CN112745554A - Polyethylene material and preparation method and application thereof - Google Patents
Polyethylene material and preparation method and application thereof Download PDFInfo
- Publication number
- CN112745554A CN112745554A CN201911046744.6A CN201911046744A CN112745554A CN 112745554 A CN112745554 A CN 112745554A CN 201911046744 A CN201911046744 A CN 201911046744A CN 112745554 A CN112745554 A CN 112745554A
- Authority
- CN
- China
- Prior art keywords
- polyethylene material
- temperature
- antioxidant
- polyethylene
- tert
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Multicomponent Fibers (AREA)
- Artificial Filaments (AREA)
Abstract
The invention relates to a polyethylene material and a preparation method and application thereof, wherein the polyethylene material is prepared by granulating raw materials; the raw materials comprise the following components in parts by weight: 100 parts of polyethylene resin, 0.02-0.1 part of main antioxidant, 0.01-0.1 part of auxiliary antioxidant, 0.01-0.1 part of acid acceptor and 0.01-0.1 part of antistatic agent. The sheath-core fiber prepared from the polyethylene material has the advantages of environmental protection and high glossiness, and meets the requirements of people on products.
Description
Technical Field
The invention belongs to the field of chemical materials, and particularly relates to a polyethylene material, a preparation method thereof and application thereof in sheath-core fibers.
Background
The flexible sheath-core polyolefin fiber is one of polyolefin fibers developed by Nippon Chineso corporation, and the sheath-core polyolefin fiber is a bicomponent fiber with a sheath-core structure and is mainly used for producing hot-melt adhesive non-woven fabrics. The sheath-core polyolefin fiber is formed by combining two resins with different melting points, and can realize bonding between fibers only through heat treatment by utilizing the difference of the melting points of the two resins, wherein the low-melting-point component PE (usually a sheath) is used as a hot-melt bonding component of the non-woven fabric, and the high-melting-point component PP (usually a core) is used as a main body of the non-woven fabric. Since the sheath-core polyolefin fiber is a clean fiber without using an adhesive, it is widely used for sanitary materials such as disposable diapers. Compared with the advanced countries in the world, the application of the sheath-core polyolefin fiber in China starts later, but the development is fast, the raw material demand is increased rapidly, and the sheath-core fiber polyethylene material commonly used in the market at present can not meet the market demand far. The development and production of the polyethylene material for the sheath-core fiber which meets the requirements have better benefits.
The polyethylene material for the sheath-core fiber mainly adopts High Density Polyethylene (HDPE), the method for producing the HDPE has various processes, including a loop slurry process, a gas phase fluidized bed process and the like, and the produced products have great difference in product performance due to different molecular weights and densities. The loop slurry process has high stability, and the produced HDPE product has wide molecular weight distribution and high processability. HDPE products produced by the gas-phase fluidized bed process have the characteristics of narrow molecular weight distribution and high strength. At present, the domestic polyethylene products are used for producing sheath-core fiber materials, but the fiber glossiness of the existing products is not high, the products are not bright, and customers prefer bright products in terms of aesthetic appearance, so that the customers' eyes are attracted, the use intentions of the customers are improved, but the products are required to be absolutely incapable of adding fluorescent whitening agents, and the influence on the skin is avoided.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a novel polyethylene material, and the sheath-core fiber prepared from the polyethylene material has the advantages of environmental protection and high glossiness, and meets the requirements of people on products.
To this end, the invention provides, in a first aspect, a polyethylene material obtained by granulating a starting material; the raw materials comprise the following components in parts by weight:
the antioxidant contained in the raw materials is used for improving the processing stability and the long-acting heat and oxygen aging resistance of the materials, and the primary antioxidant and the secondary antioxidant are used in a matching way.
To improve the stability of production and the stability of product quality, in some embodiments of the invention, the primary antioxidant is selected from phenolic antioxidants; preferably, the phenolic antioxidant is selected from pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] or octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
In other embodiments of the present invention, the secondary antioxidant is selected from phosphite antioxidants; preferably, the secondary antioxidant is selected from tris (2, 4-di-tert-butylphenyl) phosphite or bis (2, 4-di-tert-butylphenyl) propanoic acid ] pentaerythritol diphosphite.
The acid absorbent in the raw material of the invention is an acid absorbent commonly used in the production of polyethylene materials, such as zinc stearate.
In some embodiments of the invention, the antistatic agent is selected from organic antistatic agents, which are white waxy solids, non-toxic.
In the present invention, the polyethylene resin used is a copolymerized polyethylene resin. In an embodiment of the invention, the polyethyleneThe melt index of the olefinic resin is 18.0-22.0 g/10min, and the density is 0.944-0.960 g/cm3The weight average molecular weight is 5-9 ten thousand, the crystallinity is 60-70%, and the content of comonomer in the resin is 0.01-0.1 wt%.
In a second aspect, the present invention provides a process for preparing a polyethylene material according to the first aspect of the present invention, comprising the steps of:
s1, preparing polyethylene resin;
s2, mixing the polyethylene resin with a main antioxidant, an auxiliary antioxidant, an acid-absorbing agent and an antistatic agent, and then granulating, and cooling the obtained granules with cooling water.
In some embodiments of the present invention, the method for preparing the polyethylene resin comprises: and continuously introducing the ethylene, the polymerized monomer and the molecular weight regulator into the fluidized bed reactor under the condition that the ethylene and the polymerized monomer are in a circulating state, and reacting after contacting with a catalyst to obtain the polyethylene resin.
The method adopts a gas-phase fluidized bed process, utilizes a novel high-activity catalyst, effectively removes product impurities, and realizes the stable production of products.
The gas-phase fluidized bed process refers to the process of directly polymerizing ethylene and polymerization monomer gas in a fluidized bed reactor or a stirred bed reactor to generate solid polyethylene. The gas phase fluidized bed process produces polyethylene without the need for a solvent and therefore does not require separation to recover the solvent. The gas phase method has the advantages of short flow, small occupied area of the device, low equipment investment, mild operation condition, low production unit consumption, small environmental pollution and the like, and is the mainstream technology of polyethylene production.
The polymerized monomer is selected from any one of ethylene and alpha-olefin of C4-C8; preferably, the α -olefin is selected from any one of 1-butene, 1-hexene and 1-octene; further preferably, the alpha-olefin is 1-butene.
The catalyst is a titanium catalyst; preferably, the titanium-based catalyst comprises a titanium tetrachloride-triethylaluminum catalytic system.
The molecular weight regulator in the present invention may be hydrogen gas.
In some embodiments of the invention, the temperature of the reaction is 100 to 110 ℃; preferably 104 to 108 ℃.
The obtained granules are cooled by using cooling water and entrained with the granules. In some embodiments of the present invention, the cooling water has a temperature of 50 to 70 ℃ and a flow rate of 600 to 700m3H is used as the reference value. And (3) separating moisture from the cooled particles, feeding the particles into a hopper, and then feeding the particles into the mixing, storage and transportation and packaging processes by using air to obtain the polyethylene material for the sheath-core fibers.
In some embodiments of the present invention, the method for preparing the polyethylene resin specifically comprises:
(1) purifying the monomer, wherein the ethylene and the polymerized monomer entering the polymerization reactor are respectively subjected to oxygen removal, carbon monoxide, carbon dioxide, water, sulfide, methanol, alkyne and other impurities which are toxic to the catalyst through the purifier, and the impurities are removed by a catalyst bed and a molecular sieve of the oxygen removal and the oxide.
(2) The polymerization reaction is carried out in a fluidized bed reactor, the lower part of the reactor is cylindrical, and the upper part of the reactor consists of an inverted cone and a hemisphere. The bottom of the reactor is provided with a gas distribution plate on which is a fluidized bed layer formed by powdery resin. The catalyst and optional cocatalyst are directly introduced into the reaction bed layer from the distribution plate, the circulating gas compressor feeds circulating gas to keep the bed layer in a fluidized state, the reaction monomer and the catalyst are uniformly mixed, reaction heat is taken away, and the reaction heat is removed out of the system in the circulating gas cooler. The molecular weight regulator hydrogen is also introduced into the system from the bottom of the reactor together with the polymerization monomer, and the reaction residence time is about 3 hours. The properties of polyethylene resins are mainly regulated by the amounts of catalyst, cocatalyst, comonomer and hydrogen added. In the invention, ethylene and a polymeric monomer are continuously introduced and added with a catalyst under the condition that the ethylene and the polymeric monomer are always in a circulating state, the reaction temperature in a reactor is adjusted to be 104-108 ℃, and the melt index (melt flow rate) of a reaction product is 18-22.0 g/10min and the density is 0.944-0.960 kg/m3Then, the polyethylene resin with the weight average molecular weight of 4-6 ten thousand and the crystallinity of 60-70 percent is obtained.
Optionally, the resin obtained can be degassed and the polyethylene resin is freed from unreacted monomers from the reactor by means of a special discharge system; the resin with the recovered monomer enters a degassing bin, hydrocarbons adsorbed in the polyethylene resin are further removed in the bin, dry air is introduced from the bottom of the degassing bin and contacts with the polyethylene resin in a countercurrent manner, and the hydrocarbon gas is taken away.
In a third aspect, the present invention provides a polyethylene material according to the first aspect of the present invention or prepared by the method of the second aspect, for use in preparing a sheath-core fibre. The sheath-core fiber prepared by the polyethylene material has higher glossiness, so that the sheath-core fiber looks brighter and meets the requirements of people on products.
Compared with the prior art, the invention has the following advantages:
(1) in the preparation method of the environment-friendly high-glossiness polyethylene material for the sheath-core fiber, the polymerization reaction adopts a gas-phase fluidized bed reaction process, the obtained polyethylene material has narrow molecular weight distribution and good mechanical property, and the obtained polyethylene material has good processability when being used for producing the sheath-core fiber, so that the normal production in the fiber drawing process is ensured, and the phenomenon of filament breakage is not easy to occur.
(2) The polyethylene material is added with the organic antistatic agent, so that the product has an antistatic function, and the inventor finds that the glossiness of the sheath-core fiber prepared from the polyethylene material is obviously higher than that of a similar product after the antistatic agent is added, the fiber product has smooth and bright hand feeling, and the appearance performance is obviously improved. More importantly, the product is environment-friendly and nontoxic, no fluorescent whitening agent is added, and the fibers have good sensory property and are easy to be noticed by customers.
(3) The catalyst adopted by the invention has high activity and stable production process, and the reaction can stably produce the polyethylene material for the sheath-core fiber under higher load (ethylene feeding amount). When the catalyst is used for production by a gas-phase fluidized bed process, the catalyst has good responsiveness to a polymerized monomer, can effectively improve the grafting efficiency of the polymerized monomer, produces the copolymerized polyethylene resin with narrow molecular weight distribution and good mechanical property, has stable polymerization production, is not easy to generate abnormal phenomena such as deviation of the actual temperature of a reactor from a set value due to reaction fluctuation, obviously reduces the yield of transition materials, and obviously improves the conversion efficiency of products.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description will proceed with reference being made to examples, which are intended to be illustrative only and are not intended to limit the scope of the invention. The starting materials or components used in the present invention may be commercially or conventionally prepared unless otherwise specified.
In the polymerization reaction of the following examples, the main reaction process is to continuously introduce ethylene, 1-butene and hydrogen into the reactor while ethylene and 1-butene are always in a circulating state, and to add a catalyst, to adjust the reaction temperature in the reactor to 106 ℃, until the melt flow rate of the reaction product is 18.0-22.0 g/10min and the density is 0.944-0.960 g/cm3Then, the ethylene-butylene copolymer polyethylene resin with the weight-average molecular weight of 5-9 ten thousand, the 1-butylene content of 0.01-0.1 wt% and the crystallinity of 60-70% is obtained. The catalyst is titanium catalyst, and slurry SLC-S catalyst produced by Shanghai Li catalyst Co.
Ethylene: purity is more than or equal to 99.90 percent C2H2≤5×10-6ppm CO≤1×10-6Kg/Kg
O2≤1×10-6Kg/Kg H2O≤1×10-6Kg/Kg
1-butene: purity is more than or equal to 99.0 percent H2O≤100×10-6Kg/Kg CO≤5×10-6Kg/Kg
CO2≤10×10-6Kg/Kg O2≤1×10-6Kg/Kg
CH3OH≤10×10-6Kg/Kg
Hydrogen gas: purity is more than or equal to 95.0 percent H2O≤5×10-6Kg/Kg O2≤10×10-6Kg/Kg
CO+CO2≤5×10-6Kg/Kg
The polymerization reactions of the following examples were carried out according to the above reaction parameters.
Example 1
The ethylene-butylene copolymer polyethylene resin obtained by the polymerization reaction is added with additives according to the following formula.
Raw materials of the polyethylene material (parts by weight):
the main antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4 hydroxyphenyl) propionic acid ] pentaerythritol ester, the auxiliary antioxidant is tri (2, 4-di-tert-butylphenyl) phosphite, the acid acceptor is zinc stearate, and the antistatic agent is an organic antistatic agent which is white waxy solid and is non-toxic.
The preparation method of the sheath-core fiber polyethylene material comprises the following steps:
uniformly mixing the ethylene-butylene copolymer polyethylene resin, the main antioxidant, the auxiliary antioxidant, the acid-absorbing agent and the antistatic agent according to the mixture ratio of the raw materials, adding the mixture into a mixing roll for granulation, and extruding granules into cooling water to obtain the granular polyethylene material. When the mixing roll is used for mixing, the temperature of a second section of barrel of the mixing roll is adjusted to be 190 ℃, the temperature of a third section of barrel is adjusted to be 225 ℃, the temperature of a fourth section of barrel is adjusted to be 225 ℃, the temperature of a fifth section of barrel is adjusted to be 225 ℃, the temperature of a sixth section of barrel is adjusted to be 225 ℃ and the temperature of a seventh section of barrel is adjusted to be 225 ℃; the temperature of the cooling water is 70 ℃, and the flow of the cooling water is 650m3/h。
Example 2
The ethylene-butylene copolymer polyethylene resin obtained by the polymerization reaction is added with additives according to the following formula.
Raw materials of the polyethylene material (parts by weight):
the main antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4 hydroxyphenyl) propionic acid ] pentaerythritol ester, the auxiliary antioxidant is tri (2, 4-di-tert-butylphenyl) phosphite ester, and the acid-absorbing agent is zinc stearate. The antistatic agent is an organic antistatic agent which is a white waxy solid and is non-toxic.
The preparation method of the sheath-core fiber polyethylene material comprises the following steps:
uniformly mixing the ethylene-butylene copolymer polyethylene resin, the main antioxidant, the auxiliary antioxidant, the acid-absorbing agent and the antistatic agent according to the mixture ratio of the raw materials, adding the mixture into a mixing roll for granulation, and extruding granules into cooling water to obtain the granular polyethylene material. When the mixing roll is used for mixing, the temperature of a second section of barrel of the mixing roll is adjusted to be 190 ℃, the temperature of a third section of barrel is adjusted to be 225 ℃, the temperature of a fourth section of barrel is adjusted to be 225 ℃, the temperature of a fifth section of barrel is adjusted to be 225 ℃, the temperature of a sixth section of barrel is adjusted to be 225 ℃ and the temperature of a seventh section of barrel is adjusted to be 225 ℃; the temperature of the cooling water is 70 ℃, and the flow of the cooling water is 650m3/h。
Example 3
The ethylene-butylene copolymer polyethylene resin obtained by the polymerization reaction is added with additives according to the following formula.
Raw materials of the polyethylene material (parts by weight):
the main antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4 hydroxyphenyl) propionic acid ] pentaerythritol ester, the auxiliary antioxidant is tri (2, 4-di-tert-butylphenyl) phosphite ester, and the acid-absorbing agent is zinc stearate. The antistatic agent is an organic antistatic agent which is a white waxy solid and is non-toxic.
The preparation method of the sheath-core fiber polyethylene material comprises the following steps:
uniformly mixing the ethylene-butylene copolymer polyethylene resin, the main antioxidant, the auxiliary antioxidant, the acid-absorbing agent and the antistatic agent according to the mixture ratio of the raw materials, adding the mixture into a mixing roll for granulation, and extruding granules into cooling water to obtain the granular polyethylene material. Wherein, when the mixing roll is used for mixing, the temperature of the second section of the cylinder of the mixing roll is adjusted to 190 ℃, the temperature of the third section of the cylinder is adjusted to 225 ℃, the temperature of the fourth section of the cylinder is adjusted to 225 ℃, the temperature of the fifth section of the cylinder is adjusted to 225 ℃, the temperature of the sixth section of the cylinder is adjusted to 225 ℃, and the temperature of the seventh section of the cylinder is adjusted to 225 DEG C(ii) a The temperature of the cooling water is 70 ℃, and the flow of the cooling water is 650m3/h。
Example 4
The ethylene-butylene copolymer polyethylene resin obtained by the polymerization reaction is added with additives according to the following formula.
Raw materials of the polyethylene material (parts by weight):
the main antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4 hydroxyphenyl) propionic acid ] pentaerythritol ester, the auxiliary antioxidant is bis (2, 4-di-tert-butylphenyl) propionic acid ] pentaerythritol diphosphite, and the acid acceptor is zinc stearate. The antistatic agent is an organic antistatic agent which is a white waxy solid and is non-toxic.
The preparation method of the sheath-core fiber polyethylene material comprises the following steps:
uniformly mixing the ethylene-butylene copolymer polyethylene resin, the main antioxidant, the auxiliary antioxidant, the acid-absorbing agent and the antistatic agent according to the mixture ratio of the raw materials, adding the mixture into a mixing roll for granulation, and extruding granules into cooling water to obtain the granular polyethylene material. When the mixing roll is used for mixing, the temperature of a second section of barrel of the mixing roll is adjusted to be 190 ℃, the temperature of a third section of barrel is adjusted to be 225 ℃, the temperature of a fourth section of barrel is adjusted to be 225 ℃, the temperature of a fifth section of barrel is adjusted to be 225 ℃, the temperature of a sixth section of barrel is adjusted to be 225 ℃ and the temperature of a seventh section of barrel is adjusted to be 225 ℃; the temperature of the cooling water is 70 ℃, and the flow of the cooling water is 650m3/h。
Example 5
The ethylene-butylene copolymer polyethylene resin obtained by the polymerization reaction is added with additives according to the following formula.
Raw materials of the polyethylene material (parts by weight):
the main antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4 hydroxyphenyl) propionic acid ] pentaerythritol ester, the auxiliary antioxidant is bis (2, 4-di-tert-butylphenyl) propionic acid ] pentaerythritol diphosphite, and the acid acceptor is zinc stearate. The antistatic agent is an organic antistatic agent which is a white waxy solid and is non-toxic.
The preparation method of the sheath-core fiber polyethylene material comprises the following steps:
uniformly mixing the ethylene-butylene copolymer polyethylene resin, the main antioxidant, the auxiliary antioxidant, the acid-absorbing agent and the antistatic agent according to the mixture ratio of the raw materials, adding the mixture into a mixing roll for granulation, and extruding granules into cooling water to obtain the granular polyethylene material. When the mixing roll is used for mixing, the temperature of a second section of barrel of the mixing roll is adjusted to be 190 ℃, the temperature of a third section of barrel is adjusted to be 225 ℃, the temperature of a fourth section of barrel is adjusted to be 225 ℃, the temperature of a fifth section of barrel is adjusted to be 225 ℃, the temperature of a sixth section of barrel is adjusted to be 225 ℃ and the temperature of a seventh section of barrel is adjusted to be 225 ℃; the temperature of the cooling water is 70 ℃, and the flow of the cooling water is 650m3/h。
Example 6
The ethylene-butylene copolymer polyethylene resin obtained by the polymerization reaction is added with additives according to the following formula.
Raw materials of the polyethylene material (parts by weight):
the main antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4 hydroxyphenyl) propionic acid ] pentaerythritol ester, the auxiliary antioxidant is bis (2, 4-di-tert-butylphenyl) propionic acid ] pentaerythritol diphosphite, and the acid acceptor is zinc stearate. The antistatic agent is an organic antistatic agent which is a white waxy solid and is non-toxic.
The preparation method of the sheath-core fiber polyethylene material comprises the following steps:
uniformly mixing the ethylene-butylene copolymer polyethylene resin, the main antioxidant, the auxiliary antioxidant, the acid-absorbing agent and the antistatic agent according to the mixture ratio of the raw materials, adding the mixture into a mixing roll for granulation, and extruding granules into cooling water to obtain the granular polyethylene material. Wherein, when the mixing roll is used for mixing, the temperature of the second section of the cylinder body of the mixing roll is adjusted to 190 ℃, the temperature of the third section of the cylinder body is adjusted to 225 ℃, and the temperature of the fourth section of the cylinder body of the mixing roll is adjusted to 190 ℃The temperature is 225 ℃, the temperature of the cylinder body at the fifth section is 225 ℃, the temperature of the cylinder body at the sixth section is 225 ℃, and the temperature of the cylinder body at the seventh section is 225 ℃; the temperature of the cooling water is 70 ℃, and the flow of the cooling water is 650m3/h。
Example 7
The ethylene-butylene copolymer polyethylene resin obtained by the polymerization reaction is added with additives according to the following formula.
Raw materials of the polyethylene material (parts by weight):
the main antioxidant is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester, the auxiliary antioxidant is bis (2, 4-di-tert-butylphenyl) propionic acid ] pentaerythritol diphosphite, and the acid-absorbing agent is zinc stearate. The antistatic agent is an organic antistatic agent which is a white waxy solid and is non-toxic.
The preparation method of the sheath-core fiber polyethylene material comprises the following steps:
uniformly mixing the ethylene-butylene copolymer polyethylene resin, the main antioxidant, the auxiliary antioxidant, the acid-absorbing agent and the antistatic agent according to the mixture ratio of the raw materials, adding the mixture into a mixing roll for granulation, and extruding granules into cooling water to obtain the granular polyethylene material. When the mixing roll is used for mixing, the temperature of a second section of barrel of the mixing roll is adjusted to be 190 ℃, the temperature of a third section of barrel is adjusted to be 225 ℃, the temperature of a fourth section of barrel is adjusted to be 225 ℃, the temperature of a fifth section of barrel is adjusted to be 225 ℃, the temperature of a sixth section of barrel is adjusted to be 225 ℃ and the temperature of a seventh section of barrel is adjusted to be 225 ℃; the temperature of the cooling water is 70 ℃, and the flow of the cooling water is 650m3/h。
Example 8
The ethylene-butylene copolymer polyethylene resin obtained by the polymerization reaction is added with additives according to the following formula.
Raw materials of the polyethylene material (parts by weight):
the main antioxidant is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester, the auxiliary antioxidant is (2, 4-di-tert-butylphenyl) propionic acid ] pentaerythritol diphosphite, and the acid acceptor is zinc stearate. The antistatic agent is an organic antistatic agent which is a white waxy solid and is non-toxic.
The preparation method of the sheath-core fiber polyethylene material comprises the following steps:
uniformly mixing the ethylene-butylene copolymer polyethylene resin, the main antioxidant, the auxiliary antioxidant, the acid-absorbing agent and the antistatic agent according to the mixture ratio of the raw materials, adding the mixture into a mixing roll for granulation, and extruding granules into cooling water to obtain the granular polyethylene material. When the mixing roll is used for mixing, the temperature of a second section of barrel of the mixing roll is adjusted to be 190 ℃, the temperature of a third section of barrel is adjusted to be 225 ℃, the temperature of a fourth section of barrel is adjusted to be 225 ℃, the temperature of a fifth section of barrel is adjusted to be 225 ℃, the temperature of a sixth section of barrel is adjusted to be 225 ℃ and the temperature of a seventh section of barrel is adjusted to be 225 ℃; the temperature of the cooling water is 70 ℃, and the flow of the cooling water is 650m3/h。
Example 9
The ethylene-butylene copolymer polyethylene resin obtained by the polymerization reaction is added with additives according to the following formula.
Raw materials of the polyethylene material (parts by weight):
the main antioxidant is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester, the auxiliary antioxidant is bis (2, 4-di-tert-butylphenyl) propionic acid ] pentaerythritol diphosphite, and the acid-absorbing agent is zinc stearate. The antistatic agent is an organic antistatic agent which is a white waxy solid and is non-toxic.
The preparation method of the sheath-core fiber polyethylene material comprises the following steps:
uniformly mixing the ethylene-butylene copolymer polyethylene resin, the main antioxidant, the auxiliary antioxidant, the acid-absorbing agent and the antistatic agent according to the mixture ratio of the raw materials, adding the mixture into a mixing roll for granulation, and extruding granules into cooling water to obtain the granular polyethylene material. Wherein, when the mixing machine is used for mixing, the mixing is adjustedThe temperature of the second section of the cylinder body of the mixer is 190 ℃, the temperature of the third section of the cylinder body is 225 ℃, the temperature of the fourth section of the cylinder body is 225 ℃, the temperature of the fifth section of the cylinder body is 225 ℃, the temperature of the sixth section of the cylinder body is 225 ℃ and the temperature of the seventh section of the cylinder body is 225 ℃; the temperature of the cooling water is 70 ℃, and the flow of the cooling water is 650m3/h。
Comparative example 1
The comparative product is a certain sheath-core fiber polyethylene product which is most commonly used in China, and the product is granular.
The products of inventive examples 1-9 were compared to comparative example 1, and the melt indices were compared as shown in Table 1.
TABLE 1
Detection by the method provided in GB3682-2000
As shown in table 1, the melt flow rates of the polyethylene materials of the invention were substantially comparable, as compared to comparative example 1, measured under the same conditions, indicating that the average molecular weights of the polyethylene materials were substantially comparable.
The gloss and transmittance of the products of examples 1-9 and comparative example 1 were measured, and the results are shown in table 2:
TABLE 2
Note: the test material was a sheet having a thickness of 1mm
As can be seen from the results in tables 1 and 2, compared with the similar products, the molecular weight of the product is basically equivalent, the glossiness and the light transmittance of the polyethylene material are higher than those of the comparative product, the product has the advantage of high glossiness, and the product is bright and bright, has good sensory effect and is easily welcomed by customers.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A polyethylene material, which is prepared by granulating raw materials; the raw materials comprise the following components in parts by weight:
2. polyethylene material according to claim 1, wherein the primary antioxidant is selected from phenolic antioxidants; preferably, the phenolic antioxidant is selected from pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] or octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
3. Polyethylene material according to claim 1 or 2, wherein the secondary antioxidant is selected from phosphite antioxidants; preferably, the secondary antioxidant is selected from tris (2, 4-di-tert-butylphenyl) phosphite or bis (2, 4-di-tert-butylphenyl) propanoic acid ] pentaerythritol diphosphite; and/or the antistatic agent is selected from organic antistatic agents.
4. Polyethylene material according to any of claims 1 to 3, characterized in thatCharacterized in that the polyethylene resin has a melt index of 18.0 to 22.0g/10min and a density of 0.944 to 0.960g/cm3The weight average molecular weight is 5-9 ten thousand, and the crystallinity is 60-70%.
5. A process for the preparation of a polyethylene material according to any one of claims 1 to 4, comprising the steps of:
s1, preparing polyethylene resin;
s2, mixing the polyethylene resin with a main antioxidant, an auxiliary antioxidant, an acid-absorbing agent and an antistatic agent, and then granulating, and cooling the obtained granules with cooling water.
6. The method according to claim 5, wherein the preparation method of the polyethylene resin comprises: and continuously introducing the ethylene, the polymerized monomer and the molecular weight regulator into the fluidized bed reactor under the condition that the ethylene and the polymerized monomer are in a circulating state, and reacting after contacting with a catalyst to obtain the polyethylene resin.
7. The method of claim 6, wherein the polymerized monomer is selected from any one of C4-C8 alpha-olefins; preferably, the α -olefin is selected from any one of 1-butene, 1-hexene and 1-octene; further preferably, the alpha-olefin is 1-butene.
8. The method according to claim 6 or 7, wherein the catalyst is a titanium-based catalyst; preferably, the titanium-based catalyst comprises a titanium tetrachloride-triethylaluminum system; and/or the temperature of the reaction is 100-110 ℃; preferably 104 to 108 ℃.
9. The method according to any one of claims 5 to 8, wherein the cooling water has a temperature of 50 to 70 ℃ and a flow rate of 600 to 700m3/h。
10. Use of a polyethylene material according to any one of claims 1 to 4 or prepared by a process according to any one of claims 5 to 9 for the preparation of a sheath-core fibre.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911046744.6A CN112745554A (en) | 2019-10-30 | 2019-10-30 | Polyethylene material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911046744.6A CN112745554A (en) | 2019-10-30 | 2019-10-30 | Polyethylene material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112745554A true CN112745554A (en) | 2021-05-04 |
Family
ID=75640753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911046744.6A Pending CN112745554A (en) | 2019-10-30 | 2019-10-30 | Polyethylene material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112745554A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1646739A (en) * | 2002-04-09 | 2005-07-27 | 东洋纺织株式会社 | Polyethylene fiber and process for producing the same |
| CN103370459A (en) * | 2011-02-14 | 2013-10-23 | 捷恩智株式会社 | Polyolefin-based antistatic fiber as monocomponent fiber or composite fiber and nonwoven fabric including the same |
| CN103554631A (en) * | 2013-10-16 | 2014-02-05 | 中国石油化工股份有限公司 | Blown plastic material for small hollow containers and preparation method thereof |
| CN104292595A (en) * | 2013-07-18 | 2015-01-21 | 中国石油化工股份有限公司 | High-rigid linear low-density polyethylene injection moulding resin |
| CN104356494A (en) * | 2014-10-10 | 2015-02-18 | 中国石油化工股份有限公司 | Polyethylene material for rotational thermal forming and preparation method thereof |
| CN106496802A (en) * | 2015-09-07 | 2017-03-15 | 中国石油天然气股份有限公司 | High-density polyethylene resin for melt-blown composite fiber |
| CN107365444A (en) * | 2016-05-13 | 2017-11-21 | 中国石化扬子石油化工有限公司 | A kind of film anti-static polyethylene composition and preparation method thereof |
| CN109385002A (en) * | 2017-08-09 | 2019-02-26 | 中国石化扬子石油化工有限公司 | A kind of 3D printing self-lubricating polyethylene composition and preparation method thereof |
-
2019
- 2019-10-30 CN CN201911046744.6A patent/CN112745554A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1646739A (en) * | 2002-04-09 | 2005-07-27 | 东洋纺织株式会社 | Polyethylene fiber and process for producing the same |
| CN103370459A (en) * | 2011-02-14 | 2013-10-23 | 捷恩智株式会社 | Polyolefin-based antistatic fiber as monocomponent fiber or composite fiber and nonwoven fabric including the same |
| CN104292595A (en) * | 2013-07-18 | 2015-01-21 | 中国石油化工股份有限公司 | High-rigid linear low-density polyethylene injection moulding resin |
| CN103554631A (en) * | 2013-10-16 | 2014-02-05 | 中国石油化工股份有限公司 | Blown plastic material for small hollow containers and preparation method thereof |
| CN104356494A (en) * | 2014-10-10 | 2015-02-18 | 中国石油化工股份有限公司 | Polyethylene material for rotational thermal forming and preparation method thereof |
| CN106496802A (en) * | 2015-09-07 | 2017-03-15 | 中国石油天然气股份有限公司 | High-density polyethylene resin for melt-blown composite fiber |
| CN107365444A (en) * | 2016-05-13 | 2017-11-21 | 中国石化扬子石油化工有限公司 | A kind of film anti-static polyethylene composition and preparation method thereof |
| CN109385002A (en) * | 2017-08-09 | 2019-02-26 | 中国石化扬子石油化工有限公司 | A kind of 3D printing self-lubricating polyethylene composition and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU615804B2 (en) | Linear ethylene interpolymer blends of interpolymers having narrow molecular weight and composition distributions | |
| US8802762B2 (en) | Additive composition and polymer composition comprising the same | |
| EP1303547B1 (en) | Propylene polymers with an ultra high melt flow rate | |
| EP1244717A1 (en) | Heterophasic copolymers | |
| AU728337B2 (en) | High-molecular-weight ethylene-propylene reactor blend with a broad molecular weight distribution | |
| KR101590998B1 (en) | Process and apparatus for continuous solution polymerization of olefins | |
| EP3234005A1 (en) | Low haze polyethylene polymer compositions | |
| JP2017078100A (en) | Resin composition, molding comprising the composition, and pipe | |
| CN102690378A (en) | Modified propylene polymer | |
| EP3467022B1 (en) | Propylene-based resin composition and injection-molded object thereof | |
| DE69924965T3 (en) | PROCESSES FOR THE POLYMERIZATION OF OLEFINS; POLYETHYLENES, AND FILMS, AND ARTICLES MADE THEREOF | |
| JPS62149711A (en) | Continuous production of high-melt viscoelasticity ethylene/propylene copolymer | |
| CN110724332B (en) | Polyethylene composition with excellent comprehensive performance for double-wall corrugated pipe and preparation method thereof | |
| JP2024540075A (en) | Sustainable high density polyethylene and method for its production | |
| CN112745554A (en) | Polyethylene material and preparation method and application thereof | |
| CN114573742B (en) | High-density polyethylene resin and preparation method and application thereof | |
| CN115304695A (en) | Special polypropylene material suitable for lithium battery diaphragm and preparation method thereof | |
| CN113583167A (en) | Device and method for producing propylene-butylene random copolymerization polypropylene by gas phase process | |
| CN114316110B (en) | Propylene-butene random copolymer production system and preparation method | |
| JP5128233B2 (en) | Polyolefin resin composition, molded product thereof, and electric wire / cable | |
| CN109627368B (en) | Production process of polyethylene wire drawing material product | |
| CN113136074A (en) | High-toughness homo-polypropylene composition and preparation method thereof | |
| CN114426731A (en) | Polypropylene material and preparation method and application thereof | |
| CN115505057B (en) | Low ash polyethylene powder production system and production method | |
| CN112457441B (en) | Random copolymerization polypropylene, preparation method thereof, polypropylene cast film containing random copolymerization polypropylene and application of polypropylene cast film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210504 |
|
| RJ01 | Rejection of invention patent application after publication |