CN105985561A - Polyethylene hollow container material used for drinking water package and preparation method thereof - Google Patents
Polyethylene hollow container material used for drinking water package and preparation method thereof Download PDFInfo
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- CN105985561A CN105985561A CN201510062404.8A CN201510062404A CN105985561A CN 105985561 A CN105985561 A CN 105985561A CN 201510062404 A CN201510062404 A CN 201510062404A CN 105985561 A CN105985561 A CN 105985561A
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Abstract
The invention relates to a polyethylene hollow container material used for drinking water package and a preparation method thereof. The method comprises the following steps: melting ethylene homopolymerization polyethylene base resin and an anti-oxidant in a mixing mill, uniformly mixing the raw materials, and cutting a mixture by a underwater pelletizer to obtain the polyethylene hollow container material.
Description
Technical field
The present invention relates to a kind of drinking water packaging PE Hollow Containers material and preparation method thereof, belong to and mould
Material technical field.
Background technology
Polyethylene (PE) is the kind realizing merchandized handling in plastic hollow moulding material the earliest, is also
With fastest developing speed, most widely used kind.At present, the yield of the Blow Molded Articles with PE as raw material production
Accounting for world's blow-molded article total output about 2/3rds, consumption firmly occupies leading position.Polyethylene hollow system
Product are of a great variety, and product is based on packing container, including small package packaging container, such as: drug bottle, carafe,
Bottle for cosmetics, Detergent bottle, and heavy packages container, such as fuel tank, storage tank etc..Comparatively speaking,
Middle-size and small-size hollow product is relatively big to the demand of polyethylene, accounts for 80%, and large-scale hollow product is to polyethylene
Demand only accounts for 20%.The mechanical performance of high density polyethylene (HDPE) (HDPE), rigidity, environmental stress resistance are opened
Fragility and detergent resistance performance are superior to Low Density Polyethylene (LDPE).Therefore, in PE
In empty, the proportion shared by HDPE hollow container is maximum.
1949, Norbert and the Reinold brother of Germany invented and has produced bottle by thermoplastic
Processing technique and device.Within 1956, German Hoechst company achieves HDPE with Phillips company of the U.S.
Industrialization produce, the two event is that the development of polyethylene hollow molding technology brings opportunity.1957
Year, Plax company is blow molded out first HDPE bottle, within 1958, is blow molded successfully first packaging HDPE
Bottle, has been used for the commercial packing of detergent, bleach and acidic cleaner to nineteen fifty-nine HDPE bottle, and 1963
Year U.S. Continental, can company was blow molded successfully liquid milk packaging HDPE bottle.Since then, HDPE
Small hollow goods start to be used widely at packaging field, have the most also driven flying of polyethylene industry
Speed development.From raw material, all there is the PP Pipe Compound being suitable for producing small hollow container in external major company, such as Korea Spro
The B210A of Samsung of state, Korea S great Lin and the HHM5502 of Philips Corporate of Singapore, Germany
The 6041D of BASF AG, the BC900 etc. of oil public company of Korea S；Domestic raise sub-petrochemical industry, Yanshan Petrochemical,
Daqing petrochemical, Maoming Petrochemical, Dushanzi petrochemical industry the most all carry out the exploitation of too small hollow PP Pipe Compound or introduce board
Number production domesticization work.
Domestic hollow PP Pipe Compound such as 5300B, HHM5502 and 5000B etc., all use slurry process, Z-N
Catalyst, butylene or hexene are that the little hollow that comonomer produces is resin dedicated.5300B and HHM5502
Melt index is all at about 0.35g/10min, and melt strength is high, environmental stress cracking resistance is good, but molten
Melting index on the low side, when producing 3～6L bucket, processing characteristics is poor；5000B melt index is 1.0g/10min,
Melt index is higher, good processability, but parison intensity is poor when processing 3～6L bucket, sag phenomenon
The most serious.It addition, as drinking water packing container, it is desirable to water product abnormal smells from the patient without exception after packaging, existing state
Produce resin and generally there is odor problem.The present invention have developed a kind of drinking water bag meeting sanitation performance requirement
Dress high density polyethylene (HDPE) hollow container material and preparation method thereof.
CN201110086542.1 high density polyethylene (HDPE) hollow container PP Pipe Compound and preparation method thereof, discloses
A kind of high density polyethylene (HDPE) hollow container PP Pipe Compound and preparation method thereof.In the described high density polyethylene (HDPE) of this invention
Empty PP Pipe Compound has bimodal molecular weight distribution, by low-molecular-weight ethylenic homopolymer and ethylene and containing 3～6
The high molecular weight ethylene copolymer composition of the а-olefin-copolymerization of individual carbon, wherein the melt flows speed of Alathon
Rate is 10～30g/10min, and the melt flow rate (MFR) of ethylene copolymer is 0.02～0.2g/10min, and ethylene is equal
Vinyl monomer quality in polymers is vinyl monomer quality in high density polyethylene (HDPE) hollow container PP Pipe Compound
30%～60%.Described high density polyethylene (HDPE) hollow container PP Pipe Compound molecular weight distribution is bimodal morphology, it is ensured that
PP Pipe Compound has stronger mechanical strength and a good processing characteristics, has higher melt strength simultaneously,
Ensure that the sag resistant performance in the course of processing, it is possible to the large-scale hollow meeting more than 200L range of capacity is held
The processing of device and use requirement.
CN03101837.8 hollow molded body polyethylene-based resin and the hollow molding being made up of this resin
Body, it is provided that a kind of density is high, bending strength is excellent and bottle ESCR is excellent and is difficult to produce environmental stress Testudinis
The hollow molded body polyethylene-based resin split and the hollow molded body being made up of this resin.Use melt index
(MFR:JIS K7210,190 DEG C, 2.16kg load, unit for gram/10 minutes) be 0.1～2.0, close
(JIS K6922.2, the meter wire rod boiling water slow cooling in 30 minutes of test sample MFR, unit is kg/m to degree3)
In the range of 957～967 and Mz (Z mean molecule quantity) meets formula Mz >=-4 × 105㏒MFR+1.2×106
Hollow molded body polyethylene-based resin.For above-mentioned polyethylene-based resin, it is preferably with 21.6kg
Melt index (the MFR of load measurement21.6) melt index (MFR of value and 2.16kg load measurement2.16)
The ratio [(MFR of value21.6)/(MFR2.16)] be less than 200 polyethylene.
CN200980159486.0 polyethylene-based resin, its catalyst for producing and manufacture method and bag
Hollow plastic molded article containing polyethylene-based resin and application thereof, it is provided that formability, excellent in te pins of durability and resistance to
The polyethylene-based resin of the balancing good of impact and rigidity, and formability, durability, shielding are excellent,
And the hollow plastic molded article employing above-mentioned resin of the balancing good of resistance to impact and rigidity.Described poly-second
Alkene system resin meets following (1)～the essential condition of (4): (1) high load capacity melt flow rate (MFR) (HLMFR)
It is 1～100g/10 minute；(2) density is 0.940～0.960g/cm3；(3) tensile viscosity should be hardening
Changing parameter (λ max) is 1.05～1.50；And the rupture time of (4) full gap type tensile test is with close
Spend and meet following formula (A): (rupture time) >=-355 × (density)+337.6 ... (A).
CN201210152271.X mono-kind blows the high-density polyethylene resin of special-shape bottle, relates to one and blows
The high-density polyethylene resin of special-shape bottle processed；It is on the basis of producing general hollow resin 5000B,
By 78 DEG C, polymerization temperature is brought up to 82 DEG C, and polymerization pressure is brought up to 0.55MPa by 0.45MPa and gathers
Symphysis is produced, and at prilling section, adds high density polyethylene (HDPE) mass percent 0.01～0.8% composite auxiliary for processing,
The directly high-density polyethylene resin of the blowing special-shape bottle of preparation；Composite auxiliary for processing is by antioxidant, lubrication
Agent, fluoroelastomer and OPE are prepared according to 10～20/35～50/20～30/15～20 mass percents；
This resin has the spy that essential to the PP Pipe Compound of blowing special-shape bottle, melt strength is moderate, molecular weight distribution is wider
Property, processing characteristics is excellent, and sanitation performance and serviceability are good, solve current domestic general hollow resin without
The problem of method blowing special-shape bottle.
CN103554631A small hollow container construct blow-molded and preparation method thereof.The invention discloses one
Plant little hollow blow molding material, be made up of the raw material of following weight portion: ethylene hervene copolymer polyethylene base resin
99.95～98.80 antioxidant 0.02～0.4 aid anti-oxidants 0.03～0.8, also disclose above-mentioned little hollow blow molding material
Preparation method.This little hollow blow molding material uses ethylene hervene copolymer polyethylene base resin, has had
Environmental stress crack resistance energy, has prominent oxidation resistance, corrosion resistance and good simultaneously, and has
Low n-hexane extract, is suitable for blowing all kinds of corrosion resistance small hollow containers, as contained chemical reagent, agriculture
Medicine, herbicide, detergent, industrial lubricant small packaging container it can also be used to wholesomeness is had and strictly wants
The food asked, drug packaging, product pelletize is easy, and supply is stable.This technology is to use slurry method to produce
Hervene copolymer polyethylene, solvent is iso-butane, and solvent is the most completely out causes product to use the production of this technology to exist
The risk of product odor problem, uses polyethylene copolymer to easily cause the lower-molecular-weight component content in product simultaneously
More.
In sum, high density polyethylene (HDPE) hollow container material uses slurry method technology to produce mostly, and mostly is
Polyethylene copolymer, is mostly used in the packaging for foodstuff of corrosion resistant hollow package or less.Present invention innovation
Use vapor phase method to produce the homopolymerisation polyethylene hollow container material of pack for drinking water 3～6L, have molten
The features such as body flow rate is moderate, and molecular weight distribution is wider, and processing characteristics is good, and sanitation performance is excellent.
Summary of the invention
It is an object of the invention to provide a kind of drinking water packaging PE Hollow Containers material, this drinking water bag
It is moderate that dress PE Hollow Containers material has melt flow rate (MFR), and molecular weight distribution is wider, processing characteristics
Well, the features such as sanitation performance is excellent, it is adaptable to the drinking water packaging hollow container of blowing 3～6L, system
Product have good outward appearance and feel, and odorlessness.
The present invention provides the preparation method of a kind of drinking water packaging PE Hollow Containers material, including following
Step: ethylene homo polyethylene base resin, antioxidant are melted in mixing roll and mix homogeneously, and warp
Underwater pelletizer cuts, it is thus achieved that graininess drinking water packaging PE Hollow Containers material.
The preparation method of drinking water packaging PE Hollow Containers material of the present invention, wherein, preferably
Be the raw material containing following weight portion:
Ethylene homo polyethylene base resin 99.95～99.99；
Antioxidant 0.01～0.05.
The preparation method of drinking water packaging PE Hollow Containers material of the present invention, wherein, preferably
Be that ethylene homo polyethylene base resin is prepared by the following method acquisition: be in all the time in mixed gas and follow
Under ring status, adding catalyst, the reaction temperature in regulation reaction vessel is preferably 105～111 DEG C, reaction
Pressure is preferably 2000～2200kPa, the melt flow rate (MFR) to product be 0.4～1.0g/10min and
Density is 0.952～0.960g/cm3Time, prepare ethylene homo polyethylene base resin.
The preparation method of drinking water packaging PE Hollow Containers material of the present invention, wherein, ethylene
The mixed gas used in homopolymerisation polyethylene base resin preparation process is preferably ethylene, hydrogen, nitrogen and second
Alkane.
The preparation method of drinking water packaging PE Hollow Containers material of the present invention, wherein, ethylene
The mixed gas volume ratio used in homopolymerisation polyethylene base resin preparation process is preferably:
Ethylene: hydrogen: nitrogen: ethane=60.0～65.0:6.0～8.0:24.0～28.0:1.0～2.0
The preparation method of drinking water packaging PE Hollow Containers material of the present invention, wherein, ethylene
In homopolymerisation polyethylene base resin preparation process, the amount ratio of ethylene and catalyst is preferably 1 ton:
0.12～0.16kg.
The preparation method of drinking water packaging PE Hollow Containers material of the present invention, wherein, ethylene
The catalyst used in homopolymerisation polyethylene base resin preparation process is preferably chromium-based catalysts.
The preparation method of drinking water packaging PE Hollow Containers material of the present invention, wherein, antioxygen
Agent is preferably Hinered phenols antioxidant.
The preparation method of drinking water packaging PE Hollow Containers material of the present invention, wherein, is obstructed
Phenolic antioxidant be preferably four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester, β-
(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester or N, N'-pair-(3-(3,5-di-t-butyls
-4-hydroxy phenyl) propiono) hexamethylene diamine.
Heretofore described antioxidant uses phenolic antioxidant, and its effect is to produce because of oxidation in plastic material
Raw oxyradical R, ROO reaction, interrupts the growth of living chain.Use this antioxidant systems can
Enough processing stabilities and thermo-oxidative ageing is provided for material.
The preparation method of drinking water packaging PE Hollow Containers material of the present invention, wherein, mixing
Machine is the reverse non-engagement type mixing roll of twin screw, when mixing roll is mixing, regulates the 5th section of barrel temperature of mixing roll
Being preferably 200～205 DEG C, the 6th section of barrel temperature is preferably 200～210 DEG C, and the 7th section of barrel temperature is preferred
It it is 190～200 DEG C；And the temperature regulating granule cooling water is preferably 60～70 DEG C, granule cooling water flow root
Regulate according to cooling water temperature.
The present invention also provides for the drinking water packaging polyethylene hollow appearance that a kind of above-mentioned preparation method prepares simultaneously
Equipment material.
The ethylene of the employing in the present invention is preferably the ethylene of following specification:
The present invention compared with prior art has the advantage that
The present invention, by process conditions such as polymerization temperature, pressure, reaction gas composition, catalyst, controls to drink
Water packaging PE Hollow Containers material has suitable melt flow rate (MFR), density, wider molecular weight
Distribution, meets its good processing characteristics required by blowing and every physical and mechanical property, wholesomenesses etc..
Detailed description of the invention
Hereinafter embodiments of the invention are elaborated: the present embodiment is premised on technical solution of the present invention
Under implement, give detailed embodiment and process, but protection scope of the present invention be not limited to following
Embodiment, the experimental technique of unreceipted actual conditions in the following example, generally according to normal condition.
Ethylene homo polyethylene base resin and antioxidant consumption:
In the present invention, being not particularly limited ethylene homo polyethylene base resin consumption, usual ethylene is equal
Poly-polyethylene base resin 99.95～99.99 weight portion, antioxidant is 0.01～0.05 weight portion；
If antioxidant is less than 0.01 weight portion, owing to antioxidant consumption is very few, cause the antioxidation of product
Performance is defective, the oxidizable degeneration of product, and antioxidant is more than 0.05 weight portion, due to antioxidant consumption
Too much, cause waste, and base resin content is too low causes properties of product defective, there is no other useful effect
Really.
Ethylene homo polyethylene base resin preparation condition:
In the present invention, the preparation condition of ethylene homo polyethylene base resin is not particularly limited, generally
Under mixed gas is in recurrent state all the time, adding catalyst, the reaction temperature in regulation reaction vessel is
105～111 DEG C, reaction pressure is 2000～2200kPa, the melt flow rate (MFR) to product be 0.4～
1.0g/10min and density are 0.952～0.960g/cm3Time, prepare ethylene homo polyethylene base resin；
If reaction temperature is less than 105 DEG C, owing to reaction temperature is too low, cause catalyst activity too low, produce
Amount declines, and reaction temperature is more than 111 DEG C, owing to reaction temperature is too high, causes catalyst activity too high,
React wayward, and affect properties of product, without other beneficial effect；
If reaction pressure is less than 2000kPa, due to hypotony, cause catalyst activity too low, reaction
Device fluidisation is bad, and impact produces, and reaction pressure is more than 2200kPa, owing to pressure is excessive, causes catalysis
Agent hyperactivity, the too high impact of fluid height produces, and affects properties of product, without other beneficial effect；
If the melt flow rate (MFR) of product is less than 0.4g/10min, due to the melt flows of product
Speed is too small, causes processing difficulties, and the melt flow rate (MFR) of product is more than 1.0g/10min, by
Excessive in the melt flow rate (MFR) of product, cause properties of product defective, there is no other beneficial effect；
If the density of product is less than 0.952g/cm3, owing to density is too small, cause properties of product not conform to
Lattice, and the density of product is more than 0.960g/cm3, owing to density is excessive, cause properties of product defective,
There is no other beneficial effects.
Mixed gas:
In the present invention, the mixed gas used in ethylene homo polyethylene base resin preparation process be there is no
Being particularly limited to, the mixed gas used in usual ethylene homo polyethylene base resin preparation process can be enumerated as
Ethylene, hydrogen, nitrogen and ethane.
Ethylene and the amount ratio of catalyst:
In the present invention, the amount ratio of ethylene and catalyst is not particularly limited, usual described ethylene homo
In polyethylene base resin preparation process, the amount ratio of ethylene and catalyst is 1 ton: 0.12～0.16kg；
If the amount ratio of ethylene and catalyst is less than 1 ton: 0.16kg, owing to catalyst amount is too big,
Cause catalyst activity on the low side, affect molecular weight product, and the amount ratio of ethylene and catalyst is more than 1 ton:
0.12kg, owing to catalyst amount is very few, causes ethylene reaction incomplete, causes waste, and there is no other has
Benefit effect.
The catalyst used in ethylene homo polyethylene base resin preparation process:
In the present invention, the catalyst used in ethylene homo polyethylene base resin preparation process be there is no spy
Not limiting, the catalyst used in usual ethylene homo polyethylene base resin preparation process can be that chromium system urges
Agent.
Antioxidant:
In the present invention, being not particularly limited the type of antioxidant, usual antioxidant is Hinered phenols antioxygen
Agent, can be enumerated as four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester, β-
(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester or N, N'-pair-(3-(3,5-di-t-butyls
-4-hydroxy phenyl) propiono) hexamethylene diamine.
Embodiment 1
The raw material of ethylene homo base resin:
The raw material producing base resin is following material:
(1) polymer grade ethylene inlet amount 29.6 ton hour
| Ingredient names | Unit | Con trolling index |
| Ethylene | % (vol) | ≥99.90 |
| (methane ethane) | (ml/m3) | 500 |
| Acetylene | (ml/m3) | ≤8 |
| CO | (ml/m3) | ≤5 |
| CO2 | (ml/m3) | ≤10 |
| Oxygen | (ml/m3) | ≤2 |
| Water | (ml/m3) | ≤10 |
| Sulfur | (ml/m3) with H2S counts | ≤1 |
(2) catalyst: chromium-based catalysts addition 3.55kg/ hour
(3) polymer grade added hydrogen 3.08kg/ hour
(4) nitrogen and ethane are inert component, are not involved in reaction.
Ratio of gas mixture is:
The preparation method of ethylene homo base resin:
Under mixed gas is in recurrent state all the time, add catalyst, the reaction temperature in regulation reaction vessel
Degree is 105～111 DEG C, and reaction pressure is 2000～2200kPa, and the melt flow rate (MFR) to product is
0.4～1.0g/10min and density be 0.952～0.960g/cm3Time, prepare ethylene homo polyethylene basic tree
Fat.
The raw material (weight portion) of drinking water packaging PE Hollow Containers material:
Homopolymerisation polyethylene base resin 99.96
Antioxidant 0.04.
Wherein antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester.
The preparation method of drinking water packaging PE Hollow Containers material:
By above-mentioned metering ratio, ethylene homo polyethylene base resin, antioxidant are melted in mixing roll and mixes
Close uniformly, and cut through underwater pelletizer, it is thus achieved that graininess drinking water packaging PE Hollow Containers material.
Mixing roll is the reverse non-engagement type mixing roll of LCM400H twin screw, and underwater pelletizer is UP-850N
Type；When mixing roll is mixing, regulation the 5th section of barrel temperature of mixing roll is 201 DEG C, and the 6th section of barrel temperature is
205 DEG C, the 7th section of barrel temperature is 195 DEG C；And the temperature regulating granule cooling water is 65 DEG C, granule is cold
But discharge regulates according to cooling water temperature.
Embodiment 2
The raw material of ethylene homo base resin:
The raw material producing base resin is following material:
(1) polymer grade ethylene inlet amount 32.8 ton hour
| Ingredient names | Unit | Con trolling index |
| Ethylene | % (vol) | ≥99.90 |
| (methane ethane) | (ml/m3) | 500 |
| Acetylene | (ml/m3) | ≤8 |
| CO | (ml/m3) | ≤5 |
| CO2 | (ml/m3) | ≤10 |
| Oxygen | (ml/m3) | ≤2 |
| Water | (ml/m3) | ≤10 |
| Sulfur | (ml/m3) with H2S counts | ≤1 |
(2) catalyst: chromium-based catalysts addition 4.26kg/ hour
(3) polymer grade added hydrogen 3.35kg/ hour
(4) nitrogen and ethane are inert component, are not involved in reaction.
Ratio of gas mixture is:
The preparation method of ethylene homo base resin:
Under mixed gas is in recurrent state all the time, add catalyst, the reaction temperature in regulation reaction vessel
Degree is 105～111 DEG C, and reaction pressure is 2000～2200kPa, and the melt flow rate (MFR) to product is
0.4～1.0g/10min and density be 0.952～0.960g/cm3Time, prepare ethylene homo polyethylene basic tree
Fat.
The raw material (weight portion) of drinking water packaging PE Hollow Containers material:
Homopolymerisation polyethylene base resin 99.97
Antioxidant 0.03.
Wherein antioxidant is β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester.
The preparation method of drinking water packaging PE Hollow Containers material:
By above-mentioned metering ratio, ethylene homo polyethylene base resin, antioxidant are melted in mixing roll and mixes
Close uniformly, and cut through underwater pelletizer, it is thus achieved that graininess drinking water packaging PE Hollow Containers material.
Mixing roll is the reverse non-engagement type mixing roll of LCM400H twin screw, and underwater pelletizer is UP-850N
Type；When mixing roll is mixing, regulation the 5th section of barrel temperature of mixing roll is 204 DEG C, and the 6th section of barrel temperature is
206 DEG C, the 7th section of barrel temperature is 193 DEG C；And the temperature regulating granule cooling water is 63 DEG C, granule is cold
But discharge regulates according to cooling water temperature.
Embodiment 3
The raw material of ethylene homo base resin:
The raw material producing base resin is following material:
(1) polymer grade ethylene inlet amount 28.8 ton hour
| Ingredient names | Unit | Con trolling index |
| Ethylene | % (vol) | ≥99.90 |
| (methane ethane) | (ml/m3) | 500 |
| Acetylene | (ml/m3) | ≤8 |
| CO | (ml/m3) | ≤5 |
| CO2 | (ml/m3) | ≤10 |
| Oxygen | (ml/m3) | ≤2 |
| Water | (ml/m3) | ≤10 |
| Sulfur | (ml/m3) with H2S counts | ≤1 |
(2) catalyst: chromium-based catalysts addition 4.32kg/ hour
(3) polymer grade added hydrogen 2.95kg/ hour
(4) nitrogen and ethane are inert component, are not involved in reaction.
Ratio of gas mixture is:
The preparation method of ethylene homo base resin:
Under mixed gas is in recurrent state all the time, add catalyst, the reaction temperature in regulation reaction vessel
Degree is 105～111 DEG C, and reaction pressure is 2000～2200kPa, and the melt flow rate (MFR) to product is
0.4～1.0g/10min and density be 0.952～0.960g/cm3Time, prepare ethylene homo polyethylene basic tree
Fat.
The raw material (weight portion) of drinking water packaging PE Hollow Containers material:
Homopolymerisation polyethylene base resin 99.98
Antioxidant 0.02.
Wherein antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester.
The preparation method of drinking water packaging PE Hollow Containers material:
By above-mentioned metering ratio, ethylene homo polyethylene base resin, antioxidant are melted in mixing roll and mixes
Close uniformly, and cut through underwater pelletizer, it is thus achieved that graininess drinking water packaging PE Hollow Containers material.
Mixing roll is the reverse non-engagement type mixing roll of LCM400H twin screw, and underwater pelletizer is UP-850N
Type；When mixing roll is mixing, regulation the 5th section of barrel temperature of mixing roll is 201 DEG C, and the 6th section of barrel temperature is
203 DEG C, the 7th section of barrel temperature is 198 DEG C；And the temperature regulating granule cooling water is 64 DEG C, granule is cold
But discharge regulates according to cooling water temperature.
Embodiment 4
The raw material of ethylene homo base resin:
The raw material producing base resin is following material:
(1) polymer grade ethylene inlet amount 34.7 ton hour
| Ingredient names | Unit | Con trolling index |
| Ethylene | % (vol) | ≥99.90 |
| (methane ethane) | (ml/m3) | 500 |
| Acetylene | (ml/m3) | ≤8 |
| CO | (ml/m3) | ≤5 |
| CO2 | (ml/m3) | ≤10 |
| Oxygen | (ml/m3) | ≤2 |
| Water | (ml/m3) | ≤10 |
| Sulfur | (ml/m3) with H2S counts | ≤1 |
(2) catalyst: chromium-based catalysts addition 4.86kg/ hour
(3) polymer grade added hydrogen 3.58kg/ hour
(4) nitrogen and ethane are inert component, are not involved in reaction.
Ratio of gas mixture is:
The preparation method of ethylene homo base resin:
Under mixed gas is in recurrent state all the time, add catalyst, the reaction temperature in regulation reaction vessel
Degree is 105～111 DEG C, and reaction pressure is 2000～2200kPa, and the melt flow rate (MFR) to product is
0.4～1.0g/10min and density be 0.952～0.960g/cm3Time, prepare ethylene homo polyethylene basic tree
Fat.
The raw material (weight portion) of drinking water packaging PE Hollow Containers material:
Homopolymerisation polyethylene base resin 99.96
Antioxidant 0.04.
Wherein antioxidant is N, N'-pair-(3-(3,5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine.
The preparation method of drinking water packaging PE Hollow Containers material:
By above-mentioned metering ratio, ethylene homo polyethylene base resin, antioxidant are melted in mixing roll and mixes
Close uniformly, and cut through underwater pelletizer, it is thus achieved that graininess drinking water packaging PE Hollow Containers material.
Mixing roll is the reverse non-engagement type mixing roll of LCM400H twin screw, and underwater pelletizer is UP-850N
Type；When mixing roll is mixing, regulation the 5th section of barrel temperature of mixing roll is 205 DEG C, and the 6th section of barrel temperature is
208 DEG C, the 7th section of barrel temperature is 197 DEG C；And the temperature regulating granule cooling water is 61 DEG C, granule is cold
But discharge regulates according to cooling water temperature.
Embodiment 5
The raw material of ethylene homo base resin:
The raw material producing base resin is following material:
(1) polymer grade ethylene inlet amount 31.2 ton hour
| Ingredient names | Unit | Con trolling index |
| Ethylene | % (vol) | ≥99.90 |
| (methane ethane) | (ml/m3) | 500 |
| Acetylene | (ml/m3) | ≤8 |
| CO | (ml/m3) | ≤5 |
| CO2 | (ml/m3) | ≤10 |
| Oxygen | (ml/m3) | ≤2 |
| Water | (ml/m3) | ≤10 |
| Sulfur | (ml/m3) with H2S counts | ≤1 |
(2) catalyst: chromium-based catalysts addition 4.06kg/ hour
(3) polymer grade added hydrogen 3.22kg/ hour
(4) nitrogen and ethane are inert component, are not involved in reaction.
Ratio of gas mixture is:
The preparation method of ethylene homo base resin:
Under mixed gas is in recurrent state all the time, add catalyst, the reaction temperature in regulation reaction vessel
Degree is 105～111 DEG C, and reaction pressure is 2000～2200kPa, and the melt flow rate (MFR) to product is
0.4～1.0g/10min and density be 0.952～0.960g/cm3Time, prepare ethylene homo polyethylene basic tree
Fat.
The raw material (weight portion) of drinking water packaging PE Hollow Containers material:
Homopolymerisation polyethylene base resin 99.98
Antioxidant 0.02.
Wherein antioxidant is β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester.
The preparation method of drinking water packaging PE Hollow Containers material:
By above-mentioned metering ratio, ethylene homo polyethylene base resin, antioxidant are melted in mixing roll and mixes
Close uniformly, and cut through underwater pelletizer, it is thus achieved that graininess drinking water packaging PE Hollow Containers material.
Mixing roll is the reverse non-engagement type mixing roll of LCM400H twin screw, and underwater pelletizer is UP-850N
Type；When mixing roll is mixing, regulation the 5th section of barrel temperature of mixing roll is 202 DEG C, and the 6th section of barrel temperature is
210 DEG C, the 7th section of barrel temperature is 196 DEG C；And the temperature regulating granule cooling water is 67 DEG C, granule is cold
But discharge regulates according to cooling water temperature.
Embodiment 6
The raw material of ethylene homo base resin:
The raw material producing base resin is following material:
(1) polymer grade ethylene inlet amount 29.3 ton hour
| Ingredient names | Unit | Con trolling index |
| Ethylene | % (vol) | ≥99.90 |
| (methane ethane) | (ml/m3) | 500 |
| Acetylene | (ml/m3) | ≤8 |
| CO | (ml/m3) | ≤5 |
| CO2 | (ml/m3) | ≤10 |
| Oxygen | (ml/m3) | ≤2 |
| Water | (ml/m3) | ≤10 |
| Sulfur | (ml/m3) with H2S counts | ≤1 |
(2) catalyst: chromium-based catalysts addition 4.39kg/ hour
(3) polymer grade added hydrogen 3.02kg/ hour
(4) nitrogen and ethane are inert component, are not involved in reaction.
Ratio of gas mixture is:
The preparation method of ethylene homo base resin:
Under mixed gas is in recurrent state all the time, add catalyst, the reaction temperature in regulation reaction vessel
Degree is 105～111 DEG C, and reaction pressure is 2000～2200kPa, and the melt flow rate (MFR) to product is
0.4～1.0g/10min and density be 0.952～0.960g/cm3Time, prepare ethylene homo polyethylene basic tree
Fat.
The raw material (weight portion) of drinking water packaging PE Hollow Containers material:
Homopolymerisation polyethylene base resin 99.96
Antioxidant 0.04.
Wherein antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester.
The preparation method of drinking water packaging PE Hollow Containers material:
By above-mentioned metering ratio, ethylene homo polyethylene base resin, antioxidant are melted in mixing roll and mixes
Close uniformly, and cut through underwater pelletizer, it is thus achieved that graininess drinking water packaging PE Hollow Containers material.
Mixing roll is the reverse non-engagement type mixing roll of LCM400H twin screw, and underwater pelletizer is UP-850N
Type；When mixing roll is mixing, regulation the 5th section of barrel temperature of mixing roll is 204 DEG C, and the 6th section of barrel temperature is
209 DEG C, the 7th section of barrel temperature is 195 DEG C；And the temperature regulating granule cooling water is 61 DEG C, granule is cold
But discharge regulates according to cooling water temperature.
The present invention can summarize with other the concrete form without prejudice to the spirit or essential characteristics of the present invention, this
Above-described embodiment of invention all can only be considered the description of the invention rather than restriction, every according to the present invention
Substantial technological any trickle amendment, equivalent variations and modification that above example is made, belong to this
In the range of bright technical scheme.
Comparative example 1
The raw material of ethylene hervene copolymer base resin:
The raw material producing base resin is following material:
(1) polymer grade ethylene inlet amount 28.5 ton hour
| Ingredient names | Unit | Con trolling index |
| Ethylene | % (vol) | ≥99.90 |
| (methane ethane) | (ml/m3) | 500 |
| Acetylene | (ml/m3) | ≤8 |
| CO | (ml/m3) | ≤5 |
| CO2 | (ml/m3) | ≤10 |
| Oxygen | (ml/m3) | ≤2 |
| Water | (ml/m3) | ≤10 |
| Sulfur | (ml/m3) with H2S counts | ≤1 |
(2) polymer grade hexene-1 inlet amount 165kg/ hour
| Ingredient names | Unit | Con trolling index |
| C6 | % (wt) | ≥99.0 |
| Monoolefine | % (wt) | ≥98.5 |
| N-alhpa olefin | % (wt) | ≥96.0 |
| Total inert substance | ppm(wt) | ≤4 |
| Peroxide | ppm(wt) | ≤1 |
| Water | ppm(wt) | ≤25 |
| Benzene | ppm(wt) | ≤1 |
| Outward appearance | -- | Limpid without visible foreign |
(3) catalyst: chromium-based catalysts addition 4.31kg/ hour
(4) polymer grade added hydrogen 2.67kg/ hour
(4) nitrogen and ethane are inert component, are not involved in reaction.
Ratio of gas mixture is:
The preparation method of polyethylene-hexene-1 copolymeric base resin:
Under mixed gas is in recurrent state all the time, add catalyst, the reaction temperature in regulation reaction vessel
Degree is 105～111 DEG C, and reaction pressure is 2000～2200kPa, and the melt flow rate (MFR) to product is
0.4～1.0g/10min and density be 0.952～0.960g/cm3Time, prepare polyethylene-hexene-1 polyethylene copolymer
Base resin.
The raw material (weight portion) of drinking water packaging PE Hollow Containers material:
Polyethylene copolymer base resin 99.95
Antioxidant 0.05.
Wherein antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester.
The preparation method of drinking water packaging PE Hollow Containers material:
By above-mentioned metering ratio, polyethylene copolymer base resin, antioxidant are melted in mixing roll and mixes all
Even, and cut through underwater pelletizer, it is thus achieved that graininess drinking water packaging PE Hollow Containers material.
Mixing roll is the reverse non-engagement type mixing roll of LCM400H twin screw, and underwater pelletizer is UP-850N
Type；When mixing roll is mixing, regulation the 5th section of barrel temperature of mixing roll is 203 DEG C, and the 6th section of barrel temperature is
206 DEG C, the 7th section of barrel temperature is 193 DEG C；And the temperature regulating granule cooling water is 59 DEG C, granule is cold
But discharge regulates according to cooling water temperature.
The present invention can summarize with other the concrete form without prejudice to the spirit or essential characteristics of the present invention, this
Above-described embodiment of invention all can only be considered the description of the invention rather than restriction, every according to the present invention
Substantial technological any trickle amendment, equivalent variations and modification that above example is made, belong to this
In the range of bright technical scheme.
Table 1
By data in table it can be seen that use homopolymerisation polyethylene relatively polyethylene copolymer significantly to reduce in product
The content of low molecular weight part so that the abnormal smells from the patient of product is less, when containing drinking water, its taste is more preferably.
Use polyethylene copolymer finished product bucket homopolymerisation polyethylene cannot be used then full by using the test of unit
Foot uses the requirement of unit.
Claims (11)
1. a preparation method for drinking water packaging PE Hollow Containers material, comprises the following steps:
Ethylene homo polyethylene base resin, antioxidant are melted in mixing roll and mix homogeneously, and cut through under water
Grain machine cutting, it is thus achieved that graininess drinking water packaging PE Hollow Containers material.
The preparation side of drinking water packaging PE Hollow Containers material the most according to claim 1
Method, is characterized in that: containing the raw material of following weight portion:
Ethylene homo polyethylene base resin 99.95～99.99；
Antioxidant 0.01～0.05.
The preparation method of drinking water packaging PE Hollow Containers material the most according to claim 1,
It is characterized in that: described ethylene homo polyethylene base resin is prepared by the following method acquisition: in mixed gas
All the time being under recurrent state, add catalyst, the reaction temperature in regulation reaction vessel is 105～111 DEG C,
Reaction pressure is 2000～2200kPa, the melt flow rate (MFR) to product be 0.4～1.0g/10min and
Density is 0.952～0.960g/cm3Time, prepare ethylene homo polyethylene base resin.
The preparation side of drinking water packaging PE Hollow Containers material the most according to claim 3
Method, is characterized in that: the mixed gas used in described ethylene homo polyethylene base resin preparation process is second
Alkene, hydrogen, nitrogen and ethane.
The preparation side of drinking water packaging PE Hollow Containers material the most according to claim 4
Method, is characterized in that: the mixed gas volume used in described ethylene homo polyethylene base resin preparation process
Ratio is: ethylene: hydrogen: nitrogen: ethane=60.0～65.0:6.0～8.0:24.0～28.0:1.0～2.0.
The preparation side of drinking water packaging PE Hollow Containers material the most according to claim 3
Method, is characterized in that: in described ethylene homo polyethylene base resin preparation process, ethylene and the use of catalyst
Amount ratio is 1 ton: 0.12～0.16kg.
7. according to the drinking water packaging PE Hollow Containers material described in any one of claim 3～6
Preparation method, is characterized in that: the catalyst used in described ethylene homo polyethylene base resin preparation process
For chromium-based catalysts.
8. according to the drinking water packaging PE Hollow Containers material described in any one of claim 1～6
Preparation method, is characterized in that: described antioxidant is Hinered phenols antioxidant.
The preparation method of drinking water packaging PE Hollow Containers material the most according to claim 8,
It is characterized in that: described Hinered phenols antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid]
Pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester or N, N'-
Double-(3-(3,5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine.
10. according to the drinking water packaging PE Hollow Containers material described in any one of claim 1～6
Preparation method, is characterized in that: when mixing roll is mixing, and regulation the 5th section of barrel temperature of mixing roll is 200～205
DEG C, the 6th section of barrel temperature is 200～210 DEG C, and the 7th section of barrel temperature is 190～200 DEG C；And regulation
The temperature of grain cooling water is 60～70 DEG C, and granule cooling water flow regulates according to cooling water temperature.
11. 1 kinds of drinking water packaging PE Hollow Containers materials, it is any one of claim 1～10 institute
The poly-second of drinking water packaging that the preparation method of the drinking water packaging PE Hollow Containers material stated prepares
Alkene hollow container material.
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|---|---|---|---|---|
| US20130228308A1 (en) * | 2010-09-01 | 2013-09-05 | Syntroleum Corporation | Plastic phase change material and articles made therefrom |
| CN103554631A (en) * | 2013-10-16 | 2014-02-05 | 中国石油化工股份有限公司 | Blown plastic material for small hollow containers and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130228308A1 (en) * | 2010-09-01 | 2013-09-05 | Syntroleum Corporation | Plastic phase change material and articles made therefrom |
| CN103554631A (en) * | 2013-10-16 | 2014-02-05 | 中国石油化工股份有限公司 | Blown plastic material for small hollow containers and preparation method thereof |
Cited By (2)
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|---|---|---|---|---|
| CN114573902A (en) * | 2020-12-01 | 2022-06-03 | 中国石油天然气股份有限公司 | Polyethylene composition and preparation method thereof |
| CN114573902B (en) * | 2020-12-01 | 2023-11-28 | 中国石油天然气股份有限公司 | Polyethylene composition and method for producing the same |
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