CN114426733A - Low-shrinkage impact-resistant co-polypropylene material and preparation method thereof - Google Patents
Low-shrinkage impact-resistant co-polypropylene material and preparation method thereof Download PDFInfo
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 68
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 68
- 239000000463 material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 10
- -1 polypropylene Polymers 0.000 claims abstract description 58
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005977 Ethylene Substances 0.000 claims abstract description 11
- 239000000155 melt Substances 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 30
- 230000003078 antioxidant effect Effects 0.000 claims description 29
- 239000002667 nucleating agent Substances 0.000 claims description 22
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 22
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 21
- 239000002954 polymerization reaction product Substances 0.000 claims description 19
- 229910052736 halogen Inorganic materials 0.000 claims description 18
- 150000002367 halogens Chemical class 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 230000002745 absorbent Effects 0.000 claims description 16
- 239000002250 absorbent Substances 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 7
- 238000010574 gas phase reaction Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 4
- 235000013539 calcium stearate Nutrition 0.000 claims description 4
- 239000008116 calcium stearate Substances 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical group CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- BGHBLQKNCVRIKV-UHFFFAOYSA-N OP(O)OP(O)O.OCC(CO)(CO)CO.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O BGHBLQKNCVRIKV-UHFFFAOYSA-N 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims 1
- 239000002530 phenolic antioxidant Substances 0.000 claims 1
- 238000001746 injection moulding Methods 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 238000005452 bending Methods 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 13
- 239000012071 phase Substances 0.000 description 7
- 239000000498 cooling water Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000003484 crystal nucleating agent Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000012261 overproduction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides a low-shrinkage impact-resistant co-polypropylene material and a preparation method thereof, and particularly relates to a low-shrinkage impact-resistant polypropylene material. The low-shrinkage impact-resistant polypropylene material has a melt flow rate of 20-40 g/10min, an ethylene content of 5-11%, a rubber content of 14-19%, and a simple beam notch impact strength of more than 7KJ/m2Flexural modulus of greater than 900MPa and transverse shrinkage<1.0% and longitudinal shrinkage<1.0 percent. The material has a low shrinkage rate and is suitable for the production of the plastic material,meanwhile, the modified polypropylene composite material has good flow property, impact resistance and bending property, and good comprehensive performance, and can be directly used for large injection molding products such as automobiles, household products, toys, packages and the like without modification. Also discloses a preparation method of the polypropylene material.
Description
Technical Field
The invention relates to a polypropylene material, in particular to a low-shrinkage impact-resistant polypropylene material and a preparation method thereof.
Background
With the increasingly fierce market competition of synthetic resins, the phenomenon of the over-production capability of global polypropylene is gradually revealed, the harsh market competition is inevitable, and the structure of global polypropylene products is forced to develop towards diversification and functionalization. Polypropylene, as a highly crystalline polymer material, tends to exhibit some shrinkage behavior during injection molding, storage and use of the article, resulting in warpage of the article. Therefore, reducing the shrinkage of polypropylene is an important direction to improve the performance of polypropylene, and is also a development need for the aesthetic design of plastic parts. The material has low shrinkage rate, good flow property, impact resistance and bending property, and good comprehensive performance, and can be widely applied to large injection molding products such as automobiles, household products, packages and the like.
Disclosure of Invention
The invention aims to provide a low-shrinkage impact-resistant co-polypropylene material which has good mechanical properties and low shrinkage.
In order to achieve the above object, the first aspect of the present invention provides a low shrinkage impact resistant co-polypropylene material, which has a melt flow rate of 20-40 g/10min, an ethylene content of 5-11%, a rubber content of 14-19%, a transverse shrinkage rate of less than 1.0%, and a longitudinal shrinkage rate of less than 1.0%.
In a preferred embodiment of the invention, the polypropylene material is prepared by taking polypropylene powder, a primary antioxidant, a secondary antioxidant, a halogen absorbent and a nucleating agent as main raw materials. The material has low shrinkage rate, good flow property and impact resistance, is suitable for injection molding of large-scale thin-wall products, and is easy to assemble and not easy to deform. The material can be directly used for large injection molding products such as automobiles, household products, packaging and the like without modification, thereby reducing intermediate links and lowering production cost.
In a further preferred embodiment of the present invention, the polypropylene material is prepared from the following raw materials:
90.5-99.8 parts by weight of polypropylene powder;
0.05-0.15 part by weight of a main antioxidant;
0.05-0.15 part by weight of auxiliary antioxidant;
0.05-0.15 parts by weight of a halogen absorbent; and
0.05 to 0.25 part by weight of a nucleating agent.
In a further preferred embodiment of the present invention, wherein the primary antioxidant is selected from one or more of the antioxidants of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] or 3- (3, 5-bis-tert-butyl-4-hydroxycyclohexyl) propionate.
In a further preferred embodiment of the present invention, wherein the secondary antioxidant is selected from one or more of bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite or tris (2, 4-di-tert-butylphenyl) phosphite.
In a further preferred embodiment of the present invention, wherein the halogen absorbent is selected from one or more of calcium stearate or zinc stearate or hydrotalcite.
In a further preferred embodiment of the present invention, the nucleating agent is an α -crystal nucleating agent, and preferably comprises one or more selected from inorganic α -crystal nucleating agents, sorbitol nucleating agents and organic phosphate nucleating agents. Organic phosphate nucleating agents are preferred.
The second aspect of the invention provides a preparation method of the low-shrinkage impact-resistant co-polypropylene material, which comprises the following steps: and uniformly mixing the polypropylene powder with the antioxidant, the auxiliary antioxidant, the halogen absorbent and the nucleating agent, and adding the mixture into an extruder for extrusion and granulation to obtain the polypropylene material.
In some preferred embodiments of the present invention, the polypropylene powder is prepared by a Spheripol process device, and the preparation steps are as follows:
(1) synthesizing propylene into polypropylene by propylene through a prepolymerization reactor under the combined action of a main catalyst, a cocatalyst and an external electron donor;
(2) feeding the polypropylene obtained in the step (1), fresh propylene and hydrogen into a first loop reactor to obtain a first polymerization reaction product;
(3) feeding the first polymerization reaction product obtained in the step (2), fresh propylene and hydrogen into a second loop reactor to obtain a second polymerization reaction product;
(4) and (4) after flash evaporation and liquid phase propylene removal are carried out on the second polymerization reaction product obtained in the step (3), feeding the second polymerization reaction product into a gas phase reaction kettle for reaction, and obtaining polypropylene powder with 5-11% of ethylene content, 14-19% of rubber content and 20-40 g/10min of melt flow rate.
In a preferred embodiment of the invention, the catalyst is a fourth generation Z-N catalyst, such as Basel's ZN118, the cocatalyst is triethylaluminium and the external electron donor is DIPDMS.
In a further preferred embodiment of the present invention, the hydrogen concentration in the first loop reactor in the step (1) is 2500. + -. 200ppm, and the loop density is 530 to 560kg/m3(ii) a The hydrogen concentration of the second loop reactor in the step (2) is 2500 +/-200 ppm, and the loop density is 550-580 kg/m3。
In other preferred embodiments of the present invention, the first polymerization reaction and the second polymerization reaction of steps (1) and (2) have the same reaction temperature and pressure, specifically, the reaction temperature is 69 ± 1 ℃ and the reaction pressure is 3.3 ± 0.1 MPa.
In other preferred embodiments of the present invention, in the step (3), the temperature of the gas phase reaction kettle is controlled to be 70 ± 5 ℃, the material level is controlled to be 70-80%, and the gas phase ratio is controlled to be 0.43-0.45.
In other preferred embodiments of the present invention, the halogen absorbent is calcium stearate; the main antioxidant is 3- (3, 5-bi-tert-butyl-4-hydroxycyclohexyl) propionate; the auxiliary antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite.
In other preferred embodiments of the present invention, the load of the extruder is 8 to 12 tons/hour, the barrel temperature is 180 to 230 ℃, and the cooling water temperature is 55 to 65 ℃.
The invention has the following advantages:
the low-shrinkage impact-resistant co-polypropylene is obtained by mixing the nucleating agent, the antioxidant and the halogen absorbent with polypropylene powder and extruding the mixture by an extruder. The material has low shrinkage rate, good flow property and impact resistance, and can be directly used for large injection molding products such as automobiles, household products, toys, packages and the like without modification, thereby reducing intermediate links and lowering production cost.
Detailed Description
In order to make the technical solutions and advantages of the present invention clearer, the following embodiments are used to clearly and completely describe the solutions of the present invention.
The extrusion granulation system used in the examples is a model CMP215 twin-screw extrusion granulator manufactured by JSW of Japan, and the design capacity is 6 to 14 tons/hour.
In the following examples, the antioxidant was 3- (3, 5-bis-butyl-4-hydroxycyclohexyl) propionate (1010).
The auxiliary antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite (168).
The halogen absorbent is calcium stearate.
The nucleating agent is phosphate nucleating agent.
The main catalyst is Bazier ZN118, the cocatalyst is triethyl aluminum, and the external electron donor is DIPDMS.
Example 1
99.55 parts of polypropylene material, 10100.1 parts of antioxidant, 1680.1 parts of auxiliary antioxidant, 0.05 part of halogen absorbent and 0.2 part of nucleating agent.
The preparation method comprises the following steps:
step 1: and (3) preparing polypropylene powder.
(1) Propylene is polymerized to generate polypropylene by a prepolymerization reactor under the combined action of a main catalyst, a cocatalyst and an external electron donor.
(2) The prepolymerization reaction product obtained in the step (1), fresh propylene and hydrogen enter a first loop reactor to continue polymerization reaction, the concentration of the hydrogen in the first loop is controlled to be 2500 +/-200 ppm, the reaction temperature is controlled to be 69 +/-1 ℃, and the reaction is carried outThe stress is 3.3 +/-0.1 MPa, and the density of a ring pipe is 540kg/m3。
(3) Feeding the polymerization reaction product obtained in the step (2), fresh propylene and hydrogen into a second loop reactor for continuous polymerization, controlling the hydrogen concentration of the second loop to be 1500 +/-200 ppm, the reaction temperature to be 69 +/-1 ℃, the reaction pressure to be 3.3 +/-0.1 MPa and the loop density to be 570kg/m3。
(4) And (4) carrying out flash evaporation to remove liquid-phase propylene from the polymerization reaction product obtained in the step (3), then feeding the polymerization reaction product into a gas-phase reaction kettle, controlling the temperature of the gas-phase kettle to be 70 +/-5 ℃, the material level to be 75%, the gas phase ratio to be 0.44, and finally the ethylene content to be 7%, thus obtaining the polypropylene powder with the melt flow rate of 24g/10 min.
Step 2: mixing polypropylene powder, an antioxidant 1010, an auxiliary antioxidant 168, a halogen absorbent and a nucleating agent, and then adding the mixture into an extruder, wherein the load is 10 tons/hour, the temperature of each section of a barrel of the extruder is 195 ℃, and the temperature of cooling water is 58 ℃. The prepared low-shrinkage impact-resistant co-polypropylene material has the ethylene content of 6.5 percent, the melt flow rate of 24.5g/10min, the transverse shrinkage rate of 0.95 percent and the longitudinal shrinkage rate of 0.93 percent.
The mechanical properties of the obtained product are shown in the invention effect attached table 1.
Example 2
99.64 parts of polypropylene material, 10100.07 parts of antioxidant, 1680.1 parts of auxiliary antioxidant, 0.04 part of halogen absorbent and 0.15 part of nucleating agent.
The preparation method comprises the following steps:
step 1: and (3) preparing polypropylene powder.
(1) Propylene is polymerized to generate polypropylene by a prepolymerization reactor under the combined action of a main catalyst, a cocatalyst and an external electron donor.
(2) Enabling the prepolymerization reaction product obtained in the step (1), fresh propylene and hydrogen to enter a first loop reactor for continuous polymerization reaction, controlling the hydrogen concentration of a first loop to be 2500 +/-200 ppm, the reaction temperature to be 69 +/-1 ℃, the reaction pressure to be 3.3 +/-0.1 MPa, and the loop density to be 538kg/m3。
(3) The polymerization reaction product obtained in the step (2) and fresh propylene and hydrogen enter a second loop reactor and thenThe polymerization is continued, the hydrogen concentration of the second loop is controlled to be 1500 plus or minus 200ppm, the reaction temperature is 69 plus or minus 1 ℃, the reaction pressure is 3.3 plus or minus 0.1MPa, and the loop density is 580kg/m3。
(4) And (4) carrying out flash evaporation to remove liquid-phase propylene from the polymerization reaction product obtained in the step (3), then feeding the polymerization reaction product into a gas-phase reaction kettle, controlling the temperature of the gas-phase kettle to be 70 +/-5 ℃, the material level to be 75 percent, the gas phase ratio to be 0.45, and finally the ethylene content to be 8.0 percent, thus obtaining the polypropylene powder with the melt flow rate of 30.7g/10 min.
Step 2: mixing polypropylene powder, an antioxidant 1010, an auxiliary antioxidant 168, a halogen absorbent and a nucleating agent, and then adding the mixture into an extruder, wherein the load is 9 tons/hour, the temperature of each section of a barrel of the extruder is 195 ℃, and the temperature of cooling water is 63 ℃. The prepared low-shrinkage impact-resistant co-polypropylene material has the ethylene content of 8.2 percent, the melt flow rate of 29.6g/10min, the transverse shrinkage of 0.83 percent and the longitudinal shrinkage of 0.85 percent.
The mechanical properties of the obtained product are shown in the invention effect attached table 1.
Example 3
99.49 parts of polypropylene material, 10100.1 parts of antioxidant, 1680.15 parts of auxiliary antioxidant, 0.08 part of halogen absorbent and 0.18 part of nucleating agent.
The preparation method comprises the following steps:
step 1: and (3) preparing polypropylene powder.
(1) Propylene is polymerized to generate polypropylene by a prepolymerization reactor under the combined action of a main catalyst, a cocatalyst and an external electron donor.
(2) The prepolymerization reaction product obtained in the step (1), fresh propylene and hydrogen enter a first loop reactor to continue polymerization reaction, the concentration of the hydrogen in the first loop is controlled to be 2500 +/-200 ppm, the reaction temperature is controlled to be 69 +/-1 ℃, the reaction pressure is controlled to be 3.3 +/-0.1 MPa, and the loop density is 535kg/m3。
(3) Feeding the polymerization reaction product obtained in the step (2), fresh propylene and hydrogen into a second loop reactor for continuous polymerization, controlling the hydrogen concentration of the second loop to be 1500 +/-200 ppm, the reaction temperature to be 69 +/-1 ℃, the reaction pressure to be 3.3 +/-0.1 MPa and the loop density to be 585kg/m3。
(4) And (4) carrying out flash evaporation to remove liquid-phase propylene from the polymerization reaction product obtained in the step (3), then feeding the polymerization reaction product into a gas-phase reaction kettle, controlling the temperature of the gas-phase kettle to be 70 +/-5 ℃, the material level to be 75%, the gas phase ratio to be 0.45, and finally the ethylene content to be 7.8%, thus obtaining the polypropylene powder with the melt flow rate of 28.5g/10 min.
Step 2: mixing polypropylene powder, an antioxidant 1010, an auxiliary antioxidant 168, a halogen absorbent and a nucleating agent, and then adding the mixture into an extruder, wherein the load is 11 tons/hour, the temperature of each section of a barrel of the extruder is 201 ℃, and the temperature of cooling water is 58 ℃. The prepared low-shrinkage impact-resistant co-polypropylene material has the ethylene content of 7.4%, the melt flow rate of 27.2g/10min, the transverse shrinkage of 0.92% and the longitudinal shrinkage of 0.92%.
The mechanical properties of the obtained product are shown in the invention effect attached table 1.
The results in the above table show that examples 1, 2 and 3 directly obtained high flow, high impact polypropylene by mixing polypropylene powder with nucleating agent, antioxidant, secondary antioxidant, halogen absorber and extruding through an extruder. The material can be directly used for large injection molding products such as automobiles, household products, toys, packages and the like without modification, thereby reducing intermediate links and lowering production cost.
While the invention has been described with reference to a preferred embodiment, various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In particular, the technical features mentioned in the embodiments can be combined in any way as long as there is no structural conflict. It is intended that the invention not be limited to the particular embodiments disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (11)
1. A low-shrinkage impact-resistant co-polypropylene material is characterized in that: the melt flow rate of the polypropylene material is 20-40 g/10min, and the ethylene content is 5-11%The rubber content is 14-19%, and the impact strength of the simple beam notch is more than 7KJ/m2Flexural modulus of greater than 900MPa and transverse shrinkage<1.0% and longitudinal shrinkage<1.0％。
2. The polypropylene material according to claim 1, wherein the polypropylene material is prepared from polypropylene powder, a primary antioxidant, a secondary antioxidant, a halogen absorbent and a nucleating agent as main raw materials.
3. The polypropylene material according to claim 1 or 2, wherein the polypropylene material is prepared from the following raw materials:
90.5-99.8 parts by weight of polypropylene powder;
0.05-0.15 part by weight of a main antioxidant;
0.05-0.15 part by weight of auxiliary antioxidant;
0.05-0.15 parts by weight of a halogen absorbent; and
0.05 to 0.25 part by weight of a nucleating agent.
4. The polypropylene material according to any one of claims 1 to 3, wherein the primary antioxidant is selected from phenolic antioxidants, preferably comprising one or more of pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] or n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
5. The polypropylene material according to any one of claims 1 to 3, wherein the secondary antioxidant is selected from one or more of bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite or tris [2, 4-di-tert-butylphenyl ] phosphite.
6. The polypropylene material according to any one of claims 1 to 3, wherein the halogen absorber is selected from one or more of calcium stearate or zinc stearate or hydrotalcite.
7. The polypropylene material according to any one of claims 1 to 3, wherein the nucleating agent is an organophosphate type nucleating agent.
8. A method of making a low shrink impact co-polypropylene material according to any one of claims 1-4, comprising: and uniformly mixing the polypropylene powder with the antioxidant, the auxiliary antioxidant, the halogen absorbent and the nucleating agent, and adding the mixture into an extruder for extrusion and granulation to obtain the polypropylene material.
9. The process of claim 8 wherein the polypropylene powder is produced by hydrogen blending in a Spheripol polymerization process by the steps of:
(1) synthesizing propylene into polypropylene by propylene through a prepolymerization reactor under the combined action of a main catalyst, a cocatalyst and an external electron donor;
(2) feeding the polypropylene obtained in the step (1), fresh propylene and hydrogen into a first loop reactor to obtain a first polymerization reaction product;
(3) feeding the first polymerization reaction product obtained in the step (2), fresh propylene and hydrogen into a second loop reactor to obtain a second polymerization reaction product;
(4) and (4) after flash evaporation and liquid phase propylene removal are carried out on the second polymerization reaction product obtained in the step (3), feeding the second polymerization reaction product into a gas phase reaction kettle for reaction, and obtaining polypropylene powder with 5-11% of ethylene content, 14-19% of rubber content and 20-40 g/10min of melt flow rate.
10. The process of claim 9, wherein the catalyst is a fourth generation Z-N catalyst, the cocatalyst is triethylaluminum, and the external electron donor is DIPDMS.
11. The method as claimed in claim 9, wherein the hydrogen concentration in the first loop reactor in the step (1) is 2500 ± 200ppm, and the loop density is 530-560 kg/m3；
The hydrogen concentration of the second loop in the step (2) is 2500 +/-200 ppm, and the loop density is 550 to E580kg/m3。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101309961A (en) * | 2005-11-16 | 2008-11-19 | 北方科技有限公司 | Polypropylene resin with low shrinkage, high impact strength, stiffness and scratch resistance |
| CN108948521A (en) * | 2018-06-15 | 2018-12-07 | 中国石油化工股份有限公司 | A kind of high fluidity punching proof acrylic material |
| CN108948522A (en) * | 2018-06-15 | 2018-12-07 | 中国石油化工股份有限公司 | A kind of preparation method of high fluidity punching proof acrylic material |
| US20190031869A1 (en) * | 2016-01-29 | 2019-01-31 | Borealis Ag | Heterophasic propylene copolymer with low shrinkage |
| CN110746703A (en) * | 2019-10-30 | 2020-02-04 | 中国石油化工股份有限公司 | High-rigidity high-toughness polypropylene composition and preparation method thereof |
-
2020
- 2020-10-29 CN CN202011185763.XA patent/CN114426733A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101309961A (en) * | 2005-11-16 | 2008-11-19 | 北方科技有限公司 | Polypropylene resin with low shrinkage, high impact strength, stiffness and scratch resistance |
| US20190031869A1 (en) * | 2016-01-29 | 2019-01-31 | Borealis Ag | Heterophasic propylene copolymer with low shrinkage |
| CN108948521A (en) * | 2018-06-15 | 2018-12-07 | 中国石油化工股份有限公司 | A kind of high fluidity punching proof acrylic material |
| CN108948522A (en) * | 2018-06-15 | 2018-12-07 | 中国石油化工股份有限公司 | A kind of preparation method of high fluidity punching proof acrylic material |
| CN110746703A (en) * | 2019-10-30 | 2020-02-04 | 中国石油化工股份有限公司 | High-rigidity high-toughness polypropylene composition and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 范维 等: "聚丙烯收缩率影响因素研究进展", 《塑料科技》 * |
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