CN112745665B - Polypropylene material injection molding flow pattern effect master batch and preparation method thereof - Google Patents
Polypropylene material injection molding flow pattern effect master batch and preparation method thereof Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
Abstract
The invention provides polypropylene material injection molding manifold effect master batch, a preparation method and application thereof, wherein the master batch comprises the following components in parts by weight: 40-70 parts of PA6 resin; 10-20 parts of HDPE resin; 4-10 parts of a compatilizer; 4-10 parts of a styrene-based elastomer; 2-5 parts of PP resin; 1-3 parts of a dispersing agent; 0.1-1 part of antioxidant; 1-30 parts of pigment; 0-30 parts of a filling material; the relative viscosity value of the PA6 resin is less than or equal to 2.8; the HDPE resin has a melt index less than or equal to 3g/10min at 190 ℃ under the load of 2.16 Kg. The product prepared from the master batch has a good flow pattern effect.
Description
Technical Field
The invention relates to the technical field of color master batches, in particular to a polypropylene material injection molding flow line effect master batch and a preparation method thereof.
Background
Along with the application and popularization of plastic products, new modification schemes and appearance effect schemes are continuously developed in the application of plastic products in daily necessities, packages, artware, household appliances and automobile accessories, the trend of plastic engineering and appearance spraying-free trend is greatly broken through, particularly, polypropylene materials realize high-gloss modification and spraying-free coloring in household appliance series due to good processing and forming performance, heat resistance, rigidity and the like, the polypropylene materials also become structural parts and appearance parts in the automobile field, the requirement of personalized design cannot be met by using the traditional color master batch coloring to present single color effect, the pushing of the spraying-free coloring effect solves the complex process and the pollution to the environment in the traditional spraying process in a certain sense, the cost also has great advantage, and the realization of the flow line effect makes us more choices in the spraying-free appearance design, meanwhile, the printing-free personalized effect is realized, the bright surface effect is achieved, the texture of different layers is contained, and the texture imitating natural ecology is realized.
Chinese patent (CN108976602A) discloses an imitation marble master batch suitable for PP, the design method mainly uses a formula mode of PA + PP + flexibilizer to prepare the master batch, a more prominent defect exists in the design that PA and PP are originally non-meltable polymers, a blend can not achieve the uniform dispersion of a two-phase structure when no effective graft modification polymer is added, the blend is still in a mutually separated two-phase structure, when the PA is added into PP matrix resin, the PP can be easily melted in a PP matrix to form a conventional coloring effect, and the PA non-meltable phase can form concentrated and separated point-like or block-like objects in a product, at the moment, the appearance of the colored product is not beneficial to forming texture in the uniform flow direction and can also generate local flaws; in addition, if a melt finger or an improperly viscous formulation is selected, either the melt disperses completely or an unmelted mass is present during the molding process.
Disclosure of Invention
The invention provides a polypropylene material injection molding master batch with the flow pattern effect, aiming at overcoming the defect of poor flow pattern effect in the prior art.
The invention also aims to provide a preparation method of the polypropylene material injection molding flow pattern effect master batch.
The invention also aims to provide a product of the polypropylene material injection molding manifold effect master batch.
In order to achieve the purpose, the invention adopts the technical scheme that:
a polypropylene material injection molding flow pattern effect master batch comprises the following components by weight:
the relative viscosity value of the PA6 resin is less than or equal to 2.8;
the HDPE resin has a melt index less than or equal to 3g/10min at 190 ℃ under the load of 2.16 Kg.
The invention adopts PA6 resin and HDPE resin as matrix resin, and realizes the flow pattern effect by adjusting the relative viscosity value of PA6 resin and the melt index of HDPE resin; the compatilizer is adopted to improve the compatibility of the resin, the PP resin is adopted to improve the compatibility of the master batch with the flow pattern effect and the PP matrix resin, and the styrene elastomer is added to improve the toughness of the master batch and improve the flow pattern effect.
Preferably, the styrene-based elastomer is a styrene block copolymer.
Preferably, characterized in that said styrene block copolymer is a linear SBS block copolymer.
Preferably, the compatibilizer is one selected from maleic anhydride grafted PP, maleic anhydride grafted PE, and maleic anhydride grafted POE.
More preferably, the compatibilizer is maleic anhydride grafted POE.
More preferably, the grafting ratio of the compatilizer is more than or equal to 0.5-1%.
Preferably, the PP resin has a melt index of 10g/10min or less at 230 ℃ under a load of 2.16 Kg.
Preferably, the dispersant is one of polyethylene wax, polypropylene wax, EVA wax, EBS, polyester wax or stearate.
The antioxidant is one of phenol antioxidant, amine antioxidant, phosphite antioxidant or sulfur-containing antioxidant.
The classes of such pigments include, but are not limited to, commercially available inorganic pigments, organic pigments, and metal effect pigments, for example, inorganic pigments including titanium dioxide, zinc sulfide, carbon black, ultramarine, titanium yellow, iron red, and other metal oxide pigments; the organic pigment includes azo-structured pigments, phthalocyanine-structured pigments, dioxazines, quinacridones, isoindolines, isoindolinones, perylenes, quinophthalones, pyrrolopyrroles, anthraquinones, metal complex pigments, and the like; the metal effect pigment comprises one or a mixture of mica pearl powder, noctilucent pigment and fiber point effect material.
The filling material also comprises one or a mixture of more of powdery calcium carbonate, talcum powder, barium sulfate, titanium dioxide, wollastonite, glass beads, wollastonite and high clay.
The invention also provides a preparation method of the polypropylene material injection molding flow pattern effect master batch, which comprises the following steps:
s1, weighing PA6 resin, HDPE resin, compatilizer, styrene elastomer, PP resin, dispersant, antioxidant, pigment and filling material in proportion, and mixing and pre-dispersing to obtain a pre-dispersed mixture;
and S2, putting the pre-dispersed mixture obtained in the step S1 into an extruder for extrusion, bracing, granulating and granulating to obtain the master batch.
And drying the cut mother grain product in a drying material tank at 100 ℃ for 1 hour, and then sealing, packaging and packaging.
The screw rotating speed of the extruder is 400-600 revolutions per minute, and the extrusion feeding rotating speed is 30-45 HZ.
A product with the flow pattern effect contains the polypropylene material injection molding flow pattern effect master batch.
The product with the flow pattern effect can be obtained by a conventional injection molding preparation method; the preparation method comprises the following steps:
adding 0.5-5% of single-component flow pattern master batch and traditional PP coloring master batch into the prepared flow pattern master batch and traditional PP coloring master batch according to formula requirements, stirring and mixing the single-component flow pattern master batch and the traditional PP coloring master batch with a coloring PP base material, and then putting the mixture into an injection molding machine for injection molding of a workpiece;
setting the temperature of an injection molding machine at 200 ℃, 220 ℃, 225 ℃, 230 ℃, the plasticizing backpressure at 0-0.5 Mpa, the injection molding pressure at one section of 30Mpa, at two sections of 60Mpa and at three sections of 45Mpa, and keeping the pressure and cooling for 10 seconds;
the injection molded article is a PP article with a flow pattern appearance effect, and each sample has uniqueness.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts PA6 resin and HDPE resin as matrix resin, and realizes the flow pattern effect by adjusting the relative viscosity value of PA6 resin and the melt index of HDPE resin; the styrene-based elastomer is selected, so that the toughness of the master batch can be improved, and the flow pattern effect can be further improved.
Drawings
FIG. 1 is a schematic representation of an article prepared from the flow-textured masterbatch prepared in example 1;
FIG. 2 is a schematic representation of an article prepared from the fluid-textured masterbatch prepared in example 11;
FIG. 3 is a schematic representation of an article prepared from the fluid-textured masterbatch prepared in example 10;
FIG. 4 is a schematic representation of an article prepared from the fluid-textured masterbatch prepared in example 12;
FIG. 5 is a schematic representation of an article prepared from the flow-textured masterbatch prepared in example 1;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, but the embodiments of the present invention are not limited thereto.
The reagents, methods and equipment used in the invention are conventional in the technical field unless otherwise specified.
The following examples and comparative examples employ the following starting materials:
PA6 resin a: PA 6M 2800, medada polyamide; the relative viscosity number was 2.8;
PA6 resin B: PA6 BL3200H, barlingite; the relative viscosity number is 2;
PA6 resin C: PA 61340, barlington; the relative viscosity number was 3.3;
HDPE resin A: HDPE 7750P, liaoyang petrochemical; a melt index at 190 ℃ of 3g/10min under 2.16 Kg;
HDPE resin B: HDPE 3300F, winnowing; melt index at 190 ℃ under 2.16Kg of 1g/10 min;
HDPE resin C: HDPE5502, chrysene shanghai; a melt index of 0.5g/10min at 190 ℃ under 2.16 Kg;
HDPE resin D: HDPE 2200J, yanshan petrochemical; a melt index at 190 ℃ under 2.16Kg of 5g/10 min;
a compatilizer A: LEP-1A, Shenyang Ketong; maleic anhydride grafted POE with grafting rate of 0.5-0.8%;
a compatilizer B: PC-28A, south China sea cypress morning; maleic anhydride grafted POE with grafting rate of 0.7-1%;
a compatilizer C: n406, light of Nile energy; maleic anhydride-grafted POE with a grafting rate of 0.35%;
a compatilizer D: PC-8C, south China sea cypress morning; maleic anhydride grafted POE with a grafting rate > 1%;
styrene-based elastomer: SBS YH-792E, Basil petrochemical;
PP resin: PP HP500N zhonghai shell;
dispersing agent: A-C6A HELLYWELL;
antioxidant: IRGANOX 1076, IRGANOX 1098, IRGANOX 168. basf;
pigment A: phthalocyanine green GNX colain;
pigment B: phthalocyanine blue BS chanzhou yapa;
pigment C: iron red 130M germany bayer;
pigment D: titanium white RCL-69 American couplet;
filling materials: wollastonite Cabot;
the present invention will be described in detail below with reference to examples and comparative examples.
The following examples and comparative examples were prepared into a flow grain effect master batch by the following method, and the components were weighed according to the weight ratios in tables 1 to 3; the method comprises the following specific steps:
s1, weighing PA6 resin, HDPE resin, compatilizer, styrene elastomer, PP resin, dispersant, antioxidant, pigment and filling material in proportion, and mixing and pre-dispersing to obtain a pre-dispersed mixture;
s2, putting the pre-dispersed mixture obtained in the step S1 into an extruder for extrusion, bracing, granulating and granulating to obtain the master batch.
And drying the cut mother particle product in a drying material tank with the temperature of 100 ℃ for 1 hour, and then sealing, packaging and packaging.
The rotating speed of a screw of the extruder is 400-600 revolutions per minute, and the rotating speed of the extrusion feeding is 30-45 HZ.
The product with the flow pattern effect is further prepared from the flow pattern master batch prepared in the embodiment, and the method comprises the following specific steps:
combining the flow line master batch and the traditional PP coloring master batch, stirring and mixing the flow line master batch and the coloring PP base material, and then putting the mixture into an injection molding machine for injection molding of a workpiece; the flow line master batch accounts for 2 percent of the total mass.
The temperature of the injection molding machine is set to be 200 ℃, 220 ℃, 225 ℃, 230 ℃, the plasticizing backpressure is 0-0.5 Mpa, the injection molding pressure is 30Mpa at one section, 60Mpa at two sections and 45Mpa at three sections, and the pressure maintaining and cooling time is 10 seconds.
Examples 1 to 6
TABLE 1 formulations (parts) of examples 1 to 6
Examples 7 to 12
TABLE 2 formulations (parts) of examples 7 to 12
Examples 14 to 16
TABLE 3 formulations (parts) of examples 14 to 16
Comparative examples 1 to 6
TABLE 4 formulations (parts) of comparative examples 1 to 6
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| PA6 resin A | 48 | 48 | — | 48 | 48 | 48 |
| PA6 resin C | — | — | 48 | — | — | — |
| HDPE resin A | — | 20 | 20 | — | 20 | 20 |
| HDPE resin D | — | — | — | 20 | — | — |
| Compatibilizer C | — | — | — | — | 4 | — |
| Compatibilizer B | 4 | 4 | 4 | 4 | — | — |
| Compatibilizing agent D | — | — | — | — | — | 4 |
| Styrene-based elastomersBody | 4 | — | 4 | 4 | 4 | 4 |
| PP resin | 5 | 5 | 5 | 5 | 5 | 5 |
| Dispersing agent | 2 | 2 | 2 | 2 | 2 | 2 |
| Antioxidant agent | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| Pigment A | 7 | 7 | 7 | 7 | 7 | 7 |
| Filling material | 10 | 10 | 10 | 10 | 10 | 10 |
The examples and comparative examples described above were all examined by the appearance of "flow marks, color lumps or color spots, fusibility".
TABLE 5 data for examples and comparative examples
From examples 1 to 3, the flow pattern effect was more pronounced with increasing HDPE resin, and the color also became darker
From examples 3 to 6, the flow pattern layering was more intense as the content of the styrene-based elastomer was increased
From examples 3 and 7-8, with the increase of the content of PA6, the flow lines are changed from the radioactive thin strips into the cloud irregular distribution, and the layering effect is obvious
From examples 8 and 9, it can be seen that good flow marks can be achieved with a grafting degree of the compatibilizer in the range of 0.5 to 1%.
From examples 9 to 12, it can be seen that different colors of flow marks can be obtained by adding different colors of pigments.
From examples 3 and 13, PA6 having a viscosity within 2.8 had a desirable flow pattern
From examples 3 and 13-15, the HDPE resin has a melt index within 3.0 and a good flow pattern effect, which changes from fine-grained to cloud-like as the melt index of the HDPE decreases.
From example 16, no filler material was added, and the flow pattern effect was not affected.
As can be seen from the results and expected designs obtained in the above examples, too high viscosity of the PA resin is not favorable for system flow and formation of flow texture, which results in lump formation, while too high melt index of HDPE is also easy to cause excessive melt dispersion during molding and failure of texture formation, and also, the control of the grafting ratio of the solubilizer is important, and both too high and too low have an influence on the formation of texture. Different patterns with different flow line effects can be realized by adding different colors, and the functional filler can be added according to the actual requirements of the formula without generating negative effects on the flow line effects.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (6)
1. The polypropylene material injection molding manifold effect master batch is characterized by comprising the following components in parts by weight:
the relative viscosity value of the PA6 resin is 2-2.8;
the HDPE resin has a melt index of 1-3 g/10min at 190 ℃ under a load of 2.16 Kg;
the compatilizer is maleic anhydride grafted POE;
the grafting rate of the compatilizer is 0.5-1%;
the melt index of the PP resin is less than or equal to 3g/10min under the conditions of 230 ℃ and 2.16Kg of load.
2. The polypropylene material injection molding manifold effect masterbatch of claim 1, wherein the styrene-based elastomer is a styrene block copolymer.
3. The injection molded streaming effect masterbatch of polypropylene material of claim 2, wherein the styrene block copolymer is a linear SBS block copolymer.
4. The polypropylene material injection molding flow pattern effect master batch according to claim 1, wherein the dispersing agent is one of polyethylene wax, polypropylene wax, EVA wax, EBS, polyester wax or stearate.
5. The preparation method of the polypropylene material injection molding flow line effect master batch according to any one of claims 1 to 4, characterized by comprising the following steps:
s1, weighing PA6 resin, HDPE resin, compatilizer, styrene elastomer, PP resin, dispersant, antioxidant, pigment and filling material in proportion, and mixing and pre-dispersing to obtain a pre-dispersed mixture;
and S2, putting the pre-dispersed mixture obtained in the step S1 into an extruder for extrusion, bracing, granulating and granulating to obtain the master batch.
6. A product with a flow pattern effect, characterized by comprising the polypropylene material injection molded flow pattern effect master batch of any one of claims 1 to 4.
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| CN104151710A (en) * | 2014-08-21 | 2014-11-19 | 青岛骏泽盛泰智能科技有限公司 | PP/PA6/PE composite material |
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| CN108976602A (en) * | 2018-08-07 | 2018-12-11 | 东莞市荣晟颜料有限公司 | A kind of marbling master batch suitable for PP |
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