CN116120630A - Application of nucleating agent in preparation of high-gloss polyolefin resin - Google Patents
Application of nucleating agent in preparation of high-gloss polyolefin resin Download PDFInfo
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- CN116120630A CN116120630A CN202211634904.0A CN202211634904A CN116120630A CN 116120630 A CN116120630 A CN 116120630A CN 202211634904 A CN202211634904 A CN 202211634904A CN 116120630 A CN116120630 A CN 116120630A
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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
- C08K3/32—Phosphorus-containing compounds
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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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
- C08L23/10—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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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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
- C08L2205/24—Crystallisation aids
Abstract
The invention relates to the technical field of plastic products, in particular to application of a nucleating agent in preparing high-gloss polyolefin resin, wherein 3-7 parts of the nucleating agent is added into 1000 parts of polyolefin resin, the grain diameter D (97) of the nucleating agent is 1-7 mu m, and the nucleating agent is phosphate nucleating agent. Through a great deal of experimental study, the invention discovers that the nucleating agent particle size can be controlled to prepare high-gloss polyolefin resin. The reason is that when preparing high-gloss polypropylene resin, the particle sizes of the nucleating agent and various processing aids are uniform, the meltability and the dispersibility are good in the double-screw conveying process, and the granulated polypropylene resin has regular surface and good glossiness; when the particle size difference between the processing aid and the nucleating agent is large, in the conveying process of the double screws, the melting property is uneven due to the non-uniformity of the particle size, and agglomeration of the small-particle-size aid due to intermolecular acting force is likely to occur, so that the dispersibility is poor, and finally, the glossiness of the product is reduced.
Description
Technical Field
The invention relates to the technical field of plastic products, in particular to application of a nucleating agent in preparation of high-gloss polyolefin resin.
Background
Polypropylene (PP) resin is the most light density of the current common resin, is thermoplastic synthetic resin with excellent performance, is colorless semitransparent thermoplastic light general plastic, has the characteristics of chemical resistance, heat resistance, electrical insulation, high strength mechanical property, good high wear-resistant processability, no odor, no toxicity and the like, and is widely applied to various fields of automobiles, household appliances, foods and the like. With the development of technology and the improvement of aesthetic requirements of the public, in the current application fields of household appliances and daily necessities, higher requirements are gradually put on the surface glossiness of plastic products.
The high gloss plastics in the prior art are mainly PC (polycarbonate) materials. As CN112795166a discloses a polycarbonate composite material for high-gloss plastic products and a preparation method thereof, the preparation method thereof is as follows (expressed in parts by weight): 60-99 parts of Polycarbonate (PC), 0-20 parts of polymethyl methacrylate (PMMA), 1-20 parts of polyvinylidene fluoride (PVDF), 0.1-0.5 part of antioxidant and 0.1-2 parts of lubricant are put into a high-speed mixer at 300-1500 rpm, mixed for 3-15 minutes, then added into a double screw extruder, and melted and granulated to obtain the high-gloss composite material, wherein pearl powder or metal powder is not required to be additionally added in the preparation process, and the high-gloss effect can be achieved. However, PC materials are very tough and very brittle, and are not suitable for applications in the household appliance field.
In addition, the brightening agent is sprayed on the surface of the plastic product, and a thin film layer is formed on the surface of the plastic product, so that the glossiness of the surface of the product is improved. As CN111113851a discloses a method and apparatus for preparing a high gloss plastic product, the plastic is as follows by weight: resin: 98-99.9 parts; pearlescent resin: and 0.1-2.0 parts of pearl resin is added from a pearl resin feeding device close to a metering section of an injection molding machine in the preparation process, so that the size integrity of the pearl resin in the injection molding preparation process is greatly reserved, a considerable part of pearl resin is selectively dispersed on the surface layer of plastic, the content of the pearl resin on the surface layer of the product is improved, and the glossiness of the plastic product is greatly improved.
As another example, CN110194868A discloses a high-gloss polypropylene resin composition, the high-gloss polypropylene resin composition of the present invention uses the prepared high-gloss polypropylene matrix resin as a raw material, and is supplemented with selected nucleating agent and brightening agent components, and the preparation raw material comprises the following components in mass content: 92-98wt% of high-gloss polypropylene resin matrix; 0.2-0.5wt% of a first nucleating agent; 0.05-0.2wt% of a second nucleating agent; 1-5wt% of brightening agent; the first nucleating agent comprises a sorbitol nucleating agent; the second nucleating agent comprises a phosphate-based nucleating agent; an impact-resistant polypropylene resin with good glossiness, impact resistance, rigidity, high rigidity-toughness balance and low shrinkage rate is obtained.
However, the coating or brightening agent is often not fully compatible with polypropylene plastic, and the coating can fall off along with the repeated use of the product, so that the surface of the product is mottled, and the quality and the appearance of the product are affected.
Therefore, developing a polyolefin resin with more stable properties and high gloss is one of the problems to be solved in the art.
Disclosure of Invention
The invention aims to provide an application of a nucleating agent in preparing high-gloss polyolefin resin.
In order to solve the technical problems, the application provides the following technical scheme:
the application of the nucleating agent in preparing the high-gloss polyolefin resin is as follows: 3 to 7 parts of nucleating agent is added to 1000 parts of polyolefin resin, and the particle diameter D (97) of the nucleating agent is 1 to 7 mu m. Experiments show that when the particle size of the nucleating agent is selected to be 1 mu m < D (97) < 2 mu m, the glossiness of the sample is 72.8 degrees, the glossiness is reduced, and the analysis reasons are probably that the particle size is too small, and the interaction force among the molecules of the nucleating agent causes aggregation, so that the surface glossiness of the sample is influenced.
Further, the nucleating agent is a phosphate nucleating agent.
Further, the nucleating agent particle diameter D (97) is 5.0.+ -. 0.2. Mu.m.
Further, 5 parts of a nucleating agent is added per 100 parts of the polyolefin resin.
Further, an antioxidant and/or an acid absorber having a particle diameter D (97) of 5.0.+ -. 0.2 μm is added to the polyolefin resin. As a result of a large number of experimental studies, it was found that the surface gloss of the sample was also affected by the particle size of the other auxiliary agent, and therefore, the optimum particle size D (97) was selected to be 5.0.+ -. 0.2. Mu.m.
Wherein the antioxidant is a phenolic antioxidant and/or a phosphite antioxidant.
Wherein the phenolic antioxidant is phenolic antioxidant 1076 or phenolic antioxidant 1010.
Wherein the phosphite antioxidant is phosphite antioxidant 168 or phosphite antioxidant 618.
Wherein the acid absorber is calcium stearate and/or zinc stearate.
Compared with the prior art, the application of the nucleating agent in preparing the high-gloss polyolefin resin has at least the following beneficial effects:
through a great deal of experimental study, the invention discovers that the nucleating agent particle size can be controlled to prepare high-gloss polyolefin resin. The possible reasons are that the particle sizes of the nucleating agent and various processing aids are uniform when the high-gloss polypropylene resin is prepared, the meltability and the dispersibility are good in the conveying process of the double screws, and the granulated polypropylene resin has regular surface and good glossiness; when the particle size difference between various processing aids and nucleating agents is large, in the conveying process of the twin-screw, the situation of uneven melting property can occur due to uneven particle size, and agglomeration of the small-particle-size auxiliary agents can occur due to intermolecular acting force, so that the dispersibility becomes worse, and finally, the glossiness of the product is reduced. The present inventors have found that the surface gloss of the sample is preferably 83.1℃when the particle diameter D (97) of the nucleating agent is 5 μm.+ -. 0.2. Mu.m.
The use of the nucleating agent of the present invention for preparing a high gloss polyolefin resin is further described below with reference to specific examples.
Detailed Description
Example 1
The application of a nucleating agent in preparing high-gloss polyolefin resin comprises the following specific formula:
polypropylene resin: petrifaction of Dushan mountain with the brand number of K9928H and 1000 parts;
nucleating agent: shanghai Ji Run QSZ-9512 is phosphate nucleating agent, D (97) is 5 mu m plus or minus 0.2 mu m, and 5 parts;
antioxidant 1010: commercially available, and crushing, wherein D (97) is 5 [ mu ] m+/-0.2 [ mu ] m and 10 parts;
antioxidant 168: commercially available, and crushing, wherein D (97) is 5 [ mu ] m+/-0.2 [ mu ] m and 10 parts;
acid absorber calcium stearate: commercially available, and further pulverized to give a D (97) of 5 μm.+ -. 0.2 μm and 8 parts.
Sample preparation process: the polypropylene resin, the nucleating agent, the antioxidant and the acid absorber are mixed in proportion, are placed in a high-speed mixer to be evenly mixed for 10-20min, the mixed materials reach a discharging bin of a double-screw extruder through a discharging opening, the double-screw extruder is preheated, after the preheating, the materials are conveyed to the double-screw extruder through the discharging bin to be extruded and granulated, and the temperature of the double-screw extruder is controlled as shown in the table 1 below.
TABLE 1
| Temperature zone | A zone of | Two-zone | Three zones | Four zones | Five zones | Six zones | Seven areas | Eight areas | Nine zones | Ten zones | Eleven zones |
| Temperature, DEG C | 160 | 170 | 180 | 190 | 195 | 190 | 185 | 175 | 180 | 185 | 190 |
And then injection molding the sample into test strips (the temperature of the injection molding machine is 260 ℃) in an injection molding machine, carrying out state adjustment on the test strips in an environment with the temperature of 23+/-2 ℃ and the humidity of 50+/-5%, wherein the state adjustment time is more than 48 hours, and then carrying out performance test.
Aging test the test was carried out according to the test method of method A in GB/T16422.3-2022 and the gloss of the test specimens after exposure was again tested.
The test standard of glossiness is GB/T8807-1988 method for testing specular gloss of plastics. The sample has smooth and flat surface, and has no defects of dirt, scratch and the like. At an incident angle of 60 degrees, the surface glossiness of the test sample is high, and the glossiness is more than or equal to 70.0 degrees.
Example 2
The use of a nucleating agent in the preparation of a high gloss polyolefin resin differs from example 1 only in that: the addition amount of the nucleating agent was 3 parts, and the other conditions and the preparation process were the same as in example 1.
Example 3
The use of a nucleating agent in the preparation of a high gloss polyolefin resin differs from example 1 only in that: the nucleating agent was added in an amount of 7 parts, and the other conditions and the preparation process were the same as in example 1.
Example 4
The use of a nucleating agent in the preparation of a high gloss polyolefin resin differs from example 1 only in that:
the nucleating agent is selected from 6 μm < D (97) < 7 μm;
antioxidant 1010: commercially available, and crushing, wherein D (97) is less than 7 μm and more than 6 μm;
antioxidant 168: commercially available, and crushing, wherein D (97) is less than 7 μm and more than 6 μm;
acid absorber calcium stearate: commercially available, and crushing, wherein D (97) is less than 7 μm and more than 6 μm;
the other conditions and preparation were the same as in example 1.
Example 5
The use of a nucleating agent in the preparation of a high gloss polyolefin resin differs from example 1 only in that:
the nucleating agent is selected from the group consisting of D (97) which is more than 1 mu m and less than 2 mu m;
antioxidant 1010: commercially available, and crushing, wherein D (97) is less than 2 μm and more than 1 μm;
antioxidant 168: commercially available, and crushing, wherein D (97) is less than 2 μm and more than 1 μm;
acid absorber calcium stearate: commercially available, and crushing, wherein D (97) is less than 2 μm and more than 1 μm;
the other conditions and preparation were the same as in example 1.
Example 6
The use of a nucleating agent in the preparation of a high gloss polyolefin resin differs from example 1 only in that:
the nucleating agent is selected from 6 μm < D (97) < 7 μm;
antioxidant 1010: commercially available, and crushing, wherein D (97) is less than 3 mu m and less than 4 mu m;
antioxidant 168: commercially available, and crushing, wherein D (97) is less than 3 mu m and less than 4 mu m;
acid absorber calcium stearate: commercially available, and crushing, wherein D (97) is less than 3 mu m and less than 4 mu m;
the other conditions and preparation were the same as in example 1.
To highlight the advantageous effects of the present invention, the following comparative examples are exemplified.
Comparative example 1
Raw materials:
polypropylene resin: petrifaction of Dushan mountain with the brand number of K9928H and 1000 parts;
antioxidant 1010: commercially available was used as it is, tested for D (97) of 185 μm,10 parts;
antioxidant 168: commercially available was used as it is, and tested for D (97) of 132 μm,10 parts;
acid absorber calcium stearate: commercially available for direct use, tested for D (97) of 89.3 μm;8 parts.
The sample preparation process and related parameters were the same as in example 1.
Comparative example 2
Raw materials:
polypropylene resin: petrifaction of Dushan mountain with the brand number of K9928H and 1000 parts;
nucleating agent: shanghai Ji Run QSZ-9512, a phosphate nucleating agent, is produced into a finished product which is not crushed, and has a D (97) of 44.9 mu m and 5 parts
Antioxidant 1010: commercially available was used as it is, tested for D (97) of 185 μm,10 parts;
antioxidant 168: commercially available was used as it is, and tested for D (97) of 132 μm,10 parts;
acid absorber calcium stearate: commercially available for direct use, tested for D (97) of 89.3 μm;8 parts.
The sample preparation process and related parameters were the same as in example 1.
Comparative example 3
In contrast to example 1, the only difference is that: the nucleating agent is D (97) less than 1 mu m, and the other conditions and the preparation process are the same as those of the example 1.
Comparative example 4
In contrast to example 1, the only difference is that: the nucleating agent is 7 μm < D (97) < 10 μm, and the other conditions and preparation process are the same as in example 1.
Comparative example 5
The procedure was as in example 1 except that the addition amount of the nucleating agent was adjusted to 10 parts, and the other conditions and the production process were the same as in example 1.
Comparative example 6
The procedure was as in example 1 except that the addition amount of the nucleating agent was adjusted to 2 parts, and the other conditions and the production process were the same as in example 1.
Comparative example 7
In contrast to example 1, the difference is that:
the nucleating agent is selected from 6 μm < D (97) < 7 μm;
antioxidant 1010: commercially available, and crushing, wherein D (97) is less than 12 μm and more than 10 μm;
antioxidant 168: commercially available, and crushing, wherein D (97) is less than 12 μm and more than 10 μm;
acid absorber calcium stearate: commercially available, and crushing, wherein D (97) is less than 12 μm and more than 10 μm;
the other conditions and preparation were the same as in example 1.
The above examples and comparative examples were subjected to performance tests, and the test results are shown in table 2 below.
TABLE 2
As can be seen from the above experimental results, in the process of preparing the high-gloss polypropylene resin, the particle size of the nucleating agent and other processing aids is strictly controlled, and the larger or smaller particle size affects the glossiness of the product, because the meltability in the process of conveying and extruding by the twin screw is possibly poor when the particle size of the nucleating agent or other processing aids is larger, and the surface regularity of the polypropylene resin is affected; when the grain diameter of the nucleating agent or other processing aids is smaller, the nucleating agent and other processing aids are agglomerated due to the action force in molecules or among molecules in the mixing and dispersing process, so that the regularity of the surface of the polypropylene resin is reduced, and the glossiness of the product is obviously reduced.
Secondly, when the glossiness of the product is tested after the aging test, the influence of the aging test on the glossiness is not great when the glossiness of the nucleating agent, other processing aids, the addition amount and the particle size are in a certain range, and when the particle size of the nucleating agent and the other processing aids is bigger or smaller, the glossiness after aging is obviously influenced greatly, which is probably because the problem of poor meltability and poor dispersibility of the nucleating agent and the other processing aids caused by the bigger or smaller particle size further influences the quality of the product after the aging test. Moreover, as can be seen from comparative examples 5 to 6, if the addition amount of the nucleating agent is too high, the nucleating agent is unevenly dispersed in the polypropylene resin, the phenomenon of nucleating agent agglomeration occurs, the particle size is uneven, and the glossiness is affected; too low an amount of the nucleating agent added, too dispersed cells for crystallization nucleation of the nucleating agent, can lead to uneven surface gloss, and ultimately affect product quality.
The above examples are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solution of the present invention should fall within the scope of protection defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (9)
1. The application of a nucleating agent in preparing high-gloss polyolefin resin is characterized in that: 3 to 7 parts of nucleating agent is added to 1000 parts of polyolefin resin, and the particle diameter D (97) of the nucleating agent is 1 to 7 mu m.
2. Use of a nucleating agent according to claim 1 for the preparation of a high gloss polyolefin resin characterized in that: the nucleating agent is phosphate nucleating agent.
3. Use of a nucleating agent according to claim 1 or 2 for the preparation of a high gloss polyolefin resin, characterized in that: the particle diameter D (97) of the nucleating agent is 5+/-0.2 mu m.
4. Use of a nucleating agent according to any one of claims 1-3 for the preparation of high gloss polyolefin resins, characterized in that: 5 parts of a nucleating agent is added per 1000 parts of a polyolefin resin.
5. The use of the nucleating agent according to claim 4 for the preparation of high gloss polyolefin resins, characterized in that: an antioxidant and/or an acid absorber having a particle diameter D (97) of 5.+ -. 0.2 μm is further added to the polyolefin resin.
6. The use of the nucleating agent according to claim 5 for the preparation of high gloss polyolefin resins, characterized in that: the antioxidant is a phenolic antioxidant and/or a phosphite antioxidant.
7. The use of the nucleating agent according to claim 6 for the preparation of high gloss polyolefin resins, characterized in that: the phenolic antioxidant is phenolic antioxidant 1076 or phenolic antioxidant 1010.
8. The use of the nucleating agent according to claim 6 for the preparation of high gloss polyolefin resins, characterized in that: the phosphite antioxidant is phosphite antioxidant 168 or phosphite antioxidant 618.
9. The use of the nucleating agent according to claim 5 for the preparation of high gloss polyolefin resins, characterized in that: the acid absorbing agent is calcium stearate and/or zinc stearate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211634904.0A CN116120630A (en) | 2022-12-19 | 2022-12-19 | Application of nucleating agent in preparation of high-gloss polyolefin resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211634904.0A CN116120630A (en) | 2022-12-19 | 2022-12-19 | Application of nucleating agent in preparation of high-gloss polyolefin resin |
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| CN202211634904.0A Pending CN116120630A (en) | 2022-12-19 | 2022-12-19 | Application of nucleating agent in preparation of high-gloss polyolefin resin |
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- 2022-12-19 CN CN202211634904.0A patent/CN116120630A/en active Pending
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