CN111303327A - Special high-transparency food-grade polypropylene material and production method thereof - Google Patents
Special high-transparency food-grade polypropylene material and production method thereof Download PDFInfo
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- CN111303327A CN111303327A CN202010176631.4A CN202010176631A CN111303327A CN 111303327 A CN111303327 A CN 111303327A CN 202010176631 A CN202010176631 A CN 202010176631A CN 111303327 A CN111303327 A CN 111303327A
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- 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
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Abstract
The invention discloses a high-transparency food-grade polypropylene special material, which comprises the following steps: (1) refining propylene and ethylene raw materials; (2) carrying out binary random copolymerization on ethylene and propylene in a gas-phase fluidized bed reactor of a Unipol process polypropylene device under a specific catalyst Cat-II and external electron donor D-II system, (3) degassing a polymerization product, and (4) co-extruding and granulating polymerization powder and a specific additive to obtain the product. The transparent polypropylene special material obtained by the production formula is green, environment-friendly, free of any plasticizer, high in melt index, moderate in impact strength and bending modulus.
Description
Technical Field
The invention relates to the technical field of polypropylene production, in particular to a high-transparency food-grade polypropylene special material and a production method thereof.
Background
Polypropylene has become the most rapidly growing and actively developing new products among five general synthetic resins because of its outstanding mechanical properties, heat resistance, electrical insulation properties, low price and excellent processability. Due to the crystallization property of the homopolymerized polypropylene, the luster and the transparency of the product are poor, the appearance is not beautiful, and the development of the product in the application fields of transparent packaging, daily necessities and the like is restricted. After PP is subjected to transparent modification, the PP has the advantages of light weight, low price, sanitation, high temperature resistance, easiness in processing and forming and the like, the transparency and the surface gloss can be comparable to those of other transparent resins (polycarbonate PC, polystyrene PS and the like), the cost performance is high, and the PP can be widely applied to the fields of transparent packaging, medical appliances, household articles, general industry and the like.
The polypropylene which is a transparent material is mainly applied to the fields of preservation boxes, transparent storage boxes, sports water cups, small household appliances and the like, and is gradually applied to the field of fruit tea/milk tea cups in recent years, and the demand is increased rapidly.
At present, the mainstream transparent polypropylene production process at home and abroad comprises a loop process, a three-well oiling process and an Enlishi gas phase process, and related patent technologies are more. Patent technologies CN 104327207 and CN103030886A disclose a heat-resistant transparent polypropylene and a preparation method thereof, wherein the production process is a loop reactor, although the rigidity and toughness balance is good, the melt index of the product is low (8-10 g/10 min), and the molecular weight distribution is narrow, which cannot meet the requirement of rapid injection molding. Patent technology CN 105218718A discloses a transparent material ternary copolymerized by ethylene, propylene and butylene, the product uses innoven gas phase process technology, although the product has better heat resistance and transparency, the catalyst system is phthalate catalyst, which contains "plasticizer", and cannot meet the requirements related to food contact, and the melt index of the final product cannot meet the requirements of fast injection molding. Patent technology CN 106554448A discloses an impact-resistant copolymerized transparent polypropylene produced by a Sphripol polymerization process, and although the product introduces an ethylene propylene rubber phase and has higher impact resistance, the bending modulus of the product is lower and is only 890-980MPa, and the final injection-molded product is easy to warp. The special transparent polypropylene material related to the patent technology has the defects of low melt index, narrow molecular weight distribution and containing plasticizer, and can not meet the requirement of downstream rapid processing and molding. The Unipol gas-phase fluidized bed polypropylene process is still in the technical digestion stage, and the patented technology of the technology in the related field of transparent polypropylene is not searched.
Disclosure of Invention
The invention aims to provide a high-transparency food-grade polypropylene special material and a production method thereof, and relates to the high-transparency food-grade polypropylene special material and the production method thereof on the Unipol gas-phase fluidized bed process.
In order to solve the technical problems, the invention adopts the following technical scheme:
a special material for high-transparency food-grade polypropylene is prepared by the following steps:
(1) refining propylene and ethylene raw materials;
(2) ethylene and propylene are subjected to binary random copolymerization reaction in a gas-phase fluidized bed reactor of a Unipol process polypropylene device under a specific catalyst Cat-II and an external electron donor D-II system,
(3) the polymerization product is degassed and then the polymerization product is polymerized,
(4) and co-extruding and granulating the polymerized powder and a specific additive to obtain the product.
Further, the method comprises the following steps of; the Cat-II catalyst is MgCl2Or C4H10MgO2As a carrier, TiCl4As active center, Al (C)2H5)3Is a cocatalyst; the external electron donor D-II is a silane substance.
Further, the method comprises the following steps of; the specific additives comprise a main antioxidant, an auxiliary antioxidant, an acid scavenger, an antistatic agent and an anti-reflection agent.
Further, the method comprises the following steps of; the secondary antioxidant is as follows: one or two of Irgafos 168 and Ultranox 626.
Further, the method comprises the following steps of; the acid scavenger is calcium stearate; the antistatic agent is one of Armostat 600 and GMS;
the permeability-increasing agent is: millad 3905, Millad 3988, and Millad NX 8000K.
Further, the method comprises the following steps of; the addition amount of the primary antioxidant is 400-1000 ppm; the addition amount of the auxiliary antioxidant is 200-1000 ppm; the addition amount of the antistatic agent is 100-500 ppm; the addition amount of the anti-reflection agent is 1500-.
Further, the method comprises the following steps of; when the auxiliary antioxidant is used in a compounding way, the content of Irgafos-168: the addition ratio of Ultranox626 is 2-4: 1.
Further, the method comprises the following steps of; the production method comprises the following steps:
a: gradually reducing the propylene partial pressure at the speed of 0.05-0.2Mpa/h, and gradually reducing the reactor temperature at the speed of 0.03-0.1 ℃/min;
b, gradually establishing an ethylene component at the rate of 200-300 kg/h;
c: reducing the opening degree of a guide vane of a circulating gas compressor to increase the apparent gas velocity and ensure good fluidization of the reactor;
d; the condensation amount of the reactor is adjusted by properly adjusting the temperature and the propylene partial pressure, so that the dry-wet balance in the reactor is ensured;
e, after the reaction is stable, H is gradually increased2/C3Molar ratio, adjusting the desired melt index product;
and F, when the melt index reaches the set target value, adding the transparent material additive and cutting into a qualified storage bin.
Further, the method comprises the following steps of; in the gas-phase fluidized bed reactor, the propylene partial pressure is 1.5-2.5Mpa, the ethylene partial pressure is 0.02-0.09Mpa, the condensation amount is 5-15%, the catalyst solid flow is 0.2-1.0kg/h, and the catalyst propylene carrier flow is 60-100 kg/h;
the reactor is 1-2 fluidized bed reactors connected in series.
Further, the method comprises the following steps of; in the phase fluidized bed reactor H2/C3The molar ratio is 0.05-0.1, C2/C3The molar ratio is 0.01-0.04.
Compared with the prior art, the invention has the beneficial effects that:
1. the melt index range of the polypropylene is controllable, the melt index range is 20-65g/10min, the flexural modulus is more than or equal to 900Mpa, and the impact strength of a simple beam notch is more than or equal to 3.5KJ/m2The heat distortion temperature is more than or equal to 65 ℃, the ash content is less than or equal to 250ppm, the yellow index is less than or equal to-4, and the environment-friendly flame-retardant coating does not contain phthalate plasticizer.
2. The produced polypropylene product has adjustable melt index, low haze, moderate impact strength and flexural modulus. Under the formula provided by the invention, the transparent product has smooth appearance, low molding shrinkage and high transparency, and meets the requirements of food contact and national relevant standards.
3. The catalyst system disclosed by the invention is high in activity, does not contain a plasticizer, is green and environment-friendly, and can meet the requirements of relevant specifications of food contact.
4. The final product of the invention has wide adjustable range of melt index and wide molecular weight distribution, and is easy for downstream rapid injection molding processing.
5. The invention only uses a single fluidized bed reactor to produce the transparent special material for polypropylene, thereby reducing the equipment investment and the production cost, and the yield of the method reaches 20 t/h.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a special material for high-transparency food-grade polypropylene is prepared by the following steps:
(1) refining propylene and ethylene raw materials;
(2) ethylene and propylene are subjected to binary random copolymerization reaction in a gas-phase fluidized bed reactor of a Unipol process polypropylene device under a specific catalyst Cat-II and an external electron donor D-II system,
(3) the polymerization product is degassed and then the polymerization product is polymerized,
(4) co-extruding and granulating the polymerized powder and a specific additive to obtain a product; propylene and ethylene are taken as raw materials, the propylene and the ethylene are refined and then enter a gas-phase fluidized bed reactor of a Unipol process polypropylene device, a specific catalyst Cat-II is added, and binary random copolymerization is carried out under an external electron donor D-II system to obtain the polypropylene with controllable melt index range, the flexural modulus is more than or equal to 900Mpa in 20-65g/10min, the impact strength of a simply supported beam gap is more than or equal to 3.5KJ/m2The heat distortion temperature is more than or equal to 65 ℃, the ash content is less than or equal to 250ppm, the yellow index is less than or equal to-4, and the product does not contain phthalate plasticizer.
Example 2:
on the basis of example 1, Cat-II catalyst, with MgCl2Or C4H10MgO2As a carrier, TiCl4As active center, Al (C)2H5)3Is a cocatalyst; the external electron donor D-II is a silane substance; the ethylene and the propylene can be conveniently subjected to binary random copolymerization reaction in a Unipol process polypropylene device gas-phase fluidized bed reactor.
Example 3:
on the basis of the examples 1-2, the specific additives comprise a main antioxidant, an auxiliary antioxidant, an acid scavenger, an antistatic agent and an anti-reflection agent; the specific additive and the polymerization powder material ensure that the prepared product has smooth appearance, low molding shrinkage and high transparency.
Example 4:
on the basis of examples 1 to 3, the secondary antioxidants were: one or two of Irgafos 168 and Ultranox626 are compounded; the selection of the auxiliary antioxidant enables the specific additive to obtain a product with wide adjustable range of melt index and wide molecular weight distribution during preparation.
Example 5:
based on examples 1-4, the acid scavenger is calcium stearate; the antistatic agent is one of Armostat 600 and GMS; the permeability-increasing agent is: one of Millad 3905, Millad 3988, Millad NX 8000K;
the acid scavenger is good and the antistatic agent is selected, so that the product obtained by the specific additive during preparation has wide adjustable range of melt index and wide molecular weight distribution.
Example 6:
on the basis of examples 1 to 5, the amount of primary antioxidant added was 400 ppm; the addition amount of the auxiliary antioxidant is 200 ppm; the addition amount of the antistatic agent is 100 ppm; the addition amount of the anti-reflection agent is 1500 ppm; the addition amounts of the main antioxidant, the auxiliary antioxidant, the antistatic agent and the anti-reflection agent are controlled, so that the prepared special additive is beneficial to coextrusion.
Example 7:
on the basis of examples 1 to 6, the amount of primary antioxidant added was 1000 ppm; the addition amount of the auxiliary antioxidant is 1000 ppm; the addition amount of the antistatic agent is 500 ppm; the addition amount of the anti-reflection agent is 2500 ppm; the addition amounts of the main antioxidant, the auxiliary antioxidant, the antistatic agent and the anti-reflection agent are controlled, so that the prepared special additive is beneficial to coextrusion.
Example 8:
based on examples 1-7, the amount of primary antioxidant added was 700 ppm; the addition amount of the auxiliary antioxidant is 600 ppm; the addition amount of the antistatic agent is 300 ppm; the addition amount of the anti-reflection agent is 2000 ppm; the addition amounts of the main antioxidant, the auxiliary antioxidant, the antistatic agent and the anti-reflection agent are controlled, so that the prepared special additive is beneficial to coextrusion.
Example 9:
based on examples 1-8, when the auxiliary antioxidant is used in a compounding way, the content of Irgafos-168: the adding amount ratio of Ultranox626 is 2: 1; compounding auxiliary antioxidant with Irgafos-168: the proportion of the addition amount of Ultranox626 is controlled, so that the auxiliary antioxidant has a better effect when in use.
Example 10:
based on examples 1-9, when the auxiliary antioxidant is used in a compounding way, the content of Irgafos-168: the adding amount ratio of Ultranox626 is 3: 1; compounding auxiliary antioxidant with Irgafos-168: the proportion of the addition amount of Ultranox626 is controlled, so that the auxiliary antioxidant has a better effect when in use.
Example 11:
based on the examples 1-10, when the auxiliary antioxidant is used in a compounding way, the content of Irgafos-168: the adding amount ratio of Ultranox626 is 4: 1; compounding auxiliary antioxidant with Irgafos-168: the proportion of the addition amount of Ultranox626 is controlled, so that the auxiliary antioxidant has a better effect when in use.
Example 12:
on the basis of examples 1 to 11, the production process:
a: gradually reducing the propylene partial pressure at the rate of 0.05Mpa/h, and gradually reducing the reactor temperature at the rate of 0.03 ℃/min;
b, gradually establishing an ethylene component at a rate of 200 kg/h;
c: reducing the opening degree of a guide vane of a circulating gas compressor to increase the apparent gas velocity and ensure good fluidization of the reactor;
d; the condensation amount of the reactor is adjusted by properly adjusting the temperature and the propylene partial pressure, so that the dry-wet balance in the reactor is ensured;
e, after the reaction is stable, H is gradually increased2/C3Molar ratio, adjusting the desired melt index product;
f, when the melt index reaches a set target value, adding a transparent material additive, and cutting into a qualified stock bin; when preparing the high-transparency food-grade polypropylene special materialThe melt index range of the polypropylene is controllable under the control of the process conditions, the melt index range is 20-65g/10min, the flexural modulus is more than or equal to 900Mpa, and the impact strength of a simple beam notch is more than or equal to 3.5KJ/m2The heat distortion temperature is more than or equal to 65 ℃, the ash content is less than or equal to 250ppm, the yellow index is less than or equal to-4, and the polyester-based heat-shrinkable tube does not contain phthalate plasticizer, and has adjustable melt index, lower haze, moderate impact strength and flexural modulus. Under the formula provided by the invention, the transparent product has smooth appearance, low molding shrinkage and high transparency, and meets the requirements of food contact and national relevant standards.
Example 13:
on the basis of examples 1 to 12, the production method:
a: gradually reducing the propylene partial pressure at the rate of 0.2Mpa/h, and gradually reducing the reactor temperature at the rate of 0.1 ℃/min;
b, gradually establishing an ethylene component at a rate of 300 kg/h;
c: reducing the opening degree of a guide vane of a circulating gas compressor to increase the apparent gas velocity and ensure good fluidization of the reactor;
d; the condensation amount of the reactor is adjusted by properly adjusting the temperature and the propylene partial pressure, so that the dry-wet balance in the reactor is ensured;
e, after the reaction is stable, H is gradually increased2/C3Molar ratio, adjusting the desired melt index product;
3. f, when the melt index reaches a set target value, adding a transparent material additive, and cutting into a qualified stock bin; when the special material for the high-transparency food-grade polypropylene is prepared, the melt index range of the polypropylene is controllable under the control of process conditions, the melt index range is 20-65g/10min, the bending modulus is more than or equal to 900Mpa, and the notch impact strength of a simply supported beam is more than or equal to 3.5KJ/m2The heat distortion temperature is more than or equal to 65 ℃, the ash content is less than or equal to 250ppm, the yellow index is less than or equal to-4, and the polyester-based heat-shrinkable tube does not contain phthalate plasticizer, and has adjustable melt index, lower haze, moderate impact strength and flexural modulus. Under the formula provided by the invention, the transparent product has smooth appearance, low molding shrinkage and high transparency, and meets the requirements of food contact and national relevant standards.
Example 14:
on the basis of examples 1 to 13, the production process:
a: gradually reducing the propylene partial pressure at the rate of 0.1Mpa/h, and gradually reducing the reactor temperature at the rate of 0.06 ℃/min;
b, gradually establishing an ethylene component at a rate of 250 kg/h;
c: reducing the opening degree of a guide vane of a circulating gas compressor to increase the apparent gas velocity and ensure good fluidization of the reactor;
d; the condensation amount of the reactor is adjusted by properly adjusting the temperature and the propylene partial pressure, so that the dry-wet balance in the reactor is ensured;
e, after the reaction is stable, H is gradually increased2/C3Molar ratio, adjusting the desired melt index product;
f, when the melt index reaches a set target value, adding a transparent material additive, and cutting into a qualified stock bin; when the special material for the high-transparency food-grade polypropylene is prepared, the melt index range of the polypropylene is controllable under the control of process conditions, the melt index range is 20-65g/10min, the bending modulus is more than or equal to 900Mpa, and the notch impact strength of a simply supported beam is more than or equal to 3.5KJ/m2The heat distortion temperature is more than or equal to 65 ℃, the ash content is less than or equal to 250ppm, the yellow index is less than or equal to-4, and the polyester-based heat-shrinkable tube does not contain phthalate plasticizer, and has adjustable melt index, lower haze, moderate impact strength and flexural modulus. Under the formula provided by the invention, the transparent product has smooth appearance, low molding shrinkage and high transparency, and meets the requirements of food contact and national relevant standards.
Example 15:
on the basis of examples 1 to 14, the partial pressure of propylene in the gas phase fluidized bed reactor was 1.5Mpa, the partial pressure of ethylene was 0.02Mpa, the amount of condensation was 5%, the flow rate of the catalyst solid was 0.2kg/h, and the flow rate of the catalyst propylene carrier was 600 kg/h;
the reactor is 1 fluidized bed reactor; the control of the process conditions in the gas-phase fluidized bed reactor is convenient for the ethylene and the propylene to carry out binary random copolymerization reaction in the gas-phase fluidized bed reactor of the Unipol process polypropylene device.
Example 16:
on the basis of examples 1 to 15, the partial pressure of propylene in the gas phase fluidized bed reactor was 2.5Mpa, the partial pressure of ethylene was 0.09Mpa, the amount of condensation was 15%, the flow rate of the catalyst solid was 1.0kg/h, and the flow rate of the catalyst propylene carrier was 100 kg/h;
the reactor is 2 fluidized bed reactors connected in series; the control of the process conditions in the gas-phase fluidized bed reactor is convenient for the ethylene and the propylene to carry out binary random copolymerization reaction in the gas-phase fluidized bed reactor of the Unipol process polypropylene device.
Example 17:
on the basis of examples 1 to 16, the partial pressure of propylene in the gas phase fluidized bed reactor was 2MPa, the partial pressure of ethylene was 0.05MPa, the amount of condensation was 10%, the flow rate of the catalyst solid was 0.6kg/h, and the flow rate of the catalyst propylene carrier was 80 kg/h;
the reactor is 2 fluidized bed reactors connected in series; the control of the process conditions in the gas-phase fluidized bed reactor is convenient for the ethylene and the propylene to carry out binary random copolymerization reaction in the gas-phase fluidized bed reactor of the Unipol process polypropylene device.
Example 18:
in a phase fluidized bed reactor, based on examples 1 to 17, H2/C3Molar ratio of 0.05, C2/C3The molar ratio is 0.01; in gas-phase fluidized-bed reactors2/C3Molar ratio of、C2/C3The control of the molar ratio and the control of the melt index range of the polypropylene are controllable.
Example 19:
in a phase fluidized bed reactor, based on examples 1 to 18, H2/C3Molar ratio of 0.1, C2/C3The molar ratio is-0.04; in gas-phase fluidized-bed reactors2/C3Molar ratio of、C2/C3The control of the molar ratio and the control of the melt index range of the polypropylene are controllable.
Example 20:
in a phase fluidized bed reactor based on examples 1 to 19, H2/C3Molar ratio of 0.07, C2/C3The molar ratio is 0.03; in gas-phase fluidized-bed reactors2/C3Molar ratio of、C2/C3The control of the molar ratio and the control of the melt index range of the polypropylene are controllable.
Test of
Test 1
The production formula of the polypropylene transparent special material comprises the following steps:
(1) gradually reducing the propylene partial pressure to 2.2 at the speed of 0.06Mpa/h, and gradually reducing the reactor temperature to 60 ℃ at the speed of 0.03-0.1 ℃/min;
(2) gradually establishing ethylene component at a rate of 200kg/h, wherein the final ethylene addition is 390kg/h, and the ethylene partial pressure is 0.05 Mpa;
(3) reducing the opening of the guide vane of the circulating gas compressor to 67 percent to increase the superficial gas velocity to 0.4m/s and ensure good fluidization of the reactor;
(4) the condensation amount of the reactor is controlled to be about 8 percent by adjusting the temperature and the propylene partial pressure, and the dry-wet balance in the reactor is ensured;
(5) after the reaction is stable, H is gradually increased2/C3The molar ratio is increased to 0.0475, and the melt index is gradually increased;
(6) when the melt index reaches 25g/10min, adding the special transparent additive, cutting into a qualified bin, and controlling the final melt index to be 25 +/-3 g/10min and the xylene soluble substance to be 6.0 +/-0.3%;
(7) wherein the additive comprises the following components: 700ppm of primary antioxidant Irganox 1010 is added; 800ppm of auxiliary antioxidant Irgafos 168 is added; adding 400ppm of calcium stearate; 300ppm of mold release agent GMS; the addition amount of the anti-reflection agent NX8000K is 1700 ppm.
Said H2/C3The molar ratio is 0.0484;
said C is2/C3The molar ratio is 0.02;
the propylene partial pressure is 2.2Mpa, and the ethylene partial pressure is 0.05 Mpa;
the condensation capacity of the reactor is 8%;
the solid flow rate of the catalyst is 0.5 kg/h;
the flow rate of the catalyst propylene carrier is 70 kg/h.
Test 2
The production formula of the polypropylene transparent special material comprises the following steps:
(1) gradually reducing the propylene partial pressure to 2.2 at the speed of 0.06Mpa/h, and gradually reducing the reactor temperature to 60 ℃ at the speed of 0.03-0.1 ℃/min;
(2) gradually establishing ethylene component at a rate of 200kg/h, wherein the final ethylene addition is 390kg/h, and the ethylene partial pressure is 0.05 Mpa;
(3) reducing the opening of the guide vane of the circulating gas compressor to 67 percent to increase the superficial gas velocity to 0.4m/s and ensure good fluidization of the reactor;
(4) the condensation amount of the reactor is controlled to be about 8 percent by adjusting the temperature and the propylene partial pressure, and the dry-wet balance in the reactor is ensured;
(5) after the reaction is stable, H is gradually increased2/C3The molar ratio is 0.0485, and the melt index is gradually increased;
(6) when the melt index reaches 25g/10min, adding the special transparent additive, cutting into a qualified bin, and controlling the final melt index to be 25 +/-3 g/10min and the xylene soluble substance to be 6.0 +/-0.3%;
(7) wherein the additive comprises the following components: 500ppm of primary antioxidant Irganox 1010 is added; adding 400ppm of auxiliary antioxidant Irgafos 168; adding 200ppm of calcium stearate into an auxiliary antioxidant Ultranox626, and adding 400ppm of calcium stearate; 300ppm of Armostat 600 as a release agent is added; the addition amount of an anti-reflection agent NX8000K is 2200 ppm.
Said H2/C3The molar ratio is 0.0484;
said C is2/C3The molar ratio is 0.03;
the propylene partial pressure is 2.2Mpa, and the ethylene partial pressure is 0.05 Mpa;
the condensation capacity of the reactor is 8%;
the solid flow rate of the catalyst is 0.4 kg/h;
the flow rate of the catalyst propylene carrier is 80 kg/h.
Test 3
The production formula of the polypropylene transparent special material comprises the following steps:
(1) gradually reducing the propylene partial pressure to 2.2 at the speed of 0.06Mpa/h, and gradually reducing the reactor temperature to 60 ℃ at the speed of 0.08 ℃/min;
(2) gradually establishing ethylene component at a rate of 200kg/h, wherein the final ethylene addition is 670kg/h, and the ethylene partial pressure is 0.05 Mpa;
(3) reducing the opening of the guide vane of the circulating gas compressor to 68 percent to increase the superficial gas velocity to 0.4m/s and ensure good fluidization of the reactor;
(4) the condensation amount of the reactor is controlled to be about 8 percent by adjusting the temperature and the propylene partial pressure, and the dry-wet balance in the reactor is ensured;
(5) after the reaction is stable, H is gradually increased2/C3The molar ratio is increased to 0.08, and the melt index is gradually increased;
(6) when the melt index reaches 45g/10min, adding the special transparent additive, cutting into a qualified bin, and controlling the final melt index to be 45 +/-4 g/10min and the xylene soluble substance to be 5.8 +/-0.3%;
(7) wherein the additive comprises the following components: adding 600ppm of primary antioxidant Irganox 1010; adding 600ppm of auxiliary antioxidant Irgafos 168; adding 100ppm of calcium stearate into an auxiliary antioxidant Ultranox626, and adding 500ppm of calcium stearate; adding 200ppm of release agent Armostat 600; the amount of an anti-reflection agent NX8000K added was 1900 ppm.
Said H2/C3The molar ratio is 0.08;
said C is2/C3The molar ratio is 0.03;
the propylene partial pressure is 2.4Mpa, and the ethylene partial pressure is 0.05 Mpa;
the condensation capacity of the reactor is 8%;
the solid flow rate of the catalyst is 0.6 kg/h;
the flow rate of the catalyst propylene carrier is 90 kg/h.
Test 4
The production formula of the polypropylene transparent special material comprises the following steps:
(1) gradually reducing the propylene partial pressure to 2.0 at the speed of 0.06Mpa/h, and gradually reducing the reactor temperature to 60 ℃ at the speed of 0.08 ℃/min;
(2) gradually establishing ethylene component at a rate of 100kg/h, wherein the final ethylene addition is 770kg/h and the ethylene partial pressure is 0.06 MPa;
(3) reducing the opening of the guide vane of the circulating gas compressor to 68 percent to increase the superficial gas velocity to 0.4m/s and ensure good fluidization of the reactor;
(4) the condensation amount of the reactor is controlled to be about 10 percent by adjusting the temperature and the propylene partial pressure, and the dry-wet balance in the reactor is ensured;
(5) after the reaction is stable, H is gradually increased2/C3The molar ratio is increased to 0.095, and the melt index is gradually increased;
(6) when the melt index reaches 60g/10min, adding a special transparent additive, cutting into a qualified bin, and controlling the final melt index to be 60 +/-5 g/10min and the xylene soluble to be 5.5 +/-0.3%;
(7) wherein the additive comprises the following components: adding 600ppm of primary antioxidant Irganox 1010; adding 600ppm of auxiliary antioxidant Irgafos 168; adding 100ppm of calcium stearate into an auxiliary antioxidant Ultranox626, and adding 500ppm of calcium stearate; adding 200ppm of release agent Armostat 600; the amount of an anti-reflection agent NX8000K added was 1900 ppm.
Said H2/C3The molar ratio is 0.095;
said C is2/C3The molar ratio is 0.02;
the propylene partial pressure is 2.0Mpa, and the ethylene partial pressure is 0.06 Mpa;
the condensation capacity of the reactor is 10%;
the solid flow rate of the catalyst is 0.7 kg/h;
the flow rate of the catalyst propylene carrier is 80 kg/h.
Test 5
The production formula of the polypropylene transparent special material comprises the following steps:
(1) gradually reducing the propylene partial pressure to 2.0 at the speed of 0.06Mpa/h, and gradually reducing the reactor temperature to 60 ℃ at the speed of 0.08 ℃/min;
(2) gradually establishing ethylene component at a rate of 200kg/h, wherein the final ethylene addition is 670kg/h, and the ethylene partial pressure is 0.05 Mpa;
(3) reducing the opening of the guide vane of the circulating gas compressor to 70 percent to increase the apparent gas velocity to 0.41 m/s and ensure good fluidization of the reactor;
(4) the condensation amount of the reactor is controlled to be about 10 percent by adjusting the temperature and the propylene partial pressure, and the dry-wet balance in the reactor is ensured;
(5) after the reaction is stable, H is gradually increased2/C3The molar ratio is increased to 0.093, and the melt index is gradually increased;
(6) when the melt index reaches 60g/10min, adding a special transparent additive, cutting into a qualified bin, and controlling the final melt index to be 60 +/-5 g/10min and the xylene soluble to be 5.5 +/-0.3%;
(7) wherein the additive comprises the following components: adding 600ppm of primary antioxidant Irganox 1010; adding 1000ppm of auxiliary antioxidant Irgafos 168; adding 500ppm of calcium stearate; 300ppm of mold release agent GMS; the addition amount of an anti-reflection agent NX8000K is 2000 ppm.
Said H2/C3The molar ratio is 0.094;
said C is2/C3The molar ratio is 0.02;
the propylene partial pressure is 2.0Mpa, and the ethylene partial pressure is 0.05 Mpa;
the condensation capacity of the reactor is 10%;
the solid flow rate of the catalyst is 0.7 kg/h;
the flow rate of the catalyst propylene carrier is 90 kg/h.
Quality table of comparative products of each test
As can be seen from the table, the product produced by the formula of the invention achieves higher levels in the aspects of molecular weight distribution and impact strength, all indexes are superior to the industrial standard, and the product quality is adjustable.
Although the invention has been described herein with reference to a number of illustrative embodiments thereof, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure. More specifically, various variations and modifications are possible in the component parts and/or arrangements of the subject combination arrangement within the scope of the disclosure and claims of this application. In addition to variations and modifications in the component parts and/or arrangements, other uses will also be apparent to those skilled in the art.
Claims (10)
1. The special material for the high-transparency food-grade polypropylene is characterized by comprising the following components in parts by weight: the preparation method comprises the following steps:
(1) refining propylene and ethylene raw materials;
(2) ethylene and propylene are subjected to binary random copolymerization reaction in a gas-phase fluidized bed reactor of a Unipol process polypropylene device under a specific catalyst Cat-II and an external electron donor D-II system,
(3) the polymerization product is degassed and then the polymerization product is polymerized,
(4) and co-extruding and granulating the polymerized powder and a specific additive to obtain the product.
2. The special material for high-transparency food-grade polypropylene according to claim 1, wherein the special material comprises the following components: said Cat-II catalyst is MgCl2Or C4H10MgO2As a carrier, TiCl4As active center, Al (C)2H5)3Is a cocatalyst; the external electron donor D-II is a silane substance.
3. The special material for high-transparency food-grade polypropylene according to claim 1, wherein the special material comprises the following components: the specific additives comprise a main antioxidant, an auxiliary antioxidant, an acid scavenger, an antistatic agent and an anti-reflection agent.
4. The special material for high-transparency food-grade polypropylene according to claim 3, wherein the special material comprises the following components in percentage by weight: the secondary antioxidant is as follows: one or two of Irgafos 168 and Ultranox 626.
5. The special material for high-transparency food-grade polypropylene according to claim 3, wherein the special material comprises the following components in percentage by weight: the acid scavenger is calcium stearate; the antistatic agent is one of Armostat 600 and GMS;
the permeability-increasing agent is: millad 3905, Millad 3988, and Millad NX 8000K.
6. The special material for high-transparency food-grade polypropylene according to claim 3, wherein the special material comprises the following components in percentage by weight: the addition amount of the primary antioxidant is 400-1000 ppm; the addition amount of the auxiliary antioxidant is 200-1000 ppm; the addition amount of the antistatic agent is 100-500 ppm; the addition amount of the anti-reflection agent is 1500-.
7. The special material for high-transparency food-grade polypropylene according to claim 6, wherein the special material comprises the following components: when the auxiliary antioxidant is used in a compounding way, the content of Irgafos-168: the addition ratio of Ultranox626 is 2-4: 1.
8. The production method of the special material for high-transparency food-grade polypropylene according to claim 1, characterized in that: the production method comprises the following steps:
a: gradually reducing the propylene partial pressure at the speed of 0.05-0.2Mpa/h, and gradually reducing the reactor temperature at the speed of 0.03-0.1 ℃/min;
b, gradually establishing an ethylene component at the rate of 200-300 kg/h;
c: reducing the opening degree of a guide vane of a circulating gas compressor to increase the apparent gas velocity and ensure good fluidization of the reactor;
d; the condensation amount of the reactor is adjusted by properly adjusting the temperature and the propylene partial pressure, so that the dry-wet balance in the reactor is ensured;
e, after the reaction is stable, H is gradually increased2/C3Molar ratio, adjusting the desired melt index product;
and F, when the melt index reaches the set target value, adding the transparent material additive and cutting into a qualified storage bin.
9. The production method of the special material for high-transparency food-grade polypropylene according to claim 1, characterized in that: in the gas-phase fluidized bed reactor, the propylene partial pressure is 1.5-2.5Mpa, the ethylene partial pressure is 0.02-0.09Mpa, the condensation amount is 5-15%, the catalyst solid flow is 0.2-1.0kg/h, and the catalyst propylene carrier flow is 60-100 kg/h;
the reactor is 1-2 fluidized bed reactors connected in series.
10. The production method of the special material for high-transparency food-grade polypropylene according to claim 1, characterized in that: in the phase fluidized bed reactor H2/C3The molar ratio is 0.05-0.1, C2/C3The molar ratio is 0.01-0.04.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113980383A (en) * | 2021-10-25 | 2022-01-28 | 成都金发科技新材料有限公司 | Polypropylene composition with high light transmission and low-temperature toughness as well as preparation method and application thereof |
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| US20050277719A1 (en) * | 2004-05-27 | 2005-12-15 | Thomas Gallagher | Clarity, low haze polymer |
| CN108864347A (en) * | 2018-06-22 | 2018-11-23 | 云南云天化石化有限公司 | The production method of PPR pipe PP Pipe Compound |
| CN110527197A (en) * | 2019-09-30 | 2019-12-03 | 东华能源(宁波)新材料有限公司 | A kind of atactic copolymerized polypropene thermoset resin and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20050277719A1 (en) * | 2004-05-27 | 2005-12-15 | Thomas Gallagher | Clarity, low haze polymer |
| CN108864347A (en) * | 2018-06-22 | 2018-11-23 | 云南云天化石化有限公司 | The production method of PPR pipe PP Pipe Compound |
| CN110527197A (en) * | 2019-09-30 | 2019-12-03 | 东华能源(宁波)新材料有限公司 | A kind of atactic copolymerized polypropene thermoset resin and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113980383A (en) * | 2021-10-25 | 2022-01-28 | 成都金发科技新材料有限公司 | Polypropylene composition with high light transmission and low-temperature toughness as well as preparation method and application thereof |
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Application publication date: 20200619 |