about 70, preferably surpasses about 75 (for example 77), most preferably surpasses about 80 L* value (that is brightness).In addition, pet resin preferably have as with the classification of the CIE L*a*b* color space less than about 2, be more preferably less than about 0 b* colour.Most preferably, pet resin has as approximately-3 to 2 the b* colour with the classification of the CIEL*a*b* color space.

What those of ordinary skills will appreciate that is though can measure the color of polyester preform and polyester bottles, to measure polyester granules or polyester sheet usually more aptly.(typically referring to fragment, pellet etc.) at this given term " pellet ".

Those of ordinary skills can know that pet resin formed pellet usually before experience crystallization and solid state polymerization.Therefore, still in polymer processing (for example, injection-molded) before, pet resin of the present invention is the crystallization pellet after solid state polymerization; Preferably measure color in this state.In this respect and except as otherwise noted (for example, as for noncrystalline plate), this paper relates to crystalline polyethylene terephthalate pellet for the CIE L*a*b* color space values of pet resin report of the present invention.

Use (light source/observer: D65/10 ° in HunterLab LabScan XE spectrophotometer; 45 °/0 ° geometry; Reflect diffusing globe NBS78 fully; Reference colour rules LX16697) measures the CIEL*a*b* color space values of this crystallization polyethylene terephthalate pellet.What those of ordinary skills will appreciate that is that the crystalline polyester pellet is translucent, so use transparent sample cup to measure by reflecting usually.In this respect, the testing sequence (for example, standard and correction) that is suitable for measuring the color characteristics of the crystalline polyester be various forms (for example, pellet) is that those of ordinary skills obtain easily and should be appreciated that.Referring to http://www.hunterlab.com/measurementmethods.

As described herein, pet resin of the present invention can be moulded preform by injection mould, and the latter can be blow molded into bottle again.Yet the color of measuring preform and bottle may be uncontrolled.Therefore, preferably preform is become plate with doleiform so that the contrast color measuring.In this respect, will be ground according to polyethylene terephthalate preform of the present invention and bottle,, be injected cold mould then to form 3 millimeters non-crystalline polyester test boards of standard 280 ℃ of following fusions.This paper relates to the observed value that this type of standard test block is measured for the CIE L*a*b* color space values of polyethylene terephthalate preform of the present invention and bottle report.

When forming these standard test blocks by polyester preform or polyester bottles, the polyester moiety may have disadvantageous thermal history.Those of ordinary skills it should be understood that this may make the degraded of polyester moiety a little.In this respect, notice, may introduce a little yellowing (that is, the b* colour raises slightly) by the preform (after this forming standard test block) that crystallization polyethylene terephthalate pellet injection mould of the present invention is moulded.

Therefore, polyethylene terephthalate preform of the present invention and bottle preferably have as in the CIE L*a*b* color space, classify less than about 4, be more preferably less than the b* colour of about 2 (for example less than about 0).This polyethylene terephthalate preform and bottle very preferably have approximately-3 to 3 the b* colour as classifying in the CIE L*a*b* color space.

Yet, as above-mentioned crystallization polyethylene terephthalate pellet, polyethylene terephthalate preform of the present invention and bottle have as what classify in the CIE L*a*b* color space and surpass about 70, preferably surpass about 75 (for example 77), most preferably surpass the L* value of about 80 (for example 83 or higher).

As point out that these CIE L*a*b* color space values are meant the observed value from standard non-crystalline polyester test board.

Use (light source/observer: D65/10 ° in HunterLab LabScan XE spectrophotometer; 45 °/0 ° geometry; Penetrate the 8 ° of standards of overflowing; Light-transmissive port) measures 3 millimeters, the CIE L*a*b* color space values of amorphous polyethylene terephthalate test board.So it is transparently to measure by printing opacity basically that those of ordinary skills it should be understood that the non-crystalline polyester plate.In this respect, the testing sequence (for example, standard and correction) that is suitable for measuring the color characteristics of the non-crystalline polyester that is various forms is that those of ordinary skills obtain easily and should be appreciated that.Referring to http://www.hunterlab.com/measurementmethods.

According to the present invention, this type of color is by adding about 10 to the 50ppm element cobalt, and preferably approximately 15 is to the 40ppm element cobalt, very preferably 20 to 30ppm element cobalt and obtaining.Do not having under the situation of cobalt, pet resin of the present invention often looks like yellowy.Pet resin of the present invention has excellent color under the situation that does not comprise tinting material (except cobalt catalyst).(those of ordinary skills it should be understood that cobalt not only provides catalytic activity, and can give the pet resin blueness).

If pet resin is intended for use packing (for example polyester preform and bottle), it preferably includes the heating rate additive.In this respect, the heating rate additive is present in the resin with the amount of the reheat performance (profile) of enough improvement resins.Will be understood that as those of ordinary skill in the art the heating rate additive helps preform to absorb energy in preform reheat process.In the reheat preform, the inside of this preform should be the same with the outside of preform at least hot, because inside has experienced more stretching in the blowing process.

For the person of ordinary skill of the art, it is counterintuitive adopting slow crystallization pet resin in the manufacturing of thermal-setting bottle.For example, US patent No.6,699,546 (Tseng) instruction is introduced nucleator and is quickened the resin crystallization rate, is used to obtain improved thermal-setting bottle.

Illustrated as the front, slow crystallization pet resin has with those of the catalytic pet resin of antimony compares obviously higher heating crystalline exotherm peak temperature (T _CH).The purpose of thermal-setting method is to make bottle degree of crystallinity and stress relaxation reach maximum when keeping transparency.As if slow crystalline resins have lower thermal-setting ability.Therefore, introduce the heating rate additive and obtain higher preform temperature-and therefore improve the degree of crystallinity of slow crystalline resins-seem there is not practical benefits.In this case, those of ordinary skill in the art's expection can not obtain improved bottle performance (for example, transparency and contraction).

For example, can consider bottle preform by the slow crystallization pet resin that further comprises the heating rate additive (for example, the catalytic vibrin of titanium disclosed herein) preparation.As mentioned above, when heating during preform, compare with antimony, titanium has slowed down thermal crystalline initial of preform.Yet the heating rate additive makes preform absorb more multipotency, therefore reaches obviously higher temperature before crystallization is initial.Therefore, even under the preform temperature that raises, also kept good preform transparency.

Surprisingly, the contriver has been found that introducing the reheat performance that enough additive agent modified slow-crystallizing polyester resins of heating rate improve resin has in fact improved a blowing performance and a bottle performance, such as contraction.The preform temperature that increases in blowing and thermosetting process has improved bottle crystallization and stress relaxation, produces the bottle that transparency is better than the catalytic pet resin of antimony simultaneously.

In one embodiment, the heating rate additive is a carbon back heating rate additive.Carbon back heating rate additive is present in the pet resin with the amount that is lower than about 25ppm usually.More preferably, carbon back heating rate additive most preferably is present in the pet resin with about amount of 6 to 10ppm with about 4 to the amount of 16ppm (for example 8-12ppm).The carbon back additive that is fit to comprises carbon black, gac and graphite.For example, gratifying carbon black heating rate additive is disclosed in US patent No.4, and among 408,004 (Pengilly), this patent is introduced for reference here comprehensively.

In another embodiment, the heating rate additive is metallic heating rate additive.Metallic heating rate additive generally with the amount of about 10-300ppm, more generally is present in the pet resin with the amount (for example, about 150 to 250ppm) that is higher than about 75ppm.The metallic heating rate additive that is fit to comprises metal, metal oxide, mineral (for example, the copper chromite spinel), and dyestuff.For example, US patent No.6,503,586 (Wu) disclose gratifying inorganic mineral black and particle, and this patent is introduced for reference thus in full.

Preferred metallic heating rate additive is the tungsten based additive, for example tungsten metal or wolfram varbide.In this respect, the heating rate additive powder of tungstenic preferably has about 0.7 to 5.0 micron, more preferably about 0.9 to 2.0 micron mean particle size.

As those skilled in the art can understand, granularity was measured by the technology based on scattering of light usually.Granularity and size-grade distribution usually characterize according to ASTM B330-2 (" Standard TestMethod for Fisher Number of Metal Powders and Related Compounds).

Other preferred metallic heating rate additive is the molybdenum based additive, especially moly-sulfide (MoS ₂).In this respect, moly-sulfide has outstanding heat-absorption properties, so it can be introduced with the amount of lacking slightly than other metallic heating rate additive (for example 5-100ppm).

Most preferred heating rate additive is natural spinel and synthetic spinel.Spinel preferably is included in the pet resin with about 10 amounts that arrive 100ppm (for example, about 15 to 25ppm).Especially Tu Chu spinel pigments is copper chromite black spinel and ferrochrome nickel black look spinel.

These spinels are disclosed in the following document: the US patent application serial number 09/247,355 of proposition on February 10th, 1999, existing resigned common transfer, " having the thermoplastic polymer that improves infrared rays reheat performance " and division thereof; In the US patent application serial number of publishing on January 31st, 2,002 09/973,499 as US patent publications 2002/0011694A1; The US patent application serial number 09/973,520 that on March 7th, 2002 published as US patent publications 2002-0027314A1; And the US patent application serial number of publishing as US patent publications 2002-0033560A1 on March 21st, 2,002 09/973,436.These patent applications and patent publications are introduced for reference separately in full.

For specific bottle throughput rate, the heating rate of polyethylene terephthalate preform can be described by the surface temperature measurement of the fixed position on preform.

In the manufacturing of polyethylene terephthalate bottle, allow preform come reheat polyethylene terephthalate bottle preform by the reheating furnace of blow moulding machine.Reheating furnace is made up of one group of radiating quartz lamp (3,000 and 2,500 watts of lamps) of mainly launching infra-red range.Preform absorbs this radiation and is translated into heat, thereby the ability that makes preform reach the orientation temperature of blowing is important for best bottle performance and effective production.Important bottle performance for the bottle service performance is distribution of material, orientation and sidewall degree of crystallinity.

Preform reheat temperature is important for these performances of control.Depend on the type of the bottle that will make, preform reheat temperature generally is the second-order transition temperature (T at polyethylene terephthalate _g) in the scope of above 30-50 ℃.The reheat temperature depends on application (for example, heat is filled beverage bottle or carbonated Sofe drink bottle).At high speed polyethylene terephthalate blow moulding machine, for example by Sidel, in those of Inc. (French LeHavre) manufacturing, the speed that preform can be reheated orientation temperature is important for a best bottle service performance.For the thermal-setting bottle of planning to fill with the hot liquid that surpasses 185 , situation is especially true.In the manufacturing of thermal-setting bottle, this preform is rapidly heated to high as far as possible temperature.This makes crystallization reach maximum when blowing, and has avoided the thermal crystalline of preform.Those of ordinary skill in the art can know that this thermal crystalline may be owing to spheroidal crystal causes unacceptable turbidity.

In view of the importance of preform reheat, adopted following method to estimate the reheat characteristic of polyethylene terephthalate preform.As the thing that at first will do, this test method is analyzed the reheat characteristic of polyethylene terephthalate preform (or resin) by formed the test parison by one or more pet resin formulations.In fact test is the test parison, but not industrial preform:

At first, be 5.25 inches test parisons with trying resin forming with necklace (neck finish) of 47 gram weight, 1.125 inches overall diameter and 0.75 inch.In order to form this test parison, pet resin in moisture eliminator under 350  dry 4 hours.Dry resin is incorporated in 4 ounces of Newbury injection moulding machines.This resin is mediated and fusion, the molten resin of the temperature with 500-520  is provided.Then, molten resin is expelled in the preform mould that is designed for the carbonated Sofe drink bottle of 2L.Total cycle time is 60 seconds, comprises injection, filling and cooling time.Continuously with this mold cools down to 45 .These injecting conditions have obtained to be mainly the transparent test parison of amorphous (that is, being lower than about 4% degree of crystallinity).

5.25 the reheat performance of inch test parison is tested with Sidel SBO1 laboratory blow moulding machine.This machine has one and contains one group of reheating furnace of the quartz lamp of 10 independent regulation at the most, be used to measure the infrared camera of preform surface temperature, be transferred to the mechanical manipulator of blow mold from stove, a blow mold, and the bottle mechanical manipulator that extends to machine exit from blow mold.

In this test method, SBO1 laboratory blow moulding machine continuously with 1,000 bottle/hour speed adopt 8 quartz lamps to produce the polyethylene terephthalate bottles.Baking oven has and can control as the power that the percentage of total baking oven power output is regulated.Equally, each lamp can be regulated as the percentage of independently lamp power output.

In order to measure the reheat characteristic of 5.25 inches parisons, this machine be arranged on 1,000 bottle/hour the bottle production rate under.The choice criteria resin is produced the prototype version base.Then, determine the reheat characteristic of this test parison.Use the reheat characteristic, acceptable bottle on manufacture under 80% the total power output.After this, the percentage of total power changes between 65 to 90%, and the fixed position replicate measurement surface temperature on the test parison.

5.25 the reheat performance of inch test parison is 1.4 inches mensuration below the support ring of necklace unchangeably.At this position (be below the support ring 1.4 inches), the test parison has 0.157 inch wall thickness.

Embodiment 1

Produce two liters of polyethylene terephthalate bottle test parisons by normal resin (that is Wellman ' s PermaClear  HP806 vibrin).This test parison needs eight reheat districts, is used to make straight wall two litre flasks.Under total baking oven power percentage of 80%, the reheat characteristic of this PermaClear  HP806 test parison is shown in the table 1:

Table 1

The heating zone	Power output (%)
		1	74
2	60
		3	55
4	55
		5	55
6	68
		7	86
8	74

After setting up this reheat characteristic, by having two kinds of samples of the catalytic pet resin preparation of the antimony that is lower than about 6mol% comonomer substitution rate.A kind of sample comprises carbon back heating rate additive (Resin A) and another sample of about 11ppm, and promptly contrast does not comprise heating rate additive (resin B).Except having the reheat rate additive, Resin A is identical with B in others.Under total baking oven power output of 65-90%, measure the reheat performance (that is, measuring) of (increment) Resin A and resin B then by 5% via surface temperature:

Table 2

Total baking oven power output (%)	Resin A (surface temperature ℃)	Resin B (surface temperature ℃)
			65	87.3	81.0
70	92.0	85.0
			75	95.8	87.5
80	100.5	92.0
			85	107.0	97.3
90	113.0	101.0

Table 2 explanation, the result as introducing the heating rate additive has obtained improved preform reheat characteristic.

Therefore, in order to improve preform reheat characteristic, pet resin of the present invention preferably includes the reheat surface temperature that concentration is enough to make above-mentioned 5.25 inches test parisons to obtain (be at wall thickness below 0.157 inch the support ring of necklace 1.4 inches locate to measure) than by at the identical 5.25 inches test parisons of others (promptly, do not have the reheat rate additive) the about at least 4 ℃ heating rate additive of corresponding reheat temperature height that obtains, wherein this reheat surface temperature is respectively 65%, 70%, 75%, 80%, under 85% and 90% the total power level with 1,000 bottle/hour throughput rate operation and adopt the Sidel SBO1 laboratory blowing aircraft measurements of 8 lamps.Each reheat surface temperature difference is more preferably about at least 7 ℃, most preferably about at least 10 ℃.

In another embodiment, polyethylene terephthalate of the present invention preferably includes the average reheat surface temperature that concentration is enough to make above-mentioned 5.25 inches test parisons to obtain (be at wall thickness below 0.157 inch the support ring of necklace 1.4 inches locate to measure) than by at the identical 5.25 inches test parisons of others (promptly, do not have the reheat rate additive) about at least 5 ℃ of obtainable average reheat surface temperature height, the heating rate additive that preferably approximately is 10 ℃, wherein this reheat surface temperature under the total power level between 65% and 90% with 1,000 bottle/hour throughput rate operation and adopt the Sidel SBO1 laboratory blowing aircraft measurements of 8 lamps.

Perhaps, the intrinsic heating rate of vibrin can be described by its characteristic energy absorption.In this respect, electromagnetic radiation is present in several spectrums.For example, electromagnetic radiation can be measured in ultraviolet ray, visible light, near infrared ray and far infrared rays scope.Visible spectrum is between the 690nm at about 430nm.This spectrum is a boundary with ultraviolet radiation and far infrared radiation respectively.For the reheat characteristic (profile) of polyester, near infrared radiation (NIR) is significant especially.

More particularly, the intrinsic heating rate of vibrin can characterize by its absorption of electromagnetic radiation rate.Specific absorption is described by Beer's law, and it is represented with equation 1:

Equation 1 A=ε 1c

Wherein

A is the absorption of electromagnetic radiation rate of sample,

ε is the rate constant (that is, " molar absorptivity ") of sample,

L be the electromagnetic radiation sample that must pass through path length and

C is the concentration (pressing mol/L usually weighs) of sample.

Yet for vibrin, equation 1 can be simplified.For specific vibrin, molar absorptivity and sample concentration can be ignored.And, between specific absorption and path length (that is thickness of sample), there is linear relationship.Therefore, for fluoropolymer resin, specific absorption (A) can as followsly be calculated by transmissivity (T):

Equation 2 A=log (100)-log (%T)

As represented in equation 3, equation 2 further is simplified:

Equation 3 A=2-log (%T)

In brief, transmissivity is the ratio of intensity and the intensity of the electromagnetic radiation that enters fluoropolymer resin that sees through the electromagnetic radiation of fluoropolymer resin.As the specific absorption of reporting (calculating) the not transmissible electromagnetic radiation of noncrystalline pet resin has been described here by relational expression represented in equation 3.

As mentioned before, pet resin of the present invention generally has at least approximately 0.18cm under the wavelength of 1100nm or under the wavelength at 1280nm ^-1Specific absorption (A).And pet resin of the present invention generally has at least approximately 0.20cm under the wavelength of 1100nm or under the wavelength at 1280nm ^-1Specific absorption (A), preferably generally have at least approximately 0.24cm under the wavelength of 1100nm or under the wavelength at 1280nm ^-1Specific absorption (A), more preferably generally have at least approximately 0.28cm under the wavelength of 1100nm or under the wavelength at 1280nm ^-1Specific absorption (A).

Those of ordinary skill in the art will appreciate that, as comprise coordinating conjunction (that is, " with ") at the employed adversative conjunction of this paper (promptly " or ").And, for the disclosure, to non-crystalline polyester report specific absorption.

In its most preferred embodiment, pet resin has at least approximately 0.25cm under the wavelength of 1100nm or under the wavelength at 1280nm ^-1Specific absorption (A), preferably have at least approximately 0.30cm under the wavelength of 1100nm or under the wavelength at 1280nm ^-1Specific absorption (A).In certain embodiments, pet resin has at least approximately 0.30cm under the wavelength of 1100nm or under the wavelength at 1280nm ^-1Specific absorption (A), in specific embodiments, have at least approximately 0.40cm under the wavelength of 1100nm or under the wavelength at 1280nm ^-1Specific absorption (A).These pet resins can obtain by the copper chromite black spinel of introducing about 10-100ppm.

In this respect, in visible light and NIR spectral range to noncrystalline, enhanced pet resin (PET) is identical with others but measure specific absorption with the copper chromite black spinel heating rate additive enhanced pet resin (PET/ spinel) of 22ppm.Table 3 has been reported the specific absorption of these vibrin under 550nm, 700nm, 1100nm and 1280nm:

Table 3

Specific absorption (cm -1)	550nm	700nm	1100nm	1280nm
					PET	0.209	0.170	0.145	0.144
The PET/ spinel	0.399	0.374	0.314	0.314

The wavelength of table 3 report is meaningful.Especially, 550nm is near the mid point of visible spectrum, and 700nm is near the upper end of visible spectrum.And as describing in Figure 12-13, the specific absorption of enhanced PET is not almost smooth (that is, slope is about 0) under 1100nm and 1280nm, thereby but helps the replicate measurement under these wavelength in the NIR spectral range.

In order to strengthen color, preferably, the heating rate additive has promoted the more NIR radiation and the absorption of more a spot of visible radiation.This can recently describe by absorption as defined herein.In brief, for vibrin, specific absorption is at the antilogarithm of the specific absorption under first wavelength antilogarithm divided by the specific absorption under second wavelength simply.This represents in equation 4:

Equation 4 specific absorptions=(antilogarithm A ₁)/(antilogarithm A ₂)

Wherein

A ₁Be under first wavelength specific absorption and

A ₂It is the specific absorption under second wavelength.

For specific absorption, normally (for example, 1280nm) in the scope, second wavelength is normally at visible spectrum (for example, 550nm) in the scope at NIR spectrum for first wavelength.Table 4 shows, have with enhanced polyethylene terephthalate not with 22ppm copper chromite spinel enhanced polyethylene terephthalate and similarly to absorb selectivity, but have obviously higher specific absorption (for example, is higher than 0.30cm under 1100nm and 1280nm ^-1Specific absorption).

Table 4

Specific absorption	1100∶550	1280∶550	1100∶700	1280∶700
					PET	0.864	0.862	0.945	0.943
The PET/ spinel	0.822	0.822	0.871	0.871

Pet resin of the present invention preferably has 1100: 550 specific absorptions of about at least 70%, or 1280: 550 specific absorptions of about at least 70%.More preferably, pet resin of the present invention has 1100: 550 specific absorptions of about at least 75%, or 1280: 550 specific absorptions of about at least 75%.In certain embodiments, pet resin of the present invention preferably has 1100: 550 specific absorptions of about at least 80%, or 1280: 550 specific absorptions of about at least 80%.

Similarly, pet resin of the present invention preferably has 1100: 700 specific absorptions of about at least 85%, or 1280: 700 specific absorptions of about at least 85%.In certain embodiments, 1100: 700 specific absorptions that pet resin of the present invention preferably has is about at least 90% (promptly 95% or higher), or 1280: 700 specific absorptions of about at least 90% (promptly 95% or higher).

For the disclosure, adopt Foss Series 6500 Transport Analyzer to measure the specific absorption of three millimeters (3mm) non-crystalline polyester plates.This instrument is those typical case's representative that can be determined at transmissivity in visible light and the NIR spectrum, measures because instrument coefficient (for example, lamp, detector, vibration and air filtration) can influence specific absorption.Certainly, the use of proper standard and calibration is in those of ordinary skills' intellect scope.

For the control test mobility, absorbance data must stdn under the incident wavelength of 2132nm, makes that corresponding specific absorption is 0.473mm ^-1(that is 4.73cm, ^-1).Under this wavelength, additive has the influence of appropriateness to the specific absorption of noncrystalline polyethylene terephthalate.

The inventor has also considered the influence of sample reflectivity, but determines, it can be out in the cold when measuring the specific absorption of vibrin.In brief, reflectivity is the radiation of scattering from the surface of solid, liquid or gas.As represented in equation 5, the electromagnetic energy of reflection is represented according to the energy that absorbs and the energy of transmission:

Equation 5 I _O=I _A+ I _T+ I _R

Wherein

I _OBe projectile energy,

I _ABe to absorb energy,

I _YBe transmission potential and

I _RIt is reflected energy.

As mentioned before, specific absorption is obtained by transmissivity.Referring to equation 3.Reflectivity is not generally measured, and whether has introduced big error so the contriver has considered to ignore reflectivity in the mensuration of specific absorption.

In this respect, as if the polyester sheet with glazed surface has than the higher reflectivity of polyester sheet with " unglazed " or other non-reflectivity facing.If do not consider reflectivity, increase reflectivity and as if reduced transmissivity.According to equation 3, this will have the effect that phonily increases the specific absorption of calculating.

Therefore, in order to reduce absolute reflectance and control reflectivity mobility, each batch of material of this polyester sheet should have consistent facing (that is semi-gloss).It is believed that in estimating specific absorption and specific absorption, reflectivity can be ignored by controlling the physicals of polyester sheet by this way.

Those ordinarily skilled in the art know that forming polyethylene terephthalate has two kinds of usual ways.These methods are as well known to those skilled in the art.

A kind of method adopts the direct esterification reaction of using terephthalic acid and excessive ethylene glycol.In this technology, the above-mentioned steps that allows terephthalic acid component and diol component react comprises allows terephthalic acid and ethylene glycol react in the heating esterification, thereby forms the monomer and the oligopolymer of terephthalic acid and ethylene glycol, and the water by product.For esterification is proceeded to fully substantially,, must remove continuously and anhydrate if form.Monomer and oligopolymer carry out catalyzed polymerization via polycondensation subsequently, form polyethylene terephthalate polyester.As mentioned above, ethylene glycol is removed in polycondensation process continuously, thereby produces favourable reaction kinetics.

Other method relates to two step transesterification reaction and the polymerizations of using dimethyl terephthalate (DMT) and excessive ethylene glycol.In this technology, the above-mentioned steps that allows terephthalic acid component and diol component react comprises allows dimethyl terephthalate (DMT) and ethylene glycol react in heating, catalyzed transesterification (being transesterification), form two (2-hydroxyethyl) the ester monomers of terephthalic acid, and as the methyl alcohol of by product.

For transesterification reaction is proceeded to fully basically, when forming, methyl alcohol must be removed continuously.Two (2-hydroxyethyl) the ester monomeric products of terephthalic acid are carried out catalyzed polymerization via polycondensation then, form polyethylene terephthalate polymer.The gained polyethylene terephthalate polymer is identical with the polyethylene terephthalate polymer that is obtained by the direct esterification of using terephthalic acid basically, but has some little chemical differences (for example, end group difference).

Polyethylene terephthalate can wherein form the product of transesterify or esterification by discontinuous method production in a container, transfer to then in second container to be used for polymerization.Generally, stir second container, polyreaction lasts till that the used power of agitator reaches that the indication polyester fondant reaches required limiting viscosity and therefore till the level of required molecular weight.Yet the industrial way that more gears to actual circumstances is to carry out esterification or transesterification reaction, carries out the polyreaction as continuation method then.The continuous production of polyethylene terephthalate has caused higher output, so be more typical in the scale operation facility.

In the present invention, the direct esterification reaction is more preferred than two old-fashioned step transesterification reactions, and the latter is uneconomic, and has usually obtained to have the polyethylene terephthalate of bad color.

In this respect, and as mentioned above, the direct esterification technology allows terephthalic acid and ethylene glycol and be no more than the 6mol% diacid and glycol modification agent reaction, forms low molecular weight monomers, oligopolymer and water.Especially, titanium and cobalt catalyst preferably add in esterification process, because find to do like this color of having improved the gained pet resin.Pet resin can randomly comprise other catalyzer, such as aluminium-based catalyst, and manganese-based catalyst, or zinc-base catalyzer.

More particularly, titanium catalyst is introduced enough to make final pet resin comprise about 2 amounts that arrive the element titanium of 50ppm.Equally, cobalt catalyst comprises the about 10 amount introducings to the 50ppm element cobalt enough to make final pet resin.In order to prevent technology trouble (for example, blocking pipe), suggestion is incorporated into titanium and cobalt catalyst in the esterification vessel with different handling equipments.

The introducing of titanium or cobalt catalyst has increased the speed of esterification and polycondensation, therefore, has increased the production of poly terephthalic acid ethylene glycol resin.Yet these catalyzer finally make the grade of polyethylene terephthalate reduce.For example, degradation can comprise polymkeric substance variable color (for example, yellowing), and acetaldehyde forms, or molecular weight lowers.In order to lower these undesirable effects, can use stable compound to isolate (" cooling ") catalyzer.The stablizer of normal use contains phosphorus, usually with the form of phosphoric acid ester and phosphorous acid ester.

Therefore, resin of the present invention generally comprises the phosphorus stabilizer agent.In this respect, the phosphorus stabilizer agent preferably is incorporated in the polyethylene terephthalate polymer, make by the element benchmark, phosphorus is to be lower than about 60ppm, common about 2 to 40ppm amount, preferably, more preferably be present in the gained resin with the amount that is lower than about 10ppm (that is, about 2 to 10ppm) to be lower than the amount of about 15ppm (for example about 5 to 15ppm).The phosphorus stabilizer agent can be incorporated into any time after esterification melt mutually in, but preferably the phosphorus stabilizer agent is joined in the melt after fully basically in polycondensation.

Though in batch reactor the phosphorus stabilizer agent being joined in the polymer melt is simple relatively method, if stablizer adds stablizer in the continuous production of polyethylene terephthalate, many problems occurred.For example, though add variable color and the degradation that stablizer has prevented polyester in early days, it has also caused the attenuating (that is, reducing polycondensation speed) of turnout.And the phosphorus stabilizer agent is dissolved in the ethylene glycol usually, its interpolation polymerization process that further slowed down.Therefore, the early stage stablizer that adds requires to do undesirable selection between the turnout of polymkeric substance and thermostability in polymerization process.As used herein " thermostability " is meant that the speed of acetaldehyde generation is low, and variable color is little, and molecular weight keeps after subsequent heat treatment or other processing.

Later stage is added the chance that the phosphorus stabilizer agent may provide inadequate stablizer and the complete blend of polymkeric substance.Therefore, the phosphorus stabilizer agent may not can prevent the degradation and the variable color of polyester.In addition, it usually is inconvenient adding the phosphorus stabilizer agent in polymer processing, and scale economics is not provided.

Title is the US patent No.5 of " method and apparatus that is used for the direct and continuous modification of polymer melt ", and 376,702 disclose the branch's materials flow that the polymer melt materials flow is divided into unmodified materials flow and reception additive.Especially, effluent (side stream) is incorporated into forcing machine with the part of branch's materials flow, introduces additive there.Yet this technology is not only complicated, and the cost height, requires screw extrusion press and melt pipe to come treatment additive.Therefore, this preparation is inconvenient, even (for example being lower than 1wt%) is unpractical under the low situation of total additive concentration.

Add the US patent No.5 that some relevant problem of stablizer be " continuously in the polyethylene terephthalate production after the polymerization of high activated catalyst stabilising method " at title with the later stage, solved in 898,058; This patent disclosure in continuously ethylene glycol terephthalate is produced, stablize the method for high reactivity polymerizing catalyst.This patent of being transferred the possession of jointly with this application is incorporated herein for reference thus comprehensively.

Especially, US patent No.5,898,058 disclose when polyreaction finishes or afterwards and before polymer processing, have added the stablizer that preferably contains phosphorus.This passivation polymerizing catalyst, increased the turnout of polyester, do not influence the thermostability of polyethylene terephthalate polyester unfriendly.Though compared significant improvement with ordinary skill, US patent No.5, the stablizer that does not have carrier is added in 898,058 instructions.As a result, solid is joined essential expensive use forcing machine in the polymkeric substance.

Title is the above-mentioned US application serial 09/738 of " injecting method after the polymerization during poly terephthalic acid ethylene glycol is produced continuously ", 150 (existing US patent No.6,599,596) the US patent No.5 that uses by common transfer is disclosed, the method of the improved production high quality of 898,058 disclosed stablizer adding techniques polyethylene terephthalate polyester.

More particularly, US applies for No.09/738, and 150 disclose the additive later stage is incorporated into method in the method for preparing polyethylene terephthalate.These additives are introduced during the polycondensation of polyethylene terephthalate polymer, preferably after introduce.Especially, this method adopts reactive carrier, and it is not only as the delivery vehicles of one or more additives, and with the polyethylene terephthalate reaction, thereby in pet resin in conjunction with this carrier.And US application serial 09/738,150 is open, and this can adopt does not need to use the simplification additive delivery system of forcing machine to finish.(title is the US application serial 09/932 of " forcing machine injecting method after the polymerization in the polyethylene terephthalate production ", 150, existing US patent No.6,569,991, be the part continuation application of US application serial 09/738,150, disclose the method for in the process of the method for preparing polyethylene terephthalate, introducing additive in the forcing machine later stage.)

Phosphorus stabilizer agent disclosed herein can be directly, as the enriched material in poly terephthalic acid ethylene glycol, or be incorporated in the polyethylene terephthalate polymer as the enriched material in liquid vehicle.The preferred interpolation time in the polyethylene terephthalate polymerization process is (that is, to mix with the melt polymerization streams after final aggregation container) after polycondensation is finished.

The phosphorus stabilizer agent preferably is incorporated in the polyethylene terephthalate polymer via reactive carrier, but not via inert support or complete carrier free.Preferably have and surpass about 200g/mol and be lower than approximately 10, this reactive carrier of the molecular weight of 000g/mol can be introduced during polycondensation, or more preferably, introducing polycondensation is finished after.Aspect any one, this reactive carrier should be so that the mass polymer performance be incorporated in the polyethylene terephthalate polymer by the amount of remarkably influenced.

In general, reactive carrier should be no more than about 1wt% of pet resin.Preferably, reactive carrier is so that its concentration in fluoropolymer resin is lower than approximately 1, and (that is, amount 0.1wt%) is incorporated in the polyethylene terephthalate polymer 000ppm.Reactive carrier is reduced to makes and its concentration in fluoropolymer resin be lower than 500ppm (that is, amount 0.05wt%) will further reduce the potential for adverse effects to the mass polymer performance.

Most preferably, reactive carrier has and guarantees that it is near the fusing point that under the envrionment temperature is liquid or slurry.Not only simplified device operation (for example, forcing machine, well heater and pipeline) near envrionment temperature, and the degradation of inert particle additive has been reduced to minimum.This paper employed " near envrionment temperature " comprises about 20 to 60 ℃ temperature.

Generally, the reactive carrier with carboxyl, hydroxyl or amine functional group is favourable.Polyvalent alcohol preferably, the pure and mild polyether glycol of polyester polyols especially, the pumping that has the molecular weight of the high limiting viscosity that must be enough to make the not obvious attenuating polyethylene terephthalate polymer of polyvalent alcohol and make polyvalent alcohol is viscosity easily.Polyoxyethylene glycol is a preferred polyhydric alcohols.Other exemplary polyvalent alcohol comprises functional polyethers, such as polypropylene glycol by propylene oxide production, and the random and segmented copolymer of oxyethane and propylene oxide, and the polytetramethylene glycol that obtains by the polymerization of tetrahydrofuran (THF).

In addition, this reactive carrier can comprise dimerization or trimer acid and acid anhydrides.In another embodiment, except functional end-group or replace functional end-group, this reactive carrier can have can with the internal functionality (for example, ester, acid amides and acid anhydrides) of polyethylene terephthalate polymer reaction.In another embodiment, this reactive carrier can comprise non-functionalized ester, acid amides, or acid anhydrides, they can be reacted in the polyethylene terephthalate polymer in the solid-state polymerization process and not make polyethylene terephthalate polymer suffer limiting viscosity loss in the Shooting Technique process.

In view of the above, the preferred method for preparing the catalytic pet resin of titanium of the present invention is included in the heating esterification, allows comprise the diacid component of 94mol% terephthalic acid at least and comprise the diol component reaction of 94mol% ethylene glycol at least.Should comprise diacid and glycol modification agent, make the gained polyethylene terephthalate polymer have and be lower than about 6mol% comonomer substitution rate.For example, diacid component preferably includes about 1.6 terephthalic acids to 2.4mol% m-phthalic acid and remainder, and diol component comprises the ethylene glycol of 1.6mol% glycol ether and remainder.

Esterification forms the monomer and the oligopolymer of terephthalic acid and diacid properties-correcting agent and ethylene glycol and glycol modification agent by titanium and cobalt catalysis, and water.When water forms, remove it continuously, so that esterification is proceeded to basically fully.(for example, the amount of element titanium 5-15ppm) and about element cobalt of 10 to 50ppm (for example 20-30ppm) is introduced simultaneously enough to make pet resin comprise about 2 to 50ppm for titanium catalyst and cobalt catalyst.

Monomer and oligopolymer then via melt mutually polycondensation aggregate into polyethylene terephthalate polymer.Then the phosphorus stabilizer agent is incorporated in the polyethylene terephthalate polymer, preferably adopts reactive carrier.As mentioned above, reactive carrier has promoted the even blend in polymer melt.Usually the phosphorus stabilizer agent is incorporated in the polyethylene terephthalate polymer, makes by the element benchmark, phosphorus is with about 2 to 60ppm amount, preferably be lower than about 10 or the amount of 15ppm be present in the gained resin.After this, polyethylene terephthalate polymer is configured as pellet, is polymerized under solid-state then and is lower than 0.86dl/g (for example, limiting viscosity 0.75-0.78dl/g).

Preferably, reactive carrier be polyvalent alcohol (for example, polyoxyethylene glycol), its molecular weight can make polyvalent alcohol near envrionment temperature (for example, be lower than 60 ℃) pumping down, and so that the not remarkable affected amount of the bulk properties of polyethylene terephthalate polymer (for example, making its concentration in polymkeric substance be lower than the amount of about 1wt%) is incorporated in the polyethylene terephthalate polymer.Before solid-state polymerization, polyethylene terephthalate polymer is shaped to fragment (or be shaped to pellet via the polymkeric substance cutting machine) then.Importantly, the polyol reaction carrier combines with polyethylene terephthalate polymer, makes it can not extract in following process operation (for example, forming polyester preform or beverage container) process.

Other additive can be incorporated in the pet resin of the present invention via reactive carrier.Examples of such additives comprises preform heating rate rising agent, antifriction additive, UV absorption agent, inert particle additive (for example clay or silica), tinting material, antioxidant, branching agent, oxygen barrier agent, the carbonic acid gas barrier agent, oxygen scavenqer, fire retardant, crystal controlling agent, acetaldehyde reduces agent, impact modifying agent, catalyst passivating agent, melt strength toughener, static inhibitor, lubricant, chainextender, nucleator, solvent, filler and softening agent.

When additive was volatile or is easy to thermal destruction, the later stage interpolation was special ideal.Before polycondensation, high temperature (being higher than 260 ℃) and decompression (being lower than 10 holders) condition that the early stage common additives injection for example in polyester synthetic Esterification Stage, or during polycondensation phase stood additive several hours.As a result, the additive that has remarkable vapour pressure under these conditions will lose from technology.Advantageously, add via later stage of reactive carrier and significantly reduced the time that additive contacts high condensation temperature.

As those ordinarily skilled in the art will appreciate that, polymer was considered to the polymkeric substance of the about 0.45dl/g of limiting viscosity.This is converted into about at least 13 roughly, the molecular weight of 000g/mol.On the contrary, reactive carrier according to the present invention have surpass about 200g/mol and be lower than about 10, the molecular weight of 000g/mol.The molecular weight of reactive carrier generally is lower than 6, and 000g/mol preferably is lower than 4, and 000g/mol is more preferably about 300 to 2, and 000g/mol is most preferably about 400 to 1,000g/mol.As used herein molecular weight is meant number-average molecular weight, but not weight-average molecular weight.

Figure 10 and 11 for example understands the theory loss with the limiting viscosity of reactive carrier change in concentration under several molecular weight.Figure 10 has described the influence of reactive carrier to the polyethylene terephthalate of limiting viscosity with 0.63dl/g.Similarly, Figure 11 has described the influence of reactive carrier to the polyethylene terephthalate of limiting viscosity with 0.45dl/g.Note under any concentration, having the high-molecular weight reactive carrier limiting viscosity of fluoropolymer resin is had less deleterious effect.

In typical illustrative methods, continuously feeding enters the direct esterification reaction vessel, and this container moves about 1 to 5 hour in about 240 to 290 ℃ temperature and about 5 under the pressure of 85psia.Preferred titanium and the catalytic esterification of cobalt catalyst used formed low molecular weight monomers, oligopolymer and water.Water is removed when reaction is carried out, to drive the balance of favourable reaction.

After this, low molecular weight monomers and oligopolymer come polymerization via polycondensation, form polyethylene terephthalate polyester.This polycondensation phase is general to adopt two or more container series, and moves about 1 to 4 hour under about 250 to 305 ℃ temperature.Polycondensation begins in first container that is called oligomeric device (low polymerizer) usually.This oligomeric device is operated under the pressure range of about 0 to 70 holder.Monomer and oligopolymer polycondensation form polyethylene terephthalate and ethylene glycol.

Ethylene glycol adopts the vacuum that applies to remove from polymer melt, to drive reaction to complete.In this respect, stir this polymer melt usually, to promote ethylene glycol from polymer melt, to select and to help the high viscosity polymer melt to pass through aggregation container.

When with polymer melt feeding successive container, the molecular weight of polymer melt and thus limiting viscosity increase.The temperature of each container generally increases and pressure reduces, thereby provides higher polymerization in each continuous container.

Final container is commonly referred to " high poly-device (high polymerizer) ", turns round under the pressure of about 0 to 40 holder.As oligomeric device, each aggregation container is connected in the vacuum system with condenser, and stirs usually separately, to promote the removal of ethylene glycol.The feeding rate part of the residence time in the aggregation container and ethylene glycol and terephthalic acid feeding continuous processing decides according to the target molecular weight of polyethylene terephthalate polyester.Because this molecular weight can be is easily decided according to the limiting viscosity of polymer melt, so the limiting viscosity of this polymer melt generally is used for determining polymerizing condition, such as the feeding rate of temperature, pressure, reagent, and the residence time in aggregation container.

Note, except forming polyethylene terephthalate polymer, the side reaction of undesirable by product has taken place also to form.For example, the esterification of ethylene glycol has formed glycol ether, and the latter is introduced in the polymer chain.Known as those skilled in the art, glycol ether has reduced the softening temperature of polymkeric substance.And cyclic oligomer (for example, the tripolymer of terephthalic acid and ethylene glycol and the tetramer) can exist on a small quantity.In polycondensation, when forming, ethylene glycol removes the formation that it has generally reduced these by products continuously.

After polymer melt withdraws from polycondensation phase, (withdraw from from the poly-device of height usually), introduce the phosphorus stabilizer agent via reactive carrier.After this, the common filtration and the extruded polymer melt.After extruding,, preferably pass through to use water spray, thereby make it to solidify the polyethylene terephthalate quenching.The solidified polyethylene terephthalate polyester is cut into fragment or pellet, be used for storing and handling.Polyester granules preferably has the average quality of about 15-20mg.Term as used herein " pellet " generally is used to refer to fragment, pellet etc.

Though continuous production processes has been supposed in previous argumentation, it should be understood that to the invention is not restricted to this.Instruction disclosed herein can be applied to semicontinuous method, even discontinuous method.

Known as those skilled in the art, the pellet that is formed by polyethylene terephthalate polymer can carry out crystallization, carries out solid-state polymerization subsequently, increases the molecular weight of pet resin.Compare with antimony, for example, titanium is obviously lower as the SSP activity of such catalysts.Therefore, in order to promote poly-solid state polymerization, before solid state polymerization, preferably in polycondensation process, complementary SSP catalyzer is incorporated in the polymer melt dioctyl phthalate glycol ester resin.

Preferred SSP catalyzer comprises I family and II family metal.Acetate of I family and II family metal (for example, calcium acetate, Lithium Acetate, manganese acetate, Potassium ethanoate, or sodium-acetate) or terephthalate can increase solid state polymerization rate.The SSP catalyzer is generally enough to make pet resin comprise that about 10 arrive the amounts introducing of the metal element of 70ppm.

After solid-state polymerization, then with the fusion and extruding again again of polyester fragment, form a bottle preform, after this can be shaped to polyester container (for example, beverage bottle).The bottle that forms by resin as herein described and preform preferably have be lower than about 15%, the sidewall turbidity more preferably less than about 10%.

Usually, hot filling bottle according to the present invention has shown when filling under 195  and has been lower than about 3% average circumference dimensional change, when under 205 , filling, shown to be lower than about 5% average circumference dimensional change, this average circumference dimensional change from shoulder to the bottle substrate measurement.And this hot filling bottle according to the present invention has shown that being lower than about 5%-preferably is lower than 4% the largest circumference dimensional change from shoulder to the bottle substrate-when this bottle is filled under 195 .(this shrinkage is measured with 24 hours aging bottles.)

As those of ordinary skill in the art will appreciate that, polyethylene terephthalate was converted into container via two-stage process usually.At first, be injected into preform by the amorphous bottle of bottle resins production preform (for example, being lower than about 4% degree of crystallinity and common about 4) by molten resin in forcing machine with molten polyester to 7mm thickness.The outer surface area of this preform is usually than little at least one order of magnitude of outer surface area of final container.To orientation temperature, this orientation temperature is normally at second-order transition temperature (T with this preform reheat _g) above 30 ℃.

Then the reheat preform is put in bottle blow mold,, be shaped to heating bottle by stretching with high-pressure air and expanding.Blow mold remains under about 115 to 200 ℃ temperature, about 120 to 160 ℃ usually.Those of ordinary skill in the art will appreciate that, pressurized air is incorporated into the moulding that has influenced heating bottle in the heating preform.Therefore, in a modification, discharge pressurized air by cleaning (balayage) technology turbulent flow ground from bottle, thereby promote the cooling of heating bottle.It is believed that to adopt and be used for compressed-air actuatedly being lower than non-pressurized pressure and being blow molded into the low bottle that shrinks according to preform of the present invention.

Fill polyester bottles for high-clarity of the present invention, heat, after the reheat step, be lower than (that is, under ordinary production speed) in about 6 seconds cycling time, this preform is blow molded into the low bottle that shrinks.

Those of ordinary skill in the art will appreciate that any defective of preform is transferred in the bottle usually.Therefore, the quality that is used to form the bottle resins of injection moulding preform is vital for obtaining industrial acceptable bottle.Injection moulding preform and stretch blow bottle are the US patent No.6 of " large polyester container and preparation method thereof " at title, discuss in 309,718, and this patent is introduced for reference at this paper thus comprehensively.

Those of ordinary skill in the art can further know, can with a small amount of introducing branching agent (for example be lower than about 2,000ppm), to increase rate of polymerization and to improve a bottle manufacturing process.Chain branching agent for example can close in the process at esterification or melt phase and introduce.Usually, in pet resin of the present invention, comprise and be lower than the 0.1mol% branching agent.

As used herein term " branching agent " is meant the polyfunctional monomer of promotion along the formation of the side shoot of the connection monomer molecule of host polymer chain.Referring to Odian, polymerization principle (Principlesof Polymerization), 18-20 page or leaf (second edition 1981).Chain branching agent preferentially be selected from can with trifunctional, four senses, face energy and six functional alcohol or the acid of polyethylene terephthalate copolymerization.As the skilled person will understand, trifunctional branching agent has a reactive site of the branching of being available for, four sense branching agents have two reactive site of the branching of being available for, face energy branching agent has three reactive site of the branching of being available for, and six sense branching agents have four reactive site of the branching of being available for.

Acceptable chain branching agent is including, but not limited to trimesic acid (C ₆H ₃(COOH) 3), pyromellitic acid (C ₆H ₂(COOH) ₄), pyromellitic acid dianhydride, trimellitic acid, trimellitic acid 1,2-anhydride, TriMethylolPropane(TMP) (C ₂H ₅C (CH ₂OH) ₃), ditrimethylolpropane (C ₂H ₅C (CH ₂OH) ₂C ₂H ₄OC (CH ₂OH) ₂C ₂H ₅), Dipentaerythritol (CH ₂OHC (CH ₂OH) ₂C ₂H ₄OC (CH ₂OH) ₂CH ₂OH), tetramethylolmethane (C (CH ₂H) ₄), ethoxylated glycerol, ethoxylation tetramethylolmethane (3EO/4OH and 15EO/4OH), come from Aldrich Chemicals), ethoxylated trimethylolpropane (2.5EO/OH and 20EO/3OH come from Aldrich Chemicals), with Lutrol HF-1 (ethoxylated glycerol comes from BASF).

As if preferred chains of aromatic branching agent-aromatic ring suppress stress nucleation (stressnucleation)-comprise trimellitic acid (TMLA), trimellitic acid 1,2-anhydride (TMA), pyromellitic acid (PMLA) pyromellitic acid dianhydride (PMDA), the benzophenone tetracarboxylic acid, benzophenone tetracarboxylic dianhydride, naphthalene tetracarboxylic acid, and naphthalene tetracarboxylic acid dianhydride, and their derivative:

(trihemellitic acid-TMLA)

(the trihemellitic acid acid anhydride-TMA)

(pyromellitic acid-PMLA)

(pyromellitic dianhydride-PMDA)

(benzophenone-3,3 ', 4,4 '-tetracarboxylic dianhydride)

(1,4,5,8-naphthalene tetracarboxylic acid dianhydride)

The patent of the following common transfer of the comprehensive introducing of the application is for reference, these patents have been discussed with respect to the stoichiometry mol ratio of reactive terminal group (promptly separately, " molar equivalent branch "): title is the US patent No.6 of " poly ethyldiol modified trevira and preparation method thereof ", 623,853; Title is the US patent No.6 of " supatex fabric that is formed by poly ethyldiol modified trevira and preparation method thereof ", 582,817; Title is the US patent No.6 of " poly ethyldiol modified trevira ", 509,091; Title is the US patent No.6 of " method for preparing poly ethyldiol modified polyester filament ", 454,982; Title is the US patent No.6 of " method for preparing poly ethyldiol modified polyester filament ", 399,705; Title is the US patent No.6 of " supatex fabric that is formed by poly ethyldiol modified trevira and preparation method thereof ", 322,886; Title is the US patent No.6 of " method for preparing poly ethyldiol modified polyester filament ", 303,739; And title is the US patent No.6 of " poly ethyldiol modified polyester filament and preparation method thereof ", 291,066.

Typical embodiments of the present invention is disclosed in specification sheets and accompanying drawing.Particular term is only used with the meaning of general and explanation, is not to be used for restriction.Scope of the present invention provides in following claims.

Claims (47)

1. the manufacture method of the catalytic pet resin of titanium comprises:

In esterification, allow the diol component reaction that comprises the diacid component of 94mol% terephthalic acid at least and comprise 94mol% ethylene glycol at least forming the monomer and the oligopolymer of terephthalic acid and diacid properties-correcting agent and ethylene glycol and glycol modification agent, and water;

During this esterification,, this pet resin introduces titanium catalyst and cobalt catalyst to the amount of 50ppm element cobalt so that being enough to comprise about 2 titaniums and about 10 that arrive the 50ppm element;

Remove the water that during this esterification, forms so that this esterification can be finished basically;

Monomer and oligopolymer via melt mutually polycondensation aggregate into polyethylene terephthalate polymer, wherein this polyethylene terephthalate polymer has the comonomer substitution rate less than about 6 moles of %; With

This polyethylene terephthalate polymer of solid-state polymerization.

2. according to the process of claim 1 wherein that the step of this introducing titanium catalyst and cobalt catalyst comprises so that this pet resin is enough to comprise about 2 titanium and about 15 amount introducing titanium catalyst and cobalt catalyst to the 40ppm element cobalt to the 20ppm element.

3. according to the process of claim 1 wherein that step via melt phase polycondensation polymerization single polymerization monomer and oligopolymer comprises the polyethylene terephthalate polymer that monomer and oligopolymer is aggregated into have less than about 2 and 5 moles of % comonomer substitution rates.

4. according to the process of claim 1 wherein that the step of this polyethylene terephthalate polymer of solid-state polymerization comprises this polyethylene terephthalate polymer solid-state polymerization to the limiting viscosity less than about 0.86dl/g.

5. according to the process of claim 1 wherein that the step of this polyethylene terephthalate polymer of solid-state polymerization comprises this polyethylene terephthalate polymer solid-state polymerization to the limiting viscosity greater than about 0.68dl/g.

6. according to the method for claim 1, further comprise the step of introducing the phosphorus stabilizer agent.

7. according to the method for claim 6, the step of wherein introducing the phosphorus stabilizer agent comprises: after finishing this esterification and before starting solid-state polymerization, so that this pet resin is enough to comprise the about 2 amount introducing phosphorus stabilizer agent to the 60ppm element phosphor.

8. according to the method for claim 6, wherein the step of this introducing phosphorus stabilizer agent comprises that with molecular weight be about 200g/mol to 10, the reactive carrier of 000g/mol is introduced in this polyethylene terephthalate polymer, and this reactive carrier is the delivery vehicles of phosphorus stabilizer agent.

9. method according to Claim 8, the step of wherein reactive carrier being introduced this polyethylene terephthalate polymer is included in the reactive carrier that is liquid or slurry near injection under the temperature of envrionment temperature.

10. method according to Claim 8, the step of wherein reactive carrier being introduced this polyethylene terephthalate polymer comprise to satisfy the concentration of reactive carrier in this polyethylene terephthalate polymer introduces this reactive carrier less than the about amount of 1wt%.

11. according to the method for claim 10, wherein this reactive carrier have about 300 to 2, the molecular weight of 000g/mol.

12. method according to Claim 8, the step of wherein reactive carrier being introduced this polyethylene terephthalate polymer comprises that the amount of 000ppm is introduced this reactive carrier to satisfy the concentration of reactive carrier in this polyethylene terephthalate polymer less than about 1.

13. method according to Claim 8, wherein this reactive carrier has less than about 4, the molecular weight of 000g/mol.

14. method according to Claim 8, wherein this reactive carrier have about 400 to 1, the molecular weight of 000g/mol.

15., further comprise the step of introducing the heating rate additive with the amount of the reheat performance of enough this pet resins of improvement according to the method for claim 1.

16. according to the method for claim 15, the step of wherein introducing the heating rate additive comprises to introduce carbon back heating rate additive less than the amount of about 25ppm.

17. according to 16 method of claim, the step of wherein introducing carbon back heating rate additive comprises with about amount of 4 to 16ppm introduces the carbon back heating rate additive that is selected from carbon black, activated carbon and graphite and binding substances thereof.

18. according to the method for claim 15, the step of wherein introducing the heating rate additive comprises with about 10ppm introduces metallic heating rate additive to the amount of 300ppm.

19. according to the method for claim 18, the step of wherein introducing metallic heating rate additive comprises with about 10ppm introduces spinel to the amount of 100ppm.

20., further comprise the step of introducing the SSP catalyzer that improves solid state polymerization rate according to the method for claim 1.

21. according to the method for claim 20, the step of wherein introducing the SSP catalyzer is introduced the SSP catalyzer during being included in melt phase polycondensation.

22. according to the method for claim 20, wherein this SSP catalyst pack alkali metal containing or alkaline-earth metal.

23., further be included in the step that the startup solid-state polymerization forms this polyethylene terephthalate polymer pellet before according to the method for claim 1.

24., further comprise the step that this polyethylene terephthalate polymer is formed the bottle preform and after this this bottle preform is formed bottle according to the method for claim 1.

25., further comprise with the film forming step of this polyethylene terephthalate polymer according to the method for claim 1.

26. introduce titanium catalyst and cobalt catalyst simultaneously during the step of introducing titanium catalyst and cobalt catalyst is included in this esterification according to the process of claim 1 wherein.

27. each method among the 2-25 is as requested introduced titanium catalyst and cobalt catalyst during the step of wherein introducing titanium catalyst and cobalt catalyst is included in this esterification simultaneously.

28. each method among the 1-26 as requested, wherein the step of this introducing titanium catalyst comprises so that this pet resin is enough to comprise that about 5 introduce titanium catalysts to the amounts of 15ppm element titanium.

29. each method among the 1-26 as requested, wherein the step of this introducing cobalt catalyst comprises so that this pet resin is enough to comprise that about 20 introduce cobalt catalyst to the amounts of 30ppm element cobalt.

30. each method among the 1-26 as requested wherein comprises the polyethylene terephthalate polymer that monomer and oligopolymer is aggregated into have less than about 3 and 4 moles of % comonomer substitution rates via the step of melt phase polycondensation polymerization single polymerization monomer and oligopolymer.

31. each method among the 1-26 as requested, wherein the step of this polyethylene terephthalate polymer of solid-state polymerization comprises the limiting viscosity of this polyethylene terephthalate polymer solid-state polymerization to about 0.72 to 0.84dl/g.

32. each method among the 1-26 as requested, wherein the step of this polyethylene terephthalate polymer of solid-state polymerization comprises this polyethylene terephthalate polymer solid-state polymerization to less than the about limiting viscosity of 0.80dl/g.

33. each method among the 6-14 as requested, wherein the step of this introducing phosphorus stabilizer agent comprises so that this pet resin is enough to comprise less than the about amount of 40ppm element phosphor and introduces the phosphorus stabilizer agent.

34. each method among the 6-14 as requested, wherein the step of this introducing phosphorus stabilizer agent comprises so that this pet resin is enough to comprise less than the about amount of 15ppm element phosphor and introduces the phosphorus stabilizer agent.

35. each method among the 8-14 wherein should comprise polyvalent alcohol by the reactivity carrier wave as requested, sufficiently high this polyvalent alcohol that makes of the molecular weight of this polyvalent alcohol can not reduce the limiting viscosity of this polyethylene terephthalate polymer significantly.

36. each method among the 1-26 further comprises the step that this polyethylene terephthalate polymer is formed preform as requested.

37., wherein further comprise the step that this preform is formed container according to the method for claim 36.

38. the pet resin that each method is made among the 1-26 as requested.

39. the pet resin that each method is made among the 1-26 as requested, wherein this pet resin comprises element antimony that is lower than 100ppm and the elements germanium that is lower than about 20ppm.

40. the pet resin that each method is made among the 1-26 as requested, wherein this pet resin comprises the element antimony that is lower than 50ppm.

41. the pet resin that each method is made among the 1-26 as requested, wherein this pet resin comprises element antimony that is lower than 25ppm and the elements germanium that is lower than about 5ppm.

42. the pet resin that each method is made among the 1-26 as requested, wherein this pet resin have as in the CIE L*a*b* color space, classify greater than about 75 L* value.

43. the pet resin that each method is made among the 1-26 as requested, wherein this pet resin has 2 the b* colour of being lower than as classifying in the CIE L*a*b* color space.

44. the pet resin that each method is made among the 1-26 as requested, wherein this pet resin have as in the CIE L*a*b* color space, classify greater than about 80 L* value.

45. the polyethylene terephthalate preform that each method is made among the 1-26 as requested.

46. the polyethylene terephthalate container that each method is made among the 1-26 as requested.

47. the pet film that each method is made among the 1-26 as requested.

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