CN103160005B - Special polyolefin resin composition for tubing - Google Patents
Special polyolefin resin composition for tubing Download PDFInfo
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- CN103160005B CN103160005B CN201110419925.6A CN201110419925A CN103160005B CN 103160005 B CN103160005 B CN 103160005B CN 201110419925 A CN201110419925 A CN 201110419925A CN 103160005 B CN103160005 B CN 103160005B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- Rigid Pipes And Flexible Pipes (AREA)
Abstract
A polyolefin resin composition for tubing comprises, calculated by the weight of high density polyethylene being 100%, 1) 100% of the high density polyethylene with melt flow rate of 0.1-0.5g / 10min and density of 0.945-0.957g / cm<3>, 2) 8%-18% of a ULDPE-G-HEMA graft, and 3) 2%-5% of nanometer carbon black / alumina composite. The ULDPE-G-HEMA graft contained in the composition employs bromine as an initiator, and is prepared by a graft reaction through a reactive extrusion process. The method improves environmental stress cracking resistance of the high density polyethylene (longer than 5000 h) and expands application of the high density polyethylene to tubing or other fields. The invention further discloses a preparation method of the resin composition.
Description
Technical field
The present invention relates to a kind of polyolefin resin composition for tubing, be specifically related to resin based on high density polyethylene(HDPE) (HDPE), by second component ULDPE-g-HEMA grafts and three components nano level carbon black/alumina composite material 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; Add and add nano level carbon black/alumina compound, the space structure 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) the nano level carbon black/alumina compound of 2% ~ 5%.
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 hydroxyethyl methylacrylate (HEMA) of 10 ~ 20 weight parts and the ULDPE high-speed mixing 5 ~ 10min of 100 weight parts, the material mixed is placed 12 ~ 24h in encloses container; Then the bromine that accounts for material gross weight 0.20% ~ 0.40% in encloses container is got and mixing solutions made by ethanol, the weight ratio of bromine and ethanol is 1: 2.5 ~ 1: 5, 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, extrudes, cools, granulation, obtains 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.
The preparation method of described nano level carbon black/alumina compound is: by 40 ~ 70 weight parts, preferably 50 ~ 60 weight part nano level carbon blacks and 100 parts by weight of alumina powder add the mixed device high speed of 1L height and mix 8 ~ 10min, load sealed vessel after taking out stand-by, obtain carbon black/alumina compound.Wherein the particle diameter of nano level carbon black is 15 ~ 30nm, and the particle diameter of aluminum oxide is 20 ~ 35 μm, and purity is 99.8%.
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, nano level carbon black/alumina compound, oxidation inhibitor, stearate 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.
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.
Adding of the three components in composition-nano level carbon black/alumina compound, not only can reduce HDPE molecular gap, the secondary wafer of HDPE microlitic structure can also be suppressed to a certain extent to produce, thus effectively improve composition ESCR performance.Nano level particle size carbon black is little, and specific surface area is very large, caking of thus easily reuniting.The method adopting the larger aluminum oxide of particle diameter (20 ~ 35 μm) to mix with nano level carbon black in the present invention can address this problem to a certain extent: rely on the physical force such as Van der Waals force, hydrogen bond, nano level carbon black meeting uniform adsorption is at Membranes On Alumina Particles Surface, alumina surface is made to form the coated film of one deck nanometer, thus the activity of nanoparticle is reduced due to the existence of aluminum oxide, as long as adjust the proportioning of nano level carbon black and aluminum oxide, the agglomeration of nano level carbon black just obviously can be improved.
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: by the ULDPE high-speed mixing 10min 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 nano level carbon black/alumina compound: 50 parts of nano level carbon blacks and 100 parts of alumina powders are added the mixed device high speed of 1L height and mix 10min, put into sealed vessel after taking-up, obtain carbon black/alumina compound.
(3) preparation of the special polyolefine resin composition of tubing: be the ULDPE-g-HEMA grafts of 8.6% by 8 parts of percentage of grafting, 2 parts of nano level carbon black/alumina compounds, 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 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 2
(1) preparation of ULDPE-g-HEMA is identical with embodiment 1.
(2) preparation of nano level carbon black/alumina compound is identical with embodiment 1.
(3) 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 3.5 parts of nano level carbon black/alumina compounds 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, 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 3
(1) preparation of ULDPE-g-HEMA is identical with embodiment 1.
(2) preparation of nano level carbon black/alumina compound is identical with embodiment 1.
(3) preparation of the special polyolefine resin composition of tubing: be the ULDPE-g-HEMA grafts of 8.6% by 18 parts of percentage of grafting, 5 parts of nano level carbon black/alumina compounds, 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 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: by the ULDPE high-speed mixing 5min of the hydroxyethyl methylacrylates of 18 parts (HEMA) with 100 parts, the material mixed is placed 12h 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 nano level carbon black/alumina compound: 60 parts of nano level carbon blacks and 100 parts of alumina powders are added the mixed device high speed of 1L height and mix 8 ~ 10min, put into sealed vessel after taking-up, obtain carbon black/alumina compound.
(3) preparation of the special polyolefine resin composition of tubing: be the ULDPE-g-HEMA grafts of 10.2% by 8 parts of percentage of grafting, 2 parts of nano level carbon black/alumina compounds, 0.1 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 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 is identical with embodiment 4.
(2) preparation of nano level carbon black/alumina compound is identical with embodiment 4.
(3) 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 3.5 parts of nano level carbon black/alumina compounds 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 4min, 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 6
(1) preparation of ULDPE-g-HEMA is identical with embodiment 4.
(2) preparation of nano level carbon black/alumina compound is identical with embodiment 4.
(3) 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, 5 parts of nano level carbon black/alumina compounds, 0.2 part of oxidation inhibitor B561, 0.15 part of calcium stearate puts into 10L high-speed mixer 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 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 7
(1) preparation of ULDPE-g-HEMA is identical with embodiment 1.
(2) preparation of nano level carbon black/alumina compound is identical with embodiment 4.
(3) preparation of the special polyolefine resin composition of tubing: by 8 parts of percentage of grafting be 8.6% ULDPE-g-HEMA grafts put into 10L high-speed mixer with 2 parts of nano level carbon black/alumina compounds 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.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 8
(1) preparation of ULDPE-g-HEMA is identical with embodiment 4.
(2) preparation of nano level carbon black/alumina compound is identical with embodiment 1.
(3) preparation of the special polyolefine resin composition of tubing: be the ULDPE-g-HEMA grafts of 8.6% by 18 parts of percentage of grafting, 5 parts of nano level carbon black/alumina compounds, 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 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 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: put into 10L high-speed mixer by not adding together with the pure HDPE resin 100 parts of any ULDPE-g-HEMA grafts with nano level carbon black/alumina compound, 0.15 part of oxidation inhibitor B561,0.1 part of Zinic stearas, 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, cool, granulation, prepare corresponding resin.Its quantitative measurement the results are shown in Table 1.
Comparative example 2
(1) preparation of ULDPE-g-HEMA 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 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, its quantitative measurement the results are shown in Table 1.
Comparative example 3
(1) preparation of ULDPE-g-HEMA is identical with embodiment 4.
(2) preparation of the special polyolefine resin composition of tubing: be the ULDPE-g-HEMA grafts of 8.6% 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 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 6min, extrude, cooling, granulation, prepare the special polyolefine resin composition of tubing, its quantitative measurement the results are shown in Table 1.
Comparative example 4
(1) preparation of nano level carbon black/alumina compound is identical with embodiment 1.
(2) preparation of the special polyolefine resin composition of tubing: by 2 parts of nano level carbon black/alumina compounds, 0.1 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 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, its quantitative measurement the results are shown in Table 1.
Comparative example 5
(1) preparation of nano level carbon black/alumina compound is identical with embodiment 4.
(2) preparation of the special polyolefine resin composition of tubing: 5 parts of nano level carbon black/alumina compounds are put into 10L high-speed mixer 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 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 is identical with embodiment 1.
(2) preparation of nano level carbon black/alumina compound is identical with embodiment 1.
(3) preparation of the special polyolefine resin composition of tubing: be the ULDPE-g-HEMA grafts of 8.6% by 3 parts of percentage of grafting, 3.5 parts of nano level carbon black/alumina compounds, 0.2 part of oxidation inhibitor B561, 0.15 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, its quantitative measurement the results are shown in Table 1.
Comparative example 7
(1) preparation of ULDPE-g-HEMA is identical with embodiment 1.
(2) preparation of nano level carbon black/alumina compound is identical with embodiment 1.
(3) preparation of the special polyolefine resin composition of tubing: by 22 parts of percentage of grafting be 8.6% ULDPE-g-HEMA grafts put into 10L high-speed mixer with 3.5 parts of nano level carbon black/alumina compounds 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, 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 is identical with embodiment 1.
(2) preparation of nano level carbon black/alumina compound is identical with embodiment 1.
(3) preparation of the special polyolefine resin composition of tubing: be the ULDPE-g-HEMA grafts of 8.6% by 13 parts of percentage of grafting, 1 part of nano level carbon black/alumina compound, 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 9
(1) preparation of ULDPE-g-HEMA is identical with embodiment 1.
(2) preparation of nano level carbon black/alumina compound is identical with embodiment 1.
(3) 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 7 parts of nano level carbon black/alumina compounds 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. the special polyolefine resin composition of tubing, 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) is 0.1 ~ 0.5g/10min;
2) the ULDPE-g-HEMA grafts of 8% ~ 18%;
3) the nano level carbon black/alumina compound of 2% ~ 5%;
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, 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 the bromine that accounts for material gross weight 0.20% ~ 0.40% in encloses container is got and mixing solutions made by ethanol, the weight ratio of bromine and ethanol is 1: 2.5 ~ 1: 5, 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, extrudes, cools, granulation, obtains the ULDPE-g-HEMA grafts that HEMA percentage of grafting is 8% ~ 11%.
3. resin combination as claimed in claim 1, is characterized in that described initiator is bromine.
4. resin combination as claimed in claim 1, it is characterized in that the preparation method of described nano level carbon black/alumina compound is: stand-by by loading sealed vessel after 40 ~ 70 weight part nano level carbon blacks and 100 parts by weight of alumina powder high-speed mixing 8 ~ 10min, obtaining carbon black/alumina compound.
5. resin combination as claimed in claim 1, it is characterized in that the particle diameter of wherein nano level carbon black is 15 ~ 30nm, the particle diameter of aluminum oxide is 20 ~ 35 μm.
6. the preparation method of resin combination as claimed in claim 1, is characterized in that comprising the steps:
1) HDPE, ULDPE-g-HEMA grafts, nano level carbon black/alumina compound 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.
7. preparation method as claimed in claim 6, is characterized in that adding stearate stabilizers, oxidation inhibitor in resin combination preparation process.
8. preparation method as claimed in claim 7, is characterized in that described stearate is selected from Zinic stearas or calcium stearate, and in HDPE consumption for a hundred per cent, consumption is 0.1% ~ 0.15%.
9. preparation method as claimed in claim 7, is characterized in that described oxidation inhibitor is phenols, hindered amines or phosphite ester kind antioxidant, and in HDPE consumption for a hundred per cent, oxidation inhibitor consumption is 0.1% ~ 0.2%.
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| CN1827682A (en) * | 2006-03-28 | 2006-09-06 | 华南理工大学 | Process for preparing predispersed masterbatch of polyolefin and nano calcium carbonate |
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