CN112048145B - Environment-friendly plastic with cloud and air line effects and preparation method thereof - Google Patents
Environment-friendly plastic with cloud and air line effects and preparation method thereof Download PDFInfo
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- CN112048145B CN112048145B CN202010913591.7A CN202010913591A CN112048145B CN 112048145 B CN112048145 B CN 112048145B CN 202010913591 A CN202010913591 A CN 202010913591A CN 112048145 B CN112048145 B CN 112048145B
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
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- 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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- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention belongs to the technical field of preparation of blending improved thermoplastic plastic alloy, and relates to environment-friendly plastic with a cloud and air line effect and a preparation method thereof; the composition consists of the following components in parts by weight: 800-3500 parts of main material, 20-200 parts of modified polymer, 600-3000 parts of auxiliary resin, 5-200 parts of plastic-rubber material compatilizer, 10-100 parts of auxiliary agent and 1-10 parts of pigment or dye; the auxiliary agent consists of an anti-thermal oxidant and a lubricant; the physical parameters of the final finished product can be controlled in a large range by adjusting the dosage of a specific formula, and a product with well-defined cloud air veins can be directly injected and molded, and has natural and vivid color, well-defined layers and dynamic elegant appearance; the method is simple to operate, safe and environment-friendly, avoids high cost and pollution of secondary processing of plastic products, is low in cost, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of preparation of blending improved thermoplastic plastic alloy, and particularly relates to environment-friendly plastic with a cloud and air line effect and a preparation method thereof.
Background
Since the invention of plastics in the 19 th century, plastics are applied to various fields such as industry, agriculture, medical treatment, articles for daily use and the like due to good processability, rapid development speed and improvement and development of plastic molding and processing means; the plastic product is increasingly abundant along with the fact that new high-performance and functionalized plastic products are industrialized, and people not only put higher requirements on the performance of the plastic product, but also put higher requirements on the appearance quality and the effect of the plastic.
The cloud pattern originates from Hanwei times, and the cloud pattern of Han dynasties is called as the cloud pattern in academic circles due to dynamic effect and strong air force of \36878. The Jing Shi (Dong Han Dynasty) and the literary scientist have cautions in the book Bing Wen Jie Ji (the book of explanation and literature): the cloud and the mountain air are connected together for a long time, and the linear aesthetic feeling of dynamic flowing and the thousands of grafting combinations of the weather are emphasized. In order to meet the requirements of people on nature and aesthetic feeling, the cloud air patterns are also applied to articles such as textiles, bronze ware, ceramics and the like. In recent years, moire patterns have also been used on plastic products due to their aesthetic qualities; however, the plastic products produced by printing or adding special color master batches in the current market have the appearance of moire effect, and have the defects of troublesome processing, high cost, poor yield, turbid product lines, inflexibility, no layering and the like.
Disclosure of Invention
Aiming at overcoming the defects in the prior art, the invention provides the environment-friendly plastic with the cloud pattern effect and the preparation method thereof, and the raw materials related by the invention are easily available on the market, the cost is reasonable, the yield of the preparation method is high, the production process and the final product have no three wastes, and the environment-friendly plastic is safe; the process has good compatibility with equipment, and is suitable for large-scale mass production; the product has well-arranged and dynamic and elegant cloud patterns after injection molding. Can be used for products with special requirements on appearance effect, has important use significance and large market potential.
The present invention achieves the above-described object by the following means.
The invention firstly provides an environment-friendly plastic with a cloud pattern effect, which consists of six substances of a main material, a modified polymer, auxiliary resin, a plastic-rubber material compatilizer, an auxiliary agent and pigment or dye;
the paint specifically comprises the following components in parts by weight: 800-3500 parts of main material, 20-200 parts of modified polymer, 600-3000 parts of auxiliary resin, 5-200 parts of plastic-rubber material compatilizer, 10-100 parts of auxiliary agent and 1-10 parts of pigment or dye;
the main material is styrene-butadiene transparent impact-resistant resin and a modified substance thereof.
The composite plastic is divided into a plurality of grades according to the impact resistance, the heat resistance and the strength, the grades are reasonably matched, and in addition, the modified polymers such as SIBS, branched polar SBS and the like are used, so that the properties of the main material can be adjusted in a larger range, and the environment-friendly composite plastic has a wider application range, which is a characteristic of the patent.
Preferably, the main material is SL-803G or/and SL-801G.
The modified polymer: the modified resin is any one or more of SIS (styrene-isoprene-styrene polymer), SBS (styrene-butadiene-styrene polymer), SIBS (styrene-isoprene/butadiene-styrene polymer), SEP (styrene-ethylene/propylene polymer), SEBS (styrene-ethylene/butylene-styrene polymer) and SEB (styrene-ethylene/butylene polymer).
Preferably, the modified polymer is PS, SIS and/or SBS.
The auxiliary resin comprises one or more of HIPS, GPPS, PE, PP, PS, PET, PBT, ABS, butylene and butadiene resin and trans polypentene.
The plastic-rubber material compatilizer is one or more of PP-G-MAH (maleic anhydride grafted polypropylene), MS, SAN, POE, ABS-G-MAH (maleic anhydride grafted acrylonitrile-butadiene-styrene copolymer), PP-G-PS (polypropylene grafted styrene), PE-G-MAH (maleic anhydride grafted polyethylene) and EVA (ethylene-vinyl acetate copolymer).
Preferably, the plastic-rubber material compatilizer consists of MS, EVA or PP-G-MAH.
The auxiliary agent consists of an anti-thermal oxidant and a lubricant; the anti-thermal oxygen agent is any one or more of TNPP, 1076, 1010, 168, 531, 681, HP-10 and DSTDP; the lubricant is any one or more of paraffin, microcrystalline wax, PE and PP wax, EBS, PETS, cast, erucic acid amide, stearic acid and calcium, zinc and magnesium soaps thereof.
Preferably, the auxiliary agent consists of 1076, 1010, 168, 531, EBS, PETS, cast, paraffin or TNPP.
The pigment (dye) comprises the following components: mainly comprises nontoxic organic pigment and dye; concretely, the color master batch taking PP or PS as a carrier is assisted by organic dye or pigment and TiO 2 Carbon black, znO or SiO 2 Any one or more of them.
The invention also provides a preparation method of the environment-friendly plastic with the cloud and air line effect, which comprises the following specific steps:
(1) According to the weight parts, firstly, the materials of all the components are put into a high-speed stirrer for stirring, the stirring speed is from low to high, the stirring speed is less than or equal to 3000rmp, the stirring time is 5 to 25 minutes, the temperature of the premix is 65 to 75 ℃, and the materials are stirred so that the materials do not stick to pieces, adhere to walls or precipitate at the bottom, and the powder materials do not precipitate at the bottom and are uniformly adhered to the surface of the granular materials, thus obtaining the materials of a primary mixing grid;
(2) Putting the materials in the primary mixing grid into a co-rotating double-screw mixing granulator for fine mixing granulation, controlling the temperature of the double-screw granulator, and increasing and then decreasing the temperature from a feeding port to an extrusion die head so as to keep the materials with the highest melting point fully and uniformly melted and take the lowest point of temperature as benefit; the specific temperature-raising program is as follows: the temperature of the material is gradually increased from an inlet to 190-210 ℃ from 140 ℃, and then is reduced to 180 ℃ of a model; aiming at ensuring full melting and mixing, controlling the heating temperature of a lower mixture as much as possible and reducing the degree of thermal-oxygen reaction; and finally, enabling the melt strips extruded from the die head of the extruder to enter a cold water tank and a granulator to obtain the environment-friendly plastic granules with the cloud pattern effect.
In addition, the extrusion granulator unit used in the invention is a double-screw co-rotating extruder specially designed by the company, the extruder is provided with 1-2 feed ports, and the feed ports are protected by low-pressure pure nitrogen to prevent air from being brought in. 3-4 exhaust ports, one normal pressure exhaust port and 2-3 vacuum exhaust ports, wherein the exhaust ports on the unit are used for exhausting air carried by solid materials and original organic volatile substances of various raw materials, and the vacuum exhaust ports are used for not extracting molten low molecules, so that the volatile content of the product is less than 0.2%; the double-screw unit is divided into 12 sections of independent temperature control areas, a water cooling and heating system is automatically adjusted according to a set value, 12 sections of screw jackets capable of respectively controlling and adjusting the temperature can be used for controlling the temperature independently in sections, so that the temperature of the composite plastic in different areas can meet the requirements of area functionalization, and a water-cooling strand cutting machine system is matched with the unit.
The temperature control of the twin-screw extrusion granulator set is generally from low temperature to high temperature and then from high temperature to medium temperature, the temperature range of 130-220 ℃ is commonly used in the patent, the aim of ensuring full melting and mixing is taken, the heating temperature of the mixture is controlled as much as possible, and the thermal oxidation reaction degree is reduced. The rotation speed of the screw of the machine set is set according to the output and the property of the processed material, and the rotation speed of the machine set is adjusted to match the feeding speed, the extrusion speed and the grain cutting speed.
The invention has the advantages and technical effects that:
(1) The invention can directly inject and mould the cloud pattern product with distinct layers by adjusting the components and the proportion of the specific formula, and can control the physical parameters of the final product in a large range, the operation is simple, and the cost is reduced; at present, how to obtain a specific cloud pattern effect and how to simultaneously use specific raw materials to obtain specific physical properties are not the basic common knowledge in the industry, wherein the content relates to three parts of a formula, a mixed granulation process and injection molding equipment selection and process, and creative labor is required for research; based on the method, the environment-friendly plastic with the cloud pattern effect is obtained, and has good effect and remarkable progress.
(2) The invention provides the environment-friendly plastic with the cloud pattern effect and the preparation method thereof from beautifying the packaging material, and the environment-friendly plastic can achieve the effect that the whole product has the cloud pattern effect at one time, and has distinct gradation, dynamic elegance, nature, liveliness, fine and vivid cloud patterns; meanwhile, the high cost and pollution of secondary processing of plastic products are avoided, the processing process is safe and environment-friendly, three wastes are avoided, and the added value of products is improved; meanwhile, the method has low requirements on injection molding conditions, high yield and great market potential, is suitable for large-scale production, can be used for products with special requirements on appearance effects, and has important use significance.
Drawings
FIG. 1 is a picture of the appearance of the plastic prepared in comparative example 1 of the present invention.
Fig. 2 is an appearance picture of the moire plastic prepared in example 2 of the present invention.
Fig. 3 is a picture of the appearance of the moire plastic prepared in example 3 of the present invention.
Detailed Description
The present invention is further illustrated by the following examples.
Comparative example 1:
(1) Pre-mixing: accurately weighing the components according to the mixture ratio as shown in Table 1, adding the components into a high-speed stirrer, and premixing at 2000 r/s, wherein the temperature of the premix is 65-75 ℃, and the stirring time is 11 minutes, so that the added substances are uniformly mixed without being adhered to sheets, walls or sediment at the bottom; stopping the machine, opening the cover and checking to obtain the material of the primary mixing grid;
(2) Extruding and granulating: putting the materials in the primary mixing grid into a co-rotating twin-screw mixing granulator for fine mixing granulation, controlling the temperature of the twin-screw granulator to be fed to an extrusion die head from low to high, and keeping the materials with the highest melting point fully and uniformly melted from high to medium, wherein the lowest point of the temperature is beneficial; the temperature of the twin-screw extrusion granulator of the embodiment is arranged as follows: 140 ℃, 160 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 200 ℃, 190 ℃, 180 ℃, and the screw rotation speed is as follows: 200rmp; the melt strip extruded from the extruder die head enters a cold water tank and a granulator to obtain the environment-friendly plastic; specific amounts are shown in table 1.
Table 1: the components and proportions of comparative example 1 are as follows:
example 1:
the components and the formulation of example 1 are shown in the table below, and the specific preparation process is the same as that of comparative example 1.
Table 2: composition and ratio of example 1
Example 2:
the components and the mixture ratio of the example 2 are shown in the table 3, and the specific preparation process is the same as that of the comparative example 1.
Table 3: composition and proportioning of example 2
| Name(s) | Parts by weight | Name (R) | Parts by weight |
| SL-803G | 1200 | 1010 | 6 |
| PP | 1200 | 1076 | 6 |
| HIPS | 100 | 168 | 2 |
| GPPS | 600 | 531 | 2 |
| SIS | 60 | TNPP | 2 |
| PS | 10 | Cast | 4 |
| EVA | 30 | PETS | 6 |
| SBS | 60 | Solid paraffin | 3 |
| EBS | 6 | Composite PP carrier organic pigment | 3 |
| Ms | 30 |
Example 3:
the components and the mixture ratio of the example 3 are shown in the table 4, and the specific preparation process is the same as that of the comparative example 1.
Table 4: composition and proportioning of example 3
Table 5: comparative table of properties of various examples
| Comparative example 1 | Example 1 | Example 2 | Example 3 | |
| Yield strength (Mpa) | 16.7 | 16.8 | 11.7 | 11 |
| Elongation at yield (%) | 2.2 | 2.8 | 2.2 | 2.1 |
| Breaking stress (Mpa) | 32.1 | 38.2 | 31.2 | 28.2 |
| Elongation at Break (%) | 29.7 | 52.5 | 65.5 | 331.8 |
| Flexural modulus (MPa) | 1320 | 1250 | 1260 | 1170 |
| Flexural strength (Mpa) | 29.6 | 26.1 | 17.4 | 14.2 |
| Cantilever impact strength (KJ/square meter) | 3.93 | 17.1 | 7.4 | 8.3 |
| Vicat softening point (. Degree. C.) | 90.2 | 90.3 | 100 | 99.2 |
| Heat distortion temperature (. Degree. C.) | 68.4 | 65.8 | 60.4 | 54.1 |
| Hardness (Shao D) | 79 | 73 | 72 | 72 |
| Melt index (200 ℃,5 kg) | 13.3 | 12.9 | 7.5 | 10.7 |
| Light transmittance (%) | 89 | 60 | 0 | 0 |
| Pattern coefficient (10 divisions) | 0 | 2 | 8 | 8 |
According to the data, the invention realizes the regulation and control of the pattern effect by adjusting the formula data on the premise of not influencing the performance of the plastic; more obviously, with reference to the attached drawings, fig. 1 is an appearance picture of the common plastic prepared by the comparative example 1 of the invention, which is light white and has no patterns; FIGS. 2 and 3 are pictures showing the appearance of the cloud pattern plastics prepared in examples 2 and 3 of the present invention, which are sky blue, and the dynamically flowing cloud pattern is naturally integrated with the plastic product;
in addition, the method has the advantages of high finished product rate, no three wastes in the production process and the final product, safety and environmental protection; and the process has good compatibility with equipment, and is suitable for large-scale mass production.
The above abbreviations correspond to the following specific components:
description of the invention: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, while the present invention has been described in detail with reference to the various embodiments thereof, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.
Claims (6)
1. The environment-friendly plastic with the cloud and air line effect is characterized by comprising the following components in parts by weight:
the main material consists of 1200 parts of SL-803G;
the modified polymer was composed of 10 parts of polystyrene, 60 parts of styrene-isoprene-styrene and 60 parts of styrene-butadiene-styrene polymer;
the auxiliary resin is composed of 1200 parts of polypropylene, 100 parts of high impact polystyrene and 600 parts of general-purpose polystyrene;
the plastic rubber material compatilizer consists of 30 parts of styrene-methyl methacrylate copolymer and 30 parts of ethylene-vinyl acetate copolymer;
the auxiliary agent consists of 6 parts of ethylene bis stearamide, 6 parts of 1010, 6 parts of 1076, 2 parts of 168, 2 parts of UV-531, 2 parts of trisnonylphenyl phosphite, 4 parts of calcium stearate, 6 parts of pentaerythritol stearate and 3 parts of solid paraffin;
3 parts of PP carrier color master batch supplemented with organic pigment.
2. The environment-friendly plastic with the cloud and air line effect is characterized by comprising the following components in parts by weight:
the main material consists of 1400 parts of SL-803G and 200 parts of SL-801G;
the modified polymer consists of 10 parts of polystyrene and 50 parts of styrene-isoprene-styrene;
the auxiliary resin consists of 1750 parts of polypropylene and 150 parts of high impact polystyrene;
the plastic-rubber material compatilizer consists of 30 parts of styrene-methyl methacrylate copolymer and 70 parts of PP-G-MAH;
the auxiliary agent consists of 6 parts of ethylene bis stearamide, 6 parts of 1010, 6 parts of 1076, 2 parts of 618, 6 parts of 168, 4 parts of calcium stearate, 4 parts of titanium dioxide, 6 parts of pentaerythritol stearate and 3 parts of solid paraffin;
and 2 parts of PP carrier color master batch supplemented with organic pigment.
3. The preparation method of the environment-friendly plastic with the cloud and air line effects as claimed in claim 1 or 2, characterized by comprising the following steps:
(1) According to the weight parts, firstly, adding the materials of the components into a high-speed stirrer for stirring, wherein the stirring speed is from low to high, the stirring speed is less than or equal to 3000rpm, the stirring time is 5 to 25 minutes, the temperature of the premix is 65 to 75 ℃, and the materials are stirred so that the materials do not adhere to sheets, adhere to walls or precipitate at the bottom, and are enabled to be not precipitated and uniformly adhered to the surfaces of the granules, so that the materials of a primary mixing grid are obtained;
(2) Putting the materials in the primary mixing grid into a double-screw extrusion granulator for fine mixing granulation, controlling the temperature of the double-screw extrusion granulator, and increasing and then decreasing the temperature from a feeding port to an extrusion die head so as to keep the materials with the highest melting point molten uniformly; the specific temperature-raising program is as follows: the temperature of the material is gradually increased from an inlet to 190-210 ℃ from 140 ℃, and then is reduced to 180 ℃ of a die head, and the rotating speed of a screw of a machine set is 200rpm; and finally, the melt strips extruded from the die head of the extruder enter a cold water tank and a granulator to obtain the environment-friendly plastic with the cloud pattern effect.
4. The method for preparing environment-friendly plastic with moire effect as defined in claim 3, wherein in the step (1), the rotation speed of the stirrer is 2000 rpm.
5. The method for preparing environment-friendly plastic with moire effect as claimed in claim 3, wherein in the step (1), the stirring time is 11min.
6. The method for preparing the environment-friendly plastic with the cloud and ripple effect as claimed in claim 3, wherein in the step (2), the temperature of the twin-screw extrusion granulator is arranged as follows: 140 deg.C, 160 deg.C, 180 deg.C, 190 deg.C, 200 deg.C, 210 deg.C, 200 deg.C, 190 deg.C, 180 deg.C.
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