CN106699946A - High-density polyethylene resin, and preparation method and application thereof - Google Patents
High-density polyethylene resin, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a high-density polyethylene resin with a density of 0.946 to 0.960 g/cm<3>, S value of 8 to 13, MFI of 0.3 to 25 g/10 min, an average particle size of 140 to 280 [mu]m, a bulk density of no less than 0.38 g/cm<3>, a weight average molecular weight Mw of 8 to 22 * 10 <4> g/mol, a molecular weight distribution index Mw/Mn of 4.5 to 6.1 and polyethylene wax mass content of no more than 0.5%. The invention also provides a preparation method for the high-density polyethylene resin. The high-density polyethylene resin is prepared through slurry polymerization with a supported metallocene catalyst as a main catalyst and in the presence of a cocatalyst. The prepared polyethylene resin has excellent chlorination performance; and a chlorination product has excellent tensile properties, has tensile strength maximally 50% or more than conventional products and can be directly applied to production of chlorinated polyethylene used as a rubber-plastic material.
Description
Technical field
The present invention relates to a kind of copolymer high density polyvinyl resin, its preparation method and its purposes for being used for haloflex.
Background technology
Haloflex (CPE) is to be substituted the obtained random product of reaction by polyethylene and chlorine, can be considered ethene, chlorine
Ethene and 1,2-dichloroethene terpolymer.The difference of chlorinity in molecule is depended on, CPE has from flexible plastic, bullet
Property plastics, rubber elastomer, belt like hard plastic expect the polymer of the various performances such as the crisp resin of noninflammability and extensive use.It is special
Different molecular structure assigns CPE with excellent pliability, weatherability, resistance to ozone, chemical proofing, cold resistance and fire-retardant
The features such as property, it is widely used in plastic door-window, PVC and sheet material, waterproof roll, electric wire and rubber and plastic composite wood
The industrial circles such as material.
Usually, the production of CPE use suspension chlorination method, will polyethylene powders be suspended in water phase or hydrochloric acid phase medium
The method for carrying out chlorination.Powdery polyethylene used can be directly obtained by polymerization, also can be by conventional polyvinyl pellet
Milled.Due to being easy to large-scale production, low cost is the preparation method of topmost CPE raw materials to polymerization.
Polymerization is to use Ziegler-Natta catalyst, by aq slurry process, obtains the high density containing a small amount of alpha-olefin copolymer
Polyethylene (HDPE) powder, at 250~400 microns, density is 0.950~0.960g/cm3,5 kilograms to its average grain diameter
0.4~25g/10min of melt flow rate (MFR) under load, S value (melt flow rate (MFR) ratio under 21.6kg loads and 5kg loads)
It is 11 or so.However, often have molecular weight distribution wide using the HDPE that Ziegler-Natta catalyst polymerization is obtained, it is special
It is not that there is low-molecular-weight hangover situation, the wax content that this is often led in HDPE raw materials is higher.On the one hand, in chlorination
During, more wax meeting premature melt, and the duct inside HDPE powder is blocked, shield chlorine and initiator enters
Inside powder particle so that powder surfaces externally and internally chlorination is uneven；On the other hand, excessive low-molecular-weight wax also can be to final
The performance of chlorizate-haloflex is adversely affected.
Therefore, the current present situation in this area is, it is desirable to be able to provide such a HDPE raw materials, and there is relatively low wax to contain for it
Amount, preferable chlorination performance, while chlorization product has the mechanical property of lifting.
The content of the invention
The purpose of the present invention is on existing technical foundation, there is provided one kind with have good chlorination performance, can be directly used for give birth to
The high-density polyethylene resin of the haloflex as rubber-plastics material is produced, and chlorizate has excellent tensile property, draws
It can be higher than more than the 50% of existing product to stretch intensity.
The technical solution adopted by the present invention is as follows：
A kind of high-density polyethylene resin, described high-density polyethylene resin is that density is 0.946~0.960g/cm3, S values are
8~13, melt flow rate MFI are 0.3~25g/10min, and average grain diameter is 140~280 microns, is piled up close
Degree is not less than 0.38g/cm3, weight average molecular weight Mw is 8~22 × 104G/mol, molecular weight distributing index Mw/Mn are 4.5~6.1,
Tissuemat E mass content is not higher than 0.5%, and the S values are the polymer melt flow under 21.6 kilograms and 5.0 kilograms of loads
The ratio of speed MFI.
The high-density polyethylene resin is Alathon or ethene and alpha olefin copolymer.
Described alpha-olefin is selected from propylene, butene-1, hexene -1 or octene-1, preferably butene-1 and hexene -1, more preferably butylene
-1。
The present invention also provides a kind of preparation method of above-specified high density polyvinyl resin, with carried metallocene catalyst to sponsor
Agent, in the presence of co-catalyst, makes ethylene homo or ethene be closed with alpha-olefin copolymer by slurry polymerization
Obtain described polyvinyl resin.
Specific preparation process is as follows：
1) first to alkane solvent is added in reactor, major catalyst and co-catalyst are added, with continuous stirring by reactor
It is warming up to 70~85 DEG C；
2) to adding H in reactor2And alpha-olefin as comonomer, and ethene is continuously passed through, regulation ethene is passed through maintenance reaction
0.5~0.8MPa of pressure carries out first paragraph slurry polymerization 2 hours in kettle；
3) again to adding H in reactor2And alpha-olefin as comonomer, and ethene is continuously passed through, regulation ethene is passed through maintenance
0.5~0.8MPa of pressure carries out first paragraph slurry polymerization 2 hours in reactor；
4) stop being passed through ethene, material in reactor temperature be reduced to 25 ± 1 DEG C by outer circulation water, be vented reacting kettle inner pressure,
Polymer slurries are released, the polyvinyl resin is obtained through separation of solid and liquid and after drying.
Above-mentioned preparation process can be in a stirred tank reactor or in a double slurry polymerization kettle series connection continuous polymerization technique device
On carry out；On slurry polymerization kettle series connection continuous polymerization technique device, step 1-3) carried out in the first slurry polymerization kettle,
After first paragraph slurry polymerization terminates, material by flash distillation removing volatile component after, into series connection the second slurry polymerization kettle
Carry out step 4) described in second segment slurry polymerization.
In first paragraph continuous polymerization course of reaction, described alpha-olefin as comonomer can be selected to be dividedly in some parts or disposably added
Enter；
In step 1) described in alkane solvent can be iso-butane, pentane, hexane or heptane, preferably iso-butane, pentane or
Hexane, is further preferably iso-butane or hexane, most preferably hexane.
Addition sum of the alpha-olefin during two sections of slurry polymerizations is with ethene during two sections of slurry polymerizations
The mole ratio of addition sum is 0~1.2.
Intake of the ethene during first paragraph slurry polymerization and the intake during second segment slurry polymerization
Mol ratio is 40:60~60:40.
The preparation method of described CPE HDPE resins, in step 2) and step 4) in, hydrogen is molecular-weight adjusting
Agent, H2Be added to adjust melt flow rate, and because catalyst is different, hydrogen sensitive sex differernce also pole
Greatly, therefore, the addition and addition scope of hydrogen can determine according to polymerizate melt flow rate (MFR).
Described co-catalyst is alkyl aluminum, preferably trialkylaluminium, such as triethyl aluminum, triisobutyl aluminium, three n-butylaluminums,
It is preferred that triethyl aluminum.
The present invention also provides application of the described polyvinyl resin in the haloflex as rubber-plastics material is prepared.
Carried metallocene catalyst used in the present invention is disclosed in patent US4701432A；
Using silica gel supported metallocene catalyst, with continuous and batch slurry process polymerisation method, polymerization with it is existing
The suitable HDPE powders of Ziegler-Natta catalyst molecular weight, make use of metallocene PE relative molecular mass distribution narrow,
Normal heptane can extract content it is low the characteristics of.Compared with conventional polyethylene, can effectively by the content of polyethylene wax reduction in PE
More than 50%.Additionally, the insertion of comonomer is uniform in metallocene PE macromolecular chain, more general polyethylene is formed more equal
Even chemical constitution, it is ensured that be not in a large amount of methylene sequences units long in polyethylene macromolecular chain, can avoid the formation of blocked up
Lamellar structure, be conducive to diffusion and the intercalation reaction of initiator and chlorine, improve the chlorination of polymer.
The weight average molecular weight of high density polyethylene (HDPE) of the present invention is big, and molecular weight distributing index is narrow and wax content is low, makes thereafter
Represent good chlorination performance in the chlorination process of phase, the product after chlorination has excellent tensile property, and tensile strength is maximum
Can be higher than more than the 50% of existing product, can be directly used for haloflex of the production as rubber-plastics material.
Specific embodiment
Technical solutions according to the invention are further described in detail below by specific embodiment, but it is necessary to note that
Following examples are served only for the description to the content of the invention, do not constitute limiting the scope of the invention.
Preferably to describe easy processing haloflex high-density polyethylene resin provided by the present invention and its manufacture method,
Following examples sequentially may be different with the statement in the specification content of the invention narration, but does not interfere with this area
Understanding of the technical staff to the content of the invention.
Melt flow rate (MFI) determines reference standard GB/T 3682-2008 and carries out, and is determined respectively at 190 DEG C
MFI under 5.0 kilograms and 21.6 kilograms of loads.The S values of polymer are the MFI's under 21.6 kilograms and 5.0 kilograms of loads
Ratio；
The density measurement of polymer is carried out with reference to GB 1033.1-2008；
The apparent density of polymer is determined and carried out with reference to GB/T 1636-2008；
Polymer particle size distributional analysis is carried out on Beckman Coulter LS230 type laser particle size analyzers, granulometry model
Enclose 0.04~2000 micron.
The GPCV-2000 type gel permeation chromatographies that the relative molecular mass and its distribution of polymer is produced using PL companies of Britain
Instrument is determined, and trichloro-benzenes is solvent, 150 DEG C of temperature, polystyrene standards correction.
The wax content test of polymer is carried out in such a way：
About 10 grams of polyethylene powders samples are weighed, is put into the extraction paper web of known weight, paper web and sample are together put into dress
In having an extractor of normal heptane, then extractor is put into constant temperature oil bath, is extracted 6 hours at 80 ± 2 DEG C.After extraction is finished,
Extraction paper web containing residual polymer is placed in vacuum drying oven, is dried to constant weight at 90 DEG C, then move into silica dehydrator
In case, cooling is weighed (be accurate to 0.1mg) after 30 minutes, and wax content is calculated according to the following formula：
In formula：X-wax content, %；m1Sample mass before-extraction, g；m2Sample mass, g after-extraction is dry.As a result
The average value for determining twice is taken, its deviation is not more than 5%.
Haloflex preparation method is prepared using water phase suspension in embodiment, as described in detail by patent 02135472.3.
Specifically, by weight ratio, 0.1 part of dispersant (sodium polymethacrylate) is sequentially added in 35 parts of water, is suspended surely
0.012 part of agent (SYNPERONIC PE/F68), 0.007 part of emulsifying agent (polyvinylpyrrolidone) are determined, in stirring
Under the conditions of add the haloflex high-density polyethylene resin powder (5.5 parts), after being heated to 35-45 DEG C, then to liter
Initiator dibenzoyl peroxide (BPO) 0.025~0.03 is added in water after temperature, continues to be heated to 60 DEG C under air-proof condition
Afterwards, to chlorine is passed through in the water after secondary temperature elevation, dividing three sections carries out chlorination, and one section is passed through 1.7~1.95 parts of chlorine, in temperature
75~80 DEG C, pressure<Under the conditions of 0.2MPa react 45~60 minutes, two sections are passed through 2.6~2.9 parts of chlorine, 100~110 DEG C,
Pressure<Under the conditions of 0.3MPa react 1.5~2.5 hours, three sections are passed through 1.5 parts~1.65 parts of chlorine, 125~132 DEG C of temperature,
Pressure<Reacted 95~105 minutes under the conditions of 0.4MPa.Haloflex mother liquor is obtained, neutralized through filtering, pressurization, washed,
Centrifugation, dry, prepared haloflex product of the chlorinty 33~37%.
The sample of haloflex is prepared and carried out according to HG/T 2704-2002 standards；
The chloride content determination of haloflex is carried out by the B methods in GB/T 7139-2002；
Haloflex
Melting heat determination is carried out by HG/T 2704-2002；
Continued as specified in the GB/T 531.1-2008 assay method of your hardness A of the measure of your hardness of continuing of haloflex enters
OK, 10 seconds readings；
The tensile property of haloflex is determined and carried out by GB/T 528-2009, using I type dumbbell shaped cut-off knives.
Embodiment 1
High-density polyethylene resin of the present invention, is prepared as follows：To 200 liters of addition in 300 liters of reactors
Hexane solvent；Rinsed by 1L hexanes, it is disposable to add carried metallocene catalyst and co-catalyst triethyl aluminum (hexane
Solvent, concentration is 0.88mol/L), stirring is opened, speed of agitator is 250rpm, while by outer circulation water by reactor
Material is heated to 70~85 DEG C；Ethene continuously is passed through, while disposably adding hydrogen 0.1g and being dividedly in some parts comonomer 1- fourths
Alkene 30g；0.5~0.8MPa of pressure carries out first paragraph slurry polymerization 2 hours during regulation ethene is passed through maintenance reaction kettle, this
Total addition of ethene is 11kg during first paragraph slurry polymerization；
Disposable again to add 0.3 gram of hydrogen, while being continuously passed through ethene, maintenance reaction kettle 0.5~0.8MPa of pressure is carried out
Second segment slurry polymerization 2 hours, total addition of ethene is 11kg during this second segment slurry polymerization；
Stopping is passed through ethene, and material in reactor temperature is reduced into 25 DEG C by outer circulation water, is vented reacting kettle inner pressure, puts
Go out polymer slurries, polyethylene powder resin is obtained through separation of solid and liquid and after drying.
The test result of this polyvinyl resin is shown in Table 1.
The performance of polyvinyl resin chlorization product is shown in Table 2.
Embodiment 2
Difference from Example 1 is：
The added hydrogen of first paragraph polymerization is 0.6 gram；
Second segment polymerization added hydrogen is 0.4 gram, adds comonomer butene -1, and addition is 13 grams.
The test result of this polyvinyl resin is shown in Table 1.
The performance of polyvinyl resin chlorization product is shown in Table 2.
Embodiment 3
Difference from Example 1 is：
The added hydrogen of the first polymeric segment is changed to 0.3, and comonomer is changed to hexene -1, and addition is 20 grams；
Second polymeric segment added hydrogen is changed to 0.3 gram.
The test result of this polyvinyl resin is shown in Table 1.
The performance of polyvinyl resin chlorization product is shown in Table 2.
Embodiment 4
Difference from Example 1 is：
The added hydrogen of the first polymeric segment is changed to 1.2 grams, and comonomer is changed to propylene, and addition is 5 grams；
Second polymeric segment hydrogen is changed to 0.2 gram.
The test result of this polyvinyl resin is shown in Table 1.
The performance of polyvinyl resin chlorization product is shown in Table 2.
Comparative example 1
To 200 liters of hexane solvents of addition in 300 liters of reactors；Rinsed by 1L hexanes, disposably add Ziegler-Natta
Catalyst (BCH catalyst) and co-catalyst triethyl aluminum (hexane solvent, concentration is 0.88mol/L), open stirring,
Speed of agitator is 250rpm, while material in reactor is heated into 70~85 DEG C by outer circulation water；It is disposable to add hydrogen
10 grams, ethene is continuously passed through, while being dividedly in some parts 40g comonomer butenes -1；Regulation ethene is pressed in being passed through maintenance reaction kettle
0.5~0.8MPa of power carries out slurry polymerization 2~3 hours.Stopping is passed through ethene, by outer circulation water by material in reactor
Temperature is reduced to 25 DEG C, is vented reacting kettle inner pressure, releases polymer slurries, and ethylene powder is obtained through separation of solid and liquid and after drying
Polymer.
The test result of comparative example high density polyethylene (HDPE) is shown in Table 1.
The performance of high density polyethylene (HDPE) chlorization product is shown in Table 2.
Comparative example 2
Essentially identical with comparative example 1, only alpha-olefin is changed to propylene, and addition is changed to 10 grams, and added hydrogen is changed to 50 grams.
The test result of comparative example high density polyethylene (HDPE) is shown in Table 1.
The performance of high density polyethylene (HDPE) chlorization product is shown in Table 2.
The haloflex HDPE resin performance of table 1
| Performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 |
| Density (g/cm3) | 0.946 | 0.954 | 0.950 | 0.960 | 0.952 | 0.958 |
| MFI(g/10min) | 0.3 | 2.1 | 8.2 | 24 | 0.5 | 9.1 |
| S values | 13 | 8.1 | 11.4 | 9.8 | 11.9 | 10.3 |
| Average grain diameter (μm) | 279.0 | 195.3 | 160.4 | 142.6 | 204.7 | 180.1 |
| Mn(104g/mol) | 3.3 | 3.9 | 2.7 | 1.6 | 3.9 | 2.8 |
| Mw(104l) | 20.2 | 17.6 | 14.5 | 8.1 | 22.1 | 16.3 |
| Mw/Mn | 6.1 | 4.5 | 5.4 | 5.1 | 5.7 | 5.8 |
| Bulk density (g/cm3) | 0.38 | 0.40 | 0.42 | 0.44 | 0.39 | 0.41 |
| Wax content (wt%) | 0.13 | 0.22 | 0.34 | 0.49 | 0.97 | 1.44 |
The haloflex performance of table 2
| Performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 |
| Chlorinity (%) | 35.1 | 35.8 | 34.9 | 34.2 | 35.3 | 34.7 |
| Volatile matter (%) | 0.10 | 0.12 | 0.13 | 0.15 | 0.22 | 0.25 |
| Melting heat (J/g) | ＜ 1.5 | ＜ 1.5 | ＜ 1.5 | ＜ 1.5 | ＜ 1.5 | ＜ 1.5 |
| Shore hardness (A) | 52 | 51 | 52 | 54 | 58 | 54 |
| Tensile strength (MPa) | 16.3 | 15.5 | 14.7 | 13.9 | 10.8 | 9.9 |
| Elongation at break (%) | 402 | 513 | 545 | 497 | 790 | 830 |
As seen from the results in Table 1, MFI can be effectively obtained using slurry polymerization processes of the invention5Between 0.3~25g/10min,
S values between 8~13, weight average molecular weight between 80,000~220,000, molecular weight distribution (MWD) between 4.5~6.1, density between
0.946~0.960g/cm3, average grain diameter between 140~280 microns, bulk density is not less than 0.38g/cm3, Tissuemat E quality
Content is not higher than 0.5% high density polyethylene (HDPE).
As shown in Table 2, using high-density polyethylene resin powder obtained in the present invention, the chlorine obtained after superchlorination
Change polyethylene have lower volatile content and shore hardness, compared with control sample, tensile strength maximum can improve 50% with
On, prepare HDPE better performances compared with Ziegler-Natta catalyst so as to show.
Claims (9)
1. a kind of high-density polyethylene resin, it is characterised in that described polyvinyl resin is that density is 0.946~0.960g/cm3,
S values are 8~13, and melt flow rate MFI is 0.3~25g/10min, and average grain diameter is 140~280 microns,
Bulk density is not less than 0.38g/cm3, weight average molecular weight Mw is 8~22 × 104G/mol, molecular weight distributing index Mw/Mn
It is 4.5~6.1, Tissuemat E mass content is not higher than 0.5%, and the S values are the polymerization under 21.6 kilograms and 5.0 kilograms of loads
The ratio of thing melt flow rate (MFR) MFI.
2. high-density polyethylene resin according to claim 1, it is characterised in that the polyvinyl resin is that ethene is equal
Polymers or ethene and alpha olefin copolymer.
3. high-density polyethylene resin according to claim 2, it is characterised in that described alpha-olefin is propylene, fourth
Alkene -1, hexene -1 and octene-1.
4. the preparation method of the high-density polyethylene resin described in any claims of claim 1-3, it is characterised in that with
Carried metallocene catalyst is major catalyst, in the presence of co-catalyst alkyl aluminum, is made by slurry polymerization
Ethylene homo or ethene are closed with alpha-olefin copolymer and obtain described polyvinyl resin.
5. the preparation method of high-density polyethylene resin according to claim 4, it is characterised in that specifically prepared
Journey is as follows：
1) first to alkane solvent is added in reactor, major catalyst and co-catalyst are added, with continuous stirring by reactor
It is warming up to 70~85 DEG C；
2) to adding H in reactor2And alpha-olefin as comonomer, and ethene is continuously passed through, regulation ethene is passed through maintenance reaction
0.5~0.8MPa of pressure carries out first paragraph slurry polymerization 2 hours in kettle；
3) again to adding H in reactor2And alpha-olefin as comonomer, and ethene is continuously passed through, regulation ethene is passed through maintenance
0.5~0.8MPa of pressure carries out first paragraph slurry polymerization 2 hours in reactor；
4) stop being passed through ethene, material in reactor temperature be reduced to 25 ± 1 DEG C by outer circulation water, be vented reacting kettle inner pressure,
Polymer slurries are released, the polyvinyl resin is obtained through separation of solid and liquid and after drying.
6. the preparation method of high-density polyethylene resin according to claim 5, it is characterised in that in step 1) in
Described alkane solvent is iso-butane, pentane, hexane or heptane.
7. the preparation method of high-density polyethylene resin according to claim 5, it is characterised in that alpha-olefin is at two sections
Addition sum during slurry polymerization and addition sum of the ethene during two sections of slurry polymerizations mole
Amount is than being 0~1.2.
8. the preparation method of high-density polyethylene resin according to claim 5, it is characterised in that ethene is first
Section slurry polymerization during intake be with the intake mol ratio during second segment slurry polymerization
40:60~60:40.
9. the high-density polyethylene resin described in any claims of claim 1-3 gathers in chlorination of the preparation as rubber-plastics material
Application in ethene.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114133473A (en) * | 2021-12-16 | 2022-03-04 | 万华化学集团股份有限公司 | Special resin powder for chlorinated polyethylene and preparation method and application thereof |
| CN114634587A (en) * | 2021-02-01 | 2022-06-17 | 中国石油化工股份有限公司 | Method for continuously producing ultra-high molecular weight polyethylene by slurry polymerization |
| CN115636893A (en) * | 2021-07-20 | 2023-01-24 | 中国石油天然气股份有限公司 | High-density polyethylene resin and preparation method thereof |
| CN115926034A (en) * | 2022-11-28 | 2023-04-07 | 浙江石油化工有限公司 | Preparation method of high-strength waterproof polyethylene film |
| CN115991804A (en) * | 2021-10-20 | 2023-04-21 | 中国石油化工股份有限公司 | Poly-1-butene and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114634587A (en) * | 2021-02-01 | 2022-06-17 | 中国石油化工股份有限公司 | Method for continuously producing ultra-high molecular weight polyethylene by slurry polymerization |
| CN114634587B (en) * | 2021-02-01 | 2024-04-09 | 中国石油化工股份有限公司 | Method for continuously producing ultra-high molecular weight polyethylene by slurry polymerization |
| CN115636893A (en) * | 2021-07-20 | 2023-01-24 | 中国石油天然气股份有限公司 | High-density polyethylene resin and preparation method thereof |
| CN115991804A (en) * | 2021-10-20 | 2023-04-21 | 中国石油化工股份有限公司 | Poly-1-butene and preparation method thereof |
| CN114133473A (en) * | 2021-12-16 | 2022-03-04 | 万华化学集团股份有限公司 | Special resin powder for chlorinated polyethylene and preparation method and application thereof |
| CN115926034A (en) * | 2022-11-28 | 2023-04-07 | 浙江石油化工有限公司 | Preparation method of high-strength waterproof polyethylene film |
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Application publication date: 20170524 |