CN102952323B - A kind of heat-proof polythene composition and use thereof - Google Patents
A kind of heat-proof polythene composition and use thereof Download PDFInfo
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Abstract
A kind of heat-proof polythene composition and use thereof, belong to polyethylene pipe field, it is characterized in that the component comprising following weight part: heat-proof polythene (PE-RT) 100 parts and 0.1 ~ 1.5 part, oxidation inhibitor, wherein heat-proof polythene is polyethylene-hexene-1 multipolymer, density 0.926 ~ 0.950g/cm
3, melt flow rate (MFR) (190 DEG C, 2.16Kg counterweight) 0.1 ~ 2g/10min, molecular weight is unimodal distribution, the relative degree of branching 0.08 ~ 0.50; Oxidation inhibitor comprises Hinered phenols antioxidant and phosphite ester kind antioxidant.The present invention adopts the components such as heat-resisting hervene copolymer polyethylene, oxidation inhibitor to prepare the heat-proof polythene composition having excellent mechanical property, high temperature resistant creep property, heat aging property and extrude processing characteristics, the Practical Performance of further raising PE-RT tubing, can be used for preparation hot-water pipeline system tubing and pipe fitting.
Description
Technical field
A kind of heat-proof polythene composition and use thereof, belong to polyethylene pipe field, in particular to one heat-proof polythene (being called for short PE-RT), oxidation inhibitor etc., preparation has the polyethylene composition of good heat resistance energy and long-term ageing property, for hot water or cold water's transportation art, especially for tubing and the pipe fitting of delivery system.
Background technology
PE-RT is a kind of noncrosslinking polyvinyl resin that may be used for hot-water line.Early stage PE tubing can only be used in conveying cold water field, and PE-RT is specially cold and hot water supply tubing and a kind of ethene of designing and octene, hexene or butylene copolymer, is the brand-new polyvinyl piping materials materials occurred in middle and high warm water transportation art.In recent years, PE-RT relies on the features such as the physicals of its excellence, erosion resistance, snappiness, processibility and construction and installation, and atactic copolymerized polypropene (PPR), polybutene (PB), chlorinated polyvinyl chloride (PVC-C) and crosslinked polyethylene (PEX) can be replaced for Application Areass such as floor heating tube, heat exchanger, cold and hot water conveyings.
European patent EP 0702056 is heat-resisting about preparation, the particularly plastics of hot-water line, hot-water line composition described in this invention is by the polyethylene of 1 ~ 10% (weight), the blend polymer of the polybutene composition of the polyethylene and 5 ~ 75% (weight) of 5 ~ 75% (weight).The high temperature creep property that this mixture has had, good low-temperature impact-resistant performance, good moulding processability.But the not mentioned heatproof air aging performance of this patent, for hot-water line, the heat oxygen aging resistance of material is a very important index, and it directly has influence on the work-ing life of tubing.And mix obtained material by several material, the difference due to material crystalline degree makes blend phase interface can produce defect and cause the change of material performance bad.
Described in Chinese Patent Application No. 200710114113.4, " polyethylene resin composition for pipe and preparation method thereof " relates to thermoplasticity pressure pipeline and tube material, this polyethylene resin composition has excellent short-term hydrostatic strength, slow-crack-growth ability and resistance to Rapid Crack ability, performance reaches the requirement of PE100 level tube material, can be used for delivery of fuel gas, cold water, but this invention can not reach the requirement of the resistance toheats such as delivering hot water.Chinese Patent Application No. 200710044150 " production method of heat-resisting polyethylene tube ", material therefor is medium-density polyethylene, formed by vinyl monomer and octene monomers copolymerization, different from the heat-proof polythene composition that the present invention relates to vinyl monomer and hexene monomers copolymerization, and this invention only relates to the production method of heat-proof polythene tubing.
Chinese Patent Application No. 200610085299 " a kind of modified heat resistant polyethylene material and the application in ship plastic pipeline thereof ", relate to a kind of modified heat resistant polyethylene material, bulk composition is heat-proof polythene (PE-RT) (weight percent) 98 ~ 78%, environmentally friendly fire retardant 0 ~ 15%, processing aid 0 ~ 5%, all the other are colour batch.Tubing alleged by this invention and pipe fitting are mainly used in the water supply and sewerage pipeline systems such as safe drinking water and service location on boats and ships, control station, the empty cabin of isolation, and marine air conditioner condensate system and ventilation system.This invention the long-term behaviour of the characteristic, particularly material of unexposed PE-RT used.This invention and the present invention form also different.
Chinese patent CN101148524A discloses formula and the preparation method of heat resistance reinforced polyethylene pipe.This pipe composition by high temperature resistant non-cross-linked polyvinyl (PE-RT) 100 parts, nano silicon 20 parts and antioxidant 0.1 part composition.The object of this patent is to provide a kind of relative low price, and can be used for the tubing polyethylene composition of the transport pipe such as floor heating, hot-water heating.But according to the scheme of this disclosure of the invention, gained polyvinyl piping materials in hydro-test 95 DEG C, be 1000h under ring compression 3.5MPa, these data still have larger room for promotion on the basis that scheme is changed.In addition, the kind of antioxidant and the concrete kind selected both are not disclosed in the program, and the preferred improvement in performance to PE-RT of oxidation inhibitor is very important, it directly affects the work-ing life of tubing, does not also disclose the performance of products obtained therefrom in oxidation induction period, stretching yield stress etc.Therefore in the program, PE-RT and choosing of oxidation inhibitor are urgently improved, to meet PE-RT requirement in actual applications further.
Summary of the invention
The technical problem to be solved in the present invention is: overcome the deficiencies in the prior art, a kind of heat-proof polythene composition with ad hoc structure performance is provided, the tubing thermal oxidation resistance performance obtained for raw material with this heat-proof polythene composition, anti-long-term hydrostatic performance have larger lifting, can meet the requirement that application is actual further.
The present invention solves the technical scheme that its technical problem takes: a kind of heat-proof polythene composition, it is characterized in that: comprise heat-proof polythene (PE-RT) 100 parts and 0.1 ~ 1.5 part, oxidation inhibitor (weight part), described heat-proof polythene is ethene and hexene-1 multipolymer, and density is 0.926 ~ 0.950g/cm
3, melt flow rate (MFR) (190 DEG C, 2.16Kg counterweight) is 0.1 ~ 2g/10min, and molecular weight is unimodal distribution, and the relative degree of branching is 0.08 ~ 0.50.
Described heat-proof polythene density preferably 0.930 ~ 0.945g/cm
3, melt flow rate (MFR) preferably (190 DEG C, 2.16Kg counterweight) is 0.20 ~ 1.5g/10min, and melt temperature scope is 120 ~ 135 DEG C, and peak width at half height is 5.0 ~ 8.0 DEG C.
Described heat-proof polythene melt flow rate (MFR) is preferably 0.20 ~ 1.0g/10min.
The relative degree of branching of described heat-proof polythene preferably 0.10 ~ 0.40, melt temperature scope preferably 122 ~ 132 DEG C, peak width at half height preferably 5.5 ~ 8.0 DEG C.
Described oxidation inhibitor is Hinered phenols antioxidant and phosphite ester kind antioxidant, and the weight ratio of Hinered phenols antioxidant and phosphite ester kind antioxidant is 1: 0.1 ~ 10, oxidation inhibitor parts by weight in the composition preferably: 0.2 ~ 1.0.
Described oxidation inhibitor is Hinered phenols antioxidant, phosphite ester kind antioxidant and sulphur ester antioxidant mixture, the weight ratio of Hinered phenols antioxidant and phosphite ester kind antioxidant and sulphur ester antioxidant mixture is 1: 0.1 ~ 14, wherein the weight ratio of phosphite ester kind antioxidant and sulphur ester antioxidant is 1: 0.1 ~ 4, and oxidation inhibitor parts by weight are in the composition 0.2 ~ 1.2.
Described Hinered phenols antioxidant: the weight ratio of phosphite ester kind antioxidant and sulphur ester antioxidant mixture is 1: 0.3 ~ 10, and wherein the ratio of phosphite ester kind antioxidant and sulphur ester antioxidant is 1: 0.25 ~ 1.
Described Hinered phenols antioxidant is selected from four [β-(3, 5 di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester, (2, 4, 6-trioxy--1, 3, 5-triazine-1, 3, 5 (2H, 4H, 6H)-three bases) trivinyl three [3-(3, 5-di-tert-butyl-hydroxy phenyl) acrylate, 1, 1, 3-tri-(2-methyl-4-hydroxyl-5-trimethylphenylmethane base) butane, 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-t-butyl-4-hydroxyl benzyl) benzene, 1, 3, 5-tri-(the 4-tertiary butyl-3-hydroxyl-2, 6-dimethyl benzyl)-1, 3, 5-triazine-2, 4, 6-(1H, 3H, 5H)-triketone, 1, 3, 5-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4, 6-(1H, 3H, middle one 5H) in triketone, two or more, described phosphite ester kind antioxidant is selected from the one in three (2,4-di-tert-butyl-phenyl) phosphorous acid esters or tetramethylolmethane diphosphite two (2,4-di-tert-butyl phenyl) ester.
Described sulphur ester antioxidant is two (18) ester of thio-2 acid or Tyox B.
The processing aid of 0 ~ 0.2 part is also added with in described heat-proof polythene composition.
Described processing aid is fluoroelastomer, addition preferably 0.01 ~ 0.1 part.
A kind of heat-proof polythene composition of the present invention, can be used for tubing or the pipe fitting of preparing delivering hot water.
The heat-proof polythene that the present invention selects is the multipolymer by being polymerized ethene and the hexene-1 directly obtained, and its every material index is specially: density 0.926 ~ 0.950g/cm
3, melt flow rate (MFR) (190 DEG C, 2.16Kg counterweight) 0.1 ~ 2g/10min, the relative degree of branching of examination of infrared spectrum is 0.08 ~ 0.50 (1378cm
-1difference spectrum peak area/2019cm
-1peak area); It is unimodal distribution that gel permeation chromatography GPC shows molecular weight, and the melt temperature scope that differential scanning calorimeter (DSC) measures composition is 120 ~ 135 DEG C, peak width at half height 5.0 ~ 8.0 DEG C.
For polyethylene, improving density can make elasticity modulus of materials improve, thus improve short-term hydrostatic strength, but density is too high, heat-resisting creep property and the toughness of tubing can be reduced, the long-term hydrostatic strength (LTHS) of tubing and the ability of slow-crack-growth (SCG) are reduced, and polyethylene, resin density of the present invention is 0.926 ~ 0.950g/cm
3, preferably 0.930 ~ 0.945g/cm
3.The present invention PE-RT used has moderate melt flow rate (MFR), and while maintenance composition mechanical property, have well processed mobility, melt flow rate (MFR) is 0.1 ~ 2g/10min, preferably 0.1 ~ 1.5g/10min, is preferably 0.1 ~ 1.0g/10min.
Comonomer and the degree of branching thereof determine tie molecule quantity in resin, comonomer selects hexene-1, improve PE-RT branch lengths, and its content is higher, the degree of branching is larger, along with the increase of the degree of branching, having more propping up is linked on tie molecule, resistance during pull-off is larger, and the resistivity of material On Crack Propagation is larger, but the degree of branching can not be too high, if the degree of branching is too high, degree of crystallinity will decline, and lamellae thickness reduces, thus opposing tie molecule is reduced by the force that pull-off spendes from crystalline region.Hexene-1 comonomer degree of branching of PE-RT of the present invention is 0.08 ~ 0.50, preferably reaches 0.10 ~ 0.40, thus ensure that the performance of composition excellence.PE-RT melt temperature scope of the present invention preferably 122 ~ 132 DEG C, peak width at half height preferably 5.5 ~ 8.0 DEG C, thus ensure that homogeneity and the stability of material.
In the present invention, oxidation inhibitor is selected from Hinered phenols antioxidant, phosphite ester kind antioxidant and sulphur ester antioxidant, in oxidation inhibitor, the fusing point of Hinered phenols antioxidant is between 100 DEG C ~ 260 DEG C, can choose from following material: four [β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; (2,4,6-trioxy--1,3,5-triazines-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-trimethylphenylmethane base) butane, 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-t-butyl-4-hydroxyl benzyl) benzene; 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazines-2,4,6-(1H, 3H, 5H)-triketone; 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4,6-(1H, 3H, 5H) triketone.Hinered phenols antioxidant is optional with 1 ~ 3 in above-mentioned oxidation inhibitor kind, when selecting 2 kinds and above Hinered phenols antioxidant, and can arbitrary proportion mixing.
Oxidation inhibitor phosphorous acid ester kind antioxidant fusing point of the present invention is greater than 160 DEG C, can choose from following material: three (2,4-di-tert-butyl-phenyl) phosphorous acid ester; Tetramethylolmethane diphosphite two (2,4-di-tert-butyl phenyl) ester.
In oxidation inhibitor, sulphur ester antioxidant selects two (18) ester of thio-2 acid or Tyox B.
When with Hinered phenols antioxidant and phosphite ester kind antioxidant, Hinered phenols antioxidant can select two kinds, and the mixing of available arbitrary proportion, the weight ratio of Hinered phenols antioxidant and phosphite ester kind antioxidant is 1: 0.1 ~ 10.
When with Hinered phenols antioxidant, phosphite ester kind antioxidant and sulphur ester antioxidant, weight ratio used is: Hinered phenols antioxidant: (phosphite ester kind antioxidant and sulphur ester antioxidant)=1: 0.1 ~ 14, be better 1: 0.3 ~ 10, wherein the ratio of phosphite ester kind antioxidant and sulphur ester antioxidant is 1: 0.1 ~ 4.
Can also comprise right amount of processing aids in the present composition, extrude processing characteristics with what improve tubing, processing aid can be fluoroelastomer.
The present composition can be used as cold hot water piping preparation in buildings, comprises industrial or civilian hot water or cold water, and tap water and heating system pipeline make.
Compared with prior art, the beneficial effect that a kind of heat-proof polythene composition of the present invention has is: composition of the present invention has excellent heat-resisting for a long time, oxidation resistent susceptibility and high temperature resistant creep property, and average oxidation is all greater than 50min inductive phase.According to the requirement of polyethylene hot-water line to use properties, adopt GB/T 6111 " fluid conveying thermoplastic plastic pipe-internal pressure-resistant test method " to test, its hydrostatic strength is at 95 DEG C of temperature, Zernike annular polynomial 4.2MPa, > 1000h, tubing is non-leakage, does not break.
Embodiment
Embodiment 1
This heat-proof polythene composition is by 100 parts of PE-RT resins (MI=0.45g/10min, density 0.934g/cm
3), four [β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester of 0.1 part, 0.15 part 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-t-butyl-4-hydroxyl benzyl) benzene, 0.15 part 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4,6-(1H, 3H, 5H) three (2,4-di-tert-butyl-phenyl) phosphorous acid ester composition of triketone and 0.1 part.
Said composition is carried out performance measurement by respective standard, and the feature of performance perameter and PE-RT used is in table 1.1.
Embodiment 2
This heat-proof polythene composition is by 100 parts of PE-RT resins (MI=0.53g/10min, density 0.936g/cm
3), four [β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester of 0.1 part, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters of 0.2 part and the Tyox B composition of 0.1 part.
Said composition is carried out performance measurement by respective standard, and the feature of performance perameter and PE-RT used is in table 1.1.
Embodiment 3
This heat-proof polythene composition is by 100 parts of PE-RT resins (MI=0.66g/10min, density 0.946g/cm
3), four [β-(3 of 0.2 part, 5 di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester, fluoroelastomer (the commercially available tube material rheological agent) composition of two (18) ester of three (2,4-di-tert-butyl-phenyl) phosphorous acid ester of 0.1 part, the thio-2 acid of 0.4 part and 0.01 part.
Said composition is carried out performance measurement by respective standard, and the feature of performance perameter and PE-RT used is in table 1.1.
Embodiment 4
This heat-proof polythene composition is by 100 parts of PE-RT resins (MI=0.60g/10min, density 0.937g/cm
3), four [β-(3 of 0.2 part, 5 di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester, 0.15 part 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4,6-(1H, 3H, 5H) fluoroelastomer (the commercially available tube material rheological agent) composition of triketone, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester of 0.2 part, the Tyox B of 0.1 part and 0.05 part.
Said composition is carried out performance measurement by respective standard, and the feature of performance perameter and PE-RT used is in table 1.1.
Table 1.1 embodiment 1 ~ 4 resulting composition performance and PE-RT feature
Embodiment 5
This heat-proof polythene composition is by 100 parts of PE-RT resins (MI=0.80g/10min, density 0.934g/cm
3), 0.2 part (2,4,6-trioxy--1,3,5-triazine-1,3,5 (2H, 4H, 6H)-three bases) trivinyl three [3-(3,5-di-tert-butyl-hydroxy phenyl) acrylate, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters of 0.2 part and the Tyox B composition of 0.1 part.
Said composition is carried out performance measurement by respective standard, and the feature of performance perameter and PE-RT used is in table 1.2.
Embodiment 6
This heat-proof polythene composition is by 100 parts of PE-RT resins (MI=0.43g/10min, density 0.940g/cm
3), 0.2 part 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, tetramethylolmethane diphosphite two (2, the 4-di-tert-butyl phenyl) ester of 0.4 part and the Tyox B composition of 0.1 part.
Said composition is carried out performance measurement by respective standard, and the feature of performance perameter and PE-RT used is in table 1.2.
Embodiment 7
This heat-proof polythene composition is by 100 parts of PE-RT resins (MI=0.40g/10min, density 0.940g/cm
3), 0.3 part (2,4,6-trioxy--1,3,5-triazine-1,3,5 (2H, 4H, 6H)-three bases) trivinyl three [3-(3,5-di-tert-butyl-hydroxy phenyl) acrylate, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters of 0.3 part and the Tyox B composition of 0.1 part.
Said composition is carried out performance measurement by respective standard, and the feature of performance perameter and PE-RT used is in table 1.2.
Embodiment 8
This heat-proof polythene composition is by 100 parts of PE-RT resins (MI=0.55g/10min, density 0.930g/cm
3), four [β-(3 of 0.2 part, 5 di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester, two (18) ester of three (2,4-di-tert-butyl-phenyl) phosphorous acid ester of 0.6 part, the thio-2 acid of 0.2 part and 0.1 part of fluoroelastomer (commercially available tube material rheological agent) composition.
Said composition is carried out performance measurement by respective standard, and the feature of performance perameter and PE-RT used is in table 1.2.
Embodiment 9
This heat-proof polythene composition is by 100 parts of PE-RT resins (MI=0.59g/10min, density 0.937g/cm
3), 0.1 part 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4,6-(1H, 3H, 5H) triketone, four [β-(3 of 0.1 part, 5 di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester, 1,3, the 5-trimethylammonium-2 of 0.1 part, 4,6-tri-(3,5-di-t-butyl-4-hydroxyl benzyl) benzene, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters of 0.2 part and fluoroelastomer (the commercially available tube material rheological agent) composition of 0.1 part.
Said composition is carried out performance measurement by respective standard, and the feature of performance perameter and PE-RT used is in table 1.3.
Embodiment 10
This heat-proof polythene composition is by 100 parts of PE-RT resins (MI=0.26g/10min, density 0.930g/cm
3), four [β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester of 0.3 part, 0.2 part 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, tetramethylolmethane diphosphite two (2, the 4-di-tert-butyl phenyl) ester of 0.3 part and the Tyox B composition of 0.2 part.
Said composition is carried out performance measurement by respective standard, and the feature of performance perameter and PE-RT used is in table 1.3.
Embodiment 11
This heat-proof polythene composition is by 100 parts of PE-RT resins (MI=0.59g/10min, density 0.939g/cm
3), four [β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester of 0.1 part, 0.2 part (2,4,6-trioxy--1,3,5-triazines-1,3,5 (2H, 4H, 6H)-three base) trivinyl three [3-(3,5-di-tert-butyl-hydroxy phenyl) acrylate, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters of 0.1 part and the Tyox B composition of 0.1 part.
Said composition is carried out performance measurement by respective standard, and the feature of performance perameter and PE-RT used is in table 1.3.
Table 1.2 embodiment 5 ~ 8 resulting composition performance and PE-RT feature
Table 1.3 embodiment 9 ~ 11 resulting composition performance and PE-RT feature
Melt flow rate (MFR) described in above-mentioned table 1.1 ~ 1.3, at 190 DEG C, measures under 2.16Kg counterweight; Oxidation induction period is at 200 DEG C, and Al cup measures; Hydrostatic test is at 95 DEG C, and Zernike annular polynomial 4.2MPa, tubing is non-leakage, does not break.
Embodiment 12 ~ 20
The heat-proof polythene composite formula of embodiment 12 ~ 20 is in table 2, and in table 2, each component is with listed as parts by weight, and in composition, PE-RT resin is 100 parts; The Hinered phenols antioxidant of embodiment 12 ~ 15 is four [β-(3,5 di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester, the Hinered phenols antioxidant of embodiment 16 ~ 20 is 1,1,3-tri-(2-methyl-4-hydroxyl-5-trimethylphenylmethane base) butane; The phosphite antioxidant of embodiment 12 ~ 20 is three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, and the sulphur ester antioxidant of embodiment 13,14,17 ~ 20 is Tyox B; Embodiment 12,17 processing aid is fluoroelastomer.
The composition of heat-proof polythene composition described in table 2 embodiment 12 ~ 20
| Hinered phenols antioxidant | Phosphite ester kind antioxidant | Sulphur ester antioxidant | Processing aid | |
| Embodiment 12 | 0.05 | 0.05 | - | 0.2 |
| Embodiment 13 | 0.1 | 0.05 | 0.05 | - |
| Embodiment 14 | 0.1 | 1.0 | 0.4 | - |
| Embodiment 15 | 0.1 | 0.1 | - | - |
| Embodiment 16 | 0.5 | 0.5 | - | - |
| Embodiment 17 | 1 | 0.05 | 0.05 | 0.05 |
| Embodiment 18 | 0.1 | 0.5 | 0.5 | - |
| Embodiment 19 | 0.1 | 1 | 0.1 | - |
| Embodiment 20 | 0.05 | 0.1 | 0.4 | - |
In embodiment 12 ~ 15, embodiment 16 ~ 20, gained heat-proof polythene composition carries out performance measurement by respective standard, and the feature of performance perameter and PE-RT used is respectively in table 2.1, table 2.2.
Table 2.1 embodiment 12 ~ 15 resulting composition performance and PE-RT feature
Table 2.2 embodiment 16 ~ 20 resulting composition performance and PE-RT feature
Melt flow rate (MFR) described in table 2.1 ~ 2.2, at 190 DEG C, measures under 2.16Kg counterweight; Oxidation induction period is at 200 DEG C, and Al cup measures; Hydrostatic test is at 95 DEG C, and Zernike annular polynomial 4.2MPa, tubing is non-leakage, does not break.
For the vital role of PE-RT material in heat-proof polythene composition of the present invention that this experiment adopts is described, spy sets serial comparative example 1 ~ 3.
Comparative example 1
Polyethylene composition is by PE resin (MI=2.0g/10min, the density 0.920g/cm of 100 parts
3), three (2,4-di-tert-butyl-phenyl) phosphorous acid ester composition of four [β-(3, the 5 di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters of 0.1 part and 0.1 part.Specific performance is same in table 3.
Comparative example 2
Polyethylene composition is by PE resin (MI=0.08g/10min, the density 0.950g/cm of 100 parts
3), four [β-(3 of 0.2 part, 5 di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester of 0.1 part, two (18) ester of thio-2 acid of 0.4 part and 0.05 part fluoroelastomer (commercially available tube material rheological agent) composition.Specific performance is same in table 3.
Comparative example 3
Polyethylene composition is by PE resin (MI=0.07g/10min, the density 0.951g/cm of 100 parts
3), three (2,4-di-tert-butyl-phenyl) phosphorous acid ester composition of four [β-(3, the 5 di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters of 0.04 part and 0.04 part.Specific performance is in table 3.
Table 3 embodiment 9 and comparative example 1 ~ 3 resulting composition performance and PE-RT feature
As can be seen from comparative example 1 ~ 3, select specific PE-RT material index to the vital role improving heat-proof polythene tubing.
The above is only preferred embodiment of the present invention, and be not restriction invention being made to other form, any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the Equivalent embodiments of equivalent variations.But everyly do not depart from technical solution of the present invention content, any simple modification, equivalent variations and the remodeling done above embodiment according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.
Claims (2)
1. a heat-proof polythene composition, is characterized in that: comprise heat-proof polythene 100 parts and 0.1 ~ 1.5 part, oxidation inhibitor, described heat-proof polythene is ethene and hexene-1 multipolymer, and density is 0.930 ~ 0.945 g/cm
3at 190 DEG C, melt flow rate (MFR) under 2.16Kg weight measurement condition is 0.20 ~ 1.0g/10min, molecular weight is unimodal distribution, the relative degree of branching 0.10 ~ 0.40 of examination of infrared spectrum, the melt temperature scope that differential scanning calorimeter DSC measures is 122 ~ 132 DEG C, and peak width at half height is 5.5 ~ 8.0 DEG C;
Described oxidation inhibitor is Hinered phenols antioxidant, phosphite ester kind antioxidant and sulphur ester antioxidant mixture, the weight ratio of Hinered phenols antioxidant and phosphite ester kind antioxidant and sulphur ester antioxidant mixture is 1:0.3 ~ 10, wherein the weight ratio of phosphite ester kind antioxidant and sulphur ester antioxidant is 1:0.25 ~ 1, and oxidation inhibitor parts by weight are in the composition 0.2 ~ 1.2;
Described Hinered phenols antioxidant is selected from four [β-(3, 5 di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester, (2, 4, 6-trioxy--1, 3, 5-triazine-1, 3, 5(2H, 4H, 6H)-three bases) trivinyl three [3-(3, 5-di-tert-butyl-hydroxy phenyl) acrylate, 1, 1, 3-tri-(2-methyl-4-hydroxyl-5-trimethylphenylmethane base) butane, 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-t-butyl-4-hydroxyl benzyl) benzene, 1, 3, 5-tri-(the 4-tertiary butyl-3-hydroxyl-2, 6-dimethyl benzyl)-1, 3, 5-triazine-2, 4, 6-(1H, 3H, 5H)-triketone, 1, 3, 5-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4, 6-(1H, 3H, middle one 5H) in triketone, two or more, described phosphite ester kind antioxidant is selected from the one in three (2,4-di-tert-butyl-phenyl) phosphorous acid esters or tetramethylolmethane diphosphite two (2,4-di-tert-butyl phenyl) ester,
Described sulphur ester antioxidant is two (18) ester of thio-2 acid or Tyox B;
Also processing aid is added with in described heat-proof polythene composition;
Described processing aid is fluoroelastomer, and addition is 0.01 ~ 0.1 part.
2. a kind of heat-proof polythene composition according to claim 1, is characterized in that: for the preparation of tubing or the pipe fitting of delivering hot water.
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| CN104356494B (en) * | 2014-10-10 | 2018-05-29 | 中国石油化工股份有限公司 | It is a kind of to be used to rotate polythene material of thermoforming and preparation method thereof |
| CN104962027B (en) * | 2015-07-27 | 2017-07-14 | 福建晟扬管道科技有限公司 | A kind of elastomer alloy material and preparation method thereof |
| CN106496802B (en) * | 2015-09-07 | 2019-09-03 | 中国石油天然气股份有限公司 | A kind of high-density polyethylene resin for melt-blown composite fibre |
| CN106554558B (en) * | 2015-09-30 | 2019-01-01 | 中国石油化工股份有限公司 | Easily molded heat-proof polythene composition |
| CN105623053A (en) * | 2016-04-06 | 2016-06-01 | 苏州甫众塑胶有限公司 | Novel heat-resistant polyethylene pipeline material and preparation method thereof |
| CN108503935B (en) * | 2017-02-28 | 2021-04-13 | 中国石油化工股份有限公司 | Easy-to-process heat-resistant polyethylene composition and preparation method thereof |
| WO2019099131A1 (en) | 2017-11-17 | 2019-05-23 | Exxonmobil Chemical Patents Inc. | Pe-rt pipes and processes for making the same |
| CN109990145A (en) * | 2017-12-30 | 2019-07-09 | 福建纳川管业科技有限责任公司 | Heat-resisting steel skeleton polyethylene plastic composite pipe |
| CN108263048A (en) * | 2018-01-18 | 2018-07-10 | 深圳市奥比自动控制有限公司 | A kind of preparation method of high-temperature-resistant high-pressure-resistant pipeline |
| US11931973B2 (en) * | 2018-03-02 | 2024-03-19 | Ticona Llc | Weatherable fiber-reinforced propylene composition |
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