CN109320827B - Polyethylene resin suitable for preparing blow molding tray and preparation method and application thereof - Google Patents
Polyethylene resin suitable for preparing blow molding tray and preparation method and application thereof Download PDFInfo
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- CN109320827B CN109320827B CN201810960169.XA CN201810960169A CN109320827B CN 109320827 B CN109320827 B CN 109320827B CN 201810960169 A CN201810960169 A CN 201810960169A CN 109320827 B CN109320827 B CN 109320827B
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- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic 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
- C08K5/04—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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- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
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Abstract
The invention discloses a polyethylene resin suitable for preparing blow molding trays, which is prepared from the following components in parts by weight: 100 parts of polyethylene resin base material and 0.06-0.8 part of composite auxiliary agent. The invention also discloses a blow molding tray prepared from the polyethylene resin suitable for preparing the blow molding tray. The polyethylene resin suitable for preparing blow molding trays is prepared by pertinently adjusting the molecular weight of a polyethylene resin base material, wherein the polyethylene resin base material adopts a random copolymer of ethylene and hexene, the content of hexene is low, the resin has good impact strength and bending strength, the polyethylene resin prepared by the invention can be used for blow molding trays with various specifications such as 1.4 x 1.2m, 1.3 x 1.1m, 1.2 x 1.1m and the like, and the molded trays have uniform wall thickness, very good toughness and rigidity and very long service life.
Description
Technical Field
The invention belongs to the technical field of polyethylene resin, and particularly relates to polyethylene resin suitable for preparing blow molding trays, and a preparation method and application thereof.
Background
Polyethylene (PE) is the variety of plastic hollow blow molding materials that realizes commercial production at the earliest time, and is also the most rapidly developed and widely used variety, and at present, the yield of hollow blow molding products produced by using PE as a raw material accounts for about two thirds of the total yield of blow molding products in the world, wherein the demand of medium and small hollow products for polyethylene is large, accounting for about 80%. However, the research on polyethylene resin for molding plastic trays by a blow molding process is relatively less, polypropylene or polyethylene injection molding trays are more used in the market, the toughness and the impact resistance of the trays are poorer, the service life of the trays is shorter, the developed polyethylene resin for blow molding trays has good impact strength and bending strength, the trays can be endowed with better toughness and rigidity, and the service life of the trays is greatly prolonged compared with that of the injection molding trays.
Disclosure of Invention
In order to solve the problems of low toughness, poor impact strength and short service life of common polyethylene or polypropylene resin for plastic trays in the prior art, the invention aims to provide polyethylene resin which has good impact strength and bending strength and is suitable for preparing blow molding trays, and the blow molding trays have good rigidity and toughness and long service life.
Another object of the present invention is to provide a process for the preparation of said polyethylene resin suitable for the preparation of blow-moulded trays.
It is a further object of the present invention to provide a blow molded tray prepared from the polyethylene resin suitable for preparing blow molded trays.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a polyethylene resin suitable for preparing blow-molded trays, which is prepared from the following components in parts by weight:
100 parts of polyethylene resin base stock;
0.06-0.8 part of composite auxiliary agent.
The polyethylene resin base material is a random copolymer of ethylene and hexene, the content of the hexene is 0.5 to 2.0 weight percent, and the melt flow rate (21.6kg/10min) is 1.5 to 11.0g/10 min.
The content of hexene in the polyethylene resin base material is 0.5-1.0 wt%, and the melt flow rate (21.6kg/10min) is 1.5-3.0g/10 min.
The polyethylene resin base material had a hexene content of 0.8 wt% and a melt flow rate (21.6kg/10min) of 1.5g/10 min.
The composite auxiliary agent is prepared from the following components in parts by weight:
0.02 to 0.3 part of halogen absorbent,
0.04-0.5 part of antioxidant.
The composite auxiliary agent is prepared from the following components in parts by weight:
0.1 part of halogen absorbent,
0.3 part of antioxidant.
The halogen absorbent is at least one of calcium stearate and hydrotalcite.
The antioxidant is at least one of bis- [3, 3-bis- (3-tert-butyl-4-hydroxyphenyl) -butyric acid ] glycol ester, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tris (2, 3-di-tert-butylphenyl) phosphite.
The antioxidant is a mixture of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tri (2, 3-di-tert-butylphenyl) phosphite.
The second aspect of the present invention provides a method for preparing the polyethylene resin suitable for preparing the blow-molded tray, which comprises the following steps:
and uniformly mixing the polyethylene resin base material and the composite auxiliary agent according to the proportion, and carrying out melt granulation to obtain the polyethylene resin suitable for preparing the blow molding tray.
A third aspect of the invention provides a blow molded tray prepared from the polyethylene resin suitable for preparing a blow molded tray.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the polyethylene resin suitable for preparing blow molding trays of the invention is prepared by carrying out targeted adjustment on the molecular weight of a polyethylene resin base material, wherein the polyethylene resin base material adopts a random copolymer of ethylene and hexene, the hexene content is low, and the resin has good impact strength and bending strength at the same time.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
In the case where the object of the present invention is illustrated and explained by the following examples, the components of the polyethylene resin suitable for preparing blow molded trays are all explained on the general standard of parts by weight. In the present invention, the term "part" is used in the same sense as part by weight for the sake of brevity without specific mention.
Example 1
100 parts of a random copolymer of ethylene and hexene having a hexene content of 0.8% by weight and a melt flow rate of 1.5g/10min were uniformly mixed with 0.1 part of calcium stearate, 0.2 part of pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 0.1 part of tris (2, 3-di-tert-butylphenyl) phosphite, and the mixture was fed into a twin-screw extruder to be melt-pelletized, with a screw diameter of 150mm and an aspect ratio of 25, and the temperatures in the respective zones: zone 1 180 ℃, zone 2 190 ℃, zone 3 200 ℃, zone 4 200 ℃, zone 5 200 ℃, zone 6 180 ℃, zone 7 190 ℃, zone 8 200 ℃ and zone 9 ℃ to obtain the polyethylene resin suitable for preparing blow molding trays.
Example 2
100 parts of a random copolymer of ethylene and hexene having a hexene content of 0.8% by weight and a melt flow rate of 2.5g/10min were uniformly mixed with 0.1 part of calcium stearate, 0.2 part of pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 0.1 part of tris (2, 3-di-tert-butylphenyl) phosphite, and then fed into a twin-screw extruder to be melt-pelletized, thereby obtaining a polyethylene resin suitable for preparing blow molding trays. The processing parameters were the same as in example 1.
Example 3
100 parts of a random copolymer of ethylene and hexene having a hexene content of 0.8% by weight and a melt flow rate of 6.0g/10min were uniformly mixed with 0.1 part of calcium stearate, 0.2 part of pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 0.1 part of tris (2, 3-di-tert-butylphenyl) phosphite, and then fed into a twin-screw extruder to be melt-pelletized, thereby obtaining a polyethylene resin suitable for preparing blow molding trays. The processing parameters were the same as in example 1.
Example 4
100 parts of a random copolymer of ethylene and hexene having a hexene content of 0.8% by weight and a melt flow rate of 10.0g/10min were uniformly mixed with 0.1 part of calcium stearate, 0.2 part of pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 0.1 part of tris (2, 3-di-tert-butylphenyl) phosphite, and then fed into a twin-screw extruder to be melt-pelletized, thereby obtaining a polyethylene resin suitable for preparing blow molding trays. The processing parameters were the same as in example 1.
Example 5
100 parts of a random copolymer of ethylene and hexene having a hexene content of 0.5% by weight and a melt flow rate of 1.5g/10min were uniformly mixed with 0.1 part of calcium stearate, 0.2 part of pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 0.1 part of tris (2, 3-di-tert-butylphenyl) phosphite, and then fed into a twin-screw extruder to be melt-pelletized, thereby obtaining a polyethylene resin suitable for preparing blow molding trays. The processing parameters were the same as in example 1.
Example 6
100 parts of a random copolymer of ethylene and hexene having a hexene content of 1.5% by weight and a melt flow rate of 1.5g/10min were uniformly mixed with 0.1 part of calcium stearate, 0.2 part of pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 0.1 part of tris (2, 3-di-tert-butylphenyl) phosphite, and then fed into a twin-screw extruder to be melt-pelletized, thereby obtaining a polyethylene resin suitable for preparing blow molding trays. The processing parameters were the same as in example 1.
Example 7
100 parts of a random copolymer of ethylene and hexene having a hexene content of 0.8% by weight and a melt flow rate of 1.5g/10min were uniformly mixed with 0.2 part of calcium stearate, 0.2 part of pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 0.1 part of tris (2, 3-di-tert-butylphenyl) phosphite, and then fed into a twin-screw extruder to be melt-pelletized, thereby obtaining a polyethylene resin suitable for preparing blow molding trays. The processing parameters were the same as in example 1.
Example 8
100 parts of a random copolymer of ethylene and hexene having a hexene content of 0.8% by weight and a melt flow rate of 1.5g/10min were uniformly mixed with 0.1 part of calcium stearate, 0.1 part of pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 0.1 part of tris (2, 3-di-tert-butylphenyl) phosphite, and then fed into a twin-screw extruder to be melt-pelletized, thereby obtaining a polyethylene resin suitable for preparing blow molding trays. The processing parameters were the same as in example 1.
Example 9
100 parts of a random copolymer of ethylene and hexene having a hexene content of 0.8 wt% and a melt flow rate of 1.5g/10min were uniformly mixed with 0.1 part of hydrotalcite, 0.2 part of pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 0.1 part of tris (2, 3-di-tert-butylphenyl) phosphite, and then fed into a twin-screw extruder to be melt-pelletized, thereby obtaining a polyethylene resin suitable for preparing blow molding trays. The processing parameters were the same as in example 1.
And (3) performance testing: the polyethylene resins obtained in examples 1 to 9 were subjected to conventional mechanical property tests, wherein the bending strength was obtained by the method of GB/T1040.2 to 2006, the impact strength was obtained by the method of GB/T1043 to 2008, and the polyethylene resins obtained in each example were respectively subjected to blow molding by extrusion blow molding equipment for 1.4 × 1.2m trays, and blow molding was performed by a Kautex blow molding machine, and were compared with mechanical properties of polypropylene (K8003PP is available from China petrochemical Yanggui petrochemical company, Inc.) of which the special brand number of K8003 is commonly used for injection molding trays, and the test results are shown in Table 1:
TABLE 1
| Examples | Percent of pass of blow molding | Flexural strength, MPa | Impact strength, kJ/m2，23℃ |
| Example 1 | 100％ | 23.9 | 154.2 |
| Example 2 | 100％ | 24.1 | 146.7 |
| Example 3 | 100％ | 24.0 | 135.9 |
| Example 4 | 95％ | 24.3 | 128.6 |
| Example 5 | 100％ | 25.3 | 141.2 |
| Example 6 | 100％ | 22.8 | 168.2 |
| Example 7 | 100％ | 24.0 | 152.3 |
| Example 8 | 100％ | 23.6 | 155.5 |
| Example 9 | 100％ | 24.5 | 150.3 |
| Polypropylene | —— | 24.7 | 30.1 |
As can be seen from the data in Table 1, the comparison between the polypropylene with the special injection molding tray brand K8003 and the products obtained in the embodiments 1-9 of the present invention shows that the impact strength of the products obtained in the embodiments of the present invention is high, i.e., the toughness and the impact resistance of the products are both better than those of the polypropylene with the special injection molding tray brand K8003, and meanwhile, the bending strength also basically reaches the level of polypropylene resin. Therefore, the polyethylene resin base material adopted in the embodiment of the invention adopts a random copolymer of ethylene and hexene, the hexene content is low, the resin has good impact strength and bending strength, the polyethylene resin prepared by the invention can be used for blow molding trays of various specifications such as 1.4 × 1.2m, 1.3 × 1.1m, 1.2 × 1.1m and the like, the wall thickness of the molded tray is uniform, the toughness and the rigidity are very good, and the excellent toughness endows the blow molded tray prepared by the resin with long service life.
Comparative example 1
Patent 201810019538.5 discloses a polypropylene resin suitable for blow molding process for making hollow articles: 100 parts of a random copolymer of propylene and ethylene, the ethylene content of which is 3 wt%, and the melt flow rate of which is 0.2g/10min, are uniformly mixed with 0.1 part of calcium stearate, 0.2 part of pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 0.1 part of tris (2, 3-di-tert-butylphenyl) phosphite, and then the mixture is added into a twin-screw extruder to be subjected to melt granulation, so that the polypropylene resin suitable for preparing hollow products by a blow molding process is obtained. The length-diameter ratio of the double-screw extruder is 40, the screw rotating speed is 200r/min, and the temperature of each area of the double-screw extruder is as follows: 130 ℃ in the first zone, 160 ℃ in the second zone, 190 ℃ in the third zone, 200 ℃ in the fourth zone, 200 ℃ in the fifth zone, 205 ℃ in the sixth zone, 210 ℃ in the seventh zone and 210 ℃ in the eighth zone.
Comparative examples 2 to 6
Patent 201711183177.X discloses a preparation method of a high-transparency high-impact polypropylene resin, which comprises the following steps: 100 parts of random copolymerized polypropylene (random copolymer of propylene and ethylene, the ethylene content of which is 3 wt%, 3 wt%, 3 wt%, 5 wt%, 5 wt%) and having melt flow rates of 0.3, 0.6, 1.0, 1.5 and 2.0g/10min, respectively, were uniformly mixed with 0.1 part of calcium stearate, 0.2 part of transparent nucleating agent NX8000, 0.2 part of pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 0.1 part of tris (2, 3-di-tert-butylphenyl) phosphite, and then melt-granulated, the extrusion temperature was 200 ℃, and the resulting polypropylene resin was subjected to extrusion blow molding on blow molding equipment.
The polypropylene resins prepared in the above six comparative examples cannot be prepared into blow-molded trays by a blow molding process, and in addition, the impact strength of the polypropylene resins in the comparative examples is much lower than that of the polyethylene resins prepared in the examples of the present application.
Comparative example 7
Patent 200910229289.3 discloses an ultra-high molecular weight polyethylene resin composition, component a: ultra-high molecular weight polyethylene resin, weight fraction: 100 parts of (A); and (B) component: pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] in a weight fraction of: 0.2 part; and (3) component C: calcium stearate, weight fraction: 0.03.
comparative example 8
Patent 200910229289.3 discloses an ultra-high molecular weight polyethylene resin composition, component a: ultra-high molecular weight polyethylene resin, weight fraction: 100 parts of (A); and (B) component: tris (2, 4-di-tert-butylphenyl) phosphite, weight fraction: 0.3 part; and (3) component C: calcium stearate, weight fraction: 0.06.
comparative example 9
Patent 200910229289.3 discloses an ultra-high molecular weight polyethylene resin composition, component a: ultra-high molecular weight polyethylene resin, weight fraction: 100 parts of (A); and (B) component: dilauryl thiodipropionate, weight fraction: 0.4 part, component C: zinc stearate, weight fraction: 0.1 part.
The ultra-high molecular weight polyethylene resin compositions prepared in comparative examples 7 to 9 could not be applied to tray molding by the blow molding process, and the obtained ultra-high molecular weight polyethylene had a much different molecular weight from the polyethylene resin obtained in the present application, and the melt index of the ultra-high molecular weight polyethylene resin compositions prepared in comparative examples 7 to 9 could not be measured. In addition, the polyethylene resin in the prior art cannot be used for tray molding through an injection molding process and equipment, the melt index (7-8g/10min,2.16kg) of the polyethylene resin selected by the injection molding equipment is greatly different from that of the raw materials selected by the application, and the impact strength of the polyethylene for injection molding can only reach 1/3 of the polyethylene resin prepared by the application.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (4)
1. A polyethylene resin suitable for use in the preparation of blow molded trays, characterized by: the composition is prepared from the following components in parts by weight:
100 parts of polyethylene resin base stock;
0.06-0.8 parts of a composite additive;
the polyethylene resin base material is a random copolymer of ethylene and hexene, the content of hexene is 0.8 wt%, and the melt flow rate is 1.5g/10 min;
the composite auxiliary agent is prepared from the following components in parts by weight:
0.02 to 0.3 part of halogen absorbent,
0.04-0.5 part of antioxidant;
the antioxidant is a mixture of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tri (2, 3-di-tert-butylphenyl) phosphite.
2. Polyethylene resin suitable for the preparation of blow-molded trays according to claim 1, characterized in that: the composite auxiliary agent is prepared from the following components in parts by weight:
0.1 part of halogen absorbent,
0.3 part of antioxidant.
3. Polyethylene resin suitable for the preparation of blow-molded trays according to claim 2, characterized in that: the halogen absorbent is at least one of calcium stearate and hydrotalcite.
4. A blow molded tray prepared from the polyethylene resin suitable for preparing a blow molded tray of any one of claims 1 to 3.
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