CN114058119B - Polypropylene mica master batch and preparation method and application thereof - Google Patents
Polypropylene mica master batch and preparation method and application thereof Download PDFInfo
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- CN114058119B CN114058119B CN202111314684.9A CN202111314684A CN114058119B CN 114058119 B CN114058119 B CN 114058119B CN 202111314684 A CN202111314684 A CN 202111314684A CN 114058119 B CN114058119 B CN 114058119B
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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
- 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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- 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
- 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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- 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
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- C08K3/34—Silicon-containing compounds
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Abstract
The invention discloses a polypropylene mica master batch and a preparation method and application thereof, and belongs to the technical field of plastic processing aids. The polypropylene mica master batch comprises the following components in parts by weight: 10-25 parts of homo-polymerization high melt index polypropylene; 10-25 parts of metallocene low isotacticity polypropylene; 75-90 parts of mica. According to the invention, a small amount of metallocene low-isotacticity polypropylene is added, so that a high gloss surface is easy to form, the glossiness of the polypropylene mica master batch is improved, meanwhile, the glossiness value is effectively improved and the dispersibility of a mica master batch system is improved through the synergistic effect of homopolymerization of high-melting-index polypropylene, the polypropylene mica master batch with high mica content and high glossiness is prepared, the glossiness can reach 79.6, and the 1-stage dispersion effect can be realized.
Description
Technical Field
The invention relates to the technical field of plastic processing aids, in particular to a polypropylene mica master batch, a preparation method and application thereof.
Background
The existing research on polypropylene filler master batches needs to improve various processing performances of the master batches through different carrier types and processing technologies. Such as good dispersibility and high gloss, which often also affect the appearance properties of the back end product to which the masterbatch product is applied, especially in the housing of a particular, e.g. electronic appliance. Among them, the mica master batch has high processing difficulty because of poor dispersion property of the mica itself, and a mica master batch product capable of achieving good dispersibility and glossiness is not yet available at present.
CN102532703a discloses a low-odor and high-gloss modified polypropylene material and a preparation method thereof, wherein the modified polypropylene material comprises polypropylene and mica components (inorganic filler), but the modified polypropylene material mainly comprises polypropylene, the mica is added in an amount of only 5-15%, and the high gloss is realized mainly by adding high-gloss barium sulfate, so that a mica master batch product with good dispersion performance and glossiness value cannot be provided.
Disclosure of Invention
The invention aims to overcome the defect and the defect of lack of mica master batch with good dispersibility and high glossiness value in the existing plastic processing aid, and provides a polypropylene mica master batch, wherein the dispersibility of mica and a polypropylene carrier in the mica master batch is effectively improved by adding a small amount of metallocene low-isotacticity polypropylene, and meanwhile, the glossiness value of the mica master batch is improved.
The invention further aims at providing a preparation method of the polypropylene mica master batch.
The invention also aims to provide an application of the polypropylene mica master batch in preparing plastic products.
It is still another object of the present invention to provide a plastic article.
The above object of the present invention is achieved by the following technical scheme:
the polypropylene mica master batch comprises the following components in parts by weight:
10-25 parts of homo-polymerization high melt index polypropylene; 10-25 parts of metallocene low isotacticity polypropylene; 75-90 parts of mica; the metallocene low isotacticity polypropylene content is more than 25 parts,
wherein the melt flow rate of the homo-polymerized high-melt-index polypropylene is 18-30 g/10min according to the ISO1133-2011 method under the condition of 230 ℃/2.16 kg;
the isotacticity of the metallocene low isotacticity polypropylene is 55-65%.
The following description is needed:
the polypropylene mica master batch is added with a small amount of metallocene low isotacticity polypropylene, so that when the mica master batch is mixed with polypropylene resin and then injection-molded, the metallocene low isotacticity polypropylene phase in the melt is firstly injection-molded on the surface of a mold to form a solidification layer highlight surface, thereby achieving higher glossiness.
Meanwhile, the metallocene low isotacticity polypropylene can be effectively dispersed and combined with mica under the condition of homopolymerizing high melt index polypropylene, so that a good dispersing effect is achieved, and the use of polypropylene mica master batch in the downstream industry is improved.
The mass fraction control of each component in the polypropylene mica master batch is quite critical, wherein the homo-polymerized high-melting polypropylene is used as a basic carrier resin, the influence of the homo-polymerized high-melting polypropylene on the dispersibility of the metallocene low-isotacticity polypropylene and mica of the system is considered, and the poor dispersibility can be caused by the excessively low dosage.
Similarly, the addition of the metallocene low isotacticity polypropylene is beneficial to improving the glossiness of the polypropylene mica master batch and improving the glossiness value, but the excessive use of the metallocene low isotacticity polypropylene can cause the deterioration of the overall dispersibility.
The invention improves the cantilever beam notch impact strength of the product after the polypropylene mica master batch is injection molded by adding the metallocene low isotacticity polypropylene into the polypropylene mica master batch, and the cantilever beam notch impact strength of the product after the polypropylene mica master batch is injection molded can be influenced by the excessively high or excessively low isotacticity of the metallocene low isotacticity polypropylene.
Preferably, the composition comprises the following components in parts by weight:
15-20 parts of homo-polymerization high melt index polypropylene; 13-18 parts of metallocene low isotacticity polypropylene; 78-85 parts of mica.
Preferably, the melt flow rate of the homo-high melt-index polypropylene is 20-25 g/10min according to ISO1133-2011 measured under 230 ℃/2.16 kg.
Preferably, the metallocene low isotacticity polypropylene has an isotacticity of 60 to 63%.
Preferably, the metallocene low isotacticity polypropylene has a melt flow rate of 1500-1800 g/10min measured according to ISO1133-2011 under 230 ℃/2.16kg conditions.
Preferably, the particle diameter D50 of the mica is 30-40 mu m, the particle diameter D50 of the mica is less than 30 mu m, the actual production is not facilitated, and the mother particle diameter D50 is more than 40 mu m, and the mica is not easy to disperse.
Preferably, in order to improve other use performances, the polypropylene mica master batch also comprises 0.2-1 part of antioxidant and 0.3-1 part of lubricant in parts by weight.
The following description is needed:
the antioxidant of the invention can be one or more of hindered phenol antioxidants, phosphite antioxidants or thioether antioxidants.
The lubricant of the invention can be one or more of metal soaps, stearic acid complex esters and amides.
The antioxidant has the following functions: delay or inhibit the oxidation process of polypropylene, thereby preventing the aging of polypropylene and prolonging the service life.
The lubricant functions as: the internal friction of polypropylene and mica is reduced, so that the heat energy is reduced, and the abnormal performance and appearance of the system caused by overhigh heat energy are prevented.
The invention also specifically protects a preparation method of the polypropylene mica master batch, which comprises the following steps:
adding the components into an internal mixer for banburying and mixing to obtain a mixture, adding the mixture into an extruder for granulating through main feeding, and controlling the temperature of the extruder to be 120-160 ℃ to finally obtain the polypropylene mica master batch.
The temperature of the extruder is too high, and the appearance of the mica master batch is easy to turn yellow or even black under the conditions of high temperature and shearing of the screw, so that the later use is not facilitated; when the temperature of the extruder is too low, the current of the extruder increases, so that the load of the extruder increases and the extruder is easily damaged.
In specific application, the polypropylene mica master batch can be widely applied as a plastic processing aid, and the invention also protects the application of the polypropylene mica master batch in preparing plastic products.
The invention also specifically protects a plastic product which is prepared from the raw materials of the polypropylene mica master batch.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a polypropylene mica master batch, which is easy to form a high gloss surface by adding a small amount of metallocene low-isotacticity polypropylene, so that the glossiness of the polypropylene mica master batch is improved, meanwhile, the dispersibility of a mica master batch system is improved while the glossiness value is effectively improved by the synergistic effect of homopolymerization of high-melt-index polypropylene, and the polypropylene mica master batch with high mica content and high glossiness is prepared, and meanwhile, the notch impact strength of a cantilever beam after the polypropylene mica master batch is injection molded is improved.
Detailed Description
The invention will be further described with reference to the following specific embodiments, but the examples are not intended to limit the invention in any way. Raw materials reagents used in the examples of the present invention are conventionally purchased raw materials reagents unless otherwise specified.
Among them, the test methods of the gloss value and the dispersion coefficient of the examples and comparative examples of the present invention are as follows:
dispersion coefficient: the polypropylene mica master batch is prepared into 100mm square plates with the size of 100mm and 1mm on a die with the surface subjected to polishing treatment, the surface is observed through a secondary imaging instrument, the number of black spots appearing on the 2mm and 2mm area is quantified through the secondary imaging instrument, the number of the black spots on the surface is divided into 10 grades according to the difference of the number of the black spots on the surface, wherein the 1 grade is the best, the 10 grade is the worst, the number of the 1 grade black spots is within 2, the 2-10 grades, the number of the black spots is within 4, the number of the black spots is within 6, the number of the black spots is within 8, the number of the black spots is within 10, the number of the black spots is within 12, the number of the black spots is within 14, the number of the black spots is within 16, the number of the black spots is within 18 and the number of the black spots is greater than 18.
Gloss level: according to standard GB/T8807-1988, the degree to which the surface of an object is close to specular is expressed numerically. The gloss level may be evaluated using a gloss meter, which typically uses 20 °, 45 °, 60 ° or 85 ° illumination, mainly 60 ° illumination, depending on the angle of illumination and observation of the light source. The testing method comprises the following steps: the gloss data of 60 ° were read directly using a gloss meter laid flat on a square plate of 2mm x 100 mm.
Izod notched impact strength at-40 ℃ and kJ/m 2 : after 50 parts of mica master batch and 50 parts of polypropylene PP 179 are uniformly mixed, the mixture is injection molded into standard cantilever beam notch impact splines according to ISO 180-2019, A-shaped notch is arranged in a forced convection oven at the temperature of minus 40 ℃ for 24 hours, and the low-temperature cantilever beam notch impact strength is tested.
The raw material information of the invention is specifically described as follows:
melt flow rate of the homo-polypropylene is 15g/10min measured according to ISO1133-2011 method under 230 ℃/2.16kg, and the melt flow rate is purchased from Baling petrochemical industry and has the brand of PP 150 (powder);
the melt flow rate of the homo-polymerized ultra-high melt-index polypropylene is 100g/10min according to the ISO1133-2011 method under the condition of 230 ℃/2.16kg, and the melt flow rate is purchased from Darling with the brand name of PP 3860X;
the melt flow rate of the homo-high melt-index polypropylene A is 18G/10min according to the ISO1133-2011 method under the condition of 230 ℃/2.16kg, and the melt flow rate is purchased from Hainan petrochemical industry and is named as PP V30G;
the melt flow rate of the homo-high melt-index polypropylene B is 30g/10min according to the ISO1133-2011 method under the condition of 230 ℃/2.16kg, and the melt flow rate is purchased from the petrochemical industry with a name of China and the brand name of PP 320 powder;
the melt flow rate of the homo-high melt-index polypropylene C is 20g/10min according to the ISO1133-2011 method under the condition of 230 ℃/2.16kg, and the melt flow rate is purchased from the Yanshan petrochemical industry and has the brand of PP YPJ-3860;
the melt flow rate of the homo-high melt-index polypropylene D is 25g/10min according to the ISO1133-2011 method under the condition of 230 ℃/2.16kg, and the melt flow rate is purchased from Indian Xincheng with the brand of PP HP552R;
metallocene low isotacticity polypropylene a: the isotacticity is 60%, the melt flow rate is 1600g/10min according to the ISO1133-2011 method under the condition of 230 ℃/2.16kg, and the product is purchased from Japan and has the brand L-MODU S400;
metallocene low isotacticity polypropylene B: the isotacticity is 63%, the melt flow rate is 800g/10min according to the ISO1133-2011 method under the condition of 230 ℃/2.16kg, and the product is purchased from Japan and has the brand of PP T500;
metallocene low isotacticity polypropylene C: the isotacticity is 65%, the melt flow rate is 3000g/10min according to the ISO1133-2011 method under 230 ℃/2.16kg condition, and the product is purchased from Japan and has the brand L-MODU S901;
metallocene low isotacticity polypropylene D: the isotacticity is 55%, the melt flow rate is 2500g/10min according to the ISO1133-2011 method under the condition of 230 ℃/2.16kg, and the product is purchased from Japan and has the brand L-MODU S600;
metallocene low isotacticity polypropylene E: the isotacticity is 50%, and the melt flow rate is 1200g/10min according to the ISO1133-2011 method under the condition of 230 ℃/2.16kg, and the isotacticity is purchased from Japan and has the brand of L-MODU S410;
metallocene low isotacticity polypropylene F: the isotacticity is 68%, the melt flow rate is 10g/10min according to the ISO1133-2011 method under 230 ℃/2.16kg condition, and the product is purchased from Yanshan petrochemical industry and has the brand of PP C5608M;
mica A is purchased from Jiangmen Jingda, with the brand of AY-03N and the particle size D50 of 32 μm;
mica B is purchased from the Liangshou Huajing with the brand of 60-D and the particle diameter D50 of 38 mu m;
mica C was purchased from Liang Huo Jing, trade name 300HC, particle size D50 20 μm;
mica D was purchased from Chuzhou Gerui under the trade name GM-5 and had a particle size D50 of 45. Mu.m;
polypropylene: PP SP179, available from lanzhou petrochemicals;
the antioxidants are commercially available, and the same in other examples and comparative examples;
the lubricants are commercially available, and the same is true for the other examples and comparative examples.
Examples 1 to 6
The polypropylene mica master batch comprises the following components in parts by weight in table 1.
The preparation method of the polypropylene mica master batch in the embodiments 1 to 6 comprises the following steps:
adding the components into an internal mixer, banburying and mixing for 20min to obtain a mixture, adding the mixture into a single screw extruder through main feeding, extruding and granulating, and controlling the temperature of the extruder at 140 ℃ to finally obtain the polypropylene mica master batch.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| Homo-high melt index Polypropylene A | 10 | 25 | 15 | 20 | 18 | 15 |
| Metallocene low isotacticity polypropylene A | 25 | 10 | 18 | 13 | 15 | 15 |
| Mica A | 90 | 75 | 78 | 85 | 82 | 82 |
| Antioxidant | 1 | 0.3 | 0.5 | 0.5 | 0.5 | 0 |
| Lubricant | 0.3 | 1 | 0.5 | 0.5 | 0.5 | 0 |
Example 7
The polypropylene mica master batch comprises the same components and contents as in example 5 in parts by weight, except that the homo-high melt polypropylene is homo-high melt polypropylene B.
The preparation method of the polypropylene mica master batch is the same as in example 5.
Example 8
The polypropylene mica master batch comprises the same components and contents as in example 5 in parts by weight, except that the homo-high melt polypropylene is homo-high melt polypropylene C.
The preparation method of the polypropylene mica master batch is the same as in example 5.
Example 9
The polypropylene mica master batch comprises the same components and contents as in example 5 in parts by weight, except that the homo-high melt polypropylene is homo-high melt polypropylene D.
The preparation method of the polypropylene mica master batch is the same as in example 5.
Example 10
The polypropylene mica master batch comprises the same components and contents as in example 5 in parts by weight, except that the metallocene low isotacticity polypropylene is metallocene low isotacticity polypropylene B.
The preparation method of the polypropylene mica master batch is the same as in example 5.
Example 11
The polypropylene mica master batch comprises the same components and contents as in example 5 in parts by weight, except that the metallocene low isotacticity polypropylene is metallocene low isotacticity polypropylene C.
The preparation method of the polypropylene mica master batch is the same as in example 5.
Example 12
The polypropylene mica master batch comprises the same components and contents as in example 5 in parts by weight, except that the metallocene low isotacticity polypropylene is metallocene low isotacticity polypropylene D.
The preparation method of the polypropylene mica master batch is the same as in example 5.
Example 13
The polypropylene mica master batch comprises the same components and contents as in example 5 in parts by weight, except that the mica is mica B.
The preparation method of the polypropylene mica master batch is the same as in example 5.
Example 14
The polypropylene mica master batch comprises the same components and contents as in example 5 in parts by weight, except that the mica is mica C.
The preparation method of the polypropylene mica master batch is the same as in example 5.
Example 15
The polypropylene mica master batch comprises the same components and contents as in example 5 in parts by weight, except that the mica is mica D.
The preparation method of the polypropylene mica master batch is the same as in example 5.
Comparative examples 1 to 7
The polypropylene mica master batch comprises the following components in parts by weight.
A preparation method of the polypropylene mica master batch in comparative examples 1-7 comprises the following steps:
adding the components into an internal mixer, banburying and mixing for 20min to obtain a mixture, adding the mixture into a single screw extruder through main feeding, extruding and granulating, and controlling the temperature of the extruder at 140 ℃ to finally obtain the polypropylene mica master batch.
TABLE 2
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | |
| Homo-high melt index Polypropylene A | 10 | 25 | 10 | 18 | 18 | ||
| Homo-and melt-index polypropylene | 18 | ||||||
| Homo-and ultra-high melt index polypropylene | 18 | ||||||
| Metallocene low isotacticity polypropylene A | 27 | 8 | 25 | 15 | 15 | ||
| Metallocene low isotacticity Polypropylene E | 15 | ||||||
| Metallocene low isotacticity polypropylene F | 15 | ||||||
| Mica A | 90 | 75 | 92 | 82 | 82 | 82 | 82 |
| Antioxidant | 1 | 0.3 | 1 | 0.5 | 0.5 | 0.5 | 0.5 |
| Lubricant | 0.3 | 1 | 0.3 | 0.5 | 0.5 | 0.5 | 0.5 |
Result detection
The results of the above examples and comparative examples are shown in Table 3.
The above examples of the invention are merely illustrative of the invention and are not intended to limit the embodiments of the invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (8)
1. The polypropylene mica master batch is characterized by comprising the following components in parts by weight:
10-25 parts of homo-polymerization high melt index polypropylene; 10-25 parts of metallocene low isotacticity polypropylene; 75-90 parts of mica and the balance of the mica,
wherein the melt flow rate of the homo-polymerized high-melt polypropylene is 18-30 g/10min measured according to the ISO1133-2011 method under the condition of 230 ℃/2.16kg,
the isotacticity of the metallocene low isotacticity polypropylene is 55-65%,
the metallocene low isotacticity polypropylene has a melt flow rate of 1500-1800 g/10min measured according to ISO1133-2011 method under 230 ℃/2.16kg, and the particle diameter D50 of the mica is 30-40 mu m.
2. The polypropylene mica master batch according to claim 1, which comprises the following components in parts by weight:
15-20 parts of homo-polymerization high melt index polypropylene; 13-18 parts of metallocene low isotacticity polypropylene; 78-85 parts of mica.
3. The polypropylene mica masterbatch according to claim 1, wherein the homo-high melt index polypropylene has a melt flow rate of 20 to 25g/10min measured according to ISO1133-2011 at 230 ℃/2.16 kg.
4. The polypropylene mica masterbatch according to claim 1 wherein the metallocene low isotacticity polypropylene has an isotacticity of 60 to 63%.
5. The polypropylene mica master batch according to claim 1, further comprising 0.2 to 1 part of an antioxidant and 0.3 to 1 part of a lubricant in parts by weight.
6. A method for preparing the polypropylene mica master batch according to any one of claims 1 to 5, comprising the following steps:
adding the components into an internal mixer for banburying and mixing to obtain a mixture, adding the mixture into an extruder for granulating through main feeding, and controlling the temperature of the extruder to be 120-160 ℃ to finally obtain the polypropylene mica master batch.
7. Use of the polypropylene mica masterbatch according to any one of claims 1-5 for the preparation of plastic articles.
8. A plastic article prepared from a raw material comprising the polypropylene mica masterbatch of any one of claims 1-5.
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| CN112795083A (en) * | 2020-12-23 | 2021-05-14 | 金发科技股份有限公司 | High-glossiness polypropylene composition and preparation method and application thereof |
| CN113861554A (en) * | 2021-09-07 | 2021-12-31 | 金发科技股份有限公司 | High-gloss and well-dispersed polypropylene talcum powder master batch and preparation method and application thereof |
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