CN115926030A - High-permeability high-toughness low-isotacticity polypropylene thermal forming resin and preparation process thereof - Google Patents
High-permeability high-toughness low-isotacticity polypropylene thermal forming resin and preparation process thereof Download PDFInfo
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Abstract
The invention relates to the technical field of polypropylene resin, in particular to high-permeability high-toughness low-isotacticity polypropylene thermoforming resin and a preparation process thereof. The resin comprises the following components in percentage by weight: by mass percentage, 0.04 to 0.1 percent of main antioxidant, 0.04 to 0.1 percent of auxiliary antioxidant, 0.03 to 0.06 percent of acid scavenger, 0.1 to 0.25 percent of nucleating agent and the balance of polypropylene. By polymerizing in a Unipol gas-phase fluidized reactor, the production process parameters such as hydrogen concentration, aluminum-silicon ratio and the like are controlled, the homopolymerized polypropylene powder with proper melt flow rate, high xylene content, low isotacticity and good toughness is obtained, no ethylene monomer is required to be added, the operation is simple, and the risk of local hot spots at the bottom and the wall of the reactor caused by ethylene is avoided.
Description
Technical Field
The invention relates to the technical field of polypropylene resin, in particular to high-transparency high-toughness low-isotacticity polypropylene thermoforming resin and a preparation process thereof.
Background
Thermoforming is a more specific plastic processing method for processing thermoplastic sheets into various products. The sheet is clamped on a frame and heated to a softening state, under the action of external force (vacuum, air pressure or mechanical pressure), the sheet is tightly attached to the molded surface of the mold so as to obtain a shape similar to the molded surface, and after cooling and shaping, the product is finished. The thermoforming transparent polypropylene resin has the characteristics of high transparency, good toughness, high glossiness and high temperature resistance, is widely applied to the fields of packaging materials, thermoforming utensils, medical supplies and the like, and can be made into disposable lunch boxes, water cups, dishes, trays, yogurt cups, jelly cups, stationery, automobile parts, electric appliance shells, seats and the like. In recent years, with the development of thermoforming technology, the market of thermoformed products is expanding, and the demand for special materials for thermoforming is increasing.
Currently, the materials for thermoforming are Polystyrene (PS), polyethylene terephthalate (PET), polyvinyl chloride (PVC) and polypropylene (PP). However, PVC contains harmful substances such as plasticizer and the like, and cannot be used for food packaging; PS and PET have poor heat resistance, and cannot be used for hot drinking cups and containers needing hot filling; the transparent modified PP has the characteristics of no toxicity, light weight and low price, and can be used for manufacturing clean thermoformed beverage cups.
Many manufacturers currently use conventional homopolymeric PP, such as T30S, for thermoformed articles. However, PP homopolymer has poor rigidity and toughness balance, and can cause undesirable product details, incomplete molding and cracking in the production process, product damage can be caused in the transportation process, and the product is fragile at low temperature, and meanwhile, the product has insufficient rigidity, and poor heat resistance and transparency. Downstream manufacturers generally add a transparent nucleating agent, polyethylene resin and an elastomer into homopolymerized polypropylene and increase the wall thickness to improve the transparency, flexibility and rigidity of products so as to meet the use requirements of users. However, the problems of unstable product quality, large fluctuation of transparency of the prepared water cup, uneven wall thickness, insufficient heat resistance and the like are caused. In order to solve the problem, domestic petrochemical manufacturers such as petrochemical plants, donghua energy plants and the like develop random copolymer polypropylene thermoforming materials.
The invention patent of publication No. CN104163881A discloses "a special resin for thermoforming of random copolymerization polypropylene with wide molecular weight distribution and a preparation method", on a Spheripol process unit, a catalyst with wide molecular weight distribution is adopted to produce a special resin for thermoforming of random copolymerization polypropylene with wide molecular weight distribution, a preparation method of the special resin for thermoforming of random copolymerization polypropylene with wide molecular weight distribution is designed, and particularly a novel catalyst with wide molecular weight distribution is adopted; the invention changes the catalyst, the prior device adopts the traditional Ziegler-Natta catalyst, and the produced random copolymerization polypropylene product has narrow molecular weight distribution, mw/Mn is usually less than or equal to 3.5; the invention relates to a preparation method for producing random copolymerization polypropylene resin with wider molecular weight distribution (Mw/Mn = 5.0-7.0) on a Spheripol process single-ring pipe polypropylene device.
The invention patent of publication No. CN105754232A discloses a heat-resistant high-rigidity high-toughness transparent thermo-forming polypropylene material and a preparation process thereof, the crystallization temperature is 120-122 ℃, the thermal deformation temperature is 88-96 ℃, the tensile yield strength is 34-36MPa, the flexural modulus is 1500-1650MPa, and the cantilever beam impact strength is 5.0-6.0KJ/m 2 Haze 28-38%, polymerized by the following method: in the presence of a catalyst and an external electron donor, adding propylene and ethylene into a double-loop reactor to carry out polymerization reaction, controlling the temperature of the double-loop reactor to be 70 +/-1 ℃, the reaction pressure to be 3.7-4.0MPa, the adding amount of the propylene to be 98-99.6%, the adding amount of the ethylene to be 0.4-2.0%, the adding amount of hydrogen in a first loop to be 0.04-0.06%, and the adding amount of hydrogen in a second loop to be 0.50-0.55%, obtaining polypropylene with the bonding amount of the ethylene of 0.4-2.0% and the melt flow rate of 2.5-3.5g/10min, then adding a main antioxidant, an auxiliary antioxidant, an acid scavenger and a nucleating agent to mix, extruding and granulating to obtain the heat-resistant high-rigidity high-toughness transparent thermoforming polypropylene material.
The invention patent of publication No. CN110527197A discloses "a random copolymerization polypropylene thermal forming resin and its preparation method and application" discloses a random copolymerization polypropylene thermal forming resin and its preparation method, the preparation method comprises mixing catalyst system, hydrogen, propylene and ethylene to carry out the first step polymerization reaction of propylene and ethylene, to obtain random copolymerization polypropylene; adding 1,3, 5-trimethyl-2, 4, 6-tri (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene serving as a main antioxidant, tri (2, 4-di-tert-butylphenyl) phosphite serving as an auxiliary antioxidant, calcium stearate serving as an acid scavenger, a sorbitol nucleating agent and an aldehyde remover into random copolymer polypropylene, mixing, and extruding and granulating to obtain the random copolymer polypropylene thermal forming resin.
The invention patent with publication number CN110577702A discloses a transparent rigidity-toughness balanced thermal forming homopolymerized polypropylene resin and a preparation method and application thereof, which comprises polypropylene, a main antioxidant 1010, an auxiliary antioxidant 168, an acid scavenger calcium stearate and a nucleating agent. The invention also discloses a preparation method of the transparent rigidity-toughness balanced thermoforming homopolymerized polypropylene resin, which comprises the steps of adding propylene and hydrogen into a Unipol gas-phase fluidized reactor for polymerization reaction in the presence of a main catalyst SHAPM 201, a cocatalyst triethylaluminum and an external electron donor n-propyl trimethoxy silane, and adjusting the content of xylene soluble substances of the powder to obtain polypropylene powder; then adding the main antioxidant 1010, the auxiliary antioxidant 168, the acid scavenger calcium stearate and the nucleating agent, mixing, and carrying out melt extrusion and granulation by a double screw to obtain the resin. The homo-polypropylene xylene soluble substance prepared by the method is 2.8 to 3.8 percent, and the impact strength of the simply supported beam is 3.13 to 3.57KJ/m 2 The haze value (1 mm) is 22 to 51%, and the toughness and transparency cannot reach the level of random copolymerization.
As for the preparation method of the special material for thermoforming the high-permeability high-toughness polypropylene, the impact strength of the homo-polypropylene simple supported beam is 3.0 to 3.50KJ/m 2 The haze value (1 mm) is 22-51%, and the toughness and the transparency can not reach the level of the special random copolymerization thermoforming material. However, the preparation of random copolymerized polypropylene requires the addition of a certain amount of ethylene, which requires solving the problem of ethylene source, and there are generally two schemes: the first is the matched ethylene production device; secondly, the ethylene adding system is designed, and the additional cost is increased when ethylene is purchased externally. Meanwhile, the reaction rate constant of ethylene is much higher than that of propylene, the activity of the catalyst is increased, and the activity is more and more severe along with the continuous increase of the addition of ethylene, so that the condensation state and the static balance of the reactor are damaged, and when static electricity in the reactor cannot be effectively led out and reaction heat cannot be rapidly withdrawn, local hot spots are easily caused at the bottom and the wall of the reactor.
Therefore, based on the situation, the scheme provides the high-permeability high-toughness low-isotacticity polypropylene thermoforming resin and the preparation process thereof so as to improve the toughness and comprehensive performance of polypropylene.
Disclosure of Invention
The invention aims to provide a high-permeability high-toughness low-isotacticity polypropylene thermoforming resin and a preparation process thereof, overcomes the defect that the conventional homopolymerization thermoforming polypropylene cannot reach the performance index of random copolymerization thermoforming polypropylene, and provides the high-permeability high-toughness low-isotacticity polypropylene thermoforming resin and the preparation process thereof.
In order to solve the technical problems, the invention provides the following technical scheme:
the high-permeability high-toughness low-isotacticity polypropylene thermoforming resin comprises the following components in percentage by mass: 0.04-0.1% of main antioxidant, 0.04-0.1% of auxiliary antioxidant, 0.03-0.06% of acid scavenger, 0.1-0.25% of nucleating agent and the balance of polypropylene.
According to an optimized scheme, the resin further comprises an initiator, 1, 6-hexanediol diacrylate and a comonomer, wherein the initiator is 0.03-0.04 wt%, the comonomer is 1-2 wt%, and the 1, 6-hexanediol diacrylate is 2-3 wt%.
According to an optimized scheme, the antioxidant system can maintain the oxidation resistance and aging resistance of polypropylene in the processes of granulation processing, storage and use. The antioxidant system comprises a primary antioxidant and a secondary antioxidant, wherein the primary antioxidant includes, but is not limited to, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione; the auxiliary antioxidant is phosphite ester antioxidant, including but not limited to any one of alkyl phosphite ester and bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite ester; the mass ratio of the main antioxidant to the auxiliary antioxidant is (1.
According to an optimized scheme, the acid scavenger is calcium stearate, and the nucleating agent is a dibenzylidene sorbitol nucleating agent with an asymmetric structure. The nucleating agent adopts a fourth generation transparent nucleating agent: dibenzylidene sorbitol nucleating agents with asymmetric structures. The nucleating agent has a melting point obviously lower than that of the first-generation DBS, the second-generation MDBS and the third-generation DMDBS, has a melting point of 195 ℃, is good in dispersity, high in nucleating efficiency and odorless, and does not need to be added with an aldehyde remover. The addition of a small amount of the nucleating agent can obviously improve the transparency and rigidity of the material, increase the crystallization temperature of the material and increase the molding rate of the material.
In an optimized scheme, the comonomer is mainly obtained by copolymerizing 1, 6-hexanediol diacrylate and an ultraviolet absorbent containing double bonds; the initiator is dicumyl peroxide; the ultraviolet absorbent containing double bonds is any one of 2-hydroxy-4- (3-methacrylic acid-2-hydroxyl propoxy) benzotriazole and 2- (-hydroxy-4-undecenylphenyl) -2H-benzotriazole.
In order to improve the strength and the aging resistance of the resin, a long-chain acrylate monomer 1, 6-hexanediol diacrylate is introduced into the scheme, and grafting copolymerization is carried out under the action of an initiator so as to improve the strength and the impact resistance of the product; meanwhile, in order to improve the ultraviolet aging resistance of the scheme, 1, 6-hexanediol diacrylate and an ultraviolet absorbent containing double bonds are subjected to copolymerization reaction to obtain a comonomer, and a reactive ultraviolet-resistant comonomer is grafted while an acrylate long chain is introduced, so that the ultraviolet aging resistance of the product is improved; meanwhile, in order to ensure the generation of a polypropylene long-chain branched structure, the scheme limits that the using amount of the comonomer is 1-2 percent and the using amount of the 1, 6-hexanediol diacrylate is 2-3 percent, so that the product can have the most excellent mechanical property and ultraviolet resistance.
Here also to be explained: the reactive comonomer is introduced into the resin, so that the problem of migration of the anti-ultraviolet agent caused by use time lapse can be avoided, the long-time anti-ultraviolet aging of the product can be realized, and the performance is excellent.
The optimized scheme is that the preparation process of the high-permeability high-toughness low-isotacticity polypropylene thermoforming resin comprises the following steps:
(1) Under the mixed catalysis condition of a main catalyst, a cocatalyst and an external electron donor, adding propylene into a gas phase reactor for polymerization reaction to obtain polypropylene with the isotacticity of 94.5-96.0% and the melt flow rate of 2.0-3.0 g/10 min;
(2) Premixing the polypropylene, the main antioxidant, the auxiliary antioxidant, the acid scavenger and the nucleating agent, and extruding and granulating to obtain a finished product.
In the invention, the main antioxidant, the auxiliary antioxidant, the acid scavenger and the nucleating agent can be mixed to prepare a fine strip composition, the fine strip composition is used as a compound agent to be added into polypropylene powder, and then extrusion granulation is carried out.
According to an optimized scheme, in the step (1), the external electron donor is an alkoxysilane compound; the catalyst promoter is triethyl aluminum, the main catalyst provides titanium ions, wherein the aluminum-titanium ratio of the triethyl aluminum to the main catalyst is 40-60, and the aluminum-silicon ratio of the triethyl aluminum to the external electron donor is 4.0-5.0.
The device adopted by the invention is a Unipol vapor phase method polypropylene device; the catalyst system is a main catalyst, a cocatalyst and an external electron donor, wherein titanium ions come from the main catalyst, aluminum ions come from the cocatalyst, and the addition amount of triethyl aluminum is controlled by setting the aluminum-titanium ratio of the aluminum ions to the titanium ions to be 40-60; the external electron donor is an alkoxy silane compound. The silicon ions come from an external electron donor, and the adding amount of the external electron donor is controlled by setting the ratio of aluminum ions to silicon ions to aluminum-silicon ratio to be 4.0-5.0.
The main catalyst is a fourth-generation Z-N catalyst, and comprises a titanium compound containing a titanium-halogen bond, a carrier magnesium chloride and an internal electron donor phthalic acid dimethyl ester. The carrier liquid of the main catalyst is 70-120 kg/h.
In the optimized scheme, in the step (1), during the polymerization reaction, the temperature of the gas phase reactor is 68-70 ℃, the reaction pressure is 3.2-3.4 MPa, the adding amount of hydrogen is 0.15-0.30 mol%, the adding amount of nitrogen is 8-10 mol%, and the mole percentage ratio of the adding amounts of hydrogen and propylene is 0.002-0.004.
In the optimized scheme, in the step (2), the extrusion temperature is 230-240 ℃ during extrusion granulation.
The optimized scheme is the step (2), and the specific process comprises the following steps:
premixing polypropylene, a main antioxidant, an auxiliary antioxidant, an acid scavenger and a nucleating agent to obtain a premix;
mixing 1, 6-hexanediol diacrylate, a double-bond-containing ultraviolet absorbent and azobisisobutyronitrile, and carrying out copolymerization reaction to obtain a comonomer; the ultraviolet absorbent containing double bonds is any one of 2-hydroxy-4- (3-methacrylic acid-2-hydroxyl propoxy) benzotriazole and 2- (-hydroxy-4-undecenylphenyl) -2H-benzotriazole;
mixing a comonomer, 1, 6-hexanediol diacrylate, an initiator and acetone to obtain a monomer liquid; and (3) dripping the monomer into the premix, uniformly stirring, standing for 20-24h, and extruding and granulating to obtain a finished product.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, by polymerizing in a Unipol gas-phase fluidized reactor, production process parameters such as hydrogen concentration, aluminum-silicon ratio and the like are controlled, the homopolymerized polypropylene powder with proper melt flow rate, high xylene content, low isotacticity and good toughness is obtained, no ethylene monomer is required to be added, the operation is simple, and the risk of local hot spots at the bottom and the wall of the reactor caused by ethylene is avoided.
(2) The invention reduces the isotacticity of the polypropylene to 94.5-96.0%, increases the random content in the polypropylene, reduces the crystallinity of the polypropylene, improves the melt strength, improves the melt-sagging property of the polypropylene, increases the melting range and widens the temperature range of the hot forming processing.
(3) The invention adopts the fourth generation transparent nucleating agent (dibenzylidene sorbitol nucleating agent with an asymmetric structure), has low melting point, good dispersibility, high nucleating efficiency and no odor, does not need to add an aldehyde remover, greatly improves the transparency of polypropylene, does not reduce the toughness, has the characteristics of high transparency, high toughness and quick formability, is comparable to random copolymerization thermoforming polypropylene in the aspects of transparency and toughness, and is suitable for producing products such as disposable drinking cups, tableware, jelly cups, milk tea cups, stationery sheets and the like by using a thermoforming process.
(4) According to the invention, 1, 6-hexanediol diacrylate and a comonomer are introduced, so that the ultraviolet aging resistance of the product can be ensured while the strength and the impact resistance of the thermal forming resin are improved, the migration of an ultraviolet resistant agent is avoided, the ultraviolet aging resistance is lasting, and the practicability is better.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In this example, the main catalyst
C201, the external electron donor is alkyl trialkoxysilane and a cocatalyst of triethyl aluminum. The primary antioxidant is an antioxidant 1010, and the secondary antioxidant is an antioxidant 168; the acid scavenger is calcium stearate, and the fourth generation transparent nucleating agent is specifically dibenzylidene sorbitol nucleating agent with asymmetric structure, and is specifically RY-1130; the rigidity-enhancing nucleating agent is specifically a substituted aryl heterocyclic phosphate nucleating agent, specifically NA-62A.
Example 1:
injecting materials such as nitrogen, hydrogen, propylene and the like into a gas phase reactor, establishing reaction conditions of 85mol% of propylene, 5.2mol% of propane, 9.5mol% of nitrogen and 0.23mol% of hydrogen, wherein the molar percentage of the added amount of the hydrogen and the propylene is 0.0027, and the rest is ethane, ethylene and carbon dioxide, and the concentration is about 0.1mol%; triethyl aluminum and external electron donor are injected into the reactor in 2 times of normal dosage, and a main catalyst is injected into the reactor after pretreatment for 0.5h to initiate the reaction. In the polymerization reaction, the total reaction pressure is 3.25MPa, the propylene partial pressure is 2.85MPa, the reaction temperature is 69 ℃, the catalyst carrier liquid is 80kg/h, the aluminum-titanium ratio of the addition ratio of triethyl aluminum to the main catalyst is controlled to be 45, the aluminum-silicon ratio of the addition ratio of the triethyl aluminum to the external electron donor is controlled to be 4.0, the reaction load is controlled to be 36.0t/h, and the homopolymerized polypropylene powder with the melt flow rate controlled to be 3.5g/10min is obtained through polymerization.
0.05wt% of main antioxidant, 0.10wt% of auxiliary antioxidant, 0.05wt% of acid scavenger, 0.15wt% of fourth-generation transparent nucleating agent and the balance of homopolymerized polypropylene powder are premixed, extruded and granulated, and the extrusion temperature is 230 ℃, so that a finished product is obtained.
Example 2:
injecting materials such as nitrogen, hydrogen, propylene and the like into a gas phase reactor, establishing reaction conditions of 85mol% of propylene concentration, 5.2mol% of propane concentration, 9.5mol% of nitrogen concentration and 0.23mol% of hydrogen concentration, wherein the molar percentage value of the added amount of the hydrogen and the propylene is 0.0027, and the rest is ethane, ethylene and carbon dioxide, and the concentration is about 0.1mol%; triethyl aluminum and external electron donor are injected into the reactor in 2 times of normal dosage, and a main catalyst is injected into the reactor after pretreatment for 0.5h to initiate the reaction. In the polymerization reaction, the total reaction pressure is 3.25MPa, the propylene partial pressure is 2.85MPa, the reaction temperature is 69 ℃, the catalyst carrier liquid is 80kg/h, the aluminum-titanium ratio of the addition ratio of triethyl aluminum to the main catalyst is controlled to be 45, the aluminum-silicon ratio of the addition ratio of the triethyl aluminum to the external electron donor is controlled to be 4.0, the reaction load is controlled to be 36.0t/h, and the homopolymerized polypropylene powder with the melt flow rate controlled to be 3.5g/10min is obtained through polymerization.
0.05wt% of main antioxidant, 0.10wt% of auxiliary antioxidant, 0.05wt% of acid scavenger, 0.2wt% of fourth-generation transparent nucleating agent and the balance of homopolymerized polypropylene powder are premixed, extruded and granulated, and the extrusion temperature is 235 ℃, so that a finished product is obtained.
Example 3:
injecting materials such as nitrogen, hydrogen, propylene and the like into a gas phase reactor, establishing reaction conditions of 85mol% of propylene concentration, 5.2mol% of propane concentration, 9.5mol% of nitrogen concentration and 0.23mol% of hydrogen concentration, wherein the molar percentage value of the added amount of the hydrogen and the propylene is 0.0027, and the rest is ethane, ethylene and carbon dioxide, and the concentration is about 0.1mol%; triethyl aluminum and external electron donor are injected into the reactor in 2 times of normal dosage, and a main catalyst is injected into the reactor after pretreatment for 0.5h to initiate the reaction. In the polymerization reaction, the total reaction pressure is 3.25MPa, the propylene partial pressure is 2.85MPa, the reaction temperature is 69 ℃, the catalyst carrier liquid is 80kg/h, the aluminum-titanium ratio of the addition ratio of triethyl aluminum to the main catalyst is controlled to be 45, the aluminum-silicon ratio of the addition ratio of the triethyl aluminum to the external electron donor is controlled to be 4.0, the reaction load is controlled to be 36.0t/h, and the homopolymerized polypropylene powder with the melt flow rate controlled to be 3.5g/10min is obtained through polymerization.
0.05wt% of main antioxidant, 0.10wt% of auxiliary antioxidant, 0.05wt% of acid scavenger, 0.25wt% of fourth-generation transparent nucleating agent and the balance of homopolymerized polypropylene powder are premixed, extruded and granulated, and the extrusion temperature is 235 ℃, so that a finished product is obtained.
Example 4:
injecting materials such as nitrogen, hydrogen, propylene and the like into a gas phase reactor, establishing reaction conditions of 85mol% of propylene concentration, 5.2mol% of propane concentration, 9.5mol% of nitrogen concentration and 0.20mol% of hydrogen concentration, wherein the molar percentage value of the added amount of the hydrogen and the propylene is 0.0023, and the rest is ethane, ethylene and carbon dioxide, and the concentration is about 0.1mol%; triethyl aluminum and external electron donor are injected into the reactor in 2 times of normal dosage, and a main catalyst is injected into the reactor after pretreatment for 0.5h to initiate the reaction. In the polymerization reaction, the total reaction pressure is 3.25MPa, the propylene partial pressure is 2.85MPa, the reaction temperature is 69 ℃, the catalyst carrier liquid is 80kg/h, the aluminum-titanium ratio of the addition ratio of triethyl aluminum to the main catalyst is controlled to be 45, the aluminum-silicon ratio of the addition ratio of the triethyl aluminum to the external electron donor is controlled to be 4.0, the reaction load is controlled to be 36.0t/h, and the homopolymerized polypropylene powder with the melt flow rate controlled to be 2.8g/10min is obtained through polymerization.
0.05wt% of main antioxidant, 0.10wt% of auxiliary antioxidant, 0.05wt% of acid scavenger, 0.22wt% of fourth-generation transparent nucleating agent and the balance of homopolymerized polypropylene powder are premixed, extruded and granulated, and the extrusion temperature is 235 ℃, so that a finished product is obtained.
Example 5:
injecting materials such as nitrogen, hydrogen, propylene and the like into a gas phase reactor, establishing reaction conditions of 85mol% of propylene, 5.2mol% of propane, 9.5mol% of nitrogen and 0.17mol% of hydrogen, wherein the molar percentage of the added amount of the hydrogen and the propylene is 0.0020, and the rest is ethane, ethylene and carbon dioxide, and the concentration is about 0.1mol%; triethyl aluminum and external electron donor are injected into the reactor in 2 times of normal dosage, and a main catalyst is injected into the reactor after pretreatment for 0.5h to initiate the reaction. In the polymerization reaction, the total reaction pressure is 3.25MPa, the propylene partial pressure is 2.85MPa, the reaction temperature is 69 ℃, the catalyst carrier liquid is 80kg/h, the aluminum-titanium ratio of the addition ratio of triethyl aluminum to the main catalyst is controlled to be 45, the aluminum-silicon ratio of the addition ratio of the triethyl aluminum to the external electron donor is controlled to be 4.4, the reaction load is controlled to be 36.0t/h, and the homopolymerized polypropylene powder with the melt flow rate controlled to be 2.8g/10min is obtained through polymerization.
0.05wt% of main antioxidant, 0.10wt% of auxiliary antioxidant, 0.05wt% of acid scavenger, 0.22wt% of fourth-generation transparent nucleating agent and the balance of homopolymerized polypropylene powder are premixed, extruded and granulated, and the extrusion temperature is 235 ℃, so that a finished product is obtained.
Example 6:
injecting materials such as nitrogen, hydrogen, propylene and the like into a gas phase reactor, establishing reaction conditions of 85mol% of propylene concentration, 5.2mol% of propane concentration, 9.6mol% of nitrogen concentration and 0.14mol% of hydrogen concentration, wherein the molar percentage value of the added amount of the hydrogen and the propylene is 0.0017, and the rest is ethane, ethylene and carbon dioxide, and the concentration is about 0.1mol%; triethyl aluminum and external electron donor are injected into the reactor in 2 times of normal dosage, and a main catalyst is injected into the reactor after pretreatment for 0.5h to initiate the reaction. In the polymerization reaction, the total reaction pressure is 3.25MPa, the propylene partial pressure is 2.85MPa, the reaction temperature is 69 ℃, the catalyst carrier liquid is 80kg/h, the aluminum-titanium ratio of the addition ratio of triethyl aluminum to the main catalyst is controlled to be 45, the aluminum-silicon ratio of the addition ratio of the triethyl aluminum to the external electron donor is controlled to be 4.8, the reaction load is controlled to be 36.0t/h, and the homopolymerized polypropylene powder with the melt flow rate controlled to be 2.8g/10min is obtained through polymerization.
0.05wt% of main antioxidant, 0.10wt% of auxiliary antioxidant, 0.05wt% of acid scavenger, 0.22wt% of fourth-generation transparent nucleating agent and the balance of homopolymerized polypropylene powder are premixed, extruded and granulated, and the extrusion temperature is 235 ℃, so that a finished product is obtained.
Comparative example 1:
injecting materials such as nitrogen, hydrogen, propylene and the like into a gas phase reactor, establishing reaction conditions of 85mol% of propylene, 5.2mol% of propane, 9.5mol% of nitrogen and 0.24mol% of hydrogen, wherein the molar percentage of the added amount of the hydrogen and the propylene is 0.0028, and the rest is ethane, ethylene and carbon dioxide, and the concentration is about 0.1mol%; triethyl aluminum and external electron donor are injected into the reactor in 2 times of normal dosage, and a main catalyst is injected into the reactor after pretreatment for 0.5h to initiate the reaction. In the polymerization reaction, the total reaction pressure is 3.25MPa, the propylene partial pressure is 2.85MPa, the reaction temperature is 69 ℃, the catalyst carrier liquid is 80kg/h, the aluminum-titanium ratio of the addition ratio of triethyl aluminum to the main catalyst is controlled to be 45, the aluminum-silicon ratio of the addition ratio of the triethyl aluminum to the external electron donor is controlled to be 3.9, the reaction load is controlled to be 35.0t/h, and the homopolymerized polypropylene powder with the melt flow rate controlled to be 3.7g/10min is obtained through polymerization.
0.04wt% of main antioxidant, 0.08wt% of auxiliary antioxidant, 0.04wt% of acid scavenger and the balance of homopolymerized polypropylene powder are premixed, extruded and granulated, and the extrusion temperature is 230 ℃, so that a finished product is obtained.
Comparative example 2:
injecting materials such as nitrogen, hydrogen, propylene and the like into a gas phase reactor, establishing reaction conditions of 85mol% of propylene concentration, 5.2mol% of propane concentration, 9.4mol% of nitrogen concentration and 0.32mol% of hydrogen concentration, wherein the molar percentage value of the added amount of the hydrogen and the propylene is 0.0038, and the rest is ethane, ethylene and carbon dioxide, and the concentration is about 0.1mol%; triethyl aluminum and external electron donor are injected into the reactor in 2 times of normal dosage, and a main catalyst is injected into the reactor after pretreatment for 0.5h to initiate the reaction. In the polymerization reaction, the total reaction pressure is 3.25MPa, the propylene partial pressure is 2.85MPa, the reaction temperature is 69 ℃, the catalyst carrier liquid is 80kg/h, the aluminum-titanium ratio of the addition ratio of triethyl aluminum to the main catalyst is controlled to be 45, the aluminum-silicon ratio of the addition ratio of the triethyl aluminum to the external electron donor is controlled to be 7.6, the reaction load is controlled to be 35.0t/h, and the homopolymerized polypropylene powder with the melt flow rate controlled to be 3.7g/10min is obtained through polymerization.
0.04wt% of main antioxidant, 0.08wt% of auxiliary antioxidant, 0.04wt% of acid scavenger and the balance of homopolymerized polypropylene powder are premixed, extruded and granulated, and the extrusion temperature is 235 ℃, so that a finished product is obtained.
Comparative example 3:
injecting materials such as nitrogen, hydrogen, propylene and the like into a gas phase reactor, establishing reaction conditions of 85mol% of propylene concentration, 5.2mol% of propane concentration, 9.5mol% of nitrogen concentration and 0.23mol% of hydrogen concentration, wherein the molar percentage value of the added amount of the hydrogen and the propylene is 0.0027, and the rest is ethane, ethylene and carbon dioxide, and the concentration is about 0.1mol%; triethyl aluminum and external electron donor are injected into the reactor in 2 times of normal dosage, and a main catalyst is injected into the reactor after pretreatment for 0.5h to initiate the reaction. In the polymerization reaction, the total reaction pressure is 3.25MPa, the propylene partial pressure is 2.85MPa, the reaction temperature is 69 ℃, the catalyst carrier liquid is 80kg/h, the aluminum-titanium ratio of the addition ratio of triethyl aluminum to the main catalyst is controlled to be 45, the aluminum-silicon ratio of the addition ratio of the triethyl aluminum to the external electron donor is controlled to be 4.0, the reaction load is controlled to be 36.0t/h, and the homopolymerized polypropylene powder with the melt flow rate controlled to be 3.5g/10min is obtained through polymerization.
0.05wt% of main antioxidant, 0.10wt% of auxiliary antioxidant, 0.05wt% of acid scavenger, 0.1wt% of rigidity increasing nucleating agent and the balance of homopolymerized polypropylene powder are premixed, extruded and granulated, and the extrusion temperature is 240 ℃, so that a finished product is obtained.
Example 7: using example 6 as a control experiment, comonomer was introduced and the remaining process parameters were unchanged.
Injecting materials such as nitrogen, hydrogen, propylene and the like into a gas phase reactor, establishing reaction conditions of 85mol% of propylene concentration, 5.2mol% of propane concentration, 9.6mol% of nitrogen concentration and 0.14mol% of hydrogen concentration, wherein the molar percentage value of the added amount of the hydrogen and the propylene is 0.0017, and the rest is ethane, ethylene and carbon dioxide, and the concentration is about 0.1mol%; triethyl aluminum and external electron donor are injected into the reactor in 2 times of normal dosage, and a main catalyst is injected into the reactor after pretreatment for 0.5h to initiate the reaction. In the polymerization reaction, the total reaction pressure is 3.25MPa, the propylene partial pressure is 2.85MPa, the reaction temperature is 69 ℃, the catalyst carrier liquid is 80kg/h, the aluminum-titanium ratio of the addition ratio of triethyl aluminum to the main catalyst is controlled to be 45, the aluminum-silicon ratio of the addition ratio of the triethyl aluminum to the external electron donor is controlled to be 4.8, the reaction load is controlled to be 36.0t/h, and the homopolymerized polypropylene powder with the melt flow rate controlled to be 2.8g/10min is obtained through polymerization.
The composite material is prepared by 0.05wt% of main antioxidant, 0.10wt% of auxiliary antioxidant, 0.05wt% of acid scavenger and 0.22wt% of fourth-generation transparent nucleating agent, wherein the dosage of the initiator is 0.03wt%, the dosage of the comonomer is 1.5wt%, the dosage of the 1, 6-hexanediol diacrylate is 2.5wt%, and the balance is the dosage of homopolymerized polypropylene powder;
premixing polypropylene, a main antioxidant, an auxiliary antioxidant, an acid scavenger and a nucleating agent to obtain a premix;
mixing 1, 6-hexanediol diacrylate, 2-hydroxy-4- (3-methacrylic acid-2-hydroxyl propoxy) benzotriazole and azobisisobutyronitrile, dissolving butyl acetate, and performing copolymerization reaction at 80 ℃ to obtain a comonomer; the ultraviolet absorbent containing double bonds is 2-hydroxy-4- (3-methacrylic acid-2-hydroxyl propoxy) benzotriazole. Wherein the mass ratio of 1, 6-hexanediol diacrylate to 2-hydroxy-4- (3-methacrylic acid-2-hydroxyl propoxy) benzotriazole is 3:1; the dosage of the azodiisobutyronitrile is 4wt% of the total mass of the 1, 6-hexanediol diacrylate and the 2-hydroxy-4- (3-methacrylic acid-2-hydroxyl propoxy) benzotriazole.
Mixing a comonomer, 1, 6-hexanediol diacrylate, an initiator and acetone to obtain a monomer liquid; and (3) dripping the monomer into the premix, uniformly stirring, standing for 24h, and extruding and granulating at 235 ℃ to obtain a finished product.
In summary of the above examples 1-7 and comparative examples 1-3, the specific processing parameters are shown in Table 1 below:
detection experiment:
1. taking the finished resin prepared in the examples 1-7 and the comparative examples 1-3, carrying out performance detection, wherein the specific detection data are shown in the following table 2, the tensile yield stress test standard is GB/T1040.2-2006, the sample size is 1A type, and the tensile speed is 50mm/min; the simple supported beam has the impact strength test standard of GB/T1043.1-2008 and the haze test standard of GB/T2410-2008; the oxidative induction phase test standard is GBT 19466.6-2009.
And (3) ultraviolet aging resistance test: the light source is a xenon arc lamp, and the light irradiation intensity is 0.50W/m 2 (340 nm detection point), after 2000 hours of irradiation, the impact strength of the simply supported beam of the standard specimen was measured before and after the irradiation, and the impact strength retention rate was calculated.
And (4) conclusion: from the above test results it can be seen that:
(1) As can be seen from examples 1 to 3, comparative example 1 and comparative example 3, the haze of the product is greatly reduced, the transparency is obviously improved, and the rigidity and the toughness of the product are improved after the transparent nucleating agent is added. With the increase of the concentration of the transparent nucleating agent, the haze of the product is gradually reduced when the concentration reaches more than 2000ppm, the mechanical property performance is good, and the toughness is not obviously reduced. After the stiffening nucleating agent is added, the haze of the product is not reduced as much as that of the transparent nucleating agent, and the rigidity of the product is obviously increased.
(2) It can be seen from examples 4 to 5 that the impact strength of the simply supported beam of the product of the invention is increased and the toughness is significantly improved with the decrease of the isotacticity.
(3) As can be seen from example 6 and comparative example 1, the transparency and toughness of the product of the present invention are close to those of the random copolymerized thermoformed polypropylene resin, and the process improves the melt strength of the homopolymerized polypropylene, improves the sag property, increases the melting range and widens the temperature range of the thermoformable process.
(3) As can be seen from the comparison between example 7 and comparative example 4, the finished resin has excellent UV aging resistance due to the existence of the comonomer, and the UV aging resistance is durable and long-lasting.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described above, or equivalents may be substituted for elements thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A high-permeability high-toughness low-isotacticity polypropylene thermal forming resin is characterized in that: the resin comprises the following components in percentage by mass: 0.04-0.1% of main antioxidant, 0.04-0.1% of auxiliary antioxidant, 0.03-0.06% of acid scavenger, 0.1-0.25% of nucleating agent and the balance of polypropylene.
2. The high permeability, high toughness and low isotacticity polypropylene thermoforming resin as claimed in claim 1, wherein: the resin also comprises an initiator, 1, 6-hexanediol diacrylate and a comonomer, wherein the amount of the initiator is 0.03-0.04 wt%, the amount of the comonomer is 1-2 wt%, and the amount of the 1, 6-hexanediol diacrylate is 2-3 wt%.
3. The high permeability, high toughness and low isotacticity polypropylene thermoforming resin as claimed in claim 1, wherein: the main antioxidant is 1,3, 5-tri (4-tertiary butyl-3-hydroxy-2, 6-dimethyl benzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione; the auxiliary antioxidant is any one of alkyl phosphite ester and bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite ester; the mass ratio of the main antioxidant to the auxiliary antioxidant is (1.
4. The high permeability, high toughness and low isotacticity polypropylene thermoforming resin as claimed in claim 1, wherein: the acid scavenger is calcium stearate, and the nucleating agent is dibenzylidene sorbitol nucleating agent with an asymmetric structure.
5. The high-permeability high-toughness low-isotacticity polypropylene thermoforming resin as claimed in claim 2, wherein: the comonomer is mainly obtained by copolymerizing 1, 6-hexanediol diacrylate and an ultraviolet absorbent containing double bonds; the initiator is dicumyl peroxide; the ultraviolet absorbent containing double bonds is any one of 2-hydroxy-4- (3-methacrylic acid-2-hydroxyl propoxy) benzotriazole and 2- (-hydroxy-4-undecenylphenyl) -2H-benzotriazole.
6. A preparation process of high-permeability high-toughness low-isotacticity polypropylene thermoforming resin is characterized by comprising the following steps of: the method comprises the following steps:
(1) Adding propylene into a gas phase reactor under the mixed catalysis condition of a main catalyst, a cocatalyst and an external electron donor, and carrying out polymerization reaction to obtain polypropylene;
(2) Premixing the polypropylene, the main antioxidant, the auxiliary antioxidant, the acid scavenger and the nucleating agent, and extruding and granulating to obtain a finished product.
7. The preparation process of the high-permeability high-toughness low-isotacticity polypropylene thermoforming resin as claimed in claim 6, wherein the preparation process comprises the following steps: in the step (1), the external electron donor is an alkoxysilane compound; the catalyst promoter is triethyl aluminum, the main catalyst provides titanium ions, wherein the aluminum-titanium ratio of the triethyl aluminum to the main catalyst is 40-60, and the aluminum-silicon ratio of the triethyl aluminum to the external electron donor is 4.0-5.0.
8. The preparation process of the high-permeability high-toughness low-isotacticity polypropylene thermoforming resin as claimed in claim 6, wherein the preparation process comprises the following steps: in the step (1), during the polymerization reaction, the temperature of the gas phase reactor is 68-70 ℃, the reaction pressure is 3.2-3.4 MPa, the adding amount of hydrogen is 0.15-0.30 mol%, the adding amount of nitrogen is 8-10 mol%, and the mol percentage value of the adding amount of hydrogen and propylene is 0.002-0.004.
9. The preparation process of the high-permeability high-toughness low-isotacticity polypropylene thermoforming resin as claimed in claim 6, wherein the preparation process comprises the following steps: in the step (2), the extrusion temperature is 230-240 ℃ during extrusion granulation.
10. The preparation process of the high-permeability high-toughness low-isotacticity polypropylene thermoforming resin as claimed in claim 6, wherein the preparation process comprises the following steps: the specific process of the step (2) is as follows:
premixing polypropylene, a main antioxidant, an auxiliary antioxidant, an acid scavenger and a nucleating agent to obtain a premix;
mixing 1, 6-hexanediol diacrylate, a double-bond-containing ultraviolet absorbent and azobisisobutyronitrile, and carrying out copolymerization reaction to obtain a comonomer; the ultraviolet absorbent containing double bonds is any one of 2-hydroxy-4- (3-methacrylic acid-2-hydroxyl propoxy) benzotriazole and 2- (-hydroxy-4-undecenylphenyl) -2H-benzotriazole;
mixing a comonomer, 1, 6-hexanediol diacrylate, an initiator and acetone to obtain a monomer liquid; and (3) dripping the monomer into the premix, uniformly stirring, standing for 20-24h, and extruding and granulating to obtain a finished product.
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