CN108473622A

CN108473622A - Pipeline including syndiotactic polypropylene

Info

Publication number: CN108473622A
Application number: CN201780005805.7A
Authority: CN
Inventors: C.布维; O.洛斯特
Original assignee: Total Petrochemicals Research Feluy SA
Current assignee: Total Petrochemicals Research Feluy SA; TotalEnergies One Tech Belgium SA
Priority date: 2016-01-13
Filing date: 2017-01-11
Publication date: 2018-08-31
Also published as: KR20180102577A; WO2017121756A1; JP2019503417A

Abstract

The present invention relates to pipelines comprising composition, the composition include at least one syndiotactic polypropylene of at least 50% weight of the total weight based on the composition；Wherein described at least one syndiotactic polypropylene have such as via¹³At least 70% syndiotactic index that C NMR spectroscopies measure；The melting temperature peak higher than 145 DEG C is not presented for the wherein described syndiotactic polypropylene, as measured by differential scanning calorimetry.The invention further relates to the technique for being used to prepare the pipeline and the purposes of the pipeline.

Description

Pipeline including syndiotactic polypropylene

Technical field

The present invention relates to the pipelines including acrylic resin；Preferably, include the pipeline of syndiotactic polypropylene resin.

Background technology

Polymer material is commonly used for manufacture and is suitable for various purposes (for example, period fluid can be pressurized and can have The fluid conveying of the temperature (up to 70 DEG C) of variation, that is, the conveying of liquid or gas such as water or natural gas) pipeline. These pipelines are usually prepared by polyolefin such as polyethylene and polypropylene.Due to involved high temperature, managed made of polyolefin Road has particular/special requirement.

Good heat resistance of the polypropylene compared with other polyolefin is special for the application of such as pipeline and pressure pipeline Useful.Pressure pipeline resin needs and high anti-slow crack growth and resistance to rapid crack autgmentability (impact flexibility) group The high rigidity (stiffness) (creep rupture strength) closed.All three major type of polypropylene, that is, homopolymers are randomly total to Polymers and block copolymer have been used to manufacture pipeline.

According to standard DIN 8078, the pipeline that is made up of polypropylene must satisfy destroys it under 95 DEG C and 3.5MPa pressure Preceding requirement at least 1000 hours.A kind of trial for meeting these requirements always is raising for the poly- of such pressure pipeline The rigidity (rigidity) of compositions of olefines.However, the reduction that rigidity occasionally results in anti-slow crack growth (SCGR) is improved, So as to cause brittle break earlier and therefore also there is negative effect to minimum desired strength (MRS) grade.In this way, pressure pipe Road is also flexible lower and lower.It is expected that it is the processability of pipeline material, stretching die to improve or remain high-caliber other properties Amount, short-term and chronic stress tolerance and shock feature.

Therefore, there is still a need for " as flexible as possible " polypropylene pipe that manufacture is following：It can be subjected to high pressure for a long time Power, while meeting the processability of existing standard, the standard of anti-slow crack growth and impact flexibility.The purpose that the present invention hides It is to provide following flexible duct：It can be subjected to high pressure for a long time, while meeting the processability of existing standard, resisting and split at a slow speed The standard of line growth property and impact flexibility.

Invention content

The present inventor surprisingly it has been found that, the one or more of object above can be come by using syndiotactic polypropylene It manufactures pipeline and realizes.

According in a first aspect, the present invention provides pipeline comprising composition, wherein the composition includes that syndiotaxy is poly- Propylene, wherein the syndiotactic polypropylene have such as via¹³At least 70% syndiotaxy of C-NMR spectroscopy measurements refers to Number；The melting temperature peak higher than 145 DEG C is not presented for the wherein described syndiotactic polypropylene, is such as surveyed by differential scanning calorimetry Fixed.¹³C-NMR is analyzed as follows in text described in a specific embodiment to carry out like that.Present inventors have demonstrated that being wanted Ask the pipeline of protection more flexible than prior art pipeline meanwhile, it is capable to be subjected to high stress for a long time, and at the same time, meet plus The existing standard of work, anti-slow crack growth and impact resistance.

Preferably, the present invention provides pipeline comprising composition, the composition include at least one syndiotaxy poly- third Alkene, wherein the composition include at least 80% weight of the total weight based on the composition it is described it is at least one between with vertical Structure polypropylene；Wherein described at least one syndiotactic polypropylene has as used¹³At least the 70% of C-NMR spectroscopy measurements Syndiotactic index；The melting temperature peak higher than 145 DEG C is not presented for the wherein described syndiotactic polypropylene, is such as swept by differential Retouch calorimetric determination.

According to second aspect, present invention also contemplates that the technique for manufacturing the pipeline according to first aspect comprising as follows Step：

(a) syndiotactic polypropylene is resin extruded for pipeline；

(b) tube-cooled that will be formed in step (a)；With

(c) the pipeline heating/annealing that will optionally be formed in step (a).

Preferably, present invention also contemplates that being used to manufacture the technique of the pipeline according to first aspect comprising following steps：

(a) composition is extruded as pipeline；The composition includes at least 50% of the total weight based on the composition At least one syndiotactic polypropylene of weight；Wherein described at least one syndiotactic polypropylene has as used¹³C-NMR light At least 70% syndiotactic index that spectrometry measures；The wherein described syndiotactic polypropylene does not present molten higher than 145 DEG C Melt temperature peaks, as measured by differential scanning calorimetry；

(b) tube-cooled that will be formed in step (a)；With

(c) the pipeline heating/annealing that will optionally be formed in step (a).

According to the third aspect, the present invention provides pipeline that is according to first aspect and/or being manufactured according to second aspect and is used for The purposes of fluid of the conveying under pressure.

Present invention also contemplates that according to first aspect and/or according to second aspect manufacture pipeline for manufacturing medical product Purposes.

Present invention will be further described now.In the following paragraphs, the different aspect of the present invention is defined in more detail.So The various aspects of definition can be combined with any other one or more aspects, unless clearly opposite instruction.Particularly, it is illustrated as excellent Choosing or advantageous any feature can be illustrated as a preferred or advantageous any other feature or multiple features combine.

Description of the drawings

Fig. 1 is the photo of the water-bath for carrying out creep test.

Fig. 2 indicates to draw the work of the tensile bars made of the syndiotactic polypropylene according to one embodiment of the present invention For the figure of the % elongations of the function of time.

Fig. 3 indicates to draw the tensile bars made of the syndiotactic polypropylene resin according to one embodiment of the present invention The function as applied stress the % elongations at inflection point figure.

Fig. 4 indicates to draw by the syndiotactic polypropylene resin according to one embodiment of the present invention compared with comparative example The figure of the applied stress of the function as the inflection point time of manufactured tensile bars.

Fig. 5 indicates the photo of the manufacture of the pipeline including syndiotactic polypropylene according to one embodiment of the present invention.

Fig. 6 indicates outer surface of the display according to the pipeline including syndiotactic polypropylene of one embodiment of the present invention The figure of the DSC profiles of the DSC profiles and inner surface (interior) of (outer).

Fig. 7 expressions are shown in and will be existed according to the pipeline including syndiotactic polypropylene resin of one embodiment of the present invention The figure of the DSC profiles of the inner surface of the pipeline at different time at 80 DEG C after heating/annealing.

Fig. 8 shows be shown according to the pipeline including syndiotactic polypropylene resin of one embodiment of the present invention to be existed The figure of the DSC profiles of the outer surface of the pipeline at different time at 80 DEG C after heating/annealing.

Fig. 9 indicates that display is squeezed out at 160 DEG C according to one embodiment of the present invention and persistently annealed at 80 DEG C The figure of the DSC profiles of 14 days pipelines including syndiotactic polypropylene resin.

Figure 10 indicates that display is squeezed out at 170 DEG C according to one embodiment of the present invention and persistently annealed at 80 DEG C The figure of the DSC profiles of 14 days pipelines including syndiotactic polypropylene resin.

Figure 11 indicates that display is squeezed out at 220 DEG C according to one embodiment of the present invention and persistently annealed at 80 DEG C The figure of the DSC profiles of 14 days pipelines including syndiotactic polypropylene resin.

Figure 12 indicate draw compared with comparative example according to one embodiment of the present invention by syndiotactic polypropylene system At function as the circumference stress that is applied of 32mm diameter pipes at a temperature of 20 DEG C time to rupture figure.

Specific implementation mode

Before this pipeline of the description present invention, composition, technique, product and purposes, it should be appreciated that the present invention is not limited to Described specific pipeline, composition, technique, product and purposes because such pipeline, composition, technique, product and Purposes can change certainly.It should also be understood that term used herein be not intended to it is restrictive because the scope of the present invention will only It is limited by the appended claims.

In the pipeline and technique of the description present invention, used term should be according to explanation defined below, unless context It states otherwise.

As used in this article, singulative " one (kind) (a, an) " and " being somebody's turn to do (described) " are comprising odd number and plural number Both a indicants, unless the context clearly dictates otherwise.

Term " comprising " as used in this article and " by ... structure forms (comprised of) " be with "comprising" or " contain (having) " is synonymous, and be inclusiveness or it is open and be not excluded for other, unrequited member, element or Person's method and step.Term " comprising " and " by ... structure form " also comprising term " by ... constitute (consisting of) ".

By endpoint carry out numberical range statement comprising all numbers included in respective range and part and The endpoint stated.

Refer to " embodiment " or " a kind of embodiment " it is meant that being retouched about the embodiment in the present specification The specific features stated, structure or characteristic are comprised at least one embodiment of the present invention.Therefore, in the present specification Occur phrase " in one embodiment " in different location or " in one embodiment " not necessarily each mean it is identical Embodiment, but identical embodiment can be referred to.It, can will be described specific in addition, in one or more embodiments Feature, structure or characteristic are combined apparent any suitable way by present disclosure with such as those skilled in the art.In addition, Although as it will appreciated by a person of ordinary skill, some embodiments described herein include other embodiment in include Some features but not comprising the other feature for including in the other embodiment, but the group of the feature of different embodiments Desirable figure within the scope of the invention, and forms different embodiments.For example, in the following claims, it is any to be wanted Ask the embodiment of protection that can be used in any combination.

Unless otherwise defined, all terms used in the open present invention, including technical and scientific term, has Such as the normally understood meaning of those skilled in the art.It is guided as further, in this specification The definition of the term used includes to preferably understand the teachings of the present invention.

Hereinafter illustrate the preferred statement (feature) and implementation of the pipeline, composition, technique, product and purposes of the present invention Mode.Each statement of the so defined present invention and embodiment can be combined with any other statement and/or embodiment, unless Clearly opposite instruction.Particularly, be illustrated as preferred or advantageous any feature can be illustrated as it is preferred or advantageous any Other feature or statement combination.About this, the present invention is particularly by the aspect of following number and appointing for embodiment 1-34 One or one or more and any other statement and/or the arbitrary of embodiment combine and win.

1. pipeline comprising composition, the composition include at least one syndiotactic polypropylene, wherein it is described at least A kind of syndiotactic polypropylene has as used¹³At least 70% syndiotactic index of C-NMR spectroscopy measurements；Wherein institute It states syndiotactic polypropylene and melting temperature peak higher than 145 DEG C is not presented, as measured by differential scanning calorimetry.

2. pipeline comprising composition, the composition include at least 50% weight of the total weight based on the composition At least one syndiotactic polypropylene of amount；Wherein described at least one syndiotactic polypropylene has as used¹³C-NMR spectrum At least 70% syndiotactic index that method measures；The melting higher than 145 DEG C is not presented for the wherein described syndiotactic polypropylene Temperature peaks, as measured by differential scanning calorimetry.

3. pipeline comprising at least one syndiotactic polypropylene, wherein at least one syndiotactic polypropylene tool Just like using¹³At least 70% syndiotactic index of C-NMR spectroscopy measurements；The wherein described syndiotactic polypropylene is not in Now it is higher than 145 DEG C of melting temperature peak, as measured by differential scanning calorimetry.

4. pipeline comprising at least one syndiotactic polypropylene, wherein at least one syndiotactic polypropylene tool Just like using¹³At least 70% syndiotactic index of C-NMR spectroscopy measurements；The wherein described pipeline includes being based on the pipeline Total weight at least 50% weight at least one syndiotactic polypropylene and the wherein described syndiotactic polypropylene not The melting temperature peak higher than 145 DEG C is presented, as measured by differential scanning calorimetry.

5. according to the pipeline of any one of statement 1-4, wherein the melting higher than 140 DEG C is not presented for the syndiotactic polypropylene Melting temperature peak higher than 136 DEG C is not presented preferably in temperature peaks.

6. according to the pipeline of any one of statement 1-5, wherein the melting temperature peak higher than 145 DEG C is not presented for the pipeline, such as It is measured by differential scanning calorimetry.

7. according to the pipeline of any one of statement 1-6, wherein poly- by the syndiotaxy that differential scanning calorimetry measures The maximum melting temperature of propylene is at most 145 DEG C, preferably no more than 140 DEG C.

8. according to the pipeline of any one of 1-7 of statement, have such as by ISO 178 measure less than 1000MPa, preferably Less than the flexural modulus of 700MPa, preferably less than 500MPa.

9. according to the pipeline of any one of statement 1-8, the pipeline has answering for 50 DEG C/50 years at least 7.0MPa of extrapolation Power.

10. according to the pipeline of any one of statement 1-9, wherein the composition includes the total weight based on the composition At least 60% weight, preferably at least 70% weight, preferably at least 80% weight, preferably at least 90% weight, preferably At least one of at least 95% weight, still more preferably at least 97% weight, even more preferably still at least 98% weight Syndiotactic polypropylene.

11. according to the pipeline of any one of 1-10 of statement, wherein the pipeline include the total weight based on the pipeline extremely Few 60% weight, preferably at least 70% weight, preferably at least 80% weight, preferably at least 90% weight, preferably extremely At least one syndiotactic polypropylene of few 95% weight.

12. according to the pipeline of any one of statement 1-11, wherein the pipeline is by including that at least one syndiotaxy gathers The composition of propylene is made, and the preferably wherein described composition includes at least 80% weight of the total weight based on the composition At least one syndiotactic polypropylene of amount, preferably at least 90% weight, preferably at least 95% weight.

13. according to the pipeline of any one of statement 1-12, wherein at least one syndiotactic polypropylene has as used¹³C-NMR spectrographic determinations at least 73%, more preferably at least 75%, preferably no more than 90%, preferably no more than 85%, most Syndiotactic index preferably no more than 80%.

14. according to the pipeline of any one of statement 1-13, wherein at least one syndiotactic polypropylene has as used¹³At most 90% syndiotactic index of C-NMR spectrographic determinations.

15. according to the pipeline of any one of statement 1-14, wherein at least one syndiotactic polypropylene has as used¹³The syndiotactic index of the about 74%-90% of C-NMR spectrographic determinations.

16. according to the pipeline of any one of statement 1-15, wherein at least one syndiotactic polypropylene has such as basis The at most 0.900g/cm that ASTM D-1505 are measured at 23 DEG C³, for example, at least 0.800g/cm³And at most 0.900g/cm³, it is excellent Selection of land at least 0.820g/cm³And at most 0.900g/cm³, preferably at least 0.840g/cm³And at most 0.9000g/cm³, preferably Ground at least 0.8605g/cm³And at most 0.900g/cm³, preferably at least 0.870g/cm³And at most 0.900g/cm³Density.

17. according to the pipeline of any one of statement 1-16, wherein at least one syndiotactic polypropylene has such as basis ASTM D-1238 conditions L, at least 0.3g/10min measured under the load of 2.16kg at 230 DEG C, preferably at least 0.5g/10min, preferably at least 1.0g/10min, preferably at least 1.5g/10min, preferably at least 1.8g/10min's is molten Body flow rate.

18. according to the pipeline of any one of statement 1-17, wherein at least one syndiotactic polypropylene has such as basis ASTM D-1238 conditions L, the at most 25.0g/10min measured under the load of 2.16kg at 230 DEG C, preferably no more than 20.0g/10min, the melt flow rate (MFR) preferably no more than 15.0g/10min, preferably no more than 10.0g/10min；Preferably, At least one syndiotactic polypropylene resin has the melt flows of at least 0.3g/10min and at most 25.0g/10min speed Rate；The melt flow rate (MFR) of preferably at least 0.5g/10min and at most 20.0g/10min；Preferably at least 1.0g/10min and The at most melt flow rate (MFR) of 15.0g/10min；The melt flows of preferably at least 1.0g/10min and at most 10.0g/10min Rate；Most preferably at least 1.8g/10min and at most 10.0g/10min, preferably at least 1.8g/10min and at most 9.0g/ The melt flow rate (MFR) of 10min；The melt flow rate (MFR) of preferably at least 1.9g/10min and at most 8.0g/10min；Preferably The melt flow rate (MFR) of at least 1.8g/10min and at most 7.0g/10min；Preferably at least 1.8 and at most 6.0g/10min's MFR；The melt flow rate (MFR) of preferably at least 1.8g/10min and at most 5.0g/10min；More preferably at least 1.8g/10min And the melt flow rate (MFR) of at most 4.0g/10min；The melt flow of most preferably at least 1.8g/10min and at most 3.0g/10min Dynamic rate.

19. according to the pipeline of any one of 1-18 of statement, wherein at least one syndiotactic polypropylene be with less than The ethylene of 0.7% weight or other alpha-olefin comonomers (optimal ethylene), the preferably less than ethylene of 0.5% weight, preferably Ground is less than the syndiotactic polypropylene homopolymer of the ethylene of 0.4% weight, the ethylene for being preferably less than 0.1% weight.

20. according to the pipeline of any one of 1-19 of statement, wherein at least one syndiotactic polypropylene be it is pure between it is same Vertical structure polypropylene homopolymer.

21. according to the pipeline of any one of statement 1-20, wherein at least one syndiotactic polypropylene is by single centre The syndiotactic polypropylene of catalyst, preferably by the syndiotactic polypropylene of metallocene catalysis.

22. according to the pipeline of any one of statement 1-21, there is the scratching less than 1000MPa such as measured by ISO 178 Bent modulus.

23. according to the pipeline of any one of statement 1-22, has and such as pass through the ISO 180- notched izods at 23 DEG C Test at least 40kJ/m measured²Impact resistance.

24. the technique for manufacturing the pipeline according to any one of statement 1-23 comprising following steps：

(b) tube-cooled that will be formed in step (a)；With

(c) the pipeline heating/annealing that will optionally be formed in step (a).

25. the technique for manufacturing the pipeline according to any one of statement 1-23 comprising following steps：

(a) at least one syndiotactic polypropylene is extruded as pipeline；Wherein described at least one syndiotaxy is poly- Propylene has as used¹³At least 70% syndiotactic index of C-NMR spectroscopy measurements；The wherein described pipeline includes being based on institute At least one syndiotactic polypropylene and the wherein described syndiotaxy for stating at least 50% weight of the total weight of pipeline are poly- The melting temperature peak higher than 145 DEG C is not presented for propylene, as measured by differential scanning calorimetry；

(b) tube-cooled that will be formed in step (a)；With

(c) the pipeline heating/annealing that will optionally be formed in step (a).

26. the technique for manufacturing the pipeline according to any one of statement 1-23 comprising following steps：

(a) at least one syndiotactic polypropylene is extruded as pipeline；

(b) tube-cooled that will be formed in step (a)；With

(c) the pipeline heating/annealing that will optionally be formed in step (a).

27. stating the technique of any one of 24-26, wherein step (c) carries out at a temperature of at least 60 DEG C.

28. stating the technique of any one of 24-27, wherein step (c) carries out at a temperature of at most 120 DEG C.

29. stating the technique of any one of 24-28, wherein step (c) carries out at a temperature of at least 70 DEG C-at most 120 DEG C.

30. stating the technique of any one of 24-29, wherein step (c) carries out at least 3 days.

31. stating the technique of any one of 24-30, wherein step (c) is carried out within 20 days.

32. stating the technique of any one of 24-31, wherein step (c) carries out at least 3 days-at most 14 days.

33. stating the technique of any one of 24-32, wherein step (c) is annealing steps.

34. being used for according to any one of statement 1-23's and/or according to the pipeline of the technique manufacture of any one of statement 24-33 defeated Send the purposes of the fluid under pressure.

According in a first aspect, the present invention covers pipeline comprising composition, the composition is including same vertical between at least one Structure polypropylene, wherein it is described at least one syndiotactic polypropylene have such as via¹³At least the 70% of C-NMR spectroscopy measurements Syndiotactic index；The melting temperature peak higher than 145 DEG C is not presented for the wherein described syndiotactic polypropylene, is such as swept by differential Retouch calorimetric determination.Present invention also contemplates that pipeline comprising at least one syndiotactic polypropylene, wherein at least one Syndiotactic polypropylene have such as via¹³At least 70% syndiotactic index of C-NMR spectroscopy measurements；Wherein such as pass through What differential scanning calorimetry measured, the melting temperature peak higher than 145 DEG C is not presented for the syndiotactic polypropylene, such as in embodiment Described in part.

Preferably, the present invention provides pipeline comprising composition, the composition include the gross weight based on the composition At least one syndiotactic polypropylene of at least 50% weight of amount；Wherein described at least one syndiotactic polypropylene has such as It uses¹³At least 70% syndiotactic index of C-NMR spectroscopy measurements；Height is not presented for the wherein described syndiotactic polypropylene In 145 DEG C of melting temperature peak, as measured by differential scanning calorimetry.

Present invention also contemplates that pipeline comprising at least one syndiotactic polypropylene, wherein with vertical between at least one Structure polypropylene has as used¹³At least 70% syndiotactic index of C-NMR spectroscopy measurements；The wherein described pipeline includes base In at least 50% weight of the total weight of the pipeline at least one syndiotactic polypropylene and it is wherein described between with vertical The melting temperature peak higher than 145 DEG C is not presented for structure polypropylene, as measured by differential scanning calorimetry.

As used in this article " pipeline " be intended to cover pipeline in the narrow sense and for pipeline supplement (it is attached, Supplementary) part such as connector (fitting), valve and generally for (such as conveying gas, cold water or hot water ) necessary all parts for pipe-line system.Pipeline according to the present invention is also contemplated by single layer and multi-layer piping, wherein such as institute The one or more for stating layer be metal layer and its may include gluing oxidant layer.Other constructions of pipeline such as corrugated conduit (ripple Pipe) it is also possible.

As used in this article term " syndiotactic polypropylene " or " syndiotactic polypropylene resin " refer to it is extruded, And/or melting and/or the syndiotactic polypropylene villus or powder that are granulated and can be by between described in as taught herein Same vertical structure is polyacrylic to be manufactured with mixing homogenizing (such as with mixing and/or squeezing out machine equipment).As used in this article, term " syndiotactic polypropylene " or " sPP " can be used as writing a Chinese character in simplified form for " syndiotactic polypropylene resin ".

Pipeline according to the present invention include have such as via¹³C-NMR spectroscopy measurements at least 70%, preferably at least 73%, more preferably at least 75%, the syndiotactic polypropylene of the syndiotactic index preferably no more than 90%.

¹³C-NMR analyses are to use high temperature under the operating frequency of 125MHz using 500MHz Bruker NMR spectrometers The 10mm cryoprobes condition directly proportional to the sum of the contributive carbon atom in sample in the signal strength in making spectrogram Lower progress.Such condition is well known to technical staff and includes such as enough relaxation times.In practice, signal Intensity is to integrate i.e. corresponding area by it to obtain.Data are at a temperature of 130 DEG C using proton decoupling, every spectrogram The spectrum width acquisition of 240 scanning, 11 seconds pulse repetition delays and 26000Hz.Sample is prepared by the following procedure：It will be enough The polymer of amount is dissolved at 130 DEG C in 1,2,4- trichloro-benzenes (TCB, 99%, the order of spectrum) and occasional agitation is so that sample Homogenization, adds six deuterated benzene (C later₆D₆, the order of spectrum) and less amount of hexamethyldisiloxane (HMDS, 99.5+%), Middle HMDS serves as internal standard compound.For example for, about 200mg polymer is dissolved in the TCB of 2.0mL, adds 0.5mL later C₆D₆With 2-3 drops HMDS.

After data acquisition, signal of the chemical shift with reference to internal standard compound HMDS (it is pointed out as the value of δ 2.03ppm). Degree of syndiotacticity is by entire polymer¹³C-NMR analyze and measure.In the SPECTRAL REGION of methyl, use The data of announcement point out signal corresponding with five-tuple rrrr, mrrr, mrrm, mrmr, mmrm, rrmr and mmrr.Syndiotaxy Index is calculated according to following equation：

Syndiotactic index=rrrr+mrrr+mrrm+1/2* (mrmr+mmrm+rrmr+mmrr)

In those conditions¹³C-NMR detectable limits are about 0.6/10,000C.

Syndiotactic polypropylene homopolymer is formed by the catalytic polymerization of propylene monomer.In some embodiments In, suitable syndiotactic polypropylene homopolymer has the degree of syndiotacticity degree of 70%-90% herein.Preferably, institute Stating syndiotactic polypropylene homopolymer has the degree of syndiotacticity degree of about 73%-90%, preferably 75%-90%.

Term " steric regularity " refers to the arrangement of the pendant groups in polymer.For example, polymer is in its base that dangles Group is " atactic " when being arranged in random fashion on the both sides of polymer chain.In contrast, polymer is in its base that dangles Group is all " isotactic " when being arranged on the same side of chain and in its pendant groups is when in the opposite side of chain alternately " syndyotactic ".Therefore, syndiotactic polypropylene is the methyl that wherein dangles with regular from the side of chain to the other side The alternate polypropylene of mode.

In a preferred embodiment, suitable syndiotactic polypropylene is homopolymer.As used in this article, same Vertical structure polypropylene homopolymer includes with minimal amount of ethylene or other alhpa olefin comonomers (optimal ethylene), i.e. entire polymerization Compositions (ingredient) are less than about 0.7% weight, preferably less than 0.5% weight, still more preferably less than 0.1% weight Ethylene syndiotactic polypropylene random copolymer.Syndiotactic polypropylene with the ethylene less than about 0.7% weight Copolymer behavior expression for most of physical property obtains 100% weight syndiotactic polypropylene homopolymer of extraordinary image.Unless Illustrate on the contrary, otherwise term syndiotactic polypropylene homopolymer will be understood as including pure syndiotactic polypropylene homopolymer It is total to the syndiotactic polypropylene containing various alhpa olefins, the preferably less than ethylene of 0.7% weight less than about 0.7% weight Polymers.

In some embodiments, the composition include the total weight based on the composition at least 50% weight, Preferably at least 60% weight, preferably at least 70% weight, preferably at least 80% weight, preferably at least 90% weight, Preferably at least 95% weight, still more preferably at least 97% weight, even more preferably still at least 98% weight it is described extremely A kind of few syndiotactic polypropylene.In some embodiments, the pipeline include the total weight based on the pipeline at least 50% weight, preferably at least 60% weight, preferably at least 70% weight, preferably at least 80% weight, preferably at least At least one syndiotactic polypropylene of 90% weight, preferably at least 95% weight.

In some embodiments, pipeline according to the present invention includes at least one syndiotactic polypropylene, is had such as The at most 0.900g/cm measured at 23 DEG C according to ASTM D-1505³Density.In some preferred embodiments, between described There is at least 0.800g/cm with vertical structure polypropylene³And at most 0.900g/cm³, preferably at least 0.820g/cm³And at most 0.900g/cm³, preferably at least 0.840g/cm³And at most 0.900g/cm³, preferably at least 0.8605g/cm³And at most 0.9000g/cm³, preferably at least 0.870g/cm³And at most 0.900g/cm³Density.The syndiotactic polypropylene it is close Degree refers to the density polymer of the original sample not comprising additive such as pigment such as carbon black, unless otherwise indicated.

Example suitable for the syndiotactic polypropylene in this pipeline includes as follows without limiting： 1251 and1471 syndiotactic polypropylenes, being can be from TotalPetrochemicals USA, Inc quotient What purchase obtained.

The syndiotactic polypropylene is catalyzed using metallocene catalyst system.

Being preferably adapted to the syndiotactic polypropylene of the present invention can be manufactured by the following：Make propylene and one or more Optional comonomer, optional hydrogen are deposited at least one single-site catalyst systems, preferably metallocene catalyst system In lower polymerization.

As used in this article, term " catalyst " refers to the substance for the variation for leading to polymerization rate.In this hair In bright, it is particularly suitable for being suitable for the catalyst by propylene polymerization is syndiotactic polypropylene.The invention particularly relates in list The syndiotactic polypropylene prepared in the presence of the catalyst of center.Among these catalyst, metallocene catalyst is preferred.Such as It is used herein, term " the syndiotactic polypropylene resin through metallocene catalysis " and " syndiotaxy through metallocene catalysis Polypropylene " is synonymous and is interchangeably used and refers to that the syndiotaxy prepared in the presence of a metallocene catalyst is poly- Propylene.

Term " metallocene catalyst " or write a Chinese character in simplified form " metallocene " herein for describe it is any include with it is a kind of or more The transition metal complex of the metallic atom of kind ligand bonding.Preferred metallocene catalyst is periodic table group iv transition metals Such as the compound of titanium, zirconium, hafnium etc., and have and possess following coordination structure：Metallic compound, and by cyclopentadienyl group, The ligand of one or both of indenyl, fluorenyl or their derivative group composition.Depending on desired polymer, can be changed The structure and geometry of the metallocene are to adapt to the specific requirement of manufacturer.Metallocene typically comprises in single metal The heart, this allows the branched and molecular weight distribution for more controlling polymer.Monomer is inserted into the metal and polymer growth Between chain.

In some embodiments, the metallocene catalyst is the compound of formula (I)：

R”(Ar)₂MQ_j(I),

Wherein it is the metallocene of bridge joint according to the metallocene of formula (I)；

The wherein described metallocene according to formula (I) has two Ar combined with M, can be same or different to each other；

Wherein j be selected from 1,2,3 and 4 integer, and when j be two or more when, the multiple Q can be same or different to each other； Preferably j is 2；

Wherein Ar is aromatic ring, group or part and wherein each Ar independently selected from cyclopentadienyl group, fluorenyl, indenyl (IND) and tetrahydro indenyl (THI), wherein the group be respectively optionally each independently selected from by one or more it is following Substituent group substitution：Alkyl, halogen, SiR " ' with 1-20 carbon atom₃, wherein R " ' is the hydrocarbon with 1-20 carbon atom Base, and the wherein described alkyl optionally contain one or more selected from the atom for including following group：B, Si, S, O, F, Cl and P；

Wherein M is the transition metal selected from titanium, zirconium, hafnium and vanadium；And preferably zirconium；

Oxyls of wherein each Q independently selected from halogen, with 1-20 carbon atom and the hydrocarbon with 1-20 carbon atom Base and the wherein described alkyl optionally contain one or more selected from the atom for including following group：B, Si, S, O, F, Cl and P； With

Wherein R " is to bridge the bivalent group of two Ar groups or part and be selected from C₁-C₂₀Alkylidene, germanium, silicon, silica Alkane, alkylphosphines and amine, and the wherein described R " are optionally each independently selected from substituent group below by one or more and replace： Alkyl, halogen, SiR with 1-20 carbon atom₃, wherein R is the alkyl with 1-20 carbon atom；The wherein described alkyl Optionally contain one or more selected from the atom for including following group：B, Si, S, O, F, Cl, Br, I and P.

Preferably, the metallocene includes the cyclopentadienyl-fluorenyl component of bridge joint.In some embodiments, described Metallocene catalyst is the fluorenyl type metallocene catalyst (FMC) of lower formula (II)：

Wherein M, Q and j are as hereinbefore defined；With

Wherein R¹、R²、R³And R⁴It is each independently selected from hydrogen, the alkyl with 1-20 carbon atom, halogen, SiR " '₃, Middle R " ' is the alkyl with 1-20 carbon atom, and it includes as follows that the wherein described alkyl, which optionally contains one or more be selected from, Group atom：B, Si, S, O, F, Cl, Br, I and P；Wherein R¹And R²It does not bond together and forms ring；Wherein R³And R⁴Not It bonds together and forms ring；

R⁵And R⁶It is each independently selected from hydrogen；Alkyl, halogen, SiR with 1-20 carbon atom₃, wherein R is with 1- The alkyl of 20 carbon atoms；The wherein described alkyl optionally contains one or more selected from the atom for including following group：B、 Si, S, O, F, Cl, Br, I and P.Preferably, R¹And R⁴It is identical.Preferably, R²、R³It is identical.Preferably R⁵And R⁶It is identical.

The example of suitable alkyl with 6-20 carbon atom includes：Phenyl, o- chlorphenyl, m- chlorphenyl, p- chlorobenzene For example o- bromophenyl of base, bromo aryl, m- bromophenyl, p- bromophenyl, o- iodophenyl, m- iodophenyl, p- iodophenyl, naphthalene Base, chloro naphthalene, bromo naphthalene, iodo naphthalene, o- tolyl, m- tolyl, p- tolyl, 2-bromomethylphenyl, dibromo first Base phenyl, iodomethyl phenyl, diiodomethyl phenyl, ethylphenyl, n-propyl phenyl, isopropyl phenyl, n-butylphenyl, Zhong Ding Base phenyl, tert-butyl-phenyl, xylyl, benzyl, m- chlorobenzyl, p- chlorobenzyl, m- bromobenzyl, p- bromobenzyl, m- iodine Benzyl, p- iodine benzyl, [α]-phenethyl, [β]-phenethyl, diphenyl methyl, naphthyl methyl and benzene tertiary butyl.

In some embodiments, the metallocene catalyst is the FMC, wherein R of formula (II)¹、R²、R³And R⁴Respectively solely On the spot it is selected from hydrogen, alkyl and SiR " ' with 1-20 carbon atom₃, wherein R " ' is the alkyl with 1-20 carbon atom；With Wherein R¹And R²It does not bond together and forms ring；Wherein R³And R⁴It does not bond together and forms ring.It is highly preferred that R¹And R⁴Phase Together；And R²And R³It is identical；And it is particularly preferred that R²And R³For tertiary butyl.

In some embodiments, the metallocene catalyst is the FMC, wherein R of formula (II)⁵And R⁶It selects each independently From hydrogen；Alkyl and SiR with 1-20 carbon atom₃, wherein R is the alkyl with 1-20 carbon atom；The wherein described hydrocarbon Base optionally contains one or more selected from the atom for including following group：F, Cl, Br and I.More preferably R⁵And R⁶It is identical and For the alkyl with 6-20 carbon atom.Preferably, R¹And R⁴Identical and R²And R³It is identical.

In some embodiments, the metallocene catalyst is the FMC, wherein R of formula (II)¹And R⁴Respectively preferably hydrogen Atom or alkyl with 6-20 carbon atom；More preferably hydrogen atom or the aryl with 6-10 carbon atom；It is optimal Selection of land hydrogen atom, phenyl, o- tolyl, m- tolyl, p- tolyl, o- chlorphenyl, m- chlorphenyl or p- chlorphenyl. Preferably, R¹And R⁴It is identical, R⁵And R⁶Identical and R²And R³It is identical.

In some embodiments, the metallocene catalyst is the FMC, wherein R of formula (II)⁵And R⁶Can it is mutually the same or Difference, and the respectively preferably aryl with 6-10 carbon atom or the aralkyl with 6-10 carbon atom；Preferably Phenyl, benzyl, m- chlorphenyl, p- chlorphenyl, m- chlorobenzyl or p- chlorobenzyl.Preferably, R¹And R⁴It is identical, R⁵And R⁶ Identical and R²And R³It is identical.

Illustrative example suitable for the FMC for preparing syndiotactic polypropylene used herein includes dibenzyl methylene (cyclopentadienyl group) (2,7- dimethyl -3,6- di-t-butyls fluorenyl) zirconium dichloride [also referred to as 1,3- diphenyl isopropylidene (ring penta Dialkylene) (2,7- dimethyl -3,6- di-t-butyls fluorenyl) zirconium dichloride；Hereinafter, omit the alias of each compound], dibenzyl Methylene (cyclopentadienyl group) ((2,4,6- the trimethylphenyls) -3,6- di-t-butyls of 2,7- bis- fluorenyl) zirconium dichloride, dibenzyl Methylene (cyclopentadienyl group) (2,7- diphenyl -3,6- di-t-butyls fluorenyl) zirconium dichloride, dibenzyl methylene (ring penta 2 Alkenyl) ((3,5- the 3,5-dimethylphenyls) -3,6- di-t-butyls of 2,7- bis- fluorenyl) zirconium dichloride, dibenzyl methylene (cyclopentadiene Base) ((4- the aminomethyl phenyls) -3,6- di-t-butyls of 2,7- bis- fluorenyl) zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) (2, 7- dinaphthyl -3,6- di-t-butyls fluorenyl) zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) ((the 4- tert-butyl benzenes of 2,7- bis- Base) -3,6- di-t-butyls fluorenyl) zirconium dichloride, Diphenethyl methylene (cyclopentadienyl group) (two uncles of 2,7- diphenyl -3,6- Butyl fluorenyl) zirconium dichloride, two (benzhydryl) methylene (cyclopentadienyl group) (2,7- diphenyl -3,6- di-t-butyls fluorenyl) Zirconium dichloride, two (cumyl) methylene (cyclopentadienyl group) (2,7- diphenyl -3,6- di-t-butyls fluorenyl) zirconium dichloride, hexichol Methylene (cyclopentadienyl group) (3,6- di-t-butyls fluorenyl) zirconium dichloride, two-o- toluene methylenes (cyclopentadienyl group) (3,6- di-t-butyls fluorenyl) zirconium dichloride, two-m- toluene methylenes (cyclopentadienyl group) (3,6- di-t-butyls fluorenyl) two Zirconium chloride, two-p- toluene methylene (cyclopentadienyl group) (3,6- di-t-butyls fluorenyl) zirconium dichlorides, two (o- chlorphenyls) Methylene (cyclopentadienyl group) (3,6- di-t-butyls fluorenyl) zirconium dichloride, two (m- chlorphenyl) methylene (cyclopentadienyl group) (3,6- di-t-butyls fluorenyl) zirconium dichloride, two (p- chlorphenyl) methylene (cyclopentadienyl group) (3,6- di-t-butyls fluorenyl) Zirconium dichloride, two (o- bromophenyl) methylene (cyclopentadienyl group) (3,6- di-t-butyls fluorenyl) zirconium dichlorides, two (m- bromobenzenes Base) methylene (cyclopentadienyl group) (3,6- di-t-butyls fluorenyl) zirconium dichloride, two (p- bromophenyl) methylene (cyclopentadiene Base) (3,6- di-t-butyls fluorenyl) zirconium dichloride, two (o- iodophenyl) methylene (cyclopentadienyl group) (3,6- di-tert-butyl-fluorenes Base) it is zirconium dichloride, two (m- iodophenyl) methylene (cyclopentadienyl group) (3,6- di-t-butyls fluorenyl) zirconium dichlorides, two (p- Iodophenyl) methylene (cyclopentadienyl group) (3,6- di-t-butyls fluorenyl) zirconium dichloride, two (o- trifluoromethyl) methylene (cyclopentadienyl group) (3,6- di-t-butyls fluorenyl) zirconium dichloride, two (m-trifluoromethyl phenyl) methylene (cyclopentadienyl group) (3,6- di-t-butyls fluorenyl) zirconium dichloride, two (p- trifluoromethyl) methylene (cyclopentadienyl group) (3,6- di-t-butyls Fluorenyl) zirconium dichloride, two (2- naphthalenes) methylene (cyclopentadienyl group) (3,6- di-t-butyls fluorenyl) zirconium dichlorides, dibenzyl be sub- Methyl (cyclopentadienyl group) (3,6- di-t-butyls fluorenyl) zirconium dichloride, two (o- chlorobenzyl) methylene (cyclopentadienyl group) (3, 6- di-t-butyls fluorenyl) zirconium dichloride, two (m- chlorobenzyl) methylene (cyclopentadienyl group) (3,6- di-t-butyls fluorenyl) dichloros Change zirconium, two (p- chlorobenzyl) methylene (cyclopentadienyl group) (3,6- di-t-butyls fluorenyl) zirconium dichlorides, two (o- bromobenzyls) Methylene (cyclopentadienyl group) (3,6- di-t-butyls fluorenyl) zirconium dichloride, two (m- bromobenzyl) methylene (cyclopentadienyl group) (3,6- di-t-butyls fluorenyl) zirconium dichloride, two (p- bromobenzyl) methylene (cyclopentadienyl group) (3,6- di-t-butyls fluorenyl) Zirconium dichloride, two (o- iodine benzyl) methylene (cyclopentadienyl group) (3,6- di-t-butyls fluorenyl) zirconium dichlorides, two (m- iodine benzyls Base) methylene (cyclopentadienyl group) (3,6- di-t-butyls fluorenyl) zirconium dichloride, two (p- iodine benzyl) methylene (cyclopentadiene Base) (3,6- di-t-butyls fluorenyl) zirconium dichloride, two (ortho-methyl benzyl) methylene (cyclopentadienyl group) (3,6- di-t-butyls Fluorenyl) zirconium dichloride, two (m- methylbenzyl) methylene (cyclopentadienyl group) (3,6- di-t-butyls fluorenyl) zirconium dichlorides, two (p- methylbenzyl) methylene (cyclopentadienyl group) (3,6- di-t-butyls fluorenyl) zirconium dichloride, (benzyl) (phenyl) methylene (cyclopentadienyl group) (3,6- di-t-butyls fluorenyl) zirconium dichloride, (benzyl) (phenyl) methylene (cyclopentadienyl group) (2,7- bis- Phenyl -3,6- di-t-butyls fluorenyl) zirconium dichloride, (benzyl) (phenyl) methylene (cyclopentadienyl group) (2,7- bis--o- toluene Base -3,6- di-t-butyls fluorenyl) zirconium dichloride, (benzyl) (phenyl) methylene (cyclopentadienyl group) (2,7- bis--p- chlorphenyl - 3,6- di-t-butyls fluorenyl) zirconium dichloride, (p- chlorobenzyl) (phenyl) methylene (cyclopentadienyl group) (2,7- diphenyl -3,6- Di-t-butyl fluorenyl) zirconium dichloride, (p- chlorobenzyl) (phenyl) methylene (cyclopentadienyl group) (2,7- bis--o- tolyl -3, 6- di-t-butyls fluorenyl) zirconium dichloride, (p- chlorobenzyl) (phenyl) methylene (cyclopentadienyl group) (bis- p- chlorphenyls-of 2,7- 3,6- di-t-butyls fluorenyl) zirconium dichloride, (benzyl) (p- chlorphenyl) methylene (cyclopentadienyl group) (2,7- diphenyl -3,6- Di-t-butyl fluorenyl) zirconium dichloride, (benzyl) (p- chlorphenyl) methylene (cyclopentadienyl group) (2,7- bis--o- tolyl -3, 6- di-t-butyls fluorenyl) zirconium dichloride, (benzyl) (p- chlorphenyl) methylene (cyclopentadienyl group) (2,7- bis--p- chlorphenyl- 3,6- di-t-butyls fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl group) (2,7- bis--two uncles of o- tolyl -3,6- Butyl fluorenyl) zirconium dichloride, two-p- tolyl-methylene (cyclopentadienyl group) (two tertiary fourths of 2,7- bis--o- tolyl -3,6- Base fluorenyl) zirconium dichloride, two (p- chlorphenyl) methylene (cyclopentadienyl group) (2,7- bis--o- tolyl -3,6- di-t-butyls Fluorenyl) zirconium dichloride, two (p- trifluoromethyl) methylene (cyclopentadienyl group) (2,7- bis--two uncles of o- tolyl -3,6- Butyl fluorenyl) zirconium dichloride, two (2- naphthalenes) methylene (cyclopentadienyl group) (2,7- bis--o- tolyl -3,6- di-t-butyls Fluorenyl) zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) (2,7- bis--o- tolyl -3,6- di-t-butyls fluorenyl) dichloro Change zirconium, two (p- chlorobenzyl) methylene (cyclopentadienyl group) (2,7- bis--o- tolyl -3,6- di-t-butyls fluorenyl) dichloride Zirconium, two (p- methylbenzyl) methylene (cyclopentadienyl group) (2,7- bis--o- tolyl -3,6- di-t-butyls fluorenyl) dichloride Zirconium, dibenzyl methylene (cyclopentadienyl group) (the o- tolyl-fluorenyls of 2,7- bis- -) zirconium dichloride, dibenzyl methylene (ring penta Dialkylene) [(o- the ethylphenyl) -3,6- di-t-butyls of 2,7- bis- fluorenyl] zirconium dichloride, dibenzyl methylene (cyclopentadiene Base) [2,7- bis- [o- (n-propyl) phenyl] -3,6- di-t-butyls fluorenyl] zirconium dichloride, dibenzyl methylene (cyclopentadiene Base) [2,7- bis- [o- (isopropyl) phenyl] -3,6- di-t-butyls fluorenyl] zirconium dichloride, dibenzyl methylene (cyclopentadiene Base) [2,7- bis- [o- (normal-butyl) phenyl] -3,6- di-t-butyls fluorenyl] zirconium dichloride, dibenzyl methylene (cyclopentadiene Base) [2,7- bis- [o- (isobutyl group) phenyl] -3,6- di-t-butyls fluorenyl] zirconium dichloride, dibenzyl methylene (cyclopentadiene Base) [2,7- bis- [o- (sec-butyl) phenyl] -3,6- di-t-butyls fluorenyl] zirconium dichloride, dibenzyl methylene (cyclopentadiene Base) [2,7- bis- [o- (tertiary butyl) phenyl] -3,6- di-t-butyls fluorenyl] zirconium dichloride, dibenzyl methylene (cyclopentadiene Base) [2,7- bis- [o- (n-eicosane base) phenyl] -3,6- di-t-butyls fluorenyl] zirconium dichloride, dibenzyl methylene (ring penta 2 Alkenyl) [(o- the cyclohexyl phenyl) -3,6- di-t-butyls of 2,7- bis- fluorenyl] zirconium dichloride, dibenzyl methylene (cyclopentadiene Base) [2,7- bis- (biphenyl -2- bases) -3,6- di-t-butyls fluorenyl] zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) [2,7- Two [o- (2- naphthalenes) phenyl] -3,6- di-t-butyls fluorenyls] zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) [2,7- bis- [o- (2- phenanthryl) phenyl] -3,6- di-t-butyls fluorenyl] zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) [2,7- bis- (o- trimethylsilylphenyl) -3,6- di-t-butyls fluorenyl] zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) [2, 7- bis- (o- triphenyl-silyl phenyl) -3,6- di-t-butyls fluorenyl] zirconium dichloride, diphenylmethylene (cyclopentadiene Base) (2,7- diphenyl -3,6- di-t-butyls fluorenyl) zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) (2,7- diphenyl - 3,6- di-t-butyls fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl group) (2,7- bis--two uncles of p- chlorphenyl -3,6- Butyl fluorenyl) zirconium dichloride, two-p- tolyl-methylene (cyclopentadienyl group) (two tertiary fourths of 2,7- bis--p- chlorphenyl -3,6- Base fluorenyl) zirconium dichloride, two (p- chlorphenyl) methylene (cyclopentadienyl group) (2,7- bis--p- chlorphenyl -3,6- di-t-butyls Fluorenyl) zirconium dichloride, two (p- trifluoromethyl) methylene (cyclopentadienyl group) (2,7- bis--two uncles of p- chlorphenyl -3,6- Butyl fluorenyl) zirconium dichloride, two (2- naphthalenes) methylene (cyclopentadienyl group) (2,7- bis--p- chlorphenyl -3,6- di-t-butyls Fluorenyl) zirconium dichloride, dibenzyl methylene (cyclopentadienyl group) (2,7- bis--p- chlorphenyl -3,6- di-t-butyls fluorenyl) dichloro Change zirconium, two (p- chlorobenzyl) methylene (cyclopentadienyl group) (2,7- bis--p- chlorphenyl -3,6- di-t-butyls fluorenyl) dichloride Zirconium, two (p- methylbenzyl) methylene (cyclopentadienyl group) (2,7- bis--p- chlorphenyl -3,6- di-t-butyls fluorenyl) dichloride Zirconium, dibenzyl methylene (cyclopentadienyl group) (the double trimethyl silyl fluorenyls of 2,7- bis--p- chlorphenyl -3,6-) dichloride Zirconium, dibenzyl methylene (cyclopentadienyl group) (2,7- bis--p- chlorphenyl -3,6- dicumyls fluorenyl) zirconium dichloride, dibenzyl are sub- Methyl (cyclopentadienyl group) (2,7- bis--p- chlorphenyl -3,6- adamantyls fluorenyl) zirconium dichloride, dimethylated methylene base (ring penta Dialkylene) (2,7- bis--p- trifluoromethyl -3,6- di-t-butyls fluorenyl) zirconium dichloride, diethyl methylene (ring penta 2 Alkenyl) (2,7- bis--p- trifluoromethyl -3,6- di-t-butyls fluorenyl) zirconium dichloride, diη-propyl methylene (ring penta 2 Alkenyl) (2,7- bis--p- trifluoromethyl -3,6- di-t-butyls fluorenyl) zirconium dichloride, diisopropyl methylene (ring penta 2 Alkenyl) (2,7- bis--p- trifluoromethyl -3,6- di-t-butyls fluorenyl) zirconium dichloride, di-n-butyl methylene (ring penta 2 Alkenyl) (2,7- bis--p- trifluoromethyl -3,6- di-t-butyls fluorenyl) zirconium dichloride, diisobutyl methylene (ring penta 2 Alkenyl) (2,7- bis--p- trifluoromethyl -3,6- di-t-butyls fluorenyl) zirconium dichloride, di-sec-butyl methylene (ring penta 2 Alkenyl) (2,7- bis--p- trifluoromethyl -3,6- di-t-butyls fluorenyl) zirconium dichloride, di-t-butyl methylene (ring penta 2 Alkenyl) (2,7- bis--p- trifluoromethyl -3,6- di-t-butyls fluorenyl) zirconium dichloride, di-n-octyl methylene (ring penta 2 Alkenyl) (2,7- bis--p- trifluoromethyl -3,6- di-t-butyls fluorenyl) zirconium dichloride, two positive melissyl methylene (rings Pentadienyl) (2,7- bis--p- trifluoromethyl -3,6- di-t-butyls fluorenyl) zirconium dichloride, phenylmethylene (ring penta 2 Alkenyl) (2,7- bis--p- trifluoromethyl -3,6- di-t-butyls fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadiene Base) (2,7- bis--p- trifluoromethyl -3,6- di-t-butyls fluorenyl) zirconium dichloride, two-p- toluene methylene (rings penta Dialkylene) (2,7- bis--p- trifluoromethyl -3,6- di-t-butyls fluorenyl) zirconium dichloride, two (p- chlorphenyl) methylene (cyclopentadienyl group) (2,7- bis--p- trifluoromethyl -3,6- di-t-butyls fluorenyl) zirconium dichloride, two (p- trifluoromethyls Phenyl) methylene (cyclopentadienyl group) (2,7- bis--p- trifluoromethyl -3,6- di-t-butyls fluorenyl) zirconium dichloride, two (2- naphthalenes) methylene (cyclopentadienyl group) (2,7- bis--p- trifluoromethyl -3,6- di-t-butyls fluorenyl) zirconium dichloride, Dibenzyl methylene (cyclopentadienyl group) (2,7- bis--p- trifluoromethyl -3,6- di-t-butyls fluorenyl) zirconium dichloride, two (p- chlorobenzyl) methylene (cyclopentadienyl group) (2,7- bis--p- trifluoromethyl -3,6- di-t-butyls fluorenyl) dichloride Zirconium, two (p- methylbenzyl) methylene (cyclopentadienyl group) (2,7- bis--p- trifluoromethyl -3,6- di-t-butyls fluorenyl) Zirconium dichloride；The compound that the zirconium atom hafnium atom or titanium atom of the wherein above compound replace；The wherein above compound The compound that chlorine atom methyl or benzyl replace；And combinations thereof, and it is without being limited thereto.Hafnium atom, zirconium atom and titanium atom it In, preferred zirconium atom.These compounds can be used alone, or can will be applied in combination in two or more.

As used in this article, term " alkyl with 1-20 carbon atom " is referred to selected from the portion for including following group Point：Line style or branched C₁-C₂₀Alkyl；C₃-C₂₀Naphthenic base；C₆-C₂₀Aryl；C₇-C₂₀Alkylaryl and C₇-C₂₀Aryl alkyl, Or its arbitrary combination.Illustrative alkyl be methyl, ethyl, propyl, butyl, amyl, isopentyl, hexyl, isobutyl group, heptyl, Octyl, nonyl, decyl, cetyl, 2- ethylhexyls and phenyl.

As used in this article, term " oxyl with 1-20 carbon atom " refers to the portion with formula alkyl-O- Point, wherein as described in this article, the alkyl has 1-20 carbon atom.It includes following that preferred oxyl, which is selected from, Group：Alkyl oxy, alkenyl oxygroup, cycloalkyl oxy or aralkoxy.

As used in this article, term " alkyl " (itself or as another substituent group part) refer to have 1 Or more carbon atom, such as 1-20 carbon atom, such as 1-12 carbon atom, such as 1-6 carbon atom, such as 1-4 carbon The straight chain of atom combined by carbon-to-carbon singly-bound or branched saturated hydrocarbons group.It is used after following herein in carbon atom When subscript, which refers to the carbon atom number that named group contains.Thus, for example, C_1-12Alkyl means 1-12 carbon The alkyl of atom.The example of alkyl is methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, sec-butyl, tertiary butyl, 2- methyl Butyl, amyl and its chain isomer, hexyl and its chain isomer, heptyl and its chain isomer, octyl and its chain isomer, nonyl With its chain isomer, decyl and its chain isomer, undecyl and its chain isomer, dodecyl and its chain isomer.Alkyl With general formula C_nH_2n+1。

As used in this article, term " naphthenic base " (itself or as another substituent group part) refer to saturation or The cyclic alkyl free radical that person is partly saturated.Naphthenic base has general formula C_nH_2n-1.It is used after following herein in carbon atom When subscript, which refers to the carbon atom number that named group contains.Therefore, C_3-6The example of naphthenic base include cyclopropyl, Cyclobutyl, cyclopenta or cyclohexyl.

As used in this article, term " aryl " (itself or as another substituent group part) refer to by aromatic ring Derivative free radical such as phenyl, naphthalene, indanyl or 1,2,3,4- tetrahydro-naphthalenyls.When herein follow carbon atom it When using subscript afterwards, which refers to the carbon atom number that named group contains.

As used in this article, term " alkylaryl " (itself or as another substituent group part) refer to wherein The aryl as defined herein that hydrogen atom is replaced by alkyl as defined herein.Make after following herein in carbon atom When with subscript, which refers to the carbon atom number that named group or subbase group contain.

As used in this article, term " aryl alkyl " (itself or as another substituent group part) refer to wherein The alkyl as defined herein that hydrogen atom is replaced by aryl as defined herein.Make after following herein in carbon atom When with subscript, which refers to the carbon atom number that named group contains.C_6-10Aryl C_1-6The example packet of alkyl diradical Containing benzyl, phenethyl, dibenzylmethyl, methylphenylmethyl, 3- (2- naphthalenes)-butyl etc..

As used in this article, term " alkylidene " (itself or as another substituent group part) refer to it is such Alkyl：It is divalent, that is, there are two singly-bounds for being connect with two other groups for tool.Alkylidene can be line style or branched And it can be substituted as indicated.The non-limiting examples of alkylidene include methylene (- CH₂), ethylidene (- CH₂- CH₂), methylmethylene (- CH (CH₃) -), 1- methyl-ethylenes (- CH (CH₃)-CH₂), sub- n-propyl (- CH₂-CH₂- CH₂), 2- methyl propylenes (- CH₂-CH(CH₃)-CH₂), 3- methyl propylenes (- CH₂-CH₂-CH(CH₃) -), sub- normal-butyl- CH₂-CH₂-CH₂-CH₂), 2- methylbutylenes (- CH₂-CH(CH₃)-CH₂-CH₂), 4- methylbutylenes (- CH₂-CH₂-CH₂- CH(CH₃) -), pentylidene and its chain isomer, hexylidene and its chain isomer, heptamethylene and its chain isomer, octamethylene and its Chain isomer, nonylene and its chain isomer, decylene and its chain isomer, alkylene undecyl and its chain isomer, Asia 12 Alkyl and its chain isomer.When following herein when using subscript after carbon atom, which refers to that named group can The carbon atom number contained.For example, C₁-C₂₀Alkylidene refers to the alkylidene with 1-20 carbon atom.

Illustrative halogen atom includes chlorine, bromine, fluorine and iodine, and wherein fluorine and chlorine is preferred.

Suitable metallocene catalyst used herein is preferably provided on solid carrier.The carrier can be with it is normal The arbitrary component for advising metallocene catalyst does not have chemically reactive inert organic or inorganic solid.For the supported catalyst The suitable carrier material of agent includes solid inorganic oxide such as silica, aluminium oxide, magnesia, titanium oxide, three oxidations Boron, calcium oxide, zinc oxide, barium monoxide, thorium oxide and silica and one or more 2nd or 13 family metal oxides Mixed oxide such as silica-magnesia and silica-alumina mixed oxide.Silica, aluminium oxide, and The mixed oxide of silica and one or more 2nd or 13 family metal oxides is preferred carrier material.It is such mixed The preferred embodiment for closing oxide is silica-alumina.Most preferably silicon dioxide compound.In a kind of preferred implementation side In formula, the metallocene catalyst is provided on solid carrier, preferably silica supports.The silica can be granular , agglomeration, pyrolysis or other forms.

The FMC can be used together with one or more co-catalysts to form catalyst system.As used in this article " catalyst system " refers to consistently working to improve one or more chemical reagent of reaction rate.Including public herein The catalyst system of the FMC for the type opened can be used for being catalyzed propylene polymerization into syndiotactic polypropylene.

In some embodiments, the catalyst system for manufacturing syndiotactic polypropylene used herein includes helping Catalyst.When in by the catalytic component of present disclosure (i.e. FMC) for polymerization procedure, they can be with activation co-catalysis Agent is used together.Suitable activation co-catalyst can be any co-catalyst such as co-catalysis containing aluminium for becoming known for the purpose Agent, boracic co-catalyst or fluorinated catalyst.It is described to may include aikyiaiurnirsoxan beta, alkyl aluminum, lewis acid containing aluminum cocatalyst And/or fluorinated catalytic carrier.

In some embodiments, using aikyiaiurnirsoxan beta as the activator for the metallocene catalyst.As herein It uses, term " aikyiaiurnirsoxan beta " and " aluminiumAlkane " is interchangeably used and refers to that the metallocene catalyst can be activated Substance.In one embodiment, aikyiaiurnirsoxan beta includes oligomeric line style and/or cricoid alkylaluminoxane.Further real It applies in mode, the aikyiaiurnirsoxan beta has formula (V) or (VI)：

R^a-(Al(R^a)-O)x-AlR^a2 (V), for oligomeric linear alumoxanes；Or

(-Al(R^a)-O-)_y(VI), for oligomeric Cyclic aluminoxane

Wherein x is 1-40 and preferably 10-20；

Wherein y is 3-40 and preferably 3-20；With

Wherein each R^aIndependently selected from C₁-C₈Alkyl, and preferably methyl.In a preferred embodiment, the alumina Alkane is methylaluminoxane (MAO).

In a preferred embodiment, the metallocene catalyst is the metallocene-aluminoxane catalyst of load, packet Include the metallocene being incorporated on porous silicon dioxide carrier and aikyiaiurnirsoxan beta.

It can be used one or more by formula AIR^b _xThe alkyl aluminum of expression is as other co-catalyst, wherein each R^bIt is identical or It is different and selected from the halogen either alkoxy with 1-12 carbon atom or alkyl and x is 1-3.Non-limiting examples are Triethyl aluminum (TEAL), triisobutyl aluminium (TIBAL), trimethyl aluminium (TMA) and methyl-methyl-ethyl aluminium (MMEAL).Especially Suitably trialkylaluminium, most preferably triisobutyl aluminium (TIBAL) and triethyl aluminum (TEAL).

The alkylaluminoxane promoter and FMC can any suitable amount use to provide olefin polymerization catalysis. Suitable aluminium:FMC molar ratios are 10:1-20,000:In the range of 1, alternatively, 50:1-10,000:In the range of 1, substitute Ground, 100:1-5,000:In the range of 1.

Such as solution phase, gas phase, slurry phase, ontology phase, high pressure can be used to form syndiotactic polypropylene in propylene polymerization Technique or combinations thereof carries out.One example of gas-phase polymerization process include continuous circulation system, wherein by recycle gas stream ( Referred to as recirculation stream or fluidizing agent) it is heated in the reactor by heat of polymerization.By outside the reactor Heat is moved out to from the recycle gas stream in another part of the cycle by cooling system.It can will contain one or more lists The recycle gas stream of body is continuously circulated through fluid bed in the presence of a catalyst at reaction conditions.The recyclegas Logistics is usually taken out from the fluid bed and is recycled in the reactor.Meanwhile it can be by polymer product from institute Reactor is stated to take out and fresh monomer can be added to substitute the monomer of polymerization.Temperature of reactor in gas phase process can be such as From -30 DEG C to 120 DEG C or from 60 DEG C to 115 DEG C or from 70 DEG C to 110 DEG C or DEG C variation from 70 DEG C to 95.

Slurry phase processes are generally comprised within added in monomer and the liquid polymerizaton medium of optional hydrogen and catalyst Form the suspension of the granulated polymer of solid.It can be by the suspension (it may include diluent) intermittently or continuously It is removed from the reactor, wherein can detach and recycle (optionally after the distillation again from polymer by volatile component Cycle) to the reactor.The liquefied diluent used in polymerisation medium may include such as C_3-7Alkane (such as hexane or different Butylene).Used medium is usually liquid under polymerization conditions and is relative inertness.Bulk phase process and slurry process It is similar.However, technique can be such as bulk process, slurry process or bulk slurry technique.

Slurry polymerization is preferably used prepare the syndiotactic polypropylene, preferably in slurry loop reactor or The syndiotactic polypropylene is prepared in continuous-stirring reactor.As used in this article, term " annular-pipe reactor " and " slurry Annular-pipe reactor " can be used interchangeably herein.The annular-pipe reactor can be maintained at such as 27 bars -45 bars pressure and At a temperature of 38 DEG C -121 DEG C.

Polymerization can carry out in a reactor or in a serial response device.The blending of a variety of syndiotactic polypropylenes Object is also suitable for the present invention.

In some embodiments, the pipeline is by including the syndiotactic polypropylene and can further comprise at least A kind of composition of processing aid is made.Non-limiting examples for the suitable processing aid in the present invention include to be based on fluorine Or the processing aid of silicon.

Preferred processing aid can be selected from fluoropolymer, including fluoroelastomer and crystallinity or hemicrystalline fluoroplastics Or its blend.Can be any polymer containing fluorine by the fluoropolymer being blended with the syndiotactic polypropylene.As A kind of fluoropolymer can be crystalline or generally unbodied.It is obtained suitable for commercially available in the present invention Processing aid example include can the material that obtains of following title：Viton Freeflow Z100 of DuPont, Viton Freeflow Z110、Viton Freeflow Z200、Viton Freeflow Z210、Viton Freeflow Z300、Viton Freeflow 10、Viton Freeflow RC；The Dynamar FX 5911 of 3M, Dynamar FX 5912, Dynamar FX5920A、Dynamar FX 5926、Dynamar FX 5927、Dynamar FX 9613、Dynamar FX 9614, the Tecnoflon NM and SOLEF 11010 of the DAI-EL DA-410 of Daikin, DAI-EL DA-910 and Solvay. The fluoropolymer of a suitable class in for the present invention be by following material it is one or more obtain it is poly- Close object：Vinylidene, hexafluoropropene and tetrafluoroethene.

The processing aid can with masterbatch or pure substance in any stage of manufacture (for example, be granulated, compounding during Or at pipeline production line) addition, as known in the art.

E.g., including the composition of the syndiotactic polypropylene may include at least one processing of at least 50ppm At least one processing aid of auxiliary agent, preferably at least 100ppm, preferably at least 200ppm, be based preferably on silicon or fluorine plus Work auxiliary agent such as fluoroelastomer.

The composition including the syndiotactic polypropylene can additionally comprise a effective amount of as known in the art Any conventional additives are such as antioxidant, antiacid, wetting agent, nucleating agent.

Preferred antioxidant can be found in Zweifel, Hans, ISBN 354061690X, Springer-Verlag 1998.Preferred antioxidant is Irganox 1010 and Irgafos 168 as shown below.

Irganox 1010：

Irgafos 168：

Calcium stearate can be added as processing aid.The additive can be used as masterbatch or pure substance in any of manufacture (for example, being granulated, during compounding or at pipeline production line) addition in stage, as known in the art.

In some embodiments, it can be contained for the composition including the syndiotactic polypropylene of pipeline Its auxiliary material such as filler and/or stabilizer and/or antistatic agent and/or pigment and/or reinforcing agent.

The blend of syndiotactic polypropylene and other polymer is also feasible.In this case, described another The ratio of outer polymer has to be lower than 30% weight, is preferably lower than 10% weight, even more preferably less than 2% weight. Among possible polymer, add small polymerized ethylene content (typically 1% weight) be preferably as polyethylene plays between With the effect of the polyacrylic nucleating agent of vertical structure.Also other nucleating agents can be added to the syndiotactic polypropylene.

For the purpose of the application, nucleating agent is defined as improving the compound of the polyacrylic crystallized temperature. Any nucleating agent known to technical staff is can be selected from for the suitable nucleating agent in the present invention.In some embodiments, institute It includes following group to state nucleating agent and be selected from：Talcum, carboxylate, sorbitol acetal, phosphate ester salt, substituted benzene trimethamide and poly- Close object type nucleating agent and its blend.

The example of suitable carboxylate includes organic carboxylate.Specific example is sodium benzoate and lithium benzoate.It is described to have Machine carboxylate can also be for example bicyclic organic dicarboxylic acid salts of alicyclic organic carboxylate and especially bicyclic [2.2.1] heptane dicarboxyl Hydrochlorate.The nucleating agent of the type is by Milliken Chemical conductsHPN-68 is sold.Suitable mountain The example of pears acetal includes dibenzyl sorbitol (DBS), bis- (p- methyl-dibenzyl sorbitol) (MDBS), bis- (p- Ethyl-dibenzyl sorbitol), it is bis- (3,4- dimethyl-dibenzyl sorbitol) (DMDBS) and bis- (4- propyl benzal) Propyl sorbierite.Bis- (3,4- dimethyl-dibenzyl sorbitol) (DMDBS) and bis- (4- propyl benzal) propyl sorbierites are Preferably.These can be for example from Milliken Chemical with Millad 3905, Millad 3940,3988 and of Millad The trade name of Millad NX8000 obtains.The example of suitable phosphate ester salt includes bis- (the 4,6- di-t-butyls of 2,2'- methylene- Phenyl) phosphate salt.Such phosphate ester salt can for example be obtained from Asahi Denka as NA-11 or NA-21.Suitably The example of substituted trimethamide includes the compound of logical formula (III)：

Wherein, in the compound of formula (III), R1, R2 and R3 are independently from each other C₁-C₂₀Alkyl, C₅-C₁₂Cycloalkanes Base or phenyl, respectively itself again can be by one or more C₁-C₂₀Alkyl, C₅-C₁₂Naphthenic base, phenyl, hydroxyl, C₁-C₂₀Alkane Base amino or C₁-C₂₀The substitutions such as alkyl oxy.C₁-C₂₀The example of alkyl includes methyl, ethyl, n-propyl, normal-butyl, isobutyl It is base, tertiary butyl, n-pentyl, isopentyl, 1,1- dimethyl propyls, 1,2- dimethyl propyls, 3- methyl butyls, hexyl, heptyl, pungent Base or 1,1,3,3- tetramethyl butyls.C₅-C₁₂The example of naphthenic base include cyclopenta, cyclohexyl, cyclooctyl, cyclo-dodecyl, Adamantyl, 2- methylcyclohexyls, 3- methylcyclohexyls or 2,3- Dimethylcyclohexyls.In WO 03/102069 and Blomenhofer et al. discloses such nucleating agent in Macromolecules 2005,38,3688-3695.Polymer The non-limiting examples of type nucleating agent include the Polymeric Nucleating Agent containing vinyl compound, e.g., as disclosed in EP-A1- Those of in 0152701 and EP-A2-0368577.Polymeric Nucleating Agent containing vinyl compound can be with the polypropylene Physically or chemically it is blended.Suitable vinyl compound includes vinyl cycloalkane or vinyl at least six carbon atom Cycloolefin for example vinyl cyclopentane, vinyl -3- methyl cyclopentanes, vinyl cyclohexane, vinyl -2- hexahydrotoluenes, Vinyl -3- hexahydrotoluenes, vinyl norcamphane, vinylcyclopentene, vinylcyclohexene, vinyl -2- methyl cyclohexanes Alkene.The further example of Polymeric Nucleating Agent includes poly- 3-methyl-1-butene, poly dimethyl styrene, polysilane and poly- alkane Base dimethylbenzene.These Polymeric Nucleating Agents can be introduced by being chemically or physically blended in the polypropylene.

Useful other nucleating agents may include various organic and inorganic nucleator example in embodiment disclosed herein Such as：The quinacridone colorant permanent red E3B " Q-Dye " of γ-crystalline form；The disodium salt of phthalic acid；The aluminium of 6- quinizarin sulfonic acids Salt；M-phthalic acid and terephthalic acid (TPA)；N', N'- dicyclohexyl -2,6- aphthalimide, also referred to as NJStar NU-100, It is available from New Japan Chemical Co.；The nucleating agent of salt based on rosin/resin acid (adiebetic acid)；It is single sweet Oily zinc (II)；Such as nucleating agent based on diamide compound disclosed in United States Patent (USP) No.6,235,823, such as N- hexamethylenes Base -4- (N- cyclohexylcarbonylaminos) benzamides and N, N'-1,4- hexamethylene-bis--benzamide；Derived based on trimesic acid The nucleating agent of object, such as disclosed in WO 02/46300, WO 03/102069, WO 2004/072168, it includes such as 1, Three (uncle of 3,5- benzene tricarbonic acids three (cyclopentyl amide), 1,3,5- benzene tricarbonic acids three (cyclohexyl amide) and 1,3,5- benzene tricarbonic acids Butyl) amide.

The nucleating agent can by powder, pellet, liquid, it is other usually it is available in the form of or a combination thereof use with gather Propylene blends (melt blending).In other embodiment, the nucleating agent can be compounded with polypropylene to form nucleation with adding Masterbatch is added to blend (melt blending) with polypropylene.Including according to the polypropylene of embodiment disclosed herein (it is a kind of or It is a variety of) and the composition of nucleating agent (one or more) can be prepared by the following procedure：By each component in the blend component One or more melting temperatures near or above at a temperature of mix or mediate.Can be used can reach desired temperature and By the typical mixed with polymers or kneader device of the mixture fusion plastification.These include grinding machine, kneader, extruder (both single screw rod and twin-screw),Mixer, calender etc..Order by merging and method may depend on finally The form (powder, pellet, masterbatch etc.) of composition (composition) and starting ingredient.

In some preferred embodiments, including the composition of the syndiotactic polypropylene may include pigment.Institute The specific color for stating pigment may depend on the fluid (water or gas) that will be conveyed in the pipeline and country (depends on forcing The regulation of execution).

The composition including the syndiotactic polypropylene for pipeline according to the present invention can contain for example most The up to stabilizer of the filler of 40% weight and/or 0.01%-2.5% weight and/or the antistatic agent of 0.1%-1% weight And/or the pigment of 0.2%-3% weight and/or the reinforcing agent of 0.2%-3% weight, it is based on the syndiotaxy in every case Polyacrylic total weight.

Pipeline according to the present invention can manufacture according to procedures known in the art.According to second aspect, the present invention is also contained Technique of the lid for manufacturing the pipeline according to first aspect comprising following steps：

(a) composition including the syndiotactic polypropylene is extruded as pipeline；

(b) tube-cooled that will be formed in step (a)；With

(c) the pipeline heating/annealing that will optionally be formed in step (a).

Extrusion step (a) can carry out at a temperature of at least 150 DEG C.Such as extrusion step (a) can be ranging from least 150 It is carried out at a temperature of DEG C-at most 250 DEG C, preferably at least 160 DEG C-at most 230 DEG C.In some embodiments, step (a) is wrapped It includes and first for example moulds the syndiotactic polypropylene composition at a temperature of at least 150 DEG C-at most 250 DEG C in an extruder Change, it is then extruded as desired internal diameter by ring moulds head.

Extruder for manufacturing pipeline according to the present invention can be single screw extrusion machine or double screw extruder or equal Change and is cascaded with the extruder of extruder (single screw rod or twin-screw).In order to (be added described in homogenizing and introducing by villus manufacture pellet When adding agent), single screw extrusion machine (the preferably L/D with 20-40) can be used, or (preferably using double screw extruder L/D with 20-40), it is preferred to use extruder cascades.In some embodiments, supercritical CO is used during extrusion₂ Or water is to help to be homogenized.It is contemplated that a variety of modifications, such as uses supercritical CO₂To help to be homogenized, use water during extrusion.Appoint In addition selection of land can use Melt Pump and/or static mixer between extruder and ring moulds head.With ranging from about 16- The annular die of 2000mm and even greater diameter is possible.

Melt from extruder can be first via the pore size distribution arranged in a conical manner on ring shaped cross-section, then It is fed to core/die-head combination via coil pipe (coil) distributor or sieve.If necessary, can in addition pacify before die head exit Fill the restrictor ring or other structures element for ensureing uniform melt flows.

After leaving ring moulds head, pipeline can be detached to above calibration mandrel.Once pipeline has been formed into expectation Diameter and thickness, then the cooling of step (b) pipeline occur.The cooling of pipeline by air cooling and/or can pass through water cooling It carries out, optionally also there is internal water cooling.

After cooling, pipeline can be made to be optionally subjected to heating/annealing steps (c).Heating/the annealing steps can dry The time of length is determined in case or any other suitable equipment；The technique (process) is referred to as heat in the art Annealing.In some embodiments, pipeline is made to undergo thermal annealing at a temperature of at least 60 DEG C.In some embodiments, Make pipeline experience at a temperature of at least 60 DEG C-at most 120 DEG C；Preferably at a temperature of at least 70 DEG C-at most 110 DEG C；More Thermal annealing preferably at a temperature of at least 75 DEG C-at most 90 DEG C.In some embodiments, make pipeline experience thermal annealing extremely It is 3 days few.In some embodiments, make pipeline experience thermal annealing at least 3 days-at most 20 days, such as at most 14 days；Preferably extremely It is 4 days-at most 12 days few；More preferably at least 5 days-at most 10 days；Most preferably at least 6 days-at most 8 days.

In some embodiments, pipeline is made to undergo the thermal annealing at least 3 at a temperature of at least 70 DEG C-at most 120 DEG C It is-at most 14 days.

Pipeline according to the present invention surprisingly shows improved engineering properties and/or intensity.In some embodiment party In formula, pipeline according to the present invention, which has, such as to be measured at least by the ISO 180- Notched Izod tests at 23 DEG C 20kJ/m²；Preferably at least 30kJ/m²；Preferably at least 35kJ/m²；Preferably at least 38kJ/m²；Preferably at least 40kJ/ m²；Preferably no more than 45kJ/m²Impact resistance.

Pipeline according to the present invention surprisingly shows improved flexible nature, is such as scratched by it according to ISO 178 Bent modulus measurement.In some embodiments, pipeline according to the present invention, which has, is less than 1000MPa；Preferably less than 900MPa；Preferably less than 800MPa；Preferably less than 700MPa；Preferably less than 600MPa；Even more preferably less than 500MPa Flexural modulus.

In some embodiments, pipeline according to the present invention usually have so that they can be attributed to according to ISO/TR The creep resistance of minimum desired strength (MRS) grade (10 grades of MRS) (for PE100 resins) of 9080 standards.The grade is Desired strength MRS measured according to statistical method and minimum is defined as under the prediction classified under 97.5% confidence interval It limits (LPL).

In some embodiments, pipeline according to the present invention usually has 50 DEG C/50 years at least 7.0MPa's of extrapolation Stress.

Pipeline according to the present invention has excellent tensile strength, modulus and impact resistance, and with outstanding transparent Property, and can transparent to be enough not to the pipeline add individual fining agent in the case of use.

According to the third aspect, the present invention provides pipeline that is according to first aspect and/or being manufactured according to second aspect and is used for The purposes of fluid of the conveying under pressure.Pipeline according to the present invention is very suitable for fluid of the conveying under pressure for example Water and gas.They can be used within the scope of very wide temperature.

Pipeline according to the present invention is also adapted to the trandfer fluid in pharmacy, chemistry and food-stuff production industry.

Present invention also contemplates that according to first aspect and/or according to second aspect manufacture pipeline for manufacturing medical product Purposes.Preferred product is to need to have an X-rayed those of performance.Most preferred product has about 2mm or smaller wall thickness, such as Heparin tube, centrifuge tube, culture bottle, syringe plug and cylinder etc..

It is illustrated by the following examples the present invention, but the present invention is not limited by the following examples.

Embodiment

Test method：

Unless otherwise stated, density is measured at 23 DEG C according to the method for standard ASTM D-1505.

Creep test carries out (table 2) in two different creep test equipment.Syndiotactic polypropylene (sPP) is passed through It compresses and is molded as 2mm sheet materials, ISO527 5A type tensile bars are then sampled in the sheet material.By the sample in perseverance It is inserted into the fixture of creep machine under constant temperature degree (being realized with water-bath or chamber), and applies load to the sample.For various kinds Product, record destroy (the deformation or fracture) time.

Bending test for characterizing pipeline flexible is from the modification of 178 three point bending tests of ISO.Unique difference It is that polymer samples are replaced by 40cm duct sections (diameter 32mm-SDR 11).The duct section is introduced into Zwick types 1445 In machine, in the center (span=200mm) of three point bending test.During experiment, the center of the span is applied a force upon Place, also corresponds to the center of the duct section.The actual conditions of experiment be (if not referring to the parameter or condition of experiment, Then this means that the value is applied with for the flexural modulus based on 178 three point bending tests of ISO measurement polymer samples Value it is identical)：

The radius at the edge load (load, loading)：10mm

The radius of supporter：5mm

Pre-loaded (pre-charge)：5N

Test speed：1mm/min

Temperature：23℃

Record the power as elongation function.Power is lower, then pipeline is more flexible.

Use the Perkin-Elmer Pyris Diamond differential scanning calorimeters (DSC) for using indium to be calibrated as reference substance The thermal property of analyzing polymers pellet or pipeline.Sample (is derived from the 2mg-10mg of the polymeric aggregate or the pipeline Sample) with the rate of 20 DEG C/min 220 DEG C are heated to from -50 DEG C, isothermal 3min later, then for the rate of -20 DEG C/min To -50 DEG C of cooling scanning, isothermal 3min, is then reheated to 220 DEG C with 20 DEG C/min later.It is heated at this second Melting temperature (Tm) is measured during journey, corresponds to the temperature at the maximum value at peak.

Circumference stress experiment is according to ISO 1167:What 1996 (E) were carried out.

Embodiment 1

By using1251 (by the syndiotactic polypropylene homopolymer of metallocene catalysis, having such as makes With¹³75% syndiotactic index that C-NMR is measured, can be from Total Petrochemicals USA, and Inc. is commercially available, property Matter is shown in Table 1) it is compression molded at 50 DEG C and prepares 527 type 5A tensile bars of ISO.Before carrying out creep test, by this A little tensile bars are persistently aged 3 days in simple stove at 60 DEG C.

Table 1

It is carried out in creep test water-bath shown in Fig. 1 and as listed in table 2.

Table 2

Temperature regulates and controls	Water-bath
		The application of constant stress	Stepping engine (engine)
The record of elongation	The distance between fixture
		The quantity of simultaneous test	6
Usage	Low stress

The following operation of experiment：Apply stabilization to the tensile bars under 50 DEG C of steady temperature are maintained at through entire experiment Tensile load measures the deformation (elongation) of sample at any time, until the destruction of sample occurs；The time of gained extends % The data of rate are mapped.

Fig. 2 shows the creep curve obtained when applying the constant stress of 8.5MPa.In on-test, the deformation of sample Sharp occur；However, deformation velocity is gradually slack-off up to reaching constant rate of deformation (middle section of curve), then send out The necking down (point of inflexion on a curve) of raw tensile bars, it means that having reached the yield strength of sample, (surrender corresponds to described Boundary between the reversible elasticity area and irreversible plastic zone of polymer).The inflection point of creep curve is soft by using Matlab Part as described in this article such Mathematical Fitting and measure.The time for introducing deformation epsilon (between ε=20% and 50%) drills Become as " data " in statistics.The dependence has been used to lower equation model：

ε (t)=x (1) * exp (x (2) * (t-x (3)))+x (4) * t+x (5)-x (6) * exp (- x (7) * (t-x (8))).

Wherein x (i) is that height can free adjusting parameter.Substantially, the equation contains Burger models and (is used plus exponential term In time-evolution of the description under high deformation/time).In addition, it does not force (0,0) point (in fact, (0,0) nearby coordinates Small fluctuation allow by caused by the mode that stress is applied some experimental errors take into account).

Once it is determined that x (i) parameters, then via the cyclisation of the second dervative of the elongation function as the function of time (annulation) inflection point is analytically calculated.

Under the concrete condition of Fig. 2, inflection point 1047h after on-test occurs, and the elongation recorded is 35.5%.

Table 3 is shown in carries out average inflection point time obtained after Mathematical Fitting and corresponding by the creep curve obtained Elongation.

Table 3

Fig. 3 is shown in the elongation of the inflection point of the creep test carried out under a variety of constant stress at 50 DEG C.

Comparative example 1

To using(polythene PE 100, can be from Total Petrochemicals USA Inc quotient by XT10N Purchase obtains, density 0.949g/cm³(ASTM D-792), melt index (MI) 7.5g/10min (21.6kg-190 DEG C of ASTM D-1238) (polypropylene random copolymer is provided by Borealis A/S, density 0.905g/cm with RA130E-8427³(ISO 1183), MI2 0.25g/10min (230 DEG C/2.16kg ISO 1133)) 527 types of ISO that are prepared by being compression molded at 50 DEG C 5A tensile bars carry out creep test as described in Example 1.

Fig. 4 shows both samples for embodiment 1 and comparative example 1, figure of the average inflection point time to applied stress.By The figure can determine, the tensile bars made of syndiotactic polypropylene can be subjected to with polyethylene (XT10N it) makes At equally big (or higher) stress of tensile bars.Fig. 4 further displays the syndiotactic polypropylene tested in embodiment 1 (1251) gained regression curve (and equation)；Based on the curve extrapolation pressure resistance of about 8MPa has been obtained to 50 years Property.

Measure in embodiment 1 tensile bars that obtain andThe flexural modulus of XT10N battens and shock resistance Property.Impact resistance is used in the measurement of the ISO 180- Notched Izod tests at 23 DEG C.As a result it is shown in Table 5.

Table 5

Embodiment 2

It will1251 (syndiotactic polypropylene is provided by Total Petrochemicals USA, Inc., Property is shown in embodiment 1) it is squeezed on the single screw extrusion machine (Reifenhauser) with 70mm diameters and L/D=25 Go out.Output is in range 15-20kg/h.Using 25mm die heads so that the polymer of melting meets the final diameter of 32mm.So Afterwards, using 32mm calibrators, to manufacture pipeline, (melting before Fig. 5 is shown in the entrance at die head exit and in calibrator is poly- Close the photo of object).It is~the rate of 2mm to allow the final thickness of the wall of pipeline after cooling in water-bath (10-15 DEG C) Pipeline is slowly drawn.Table 6 shows the machined parameters for manufacturing pipeline.Pipeline 1 be by1251 and 1% What the dry-blended mixture of the HD6081 (high density polyethylene (HDPE) is provided by TOTAL Petrochemicals) of weight squeezed out, and manage Road 2-6 is by 100%1251 extrusions.Pipeline 1 is slightly whiter than the pipeline manufactured by pure sPP.In higher melt At a temperature of the pipeline that manufactures there is more smooth outer surface.

Table 6

According to the flexural modulus of the measurement gained pipelines of ISO 178 and it is surprisingly for all tested pipelines All it is low (~450MPa).

Evaluate the aging condition of sPP.

Fig. 6 shows the DSC thermograms of the inner surface and the outer surface of sPP pipelines 2.Outer surface (due to pipeline quenching and) do not have Have time to crystallize, and therefore, DSC thermograms (be labeled as "outside") only nearby showed at 125 DEG C one it is sharp molten Melt peak.Inner surface has time to crystallize, and its DSC thermogram (being labeled as "inner") present two apparent melting peaks (~ 113 DEG C and 125 DEG C).Therefore, the inside of pipeline has more stable microstructure.

Table 7 shows the data of the DSC thermograms from the pipeline manufactured under different extrusion temperatures.The data show, with Extrusion temperature raising, cooling rate also increases, and the sPP forms of middle appearance have " low " melt between 110 DEG C and 120 DEG C Melt fading away for peak (~110 DEG C).With 1%HD6081 prepare pipeline (pipeline 1) provide have maximum low melt peak (~ 115 DEG C) thermogram, show HD6081 auxiliary sPP crystallization in terms of effect.

Table 7

In another experiment, one piece of sPP pipeline 2 is placed in the baking oven being arranged under 80 DEG C of steady temperature.To there is rule The sub-fraction of the pipeline is cut to be analyzed by DSC in the interval of rule.Fig. 7 shows the temperature spectrum inside recorded pipeline Figure, and Fig. 8 shows the thermogram of recorded pipeline external.The relative intensity of melting peak is allowed to determine, persistently be moved back at 80 DEG C For making the sPP microstructures in pipeline in the inner surface and the outer surface the two, further stabilisation is useful to fire within 3 days.

Pipeline 1,2 and 6 is persistently placed 14 days at 80 DEG C in an oven, dsc analysis is carried out after the time.Table 8 converges The percentage and total melting enthalpy of total area (subregion, partial area) of " low " warm melting peak.It is squeezed in difference It is manufactured at a temperature of going out, the DSC thermograms for the sPP pipelines then persistently annealed at 80 DEG C 14 days are shown in Fig. 9-11.Fig. 9 is shown For pipeline 1 (sPP+1%HD6081, at 160 DEG C) obtain DSC thermograms, Figure 10 show for pipeline 2 (pure sPP, At 170 DEG C) obtain DSC thermograms and Figure 11 show the DSC thermograms obtained for pipeline 6 (pure sPP, at 220 DEG C). For all samples, total melting enthalpy is increased to~39J/g from~29J/g.Thermogram (Fig. 9) display of pipeline 1, two melting peaks With almost the same relative intensity.The integral of the area is estimated as about 70%.After the anneal step, pipeline 2 The DSC thermograms (Figure 11) of DSC thermograms (Figure 10) and pipeline 6 are almost the same, show their microstructure during annealing It has developed and has generated stable and comparable (equivalent) crystalline state.

Table 8

Make annealing steps of the experience of pipeline 1 and 2 at 80 DEG C 7 days, the temperature at 20 DEG C is then carried out to manufactured pipeline Circumference stress experiment under degree.As a result it is shown in Table 9.

Table 9

Pipeline	Circumference stress (MPa)	Thickness/diameter (mm)	Time to rupture (h)
				1	12.5	1.95/28.6	6
1	12.3	2.20/26.9	43
				1	12.0	2.03/28.0	186
2	13.0	2.30/31.0	25
				2	12.7	2.47/31.9	1121
2	12.5	2.40/30.7	851
				2	12.3	2.41/31.5	2416

Comparative example 2

It usesXT10N (PE100, can be commercially available from Total Petrochemicals USA Inc, Density 0.949g/cm³(ASTM D-792), melt index (MI) 7.5g/10min (21.6kg, 190 DEG C, ASTM D-1238) manufacture tools There is the pipeline of 32mm diameters.Using RA130E-8427, (polypropylene random copolymer, can be commercially available from Borealis A/S, close Spend 0.905g/cm³(ISO 1183), MI2 0.25g/10min (230 DEG C/2.16kg ISO 1133)) manufacture have 32mm it is straight The pipeline of diameter.Using MDPE 3802, (PE80 polyethylene, can be commercially available from TOTAL Refining＆Chemicals, density 0.938g/cm³(ISO 1183), MI2 20g/10min (230 DEG C/21.6kg ISO 1133-G)) it manufactures with 32mm diameters Pipeline.Each pipeline be using 45mm die heads manufacture so that the polymer of melting meets final 32mm diameters.Make institute State annealing steps of the pipeline experience at 80 DEG C 7 days.

The flexural modulus (1100-1300MPa) of gained pipeline is measured according to ISO 178.Pipeline ratio including sPP includes complete With the polyacrylic pipeline flexible of vertical structure.

The circumference stress experiment at 20 DEG C is carried out to manufactured pipeline.Figure 12 is shown for manufacturing in example 2 Pipeline (pipeline 5) and the pipeline for being tested in comparative example 2, figure of the time to rupture to the circumference stress applied.By this Figure can determine, at a temperature of 20 DEG C, with syndiotactic polypropylene (1251) pipeline made of can be subjected to and use Polyethylene (XT10N, MDPE3802) made of equally big (or higher) stress of pipeline.

Claims

1. pipeline comprising composition, the composition include at least 50% weight of the total weight based on the composition At least one syndiotactic polypropylene；Wherein described at least one syndiotactic polypropylene, which has, to be used¹³C-NMR spectroscopy measurements At least 70% syndiotactic index；The melting temperature peak higher than 145 DEG C is not presented for the wherein described syndiotactic polypropylene, It is measured by differential scanning calorimetry.

2. pipeline according to claim 1 has the flexural modulus less than 1000MPa measured by ISO 178.

3. according to the pipeline of claims 1 or 2, the pipeline has 50 DEG C/50 years to extrapolate at least stress of 7.0MPa.

4. according to the pipeline of any one of claim 1-3, used wherein the syndiotactic polypropylene has¹³C-NMR spectroscopic methodologies At most 90% syndiotactic index measured.

5. according to the pipeline of any one of claim 1-4, wherein the syndiotactic polypropylene does not show melting higher than 136 DEG C Melt temperature peaks.

6. according to the pipeline of any one of claim 1-5, wherein the syndiotactic polypropylene has according to ASTM D-1238 items Part L, at least melt flow rate (MFR) of 0.3g/10min measured under the load of 2.16kg at 230 DEG C.

7. according to the pipeline of any one of claim 1-6, wherein the syndiotactic polypropylene has according to ASTM D-1238 items Part L, the at most melt flow rate (MFR) of 25.0g/10min measured under the load of 2.16kg at 230 DEG C.

8. according to the pipeline of any one of claim 1-7, wherein the syndiotactic polypropylene is with less than 0.7% weight The syndiotactic polypropylene homopolymer of alpha-olefin comonomer.

9. according to the pipeline of any one of claim 1-8, wherein the syndiotactic polypropylene is pure syndiotactic polypropylene Homopolymer.

10. according to the pipeline of any one of claim 1-9, wherein the syndiotactic polypropylene is to be catalyzed by single-site catalysts Syndiotactic polypropylene.

11. according to the pipeline of any one of claim 1-10, has and tried by the ISO 180- notched izods at 23 DEG C The fixed at least 40kJ/m of test²Impact resistance.

12. the technique for manufacturing the pipeline according to any one of claim 1-11 comprising following steps：

(a) composition is extruded as pipeline；The composition includes at least 50% weight of the total weight based on the composition At least one syndiotactic polypropylene；Wherein described at least one syndiotactic polypropylene, which has, to be used¹³C-NMR spectroscopic methodologies are surveyed At least 70% syndiotactic index of amount；The melting temperature higher than 145 DEG C is not presented for the wherein described syndiotactic polypropylene Peak is measured by differential scanning calorimetry；

(b) tube-cooled that will be formed in step (a)；With

(c) the pipeline heating/annealing that will optionally be formed in step (a).

13. technique according to claim 12, wherein step (c) carry out at a temperature of at least 60 DEG C-at most 120 DEG C.

14. according to the technique of any one of claim 12 or 13, wherein step (c) carries out at least 3 days.

15. according to any one of claim 1-11's and/or according to the pipe manufactured according to the technique of any one of claim 12-14 Road is used to convey the purposes of the fluid under pressure.