CN112142997A - Functional master batch for improving appearance flow mark defect of spraying-free material and preparation method - Google Patents
Functional master batch for improving appearance flow mark defect of spraying-free material and preparation method Download PDFInfo
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- 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
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- 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
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- C08J2423/14—Copolymers of propene
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- 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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- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K2003/0806—Silver
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K2003/0812—Aluminium
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- C08K2003/0831—Gold
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C08K2003/085—Copper
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0893—Zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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Abstract
The invention discloses a functional master batch for improving the appearance flow mark defect of a spraying-free material and a preparation method thereof, and relates to the technical field of high polymers, wherein the metal silver polypropylene functional master batch comprises 15-40 parts of polypropylene, 30-50 parts of modified nano silicon dioxide, 20-35 parts of surface modified metal pigment, 1-5 parts of compatilizer and 3-6 parts of other auxiliary agents by weight; the invention prepares the fluid silicon dioxide nanometer ionic material with a core-shell structure by an acid-base neutralization method. The modified nano silicon dioxide fluid is coated on the surface of the metal pigment to form a protective layer, and strong-polarity amino groups are introduced on a nonpolar molecular main chain, so that the dispersion of the metal pigment in polypropylene is greatly improved, the flow direction stability of the metal pigment in molten polypropylene plastic in a mold cavity can be effectively improved, the change of the arrangement direction of the flaky metal pigment in a melt is greatly reduced, the original parallel arrangement is kept, and the flow mark or water inclusion mark symptoms on the surface of a product are improved.
Description
Technical Field
The invention relates to the technical field of macromolecules, in particular to a functional master batch for improving the appearance flow mark defect of a spraying-free material and a preparation method thereof.
Background
In recent years, with the continuous improvement of living standard and the continuous improvement of national requirements for environmental protection, the paint spraying process has the defects of easy paint dropping, difficult repair after paint dropping, complex process, non-recyclable production defective products and the like due to large environmental pollution, and is more and more concerned by people. With the development of materials and mold processes, spray-free materials replacing spray coating processes become a new application trend of plastic products.
The spraying-free plastic is a product which is prepared by adding pigments with special color effects such as metal pigments, pearlescent pigments and the like into resin and further has the effect similar to that of spray painting. The existing surface spraying plastic is influenced by the structure of parts, rib positions and the like when an injection molding manufacturer performs injection molding, and the appearance defects such as flow marks and the like easily appear on the surface of a spraying-free plastic product, so that the batch use of the spraying-free plastic is influenced. In recent years, bimodal polypropylene is proposed to improve appearance flow marks, but through the verification of practical projects, the bimodal polypropylene metal silver cannot well solve the flow mark problem. Therefore, the functional master batch for improving the flow marks has wide market prospect.
Disclosure of Invention
In order to solve the defects in the background art, the invention aims to provide a functional master batch for improving the defect of flow marks on the appearance of a spraying-free material and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
a functional master batch for improving the appearance flow mark defect of a spraying-free material comprises the following raw materials in parts by weight:
15-40 parts of polypropylene;
30-50 parts of modified nano silicon dioxide;
20-35 parts of a surface modified metal pigment;
1-5 parts of a compatilizer;
3-6 parts of other auxiliary agents.
Further, the polypropylene is copolymerized polypropylene, and the melt index of the copolymerized polypropylene is 3-60g/10 min.
Further, the preparation method of the modified nano-silica comprises the following steps:
1) respectively dissolving silica sol, 1, 3-propane sultone and sodium hydroxide into distilled water to respectively obtain diluent a, diluent b and diluent c, dropwise adding a into the solution b to obtain a silicon dioxide modified solution d, then adding c into d, stirring and heating, dialyzing by using a biological dialysis bag, and removing small molecular substances to obtain a mixed solution e.
2) Taking a polyether monoamine solution, diluting with water to obtain a diluent f, titrating e on a constant-temperature magnetic stirrer to obtain a polyether amine/silicon dioxide aqueous solution, and then placing the solution in an electric heating drying oven for vacuum drying to obtain the modified silicon dioxide.
Further, the preparation method of the surface modified metal pigment comprises the following steps:
(1) carrying out ion exchange by using the mixed solution e to obtain a first solution;
(2) soaking the metallic pigment in a sodium bicarbonate solution, performing ultrasonic treatment by using ultrasonic waves, adding the metallic pigment into a silane coupling agent aqueous solution, stirring for reaction, adding a first solution into the solution, and continuously stirring to obtain a reaction solution;
(3) and (3) adjusting the reaction liquid by using an ammonia water solution, heating and stirring in a water bath, cooling, filtering, washing with water, and drying to obtain the required surface modified metal pigment.
Further, the surface modified metal pigment is one or a mixture of more of modified aluminum powder, silver powder, gold powder, zinc powder and copper powder, and the metal pigment is flaky, rod-shaped or spherical and has a particle size of 5-200 um.
Further, the compatilizer is maleic anhydride polypropylene grafted compatilizer.
Further, the other auxiliary agents comprise an antioxidant 1010, an antioxidant 168 and a lubricant polyethylene wax.
A preparation method of a functional master batch for improving the flow mark defect of the appearance of a spraying-free material comprises the following steps:
s1, weighing 15-40 parts of polypropylene, 30-50 parts of modified nano silicon dioxide, 20-35 parts of surface modified metal pigment, 1-5 parts of compatilizer and 3-6 parts of other auxiliary agents in parts by weight;
s2, putting the weighed raw materials into a high-speed mixer and uniformly mixing;
s3, after mixing, transferring the mixture into a rheometer for mixing;
and S4, adding the mixed material into a double-screw extruder, and carrying out melt granulation.
The invention has the beneficial effects that:
1. the invention prepares the fluid silicon dioxide nanometer ionic material with a core-shell structure by an acid-base neutralization method. The modified nano silicon dioxide fluid is coated on the surface of the metal pigment to form a protective layer, and strong-polarity amino groups are introduced on a nonpolar molecular main chain, so that the dispersion of the metal pigment in polypropylene is greatly improved, the flow direction stability of the metal pigment in molten polypropylene plastic in a mold cavity can be effectively improved, the change of the arrangement direction of the flaky metal pigment in a melt is greatly reduced, the original parallel arrangement is kept, and the flow mark or water inclusion mark symptoms on the surface of a product are improved.
2. The functional master batch for improving the appearance flow mark defect of the spraying-free metal silver polypropylene is added into the modified polypropylene, the performance requirement of the material is not influenced, the processing technology does not need special adjustment, and the product adaptability is strong.
3. The functional master batch for improving the appearance flow mark defect of the spraying-free metal silver polypropylene prepared by the invention can be recycled and can be directly used for industrial production.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A functional master batch for improving the appearance flow mark defect of a spraying-free material comprises the following raw materials in parts by weight:
15-40 parts of polypropylene;
30-50 parts of modified nano silicon dioxide;
20-35 parts of a surface modified metal pigment;
1-5 parts of a compatilizer;
3-6 parts of other auxiliary agents.
As shown in detail in table 1 below, the following examples,
table 1 composition of the starting materials prepared in the specific examples
Wherein the content of the first and second substances,
the polypropylene is copolymerized polypropylene with the melt index of 3-60g/10 min;
the compatilizer is maleic anhydride grafted polypropylene;
the modified nano silicon dioxide is obtained by self-making and comprises the following steps:
1) respectively dissolving 50g of silica sol, 25g of 1, 3-propane sultone and 8g of sodium hydroxide into a certain amount of distilled water to respectively obtain diluents a, b and c, dropwise adding the a into the solution b at 5ml/min by using an alkaline burette to obtain a silicon dioxide modified solution d, then adjusting the pH of the solution d to 5.2 by using the c, stirring and heating the solution, stirring the solution at 75 ℃ for 24 hours, dialyzing the solution in the distilled water for 40 hours by using a biological dialysis bag to remove small molecular substances to obtain a mixed solution e, and finally performing ion exchange on the e by using cation exchange resin 732 to obtain a solution (No.: I).
2) Taking 5ml of polyether monoamine solution, diluting with 30ml of water to obtain a diluent f, titrating e on a constant-temperature magnetic stirrer at 25 ℃ until the pH value is equal to 6.5 to obtain a polyether amine/silicon dioxide aqueous solution, then placing the solution in an electric heating drying oven, and drying in vacuum at 75 ℃ to obtain the modified silicon dioxide.
The metal pigment is a surface modified metal pigment obtained by self-treatment, the metal pigment is one or a mixture of more than two of modified aluminum powder, silver powder, gold powder, zinc powder and copper powder, the shape of the metal pigment is flake, rod or sphere, and the particle size of the metal pigment is 5-200 um. The preparation method comprises the following steps:
(1) soaking the metal pigment in a sodium bicarbonate solution with the mass fraction of 10%, performing ultrasonic treatment for 2 hours at the temperature of 40 ℃ by using ultrasonic waves, adding an aqueous solution of a KH550 silane coupling agent with the mass fraction of 8%, stirring and reacting for 60 minutes, adding the solution I obtained in the step, and continuing stirring and reacting for 2 hours to obtain a reaction solution.
(2) Adjusting the pH value of the reaction solution to 4.5 by using an ammonia water solution with the mass fraction of 15%, heating and stirring the reaction solution in a water bath kettle at the temperature of 90 ℃ for reaction for 4 hours, cooling the reaction solution, filtering, washing with water, drying the reaction solution to obtain the required surface modified metal pigment, and reserving the metal pigment for later use.
Other auxiliary agents include antioxidant 1010, antioxidant 168, lubricant polyethylene wax, etc.
A preparation method of a functional master batch for improving the flow mark defect of the appearance of a spraying-free material comprises the following steps:
weighing the raw materials according to the weight parts of the preparation raw materials, putting the polypropylene, the modified nano-silica, the surface modified metal pigment, the compatilizer, the antioxidant, the lubricant and the like into a high-speed mixer, mixing for 5min, then mixing for 15min in a rheometer at 180 ℃ and 40-60r/min, adding the mixed material into a double-screw extruder, and carrying out melt granulation at 190-.
TABLE 2 composition of the raw materials prepared in the specific examples
As shown in Table 2, for the specific examples 1-5 and the comparative example, the prepared functional master batch was added to the polypropylene composite material in a ratio of 4% according to the relevant detection standards to prepare a spray-free metallic silver material, the physical properties of the modified composite material were tested, and the evaluation results of the flow marks of the appearance of the modified composite material by injection molding samples at an injection temperature of 230 ℃ are shown in Table 3,
TABLE 3 Main physical Properties index
As can be seen from Table 3, the functional masterbatch is added into the modified polypropylene composite material, so that the defect of the appearance flow mark of the spray-free metallic silver polypropylene is well improved.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed.
Claims (8)
1. The functional master batch for improving the appearance flow mark defect of the spraying-free material is characterized by comprising the following raw materials in parts by weight:
15-40 parts of polypropylene;
30-50 parts of modified nano silicon dioxide;
20-35 parts of a surface modified metal pigment;
1-5 parts of a compatilizer;
3-6 parts of other auxiliary agents.
2. The functional master batch for improving the flow mark defect of the appearance of the spray-free material according to claim 1, wherein the polypropylene is a polypropylene copolymer, and the melt index of the polypropylene copolymer is 3-60g/10 min.
3. The functional master batch for improving the flow mark defect of the appearance of the spraying-free material according to claim 1, wherein the preparation method of the modified nano silicon dioxide comprises the following steps:
1) respectively dissolving silica sol, 1, 3-propane sultone and sodium hydroxide into distilled water to respectively obtain diluent a, diluent b and diluent c, dropwise adding a into the solution b to obtain a silicon dioxide modified solution d, then adding c into d, stirring and heating, dialyzing by using a biological dialysis bag, and removing small molecular substances to obtain a mixed solution e.
2) Taking a polyether monoamine solution, diluting with water to obtain a diluent f, titrating e on a constant-temperature magnetic stirrer to obtain a polyether amine/silicon dioxide aqueous solution, and then placing the solution in an electric heating drying oven for vacuum drying to obtain the modified silicon dioxide.
4. The functional master batch for improving the flow mark defect of the appearance of the spray-free material according to claim 3, wherein the preparation method of the surface modified metal pigment comprises the following steps:
(1) carrying out ion exchange by using the mixed solution e to obtain a first solution;
(2) soaking the metallic pigment in a sodium bicarbonate solution, performing ultrasonic treatment by using ultrasonic waves, adding the metallic pigment into a silane coupling agent aqueous solution, stirring for reaction, adding a first solution into the solution, and continuously stirring to obtain a reaction solution;
(3) and (3) adjusting the reaction liquid by using an ammonia water solution, heating and stirring in a water bath, cooling, filtering, washing with water, and drying to obtain the required surface modified metal pigment.
5. The functional master batch for improving the flow mark defect of the appearance of the spray-free material according to claim 1, wherein the surface modified metal pigment is one or a mixture of modified aluminum powder, silver powder, gold powder, zinc powder and copper powder, and the metal pigment is in a shape of a flake, a rod or a sphere and has a particle size of 5-200 um.
6. The functional master batch for improving the flow mark defect of the appearance of the spray-free material according to claim 1, wherein the compatilizer is a maleic anhydride polypropylene graft compatilizer.
7. The functional master batch for improving the flow mark defect of the appearance of the spray-free material according to claim 1, wherein the other auxiliary agents comprise an antioxidant 1010, an antioxidant 168 and a lubricant polyethylene wax.
8. A preparation method of a functional master batch for improving the flow mark defect of the appearance of a spraying-free material is characterized by comprising the following steps:
s1, weighing 15-40 parts of polypropylene, 30-50 parts of modified nano silicon dioxide, 20-35 parts of surface modified metal pigment, 1-5 parts of compatilizer and 3-6 parts of other auxiliary agents in parts by weight;
s2, putting the weighed raw materials into a high-speed mixer and uniformly mixing;
s3, after mixing, transferring the mixture into a rheometer for mixing;
and S4, adding the mixed material into a double-screw extruder, and carrying out melt granulation.
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| CN103910937A (en) * | 2014-04-04 | 2014-07-09 | 金发科技股份有限公司 | Scratch-resistant high-gloss spraying-free polypropylene composition with aesthetic effect as well as preparation method and application of composition |
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| CN107459713A (en) * | 2017-07-27 | 2017-12-12 | 中广核俊尔新材料有限公司 | PP composite material that a kind of proof stress turns white and its preparation method and application |
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