CN106317546A - High-density polyethylene resin for large hollow containers - Google Patents
High-density polyethylene resin for large hollow containers Download PDFInfo
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- CN106317546A CN106317546A CN201510379412.5A CN201510379412A CN106317546A CN 106317546 A CN106317546 A CN 106317546A CN 201510379412 A CN201510379412 A CN 201510379412A CN 106317546 A CN106317546 A CN 106317546A
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- Prior art keywords
- reactor
- ethylene
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- density polyethylene
- polyethylene resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- 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
- B29C2948/92704—Temperature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/02—Ziegler natta catalyst
Abstract
The invention relates to high-density polyethylene resin for large hollow containers. A kettle-type slurry polymerization process with three kettles connected in series is adopted. Ethylene is added into a first reaction kettle, and is subjected to polymerization under the effect of a catalyst, such that a low-molecular-weight ethylene homopolymer is formed; ethylene and 1-butene are added into a second reaction kettle, and copolymerization is carried out, such that a high-molecular-weight ethylene copolymer is formed; and ethylene and 1-butene are added into the third reaction kettle. With the process provided by the invention, the content of the high-molecular-weight part comonomer can be increased, such that a final product shows multi-peak distribution. Therefore, the high-density polyethylene resin has excellent environmental stress cracking resistance and tensile properties.
Description
Technical field
The present invention relates to a kind of Large Hollow Container high-density polyethylene resin.
Background technology
Owing to high density polyethylene (HDPE) (being abbreviated as HDPE) density is big, rigidity, good toughness, good processability,
Therefore it is usually used in producing milk bottle, juice bottle, bottle for cosmetics, medicine bottle, detergent and food containers, industry bottle
Etc. all kinds of large, medium and small hollow containers.Large Hollow Container include a ton packing plastics collection barrelling, fuel tank of vehicle,
Storage tank, Turnover Box, ring Plastic Drum etc..For produce the HDPE of Large Hollow Container have to have with
Lower feature: 1) melt flow rate (MFR) is the least, HLMFR < 10g/10min；2) melt strength is high, in temperature
Be 230 DEG C, velocity of plunger be 10mm/min, under conditions of draft speed is 5m/min, melt strength is high
Reach 7-8g, low between 3-4g；3) density is at 0.945-0.952g/m3Between；4) resistance to ambient pressure
Cracking performance is preferable；5) ageing-resistant performance is relatively good, and under the conditions of 200 DEG C of Cu cup, the oxidation of each sample lures
Phase of leading is more than 6min.
Current domestic Large Hollow Container HDPE resin has the DMDY1158 of Qilu Petrochemical, Dushanzi stone
HXM50100, the CH202 etc. of oil of SPC that the HD5420GA of change, Shanghai gold are luxuriant and rich with fragrance.These HDPE
Resin all uses one-pot or two still techniques to produce when producing, and its molecular weight distribution is narrower, and comonomer is at high score
The upper content of son amount part is the lowest, and the environmental stress cracking resistance ultimately resulting in product is poor, typically exists
Between 480-600h, and produce Large Hollow Container and the environmental stress cracking resistance of raw material is required higher, its
The highest more good, preferably higher than 700h.
Summary of the invention
Present invention aim to address the deficiency of HDPE resin in prior art, it is provided that a kind of Large Hollow Container
With high-density polyethylene resin so that it is there is the environmental stress cracking resistance of excellence, and there is the power of excellence
Learn performance.
Technical scheme
The present invention is on the basis of two still tandem process of existing three well autoclave slurry polymerization devices, then connects one
Reactor, the first reactor only adds ethylene, the second reactor and the 3rd reactor and adds ethylene and 1-butylene,
Widened the molecular weight distribution of HDPE by the polymerization of the 3rd reactor further, increase high molecular simultaneously
The content of the comonomer 1-butylene of part, to reach the requirement of Large Hollow Container HDPE.The most such as
Under:
A kind of Large Hollow Container high-density polyethylene resin, uses the autoclave slurry polymerization work of three still series connection
Skill, adds ethylene in the first reactor, is polymerized under the effect of catalyst, form low-molecular-weight ethylenic
Homopolymer, adds ethylene and 1-butylene in the second reactor, and copolymerization generates the ethylene copolymer of high molecular,
Ethylene and 1-butylene is added in the 3rd reactor；In first reactor, hydrogen/volume of ethylene ratio is 1.0～6.0,
Temperature of reaction kettle is 70～85 DEG C, and reactor pressure is 0.55～0.75MPa；Hydrogen/second in second reactor
Alkene volume ratio is 0.03～0.20, and temperature of reaction kettle is 70～85 DEG C, and reactor pressure is 0.30～0.50MPa；
In 3rd reactor, hydrogen/volume of ethylene ratio is 0.02～0.15, and temperature of reaction kettle is 75～82 DEG C, reactor
Pressure is 0.20～0.40MPa, and the content of the 1-butylene in the second reactor and the 3rd reactor is and accounts for each
Add the 0.2～0.4wt% of ethylene, help toward addition Compound Machining from the 3rd reactor HDPE powder out
Agent, then through double screw extruder extruding pelletization, then after drying, screening, obtains product.
In the course of the polymerization process by measure the melt index of product powder in three reactors regulate 1-butylene,
The intake of hydrogen, controls powder melts index 100～120g/10min in the first reactor, controls second anti-
Answer powder melts index 1.0～3.0g/10min in still, control in the 3rd reactor powder melts index 1.0～
5.0g/10min, wherein the melt index of the first reactor 190 DEG C, measure under 2.16Kg load, the
The melt index of two reactors 190 DEG C, measure under 5.0Kg load, the melt index of the 3rd reactor
190 DEG C, measure under 21.6Kg load.
In catalyst used in the present invention, major catalyst is Ziegler-Natta catalyst commonly used in the art,
Such as Beijing Chemical Research Institute BCH or BCE catalyst, Mitsui company PZ or RZ catalyst, join
Concentration processed was 2.5～5mmolTi/LHX (1g catalyst contains 55 ± 10mgTi)；The promoter used is
Triethyl aluminum, compound concentration is 90～100mmolAl/LHX.
Being in terms of 1,000 ‰ by the weight of HDPE powder, heretofore described composite auxiliary for processing comprises:
Four [B-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] tetramethylolmethane (antioxidant 1010) of 0.3～1.0 ‰, 0.5～
Three (2,4-di-tert-butyl phenyl) phosphite (irgasfos 168) of 1.0 ‰, the 2 of 0.2～0.8 ‰, 6-di-tert-butyl
P-Cresol (antioxidant DHT), the stabilizer of 0.5～1.2 ‰, the slipping agent of 0.3～1.0 ‰.
Aforementioned stable agent is any one in calcium stearate or zinc stearate.
Above-mentioned slipping agent is any one in erucyl amide or oleamide.
Granulating working procedure in the present invention, district's temperature of double screw extruder is 165 ± 10 DEG C, and two district's temperature are
210 ± 10 DEG C, three district's temperature are 180 ± 10 DEG C, and die plate temperature is 175 ± 10 DEG C.
Polyethylene process of the present invention is for raising sub-petrochemical industry Polyethylene slurry polymerisation three still tandem process, three still strings
Connection technique can realize the raising of high molecular weight moieties co-monomer content, and its final products present multimodal and divide
Cloth: low molecular mass homopolymers, high molecular weight copolymer, ultrahigh molecular weight copolymer, can make HDPE have
Excellent environmental stress cracking resistance.
The Large Hollow Container HDPE that the present invention is produced by three still tandem process, shows in mechanical property
Excellence, tensile yield strength can reach 27MPa, and environmental stress cracking resistance is more than 700h.
Detailed description of the invention
Embodiment 1
Polymerization process condition
Composite auxiliary for processing in the present embodiment is: the antioxidant 1010 of 0.5wt ‰, the antioxidant of 0.6wt ‰
The calcium stearate of the antioxidant DHT, 1.0wt ‰ of 168,0.3wt ‰, the erucyl amide of 0.5wt ‰.Twin screw
One district's temperature of extruder is 165 DEG C, and two district's temperature are 210 DEG C, and three district's temperature are 180 DEG C, die plate temperature
It it is 175 DEG C.
Embodiment 2
Polymerization process condition
Composite auxiliary for processing in the present embodiment is: the antioxidant 1010 of 0.8wt ‰, the antioxidant of 0.5wt ‰
The zinc stearate of the antioxidant DHT, 0.8wt ‰ of 168,0.3wt ‰, the oleamide of 0.8wt ‰.Twin screw
One district's temperature of extruder is 160 DEG C, and two district's temperature are 215 DEG C, and three district's temperature are 175 DEG C, die plate temperature
It it is 180 DEG C.
Embodiment 3
Polymerization process condition
Composite auxiliary for processing in the present embodiment is: the antioxidant 1010 of 0.3wt ‰, the antioxidant of 0.9wt ‰
The calcium stearate of the antioxidant DHT, 0.6wt ‰ of 168,0.5wt ‰, the erucyl amide of 0.3wt ‰.Twin screw
One district's temperature of extruder is 170 DEG C, and two district's temperature are 210 DEG C, and three district's temperature are 175 DEG C, die plate temperature
It it is 170 DEG C.
Performance test
The high-density polyethylene resin that embodiment prepares is carried out melt index, tensile yield strength and resistance to environment should
Power cracking test, and contrast with commercially available DMDY1158, HXM50100, CH202, wherein,
Described melt index is according to GB/T3682-2000 standard testing, and test condition is 190 DEG C, 21.6Kg, stretching
Performance is according to GB/T2546.2-2003 standard testing, and draw speed is 50mm/min, resisting environmental stress and cracking
Performance is according to GB 1842-1999 standard testing.
Result see table:
By the test result of upper table it can be seen that the tensile property of the high-density polyethylene resin of the embodiment of the present invention
And resisting environmental stress and cracking is substantially better than commercially available product.
Claims (5)
1. a Large Hollow Container high-density polyethylene resin, it is characterised in that use three still series connection
Autoclave slurry polymerization processes, adds ethylene in the first reactor, is polymerized, shape under the effect of catalyst
Becoming low-molecular-weight ethylenic homopolymer, add ethylene and 1-butylene in the second reactor, copolymerization generates high molecular
Ethylene copolymer, the 3rd reactor adds ethylene and 1-butylene；Hydrogen/ethylene body in first reactor
Long-pending ratio is 1.0～6.0, and temperature of reaction kettle is 70～85 DEG C, and reactor pressure is 0.55～0.75MPa；Second
In reactor, hydrogen/volume of ethylene ratio is 0.03～0.20, and temperature of reaction kettle is 70～85 DEG C, reactor pressure
It is 0.30～0.50MPa；In 3rd reactor, hydrogen/volume of ethylene ratio is 0.02～0.15, and temperature of reaction kettle is
75～82 DEG C, reactor pressure is 0.20～0.40MPa, the 1-butylene in the second reactor and the 3rd reactor
Content be to account for and each add the 0.2～0.4wt% of ethylene, toward from the 3rd reactor HDPE powder out
Middle addition composite auxiliary for processing, then through double screw extruder extruding pelletization, then after drying, screening, obtains
Product.
2. Large Hollow Container high-density polyethylene resin as claimed in claim 1, it is characterised in that
Being in terms of 1,000 ‰ by the weight of HDPE powder, described composite auxiliary for processing comprises: the four of 0.3～1.0 ‰
[B-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] tetramethylolmethane, three (2, the 4-di-tert-butyl phenyl) of 0.5～1.0 ‰
Phosphite, the 2 of 0.2～0.8 ‰, 6-di-tert-butyl p-Cresol, the stabilizer of 0.5～1.2 ‰, 0.3～1.0 ‰
Slipping agent.
3. Large Hollow Container high-density polyethylene resin as claimed in claim 2, it is characterised in that
Described stabilizer is any one in calcium stearate or zinc stearate.
4. Large Hollow Container high-density polyethylene resin as claimed in claim 2, it is characterised in that
Above-mentioned slipping agent is any one in erucyl amide or oleamide.
5. the Large Hollow Container high-density polyethylene resin as described in any one of Claims 1-4, its
Being characterised by, in described granulating working procedure, district's temperature of double screw extruder is 165 ± 10 DEG C, two district's temperature
Being 210 ± 10 DEG C, three district's temperature are 180 ± 10 DEG C, and die plate temperature is 175 ± 10 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510379412.5A CN106317546A (en) | 2015-07-01 | 2015-07-01 | High-density polyethylene resin for large hollow containers |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510379412.5A CN106317546A (en) | 2015-07-01 | 2015-07-01 | High-density polyethylene resin for large hollow containers |
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| Publication Number | Publication Date |
|---|---|
| CN106317546A true CN106317546A (en) | 2017-01-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201510379412.5A Pending CN106317546A (en) | 2015-07-01 | 2015-07-01 | High-density polyethylene resin for large hollow containers |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286420A (en) * | 2016-04-11 | 2017-10-24 | 中国石化扬子石油化工有限公司 | A kind of small hollow product high-density polyethylene resin of extrusion-blown modling |
| CN109422947A (en) * | 2017-08-29 | 2019-03-05 | 中国石油天然气股份有限公司 | Multimodal polyethylene and preparation method thereof |
| CN114133489A (en) * | 2021-12-28 | 2022-03-04 | 中国石油天然气股份有限公司 | Blow molding material for hollow container and preparation method and application thereof |
| CN114181349A (en) * | 2021-12-28 | 2022-03-15 | 中国石油天然气股份有限公司 | Polyethylene pipe material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1717448A (en) * | 2002-12-19 | 2006-01-04 | 巴塞尔聚烯烃有限公司 | Polyethylene blow molding composition for producing small containers |
| CN102753590A (en) * | 2009-11-20 | 2012-10-24 | 巴塞尔聚烯烃股份有限公司 | Novel trimodal polyethylene for use in blow moulding |
| WO2013113797A1 (en) * | 2012-01-31 | 2013-08-08 | Norner As | Multimodal polyethylene polymers and process preparing said polymer |
-
2015
- 2015-07-01 CN CN201510379412.5A patent/CN106317546A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1717448A (en) * | 2002-12-19 | 2006-01-04 | 巴塞尔聚烯烃有限公司 | Polyethylene blow molding composition for producing small containers |
| CN102753590A (en) * | 2009-11-20 | 2012-10-24 | 巴塞尔聚烯烃股份有限公司 | Novel trimodal polyethylene for use in blow moulding |
| WO2013113797A1 (en) * | 2012-01-31 | 2013-08-08 | Norner As | Multimodal polyethylene polymers and process preparing said polymer |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286420A (en) * | 2016-04-11 | 2017-10-24 | 中国石化扬子石油化工有限公司 | A kind of small hollow product high-density polyethylene resin of extrusion-blown modling |
| CN109422947A (en) * | 2017-08-29 | 2019-03-05 | 中国石油天然气股份有限公司 | Multimodal polyethylene and preparation method thereof |
| CN114133489A (en) * | 2021-12-28 | 2022-03-04 | 中国石油天然气股份有限公司 | Blow molding material for hollow container and preparation method and application thereof |
| CN114181349A (en) * | 2021-12-28 | 2022-03-15 | 中国石油天然气股份有限公司 | Polyethylene pipe material and preparation method and application thereof |
| CN114181349B (en) * | 2021-12-28 | 2023-11-17 | 中国石油天然气股份有限公司 | Polyethylene pipe material and preparation method and application thereof |
| CN114133489B (en) * | 2021-12-28 | 2024-02-02 | 中国石油天然气股份有限公司 | Blow molding material for hollow container, preparation method and application thereof |
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