CN102954980B - A kind of method of quick detection Polyethylene Pipe Resin grade - Google Patents
A kind of method of quick detection Polyethylene Pipe Resin grade Download PDFInfo
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Abstract
The present invention relates to a kind of method of quick detection Polyethylene Pipe Resin grade, (1) test sample obtains differential scanning calorimetric curve; (2) the multiple melting peak on curve is more than or equal to 127 DEG C according to temperature; 127-120 DEG C; 110-120 DEG C; Be less than or equal to 110 DEG C to be divided into four groups and to calculate corresponding integral area; Calculated weight number percent and the crystallizable sequence length of correspondence: long sequence is >=260 methylene; Longer sequence is 260 ~ 160 methylene; Not long sequence is 160 ~ 90 methylene and short data records is≤90 methylene; According to crystallizable sequence length, carry out polyethylene pipe material deciding grade and level by mass content: long sequence is 30-86%; Longer sequence is 3-25%; Not long sequence is 3-30%; Short data records is 0-50%; This method has convenient and swift, to save fund advantage, can accelerate the research and development process of tube material new product, can carry out on-line checkingi.
Description
Technical field
The present invention relates to a kind of performance evaluation of polyethylene pipe material and the method for deciding grade and level, especially a kind of method of ISO9080 grade of quick detection polyvinyl piping materials.
Background technology
Polyethylene Pipe Resin refers to for the raw material used of the pressure pipeline in industrial or agricultural, daily life, mainly containing high density polyethylene (HDPE), medium density polyethylene (MDPE), is the Research Emphasis of recent domestic production of resins enterprise-specific material.Tubing is produced owing to adopting special material for tube, this kind of tubing with outstanding chemical resistance, lower temperature resistance, heat-resisting, wear-resisting, friction factor is low, good welding performance, the excellent properties such as, long service life, making and installation expense pollution-free to pumped (conveying) medium are low, more and more be widely used in fuel gas transmission, water supply, blowdown, heat supply, agricultural irrigation, the conveying of mine fine particle solid, and the field such as oil field, chemical industry and post and telecommunications.In the world according to the long-term hydrostatic strength (MRS) of tygon (PE) pipe to tubing and raw material taxonomy and nomenclature thereof.MRS refers to that being applied to this PE tube wall continuously to cause hoop tension stress on the tube wall that calculates during pipe failure upper 50 year, and this value is the basis of pipe structure design.According to the MRS of PE pipe, in the world PE tube material is divided into PE 32, PE 40, PE 63, PE 80 and PE100 five grades.
The lifting of tube material grade is along with the progress of new technology.Along with the development of new catalyst and polymerization technique, alpha-olefin comonomer is incorporated in HDPE linear molecule amount by people, have developed PE-80, PE100 tube material with higher authentication grade, even has report can reach PE125 level.This resin adopts and hexene, octene or butene copolymerization, the relative molecular mass of product is mostly in bimodal distribution. while raising MRS. and also improve resistance to Slow Crack and increase and the scalability of resistance to rapid crack propagation, and there is good processability, for raising pipe network discharge pressure, increase pipe diameter, expansion pipeline range of application create condition.At present, the use amount of PE100 tube material, the consumption particularly on heavy caliber pipe rises just rapidly.Why this ethylene/alpha-olefin copolymer has the premium properties that common polythene does not have, and by regulating the content of alpha-olefin to obtain the changeable polythene material (from plastics to elastic body) of performance, after all, be cause because the existence of side chain makes macromolecular structure have heterogeneity.This Structural inhomogeneity mainly comprises the intermolecular and intramolecular heterogeneity that the type of branched chain, content, length and distribution cause, and the heterogeneity on molecular mass and distribution, these factors have impact on its aggregated structure to a great extent, and aggregated structure directly affects its processing and mechanical property.Therefore, short chain branch content and distribution affect a key of PE-100 tube material performance and important factor.
The deciding grade and level of PE tube material is the basis of PE pipe application.When defining the level to PE pipe, need the requirement according to ISO9080, under 20 DEG C, 60 DEG C and 80 DEG C of these three temperature conditions, carry out the hydrostatic test of more than at least 9000 hours respectively, and then carry out complicated multiple linear regression analysis, be extrapolated to the confidence lower limit σ of the hydrostatic strength 97.5% of prediction in 20.C and 50 year
lCL.σ
lCLbe PE80 level tube material at the polythene material of 8.00 ~ 9.999.99MPa.Tube material only completes above-mentioned test and under obtaining the prerequisite of corresponding level authentication, just can be used as production Gas Pipe.The minimum requirement of Gas Pipe to material grade is PE80 level.Now, along with the development of polyethylene production technology, developed third generation polyvinyl piping materials PE100 and captured rapidly high-end polyvinyl piping materials market.
As previously mentioned, long-term hydrostatic test need be carried out at internationally recognized certification authority (as Sweden Bodycote) when PE pipeline being defined the level.The PE pipeline stage that this evaluation method is determined is with a high credibility, but its shortcoming is that test period is long, and the stand-by period of manufacturer is of a specified duration, particularly unfavorable for the research and development of more high-grade tube material.Therefore, a kind of tube material method of evaluating performance of quick test can be proposed, be preferred for the PE tubing of certification, accelerate the paces of research and development, have important practical significance.Reaching this purpose, by greatly reducing the risk of manufacturer's pipe resin by certification, reducing unnecessary expenditure to enterprise.
Hot classification technique development based on differential scanning calorimeter starts from 19th-century seventies.Hot classification technique be a kind of can a kind of new technology of molecular chain structure heterogeneous (chain heretogeneities) degree of rapid evaluation thermoplastic semi-crystalline material via well-designed thermal cycle testing procedure.This new technology is especially effective to the short-chain branched degree and short-chain branched distribution of investigating ethylene/alpha-olefin copolymer.Wherein, hot classification (SSA) technical development of annealing of continuous spontaneous nucleation starts from 19th-century nineties, is a kind ofly to have more the ageing a kind of Novel hot classification technique more having development potentiality.SSA technology is, based on the one of means of differential scanning calorimetry equipment, a series of spontaneous nucleation and annealing steps are applied to a kind of hot stage division on macromolecule sample.Nearly decades, due to DSC equipment have easy and simple to handle, amount of samples is few, the advantage such as short consuming time, the hot classification technique based on DSC obtains develop rapidly, is tending towards ripe gradually.By polyethylene specimen after the hot classification process of some specific DSC, also can obtain a series of chain structure information similar with temperature rising elution classification (TREF).The multiple melting peaks obtained after hot classification process is corresponding from the segment of different crystallizable sequence length, the segment of different crystallizable sequence length and the different chips thickness one_to_one corresponding of the degree of branching and formation.The content of corresponding segment number can quantize by the size of the integral area of the multiple melting peaks curve obtained after hot classification process.Hot classification technique has been widely used in investigating the short-chain branched degree of linear low density polyethylene and short-chain branched distribution.Hot classification technique is very suitable for one effective hand fast of the ethylene/alpha-olefin copolymer quality testing being used as petroleum chemical enterprise or other scientific research institutions.But up to the present, this technology is not also on the actual application in polyvinyl piping materials field.
Summary of the invention
The object of this invention is to provide a kind of method detecting polyethylene pipe material, by the test analysis to the resin chain structure degree of branching and the distribution of aggregated structure wafer thickness, conveniently performance evaluation and quality control are carried out to PE tube material.The test analysis of the resin chain structure degree of branching and the distribution of aggregated structure wafer thickness is applied continuous spontaneous nucleation hot classification (SSA) technology of annealing and is completed at differential scanning calorimeter.This test specific procedure setting reference literature [Arnal, M.L.; Sanchez, J.J.; Muller, A.J.Polymer 2001,42,6877-6890].Illustrate the program setting on differential scanning calorimeter: sample is warming up to high temperature (ensureing the abundant melting of sample) constant temperature a period of time to eliminate thermal history by a. under nitrogen protection; B. sample is down to low temperature (be generally 0 ~ 50 DEG C, sample at this temperature sample is crystallizable) with certain rate of temperature fall, and at such a temperature constant temperature a period of time in order to set up the standard thermal history of sample; C. sample is risen to a spontaneous nucleation temperature T set with certain heating rate
s, and constant temperature a period of time (1 ~ 30min); D. step b is repeated; E. sample is risen to next spontaneous nucleation temperature by certain heating rate, and constant temperature certain hour, so circulate.Initial spontaneous nucleation temperature T
s1it is the most important experiment parameter carrying out SSA research.Usually the minimum temperature in melting microfacies district will be there is in sample as the initial spontaneous nucleation temperature of carrying out SSA research.At such a temperature, temperature is enough to most polymer crystallization melting, and simultaneous temperature is enough low can make to exist in sample the nucleus that fraction crystallization serves as spontaneous nucleation.[M ü ller, the A.J. such as application M ü ller; Arnal, M.L.Prog.Polym.Sci.2005,30,559-603.] the single step spontaneous nucleation program reported determines the initial spontaneous nucleation temperature of three samples.Shown by lot of experiments, for herein for Polyethylene Pipe Resin, the initial spontaneous nucleation temperature of detection preferably 140 ~ 115 DEG C.After hot classification process completes, the rate of heat addition of 1 ~ 20 DEG C/min is adopted to record the melting curve of sample.
The method of the ISO9080 grade of quick detection polyethylene pipe material of the present invention, comprises the steps:
(1) continuous spontaneous nucleation hot classification technique of annealing is adopted to obtain melting curve after hot classification based on differential scanning calorimeter, detect the distribution of polyethylene pipe material chain structure, described chain structure distribution comprises the mass percentage distribution of different crystallizable methylene sequence lengths, the mass percentage distribution of short-chain branched degree and the mass percentage distribution of wafer thickness.
(2) the multiple melting peak on differential scanning calorimetric curve is divided into four groups according to temperature section and calculates corresponding integral area: be more than or equal to 127 DEG C of corresponding melting peak integral areas; Temperature section 127-120 DEG C of corresponding melting peak integral area; Temperature section 110-120 DEG C of corresponding melting peak integral area; Be less than or equal to the corresponding melting peak integral area of 110 DEG C of temperature sections.Crystallinity corresponding for the integral area of each temperature section/each temperature section component is calculated the weight of component corresponding to each temperature section, then calculate the number percent of weight of the corresponding each component of each temperature section.According to the length of crystallizable sequence length corresponding to four components by four part names be: long sequence (>=260 methylene), longer sequence (260 ~ 160 methylene), not long sequence (160 ~ 90 methylene) and short data records (≤90 methylene).
(3) according to the result of step (2), the ISO9080 deciding grade and level of polyethylene pipe material is carried out: mass percentage content is 30-86% to the long sequence (low branching or thick wafer) of the polyethylene pipe material of PE80 and above grade, mass percentage content is 3-25% to longer sequence (lower branching or thicker wafer), the mass percentage content of not long sequence (higher branch or comparatively LED reverse mounting type) is 3-30%, the mass percentage of short data records (highly-branched or LED reverse mounting type) is 0-50%.In described method, when the thick wafer quality degree of polyethylene pipe material be 50-80%, thicker wafer degree be 7-15%, comparatively LED reverse mounting type mass percentage content is 5-25%, when LED reverse mounting type mass percentage is 0-40, its performance is more excellent, can illustrate that polyethylene pipe material reaches PE80 and above grade in other words more accurately.Described polyethylene pipe material tygon used is Alathon and/or ethene and the C3-C12 alkene multipolymer through comonomer.The described short comonomer of C3-C12 alkene is one or more in butylene, hexene or octene.Described polyethylene pipe material comprises polyethylene powder, true qualities pellet, carbon black mixture pellet, compressing tablet material, extruded stock or pipe finished material.Described detection polyethylene pipe material chain structure and wafer thickness distribution adopt the hot classification technique based on differential scanning calorimeter, obtain result more accurately.The present invention carries out pipe performance evaluation with the chain structure of PE tube material resin composition and wafer thickness distribution as basis, is characterized in:
A polymer molecular structure and condensed state structure combine by (), can to the solid powder of pipe resin, granulation material and sheet stock even tube forming material structure analyze.This method not only closer to the actual use procedure of tubing, and covers each stage of its processing.Therefore testing and analysis is carried out to this multi-level structure, to the evaluation of pipe performance with control more effective.And the method is from affecting the most Fundamentals of material property, raw molecule structure and aggregated structure is associated and resolves pipe performance.
B () is compared to short-term Mechanics Performance Testing, be deep into the analysis of condensed state structure the level that solid material Middle molecule piles up and move, and the understanding for material microstructure is more deep, therefore has more accuracy to the evaluation of performance.
C () this method of testing adopts extensively universal this common existing equipment of differential scanning calorimeter to obtain chain structure or the wafer thickness distribution of material, the on-line analysis of even practicable production run, therefore range of application is more extensive.Thus, key of the present invention is the method that develops from the testing and analysis of solid polyethylene chain structure PE tube material performance evaluation and even deciding grade and level.Feature of the present invention is that the chain structure of quantitatively characterizing tube material or wafer thickness distribution are also evaluated tube material performance accordingly.From the performance of tubing, tube material needs good resistance to low speed cracking and high speed cracking performance.Resistance to low speed cracking requires there are enough Tie chains between molecule crystal grain; Resistance to rapid crack propagation, low-temperature flexibility is good.In fact creep resisting ability height requires its good rigidly, and crystal size wants large, and wafer thickness wants enough.Crystallinity is high, and density is high, then instantaneous good rigidly, the good rigidly that is in short-term.Two requirements to be met: one is that tubing requirement rigidity in short-term will be got well, and long creep-resistant property will be got well concerning material; Two is need excellent welding performance, and tube material needs to weld in places such as such as turning, and also require reducing, this is the requirement of our usability.The stress cracking performance of resistance to low speed, requires that the amorphous domain between specific wafer and wafer has Tie chain exactly, and wafer is enough thick.Thickness low LCL, easily collapses time stressed.Wafer is too thick, and be easy to collapse between wafer, this just needs to have enough Tie chains between wafer and wafer.Molecular weight is larger, and Tie chain is more easily formed.But the too large processing characteristics of molecular weight can be deteriorated.If by copolymerization, due to the existence of large side base, large side base cannot enter wafer, can enter amorphous area, form Tie chain.Therefore, due to the existence of comonomer, in tube material molecule, chain structure just there occurs change, crystallizable methylene sequence lengths (degree of branching) between intermolecular or strand has just had difference, and crystallizable methylene sequence lengths changes and to change with regard to result in the wafer thickness affecting tube material critical nature.The size of wafer thickness and distribution directly determine the performance of tube material.Therefore, high molecular chain structure is the principal element determining superpolymer fundamental property, and one of high molecular condensed state structure wafer thickness size and distribution are the principal elements determining superpolymer bulk properties.Crystallizable for the principal element affecting superpolymer most basic performance methylene sequences distributes (degree of branching and distribution) and affects the principal element wafer thickness of superpolymer bulk properties and distribution associates by this invention, and institute's accepted standard when tube material being defined the level according to this invention, be sum up based on the analytical test result of the PE tube material to a large amount of different brackets.The sample adopted comprises PE63, PE80, PEI00 tube material resin that Ziegler-Natta catalyst and Cr series catalysts are produced.These resins also have from reactor powder, true qualities pellet, carbon black mixed ingredients and thus gained compressing tablet material, melt extrude the broad form of the even final pipe finished material of material.The chain structure of PE80 and above tube material resin thereof and wafer thickness analysis result show to have different chain structure distributions or wafer thickness distribution in this kind of material.Mass percentage content is 30-90% to the long sequence (low branching or thick wafer) of the polyethylene pipe material of PE80 and above grade, longer sequence (lower branching or thicker wafer) mass percentage content is 3-25%, the mass percentage content of not long sequence (higher branch or comparatively LED reverse mounting type) is 3-30%, the mass percentage of short data records (highly-branched or LED reverse mounting type) is 0-50%.In described method, when the thick wafer quality degree of polyethylene pipe material be 50-80%, thicker wafer degree be 7-15%, comparatively LED reverse mounting type mass percentage content is 5-25%, when LED reverse mounting type mass percentage is 0-40, its performance is more excellent, can illustrate that polyethylene pipe material reaches PE80 and above grade in other words more accurately.Below PE80 grade tube material then generally lacks this feature, can define the level accordingly to tube material.Further, due to PE80 and above grade pipe material thereof, particularly PEI00 tube material, there is splendid environmental stress crack resistance (ESCR), therefore wafer thickness distribution can be associated with the long-term mechanical property of tube material, namely higher LED reverse mounting type content corresponds to better resistance to stress cracking performance at a slow speed, can carry out the long-term mechanical property prediction of tube material accordingly.Obviously different without branching molecule sequential structure (thick wafer) content, along with content improves, the crystallinity of material, rigidity, creep resisting ability all improve.High branched chain structural content also there are differences, highly-branched, and the highly-branched especially in high molecular will effectively improve the processing characteristics of PE-100 tube material.The strand branching of comprehensive polyethylene pipe material or wafer thickness analysis result, can evaluate long-term and short-term mechanical property and the part processing characteristics of PE80 and above grade polyethylene tube material, particular content comprises:
(a) comparatively LED reverse mounting type and LED reverse mounting type content higher, mean that in chain, the degree of branching is higher, between the so-called wafer of formation, tie chain is more, and molecular motion is more obstructed, then the resistance to cracking performance at a slow speed (SCG) of tubing is better.
B () thick wafer content is higher, then the rigidity of material, creep resisting ability are better, and processing characteristics is poor.
C () wafer thickness presents percentage composition and unifies decline gradual change trend from thick to thin, change gentler, and sample kind exists LED reverse mounting type (highly-branched) component.The distribution of this wafer thickness is more homogeneous and tax is had good combination property by the material that there is LED reverse mounting type component, and namely the rigidity of material, creep resisting ability, resistance to quick stress and resistance to stress performance are at a slow speed all better.
Accompanying drawing explanation
Fig. 1-Figure 12 is the means of differential scanning calorimetry heating curve after the hot classification process of polyethylene pipe product in corresponding embodiment 1-6.
Embodiment
The hot classification technique of embodiment 1 means of differential scanning calorimetry judges the grade of PE tube material
The powder of two kinds of tube material resins, its DSC heating scan curve after the technical finesse of continuous annealing spontaneous nucleation as depicted in figs. 1 and 2.The integral area that the multiple melting peak of curve is corresponding is provided by the integral area percent of respective corresponding model curve, and result is as shown in table 1.
The mass percentage analysis result of the different sequence lengths (different chips thickness) of table 1PE1, PE2 two kinds of samples
Note: sample 1 and sample 2 are respectively true qualities powder
Can judge according to the result in table 1, tube material corresponding to sample P E1 sample is PE63 or more inferior grade, and tube material grade corresponding to PE2 sample is PE80 or more high-grade.This result is consistent with sample instructions markup information.
The hot classification technique of embodiment 2 means of differential scanning calorimetry judges the grade of PE tube material
The true qualities pellet of two kinds of tube material resins and the black material of mixture, its DSC heating scan curve after the technical finesse of continuous annealing spontaneous nucleation as shown in Figure 3 and Figure 4.The integral area that the multiple melting peak of curve is corresponding is provided by the integral area percent of respective corresponding model curve, and result is as shown in table 2.
The mass percentage analysis result of the different sequence lengths (different chips thickness) of table 2PE1, PE2 two kinds of samples
Note: sample 1 and be this colorant of pellet; Sample 2 is that the black pellet of mixture can judge according to the result in table 2, and tube material corresponding to sample P E1 sample is PE63 or more inferior grade, and tube material grade corresponding to PE2 sample is PE80 or more high-grade.This result is consistent with sample instructions markup information.
The grade of the hot classification technique of embodiment 3 means of differential scanning calorimetry to PE tube material judges the powder of two kinds of tube material resins, and its DSC heating scan curve after the technical finesse of continuous annealing spontaneous nucleation as shown in Figure 5 and Figure 6.The integral area that the multiple melting peak of curve is corresponding is provided by the integral area percent of respective corresponding model curve, and result is as shown in table 3.
The mass percentage analysis result of the different sequence lengths (different chips thickness) of table 3PE1, PE2 two kinds of samples
Note: sample 1 and be this colorant of pellet; Sample 2 is tubing sheet stock
Can judge according to the result in table 3, tube material corresponding to sample P E1 sample is PE63 or more inferior grade, and tube material grade corresponding to PE2 sample is PE80 or more high-grade.This result provides information consistent with sample manufacturer.
The grade of the hot classification technique of embodiment 4 means of differential scanning calorimetry to PE tube material judges the powder of two kinds of tube material resins, and its DSC heating scan curve after the technical finesse of continuous annealing spontaneous nucleation as shown in Figure 7 and Figure 8.The integral area that the multiple melting peak of curve is corresponding is provided by the integral area percent of respective corresponding model curve, and result is as shown in table 4.
The mass percentage analysis result of the different sequence lengths (different chips thickness) of table 4PE1, PE2 two kinds of samples
Note: sample 1 and be this colorant of pellet; Sample 2 is yellow material
Can judge according to the result in table 4, tube material corresponding to sample P E1 sample is PE63 or more inferior grade, and tube material grade corresponding to PE2 sample is PE80 or more high-grade.This result provides information consistent with sample producer.
The hot classification technique of embodiment 5 means of differential scanning calorimetry judges the grade of PE tube material
The powder of two kinds of tube material resins, its DSC heating scan curve after the technical finesse of continuous annealing spontaneous nucleation as shown in Figure 9 and Figure 10.The integral area that the multiple melting peak of curve is corresponding is provided by the integral area percent of respective corresponding model curve, and result is as shown in table 5.
The mass percentage analysis result of the different sequence lengths (different chips thickness) of table 5PE1, PE2 two kinds of samples
Note: sample 1 and be pellet true qualities pellets; Sample 2 is true qualities pellet
Can judge according to the result in table 5, tube material corresponding to sample P E1 sample is PE63 or more inferior grade, and tube material grade corresponding to PE2 sample is PE80 or more high-grade.This result is consistent with sample instructions markup information.
The hot classification technique of embodiment 6 means of differential scanning calorimetry judges the grade of PE tube material
The powder of two kinds of tube material resins, its DSC heating scan curve after the technical finesse of continuous annealing spontaneous nucleation as is illustrated by figs. 11 and 12.The integral area that the multiple melting peak of curve is corresponding is provided by the integral area percent of respective corresponding model curve, and result is as shown in table 6.
The mass percentage analysis result of the different sequence lengths (different chips thickness) of table 6PE1, PE2 two kinds of samples
Note: sample 1 and be pellet; Sample 2 is shaping pipe section
Can judge according to the result in table 6, tube material corresponding to sample P E1 sample is PE63 or more inferior grade, and tube material grade corresponding to PE2 sample is PE80 or more high-grade.This result is consistent with sample instructions markup information.
Claims (4)
1. detect a method for Polyethylene Pipe Resin grade fast, it is characterized in that: comprise the steps:
(1) apply continuous spontaneous nucleation hot stage division of annealing on differential scanning calorimeter, to carry out continuous spontaneous nucleation program test sample obtain differential scanning calorimetric curve;
(2) the multiple melting peak on differential scanning calorimetric curve is divided into four groups according to temperature section and calculates corresponding integral area, they are respectively: be more than or equal to 127 DEG C of corresponding melting peak integral areas; Temperature section 127-120 DEG C of corresponding melting peak integral area; Temperature section 110-120 DEG C of corresponding melting peak integral area; Be less than or equal to the corresponding melting peak integral area of 110 DEG C of temperature sections; Crystallinity corresponding for the integral area of each temperature section/each temperature section component is calculated the weight of component corresponding to each temperature section, then calculate the number percent of weight of the corresponding each component of each temperature section; Be divided into according to the length of crystallizable sequence length corresponding to four components: >=260 methylene; 260 ~ 160 methylene; 160 ~ 90 methylene and≤90 methylene;
(3) according to the result of step (2), the ISO9080 deciding grade and level of polyethylene pipe material is carried out: the polyethylene pipe material of PE80 and above grade: >=260 methylene mass percentage content are 30-86%; 260 ~ 160 methylene mass percentage content are 3-25%; The mass percentage content of 160 ~ 90 methylene is 3-30%; The mass percentage of≤90 methylene is 0-50%;
The program setting that differential scanning calorimeter has of one's own nuclear heat classification procedure test sample is continuously:
A. sample is warming up to the abundant melting of sample under nitrogen protection, constant temperature eliminates thermal history;
B. sample is cooled to 0 ~ 50 DEG C, constant temperature sets up the standard thermal history of sample at such a temperature;
C. sample is risen to the spontaneous nucleation temperature T set
s, constant temperature 1 ~ 30min;
D. step b is repeated;
E. sample is warming up to next spontaneous nucleation temperature, constant temperature, so circulates; Usually the minimum temperature in melting microfacies district will be there is in sample as the initial spontaneous nucleation temperature of carrying out SSA research, at such a temperature, most polymer crystallization melting, simultaneous temperature is enough low can make to exist in sample the nucleus that fraction crystallization serves as spontaneous nucleation; Application single step spontaneous nucleation program determines the initial spontaneous nucleation temperature of three samples, and the initial spontaneous nucleation temperature of detection is 140 ~ 115 DEG C, after hot classification process completes, adopts the rate of heat addition of 1 ~ 20 DEG C/min to record the melting curve of sample.
2. method according to claim 1, is characterized in that: described polyethylene pipe material >=260 methylene mass percentage content are 50-80%; 260 ~ 160 methylene degrees are 7-15%; 160 ~ 90 methylene mass percentage content are 5-25%; ≤ 90 methylene mass percentage are 0-40%.
3. method according to claim 1, is characterized in that: described polyethylene pipe material tygon used is one or more the multipolymer in Alathon and/or ethene and butylene, hexene or octene.
4. method according to claim 1, is characterized in that: described polyethylene pipe material comprises polyethylene powder, true qualities pellet, carbon black mixture pellet, compressing tablet material, extruded stock or pipe finished material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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Non-Patent Citations (4)
| Title |
|---|
| Miscibility of linear and branched polyethylene blends by thermal fractionation: use of the successive self-nucleation and annealing (SSA) technique;M.L Arnal et al.;《Polymer》;20010731;第42卷(第16期);6877-6890 * |
| Thermal fractionation of ethylene polymers in packaging applications;Keating, M et al.;《THERMOCHIMICA ACTA》;19960725;第284卷(第1期);47-56 * |
| 热分级-示差扫描量热方法表征聚合物支化结构;滕洪祥 等;《现代仪器》;20021231(第6期);11-13 * |
| 结晶分级技术在支化聚乙烯研究中的应用;宋士杰 等;《高分子通报》;20080331(第3期);15-28 * |
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