CN103160022B - Special polyolefin resin composition for pipes - Google Patents
Special polyolefin resin composition for pipes Download PDFInfo
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- CN103160022B CN103160022B CN201110419924.1A CN201110419924A CN103160022B CN 103160022 B CN103160022 B CN 103160022B CN 201110419924 A CN201110419924 A CN 201110419924A CN 103160022 B CN103160022 B CN 103160022B
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- 239000011342 resin composition Substances 0.000 title claims abstract description 38
- 229920005672 polyolefin resin Polymers 0.000 title abstract description 4
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 63
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 63
- 238000002360 preparation method Methods 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 229920001084 poly(chloroprene) Polymers 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 238000005469 granulation Methods 0.000 claims abstract description 22
- 230000003179 granulation Effects 0.000 claims abstract description 22
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 5
- 229920005989 resin Polymers 0.000 claims description 46
- 239000011347 resin Substances 0.000 claims description 45
- 229920000098 polyolefin Polymers 0.000 claims description 35
- 238000002156 mixing Methods 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 28
- 239000003112 inhibitor Substances 0.000 claims description 19
- 230000003647 oxidation Effects 0.000 claims description 19
- 238000007254 oxidation reaction Methods 0.000 claims description 19
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 12
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 claims description 11
- -1 -isopropyl xanthogenic acid Chemical compound 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 7
- 235000013539 calcium stearate Nutrition 0.000 claims description 7
- 239000008116 calcium stearate Substances 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 claims description 2
- 230000003750 conditioning effect Effects 0.000 claims description 2
- 229920000578 graft copolymer Polymers 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002989 phenols Chemical group 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 abstract description 19
- 230000006353 environmental stress Effects 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 10
- 238000005336 cracking Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 238000005259 measurement Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical class CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002262 irrigation Effects 0.000 description 2
- 238000003973 irrigation Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004567 concrete Substances 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
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 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
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Rigid Pipes And Flexible Pipes (AREA)
Abstract
A polyolefin resin composition for pipes comprising, in one hundred percent by weight of high density polyethylene: 1) 100% high density polyethylene; 2) 8-18% of ULDPE-g-HEMA graft. 3)5 to 12 percent of chloroprene rubber. The ULDPE-g-HEMA graft contained in the composition is prepared by adopting bromine as an initiator and carrying out grafting reaction through a reactive extrusion process. The ULDPE-g-HEMA graft and CR are added into HDPE according to specific content, and the polyolefin resin composition for pipes is obtained after extrusion and granulation by a double screw extruder. The method improves the environmental stress cracking resistance (more than 5000 hours) of the high-density polyethylene, and expands the application of the high-density polyethylene in pipes or other fields. The invention further discloses a preparation method of the resin composition.
Description
Technical field
The present invention relates to the special polyolefine resin composition of a kind of tubing, be specifically related to resin based on high density polyethylene(HDPE) (HDPE), by second component ULDPE-g-HEMA grafts and three components chloroprene rubber (CR) modification, tubing polyolefin compositions preparing environmental stress cracking resistance excellence and preparation method thereof.
Background technology
In recent years, along with the development of plastics industry, polyvinyl piping materials is lightweight with it, corrosion-resistant, thermal conductivity is low, good insulation preformance, construction and installation and the feature such as easy to maintenance are more and more subject to people's attention, and become after PVC, the plastic conduit kind that world consumption amount is maximum, Application Areas is throughout fields such as engineering and oil field, chemical industry and post and telecommunications such as feedwater, agricultural irrigation, fuel gas transmission, blowdown, mine mortar conveyings.
In polyvinyl piping materials, high density polyethylene(HDPE) (HDPE) pipe has the features such as light weight, excellent in mechanical performance, crimp tendency and flexibility are excellent, is the tubing kind having competitive capacity most.But due to structure, the form of HDPE resin itself, tubing is easily caused to there will be fracture phenomena under certain hour, certain load effect, namely environmental stress cracking resistance (ESCR) is poor, thus have impact on the application of HDPE tubing in fields such as outdoor water supply pipe, gas line, irrigation pipes.Therefore, ESCR is the important indicator evaluating and affect the HDPE tubing life-span.
There are some researches show, the ESCR of HDPE resin is subject to the impact of the extraneous factor such as temperature, external force, but it is larger with the molecular weight of resin itself, molecular weight distribution, the degree of branching and the internal cause relation such as branch lengths, crystallization situation, therefore, in prior art, there is the angle from polymerization, by reactors in series, add the polyvinyl resin that the modes such as long-chain branch monomer, control reaction conditions, change catalyst system can produce high ESCR, as reports such as CN1903896, CN1513002.Although improve the ESCR performance effect of HDPE better by changing catalyst system, shortcoming is that research and development difficulty is large, and be only applicable to possess poly-unit large-scale petrochemical factory, small-sized petrochemical plant is difficult to carry out technique.From the angle of resin post-treatment modification, the more of the method application of the ESCR of material are improved by modulation resinous molecular structure, main path has two kinds: one to be mixed into the second component such as polyolefine, elastomerics in resin to carry out modification, the effect that second component plays refinement spherocrystal, reduces degree of crystallinity and stop crackle to stretch in polyethylene.The method is method the most frequently used at present, relevant report is more, as CN1556835, CN1247204, CN1262972, US2007282071 (A1), US2006276593 (A1), US2003088021 (A1), US7153909, WO0105852 (A1), JP57031945 (A) etc.Two is by chemical crosslinking modified, forms crosslinked structure, increases the connection between molecular chain, improves the environmental stress cracking resistance of polythene material.As CN2492729 adopts organosilane crosslinked polyethylene layer; The polyvinyl resin of two kinds of different molecular weights mixes by US4390666, and the polyethylene composition that recycling organo-peroxide carries out crosslinked preparation has good physical property, as having high rigidity, high ESCR, high impact resistance etc.Improved the patented technology of resin ESCR above by the modification of resin post-treatment, although simple process, be beneficial to enforcement, generally to the ESCR improved performance limited efficiency of HDPE, be generally no more than 2000 hours.
Summary of the invention
The object of the invention is to provide a kind of polyolefin resin composition for tubing, with HDPE resin for base-material, by the modification of second component ULDPE-g-HEMA grafts, and its molecular structure of modulation; Again by adding chloroprene rubber (CR), the crystallization behavior of adjustment HDPE molecule, thus make resin have good ESCR (> 5000 hours) performance.The present invention proposes the preparation method of resin combination further.
Particularly, in the weight of high density polyethylene(HDPE) for a hundred per cent, resin combination of the present invention comprises:
1) high density polyethylene(HDPE) of 100%, melt flow rate (MFR) 0.1 ~ 0.5g/10min;
2) the ULDPE-g-HEMA grafts of 8% ~ 18%;
3) chloroprene rubber (CR) of 5% ~ 12%.
Described ULDPE-g-HEMA grafts is the graft copolymer be grafted to by grafted monomer under the effect of initiator on ultra-low density polyethylene (ULDPE) main chain, and initiator is bromine (Br
2).Grafted monomer is hydroxyethyl methylacrylate (HEMA), purity > 99.5%.Polymkeric substance ULDPE is the multipolymer of the multipolymer of ethene and propylene, butylene, octene or hexene, optimal ethylene and butylene.Wherein melt flow rate (MFR) (MFR) is 0.1 ~ 20g/10min, and density (ρ) is 0.860 ~ 0.900g/cm
3;
Described melt flow rate (MFR) (MFR) is at 190 DEG C, the measured value under 2.16Kg load.
The preparation method of described ULDPE-g-HEMA grafts is: by the ULDPE high-speed mixing 5 ~ 10min of the hydroxyethyl methylacrylates of 10 ~ 20 parts (HEMA) with 100 parts, the material mixed is placed 12 ~ 24hr in encloses container; Then getting the bromine that accounts for material gross weight 0.2% ~ 0.4% in encloses container and ethanol is be mixed with mixing solutions at 1: 2.5 ~ 1: 5 by weight, again by mixing solutions and the mixture high-speed mixing 8 ~ 10min placed, melting graft reaction is carried out finally by twin screw extruder, temperature of reaction 140 ~ 220 DEG C, reaction times 6 ~ 8min, extrude, cool, granulation, obtain the ULDPE-g-HEMA grafts that HEMA percentage of grafting is 8% ~ 11%.
Described bromine is the technical purity of 99.7%, and can be commercially available prod, wherein chloride ion content be below 0.002%, and non-volatile matter is below 0.05%.
HDPE can be Alathon, also can be the multipolymer of ethene and 1% ~ 2% butene-1, general Mw:10 ~ 20 × 10
4; Mw/Mn:10 ~ 20, density 0.945 ~ 0.957g/cm
3.Can be powdery or granular resin, best with powdered resin.
Described chloroprene rubber (CR) is with curing di-isopropyl xanthogenic acid fat be conditioning agent chloroprene and dichloroprene multipolymer.Density 1.23g/cm
3, beige or granulated brown thing.
According to resin treatment needs in the present invention, in preparation process, the processing aid such as stearate stabilizers, oxidation inhibitor can be added.
Described stearate is selected from Zinic stearas or calcium stearate, for improvement of mobility and the stability of resin in Reaction extrusion process.In HDPE consumption for a hundred per cent, stearate consumption 0.1% ~ 0.15%.
Described oxidation inhibitor is phenols, hindered amines or phosphite ester kind antioxidant, conventional as antioxidant 1010, irgasfos 168, antioxidant 1076 and antioxidant 2246 etc., in HDPE consumption for absolutely, oxidation inhibitor consumption 0.1% ~ 0.2%, preferably 0.1% ~ 0.15%.
For meeting the needs of product application, in composition of the present invention, the various auxiliary agent such as UV light absorber or filler also can be added.
The preparation of resin combination can select various mixing roll, mixing machine, forcing machine as conversion unit, wherein, is prepared in suitability for industrialized production more feasible in an extruder.Select forcing machine as conversion unit, raw material can be adopted to be pre-mixed, carry out again reacting in forcing machine; Also the technique that raw material reacts in an extruder online can be adopted.Method was an example in the past, and concrete preparation process comprises the steps:
1) HDPE, ULDPE-g-HEMA grafts, CR, oxidation inhibitor, stearate are mixed 6 ~ 10 minutes in super mixer;
2) mixed raw material adds twin screw extruder, temperature of reaction 160 ~ 210 DEG C, reaction times 3 ~ 6min, extrudes, granulation obtains the special polyolefine resin composition of tubing.
Composition of the present invention, wherein containing second component ULDPE-g-HEMA grafts.Because ULDPE density is low, short-chain branch is many, can resist the invasion and attack of extraneous medium to a certain extent.But, because ULDPE is large due to intermolecular space, often easily assemble some amorphous substances and internal stress, cause the adaptive faculty of resin environment to external world enough not good.And ULDPE is by grafting HEMA, not only can increases branch lengths, but also effectively can reduce molecule gap, the content of amorphous substance is obviously reduced, greatly can reduce the susceptibility of resin medium to external world.In addition, owing to adding second component ULDPE-g-HEMA grafts in HDPE system, the phase of base resin is changed, ULDPE-g-HEMA grafts is evenly distributed in HDPE phase with extremely trickle island structure, long-chain branchs a large amount of in ULDPE-g-HEMA grafts penetrates in HDPE molecular grouping, greatly strengthen HDPE molecule effectively to tangle, avoid the generation of the secondary wafer of HDPE microlitic structure to a certain extent, have remarkable help to the ESCR performance improving composition.
Three components CR in composition adds, not only can reduce HDPE molecular gap, and a part of CR molecule segment during HDPE molecular crystal, can be clamped, these be further limit the diffusibility of neighbour's segment by the segment clamped, and make it more easily clamped by crystalline region and form blend.Destroyed the regularity of HDPE crystalline region by the segment clamped, melting range is broadened, degree of crystallinity declines, so the secondary wafer of HDPE microlitic structure can be suppressed to a certain extent to produce.Because the different segments of same CR molecule can be clamped by different crystalline regions, a molecule can pass multiple crystalline region and non-crystalline region, so also can play the effect connecting molecule, thus effectively improves composition ESCR performance.Owing to containing polarity and nonpolar segment in second component ULDPE-g-HEMA grafts molecule, therefore its existence effectively can help the consistency of HDPE and CR, that three components in composition are farthest uniformly dispersed, reduce the degree that phase is separated, make every physics of composition, chemical property obviously optimized.
In composition, second component ULDPE-g-HEMA grafts and the improved performance of three components CR to base resin HDPE are complementary, it not simple additive effect, but there is certain synergistic effect, net result is exactly the ESCR performance substantially improving HDPE resin.
This resin combination has good processibility, can without the tubing common pipe extruder group of any transformation stably processing various internal diameter, and tubing has good environmental stress cracking resistance (> 5000h), solve the problem of common HDPE resin environmental stress crack resistance deficiency.
Embodiment
1 raw material
Hydroxyethyl methylacrylate (HEMA) purity > 99.5%, BASF AG
Bromine (Br
2) purity > 99.7%, Shouguang Lu Yuan salinization
Nano level carbon black median size 22nm Tianjin Li Huajin Chemical Co., Ltd.
Aluminum oxide powder median size 25 μm of Solution on Chemical Reagents in Shanghai companies
The oxidation inhibitor B561 composite mixture of 1: 4 (antioxidant 1010 and the irgasfos 168 with) Switzerland's vapour Bagong department
2 performance test standards
3 equipment and instrument
The German Lestreiz company in Φ 67 twin-screw extrusion captain/footpath=34/1
10 liters of high-speed mixer Fuxin plastics machinery factories
Embodiment and comparative example
Enumerate following examples so that invention effect of the present invention to be described, but protection scope of the present invention is not limited in these embodiments, in composition, each component is with the weight parts of base resin HDPE.
Embodiment 1
(1) preparation of ULDPE-g-HEMA grafts: by the ULDPE high-speed mixing 8min of the hydroxyethyl methylacrylates of 12 parts (HEMA) with 100 parts, the material mixed is placed 24h in encloses container; Then the ethanol getting 0.25 part of bromine and 1 part is put into beaker and is mixed, then the solution mixed is put into 10L high-speed mixer together with the mixture placed, high-speed mixing 8min; Finally joined in Φ 67 twin screw extruder by the material mixed, screw zones temperature of reaction (DEG C) is followed successively by: 140, and 165,190,200,210,220,200,190,170; Carry out melting graft reaction, after reaction 6min, extrude, cool, granulation, obtained percentage of grafting is the ULDPE-g-HEMA grafts of 6.2%.
(2) preparation of the special polyolefine resin composition of tubing: be ULDPE-g-HEMA grafts and 5 parts of CR of 8.6% by 8 parts of percentage of grafting, 0.15 part of oxidation inhibitor B561, 0.1 part of Zinic stearas puts into 10L high-speed mixer together with 100 parts of HDPE resins, high-speed mixing 10min, then mixed material is joined in Φ 67 twin screw extruder by charging opening, be followed successively by barrel temperature (DEG C): 160, 180, 195, 200, 210, 210, 200, 185, 175, after extrusion reaction 3min, extrude, cooling, granulation, prepare the special polyolefine resin composition of tubing.The environmental stress crack resistance energy of said composition can more than 5000h, and its quantitative measurement the results are shown in Table 1.
Embodiment 2
(1) preparation of ULDPE-g-HEMA grafts is identical with embodiment 1.
(2) preparation of the special polyolefine resin composition of tubing: by 13 parts of percentage of grafting be 8.6% ULDPE-g-HEMA grafts put into 10L high-speed mixer with 8.5 parts of CR together with 100 parts of HDPE resins, high-speed mixing 8min, then mixed material is joined in Φ 67 twin screw extruder by charging opening, be followed successively by barrel temperature (DEG C): 160,180,195,200,210,210,200,185,175, after extrusion reaction 4min, extrude, cool, granulation, prepare the special polyolefine resin composition of tubing.The environmental stress crack resistance energy of said composition can more than 5000h, and its quantitative measurement the results are shown in Table 1.
Embodiment 3
(1) preparation of ULDPE-g-HEMA grafts is identical with embodiment 1.
(2) preparation of the special polyolefine resin composition of tubing: be ULDPE-g-HEMA grafts and 12 parts of CR of 8.6% by 18 parts of percentage of grafting, 0.15 part of oxidation inhibitor B561, 0.1 part of Zinic stearas puts into 10L high-speed mixer together with 100 parts of HDPE resins, high-speed mixing 9min, then mixed material is joined in Φ 67 twin screw extruder by charging opening, be followed successively by barrel temperature (DEG C): 160, 180, 195, 200, 210, 210, 200, 185, 175, after extrusion reaction 6min, extrude, cooling, granulation, prepare the special polyolefine resin composition of tubing.The environmental stress crack resistance energy of said composition can more than 5000h, and its quantitative measurement the results are shown in Table 1.
Embodiment 4
(1) preparation of ULDPE-g-HEMA grafts: by the ULDPE high-speed mixing 10min of the hydroxyethyl methylacrylates of 18 parts (HEMA) with 100 parts, the material mixed is placed 24h in encloses container; Then the ethanol getting 0.4 part of bromine and 2 parts is put into beaker and is mixed, then the solution mixed is put into 10L high-speed mixer together with the mixture placed, high-speed mixing 10min; Finally joined in Φ 67 twin screw extruder by the material mixed, screw zones temperature of reaction (DEG C) is followed successively by: 140, and 165,190,200,210,220,200,190,170; Carry out melting graft reaction, after reaction 8min, extrude, cool, granulation, obtained percentage of grafting is the ULDPE-g-HEMA grafts of 10.2%.
(2) preparation of the special polyolefine resin composition of tubing: be ULDPE-g-HEMA grafts and 5 parts of CR of 10.2% by 8 parts of percentage of grafting, 0.15 part of oxidation inhibitor B561, 0.1 part of calcium stearate puts into 10L high-speed mixer together with 100 parts of HDPE resins, high-speed mixing 6min, then mixed material is joined in Φ 67 twin screw extruder by charging opening, be followed successively by barrel temperature (DEG C): 160, 180, 195, 200, 210, 210, 200, 185, 175, after extrusion reaction 3min, extrude, cooling, granulation, prepare the special polyolefine resin composition of tubing.The environmental stress crack resistance energy of said composition can more than 5000h, and its quantitative measurement the results are shown in Table 1.
Embodiment 5
(1) preparation of ULDPE-g-HEMA grafts is identical with embodiment 4.
(2) preparation of the special polyolefine resin composition of tubing: by 13 parts of percentage of grafting be 10.2% ULDPE-g-HEMA grafts put into 10L high-speed mixer with 8.5 parts of CR together with 100 parts of HDPE resins, high-speed mixing 8min, then mixed material is joined in Φ 67 twin screw extruder by charging opening, be followed successively by barrel temperature (DEG C): 160,180,195,200,210,210,200,185,175, after extrusion reaction 5min, extrude, cool, granulation, prepare the special polyolefine resin composition of tubing.The environmental stress crack resistance energy of said composition can more than 5000h, and its quantitative measurement the results are shown in Table 1.
Embodiment 6
(1) preparation of ULDPE-g-HEMA grafts is identical with embodiment 4.
(2) preparation of the special polyolefine resin composition of tubing: be ULDPE-g-HEMA grafts and 12 parts of CR of 10.2% by 18 parts of percentage of grafting, 0.15 part of oxidation inhibitor B561, 0.1 part of calcium stearate puts into 10L high-speed mixer together with 100 parts of HDPE resins, high-speed mixing 10min, then mixed material is joined in Φ 67 twin screw extruder by charging opening, be followed successively by barrel temperature (DEG C): 160, 180, 195, 200, 210, 210, 200, 185, 175, after extrusion reaction 6min, extrude, cooling, granulation, prepare the special polyolefine resin composition of tubing.The environmental stress crack resistance energy of said composition can more than 5000h, and its quantitative measurement the results are shown in Table 1.
Comparative example 1
Resin-made is standby: putting into 10L high-speed mixer, high-speed mixing 10min by not adding together with the pure HDPE resin 100 parts of any ULDPE-g-HEMA grafts with CR, 0.15 part of oxidation inhibitor B561,0.1 part of Zinic stearas, then joining in Φ 67 twin screw extruder by mixed material by charging opening, be followed successively by barrel temperature (DEG C): 160,180,195,200,210,210,200,185,175, after extrusion reaction 3min, extrude, cool, granulation, prepare corresponding resin.Its quantitative measurement the results are shown in Table 1.
Comparative example 2
(1) preparation of ULDPE-g-HEMA grafts is identical with embodiment 1.
(2) preparation of the special polyolefine resin composition of tubing: by 13 parts of percentage of grafting be 8.6% ULDPE-g-HEMA grafts put into 10L high-speed mixer together with 100 parts of HDPE resins, high-speed mixing 10min, then mixed material is joined in Φ 67 twin screw extruder by charging opening, be followed successively by barrel temperature (DEG C): 160,180,195,200,210,210,200,185,175, after extrusion reaction 4min, extrude, cool, granulation, prepare the special polyolefine resin composition of tubing, its quantitative measurement the results are shown in Table 1.
Comparative example 3
(1) preparation of ULDPE-g-HEMA grafts is identical with embodiment 4.
(2) preparation of the special polyolefine resin composition of tubing: be the ULDPE-g-HEMA grafts of 10.2% by 18 parts of percentage of grafting, 0.15 part of oxidation inhibitor B561, 0.1 part of calcium stearate puts into 10L high-speed mixer together with 100 parts of HDPE resins, high-speed mixing 10min, then mixed material is joined in Φ 67 twin screw extruder by charging opening, be followed successively by barrel temperature (DEG C): 160, 180, 195, 200, 210, 210, 200, 185, 175, after extrusion reaction 5min, extrude, cooling, granulation, prepare the special polyolefine resin composition of tubing, its quantitative measurement the results are shown in Table 1.
Comparative example 4
The preparation of the special polyolefine resin composition of tubing: 8.5 parts of CR, 0.15 part of oxidation inhibitor B561,0.1 part of Zinic stearas are put into 10L high-speed mixer together with 100 parts of HDPE resins, high-speed mixing 10min, then mixed material is joined in Φ 67 twin screw extruder by charging opening, be followed successively by barrel temperature (DEG C): 160,180,195,200,210,210,200,185,175, after extrusion reaction 3min, extrude, cool, granulation, prepare the special polyolefine resin composition of tubing, its quantitative measurement the results are shown in Table 1.
Comparative example 5
The preparation of the special polyolefine resin composition of tubing: 5 parts of CR, 0.15 part of oxidation inhibitor B561,0.1 part of calcium stearate are put into 10L high-speed mixer together with 100 parts of HDPE resins, high-speed mixing 10min, then mixed material is joined in Φ 67 twin screw extruder by charging opening, be followed successively by barrel temperature (DEG C): 160,180,195,200,210,210,200,185,175, after extrusion reaction 6min, extrude, cool, granulation, prepare the special polyolefine resin composition of tubing, its quantitative measurement the results are shown in Table 1.
Comparative example 6
(1) preparation of ULDPE-g-HEMA grafts is identical with embodiment 1.
(2) preparation of the special polyolefine resin composition of tubing: by 3 parts of percentage of grafting be 8.6% ULDPE-g-HEMA grafts put into 10L high-speed mixer with 8.5 parts of CR together with 100 parts of HDPE resins, high-speed mixing 10min, then mixed material is joined in Φ 67 twin screw extruder by charging opening, be followed successively by barrel temperature (DEG C): 160, 180, 195, 200, 210, 210, 200, 185, 175, after extrusion reaction 3min, extrude, cooling, granulation, prepare the special polyolefine resin composition of tubing, its quantitative measurement the results are shown in Table 1.
Comparative example 7
(1) preparation of ULDPE-g-HEMA grafts is identical with embodiment 1.
(2) preparation of the special polyolefine resin composition of tubing: be ULDPE-g-HEMA grafts and 8.5 parts of CR of 8.6% by 22 parts of percentage of grafting, 0.15 part of oxidation inhibitor B561, 0.1 part of calcium stearate puts into 10L high-speed mixer together with 100 parts of HDPE resins, high-speed mixing 10min, then mixed material is joined in Φ 67 twin screw extruder by charging opening, be followed successively by barrel temperature (DEG C): 160, 180, 195, 200, 210, 210, 200, 185, 175, after extrusion reaction 6min, extrude, cooling, granulation, prepare the special polyolefine resin composition of tubing, its quantitative measurement the results are shown in Table 1.
Comparative example 8
(1) preparation of ULDPE-g-HEMA grafts is identical with embodiment 1.
(2) preparation of the special polyolefine resin composition of tubing: be ULDPE-g-HEMA grafts and 2 parts of CR of 8.6% by 13 parts of percentage of grafting, 0.15 part of oxidation inhibitor B561, 10L high-speed mixer put into by 0.1 part of Zinic stearas, 100 parts of HDPE resins together, high-speed mixing 10min, then mixed material is joined in Φ 67 twin screw extruder by charging opening, be followed successively by barrel temperature (DEG C): 160, 180, 195, 200, 210, 210, 200, 185, 175, after extrusion reaction 5min, extrude, cooling, granulation, prepare the special polyolefine resin composition of tubing, its quantitative measurement the results are shown in Table 1.
Comparative example 9
(1) preparation of ULDPE-g-HEMA grafts is identical with embodiment 1.
(2) preparation of the special polyolefine resin composition of tubing: by 13 parts of percentage of grafting be 8.6% ULDPE-g-HEMA grafts put into 10L high-speed mixer with 15 parts of CR together with 100 parts of HDPE resins, high-speed mixing 10min, then mixed material is joined in Φ 67 twin screw extruder by charging opening, be followed successively by barrel temperature (DEG C): 160, 180, 195, 200, 210, 210, 200, 185, 175, after extrusion reaction 6min, extrude, cooling, granulation, prepare the special polyolefine resin composition of tubing, its quantitative measurement the results are shown in Table 1.
Table 1 test result
Claims (9)
1. a polyolefine resin composition, to is characterized in that in the weight of high density polyethylene(HDPE) for absolutely, comprising:
1) high density polyethylene(HDPE) of 100%, melt flow rate (MFR) 0.1 ~ 0.5g/10min;
2) the ULDPE-g-HEMA grafts of 8% ~ 18%;
3) chloroprene rubber of 5% ~ 12%;
Described ULDPE-g-HEMA grafts be under the effect of initiator by monomer-grafted for hydroxyethyl methylacrylate to the graft copolymer on ultra-low density polyethylene main chain.
2. resin combination as claimed in claim 1, is characterized in that described initiator is bromine.
3. resin combination as claimed in claim 1, is characterized in that described chloroprene rubber is with curing di-isopropyl xanthogenic acid fat be conditioning agent chloroprene and dichloroprene multipolymer.
4. resin combination as claimed in claim 1, it is characterized in that the preparation method of described ULDPE-g-HEMA grafts is: by the ULDPE high-speed mixing 5 ~ 10min of the hydroxyethyl methylacrylate of 10 ~ 20 weight parts and 100 weight parts, the material mixed is placed 12 ~ 24h in encloses container; Then getting the bromine that accounts for material gross weight 0.2% ~ 0.4% in encloses container and ethanol is be mixed with mixing solutions at 1: 2.5 ~ 1: 5 by weight, again by mixing solutions and the mixture high-speed mixing 8 ~ 10min placed, melting graft reaction is carried out finally by twin screw extruder, temperature of reaction 140 ~ 220 DEG C, reaction times 6 ~ 8min, extrude, cool, granulation, obtain the ULDPE-g-HEMA grafts that hydroxyethyl methylacrylate percentage of grafting is 8% ~ 11%.
5. a preparation method for resin combination as claimed in claim 1, comprises the steps:
1) HDPE, ULDPE-g-HEMA grafts, chloroprene rubber are mixed 6 ~ 10min in super mixer;
2) mixed raw material adds twin screw extruder, temperature of reaction 160 ~ 210 DEG C, reaction times 3 ~ 6min, extrudes, granulation obtains the special polyolefine resin composition of tubing.
6. preparation method as claimed in claim 5, is characterized in that adding stearate stabilizers and oxidation inhibitor in resin combination preparation process.
7. preparation method as claimed in claim 5, is characterized in that described stearate is selected from Zinic stearas or calcium stearate, and in HDPE weight for a hundred per cent, stearate consumption is 0.1% ~ 0.15%.
8. preparation method as claimed in claim 5, is characterized in that described oxidation inhibitor is phenols, hindered amines or phosphite ester kind antioxidant, in HDPE weight for a hundred per cent, and oxidation inhibitor consumption 0.1% ~ 0.2%.
9. preparation method as claimed in claim 5, is characterized in that described oxidation inhibitor is selected from antioxidant 1010, irgasfos 168, antioxidant 1076 or antioxidant 2246.
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|---|---|---|---|
| CN201110419924.1A CN103160022B (en) | 2011-12-15 | 2011-12-15 | Special polyolefin resin composition for pipes |
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| CN201110419924.1A CN103160022B (en) | 2011-12-15 | 2011-12-15 | Special polyolefin resin composition for pipes |
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| CN103160022B true CN103160022B (en) | 2015-02-25 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1240456A (en) * | 1996-10-18 | 2000-01-05 | 金伯利-克拉克环球有限公司 | Polyolefins having greater than 5 percent 2-hydroxyethyl methacrylate grafted thereto |
| CN102276891A (en) * | 2010-06-11 | 2011-12-14 | 中国石油天然气股份有限公司 | Polyolefin resin composition for pipe |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1240456A (en) * | 1996-10-18 | 2000-01-05 | 金伯利-克拉克环球有限公司 | Polyolefins having greater than 5 percent 2-hydroxyethyl methacrylate grafted thereto |
| CN102276891A (en) * | 2010-06-11 | 2011-12-14 | 中国石油天然气股份有限公司 | Polyolefin resin composition for pipe |
Non-Patent Citations (1)
| Title |
|---|
| 氯丁橡胶/高密度聚乙烯共混物的研究;方征平;《合成橡胶工业》;19930829;第16卷(第4期);第224页摘要 * |
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