CN103012902B - Black master-batch and preparation method thereof - Google Patents
Black master-batch and preparation method thereof Download PDFInfo
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- CN103012902B CN103012902B CN201210349504.5A CN201210349504A CN103012902B CN 103012902 B CN103012902 B CN 103012902B CN 201210349504 A CN201210349504 A CN 201210349504A CN 103012902 B CN103012902 B CN 103012902B
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- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 63
- 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
- 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 22
- 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
- 239000000155 melt Substances 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
- 230000007423 decrease Effects 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
- 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
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 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 production of carbon black mixed ingredients, and the 2nd, with carbonarius master batch, produce mixed ingredients.Due to the advantage of the aspects such as environmental protection, performance and usability, the coloring mode of black masterbatch obtains applying the most widely.
As everyone knows, carbon black is a kind of nano material, and its primary particle diameter, between 15-120nm, is generally efficient UV light absorber and photomask agent.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; In master batch, the content of carbon black is higher simultaneously, and adding proportion is less, and cost is lower, 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 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 formula, EBS are to improve the dispersiveness of carbon black.Adding of low molecule lubricant, will inevitably make material extending yield strength, flexural strength, shock strength performance significantly decline.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 one of this area always, is also the problem that the present invention solves emphatically.
Because polyethylene and polypropylene are all non-polar polyolefinic material, therefore polyethylene black masterbatch can successful Application in Pp System, but the consistency reason due 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 causing due to resin compatible problem, but due to the compatibility problem with Other Engineering plastics, make its scope of application very narrow.As AS black masterbatch can be in AS, ABS product, but cannot be for products such as polypropylene, nylon, polyester; Nylon 6 black masterbatchs can be in nylon 6 and nylon 66 products, but cannot be for products such as polypropylene, ABS, polyester.Due to aspects such as molecular chain characteristics, be not the high-quality carbon black master batch that every various engineering plastics may be used to produce high-content, high dispersive simultaneously.
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 ABS isopolarity polymkeric substance.
One of object of the present invention is to provide 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.Conventionally the product matrix resin of automobile and the application of electronic product field 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, 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 be greater than 5g/10min (190 ℃, 2.16kg); From the dispersiveness of carbon black, consider, be preferably more than 10g/10min (190 ℃, 2.16kg).
The choice relation of carbon black is the dispersiveness in matrix resin and look female processing characteristics to carbon black, and it is also 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 prior art.For requiring the injection-molded item of high blackness, generally select the carbon black that average primary particle diameter is 15～120nm.In polyethylene color masterbatch of the present invention, the average primary particle diameter of carbon black is less than or equal to 100nm, is preferably 15～50nm.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, and 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 obtaining 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 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, 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, 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 melt blending process, in polymer compatibilizer there is situ-formed graft chemical reaction in the functional group such as the active function groups of main chain and the carboxyl of carbon blacksurface, amino and hydroxyl, forms chemical bonding force and mortise.The polyethylene matrix resin of non-polar sidechain and black masterbatch has good consistency, between molecular chain, is intertwined mutually, and the polyethylene matrix resin of black masterbatch and the boundary strength between carbon black can improve greatly like this.The raising of boundary strength, can transmit 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 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 at least one or homopolymer or the multipolymer of several monomers in vinylidene, R 1216, tetrafluoroethylene, is preferably the multipolymer of vinylidene and tetrafluoroethylene.Take polyvinyl resin weight as 100 parts of calculating, and 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, with traditional dispersion agents such as polyethylene wax, to compare, 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 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 not exert an influence to the physical and mechanical properties of engineering plastics.
Two of object of the present invention is to provide a kind of preparation method of black masterbatch.
Comprise: described component is made to described black masterbatch after by described consumption melt blending.
Particularly, by 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.
In the preparation method of above-described black masterbatch of the present invention, can be by Banbury mixer general in prior art or twin screw extruder by described polyvinyl resin, carbon black in interior component melts blend.Described production unit can be Banbury mixer or twin screw extruder, preferably Banbury mixer.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 carbon black, carbon black coacervate is broken and carbon black is dispersed in vector resin uniformly; The melt blending time is 2～20min.
Black masterbatch of the present invention and true qualities engineering plastics, mix 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 blend granulation by 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, by melt blending, prepare mixed ingredients, again mixed ingredients is adopted to conventional injection moulding machine injection moulding, just can obtain high blackness, high performance engineering plastics product.
Embodiment
Below in conjunction with embodiment, further illustrate the present invention.
physical and mechanical properties:
Engineering plastics true qualities material mixing is made injection moulding sample preparation after mixed ingredients, test physical and mechanical properties.The kind of engineering plastics has ABS (trade mark 15A1, Tai Hua limited-liability company produce), acrylic resin PP (trade mark: 4220, Yanshan Petrochemical).Its test method is: true qualities engineering plastic resin is mixed with the ratio of black masterbatch according to 100: 2, and by 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: the blending ratio by engineering plastics base-material and black masterbatch according to 100: 2, then in twin screw extruder, granulation mixes, by mixed ingredients by injection moulding machine sample preparation, with the color (L of spectrophotometer test sample
*, a
*, b
*).L wherein
*numerical value for the blackness of exosyndrome material, numerical value is less, blackness is higher.
Embodiment 1
Control the mass content of carbon black 45%, add 0.5% parents' comb shaped polymer expanding material, 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 formula is as follows:
Ldpe resin (1F7B, China Petrochemical Corp. produces, 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
After mixing, put into Banbury mixer, discharging granulation after melt blending, obtains black masterbatch of the present invention, and melt blending temperature is 150 ℃.
To after the ABS melt blending described in above-mentioned black masterbatch and embodiment of the present invention, carry out performance test.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 formula is as follows:
Ldpe resin 100 weight parts
Carbon black 90 weight parts
BH-27 10 weight parts
After mixing, put into Banbury mixer, discharging granulation after melt blending, obtains black masterbatch of the present invention, and melt blending temperature is 150 ℃.
To after the ABS melt blending described in above-mentioned black masterbatch and embodiment of the present invention, carry out performance test.Specific performance test result is as shown in table 1.
Embodiment 3
Control the mass content of carbon black 45%, add 5% parents' comb shaped polymer expanding material, 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 grafting long-chain is 1-lauryl alcohol.Concrete formula is as follows:
Ldpe resin 100 weight parts
Carbon black 90 weight parts
PL-1 1 weight part
After mixing, put into Banbury mixer, discharging granulation after melt blending, obtains black masterbatch of the present invention, and melt blending temperature is 150 ℃.
To after the ABS melt blending described in above-mentioned black masterbatch and embodiment of the present invention, carry out performance test.Specific performance test result is as shown in table 1.
Comparative example 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 formula, other conditions as described in Example 2.Concrete formula is as follows:
Ldpe resin 100 weight parts
Carbon black 90 weight parts
100D 10 weight parts
After mixing, put into Banbury mixer, discharging granulation after melt blending, obtains black masterbatch of the present invention, and melt blending temperature is 150 ℃.
To after the ABS melt blending described in above-mentioned black masterbatch and embodiment of the present invention, carry out performance test.Specific performance test result is as shown in table 1.
Embodiment 4
Control the mass content of carbon black 45%, concrete formula is as follows:
Concrete formula is as follows:
Ldpe resin 100 weight parts
Carbon black 90 weight parts
BH-27 10 weight parts
After mixing, put into Banbury mixer, discharging granulation after melt blending, obtains black masterbatch of the present invention, and melt blending temperature is 150 ℃.
To after above-mentioned black masterbatch and acrylic resin PP (trade mark: 4220, Yanshan Petrochemical) melt blending, carry out performance test.Specific performance test result is as shown in table 1.
Comparative example 2
Except do not add parents' comb-shaped polymer expanding material in formula, other conditions as described in Example 4:
Ldpe resin (1F7B, China Petrochemical Corp. produces, MFR be 15g/10min (190 ℃, 2.16kg) 100 weight parts
Carbon black (BP800, average primary particle diameter is 30nm, Cabot company) 82 weight parts
After mixing, put into Banbury mixer, discharging granulation after melt blending, obtains black masterbatch of the present invention, and melt blending temperature is 150 ℃.
To after above-mentioned black masterbatch and acrylic resin PP (trade mark: 4220, Yanshan Petrochemical) melt blending, carry out performance test.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 formula is as follows:
After mixing, put into Banbury mixer, discharging granulation after melt blending, obtains black masterbatch of the present invention, and melt blending temperature is 150 ℃.
To after the ABS melt blending described in above-mentioned black masterbatch and embodiment of the present invention, carry out performance test.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 formula is as follows:
After mixing, put into Banbury mixer, discharging granulation after melt blending, obtains black masterbatch of the present invention, and melt blending temperature is 150 ℃.
To after the ABS melt blending described in above-mentioned black masterbatch and embodiment of the present invention, carry out performance test.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 formula is as follows:
After mixing, put into Banbury mixer, discharging granulation after melt blending, obtains black masterbatch of the present invention, and melt blending temperature is 150 ℃.
To after the ABS melt blending described in above-mentioned black masterbatch and embodiment of the present invention, carry out performance test.Specific performance test result is as shown in table 1.
Comparative example 3
Keep content of carbon black constant 45%, with other polymkeric substance solubilizing agent, replace parents' comb-shaped polymer expanding material, 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 formula is as follows:
After mixing, put into Banbury mixer, discharging granulation after melt blending, obtains black masterbatch of the present invention, and melt blending temperature is 150 ℃.
To after the ABS melt blending described in above-mentioned black masterbatch and embodiment of the present invention, carry out performance test.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 example 1 | 28.22 | 19.4 | 18.65 |
| Comparative example 2 | 24.1 | 18.2 | 20.26 |
| Comparative example 3 | 28.14 | 19.19 | 17.2 |
According to the testing data of the embodiment of upper table and comparative example, can find out, adopt black masterbatch of the present invention, not only have good consistency with polyolefine, and have good consistency with polar resin ABS; Under identical condition, the data of comparative example 1 and embodiment 2, comparative example 3 and embodiment 6 can be found out, with traditional technology, compare, and the present invention can give blackness and the better physical and mechanical properties that engineering plastics are higher.
Claims (7)
1. a black masterbatch, comprises the following component of blend:
The melt flow rate (MFR) of described polyvinyl resin is greater than 5g/10min, and 190 ℃, 2.16 ㎏;
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 obtaining 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 a kind of or composition in vinylformic acid, methacrylic acid, acrylate chloride, methacrylic chloride, Hydroxyethyl acrylate, 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, oleic acid;
Fluorocarbon polymer is homopolymer or the multipolymer of one or more monomers in vinylidene, R 1216, 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 is greater than 10g/10min, and 190 ℃, 2.16 ㎏.
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:
Described fluorocarbon polymer is the multipolymer of vinylidene and tetrafluoroethylene.
7. a preparation method for the black masterbatch as described in one of claim 1～6, comprising:
Described component is made to described black masterbatch after by described consumption melt blending.
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| 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 |
| CN107619544B (en) * | 2017-09-04 | 2020-03-17 | 珠海市南蓝塑胶科技有限公司 | Blue-phase black master batch 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 |
| CN114921016B (en) * | 2022-06-29 | 2023-07-07 | 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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| CN101148523A (en) * | 2007-11-01 | 2008-03-26 | 北京北化高科新技术有限公司 | Polyethylene color masterbatch and preparing method thereof |
| CN101528866A (en) * | 2006-10-31 | 2009-09-09 | 高帝斯股份有限公司 | Use of a comb polymer with at least one polyalkylene oxide grafted function as a mineral charge compatibility agent for chlorinated thermoplastic materials |
| 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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| CN101528866A (en) * | 2006-10-31 | 2009-09-09 | 高帝斯股份有限公司 | Use of a comb polymer with at least one polyalkylene oxide grafted function as a mineral charge compatibility agent for chlorinated thermoplastic materials |
| CN101148523A (en) * | 2007-11-01 | 2008-03-26 | 北京北化高科新技术有限公司 | Polyethylene color masterbatch and preparing method thereof |
| CN101870750A (en) * | 2010-06-02 | 2010-10-27 | 华东理工大学 | Comb copolymer, preparation method and application thereof |
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