CN113150419B - Crosslinkable polyethylene composition, preparation method thereof and rotational molding product - Google Patents

Crosslinkable polyethylene composition, preparation method thereof and rotational molding product Download PDF

Info

Publication number
CN113150419B
CN113150419B CN202010014988.2A CN202010014988A CN113150419B CN 113150419 B CN113150419 B CN 113150419B CN 202010014988 A CN202010014988 A CN 202010014988A CN 113150419 B CN113150419 B CN 113150419B
Authority
CN
China
Prior art keywords
polyethylene
antioxidant
weight
rotational molding
inhibitor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010014988.2A
Other languages
Chinese (zh)
Other versions
CN113150419A (en
Inventor
任月庆
孙小杰
李亚飞
孙苗苗
陈兰兰
梁文斌
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenhua Beijing New Material Technology Co ltd
Original Assignee
China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Energy Investment Corp Ltd, National Institute of Clean and Low Carbon Energy filed Critical China Energy Investment Corp Ltd
Priority to CN202010014988.2A priority Critical patent/CN113150419B/en
Publication of CN113150419A publication Critical patent/CN113150419A/en
Application granted granted Critical
Publication of CN113150419B publication Critical patent/CN113150419B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Moulding By Coating Moulds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The invention relates to the field of crosslinked polyethylene, and relates to a crosslinkable polyethylene composition, a preparation method thereof and a rotational molding product prepared from the crosslinked polyethylene composition. The crosslinkable polyethylene composition of the invention comprises polyethylene resin, a crosslinking agent, an auxiliary crosslinking agent, an inhibitor and an antioxidant, and relative to 100 parts by weight of the polyethylene resin, the composition comprises 0.05-3 parts by weight of the crosslinking agent, 0.05-3 parts by weight of the auxiliary crosslinking agent, 0.02-1.5 parts by weight of the inhibitor and 0.02-1.5 parts by weight of the antioxidant; the polyethylene resin has a melt index of 18-50g/10min at 190 ℃ under a load of 2.16kg and a density of 0.91-0.97g/cm 3 . The rotational molding product prepared from the crosslinkable polyethylene composition provided by the invention has excellent mechanical properties, particularly impact resistance at 40 ℃ below zero, higher processing efficiency and smooth inner wall surface of the product.

Description

Crosslinkable polyethylene composition, preparation method thereof and rotational molding product
Technical Field
The invention relates to the field of crosslinked polyethylene, in particular to a crosslinkable polyethylene composition, a preparation method thereof and a rotational molding product prepared from the crosslinked polyethylene composition.
Background
Polyethylene is the most important raw material in the rotational molding industry due to its excellent processability, accounting for more than 80% of the rotational molding market, but due to the linear structure of traditional polyethylene, it has poor solvent resistance, high temperature creep resistance and environmental stress cracking resistance. The cross-linked polyethylene cross-linked by peroxide has a perfect network structure after cross-linking, has high gel content, and the obtained sample has excellent solvent resistance, high temperature resistance and environmental stress cracking resistance, so the cross-linked polyethylene becomes the most important material in the rotational molding market.
The polyethylene has a linear molecular structure before cross-linking, can flow after being melted, is uniformly coated on the surface of a grinding tool under the action of gravity for forming, and is changed into a body structure after cross-linking, so that the polyethylene has high viscosity and cannot flow for forming. The crosslinked polyethylene has excellent high-temperature creep resistance, environmental stress cracking resistance and mechanical properties, so that the crosslinked polyethylene can be applied to the field of rotational molding to prepare rotational molding products such as chemical storage tanks, oil tanks, submarines and the like.
In the rotational molding process, rotational molding heating is one-way heat transfer, and heat is transferred to the interior of the mold by the oven, so that the rotational molding processing heat transfer efficiency is lower than that of mold pressing and injection molding, and the rotational molding processing efficiency is lower. In the rotational molding process of the crosslinked polyethylene, the raw material of the crosslinked polyethylene needs to be melted and leveled, and the crosslinking system needs to be completely crosslinked and cured into a three-dimensional crosslinking system, so that the crosslinked polyethylene has long heating time and low processing efficiency.
In the prior art, the cross-linking agent used in the cross-linked polyethylene for rotational molding has high reaction temperature, and has better melt processing safety, but the high reaction temperature of the cross-linking agent means that the heating time is longer in the rotational molding process so as to complete the cross-linking, and in addition, because the heating time is longer, the temperature of the inner wall of the rotational molding is higher, the inner wall of the rotational molding is close to the internal air, so that the inner wall of the rotational molding product is oxidized, and the performance, particularly the impact resistance, of the rotational molding product is obviously reduced.
Therefore, it is desirable to provide a cross-linked polyethylene which can be efficiently processed and has a wide processing window, which can be suitable for rotational molding, and which can provide a rotational molded article having excellent mechanical properties.
Disclosure of Invention
The invention aims to overcome the problems of poor processability and mechanical properties of rotational molding products, particularly poor impact resistance at 40 ℃ below zero, more defects on inner walls of the products and unsmooth inner wall surfaces in the prior art, and provides a polyethylene cross-linked polyethylene composition, a preparation method thereof and a rotational molding product prepared from the cross-linked polyethylene composition.
In order to achieve the above objects, the first aspect of the present invention provides a crosslinkable polyethylene composition, wherein the composition comprises a polyethylene resin, a crosslinking agent, a co-crosslinking agent, an inhibitor, and an antioxidant, and the composition comprises, relative to 100 parts by weight of the polyethylene resin, 0.05 to 3 parts by weight of the crosslinking agent, 0.05 to 3 parts by weight of the co-crosslinking agent, 0.02 to 1.5 parts by weight of the inhibitor, and 0.02 to 1.5 parts by weight of the antioxidant;
the polyethylene resin has a melt index of 18-50g/10min at 190 ℃ and under a load of 2.16kg, and a density of 0.91-0.97g/cm 3 。
Preferably, the composition comprises 0.1 to 2 parts by weight of a crosslinking agent, 0.1 to 2 parts by weight of a co-crosslinking agent, 0.03 to 1 part by weight of an inhibitor, and 0.05 to 1 part by weight of an antioxidant, relative to 100 parts by weight of the polyethylene resin.
More preferably, the composition comprises 0.1 to 1.0 parts by weight of a crosslinking agent, 0.1 to 1.0 parts by weight of a co-crosslinking agent, 0.05 to 0.5 parts by weight of an inhibitor and 0.1 to 0.5 parts by weight of an antioxidant, relative to 100 parts by weight of the polyethylene resin.
Preferably, the polyethylene resin has a melt index of 20 to 30g/10min and a density of 0.94 to 0.965g/cm at 190 ℃ under a load of 2.16kg 3 。
Preferably, the polyethylene resin is polyethylene a and optionally polyethylene B.
More preferably, the polyethylene a is a high density polyethylene.
More preferably, the polyethylene B is a linear low density polyethylene and/or a low density polyethylene.
Preferably, the polyethylene resin is polyethylene A and polyethylene B, wherein the amount of the polyethylene A is 99-60 parts by weight, and the amount of the polyethylene B is 1-40 parts by weight.
More preferably, the polyethylene a is used in an amount of 95 to 70 parts by weight and the polyethylene B is used in an amount of 5 to 30 parts by weight.
Preferably, the high density polyethylene has a melt index of 18 to 50g/10min at 190 ℃ and a load of 2.16kg and a density of 0.941 to 0.965g/cm 3 (ii) a The linear low density polyethylene and/or the low density polyethylene has a melt index of 2-50g/10min at 190 deg.C under a load of 2.16kg, and a density of 0.91-0.93g/cm 3 。
More preferably, the high density polyethylene has a melt index of 20 to 30g/10min at 190 ℃ and a load of 2.16kg and a density of 0.941 to 0.960g/cm 3 (ii) a The linear low density polyethylene and/or the low density polyethylene has a melt index of 2-10g/10min at 190 ℃ and under a load of 2.16kg, and a density of 0.91-0.925g/cm 3 。
Preferably, the crosslinking agent is a peroxide.
Preferably, the thermal weight loss temperature T of the cross-linking agent onset Not less than 90 ℃; wherein, for the unsupported crosslinker, the T onset Namely the temperature when the weight loss rate of the cross-linking agent is 5wt% when a thermal gravimetric method TGA test is adopted; for supported crosslinkers, the T onset I.e. the temperature at which the percentage weight loss of the crosslinker/the effective content of the crosslinker is 5wt% when tested by thermogravimetric analysis TGA.
More preferably, the cross-linking agent is selected from one or more of dicumyl peroxide, 1, 3-bis (t-butylperoxyisopropyl) benzene, 1, 4-bis (t-butylperoxyisopropyl) benzene, t-butylcumyl peroxide, t-butyl peroxybenzoate, 2, 5-dimethyl 2, 5-bis (benzoyl) peroxy-hexane and t-butylcumyl peroxide.
Preferably, the co-crosslinking agent is selected from one or more of triallyl isocyanurate, trimethylolpropane triacrylate and trimethylolpropane trimethacrylate.
Preferably, the inhibitor is a free radical inhibitor.
More preferably, the inhibitor is a nitroxide radical inhibitor.
<xnotran> , 2,2,6,6- -1- (TEMPO), 4- -2,2,6,6- -1- ( -Tempo), 4- -2,2,6,6- -1- [4- -Tempo ], 4- -2,2,6,6- -1- [4- -Tempo ] 4- -2,2,6,6- -1- [4- -Tempo ] . </xnotran>
Preferably, the antioxidant is selected from one or more of antioxidant 1010, antioxidant 168, antioxidant DSTP, antioxidant DLTP, antioxidant 1076, antioxidant 1330 and antioxidant 3114.
Preferably, the composition has a minimum heating time t for rotational moulding processing at a rotational moulding temperature of 280 ℃ and a rotational moulded product thickness of 4mm min Less than or equal to 27min, and the heating time is t min To t min When the steel plate is in PW, the drop hammer impact strength at 40 ℃ below zero is more than or equal to 29J/mm, and the machining window PW is more than or equal to 6min.
In a second aspect, the present invention provides a method of producing the crosslinkable polyethylene composition of the instant invention, comprising the steps of:
and mixing the cross-linking agent, the cross-linking assistant, the antioxidant and the polyethylene resin, and then carrying out melt blending extrusion, cooling, granulation and drying to obtain the cross-linkable polyethylene composition.
Preferably, the method comprises:
(1) Mixing a cross-linking agent, a cross-linking assistant agent and an antioxidant with more than one tenth of polyethylene resin, and then carrying out melt blending extrusion, cooling, granulation and drying to obtain a cross-linked polyethylene master batch;
(2) And mixing the crosslinked polyethylene master batch with the rest polyethylene resin, and then carrying out melt blending extrusion, cooling, granulation and drying to obtain the crosslinkable polyethylene composition.
In a third aspect, the invention provides a rotational molding product, which is prepared by crosslinking the crosslinkable polyethylene composition of the invention.
The fourth aspect of the invention provides a preparation method of the rotational moulding product, wherein the preparation method comprises the following steps:
I. crushing and screening the crosslinkable polyethylene composition to obtain crosslinkable polyethylene fine powder;
II. And placing the crosslinkable polyethylene fine powder in a rotational molding grinding tool, crosslinking and simultaneously performing rotational molding to obtain the rotational molding product.
Preferably, the conditions of the rotational moulding include: the rotation speed in the horizontal axis direction is 3-8r/min, the rotation speed in the vertical axis direction is 4-10r/min, the molding temperature is 200-350 ℃, and the molding time is 25-32min.
Through the technical scheme, the cross-linked polyethylene composition provided by the invention has excellent processability and meets the requirements of a rotational molding process on the processability of a polymer.
The cross-linked polyethylene polymer provided by the invention has short heating time and can realize high-efficiency processing; the crosslinked polyethylene composition has a wide processing window, and is beneficial to product quality control in the production process; excellent low temperature impact strength.
Specifically, when the rotational molding temperature of the crosslinked polyethylene composition is 280 ℃ and the thickness of a rotational molding product is 4mm, the shortest heating time t of rotational molding processing is min Less than or equal to 27min, and the heating time is t min To t min When the material is PW, the drop hammer impact strength at minus 40 ℃ is more than or equal to 29J/mm, wherein the processing window PW is more than or equal to 6min.
Drawings
FIG. 1 is a TGA thermogravimetric plot of a crosslinking agent used in an example of the present invention;
fig. 2 is a photograph of the inner wall topography of rotomoulded articles provided by examples 1,4, 7 of the present invention and comparative examples 1, 2, = and 4.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a crosslinkable polyethylene composition, wherein the composition comprises a polyethylene resin, a crosslinking agent, an auxiliary crosslinking agent, an inhibitor and an antioxidant, and relative to 100 parts by weight of the polyethylene resin, the composition comprises 0.05 to 3 parts by weight of the crosslinking agent, 0.05 to 3 parts by weight of the auxiliary crosslinking agent, 0.02 to 1.5 parts by weight of the inhibitor and 0.02 to 1.5 parts by weight of the antioxidant;
the polyethylene resin has a melt index of 18-50g/10min at 190 ℃ under a load of 2.16kg and a density of 0.91-0.97g/cm 3 。
According to the present invention, the composition comprises 0.1 to 2 parts by weight of a crosslinking agent, 0.1 to 2 parts by weight of a co-crosslinking agent, 0.03 to 1 part by weight of an inhibitor, and 0.05 to 1 part by weight of an antioxidant, relative to 100 parts by weight of a polyethylene resin.
According to the present invention, the composition comprises 0.1 to 1.0 parts by weight of a crosslinking agent, 0.1 to 1.0 parts by weight of a co-crosslinking agent, 0.05 to 0.5 parts by weight of an inhibitor, and 0.1 to 0.5 parts by weight of an antioxidant, relative to 100 parts by weight of a polyethylene resin.
According to the invention, the polyethylene resin has a melt index of 20 to 30g/10min at 190 ℃ and under a load of 2.16kg, and a density of 0.94 to 0.965g/cm 3 。
According to the invention, the polyethylene resin has a higher melt index, the processing fluidity of the polyethylene resin is obviously improved, the phenomena of inner wall defects, unsmooth inner wall surface and the like of a rotational molding product caused by uneven resin flow can be obviously improved, and the quality of the rotational molding product is improved.
In the rotational molding process, the used crosslinked polyethylene raw material is 30-80 mesh powdery polyethylene particles, the temperature of a mold rises along with the extension of rotational molding heating time, the polyethylene particles firstly melt and flow, adhere to the surface of the mold and gradually level, the temperature of the mold rises along with the further rise of the rotational molding heating time to reach the decomposition temperature of a peroxide crosslinking agent, the peroxide decomposes to generate free radicals to initiate crosslinking reaction, and the crosslinking reaction is initiated along with the further rise of the rotational molding heating timeFurther extension, the peroxide rapidly generates free radicals, the crosslinking reaction is rapidly completed, and after a certain heating time (the time is a time period as much as possible, but not a time point, i.e. t) min The crosslinking reaction is complete, but t min To t min And+ PW finishes crosslinking, but the performance is not different, PW is a processing window, the wider the processing window is, the wider the processing window represents that the processing technology has less influence on performance indexes, and the processing control is easy), the crosslinking reaction is finished, and the product is taken out after being cooled to room temperature.
According to the invention, the polyethylene resin is polyethylene a and optionally polyethylene B.
According to the invention, the polyethylene a is a high density polyethylene.
According to the invention, the polyethylene B is a linear low density polyethylene and/or a low density polyethylene.
In the present invention, the weight ratio of the linear low density polyethylene to the low density polyethylene is from 100 to 40.
According to the invention, the polyethylene resin comprises polyethylene A and polyethylene B, wherein the amount of the polyethylene A is 99-60 parts by weight, and the amount of the polyethylene B is 1-40 parts by weight.
Preferably, the polyethylene A is used in an amount of 95 to 70 parts by weight and the polyethylene B is used in an amount of 5 to 30 parts by weight.
According to the invention, the high-density polyethylene has a melt index of 18 to 50g/10min at 190 ℃ and under a load of 2.16kg, and a density of 0.941 to 0.965g/cm 3 (ii) a The linear low density polyethylene and/or the low density polyethylene has a melt index of 2-50g/10min at 190 deg.C under a load of 2.16kg, and a density of 0.91-0.93g/cm 3 。
Preferably, the high density polyethylene has a melt index of 20 to 30g/10min at 190 ℃ and a load of 2.16kg and a density of 0.941 to 0.96g/cm 3 (ii) a The linear low density polyethylene and/or the low density polyethylene has a melt index of 2-10g/10min at 190 ℃ and under a load of 2.16kg, and a density of 0.91-0.925g/cm 3 。
According to the invention, the crosslinking agent is a peroxide.
According to the inventionTemperature T of thermal weight loss of said crosslinking agent onset More than or equal to 90 ℃; wherein, for the unsupported crosslinker, the T onset Namely the temperature when the weight loss rate of the cross-linking agent is 5wt% when a thermal gravimetric method TGA test is adopted; for supported crosslinkers, the T onset I.e. the temperature at which the percentage weight loss of the cross-linking agent/the effective content of the cross-linking agent is 5wt% when tested by thermogravimetric analysis TGA.
In the present invention, the supported crosslinking agent is a solid crosslinking agent obtained by mixing a crosslinking agent which is liquid at room temperature with inorganic particles as a carrier. Wherein, the effective component in the load type cross-linking agent is the cross-linking agent, and the inorganic particles as the carrier are the non-effective component.
More preferably, the cross-linking agent is selected from one or more of dicumyl peroxide, 1, 3-bis (t-butylperoxyisopropyl) benzene, 1, 4-bis (t-butylperoxyisopropyl) benzene, t-butylcumyl peroxide, t-butylperoxybenzoate, 2, 5-dimethyl 2, 5-bis (benzoyl) peroxy-hexane, and t-butylcumyl peroxide;
in the present invention, the crosslinking agent contains at least 1, 4-bis (tert-butylperoxyisopropyl) benzene (BIPB).
According to the invention, the co-crosslinking agent is selected from one or more of triallyl isocyanurate, trimethylolpropane triacrylate and trimethylolpropane trimethacrylate.
According to the invention, the inhibitor is a free radical inhibitor.
Preferably, the inhibitor is a nitroxide radical inhibitor.
<xnotran> , 2,2,6,6- -1- (Tempo), 4- -2,2,6,6- -1- ( -Tempo), 4- -2,2,6,6- -1- [4- -Tempo ], 4- -2,2,6,6- -1- [4- -Tempo ] 4- -2,2,6,6- -1- [4- -Tempo ] . </xnotran>
According to the invention, the antioxidant is selected from one or more of antioxidant 1010, antioxidant 168, antioxidant DSTP, antioxidant DLTP, antioxidant 1076, antioxidant 1330 and antioxidant 3114.
In the prior art, in order to ensure that the rotational molding product has excellent crosslinking efficiency and obtain a product with smooth inner wall, a crosslinking agent with higher initial crosslinking temperature is preferably used to be matched with an auxiliary crosslinking agent and an inhibitor so as to prevent the premature crosslinking of polyethylene, thereby obtaining a crosslinked polyethylene rotational molding product with excellent performance. However, the requirements for the type of the crosslinking agent are high, and the energy consumption for production is remarkably increased and the production efficiency is reduced due to the high crosslinking initiation temperature.
The inventor finds that when the polyethylene resin with the high melt index is selected as the polyethylene matrix for the rotational molding product, the cross-linking agent with the lower initial cross-linking temperature can be selected, so that the selection range of the cross-linking agent is widened, the cross-linking temperature is reduced, the production energy consumption is reduced, and the production efficiency is improved.
In addition, the polyethylene resin with high melt index can ensure excellent mechanical property and crosslinking efficiency of the rotational molding product, greatly reduce the dosage of the inhibitor and reduce the production cost.
According to the invention, the composition has a minimum heating time t for rotational moulding processing when the rotational moulding temperature is 280 ℃ and the thickness of a rotational moulding product is 4mm min Less than or equal to 27min, and the heating time is t min To t min When the material is PW, the drop hammer impact strength at minus 40 ℃ is more than or equal to 29J/mm, wherein the processing window PW is more than or equal to 6min.
In the invention, the processing window PW refers to a rotational molding heating time interval during which the drop hammer impact strength of a prepared rotational molding product at the temperature of-40 ℃ is greater than 90% of the maximum drop hammer impact strength along with the change of heating time in the rotational molding process of the composition.
The second aspect of the present invention provides a method for preparing said crosslinkable polyethylene composition, comprising the steps of: and mixing the cross-linking agent, the cross-linking assistant, the antioxidant and the polyethylene resin, and then carrying out melt blending extrusion, cooling, granulation and drying to obtain the cross-linkable polyethylene composition.
According to the invention, the method comprises:
(1) Mixing a cross-linking agent, a cross-linking auxiliary agent and an antioxidant with more than one tenth of polyethylene resin, and then carrying out melt blending extrusion, cooling, granulation and drying to obtain a cross-linked polyethylene master batch;
(2) And mixing the crosslinked polyethylene master batch with the rest polyethylene resin, and then carrying out melt blending extrusion, cooling, granulation and drying to obtain the crosslinkable polyethylene composition.
In the invention, the cross-linking agent, the cross-linking auxiliary agent, the antioxidant and the polyethylene resin or the cross-linked polyethylene master batch are mixed with the rest polyethylene resin by a high-speed mixer, wherein the rotating speed of the high-speed mixer is 10-1000r/min, preferably 50-300r/min.
In the invention, the mixture is placed in an internal mixer or a double-screw extruder for melt blending extrusion, wherein the temperature of the melt blending extrusion is 100-180 ℃, and preferably 120-140 ℃.
In the invention, the mixture obtained by melt blending and extrusion is subjected to melt extrusion granulation by adopting twin-screw extrusion, wherein the temperature of the melt extrusion granulation is 100-200 ℃, preferably 120-160 ℃, the length-diameter ratio of a screw of a twin-screw extruder is 16/1-35/1, preferably 20/1-30/1, and the rotating speed of the screw is 50-200 r/min, preferably 80-100 r/min.
In a third aspect, the present invention provides a rotomoulded article made from the crosslinkable polyethylene composition of the present invention by crosslinking.
The fourth aspect of the invention provides a preparation method of the rotational moulding product, wherein the preparation method comprises the following steps:
I. crushing and screening the crosslinkable polyethylene composition to obtain crosslinkable polyethylene fine powder;
II. And placing the crosslinkable polyethylene fine powder in a rotational molding grinding tool, crosslinking and simultaneously performing rotational molding to obtain the rotational molding product.
In the invention, a pulverizer or a ball mill is adopted to crush the crosslinked polyethylene composition, and the crushed composition is sieved by a 20-40 mesh sieve powder machine to obtain the crosslinked polyethylene fine powder.
According to the invention, the conditions of the rotational moulding include: the rotating speed in the horizontal axis (small axis) direction is 3-8r/min, the rotating speed in the vertical axis (large axis) direction is 4-10r/min, the molding temperature is 200-350 ℃, and the molding time is 25-32min.
The present invention will be described in detail below by way of examples.
-40 ℃ drop hammer impact strength test method
According to the T/CAS 263-2017 test standard, cutting a rotational molding sample into square sample pieces with the size of 120mm multiplied by 120mm, and placing the square sample pieces in a low-temperature freezer for 24 hours at the constant temperature of-40 ℃. And (3) quickly placing the sample after constant temperature in an impact testing machine, releasing an impact hammer with the mass of 9.072kg, and impacting the outer surface of the rotational molding product. The calculation of drop hammer impact strength (ARM) is shown in formula (1):
ARM＝m×g×h/t (1)
in the formula, ARM-drop hammer impact strength is J/mm; m-drop weight, kg; g-acceleration of gravity, m/s 2 (ii) a h-weighted average height, m; t-average thickness of sample, mm.
Thermogravimetric temperature measurement
Thermal Gravimetric Analysis (TGA) for testing thermal gravimetric temperature T of cross-linking agent onset Putting 10mg of sample into a ceramic crucible, taking nitrogen as atmosphere, heating the sample from 40 ℃ to 500 ℃ at a heating rate of 10 ℃/min, and measuring the temperature when the thermal weight loss rate of the effective content of peroxide in the peroxide heating process is 5 percent, namely T onset 。
The following examples and comparative examples used the following starting materials:
high density polyethylene HDPE DMDA 8920 available from Dushan petrochemical Co., ltd of China, having a melt index of 23g/10min (190 deg.C, 2.16 kg) and a density of 0.954g/cm 3 ；
High density polyethylene HDPE DMDA8007, available from Shenhua Baotou coal chemical industry Co., ltd., melt index of 8g/10min (190 ℃,2.16 kg), density of 0.960g/cm 3 ；
Linear Low Density polyethylene LLDPE 5230G, available from Dow chemical, having a melt index of 4G/10min (190 ℃,2.16 kg) and a density of 0.916G/cm 3 ；
Cross-linker 1, 4-bis-tert-butylperoxyIsopropylbenzene BIPB (isopropyl benzene BIPB) purchased from ARKAMA China investment Limited company, with the initial crosslinking temperature of 158 ℃ and the TGA thermal weight loss temperature T in high-density polyethylene onset The temperature was 126 ℃.
Cross-linking agent 2, 5-dimethyl-2, 5-bis (T-butylperoxy) hexane (DHBP), available from Allan reagent, with an onset cross-linking temperature of 167 ℃ in high density polyethylene, TGA thermogravimetric loss temperature T onset Is 80 ℃;
cross-linking agent 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexyne-3 (DTBH) purchased from ARKAMA, china investment Limited, with an initial cross-linking temperature of 181 ℃ and a TGA thermogravimetric loss temperature T in high density polyethylene onset Is 83 ℃;
the crosslinking agents used in the examples of the present invention are all unsupported crosslinking agents.
The other raw materials used in the examples and comparative examples are commercially available.
Preparation example
Heating F01-1000 of cigarette table square large rotational molding company Limited to 280 ℃, adding 4kg of crosslinked polyethylene fine powder into a mold of 50cm multiplied by 25cm, pushing a rotational molding grinding tool into an oven to heat, setting the heating time to be 25-32min respectively, setting the revolution of a large rotating shaft to be 5r/min and the revolution of a small rotating shaft to be 8r/min, heating at 280 ℃ for 25-32min, cooling the grinding tool to about 40 ℃ by adopting air cooling after heating is finished (the cooling time is about 30 min), and opening the mold to obtain a rotational molding product.
Examples 1 to 10
The kinds and amounts of the respective materials used in examples are shown in Table 1.
(1) Adding polyethylene I, a cross-linking agent, an auxiliary cross-linking agent, an inhibitor and an antioxidant into a high-speed mixer for mixing, then adding into a hopper of a double-screw extruder, and carrying out melt blending extrusion, cooling, granulation and drying at 130 ℃ to obtain the cross-linked master batch.
(2) And blending the crosslinking master batch and the polyethylene II in a high-speed mixer, and then performing melt extrusion granulation at 140 ℃ by adopting a double-screw extruder to obtain the crosslinking polyethylene composition. Wherein the length-diameter ratio of a screw of the double-screw extruder is 26/1, and the rotating speed of the screw is 100 revolutions per minute.
(3) The prepared crosslinked polyethylene composition is crushed and screened to obtain crosslinked polyethylene fine powder with about 35 meshes, and the crosslinked polyethylene fine powder is rotationally molded according to the method of the preparation example to obtain rotational molding products A1-10.
Example 11
Rotomoulded articles were prepared in the same way as in example 1, except that: mixing all the high-density polyethylene with a cross-linking agent, an auxiliary cross-linking agent, an inhibitor and an antioxidant at one time, and carrying out melt blending extrusion, cooling, granulation and drying to obtain the cross-linked polyethylene composition. A rotomoulded article a11 was prepared.
Comparative examples 1 to 5
Rotomoulded articles were prepared in the same way as in example 1, except that: the kinds and amounts of the respective materials were different, and the kinds and amounts of the respective materials used in comparative examples are shown in Table 1.
Table 1 composition and performance testing of rotomoulded articles from example 1 to comparative example 5
Figure BDA0002358540980000131
Note: the inner wall topography of the rotomoulded article is shown in FIG. 2
TABLE 1 (continue)
Figure BDA0002358540980000141
Note: the inner wall topography of the rotomoulded article is shown in FIG. 2
As can be seen from the TGA thermogravimetry curve of the cross-linking agent shown in FIG. 1, the thermogravimetry temperatures T of the cross-linking agent BIPB used in the examples and comparative examples of the present invention onset At 126 ℃, the thermal weight loss temperature T of the crosslinking agent DHBP onset The thermal weight loss temperature T of the crosslinking agent DTBH is 80 DEG C onset The temperature was 83 ℃.
From the results in the table 1 and the inner wall morphology of the rotational molding product provided by the invention shown in fig. 2, it can be seen that the rotational molding products provided by the embodiments 1-8 of the invention have excellent low-temperature impact strength at-40 ℃, the inner wall of the product is smooth, the low-temperature drop hammer impact strength at-40 ℃ is about 30-32J/mm when the rotational molding heating time is 26-32min, the processing window PW is more than 6min, the shortest rotational molding heating time is only about 26min, and the rotational molding processing period and the heating energy consumption in the rotational molding process can be reduced. The composition provided by the invention has short processing time, and the product has excellent low-temperature impact resistance.
The rotomoulded articles provided in examples 9-10 had smooth interior walls, but the rotomoulded articles had rotomoulded heating times of > 30min at-40 ℃ low temperature impact strengths of greater than 29J/mm, long rotomoulded heating times and high energy consumption.
Comparative examples 1-5 provide rotomoulded articles having low-40 ℃ impact strength (both less than 29J/mm) and limited applicability in low temperature article applications. Of these, comparative example 2 provides a rotomoulded article with uneven inner walls and marked irregularities.
Comparative example 1 adopts high melt index polyethylene, no antioxidant system, and even if a crosslinking agent with low crosslinking temperature is added, the impact strength at the low temperature of-40 ℃ of the rotational molding product is obviously lower than that of the embodiment, and the product performance can not meet the requirements of practical production and application.
In comparative example 2 using the low melt index polyethylene resin, even if the initial crosslinking time is prolonged and the crosslinking temperature is increased in the same amount of the inhibitor, the impact strength at-40 ℃ of the prepared rotomolded article is significantly lower than that of the examples, and the surface of the rotomolded article is uneven, which cannot meet the requirements of practical production and application.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (21)

1. A crosslinkable polyethylene composition, wherein the composition comprises a polyethylene resin, a crosslinking agent, a co-crosslinking agent, an inhibitor and an antioxidant, and the composition comprises, relative to 100 parts by weight of the polyethylene resin, 0.05 to 3 parts by weight of the crosslinking agent, 0.05 to 3 parts by weight of the co-crosslinking agent, 0.02 to 1.5 parts by weight of the inhibitor and 0.02 to 1.5 parts by weight of the antioxidant;
the polyethylene resin has a melt index of 18-50g/10min at 190 ℃ under a load of 2.16kg and a density of 0.91-0.97g/cm 3 ；
The thermal weight loss temperature T of the cross-linking agent onset More than or equal to 90 ℃; wherein, for the unsupported crosslinker, the T onset Namely the temperature when the weight loss rate of the cross-linking agent is 5wt% when a thermal gravimetric method TGA test is adopted; for supported crosslinkers, the T onset Namely, the temperature when the weight loss percentage of the cross-linking agent/the effective content of the cross-linking agent is 5wt% when a thermal gravimetric analysis TGA test is adopted;
the cross-linking agent is selected from one or more of dicumyl peroxide, 1, 3-bis (t-butylperoxyisopropyl) benzene, 1, 4-bis (t-butylperoxyisopropyl) benzene, t-butylcumyl peroxide, t-butylperoxybenzoate, 2, 5-dimethyl 2, 5-bis (benzoyl) peroxy-hexane and t-butylcumyl peroxide.
2. The crosslinkable polyethylene composition according to claim 1, wherein the composition comprises 0.1-2 parts by weight of the crosslinking agent, 0.1-2 parts by weight of the co-crosslinking agent, 0.03-1 part by weight of the inhibitor and 0.05-1 part by weight of the antioxidant, relative to 100 parts by weight of the polyethylene resin.
3. The crosslinkable polyethylene composition according to claim 1 or 2, wherein the polyethylene resin has a melt index at 190 ℃ and under a load of 2.16kg of from 20 to 30g/10min and a density of from 0.94 to 0.965g/cm 3 ；
And/or, the composition comprises 0.1-1.0 weight part of cross-linking agent, 0.1-1.0 weight part of auxiliary cross-linking agent, 0.05-0.5 weight part of inhibitor and 0.1-0.5 weight part of antioxidant relative to 100 weight parts of polyethylene resin.
4. The crosslinkable polyethylene composition according to claim 1, wherein the polyethylene resin is polyethylene a and optionally polyethylene B.
5. The crosslinkable polyethylene composition according to claim 4, wherein the polyethylene resins are polyethylene A and polyethylene B, wherein the amount of polyethylene A is 99-60 parts by weight and the amount of polyethylene B is 1-40 parts by weight;
and/or the polyethylene A is high density polyethylene;
and/or the polyethylene B is linear low density polyethylene and/or low density polyethylene.
6. The crosslinkable polyethylene composition according to claim 5, wherein said high density polyethylene has a melt index at 190 ℃ and under a load of 2.16kg of from 18 to 50g/10min, and a density of from 0.941 to 0.965g/cm 3 (ii) a The linear low density polyethylene and/or the low density polyethylene has a melt index of 2-50g/10min at 190 ℃ under a load of 2.16kg and a density of 0.91-0.93g/cm 3 ；
And/or the polyethylene resin is polyethylene A and polyethylene B, wherein the amount of the polyethylene A is 95-70 parts by weight, and the amount of the polyethylene B is 5-30 parts by weight.
7. The crosslinkable polyethylene composition according to claim 6, wherein the high density polyethylene has a melt index of 20-30g/10min at 190 ℃ and 2.16kg load and a density of 0.941-0.96g/cm 3 (ii) a The linear low density polyethylene and/or the low density polyethylene has a melt index of 2-10g/10min at 190 ℃ and under a load of 2.16kg, and a density of 0.91-0.925g/cm 3 。
8. The crosslinkable polyethylene composition of any one of claims 1, 2, 4, 5 or 7,
the auxiliary crosslinking agent is selected from one or more of triallyl isocyanurate, trimethylolpropane triacrylate and trimethylolpropane trimethacrylate;
and/or, the inhibitor is a free radical inhibitor; and/or the antioxidant is selected from one or more of an antioxidant 1010, an antioxidant 168, an antioxidant DSTP, an antioxidant DLTP, an antioxidant 1076, an antioxidant 1330 and an antioxidant 3114;
and/or the composition has the shortest heating time t of rotational molding processing when the rotational molding temperature is 280 ℃ and the thickness of a rotational molding product is 4mm min Less than or equal to 27min, and the heating time is t min To t min When the material is PW, the drop hammer impact strength at minus 40 ℃ is more than or equal to 29J/mm, wherein the processing window PW is more than or equal to 6min.
9. The crosslinkable polyethylene composition according to claim 8, wherein said inhibitor is a nitrogen oxygen radical based inhibitor.
10. <xnotran> 9 , , 2,2,6,6- -1- ,4- -2,2,6,6- -1- ,4- -2,2,6,6- -1- ,4- -2,2,6,6- -1- 4- -2,2,6,6- -1- . </xnotran>
11. The crosslinkable polyethylene composition according to claim 3, wherein the co-crosslinking agent is selected from one or more of triallyl isocyanurate, trimethylolpropane triacrylate and trimethylolpropane trimethacrylate;
and/or, the inhibitor is a free radical inhibitor;
and/or the antioxidant is selected from one or more of antioxidant 1010, antioxidant 168, antioxidant DSTP, antioxidant DLTP, antioxidant 1076, antioxidant 1330 and antioxidant 3114;
and/or the composition has the shortest heating time t of rotational molding processing when the rotational molding temperature is 280 ℃ and the thickness of a rotational molding product is 4mm min Less than or equal to 27min, and the heating time is t min To t min When the material is PW, the drop hammer impact strength at minus 40 ℃ is more than or equal to 29J/mm, wherein the processing window PW is more than or equal to 6min.
12. The crosslinkable polyethylene composition according to claim 11, wherein said inhibitor is a nitroxide radical inhibitor.
13. <xnotran> 12 , , 2,2,6,6- -1- ,4- -2,2,6,6- -1- ,4- -2,2,6,6- -1- ,4- -2,2,6,6- -1- 4- -2,2,6,6- -1- . </xnotran>
14. The crosslinkable polyethylene composition according to claim 6,
the auxiliary crosslinking agent is selected from one or more of triallyl isocyanurate, trimethylolpropane triacrylate and trimethylolpropane trimethacrylate;
and/or the inhibitor is a free radical inhibitor;
and/or the antioxidant is selected from one or more of an antioxidant 1010, an antioxidant 168, an antioxidant DSTP, an antioxidant DLTP, an antioxidant 1076, an antioxidant 1330 and an antioxidant 3114;
and/or the composition has the shortest heating time t of rotational molding processing when the rotational molding temperature is 280 ℃ and the thickness of a rotational molding product is 4mm min Less than or equal to 27min, and the heating time is t min To t min When the material is PW, the drop hammer impact strength at minus 40 ℃ is more than or equal to 29J/mm, wherein the processing window PW is more than or equal to 6min.
15. The crosslinkable polyethylene composition according to claim 14, wherein the inhibitor is a nitrogen oxygen radical based inhibitor.
16. <xnotran> 15 , , 2,2,6,6- -1- ,4- -2,2,6,6- -1- ,4- -2,2,6,6- -1- ,4- -2,2,6,6- -1- 4- -2,2,6,6- -1- . </xnotran>
17. A process for producing a crosslinkable polyethylene composition according to any one of claims 1-16, comprising the steps of: and mixing the cross-linking agent, the cross-linking assistant, the antioxidant and the polyethylene resin, and then carrying out melt blending extrusion, cooling, granulation and drying to obtain the cross-linkable polyethylene composition.
18. A method of producing the crosslinkable polyethylene composition of claim 17, wherein,
the method comprises the following steps: (1) Mixing a cross-linking agent, a cross-linking auxiliary agent and an antioxidant with more than one tenth of polyethylene resin, and then carrying out melt blending extrusion, cooling, granulation and drying to obtain a cross-linked polyethylene master batch;
(2) And mixing the crosslinked polyethylene master batch with the rest polyethylene resin, and then carrying out melt blending extrusion, cooling, granulation and drying to obtain the crosslinkable polyethylene composition.
19. A rotomoulded article prepared from the crosslinkable polyethylene composition of any one of claims 1-16 by crosslinking.
20. A process for the preparation of a rotomoulded article as claimed in claim 19 comprising the steps of:
I. crushing and screening the crosslinkable polyethylene composition to obtain crosslinkable polyethylene fine powder;
II. And placing the crosslinkable polyethylene fine powder into a rotational molding grinding tool, crosslinking and simultaneously performing rotational molding to obtain the rotational molding product.
21. The production method according to claim 20, wherein the condition of the rotational molding includes: the rotation speed in the horizontal axis direction is 3-8r/min, the rotation speed in the vertical axis direction is 4-10r/min, the molding temperature is 200-350 ℃, and the molding time is 25-32min.
CN202010014988.2A 2020-01-07 2020-01-07 Crosslinkable polyethylene composition, preparation method thereof and rotational molding product Active CN113150419B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010014988.2A CN113150419B (en) 2020-01-07 2020-01-07 Crosslinkable polyethylene composition, preparation method thereof and rotational molding product

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010014988.2A CN113150419B (en) 2020-01-07 2020-01-07 Crosslinkable polyethylene composition, preparation method thereof and rotational molding product

Publications (2)

Publication Number Publication Date
CN113150419A CN113150419A (en) 2021-07-23
CN113150419B true CN113150419B (en) 2022-12-27

Family

ID=76881515

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010014988.2A Active CN113150419B (en) 2020-01-07 2020-01-07 Crosslinkable polyethylene composition, preparation method thereof and rotational molding product

Country Status (1)

Country Link
CN (1) CN113150419B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115895075B (en) * 2021-08-20 2024-05-17 中国石油化工股份有限公司 Rotational molding high-density polyethylene composition, and preparation method and application thereof
CN113969011A (en) * 2021-11-29 2022-01-25 江南大学 Low-temperature-resistant crosslinked polyethylene material and preparation method thereof
CN114800985B (en) * 2022-05-05 2024-01-26 安徽锐途新材料科技有限公司 Rotational molding crosslinked polyethylene hand mold, composition and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106336568A (en) * 2016-09-20 2017-01-18 神华集团有限责任公司 Crosslinked polyethylene and preparation method and application thereof
CN106366430A (en) * 2016-09-20 2017-02-01 神华集团有限责任公司 Crosslinkable polyethylene composition, crosslinked polyethylene, preparing method, product and application
CN106715567A (en) * 2014-10-09 2017-05-24 维尔萨利斯股份公司 Styrene-butadiene rubber (sbr)-nanocarbon filled masterbatches and uses thereof
CN107814996A (en) * 2016-09-14 2018-03-20 神华集团有限责任公司 A kind of preparation method of crosslinkable polyethylene modified materials
CN108034105A (en) * 2017-11-17 2018-05-15 神华集团有限责任公司 Crosslinked polyethylene composition and crosslinked polyethylene and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2049588B1 (en) * 2006-08-02 2010-10-13 Dow Global Technologies Inc. High-density polyethylene compositions, method of producing the same, articles made therefrom, and method of making such articles

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106715567A (en) * 2014-10-09 2017-05-24 维尔萨利斯股份公司 Styrene-butadiene rubber (sbr)-nanocarbon filled masterbatches and uses thereof
CN107814996A (en) * 2016-09-14 2018-03-20 神华集团有限责任公司 A kind of preparation method of crosslinkable polyethylene modified materials
CN106336568A (en) * 2016-09-20 2017-01-18 神华集团有限责任公司 Crosslinked polyethylene and preparation method and application thereof
CN106366430A (en) * 2016-09-20 2017-02-01 神华集团有限责任公司 Crosslinkable polyethylene composition, crosslinked polyethylene, preparing method, product and application
CN108034105A (en) * 2017-11-17 2018-05-15 神华集团有限责任公司 Crosslinked polyethylene composition and crosslinked polyethylene and preparation method thereof

Also Published As

Publication number Publication date
CN113150419A (en) 2021-07-23

Similar Documents

Publication Publication Date Title
CN113150419B (en) Crosslinkable polyethylene composition, preparation method thereof and rotational molding product
CN1105135C (en) High density polyethylene films with improved barrier
CN101580680B (en) Crosslinkable polyethylene hot-melt adhesive composition and preparation method and application thereof
US9359499B2 (en) Radiation curable polymers
KR20010040930A (en) Mixtures of thermoplastic fluoropolymers
CN107540920B (en) Metallocene polyethylene composition and preparation method thereof
EP0028536B1 (en) Process for producing articles of ultra high molecular weight high density polyethylene
US4171338A (en) Process for ultra-high molecular weight, high abrasion resistance, cross-linked polyethylene
CN103351557A (en) PVC wood-plastic composite material and machine shaping method thereof
CN108794847A (en) Rotational moulding polyolefin composition and preparation method thereof
JPH05254919A (en) Molding material for production of inorganic sintered product
JPH08252813A (en) Ceramic and metal composition which can be injection-molded, and its manufacture
JPH10195268A (en) Poly(vinyl chloride) having improved low-temperature melting property and improved impact resistance
CN114920881A (en) HDPE/PEW-g- (MAH-co-HEMA) micro powder for powder coating and preparation method thereof
CN109627587A (en) A kind of polypropylene agglomerate and its preparation process
WO2016036402A1 (en) Moldable engineered stone
CN110483889B (en) Rotational molding polypropylene alloy material and preparation method thereof
CN114644778A (en) Low-breakage-rate and high-hardness talcum powder master batch and preparation method and application thereof
CN109851901B (en) Crosslinked polyethylene roll plastic for water heater liner and preparation method and application thereof
CN114479224A (en) Thermoplastic resin porous foam and preparation method and application thereof
CN109401031A (en) A kind of rotational moulding PP Pipe Compound and preparation method thereof that can improve bond strength between polyurethane foaming layer and product
CN113929998B (en) Polyolefin composition for rotational molding, polyolefin powder for rotational molding, and preparation method and application thereof
CN112457748A (en) High-toughness low-temperature-resistant powder coating and preparation method thereof
CN116462916A (en) Modified polypropylene for injection molding and preparation method thereof
EP1938941A1 (en) Rotational moulding process of metallocene polymers or copolymers having a low melting point and a low melt viscosity

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20230712

Address after: 102211 Shenhua Low Carbon 001 Mailbox, Naukograd, Changping District, Beijing

Patentee after: Beijing low carbon clean energy Research Institute

Address before: 100011 Beijing Dongcheng District, West Binhe Road, No. 22

Patentee before: CHINA ENERGY INVESTMENT Corp.,Ltd.

Patentee before: Beijing low carbon clean energy Research Institute

TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20230818

Address after: 102211 unit 201, Shenhua science and technology innovation base, Beibinhe Road, Xiaotangshan Town, Changping District, Beijing

Patentee after: SHENHUA (BEIJING) NEW MATERIAL TECHNOLOGY Co.,Ltd.

Address before: 102211 Shenhua Low Carbon 001 Mailbox, Naukograd, Changping District, Beijing

Patentee before: Beijing low carbon clean energy Research Institute