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
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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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.
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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 |
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- 2022-10-21 CN CN202211300128.0A patent/CN115521544A/en active Pending
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 * |
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