CN112745580B - High-fluidity, high-impact-resistance and high-temperature-resistance polypropylene material as well as preparation method and application thereof - Google Patents
High-fluidity, high-impact-resistance and high-temperature-resistance polypropylene material as well as preparation method and application thereof Download PDFInfo
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- CN112745580B CN112745580B CN201911043541.1A CN201911043541A CN112745580B CN 112745580 B CN112745580 B CN 112745580B CN 201911043541 A CN201911043541 A CN 201911043541A CN 112745580 B CN112745580 B CN 112745580B
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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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
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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
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic 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
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention provides a high-flow high-impact-resistance high-temperature-resistance polypropylene material which is characterized in that the ethylene content of the polypropylene material is 8-14%, the rubber content is 14-17%, the melt flow rate is 20-30 g/10min, the cantilever beam impact strength is greater than 70J/m, and the thermal deformation temperature is greater than 100 ℃. The polypropylene material provided by the invention can be directly used for washing machine inner barrel products without modification, thereby reducing intermediate links and lowering production cost.
Description
Technical Field
The invention relates to the field of polypropylene materials, in particular to a high-fluidity, high-impact and high-temperature resistant polypropylene material, and a preparation method and application thereof.
Background
In the field of polypropylene resins, polypropylene is rapidly becoming one of the most popular products in the market by virtue of its excellent properties in hardness, impact resistance, transparency, etc., and recyclability. The high-flow impact polypropylene generally refers to impact polypropylene with the Melt Flow Rate (MFR) of more than or equal to 20g/10min, and the resin has high melt fluidity, high impact strength and better rigidity and toughness.
The fluidity of the polypropylene resin is improved, and the pressure of a mold cavity can be reduced during molding processing. Generally, the injection pressure is reduced by increasing the processing temperature, thereby reducing the deformation of the product. After the high-fluidity impact-resistant polypropylene is selected, the processing temperature and the injection pressure can be reduced, the product deformation can be inhibited to a certain extent, the product quality is improved, and the processing energy consumption is reduced.
At present, the high-fluidity impact-resistant polypropylene is mainly applied to injection molding of large-scale thin-wall products, such as household electrical appliances, automobile parts, industrial parts, office supplies, furniture, toys, food and medical packages and the like, and the development of large-scale thin-wall manufacturing industries of automobiles, household products, packages and the like is greatly increased.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a high-flow high-impact-resistance high-temperature-resistance polypropylene material, and a preparation method and application thereof.
The invention provides a high-fluidity high-impact-resistance high-temperature-resistance polypropylene material, wherein the ethylene content of the polypropylene material is 8-14%, the rubber content is 14-17%, the melt flow rate is 20-10 min-30 g/10min, the cantilever beam impact strength is greater than 70J/m, and the heat deformation temperature is greater than 100 ℃.
In another aspect, the present invention provides a preparation method of the polypropylene material, including: the polypropylene material is prepared from raw materials including copolymerized polypropylene powder and an auxiliary agent through mixing, extruding and granulating.
In some preferred embodiments of the present invention, the copolymerized polypropylene powder has an ethylene content of 8% to 14%, a rubber content of 14% to 17%, and a melt flow rate of 20g/10min to 30g/10 min.
According to the invention, the polypropylene copolymer powder can be obtained by methods known in the art, provided that the ethylene content is 8-14%, the rubber content is 14-17%, and the melt flow rate is 20-30 g/10 min.
In some preferred embodiments of the invention, the mass fraction of the polypropylene copolymer powder is 87.5-95.5 parts, and the mass fraction of the auxiliary agent is 0.45-1.25 parts.
In some preferred embodiments of the present invention, the co-agent is selected from at least one of a first primary antioxidant, a second primary antioxidant, a secondary antioxidant, a halogen absorbent, a lubricant, and a nucleating agent; preferably, the auxiliary agent comprises a first primary antioxidant, a second primary antioxidant, a secondary antioxidant, a halogen absorbent, a lubricant, and a nucleating agent.
In some preferred embodiments of the present invention, the amount of the organic acid is, in parts by mass,
87.5-95.5 parts of copolymerized polypropylene powder, 0.2-0.4 part of first main antioxidant, 0.05-0.15 part of second main antioxidant, 0.05-0.15 part of auxiliary antioxidant, 0.05-0.15 part of halogen absorbent, 0.05-0.15 part of lubricant and 0.05-0.25 part of nucleating agent.
In some preferred embodiments of the present invention, the first primary antioxidant is dioctadecyl thiodipropionate; and/or the second primary antioxidant is 3- (3, 5-bis-butyl-4-hydroxycyclohexyl) propionate; and/or the auxiliary antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite; and/or the halogen absorbent is calcium stearate; and/or the lubricant is glyceryl monostearate; and/or the nucleating agent is cadmium carboxylate.
In some preferred embodiments of the present invention, the extruder barrel temperature is 180 ℃ to 230 ℃ and the cooling water temperature is 55 ℃ to 65 ℃ during extrusion granulation.
The invention further provides application of the polypropylene material or the polypropylene material prepared by the preparation method in the field of injection molding of large-sized thin-walled products.
In some preferred embodiments of the present invention, the polypropylene material or the polypropylene material prepared by the preparation method is applied to the field of washing machine inner barrel products.
Compared with the prior art, the invention has the following beneficial effects:
the high-fluidity and high-impact polypropylene is obtained by mixing a high-efficiency antioxidant, a high-efficiency nucleating agent, a lubricant, an antioxidant and a halogen absorbent with polypropylene powder and extruding the mixture by an extruder. The material can be directly used for inner barrel products of the washing machine without modification, thereby reducing intermediate links and lowering production cost.
Detailed Description
The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In the following examples:
melt Flow Rate (MFR): measured according to GB3682 at 230 ℃ under a load of 2.16 kg.
Ethylene content: determined by means of known FTIR tests based on calibration with 13C-NMR.
Rubber content: determined according to GB/T24282-.
Tensile strength: measured according to GB/T1040.
Cantilever beam impact: measured according to GB/T1843-1996.
Flexural modulus: measured according to GB/T9341-2008.
Heat distortion temperature: measured according to GB/T1634.2-2004.
In the following examples 1 to 3 and comparative examples 1 to 5, unless otherwise specified:
the first main antioxidant is dioctadecyl thiodipropionate;
the second main antioxidant is 3- (3, 5-bi-tert-butyl-4-hydroxycyclohexyl) propionate;
the auxiliary antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite;
the halogen absorbent is calcium stearate;
the lubricant is glyceryl monostearate;
the nucleating agent is cadmium benzoate.
Example 1
In the embodiment, the raw materials are as follows in parts by weight:
99.37 parts of copolymerized polypropylene powder; 0.06 part of lubricant, 0.2 part of first main antioxidant, 0.1 part of second main antioxidant, 0.1 part of auxiliary antioxidant, 0.07 part of halogen absorbent and 0.1 part of nucleating agent.
The preparation method of the polypropylene material comprises the following steps:
step 1: high-purity propylene, ethylene and hydrogen are used as raw materials to produce polypropylene powder with the ethylene content of 12.2 percent, the rubber content of 14.3 percent and the melt flow rate of 24g/10 min.
Step 2: and mixing the polypropylene powder with a lubricant, a first main antioxidant, a second main antioxidant, an auxiliary antioxidant, a halogen absorbent and a nucleating agent to obtain a mixed material.
And step 3: and adding the prepared mixed material into an extruder to prepare the polypropylene material. The load of the extruder is 10 tons/hour, the temperature of each section of the barrel of the extruder is 200 ℃, and the temperature of cooling water is 60 ℃.
The prepared polypropylene material has the ethylene content of 12.1 percent, the rubber content of 14.3 percent and the melt flow rate of 24g/10 min. The indexes are shown in table 1.
Example 2
In the embodiment, the raw materials are as follows in parts by weight:
99.3 parts of copolymerized polypropylene powder; 0.07 part of lubricant, 0.25 part of first main antioxidant, 0.08 part of second main antioxidant, 0.08 part of auxiliary antioxidant, 0.07 part of halogen absorbent and 0.15 part of nucleating agent.
The preparation method of the polypropylene material comprises the following steps:
step 1: high-purity propylene, ethylene and hydrogen are used as raw materials to produce polypropylene powder with the ethylene content of 12.4 percent, the rubber content of 15.3 percent and the melt flow rate of 24.6g/10 min.
Step 2: and mixing the polypropylene powder with a lubricant, a first main antioxidant, a second main antioxidant, an auxiliary antioxidant, a halogen absorbent and a nucleating agent to obtain a mixed material.
And step 3: and adding the prepared mixed material into an extruder to prepare the polypropylene material. The load of the extruder is 10 tons/hour, the temperature of each section of the barrel of the extruder is 200 ℃, and the temperature of cooling water is 60 ℃.
The prepared polypropylene material has the ethylene content of 12.4 percent, the rubber content of 15.3 percent and the melt flow rate of 24.6g/10 min. The indexes are shown in table 1.
Example 3
In the embodiment, the raw materials are as follows in parts by weight:
99.44 parts of copolymerized polypropylene powder; 0.05 part of lubricant, 0.25 part of first main antioxidant, 0.1 part of second main antioxidant, 0.05 part of auxiliary antioxidant, 0.1 part of halogen absorbent and 0.23 part of nucleating agent.
The preparation method of the polypropylene material comprises the following steps:
step 1: high-purity propylene, ethylene and hydrogen are used as raw materials to produce polypropylene powder with 11.8% of ethylene content, 15.7% of rubber content and 25g/10min of melt flow rate.
Step 2: and mixing the polypropylene powder with a lubricant, a first main antioxidant, a second main antioxidant, an auxiliary antioxidant, a halogen absorbent and a nucleating agent to obtain a mixed material.
And step 3: and adding the prepared mixed material into an extruder to prepare the polypropylene material. The load of the extruder is 10 tons/hour, the temperature of each section of the barrel of the extruder is 200 ℃, and the temperature of cooling water is 60 ℃.
The prepared polypropylene material has the ethylene content of 11.8 percent, the rubber content of 15.7 percent and the melt flow rate of 25g/10 min. The indexes are shown in table 1.
Comparative example 1
A polypropylene material was prepared as in example 1, except that pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] was used as the primary antioxidant.
The prepared polypropylene material has the ethylene content of 12.1 percent, the rubber content of 14.3 percent and the melt flow rate of 26g/10 min. The indexes are shown in table 1.
Comparative example 2
A polypropylene material was prepared as in example 1, except that the first primary antioxidant was not used, and the amount of the second primary antioxidant was adjusted to 0.3 parts.
The prepared polypropylene material has the ethylene content of 12 percent, the rubber content of 14.3 percent and the melt flow rate of 24.5g/10 min. The indexes are shown in table 1.
Comparative example 3
A polypropylene material was prepared as in example 1, except that sodium benzoate was used as the nucleating agent.
The prepared polypropylene material has the ethylene content of 12 percent, the rubber content of 14.3 percent and the melt flow rate of 24.5g/10 min. The indexes are shown in table 1.
Comparative example 4
A polypropylene material was prepared as in example 1, except that a polypropylene powder having an ethylene content of 11.8%, a rubber content of 15.2% and a melt flow rate of 35g/10min was used.
The prepared polypropylene material has 11.8 percent of ethylene content, 15.2 percent of rubber content and 35g/10min of melt flow rate. The indexes are shown in table 1.
Comparative example 5
A polypropylene material was prepared as in example 1, except that a polypropylene powder having an ethylene content of 12.6%, a rubber content of 20% and a melt flow rate of 24.6g/10min was used.
The prepared polypropylene material has the ethylene content of 12.6 percent, the rubber content of 20 percent and the melt flow rate of 24.6g/10 min. The indexes are shown in table 1.
TABLE 1
The results in the table show that examples 1-3 directly obtained a high-fluidity and high-impact polypropylene by mixing a high-efficiency nucleating agent, a lubricant, an antioxidant and a halogen absorbent with polypropylene powder and extruding the mixture through an extruder. The material can be directly used for large thin-wall products such as automobiles, household products, packaging and the like without modification, thereby reducing intermediate links and lowering production cost.
As can be seen from the comparison of examples 1-3 with comparative examples 1-5, the properties of the material were reduced by changing the antioxidant and the nucleating agent. The material properties are degraded by increasing the melt flow rate of the material. The ethylene and rubber content of the material is increased, and although the impact of the material is increased, the bending performance is reduced greatly, so that the rigidity and toughness balance performance of the material is reduced.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (7)
1. The high-flow high-impact-resistance high-temperature-resistance polypropylene material is characterized in that the ethylene content of the polypropylene material is 8-14%, the rubber content is 14-17%, the melt flow rate is 20g/10 min-30 g/10min, the cantilever beam impact strength is greater than 70J/m, and the heat deformation temperature is greater than 100 ℃;
the preparation method of the polypropylene material comprises the following steps: the polypropylene material is prepared by mixing, extruding and granulating raw materials comprising copolymerized polypropylene powder and an auxiliary agent;
by mass fraction, 87.5-95.5 parts of copolymerized polypropylene powder and 0.45-1.25 parts of auxiliary agent;
the auxiliary agent comprises a first main antioxidant, a second main antioxidant, an auxiliary antioxidant, a halogen absorbent, a lubricant and a nucleating agent;
0.05-0.25 part of nucleating agent;
the nucleating agent is cadmium carboxylate.
2. The polypropylene material according to claim 1, wherein the copolymerized polypropylene powder has an ethylene content of 8-14%, a rubber content of 14-17%, and a melt flow rate of 20-30 g/10 min.
3. The polypropylene material according to claim 1, wherein the polypropylene material is characterized in that the polypropylene material comprises, in parts by mass,
87.5-95.5 parts of copolymerized polypropylene powder, 0.2-0.4 part of first main antioxidant, 0.05-0.15 part of second main antioxidant, 0.05-0.15 part of auxiliary antioxidant, 0.05-0.15 part of halogen absorbent, 0.05-0.15 part of lubricant and 0.05-0.25 part of nucleating agent.
4. The polypropylene material of claim 1, wherein the first primary antioxidant is dioctadecyl thiodipropionate; and/or the second primary antioxidant is 3- (3, 5-bis-butyl-4-hydroxycyclohexyl) propionate; and/or the auxiliary antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite; and/or the halogen absorbent is calcium stearate; and/or the lubricant is glyceryl monostearate.
5. The polypropylene material according to any one of claims 1 to 4, wherein the extruder barrel temperature is 180 ℃ to 230 ℃ and the cooling water temperature is 55 ℃ to 65 ℃ during extrusion granulation.
6. Use of a polypropylene material according to any one of claims 1 to 5 in the field of injection moulding of large thin-walled articles.
7. Use according to claim 6, wherein the polypropylene material according to any one of claims 1 to 5 is used in the field of inner drum products for washing machines.
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2019
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