CN103012902A - Black master-batch and preparation method thereof - Google Patents
Black master-batch and preparation method thereof Download PDFInfo
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- CN103012902A CN103012902A CN2012103495045A CN201210349504A CN103012902A CN 103012902 A CN103012902 A CN 103012902A CN 2012103495045 A CN2012103495045 A CN 2012103495045A CN 201210349504 A CN201210349504 A CN 201210349504A CN 103012902 A CN103012902 A CN 103012902A
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- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000006229 carbon black Substances 0.000 claims abstract description 56
- 238000002156 mixing Methods 0.000 claims abstract description 51
- 229920002313 fluoropolymer Polymers 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 239000000155 melt Substances 0.000 claims description 26
- 239000011347 resin Substances 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 25
- -1 1-lauryl alcohol Chemical compound 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 11
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 7
- 239000011164 primary particle Substances 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 4
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 241001597008 Nomeidae Species 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005968 1-Decanol Substances 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims description 2
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- NPSSWQJHYLDCNV-UHFFFAOYSA-N prop-2-enoic acid;hydrochloride Chemical compound Cl.OC(=O)C=C NPSSWQJHYLDCNV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003039 volatile agent Substances 0.000 claims description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 abstract description 20
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 7
- 229920006113 non-polar polymer Polymers 0.000 abstract description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 abstract 2
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 229920006112 polar polymer Polymers 0.000 abstract 1
- 229920013716 polyethylene resin Polymers 0.000 abstract 1
- 229920006351 engineering plastic Polymers 0.000 description 22
- 238000011056 performance test Methods 0.000 description 20
- 238000005469 granulation Methods 0.000 description 13
- 230000003179 granulation Effects 0.000 description 13
- 239000004698 Polyethylene Substances 0.000 description 12
- 239000011159 matrix material Substances 0.000 description 12
- 229920000573 polyethylene Polymers 0.000 description 12
- 238000007599 discharging Methods 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000001746 injection moulding Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000004677 Nylon Substances 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 229920001778 nylon Polymers 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000004595 color masterbatch Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 238000010094 polymer processing Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a black master-batch and a preparation method thereof. The black master-batch comprises the following components in parts by weight: 100 parts of polyethylene resin, 50 to 150 parts of carbon black, 0.1 to 14 parts of amphipathic brushed polymer compatibilizer, and 0 to 10 parts of fluorocarbon polymer. The method comprises the step of melting and blending the components based on the dosage. The black master-batch disclosed by the invention is high in compatibility respect to the non-polar polymer, and can be applicable to polar polymers such as ABS (Acrylonitrile Butadiene Styrene).
Description
Technical field
The present invention relates to the plastics field, say further, relate to a kind of black masterbatch and preparation method thereof.
Background technology
Fast development along with plastics industry, the engineering plastics such as nylon, polyester, polycarbonate and ABS are widely used in the fields such as automobile, household electrical appliance and daily necessities, for requirements such as product appearance and weathering resistancies, the ratio of black engineering plastic product improves constantly.
The production of engineering plastics black mixed ingredients has two kinds of methods: the one, directly in resin, add the production of carbon black mixed ingredients, and the 2nd, produce mixed ingredients with the carbonarius master batch.Because the advantage of the aspects such as environmental protection, performance and usability, the coloring mode of black masterbatch obtains using the most widely.
As everyone knows, carbon black is a kind of nano material, and its primary particle diameter between 15-120nm, is efficient UV light absorber and photomask agent generally.The primary particle diameter of carbon black is less, the content of carbon black is higher, the dispersiveness of carbon black is better, and tinting strength and the blackness of black masterbatch are higher; The content of carbon black is higher in the master batch simultaneously, and adding proportion is less, and cost is lower, and is also less on the impact of engineering plastics performance.The particle diameter of carbon black is less, content of carbon black is higher, and its specific surface area is just larger, and the Intermolecular Forces between the carbon black aggregate is stronger, more be not easy to disperse, at present current techique is that the low molecule lubricants such as the polyethylene wax that adds high level in prescription, EBS are to improve the dispersiveness of carbon black.The adding of low molecule lubricant will inevitably make material extending yield strength, flexural strength, shock strength performance significantly descend.Therefore do not use low dispersal agent molecule, adopt special dispersion system, prepare high blackness, high-performance carbon black masterbatch, be the insoluble problem in this area always, also is the problem that the present invention solves emphatically.
Because polyethylene and polypropylene are all the non-polar polyolefinic material, therefore the polyethylene black masterbatch can successful Application in Pp System, but the consistency reason owing to matrix resin, in the engineering plastics such as ABS, nylon, polyester, very low black masterbatch content just makes the degradation of engineering plastics very large.And adopt the matrix resin identical with engineering plastics of the same race to prepare black masterbatch, can reduce the degradation that causes owing to the resin compatible problem, but owing to the compatibility problem of Other Engineering plastics, make its scope of application very narrow.AS, ABS product can be used for such as the AS black masterbatch, but the products such as polypropylene, nylon, polyester can't be used for; Nylon 6 black masterbatchs can be used for nylon 6 and nylon 66 products, but can't be used for the products such as polypropylene, ABS, polyester.Simultaneously because the aspects such as molecular chain characteristic are not the high-quality carbon black master batch that every various engineering plastics may be used to produce high-content, high dispersive.
Summary of the invention
For solving problems of the prior art, the invention provides a kind of black masterbatch and preparation method thereof, black masterbatch of the present invention and non-polar polymer have good consistency, can be applied in nylon, polyester and the ABS isopolarity polymkeric substance.
One of purpose of the present invention provides a kind of black masterbatch.
The following component that comprises blend:
The type of matrix resin has a great impact the physical and mechanical properties of plastics, directly affects the Long-Term Properties of product.Usually the product matrix resin of automobile and electronic product field application is the goods such as polypropylene, ABS and nylon.Different for the polarity of its resin own, the present invention adopt in linear low density polyethylene, ultra-low density polyethylene, Low Density Polyethylene, medium-density polyethylene, the high density polyethylene(HDPE) any one or its be combined as the matrix resin of black masterbatch, be preferably Low Density Polyethylene.The melt flow rate (MFR) of matrix resin greater than 5g/10min (190 ℃, 2.16kg); Consider from the dispersiveness of carbon black, be preferably more than 10g/10min (190 ℃, 2.16kg).
The choice relation of carbon black is to dispersiveness and the look female processing characteristics of carbon black in matrix resin, and it also is the key factor that affects product appearance and surface gloss simultaneously.Carbon black in the above component can comprise disclosed all kinds carbon black in the prior art.For requiring the injection-molded item of high blackness, generally selecting average primary particle diameter is the carbon black of 15～120nm.The average primary particle diameter of carbon black is preferably 15～50nm less than or equal to 100nm in the polyethylene color masterbatch of the present invention.The volatiles of selected carbon black is the oxygen-containing functional group (carboxyl, hydroxyl) of carbon blacksurface absorption, and volatile content is less than 3.5wt.%.Take polyvinyl resin weight as 100 parts of calculating, the content of carbon black is 50～150 parts, is preferably 50～130 parts, more preferably 80～100 parts.
The main chain of described parents' comb-shaped polymer expanding material is the series of acrylate polymer derivant with high reaction activity polarity side group that obtains by Raolical polymerizable, and the nonpolar side group of comb type is the long carbon-chain structure of grafting on main chain, the main chain of parents' comb-shaped polymer expanding material is the series of acrylate polymer derivant, and its composition is a kind of or composition in vinylformic acid, methacrylic acid, acrylate chloride, methacrylic chloride, Hydroxyethyl acrylate, the hydroxyethyl methylacrylate; Long carbon-chain structure is a kind of or composition in 1-decanol, 1-lauryl alcohol, 1-stearyl alcohol, 1-amino dodecane, 1-stearylamine, stearic acid, the oleic acid.Compatibilizer Content is 0.1～14 part, is preferably 0.5～11 part.
On parents' comb-shaped polymer expanding material Semi-polarity main chain part side chain or the end of the chain with the carboxyl functional group with reactive behavior.In the melt blending process, the situ-formed graft chemical reaction occurs in the functional groups such as the carboxyl of the active function groups of main chain and carbon blacksurface, amino and hydroxyl in the polymer compatibilizer, forms chemical bonding force and mortise.The polyethylene matrix resin of non-polar sidechain and black masterbatch has good consistency, is intertwined mutually between the molecular chain, and the polyethylene matrix resin of black masterbatch and the boundary strength between the carbon black can improve greatly like this.The raising of boundary strength can be transmitted higher dispersion shearing force on the one hand, reduces the quantity of large size carbon black aggregate, has further put forward the dispersiveness of high carbon black, and the blackness of black masterbatch is higher; On the other hand, the intensity between carbon black and the matrix resin is also just higher, and the physical and mechanical properties of material is also just better.
Simultaneously the polar group of this compatilizer can also with the polar group generation chemical reaction of the engineering plastics such as nylon, polyester, improve the consistency of black masterbatch and polarity engineering plastics, to a certain extent the physical and mechanical properties of betterment works plastics.
Fluorocarbon polymer processing aid (Polymer Processing Additives) is as the dispersion agent of carbon black.PPA comprises carbon fluorine homopolymer and carbon fluo-copolymer, is homopolymer or the multipolymer of at least a or several monomers in vinylidene, R 1216, the tetrafluoroethylene, is preferably the multipolymer of vinylidene and tetrafluoroethylene.Take polyvinyl resin weight as 100 parts of calculating, content is 0～10 part, is preferably 0.01～10 part, more preferably 0.5～8 part.Adopt PPA as the dispersion agent of carbon black, the addition of 1000PPM just can obviously improve the blackness of black masterbatch.And adopt the dispersion agents such as polyethylene wax of the prior art, EBS, and need larger consumption, can affect the performance of engineering plastics.
As the dispersion agent of carbon black, to compare with traditional dispersion agents such as polyethylene wax, macromolecule carbon fluoropolymer very in a small amount just can reach good dispersion effect.In the mixing process of black masterbatch, fluorocarbon polymer is to the carbon blacksurface enrichment, do not react with polyethylene matrix resin, between carbon black aggregate, formed a dynamic user interface, weakened widely the secondary aggregation effect of carbon black dispersion process, the size decreases of carbon black aggregate, number obviously reduces, thereby has improved the dispersiveness of carbon black in matrix resin.Different from traditional low-molecular-weight wax dispersion agent, fluorocarbon polymer is high-molecular weight polymer, and addition is very little simultaneously, therefore can the physical and mechanical properties of engineering plastics not exerted an influence.
Two of purpose of the present invention provides a kind of preparation method of black masterbatch.
Comprise: described component is made described black masterbatch after by described consumption melt blending.
Particularly, with described polyvinyl resin, carbon black in interior component by described umber melt blending in Banbury mixer or twin screw extruder, mix rear discharging and make described black masterbatch.
Among the preparation method of above-described black masterbatch of the present invention, can be by Banbury mixer general in the prior art or twin screw extruder with described polyvinyl resin, carbon black in interior component melts blend.Described production unit can be Banbury mixer or twin screw extruder, preferred Banbury mixer.The banburying built-in temperature adopts the processing temperature of conventional Low Density Polyethylene melt blending, is generally 110～180 ℃, and better effects if is 120～160 ℃.In this step, by the powerful frictional force between resin and the carbon black carbon black coacervate is broken and be dispersed in uniformly carbon black in the vector resin; The melt blending time is 2～20min.
Black masterbatch of the present invention and true qualities engineering plastics mix such as ABS resin, and the part by weight of common engineering plastics and polyethylene color masterbatch of the present invention is 100: 1 to 100: 4.Compound carries out injection moulding after extruding the blend granulation by the common double screw extrusion press, and its moulding process and equipment all adopt Shooting Technique of the prior art and equipment.
The consistency of the various engineering plastics systems such as black masterbatch of the present invention and nylon, polyester, polycarbonate and ABS is good, prepare mixed ingredients by melt blending, again mixed ingredients is adopted conventional injection moulding machine injection moulding, just can obtain high blackness, high performance engineering plastics product.
Embodiment
Below in conjunction with embodiment, further specify the present invention.
Physical and mechanical properties:
Engineering plastics true qualities material mixing is made injection moulding sample preparation behind the mixed ingredients, the test physical and mechanical properties.The kind of engineering plastics has ABS (trade mark 15A1, platform limited-liability company produce), acrylic resin PP (trade mark: 4220, Yanshan Petrochemical).Its test method is: true qualities engineering plastic resin and the black masterbatch ratio according to 100: 2 is mixed, and by the twin screw extruder extruding pelletization, by injection moulding machine injection moulding sample preparation, the processing condition of granulation and injection moulding are with reference to material supplier's guidance.According to GB GB/T1040.2-2006 test tensile yield strength; According to GB/T1843-2008 test cantilever beam impact strength.
Blackness:
Test method is as follows: with engineering plastics base-material and the black masterbatch blending ratio according to 100: 2, then granulation mixes in twin screw extruder, with mixed ingredients by the injection moulding machine sample preparation, with the color (L of spectrophotometer test sample
*, a
*, b
*).L wherein
*Numerical value be used for the blackness of exosyndrome material, numerical value is less, blackness is higher.
Embodiment 1
The mass content of control carbon black is added 0.5% parents' comb shaped polymer expanding material 45%, and parents herein dredge type polymkeric substance solubilizing agent and select the BH-27 of Beijing University of Chemical Technology, and its main chain is polymethacrylate, and side chain is stearic acid.Concrete prescription is as follows:
Ldpe resin (1F7B, China Petrochemical Corp. produce, MFR be 15g/10min (190 ℃, 2.16kg) 100 weight parts
Carbon black (BP800, average primary particle diameter is 30nm, Cabot company) 82 weight parts
BH-27 1 weight part
Put into Banbury mixer after mixing, discharging granulation behind the melt blending obtains black masterbatch of the present invention, and the melt blending temperature is 150 ℃.
To carry out performance test behind the ABS melt blending described in above-mentioned black masterbatch and the embodiment of the present invention.The specific performance test result is as shown in table 1.
Embodiment 2
Keep content of carbon black 45% constant, increase Compatibilizer Content to 5%, other conditions as described in Example 1.Concrete prescription is as follows:
Ldpe resin 100 weight parts
Carbon black 90 weight parts
BH-27 10 weight parts
Put into Banbury mixer after mixing, discharging granulation behind the melt blending obtains black masterbatch of the present invention, and the melt blending temperature is 150 ℃.
To carry out performance test behind the ABS melt blending described in above-mentioned black masterbatch and the embodiment of the present invention.The specific performance test result is as shown in table 1.
Embodiment 3
The mass content of control carbon black is added 5% parents' comb shaped polymer expanding material 45%, and parents herein dredge type polymkeric substance solubilizing agent and select the PL-1 of Beijing University of Chemical Technology, and its main chain is methacrylic acid, and the grafting long-chain is the 1-lauryl alcohol.Concrete prescription is as follows:
Ldpe resin 100 weight parts
Carbon black 90 weight parts
PL-1 1 weight part
Put into Banbury mixer after mixing, discharging granulation behind the melt blending obtains black masterbatch of the present invention, and the melt blending temperature is 150 ℃.
To carry out performance test behind the ABS melt blending described in above-mentioned black masterbatch and the embodiment of the present invention.The specific performance test result is as shown in table 1.
Comparative Examples 1
Keep content of carbon black 45% constant, except replace BH-27 with polyolefine expanding material modified by maleic acid anhydride graft polyethylene (100D, Du Pont) in prescription, other conditions as described in Example 2.Concrete prescription is as follows:
Ldpe resin 100 weight parts
Carbon black 90 weight parts
100D 10 weight parts
Put into Banbury mixer after mixing, discharging granulation behind the melt blending obtains black masterbatch of the present invention, and the melt blending temperature is 150 ℃.
To carry out performance test behind the ABS melt blending described in above-mentioned black masterbatch and the embodiment of the present invention.The specific performance test result is as shown in table 1.
Embodiment 4
The mass content of control carbon black is 45%, and it is as follows specifically to fill a prescription:
Concrete prescription is as follows:
Ldpe resin 100 weight parts
Carbon black 90 weight parts
BH-27 10 weight parts
Put into Banbury mixer after mixing, discharging granulation behind the melt blending obtains black masterbatch of the present invention, and the melt blending temperature is 150 ℃.
To carry out performance test behind above-mentioned black masterbatch and acrylic resin PP (trade mark: 4220, the Yanshan Petrochemical) melt blending.The specific performance test result is as shown in table 1.
Comparative Examples 2
Except in prescription, not adding parents' comb-shaped polymer expanding material, other conditions as described in Example 4:
Ldpe resin (1F7B, China Petrochemical Corp. produce, MFR be 15g/10min (190 ℃, 2.16kg) 100 weight parts
Carbon black (BP800, average primary particle diameter is 30nm, Cabot company) 82 weight parts
Put into Banbury mixer after mixing, discharging granulation behind the melt blending obtains black masterbatch of the present invention, and the melt blending temperature is 150 ℃.
To carry out performance test behind above-mentioned black masterbatch and acrylic resin PP (trade mark: 4220, the Yanshan Petrochemical) melt blending.The specific performance test result is as shown in table 1.
Embodiment 5
Keep content of carbon black 45% constant, add 0.3% fluorocarbon polymer PPA (trade mark FX5911, Minnesota Mining and Manufacturing Company produces) in system, other conditions as described in Example 2.Concrete prescription is as follows:
Put into Banbury mixer after mixing, discharging granulation behind the melt blending obtains black masterbatch of the present invention, and the melt blending temperature is 150 ℃.
To carry out performance test behind the ABS melt blending described in above-mentioned black masterbatch and the embodiment of the present invention.The specific performance test result is as shown in table 1.
Embodiment 6
Keep content of carbon black 45% constant, improve the content of fluorocarbon polymer PPA (trade mark FX5911, Minnesota Mining and Manufacturing Company produces) and bring up to 1.0%, other conditions as described in Example 5.Concrete prescription is as follows:
Put into Banbury mixer after mixing, discharging granulation behind the melt blending obtains black masterbatch of the present invention, and the melt blending temperature is 150 ℃.
To carry out performance test behind the ABS melt blending described in above-mentioned black masterbatch and the embodiment of the present invention.The specific performance test result is as shown in table 1.
Embodiment 7
Keep content of carbon black 45% constant, improve the content of fluorocarbon polymer PPA (trade mark FX5911, Minnesota Mining and Manufacturing Company produces) and bring up to 4.5%, other conditions as described in Example 5.Concrete prescription is as follows:
Put into Banbury mixer after mixing, discharging granulation behind the melt blending obtains black masterbatch of the present invention, and the melt blending temperature is 150 ℃.
To carry out performance test behind the ABS melt blending described in above-mentioned black masterbatch and the embodiment of the present invention.The specific performance test result is as shown in table 1.
Comparative Examples 3
Keep content of carbon black constant 45%, replace parents' comb-shaped polymer expanding material with other polymkeric substance solubilizing agent, with other polyethylene of dispersing agent wax (4 types, Fine Chemical Factory of Beijing University of Chemical Technology, number-average molecular weight 7000) substitute PPA, other conditions as described in Example 6.Concrete prescription is as follows:
Put into Banbury mixer after mixing, discharging granulation behind the melt blending obtains black masterbatch of the present invention, and the melt blending temperature is 150 ℃.
To carry out performance test behind the ABS melt blending described in above-mentioned black masterbatch and the embodiment of the present invention.The specific performance test result is as shown in table 1.
Table 1
| Project | Tensile yield strength | Shock strength | Blackness |
| Unit | MPa | KJ/m2 | L * |
| Embodiment 1 | 28.53 | 21 | 19 |
| Embodiment 2 | 28.6 | 21.02 | 17.94 |
| Embodiment 3 | 29.23 | 21.21 | 18.1 |
| Embodiment 4 | 24.32 | 18.23 | 19.98 |
| Embodiment 5 | 29.62 | 21.76 | 17.13 |
| Embodiment 6 | 29.98 | 22.63 | 17.1 |
| Embodiment 7 | 30.04 | 23.32 | 17.08 |
| Comparative Examples 1 | 28.22 | 19.4 | 18.65 |
| Comparative Examples 2 | 24.1 | 18.2 | 20.26 |
| Comparative Examples 3 | 28.14 | 19.19 | 17.2 |
Can find out according to the embodiment of upper table and the testing data of Comparative Examples, adopt black masterbatch of the present invention, not only with polyolefine good consistency be arranged, and with polar resin ABS good consistency be arranged; Under identical condition, the data of Comparative Examples 1 and embodiment 2, Comparative Examples 3 and embodiment 6 can be found out, compare with traditional technology, and the present invention can give the higher blackness of engineering plastics and better physical and mechanical properties.
Claims (8)
1. black masterbatch comprises the following component of blend:
The melt flow rate (MFR) of described polyvinyl resin greater than 5g/10min (190 ℃, 2.16kg);
The main chain of described parents' comb-shaped polymer expanding material is the series of acrylate polymer derivant with high reaction activity polarity side group that obtains by Raolical polymerizable, and the nonpolar side group of comb type is the long carbon-chain structure of grafting on main chain;
Fluorocarbon polymer is homopolymer or the multipolymer of one or more monomers in vinylidene, R 1216, the tetrafluoroethylene.
2. black masterbatch as claimed in claim 1 is characterized in that:
Carbon black 50～130 weight parts
Parents' comb-shaped polymer expanding material 0.5～11 weight part
Fluorocarbon polymer 0.01～10 weight part.
3. black masterbatch as claimed in claim 2 is characterized in that:
Carbon black 80～100 weight parts
Fluorocarbon polymer 0.5～8 weight part.
4. black masterbatch as claimed in claim 1 is characterized in that:
Described polyvinyl resin is ldpe resin;
The melt flow rate (MFR) of described polyvinyl resin greater than 10g/10min (190 ℃, 2.16kg).
5. black masterbatch as claimed in claim 1 is characterized in that:
The average primary particle diameter of described carbon black is 15～120nm, and oil-absorption(number) is greater than 50ml/100g, and volatiles is less than 3.5wt.%.
6. black masterbatch as claimed in claim 1 is characterized in that:
The main chain of parents' comb-shaped polymer expanding material is a kind of or composition in vinylformic acid, methacrylic acid, acrylate chloride, methacrylic chloride, Hydroxyethyl acrylate, the hydroxyethyl methylacrylate; Described long carbon-chain structure is a kind of or composition in 1-decanol, 1-lauryl alcohol, 1-stearyl alcohol, 1-amino dodecane, 1-stearylamine, stearic acid, the oleic acid.
7. black masterbatch as claimed in claim 1 is characterized in that:
Described fluorocarbon polymer is the multipolymer of vinylidene and tetrafluoroethylene.
8. preparation method such as the described black masterbatch of one of claim 1～7 comprises:
Described component is made described black masterbatch after by described consumption melt blending.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103421154A (en) * | 2013-07-25 | 2013-12-04 | 杭州师范大学 | Comb-shaped stem grafting copolymer containing reactive group and preparation method and application thereof |
| CN105542279A (en) * | 2016-01-18 | 2016-05-04 | 常州市双成塑母料有限公司 | Preparation method of highly-filled polyethylene master batch |
| CN107619544A (en) * | 2017-09-04 | 2018-01-23 | 珠海市南蓝塑胶科技有限公司 | Blue phase black agglomerate for AS or ABS and preparation method thereof |
| CN110760133A (en) * | 2019-11-25 | 2020-02-07 | 怀化东庆科技有限公司 | High-content carbon black master batch and preparation method thereof |
| CN112795069A (en) * | 2020-12-31 | 2021-05-14 | 山东环海塑业有限公司 | Preparation method of nano carbon black high-dispersion modified polyethylene pipe material |
| CN114921016A (en) * | 2022-06-29 | 2022-08-19 | 深圳市***新材料科技有限公司 | Black master batch for polyethylene modification and preparation method thereof |
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| CN101870750A (en) * | 2010-06-02 | 2010-10-27 | 华东理工大学 | Comb copolymer, preparation method and application thereof |
| CN102477180A (en) * | 2010-11-25 | 2012-05-30 | 新疆天业（集团）有限公司 | Linear low-density polyethylene composition |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103421154A (en) * | 2013-07-25 | 2013-12-04 | 杭州师范大学 | Comb-shaped stem grafting copolymer containing reactive group and preparation method and application thereof |
| CN103421154B (en) * | 2013-07-25 | 2015-07-15 | 杭州师范大学 | Comb-shaped stem grafting copolymer containing reactive group and preparation method and application thereof |
| CN105542279A (en) * | 2016-01-18 | 2016-05-04 | 常州市双成塑母料有限公司 | Preparation method of highly-filled polyethylene master batch |
| CN107619544A (en) * | 2017-09-04 | 2018-01-23 | 珠海市南蓝塑胶科技有限公司 | Blue phase black agglomerate for AS or ABS and preparation method thereof |
| CN110760133A (en) * | 2019-11-25 | 2020-02-07 | 怀化东庆科技有限公司 | High-content carbon black master batch and preparation method thereof |
| CN112795069A (en) * | 2020-12-31 | 2021-05-14 | 山东环海塑业有限公司 | Preparation method of nano carbon black high-dispersion modified polyethylene pipe material |
| CN114921016A (en) * | 2022-06-29 | 2022-08-19 | 深圳市***新材料科技有限公司 | Black master batch for polyethylene modification and preparation method thereof |
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| CN103012902B (en) | 2014-11-05 |
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