CN1152078C - Copolymerized polyester suitable for extrusion - Google Patents

Abstract

Copolyester mainly contains para-position phthalic acid and ethylene glycol, which also comprises at least one kind of special glycol selected from 2-ethyl-2-butyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, 2, 4-diethyl-1, 5-pentanediol and 1-hydroxy-2, 2-dimethyl-propyl-trihydroxymethyl acetyl ester. The addition range of the special glycol is from 1 wt% to 15 wt%, or 0 to 1.0 mol% of trimellitic acid, trimellitic anhydride or trimethylol propane is added. The viscosity of the copolyester is enhanced to 0.8 to 1.4 dl/g, and the copolyester can be used for processing and making various moulding products by fusing and extruding. The present invention has the advantages of good processability, smooth surface of finished products, good transparence, high shock resistance, heat resistance, hydrolysis resistance and chemical reagent resistance, and fusant dripping phenomena can not occur in a processing process.

Description

Be applicable to the copolyesters of extrusion processing

The prescription, the method that the present invention relates to make a kind of copolyesters reach the method for its mouldings of copolyesters processing and manufacturing thus.

This copolyesters has the characteristic of non-newtonian flow, it can present low viscosity characteristics under high shear rate, but under low shear rate, present the high viscosity characteristic, therefore can make various mouldings with melt extruded, do not have vertical (sag) the too fast problem of dripping of colloidal sol, be particularly suitable for making the peculiar hollow container of various patterns with extrusion blow.With the hollow container thickness homogeneous that this copolyesters is made, wall of container does not also have the jointing line of generation phenomenon.

This copolyesters has the slow characteristic of crystallization rate, therefore when making long, darker molded articles, does not have the problem of crystallization albefaction.When especially factory length surpasses 30 centimetres molding, if during with melt extruded manufacturing molding, be easy to produce the crystallization albinism with general traditional polyester.

Container with this copolyesters extrusion blow manufacturing has shock-resistant characteristic, and being different from general polyester has the problem of easily breaking through the container of extrusion blow.

Its smooth surface of molded article so that this copolyesters extrusion blow is made can not produce shark skin surface (shark-skin surface), does not have excessively crosslinked gel (gel) phenomenon that causes yet, and causes flake (fish eye) surface.

The fusing point of this copolyesters is lower than general traditional polyester, fills perhaps and carries out under lower processing temperature.

Used catalyzer, stablizer, the colorant of the manufacturing processed of this copolyesters is that existing mass-produced packaging polyester material use, do not fear the hygienic safety consideration that its poisonous additive is separated out with the product of polyvinyl chloride (PVC) manufacturing.

This copolyesters and other are applicable to the polyester of extrusion processing relatively, and lay special stress on must not add crosslinked modification agent again and hangs down and drip to improve melten gel, and improves the speed of solid state polymerization.

Prior art

Polyethylene terephthalate (PET) after making the slush molding object because of having the transparency, if be used for stretch-blow have the height shock-resistance, and has good barrier properties for gases, and its additive toxicity is very low, the consideration of hygienic safety is probably arranged unlike the PVC container when filling eats content, therefore be widely used as packaging material for food.

The method of making the slush molding object has two kinds, and is a kind of for extruding (or claiming to extrude) blow molding method, another kind of for penetrating blow molding method; Extrusion is to form column type embryo (Parison) with screw rod or piston extruding melten gel through mold (Die) after the resin fusion, when the type embryo still is the softish molten state, left and right two leaf moulds are closed, this template embryo is located in the die cavity, blow into air in the type embryo this this moment apace, so promptly obtains a hollow and mould the system object.Penetrating blow molding method is that molten resin is injected in the die cavity, forms idiosome, and this idiosome is inserted in the blow mold after taking out again, and air is blown in the idiosome, so promptly obtains a hollow and moulds the system object.

Compare the extrusion blow method of forming and penetrate blow molding method, its processing characteristics difference is as follows:

The technology of the extrusion blow method of forming is simple and easy, and processing mechanical apparatus is cheap, and die cost is low, more mold exchange easily and can make complex-shaped, the bottle that length is long, but its process velocity is slower; Therefore this processing method is applicable to various in a small amount order production.Penetrate the blow molding rule and be applicable to mass production, simple shape and its processing technology are very high, mould and mechanical means cost height, the needs of therefore suitable a large amount of orders.With two kinds of processing methods of practical viewpoint its advantage and weak point are arranged all, so present this two kinds of processors still in the ubiquity plastic cement processing industry.

The SILVER REAGENT ethylene glycol terephthalate is to penetrate the various hollow containers of blow molding manufactured, if add man-hour with the extrusion blow method of forming, has melten gel through the type embryo of melt extruded gained and hangs down and drip a phenomenon and cause moulding to be difficult for, and this is because of due to its low melting viscosity.In addition, the reagent level PET easily produces crystallization, and albinism is arranged, and when processing long object, this can't make acceptable product especially.In addition, since very lower with its blowing extension ratio of object of extrusion blow method of forming manufacturing than penetrating blow molding method, so the poor impact resistance of its finished product is easily broken.No matter all can't process the course of processing or final finished with the extrusion blow method of forming by above practical experience visualizingre agent level PET.

Based on above result, there are many patents to propose to be fit to the vibrin of extrusion processing, now be summarized as follows:

1.US-A-5,182,359, EP-A-0532943, JP-A-5-125165/1993 deliver with two acids or its deutero-ester class and the glycols reaction that contains 2 to 8 carbon, add the ethylene oxide adduct of dihydroxyphenyl propane in addition again, make the copolyesters that is fit to the extrusion processing method.

2.US-A-4,161,579,4,219,527,4,234,708 are published in and add TriMethylolPropane(TMP) (Trimethylol propane) or tetramethylolmethane (Pentaerythritol) or trimellitic acid (Trimellitic acid) in terephthalic acid and the glycol reaction process again as linking agent, and add phenylformic acid (Benzoic acid) again or stearic acid (Stearic acid) blocks agent as chain.Polyester with this gained is used as extruding blowing.

3.US-A-4,182,841, JP-A-55-92730/1980 proposes terephthalic acid and the synthetic prepolymer of ethylene glycol, with TriMethylolPropane(TMP) or tetramethylolmethane or trimellitic acid adding, manufacture the ester grain and obtain being applicable to the polymkeric substance that extrudes processing through solid state polymerization more again.

4.US-A-4 554,329 deliver that adding tetramethylolmethane again does the side chain agent in addition with terephthalic acid and m-phthalic acid (Isophthalicacid) and ethylene glycol, and position anisic acid (m-Anisicacid) manufacturing is applicable to the copolyesters that extrudes blowing between adding.

5.US-A-3 558,557,4,188,357,4,196,275 deliver with terephthalic acid, ethylene glycol, dihydroxyphenyl propane glycol ether ether (Bisphenol A diglycol ether) and the agent of a spot of multiple functional radical side chain manufacture be applicable to extrude processing get ester altogether.

6.EP being published in the alicyclic or aliphatics of the difunctionality base that adds 1-4 mole % in terephthalic acid and the ethylene glycol again, 0774 477A2 (is called the a1 unit, cyclohexanedimethanol for example, cyclohexane cyclohexanedimethanodibasic), or the aromatic diol class of 0.5-7 mole % (be called the a2 unit, for example 2, two [4-(the 2-hydroxyl ethoxy) phenyl] propane of 2-, 1, two (the 2-hydroxyl ethoxy) benzene of 4-), or the two carboxylic-acids of aromatic series (be called the a3 unit, for example naphthalene dicarboxylic acids, 4, the two phenyl dicarboxylic acid of 4-), (be called the b1 unit, for example TriMethylolPropane(TMP) by above wherein three functional group's materials that contain at least with 0.005-1 mole %, trimellitic acid 1,2-anhydride, tetramethylolmethane), (be called the c unit, for example phenylformic acid with the monofunctional material of specified quantitative again, naphthoic acid, the trimethoxy benzoic acid, stearic acid, a position anisic acid) a kind of copolyesters of reaction manufacturing.Perhaps, the difunctionality base material that adds 0.5-7 mole % in terephthalic acid and ethylene glycol again (is called the a2 unit, for example 2, two [4-(the 2-hydroxyl ethoxy) phenyl] propane of 2-, 1, two (the 2-hydroxyl ethoxy) benzene of 4-), (be called the b2 unit, TriMethylolPropane(TMP) for example, trimellitic acid 1,2-anhydride with three the functional group's materials that contain at least of 0.005-1 mole %, tetramethylolmethane), the another kind of copolyesters of the specific intrinsic viscosity of tool is made in reaction.Or, the difunctionality base material that adds 0.5-7 mole % in terephthalic acid and ethylene glycol again (is called the a3 unit, naphthalene dicarboxylic acids for example, 4, the two phenyl dicarboxylic acid of 4-), (be called the b1 unit by above wherein three functional group's materials that contain at least with 0.005-0.5 mole %, TriMethylolPropane(TMP) for example, trimellitic acid 1,2-anhydride, tetramethylolmethane), another kind of again copolyesters is made in reaction.Above copolyesters is all declared to be applicable to extrusion blow molding engineering.

7.US-A-5,376,375 are published in the side chain agent that adds 0.01-3 mole % in terephthalic acid and the ethylene glycol again, and these side chain agent can be the mixtures of trimellitic acid, trimellitic acid 1,2-anhydride, trimesic acid, tetramethylolmethane or TriMethylolPropane(TMP) one of them or several.Make low-molecular-weight prepolymer thus earlier, this prepolymer ground to form add position phthalic acid between the 0.1-5.0 weight % behind the powdery again, extruding machine with the Brabender board mixes and carries out solid-phase polymerization after (blend) is cut into the ester grain, and molecular weight is reached more than 11,000.Can the extrusion blow moulding.

The TaiWan, China patent of invention disclose for No. 307780 a kind of copolyesters in terephthalic acid and ethylene glycol, add again contain 2-[4-(2-hydroxyl ethoxy) phenyl]-2-[3 '-(2-hydroxyethyl)-4 '-(2-hydroxyethyl) phenyl] propane and/or 1, three alcohols materials of two (2-hydroxyl ethoxy)-2-(2-hydroxyethyl) benzene of 4-, its content is the 0.01-1 mole % of glycols and three alcohols summations.This copolyesters also can the extrusion blow moulding.

Yet, in aforementioned the 1st method for making, can run into the melt viscosity deficiency, the molten state idiosome hangs down and drips seriously, can't stablize processing; And when low temperature molding, have shaggy phenomenon.

In aforementioned the 2nd method for making, can improve molten state viscosity though use cross linking agent and chain to block agent, also causing than upgrading polyester not has crystallization rate faster, can produce the crystallization albinism when making the finished product of length.And the finished product of copolyesters made is also just like the surface irregularity phenomenon of the 1st generation thus.

In aforementioned the 3rd method for making, also just like the 2nd crystallization rate phenomenon faster.Have in addition the 3rd method for making and to add as m-phthalic acid or neopentyl glycol (neopentyl glycol) inhibition crystallization rate, cause shaggy phenomenon but still can't improve because of excessive crosslinked generation gel.

In aforementioned the 4th method for making, a position fennel libation at an ancient wedding ceremony can obtain higher melt viscosity and produce less gel between the adding tetramethylolmethane reached, and position phthalic acid inhibition crystallization rate between adding.Yet, make length when surpassing 30 centimetres molding finished product, still can run into the phenomenon of the slight coarse and crystallization albefaction in surface.

In aforementioned the 5th method for making, because its structure of bisphenol A modification agent causes amorphous phase, can only improve molecular weight with the melt-phase polymerization, this will cause the melt viscosity that can't reach higher, can cause the serious sagging of fusion idiosome when machine-shaping.If will solve this phenomenon, some method for making is to add a large amount of dihydroxyphenyl propane glycol ether ether, and this will make polymer experience the reaction times too of a specified duration when the melt-phase polymerization, cause thermo-cracking, and polymer its colour changed into yellow and melt viscosity can not suitably be controlled.

In above-mentioned and the 6th and 8 method for making, its copolyesters can be accepted in extrusion processing really, and can obtain good molded articles; Yet, materials such as alicyclic or aliphatics that its patent of delivering is added or aromatic diol class or aromatic series dual-hydroxy acid class, all be set in below the specific content, meet with the sticking mutually work of polymer chips when carrying out solid state polymerization or slow down for avoiding sticking work must reduction solid state reaction temperature to cause speed of reaction to avoid causing, but so the shock-resistance of its molded articles is partly suppressed, especially when manufacturing big volume and complex-shaped hollow container, still have the worry of breaking.In addition,, the embodiment of the 6th method for making makes 1.8 liters of hollow containers, and the embodiment of the 8th method for making then only makes 1.0 liters of hollow containers; The applicant then makes 2.0 liters and with the hollow container of handgrip with the actual production board.Again in addition,, the glycols or the three alcohols modification agents that add in the 6th and 8 method for making mostly are structure of bisphenol A greatly, and are comparatively more unfavorable than the employed method for making of the applicant with the influence of health for environment.

In aforementioned the 7th method for making, a copolyesters and a position phthalic acid are mixed, suppress forming the fish eyes phenomenon of gel, but, so can cause the fusion idiosome seriously to hang down and drip a phenomenon by the applicant's case verification.

Therefore, based on the understanding of above various technology, the applicant proposes multiple copolyesters, can have following several characteristics:

1. this copolyesters can present the behavior of non-Newtonian fluid, and low melt viscosity is arranged when high shear rate, and high melt viscosity is arranged when low shear rate.

2. this copolyesters and general purpose polyester relatively can be assigned capable fusion in lower temperature.

3. the fusion idiosome did not have to hang down and drips excessive phenomenon when this copolyesters was with extrusion processing; In fact, after squeezing out mold, present the vertical flow phenomenon of stable and uniform, do not have the excessive idiosome situation of uneven thickness up and down that causes that stretches.Especially when processing length surpasses 30 centimetres model object, more can manifest the advantage of these copolyesters.

4. the crystallization rate of this copolyesters is very slow, through squeezing out mold to making in the finished product, can not produce the crystallization albefaction, and therefore whole molded articles can present transparent and have good glossiness.Especially when processing length surpasses 30 centimetres molded articles, more can manifest the advantage of this copolyesters.

5. the molded articles smooth surface of this copolyesters does not produce the excessively crosslinked gelatin phenomenon that causes.

6. the molded articles of this copolyesters can be made the bottle of 2.0 liters of additional grip straight formings with business-like extrusion blow molding machine through reality.The smooth in appearance of this bottle has heigh clarity, and whole bottle thickness distribution is even, gel-free or infusible particle phenomenon, and the position moulding of bottle head bottle cap is good, and the jointing line of two leaf moulds is good about the bottle bottom, no buildup projection phenomenon; And fracture phenomena can not take place by the test of dropping of 1.2 meters height in the bottle that so makes.

7. when example is tested, find to select the special two alcohols of certain structure, can reduce the linking agent addition, even the present invention to obtain best effect be that the special two alcohols of choice structure needn't add linking agent again, can reach the character of non-Newtonian fluid, so can avoid adding linking agent and produce excessive interlinkage effect and cause gelatin phenomenon.

8. copolyesters of the present invention can utilize the tool sky, and decompression or rare gas element (as nitrogen) circulation in the temperature that is lower than the copolyesters fusing point, are carried out solid state polymerization down, improves intrinsic viscosity (Intrinsicviscosity is called for short IV).

(summary of the invention).

The present invention is for reaching the above object, so arrange a series of research, adds in the reactive system of dicarboxylic acid that terephthalic acid or its derivative that forms ester are formed and ethylene glycol:

(1). a spot of side chain agent such as trimellitic acid or trimellitic acid 1,2-anhydride or TriMethylolPropane(TMP); Perhaps, do not add the side chain agent.

(2). add two alcohols of some special construction, but produce and back segment processing feasibility and cost consideration for taking into account, preferably the addition of the two alcohols of control is in specified range.

The purpose of above-mentioned interpolation side chain agent is for making copolyesters can reach non-Newton fluid characteristic, promptly under high shear rate, low viscosity characteristics is arranged, and the high viscosity characteristic is arranged under low shear rate, so when the extrusion blow moulding, do not have the vertical serious problem of idiosome, therefore have good blown-moulding ability, and homogeneous about the thickness distribution of its idiosome.The applicant also finds two alcohols of selecting some structure special also can not reach above-mentioned effect even do not add above-mentioned side chain agent.Mention herein and avoid the vertical phenomenon of dripping of idiosome when processing long shaped article, must to be emphasized that more copolyesters of the present invention can be fit to produce 30 centimetres of idiosome length or longer object, do not have the serious phenomenon that causes uneven thickness of drawing down of idiosome.Though add the melt strength of side chain agent can raising idiosome, add can produce excessively crosslinked gelatin phenomenon when excessive, on shaped article, present the infusible particle of fish-eye shaped.Multiple prior art is can reduce gelatin phenomenon takes place; usually can cooperate interpolation monofunctional material to block agent as chain; though but example of the present invention test discovery interpolation monofunctional material can have the inhibition effect; but can cause rate of polymerization also partly to be suppressed; if addition is inappropriate and desire is held concurrently when reaching melt viscosity; it is yellow partially to run into color through regular meeting, so the present invention does not emphasize to add the monofunctional material.

The purpose of the two alcohols of above-mentioned interpolation is to make shaped article produce superior mechanical property, for example good shock-resistance; And two alcohols decapacitation of special construction are given outside the good shock-resistance, and can suppress crystallization rate, and idiosome can not produce the crystallization albinism in the extrusion processing process; Especially the easier idiosome bottom crystallization albinism that runs into when factory length surpasses 30 centimetres object.Copolyesters of the present invention can be fit to produce 30 centimetres of idiosome length or longer object, does not have idiosome and produces the crystallization albinism.In addition,, the copolyesters of making after two alcohols that the present invention selects add can cause fusing point to descend; So, continue when improving the manufacturing processed of viscosity, the temperature of reaction appropriateness of solid-state polymerization must be reduced to avoid taking place ester grain agglutinating problem with solid state polymerization.Again in addition,, to add two alcohols and can cause melt viscosity to descend, the temperature of therefore carrying out melt extruded also must goodness of fit reduce.Therefore, suppress effect, solid state polymerization feasibility and avoid melt viscosity to descend excessive and take into account manufacturing cost, so the present invention proposes special pair of alcohols of several interpolations and selects the copolyesters of suitable addition manufacturing for taking shock-resistance, crystallization rate into account.

Copolyesters of the present invention is to utilize general known polyester production facility and production stage to manufacture prepolymer, and it is the continous way or the groove time formula production method of initial reactant that this kind procedure for producing comprises with terephthalic acid or with dimethyl terephthalate (DMT) (DMT).Prepolymer with aforementioned gained carries out the intrinsic viscosity of solid state polymerization raising copolyesters to 0.8-1.4dl/g again; This invents the mode of production of used solid state polymerization a kind of is with groove time formula, under turning slot internal heating ester grain and environment, carry out in vacuum, another kind is with continous way, after experience crystallization of ester grain and the drying, feeds rare gas element (for example nitrogen) again and improve polymer viscosity in polymerization tank.

By above narration, the present invention proposes a kind of copolyesters, comprises to use following material to carry out ester conversion or transesterification:

(1). two carboxylic acid compositions that form by terephthalic acid or its derivative that forms ester in essence;

(2). the two pure unit of forming by ethylene glycol in essence; Add again in addition:

(3). at least a material that is selected from following each group:

(a) 2-ethyl-2-butyl-1, ammediol

(2-Butyl-2-Ethyl-1,3-Propanediol is hereinafter to be referred as BEPG), its chemical formula (1) is as follows:

(b) 3-methyl isophthalic acid, the 5-pentanediol

(3-Methyl-1,5-Pentanediol is hereinafter to be referred as MPG), its chemical formula (2) is as follows:

(c) 2,4-diethyl-1,5-pentanediol

(2,4-D-1,5-Pentanediol is hereinafter to be referred as DPG), its chemical formula (3) is as follows:

(d) 1-hydroxyl-2,2-dimethyl-propyl group-hydroxyl dimethyl acetonyl ester

(Hydroxypivalyl Hydroxypivalate is hereinafter to be referred as HPHP), its chemical formula (4) is as follows:

Its weight is 1 to 15 weight % based on the weight of whole copolyesters;

When making this copolyesters, perhaps, add again in addition again:

(4) at least a material that is selected from following each group is as cross linking agent:

(a) trimellitic acid

(b) trimellitic acid 1,2-anhydride

(c) TriMethylolPropane(TMP)

Its weight is 0 to 1.0 mole of % based on the weight of whole copolyesters; When the weight of its weight based on whole copolyesters, during greater than 0.25 mole of %, the molded article of copolyesters can produce tangible gelatin phenomenon, and the present invention's appropriateness is added phenylformic acid (Benzoic acid), and its scope is 0 to 1.0 mole of % based on whole copolyesters.But the best composition combination that must emphasize copolyesters of the present invention need not added the monofunctional material, to avoid melt polymerization speed to slow down and therefore to cause color and luster and other rerum natura variation.

Above initiator is carried out melt phase polycondensation close, form polyester prepolyer; Again this polyester prepolyer is carried out solid state polymerization.

Most preferred embodiment

Preferable copolyesters of the present invention consists essentially of dicarboxylic acid units and the essential diol units of being made up of ethylene glycol that essence is made up of terephthalic acid, and must further comprise at least a material that is selected from above-mentioned formula (1) to formula (4).

In some preferable copolyesters, consider copolymerization ease of manufacture and manufacturing cost, preferably select formula (1) and formula (2) for use; If only consider processing characteristics and molded article, can be selected from formula (1) arbitrary or wantonly two to the material of formula (4) arbitrarily, even the mixture of more material add.

Copolyesters of the present invention be necessary to comprise at least a be selected from that above-mentioned formula (1) to formula (4) formed respectively organize the unit; This is selected from formula (1) to the indivedual single ingredients substance of formula (4) or the mixture of polynary ingredients substance, and its content is 1 to 15 weight % based on the weight of copolyesters.

If the content of this element is lower than 1 weight %, the solid phase polymerization rates when then making copolyesters is with step-down.In addition, the fusing point of gained copolyesters will be too high, carry out extrusion blow when molded, and its operating time will increase.And its idiosome through the melt extruded gained very easily produces the crystallization albinism, especially more can run into this phenomenon when factory length surpasses 20 centimetres molded article.Again and, the molded article that is obtained thus, its shock-resistance is not good, when making hollow container, it is dropped to ground by eminence especially, and fracture phenomena very easily takes place.

If the content of this element is higher than 15 weight %, then the prepolymer fusing point of copolyesters descends excessive, can make polymer become amorphousness attitude (Amorphous State), when causing follow-up solid-phase polymerization, the sticking mutually work of prepolymer takes place easily, cause solid-phase polymerization to stablize and carry out, so can't improve the prepolymer intrinsic viscosity, moulding is bad when causing extrusion processing.

Copolyesters of the present invention comprises the material of the formula of being selected from (1) to formula (4), its content especially is preferably weight 1 to the 10 weight % based on copolyesters, when can making prepolymer carry out solid-phase polymerization, it can not be easy to sticking mutually work, so can guarantee the high productivity of solid-phase polymerization, and can obtain high intrinsic viscosity product.Gu and fusing point appropriateness descends, the solid-phase polymerization speed of prepolymer there is promoter action.In addition, institute in this special more suitable scope obtained have high intrinsic viscosity copolyesters and add man-hour, do not have the phenomenon that idiosome seriously hangs down droplet at compression moulding.Again in addition,, the mould process cycle of this copolyesters is suitable, can carry out stable production.The molded articles of gained has the favorable mechanical characteristic thus, especially has good shock-resistance.The copolyesters that the present invention will be obtained is especially thus made 2 liters of hollow containers with integrated handle, by height greater than dropping to ground at 1 meter, also unlikely generation fracture phenomena.

Copolyesters of the present invention, except above-mentioned terephthalic acid units, the ethylene glycol unit reaches and comprises that further at least a above-mentioned formula (1) that is selected from is to the unit of formula (4); When some particular cases, still can comprise a kind of also urstoff to formula (7) from formula (5); As if the production machine that this particular case is included in different labels carries out compression moulding processing, and some machinery equipment has higher requirement to the polymeric melt strength of melt.In addition, when making the molded articles that some shape is more special or volume is bigger, some need have higher melt strength, also will consider to add this urstoff.Under above-mentioned particular case, be selected from the urstoff of formula (5) to formula (7), its content is 0.05 to 1.0 mole of % based on the molal quantity of copolyesters.

If the content of this element is lower than 0.05 mole of %, then copolyesters is at some particular cases, and the type embryo that squeezes out when compression moulding has an excessive rule of hanging down and resembles.Especially when surpassing 20 centimetres molded article, factory length more can run into this phenomenon.

If the content of this element is higher than 0.25 mole of %, the gained copolyesters will produce excessive crosslinking structure and form gelatin phenomenon, and consequently all there is infusible particle on the type embryo that squeezes out when compression moulding and the surface of shaped article thereof, undermine the outward appearance of shaped article.This phenomenon is more obvious with the content increase of this element.The present invention also proposes to add a spot of monofunctional material for can solve this phenomenon, for example adds phenylformic acid, and it mainly act as the blockade crosslinking reaction, to avoid excessively crosslinked.But add the speed that excessive monofunctional material suppresses melt polymerization and solid state polymerization simultaneously by practical experience, this will cause the rerum natura of copolyesters and color and luster inferior.

The present invention takes into account the situation that is common to part special requirement melt strength, and can not take place excessively crosslinkedly, can take to add and is lower than 1.0 moles of % and is selected from a certain urstoff of formula (5) to formula (7), but not add the monofunctional material.And emphasize that again the present invention uses interpolation to be selected from the urstoff of formula (1) to formula (4), also can not reach non-Newton fluid characteristic even do not add the side chain agent.

Copolyesters of the present invention if necessary, remove aforementioned terephthalic acid units, the ethylene glycol unit reaches and further comprises at least a unit that is selected from above-mentioned formula (1) to formula (4), or comprise that more a kind of above-mentioned formula (5) that is selected from is to the unit of formula (7), Shang Kehe has based on entire infrastructure unit mole number, is lower than other difunctionality based compounds of 10 moles of %; For example, m-phthalic acid (Isophthalucacid), naphthalene dicarboxylic acids, propylene glycol and cyclohexanedimethanol etc.

Copolyesters intrinsic viscosity of the present invention (IV) has different viscosity requirements according to its employed molded pattern, when carrying out extrusion blow mold system with molding equipment, be preferably 0.8 to 1.4dl/g, if with physical strength, the productivity and the qualification rate of outward appearance and mouldings are seen, more are preferably 0.9 to 1.3dl/g.If the intrinsic viscosity of copolyesters is less than 0.8dl/g, formed molten state type embryo was obviously sagging when extrusion blow was molded, caused bad moulding and gained molded article to have low physical strength thus.

In addition, if the intrinsic viscosity of copolyesters is greater than 1.4dl/g, carrying out extrusion blow when molded, melt viscosity can be excessive, and the cycle of process for processing can be elongated, and production efficiency lowers, and causes the thermal crystalline effect obvious, and transparency is descended.On the other hand, because of too high intrinsic viscosity, also can cause blow-molded object bottom about two leaf mould jointing lines produce weld bond, influence the outward appearance of object.

Copolyesters of the present invention, its glass tansition temperature (Glass transition temperature is called for short Tg) is higher than more than 70 ℃, and molded article wherein takes out the back because remaining stress by mould in the time of therefore can avoiding blown-moulding, shrink phenomenon because of lax, influence the outward appearance of object.

Copolyesters of the present invention, after solid state polymerization raising intrinsic viscosity, its terminal carboxyl(group) (Carboxyl end group) content is lower than 30 microequivalents/g (μ equivalent ent/g), be preferably lower than 20 μ equivalent/gram, so avoid causing the fusion deterioration, its colour changed into yellow and produce shaggy phenomenon.

Copolyesters of the present invention, after solid state polymerization raising intrinsic viscosity, its copolyesters is analyzed degree of crystallinity with tubing string ladder densimetry, between 20 to 40%; If degree of crystallinity is lower than 20%, then the ester grain is easy to mutual bonding to each other, is unfavorable for carrying out solid state polymerization, and squeezes to add at back segment and be difficult for carrying out drying man-hour.If degree of crystallinity is higher than 40%, then the ester grain is difficult for dissolving, and when extrusion processing, extruding machine has the overweight problem of load.The outward appearance that can find on some separately extrusion machining equipments not fusant appearance is arranged and influence object.The degree of crystallinity of copolyesters of the present invention is preferably between 25 to 35% most.

Copolyesters of the present invention, after solid state polymerization raising intrinsic viscosity, with elementary errors scanning calorimeter (Differential Scanning Calometrics, be called for short DSC) analyze, its fusing point is between 225 ℃ to 240 ℃, its cold crystallization temperature is lower than below 150 ℃, even does not have the crest appearance of cold crystallization temperature.

Copolyesters of the present invention, production stability with extrusion blow when molded, the uniformity coefficient of molded article, physical strength, and productivity see, when being higher than the temperature of 40 ℃ of copolyesters fusing points, its melt flow index (Melt flow rate, be called for short MFR) be 1.0 to 10.0g/10min, more be preferably 2.0 to 7.0g/10min.

Copolyesters of the present invention, its manufacture method process is as follows:

(1) in reactor, adds following material, and carry out esterification;

(a) terephthalic acid or derivatives thereof

(b) ethylene glycol

(c) at least a material that is selected from formula (1) to formula (4), or (d) a kind of material that is selected from formula (5) to formula (7), or (e) phenylformic acid

Wherein (ethylene glycol): the initial metering mole ratio of (terephthalic acid) is between 1.1 to 1.6; (c) the initial metering content of material based on the weight of copolyesters between 1 to 15 weight %; (d) the initial metering content of material based on the mole number of copolyesters between 0 to 1.0 mole of %; (e) the initial metering content of material based on the mole number of copolyesters between 0 to 0.5 mole of %.

The temperature of esterification is between 220 to 260 ℃, esterification pressure between normal pressure to 2.0kg/cm ², carry out water and the alcohols that generates to be distilled out in the process.Proceed to transformation efficiency between 95 to 98% o'clock in esterification, promptly finish esterification and enter the prepolymerization step of reaction; Must add catalyst before finishing esterification, the copolyesters of this invention can use antimony acetate or ANTIMONY TRIOXIDE SB 203 99.8 PCT or germanium dioxide or above mixed form as catalyst.Must add stablizer, for example phosphoric acid, phosphorous acid, trimethylammonium base phosphoric acid ester, the stupid ester of tricresyl phosphate, triethyl phosphate etc. in addition; Add in addition colorant again, for example Cobaltous diacetate etc.

(2) carry out the melt phase condensation reaction: be divided into prepolymerization reaction and main polyreaction, be lower than under the high vacuum of 1mmHg, carry out polycondensation reaction, polymeric intrinsic viscosity is increased to 0.5 to 0.7dl/g, unloads polymer in refrigerated water again and be cut into columned ester grain (Chip).

(3) carry out solid-phase polymerization: with above-mentioned polyester ester grain through condensation polymerization reaction gained, carry out drying and crystallization being lower than under 180 ℃ the temperature, when the outward appearance of polyester ester grain becomes White-opalescent by original transparent lens, representative has produced crystallization, again this ester grain temperature is increased to 180 to 240 ℃ and carries out solid-phase polymerization, reach required target value until intrinsic viscosity and MFR index.

When carrying out solid-phase polymerization, when drying, crystallization and polymerization, preferably use cylinder mode or alr mode or gaseous fluid bed mode to make polyester slice can constantly continue to bond together to avoid causing mutually moving.In the solid-phase polymerization process, must carry out in vacuum or under rare gas element round-robin environment.The solid phase complex reaction temperature of copolyesters of the present invention is generally carried out under 180 to 240 ℃ more fortunately, is preferably 200 to 220 ℃ and carries out; If be bonded as mutually and mainly consider a little between section avoiding, suggestion is set in the temperature of solid state polymerization and is lower than at least 15 ℃ of copolyesters fusing points, and the more conservative practice is for being lower than at least 20 ℃ of copolyesters fusing points.

Copolyesters of the present invention can be made under short period of time and high yield with the aforesaid practice and finish.

Copolyesters of the present invention has good molded performance, can be molded by extrusion blow, penetrate compression moulding, compression moulding or penetrate method of moulding such as molded and manufacture various different shapeies, the molded articles of different volumes.Object by this molded program gained can be with good productivity and produce stably have good size precision, not fusant or gel, good heat resistance and height shock-resistance do not take place in high degree of transparency, smooth surface.Copolyesters of the present invention adds man-hour with melt extruded, and its melt temperature can be set than low 20 to 30 ℃ of SILVER REAGENT polyester, infusible phenomenon can not take place.Copolyesters of the present invention is specially adapted to make hollow container with the melt extruded blown-moulding, utilize this mode to add man-hour, copolyesters of the present invention can represent to be stablized suitable hanging down and drips a characteristic, drip a time dimension and be held in the proper range so hang down, and a bottle embryo has uniform diameter.In addition, the hollow container of manufacturing has good size precision, high degree of transparency, smooth surface not fusant or gel, good heat resistance and height shock-resistance does not take place thus, when factory length surpasses 30 centimetres hollow container, can not meet with especially as the phenomenon of crystallization albefaction is arranged with the object of melt extruded processing and manufacturing with the SILVER REAGENT polyester.What the present invention especially need emphasize is, this copolyesters can create two liters of internal volumes, length is above 30 centimetres, and copolyesters can create two liters of internal volumes, length is above 30 centimetres, and directly process the hollow container that blowing goes out to possess handle shapes, fracture phenomena can not take place by highly dropping test by 1.2 meters in the hollow container that makes thus.

When copolyesters of the present invention utilizes the melt extruded blown-moulding, consider the viewpoint of moldability and fusing point, preferably melt temperature is set in the scope of (fusing point of copolyesters+10 ℃) to (molten point+50 of copolyesters ℃).

The forming composition of copolyesters of the present invention can be Any shape, there is no specific limited, for example can be hollow object, pipe, dish, sheet, film etc.

Copolyesters of the present invention also can be applicable to that known multilayer cascode goes out (Co-Injection) or multilayer extrudes the internal layer or the skin of (Co-Extrusion) altogether.

Copolyesters of the present invention also can be according to need mixes use with general known additive such as dyestuff, pigment stabiliser, static inhibitor, fire retardant, lubrication prescription, inorganic filler etc.; Also available other known resin and copolyesters of the present invention normal and that the SILVER REAGENT polyester mixes mix.

(embodiment)

Copolymerization fat of the present invention can be confirmed in following some embodiment, but must be explanation the present invention by the employed embodiment of statement, but and unrestricted this invention.In the following example and the comparative example, the physical properties of its polyester (containing copolyesters and equal polyester) and the effect analysis of chemical property and molded and shaped object are undertaken by following method.

(1) intrinsic viscosity of polyester (IV):

, under 25 ℃, measure with Ubelohde viscometer (platform system) with the mixed solvent of phenol and 3: 2 weight ratio of tetrachloroethane.

(2) melt flow rate of polyester (MFR):

With melting index instrumentation amount (the smart machine manufacturing of Japan).Its metering system carries out according to the method for ASTM D1238.The polyester that desire is measured in all inserting 150 ℃ vacuum drying oven earlier 4 hours.With 270 ℃ of fusions, under the load of 2160 grams, extrude the die orifice of diameter 2.1mm again, measure its discharge rate (g/10min).

(3) the terminal hydroxyl content of polyester:

The polyester that takes by weighing 0.5 to 0.6 gram adds 50 milliliters oil of mirbane, be heated to 180 ℃ of dissolvings after, be cooled to 80 ℃, add 20 milliliters isopropanol (weight ratio 9: 1), titrating with the KOH of 0.01N; Calculate the acid value number of μ equivalent/gram.

(4) the glass tansition temperature (Tg) of polyester and melt temperature (Tm):

Analyze with elementary errors scanning calorimeter (type is the DSC-7 that Perkin-Elmer makes), the ester grain is earlier through 80 ℃, and after 2 hours the vacuum-drying, quick cooling after 300 ℃ of fusions is carried out the thermal properties analysis with the saturating rate of the intensification of 20 ℃/min again.

(5) cold crystallization temperature of polyester (Tcc):

With (4) Analytical equipment, the ester grain carries out the thermal properties analysis with the rate of temperature fall of 10 ℃/min after 280 ℃ of fusions.

(6) measurement of degree of crystallinity: with tetracol phenixin (CCl ₄) and after normal heptane (n-heptane) is deployed into solution, be poured in the density gradient tubing string,

Ester grain (final product) is inserted in the tubing string, and the position that is stopped by the ester grain its density that converts is calculated degree of crystallinity according to following formula again.

χc(％)＝(dc(d-da)/d(dc-da)}×100

Da represents the density of complete amorphous polyester, and its value is 1.335; Dc represents the density of complete crystal form polyester, and its value is 1.501.

(7) rheological property analysis: with capillary rheometer analysis (label: Gottfert); The polyester grain is earlier through 150 ℃, after 4 hours the vacuum-drying, on rheometer with 270 ℃ of fusions, if the SILVER REAGENT polyester is analyzed the interdependence of melt viscosity to shearing rate then with (fusing point+40 ℃) fusion.

(8) anti-the falling property analysis of slush molding object: the hollow container by extrusion blow is made, be positioned over room temperature after following 24 hours, be full of water and with the bottleneck sealing, vertically fall on the concrete floor by 1.2 meters height again, the bottom is contacted with the floor.Repeat above-mentioned test 5 times with identical bottle, the gained result is according to following table 1 listed criterion evaluation.

Table 1

The shock-resistance evaluation criteria of bottle

◎ (excellent): by testing the back leakless more than three times or splitting

Zero (very): first and second time tested leakless or split, but finds the crack or split in test for the third time

△ (bottom line): test leakless or split the first time, but testing with existing crack for the second time or splitting

* (bad): the crack takes place when testing or splits in the first time

(9) the gelatin phenomenon analysis of slush molding article surface: by the hollow container that extrusion blow is made, by the fish-eye shaped numbers of particles of calculated for gel in the areal extent of body position 10cm * 10cm, the gained result is according to following table 2 listed criterion evaluations.

Table 2

The gelatin phenomenon evaluation criteria of bottle

◎ (excellent): occur below 1 in the areal extent of 10cm * 10cm

Occur below 3 in the areal extent of zero (very): 10cm * 10cm

△ (bottom line): occur below 5 in the areal extent of 10cm * 10cm

Occur more than 5 in the areal extent of * (bad): 10cm * 10cm

(10) transparency of slush molding object assessment:

The assessment of transparency is directly to judge with naked eyes, is standard as following table 3:

Table 3

◎ (excellent): with naked eyes direct-view, tool heigh clarity and glossiness

Zero (very): with naked eyes direct-views, the tool transparency but a little less than the glossiness

△ (bottom line): with naked eyes direct-views, the tool transparency but low in glossiness

* (bad): bottle produces opaque or the partial crystallization albinism is arranged

(11) body thickness distribution assessment:

The thickness analyser (Hall EffectDigital Thickness Gage) that uses US business Pu Namei (PANAETRIC) company to make is analyzed the thickness of body top and fixed position, bottom, with its thickness difference as assessment body thick standard, its standard row in table 4:

Table 4

◎ (excellent): thickness difference is lower than 0.1mm up and down

Zero (common): thickness difference 0.1 is to 0.2mm up and down

△ (bottom line): thickness difference 0.2 is to 0.25mm up and down

* (bad): thickness difference is greater than 0.25mm up and down

(embodiment 1)

(1) get the terephthalic acid of 100 weight parts, the 2-ethyl-2-butyl-1 of the ethylene glycol of 57.48 weight parts and 7.29 weight parts, ammediol (BEPG, formula (1)) is made slurries.

In slurries, add the antimony acetate of 0.4 weight part, 0.01 part Cobaltous diacetate, 0.01 part phosphoric acid.At absolute pressure 1.0Kg/cm ²Down slurries are heated to 260 ℃, carry out esterification, reach more than 95% to ester conversion rate; Continuing to vacuumize to make to press in the reactor reduces to below the 1mmHg, and carries out first section polycondensation reaction 270 ℃ of temperature of reaction, follow-uply makes prepolymer to carry out second section polycondensation reaction under 280 ℃ of higher vacuum tightness and the temperature again.Prepolymer is cut into cylindric ester grain.Be fixing time of polyreaction, and the intrinsic viscosity of prepolymer is dropped in 0.6 to the 0.63dl/g scope as far as possible.

The prepolymer section that obtains above was carried out drying and crystallization 6 hours being lower than earlier under 180 ℃ the temperature, continuing is heated to 215 ℃ with polyester slice under the vacuum of 1.5mmHg, continued to carry out 40 hours, manufactures final copolyesters.

(2) copolyesters of gained in above-mentioned (1) is analyzed its DEG content respectively, melt flow rate, Tg, Tm, Tcc, acid value and degree of crystallinity; Every analytical results row in table 6.

(3) copolyesters with gained is molded as bottle by extrusion blow moulding press extrusion blow; The design content of this kind bottle is long-pending to be 2000 milliliters, and directly the pattern that contains handle is made in blowing

The gained bottle is assessed its effect with preceding method, and every quality project evaluation be the results are shown in table 10.

(embodiment 2)

Repeat embodiment 1, but solid state polymerization time ratio embodiment 1 increases by 10 hours, to improve its melt strength.The copolyesters of gained repeats the analytical procedure among the embodiment 1; Every analytical results row in table 6.The gained bottle is assessed its effect with preceding method, and with every quality project evaluation result row in table 10.

(embodiment 3 to 5)

Repeat embodiment 1, but add the trimellitic acid 1,2-anhydride of part different content respectively, to improve its melt strength.The copolyesters of gained repeats the analytical procedure among the embodiment 1; Every analytical results is listed in table 6.The gained bottle is assessed its effect with preceding method, and every quality project evaluation be the results are shown in table 10.

(embodiment 6 and 7)

Repeat embodiment 1, but add the trimellitic acid 1,2-anhydride of part content respectively, other is the phenylformic acid of Extra Section different content again, to suppress gelatin phenomenon.The copolyesters of gained repeats the analytical procedure among the embodiment 1; Every analytical results is listed in table 7.The gained bottle is assessed its effect with preceding method, and every quality project evaluation be the results are shown in table 10.

(embodiment 8 and 9)

Repeat embodiment 1, but add the TriMethylolPropane(TMP) of part content respectively, embodiment 9 is the phenylformic acid of Extra Section different content more in addition, to suppress gelatin phenomenon.The copolyesters of gained repeats the analytical procedure among the embodiment 1; Every analytical results row in table 7.The gained bottle is assessed its effect with preceding method, and every quality project evaluation be the results are shown in table 10.

(embodiment 10 and 11)

Repeat embodiment 1, but with the 3-methyl isophthalic acid, the 5-pentanediol replaces 2-ethyl-2-butyl-1, ammediol; Embodiment 11 adds the trimellitic acid 1,2-anhydride of part content in addition, and the copolyesters of gained repeats the analytical procedure among the embodiment 1; Every analytical results is listed in table 7 and 8.The gained bottle is assessed its effect with preceding method, and every quality project evaluation be the results are shown in table 10.

(embodiment 12 and 13)

Repeat embodiment 1, but with 2,4-diethyl-1, the 5-pentanediol replaces aforesaid pair of alcohols modification agent; Embodiment 13 adds the trimellitic acid 1,2-anhydride of part content in addition, and the copolyesters of gained repeats the analytical procedure among the embodiment 1; Every analytical results is listed in table 8.The gained bottle is assessed its effect with preceding method, and every quality project evaluation be the results are shown in table 10.

(embodiment 14)

Repeat embodiment 1, but with 1-hydroxyl-2,2-dimethyl-propyl group-hydroxyl pivalyl ester replaces aforesaid pair of alcohols modification agent; The copolyesters of gained repeats the analytical procedure among the embodiment 1; Every analytical results row in table 8.The gained bottle is assessed its effect with preceding method, and with every quality project evaluation result row in table 10.

(comparative example 1)

Carry out reaction with the ethylene glycol of the m-phthalic acid of the terephthalic acid of 97 weight parts and 3 weight parts and 57.48 weight parts, but its solid state polymerization carries out according to the listed condition of table 9 as embodiment 1.Every analytical results is listed in table 8.The gained bottle is assessed its effect with preceding method, and every quality project evaluation be the results are shown in table 10.

(comparative example 2)

Carry out reaction with the ethylene glycol of the terephthalic acid of 100 weight parts and 57.48 weight parts as comparative example 1, but the trimellitic acid 1,2-anhydride of Extra Section content again, to improve its melt strength.Every analytical results is listed in table 8.The gained bottle is assessed its effect with preceding method, and every quality project evaluation be the results are shown in table 10.

(comparative example 3 and 4)

Carry out reaction with the ethylene glycol of the m-phthalic acid of the terephthalic acid of 97 weight parts and 3 weight parts and 57.48 weight parts as comparative example 1, but the different trimellitic acid 1,2-anhydride of Extra Section content again, to improve its melt strength.Every analytical results is listed in table 8.The gained bottle is assessed its effect with preceding method, and every quality project evaluation be the results are shown in table 10.

(comparative example 5)

Carry out reaction with the ethylene glycol of the terephthalic acid of 100 weight parts and 57.48 weight parts as comparative example 1, the trimellitic acid 1,2-anhydride of Extra Section content again, again again the phenylformic acid of Extra Section content to suppress its gelatin phenomenon.Every analytical results is listed in table 8.The gained bottle is assessed its effect with preceding method, and every quality project evaluation be the results are shown in table 10.

(comparative example 6)

Carry out reaction as comparative example 1, the 1,4 cyclohexane dimethanol of Extra Section content again with the ethylene glycol of the terephthalic acid of 100 weight parts and 57.48 weight parts.Every analytical results is listed in table 8.The gained bottle is assessed its effect with preceding method, and every quality project evaluation be the results are shown in table 10.

The employed compound code of the above embodiments and comparative example is shown in following table 5.

Table 5

The BA phenylformic acid

BEPG 2-ethyl-2-butyl-1, ammediol

1, the 4-CHDM 1,4 cyclohexane dimethanol

DPG 2,4-diethyl-1,5-pentanediol

EG ethylene glycol

HPHP 1-hydroxyl-2,2-dimethyl-propyl group-hydroxyl pivalyl ester

The IPA m-phthalic acid

MPG 3-methyl isophthalic acid, the 5-pentanediol

The PTA pure terephthalic acid (PTA)

The inclined to one side terephthalic acid of TMA

The TMP TriMethylolPropane(TMP)

Table 6

Embodiment		Unit	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5
								Initial composition	Dicarboxylic acid units	Weight part	PTA 100	PTA 100	PTA 100	PTA 100	PTA 100
Ethylene glycol	Weight part	EG 57.48	EG 57.48	EG 57.48	EG 57.48	EG 57.48
							Be selected from formula (1) to formula (4) unit		Composition weight part (weight part %)	BEPG 7.29 (6％)	BEPG 7.29 (6％)	BBPG 7.29 (6％)	BEPG 7.29 (6％)	BEPG 7.29 (6％)
Be selected from formula (5) to formula (7) unit	Composition weight part (mole %)	0	0	TMA 0.0363 (0.03％)	TMA 0.0729 (0.06％)	TMA 0.0145 (0.13％)
							The monofunctional material		Composition weight part (mole %)	0	0	0	0	0
The prepolymer intrinsic viscosity		dl/g	0.615	0.610	0.611	0.623									0.628
							Solid state polymerization vacuum tightness/temperature/time		The holder ℃/hr	1.5 hold in the palm 215 ℃/40hr	1.5 hold in the palm 215 ℃/50hr	1.5 hold in the palm 215 ℃/50hr	1.5 hold in the palm 215 ℃/50hr	1.5 hold in the palm 215 ℃/50hr
The polyester intrinsic viscosity		dl/g	0.95	1.10	1.15	1.28									1.25
							Polyester DEF content		mol％	2.11	2.24	2.30	2.47	2.35
Polyester MFR		g/10min	8.8	5.5	5.3	7.1									3.17
							Polyester Tg		℃	75.6	76.0	74.5	74.8	74.1
Polyester Tm		℃	230	230	230	230									230
							Polyester Tcc		℃	Do not have	Do not have	Do not have	Do not have	Do not have
Polyester acid value number		μ equivalent/gram	15	11	13	9									11
							Ester crystalline polyimide degree		％	25％	28％	29％	32％	29％

Table 7

Embodiment		Unit	Embodiment 6	Embodiment 7	Embodiment 8	Embodiment 9	Embodiment 10
								Initial composition	Dicarboxylic acid units	Weight part	PTA 100	PTA 100	PTA 100	PTA 100	PTA 100
Ethylene glycol	Weight part	EG 57.48	EG 57.48	EG 57.48	EG 57.48	EG 57.48
							Be selected from formula (1) to formula (4) unit		Composition weight part (weight part %)	BEPG 7.29 (6％)	BEPG 7.29 (6％)	BEPG 7.29 (6％)	BEPG 7.29 (6％)	BEPG 7.29 (6％)
Be selected from formula (5) to formula (7) unit	Composition weight part (mole %)	TMA 0.289 (0.25％)	TMA 0.289 (0.25％)	TMP 0.180	TMP 0.180	0
							The monofunctional material		Composition weight part (mole %)	BA 0.184 (0.25％)	BA 0.368 (0.50％)	0	BA 0.284	0
The prepolymer intrinsic viscosity		dl/g	0.635	0.590	0.610	0.612									0.595
							Solid state polymerization vacuum tightness/temperature/time		The holder ℃/hr	1.5 hold in the palm 215 ℃/50hr	1.5 hold in the palm 215 ℃/50hr	1.5 hold in the palm 215 ℃/50hr	1.5 hold in the palm 215 ℃/50hr	1.5 hold in the palm 215 ℃/50hr
The polyester intrinsic viscosity		dl/g	1.38	1.07	1.00	0.98									1.05
							Polyester DEF content		mol％	2.51	2.40	2.37	2.41	2.35
Polyester MFR		g/10min	1.6	2.0	7.0	7.5									10.0
							Polyester Tg		℃	73.8	73.6	73.9	74.0	72.0
Polyester Tm		℃	230	230	230	230									235
							Polyester Tcc		℃	Do not have	Do not have	Do not have	Do not have	150
The polyester acid value is applied		μ equivalent/gram	8	13	16	15									11
							Ester crystalline polyimide degree		％	34％	32％	31％	29％	43％

Table 8

Embodiment		Unit	Embodiment 11	Embodiment 12	Embodiment 13	Embodiment 14
							Initial composition	Dicarboxylic acid units	Weight part	PTA 100	PTA 100	PTA 100	PTA 100
Ethylene glycol	Weight part	EG 57.48	EG 57.48	EG 57.48	EG 57.48
						Be selected from formula (1) to formula (4) unit		Composition weight part (weight part %)	BEPG 7.29 (6％)	BEPG 7.29 (6％)	BEPG 7.29 (6％)	BEPG 7.29 (6％)
Be selected from formula (5) to formula (7) unit	Composition weight part (mole %)	TMA 0.0729 (0.06％)	0	TMA 0.0729 (0.06％)	0
						The monofunctional material		Composition weight part (mole %)	0	0	0	0
The prepolymer intrinsic viscosity		dl/g	0.605	0.601	0.612								0.592
						Solid state polymerization vacuum tightness/temperature/time		The holder ℃/hr	1.5 hold in the palm 215 ℃/50hr	1.5 hold in the palm 215 ℃/50hr	1.5 hold in the palm 215 ℃/50hr	1.5 hold in the palm 215 ℃/50hr
The polyester intrinsic viscosity		dl/g	1.10	1.09	1.12								1.06
						Polyester DEF content		mol％	2.40	2.43	2.45	2.21
Polyester MFR		g/10min	4.8	10.5	5.8								9.5
						Polyester Tg		℃	72.0	72.5	72.5	70.2
Polyester Tm		℃	235	233	233								225
						Polyester Tcc		℃	150	145	145	Do not have
Polyester acid value number		μ equivalent/gram	13	13	12								15
						Ester crystalline polyimide degree		％	41％	38％	35％	20％

Table 9

Embodiment		Unit	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5	Comparative example 6
									Initial composition	Dicarboxylic acid units	Weight part	PTA/IPA 97/3	PTA 100	PTA/IPA 97/3	PTA/IPA 97/3	PrA 100	PTA 100
Ethylene glycol	Weight part	EG 57.43	EG 57.48	EG 57.48	EG 57.48	EG 57.48	EG 57.48
								Special pair of alcohols modification agent		Composition weight part (weight part %)	0	0	0	0	0	CHDM 4.34 (3.75％)
The interlinkage modification agent	Composition weight part (mole %)	0	TMA 0.289 (0.25％)	TMA 0.289 (0.25％)	TMA 0.145 (0.125％)	TMA 0.289 (0.25％)	0
								The monofunctional material		Composition weight part (mole %)	0	0	0	0	BA 0.184 (0.25％)	0
The prepolymer intrinsic viscosity		dl/g	0.635	0.620	0.631	0.620	0.625										0.640
								Solid state polymerization vacuum tightness/temperature/time		The holder ℃/hr	1.5 hold in the palm 225 ℃/40hr	1.5 hold in the palm 225 ℃/50hr	1.5 hold in the palm 225 ℃/50hr	1.5 hold in the palm 225 ℃/50hr	1.5 hold in the palm 225 ℃/50hr	1.5 hold in the palm 215 ℃/50hr
The polyester intrinsic viscosity		dl/g	1.09	1.21	1.386	1.10	0.95										1.05
								Polyester DEF content		mol％	2.5	2.47	2.45	2.52	2.44	2.1
Polyester MFR		g/10min	11*	1.6*	3.8*	5.6*	10.1*										13.1*
								Polyester Tg		℃	78.0	76.5	75.3	75.0	76.2	82
Polyester Tm		℃	242	242	240	240	241										237
								Polyester Tcc		℃	170	172	178	175	170	Do not have
Polyester acid value number		μ equivalent/gram	15	9	9	14	13										15
								Ester crystalline polyimide degree		％	55％	55％	55％	55％	55％	40％

Remarks: *: carry out fusion test with 280 ℃.

Table 10

Embodiment/comparative example	The blown-mold result of melt extruded
								The bottle embryo hangs down and drips tendency	The bottle thickness distribution	The bottle transparency	Bottle seam situation	The bottle gelatin phenomenon	The bottle shock-resistance
Embodiment 1	Big slightly	○	◎	Good	◎	◎
							Embodiment 2	Suitably	◎	◎	Good	◎	◎
Embodiment 3	Suitably	◎	◎	Good	◎	◎
							Embodiment 4	Suitably	◎	◎	Good	◎	○
Embodiment 5	Suitably	◎	○	Good	○	○
							Embodiment 6	Too small	◎	○	The seam dimpling	×	△
Embodiment 7	Too small	◎	○	The seam dimpling	△	△
							Embodiment 8	Suitably	◎	○	Good	×	△
Embodiment 9	Suitably	◎	○	Good	×	△
							Embodiment 10	Big slightly	◎	◎	Good	◎	◎
Embodiment 11	Suitably	◎	◎	Good	○	○
							Embodiment 12	Big slightly	◎	◎	Good	◎	◎
Embodiment 13	Suitably	◎	◎	Good	○	△
							Embodiment 14	Suitably	○	◎	Good	◎	◎
Comparative example 1	Excessive	×	×	Good	◎	×
							Comparative example 2	Too small	◎	×	The seam dimpling	×	×
Comparative example 3	Too small	◎	×	The seam dimpling	×	×
							Comparative example 4	Suitably	◎	×	Good	△	×
Comparative example 5	Big slightly	×	×	Good	×	×
							Comparative example 6	Excessive	×	◎	Good	◎	◎

By the result of table 6 to table 10, embodiment 1 to 9 adds 2-ethyl-2-butyl-1, ammediol, embodiment 10 and 11 adds the 3-methyl isophthalic acid, the 5-pentanediol, and embodiment 12 and 13 adds 2,4-diethyl-1, the 5-pentanediol, embodiment 14 adds 1-hydroxyl-2,2-dimethyl-propyl group-hydroxyl pivalyl ester; Its consumption has good molding effect all within the scope of the invention; Especially embodiment 1 to 5, and embodiment 10 to 12 and embodiment 14 more show superior processing effect and good molded article performance.But embodiment 6 and 7 because of too high cross-linking effect causes excessive melt strength, cause the finished product jointing line protruding phenomenon to occur, and gelatin phenomenon are obvious.Embodiment 8 and 9 produces tangible gelatin phenomenon, shows to still have too high cross-linking effect.

On the other hand, by comparative example 1 to 5, only general PET is improved viscosity or only adds linking agent or the monofunctional material, or comparative example 6 is to add 1 in addition, the 4-cyclohexanedimethanol carries out upgrading, all can't make molded articles, if make finished product, its finished product shock-resistance deficiency or bad order reluctantly so that extrusion blow is stable.

Claims (7)

1. copolyesters that is applicable to extrusion processing comprises:

(1). two carboxylic acid compositions that form by terephthalic acid or its derivative that forms ester in essence, or add the m-phthalic acid or the naphthalene dicarboxylic acids of part content in addition again; And

(2). the two pure unit of forming by ethylene glycol in essence; And add again in addition:

(3). at least a material that is selected from following each group, its content range is 1 to 15 weight % based on copolyesters weight:

(a) 2-ethyl-2-butyl-1, ammediol (BEPG), its chemical formula (1) is as follows:

(b) 3-methyl isophthalic acid, 5-pentanediol (MPG), its chemical formula (2) is as follows:

(c) 2,4-diethyl-1,5-pentanediol (DPG), its chemical formula (3) is as follows:

(d) 1-hydroxyl-2,2-dimethyl-propyl group-hydroxyl pivalyl ester (HPHP), its chemical formula

(4) as follows:

Perhaps, add again:

(4) at least a material that is selected from down group is as cross linking agent, and its content range is 0 to 1 mole of % based on the copolyesters mole number:

(a) trimellitic acid (chemical formula (5))

(b) trimellitic acid 1,2-anhydride (chemical formula (6))

(c) TriMethylolPropane(TMP) (chemical formula (7))

Perhaps, and again add part content in addition again

(5) phenylformic acid,

The intrinsic viscosity of wherein said copolyesters is 0.8 to 1.4dl/g.

2. the copolyesters that is applicable to extrusion processing according to claim 1 wherein is selected from formula (1) to a kind of material of formula (4) or the mixture of multiple material, and its content range is 1 to 10 weight % based on the weight of copolyesters.

3. the copolyesters that is applicable to extrusion processing according to claim 1, the wherein at least a material that is selected from formula (5) to formula (7), its content range are 0 to 0.25 mole of % based on the copolyesters mole number, perhaps even do not add this element material.

4. the copolyesters that is applicable to extrusion processing according to claim 1 wherein no longer adds phenylformic acid.

5. the copolyesters that is applicable to extrusion processing according to claim 1 wherein adds m-phthalic acid or naphthalene dicarboxylic acids again, and its content range is not higher than 10 moles of % based on the copolyesters mole number.

6. the copolyesters that is applicable to extrusion processing according to claim 1 is to make molding substance for compression moulding.

7. the copolyesters that is applicable to extrusion processing according to claim 1 is to make hollow object for extrusion blow.