CN102924774A - Polyethylene resin composition for pipes - Google Patents
Polyethylene resin composition for pipes Download PDFInfo
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- CN102924774A CN102924774A CN2011102280395A CN201110228039A CN102924774A CN 102924774 A CN102924774 A CN 102924774A CN 2011102280395 A CN2011102280395 A CN 2011102280395A CN 201110228039 A CN201110228039 A CN 201110228039A CN 102924774 A CN102924774 A CN 102924774A
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- 239000011342 resin composition Substances 0.000 title claims abstract description 10
- 229920013716 polyethylene resin Polymers 0.000 title claims abstract description 7
- 239000011347 resin Substances 0.000 claims abstract description 105
- 229920005989 resin Polymers 0.000 claims abstract description 105
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 claims abstract description 101
- 239000000203 mixture Substances 0.000 claims abstract description 88
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 84
- 238000002360 preparation method Methods 0.000 claims abstract description 69
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 57
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 57
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 238000004132 cross linking Methods 0.000 claims abstract description 20
- 239000004611 light stabiliser Substances 0.000 claims abstract description 15
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 50
- 239000004698 Polyethylene Substances 0.000 claims description 47
- -1 polyethylene Polymers 0.000 claims description 47
- 229920000573 polyethylene Polymers 0.000 claims description 45
- 238000002156 mixing Methods 0.000 claims description 39
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 31
- 238000001816 cooling Methods 0.000 claims description 24
- 238000005469 granulation Methods 0.000 claims description 24
- 230000003179 granulation Effects 0.000 claims description 24
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 23
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 16
- 229920003023 plastic Polymers 0.000 claims description 12
- 239000004033 plastic Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 150000001412 amines Chemical class 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 8
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000001993 wax Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- NFZJABPIWWKYPF-UHFFFAOYSA-N [O].C(CCCCCCC)C1=CC=C(C=C1)O Chemical compound [O].C(CCCCCCC)C1=CC=C(C=C1)O NFZJABPIWWKYPF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000002516 radical scavenger Substances 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 claims description 3
- VCSCKXNPGKIQRY-UHFFFAOYSA-N [Ni].C(CCCCCCC)N(C(S)=S)CCCCCCCC Chemical compound [Ni].C(CCCCCCC)N(C(S)=S)CCCCCCCC VCSCKXNPGKIQRY-UHFFFAOYSA-N 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 229920000578 graft copolymer Polymers 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 239000012808 vapor phase Substances 0.000 claims description 2
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 150000001451 organic peroxides Chemical class 0.000 abstract 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 19
- 239000003112 inhibitor Substances 0.000 description 17
- 230000003647 oxidation Effects 0.000 description 17
- 238000007254 oxidation reaction Methods 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 9
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical group [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 8
- 235000013539 calcium stearate Nutrition 0.000 description 7
- 239000008116 calcium stearate Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 230000006353 environmental stress Effects 0.000 description 6
- 230000000630 rising effect Effects 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- 238000005336 cracking Methods 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 238000003973 irrigation Methods 0.000 description 2
- 230000002262 irrigation Effects 0.000 description 2
- 150000002816 nickel compounds Chemical class 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WPRMJBJYCFNTKE-UHFFFAOYSA-L (3,5-ditert-butyl-4-hydroxyphenyl)methyl-ethoxyphosphinate;nickel(2+) Chemical compound [Ni+2].CCOP([O-])(=O)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1.CCOP([O-])(=O)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 WPRMJBJYCFNTKE-UHFFFAOYSA-L 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- SWZOQAGVRGQLDV-UHFFFAOYSA-N 4-[2-(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)ethoxy]-4-oxobutanoic acid Chemical compound CC1(C)CC(O)CC(C)(C)N1CCOC(=O)CCC(O)=O SWZOQAGVRGQLDV-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004717 peroxide crosslinked polyethylene Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Classifications
-
- B29C47/92—
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention aims to provide a polyethylene resin composition for pipes, which is prepared by using HDPE resin as a base material and carrying out micro-crosslinking modification on ultra-low density polyethylene (ULDPE) weather-resistant master batches and organic peroxide. The resin composition has excellent ESCR performance (> 3000 hours). The resin composition comprises, in one hundred percent by weight of High Density Polyethylene (HDPE): 100 percent of HDPE, 0.05 to 0.2 percent of compound crosslinking auxiliary agent and 10 to 35 percent of ULDPE weather resistant master batch; the ULDPE weather-resistant master batch is a blend consisting of ULDPE, a composite light stabilizer, an ULDPE-g-VA graft and a dispersing agent, wherein the ULDPE-g-VA graft is a graft of ULDPE and vinyl acetate. The invention further provides a preparation method of the resin composition.
Description
Technical field
The present invention relates to a kind of polyethylene resin composition, be specifically related to the tubing resin combination with good environmental stress cracking resistance take high density polyethylene(HDPE) (HDPE) as base-material.
Background technology
In recent years, development along with plastics industry, polyvinyl piping materials is so that it is lightweight, corrosion-resistant, thermal conductivity is low, good insulation preformance, construction and installation and the characteristics such as easy to maintenance more and more are subject to people's attention, and become after PVC, the plastic conduit kind of world consumption amount maximum, Application Areas spread all over engineering and the fields such as oil field, chemical industry and post and telecommunications such as feedwater, agricultural irrigation, combustion gas conveying, blowdown, mine mortar conveying.
In polyvinyl piping materials, high density polyethylene(HDPE) (HDPE) pipe has the characteristics such as light weight, mechanical property excellence, crimp tendency and flexibility are good, is the tubing kind that competitive capacity is arranged most.But because structure, the form of HDPE resin itself, easily cause tubing under certain hour, certain load effect, fracture phenomena can occur, be that environmental stress cracking resistance (ESCR) is relatively poor, thereby affected the application of HDPE tubing in fields such as outdoor water supply pipe, gas line, irrigation usefulness pipes.Therefore, ESCR is an important indicator estimating and affect the HDPE tubing life-span.
" supply water and use the polyvinyl piping materials standard " (ISO 4427:1996) is divided into PE the different gradess such as PE 32, PE40, PE 63, PE 80, PE 100 according to the tubing longterm strength.In China, modal tubing speciality resin is the PE63 level on the market, such as trades mark such as 6100M, HD4810EX.Therefore the ESCR of PE63 grade resins has limited use range all less than 1000 hours, and price and class all can't contend with PE80, other tubing speciality resin of PE100 level.And the polyvinyl piping materials of PE80, PE100 or higher category is resin dedicated, and ESCR is all above 1000 hours, but resin is directly to obtain from polyreaction, and technical sophistication and cost are higher.
There are some researches show that the ESCR of HDPE resin not only is subjected to the impact of the extraneous factors such as temperature, external force, and larger with the relation of the internal factors such as the molecular weight of resin itself, molecular weight distribution, the degree of branching and a chain length, crystallization situation.Therefore, in the prior art, the angle from polymerization is arranged, by reactors in series, add long-chain branch monomer, control reaction conditions, change the polyvinyl resin that the modes such as catalyst system can be produced high ESCR, such as reports such as CN1903896, CN1513002.But more be the angle from the modification of resin post-treatment, improve the ESCR of material by the modulation resinous molecular structure, main path has two kinds: the one, and sneak into second components such as polyolefine, elastomerics in the resin and carry out modification, second component plays the refinement spherocrystal, reduces degree of crystallinity and stop crackle to stretch in polyethylene effect.The method is present the most frequently used method, relevant report is more, such as CN1556835, CN1247204, CN1262972, US2007282071 (A1), US2006276593 (A1), US2003088021 (A1), US7153909, WO0105852 (A1), JP57031945 (A) etc.The 2nd, by chemical crosslinking modified, form crosslinked structure, increase the connection between molecular chain, improve the environmental stress cracking resistance of polythene material.Adopt the organosilane crosslinked polyethylene layer such as CN2492729; US4390666 mixes the polyvinyl resin of two kinds of different molecular weights, and the polyethylene composition that the recycling organo-peroxide carries out crosslinked preparation has good physical property, as has high rigidity, high ESCR, high impact resistance etc.; CN200410066408.5 promotes the peroxide crosslinked polyethylene resin by using infrared irridiation in the process of preparation tubing, thus the mechanical property of raising polyvinyl piping materials and resistance toheat etc.
Summary of the invention
The object of the invention provides a kind of polyethylene resin composition for pipe, take the HDPE resin as base-material, by the weather-proof master batch of ultra-low density polyethylene (ULDPE) and little cross-linking modified realization of organo-peroxide.This resin combination has good ESCR performance (＞3000 hours).The present invention further proposes the preparation method of composition.
Take the weight of high density polyethylene(HDPE) (HDPE) as absolutely, resin combination of the present invention comprises:
1)HDPE 100％；
2) composite crosslinking coagent 0.05%～0.2%;
3) the weather-proof master batch 10%～35% of ULDPE;
Wherein said composite crosslinking coagent is tertbutyl peroxide (TBHP) and dibenzoyl peroxide (BPO), and the mass ratio of two kinds of linking agents is TBHP/BPO=25: 1～5: 1.
The blend that the weather-proof master batch of described ULDPE is comprised of grafts (ULDPE-g-VA) and the dispersion agent of ULDPE, composite light stabilizer, ULDPE and vinyl acetate between to for plastic.Polymkeric substance ULDPE makes the multipolymer of optimal ethylene and butylene, wherein density: 0.860～0.915g/cm3 by ethene and a-alkene (propylene, butylene, hexene and octene) by vapor phase process, solution method or high-pressure process copolymerization; Melt flow rate (MFR) (MFR) is: 0.1～20g/10min.Described melt flow rate (MFR) (MFR) is at 190 ℃, the measured value under the 2.16Kg load.
The compound system that composite light stabilizer is comprised of quencher and radical scavenger.Quencher is the organic nickel compound, as: two (3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl ester) nickel (Irgastab 2002), 2,2-thiobis (uncle's 4-octyl phenol oxygen base) nickel-n-Butyl Amine 99 complex compound (UV-1084), 2,2-thiobis (uncle's 4-octyl phenol oxygen base) nickel (AM-101), dioctyl dithiocarbamic acid nickel (AM-108), N, a kind of in the N-nickel dibutyl dithiocarbamate (NBC), the organic nickel compound is because of the toxicity problem of heavy metal ion, and its consumption should be strict controlled in 0.01%～0.04% (pressing the weight percent meter of ULDPE).Radical scavenger is selected the hindered amine as light stabilizer (HALS) with space steric effect, as: a kind of among Tinuvin123, Tinuvin622, Tinuvin791, Tinuvin328, Tinuvin326, GW-540, GW-480, GW-544, the CH944, its consumption is 0.1%～0.5% (pressing the weight percent meter of ULDPE).This compound system can reduce the excited state functional group that has reactive behavior in the molecular resin after cross-linking modified effectively, promptly catch free radical R, ROO that linking agent produces, destroy the growth of living chain, improve the stability of base resin molecular structure, reached the work-ing life that prolongs resin.
ULDPE-g-VA is at the graft copolymer that under the effect of initiator grafted monomer is grafted on the ULDPE main chain; initiator was selected from the sad tert-butyl ester, t-butyl peroxy-acetate (TBPA), tertbutyl peroxide, 2; 5-dimethyl-2; a kind of in 5-di-t-butyl hexane peroxide (BPDH), ditertiary butyl peroxide (DTBP), dicumyl peroxide (DCP), diisopropylbenzenehydroperoxide (DBHP), benzoyl peroxide or the peroxide di-t-butyl preferably adopts dicumyl peroxide (DCP).Grafted monomer is selected from polymerization-grade vinyl acetate between to for plastic (VA).
Dispersion agent can be wherein a kind of or composite such as sherwood oil, paraffin, whiteruss, naphthenic oil, polyethylene wax, white oil, preferably adopts polyethylene wax.
The weather-proof agglomerate preparation method of ULDPE provided by the invention comprises:
(1) preparation method of ULDPE-g-VA grafts:
Press the weight percent meter of ULDPE, with the ULDPE high-speed mixing 5～10min of 5～15 parts vinyl acetate between to for plastics (VA) with 100 parts, the material that mixes is placed 5～10hr in encloses container; Then get 0.01～0.1 part initiator and acetone and be by weight and be mixed with mixing solutions in 1: 10～1: 20, again with mixing solutions and the mixture high-speed mixing 5～10min that places, at last by carrying out melting graft reaction in the twin screw extruder, 160～200 ℃ of temperature of reaction, reaction times 5～10min, extrude, cooling, granulation, obtain the VA percentage of grafting and be 2～9% ULDPE-g-VA grafts.
(2) preparation of the weather-proof master batch of ULDPE
Press the weight percent meter of ULDPE, 100 parts ULDPE and 5～12 parts ULDPE-g-VA grafts, 0.5～1.0 part dispersion agent are put in the super mixer high-speed mixing 3～5min together; And then add 0.11～0.54 part composite light stabilizer, high-speed mixing 5～10min; Mixed material is added twin screw extruder, 165～210 ℃ of temperature of reaction, reaction times 3～5min extrudes, cooling, granulation, obtains the weather-proof master batch of ULDPE.
HDPE described in the composition is for adopting the high density polyethylene(HDPE) of efficient ziegler-natta catalyst systems preparation, MFR:0.1～10g/10min; Density: 0.945～0.957g/cm
3Mw:10～20 * 10
4Mw/Mn:10～20, molecular weight can be unimodal distribution, also can be bimodal distributions.Middle-high density polyethylene of the present invention can be powdery or granular resin, but best with powdered resin for reaching better mixed effect.
Composite crosslinking coagent described in the composition is that TBHP and BPO are by the composite composition of different ratios.Wherein the scope of total add-on of composite crosslinking coagent is that the optimum mixture ratio of 0.05%～0.2%, two kinds of crosslinking coagents is TBHP/BPO=20: 1～10: 1.Two kinds of superoxide are the commercially available prod, and its half life temperature is because of manufacturer's difference difference slightly, the transformation period T=246 of general TBHP～267 ℃/1min; The transformation period T=131 of BPO～134 ℃/1min.
The preparation of resin combination of the present invention also can be carried out in Banbury mixer, kneader, forcing machine, but take twin screw extruder as best.
Particularly, the preparation method of polyethylene pipe resins composition provided by the invention comprises: first with two kinds of crosslinking coagents composite rear adding solvent in proportion, add again the HDPE that accounts for total amount 5%～10% (wt), then behind high-speed mixing 3～5min, make the premix masterbatch; Then remaining HDPE, premix masterbatch and the weather-proof master batch of ULDPE are joined together by charging opening and carry out extrusion reaction in the forcing machine, temperature of reaction is 160～220 ℃, reaction times is 3～5min, extrudes, cooling, granulation, makes the polyethylene pipe resins composition.
The present invention also can add a certain amount of thermo-stabilizer and oxidation inhibitor in the preparation process of the weather-proof master batch of ULDPE and polyethylene pipe resins composition, its total add-on is 0.2%～0.5% (take the weight of HDPE as per-cent).Wherein, oxidation inhibitor can be one or several compounds in phenols, hindered amines, the phosphite ester kind antioxidant, and its consumption is 0.1%～0.2%.Thermo-stabilizer can be stearates, and such as Zinic stearas, calcium stearate etc., consumption is generally 0.1%～0.3%.
In the resin combination preparation process of the present invention, add solvent in composite crosslinking coagent, described solvent is a kind of in toluene, dimethylbenzene, the acetone, and its add-on is 2～4 times of composite crosslinking coagent weight.
In the composition of the present invention, on the one hand, low, the intermolecular freeboard of the ULDPE density in the weather-proof master batch of ULDPE is large, degree of crystallinity is low, it is larger to have and more complete spherocrystal, will reduce refraction and the range of light in resin; Simultaneously again owing to short-chain branch in the molecular structure is many, and with crosslinking coagent certain crosslinked action occuring, can form more physical crosslinking point in molecular structure, can greatly improve the ESCR performance of base resin HDPE.Secondly, the ULDPE-g-VA grafts has improved the consistency of resin and photostabilizer, has improved the dispersion effect of photostabilizer in resin; The ULDPE-g-VA grafts has certain adsorption to photostabilizer in addition, avoided photostabilizer in resin migration and separate out problem, greatly improved persistence and the high efficiency of photostabilizer.ULDPE and photostabilizer can produce certain positive cooperativity like this, and this has fairly obvious effect to the ESCR performance of improving polyethylene pipe resins, and the add-on, the minimum cost that have reached with minimum obtain best ESCR performance.On the other hand, the composite cross-linking system that the superoxide of selecting two kinds of transformation period to differ larger forms, can effectively control cross-linked speed and the crosslinking degree of base resin, realize little crosslinking structure, under the prerequisite that guarantees processibility, give resin good physical property, especially environmental stress cracking resistance.Like this so that said composition can stably process the tubing of various internal diameters on the common pipe extruder group without any transformation, and with the tubing that this resin combination processes have good environmental stress cracking resistance (＞3000h).Solved the problem of common HDPE resin environmental stress crack resistance deficiency.
Embodiment
(1) raw material
1) resin
2) superoxide
3) auxiliary agent
(2) performance test standard
(3) equipment and instrument
The German Lestreiz of Φ 67 twin-screw extrusion captains/directly=34/1 company
The fast mixing machine of 10 risings Fuxin plastics machinery factory
Embodiment and Comparative Examples
Enumerate following examples invention effect of the present invention is described, but protection scope of the present invention is not limited in these embodiment, each component is in the parts by weight of base resin HDPE in the composition.
Embodiment 1
(1) preparation of ULDPE-g-VA grafts: press the weight percent meter of ULDPE, with ULDPE (4703G) the high-speed mixing 7min of 7 parts vinyl acetate between to for plastics (VA) with 100 parts, the material that mixes is placed 10hr in encloses container; Then the acetone of getting 0.03 part of DCP and 0.3 part is put into beaker and is mixed, and again the solution that mixes and mixture, 0.15 part of antioxidant 1010,0.15 part of calcium stearate of placing is put into 10L high-speed mixer, high-speed mixing 5min together; At last the material that mixes is joined in Φ 67 twin screw extruders, the screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,190,180,175,170; Carry out melting graft reaction, behind the reaction 7min, extrude, cooling, granulation, obtain ULDPE-g-VA grafts (percentage of grafting: 3.1%).
(2) preparation of the weather-proof master batch of ULDPE: the weight percent meter of pressing ULDPE, 3.1%), 0.6 part polyethylene wax puts in the high-speed mixer high-speed mixing 5min together with the ULDPE-g-VA grafts of 100 parts ULDPE (4703G) and 8 parts (percentage of grafting:; And then add 0.22 part hindered amine as light stabilizer CH944 and 2002,0.15 parts of oxidation inhibitor B561 of quencher of 0.02 part, 0.15 part of calcium stearate, high-speed mixing 10min; Mixed material is joined Φ 67 twin screw extruders, the screw zones temperature of reaction (℃) be followed successively by: 165,170,180,190,200,210,190,180,170; Behind the reaction 5min, extrude, cooling, granulation, obtain the weather-proof master batch a of ULDPE.
(3) preparation of polyethylene pipe resins composition: 0.002 part of BPO and 0.048 part of TBHP with after 0.2 part of acetone solvent mixes, are then added 5 parts of HDPE (6100M) pellet resin, raise 10 and mix 5min in the fast mixing machine, make the premix masterbatch; Taking out 13 parts of weather-proof master batch a of ULDPE is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 95 parts of HDPE (6100M) resins and 0.15 part of oxidation inhibitor B561,0.2 part of Zinic stearas, the screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; Behind the reaction 4min, extrude, cooling, granulation, prepare the polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance sees Table 1 after tested.
Embodiment 2
(1) preparation of ULDPE-g-VA grafts is fully identical with embodiment 1.
(2) preparation of the weather-proof master batch of ULDPE is fully identical with embodiment 1.
(3) preparation of polyethylene pipe resins composition: 0.003 part of BPO and 0.06 part of TBHP with after 0.2 part of acetone solvent mixes, are then added 5 parts of HDPE (6100M) pellet resin, raise 10 and mix 3min in the fast mixing machine, make the premix masterbatch; Taking out 16 parts of weather-proof master batch a of ULDPE is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 95 parts of HDPE (6100M) resins and 0.15 part of oxidation inhibitor B561,0.2 part of Zinic stearas, the screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; Behind the reaction 4min, extrude, cooling, granulation, prepare the polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance sees Table 1 after tested.
Embodiment 3
(1) preparation of ULDPE-g-VA grafts is fully identical with embodiment 1.
(2) preparation of the weather-proof master batch of ULDPE is fully identical with embodiment 1.
(3) preparation of polyethylene pipe resins composition: 0.004 part of BPO and 0.07 part of TBHP with after 0.2 part of acetone solvent mixes, are then added 5 parts of HDPE (6100M) pellet resin, raise 10 and mix 3min in the fast mixing machine, make the premix masterbatch; Taking out 20 parts of weather-proof master batch a of ULDPE is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 95 parts of HDPE (6100M) resins and 0.15 part of oxidation inhibitor B561,0.2 part of Zinic stearas, the screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; Behind the reaction 4min, extrude, cooling, granulation, prepare the polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance sees Table 1 after tested.
Embodiment 4
(1) preparation of ULDPE-g-VA grafts is fully identical with embodiment 1.
(2) preparation of the weather-proof master batch of ULDPE is fully identical with embodiment 1.
(3) preparation of polyethylene pipe resins composition: 0.005 part of BPO and 0.09 part of TBHP with after 0.3 part of acetone solvent mixes, are then added 5 parts of HDPE (6100M) pellet resin, raise 10 and mix 3min in the fast mixing machine, make the premix masterbatch; Taking out 22 parts of weather-proof master batch a of ULDPE is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 95 parts of HDPE (6100M) resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas, the screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; Behind the reaction 4min, extrude, cooling, granulation, prepare the polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance sees Table 1 after tested.
Embodiment 5
(1) preparation of ULDPE-g-VA grafts: press the weight percent meter of ULDPE, with ULDPE (4703G) the high-speed mixing 7min of 9 parts vinyl acetate between to for plastics (VA) with 100 parts, the material that mixes is placed 10hr in encloses container; Then the acetone of getting 0.05 part of DCP and 0.6 part is put into beaker and is mixed, and again the solution that mixes and mixture, 0.15 part of antioxidant 1010,0.2 part of calcium stearate of placing is put into 10L high-speed mixer, high-speed mixing 5min together; At last the material that mixes is joined in Φ 67 twin screw extruders, the screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,190,180,175,170; Carry out melting graft reaction, behind the reaction 7min, extrude, cooling, granulation, obtain ULDPE-g-VA grafts (percentage of grafting: 4.8%).
(2) preparation of the weather-proof master batch of ULDPE: the weight percent meter of pressing ULDPE, 4.8%), 0.7 part polyethylene wax puts in the high-speed mixer high-speed mixing 5min together with the ULDPE-g-VA grafts of 100 parts ULDPE (4703G) and 9 parts (percentage of grafting:; And then add 0.31 part hindered amine as light stabilizer CH944 and 2002,0.15 parts of oxidation inhibitor B561 of quencher of 0.025 part, 0.2 part of calcium stearate, high-speed mixing 10min; Mixed material is joined Φ 67 twin screw extruders, the screw zones temperature of reaction (℃) be followed successively by: 165,170,180,190,200,210,190,180,170; Behind the reaction 5min, extrude, cooling, granulation, obtain the weather-proof master batch b of ULDPE.
(3) preparation of polyethylene pipe resins composition: 0.006 part of BPO and 0.1 part of TBHP with after 0.3 part of acetone solvent mixes, are then added 5 parts of HDPE (60550) powder resin, raise 10 and mix 3min in the fast mixing machine, make the premix masterbatch; Taking out 25 parts of weather-proof master batch b of ULDPE is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 95 parts of HDPE (60550) resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas, the screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; Behind the reaction 4min, extrude, cooling, granulation, prepare the polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance sees Table 1 after tested.
Embodiment 6
(1) preparation of ULDPE-g-VA grafts is fully identical with embodiment 5.
(2) preparation of the weather-proof master batch of ULDPE is fully identical with embodiment 5.
(3) preparation of polyethylene pipe resins composition: 0.007 part of BPO and 0.12 part of TBHP with after 0.5 part of acetone solvent mixes, are then added 5 parts of HDPE (60550) powder resin, raise 10 and mix 3min in the fast mixing machine, make the premix masterbatch; Taking out 28 parts of weather-proof master batch b of ULDPE is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 95 parts of HDPE (60550) resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas, the screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; Behind the reaction 4min, extrude, cooling, granulation, prepare the polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance sees Table 1 after tested.
Embodiment 7
(1) preparation of ULDPE-g-VA grafts is fully identical with embodiment 5.
(2) preparation of the weather-proof master batch of ULDPE is fully identical with embodiment 5.
(3) preparation of polyethylene pipe resins composition: 0.008 part of BPO and 0.11 part of TBHP with after 0.5 part of acetone solvent mixes, are then added 5 parts of HDPE (60550) powder resin, raise 10 and mix 3min in the fast mixing machine, make the premix masterbatch; Taking out 30 parts of weather-proof master batch b of ULDPE is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 95 parts of HDPE (60550) resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas, the screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; Behind the reaction 4min, extrude, cooling, granulation, prepare the polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance sees Table 1 after tested.
Embodiment 8
(1) preparation of ULDPE-g-VA grafts: press the weight percent meter of ULDPE, with ULDPE (4703G) the high-speed mixing 7min of 11 parts vinyl acetate between to for plastics (VA) with 100 parts, the material that mixes is placed 10hr in encloses container; Then the acetone of getting 0.06 part of DTBP and 0.8 part is put into beaker and is mixed, and again the solution that mixes and mixture, 0.15 part of antioxidant 1010,0.2 part of calcium stearate of placing is put into 10L high-speed mixer, high-speed mixing 5min together; At last the material that mixes is joined in Φ 67 twin screw extruders, the screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,190,180,175,170; Carry out melting graft reaction, behind the reaction 7min, extrude, cooling, granulation, obtain ULDPE-g-VA grafts (percentage of grafting: 5.7%).
(2) preparation of the weather-proof master batch of ULDPE: the weight percent meter of pressing ULDPE, 5.7%), 0.8 part polyethylene wax puts in the high-speed mixer high-speed mixing 5min together with the ULDPE-g-VA grafts of 100 parts ULDPE (4703G) and 10 parts (percentage of grafting:; And then add 0.42 part hindered amine as light stabilizer Tinuvin 791 and 0.03 part quencher NBC, 0.2 part of oxidation inhibitor B561,0.2 part of calcium stearate, high-speed mixing 10min; Mixed material is joined Φ 67 twin screw extruders, the screw zones temperature of reaction (℃) be followed successively by: 165,170,180,190,200,210,190,180,170; Behind the reaction 5min, extrude, cooling, granulation, obtain the weather-proof master batch c of ULDPE.
(3) preparation of polyethylene pipe resins composition: with 0.015 part of BPO and 0.15 part of TBHP with after 0.5 part of xylene solvent mixes, then add 5 parts of HDPE (60550) powder resin, in the fast mixing machine of 10 risings, mix 3min, make the premix masterbatch; Taking out 33 parts of weather-proof master batch c of ULDPE is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 95 parts of HDPE (60550) resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas, the screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; Behind the reaction 4min, extrude, cooling, granulation, prepare the polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance sees Table 1 after tested.
Comparative Examples 1
(1) preparation of ULDPE-g-VA grafts is fully identical with embodiment 1.
(2) preparation of the weather-proof master batch of ULDPE is fully identical with embodiment 1.
(3) preparation of polyethylene pipe resins composition: difference is not add in the composition preparation process BPO, and the add-on of TBHP is 0.05 part, and other condition and embodiment 1 are identical, prepare the polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance sees Table 1 after tested.
Comparative Examples 2
(1) preparation of ULDPE-g-VA grafts is fully identical with embodiment 1.
(2) preparation of the weather-proof master batch of ULDPE is fully identical with embodiment 1.
(3) preparation of polyethylene pipe resins composition: difference is not add in the composition preparation process TBHP, and the add-on of BPO is 0.063 part, and other condition and embodiment 2 are identical, prepare the polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance sees Table 1 after tested.
Comparative Examples 3
(1) preparation of the weather-proof master batch of ULDPE: difference is not add the ULDPE-g-VA grafts in the weather-proof master batch preparation process of ULDPE, and other processes and embodiment 1 are identical, make the weather-proof master batch of ULDPE (a-1).
(2) preparation of polyethylene pipe resins composition: other condition is identical with embodiment 3, difference is that the weather-proof master batch of the ULDPE that adds in the composition preparation process does not contain the ULDPE-g-VA grafts, 20 parts of the add-ons of the weather-proof master batch of ULDPE (a-1), that is: with 0.004 part of BPO and 0.07 part of TBHP with after 0.2 part of acetone solvent mixes, then add 5 parts of HDPE (6100M) pellet resin, in the fast mixing machine of 10 risings, mix 3min, make the premix masterbatch; Taking out 20 parts of weather-proof master batches of ULDPE (a-1) is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 95 parts of HDPE (6100M) resins and 0.15 part of oxidation inhibitor B561,0.2 part of Zinic stearas, the screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; Behind the reaction 4min, extrude, cooling, granulation, prepare the polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance sees Table 1 after tested.
Comparative Examples 4
The preparation of polyethylene pipe resins composition: difference is not add in the resin combination preparation process the weather-proof master batch a of ULDPE, and other processes and embodiment 4 are identical, prepare the polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance sees Table 1 after tested.
Comparative Examples 5
(1) preparation of ULDPE-g-VA grafts is fully identical with embodiment 5.
(2) preparation of the weather-proof master batch of ULDPE: difference is not add quencher 2002 in the weather-proof master batch preparation process of ULDPE, the add-on of hindered amine as light stabilizer CH944 is 0.335 part, other processes and embodiment 5 are identical, make the weather-proof master batch of ULDPE (b-1).
(3) preparation of polyethylene pipe resins composition: other condition is identical with embodiment 5, difference is that the weather-proof master batch of the ULDPE that adds in the composition preparation process does not contain quencher 2002,25 parts of the add-ons of the weather-proof master batch of ULDPE (b-1), that is: with 0.006 part of BPO and 0.1 part of TBHP with after 0.3 part of acetone solvent mixes, then add 5 parts of HDPE (60550) powder resin, in the fast mixing machine of 10 risings, mix 3min, make the premix masterbatch; Taking out 25 parts of weather-proof master batches of ULDPE (b-1) is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 95 parts of HDPE (60550) resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas, the screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; Behind the reaction 4min, extrude, cooling, granulation, prepare the polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance sees Table 1 after tested.
Comparative Examples 6
(1) preparation of ULDPE-g-VA grafts is fully identical with embodiment 5.
(2) preparation of the weather-proof master batch of ULDPE is fully identical with embodiment 5.
(3) preparation of polyethylene pipe resins composition: other condition is identical with embodiment 6, difference is that the add-on of the weather-proof master batch b of ULDPE in the composition preparation process is 6 parts, that is: with 0.007 part of BPO and 0.12 part of TBHP with after 0.5 part of acetone solvent mixes, then add 5 parts of HDPE (60550) powder resin, in the fast mixing machine of 10 risings, mix 3min, make the premix masterbatch; Taking out 6 parts of weather-proof master batch b of ULDPE is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 95 parts of HDPE (60550) resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas, the screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; Behind the reaction 4min, extrude, cooling, granulation, prepare the polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance sees Table 1 after tested.
Comparative Examples 7
The preparation of polyethylene pipe resins composition: difference is not add in the composition preparation process the weather-proof master batch b of ULDPE, but add ULDPE (4703G), 30 parts of the add-ons of ULDPE (4703G), other condition is identical with embodiment 7, prepares the polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance sees Table 1 after tested.
Comparative Examples 8
(1) preparation of ULDPE-g-VA grafts is fully identical with embodiment 8.
(2) preparation of the weather-proof master batch of ULDPE: difference is not add hindered amine as light stabilizer Tinuvin 791 in the weather-proof master batch preparation process of ULDPE, the add-on of quencher NBC is 0.45 part, other processes and embodiment 8 are identical, make the weather-proof master batch of ULDPE (c-1).
(3) preparation of polyethylene pipe resins composition: other condition is identical with embodiment 8, difference is that the weather-proof master batch of the ULDPE that adds in the composition preparation process does not contain hindered amine as light stabilizer Tinuvin 791,33 parts of the add-ons of the weather-proof master batch of ULDPE (c-1), that is: with 0.015 part of BPO and 0.15 part of TBHP with after 0.5 part of xylene solvent mixes, then add 5 parts of HDPE (60550) powder resin, in the fast mixing machine of 10 risings, mix 3min, make the premix masterbatch; Taking out 33 parts of weather-proof master batches of ULDPE (c-1) is joined in Φ 67 twin screw extruders by charging opening with premix masterbatch and 95 parts of HDPE (60550) resins and 0.2 part of oxidation inhibitor B561,0.2 part of Zinic stearas, the screw zones temperature of reaction (℃) be followed successively by: 160,170,180,190,200,210,220,200,190; Behind the reaction 4min, extrude, cooling, granulation, prepare the polyethylene pipe resins composition.Said composition is made standard test specimen with injecting method, and performance sees Table 1 after tested.
The physical property measurement result of table 1 polyvinyl piping materials
Claims (11)
1. polyethylene resin composition for pipe take the weight of HDPE as absolutely, is characterized in that comprising:
1)HDPE 100％；
2) composite crosslinking coagent 0.05%～0.2%;
3) the weather-proof master batch 10%～35% of ULDPE;
The blend that the weather-proof master batch of described ULDPE is comprised of ULDPE, composite light stabilizer, ULDPE-g-VA grafts and dispersion agent, described ULDPE-g-VA grafts refers to the grafts of ULDPE and vinyl acetate between to for plastic.
2. resin combination as claimed in claim 1 is characterized in that described composite crosslinking coagent is tertbutyl peroxide and the composite composition of dibenzoyl peroxide, and the mass ratio of two kinds of linking agents is 25: 1～5: 1.
3. resin combination as claimed in claim 1 is characterized in that ULDPE is made by vapor phase process, solution method or high-pressure process copolymerization by ethene and a-alkene.
4. resin combination as claimed in claim 1 is characterized in that the compound system that described composite light stabilizer is comprised of quencher and radical scavenger.
5. resin combination as claimed in claim 4, it is characterized in that described quencher is selected from two (3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl ester) nickel, 2,2-thiobis (uncle's 4-octyl phenol oxygen base) nickel-n-Butyl Amine 99 complex compound, 2,2-thiobis (uncle's 4-octyl phenol oxygen base) nickel, dioctyl dithiocarbamic acid nickel, N, a kind of in the N-nickel dibutyl dithiocarbamate, its consumption accounts for 0.01%～0.04% of ULDPE weight.
6. resin combination as claimed in claim 4 is characterized in that described radical scavenger is hindered amine as light stabilizer, and its consumption accounts for 0.1%～0.5% of ULDPE weight.
7. resin combination as claimed in claim 1; it is characterized in that described ULDPE-g-VA grafts is at the graft copolymer that under the effect of initiator Vinyl Acetate Monomer is grafted on the ULDPE main chain; described initiator was selected from the sad tert-butyl ester, t-butyl peroxy-acetate, tertbutyl peroxide, 2; 5-dimethyl-2, a kind of in 5-di-t-butyl hexane peroxide, ditertiary butyl peroxide, dicumyl peroxide, diisopropylbenzenehydroperoxide, benzoyl peroxide or the peroxide di-t-butyl.
8. resin combination as claimed in claim 1 is characterized in that described dispersion agent is selected from one or more in sherwood oil, paraffin, whiteruss, naphthenic oil, polyethylene wax, the white oil.
9. resin combination as claimed in claim 1, the preparation method who it is characterized in that described ULDPE-g-VA grafts comprises: the weight percent meter of pressing ULDPE, ULDPE high-speed mixing 5～10min with 5～15 parts vinyl acetate between to for plastics and 100 parts places 5～10h with the material that mixes in encloses container; Then get 0.01～0.1 part initiator and acetone and be by weight and be mixed with mixing solutions in 1: 10～1: 20, again with mixing solutions and the mixture high-speed mixing 5～10min that places, at last by carrying out melting graft reaction in the twin screw extruder, 160～200 ℃ of temperature of reaction, reaction times 5～10min, extrude, cooling, granulation, obtain the vinyl acetate between to for plastic percentage of grafting and be 2%～9% ULDPE-g-VA grafts.
10. resin combination as claimed in claim 1, the preparation method who it is characterized in that the weather-proof master batch of described ULDPE comprises: the weight percent meter of pressing ULDPE, 100 parts ULDPE and 5～12 parts ULDPE-g-VA grafts, 0.5～1.0 part dispersion agent are put in the super mixer high-speed mixing 3～5min together; And then add 0.11～0.54 part composite light stabilizer, high-speed mixing 5～10min; Mixed material is added twin screw extruder, 165～210 ℃ of temperature of reaction, reaction times 3～5min extrudes, cooling, granulation, obtains the weather-proof master batch of ULDPE.
11. the preparation method of a resin combination as claimed in claim 1, it is characterized in that comprising: first with two kinds of crosslinking coagents composite rear adding solvent in proportion, add again the HDPE that accounts for total amount 5%～10% (wt), then behind high-speed mixing 3～5min, make the premix masterbatch; Then remaining HDPE, premix masterbatch and the weather-proof master batch of ULDPE are joined together by charging opening and carry out extrusion reaction in the forcing machine, temperature of reaction is 160～220 ℃, and the reaction times is 3～5min, extrudes, cooling, granulation, makes polyethylene resin composition.
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| CN104211862A (en) * | 2014-09-30 | 2014-12-17 | 山东瑞丰高分子材料股份有限公司 | Preparation method of grafted polyethylene |
| CN114479225A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Stress cracking resistant polyethylene sheath material for bridge cable and preparation method thereof |
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| US4614764A (en) * | 1985-03-06 | 1986-09-30 | Mobil Oil Corporation | Linear low density ethylene polymers blended with modified linear low density ethylene polymers |
| CN1135496A (en) * | 1995-05-11 | 1996-11-13 | 成都市柯力化工研究所 | Starch/polyethylene modified masterbatch |
| CN101143945A (en) * | 2007-09-04 | 2008-03-19 | 上海新上化高分子材料有限公司 | Color weatherable silane crosslinked polyethylene plastic and application thereof |
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| US4578431A (en) * | 1983-08-31 | 1986-03-25 | Mobil Oil Corporation | Process for improving melt strength of ethylene polymers by treatment with organic peroxide |
| US4614764A (en) * | 1985-03-06 | 1986-09-30 | Mobil Oil Corporation | Linear low density ethylene polymers blended with modified linear low density ethylene polymers |
| CN1135496A (en) * | 1995-05-11 | 1996-11-13 | 成都市柯力化工研究所 | Starch/polyethylene modified masterbatch |
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| CN104211862A (en) * | 2014-09-30 | 2014-12-17 | 山东瑞丰高分子材料股份有限公司 | Preparation method of grafted polyethylene |
| CN114479225A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Stress cracking resistant polyethylene sheath material for bridge cable and preparation method thereof |
| CN114479225B (en) * | 2020-10-23 | 2023-10-20 | 中国石油化工股份有限公司 | Stress cracking-resistant polyethylene sheath material for bridge cable and preparation method thereof |
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