CN115926317A - Color master batch, color-reinforced polypropylene material, and preparation method and application thereof - Google Patents
Color master batch, color-reinforced polypropylene material, and preparation method and application thereof Download PDFInfo
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- CN115926317A CN115926317A CN202211655349.XA CN202211655349A CN115926317A CN 115926317 A CN115926317 A CN 115926317A CN 202211655349 A CN202211655349 A CN 202211655349A CN 115926317 A CN115926317 A CN 115926317A
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- color
- master batch
- polypropylene material
- reinforced polypropylene
- titanium dioxide
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- -1 polypropylene Polymers 0.000 title claims abstract description 153
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 122
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 122
- 239000000463 material Substances 0.000 title claims abstract description 84
- 239000004595 color masterbatch Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 34
- 239000000314 lubricant Substances 0.000 claims abstract description 17
- 239000002981 blocking agent Substances 0.000 claims abstract description 16
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 14
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 9
- 239000003365 glass fiber Substances 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 21
- 239000000155 melt Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 9
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 7
- 229920001843 polymethylhydrosiloxane Polymers 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- HNMCSUXJLGGQFO-UHFFFAOYSA-N hexaaluminum;hexasodium;tetrathietane;hexasilicate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].S1SSS1.S1SSS1.[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] HNMCSUXJLGGQFO-UHFFFAOYSA-N 0.000 claims description 3
- 235000013799 ultramarine blue Nutrition 0.000 claims description 3
- BYUANIDVEAKBHT-UHFFFAOYSA-N [Mo].[Bi] Chemical compound [Mo].[Bi] BYUANIDVEAKBHT-UHFFFAOYSA-N 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 34
- 230000014759 maintenance of location Effects 0.000 abstract description 6
- 238000010298 pulverizing process Methods 0.000 abstract description 5
- 239000004033 plastic Substances 0.000 abstract description 4
- 229920003023 plastic Polymers 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 20
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 12
- 239000004611 light stabiliser Substances 0.000 description 7
- VPKQPPJQTZJZDB-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOC(=O)C=C VPKQPPJQTZJZDB-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 238000000227 grinding Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- QUKRIOLKOHUUBM-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOC(=O)C=C QUKRIOLKOHUUBM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000012754 barrier agent Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 238000004891 communication Methods 0.000 description 1
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- 230000005611 electricity Effects 0.000 description 1
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- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- ZZAMUZWGTXZGKY-UHFFFAOYSA-N n-(6-aminohexyl)-3-(3,5-ditert-butyl-4-hydroxyphenyl)propanamide Chemical compound CC(C)(C)C1=CC(CCC(=O)NCCCCCCN)=CC(C(C)(C)C)=C1O ZZAMUZWGTXZGKY-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
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- GKAVWWCJCPVMNR-UHFFFAOYSA-N tridecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCCCCCCCCCCC GKAVWWCJCPVMNR-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention provides a color master batch, a color reinforced polypropylene material, and a preparation method and application thereof, and belongs to the technical field of modified plastics. The color master batch comprises the following components in parts by weight: 100 parts of first polypropylene, 0.5-10 parts of inorganic color powder, 1-5 parts of titanium dioxide, 0.5-10 parts of blocking agent, 0.3-1 part of lubricant and 0.1-0.5 part of antioxidant; the blocking agent is perfluoroalkyl acrylate, and the surface of the titanium dioxide is coated with polysiloxane. The color reinforced polypropylene material contains the color master batch. The color reinforced polypropylene material has excellent weather resistance, small color difference after aging treatment, low material pulverization degree and high strength retention rate.
Description
Technical Field
The invention relates to the technical field of modified plastics, in particular to a color master batch, a color reinforced polypropylene material, and a preparation method and application thereof.
Background
Polypropylene (PP) is one of five common plastics, has the advantages of low specific gravity, temperature resistance, corrosion resistance, fatigue resistance, no toxicity, safety, easiness in processing and forming and the like, and is widely applied to the industries of household appliances, automobiles, industrial electronics and electricity and the like. In recent years, glass fiber reinforced polypropylene materials are more and more widely applied, and the application environment of the industries mainly outdoors and is particularly applied to colored polypropylene products, from the traditional household appliances to the fields of communication, low-speed travel, buildings, gardens/electric tools and the like.
In the field of modified plastics, the weather resistance of the material is improved by adding a light stabilizer or an ultraviolet absorber, and the method is a common technical means, and the method has a very obvious effect in the field of non-glass fiber reinforced polypropylene. However, for the glass fiber reinforced polypropylene material, polypropylene and glass fiber coexist on the surface of the material, after aging, a small amount of PP on the surface is degraded to enable the glass fiber to leak outwards, and the polypropylene-glass fiber interface is damaged in the aging process, so that the glass fiber is further easy to leak outwards, and the glass fiber leakage not only causes color difference of the material, but also reduces the strength of the material. Therefore, the effect of modifying the weather resistance of the glass fiber reinforced polypropylene material is very limited only by adding a light stabilizer or an ultraviolet absorber.
In addition, colored polypropylene materials are prone to fading and surface chalking in outdoor environments. The addition of the light stabilizer or the ultraviolet absorbent can not solve the problems of surface chalking and fading color difference caused by long-term outdoor aging of the colored polypropylene material.
Chinese patent CN105111590A discloses a high weather-resistant anti-aging glass fiber reinforced polypropylene and a preparation method thereof, which improves the color difference and the mechanical property of a colorful glass fiber reinforced PP material under the conditions of light and heat aging to a certain extent through the synergistic effect of components such as a compatible toughening agent, an antioxidant, a lubricant, a coupling agent, an ultraviolet absorbent, a thermal oxygen stabilizer and the like. However, the weather resistance of the colored glass fiber reinforced PP is improved to a limited extent, and the problem of pulverization of the material after aging is not solved.
Therefore, it is necessary to develop a color reinforced polypropylene material, which has excellent weather resistance, good strength after aging, low color difference and low pulverization degree.
Disclosure of Invention
The invention aims to overcome the defect of poor weather-resistant effect in the prior art, and provides a color master batch, which takes polypropylene as matrix resin of the master batch, and the color master batch has excellent weather resistance through the interaction of titanium dioxide, a blocking agent and other components with inorganic color powder.
The invention also aims to provide a preparation method of the color master batch.
The invention also aims to provide a color reinforced polypropylene material which contains the color master batch and has excellent weather resistance.
The invention also aims to provide a preparation method of the color reinforced polypropylene material.
The invention also aims to provide application of the color reinforced polypropylene material.
In order to achieve the purpose, the invention adopts the following technical scheme:
the color master batch comprises the following components in parts by weight:
the blocking agent is perfluoroalkyl acrylate, and the surface of the titanium dioxide is coated with polysiloxane.
The color master batch disclosed by the invention takes polypropylene as matrix resin of the master batch, and the color master batch has excellent weather resistance through the interaction of titanium dioxide, a blocking agent and other components with inorganic color powder, and a color polypropylene material prepared by subsequently adding the color master batch into a polypropylene material has good weather resistance.
The addition of the titanium dioxide enables the color polypropylene material to have good color stability, and is not easy to fade and generate color difference. The titanium dioxide has excellent hydrophobicity due to the fact that the surface of the titanium dioxide is coated with polysiloxane, toner aging caused by the existence of water in the outdoor environment is effectively slowed down, and further the color polypropylene material containing the color master batch has smaller color difference and better weather resistance after being used in the outdoor environment for a long time.
The invention adopts perfluoroalkyl acrylate as the blocking agent, the perfluoroalkyl acrylate has hydrophobic and oleophobic 'double-hydrophobic' protection effect, and has synergistic effect with titanium dioxide coated with polysiloxane on the surface, thereby further improving the weather resistance of the color master batch, and particularly aiming at the color difference and pulverization conditions possibly existing outdoors and caused by ultraviolet irradiation. The perfluoroalkyl acrylate has lower molecular weight, and is easy to migrate to the surface of a material by high-temperature processing in a polypropylene system, thereby greatly playing a role in protecting inorganic color powder.
Meanwhile, as the molecular chain of the perfluoroalkyl acrylate has strong polarity, the perfluoroalkyl acrylate can improve the interface effect between the polypropylene and the glass fiber, enhance the binding force between the glass fiber and the polypropylene, reduce the glass fiber leakage caused by the degradation of the polypropylene under the long-term ultraviolet irradiation, and avoid the material color whitening caused by the glass fiber leakage.
Preferably, the blocking agent is perfluoroalkyl ethyl acrylate, wherein the carbon number of the perfluoroalkyl is 4-8.
Specifically, the perfluoroalkylethyl acrylate may be at least one of perfluorobutyl ethyl acrylate, perfluorooctyl ethyl acrylate, and perfluorohexyl ethyl acrylate.
More preferably, the blocking agent is perfluorohexylethyl acrylate. The perfluorohexyl ethyl acrylate is more remarkably improved in weather resistance.
Preferably, the weight of polysiloxane in the titanium dioxide accounts for 0.5-2 wt% of the total weight of the titanium dioxide.
When the coating proportion of the polysiloxane is 0.5 to 2wt.%, the titanium dioxide has good hydrophobic property. The proportion of polysiloxane is too low, and the hydrophobicity of titanium dioxide is slightly poor; the color stabilizing effect of titanium dioxide on polypropylene materials can be influenced by the fact that the proportion of polysiloxane is too high.
Preferably, the polysiloxane is at least one of polydimethylsiloxane, phenyl polydimethylsiloxane and polymethylhydrosiloxane. More preferably, the polysiloxane is polymethylhydrosiloxane. The polymethylhydrosiloxane can enable the titanium dioxide to have more excellent hydrophobicity.
Preferably, the inorganic color powder is at least one of iron oxide red, ultramarine violet, ultramarine blue, molybdenum bismuth yellow and bismuth vanadate.
Preferably, the first polypropylene has a melt flow rate of 50 to 80g/10min at 230 ℃ under 2.16 kg.
The melt flow rate of the first polypropylene in the color master batch is not suitable to be too low, and when the melt flow rate is too low, the dispersion of the color master batch is influenced.
The melt flow rate of the polypropylene is measured according to ISO 1133-2011 standard method.
The lubricant may be a lubricant commonly used in polypropylene materials.
Optionally, the lubricant is at least one of an amide lubricant, a polyethylene lubricant, a stearic acid lubricant, and an ester lubricant.
Optionally, the amide lubricant is at least one of ethylene bis stearamide, oleamide, erucamide, stearamide.
Optionally, the polyethylene lubricant is at least one of polyethylene wax, oxidized polyethylene wax, and ethylene acrylic acid copolymer.
Optionally, the stearic acid-based lubricant is at least one of stearic acid and tridecyl stearate.
Optionally, the ester lubricant is at least one of a triglyceride and a monoglyceride.
The invention also provides a preparation method of the color master batch, which comprises the following steps:
mixing the first polypropylene, the inorganic color powder, the titanium dioxide, the blocking agent, the lubricant and the antioxidant, adding the mixture into an extruder, and performing melt mixing and extrusion granulation to obtain the color master batch.
Preferably, in the preparation method of the color master batch, the extruder is a double-screw extruder, the screw rotating speed of the double-screw extruder is 300-500rpm, and the melting temperature of the double-screw extruder is 190-220 ℃.
The invention also discloses a color reinforced polypropylene material which comprises the following components in parts by weight:
the color reinforced polypropylene material contains the color master batch, and has good weather resistance. The titanium dioxide in the color master batch is not directly blended and extruded with other components in the color enhanced polypropylene material, but is added in the form of master batch, so that the reduction of the material strength caused by the direct addition of the titanium dioxide is avoided, and the higher strength of the color enhanced polypropylene material is ensured.
Preferably, the second polypropylene is a mixture of medium melt index polypropylene resin and ultrahigh melt index polypropylene resin which are compounded in a weight ratio of (3-5) to 1;
the melt flow rate of the medium melt index polypropylene resin is 10-40 g/10min at 230 ℃ and 2.16kg, and the melt flow rate of the ultrahigh melt index polypropylene resin is more than or equal to 100g/10min at 230 ℃ and 2.16 kg.
The second polypropylene is a mixture of medium-melt-index polypropylene resin and ultrahigh-melt-index polypropylene resin, and the polypropylene resins with different melt flow rates are compounded according to the weight ratio of (3-5) to 1, so that on one hand, the good mechanical property of the color reinforced polypropylene material is ensured, on the other hand, the good coating of the polypropylene on glass fibers is realized, and the problem of material whitening caused by the leakage of the glass fibers is reduced.
Preferably, the melt flow rate of the medium-melt-index polypropylene resin at 230 ℃ and 2.16kg is 20-30 g/10min, and the melt flow rate of the ultrahigh-melt-index polypropylene resin at 230 ℃ and 2.16kg is 105-110 g/10min.
Preferably, the weight ratio of the melt index polypropylene resin to the ultrahigh melt index polypropylene resin in the second polypropylene is (3-4): 1.
Preferably, the glass fibers have an average diameter of 10 to 17 μm.
Preferably, the compatibilizer is maleic anhydride grafted polypropylene. More preferably, the grafting ratio of the maleic anhydride in the maleic anhydride grafted polypropylene is 0.5-1.5%.
Preferably, the weather resisting agent is a benzophenone light stabilizer and/or a hindered benzoate light stabilizer.
Optionally, the benzophenone light stabilizer is at least one of UV-9, UV-531 and UV-81.
Optionally, the hindered benzoate light stabilizer is at least one of UV-2908 and UV-120.
The antioxidant in the color reinforced polypropylene material and the antioxidant in the color master batch can be the same or different.
Preferably, the antioxidant is a hindered phenol antioxidant and/or a phosphite antioxidant.
More preferably, the antioxidant is at least one of 3, 5-di-tert-butyl-4-hydroxyphenylpropionyl-hexamethylenediamine (antioxidant 1098), tris (2, 4-di-tert-butylphenol phosphite) (antioxidant 168), and pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010).
The invention also provides a preparation method of the color reinforced polypropylene material, which comprises the following steps:
s1, mixing second polypropylene, a compatilizer, a weather-resistant agent and an antioxidant, adding the mixture into a main feeding port of an extruder, adding glass fibers into a side feeding port of the extruder, and performing mixing melting, extrusion and granulation to obtain a natural color reinforced polypropylene material;
and S2, mixing the natural color reinforced polypropylene material with the color master batch to obtain the color reinforced polypropylene material.
Preferably, in the step S1. Of the preparation method of the color reinforced polypropylene material, the extruder is a double-screw extruder, the screw rotating speed of the double-screw extruder is 300-500rpm, and the melting temperature of the double-screw extruder is 200-230 ℃.
The invention also protects the application of the color reinforced polypropylene material in the preparation of garden tool shells, outdoor stadium seats and exterior trimming parts of two-wheeled electric vehicles.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a color master batch and a color reinforced polypropylene material containing the color master batch, wherein the color reinforced polypropylene material has excellent weather resistance, small color difference after aging treatment, low material pulverization degree and high strength retention rate. The color master batch disclosed by the invention takes polypropylene as matrix resin of the master batch, and the color master batch has excellent weather resistance through the interaction of titanium dioxide, a blocking agent and other components with inorganic color powder, and a color polypropylene material prepared by subsequently adding the color master batch into a polypropylene material has good weather resistance. .
Detailed Description
The present invention will be further described with reference to specific examples for better illustrating the objects, technical solutions and advantages of the present invention, but the examples are not intended to limit the present invention in any way.
The examples and comparative examples in this application use the following raw material sources:
PP-1, polypropylene, H9018, lanzhou petrochemical company, with a melt flow rate of 50g/10min at 230 ℃ under 2.16 kg;
PP-2, polypropylene, BJ380MO, bolu corporation, melt flow rate of 80g/10min at 230 ℃ under 2.16 kg;
PP-3, polypropylene, S2040, shanghai Seiki Co., ltd., melt flow rate of 40g/10min at 230 ℃ under 2.16 kg;
PP-4, polypropylene, HP500N, mediterranean Shell, melt flow rate at 230 ℃ under 2.16kg of conditions of 10g/10min;
PP-5, polypropylene, PPH-Y26 Zhenhai refinery, melt flow rate at 230 deg.C under 2.16kg is 25g/10min;
PP-6, polypropylene, K7100 Yanshan petrochemical, with a melt flow rate of 105g/10min at 230 ℃ under 2.16 kg;
PP-7, polypropylene, PP MH7900, LG Chemicals, melt flow rate of 110g/10min at 230 ℃ under 2.16 kg;
inorganic color powder-1, red iron oxide, R206 langerhan corporation;
inorganic color powder-2, ultramarine blue, L303 floride corporation;
inorganic color powder-3, bismuth yellow, Y229C Heubach Co;
organic toner, red Arrovide Red DG, craiden;
titanium dioxide-1, coating 2wt.% of polydimethylsiloxane titanium dioxide on the surface, and self-made;
titanium dioxide-2, which is self-made by coating titanium dioxide with 0.5wt.% of polydimethylsiloxane on the surface;
titanium dioxide-3, coating 2wt.% of polymethylhydrosiloxane titanium dioxide on the surface, and self-made;
the self-making method of the titanium dioxide 1-3 comprises the following steps: placing titanium dioxide (R104, ke Si Ltd., untreated titanium dioxide) and polydimethylsiloxane or polymethylhydrosiloxane in a high-speed mixer according to the weight ratio, wherein the temperature is 60 ℃, the rotating speed is 500R/min, and the mixing time is 60min;
titanium dioxide-4, untreated titanium dioxide, R104 kovic;
barrier agent-1, perfluorohexylethyl acrylate, merck;
blocking agent-2, perfluoro octyl ethyl acrylate, SF-000121 upper fluorine technology;
a barrier agent-3, perfluorobutyl ethyl acrylate, and a Jinan Tutai Fuchu chemical industry;
lubricants, ethylene bis stearamide, commercially available;
antioxidant, a mixture of antioxidant 1010 and antioxidant 168, commercially available;
compatibilizer, maleic anhydride grafted polypropylene, with a grafting rate of 1%, BONDYRAM 1001CN pleron corporation;
glass fibers, 13 μm in diameter and 4mm in length, commercially available;
weather resistant agent, benzophenone weather resistant agent, UV-531, commercially available.
Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. Unless otherwise indicated, reagents and materials used in the present invention are commercially available.
Examples 1 to 12
Examples 1-12 provide a masterbatch, having the component contents shown in tables 1-1 and 1-2, prepared as follows:
mixing the components according to the table 1, wherein the rotating speed of a mixing machine for mixing is 300-500rpm, the mixing time is 10-30min, then adding the mixture into a double-screw extruder, and carrying out melt mixing and extrusion granulation, wherein the rotating speed of a screw of the double-screw extruder is 300-500rpm, and the melting temperature is 190-220 ℃ to obtain the color master batch.
Table 1-1 examples 1-6 color concentrates the component content (parts by weight)
TABLE 1-2 color masterbatch component contents (parts by weight) of examples 7-12
Examples 13 to 28
Examples 13-28 provide a color-reinforced polypropylene material having the component contents shown in tables 2-1 and 2-2, prepared as follows:
according to the table 2, all the components except the glass fiber and the color master batch are mixed and added into a main feeding port of a double-screw extruder, the glass fiber is added into a side feeding port of the double-screw extruder, and the mixture is melted and extruded for granulation, wherein the screw rotating speed of the double-screw extruder is 300-500rpm, and the melting temperature is 200-230 ℃, so that the natural color reinforced polypropylene material is obtained;
s2, placing the natural color reinforced polypropylene material and the color master batch into a low-speed mixer for mixing at a rotating speed of 100r/min for 10min to obtain the color reinforced polypropylene material.
TABLE 2-1 example 13-20 color-reinforced Polypropylene materials component amounts (parts by weight)
TABLE 2-2 component contents (in parts by weight) of color-reinforced polypropylene materials of examples 21 to 28
Comparative examples 1 to 4
Comparative examples 1 to 4 provide a masterbatch, the component contents of which are shown in table 3, and the preparation method is as follows:
the components are mixed according to the table 3, and then added into a double-screw extruder, and subjected to melt mixing, extrusion granulation, wherein the screw rotating speed of the double-screw extruder is 300-500rpm, and the melting temperature is 190-220 ℃, so that the color master batch is obtained.
TABLE 3 ingredient contents (parts by weight) of comparative examples 1 to 4 color master batches
Comparative examples 5 to 8
Comparative examples 5 to 8 provide a color-reinforced polypropylene material having the component contents shown in Table 4, and the preparation method was as follows:
according to the table 4, all the components except the glass fiber and the color master batch are mixed and added into a main feeding port of a double-screw extruder, the glass fiber is added into a side feeding port of the double-screw extruder, and the mixture is melted and extruded for granulation, wherein the screw rotating speed of the double-screw extruder is 300-500rpm, and the melting temperature is 200-230 ℃, so that the natural color reinforced polypropylene material is obtained;
s2, placing the natural color reinforced polypropylene material and the color master batch into a low-speed mixer for mixing at a rotating speed of 100r/min for 10min to obtain the color reinforced polypropylene material.
TABLE 4 comparative examples 5 to 8 component contents (parts by weight) of color-reinforced polypropylene materials
Comparative example 9
Comparative example 9 provides a color-reinforced polypropylene material having the following components in parts by weight: PP-3 parts, PP-6 parts, glass fiber 30 parts, weather resistant agent 0.5 part, antioxidant 0.53 part, PP-1 part, titanium dioxide-1.3 parts, inorganic color powder-1.18 parts, blocking agent 0.48 part and lubricant 0.03 part;
the preparation method comprises the following steps:
mixing all the components except the glass fiber, adding the mixture into a main feeding port of a double-screw extruder, adding the glass fiber into a side feeding port of the double-screw extruder, and performing mixing melting, extrusion and granulation, wherein the screw rotating speed of the double-screw extruder is 300-500rpm, and the melting temperature is 200-230 ℃, so as to obtain the color reinforced polypropylene material.
Namely, the difference from example 13 is that: the color master batch is not prepared first, but all the components are directly mixed and extruded.
Performance testing
The properties of the color reinforced polypropylene materials obtained in the above examples and comparative examples are characterized, and the specific test items and test methods are as follows:
and (3) outdoor aging: preparing a 50mm color plate from a color reinforced polypropylene material, placing the color plate under outdoor conditions, placing the color plate on a frame, forming an angle of 135 degrees between the front surface and the horizontal plane, carrying out natural aging in outdoor environment, testing the period for 12 months, testing the color difference of a sample before and after the outdoor aging, observing the powdering condition of the sample after the outdoor aging, and recording the time (unit: day) for starting the powdering;
indoor accelerated aging: preparing a color reinforced polypropylene material into a 50mm per 50mm color plate and a tensile sample bar, carrying out aging treatment for 1500h according to an ISO 4892-2-2013Cycle1 standard method, testing the tensile strength retention rate and the color difference of a sample before and after indoor accelerated aging, observing the powdering condition of the sample after indoor accelerated aging, and recording the time (unit: hour) for starting powdering;
wherein the tensile strength is tested according to the method of ISO 527-2012, the tensile speed is 10mm/min, and the tensile strength retention rate = (tensile strength after aging/tensile strength before aging) × 100%;
the color difference before and after aging was measured using a color difference meter under a D65 illuminant.
The test results of examples and comparative examples are shown in tables 5 and 6.
TABLE 5 test results of the examples
Table 6 test results of comparative examples
According to the test results in table 5, in combination with the component contents in tables 1 and 2, it can be seen that the color master batch of the embodiments of the present invention has good aging resistance, and the color reinforced polypropylene material containing the color master batch has characteristics of small color difference, chalking resistance, and high mechanical property retention rate after aging.
According to the test results of the embodiments 13, 21 and 22, the color reinforced polypropylene material using the color master batch 10 has relatively better aging resistance, less color difference generated by outdoor aging and indoor accelerated aging, no chalking, and a retention rate of tensile strength of 95.4% after indoor accelerated aging. It can be seen that the titanium dioxide coated by the polymethylhydrosiloxane can make the color master batch have more excellent weather resistance.
According to the test results of examples 13, 23 and 24, the color reinforced polypropylene material adopting the color master batch 1 has relatively better aging resistance, and particularly, the color difference after aging is obviously smaller than that of the color difference of the color master batch of the examples 23 and 24. It can be seen that perfluorohexylethyl acrylate, as a barrier agent, is more remarkably improved in weather resistance.
According to examples 25 to 28, two polypropylene resins with different melt flow rates in the second polypropylene of the color-reinforced polypropylene material also have some influence on the aging resistance of the material. When the medium melt index polypropylene resin with the melt flow rate of 10-40 g/10min and the ultrahigh melt index polypropylene resin with the melt flow rate of more than or equal to 100g/10min are compounded in the weight ratio of (3-5) to 1 to serve as second polypropylene, the prepared color reinforced polypropylene material has better aging resistance.
Table 4 shows the test results of the comparative examples. The color master batch used in the color enhanced polypropylene material of comparative example 5 does not contain titanium dioxide, and the color master batch used in the color enhanced polypropylene material of comparative example 7 does not contain a barrier agent. It can be seen that the aging resistance of the prepared material is poor when the titanium dioxide or the blocking agent is lacked; and the titanium dioxide and the blocking agent play a certain role in synergy, and the aging resistance of the prepared color reinforced polypropylene material is obviously improved under the condition of cooperative use.
The titanium dioxide in the color master batch used in the comparative example 6 is not modified, and although the weather resistance of the comparative example 6 is improved to a certain extent compared with that of the comparative example 5, such as slightly reduced color difference and slightly increased chalking time, the aging resistance is still poorer compared with that of the example.
Comparative example 9 is a one-step process, i.e. differs from example 13 in that: the color master batch is not prepared first, but all the components are directly mixed and extruded. Due to one-step and machine-through production, the initial tensile strength of the prepared color reinforced polypropylene material is lower than that of the other schemes by more than 20%. The colored reinforced polypropylene material of comparative example 12 also had poor aging resistance at lower initial tensile strength.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The color master batch is characterized by comprising the following components in parts by weight:
the blocking agent is perfluoroalkyl acrylate, and the surface of the titanium dioxide is coated with polysiloxane.
2. The color masterbatch of claim 1, wherein the blocking agent is a perfluoroalkyl ethyl acrylate, wherein the number of carbon atoms of the perfluoroalkyl group is 4-8.
3. The color master batch according to claim 1, wherein the weight of the polysiloxane in the titanium dioxide accounts for 0.5-2% of the total weight of the titanium dioxide.
4. The masterbatch according to claim 1 or 3, wherein the polysiloxane is at least one of polydimethylsiloxane, phenyl polydimethylsiloxane, and polymethylhydrosiloxane.
5. The color masterbatch according to claim 1, wherein the inorganic color powder is at least one of red iron oxide, ultramarine red, ultramarine violet, ultramarine blue, bismuth molybdenum yellow, and bismuth vanadate.
6. The masterbatch of claim 1, wherein the first polypropylene has a melt flow rate of 50-80 g/10min at 230 ℃ and 2.16 kg.
7. A process for the preparation of the masterbatch according to any one of claims 1 to 6, comprising the steps of:
mixing the first polypropylene, the inorganic color powder, the titanium dioxide, the blocking agent, the lubricant and the antioxidant, adding the mixture into an extruder, and performing melt mixing and extrusion granulation to obtain the color master batch.
8. The color reinforced polypropylene material is characterized by comprising the following components in parts by weight:
9. a method for preparing a color-reinforced polypropylene material according to claim 8, comprising the steps of:
s1, mixing second polypropylene, a compatilizer, a weather-resistant agent and an antioxidant, adding the mixture into a main feeding port of an extruder, adding glass fibers into a side feeding port of the extruder, and performing mixing melting, extrusion and granulation to obtain a natural color reinforced polypropylene material;
s2, mixing the natural color reinforced polypropylene material with the color master batch of any one of claims 1 to 6 to obtain the color reinforced polypropylene material.
10. Use of the color-reinforced polypropylene material according to claim 8 for the production of housings for garden tools, seats for outdoor stadiums, exterior trim for two-wheeled electric vehicles.
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