CN106317585A - Heat-resistant polyethylene resin composition and application thereof - Google Patents

Heat-resistant polyethylene resin composition and application thereof Download PDF

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Publication number
CN106317585A
CN106317585A CN201510379901.0A CN201510379901A CN106317585A CN 106317585 A CN106317585 A CN 106317585A CN 201510379901 A CN201510379901 A CN 201510379901A CN 106317585 A CN106317585 A CN 106317585A
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heat
antioxidant
butyl
ester
tert
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CN201510379901.0A
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CN106317585B (en
Inventor
王立娟
姜涛
宋磊
曹晨刚
高宇新
王焱鹏
王斯晗
何书艳
姜进宪
赵成才
付义
张瑀健
任鹤
赵增辉
任合刚
王登飞
门亚男
王淑英
熊国辉
王立文
曹婷婷
刘显圣
崔磊
杜小吉
蔡小仲
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Petrochina Co Ltd
China Petroleum and Natural Gas Co Ltd
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China Petroleum and Natural Gas Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0807Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815Copolymers of ethene with aliphatic 1-olefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/014Additives containing two or more different additives of the same subgroup in C08K
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/18Applications used for pipes

Abstract

The invention relates to a heat-resistant polyethylene resin composition and application thereof. The composition comprises the following components in parts by mass: 100 parts of heat-resistant polyethylene, 0.1 to 0.3 part of an antioxidant, 0.01 to 0.1 part of a processing auxiliary agent and 0.01 to 0.25 part of an acid removal agent, wherein the heat-resistant polyethylene is a copolymer of ethylene and 1-butene; the molecular weight of the heat-resistant polyethylene is distributed in dual modes; and the molecular weight distribution has a width (MW/MN) of 18 to 28, a weight-average molecular weight of 200 to 250 thousand, a melting temperature of 133 to 140 DEG C, a crystallinity of 63 to 65%, and a wafer thickness of 31 to 39 nm. The heat-resistant flexible polyethylene provided by the invention has excellent mechanical properties, high-temperature-resistant creep properties, heat-aging resistance and extrusion processing performance, and can be used for preparation of cool and hot water pipeline systems.

Description

A kind of heat-proof polythene resin combination and application thereof
Technical field
The invention belongs to polymeric material field, particularly to a kind of heat-resisting, high temperature resistant, flexible polyethylene Resin combination and application thereof.
Background technology
Heat-proof polythene (PE-RT) is the non-cross-linked polyvinyl that ethylene produces with alpha-olefin copolymer, passes through The quantity and the distribution that control side chain obtain unique molecular structure, improve the heat resistance of PE.Due to The existence of short-chain branch makes the macromole of PE uncrystallizable in a flat crystal, but is applied in several In crystal, defining the connection between crystal, it remains the pliability that PE is good, high thermal conductivity And inertia, it is allowed to resistance to pressure more preferable simultaneously.Compared with metal and other plastics pipe for hot water applications, there is hot melt even The outstanding advantages such as connecing property is good, length in service life, environmental protection, high temperature resistant and pliability are good, is mainly used in adding Work terrestrial heating pipe.PE tubing heat resistance in early days is poor, can only be used in cold water pipe field, PE- RT resin be a kind of ethylene of designing exclusively for cold and hot water supply tubing with octene, ethylene and hexene or Ethylene and the copolymer of butylene, be that the brand-new polyvinyl piping materials occurred in middle and high warm water transportation art is used Material.In recent years, PE-RT resin by the physical property of itself excellence, corrosion resistance, pliability, The feature such as processability and construction and installation, imparting pipe performance good stability, degree of safety are high, recoverable Feature, can replace atactic copolymerized polypropene (PPR), polybutene (PB), chliorinated polyvinyl chloride (PVC-C) and Crosslinked polyethylene (PEX), for applications such as floor heating tube, heat exchanger, hot and cold water conveyings.
Chinese patent CN102875885 discloses a kind of PE-RT floor heating pipe material, is by PE-RT tree Fat, the Nano-meter CaCO3 of surface preparation3, pigment, resistance cross-linking agent, antioxidant, surfactant Forming with dispersant, complicated components, production cost are high.European patent EP 0702056 discloses one Preparing the resin of hot-water line, the hot-water line compositions described in this invention is by 1~10% (weight) poly- Ethylene, the polymer of the polybutene composition of 5~the polypropylene of 75% (weight) and 5~75% (weight) Blend.This blend has a preferable high temperature creep property, preferable low-temperature impact-resistant performance, preferably Moulding processability.But the heat aging property of this patent this blend not mentioned, comes for hot-water line Saying, the heat aging property of material is a critically important index, and it directly influences the use longevity of tubing Life.And the material being mixed to prepare by several materials, owing to the difference of material crystalline degree makes blend phase boundary Face can produce defect and cause deteriorating of material performance.
Chinese patent CN101423573B disclose a kind of polyethylene resin for tubular material, its preparation method and A combination thereof thing.This polyvinyl resin melt mass flow rate is 0.25-1.0g/10min, and density is 0.930-0.955g/cm3, molecular weight is Unimodal Distribution, and the ratio of Mw/Mn is 20-90, comonomer For hexene, the degree of branching is (20-80)/10000C.The polyethylene resin composition for pipe of this invention, Comprise following components by weight: polyvinyl resin: 100 parts, antioxidant: 0.1-0.5 part, face Material: 0-5 part.Polyvinyl resin of this invention and combinations thereof thing long-term hydrostatic strength is high, and has excellent Different slow-crack-growth ability and resistance to Rapid Crack ability, performance reaches PE100 level tubing The requirement of material, can be used for delivery of fuel gas, cold water, but this invention can not reach to carry the thermostabilitys such as hot water The requirement of energy.
Chinese patent CN1858100 discloses " a kind of modified heat resistant polyethylene material and moulding at boats and ships Application in material piping ", relate to a kind of modified heat resistant polyethylene material, bulk composition is heat-proof polythene (PE-RT) (percentage by weight) 98~78%, environmentally friendly fire retardant 0~15%, processing helps Agent 0~5%, remaining is color masterbatch.Tubing and pipe fitting alleged by this invention are mainly used in health on boats and ships The water supply and sewerage pipeline systems such as drinking water and service location, control station, isolation sky cabin, and marine air conditioner condensation Water system and ventilating system, be not suitable for hot water pipeline induction system.
Chinese patent CN101148524A discloses formula and the preparation of heat-resistant flexible enhanced polyethylene tubing Method.This pipe composition is by high temperature resistant non-cross-linked polyvinyl (PE-RT) 100 parts, nanometer titanium dioxide Silicon 20 parts and antioxidant 0.1 part composition.The purpose of this patent is to provide a kind of relative low price, And the tubing polyethylene composition of the conveyance conduit such as floor heating, hot-water heating can be used for.But it is based on this invention Disclosed scheme, gained polyvinyl piping materials in hydraulic test 95 DEG C, under ring compression 3.5MPa be 1000h, these data still have bigger room for promotion on the basis of scheme is changed.Additionally, in the program The kind of antioxidant and specifically chosen kind the most do not disclosed, and antioxidant preferably to PE-RT Performance improvement particularly significant, it directly affects the service life of tubing, does not the most disclose products obtained therefrom and exists The performance of the aspect such as oxidation induction period, stretching yield stress.Therefore PE-RT and antioxidant in the program Choose and urgently improve, to meet PE-RT requirement in actual applications further.
Summary of the invention
It is an object of the invention to provide a kind of heat-proof polythene resin combination and application thereof, existing to overcome In technology, polyethylene resin composition is heat-resisting, voltage endurance capability is weak, Long-term Anti fluid power is unstable lacks Point.
The object of the present invention is achieved like this, and a kind of heat-proof polythene resin combination, with mass parts Meter, said composition includes heat-proof polythene 100 parts, antioxidant 0.1~0.3 part, processing aid 0.01~0.1 part, plumper 0.01~0.25 part;
Wherein, described heat-proof polythene is the copolymer of ethylene and 1-butylene, this heat-proof polythene molecule Measure in bi-modal distribution, molecular weight distribution width (MW/MN) it is 18~28, weight average molecular weight is 20~250,000, melt temperature is 133~140 DEG C, and degree of crystallinity is 63~65%, and wafer thickness is 31~39nm.
Wherein, described heat-proof polythene density is 0.945~0.948g/cm3, preferably 0.946~0.947 g/cm3;Melt flow rate (MFR) is 0.46~0.47g/10min (5.0kg).
Wherein, the degree of branching of described heat-proof polythene is 3.0~3.5 side chain C/1000C.
Wherein, described antioxidant is Hinered phenols antioxidant, phosphite ester kind antioxidant and thioesters class antioxygen The mixture of agent, the weight ratio of Hinered phenols antioxidant, phosphite ester kind antioxidant and sulphur ester antioxidant For 1:0.1~10:0.1~4, preferably 1:0.3~10:0.1~4, the concentration of antioxidant is 1000~3000ppm.
Wherein, described Hinered phenols antioxidant was selected from for four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] seasons Doutrate, (2,4,6-trioxy--1,3,5-triazine-1,3,5 (2H, 4H, 6H)-three base) trivinyl three [3- (3,5-di-tert-butyl-hydroxy phenyl) acrylate, 1,1,3-tri-(2-methyl-4-hydroxyl-5-2-methyl-2-phenylpropane base) fourth Alkane, 1,3,5-trimethyl-2,4,6-three (3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, 1,3,5-tri-(the 4-tert-butyl group- 3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone and 1,3,5-tri-(3,5-bis- Tertiary butyl-4-hydroxy benzyl) guanamine, the one or several in the formed group of 4,6-(1H, 3H, 5H) triketone Kind;The fusing point of Hinered phenols antioxidant is between 100 DEG C~260 DEG C, when selecting two kinds and above being subject to During resistance phenolic antioxidant, can mix with arbitrary proportion.
Wherein, described phosphite ester kind antioxidant fusing point be more than 160 DEG C, have preferable high temperature resistance and Hydrolytic resistance, selected from three (2,4-di-tert-butyl-phenyl)-phosphite ester, double [2-methyl-4,6-bis-(1,1 ' -dimethyl ethyl) phenol] ethyl ester, (2,4,6-tri-tert phenyl-2-butyl-2-ethyl)-1, Ammediol phosphite ester, two (2,4-bis-p-isopropyl phenyl) pentaerythritol bis-phosphite, 2,2 ' -ethylenebis (4,6-di-tert-butyl-phenyl) fluorophosphite, four (2,4-di-tert-butyl-phenyl-4,4- Xenyl) biphosphonate, spiral shell ethylene glycol bisthioglycolate [2,2 '-di-2-ethylhexylphosphine oxide (4,6-di-tert-butyl-phenyl)] phosphorous One in acid esters and tetramethylolmethane-diphosphite-two (2,4-di-tert-butyl phenyl) the formed group of ester;.
Wherein, described sulphur ester antioxidant is thio-2 acid double (18) ester, thiodipropionic acid dilauryl One in osmanthus ester and the formed group of Thiodiglycol distearate.
Wherein, described processing aid is fluoroelastomer.Described fluoroelastomer is fluoroolefin homopolymer or fluorine For olefin copolymer;It is preferably tetrafluoroethene, hexafluoropropene and the terpolymer of vinylidene fluoride or inclined Fluorothene and the bipolymer of hexafluoropropene;In terms of mass parts, its addition is preferably 0.03~0.06 Part.
Wherein, described plumper be calcium stearate, zinc stearate, zinc oxide and calcium oxide formed group In one or more;In terms of mass parts, its addition is preferably 0.05~0.15 part.
Wherein, the co-monomer content of described heat-proof polythene is 0.20~0.40%mol, is preferably 0.25~0.35%mol, comonomer more than 300,000 in weight molecule chain total content be 0.19~0.27%mol.
Present invention also offers above-mentioned heat-proof polythene resin combination conveying hot water, the tubing of cold water or Application in pipe fitting.
The heat-proof polythene of the present invention is by Ziegler-Natta catalyst system, ethylene slurry polymerization work The double still series system of skill is standby, is characterized in the increase along with molecular weight, and the content of comonomer gradually increases Add, as shown in Figure 1.
Beneficial effects of the present invention:
Compared with prior art, the useful effect that a kind of heat-proof polythene resin combination of the present invention is had Fruit is: the compositions of the present invention has excellent long-term pressure resistance, oxidation resistent susceptibility and high temperature resistant creep properties Energy.The comparison polyethylene hot-water line requirement to serviceability, uses GB/T 6111 " fluid conveying heat Thermoplastic plastic tubing-internal pressure-resistant test method " test, its hydrostatic strength at a temperature of 95 DEG C, Zernike annular polynomial 4.2MPa, more than 1000h, tubing is non-leakage, does not ruptures.
Accompanying drawing explanation
Fig. 1 be heat-proof polythene resin weight average molecular weight M, branching content and at different levels parts of mass fractions it Between relation curve.
Detailed description of the invention
Hereinafter embodiments of the invention are elaborated: the present embodiment is being front with technical solution of the present invention Put and implement, give detailed embodiment and process, but protection scope of the present invention is not limited to Following embodiment, the experimental technique of unreceipted actual conditions in the following example, generally according to conventional strip Part.
Heat-proof polythene:
In the present invention, heat-proof polythene is the copolymer of ethylene and 1-butylene, this heat-proof polythene molecule Measure in bi-modal distribution, molecular weight distribution width (MW/MN) it is 18~28, weight average molecular weight is 20~250,000, melt temperature is 133~140 DEG C, and degree of crystallinity is 63~65%, and wafer thickness is 31~39nm.The melt temperature scope of heat-proof polythene of the present invention is 133~140 DEG C, within the range May insure that uniformity and the stability of polyethylene resin composition.Molecular weight of polyethylene modal distribution is certainly One of key factor determining polymer performance, weight average molecular weight is high and comonomer distribution in macromolecular chain is Form two essential conditions of tie molecule, and tie molecule is whether polymer has good thermostability And a key factor of resistance to pressure.Crystal property be affect another of resin heat resistance crucial because of Element, melt temperature is the highest, and degree of crystallinity is the highest, and the temperature capacity of the biggest then resin of wafer thickness is the strongest.
In the present invention, heat-proof polythene density is 0.945~0.948g/cm3, melt flow rate (MFR) is 0.46~0.47g/10min (5.0kg).For polyethylene, improve density and can make elastic properties of materials mould Amount improves, thus improves short-term hydrostatic strength, but density is the highest, can reduce tubing heat-resistant flexible, Croop property and toughness, make long-term hydrostatic strength (LTHS) and the slow-crack-growth (SCG) of tubing Ability reduce, density of pe of the present invention is 0.945~0.948g/cm3.Polyethylene tool used by the present invention There is moderate melt flow rate (MFR), there is while keeping compositions mechanical performance good processing flowing Property, melt flow rate (MFR) is 0.46~0.47g/10min (5.0kg).
In the present invention, the degree of branching of heat-resistant flexible polyethylene is 3.0~3.5 side chain C/1000C.Polyethylene Co-monomer content and the degree of branching determine tie molecule quantity in resin, comonomer selects 1- Butylene, by controlling side chain distribution on strand, makes side chain be primarily present in the level of high molecular Point, it is easier to form a number of tie molecule, increase resistance during pull-off, so that material counterincision The resistivity of stricture of vagina extension is the biggest.The 1-butylene comonomer degree of branching in heat-proof polythene of the present invention is 3.0~3.5 C/1000 C of side chain, preferably up to 3.4~3.5 C/1000 C of side chain, ensure that The performance that compositions is excellent.
Antioxidant:
In the present invention, antioxidant is not particularly limited, usually Hinered phenols antioxidant, phosphite ester Kind antioxidant and the mixture of sulphur ester antioxidant, Hinered phenols antioxidant, phosphite ester kind antioxidant and The weight ratio of sulphur ester antioxidant is 1:0.1~10:0.1~4, preferably 1:0.3~10:0.1~4, antioxygen The concentration of agent is 1000~3000ppm.
The preparation method of heat-proof polythene compositions is as follows:
To include that heat-proof polythene resin, antioxidant, processing rheological agent, acid-acceptor are joined according to described weight Than putting into high-speed mixer, speed of agitator 1000~2000 revs/min, mixing time 15min, stirring temperature Degree: room temperature.Adding in double screw extruder mixing by the powder of mix homogeneously, extrusion extruder respectively heats The temperature of section is respectively set as 140 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 190 DEG C, heats up Preheating more than 30 minutes, machine to be extruded each bringing-up section temperature is increased to setting value.Testing sample is added In extruder, melt, plastify, extrude, pelletize, be prepared as heat-proof polythene compositions.
Embodiment 1
Heat-proof polythene compositions is prepared by following method:
(1) 100 part of polyvinyl resin (melt flow rate (MFR) be 0.46g/10min (190 DEG C, 5kg), density 0.947g/cm3, weight average molecular weight 235000, molecular weight distribution width 20.9, melted Temperature 135 DEG C, degree of crystallinity 64%, wafer thickness 35nm;
Four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester of (2) 0.12 parts;
1,3,5-trimethyl-2,4,6-three (3,5-di-t-butyl-4-hydroxyl benzyl) benzene of (3) 0.05 parts;
1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) guanamine of (4) 0.10 parts, 4,6- (1H, 3H, 5H)-triketone;
Three (2,4-di-tert-butyl-phenyl) phosphite ester of (5) 0.03 parts;
The vinylidene of (6) 0.05 parts and the bipolymer of hexafluoropropene;
The calcium stearate of (7) 0.05 parts.
Above-mentioned polyethylene resin composition is processed and performance measurement, performance parameter and polyvinyl resin The performance of compositions is shown in Table 1.
Embodiment 2
Heat-proof polythene compositions is prepared by following method:
(1) 100 part of polyvinyl resin (melt flow rate (MFR) be 0.47g/10min (190 DEG C, 5kg), density 0.946g/cm3, weight average molecular weight 214000, molecular weight distribution width 18.2, melted Temperature 134 DEG C, degree of crystallinity 64%, wafer thickness 33nm;
Four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester of (2) 0.10 parts;
Three (2,4-di-tert-butyl-phenyl) phosphite ester of (3) 0.05 parts;
The dilauryl thiodipropionate composition of (4) 0.15 parts;
The vinylidene of (5) 0.01 parts and the bipolymer of hexafluoropropene;
The zinc oxide of (6) 0.1 parts.
Above-mentioned polyethylene resin composition is processed and performance measurement, performance parameter and polyvinyl resin The performance of compositions is shown in Table 1.
Embodiment 3
Heat-proof polythene compositions is prepared by following method:
(1) 100 part of polyvinyl resin (melt flow rate (MFR) be 0.47g/10min (190 DEG C, 5kg), density 0.946g/cm3, weight average molecular weight 250000, molecular weight distribution width 24.1, melted Temperature 140 DEG C, degree of crystallinity 65%, wafer thickness 39nm;Four [β-(3,5-bis-uncles of (2) 0.05 parts Butyl-4-hydroxy phenyl) propanoic acid] pentaerythritol ester;
Three (2,4-di-tert-butyl-phenyl) phosphite ester of (3) 0.15 parts;
Double (18) ester of the thio-2 acid of (4) 0.04 parts;
The terpolymer of tetrafluoroethene, hexafluoropropene and the vinylidene fluoride of (5) 0.03 parts;
The zinc stearate of (6) 0.1 parts.
Above-mentioned polyethylene resin composition is processed and performance measurement, performance parameter and polyvinyl resin The performance of compositions is shown in Table 1.
Embodiment 4
Heat-proof polythene compositions is prepared by following method:
(1) 100 part of polyvinyl resin (melt flow rate (MFR) be 0.46g/10min (190 DEG C, 5kg), density 0.947g/cm3, weight average molecular weight 201000, molecular weight distribution width 18.5, melted Temperature 133 DEG C, degree of crystallinity 63%, wafer thickness 34nm;
1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) guanamine of (2) 0.05 parts, 4,6- (1H, 3H, 5H)-triketone;
Three (2,4-di-tert-butyl-phenyl) phosphite ester of (3) 0.15 parts;
The terpolymer of tetrafluoroethene, hexafluoropropene and the vinylidene fluoride of (4) 0.06 parts;
The calcium stearate of (5) 0.1 parts;
The zinc stearate of (6) 0.05 parts.
Above-mentioned polyethylene resin composition is processed and performance measurement, performance parameter and polyvinyl resin The performance of compositions is shown in Table 1.
Embodiment 5
Heat-proof polythene compositions is prepared by following method:
(1) 100 part of polyvinyl resin (melt flow rate (MFR) be 0.46g/10min (190 DEG C, 5kg), density 0.945g/cm3, weight average molecular weight 231000, molecular weight distribution width 23, melted temperature Spend 134 DEG C, degree of crystallinity 64%, wafer thickness 31nm;
(2,4,6-trioxy--1,3,5-triazine-1,3,5 (2H, 4H, 6H)-three base) trivinyl of (2) 0.05 parts Three [3-(3,5-di-tert-butyl-hydroxy phenyl) acrylate;
Three (2,4-di-tert-butyl-phenyl) phosphite ester of (3) 0.10 parts;
The dilauryl thiodipropionate of (4) 0.10 parts;
The vinylidene of (4) 0.06 parts and the bipolymer of hexafluoropropene;
The calcium stearate of (5) 0.1 parts;
The zinc stearate of (6) 0.05 parts.
Above-mentioned polyethylene resin composition is processed and performance measurement, performance parameter and polyvinyl resin The performance of compositions is shown in Table 2.
Embodiment 6
Heat-proof polythene compositions is prepared by following method:
(1) 100 part of polyvinyl resin (melt flow rate (MFR) be 0.47g/10min (190 DEG C, 5kg), density 0.948g/cm3, weight average molecular weight 248000, molecular weight distribution width 28, melted temperature Spend 138 DEG C, degree of crystallinity 65%, wafer thickness 38nm;
Four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester of (2) 0.05 parts;
Three (2,4-di-tert-butyl-phenyl) phosphite ester of (3) 0.10 parts;
The dilauryl thiodipropionate of (4) 0.15 parts;
The vinylidene of (4) 0.06 parts and the bipolymer of hexafluoropropene;
The calcium stearate of (5) 0.15 parts.
Above-mentioned polyethylene resin composition is processed and performance measurement, performance parameter and polyvinyl resin The performance of compositions is shown in Table 2.
Comparative example 1
Heat-proof polythene compositions is prepared by following method:
(1) 100 part of polyvinyl resin (melt flow rate (MFR) be 0.11g/10min (190 DEG C, 2.16kg), 0.65g/10min (190 DEG C, 5.0kg), density 0.945g/cm3, weight average molecular weight 178000, molecular weight distribution width 18.0, melt temperature 128 DEG C, degree of crystallinity 55%, wafer thickness 27nm;
Four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester of (2) 0.12 parts;
1,3,5-trimethyl-2,4,6-three (3,5-di-t-butyl-4-hydroxyl benzyl) benzene of (3) 0.05 parts;
1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) guanamine of (4) 0.10 parts, 4,6- (1H, 3H, 5H)-triketone;
Three (2,4-di-tert-butyl-phenyl) phosphite ester of (5) 0.03 parts;
The vinylidene of (6) 0.05 parts and the bipolymer of hexafluoropropene;
The calcium stearate of (7) 0.05 parts.
Above-mentioned polyethylene resin composition is processed and performance measurement, performance parameter and polyvinyl resin The performance of compositions is shown in Table 2.
Comparative example 2
(1) 100 part of polyvinyl resin (melt flow rate (MFR) be 0.55g/10min (190 DEG C, 2.16kg), 2.8g/10min (190 DEG C, 5.0kg), density 0.940g/cm3, weight average molecular weight 152000, molecular weight distribution width 14.5, melt temperature 124 DEG C, degree of crystallinity 48%, wafer thickness 18nm;
Four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester of (2) 0.10 parts;
Three (2,4-di-tert-butyl-phenyl) phosphite ester of (3) 0.05 parts;
The dilauryl thiodipropionate composition of (4) 0.15 parts;
The vinylidene of (5) 0.01 parts and the bipolymer of hexafluoropropene;
The zinc oxide of (6) 0.1 parts.
Above-mentioned polyethylene resin composition is processed and performance measurement, performance parameter and polyvinyl resin The performance of compositions is shown in Table 2.
The results of performance analysis of table 1 polyethylene resin composition
The results of performance analysis of table 2 polyethylene resin composition
By being analyzed the data of table 1 and table 2, embodiment 1~6 all uses 1-butylene to be copolymerization list Body, molecular weight distribution 18~28, weight average molecular weight 20~250,000, comonomer more than 70% is distributed in On macromolecular chain level part of more than 300000, melt temperature 133~140 DEG C, melt flow rate (MFR) (190 DEG C, 5.0kg) 0.46~0.47g/10min;Density meets 0.945~0.948g/cm3.With contrast Example 1,2 is compared, the shore hardness of embodiment material, vicat softening temperature, high-temperature oxidation resistance Can significantly improve;Plural number Dynamic shear viscosity η (0.5rad/s)/η (100rad/s) is 15.0~19.0, Illustrate that it has good processing characteristics;The tubing of preparation is 20 DEG C, hydrostatic under the conditions of 11.4MPa Pressure test more than 350h, 110 DEG C, hydrostatic test under the conditions of 2.3MPa more than 2000h, say Bright material has more excellent long-term hydrostatic strength under room temperature and high temperature.
It addition, according to GB/6111 criteria for classification, tubing is 80 DEG C, hydrostatic under the conditions of 5.0MPa Test, it is the poly-of PE100 that the time to rupture of embodiment 1~6 tubing greatly exceed MRS classification grade The performance of vinyl material.
Beneficial effects of the present invention:
Compared with prior art, the useful effect that a kind of heat-proof polythene resin combination of the present invention is had Fruit is: the compositions of the present invention has excellent long-term pressure performance, oxidation resistent susceptibility and high temperature resistant creep Performance, can be used for the production of cold hot water piping
Certainly, the present invention also can have other various embodiments, spiritual and essence without departing substantially from the present invention In the case of, those of ordinary skill in the art can make various corresponding change and deformation according to the present invention, But these change accordingly and deform the protection domain that all should belong to the claims in the present invention.

Claims (12)

1. a heat-proof polythene resin combination, it is characterised in that in terms of mass parts, said composition Including heat-proof polythene 100 parts, antioxidant 0.1~0.3 part, processing aid 0.01~0.1 part, plumper 0.01~0.25 part;
Wherein, described heat-proof polythene is the copolymer of ethylene and 1-butylene, this heat-proof polythene molecule Measure in bi-modal distribution, molecular weight distribution width MW/MNBe 18~28, weight average molecular weight be 20~ 250000, melt temperature is 133~140 DEG C, and degree of crystallinity is 63~65%, and wafer thickness is 31~39nm.
Heat-proof polythene resin combination the most according to claim 1, it is characterised in that described Heat-proof polythene density is 0.945~0.948g/cm3, melt flow rate (MFR) be 0.46~ 0.47g/10min。
Heat-proof polythene resin combination the most according to claim 2, it is characterised in that described The degree of branching of heat-proof polythene is 3.0~3.5 side chain C/1000C.
Heat-proof polythene resin combination the most according to claim 1, it is characterised in that described Antioxidant is the mixture of Hinered phenols antioxidant, phosphite ester kind antioxidant and sulphur ester antioxidant, is subject to Resistance phenolic antioxidant, the weight ratio of phosphite ester kind antioxidant and sulphur ester antioxidant be 1:0.1~ 10:0.1~4, the concentration of antioxidant is 1000~3000ppm.
Heat-resistant flexible polyethylene resin composition the most according to claim 4, it is characterised in that Described Hinered phenols antioxidant selected from four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester, (2,4,6-trioxy--1,3,5-triazine-1,3,5 (2H, 4H, 6H)-three base) trivinyl three [3-(3,5-di-t-butyl- 4-hydroxy phenyl) acrylate, 1,1,3-tri-(2-methyl-4-hydroxyl-5-2-methyl-2-phenylpropane base) butane, 1,3,5-front three Base-2,4,6-three (3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, 1,3,5-tri-(the 4-tert-butyl group-3-hydroxyl-2,6-diformazan Base benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone and 1,3,5-tri-(3,5-di-t-butyl-4-hydroxyl benzyl Base) guanamine, one or more in the formed group of 4,6-(1H, 3H, 5H) triketone.
Heat-resistant flexible polyethylene resin composition the most according to claim 4, it is characterised in that Described phosphite ester kind antioxidant is three (2,4-di-tert-butyl-phenyl)-phosphite ester, double [2-methyl-4,6- Two (1,1 '-dimethyl ethyl) phenol] ethyl ester, (2,4,6-tri-tert phenyl-2-butyl-2- Ethyl)-1,3-PD phosphite ester, two (2,4-bis-p-isopropyl phenyl) tetramethylolmethane diphosphite Ester, 2,2 '-ethylenebis (4,6-di-tert-butyl-phenyl) fluorophosphite, four (2,4-di-t-butyls Phenyl-4,4-xenyl) biphosphonate, spiral shell ethylene glycol bisthioglycolate [2,2 '-di-2-ethylhexylphosphine oxide (4,6-di-t-butyls Phenyl)] in phosphite ester and tetramethylolmethane-diphosphite-two (2,4-di-tert-butyl phenyl) the formed group of ester One.
Heat-resistant flexible polyethylene resin composition the most according to claim 4, it is characterised in that Described sulphur ester antioxidant is double (18) ester of thio-2 acid, dilauryl thiodipropionate and sulfur generation One in the formed group of diethylene glycol distearate.
Heat-resistant flexible polyethylene resin composition the most according to claim 1, it is characterised in that Described processing aid is fluoroelastomer.
Heat-resistant flexible polyethylene resin composition the most according to claim 8, it is characterised in that Described fluoroelastomer is fluoroolefin homopolymer or fluoroolefin copolymer.
Heat-resistant flexible polyethylene resin composition the most according to claim 9, it is characterised in that Described fluoroelastomer is terpolymer or the vinylidene of tetrafluoroethene, hexafluoropropene and vinylidene fluoride Bipolymer with hexafluoropropene.
11. heat-resistant flexible polyethylene resin compositions according to claim 1, it is characterised in that Described plumper is calcium stearate, one in zinc stearate, zinc oxide and the formed group of calcium oxide or Several.
In 12. claim 1-11, the heat-proof polythene resin combination described in any one is in conveying warm Application in water, the tubing of cold water or pipe fitting.
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CN110684140A (en) * 2018-07-04 2020-01-14 中国石油天然气股份有限公司 Method for preparing heat-resistant polyethylene, heat-resistant polyethylene prepared by same and composition thereof

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