CN117777339A - Preparation method of high-transparency polypropylene resin - Google Patents
Preparation method of high-transparency polypropylene resin Download PDFInfo
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- CN117777339A CN117777339A CN202311565073.0A CN202311565073A CN117777339A CN 117777339 A CN117777339 A CN 117777339A CN 202311565073 A CN202311565073 A CN 202311565073A CN 117777339 A CN117777339 A CN 117777339A
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- 229920001155 polypropylene Polymers 0.000 title claims abstract description 38
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 37
- -1 polypropylene Polymers 0.000 title claims abstract description 37
- 239000011347 resin Substances 0.000 title claims abstract description 30
- 229920005989 resin Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 238000001125 extrusion Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 13
- 230000000996 additive effect Effects 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005469 granulation Methods 0.000 claims abstract description 6
- 230000003179 granulation Effects 0.000 claims abstract description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 39
- 239000005977 Ethylene Substances 0.000 claims description 39
- 239000003054 catalyst Substances 0.000 claims description 16
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- NHYFIJRXGOQNFS-UHFFFAOYSA-N dimethoxy-bis(2-methylpropyl)silane Chemical compound CC(C)C[Si](OC)(CC(C)C)OC NHYFIJRXGOQNFS-UHFFFAOYSA-N 0.000 claims description 10
- 239000002667 nucleating agent Substances 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 7
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 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 3
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims 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 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 238000007872 degassing Methods 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 125000005498 phthalate group Chemical group 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 12
- 239000001257 hydrogen Substances 0.000 abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 12
- 238000013329 compounding Methods 0.000 abstract 1
- 229920003023 plastic Polymers 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a preparation method of high-transparency polypropylene resin, which is prepared by adding two different types of external electron donors into a reaction kettle in proportion, adjusting various corresponding control parameters of a polymerization process and an extrusion granulation process, and compounding additive components and adding proportions. The invention breaks through the technical bottleneck that the pressure of the reaction kettle cannot be controlled due to the higher temperature of the circulating water during the production by the traditional hydrogen regulation method, and meanwhile, the caking phenomenon does not occur during the high-load production operation process, thereby successfully realizing the goal of stably producing the products with long period and high load, and the production load can reach 42 tons/hour.
Description
Technical Field
The invention belongs to the technical field of chemical material preparation methods, and particularly relates to a preparation method of high-transparency polypropylene resin.
Background
The high transparency polypropylene resin is generally high melt random copolymer polypropylene, and the melt index thereof is about 40g/10 min. The product has the advantages of good transparency, high glossiness, low shrinkage rate of injection molding products and the like, and compared with general materials, the product has the advantages of good processing fluidity, low processing temperature, short molding period and no peculiar smell, and is mainly used for producing various high-transparency plastic vessels for food and household transparent plastic products, such as large storage boxes and the like.
The hydrogen regulation sensitivity of the catalyst used in the traditional production process of various polypropylene resins is weak, and the hydrogen content required in the production of the high-transparency polypropylene special material is often high. Meanwhile, for the high-transparency polypropylene product, a part of ethylene is added, so that the concentration of hydrogen in the polymerization reactor is further increased. Eventually, the pressure of the polymerization reaction kettle is out of control, and long-period stable production cannot be realized.
In the production process of polypropylene by the INNOVENE gas phase method, the higher hydrogen and ethylene contents can lead to the incapability of stably controlling the pressure of a polymerization reaction kettle, and further lead to the incapability of stably producing the polypropylene for a long period of time. In addition, in order to further improve the transparency of the polypropylene resin, a corresponding transparent nucleating agent is also required to be added.
Disclosure of Invention
The invention aims to provide a preparation method of high-transparency polypropylene resin, which solves the problem that the pressure of a polymerization reaction kettle cannot be controlled due to high contents of hydrogen and ethylene in the prior art.
The technical scheme adopted by the invention is as follows: the preparation method of the high transparent polypropylene resin adopts two different types of external electron donors to be added into a reaction kettle in proportion, and the preparation method is obtained by adjusting various corresponding control parameters of a polymerization process and an extrusion granulation process, and the composition and the addition proportion of the required compound additive.
The technical proposal of the invention is also characterized in that,
the two external electron donors were diisobutyldimethoxy silane and tetraethoxy silane, respectively, and the feeding ratios of diisobutyldimethoxy silane and tetraethoxy silane were 57wt% and 43wt%, respectively.
The method is implemented according to the following steps:
step 1, respectively adding two external electron donors, triethylaluminum, a main catalyst and a cocatalyst into a first reaction kettle, and then introducing ethylene and propylene into the first reaction kettle to obtain a primary product;
step 2, adding the initial product into a second reaction kettle, and introducing ethylene and propylene into the second reaction kettle to obtain a secondary product;
and step 3, degassing and deactivating the secondary product, fully mixing the secondary product with a compound additive containing a transparent nucleating agent, and then feeding the mixture into an extrusion granulator to produce the high-transparency polypropylene resin.
In the step 1, the adding amount of the main catalyst is gradually increased to 0.73kg/h, the adding amount of the cocatalyst is gradually increased to 2.8kg/h, the cocatalyst is triethylaluminum, and the main catalyst is a Ziegler-Natta catalyst system adopting the phthalate as an internal electron donor and magnesium chloride as a carrier.
In the step 1, the temperature in the first reaction kettle is 59-66 ℃, the pressure is 2.21Mpag, the material level is controlled to be 79%, the melt index of the powder is 40+/-6 g/10min, and the total ethylene content is 3.5wt%.
In the step 1, the initial addition amount of the external electron donor diisobutyldimethoxy silane is set to be 3.5kg/h, the target value is reduced to 1.7kg/h after the continuous addition for 40 minutes, and then the external electron donor tetraethoxy silane is added, and the addition amount is set to be 1.3kg/h.
In the step 1, ethylene is added into a first reaction kettle, the initial amount of the ethylene is controlled to be 100kg/h, the ethylene adding amount is controlled according to the speed of increasing 50kg every 10min, and when the molar concentration ratio of the ethylene and the propylene of the first reaction kettle is close to 1.5%, the ethylene adding amount is controlled according to 3.5% wt of the actual load of the first reaction kettle, and the molar concentration ratio of the ethylene and the propylene is maintained to be 1.7% of a final target value.
In the step 2, the temperature in the second reaction kettle is 66-68 ℃, the pressure is 2.21Mpag, the material level is controlled to 78%, the melt index of powder is 40+/-6 g/10min, the total ethylene content is 3.5wt%, and the molar concentration ratio of ethylene to propylene is maintained to be 1.2% in the second reaction kettle.
The specific components of the additive in the step 3 are as follows: the proportion of antioxidant 1010 is 11.63%, the proportion of antioxidant 168 is 23.26%, the proportion of calcium stearate is 11.63%, the proportion of GMS is 6.97%, the proportion of transparent nucleating agent is 46.51%, and the addition amount of the additive is 4300ppm.
In the step 3, the temperature of the extrusion granulating cylinder body is gradually reduced to 225-235 ℃, the opening degree of a throttle valve of an extrusion granulating machine is reduced to 40 ℃, the granulating water temperature of the extrusion granulating machine is reduced to 55 ℃, and the water flow of extrusion granulating and granulating is gradually increased to 670m 3 /h。
The preparation method of the high-transparency polypropylene resin has the beneficial effects that:
(1) The invention breaks through the technical bottleneck that the pressure of the reaction kettle cannot be controlled due to the higher temperature of the circulating water during the production by the traditional hydrogen regulation method, and meanwhile, the caking phenomenon does not occur during the high-load production operation process, thereby successfully realizing the goal of stably producing the products with long period and high load, and the production load can reach 42 tons/hour;
(2) The high-transparency polypropylene resin produced by the invention has the advantages of good transparency, high glossiness, low shrinkage rate of injection molding products and the like, and compared with general materials, the high-transparency polypropylene resin has the advantages of good processing fluidity, low processing temperature, short molding cycle and no peculiar smell.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The preparation method of the high-transparency polypropylene resin is specifically implemented according to the following steps:
step 1, respectively adding two external electron donors, triethylaluminum, a main catalyst and a cocatalyst into a first reaction kettle, and then introducing ethylene and propylene into the first reaction kettle to obtain a primary product;
step 1, gradually increasing the adding amount of a main catalyst to 0.73kg/h, and gradually increasing the adding amount of a cocatalyst to 2.8kg/h, wherein the cocatalyst is triethylaluminum, and the main catalyst is a Ziegler-Natta catalyst system taking phthalate as an internal electron donor and magnesium chloride as a carrier;
in the step 1, the temperature in the first reaction kettle is 59-66 ℃, the pressure is 2.21Mpag, the material level is controlled to be 79%, the melt index of powder is 40+/-6 g/10min, and the total ethylene content is 3.5wt%;
in the step 1, the initial addition amount of the external electron donor diisobutyldimethoxy silane is set to be 3.5kg/h, the target value is reduced to 1.7kg/h after the external electron donor diisobutyldimethoxy silane is continuously added for 40 minutes, and then the addition amount of the external electron donor tetraethoxy silane is set to be 1.3kg/h;
in the step 1, ethylene is added into a first reaction kettle, the initial amount of the ethylene is controlled to be 100kg/h, the ethylene adding amount is controlled according to the speed of increasing 50kg every 10min, when the molar concentration ratio of ethylene and propylene in the first reaction kettle is close to 1.5%, the ethylene adding amount is controlled according to 3.5% wt of the actual load of the first reaction kettle, and the molar concentration ratio of ethylene and propylene is maintained to be 1.7% of a final target value;
controlling the load of the first reaction kettle to 20t/h, and reducing the temperature of a first reaction kettle zone to 59 ℃;
step 2, adding the initial product into a second reaction kettle, and introducing ethylene and propylene into the second reaction kettle to obtain a secondary product;
in the step 2, the temperature in the second reaction kettle is 66-68 ℃, the pressure is 2.21Mpag, the material level is controlled to 78%, the melt index of powder is 40+/-6 g/10min, the total ethylene content is 3.5wt%, and the molar concentration ratio of ethylene to propylene is maintained to be 1.2% in the second reaction kettle;
step 3, degassing and deactivating the secondary product, fully mixing the secondary product with a compound additive containing a transparent nucleating agent, and then feeding the mixture into an extrusion granulator to produce high-transparency polypropylene resin;
the specific components of the additive in the step 3 are as follows: the proportion of antioxidant 1010 is 11.63%, the proportion of antioxidant 168 is 23.26%, the proportion of calcium stearate is 11.63%, the proportion of GMS is 6.97%, the proportion of transparent nucleating agent is 46.51%, and the addition amount of the additive is 4300ppm;
extruding and granulating in the step 3The temperature of the cylinder body is gradually reduced to 225-235 ℃, the opening of a throttle valve of the extrusion granulator is reduced to 40 ℃, the water temperature for granulating by the extrusion granulator is reduced to 55 ℃, and the water flow for granulating by the extrusion granulation is gradually increased to 670m 3 /h；
The addition amount of the main catalyst is increased to 1.0kg/h, the load of the first reaction kettle is increased to 30t/h, and the load of the second reaction kettle is increased to 12t/h. The total load is 42t/h;
finally, the melt index of the polypropylene resin pellets is controlled to be 40+/-5 g/10min, and the total ethylene content of the product is 3.5%.
Example 1:
aiming at the production difficulty of producing the high-transparency polypropylene special material, the method adopts the following measures:
1) The polymerization load and the temperature of a first reaction kettle zone bed are reduced in advance, and the ethylene adding rate is strictly controlled, so that the problem of abnormal severe polymerization reaction caused by high reactivity ratio of ethylene is solved, and further, the generation of sticky materials and lump materials is avoided;
2) The adding proportion of tetraethoxysilane as an external electron donor is gradually increased from 20%wt, and the most suitable feeding proportion which does not influence the isotacticity of the product and can improve the hydrogen regulation performance of the catalyst is explored;
3) The tetraethoxysilane has an inhibiting effect on the activity of the main catalyst, and the feeding amount of the main catalyst and triethylaluminum needs to be improved, so that the polymerization load is ensured.
The polypropylene device has stable running and controllable product quality during the production of PP-R, M,400 products, and typical indexes of each batch are shown in the following table:
example 2:
the two external electron donors are added into the reaction kettle according to a fixed feeding proportion, so that the hydrogen regulation sensitivity of the main catalyst can be improved, the hydrogen content can be reduced, and the high isotacticity of the polymer can be considered. The transparency of the polypropylene resin is further improved by adding a special compound additive containing a transparent nucleating agent before extrusion granulation.
Example 3:
the external electron donor is diisobutyldimethoxy silane and tetraethoxy silane, the high isotacticity of the diisobutyldimethoxy silane is utilized to improve the crystallinity of the polymer, and the tetraethoxy silane is utilized to improve the hydrogen regulation sensitivity of the main catalyst, so that the hydrogen content of the reaction kettle is reduced, and the pressure is kept controllable.
The high-transparency polypropylene resin prepared by the invention has the advantages of good transparency, high glossiness, low shrinkage rate of injection molding products and the like, and compared with general materials, the high-transparency polypropylene resin has the advantages of good processing fluidity, low processing temperature, short molding period and no peculiar smell, and is mainly used for producing various high-transparency plastic vessels for food and household transparent plastic products, such as large storage boxes and the like.
Claims (10)
1. The preparation method of the high-transparency polypropylene resin is characterized in that two different types of external electron donors are added into a reaction kettle in proportion, and the preparation method is obtained by adjusting various corresponding control parameters of a polymerization process and an extrusion granulation process, and the composition and the addition proportion of the required compound additive.
2. The method for preparing a highly transparent polypropylene resin according to claim 1, wherein the two external electron donors are diisobutyldimethoxy silane and tetraethoxy silane, respectively, and the feeding ratio of diisobutyldimethoxy silane and tetraethoxy silane is 57wt% and 43wt%, respectively.
3. The method for preparing a highly transparent polypropylene resin according to claim 1, wherein the method is specifically carried out according to the following steps:
step 1, respectively adding two external electron donors, triethylaluminum, a main catalyst and a cocatalyst into a first reaction kettle, and then introducing ethylene and propylene into the first reaction kettle to obtain a primary product;
step 2, adding the initial product into a second reaction kettle, and introducing ethylene and propylene into the second reaction kettle to obtain a secondary product;
and step 3, degassing and deactivating the secondary product, fully mixing the secondary product with a compound additive containing a transparent nucleating agent, and then feeding the mixture into an extrusion granulator to produce the high-transparency polypropylene resin.
4. The method for preparing a highly transparent polypropylene resin according to claim 3, wherein in the step 1, the addition amount of the main catalyst is gradually increased to 0.73kg/h, the addition amount of the cocatalyst is gradually increased to 2.8kg/h, the cocatalyst is triethylaluminum, and the main catalyst is a Ziegler-Natta catalyst system using a phtalate as an internal electron donor and magnesium chloride as a carrier.
5. The method for preparing a highly transparent polypropylene resin according to claim 3, wherein the temperature in the first reaction vessel in the step 1 is 59 ℃ to 66 ℃, the pressure is 2.21mpa g, the material level is 79%, the melt index of the powder is 40.+ -. 6g/10min, and the total ethylene content is 3.5wt%.
6. The method for preparing a highly transparent polypropylene resin according to claim 3, wherein the initial addition amount of diisobutyldimethoxy silane as an external donor in the step 1 is set to 3.5kg/h, the addition is continued for 40 minutes and then the target value is reduced to 1.7kg/h, and then tetraethoxy silane as an external donor is added and the addition amount is set to 1.3kg/h.
7. The method for producing a highly transparent polypropylene resin according to claim 3, wherein in the step 1, ethylene is fed into the first reactor, the initial amount of ethylene is controlled to 100kg/h, the ethylene feed amount is controlled to 50kg per 10min, and when the molar concentration ratio of ethylene to propylene in the first reactor is close to 1.5%, the ethylene feed amount is controlled to 3.5% by weight based on the actual load of the first reactor, and the final target value of the molar concentration ratio of ethylene to propylene is maintained to 1.7%.
8. The method for preparing a highly transparent polypropylene resin according to claim 3, wherein the second reaction vessel in the step 2 has a temperature of 66℃to 68℃and a pressure of 2.21Mpag, a level control of 78%, a powder melt index of 40.+ -. 6g/10min, a total ethylene content of 3.5% by weight and a molar concentration ratio of ethylene to propylene of 1.2% maintained in the second reaction vessel.
9. The method for preparing a highly transparent polypropylene resin according to claim 3, wherein the specific components of the additive in step 3 are as follows: the proportion of antioxidant 1010 is 11.63%, the proportion of antioxidant 168 is 23.26%, the proportion of calcium stearate is 11.63%, the proportion of GMS is 6.97%, the proportion of transparent nucleating agent is 46.51%, and the addition amount of the additive is 4300ppm.
10. The method for producing a highly transparent polypropylene resin according to claim 3, wherein the temperature of the extrusion granulating cylinder in step 3 is gradually reduced to 225 to 235 ℃, the throttle opening of the extrusion granulator is reduced to 40 °, the water temperature for granulating the extrusion granulator is reduced to 55 ℃, and the water flow rate for granulating the extrusion granulation is gradually increased to 670m 3 /h。
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| CN202311565073.0A CN117777339A (en) | 2023-11-22 | 2023-11-22 | Preparation method of high-transparency polypropylene resin |
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| CN202311565073.0A CN117777339A (en) | 2023-11-22 | 2023-11-22 | Preparation method of high-transparency polypropylene resin |
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| CN202311565073.0A Pending CN117777339A (en) | 2023-11-22 | 2023-11-22 | Preparation method of high-transparency polypropylene resin |
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