CN103804555B - Ethene polymers and containing this polyvinyl compositions and application thereof and a kind of pipeline - Google Patents
Ethene polymers and containing this polyvinyl compositions and application thereof and a kind of pipeline Download PDFInfo
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- CN103804555B CN103804555B CN201210441414.9A CN201210441414A CN103804555B CN 103804555 B CN103804555 B CN 103804555B CN 201210441414 A CN201210441414 A CN 201210441414A CN 103804555 B CN103804555 B CN 103804555B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92009—Measured parameter
- B29C2948/92266—Mechanical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/926—Flow or feed rate
Abstract
The invention provides a kind of ethene polymers and application thereof, on the basis of this polyvinyl total amount, this ethene polymers contains the monomeric unit formed by ethylene and by C4-C10Alpha-olefin formed monomeric unit；This polyvinyl molecular weight measured by gel permeation chromatography is bimodal distribution, wherein, the weight average molecular weight of lower-molecular-weight component is 5,000-50,000, the weight average molecular weight of high molecular weight component is 50,000-3,000,000, lower-molecular-weight component is 0.28-0.52 with separating degree DOS of high molecular weight component.Present invention also offers a kind of containing described polyvinyl compositions and application thereof.Invention further provides a kind of pipeline prepared by said composition.When the ethene polymers of the present invention prepares pipeline by the method for extrusion, it is possible to extrude at higher velocities, and the pipeline of preparation has higher resistance to hydrostatic tension destructive characteristics.
Description
Technical field
The present invention relates to a kind of ethene polymers, the invention still further relates to a kind of containing described polyvinyl compositions and application thereof, the invention further relates to a kind of pipeline prepared by described compositions.
Background technology
The ethene polymers based on ethylene monomer unit that ethylene and alpha-olefin copolymer obtain has light weight, corrosion-resistant, rigid-tough balance good, easy-formation and economic dispatch feature, is the ideal material of tubing and pipeline.The pipeline prepared by ethene polymers relies on combination property and the economy of its excellence, is widely used in industry, agricultural, daily life equal pressure or non-pressure tubing field.At present, ethene polymers the typical products of the pipeline prepared includes PE63, PE80 and PE100 grade non-pressure or pressure tubing etc..But, the use temperature of aforementioned tubes or pipeline is the most relatively low (for example, room temperature).When using temperature to improve, ethene polymers is easily deformed and creep resistance declines, and causes shorten the service life of tubing or pipeline, thus the range of application of these tubing or pipeline is restricted.
Along with catalyst for ethylene technology and the continuous progress of polymerization technique, ethene polymers intensity at high temperature is improved, some ethene polymerss can use in the higher temperature region such as 40-110 DEG C, such as, may be used for the fields such as floor heating, radiator, hot and cold water conveying, earth source heat pump.Its typical products such as heat-proof polythene (that is, PERT).
At present, disclosed heat-resisting polyvinyl preparation method typically uses single site catalysts, ethylene carry out copolymerization with such as 1-octene, 1-hexene with the alpha-olefin of 1-butylene, and obtaining molecular weight is unimodal, bimodal or the ethene polymers of multi-modal.The polymerization used can be solwution method, slurry process, vapor phase method or slurry/vapor phase method.
The polyvinyl molecular weight distribution using single site catalysts to carry out being polymerized and to prepare is narrower, although material has good mechanical property, but rheology shear thinning degree is little, process window is narrow, under higher process velocity, melt fracture or sharkskin phenomenon easily occur, the surfaces externally and internally causing the tubing of preparation is coarse, and then affects its long-term resistance to hydrostatic performance.
In order to improve its processing characteristics, general employing two sections or multi-stage polymeric technique, obtain the ethene polymers of bimodal or multimodal molecular weight distribution, all use two sections such as WO01/25328, WO03/020821 and WO08/064810 or multi-stage polymeric technique is bimodal or the ethene polymers of multi-modal to prepare molecular weight.It addition, it is bimodal or the ethene polymers of multi-modal to prepare molecular weight that KR2005/000854 discloses employing two or more single site catalysts in a reactor.EP08157848 discloses employing single site catalysts, is polymerized in a reactor, prepares the ethene polymers that molecular weight is Unimodal Distribution.
Actual application finds, uses ethene polymers prepared by single site catalysts, when the tubing that extrusion molding bore is bigger, melt viscosity is low, easily occurring in extrusion that stream hangs down phenomenon, in molding or after molding in sweat soldering, stream hangs down and then causes welding wall unevenness even.Therefore, the ethene polymers prepared is only used for molding minor caliber pipe (if caliber is the tubing of below 32mm) to single site catalysts (such as metallocene catalyst), and tubing should not use fusion weld.
In addition to single site catalysts, use Ziegler-Natta catalyst also can prepare the ethene polymers with superior heat resistance energy.Using the molecular weight prepared of Ziegler-Natta catalyst is that the ethene polymers of bimodal distribution not only has good calorific intensity and creep resistance, and has the processing characteristics of excellence, with the bigger tubing of molding bore, and can use fusion weld.
WO03/033586 discloses a kind of pipe for hot fluids (using temperature is more than 60 DEG C), and pipeline meets DIN1683395 DEG C, the requirement of 3.6MPa165h.The ethene polymers that this pipeline uses is that the molecular weight obtained by Loop Slurry/gas phase polymerization is the ethylene-butene copolymer of bimodal distribution in the presence of Ziegler-Natta catalyst, and the density of this copolymer is 0.921-0.950g/cm3, elastic modelling quantity is the highest can be 900MPa, and lower-molecular-weight component is 30:70 to 55:45 with the weight ratio of high molecular weight component.
Summary of the invention
For being mainly used in the heat-resisting ethene polymers tubing of floor irradiation heating, due to the bore of pipeline less (generally Φ 20mm), quickly extrude in molding, it is possible to production efficiency is greatly improved.Therefore in the case of meeting pipeline hydrostatic strength, it is desirable to the fastest speed extrusion.But, the present inventor finds in research process: when using existing ethene polymers to form pipeline by the technique of extrusion, material extrusion linear speed at extruding dies too fast (such as: extrusion linear speed is more than 35m/min), resistance to hydrostatic tension destruction to the pipeline of preparation is disadvantageous, unfavorable particularly with resistance to hydrostatic tension destructive characteristics at relatively high temperatures.
The present inventor is through further investigation, develop a kind of ethene polymers, this ethene polymers is when the mode using extrusion prepares tubing, even if with higher extruded velocity (such as: extrusion linear speed as 35m/min more than) extrusion, also can obtain that there is preferable resistance to hydrostatic tension destructive characteristics, the pipeline of the most high temperature resistant hydrostatic tension destructive characteristics.Complete the present invention on this basis.
A first aspect of the present invention provides a kind of ethene polymers, and this ethene polymers contains the monomeric unit and at least one formed by ethylene by C4-C10Alpha-olefin formed monomeric unit, on the basis of described polyvinyl total amount, ethylene the content of the monomeric unit formed is 95-99.9 weight %, alpha-olefin the content of the monomeric unit formed is 0.1-5 weight %；
This polyvinyl molecular weight measured by gel permeation chromatography is bimodal distribution, wherein, the weight average molecular weight of lower-molecular-weight component is 5,000-50,000, the weight average molecular weight of high molecular weight component is 50,000-3,000,000, and the weight average molecular weight of described lower-molecular-weight component is 0.28-0.52 less than the weight average molecular weight of described high molecular weight component, described lower-molecular-weight component with separating degree DOS of described high molecular weight component, this polyvinyl melt mass flow rate is 0.05-0.2g/10min, and described separating degree DOS is determined by Formulas I:
In Formulas I, MW.H.Represent the weight average molecular weight of high molecular weight component,
MW.L.Represent the weight average molecular weight of lower-molecular-weight component,
WAHWHRepresent the half-peak breadth of high molecular weight component,
WAHWLRepresent the half-peak breadth of lower-molecular-weight component.
A second aspect of the present invention provides a kind of compositions, the said composition ethene polymers containing the with good grounds present invention and at least one antioxidant.
A third aspect of the present invention provides the application in preparing pipeline of the compositions according to the present invention.
A fourth aspect of the present invention provides a kind of pipeline, and this pipeline is prepared by the compositions according to the present invention.
The pipeline prepared by the ethene polymers of the present invention has higher resistance to hydrostatic tension destructive characteristics, and the hydrostatic tension time to rupture measured at the temperature of 110 DEG C and the pressure of 2.5MPa can be higher than 4500 hours.Further, when the ethene polymers using the present invention prepares pipeline by the method for extrusion, it is possible to extruding at higher velocities, wherein, material extrusion linear speed at extruding dies can reach more than 35m/min, even up to more than 40m/min.Thus, during by the ethene polymers of the present invention is extruded to prepare pipeline, it is possible to obtain higher production efficiency.
Detailed description of the invention
A first aspect of the present invention provides a kind of ethene polymers, and this ethene polymers contains the monomeric unit and at least one formed by ethylene by C4-C10Alpha-olefin formed monomeric unit.
According to the ethene polymers of the present invention, on the basis of described polyvinyl total amount, ethylene the content of the monomeric unit formed is 95-99.9 weight %, alpha-olefin the content of the monomeric unit formed is 0.1-5 weight %.From improving polyvinyl mechanical property, processing characteristics and the angle of long-time stability further, on the basis of described polyvinyl total amount, the content of the monomeric unit formed by ethylene is preferably 97-99 weight %, alpha-olefin the content of the monomeric unit formed is preferably 1-3 weight %.
The polyvinyl molecular weight measured by gel permeation chromatography according to the present invention is bimodal distribution, and wherein, the weight average molecular weight of lower-molecular-weight component is 5,000-50,000, and preferably 8,000-30,000；The weight average molecular weight of high molecular weight component is 50,000-3,000,000, preferably 100,000-300,000, more preferably 200,000-300,000；Described lower-molecular-weight component is 0.28-0.52, preferably 0.3-0.5 with separating degree DOS of described high molecular weight component.Described separating degree DOS is determined by Formulas I:
In Formulas I, MW.H.Represent the weight average molecular weight of high molecular weight component,
MW.L.Represent the weight average molecular weight of lower-molecular-weight component,
WAHWHRepresent the half-peak breadth of high molecular weight component,
WAHWLRepresent the half-peak breadth of lower-molecular-weight component.
Polyvinyl melt mass flow rate according to the present invention is 0.05-0.2g/10min.In the present invention, melt mass flow rate is to use the method for regulation in GB/T3682-2000, is 190 DEG C in temperature, and load measures under conditions of being 2.16 kilograms.
According to the ethene polymers of the present invention, density is generally 0.94-0.955g/cm3.In the present invention, polyvinyl density is to use the method for regulation in GB/T1033.2-2010, measures in the density gradient column prepared by dehydrated alcohol and deionized water, wherein, uses the A.2 method of regulation in GB/T1033.2-2010 to prepare density gradient column.
According to the ethene polymers of the present invention, intrinsic viscosity is generally 150-450mL/g, preferably 250-400mL/g.In the present invention, intrinsic viscosity uses the method for regulation in ISO1628-3:2001 to measure.
According to the ethene polymers of the present invention, the non-newtonian index (that is, Rheological Index) of its melt is generally 50-180.
In the present invention, described non-newtonian index is to adopt to measure with the following method: use capillary rheology tester (wherein, die entrance angle is 16), at a temperature of 210 DEG C, measuring the shear rate under two shear stresses of 40kPa and 240kPa, the shear rate under 40kPa is non-newtonian index with the ratio of the shear stress under 240kPa.
Described alpha-olefin can be the conventional selection of this area, such as, can be C4-C10Alpha-olefin, its instantiation can include but not limited to: one or more in 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-octene and 1-nonene.Preferably, described alpha-olefin is selected from 1-butylene, 1-hexene and 1-octene.
Ethene polymers according to the present invention, according to concrete application scenario, can be random copolymer, it is also possible to for block copolymer, be not particularly limited.Preferably, described ethene polymers is random copolymer.
Ethene polymers according to the present invention can use the method for routine to prepare.Such as: can first ethylene be polymerized, then the Alathon obtained is carried out copolymerization with the ethylene supplemented and at least one alpha-olefin, and use molecular weight regulator that the molecular weight of the polymer of preparation is adjusted in each step is polymerized, thus obtain the ethene polymers according to the present invention；First ethylene and at least one alpha-olefin can also be carried out combined polymerization, then by the copolymer obtained supplementary ethylene and with or without supplement alpha-olefin in the presence of be polymerized, and use molecular weight regulator that the molecular weight of the polymer of preparation is adjusted in each step is polymerized, thus obtain the ethene polymers according to the present invention.Described molecular weight regulator can be the various materials can being adjusted the molecular weight of polymer commonly used in the art, preferably hydrogen.
In one embodiment of the invention, described ethene polymers can use the method comprised the following steps to prepare:
(1) under the first slurry polymerization conditions, in presence of hydrogen, ethylene is contacted with olefin polymerization catalysis；And
(2) mixture that step (1) obtains is after removing unreacted ethylene and hydrogen, under the second slurry polymerization conditions, with supplementary ethylene, at least one C4-C10Alpha-olefin and with or without supplement hydrogen contact.
In this embodiment, in step (1), ethylene and hydrogen mol ratio in the gas phase can be 1:2-15；In step (2), described supplementary ethylene can be 0.5-2:1 with the mol ratio of the ethylene in step (1), described supplementary ethylene and described alpha-olefin mol ratio in the gas phase can be 1:0.01-0.05, described supplementary hydrogen and described supplementary ethylene mol ratio in the gas phase can be 0-0.3:1, preferably 0.05-0.2:1.
In this embodiment, described first slurry polymerization conditions and described second slurry polymerization conditions can be the conventional selection of this area.Usually, described first slurry polymerization conditions includes: temperature can be 80-90 DEG C, and the time can be 1-5 hour；Described second slurry polymerization conditions includes: temperature can be 75-85 DEG C, and the time can be 1-5 hour.
In another embodiment of the invention, described ethene polymers can use the method comprised the following steps to prepare:
(1) under the 3rd slurry polymerization conditions, by ethylene, at least one C4-C10Alpha-olefin and with or without hydrogen contact with olefin polymerization catalysis；And
(2) mixture that step (1) obtains is after removing unreacted ethylene, alpha-olefin and hydrogen, under the 4th slurry polymerization conditions, with supplementary ethylene and with or without the hydrogen supplemented contact.
In this embodiment, in step (1), hydrogen and ethylene mol ratio in the gas phase can be 0-0.3:1, preferably 0.05-0.2:1, and described ethylene and described alpha-olefin mol ratio in the gas phase can be 1:0.01-0.05；In step (2), described supplementary ethylene can be 0.5-2:1 with the mol ratio of the ethylene in step (1), and described supplementary ethylene and described supplementary hydrogen mol ratio in the gas phase can be 1:2-15.
In this embodiment, described 3rd slurry polymerization conditions and described 4th slurry polymerization conditions can be the conventional selection of this area.Usually, described 3rd slurry polymerization conditions includes: temperature can be 75-85 DEG C, and the time can be 1-5 hour；Described 4th slurry polymerization conditions includes: temperature can be 75-85 DEG C, and the time can be 1-5 hour.
In another embodiment of the present invention, described ethene polymers can use the method comprised the following steps to prepare:
(1) under the 5th slurry polymerization conditions, in presence of hydrogen, by ethylene and at least one C4-C10Alpha-olefin contact with olefin polymerization catalysis；And
(2) mixture that step (1) obtains is after removing unreacted ethylene, alpha-olefin and hydrogen, under the 6th slurry polymerization conditions, with supplementary ethylene, at least one supplementary C4-C10Alpha-olefin and with or without supplement hydrogen contact.
In this embodiment, in step (1), ethylene and hydrogen mol ratio in the gas phase can be 1:2-15, and described ethylene and described alpha-olefin mol ratio in the gas phase can be 1:0.003-0.02；In step (2), the mol ratio stating the ethylene in supplementary ethylene and step (1) can be 0.5-2:1, described supplementary ethylene and the alpha-olefin supplemented mol ratio in the gas phase can be 1:0.007-0.03, described supplementary hydrogen and described supplementary ethylene mol ratio in the gas phase can be 0-0.3:1, preferably 0.05-0.2:1.
In this embodiment, described 5th slurry polymerization conditions and described 6th slurry polymerization conditions can be the conventional selection of this area.Usually, described 5th slurry polymerization conditions includes: temperature can be 75-85 DEG C, and the time can be 1-5 hour；Described 6th slurry polymerization conditions includes: temperature can be 75-85 DEG C, and the time can be 1-5 hour.
According to the present invention, polyreaction can be carried out in each leisure various polymer solvents commonly used in the art, is not particularly limited.Usually, described polymer solvent can be selected from C3-C20Straight or branched alkane, be preferably selected from C4-C20Straight or branched alkane, it is more preferably selected from normal butane, iso-butane, pentane, normal hexane, normal heptane, normal octane, n-nonane and n-decane, further preferably selected from normal hexane, normal heptane, normal octane, n-nonane and n-decane, further it is preferably selected from normal hexane and normal heptane.The present invention is not particularly limited for the consumption of described polymer solvent, can be the conventional selection of this area.
According to the present invention, described olefin polymerization catalysis can be commonly used in the art various catalyzed ethylene and alpha-olefin can to carry out the catalyst that is polymerized, can be dynamics model catalyst, it is also possible to for single site catalysts.The instantiation of described dynamics model catalyst can include but not limited to: titanium catalyst for olefine polymerization, chromium catalyst for olefine polymerization and vanadium catalyst for olefine polymerization.The instantiation of described single site catalysts can include but not limited to: metallocene catalyst and non-metallocene catalyst.Preferably, described olefin polymerization catalysis is dynamics model catalyst.It is highly preferred that described olefin polymerization catalysis is titanium catalyst for olefine polymerization (such as Ziegler-natta catalyst).
A second aspect of the present invention provides a kind of compositions, the said composition ethene polymers containing the with good grounds present invention and at least one antioxidant.
According to the compositions of the present invention, described polyvinyl composition, character and preparation method have been carried out detailed description above, do not repeat them here.
According to the compositions of the present invention, the various energy that described antioxidant can be commonly used in the art block, suppress or delay polymer oxidation or the material of autoxidation process.Such as: described antioxidant can be selected from phosphite type antioxidant, hindered phenol type antioxidant and heat stabilizer.
The instantiation of described phosphite type antioxidant can include but not limited to: three [2,4-di-tert-butyl-phenyl] phosphite ester (as168), four (2,4-di-tert-butylphenols)-4,4 '-xenyl diphosphites, three nonylated phenyl phosphite esters and double (2,4-DI-tert-butylphenol compounds) pentaerythritol diphosphites.Preferably, described phosphite type antioxidant is three [2,4-di-tert-butyl-phenyl] phosphite ester.
Described hindered phenol type antioxidant can be symmetric form hindered phenol antioxygen (such as alkyl list phenol type antioxidant, the many phenol type antioxidants of alkyl and thiobis phenol type antioxidant) and asymmetric hindered phenol antioxygen.The instantiation of described hindered phenol type antioxidant can include but not limited to: four (β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid) pentaerythritol ester (as1010), β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester (as1076), 2; 6-di-tert-butyl-4-methy phenol (such as antioxidant 264), N; N '-bis--(3-(3; 5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine (such as antioxidant 1098), 1; 3,5-trimethyl-2,4; 6-tri-(3,5-di-t-butyl-4-hydroxyphenylmethyl) benzene (as1330) and 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid (as3114).
Described heat stabilizer can be the conventional selection of this area.Usually, described heat stabilizer can be calcium stearate and/or zinc stearate.
The consumption of described phosphite type antioxidant, hindered phenol type antioxidant and heat stabilizer can be the conventional selection of this area.Usually, on the basis of total amount polyvinyl described in 100 weight portions, the content of described phosphite type antioxidant can be 0.01-1 weight portion, preferably 0.1-0.5 weight portion.On the basis of total amount polyvinyl described in 100 weight portions, the content of described hindered phenol type antioxidant can be 0.01-1 weight portion, preferably 0.1-0.6 weight portion.On the basis of total amount polyvinyl described in 100 weight portions, the content of described heat stabilizer can be 0.01-0.5 weight portion, preferably 0.1-0.3 weight portion.
According to the compositions of the present invention, it is used for preparing pipeline in said composition, and when this pipeline is used for carrying water or other fluid, described antioxidant is preferably possibly together with at least one matal deactivator.Described matal deactivator be preferably N, N '-bis-(3,5-di-tert-butyl-hydroxy phenyl propiono) shin (asMD1024).On the basis of total amount polyvinyl described in 100 weight portions, the content of described matal deactivator can be 0.01-0.5 weight portion, preferably 0.1-0.3 weight portion.
The present invention one preferred embodiment in, described antioxidant contains following antioxidant,
Antioxidant one: three [2,4-di-tert-butyl-phenyl] phosphite ester；
Antioxidant two: four (β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid) pentaerythritol ester and/or β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester；
Antioxidant three: N, N '-bis-(3,5-di-tert-butyl-hydroxy phenyl propiono) shin；
Antioxidant four: 1,3,5-trimethyl-2,4,6-three (3,5-di-t-butyl-4-hydroxyphenylmethyl) benzene and/or 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid；And
Heat stabilizer.
In a kind of embodiment being more highly preferred to of the present invention, on the basis of total amount polyvinyl described in 100 weight portions, described antioxidant contains following antioxidant: 0.01-1 weight portion, the described antioxidant one of preferred 0.1-0.5 weight portion；0.01-0.5 weight portion, the described antioxidant two of preferred 0.1-0.4 weight portion；0.01-0.5 weight portion, the antioxidant three of preferred 0.1-0.3 weight portion；0.01-0.5 weight portion, the antioxidant four of preferred 0.1-0.3 weight portion；And 0.01-0.5 weight portion, the heat stabilizer of preferred 0.1-0.3 weight portion.
Compositions according to the present invention can also be containing various auxiliary agents commonly used in the art, such as: light stabilizer and pigment.Described light stabilizer and the kind of pigment and consumption can be the conventional selection of this area, repeat no more herein.
Compositions according to the present invention is applicable to prepare various tubing, is particularly useful for making heat-resisting pipes；Further, when the compositions using the present invention prepares tubing, the tubing not only prepared has higher resistance to hydrostatic tension destructive characteristics, and when preparing pipeline by the method for extrusion, it is possible to extrude at higher velocities.
Thus, a third aspect of the present invention provides the application in preparing pipeline of the compositions according to the present invention.
A fourth aspect of the present invention provides a kind of pipeline, and this pipeline is prepared by the compositions according to the present invention.
Various methods commonly used in the art can be used to be prepared pipeline by the compositions of the present invention.Preferably, described pipeline is obtained by the compositions of the present invention being extruded.The present invention is not particularly limited for method and the condition carrying out extruding by described compositions, can be the conventional selection of this area, and such as: when extruding, material extrusion linear speed at extruding dies can be 10-25m/min.Pipeline according to the present invention is that the compositions using the present invention is prepared from, even if extruding with higher speed, still has good resistance to hydrostatic tension destructive characteristics.Therefore, according to the pipeline of the present invention, when the compositions of the present invention being extruded, material extrusion linear speed at extruding dies can be more than 35m/min, it might even be possible to for more than 40m/min.Preferably, according to the pipeline of the present invention, when the compositions of the present invention being extruded, material extrusion linear speed at extruding dies is 35-45m/min.
According to the pipeline of the present invention, the bore of described pipeline can be that this area routine selects.Usually, the bore of described pipeline can be 12-250mm, preferably 16-63mm.In the present invention, the bore of pipeline refers to the external diameter of pipeline.
Pipeline according to the present invention has good anti-hydrostatic tension destructive characteristics.Usually, according to the pipeline of the present invention, the hydrostatic tension time to rupture measured at a temperature of 110 DEG C, under the pressure of 2.5MPa is higher than 4500 hours, can be higher than 5000 hours under optimum condition；The hydrostatic tension time to rupture measured at a temperature of 95 DEG C, under the pressure of 4.0MPa is higher than 800 hours, can be higher than 1000 hours under optimum condition.In the present invention, use the method for regulation in ISO9080:2003, under the pressure of 2.5MPa, measure the hydrostatic tension time to rupture that the pipeline of preparation is at 110 DEG C, under the pressure of 4.0MPa, measure the hydrostatic tension time to rupture that the pipeline of preparation is at 95 DEG C.
The present invention is described in detail below in conjunction with embodiment and comparative example.
In following example and comparative example, PL-220 type liquid phase gel permeation chromatography (GPC) instrument using PL company of Britain to produce measures molecular weight and the molecular weight distribution of polymer.Wherein, single aperture chromatographic column is WithFlowing is trichloro-benzenes mutually, and flow velocity is 0.7mL/min；Sample solution concentration is 0.6mg/mL, and sample size is 200 μ L；Test temperature is 135 DEG C；Using single distribution polystyrene as standard sample.
In following example and comparative example, nuclear magnetic resonance spectroscopy is used to determine the polyvinyl composition of preparation.
In following example and comparative example, described melt mass flow rate is to use the method for regulation in GB/T3682-2000, is 190 DEG C in temperature, and load be 2.16 kilograms under conditions of measure.
In following example and comparative example, use the method for regulation in GB/T1033.2-2010, in the density gradient column prepared by dehydrated alcohol and deionized water, measure the polyvinyl density of preparation, use the A.2 method of regulation in GB/T1033.2-2010 to prepare density gradient column.
In following example and comparative example, polyvinyl non-newtonian index is to use capillary rheology tester (wherein, die entrance angle is 16), at a temperature of 210 DEG C, measuring the shear rate under two shear stresses of 40kPa and 240kPa, the ratio of the shear rate under two shear stresses of 40kPa and 240kPa is non-newtonian index.
In following example and comparative example, extruding, thus obtain pipeline on the plastic extruding forming machine that model is LeanEx1-60-30 commercially available from Battenfeld moral company, wherein, the specification of the pipeline of extrusion is Φ 20 × 2.0mm.
In following example and comparative example, use the method for regulation in ISO9080:2003, under the pressure of 4.0MPa, measure the hydrostatic tension time to rupture that the pipeline of preparation is at 95 DEG C；Under the pressure of 2.5MPa, measure the pipeline of preparation at the hydrostatic tension time to rupture of 110 DEG C.
Embodiment 1-7 is used for the present invention is described.
Embodiment 1
(1) it is polymerized in two polymerization stirred tanks of series connection, to prepare ethene polymers, comprises the following steps that.
Ethylene, normal hexane, Ziegler-Natta catalyst (catalyst uses the method that in CN1523044A, embodiment 1 describes to prepare), triethyl aluminum and hydrogen are added continuously in the first polymerization stirred tank of 500 liters, under conditions of table 1 is listed, carry out the polymerization of 2 hours.
By the serosity from the first polymerization stirred tank, it is consecutively transferred in flash tank, removes unreacted hydrogen, unreacted ethylene and part hexane, remaining polymer slurries is consecutively transferred in the second polymerization stirred tank.Meanwhile, in the second polymerization stirred tank, add ethylene, 1-butylene, normal hexane and hydrogen, and be polymerized under conditions of table 1 is given.
The polymer slurries of the second polymerization stirred tank output is carried out solid-liquid separation with being pumped in centrifugal separator, and the solid obtained is sent into after drying and is carried out pelletize in comminutor, thus obtains the ethene polymers according to the present invention.This polyvinyl character is listed in table 2.
(2) on the basis of ethene polymers prepared by 100 weight portion steps (1), in ethene polymers, 0.5 weight portion antioxidant is added168,0.2 weight portion antioxidant1010,0.2 weight portion antioxidant1076,0.1 weight portion antioxidantMD1024,0.2 weight portion antioxidant1330 and 0.2 parts by weight of calcium stearate, thus obtain the compositions according to the present invention.
(3) compositions that step (2) obtains is extruded under the extruded velocity that table 2 is listed, thus obtain the pipeline according to the present invention.The hydrostatic tension time to rupture of this pipeline is listed in table 2.
Embodiment 2
(1) use method same as in Example 1 to prepare ethene polymers, except for the difference that, in the first polymerization stirred tank and the second polymerization stirred tank, all add 1-butylene, thus obtain the ethene polymers according to the present invention.This polyvinyl character is listed in table 2.
(2) using method same as in Example 1 to prepare compositions, except for the difference that, ethene polymers is ethene polymers prepared by embodiment 2 step (1).
(3) under conditions of table 2 is listed, the compositions that step (2) obtains is extruded, thus obtains the pipeline according to the present invention.The hydrostatic tension time to rupture of this pipeline is listed in table 2.
Embodiment 3
(1) using method same as in Example 1 to prepare ethene polymers, except for the difference that, polymerizing condition is as shown in table 1, thus obtains the ethene polymers according to the present invention.This polyvinyl character is listed in table 2.
(2) using method same as in Example 1 to prepare compositions, except for the difference that, ethene polymers is ethene polymers prepared by embodiment 3 step (1).
(3) under conditions of table 2 is listed, the compositions that step (2) obtains is extruded, thus obtains the pipeline according to the present invention.The hydrostatic tension time to rupture of this pipeline is listed in table 2.
Embodiment 4
(1) using method same as in Example 1 to prepare ethene polymers, except for the difference that, polymerizing condition is as shown in table 1, thus obtains the ethene polymers according to the present invention.This polyvinyl character is listed in table 2.
(2) using method same as in Example 1 to prepare compositions, except for the difference that, ethene polymers is ethene polymers prepared by embodiment 4 step (1).
(3) under conditions of table 2 is listed, the compositions that step (2) obtains is extruded, thus obtains the pipeline according to the present invention.The hydrostatic tension time to rupture of this pipeline is listed in table 2.
Comparative example 1
(1) ethylene, 1-butylene, normal hexane, Ziegler-Natta catalyst (with embodiment 1), triethyl aluminum and hydrogen are added continuously in the polymerization stirred tank of 500 liters, under conditions of table 1 is listed, carry out polymerization in 2 hours.It is transported in centrifugal separator carry out solid-liquid separation by the polymer slurries of output from polymerization stirred tank, by dried for the solid obtained, send in comminutor and carry out pelletize, thus obtain ethene polymers.This polyvinyl character is listed in table 2.
(2) using method same as in Example 1 to prepare compositions, except for the difference that, ethene polymers is ethene polymers prepared by comparative example 1 step (1).
(3) use method same as in Example 1, extrude under the extruded velocity that table 2 is listed, thus obtain pipeline.The hydrostatic tension time to rupture of this pipeline is listed in table 2.
Comparative example 2
(1) method identical with comparative example 1 is used to prepare ethene polymers.
(2) method identical with comparative example 1 is used to prepare compositions.
(3) using method same as in Example 1 and condition to extrude, to prepare pipeline, except for the difference that, compositions is compositions prepared by comparative example 2 step (2), occurs melt fracture in extrusion, it is impossible to obtain the pipeline of molding.
Embodiment 5
(1) it is polymerized in two polymerization stirred tanks of series connection, to prepare ethene polymers, comprises the following steps that.
Ethylene, normal hexane, Ziegler-Natta catalyst, triethyl aluminum and hydrogen are added continuously in the first polymerization stirred tank of 500 liters, under conditions of table 1 is listed, carry out the polymerization of 2 hours.
By the serosity from the first polymerization stirred tank, it is consecutively transferred in flash tank, removes unreacted hydrogen, unreacted ethylene and part hexane, remaining polymer slurries is consecutively transferred in the second polymerization stirred tank.Meanwhile, in the second polymerization stirred tank, add ethylene, 1-butylene, normal hexane and hydrogen, and be polymerized under conditions of table 1 is given.
The polymer slurries of the second polymerization stirred tank output is carried out solid-liquid separation with being pumped in centrifugal separator, and the solid obtained after drying, is sent in comminutor and is carried out pelletize, thus obtain the ethene polymers according to the present invention.This polyvinyl character is listed in table 2.
(2) on the basis of ethene polymers prepared by 100 weight portion steps (1), in ethene polymers, 0.5 weight portion antioxidant is added168,0.2 weight portion antioxidant1010,0.1 weight portion antioxidant1076,0.2 weight portionMD1024,0.1 weight portion antioxidant1330 and 0.2 parts by weight of calcium stearate, thus obtain the compositions according to the present invention.
(3) compositions that step (2) obtains is extruded under the extruded velocity that table 2 is listed, thus obtain the pipeline according to the present invention.The hydrostatic tension time to rupture of this pipeline is listed in table 2.
Comparative example 3
(1) it is polymerized in two polymerization stirred tanks of series connection, to prepare ethene polymers, comprises the following steps that.
Ethylene, normal hexane, Ziegler-Natta catalyst, triethyl aluminum and hydrogen are added continuously in the first polymerization stirred tank of 500 liters, under conditions of table 1 is listed, carry out the polymerization of 2 hours.
By the serosity from the first polymerization stirred tank, it is consecutively transferred in flash tank, removes unreacted hydrogen, unreacted ethylene and part hexane, remaining polymer slurries is consecutively transferred in the second polymerization stirred tank.Meanwhile, in the second polymerization stirred tank, add ethylene, 1-butylene, normal hexane and hydrogen, and be polymerized under conditions of table 1 is given.
The polymer slurries of the second polymerization stirred tank output is carried out solid-liquid separation with being pumped in centrifugal separator, and the solid obtained after drying, is sent in comminutor and is carried out pelletize, thus obtain ethene polymers.This polyvinyl character is listed in table 2.
(2) using method same as in Example 5 to prepare compositions, except for the difference that, ethene polymers is ethene polymers prepared by comparative example 3 step (1).
(3) use the compositions extrusion that step (2) is prepared by method same as in Example 5, thus obtain pipeline.The hydrostatic tension time to rupture of this pipeline is listed in table 2.
Embodiment 6
(1) it is polymerized in two polymerization stirred tanks of series connection, to prepare ethene polymers, comprises the following steps that.
Ethylene, normal hexane, Ziegler-Natta catalyst, triethyl aluminum and hydrogen are added continuously in the first polymerization stirred tank of 500 liters, under conditions of table 1 is listed, carry out the polymerization of 3 hours.
By the serosity from the first polymerization stirred tank, it is consecutively transferred in flash tank, removes unreacted hydrogen, unreacted ethylene and part hexane, remaining polymer slurries is consecutively transferred in the second polymerization stirred tank.Meanwhile, in the second polymerization stirred tank, add ethylene, 1-octene, normal hexane and hydrogen, and be polymerized under conditions of table 1 is given.
The polymer slurries of the second polymerization stirred tank output is carried out solid-liquid separation with being pumped in centrifugal separator, and the solid phase obtained after drying, is sent in comminutor and is carried out pelletize, thus obtain the ethene polymers according to the present invention.This polyvinyl character is listed in table 2.
(2) on the basis of ethene polymers prepared by 100 weight portion steps (1), in ethene polymers, 0.5 weight portion antioxidant is added168,0.2 weight portion antioxidant1010,0.1 weight portion antioxidant1076,0.1 weight portionMD1024,0.1 weight portion antioxidant1330 and 0.2 parts by weight of calcium stearate, thus obtain the compositions according to the present invention.
(3) compositions that step (2) obtains is extruded under the extruded velocity that table 2 is listed, thus obtain the pipeline according to the present invention.The hydrostatic tension time to rupture of this pipeline is listed in table 2.
Comparative example 4
(1) it is polymerized in two polymerization stirred tanks of series connection, to prepare ethene polymers, comprises the following steps that.
Ethylene, normal hexane, Ziegler-Natta catalyst, triethyl aluminum and hydrogen are added continuously in the first polymerization stirred tank of 500 liters, under conditions of table 1 is listed, carry out the polymerization of 3 hours.
By the serosity from the first polymerization stirred tank, being consecutively transferred in flash tank, evaporation removes unreacted hydrogen, unreacted ethylene and part hexane, is consecutively transferred to by remaining polymer slurries in the second polymerization stirred tank.Meanwhile, in the second polymerization stirred tank, add ethylene, 1-octene, normal hexane and hydrogen, and be polymerized under conditions of table 1 is given.
By the polymer slurries of the second polymerization stirred tank output with after being pumped in centrifugal separator carrying out solid-liquid separation, send in comminutor and carry out pelletize, thus obtain ethene polymers.This polyvinyl character is listed in table 2.
(2) using method same as in Example 6 to prepare compositions, except for the difference that, ethene polymers is ethene polymers prepared by comparative example 4 step (1).
(3) use the compositions extrusion that step (2) is prepared by method same as in Example 6, thus obtain pipeline, extrusion occurs melt fracture, it is impossible to obtain the pipeline of molding.
Embodiment 7
(1) method same as in Example 1 is used to prepare ethene polymers.
(2) use method same as in Example 1 to prepare compositions, except for the difference that, do not use antioxidantMD1024。
(3) using method same as in Example 1 to prepare pipeline, the hydrostatic tension time to rupture of this pipeline is listed in table 2.
Table 1
Table 2
Claims (13)
1. an ethene polymers, this ethene polymers contains the monomeric unit and at least one formed by ethylene by C4-C10Alpha-olefin formed monomeric unit, on the basis of described polyvinyl total amount, ethylene the content of the monomeric unit formed is 95-99.9 weight %, alpha-olefin the content of the monomeric unit formed is 0.1-5 weight %；
This polyvinyl molecular weight measured by gel permeation chromatography is bimodal distribution, wherein, the weight average molecular weight of lower-molecular-weight component is 8,000-30,000, the weight average molecular weight of high molecular weight component is 100,000-300,000, and the weight average molecular weight of described lower-molecular-weight component is less than the weight average molecular weight of described high molecular weight component, described lower-molecular-weight component is 0.3-0.5 with separating degree DOS of described high molecular weight component, and this polyvinyl melt mass flow rate is 0.05-0.2g/10min, and described separating degree DOS is determined by Formulas I:
In Formulas I, MW.H.Represent the weight average molecular weight of high molecular weight component,
MW.L.Represent the weight average molecular weight of lower-molecular-weight component,
WAHWHRepresent the half-peak breadth of high molecular weight component,
WAHWLRepresent the half-peak breadth of lower-molecular-weight component.
Ethene polymers the most according to claim 1, wherein, the weight average molecular weight of described high molecular weight component is 200,000-300,000.
Ethene polymers the most according to claim 1 and 2, wherein, described alpha-olefin is selected from 1-butylene, 1-hexene and 1-octene.
4. a compositions, said composition contains in claim 1-3 the ethene polymers described in any one and at least one antioxidant.
Compositions the most according to claim 4, wherein, described antioxidant is selected from phosphite type antioxidant, hindered phenol type antioxidant, matal deactivator and heat stabilizer.
Compositions the most according to claim 5, wherein, described antioxidant contains following antioxidant,
Antioxidant one: three [2,4-di-tert-butyl-phenyl] phosphite ester；
Antioxidant two: four (β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid) pentaerythritol ester and/or β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester；
Antioxidant three: N, N '-bis-(3,5-di-tert-butyl-hydroxy phenyl propiono) shin；
Antioxidant four: 1,3,5-trimethyl-2,4,6-three (3,5-di-t-butyl-4-hydroxyphenylmethyl) benzene and/or 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid；And
Heat stabilizer.
Compositions the most according to claim 6, wherein, on the basis of total amount polyvinyl described in 100 weight portions, the content of described antioxidant one is 0.01-1 weight portion, the content of described antioxidant two is 0.01-0.5 weight portion, the content of described antioxidant three is 0.01-0.5 weight portion, and the content of described antioxidant four is 0.01-0.5 weight portion, and the content of described heat stabilizer is 0.01-0.5 weight portion.
8. compositions described in any one application in preparing pipeline in claim 4-7.
9. a pipeline, this pipeline is prepared by the compositions described in any one in claim 4-7.
Pipeline the most according to claim 9, wherein, obtains described pipeline by described compositions being extruded, and when carrying out described extrusion, material extrusion linear speed at extruding dies is more than 35m/min.
11. pipelines according to claim 10, wherein, material extrusion linear speed at extruding dies is more than 40m/min.
12. pipelines according to claim 10, wherein, material extrusion linear speed at extruding dies is 35-45m/min.
13. according to the pipeline described in any one in claim 9-12, and wherein, the hydrostatic tension time to rupture that this pipeline measures at a temperature of 110 DEG C, under the pressure of 2.5MPa is higher than 4500 hours.
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| US20050085600A1 (en) * | 2003-10-15 | 2005-04-21 | Ehrman Fred D. | Polymerization process and control of polymer composition properties |
| CN1982361A (en) * | 2001-08-17 | 2007-06-20 | 陶氏环球技术公司 | Bimodal polyethylene composition and articles made therefrom |
| CN101258197A (en) * | 2005-11-02 | 2008-09-03 | 切弗朗菲利浦化学公司 | Multimodal polyethylene compositions and pipes made from the same multimodal polyethylene composition |
| CN102365301A (en) * | 2009-04-02 | 2012-02-29 | 道达尔石油化学产品研究弗吕公司 | Method for optimizing energy consumption in an extrusion process |
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| CN1982361A (en) * | 2001-08-17 | 2007-06-20 | 陶氏环球技术公司 | Bimodal polyethylene composition and articles made therefrom |
| US20050085600A1 (en) * | 2003-10-15 | 2005-04-21 | Ehrman Fred D. | Polymerization process and control of polymer composition properties |
| CN101258197A (en) * | 2005-11-02 | 2008-09-03 | 切弗朗菲利浦化学公司 | Multimodal polyethylene compositions and pipes made from the same multimodal polyethylene composition |
| CN102365301A (en) * | 2009-04-02 | 2012-02-29 | 道达尔石油化学产品研究弗吕公司 | Method for optimizing energy consumption in an extrusion process |
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Effective date of registration: 20170221 Address after: 100029 Beijing, Chaoyangmen, North Street, No. 22, No. Patentee after: China Petroleum Chemical Co Patentee after: Beijing Yanshan Petrochemical High-Tech Technology Co., Ltd Address before: 100728 Beijing, Chaoyangmen, North Street, No. 22, No. Patentee before: China Petroleum Chemical Co |