CN115521544A - Low-VOC high-fluidity high-impact polypropylene material and preparation method thereof - Google Patents
Low-VOC high-fluidity high-impact polypropylene material and preparation method thereof Download PDFInfo
- Publication number
- CN115521544A CN115521544A CN202211300128.0A CN202211300128A CN115521544A CN 115521544 A CN115521544 A CN 115521544A CN 202211300128 A CN202211300128 A CN 202211300128A CN 115521544 A CN115521544 A CN 115521544A
- Authority
- CN
- China
- Prior art keywords
- polypropylene
- low
- impact
- polypropylene material
- gas phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 polypropylene Polymers 0.000 title abstract description 72
- 239000004743 Polypropylene Substances 0.000 title abstract description 71
- 229920001155 polypropylene Polymers 0.000 title abstract description 71
- 239000000463 material Substances 0.000 title abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 229920005989 resin Polymers 0.000 abstract description 23
- 239000011347 resin Substances 0.000 abstract description 23
- 239000001257 hydrogen Substances 0.000 abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 17
- 239000003963 antioxidant agent Substances 0.000 abstract description 14
- 239000007789 gas Substances 0.000 abstract description 14
- 230000003078 antioxidant effect Effects 0.000 abstract description 13
- 239000002667 nucleating agent Substances 0.000 abstract description 9
- 238000006116 polymerization reaction Methods 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 6
- 239000005977 Ethylene Substances 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000012855 volatile organic compound Substances 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 238000012685 gas phase polymerization Methods 0.000 description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical group [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 5
- 235000013539 calcium stearate Nutrition 0.000 description 5
- 239000008116 calcium stearate Substances 0.000 description 5
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical group CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 5
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical group C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical group CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- OYFUVZBROQZLCL-UHFFFAOYSA-K aluminum;4-tert-butylbenzoate;hydroxide Chemical compound [OH-].[Al+3].CC(C)(C)C1=CC=C(C([O-])=O)C=C1.CC(C)(C)C1=CC=C(C([O-])=O)C=C1 OYFUVZBROQZLCL-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 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 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 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
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- 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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to the technical field of polypropylene materials, and discloses a low-VOC high-fluidity high-impact polypropylene material and a preparation method thereof. The invention provides a preparation method of a low-VOC high-flow high-impact polypropylene material, which comprises the following steps: in a gas-phase polypropylene polymerization device, hydrogen, ethylene and propylene are taken as raw materials and added into a reactor; adding a main catalyst, a cocatalyst and an external electron donor into a first gas phase reactor, and adding the external electron donor into a second gas phase reactor; adding nucleating agent, antioxidant and acid acceptor, mixing, extruding, granulating, and devolatilizing. The preparation method of the low-VOC high-fluidity high-impact polypropylene material has the advantages of simple production scheme operation, high production rate and convenient industrial application and popularization, and the produced low-VOC high-fluidity high-impact polypropylene resin has lower content of organic volatile matters, higher fluidity and very good impact property.
Description
Technical Field
The invention relates to the technical field of polypropylene materials, in particular to a low-VOC high-fluidity high-impact polypropylene material and a preparation method thereof.
Background
Polypropylene resin has become one of the largest synthetic resins in global use because of its advantages of small relative density, easy processing, excellent mechanical and chemical properties, low price, etc. The polypropylene resin is widely applied to the production of fiber products such as clothes, blankets and the like, medical appliances, automobiles, bicycles, parts, conveying pipelines, chemical containers and the like, and is also used for packaging foods and medicines.
The polypropylene can be classified into homo-polypropylene, random copolymer polypropylene and impact block copolymer polypropylene according to the polymerization method. Among them, the impact-resistant block copolymer polypropylene has a wide application in automobiles, household electrical appliances, daily necessities, etc. due to its excellent impact resistance. In recent years, various industries have increasingly high requirements on environmental protection, and particularly in the automobile industry, the content of Volatile Organic Compounds (VOC) has become the most interesting index.
At present, there are two main methods for producing high-flow high-impact block copolymerized polypropylene in domestic industry.
The first method is to increase the amount of polymerization inhibitor, such as hydrogen concentration; the polypropylene resin obtained by the method has wider molecular weight distribution and high isotacticity, but has higher requirements on a polymerization process, and meanwhile, the high hydrogen concentration can generate a large amount of small molecular weight polypropylene, which can cause adverse effects on the impact resistance of the resin and increase the VOC content of the resin.
The second method adopts degradation method, such as degradation by adding peroxide; the polypropylene obtained by the method has narrow molecular weight distribution, but the melt index is not easy to control, the VOC content is higher, the residual smell is caused when the peroxide is not completely reacted, the polypropylene is not suitable for automobile interior decoration, and simultaneously, compared with polypropylene resin produced by a non-degradation method, the polypropylene needs to be added with additional peroxide and more antioxidants, so the defects are more, and the cost is higher.
Therefore, in order to meet the increasingly strict environmental requirements and develop more abundant market fields, the development of low-VOC, high-flow, high-impact polypropylene materials is the key to solve the above problems.
Disclosure of Invention
The invention aims to solve the technical problem of providing a low-VOC high-fluidity high-impact polypropylene material and a preparation method thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
in a first aspect, the invention provides a low-VOC high-flow high-impact polypropylene material, wherein the melt flow rate of the polypropylene material is 17 +/-2 g/10min, and the impact strength of a simple beam notch is more than or equal to 50kJ/m 2 The flexural modulus is more than or equal to 950MPa, and the content of organic volatile matters is less than or equal to 80 mu g (C)/g.
In a second aspect, the present invention provides a method for preparing the low-VOC high-fluidity high-impact polypropylene material, comprising the following steps:
(1) In a gas-phase polypropylene polymerization device, hydrogen, ethylene and propylene are taken as raw materials and added into a reactor; adding a main catalyst, a cocatalyst and an external electron donor into a first gas phase reactor, and adding the external electron donor into a second gas phase reactor; controlling the reaction pressure, temperature and hydrogen concentration in the first gas phase reactor, and controlling the pressure, temperature and material level of the second gas phase reactor to obtain polypropylene powder;
(2) And adding a nucleating agent, an antioxidant and an acid absorbent into the obtained polypropylene powder, uniformly mixing, extruding, granulating and devolatilizing to obtain the low-VOC high-flow high-impact polypropylene material.
The preparation method provided by the invention combines the advantages of the performance of the external electron donor with high hydrogen regulation sensitivity, and can obtain the polypropylene resin with higher melt flow rate through less hydrogen addition, so that the production difficulty of the high-flow high-impact polypropylene is effectively reduced, the content of low-molecular compounds in the polypropylene resin is reduced, and the mechanical property is kept good.
Preferably, the main catalyst is BCM; the cocatalyst is triethyl aluminum; the external electron donor in the first reactor is cyclohexyl methyl dimethoxy silane; the external electron donor in the second reactor is dicyclopentyl dimethoxy silane.
The catalyst, the cocatalyst and the external electron donor are controlled as follows: the molar ratio of Al/Mg is 4-6, and the molar ratio of Al/Si is 2-8.
Preferably, the reaction pressure in the first gas phase reactor is 2.3 plus or minus 0.15MPa, the temperature is 66 plus or minus 3 ℃, and the hydrogen concentration is 2000ppm to 2700ppm.
Preferably, the reaction pressure in the second gas phase reactor is 2.2 +/-0.15 MPa, the temperature is 66 +/-3 ℃, and the material level is 70-80%.
Preferably, the nucleating agent is a metal carboxylate and/or a substituted aryl phosphate salt, preferably aluminum hydroxy di-p-tert-butyl benzoate; the addition amount of the nucleating agent is 0.08-0.20% of the mass of the polypropylene powder. The nucleating agent can accelerate crystallization speed and refine crystal grains when polypropylene resin is processed, so that the rigidity and the impact resistance of a product are improved.
Preferably, the antioxidant is a hindered phenol antioxidant and/or a phosphite ester antioxidant; the mass ratio of the hindered phenol antioxidant to the phosphite antioxidant may be 1:2. the addition amount of the antioxidant is 0.10-0.20% of the mass of the polypropylene powder. The antioxidant can improve the heat aging resistance of the polypropylene resin during processing and use.
Preferably, the acid absorbent is calcium stearate and/or hydrotalcite; the addition amount of the acid absorbent is 0.03-0.08 percent of the mass of the polypropylene powder.
Preferably, the devolatilization treatment is performed by purging the polypropylene particles obtained by the granulation with nitrogen at 130 to 140 ℃ for 2.5 to 3.5 hours.
The polypropylene material prepared under the preferable conditions has the advantages of improved flowability, mechanical property similar to or better than that of other materials of the same type, and low content of Volatile Organic Compounds (VOC).
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the low-VOC high-flow high-impact polypropylene material has the advantages of simple production scheme operation, high production rate and convenient industrial application and popularization.
The low-VOC high-flow high-impact polypropylene resin produced by the preparation method has lower content of volatile organic compounds, higher fluidity and very good impact property.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
In the description of the present invention, it is to be understood that all equipment or devices referred to are conventional, unless otherwise indicated; the raw materials or compounds are all conventional commercial raw materials or compounds unless otherwise specified; the methods involved are conventional methods unless otherwise specified.
Example 1: preparation method of low-VOC high-fluidity high-impact polypropylene material
The method comprises the following specific steps:
(1) In a gas-phase polypropylene polymerization device, hydrogen, ethylene and propylene are used as raw materials and are added into a reactor. A main catalyst BCM, a cocatalyst triethylaluminum and an external electron donor cyclohexyl methyl dimethoxy silane are added into a first gas phase polymerization reactor, and dicyclopentyl dimethoxy silane is added into a second gas phase polymerization reactor. Controlling the reaction pressure in the loop reactor to be 2.2MPa, the reaction temperature to be 67 ℃, the hydrogen concentration to be 2500ppm, the molar ratio of Al/Mg to be 6, and the molar ratio of Al/Si to be 4; the pressure of the second gas phase reactor was controlled at 2.15MPa, the reaction temperature at 66 ℃ and the material level at 75%. Obtaining the polypropylene powder.
(2) Adding 1200ppm of a nucleating agent NAA-325p, 1200ppm of an antioxidant B225 and 300ppm of calcium stearate into the material obtained in the step (1), uniformly mixing, extruding and granulating, and devolatilizing the particles by blowing nitrogen at 135 ℃ for 3 hours to obtain the low-VOC high-flow high-impact polypropylene resin, wherein the properties of the polypropylene resin are shown in Table 1.
Example 2: preparation method of low-VOC high-fluidity high-impact polypropylene material
The method comprises the following specific steps:
(1) In a gas-phase polypropylene polymerization apparatus, hydrogen, ethylene and propylene are used as raw materials and are added into a reactor. A main catalyst BCM, a cocatalyst triethylaluminum and an external electron donor cyclohexyl methyl dimethoxy silane are added into a first gas phase polymerization reactor, and dicyclopentyl dimethoxy silane is added into a second gas phase polymerization reactor. Controlling the reaction pressure in the loop reactor to be 2.2MPa, the reaction temperature to be 65 ℃, the hydrogen concentration to be 2700ppm, the molar ratio of Al/Mg to be 6 and the molar ratio of Al/Si to be 3; the pressure of the second gas phase reactor is controlled to be 2.1MPa, the reaction temperature is 65 ℃, and the material level is 76%. Obtaining the polypropylene powder.
(2) Adding 1200ppm of nucleating agent NAA-325p, 1200ppm of antioxidant B225 and 300ppm of calcium stearate into the material obtained in the step (1), uniformly mixing, extruding and granulating, and devolatilizing the particles by nitrogen purging at 135 ℃ for 3 hours to obtain the low-VOC high-flow high-impact polypropylene resin, wherein the properties of the polypropylene resin are shown in Table 1.
Example 3: preparation method of low-VOC high-fluidity high-impact polypropylene material
The method comprises the following specific steps:
(1) In a gas-phase polypropylene polymerization device, hydrogen, ethylene and propylene are used as raw materials and are added into a reactor. Adding a main catalyst BCM, a cocatalyst triethylaluminum and an external electron donor cyclohexyl methyl dimethoxy silane into a first gas phase polymerization reactor, and adding dicyclopentyl dimethoxy silane into a second gas phase reactor. Controlling the reaction pressure in the loop reactor to be 2.2MPa, the reaction temperature to be 66 ℃, the hydrogen concentration to be 2800ppm, the molar ratio of Al/Mg to be 5, and the molar ratio of Al/Si to be 3.5; the pressure of the second gas phase reactor was controlled at 2.2MPa, the reaction temperature at 67 ℃ and the material level at 74%. Obtaining the polypropylene powder.
(2) Adding 1200ppm of nucleating agent NAA-325p, 1200ppm of antioxidant B225 and 300ppm of calcium stearate into the material obtained in the step (1), uniformly mixing, extruding and granulating, and devolatilizing the particles by nitrogen purging at 135 ℃ for 3 hours to obtain the low-VOC high-flow high-impact polypropylene resin, wherein the properties of the polypropylene resin are shown in Table 1.
Comparative example: preparation method of low-VOC high-fluidity high-impact polypropylene material
The method comprises the following specific steps:
(1) In a gas-phase polypropylene polymerization device, hydrogen, ethylene and propylene are used as raw materials and are added into a reactor. Adding a main catalyst BCM, a cocatalyst triethylaluminum and an external electron donor cyclohexyl methyl dimethoxy silane into a first gas phase polymerization reactor, and adding dicyclopentyl dimethoxy silane into a second gas phase reactor. Controlling the reaction pressure in the loop reactor to be 2.2MPa, the reaction temperature to be 65 ℃, the hydrogen concentration to be 2000ppm, the molar ratio of Al/Mg to be 5, and the molar ratio of Al/Si to be 4; the pressure of the second gas phase reactor is controlled to be 2.1MPa, the reaction temperature is 65 ℃, and the material level is 76%. Obtaining the polypropylene powder.
(2) Adding 800ppm of degradation agent Akoma LOW TBOH,1200ppm of nucleating agent and NAA-325p, 1200ppm of antioxidant B225 and 300ppm of calcium stearate into the material obtained in the step (1), uniformly mixing, extruding and granulating, and devolatilizing the particles by nitrogen purging at 135 ℃ for 3 hours to obtain the LOW-VOC high-flow high-impact polypropylene resin, wherein the properties of the polypropylene resin are shown in Table 1.
Test example:
the polypropylene resin samples of examples 1, 2 and comparative examples were tested for relevant properties against a commercially available impact polypropylene 1215C material.
The melt flow rate is measured by adopting the GB/T3682-2000 Standard of determination of melt mass flow rate and melt volume flow rate of thermoplastic plastics; the flexural modulus is measured by adopting the GB/T9341-2008 'determination of plastic flexural property'; the impact strength of the gap of the simply supported beam is measured by adopting the GB/T1043.1-2008 ' measurement of plastic and simply supported beam impact property ' part 1: non-instrumented impact test ' standard; volatile Organic Compounds (VOC) content was determined using VDA277 standards.
The detection results are as follows:
TABLE 1 test results of Performance parameters
The results in Table 1 show that the low VOC high flow high impact polypropylene resins prepared in examples 1 and 2 have melt flow rates of 17 + -2 g/10min and impact strength of the simply supported beam notch of 50kJ/m or more 2 The flexural modulus is more than or equal to 950MPa, and the content of organic volatile matters is less than or equal to 80 mu g (C)/g.
Therefore, the obtained polypropylene material has the advantages of improved fluidity, similar or better mechanical property with other materials of the same type, and low content of Volatile Organic Compounds (VOC).
In conclusion, the preparation method provided by the embodiment of the invention combines the advantages of the performance of the high-hydrogen-modulation sensitive external electron donor, the polypropylene resin with higher melt flow rate can be obtained through less hydrogen addition, the production difficulty of the high-flow high-impact polypropylene is effectively reduced, and the prepared low-VOC high-flow high-impact polypropylene material has lower content of organic volatile matters, higher fluidity and very good impact property.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and substitutions can be made without departing from the technical principle of the present invention, and these modifications and substitutions should also be regarded as the protection scope of the present invention.
Claims (10)
1. The low-VOC high-flow high-impact polypropylene material is characterized in that the melt flow rate of the polypropylene material is 17 +/-2 g/10min, and the impact strength of a simply supported beam notch is more than or equal to 50kJ/m 2 The flexural modulus is more than or equal to 950MPa, and the content of organic volatile matters is less than or equal to 80 mu g (C)/g.
2. A method for preparing the low VOC high flow high impact polypropylene material according to claim 1, comprising the steps of:
(1) Hydrogen, ethylene and propylene are taken as raw materials in a gas-phase polypropylene polymerization device and are added into a reactor; adding a main catalyst, a cocatalyst and an external electron donor into a first gas phase reactor, and adding the external electron donor into a second gas phase reactor; controlling the reaction pressure, temperature and hydrogen concentration in the first gas phase reactor, and controlling the pressure, temperature and material level of the second gas phase reactor to obtain polypropylene powder;
(2) Adding nucleating agent, antioxidant and acid absorbent into the obtained polypropylene powder, uniformly mixing, extruding, granulating and devolatilizing to obtain the polypropylene powder.
3. The method for preparing a low VOC high flow high impact polypropylene material according to claim 2, wherein said main catalyst is BCM; the cocatalyst is triethyl aluminum.
4. The preparation method of the low-VOC high-flow high-impact polypropylene material as claimed in claim 2, wherein the external electron donor of the first reactor is cyclohexylmethyldimethoxysilane; the external electron donor of the second reactor is dicyclopentyl dimethoxy silane.
5. The method for preparing a low VOC high flow high impact polypropylene material according to claim 2, wherein the reaction pressure in the first gas phase reactor is 2.3 +/-0.15 MPa, the temperature is 66 +/-3 ℃, and the hydrogen concentration is 2000ppm to 2700ppm.
6. The method for preparing a low VOC high flow high impact polypropylene material according to claim 2, wherein the reaction pressure in the second gas phase reactor is 2.2 + 0.15MPa, the temperature is 66 + 3 ℃, and the material level is 70-80%.
7. The method for preparing a low VOC high flow high impact polypropylene material according to claim 2, wherein the nucleating agent is a carboxylic acid metal salt and/or a substituted aryl phosphate salt; the addition amount of the nucleating agent is 0.08-0.20% of the mass of the polypropylene powder.
8. The method for preparing a low VOC high-flow high-impact polypropylene material according to claim 2, wherein the antioxidant is a hindered phenol antioxidant and/or a phosphite antioxidant; the addition amount of the antioxidant is 0.10-0.20% of the mass of the polypropylene powder.
9. The method for preparing a low VOC high flow high impact polypropylene material according to claim 2, wherein the acid scavenger is calcium stearate and/or hydrotalcite; the addition amount of the acid absorbent is 0.03-0.08 percent of the mass of the polypropylene powder.
10. The method for preparing a low VOC high-flow high-impact polypropylene material according to claim 2, wherein the devolatilization treatment is to blow the pelletized polypropylene particles through nitrogen at 130-140 ℃ for 2.5-3.5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211300128.0A CN115521544B (en) | 2022-10-21 | 2022-10-21 | Low-VOC (volatile organic compound) high-fluidity high-impact polypropylene material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211300128.0A CN115521544B (en) | 2022-10-21 | 2022-10-21 | Low-VOC (volatile organic compound) high-fluidity high-impact polypropylene material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115521544A true CN115521544A (en) | 2022-12-27 |
| CN115521544B CN115521544B (en) | 2024-08-20 |
Family
ID=84703155
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211300128.0A Active CN115521544B (en) | 2022-10-21 | 2022-10-21 | Low-VOC (volatile organic compound) high-fluidity high-impact polypropylene material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115521544B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116715922A (en) * | 2023-07-31 | 2023-09-08 | 天津渤化化工发展有限公司 | High-rigidity high-impact polypropylene resin and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622809A (en) * | 2014-10-31 | 2016-06-01 | 中国石油化工股份有限公司 | Method for preparing impact-resistant polypropylene with low VOC (Volatile Organic Compounds) content |
| CN112745582A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Ultrahigh impact-resistant polypropylene material and preparation method thereof |
-
2022
- 2022-10-21 CN CN202211300128.0A patent/CN115521544B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622809A (en) * | 2014-10-31 | 2016-06-01 | 中国石油化工股份有限公司 | Method for preparing impact-resistant polypropylene with low VOC (Volatile Organic Compounds) content |
| CN112745582A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Ultrahigh impact-resistant polypropylene material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 徐秀东等: "外给电子体对BCM 系列催化剂的影响", 石油化工, vol. 49, no. 7, pages 639 - 643 * |
| 邹文桢: "采用BCM催化剂在Innovene装置上开发高橡胶含量抗冲共聚聚丙烯", 合成树脂及塑料, vol. 36, no. 6, pages 51 - 55 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116715922A (en) * | 2023-07-31 | 2023-09-08 | 天津渤化化工发展有限公司 | High-rigidity high-impact polypropylene resin and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115521544B (en) | 2024-08-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107573584B (en) | Polypropylene composition for transparent high-temperature cooking film and preparation method thereof | |
| EP2527376B1 (en) | Preparation method for propylene homopolymer having high melt strength | |
| EP2028122B1 (en) | Article comprising polypropylene composition | |
| US20160200839A1 (en) | Polypropylene composition comprising a propylene copolymer component | |
| EA022161B1 (en) | Soft heterophasic propylene copolymers | |
| CN101280117B (en) | Process for producing thermoplastic resin composition | |
| CN101495520B (en) | Method of deactivating polymerization catalyst using phosphoric-or phosphonic acid salts and catalyst deactivating agent | |
| CN107325394B (en) | Polypropylene composition and high-performance flame-retardant antistatic polypropylene pipe | |
| CN115521544B (en) | Low-VOC (volatile organic compound) high-fluidity high-impact polypropylene material and preparation method thereof | |
| CN106336475A (en) | Low-melting index and wide-molecular weight distribution polypropylene random copolymer resin specially used for blow molding, and production method of resin | |
| JP2009545655A (en) | High density polyethylene composition, method for producing the same, article produced therefrom, and method for producing such article | |
| CN105111346A (en) | Polypropylene random copolymer and method for preparing same | |
| CN110437358B (en) | Preparation method of high-toughness high-transparency thin-wall injection molding polypropylene | |
| CN114349889B (en) | Preparation process of polypropylene resin special for thin-wall injection molding, prepared resin and application | |
| CN108623917B (en) | Polypropylene composition, preparation method thereof and polymer film | |
| CN114044967A (en) | Gamma irradiation resistant transparent polypropylene composition and preparation method and application thereof | |
| KR20220048537A (en) | Polypropylene Resin Composition with Excellent Transparency and Article Molded Therefrom | |
| CN114524895B (en) | Ternary random copolymer polypropylene and preparation method thereof | |
| CN1931887A (en) | Modified polypropylene resin and its prepn process | |
| CN115536792A (en) | Low-VOC high-fluidity block copolymerization polypropylene material and preparation method thereof | |
| CN116063771B (en) | Resin composition for hollow blow molding, preparation method and application thereof | |
| CN114316110B (en) | Propylene-butene random copolymer production system and preparation method | |
| WO1993020115A1 (en) | Polypropylene resins and process for the production thereof | |
| CN118165157A (en) | Polypropylene polypropylene copolymer resin and preparation method thereof, polypropylene copolymer composition and preparation method and application thereof | |
| CN114426733A (en) | Low-shrinkage impact-resistant co-polypropylene material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |