CN107746498B - Polyethylene resin for high-stiffness film, blow molding material and preparation method thereof - Google Patents
Polyethylene resin for high-stiffness film, blow molding material and preparation method thereof Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J5/18—Manufacture of films or sheets
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- 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
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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Abstract
The invention discloses a polyethylene resin for a high-stiffness film, wherein the melt flow rate is 7.0-9.0 g/10min (21.6Kg), and the density is 0.953-0.957 g/cm3The catalyst is synthesized by adopting a loop slurry process, wherein ethylene is used as a raw material, 1-hexene is used as a comonomer, and the catalyst is synthesized in the presence of an activated catalyst, a diluent and an antistatic agent, wherein the activation temperature of the catalyst is lower than 600 ℃. The invention also discloses a blow molding material containing the polyethylene resin and a preparation method of the polyethylene resin. The polyethylene resin has wider molecular weight distribution and higher tensile modulus, obviously improves the stiffness of the polyethylene film, and simultaneously has good processability and mechanical property.
Description
Technical Field
The invention relates to polyethylene resin and a preparation method thereof, in particular to polyethylene resin for a high-stiffness film and a preparation method thereof. The invention also relates to a polyethylene blow molding material for high-stiffness films.
Background
The high-stiffness polyethylene film is mainly produced by high-density polyethylene, is mainly applied to shopping bags, composite films for packaging, garbage bags and liners, heavy packaging films, agricultural films, food bags and box linings, can also be mixed with polyethylene produced by other processes to be made into pipes and hollow containers, and the domestic demand for high-stiffness polyethylene film materials is increased year by year.
The high-stiffness polyethylene film is a novel polyethylene film, has high stiffness and good mechanical property, can be independently used for film blowing, and can also be matched with other polyethylene for use. The high-density polyethylene is used for films, has better mechanical strength than low-density polyethylene films, can be used for bearing heavier objects, can be used for shopping bags and rolling bags for packaging heavy objects, and has beautiful package and comfortable hand feeling. At present, the high-density polyethylene high-stiffness film commonly used in the market mainly uses imported raw materials, and mainly takes raw materials produced by a kettle type process as main raw materials. The kettle type process for producing the high-stiffness polyethylene film material has the disadvantages of complex process, high production difficulty, frequent shutdown in the production process, large workload load of workers and low efficiency.
At present, the TR144 stiffness of the polyethylene film material prepared by the loop slurry process is low, which can not meet the requirements of shopping bags and continuous rolling bags on weight packaging, and the market urgently needs to prepare the high stiffness polyethylene film material with low cost by the loop slurry process.
Disclosure of Invention
The invention aims to provide a polyethylene resin for a high-stiffness film, which has a wider molecular weight distribution, can obviously improve the stiffness of the polyethylene film and has good processability and mechanical properties.
The invention realizes the purpose through the following technical scheme: a polyethylene resin for a high-stiffness film, having a melt flow rate of 7.0 to 9.0g/10min (21.6Kg) and a density of 0.953 to 0.957g/cm3The catalyst is synthesized by adopting a loop slurry process, wherein ethylene is used as a raw material, 1-hexene is used as a comonomer, and the catalyst is synthesized in the presence of an activated catalyst, a diluent and an antistatic agent, wherein the activation temperature of the catalyst is lower than 600 ℃.
The second object of the present invention is to provide a process for producing the above polyethylene. Specifically, the preparation method of the polyethylene takes ethylene as a raw material, 1-hexene as a comonomer, and synthesizes the polyethylene resin for the high-stiffness film in a loop slurry process polyethylene device in the presence of an activated catalyst, a diluent and an antistatic agent. In the invention, the key of the process is to control the activation temperature of the catalyst, so that the catalyst can produce a product with wide molecular weight distribution at a lower activation temperature, and the product has high stiffness. The catalyst activation temperature in the present invention is less than 600 ℃.
The catalyst is NTR-971 of Shanghai Nachuan company. NTR-971 is a chromium-based catalyst using alumina as a carrier. The chromium catalyst is optimized for loop slurry polyethylene production process, and the obtained polyethylene has wide molecular weight distribution, stable quality and good mechanical property. The catalyst must be activated before entering the polymerization reactor, and the activation means that the catalyst is added into a heating activator, and the + 3-valent chromium is converted into the + 6-valent chromium by contacting the catalyst with hot dry air. In an embodiment of the present invention, the activation temperature of the catalyst is preferably 535 to 595 ℃.
In the loop slurry process, the reaction temperature in the loop reactor is kept at 102.5-103.2 ℃, the 1-hexene/ethylene ratio feed ratio is 1.5-2.5 (kg/t), the diluent feed rate is 26-38 (t/h), the ethylene feed rate is 38-43.5 (t/h), and the antistatic agent is usually added to the reactor at a rate of 1-2 ppm of the flow rate of the circulating diluent. The antistatic agent is from Stadis 450 from Octel corporation. The diluent is isobutane.
The invention also aims to provide a high-stiffness polyethylene film blow molding material prepared from the polyethylene resin. Mainly adds a certain amount of additive into the produced polyethylene resin, so that the high-stiffness polyethylene film blow molding material meets the actual use requirement.
The additive of the present invention comprises an antioxidant and an acid acceptor. The antioxidant is used for improving the processing stability and the thermal-oxidative aging property of the material, and the antioxidant adopts a phenol antioxidant as a main antioxidant, an auxiliary antioxidant adopts a phosphite antioxidant, and the main antioxidant and the auxiliary antioxidant are matched for use. The antioxidant system can provide sufficient processing stability and thermal-oxidative aging property for materials. The phenolic antioxidant is pentaerythritol tetrakis [ methylene beta- (3, 5-di-tert-butyl-4 hydroxyphenyl) propionate ] (1010) or octadecyl beta- (3, 5-di-tert-butyl-4 hydroxyphenyl) propionate (1076), and the phosphite antioxidant is bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite (626) or tris [2, 4-di-tert-butylphenyl ] phosphite (168). The mass ratio of the phenol antioxidant to the phosphite antioxidant is 1: 1-2: 1. The acid absorbent is zinc stearate.
Specifically, the high-stiffness polyethylene film blow molding material is mainly prepared from the following raw materials in parts by weight:
compared with the prior art, the invention has the following advantages:
(1) the invention adopts the ring pipe slurry method to produce the polyethylene for the high-stiffness film, compared with the kettle type product, the production process is simple and continuous, the quality of the obtained product is stable, and the cost can be obviously reduced when the method is used for producing the high-stiffness film blow molding material.
(2) In the preparation method of the polyethylene for the high-stiffness film, the NTR-971 type chromium catalyst is adopted, so that the catalyst activity is improved, the production stability is improved, the feeding amount of ethylene during production can be increased, and the production can be carried out under high load. Meanwhile, when the special material for the high-stiffness film is produced, the number of times of switching transition marks in production is obviously reduced, the yield of the transition material is obviously reduced, the conversion efficiency is greatly improved, the cost is low, the supply is stable, and the economic benefit is improved.
(3) The activation temperature of the catalyst used in the invention is a key index and is an important control factor of the invention, and the reduction of the activation temperature widens the molecular weight distribution of the product and has a key influence on the quality of the product.
(4) The high-stiffness film provided by the invention has the advantages that the polyethylene has high molecular weight and wide molecular weight distribution, the stiffness of the polyethylene film is greatly improved, and the processability and mechanical property of the product are improved.
Detailed Description
The catalyst activation treatment method of the following examples: the catalyst falls into the activator by gravity by opening a bottom valve of the tank, the hot combustion gas and the hot fluidizing air from the hearth of the activation furnace heat the activation furnace and the catalyst, and the fluidizing gas fully contacts with the catalyst and activates the catalyst after passing upward through the distribution plate. The activation temperature is 535-595 ℃.
The mixer was a Coperion ZSK-350 extruder having 7 barrel sections.
The catalysts used in the following examples are chromium-based catalysts, model NTR-971. When the catalyst is used for producing the high-stiffness film by a loop slurry process, the prepared high-stiffness film blow molding material has high molecular weight and wide molecular weight distribution, and meets the processing performance and various physical and mechanical properties required by the high-stiffness film blow molding. Meanwhile, the high-activity catalyst can initiate production reaction under higher production load, and the conversion efficiency of production is obviously improved.
The raw materials used in the following examples all meet the following raw material requirements:
ethylene: purity is not less than 99.20 percent C2H2≤5×10-6 CO≤1×10-6
O2≤2×10-6 H2O≤1×10-6 COS≤0.02×10-6。
1-hexene: h with purity more than or equal to 98.5 percent2O≤20×10-6 CO≤5×1O-6
Mono-olefin more than or equal to 98.5 percent, isomeric alpha-olefin less than or equal to 1 percent, normal non-alpha-olefin less than or equal to 1 percent
Normal alpha olefin is greater than or equal to 96 percent, peroxide is less than or equal to 1 multiplied by 10-6Sulfur is less than or equal to 1 x 10-6。
Isobutane: purity is more than or equal to 95.0 percent, acetylene is less than or equal to 2 multiplied by 10-6Total sulfur less than or equal to 1 x 10-6
Total olefins less than or equal to 100 x 10-6Water is less than or equal to 20X 10-6 O2≤5×10-6。
Example 1
Preparation of ethylene hexene copolymerized ethylene resin:
before the catalyst is used for producing polyethylene, the catalyst must be added into a catalyst activator for activation, and the catalyst activation temperature must be strictly controlled because the catalyst activation temperature has obvious influence on the molecular weight distribution of the product. The activation temperature selected in this example was 595 ℃.
Respectively injecting monomer ethylene and 1-hexene into a loop reactor in a circulating state of a diluent isobutane, adding an antistatic agent ASA and an activated NTR-971 type chromium catalyst for reaction at the reaction temperature of 102.8 ℃, wherein the ethylene feeding amount is 38t/h, the 1-hexene feeding amount is 57-95 kg/h, the catalyst feeding amount is 149kg/h, the isobutane feeding amount is 38.0t/h, the antistatic agent is 0.039kg/h, and reacting until the melt flow rate of a reaction product is 10.0g/10min and the density is 0.953-0.957 kg/m3And then, after the reaction discharge is subjected to flash evaporation, ethylene-hexene copolymerized polyethylene resin is obtained.
The mixing formula of the high-stiffness film blow molding material is as follows: (unit: parts by weight)
Preparing a high-stiffness film blow molding material:
according to the proportion, after the ethylene-hexene copolymerized polyethylene resin and the antioxidant are mixed uniformly, the mixture is added into a mixing roll to extrude particles into cooling water, and the granular polyethylene product high-stiffness film blow molding material is obtained. When the mixing roll is used for mixing, the temperature of a second section of barrel of the mixing roll is adjusted to be 200 ℃, the temperature of a third section of barrel is adjusted to be 210 ℃, the temperature of a fourth section of barrel is adjusted to be 210 ℃, the temperature of a fifth section of barrel is adjusted to be 210 ℃, the temperature of a sixth section of barrel is adjusted to be 210 ℃, and the temperature of a seventh section of barrel is adjusted to be 210 ℃; the temperature of the heat conducting oil for heating the mixing roll is 210 ℃. The temperature of the cooling water was 70 ℃.
The ethylene-hexene copolymerized polyethylene resin is prepared into the high-stiffness film blow molding material according to the mixing formula (parts by weight) of the high-stiffness film blow molding material and the mixing method.
Example 2
The difference from example 1 is:
preparation of ethylene hexene copolymerized ethylene resin:
before the catalyst is used for producing polyethylene, the catalyst must be added into a catalyst activator for activation, and the catalyst activation temperature must be strictly controlled because the catalyst activation temperature has obvious influence on the molecular weight distribution of the product. The activation temperature of this example was selected to be 565 ℃.
Respectively injecting monomer ethylene and 1-hexene into a loop reactor in a circulating state of a diluent isobutane, adding an antistatic agent ASA and an activated NTR-971 type chromium catalyst for reaction at the reaction temperature of 102.7 ℃, wherein the ethylene feeding amount is 38t/h, the 1-hexene feeding amount is 57-95 kg/h, the catalyst feeding amount is 149kg/h, the isobutane feeding amount is 38.0t/h and the antistatic agent is 0.039kg/h, reacting until the melt flow rate of a reaction product is 10.0g/10min and the density is 0.953-0.957 kg/m3, and discharging and flashing to obtain the ethylene-hexene copolymerized polyethylene resin.
The ethylene-hexene copolymerized polyethylene resin thus obtained was subjected to the compounding formulation (parts by weight) and the compounding method of the high stiffness film blowing material of example 1 to prepare a high stiffness film blowing material.
Example 3
The difference from example 1 is:
preparation of ethylene hexene copolymerized ethylene resin:
before the catalyst is used for producing polyethylene, the catalyst must be added into a catalyst activator for activation, and the catalyst activation temperature must be strictly controlled because the catalyst activation temperature has obvious influence on the molecular weight distribution of the product. The activation temperature was chosen to be 535 ℃ in this example.
Respectively injecting monomer ethylene and 1-hexene into a loop reactor in a circulating state of a diluent isobutane, adding an antistatic agent ASA and an activated NTR-971 type chromium catalyst for reaction at the reaction temperature of 102.8 ℃, wherein the ethylene feeding amount is 38t/h, the 1-hexene feeding amount is 57-95 kg/h, the catalyst feeding amount is 149kg/h, the isobutane feeding amount is 38.0t/h and the antistatic agent is 0.039kg/h, reacting until the melt flow rate of a reaction product is 10.0g/10min and the density is 0.953-0.957 kg/m3, and discharging and flashing to obtain the ethylene-hexene copolymerized polyethylene resin.
The ethylene-hexene copolymerized polyethylene resin thus obtained was subjected to the compounding formulation (parts by weight) and the compounding method of the high stiffness film blowing material of example 1 to prepare a high stiffness film blowing material.
The similar high stiffness film stock on the market has mainly imported EGDA-6888 (comparative) to which the film blowing materials of examples 1-3 according to the invention were compared for their performance. The main properties of the examples and comparative products are compared as follows:
TABLE 1 comparison of tensile modulus of films of inventive and comparative materials
As can be seen from the results of table 1, as the activation temperature of the catalyst was lowered, the width of the molecular weight distribution was increased, and the tensile modulus of the material was increased. The tensile modulus of the material is 921Mpa which is close to imported EGDA-6888 when the activation temperature of the catalyst is 595 ℃, and the tensile modulus of the material is more than 1052Mpa which is better than the imported EGDA-6888 when the activation temperature of the catalyst is 565 ℃ or lower.
The calculation method of PET stiffness according to the PET film stiffness initial detection film (polyester industry, 3 rd 1991) is as follows:
S∝d3E
in the formula S-film stiffness
d-film thickness
E-tensile modulus of the film
The stiffness of the film is in direct proportion to the tensile modulus of the film, and the tensile modulus of the film of the product is improved, namely the insertion degree of the film of the product is improved.
TABLE 2 melt flow Rate comparison of inventive examples 1-3 materials to comparative examples
Detection by the method provided in GB3682-2000
As shown in Table 2, the high stiffness film blowing material of the invention has a slightly lower melt index at high shear (190 ℃ C., 21.6kg weight) than the comparative product, indicating a higher average molecular weight of the material.
TABLE 3 melting and crystallization parameters of inventive examples 1-3 and comparative examples
As shown in the results in Table 3, compared with the imported special material EGDA-6888, the high-stiffness film blow molding material of the invention has the advantages of higher melting point, higher crystallinity and better mechanical properties of the product.
TABLE 4 comparison of the apparent Properties of the materials of examples 1-3 according to the invention with those of the product of comparative example 1
The results in Table 4 show that the comprehensive performance is superior to that of the existing high-stiffness film blow molding material due to the wide molecular weight distribution and the improved material density, and the performance of the product for blow molding film is obviously improved.
In conclusion, the high-stiffness polyethylene for the film provided by the invention has obviously higher stiffness and mechanical properties than products produced by similar processes, and meanwhile, the preparation process uses a domestic catalyst, the production process is simple and convenient to adjust, and the realization is easier.
The above-described embodiments of the present invention are to be considered as illustrative and not restrictive, and all changes and modifications that come within the spirit of the invention and the scope of the appended claims are intended to be embraced therein.
Claims (7)
1. A polyethylene resin for a high-stiffness film, characterized in that the melt flow rate is 7.0 to 9.0g/10min under a weight of 21.6kg at 190 ℃ and the density is 0.953 to 0.957g/cm3The catalyst is synthesized by adopting a loop slurry process, wherein ethylene is used as a raw material, 1-hexene is used as a comonomer, and the catalyst is synthesized in the presence of an activated catalyst, a diluent and an antistatic agent, wherein the activation temperature of the catalyst is 535-595 ℃;
the catalyst is a chromium catalyst NTR-971;
in the loop slurry process, the reaction temperature in the loop reactor is kept at 102.5-103.2 ℃, the feeding ratio of 1-hexene to ethylene is 1.5-2.5 kg/t, the feeding amount of a diluent is 26-28 t/h, the feeding amount of ethylene is 42-43.5 t/h, and an antistatic agent is added into the reactor according to the ratio of 1-2 ppm of the flow amount of a circulating diluent.
2. The method for preparing the polyethylene resin for the high stiffness film as claimed in claim 1, wherein the polyethylene resin for the high stiffness film is synthesized in a loop slurry process polyethylene device by using ethylene as a raw material and 1-hexene as a comonomer in the presence of an activated catalyst, a diluent and an antistatic agent, wherein the activation temperature of the catalyst is 535-595 ℃;
the catalyst is a chromium catalyst NTR-971;
the reaction temperature in the loop reactor is kept at 102.5-103.2 ℃, the feeding ratio of 1-hexene to ethylene is 1.5-2.5 kg/t, the feeding amount of diluent is 26-28 t/h, the feeding amount of ethylene is 42-43.5 t/h, and the antistatic agent is added into the reactor according to the ratio of 1-2 ppm of the flow amount of the circulating diluent.
3. The method of preparing a polyethylene resin for a high stiffness film according to claim 2, wherein the antistatic agent is Stadis 450 and the diluent is isobutane.
4. A blow-molded polyethylene film having a high stiffness, which is obtained by blending the polyethylene resin as claimed in claim 1 with an additive.
5. The blown high stiffness polyethylene film material according to claim 4, wherein said additives include but are not limited to antioxidants and acid scavengers.
6. The blow molding material of polyethylene film with high stiffness as claimed in claim 5, wherein the antioxidant is phenol antioxidant as primary antioxidant, the secondary antioxidant is phosphite antioxidant, and the primary and secondary antioxidants are used in combination, the phenol antioxidant is pentaerythritol tetrakis [ methylene beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] or octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, the phosphite antioxidant is bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite or tris [2, 4-di-tert-butylphenyl ] phosphite; the mass ratio of the phenol antioxidant to the phosphite antioxidant is 1: 1-2: 1; the acid absorbent is zinc stearate.
7. The blow molding material of high stiffness polyethylene film as claimed in claim 6, wherein the mass ratio of the polyethylene resin, the primary antioxidant, the secondary antioxidant and the acid acceptor is as follows:
polyethylene resin 100 parts
0.02-0.05 part of main antioxidant
0.02-0.10 part of auxiliary antioxidant
0.02-0.05 part of acid absorbent.
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| CN109400776A (en) * | 2018-10-23 | 2019-03-01 | 南京安伦化工科技有限公司 | A kind of linear polyethylene preparation method |
| CN111483195B (en) * | 2020-04-09 | 2022-11-04 | 广州新文塑料有限公司 | Three-layer co-extrusion packaging film and preparation method thereof |
| CN114426727A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Polyethylene material for large winding forming pipe and preparation method thereof |
| CN114456474B (en) * | 2021-11-24 | 2023-12-29 | 中国石油化工股份有限公司 | Thin-wall multilayer hollow blow molding material and preparation method thereof |
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