CN112745553B - Preparation method of stacking-resistant rigid medium-sized hollow blow molding material - Google Patents
Preparation method of stacking-resistant rigid medium-sized hollow blow molding material Download PDFInfo
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- CN112745553B CN112745553B CN201911046721.5A CN201911046721A CN112745553B CN 112745553 B CN112745553 B CN 112745553B CN 201911046721 A CN201911046721 A CN 201911046721A CN 112745553 B CN112745553 B CN 112745553B
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- 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
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- 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
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Abstract
The invention discloses a preparation method of a stacking-resistant rigid medium-sized hollow blow molding material and application of the stacking-resistant rigid medium-sized hollow blow molding material, wherein the preparation method comprises the steps of mixing ethylene-hexene copolymerized polyethylene resin and an auxiliary agent, and then extruding and granulating in a mixing roll to obtain blow molding material particles, and preferably, the content of a 1-hexene comonomer in the ethylene-hexene copolymerized polyethylene resin is 0.04-0.10 mol%. The blow molding material for the medium-sized hollow container prepared by the preparation method has the advantages of moderate hexene content, wide molecular weight distribution, high density, high crystallinity, strong rigidity, high melt strength, small die-releasing expansion and stable parison, and the processing performance and various physical and mechanical properties meet the blow molding requirement of the medium-sized hollow container.
Description
Technical Field
The invention relates to a blow molding material, in particular to a preparation method of a stacking-resistant rigid medium-sized hollow blow molding material.
Background
High Density Polyethylene (HDPE) has the advantages of high molecular weight, good thermal stability, corrosion resistance, easy processing, etc., and is the most widely used raw resin in blow molded hollow articles, which have been applied to the fields of pesticides, liquid chemicals, washing products, beverages, food packaging, etc., and show a rapidly growing trend. Compared with steel barrels, the all-plastic barrel has the advantages of light weight, water resistance, moisture resistance, simple forming process, low production cost, no seam, convenience in printing and the like. Although the heat resistance, barrier property, impact resistance, etc. of the plastic drum are inferior to those of the steel drum, the plastic drum has been improved in its properties such as impact resistance, rigidity and barrier property with the progress of plastic technology. At present, the container is widely applied to containing various dangerous and non-dangerous chemicals, oil products and various liquids.
The medium-sized hollow product mainly refers to HDPE blow molding packing barrels with various specifications and the volume of 20L-160L, mainly comprises series hollow containers of 20L, 25L, 30L, 50L, 60L, 100L, 120L and 160L, and is widely applied to various transport containers, including the fields of liquid chemical tanks, agricultural chemical tanks, dangerous chemical tanks and the like. In addition, most manufacturers producing 200L large barrels and IBC ton barrels also produce medium-sized hollow containers of certain specifications between 20L and 120L at the same time.
At present, the market has great demand on medium-sized hollow special material products, and according to statistics, the yield of the medium-sized hollow container in China exceeds 10 million tons in 2013. The main market brand in south China is 5421B of Zhonghai Shell, HXM50100 by Katalr and 5401AA in Shanghai Siceao. It was found that the softness and slightly insufficient stacking rigidity of the hollow barrel blown by the inlet HXM50100 or the medium hollow blow molding material produced by using the original CPC process bag can affect the quality phase of the product. The special material for blow molding of the stacking-resistant rigid medium-sized hollow container is developed, the defects of softness and insufficient stacking-resistant rigidity of imported HXM50100 products are improved, and the market needs are met.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing a blow molding material for a medium-sized hollow container aiming at the defects of the prior art, and the blow molding material for the medium-sized hollow container prepared by the method has the advantages of moderate hexene content, wide molecular weight distribution, higher density, high crystallinity, outstanding rigidity, excellent oxidation resistance and good chemical corrosion resistance, and is suitable for processing and forming various medium-sized hollow containers. Meanwhile, the medium-sized hollow container product blown by the material prepared by the method has excellent stacking resistance.
To this end, the invention provides, in a first aspect, a process for the preparation of a rigid, stacking-resistant blow molding medium-sized hollow material. The preparation method of the stacking-resistant rigid medium-sized hollow blow molding material comprises the steps of mixing ethylene-hexene copolymerized polyethylene resin and an auxiliary agent, and then extruding and granulating in a mixing mill to obtain blow molding material particles, wherein preferably, the content of a 1-hexene comonomer in the ethylene-hexene copolymerized polyethylene resin is 0.04-0.10 mol%.
According to some embodiments of the invention, the method further comprises cooling the blow molding material pellets in cooling water to obtain a stacking-resistant rigid medium size hollow container blow molding material. The temperature of the cooling water can be 50-70 ℃, and the flow rate of the cooling water can be 600-700 m 3 H is used as the reference value. According to some embodiments of the present invention, the ethylene hexene copolymerized polyethylene resin is 99.75 to 99.92 parts by weight; and 0.08-0.25 part by weight of an auxiliary agent.
According to some embodiments of the present invention, the ethylene-hexene copolymerized polyethylene resin has a melt flow rate of 7.0 to 11.0g/10min, preferably 7.5 to 10.5g/10min, such as 8.0 to 10.0g/10min, 9.0g/10min, 9.5g/10min, and the like.
According to some embodiments of the present invention, the ethylene hexene copolymerized polyethylene resin has a weight average molecular weight of 15 ten thousand to 25 ten thousand, for example, 19 ten thousand, 20 ten thousand, 21 ten thousand, 22 ten thousand, 23 ten thousand, etc.
According to some embodiments of the invention, the ethylene hexene copolymerized polyethylene resin has a molecular weight distribution of 8 to 12, such as 8, 8.5, 9, 9.5, 10, 10.5, 11.5, 12, and the like.
According to some embodiments of the present invention, the ethylene-hexene copolymerized polyethylene resin has a melt flow rate of 10 to 11.0g/10min, a weight average molecular weight of 18 to 19 ten thousand, a molecular weight distribution of 8 to 9, and a 1-hexene comonomer content of 0.08 to 0.10mol% in the ethylene-hexene copolymerized polyethylene resin; or alternatively
According to some embodiments of the present invention, the ethylene hexene copolymerized polyethylene resin has a melt flow rate of 8.0 to 9.0g/10min, a weight average molecular weight of 19.0 to 20.0 ten thousand, a molecular weight distribution of 9 to 10, and a 1-hexene comonomer content of 0.04 mol% to 0.05mol% in the ethylene hexene copolymerized polyethylene resin; or
According to some embodiments of the present invention, the ethylene hexene copolymerized polyethylene resin has a melt flow rate of 7.0 to 8.0g/10min, a weight average molecular weight of 20.0 to 21.0 ten thousand, a molecular weight distribution of 11.0 to 12.0, and a 1-hexene comonomer content of 0.07 to 0.09mol% in the ethylene hexene copolymerized polyethylene resin;
according to some embodiments of the present invention, the ethylene-hexene copolymerized polyethylene resin has a melt flow rate of 8.0 to 9.0g/10min, a weight average molecular weight of 21.5 to 22.0 ten thousand, a molecular weight distribution of 10.0 to 10.5, and a 1-hexene comonomer content of 0.04mol to 0.06mol% in the ethylene-hexene copolymerized polyethylene resin; or alternatively
According to some embodiments of the present invention, the ethylene hexene copolymerized polyethylene resin has a melt flow rate of 9.5 to 10.0g/10min, a weight average molecular weight of 20.0 to 21.0 ten thousand, a molecular weight distribution of 11.0 to 12.0, and a 1-hexene comonomer content of 0.05mol% to 0.07mol% in the ethylene hexene copolymerized polyethylene resin.
According to other embodiments of the present invention, the ethylene-hexene copolymerized polyethylene resin has a density of 0.952 to 0.956kg/m 3 。
According to other embodiments of the present invention, the auxiliary agent comprises an antioxidant component and a processing aid component, and preferably the auxiliary agent is a compound auxiliary agent ST-510 developed and produced by Shanghai Shinetien chemical technology Limited.
According to some embodiments of the invention, the ethylene hexene copolymerized polyethylene resin is prepared by: placing monomer ethylene and 1-hexene into a reaction vessel under the condition that a diluent is always in a circulating state, adding an activated catalyst, and reacting at the reaction temperature of 95-101 ℃ until the melt flow rate of a reaction product is 7.0-11.0g/10min, preferably 7.5-10.5 g/10min and the density is 0.952-0.956 kg/m 3 Then the ethylene-hexene copolymerized polyethylene resin is obtained. In an embodiment of the present invention, the weight ratio of said ethylene to said 1-hexene is 1000: 3-12; the dosage of the 1-hexene is 0.6-2 times of the weight of the dosage of the catalyst; the feeding amount of the ethylene is 0.8-1.6 times of that of the diluent.
In an embodiment of the invention, the diluent may be an alkane, for example isobutane.
In an embodiment of the present invention, the catalyst may be a chromium-based catalyst. Preferably, the catalyst is an NTR-972 type chromium catalyst produced by Shanghai Hongshan chemical company Limited. To further enhance the activity of the reaction, an activated catalyst may be used, and the catalyst activation treatment may be carried out by a method conventional in the art.
In an embodiment of the present invention, the temperature of the cooling water is 50 to 70 ℃, and the flow rate of the cooling water is 600 to 700m 3 H is used as the reference value. The mixing may be carried out by means conventional in the art, for example using a mixer, stirrer or the like. In the present invention, the mixer may be an extruder of the Coperion ZSK-350 type, which has 7 barrel sections. In the mixing process, parameters of each section of cylinder can be set according to experimental requirements, for example, when the mixing mill is used for mixing, the temperature of the second section of cylinder of the mixing mill is adjusted to 225 ℃, the temperature of the third section of cylinder is adjusted to 230 ℃, the temperature of the fourth section of cylinder is adjusted to 240 ℃, the temperature of the fifth section of cylinder is adjusted to 245 ℃, the temperature of the sixth section of cylinder is adjusted to 250 ℃, and the temperature of the seventh section of cylinder is adjusted to 260 ℃; the temperature of the heat conducting oil of the heating mixing roll is 260 ℃.
Compared with the prior art, the invention has the advantages that:
(1) it is known in the art that the density of a material is influenced by the internal structure of molecules, the arrangement and the number of branched chains, and the like, and generally, the higher the content of 1-hexene is, the lower the density of the material is, the higher the impact resistance of the material is, and the stronger the toughness is; the lower the 1-hexene content, the higher the density of the material and the stronger the rigidity of the material. The blow molding material for the medium-sized hollow container provided by the invention has the advantages of moderate hexene content, wide molecular weight distribution, high density, high crystallinity, strong rigidity, high melt strength, small die-release expansion, stable parison, and processing performance and various physical and mechanical properties meeting the blow molding requirement of the medium-sized hollow container.
(2) The blow molding material for the medium-sized hollow container has wider molecular weight distribution and higher weight average molecular weight than the existing imported product, and has outstanding rigidity and better rigidity and toughness than imported products (such as HXM50100 of imported Sauter).
(3) According to the blow molding material and the process technology for the medium-sized hollow container, the industrial production is carried out under the process condition of the invention, compared with the prior art (such as 969ID produced by imported catalyst Grace company), the activity is doubled, and simultaneously, the production load can be increased by 25%.
Detailed Description
In order that the present invention may be more readily understood, the present invention will now be described in further detail by way of examples, which are given by way of illustration only and are not intended to limit the scope of the invention. The starting materials or components used in the present invention may be commercially or conventionally prepared unless otherwise specified.
The catalyst activation treatment of the following examples may be carried out by a conventional method, specifically: the catalyst falls into the activator by gravity by opening a bottom valve of the tank, the hot combustion gas and the hot fluidizing air from the hearth of the activation furnace heat the activation furnace and the catalyst, and the fluidizing gas passes through the distribution plate upwards and then fully contacts with the catalyst to activate the catalyst.
The mixer was a Coperion ZSK-350 extruder having 7 barrel sections.
The catalyst is a chromium catalyst, and adopts an NTR-972 chromium catalyst produced by Shanghai Hongshan chemical company Limited.
Ethylene: purity is not less than 99.20 percent C 2 H 2 ≤5×10 -6 CO≤1×10 -6
O 2 ≤2×10 -6 H 2 O≤×10 -6 COS≤0.02×10 -6 。
1-hexene: h with purity more than or equal to 98.5 percent 2 O≤20×10 -6 CO≤5×10 -6
Mono-olefin more than or equal to 98.5 percent, isomeric alpha-olefin less than or equal to 1 percent, normal non-alpha-olefin less than or equal to 1 percent
Normal alpha olefin is greater than or equal to 96 percent, peroxide is less than or equal to 1 multiplied by 10 -6 Sulfur is less than or equal to 1 x 10 -6 。
Isobutane: purity is more than or equal to 95.0 percent, acetylene is less than or equal to 2 multiplied by 10 -6 Total sulfur less than or equal to 1 x 10 -6
Total olefins less than or equal to 100 x 10 -6 Water is less than or equal to 20 multiplied by 10 -6 O 2 ≤5×10 -6 。
Example 1
The diluent isobutane is always in a circulating state, monomer ethylene and 1-hexene are respectively injected into a loop reactor, and an activated NTR-972 type chromium catalyst is added for reaction, wherein the ethylene feeding amount is 30t/h, the 1-hexene feeding amount is 360kg/h, the isobutane feeding amount is 20t/h, the catalyst feeding amount is 180kg/h, the reaction temperature is 100 ℃, and the reaction product has the melt flow rate of 10.5g/10min and the density of 0.952g/cm 3 When the reaction was stopped, an ethylene-hexene copolymerized polyethylene resin having a weight average molecular weight of 18.7 ten thousand, a molecular weight distribution of 8.7, and a 1-hexene comonomer content of 0.09mol% was obtained.
The blow molding material for the medium-sized hollow container comprises the following raw materials in parts by weight:
99.75 parts of ethylene-hexene copolymerized polyethylene resin
Compounded assistant ST-5100.25 parts
The preparation method of the blow molding material for the medium-sized hollow container comprises the following steps:
according to the proportion, the ethylene-hexene copolymerized polyethylene resin and the compound auxiliary agent are uniformly mixed and then added into a mixing roll to extrude particles into cooling water, and the granular medium-sized hollow container blow molding material is obtained. When the mixing roll is used for mixing, the temperature of a second section of barrel of the mixing roll is adjusted to 225 ℃, the temperature of a third section of barrel is adjusted to 230 ℃, the temperature of a fourth section of barrel is adjusted to 240 ℃, the temperature of a fifth section of barrel is adjusted to 245 ℃, the temperature of a sixth section of barrel is adjusted to 250 ℃, and the temperature of a seventh section of barrel is adjusted to 260 ℃; the temperature of the heat conducting oil for heating the mixing roll is 260 ℃. The temperature of the cooling water is 70 ℃, and the flow of the particle cooling water is 680m 3 /h。
Example 2
The diluent isobutane is always in a circulating state, monomer ethylene and 1-hexene are respectively injected into a loop reactor, and an activated NTR-972 type chromium catalyst is added for reaction, wherein the ethylene feeding amount is 35t/h, the 1-hexene feeding amount is 105kg/h, the isobutane feeding amount is 28t/h, the catalyst feeding amount is 175kg/h, the reaction temperature is 98 ℃, until the melt flow rate of a reaction product is 8.5g/10min, and the density is 0.956g/cm 3 When the reaction was stopped, an ethylene-hexene copolymerized polyethylene resin having a weight average molecular weight of 19.8 ten thousand, a molecular weight distribution of 9.6 and a 1-hexene comonomer content of 0.04 mol% was obtained.
The blow molding material for the medium-sized hollow container comprises the following raw materials in parts by weight:
99.90 parts of ethylene-hexene copolymerized polyethylene resin
Compounding assistant ST 5100.10 parts
The preparation method of the blow molding material for the medium-sized hollow container comprises the following steps:
and uniformly mixing the ethylene-hexene copolymerized polyethylene resin and the compound auxiliary agent according to the dosage, adding the mixture into a mixing roll to extrude particles into cooling water, and obtaining the granular polyethylene product medium-sized hollow container blow molding material. When the mixing roll is used for mixing, the temperature of a second section of barrel of the mixing roll is adjusted to 225 ℃, the temperature of a third section of barrel is adjusted to 230 ℃, the temperature of a fourth section of barrel is adjusted to 240 ℃, the temperature of a fifth section of barrel is adjusted to 245 ℃, the temperature of a sixth section of barrel is adjusted to 250 ℃, and the temperature of a seventh section of barrel is adjusted to 265 ℃; the temperature of the heat-conducting oil of the heating mixing roll is 260 ℃, the temperature of the cooling water is 65 ℃, and the flow of the particle cooling water is 680m 3 /h。
Example 3
The diluent isobutane is always in a circulating state, monomer ethylene and 1-hexene are respectively injected into a loop reactor, and an activated NTR-972 type chromium catalyst is added for reaction, wherein the ethylene feeding amount is 45t/h, the 1-hexene feeding amount is 360kg/h, the isobutane feeding amount is 22.5t/h, the catalyst feeding amount is 288kg/h, the reaction temperature is 101 ℃, until the melt flow speed of a reaction product is 7.5g/10min, and the density is 0.953g/cm 3 When the reaction was stopped, ethylene having a weight average molecular weight of 20.4 ten thousand, a molecular weight distribution of 11.7 and a 1-hexene comonomer content of 0.08 mol% was obtainedHexene copolymerized polyethylene resin.
The blow molding material for the medium-sized hollow container comprises the following raw materials in parts by weight:
99.80 parts of ethylene-hexene copolymerized polyethylene resin
Compound assistant ST 5100.20 parts
The preparation method of the blow molding material for the medium-sized hollow container comprises the following steps:
and uniformly mixing the ethylene-hexene copolymerized polyethylene resin and the compound auxiliary agent according to the above dosage, adding the mixture into a mixing roll, and extruding particles into cooling water to obtain the granular polyethylene product medium-sized hollow container blow molding material. When the mixing roll is used for mixing, the temperature of a second section of barrel of the mixing roll is adjusted to 225 ℃, the temperature of a third section of barrel is adjusted to 230 ℃, the temperature of a fourth section of barrel is adjusted to 240 ℃, the temperature of a fifth section of barrel is adjusted to 245 ℃, the temperature of a sixth section of barrel is adjusted to 250 ℃, and the temperature of a seventh section of barrel is adjusted to 265 ℃; the temperature of the heat conducting oil for heating the mixing roll is 260 ℃. The temperature of the cooling water is 60 ℃, and the flow of the particle cooling water is 620m 3 /h。
Example 4
The diluent isobutane is always in a circulating state, monomer ethylene and 1-hexene are respectively injected into a loop reactor, and an activated NTR-972 type chromium catalyst is added for reaction, wherein the ethylene feeding amount is 38t/h, the 1-hexene feeding amount is 247kg/h, the isobutane feeding amount is 38t/h, the catalyst feeding amount is 345.8kg/h, the reaction temperature is 99 ℃, until the melt flow rate of a reaction product is 8.3g/10min, and the density is 0.954g/cm 3 When the reaction was stopped, an ethylene-hexene copolymerized polyethylene resin having a weight average molecular weight of 21.9 ten thousand, a molecular weight distribution of 10.3 and a 1-hexene comonomer content of 0.05mol% was obtained.
The blow molding material for the medium-sized hollow container comprises the following raw materials in parts by weight:
99.88 parts of ethylene-hexene copolymerized polyethylene resin
Compound assistant ST 5100.12 parts
The preparation method of the blow molding material for the medium-sized hollow container comprises the following steps:
according to the dosage, the ethylene-hexene copolymerized polyethylene resin and the compound additive are evenly mixed and then added into a mixing roll to extrude particles into cooling water, and the granular polyethylene is obtainedAlkene product blow molding material for medium-sized hollow containers. When the mixing roll is used for mixing, the temperature of a second section of barrel of the mixing roll is adjusted to 225 ℃, the temperature of a third section of barrel is adjusted to 230 ℃, the temperature of a fourth section of barrel is adjusted to 240 ℃, the temperature of a fifth section of barrel is adjusted to 245 ℃, the temperature of a sixth section of barrel is adjusted to 250 ℃, and the temperature of a seventh section of barrel is adjusted to 270 ℃; the temperature of the heat conducting oil for heating the mixing roll is 260 ℃. The temperature of the cooling water is 55 ℃, and the flow of the particle cooling water is 620m 3 /h。
Example 5
The diluent isobutane is always in a circulating state, monomer ethylene and 1-hexene are respectively injected into a loop reactor, and an activated NTR-972 type chromium catalyst is added for reaction, wherein the ethylene feeding amount is 31t/h, the 1-hexene feeding amount is 248kg/h, the isobutane feeding amount is 38.75t/h, the catalyst feeding amount is 155kg/h, the reaction temperature is 95 ℃, until the melt flow speed of a reaction product is 9.8g/10min, and the density is 0.955g/cm 3 When the reaction was stopped, an ethylene-hexene copolymerized polyethylene resin having a weight average molecular weight of 20.5 ten thousand, a molecular weight distribution of 11.2 and a 1-hexene comonomer content of 0.06mol% was obtained.
The blow molding material for the medium-sized hollow container comprises the following raw materials in parts by weight:
99.92 portions of ethylene-hexene copolymerized polyethylene resin
Compound assistant ST 5100.08 parts
The preparation method of the blow molding material for the medium-sized hollow container comprises the following steps:
according to the proportion, the ethylene-hexene copolymerized polyethylene resin and the compound auxiliary agent are uniformly mixed and added into a mixing roll to extrude particles into cooling water, and the granular polyethylene product medium-sized hollow container blow molding material is obtained. When the mixing roll is used for mixing, the temperature of a second section of barrel of the mixing roll is adjusted to 225 ℃, the temperature of a third section of barrel is adjusted to 230 ℃, the temperature of a fourth section of barrel is adjusted to 240 ℃, the temperature of a fifth section of barrel is adjusted to 245 ℃, the temperature of a sixth section of barrel is adjusted to 250 ℃, and the temperature of a seventh section of barrel is adjusted to 265 ℃; the temperature of the heat conducting oil for heating the mixing roll is 260 ℃. The temperature of the cooling water is 66 ℃, and the flow of the particle cooling water is 660m 3 /h。
Comparative example 1
(1) Preparation of ethylene-hexene copolymerized polyethylene resin
Respectively injecting monomer ethylene and 1-hexene into a loop reactor under the condition that a diluent isobutane is in a circulating state all the time, and adding an activated NTR-972 chromium-based catalyst for reaction, wherein the ethylene feeding amount is 30t/h, the 1-hexene feeding amount is 240kg/h, the isobutane feeding amount is 50t/h, the catalyst feeding amount is 500kg/h, the reaction temperature is 98 ℃, until the melt flow rate of a reaction product is 7.8g/10min, and the density is 0.946g/cm 3 When the reaction was stopped, an ethylene-hexene copolymerized polyethylene resin having a weight average molecular weight of 18.3 ten thousand, a molecular weight distribution index of 4.2 and a 1-hexene content of 0.05mol% was obtained.
(2) Preparation of HDPE Material
99.72 parts of ethylene-hexene copolymerized polyethylene resin, 0.18 part of main antioxidant, 0.05 part of auxiliary antioxidant and 0.05 part of mold release agent are mixed uniformly, and then added into a mixing roll to extrude particles into cooling water, so as to obtain the granular polyethylene product medium-sized hollow container blow molding material. When the mixing roll is used for mixing, the temperature of a second section of barrel of the mixing roll is adjusted to 225 ℃, the temperature of a third section of barrel is adjusted to 230 ℃, the temperature of a fourth section of barrel is adjusted to 240 ℃, the temperature of a fifth section of barrel is adjusted to 245 ℃, the temperature of a sixth section of barrel is adjusted to 250 ℃, and the temperature of a seventh section of barrel is adjusted to 265 ℃; the temperature of the heat-conducting oil of the heating mixing roll is 260 ℃, the temperature of the particle cooling water is adjusted to be 60 ℃, and the flow of the particle cooling water is 670m 3 /h。
Comparative example 2
(1) Preparation of ethylene-hexene copolymerized polyethylene resin
Respectively injecting monomer ethylene and 1-hexene into a loop reactor under the condition that a diluent isobutane is always in a circulating state, and adding an activated NTR-972 chromium-based catalyst for reaction, wherein the ethylene feeding amount is 29t/h, the 1-hexene feeding amount is 406kg/h, the isobutane feeding amount is 34.8t/h, the catalyst feeding amount is 178kg/h, the reaction temperature is 90.2 ℃, until the melt flow speed of a reaction product is 8.3g/10min, and the density is 0.946g/cm 3 When the reaction was stopped, an ethylene-hexene copolymerized polyethylene resin having a weight average molecular weight of 20.1 ten thousand, a molecular weight distribution index of 10.9 and a 1-hexene content of 0.32 mol% was obtained.
(2) Preparation of HDPE Material
And uniformly mixing 99.88 parts of ethylene-hexene copolymerized polyethylene resin, 0.05 part of main antioxidant, 0.04 part of auxiliary antioxidant and 0.03 part of release agent, adding the mixture into a mixing roll, and extruding particles into cooling water to obtain the granular polyethylene product medium-sized hollow container blow molding material. When the mixing roll is used for mixing, the temperature of a second section of barrel of the mixing roll is adjusted to 225 ℃, the temperature of a third section of barrel is adjusted to 230 ℃, the temperature of a fourth section of barrel is adjusted to 240 ℃, the temperature of a fifth section of barrel is adjusted to 245 ℃, the temperature of a sixth section of barrel is adjusted to 250 ℃, and the temperature of a seventh section of barrel is adjusted to 265 ℃; the temperature of heat-conducting oil of the heating mixing mill is 260 ℃, the temperature of particle cooling water is adjusted to be 60 ℃, and the flow of the particle cooling water is 650m 3 /h。
Comparative example 3
(1) Preparation of ethylene-hexene copolymerized polyethylene resin
Respectively injecting monomer ethylene and 1-hexene into a loop reactor under the condition that a diluent isobutane is in a circulating state all the time, and adding an activated NTR-972 chromium-based catalyst for reaction, wherein the ethylene feeding amount is 30t/h, the 1-hexene feeding amount is 321kg/h, the isobutane feeding amount is 33.8t/h, the catalyst feeding amount is 157kg/h, the reaction temperature is 90.2 ℃, and the reaction product has the melt flow rate of 16.6g/10min and the density of 0.946g/cm 3 When the reaction was stopped, an ethylene-hexene copolymerized polyethylene resin having a weight average molecular weight of 13.2 ten thousand, a molecular weight distribution index of 8.58 and a 1-hexene content of 0.05mol% was obtained.
(2) Preparation of HDPE Material
And uniformly mixing 99.82 parts of ethylene-hexene copolymerized polyethylene resin, 0.10 part of main antioxidant, 0.05 part of auxiliary antioxidant and 0.03 part of release agent, adding the mixture into a mixing roll, and extruding particles into cooling water to obtain the granular polyethylene product medium-sized hollow container blow molding material. When the mixing roll is used for mixing, the temperature of a second section of barrel of the mixing roll is adjusted to 225 ℃, the temperature of a third section of barrel is adjusted to 230 ℃, the temperature of a fourth section of barrel is adjusted to 240 ℃, the temperature of a fifth section of barrel is adjusted to 245 ℃, the temperature of a sixth section of barrel is adjusted to 250 ℃, and the temperature of a seventh section of barrel is adjusted to 265 ℃; the temperature of the heat-conducting oil of the heating mixing roll is 260 ℃, the temperature of the particle cooling water is adjusted to be 60 ℃, and the flow of the particle cooling water is 650m 3 /h。
Comparative example 4
(1) Preparation of ethylene-hexene copolymerized polyethylene resin
Respectively injecting monomer ethylene and 1-hexene into a loop reactor under the condition that a diluent isobutane is always in a circulating state, and adding an antistatic agent ASA and a 965A chromium-based catalyst produced by activated Grace company for reaction, wherein the ethylene feeding amount is 28t/h, the 1-hexene feeding amount is 1960kg/h, the isobutane feeding amount is 34.8t/h, the catalyst feeding amount is 365kg/h, the reaction temperature is 93.7 ℃, until the melt flow speed of a reaction product is 13.2g/10min, and the density is 0.940g/cm 3 When the reaction was stopped, an ethylene-hexene copolymerized polyethylene resin having a weight average molecular weight of 25.2 ten thousand, a molecular weight distribution index of 13.0 and a 1-hexene content of 0.87 mol% was obtained.
(2) Preparation of HDPE Material
And uniformly mixing 99.76 parts of ethylene-hexene copolymerized polyethylene resin, 0.18 part of main antioxidant and 0.08 part of auxiliary antioxidant, adding the mixture into a mixing roll, and extruding particles into cooling water to obtain the blow molding material for the medium-sized hollow container of the granular polyethylene product. When the mixing roll is used for mixing, the temperature of a second section of barrel of the mixing roll is adjusted to 225 ℃, the temperature of a third section of barrel is adjusted to 230 ℃, the temperature of a fourth section of barrel is adjusted to 240 ℃, the temperature of a fifth section of barrel is adjusted to 245 ℃, the temperature of a sixth section of barrel is adjusted to 250 ℃, and the temperature of a seventh section of barrel is adjusted to 265 ℃; the temperature of the heat conducting oil of the heating mixing roll is 260 ℃, the temperature of the particle cooling water is adjusted to 65 ℃, and the flow of the particle cooling water is 680m 3 /h。
The performance of the medium-sized hollow blow molding materials of examples 1 to 5 of the invention and the performance of the HDPE blow molding materials of comparative examples 1 to 4 were compared with that of Saudi HXM50100, and the results are shown in tables 1 to 6.
TABLE 1 comparison of melt flow rates of HDPE blow molding materials of inventive examples 1-5 and comparative examples 1-4 with that of Sauter HXM50100
Note: HXM50100N is a generic name for the middle size hollow blow molding material of the present invention, and is the same as below.
TABLE 2 comparison of the molecular weights and distributions of the examples 1 to 5 of the invention, comparative examples 1 to 4 and Sauter HXM50100
TABLE 3 comparison of comonomer contents of inventive examples 1 to 5 with Saudi HXM50100
TABLE 4 comparison of crystallization Properties with Sauter HXM50100
Table 5 comparison of apparent Properties with Sauter HXM50100
P is the spline fracture morphology: partial fracture
As can be seen from table 5, the indexes of flexural modulus, flexural strength, shore hardness, vicat softening point, etc. of examples 1 to 5 of the present invention, which reflect the rigidity of the material, are all higher than those of comparative examples 1 to 4 and saute HXM50100, which reflects that the present invention has more outstanding rigidity than saute HXM 50100.
TABLE 6 comparison of the color of inventive examples 1 to 5 with Saudi HXM50100 blow-molded resins
As can be seen from Table 6, the chroma was higher in examples 1 to 5 of the present invention than in Saudi HXM 50100.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described in relation to an exemplary embodiment, and it is understood that the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (11)
1. A preparation method of a stacking-resistant rigid medium-sized hollow blow molding material comprises the steps of mixing ethylene-hexene copolymerized polyethylene resin and an auxiliary agent, and then extruding and granulating in a mixing roll to obtain blow molding material particles;
the preparation of the ethylene-hexene copolymerized polyethylene resin comprises the following steps: placing monomer ethylene and 1-hexene into a reaction vessel under the condition that a diluent is always in a circulating state, adding an activated catalyst, and reacting at the reaction temperature of 95-101 ℃ until the melt flow rate of a reaction product is 7.0-11.0g/10min and the density is 0.952-0.956 g/cm 3 Then ethylene-hexene copolymerized polyethylene resin is obtained; 99.75-99.92 parts by weight of ethylene-hexene copolymerized polyethylene resin; 0.08-0.25 part by weight of an auxiliary agent;
the auxiliary agent comprises an antioxidant component and a processing aid component, and the auxiliary agent is a compound auxiliary agent ST-510;
the content of the 1-hexene comonomer in the ethylene-hexene copolymerized polyethylene resin is 0.04-0.10 mol%.
2. The method of claim 1, further comprising cooling the blow molding material pellets in cooling water to obtain a stacking-resistant rigid medium-sized hollow container blow molding material.
3. The method according to claim 2, wherein the cooling water has a temperature of 50 to 70 ℃ and a flow rate of 600 to 700m 3 /h。
4. The preparation method according to claim 1, wherein the melt flow rate of the ethylene-hexene copolymerized polyethylene resin is 7.5 to 10.5g/10 min.
5. The preparation method according to claim 1, wherein the weight average molecular weight of the ethylene-hexene copolymerized polyethylene resin is 15 to 25 ten thousand, and the molecular weight distribution is 8 to 12.
6. The process according to claim 1, characterized in that the weight ratio of ethylene to 1-hexene used is between 1000: 3-12; the dosage of the 1-hexene is 0.6-2 times of the weight of the dosage of the catalyst; the feeding amount of the ethylene is 0.8-1.6 times of that of the diluent.
7. The method of claim 1, wherein the diluent is an alkane.
8. The method of claim 7, wherein the diluent is isobutane.
9. The method of claim 1, wherein the catalyst is a chromium-based catalyst.
10. The preparation method according to claim 1, wherein the melt flow rate of the ethylene-hexene copolymerized polyethylene resin is 10-11.0 g/10min, the weight average molecular weight is 18-19 ten thousand, the molecular weight distribution is 8-9, and the content of 1-hexene comonomer in the ethylene-hexene copolymerized polyethylene resin is 0.08-0.10 mol%; or
The melt flow rate of the ethylene-hexene copolymerized polyethylene resin is 8.0-9.0 g/10min, the weight average molecular weight is 19.0-20.0 ten thousand, the molecular weight distribution is 9-10, and the content of a 1-hexene comonomer in the ethylene-hexene copolymerized polyethylene resin is 0.04-0.05 mol%; or
The melt flow rate of the ethylene-hexene copolymerized polyethylene resin is 7.0-8.0 g/10min, the weight average molecular weight is 20.0-21.0 ten thousand, the molecular weight distribution is 11.0-12.0, and the content of a 1-hexene comonomer in the ethylene-hexene copolymerized polyethylene resin is 0.07-0.09 mol%; or
The melt flow rate of the ethylene-hexene copolymerized polyethylene resin is 8.0-9.0 g/10min, the weight average molecular weight is 21.5-22.0 ten thousand, the molecular weight distribution is 10.0-10.5, and the content of a 1-hexene comonomer in the ethylene-hexene copolymerized polyethylene resin is 0.04-0.06 mol%; or
The melt flow rate of the ethylene-hexene copolymerized polyethylene resin is 9.5-10.0 g/10min, the weight average molecular weight is 20.0-21.0 ten thousand, the molecular weight distribution is 11.0-12.0, and the content of a 1-hexene comonomer in the ethylene-hexene copolymerized polyethylene resin is 0.05-0.07 mol%.
11. Use of a stacking-resistant rigid medium hollow blow molding material prepared according to the preparation process of any one of claims 1 to 10 in medium hollow articles.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105254991A (en) * | 2015-10-23 | 2016-01-20 | 中国石油化工股份有限公司 | Preparation method of high-density polyethylene IBC inner container blow molding material |
JP2017013804A (en) * | 2015-06-29 | 2017-01-19 | コダマ樹脂工業株式会社 | Blow-molded lamination container for ultrahigh purity medicine excellent in visibility of content |
CN106543547A (en) * | 2016-10-20 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of little hollow blow molding modification high-density polyethylene resin and preparation method thereof of easy processing food-grade |
CN106866862A (en) * | 2015-12-11 | 2017-06-20 | 中国石油天然气股份有限公司 | Polyethylene base resin powder and preparation method thereof |
CN109438799A (en) * | 2018-08-22 | 2019-03-08 | 上海帆顺包装集团有限公司 | It is suitble to 200L or more hollow blow molding bucket blended polyethylene resin and the preparation method and application thereof |
-
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017013804A (en) * | 2015-06-29 | 2017-01-19 | コダマ樹脂工業株式会社 | Blow-molded lamination container for ultrahigh purity medicine excellent in visibility of content |
CN105254991A (en) * | 2015-10-23 | 2016-01-20 | 中国石油化工股份有限公司 | Preparation method of high-density polyethylene IBC inner container blow molding material |
CN106866862A (en) * | 2015-12-11 | 2017-06-20 | 中国石油天然气股份有限公司 | Polyethylene base resin powder and preparation method thereof |
CN106543547A (en) * | 2016-10-20 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of little hollow blow molding modification high-density polyethylene resin and preparation method thereof of easy processing food-grade |
CN109438799A (en) * | 2018-08-22 | 2019-03-08 | 上海帆顺包装集团有限公司 | It is suitble to 200L or more hollow blow molding bucket blended polyethylene resin and the preparation method and application thereof |
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