CN121873473A - A ternary random copolymer polypropylene resin, its preparation method and application - Google Patents
A ternary random copolymer polypropylene resin, its preparation method and applicationInfo
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- CN121873473A CN121873473A CN202411438627.5A CN202411438627A CN121873473A CN 121873473 A CN121873473 A CN 121873473A CN 202411438627 A CN202411438627 A CN 202411438627A CN 121873473 A CN121873473 A CN 121873473A
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Abstract
本发明涉及聚丙烯材料领域，具体涉及一种三元共聚聚丙烯树脂及其制备方法与应用。所述共聚聚丙烯树脂中，三元无规共聚聚丙烯树脂基料为97‑99.6重量份，抗氧剂0.1‑0.3重量份，卤素吸收剂0.01‑0.06重量份，防粘剂0.1‑0.3重量份，爽滑剂0.1‑0.2重量份。通过将部分基料与添加剂先混合后，物理共混法或者通过熔融共混法制备混合物，将其添加到剩余基料中，物理共混后送进挤出机熔融挤出造粒，即得三元无规共聚聚丙烯树脂。本发明聚丙烯树脂具有起始熔融温度和熔点低、热封效果优异、爽滑性高等特点，特别适用于低温热封聚丙烯专用树脂质量提升使用。This invention relates to the field of polypropylene materials, specifically to a ternary copolymer polypropylene resin, its preparation method, and its application. In the copolymer polypropylene resin, the ternary random copolymer polypropylene resin base material comprises 97-99.6 parts by weight, antioxidant 0.1-0.3 parts by weight, halogen absorber 0.01-0.06 parts by weight, anti-sticking agent 0.1-0.3 parts by weight, and slip agent 0.1-0.2 parts by weight. A mixture is prepared by first mixing a portion of the base material with the additives, then using a physical blending method or a melt blending method. This mixture is added to the remaining base material, and after physical blending, it is fed into an extruder for melt extrusion granulation to obtain the ternary random copolymer polypropylene resin. The polypropylene resin of this invention has the characteristics of low initial melting temperature and melting point, excellent heat-sealing effect, and high slip properties, making it particularly suitable for improving the quality of low-temperature heat-sealing polypropylene resins.
Description
Technical Field
The invention relates to the field of polypropylene materials, in particular to ternary random copolymer polypropylene resin and a preparation method and application thereof.
Background
The ternary random copolymer polypropylene (ternary polypropylene or ternary PP) is a polymer formed by the copolymerization of three components of propylene, ethylene and butylene under the action of a catalyst in a polymerization reactor. Due to the introduction of ethylene and butene comonomer, the regularity of the polypropylene molecular chain is destroyed, and the crystallization capability of the molecular chain is further reduced, so that the melting temperature of the polymer is reduced. As a heat seal layer for coextruded films, the ternary polypropylene has the unique advantage of exhibiting a lower initial heat seal temperature (100 ℃ to 115 ℃), higher heat seal strength, and a wider heat seal window, good retort resistance, good low temperature impact properties. The ternary polymerization polypropylene is mainly used for polypropylene casting films (CPP), heat shrinkage films (POF) and biaxially oriented films (BOPP).
With the development of technology, the production speed of the film is required to be higher and higher, and in order to meet the requirement of a high-speed packaging production line, the heat sealing rate of the film heat sealing layer is required to be improved, that is, the initial heat sealing temperature and the heat sealing temperature should be reduced as much as possible. At present, the preparation of the ternary random copolymer polypropylene heat-sealing film special resin with low heat-sealing temperature and high heat-sealing strength is still a great technical difficulty.
In recent years, along with the pursuit of people on the aspects of refinement, attractive appearance and the like of packaging, higher optical performance requirements are put forward on the film, the film needs to have higher transparency, higher definition and low haze, and meanwhile, defects such as crystal points, white spots and the like exist on the surface of a plurality of films, so that the performances of the appearance, printing, heat sealing, compounding and the like of the film are seriously influenced, the rejection rate is obviously improved, the product grade and selling price are greatly reduced, and the film has become a common problem and a technical problem to be solved urgently in the PP film industry.
Disclosure of Invention
The invention aims to solve the problem that the special ternary random copolymer polypropylene heat-sealing film resin in the prior art is difficult to simultaneously have low heat-sealing temperature and high optical performance, and provides the ternary random copolymer polypropylene resin with high optical performance and a preparation method thereof.
The invention provides a ternary random copolymer polypropylene resin, wherein the ternary random copolymer polypropylene resin comprises ternary random copolymer polypropylene resin base material, an antioxidant, a halogen absorbent, an anti-sticking agent and a slipping agent;
the anti-sticking agent is silicon dioxide;
the silicon dioxide has porosity ranging from 0 to 40 percent and particle size ranging from 1 to 10 mu m.
The anti-sticking agent can improve the transparency of the prepared ternary random copolymer polypropylene film material, effectively reduce the defects of white spots and crystal points of the prepared ternary random copolymer polypropylene film material and improve the optical performance of the product. The polypropylene film material prepared from the ternary random copolymer polypropylene resin with the specific components has the advantages of low heat sealing temperature, high heat sealing strength and high optical performance.
In the ternary random copolymer polypropylene resin, 97-99.6 parts by weight of ternary random copolymer polypropylene resin base material, 0.1-0.3 part by weight of antioxidant, 0.01-0.06 part by weight of halogen absorbent, 0.1-0.3 part by weight of anti-sticking agent and 0.1-0.2 part by weight of slipping agent.
When the amounts of the components satisfy the above ranges, the stability, optical properties and slip properties of the polypropylene material prepared from the composition can be further improved.
Preferably, in the ternary random copolymer polypropylene resin base material, the content of structural units from propylene is 86-95 wt%, the content of structural units from butene is 4-10 wt%, and the content of structural units from ethylene is 1-4 wt%.
Preferably, in the ternary random copolymer polypropylene resin base material, the content of structural units from propylene is 89.5-92 wt%, the content of structural units from butene is 6-8 wt%, and the content of structural units from ethylene is 1.5-2.5 wt%;
Preferably, the melt mass flow rate of the ternary random copolymer polypropylene resin binder is 1-10g/10min, preferably 6-8g/10min, at 230℃and 2.16kg load.
When the content of the propylene, ethylene and butylene structural units and the melt mass flow rate range are satisfied, the heat sealing temperature of the resin can be reduced, the transparency is improved, and the number of crystal points is reduced.
According to the invention, the antioxidants include hindered phenolic antioxidants and/or phosphite antioxidants.
According to the invention, the halogen absorber is selected from calcium stearate and/or hydrotalcite, preferably calcium stearate.
According to the invention, the silicon dioxide is at least one selected from SiO 2 prepared by a gas phase method, a precipitation method, a hydrothermal synthesis method, a microemulsion reaction method, an azeotropic distillation method and a hypergravity reaction method, and is preferably a gas phase method or a precipitation method.
Preferably, the silica has a porosity ranging from 0 to 30% and a particle size ranging from 3 to 6 μm.
Preferably, the slipping agent is selected from fatty acid and fatty amide, preferably, the fatty amide is one of ethylene bis-stearamide, erucamide and oleamide, and more preferably, oleamide or erucamide;
The anti-sticking agent and the slipping agent can play a synergistic effect of the anti-sticking agent and the slipping agent, so that the prepared ternary random copolymer polypropylene film material has excellent slipping property.
In a second aspect of the present invention, a process for producing a ternary random copolymer polypropylene resin is provided, wherein the process comprises the steps of:
(1) Preparing ternary random copolymer polypropylene resin base material by polymerization reaction of propylene, butylene and ethylene;
(2) Carrying out first physical mixing on the anti-sticking agent and the first part of ternary random copolymer polypropylene base material to form premixed master batch, and carrying out second physical mixing on the premixed master batch, the antioxidant, the halogen absorbent and the slipping agent to form an auxiliary agent mixture;
(3) And (3) physically blending the rest ternary random copolymer polypropylene base material and the auxiliary agent mixture in the step (2), and feeding the mixture into an extruder for melt extrusion and granulation to obtain the ternary random copolymer polypropylene.
According to the invention, in step (1), the weight ratio of propylene to butene is from 5 to 10:1, preferably from 5 to 7:1, and the weight ratio of propylene to ethylene is from 15 to 40:1, preferably from 25 to 35:1.
In the invention, when the dosage of propylene, butylene and ethylene satisfies the above range, the polymerization reaction can be smoothly and stably carried out, so that the prepared ternary random copolymer polypropylene resin base material has excellent heat sealing performance and optical performance.
In the invention, the catalyst can catalyze and accelerate the reaction, can adjust the molecular structure of the polymer, optimize the mechanical property and the optical property, does not limit the dosage of the catalyst, and can realize the catalytic property.
In the present invention, the catalyst is a Ziegler-Natta (Z-N) catalyst which is conventional in the polyolefin field, preferably a commercial catalyst ZN101-1 from Liandebaser company.
The cocatalyst may be selected from cocatalysts commonly used in the art, preferably the cocatalyst is an alkyl aluminum, preferably at least one of triethyl aluminum, diethyl aluminum chloride, triisobutyl aluminum and diethyl aluminum chloride, more preferably triethyl aluminum.
The external electron donor may be selected from external electron donors commonly used in the art, preferably, the external electron donor is at least one of carboxylate external electron donors, alkoxysilane external electron donors and ammonia external electron donors, preferably, alkoxysilane external electron donors. More preferably, the alkoxysilane-based external electron Donor includes at least one of cyclohexylmethyldimethoxysilane (CHMMS, donor C), dicyclopentyl dimethoxysilane (DCPMS, donor D), diisopropyldimethoxysilane (DIPMS, donor P) and diisobutyldimethoxysilane (DIBMS, donor B), more preferably dicyclopentylmethyl dimethoxysilane.
In the step (1), the polymerization reaction conditions comprise a polymerization reaction temperature of 65-85 ℃, a polymerization reaction time of 1-3h, a polymerization reaction pressure of 2-4MPa and a concentration of hydrogen of 1-5mol% in the polymerization reaction, preferably, the polymerization reaction conditions comprise a polymerization reaction temperature of 65-75 ℃, a polymerization reaction time of 1-1.5h, a polymerization reaction pressure of 2-2.5MPa and a concentration of hydrogen of 1-2mol% in the polymerization reaction.
In the present invention, the carrier gas includes hydrogen, nitrogen, and unreacted propylene, butene, and ethylene.
Preferably, the weight ratio of the anti-sticking agent in the step (2) to the partial ternary random copolymer polypropylene powder base material is 1:1-10, more preferably 1:1-5.
Preferably, the granulating in the step (3) comprises the steps of carrying out gas-solid separation on the ternary random copolymer polypropylene resin base material product obtained in the reactor to obtain a solid-phase product and carrier gas, and then carrying out granulating after mixing the solid-phase product with the auxiliary agent.
In the invention, the preparation method of the auxiliary agent mixture in the step (2) can also be that part of ternary random copolymer polypropylene base material, an anti-sticking agent, an antioxidant, a halogen absorbent and a slipping agent are physically mixed, and are subjected to melt extrusion granulation, wherein a double-screw extruder is preferably adopted for the melt extrusion, the extrusion temperature is 160-180 ℃, and the weight ratio of the anti-sticking agent to the first part of ternary random copolymer polypropylene powder base material is preferably 1:1-10, and more preferably 1:1-5.
According to the invention, by adding part of the base material in the processing process, the adsorption and dispersion of the spherical porous base material are exerted, and particularly the anti-sticking agent can migrate into holes of the base material to form a micro-scale dispersion mixing effect, so that good compatibility with the whole base material resin and other additives is ensured, and the finally prepared ternary random copolymer polypropylene film has the advantages of low heat sealing temperature, high heat sealing strength and high optical performance.
The final object of the invention is to protect the application of the ternary random copolymer polypropylene resin or the ternary random copolymer polypropylene resin prepared by the method in a polyolefin heat-shrinkable film heat-sealing layer or a polypropylene cast film heat-sealing layer.
The invention has the beneficial effects that:
(1) The polypropylene film material prepared from the ternary random copolymer polypropylene resin with specific components has the advantages of low heat sealing temperature, high heat sealing strength and high optical performance;
(2) The specific reactants, the anti-sticking agent, the slipping agent and the composite additive processing method in the preparation method enable the finally prepared ternary random copolymer polypropylene resin material to have excellent heat sealing performance and optical performance with high transparency and low crystal point.
Detailed Description
The invention is further illustrated below in connection with specific examples, which are not to be construed as limiting the invention in any way.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The present invention will be described in detail by examples.
Example 1
A preparation method of ternary random copolymer polypropylene resin, comprising the following steps:
(1) The preparation of the ternary random copolymer polypropylene resin base material comprises the steps of feeding a main catalyst, a cocatalyst, an external electron donor, hydrogen, propylene, butylene and ethylene into a gas-phase multi-zone reactor for random copolymerization reaction to obtain the ternary random copolymer polypropylene resin base material, wherein the flow of the main catalyst ZN101-1 is 1.35kg/H, the flow of the cocatalyst triethylaluminum is 5kg/H, the flow of the external electron donor cyclohexyl-methyl-dimethoxysilane is 0.5kg/H, the flow ratio of the triethylaluminum to the cyclohexyl-methyl-dimethoxysilane is 10, the pressure of the gas-phase reactor is 2MPa, the temperature is 68 ℃, the concentration of H 2 is 4mol%, the total amount of propylene, ethylene and butylene is 89.5wt%, the amount of ethylene is 2.5wt%, the amount of butylene is 8wt%, and the reaction time is 1.5H, so that the ternary random copolymer polypropylene resin base material is obtained.
(2) And preparing an auxiliary agent mixture, namely carrying out gas-solid separation on the ternary random copolymer polypropylene resin base material to obtain a solid phase product and a carrier gas, compressing and separating the carrier gas, recycling the carrier gas, mixing the solid phase product with a composite auxiliary agent, and granulating. The components and preparation process of the composite additive comprise the steps of taking a proper amount of ternary random copolymer polypropylene resin base material, carrying out first physical mixing on the ternary random copolymer polypropylene resin base material and an anti-sticking agent to form a premixed master batch, wherein the weight ratio of the anti-sticking agent to the ternary random copolymer polypropylene base material is 1:3, the anti-sticking agent is SiO 2, the SiO 2 synthesis method is a gas phase method, the porosity is about 30%, the particle size is about 6 mu m, and carrying out second physical mixing on the premixed master batch, an antioxidant B215, calcium stearate and erucamide to form the composite additive, wherein the mass ratio of the premixed master batch to the antioxidant to the halogen absorbent to the slipping agent is 4:1:0.1:0.6.
(3) And (3) mixing the ternary random copolymer polypropylene resin base material in the step (1) with the auxiliary agent mixture in the step (2), and then carrying out melt granulation, wherein the dosage of the composite auxiliary agent is 9500mg per kilogram of ternary random copolymer polypropylene powder, so as to obtain the ternary random copolymer polypropylene resin.
The content of ethylene, propylene and butene structural units in the ternary random copolymer polypropylene resin prepared in the step (2) and the melt index under 230 ℃ and 2.16kg load are shown in Table 1.
Example 2
A ternary random copolymer polypropylene resin base material was prepared in a similar manner to example 1, except that the type of the anti-sticking agent in step (2) was changed, the rest was the same, the anti-sticking agent component was SiO 2, the preparation method was a precipitation method, the porosity was about 0%, and the particle size was about 4. Mu.m.
The content of ethylene, propylene and butene structural units in the ternary random copolymer polypropylene resin prepared in the step (2) and the melt index under 230 ℃ and 2.16kg load are shown in Table 1.
Example 3
A ternary random copolymer polypropylene resin base material is prepared by adopting a method similar to the method in the embodiment 1, and the difference is that in the step (1), the dosage of propylene is 87wt%, the dosage of ethylene is 3wt% and the dosage of butene is 10wt% based on the total amount of propylene, ethylene and butene, in the step (2), the mass ratio of each component in the composite auxiliary agent is changed to be a premix master batch (the weight ratio of the anti-sticking agent to the ternary random copolymer polypropylene is 1:1), the mass ratio of the antioxidant to the halogen absorbent to the slipping agent is 2:1:0.1:0.6, and the dosage of the composite auxiliary agent is 6500mg relative to each kilogram of ternary random copolymer polypropylene powder.
The content of ethylene, propylene and butene structural units in the ternary random copolymer polypropylene resin prepared in the step (2) and the melt index under 230 ℃ and 2.16kg load are shown in Table 1.
Example 4
A ternary random copolymer polypropylene resin was prepared in a similar manner to example 1, except that the preparation method of the composite auxiliary agent in step (2) was changed, the preparation method of the composite auxiliary agent in example 1 was a physical blending method, and the preparation process of the composite auxiliary agent in example 4 was a melt granulation method. The preparation process includes the physical mixing of ternary random copolymer polypropylene resin base material, antioxidant B215, calcium stearate, silica and erucamide, and the smelting extrusion pelletizing to form the composite assistant. Wherein the mass ratio of the ternary random copolymer polypropylene resin base material to the antioxidant B215 to the calcium stearate to the silicon dioxide to the erucamide is 4:1:0.1:1:0.6. The melt extrusion was performed by a twin screw extruder in a manner conventional in the art, with an extrusion temperature of 170 ℃.
The content of ethylene, propylene and butene structural units in the ternary random copolymer polypropylene resin prepared in the step (2) and the melt index under 230 ℃ and 2.16kg load are shown in Table 1.
Example 5
A similar method to example 4 is used for preparing the ternary random copolymer polypropylene resin, and the difference is that in the step (1), the amount of propylene is 87wt%, the amount of ethylene is 3wt% and the amount of butene is 10wt%, based on the total amount of propylene, ethylene and butene, in the step (2), the type of an anti-sticking agent SiO 2 is changed, the anti-sticking agent is Japanese water-soluble JC-30, the porosity is about 0%, the particle size is about 3 mu m, the slipping agent component is erucamide, and meanwhile, in the step (2), the mass ratio of each component in the composite auxiliary agent is changed, specifically, the mass ratio of the ternary random copolymer polypropylene resin base material to the antioxidant B215 to the antioxidant JC30 to the erucamide is 1:1:0.1:0.5.
The content of ethylene, propylene and butene structural units in the ternary random copolymer polypropylene resin prepared in the step (2) and the melt index under 230 ℃ and 2.16kg load are shown in Table 1.
Example 6
A ternary random copolymer polypropylene resin is prepared by adopting a method similar to the method in the embodiment 1, except that in the step (2), the components and the preparation mode of a composite auxiliary agent are changed, and the composite auxiliary agent is not added with ternary random copolymer polypropylene powder base material, so that the components of the composite auxiliary agent are antioxidant B215, calcium stearate, silicon dioxide and erucamide, and in the composite auxiliary agent, the mass ratio of the antioxidant B215 to the calcium stearate to the silicon dioxide to the erucamide is 1:0.1:1:0.6. The preparation method comprises the steps of physically blending the auxiliary components, and then sending the mixture into a single screw extruder for dry extrusion granulation, wherein the temperature of a screw is 100 ℃.
The content of ethylene, propylene and butene structural units in the ternary random copolymer polypropylene resin prepared in the step (2) and the melt index under 230 ℃ and 2.16kg load are shown in Table 1.
Example 7
A ternary random copolymer polypropylene resin is prepared by adopting a method similar to the method in the embodiment 1, except that in the step (2), the components and the preparation mode of a composite auxiliary agent are changed, and the composite auxiliary agent is not added with ternary random copolymer polypropylene powder base material, so that the components of the composite auxiliary agent are antioxidant B215, calcium stearate, silicon dioxide and erucamide, and in the composite auxiliary agent, the mass ratio of the antioxidant B215 to the calcium stearate to the silicon dioxide to the erucamide is 1:0.1:1:0.6. The preparation method is that the auxiliary components are physically blended to obtain the composite auxiliary.
The content of ethylene, propylene and butene structural units in the ternary random copolymer polypropylene resin prepared in the step (2) and the melt index under 230 ℃ and 2.16kg load are shown in Table 1.
Comparative example 1
A ternary random copolymer polypropylene resin was prepared in a similar manner to example 1, except that the type of antiblocking agent was changed, the antiblocking agent component was SiO 2, the synthesis method was a gas phase method, the porosity was about 70%, and the particle size was about 9. Mu.m.
The content of ethylene, propylene and butene structural units in the ternary random copolymer polypropylene resin prepared in the step (2) and the melt index under 230 ℃ and 2.16kg load are shown in Table 1.
Comparative example 2
A ternary random copolymer polypropylene resin was prepared in a similar manner to example 1, except that in step (1), propylene, butene and hydrogen were introduced into the reactor to carry out polymerization, the amount of propylene was 89.5% by weight, the amount of ethylene was 1.2% by weight and the amount of butene was 5% by weight, based on the total amount of propylene, ethylene and butene. Meanwhile, in the step (2), the anti-sticking agent is SiO 2, the synthesis method is a precipitation method, the porosity is about 0%, and the particle size is about 8 mu m.
The content of ethylene, propylene and butene structural units in the ternary random copolymer polypropylene resin prepared in the step (2) and the melt index under 230 ℃ and 2.16kg load are shown in Table 1.
Comparative example 3
A ternary random copolymer polypropylene resin was prepared in a similar manner to example 1, except that in step (1), the polymerization was conducted in the presence of hydrogen (H 2 acts to adjust the melt index of the polymer) and the H 2 concentration was 1mol%.
The content of ethylene, propylene and butene structural units in the ternary random copolymer polypropylene resin prepared in the step (2) and the melt index under 230 ℃ and 2.16kg load are shown in Table 1.
Comparative example 4
A ternary random copolymer polypropylene resin was prepared in a similar manner to example 1, except that in step (2), the ratio of the premix masterbatch (weight ratio of the antiblocking agent to the ternary random copolymer polypropylene: 1:1) to the antioxidant to the halogen absorbent to the slip agent was 8:1:0.1:0.6, and the total addition amount was varied. The ternary random copolymer polypropylene resin base material and the composite auxiliary agent are mixed and then are subjected to melt granulation, and the dosage of the composite auxiliary agent is 12500mg relative to each kilogram of ternary random copolymer polypropylene powder.
The content of ethylene, propylene and butene structural units in the ternary random copolymer polypropylene resin prepared in the step (2) and the melt index under 230 ℃ and 2.16kg load are shown in Table 1.
The melting point, melt mass flow rate, and ethylene butene content of the ternary random copolymer polypropylene resins obtained in the above examples and comparative examples were measured, and the results are shown in Table 1. Meanwhile, the resins obtained in examples and comparative examples were cast into films, and the number of crystal spots, the number of white spots, the transparency and the heat-sealing temperature of the films were further tested, and the results are shown in table 2.
TABLE 1 Properties of the ternary random copolymer polypropylene resins prepared in examples 1-5 and comparative examples 1-6
TABLE 2 analysis of Properties after casting the resins of examples 1 to 5 and comparative examples 1 to 6 into films
The melt flow rate was measured in the first part of GB/T3682.1-2018 thermoplastic melt Mass Flow Rate (MFR) under test conditions including a test temperature of 230℃and a weight mass of 2.16kg. The melting point is obtained by a differential scanning method. The test method of the butene content and the ethylene content is a high-temperature 13CNMR test, the solvent is dichloro deuterated benzene, the temperature is 120 ℃, and the magnetic field frequency is 400MHz. The test method of the number of crystal points (fish eyes) and the number of white points is referred to GB/T-6595.
The initial heat seal temperature was measured using the method of GB/T27740-2011 cast polypropylene (CPP) film. The haze and clarity were measured according to GB/T2410, the thickness of the sample was 30um, the specific test method was to measure the scattered luminous flux transmitted through the sample and deviating from the incident light direction by more than 2.5 °, denoted lma, the transmitted luminous flux was denoted lmb, the haze= lma/lmb ×100%, all test items were parallel samples, and the average was determined for 5 groups.
As can be seen from Table 1, the ternary random copolymer polypropylene resin of the present invention has the characteristics of low crystallization point, low white point, low melting point, low initial heat sealing temperature and high transparency.
Examples 6 and 7 illustrate that if the preparation method of the composite auxiliary agent is changed, the ternary polymerization polypropylene powder base material is not added into the composite auxiliary agent, and the composite auxiliary agent is prepared by adopting a one-step physical blending or single screw extrusion granulation method, although the haze, definition and heat sealing temperature are not changed significantly, the number of crystal points and white points is increased.
As can be seen from comparative examples 1 and 1, the use of SiO2, which is an anti-sticking agent having an unsuitable particle size and porosity, significantly increases the number of crystal spots and white spots of the ternary random copolymer polypropylene resin, and deteriorates the optical properties. Comparative example 2 shows that low ethylene and butene content can raise the melting point and heat sealing temperature obviously. Comparative example 3 shows that when the polymer melt index is low, the number of crystal spots increases, the number of white spots does not change much, and the haze increases and the optical properties deteriorate. Comparative example 4 shows that the addition ratio and the addition amount of the compound additive are changed, which results in an increase in the number of crystal spots and white spots, an increase in the heat sealing temperature, an increase in haze, and deterioration in optical properties.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. The ternary random copolymer polypropylene resin is characterized by comprising ternary random copolymer polypropylene resin base material, antioxidant, halogen absorbent, anti-sticking agent and slipping agent, wherein the anti-sticking agent comprises silicon dioxide;
the silicon dioxide has porosity ranging from 0 to 40 percent and particle size ranging from 1 to 10 mu m.
2. The ternary random copolymer polypropylene resin according to claim 1, wherein the ternary random copolymer polypropylene resin comprises 97 to 99.6 parts by weight of ternary random copolymer polypropylene resin base material, 0.1 to 0.3 part by weight of antioxidant, 0.01 to 0.06 part by weight of halogen absorber, 0.1 to 0.3 part by weight of anti-sticking agent and 0.1 to 0.2 part by weight of slipping agent.
3. The ternary random copolymer polypropylene resin according to claim 1 or 2, wherein the ternary random copolymer polypropylene resin base material has a structural unit content of 86wt% to 95wt% derived from propylene, a structural unit content of 4wt% to 10wt% derived from butene and a structural unit content of 1 to 4wt% derived from ethylene;
Preferably, the content of structural units derived from propylene is 89.5-92 wt%, the content of structural units derived from butene is 6-8 wt%, and the content of structural units derived from ethylene is 1.5-2.5 wt%.
4. The ternary random copolymer polypropylene resin according to claim 1 or 2, wherein the ternary random copolymer polypropylene resin has a melt mass flow rate of 4-10g/10min, preferably 6-8g/10min, at 230 ℃ and under a load of 2.16 kg.
5. The ternary random copolymer polypropylene resin according to claim 1 or 2, wherein the antioxidant comprises a hindered phenolic antioxidant and/or a phosphite antioxidant;
and/or the halogen absorber is calcium stearate and/or hydrotalcite;
And/or the silicon dioxide is selected from at least one of SiO 2 prepared by a gas phase method, a precipitation method, a hydrothermal synthesis method, a microemulsion reaction method, an azeotropic distillation method and a hypergravity reaction method, and is preferably a gas phase method or a precipitation method;
Preferably, the silica has a porosity ranging from 0 to 30% and a particle size ranging from 3 to 6 μm;
And/or the slipping agent is selected from fatty acid and fatty amide, preferably, the fatty amide is one of ethylene bis-stearamide, erucamide and oleamide, and further, the fatty amide is oleamide or erucamide;
And/or the weight ratio of the anti-sticking agent to the slipping agent is 1-2:1, preferably 1-1.5:1.
6. A process for producing the ternary random copolymer polypropylene resin according to any one of claims 1 to 5, comprising the steps of:
(1) Preparing ternary random copolymer polypropylene resin base material by polymerization reaction of propylene, butylene and ethylene;
(2) Carrying out first physical mixing on the anti-sticking agent and the first part of ternary random copolymer polypropylene base material to form premixed master batch, and carrying out second physical mixing on the premixed master batch, the antioxidant, the halogen absorbent and the slipping agent to form an auxiliary agent mixture;
(3) And (3) physically blending the rest ternary random copolymer polypropylene base material and the auxiliary agent mixture in the step (2), and feeding the mixture into an extruder for melt extrusion and granulation to obtain the ternary random copolymer polypropylene.
7. The process according to claim 6, wherein the polymerization conditions in the step (1) comprise a polymerization temperature of 65 to 85 ℃, a polymerization time of 1 to 3 hours, a polymerization pressure of 2 to 4MPa, a concentration of hydrogen in the polymerization of 1 to 5mol%, an amount of 82 to 93.5wt% of propylene, an amount of 1.5 to 6wt% of ethylene, and an amount of 5 to 12wt% of butene based on the total amount of propylene, ethylene, and butene.
8. The process of claim 6 wherein the weight ratio of the antiblocking agent of step (2) to the first portion of the ternary random copolymer polypropylene powder base material is from 1:1 to 10, more preferably from 1:1 to 5.
9. The process of claim 6, wherein the process of preparing the auxiliary mixture of step (2) further comprises the steps of physically mixing the first part of the ternary random copolymer polypropylene base material, the anti-sticking agent, the antioxidant, the halogen absorber and the slipping agent, and carrying out melt extrusion granulation, wherein a twin screw extruder is preferably adopted for the melt extrusion, the extrusion temperature is 160-180 ℃, and the weight ratio of the anti-sticking agent to the first part of the ternary random copolymer polypropylene base material is preferably 1:1-10, and more preferably 1:1-5.
10. Use of the ternary random copolymer polypropylene resin according to any one of claims 1 to 5 or the ternary random copolymer polypropylene resin prepared by the method according to any one of claims 6 to 9 in a polyolefin heat-shrinkable film heat-seal layer or a polypropylene cast film heat-seal layer.
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