CN110790999B - Rotational molding composite material with pattern surface effect - Google Patents
Rotational molding composite material with pattern surface effect Download PDFInfo
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- CN110790999B CN110790999B CN201910924333.6A CN201910924333A CN110790999B CN 110790999 B CN110790999 B CN 110790999B CN 201910924333 A CN201910924333 A CN 201910924333A CN 110790999 B CN110790999 B CN 110790999B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a rotational molding composite material with a pattern surface effect, which relates to the technical field of rotational molding composite materials and is prepared by mixing the following components in percentage by mass: 1-19.9% of low mucosa temperature powder. The powder with high mucosa temperature is 80.1-99%, the rotational molding composite material with the surface effect of the patterns is prepared by controlling the material proportion and feeding once based on the difference of the mucosa temperature of the material, the surface pattern proportion is large, and the preparation method is simple, low in cost, free of complex equipment and easy to realize industrial operation.
Description
Technical Field
The invention relates to a rotational molding composite material, in particular to a rotational molding composite material with a pattern surface effect.
Background
Rotational molding is a plastic processing mode which utilizes a rotary mold to process, and the processing process comprises the steps of putting plastic powder or slurry into the mold, rotating or swinging the closed mold on equipment, heating the outside of the mold through open fire or hot air, turning and flowing the plastic powder or slurry inside the mold in a heated state, gradually coating the plastic powder or slurry on the inner surface of the mold after the temperature reaches a softening point, melting and condensing, placing the mold in a natural environment or cooling through media such as water, fog, wind and the like, and then removing the mold to take out a product. During the heating process, the temperature of the plastic powder decreases gradually in the direction of the mould face towards the interior of the mould.
In the prior art, there are various technical proposals for manufacturing products with special pattern surface effects such as imitation stone and imitation wood by using rotational molding process, for example, patent with publication number CN102010542B discloses a special material for imitation marble pattern rotational molding and a preparation method thereof, which utilizes the difference of melt flow rate and melting point of high-density polyethylene and low-density polyethylene, and simultaneously controls the particle size thickness and particle size distribution of base resin and imitation marble pattern particles, thereby solving the phenomena of pattern blurring and the like. The patent with publication number CN105754198A discloses a polyethylene material for rotational molding with special surface effect and a preparation method thereof, which is characterized in that polyethylene wax emulsion is coated on the surface of plastic powder, so that the surface energy difference of the plastic powder with different surface energy during the elimination period can be reduced, linear low-density polyethylene of the same material can be used for manufacturing rotational molding products with special surface effect, and the rotational molding products have the effects of clear and uniform patterns and prominent visual perception. However, the preparation method is complex in preparation process, uneven surface of the product is easily caused by the difference between the melt flow rate and the melting point, and the coating of the plastic powder by using the polyethylene wax emulsion is uneven, so that the process difficulty is increased.
Disclosure of Invention
The invention provides a rotational molding composite material with a pattern surface effect, which aims to overcome the problems of complex process, high difficulty, uneven product surface, uneven surface and the like of products with special pattern surface effects such as stone imitation, wood imitation and the like manufactured by the conventional rotational molding process.
In order to achieve the purpose, the invention adopts the following technical scheme:
a rotational molding composite material with a pattern surface effect is prepared by mixing the following components in percentage by mass: 1-19.9% of low mucosa temperature powder. 80.1-99% of high mucosa temperature powder.
In the present invention, the difference in the temperatures of the mucous membranes of the materials, i.e. the difference in the initial temperature at which the material begins to adhere to the mould, is a central factor contributing to the delamination of the rotomoulded material, if the temperatures of the mucous membranes of the two different materials are different, during the rotomoulding process the powder with a low film temperature will adhere to the mould first forming the outer layer and the powder with a high film temperature will adhere to the mould later forming the inner layer. When the ratio of the low-film-temperature powder is small, the uneven distribution is formed in the thickness direction, and the low-film-temperature material is concentrated in the outer layer to form the patterned surface effect.
Preferably, the difference between the mucosa temperature of the low-mucosa-temperature powder and the mucosa temperature of the high-mucosa-temperature powder is not less than 10 ℃.
The greater the difference in the mucosa temperature between the two materials, the more pronounced the tendency of the rotomoulded article to form layers, when the mucosa temperature of the two materials exceeds the minimum value of 10 ℃, a substantially divided double-layer rotomoulded article can be formed, and when the mucosa temperature is less than 10 ℃, the boundary line in the fault of the prepared rotomoulded article is very fuzzy, even no boundary line, and the rotomoulded article does not form a double layer.
Preferably, the low-film-temperature powder is prepared by mixing the following components in percentage by mass: matrix resin: 60-95% of adhesive and 5-40% of adhesive.
The mechanism of attaching the powder to the metal mold is three, namely electrostatic adsorption, fusion bonding and chemical bond formation. The addition of low-melting point substances or substances containing carbonyl, anhydride, ester and the like which can form chemical bonds with metals to the matrix resin can promote the matrix resin to be attached to a mold in advance to form low-film-temperature powder, but the content of the attaching agents cannot be too large, so that the performance of the powder is reduced or the demolding of the product is difficult.
Preferably, the adhesive is one or a combination of two or more selected from polyethylene wax, polypropylene wax, montan wax, paraffin wax, microcrystalline wax, ethylene-vinyl acetate copolymer wax, oxidized polyethylene wax, POE, EVA, EAA, polyethylene graft, and POE graft.
The adhesive has better compatibility with matrix resin, wherein the wax adhesive can enable the powder to be subjected to melt bonding at low temperature, and the EVA, the EAA and the graft can form chemical bonding force with a metal mold, so that the powder is molded in advance.
Preferably, the high mucosa temperature powder is prepared by mixing the following components in percentage by mass: matrix resin: 90 to 99.9 percent of the raw materials and 0.1 to 10 percent of the mold release agent.
The release agent has the functions of promoting the powder to eliminate electrostatic adsorption or smoothening the powder appearance in the powder preparation process, improving the powder flowability and causing the mold temperature to be higher than that of the common powder. Similarly, the content of the release agent needs to be controlled, and the high content of the release agent causes the performance deterioration of the material.
Preferably, the release agent is one or a combination of two or more selected from the group consisting of silicon dioxide, oleamide, erucamide, stearamide, stearic trimethyl ammonium chloride, stearic dimethyl amyl ammonium chloride, alkyl tertiary amine nitrate, trihydroxyethyl methyl quaternary ammonium sulfate, N-hexadecylethyl morpholine ethyl sulfate, sodium alkyl sulfonate, alkyl phosphate, polyacrylate, polystyrene sulfonate, ethoxylated alkylamine, ethoxylated amine laurate, dilauryl phosphate, glycerol monostearate, ethoxylated amine laurate, amphoteric alkyl imidazoline salt, and alkyl amino acid.
In the release agent, silicon dioxide, oleamide, erucamide and stearamide can improve the powder flowability, and dimethyl amyl ammonium stearate, alkyl tertiary amine nitrate, trihydroxyethyl methyl quaternary ammonium sulfate, N-hexadecyl ethyl morpholine sulfate ethyl ester, sodium alkyl sulfonate, alkyl phosphate, polyacrylate, polystyrene sulfonate, ethoxylated alkylamine, ethoxylated amine laurate, dilauryl phosphate, glycerol monostearate, ethoxylated amine laurate, amphoteric alkyl imidazoline salt and alkyl amino acid can eliminate the electrostatic adsorption of the powder.
Preferably, the bulk density of the low mucosa temperature powder and the high mucosa temperature powder is 0.200 to 0.500g/cm3The powder fluidity is less than or equal to 28s/100g, and the particle size distribution D95 is less than or equal to 500 um.
The powder has better processing performance under the conditions of the bulk density, the powder flowability and the particle size distribution.
Preferably, the matrix resin is selected from one or a combination of more than two of polyethylene, polypropylene, nylon, polyurethane, polylactic acid, polycarbonate, ABS, polystyrene, polyester, elastomer and derivatives thereof, and flame retardant, foaming, weather resistant, crosslinking and dyeing modified materials thereof.
The matrix resin for preparing the low-film-temperature powder and the high-film-temperature powder can be the same resin or different resins. This is because the same matrix resin can be used to change the temperature of the adhesive film by adding an adhesive or a release agent and changing the particle size, powder flowability, or the like.
Therefore, the invention has the following beneficial effects:
(1) the rotational molding composite material with the pattern surface effect is prepared by controlling the material proportion and feeding once based on the difference of the material mucosa temperature, and the surface pattern ratio is large;
(2) the preparation method is simple, low in cost, free of complex equipment and easy to realize industrial operation.
Detailed Description
The invention is further described with reference to specific embodiments.
Example 1: mixing 95Kg polyethylene (R548U, Zhenhai refining) and 5Kg EVA (742, DuPont, USA), granulating with a twin-screw extruder, grinding with a plastic mill to obtain powder with particle size D95 ═ 425um, powder fluidity of 25s/100g, and bulk density of 0.300g/cm3Low film temperature white powder of (a); 99.9Kg of polyethylene (R548U, Zhenhai refining) and 0.1Kg of silicon dioxide (AB90, American PQ) were mixed, and then pelletized by a twin-screw extruder and ground by a plastic mill to prepare a powder having a particle diameter D95 of 475um, a powder flowability of 23s/100g and a bulk density of 0.350g/cm3The high film temperature black powder of (1); 0.03Kg of low-film-temperature powder and 2.97Kg of high-film-temperature powder are mixed and then put into a rotational molding die to carry out rotational molding under the condition of 15rpm of rotation speed.
Example 2: mixing 60Kg of polyethylene (8008, Fujian union) and 40Kg of maleic anhydride grafted POE (493D, DuPont USA), granulating by a double-screw extruder, and grinding by a plastic grinder to obtain powder with particle size D95 of 435um, powder flowability of 26s/100g, and bulk density of 0.280g/cm3Low film temperature red powder of (a); mixing polyethylene (8008, Fujian union) 90Kg and sodium secondary alkylsulfonate (H95, Langshen, Germany) 10Kg, granulating with a twin-screw extruder, grinding with a plastic mill to obtain powder with particle size D95 ═ 465um, powder flowability of 25s/100g, and bulk density of 0.300g/cm3The high-viscosity-film-temperature natural-color powder; 0.3Kg of low-film-temperature powder and 2.7Kg of high-film-temperature powder are mixed and put into a rotational molding die, and rotational molding is carried out under the condition of 15rpm of rotation speed.
Example 3: mixing POE (8450, Douchi chemical) 80Kg and EAA (30307, DuPont) 20Kg, granulating with a twin-screw extruder, and grinding with a plastic grinder to obtain powder with particle diameter D95 ═ 425umThe final fluidity is 25s/100g, and the bulk density is 0.300g/cm3Low film temperature yellow powder of (a); 99Kg of polyethylene (50035E, Sautersabic), 1Kg of stearic acid ethoxy amide (A4-88, perfection) and 2Kg of silicon dioxide (AB90, American PQ) are mixed, granulated by a double-screw extruder and ground by a plastic mill to prepare the powder with the particle size of D95-475 um, the powder has the flowability of 21s/100g and the bulk density of 0.500g/cm3The high-viscosity film temperature green powder of (4); 0.597Kg of low-film-temperature powder and 2.403Kg of high-film-temperature powder are mixed and then put into a rotational molding die to carry out rotational molding under the condition of 15rpm of rotation speed.
Comparative example 1: grinding polyethylene (R548U, Zhenhai refining) by a plastic grinding machine to prepare white powder A with the particle size D95 of 425um and the powder flowability of 25s/100 g; grinding polyethylene (R548U, Zhenhai refining) into powder in a plastic grinding mill to prepare black powder B with the particle size D95 being 425um and the powder flowability being 23s/100 g; 0.3Kg of white powder A and 3Kg of black powder B are mixed and put into a rotational molding die, and rotational molding is carried out under the condition of 15rpm of rotation speed.
Comparative example 2: grinding polyethylene (8008, Fujian union) plastic mill to obtain powder with particle diameter D95 ═ 425um, powder flowability of 25s/100g, and bulk density of 0.300g/cm3Red powder a of (a); grinding polyethylene (8008, Fujian union) plastic mill to obtain powder with particle diameter D95 ═ 425um, powder flowability of 25s/100g, and bulk density of 0.300g/cm3The natural color powder B of (1); 0.3Kg of low-film-temperature powder and 3Kg of high-film-temperature powder are mixed and then put into a rotational molding die to carry out rotational molding under the condition of 15rpm of rotation speed.
Comparative example 3: grinding POE (8450, Douchi chemical) plastic powder into powder with particle diameter D95 ═ 375um, powder flowability of 30s/100g and bulk density of 0.180g/cm3Yellow powder A of (4); grinding polyethylene (50035E, Satetabic) into powder with a plastic grinding machine to obtain powder with a particle size D95 of 525um, powder flowability of 20s/100g and bulk density of 0.550g/cm3Green powder B of (4); 0.3Kg of low-film-temperature powder and 3Kg of high-film-temperature powder are mixed and then put into a rotational molding die to carry out rotational molding under the condition of 15rpm of rotation speed.
Comparative example 4: mixing POE (8450, Douchi chemical) 80Kg and EAA (30307, DuPont) 20Kg, granulating with a twin-screw extruder, grinding with a plastic mill to obtain powder with particle diameter D95 ═ 425um, powder flowability of 25s/100g, and bulk density of 0.300g/cm3Yellow powder A of (4); 99Kg of polyethylene (50035E, Sautersabic), 1Kg of stearic acid ethoxy amide (A4-88, perfection) and 2Kg of silicon dioxide (AB90, American PQ) are mixed, granulated by a double-screw extruder and ground by a plastic mill to prepare the powder with the particle size of D95-475 um, the powder flowability of 28s/100g and the bulk density of 0.250g/cm3Green powder B of (4); after 0.9kg of powder A0.9kg and 2.1kg of powder B2 were mixed, the mixture was put into a rotational molding die and rotational molding was carried out at a rotational speed of 15 rpm.
Comparative example 5: mixing 50Kg of POE (8450, Douchi chemical) and 50Kg of EAA (30307, DuPont USA), granulating by a double-screw extruder, and grinding by a plastic grinder to prepare yellow powder A with the particle size D95 being 425um and the powder fluidity being 28s/100 g; 85Kg of polyethylene (50035E, Sauterabic), 10Kg of stearic acid ethoxy amide (A4-88, perfection) and 5Kg of silicon dioxide (AB90, American PQ) are mixed, granulated by a double-screw extruder and ground by a plastic mill to prepare green powder B with the particle size of 95 ═ 475um and the powder flowability of 28s/100 g; powder A0.3Kg and powder B3Kg were mixed and put into a rotational molding die, and rotational molding was carried out at a rotational speed of 15 rpm.
The mucosa temperature in the invention is measured by using an in-mold temperature measuring instrument, the powder particle size is measured by using a laser particle size distribution instrument, and the powder flowability is measured by using an ARM standard. In addition, in order to observe the pattern effect on the surface of the rotational molding product, the low-film-temperature powder and the high-film-temperature powder are made into materials with different colors, and the dyeing and granulating technology is popular in the industry, so that special attention is not paid in the case.
The difference in the mucosa temperature of the low and high film temperature powders prepared in the examples and the powders a and B prepared in the comparative examples was examined and the surface pattern condition was observed, wherein the difference in the pattern was represented by the percentage of the surface pattern formed by the low film temperature powder to the unit area, and the ideal percentage of the pattern to the unit area was the mass ratio of the low film temperature powder to the composite powder, and the results are shown in the following table.
| Item | Difference in mucosal temperature | Percentage of ideal | Actual percentage |
| Example 1 | 19℃ | 1％ | 1.69％ |
| Example 2 | 36℃ | 10％ | 43.83％ |
| Example 3 | 50℃ | 19.9％ | 58.76％ |
| Comparative example 1 | 3℃ | 9.09％ | 4.95％ |
| Comparative example 2 | 2℃ | 9.09％ | 2.57％ |
| Comparative example 3 | 0.5℃ | 9.09％ | 0.98％ |
| Comparative example 4 | 50℃ | 30％ | 100% (section layer by layer) |
| Comparative example 5 | 5℃ | 9.09％ | 6.18％ |
As can be seen from the above table, when the adhesive and the release agent are not added, or when the addition exceeds the limited range, or when the particle size and the powder flowability of the prepared powder exceed the limited range, the mucosa temperature difference between the materials is too small, so that the percentage of the surface pattern formed by the low-film-temperature powder in the unit area is too small, and the addition of the adhesive and the release agent is the most important factor affecting the mucosa temperature difference. When the ratio of the two powders exceeds the limited range and the low-film-temperature powder is too much, the low-film-temperature powder directly forms a complete film without pattern surface effect.
It is to be understood that the practice of the invention is not limited to the embodiments described above, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.
In the invention, all parts and percentages are weight units, and all equipment, raw materials and the like can be purchased from the market or are commonly used in the industry, if not specified. Unless otherwise indicated, the examples employ methods that are within the ordinary skill in the art.
Claims (4)
1. The rotational molding composite material with the pattern surface effect is characterized by being prepared by mixing the following components in percentage by mass: 1-19.9% of low-mucosa temperature powder and 80.1-99% of high-mucosa temperature powder;
the difference of the mucosa temperature of the low-mucosa-temperature powder and the high-mucosa-temperature powder is more than or equal to 10 ℃;
the difference of the mucosa temperature is the difference of the initial temperature of the low-mucosa-temperature powder and the initial temperature of the high-mucosa-temperature powder which begin to be attached to the die; the high-viscosity film temperature powder is attached to the die to form an inner layer, and the low-viscosity film temperature powder is enriched in the outer layer to form a pattern surface effect;
the low-mucosa-temperature powder is prepared by mixing the following components in percentage by mass: matrix resin: 60% -95% of adhesive and 5% -40% of adhesive; the high mucosa temperature powder is prepared by mixing the following components in percentage by mass: matrix resin: 90 to 99.9 percent of the raw materials, and 0.1 to 10 percent of the parting agent; the bulk densities of the low-film-temperature powder and the high-film-temperature powder are 0.200-0.500g/cm3The powder fluidity is less than or equal to 28s/100g, and the particle size distribution D95 is less than or equal to 500 um.
2. The rotomolding composite with a textured surface according to claim 1, wherein the adhesive is one or a combination of two or more selected from polyethylene wax, polypropylene wax, montan wax, microcrystalline wax, ethylene-vinyl acetate copolymer wax, oxidized polyethylene wax, POE, EAA, polyethylene graft, and POE graft.
3. A rotomoulding composite material having a textured surface effect according to claim 1, wherein the release agent is selected from one or a combination of two or more of silica, oleamide, erucamide, stearamide, trimethyl ammonium chloride stearate, dimethyl amyl ammonium chloride stearate, alkyl tertiary amine nitrate, methyl trihydroxyethyl methyl quaternary ammonium sulfate, ethyl N, N-hexadecylethyl morpholine sulfate, sodium alkyl sulfonate, alkyl phosphate, polyacrylate, polystyrene sulfonate, ethoxylated alkyl amine, ethoxylated lauryl amine, dilauryl phosphate, glycerol monostearate, amphoteric alkyl imidazoline salt, and alkyl amino acids.
4. A rotomoulded composite material with a textured surface effect as claimed in claim 1, wherein the matrix resin is selected from polyethylene, polypropylene, nylon, polyurethane, polylactic acid, polycarbonate, ABS, polystyrene, elastomers and derivatives thereof, and combinations of one or more of flame retardant, foam, weatherable, cross-linked, and dye modified materials thereof.
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| CN112300497B (en) * | 2020-10-29 | 2023-04-07 | 中国石油化工股份有限公司 | Low-foam polypropylene composition for rotational molding process and preparation method thereof |
| CN113308037B (en) * | 2021-05-20 | 2022-06-17 | 浙江瑞堂塑料科技股份有限公司 | Large-particle rotational molding composite material with different color surface effects and preparation method thereof |
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| BR9810131A (en) * | 1997-06-16 | 2000-08-08 | Magna Interior Systens Inc | Process for making a panel-like structure, and, article |
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Address after: 315323 588 Industrial Avenue, Shengshan Town, Cixi City, Ningbo City, Zhejiang Province Patentee after: ZHEJIANG ROTOUN PLASTIC TECHNOLOGY Co.,Ltd. Address before: 315323 588 Industrial Avenue, Shengshan Town, Cixi City, Ningbo City, Zhejiang Province Patentee before: ZHEJIANG ROTOUN PLASTIC TECHNOLOGY Co.,Ltd. |