CN100595229C - Polyethylene color masterbatch and preparing method thereof - Google Patents
Polyethylene color masterbatch and preparing method thereof Download PDFInfo
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- CN100595229C CN100595229C CN200710176685A CN200710176685A CN100595229C CN 100595229 C CN100595229 C CN 100595229C CN 200710176685 A CN200710176685 A CN 200710176685A CN 200710176685 A CN200710176685 A CN 200710176685A CN 100595229 C CN100595229 C CN 100595229C
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- -1 Polyethylene Polymers 0.000 title claims abstract description 71
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 69
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 69
- 239000004595 color masterbatch Substances 0.000 title claims description 36
- 238000000034 method Methods 0.000 title description 25
- 239000006229 carbon black Substances 0.000 claims abstract description 69
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 58
- 239000011347 resin Substances 0.000 claims abstract description 52
- 229920005989 resin Polymers 0.000 claims abstract description 52
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 36
- 229920002313 fluoropolymer Polymers 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000003647 oxidation Effects 0.000 claims description 19
- 238000007254 oxidation reaction Methods 0.000 claims description 19
- 239000003112 inhibitor Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 12
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000011164 primary particle Substances 0.000 claims description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007983 Tris buffer Substances 0.000 claims description 3
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 claims description 2
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 claims description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 11
- 230000032683 aging Effects 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003754 machining Methods 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000003723 Smelting Methods 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 description 38
- 238000004519 manufacturing process Methods 0.000 description 34
- 238000012545 processing Methods 0.000 description 20
- 229920002554 vinyl polymer Polymers 0.000 description 17
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- 239000006185 dispersion Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 239000004594 Masterbatch (MB) Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
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- 238000009826 distribution Methods 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- 239000006057 Non-nutritive feed additive Substances 0.000 description 3
- 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 compound 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 description 3
- 239000003738 black carbon Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002706 hydrostatic effect Effects 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 230000008774 maternal effect Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 241001481833 Coryphaena hippurus Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
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- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
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- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004643 material aging Methods 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
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- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention is one kind of polyethylene premix and its preparation process. The polyethylene premix includes high density polyethylene resin in 100 weight portions, carbon lack of average grain size not greater than 25 nm in 35-100 weight portions, fluorocarbon polymer in 0-10 weight portions, and antioxidant of hindered phenol and/or phosphite in 0-15 weight portions. The polyethylene premix with high carbon black content is prepared through banburing and smelting. It may be mixed with polyethylene matrix to obtain mixed material with excellent carbon black dispersivity, excellent ultraviolet ageing resistance, high heat and oxygen stability, good machining performance, low cost and high performance.
Description
Technical field
The present invention relates to a kind of polyethylene color masterbatch, be specifically related to a kind of polyethylene pressure pipeline and use carbonarius mother and preparation method thereof.
Background technology
PE100 is the rank of the polyethylene pipe resin that at present in the world pressure rating is the highest,, is used at least 50 years under 10MPa ring stress by the tubing of this resins.Transport, deposit, under the outdoor condition such as construction, degradation with aging can take place in the true qualities polyvinyl piping materials, mechanical property descends, iso standard and national Specification, gas pipeline and the feedwater piping of producing the PE100 level must use the black mixed ingredients.The carbon black of mixed ingredients should adopt the carbon black of particle diameter less than 25nm, and content of carbon black is not less than 2.0%, and carbon black dispersion is smaller or equal to 3 grades.
The production of polyvinyl piping materials black mixed ingredients has two kinds of methods: the one, directly in polyvinyl resin, add the production of carbon black mixed ingredients, and the 2nd, produce mixed ingredients with the carbonarius master batch.The production of the special-purpose black polyethylene mixed ingredients of PE100 level polyvinyl piping materials is to add the melt blending preparation of PE100 level polyvinyl piping materials black carbon special look female by polyethylene powder or this chromoresin.The nearly all tubing mixed ingredients manufacturing enterprise of China adopts carbonarius master batch production pipes-black mixed ingredients.Shanghai petrochemical industry and Qilu Petrochemical adopt true qualities PE100 resin and the female blend of the PE100 level carbonarius of import separately respectively, have developed the PE100 level black mixed ingredients trade mark.
Domestic production carbonarius mother's enterprise is a lot, but product mainly is positioned traditional products such as farmland film, rubbish packing bag and dyeing of plastics.The polythene material that uses in these fields does not need too high anti-pressure ability.So used carbonarius mother's base material all is to use ldpe resin (LDPE).This resin melt fluidity is good, is easy to process the high look mother of content of carbon black.But because PE100 level polyvinyl piping materials needs very high compressive property, also require its used carbonarius mother's base material to have higher intensity thus, therefore need select for use high density polyethylene(HDPE) (HDPE) as base material.But the melt fluidity of HDPE is relatively poor, often can't process when adding a large amount of carbon black therein.
China does not still have PE100 level polyvinyl piping materials black carbon special look mother, and the PE100 black mixed ingredients of adopt the exploitation of domestic carbon black masterbatch, producing also is in blank.The auspicious clear technology of having studied experimental technique, prescription and the production of the special-purpose black agglomerate of PE63 level polyethylene HDPE tubing in a Tsing-Hua University left side, and delivered Master's thesis " development of the special-purpose black agglomerate of polyethylene HDPE tubing " (Tsing-Hua University's Master's thesis 2001, p.1-54).Literature research be vector resin with HDPE and LDPE, add the influence of antioxidant to pipe performance.The content of carbon black 30%wt of its finished product, dispersity of carbon black is smaller or equal to 3.For the carbonarius mother that can make HDPE can process, it adds the 20%wt polyethylene wax of look female gross weight in the look mother, but, can only satisfy the requirement of PE63 level because the adding of lubricant such as polyethylene wax makes the requirement that compressive property by the polyvinyl piping materials of the black mixed ingredients preparation that contains this kind carbonarius mother does not reach the PE100 level.
The PE100 level polyvinyl piping materials black mixed ingredients of China is all produced by the black carbon special look of external import is female at present.The female price height of external PE100 carbonarius has had a strong impact on popularization, the application of China PE100 black mixed ingredients.
Summary of the invention
At the problems of the prior art, the invention provides a kind of polyethylene carbon black function look mother of the PE100 of can be used for level polyvinyl piping materials.This look mother includes small particle size carbon black smaller or equal to 25nm, can also contain compound heat stabilizing system, can also be processing aid with fluorocarbon polymer (PPA).The purpose of this invention is to provide a kind of is the high density carbonarius mother of matrix with the high-density polyethylene resin, this look mother is prepared mixed ingredients with PE tubing base-material by melt blending, adopt conventional screw rod pipe extruder to extrude mixed ingredients again, just can obtain the polyvinyl piping materials of good reached at the PE100 level of carbon black dispension degree.
Another object of the present invention provides described high density polyethylene(HDPE) carbonarius mother's preparation method, and technology is simple, and processing ease is suitable for industrial application.
A kind of polyethylene color masterbatch of the present invention includes the following component of blend: a. high-density polyethylene resin, b. carbon black.Be 100 parts in component a high-density polyethylene resin parts by weight wherein, described carbon black is 35～100 parts, is preferably 60～85 parts by weight.
The type of matrix resin has very big influence to the long-term hydrostatic performance of plastic conduit black mixed ingredients.Having only the high density polyethylene(HDPE) of employing is the load performance that matrix resin could guarantee PE100 level tubing.In order to cooperate the bearing requirements of PE100 level tubing, the vector resin of polyethylene color masterbatch of the present invention is also selected high-density polyethylene resin for use.
Compare with ldpe resin or linear low density polyethylene resin, high-density polyethylene resin is big as its density of look maternal carrier resin, and hardness is big, fusing point is high, is unfavorable for that sooty disperses, difficulty of processing height when producing the carbonarius mother.So for the sooty choice relation to the dispersiveness of carbon black in high-density polyethylene resin and a key of the female processing characteristics quality of look.Carbon black is a kind of nano material, and its primary particle diameter between 10～100nm, is a kind of efficient UV light absorber and photomask agent generally.When polyethylene pipe was exposed to outdoor use, high-octane UV-light can make the polymkeric substance chain rupture, produced free radical, atarting material aging.Be dispersed in that carbon black can shield UV-light in the polyethylene, improved aging resistance of materials.The sooty particle diameter is more little, content of carbon black is high more, and its surface-area is big more, and light aging resisting property is good more.Yet particle size carbon black is too small, and surface-area is excessive, can make to disperse the difficulty that becomes, and is difficult to processing.The carbon black of the above components b can comprise disclosed all kinds carbon black in the prior art.For the tubing goods of long-term weatherability requirement are arranged, generally select the carbon black of average primary particle diameter smaller or equal to 25nm.The average primary particle diameter of carbon black is preferably 15～25nm smaller or equal to 25nm in the polyethylene color masterbatch of the present invention.Low, the narrow diameter distribution of sooty foreign matter content helps the dispersion of carbon black in high-density polyethylene resin, and helping with the high-density polyethylene resin is look mother's the processing of vector resin.Therefore carbon black selects for use 325 order residual quantities (325MeshResidue) smaller or equal to 1000ppm in the polyethylene color masterbatch of the present invention, preferably smaller or equal to 200ppm, is more preferably less than the carbon black that equals 100ppm.Under the situation of carbon black 325 order residual quantities smaller or equal to 100ppm, dispersity of carbon black can realize being less than or equal to 2.5 grades in look mother of the present invention and the hdpe pipe mixed ingredients.325 order residual quantities are parameters of relevant screening reject in the relevant carbon standard test method herein, promptly characterize sooty size distribution situation, and this parameter value is low can to show narrow diameter distribution, and its standard No. is ASTM D-1514.
The PE100 level tubing molecular weight height of high density polyethylene(HDPE), difficulty of processing is big.Further improve dispersity of carbon black and look female processibility in the polyethylene color masterbatch for the processing characteristics of improving PE100 level tubing reaches, can also comprise fluorocarbon polymer (PPA) in the polyethylene master batch of the present invention as processing aid.Fluorocarbon polymer comprises carbon fluorine homopolymer and carbon fluo-copolymer, is at least a or several monomeric homopolymer or the multipolymer in vinylidene, R 1216, the tetrafluoroethylene.In the tubing production process, PPA can form the stable dynamic coating of one deck at mouth mould inwall, has reduced a melt and mouthful reactive force on mould surface, has alleviated the excessive stretching and the orientation of macromolecular chain, has reached the purpose of improving processing characteristics.What of PPA content will exert an influence to degree, look mother's cost and the load performance of tubing that tubing mixed ingredients processing characteristics is improved.Reaching desirable result of use, reducing the consumption of PPA as far as possible, can not only reduce cost and can also farthest keep the pressure-bearing characteristic of PE100 resin.But,,, thereby do not have good effect because dispersion is uneven if directly add in process of production owing to need PPA content very low in the tubing mixed ingredients.PPA is added among the look mother of the present invention, makes the higher masterbatch of content, add in the production formula that advances mixed ingredients then, then effect is very good.Fluorocarbon polymer of the present invention is as the amount of component b of polyethylene color masterbatch, and its content is 100 parts in component a high-density polyethylene resin parts by weight, is 0～10 part, is preferably 0.05～5 part, more preferably 1～3 part.Fluorocarbon polymer of the present invention is selected from least a in one or more monomeric homopolymer in vinylidene, R 1216, the tetrafluoroethylene or the multipolymer.
In order to have good heatproof air aging performance, the oxidation induction time of polyethylene pipe resin requires more than or equal to 20min.For realizing this purpose, can also contain oxidation inhibitor in the polyethylene color masterbatch of the present invention.Oxidation inhibitor is as the component d of polyethylene color masterbatch, and its content is 100 parts in component a high-density polyethylene resin parts by weight, is 0～15 part, is preferably 0.1～10 part, more preferably 4～10 parts.The oxidation inhibitor of described component d is selected from least a in Hinered phenols antioxidant and the phosphite ester kind antioxidant, specifically be preferably at least a in the following material: four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, (2, the 4-di-tert-butyl-phenyl) tris phosphite, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, β-(4-hydroxy phenyl-3, the 5-di-t-butyl) the positive octadecanol ester of propionic acid, 4,4 '-methylene-bis (2,2,2 the 6-DI-tert-butylphenol compounds), '-methylene-bis (4-methyl-6-tert butyl phenol).Thus, adopt the female tubing mixed ingredients of producing of polyethylene carbonarius of the present invention, can not add compound heat stabilizing system in the prescription of mixed ingredients, or reduce its consumption, to simplify production formula.
In addition, polyethylene color masterbatch of the present invention also can include the conventional auxiliary agent that polyethylene is used, as calcium stearate etc.Its consumption is a conventional amount used, or adjusts according to practical requirements.
The preparation method of color masterbatch for polythene of the present invention comprises component with described high-density polyethylene resin, carbon black by described umber melt blending in Banbury mixer, mixes the back discharging and makes described polyethylene color masterbatch.
Specifically, among the preparation method of above-described polyethylene color masterbatch of the present invention, can be by Banbury mixer general in the prior art with described high-density polyethylene resin, carbon black in interior component melts blend.Described Banbury mixer can be continous way Banbury mixer or abbreviated formula Banbury mixer, preferred continous way Banbury mixer.The banburying built-in temperature adopts the processing temperature of conventional high density polyethylene(HDPE) melt blending, is generally 110～180 ℃, and better effects if is 120～160 ℃.In this step, carbon black pellet is pulverized and be dispersed in carbon black in the vector resin uniformly by the powerful frictional force between resin and the carbon black; Banburying mixes the back discharging.In order to improve the dispersion effect of carbon black in high-density polyethylene resin, can realize by increasing banburying number of times (repeating the banburying process) or single banburying time, but can influence working (machining) efficiency simultaneously, and number of times is too much or the single overlong time, can reduce the mechanical property of look maternal carrier polyvinyl resin, and then have influence on the mechanical property of tubing.So the banburying number of times is generally 1～3 time, the single banburying time is 2～20min.
Can also be after the banburying discharging in the above method with the gained colour batch through the screw extrusion press extruding pelletization.Described screw extrusion press can be single screw extrusion machine or twin screw extruder.Extrusion temperature is the conventional temperature of high density polyethylene(HDPE) processing, is generally 150～250 ℃.
Polyethylene color masterbatch of the present invention by with the pellet or the powder of the special-purpose matrix resin of true qualities tubing, the mixture that obtains as the high-density polyethylene resin melt blending is a mixed ingredients, and the part by weight of general tubing matrix resin and polyethylene color masterbatch of the present invention is 100: 5 to 100: 9.Mixed ingredients can obtain final tubing goods by common tubing expressing technique.Melt blending can adopt polyethylene melt blending technology of the prior art and blending equipment.Tubing mixed ingredients by polyethylene color masterbatch preparation of the present invention carries out the tubing extrusion moulding, and its moulding process and equipment all adopt tubing expressing technique of the prior art and equipment.
Polyethylene color masterbatch provided by the present invention has ultraviolet aging resistance, heat oxygen aging resistance concurrently and improves the triple functions of processing characteristics, belongs to functional look mother.Have following characteristics and effect:
1. the polyethylene color masterbatch that can be used for PE100 level polyvinyl piping materials of the present invention, adopting high density polyethylene(HDPE) (HDPE) is matrix resin, includes carbon black, can also further include processing aids such as fluorocarbon polymer and oxidation inhibitor.
2. dispersity of carbon black directly influences the ageing-resistant performance and the load performance of tubing.Dispersity of carbon black is high more, and the aging resistance of then going sightseeing is good more, and is more little to the influence of tubing load performance.Dispersity of carbon black should be smaller or equal to 3 grades in the various standard code polyvinyl piping materials.The primary particle diameter of sooty is less than 25nm in the polyethylene color masterbatch of the present invention, and carbon black can reach 30～50%wt of look female gross weight.In the tubing mixed ingredients by polyethylene color masterbatch of the present invention preparation, this small particle size, high-load carbon black dispersion are good, and dispersity of carbon black can be less than or equal to 3 grades, and more excellent situation can reach below 2.5 grades.
3. carbon black has reinforcement to polymkeric substance and adds sticking effect, and full-bodied carbonarius mother helps improving the physicals of compound.But viscosity again can not be too high, must have certain fluidity, just can help Masterbatch and be diluted in the PE100 matrix resin.Polyethylene color masterbatch of the present invention is owing to be selected from and adjust what each component was formed, its melt flow rate (MFR) 15～50g/10min (190 ℃, 21.6kg) between, be easy to processing and disperse, its over-all properties is better.
4. in preparation during polyvinyl piping materials, with the true qualities polyvinyl resin with contain in the mixed technology of sooty polyethylene color masterbatch blend, the production unit of different mixed ingredients and production technique will produce very big influence to the performance of mixed ingredients.Guaranteeing to alleviate shearing as best one can under the carbon black master batch dispersive prerequisite, be the key problem in technology of mixed technology to polymer melt.Polyethylene color masterbatch of the present invention be owing to just can well realize sooty dispersion under the processing of weak shearing force, thereby ensured the performance of mixed ingredients.
5. the adding of PPA in the polyethylene color masterbatch of the present invention has improved tubing mixed ingredients processing characteristics, has reduced look mother's the cost and the load performance of raising tubing.It is well functional that polyethylene color masterbatch is had.
The mixed ingredients of polyethylene color masterbatch of the present invention by obtaining with tubing matrix resin melt blending just can be realized small particle size, high-content sooty good distribution under the situation of weak shearing processing.Under the prerequisite of the final performance requriements of collapsing pressure tubing not, provide most economical effective means to give the uvioresistant performance of polyethylene pipe necessity.The life-time service life-span (LTHS) that polyethylene color masterbatch of the present invention and the black mixed ingredients that obtains with the true qualities resin alloy carried out more than 1 year is estimated, confirmed that it meets PE100 deciding grade and level regulation, minimum permissible stress is not less than 10MPa.This mixed ingredients also should possess better heat-resisting oxidative stability, good processing characteristics, final low cost, the high performance industrial production of realizing.Compare with external like product, this project product not only cost lower, also given better heat-resisting oxidative stability of mixed ingredients and good processing characteristics simultaneously, be a kind of low cost, high performance material.
Embodiment:
Below in conjunction with embodiment, further specify the present invention.
Tubing deciding grade and level test (LTHS):
According to design requirements, polyvinyl piping materials should be 50 years under certain condition work-ing life at least, and this just requires special material for tube is carried out long term life deciding grade and level test (LTHS).Its test principle is: by tubing is carried out hydrostatic test under two above temperature and a plurality of pressure rating condition, obtain the data set that a series of tubing temperature T, stress σ and time t three have corresponding relation.When utilizing-and the Wen principle of equivalence, adopt that extrapotation calculates T=20 ℃, the minimum permissible stress (MRS) of tubing during t=50.Long term life (LTHS) the deciding grade and level authentication of the polyethylene black mixed ingredients of PE100 level polyvinyl piping materials is to adopt the black mixed ingredients of PE100 true qualities production of resins to carry out the long term life deciding grade and level test (LTHS) of ISO 9080 standard codes, after having only its MRS of determining to be not less than 10.0MPa, just can regard as PE100 level polyvinyl piping materials black mixed ingredients.
The degree of scatter testing method:
Carbon black microcosmic degree of scatter testing method is to detect according to GB/T182512000 in the specific embodiment of the invention, this standard adopting by equation international standard ISO11420:1996.This method is under transmitted ray, checked by hot-forming film sample with opticmicroscope team from compound, according to the size and the quantity that are the dispersive carbon black aggregate, can determine the grade of the microcosmic degree of scatter of product.The apparent descriptive grade of sooty dispersive is to record under the condition of " * 70 " at enlargement ratio.Dispersity of carbon black among the polyethylene carbonarius mother of the present invention is all smaller or equal to 3 grades, and more excellent situation can reach below 2.5 grades.
Embodiment 1
With the carbon black (trade mark: ELFTEX 254, average primary particle diameter＜25nm, U.S. Cabot Co.,Ltd (CabotCorporation) produces, 325 order residual quantities＜20ppm), high-density polyethylene resin (trade mark 2200J, the production of Sinopec Yanshan Petrochemical limited-liability company), antioxidant 1010 (four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, it is pentaerythritol tetrathioglycollate, Switzerland's Ciba production) put into Banbury mixer, discharging granulation behind the melt blending, obtain polyethylene color masterbatch of the present invention, the banburying temperature is 150 ℃.Wherein, high density polyethylene(HDPE) 100 weight parts, carbon black 65 weight parts, oxidation inhibitor 0.2 weight part.
With the hdpe pipe base-material, (trade mark YJH041, Sinopec Shanghai oil part limited-liability company produces) and above prepared look female presses 100: 6 weight ratios in homogenizer after the simple and mechanical blend, in twin screw extruder (the ZSK-58 twin screw extruder of WP company) melt blending extruding pelletization, obtain PE black mixed ingredients.The temperature of each section of forcing machine is respectively 180 ℃, 200 ℃, 200 ℃, 200 ℃, 205 ℃ (die temperature).At single screw rod polyolefin pipe extrusion equipment (JWS65-33, Shanghai Jwell Machinary Co., Ltd's production) going up the extrusion moulding specification is the tubing of DN 90, the temperature of each section of forcing machine is respectively 170 ℃, 190 ℃, 190 ℃, 190 ℃, 195 ℃ (die temperature), adjust screw speed, make head pressure constant at 11.5MPa.The production capacity of record unit time, and the timed interval of statistics mouthful mould buildup cleaning, the production capacity of unit time long more explanation processing characteristics of the timed interval high more, mouthful mould buildup cleaning is good more.
Gained tubing is carried out the test of carbon black dispension degree by GB/T 18251-2000, carry out the test of content of carbon black by GB/T13021-1991.Produce the dumbbell shape tensile bars by standard GB/T 8804.3-2000 from tubing, test tensile yield strength, oxidation induction period are pressed GB/T 17391-1998 test.The specific performance test result is as shown in table 1.
Embodiment 2
Polyethylene carbonarius mother's production technique is identical with embodiment 1.Look female concrete prescription is: total umber of high-density polyethylene resin is 100 weight parts, high-density polyethylene resin (trade mark 2200J wherein, Sinopec Yanshan Petrochemical limited-liability company produces) and high-density polyethylene resin (trade mark 6380M, Sinopec Yanshan Petrochemical limited-liability company produces) each 50 weight part, the umber of carbon black (with embodiment 1) changes 40 weight parts into, antioxidant 1010 (with embodiment 1) 0.2 weight part.
Except that the part by weight with hdpe pipe base-material and look mother changes into 100: 8.5, the production of tubing is identical with embodiment 1.
The specific performance test result is as shown in table 1.
Embodiment 3
Polyethylene carbonarius mother's production technique is identical with embodiment 1.Look female concrete prescription is: the trade mark that high-density polyethylene resin adopts Sinopec Yanshan Petrochemical limited-liability company to produce is the high-density polyethylene resin of 1600J, wherein the umber of carbon black (with embodiment 1) changes 85 weight parts into, antioxidant 1010 (with embodiment 1) 0.2 weight part.
Except that the part by weight with hdpe pipe base-material and look mother changes into 100: 5, the production of tubing is identical with embodiment 1.
The specific performance test result is as shown in table 1.
Embodiment 4
Removing carbon black selects new process carbon black for use (Tianjin dolphin carbon black plant produces for trade mark N234, average primary particle diameter＜25nm, and outside the 325 order residual quantities＜200ppm), other conditions and prescription are identical with embodiment 1.The specific performance test result is as shown in table 1.
Comparative Examples 1
Removing carbon black selects the General Purpose Rubber industrial carbon black for use (the Tianjin autumn, real carbon black plant produced for trade mark N220, average primary particle diameter＜25nm, and outside the 325 order residual quantities＜2000ppm), other conditions and prescription are identical with embodiment 1.The specific performance test result is as shown in table 1.
Comparative Examples 2
Remove look female matrix resin and select for use outside the new LDPE (film grade) (Sinopec Yanshan Petrochemical limited-liability company produces for the trade mark, 1F7B), other conditions and prescription are all identical with embodiment 1.
The specific performance test result is as shown in table 1.
Comparative Examples 3
Be that with the difference of embodiment 2 matrix resin is made up of high-density polyethylene resin and low molecular weight polyethylene wax, the gross weight umber is 100 weight parts, high-density polyethylene resin (trade mark 6100J wherein, Sinopec Yanshan Petrochemical limited-liability company produces) 70 weight parts, low molecular weight polyethylene wax (IV type, Fine Chemical Factory of Beijing University of Chemical Technology produces) 30 parts by weight, the kind of carbon black and oxidation inhibitor is identical with embodiment 2 with consumption.Polyethylene carbonarius mother's production technique is identical with embodiment 1.
Except that the part by weight with hdpe pipe base-material and look mother changes into 100: 8.5, the production of tubing is identical with embodiment 1.
Embodiment 5
Remove and add in look mother's prescription outside the 0.1 weight part fluorocarbon polymer PPA (Minnesota Mining and Manufacturing Company produces for vinylidene, R 1216, tetrafluoroethylene terpolymer, trade mark FX5911), other conditions and prescription are all identical with embodiment 3.
The specific performance test result is as shown in table 1.
Embodiment 6
Except that adding in look mother's prescription the 5 weight part fluorocarbon polymer PPA (with embodiment 4), other polyethylene carbonarius mothers' production technique and prescription are all identical with embodiment 3.
Except that the part by weight with hdpe pipe base-material and look mother changes into 100: 5.2, the production technique of tubing is identical with embodiment 1.
The specific performance test result is as shown in table 1.
Embodiment 7
Except that adding in look mother's prescription the 10 weight part fluorocarbon polymer PPA (with embodiment 4), other polyethylene carbonarius mothers' production technique and prescription are all identical with embodiment 3.
Except that the part by weight with hdpe pipe base-material and look mother changes into 100: 5.5, the production technique of tubing is identical with embodiment 1.
The specific performance test result is as shown in table 1.
Embodiment 8
Except that the component and the content of oxidation inhibitor in look mother's prescription changes into: oxidation inhibitor is 168 ((2,4 di-tert-butyl-phenyls) tris phosphite, the Switzerland Ciba is produced) 2.5 parts, oxidation inhibitor are 1010 (with embodiment 1), 2.5 weight parts, other polyethylene carbonarius mothers' production technique and prescription are all identical with embodiment 6.
Except that the part by weight with hdpe pipe base-material and look mother changes into 100: 5.5, the production technique of tubing is identical with embodiment 1.
The specific performance test result is as shown in table 1.
Embodiment 9
Except that the component and the content of oxidation inhibitor in look mother's prescription changes into: oxidation inhibitor is that 5 parts of 168 (with embodiment 7), oxidation inhibitor are 1010 (with embodiment 1), 5 weight parts, and other polyethylene carbonarius mothers' production technique and prescription are all identical with embodiment 6.
Except that the part by weight with hdpe pipe base-material and look mother changes into 100: 5.5, the production technique of tubing is identical with embodiment 1.
The specific performance test result is as shown in table 1.
Table 1
| Project | Content of carbon black | Carbon black dispersion | 200 ℃ of oxidation induction periods | Tensile yield strength | The tubing pressure-bearing time | Production capacity | Average mouthful of mould buildup cleaning room every |
| Unit | ％wt | Level | min | MPa | h | kg/h | h |
| PE100 grade standard prescribed value | 2-2.5 | ≤3 | ＞20 | - | ＞100 | - | - |
| Embodiment 1 | 2.21 | 2.2 | 52 | 24.1 | 248 | 220 | 24 |
| Embodiment 2 | 2.22 | 2.1 | 50 | 23.8 | 234 | 218 | 24 |
| Embodiment 3 | 2.18 | 2.3 | 52 | 24.2 | 267 | 222 | 24 |
| Embodiment 4 | 2.20 | 2.7 | 49 | 23.6 | 237 | 221 | 24 |
| Embodiment 5 | 2.18 | 1.8 | 48 | 24.5 | 249 | 234 | 24 |
| Embodiment 6 | 2.21 | 1.6 | 47 | 24.3 | 245 | 265 | 36 |
| Embodiment 7 | 2.24 | 1.5 | 48 | 23.9 | 263 | 276 | 72 |
| Embodiment 8 | 2.25 | 1.6 | 83 | 23.7 | 232 | 257 | 72 |
| Embodiment 9 | 2.21 | 1.7 | 120 | 23.7 | 256 | 262 | 72 |
| Comparative Examples 1 | 2.20 | 3.7 | 44 | 23.2 | 156 | 222 | 24 |
| Comparative Examples 2 | 2.21 | 2.4 | 46 | 22.3 | 73 | 226 | 24 |
| Comparative Examples 3 | 2.21 | 1.8 | 36 | 22.8 | 85 | 267 | 8 |
According to the testing data of the embodiment of last table and Comparative Examples as can be seen, adopt polyethylene carbonarius mother of the present invention, the load performance of polyvinyl piping materials is good, and the processing characteristics and the antioxidant property of carbon black dispersion and tubing obviously improve.
Claims (5)
1. polyethylene color masterbatch includes the following component of blend:
A. high-density polyethylene resin 100 parts by weight
B. carbon black 35～100 parts by weight
C. fluorocarbon polymer 0.05～10 parts by weight
D. oxidation inhibitor 0～15 parts by weight
The average primary particle diameter of the above components b sooty is smaller or equal to 25nm, and 325 screen cloth residual quantities are smaller or equal to 200ppm; The oxidation inhibitor of described component d is selected from least a in Hinered phenols antioxidant and the phosphite ester kind antioxidant; The fluorocarbon polymer of described amount of component b is at least a in the following material: monomeric homopolymer of one or more in vinylidene, R 1216, the tetrafluoroethylene or multipolymer.
2. polyethylene color masterbatch according to claim 1 includes the following component of blend:
A. high-density polyethylene resin 100 parts by weight
B. carbon black 60～85 parts by weight
C. fluorocarbon polymer 0.05～5 parts by weight
D. oxidation inhibitor 0.1～10 parts by weight.
3. polyethylene color masterbatch according to claim 1, wherein the average primary particle diameter of the sooty of components b is 15～25nm.
4. polyethylene color masterbatch according to claim 1, wherein the oxidation inhibitor of component d comprises at least a in the following material: four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, (2, the 4-di-tert-butyl-phenyl) tris phosphite, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, β-(4-hydroxy phenyl-3, the 5-di-t-butyl) the positive octadecanol ester of propionic acid, 4,4 '-methylene-bis (2,2,2 the 6-DI-tert-butylphenol compounds), '-methylene-bis (4-methyl-6-tert butyl phenol).
5. according to the preparation method of each described polyethylene color masterbatch of claim 1～4, comprise component with described high-density polyethylene resin, carbon black by described umber melt blending in Banbury mixer, mix the back discharging and make described polyethylene color masterbatch.
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| CN103012902B (en) * | 2012-09-19 | 2014-11-05 | 北京北化高科新技术股份有限公司 | Black master-batch and preparation method thereof |
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