CN106700224B - Polypropylene composition and preparation method thereof - Google Patents
Polypropylene composition and preparation method thereof Download PDFInfo
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- CN106700224B CN106700224B CN201510439721.7A CN201510439721A CN106700224B CN 106700224 B CN106700224 B CN 106700224B CN 201510439721 A CN201510439721 A CN 201510439721A CN 106700224 B CN106700224 B CN 106700224B
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Abstract
The invention discloses a polypropylene composition, which comprises the following components in parts by weight: 100 parts of propylene polymer, 0.05-0.15 part of main antioxidant, 0.1-0.3 part of auxiliary antioxidant, 0.01-0.05 part of halogen absorbent and 0.05-0.3 part of beta crystal nucleating agent; the invention also discloses a preparation method of the polypropylene composition, which is simple and suitable for large-scale production; the polypropylene microporous membrane prepared by melt stretch forming of the polypropylene composition provided by the invention has excellent forming and processing properties and mechanical properties, and few crystal points and defects of the membrane, so that the severe requirements of lithium battery diaphragms can be met; the polypropylene microporous membrane can be used for dry-method double-drawing pore-forming manufacturing, and the membrane can be used in the fields of artificial kidney dialysis membranes, artificial lung membranes, sterile filtration and packaging membranes, lithium battery membranes, air purification membranes, water treatment membranes, gas separation membranes, food preservative films and the like.
Description
Technical Field
The invention belongs to the field of new materials, and particularly relates to a polypropylene composition and a preparation method thereof.
Background
The polypropylene microporous membrane is a microporous membrane with the average pore diameter of 0.01-10 microns, which is obtained by taking polypropylene as a raw material through a special forming mode, can completely block various bacteria larger than 0.2-0.5 microns and dust larger than 0.1 micron and even block partial larger viruses due to the high-efficiency separation capacity of a functional membrane and the excellent mechanical property of a plastic film, and is widely applied to the fields of medicines, batteries, air purification, food industry, daily life and the like.
At present, the preparation method of the polypropylene microporous membrane mainly adopts a dry process for forming, and the dry process can be further divided into a unidirectional stretching process and a bidirectional stretching process. The pore-forming principle of the biaxial stretching process can be briefly described as follows: the microporous membrane is obtained by stretching a polypropylene sheet with high beta crystal content, and forming a micro interface or a gap in the membrane through the difference of beta and alpha crystal densities and defects in the membrane. The dry-method melt-stretching method does not comprise a phase separation process, so that the process is relatively simple, and no pollution is produced in the production process, so that the dry-method melt-stretching method becomes one of the most main forming methods of microporous membranes such as lithium ion battery diaphragms in China.
Chinese patent application 201180050627 discloses a method for producing high purity propylene polymers with medium molecular weight distribution, high crystallinity and low ash content by gas phase reactor using internal diester electron donors, but does not relate to the application of resins in the field of microporous membranes. Korean patent KR101300346 discloses a method for preparing a high purity polypropylene resin having a low content of inorganic compounds by using a catalyst comprising a solid titanium composite procatalyst, a cocatalyst and an external electron donor, and performing a reaction of a refined propylene monomer and hydrogen. However, the total ash content is still high due to the adoption of the external electron donor, and the application of the resin in the field of microporous films is not involved.
Chinese patent application 201210105083.1 discloses a polyethylene composition for manufacturing a power battery diaphragm, which is prepared by mixing common ultra-high molecular weight polyethylene resin, high molecular weight ultra-high molecular weight polyethylene resin and high density polyethylene resin with a diluent, and is suitable for manufacturing a lithium battery diaphragm with high puncture resistance and high tear resistance. Chinese patent application 201310303894.7 discloses a high density polyethylene resin composition for microporous films comprising the following components in weight percent: 17 wt% -50 wt% of polyethylene powder, 0.1 wt% -1 wt% of antioxidant and 50 wt% -83 wt% of diluent. The high-density polyethylene resin composition for the microporous membrane is a uniform system which is suitable for industrial production and can be well mixed, and is particularly suitable for being used as a polyethylene composition raw material for a microporous membrane of a lithium ion battery in a wet process. Both are suitable for wet forming lithium battery separators.
The first step in the dry biaxial stretching process for preparing the polypropylene microporous membrane is to select or prepare a proper propylene polymer raw material to provide good processability and mechanical properties of the formed microporous membrane, and simultaneously, to ensure good pore forming property. The traditional propylene polymer is adopted as a raw material, and the phenomena of excessive surface crystal points or defects, self-discharge and the like of the diaphragm are easily caused due to the high ash content and metal ion content of the traditional propylene polymer, so that the battery capacity, the cruising ability and the batch production are seriously influenced. Therefore, the current situation is that there is still a need to provide a PP material with low ash (impurity) content, good micropore porosification, while providing good tensile properties, puncture resistance and less surface crystal point defects, to meet the application as filtration membrane or lithium battery separator, etc.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the problem that propylene polymers in the prior art cannot meet the application requirements of a filtering membrane or a lithium battery diaphragm, and provides a polypropylene composition which has low ash content (impurity) and good micropore forming property, and simultaneously provides good tensile property, puncture resistance and fewer surface crystal point defects, and a preparation method thereof, so as to meet the application requirements of the polypropylene composition as the filtering membrane or the lithium battery diaphragm.
The technical scheme is as follows:
the polypropylene composition comprises the following components in parts by weight:
wherein the propylene polymer is homo-polypropylene or linear propylene/hexene-1 random copolymer, the main antioxidant is hindered phenol compound, the auxiliary antioxidant is (2, 4-di-tert-butylphenyl) phosphite triester or pentaerythritol diphosphite di (2, 4-di-tert-butylphenyl) ester, the beta-crystal nucleating agent is one of polycyclic aromatic hydrocarbon nucleating agent, organic carboxylic acid and salt nucleating agent thereof, aromatic amide nucleating agent or rare earth nucleating agent;
the homo-polypropylene has the following characteristics:
(1) the melt flow rate is 1.0-8 g/10 min;
(2) the ratio of the melt flow rate under 10 kg load to the melt flow rate under 2.16 kg load is 18-30;
(3) the isotactic index is between 96 and 99 percent;
(4) the content of xylene solubles is not more than 5.0%;
(5) the total ash content of the composition is less than or equal to 70 ppm;
the linear propylene/hexene-1 random copolymer has the following characteristics:
(1) the melt flow rate is 1.0-8 g/10 min;
(2) the ratio of the melt flow rate under 10 kg load to the melt flow rate under 2.16 kg load is 18-30;
(3) the content of the comonomer hexene-1 is 0.5 to 2.5 wt%, preferably 0.5 to 2.0 wt%;
(4) the content of xylene solubles is not more than 4.0%;
(5) having two distinct melting points or broad melting peaks greater and less than 160 c, respectively.
Further, the main antioxidant is one or two of beta- (4-hydroxy-3, 5-di-tert-butylphenyl) propionic acid n-octadecyl ester or tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
Further, the beta crystal nucleating agent is one of N' N-dicyclohexyl terephthalamide, naphthalene dicyclohexyl amide, trimesoyl-tris (2, 3-dimethylcyclohexylamine), 2, 6-bis (N-2, 2, 6, 6-tetramethyl piperidyl) naphthalene diamide or rare earth organic complex.
Further, the halogen absorbent is one or more of calcium stearate, zinc stearate and hydrated magnesium silicate.
The main antioxidant, the auxiliary antioxidant and the beta-crystal nucleating agent can be added in a pure form or a master batch or a composite additive form.
A preparation method of a polypropylene composition comprises the following steps:
adding propylene polymer powder into a high-speed mixer, mixing a main antioxidant, an auxiliary antioxidant, a halogen absorbent and a beta crystal nucleating agent, adding the mixture into the high-speed mixer, stirring and mixing, discharging after mixing, immediately adding the premix into a double-screw extruder with a set temperature, and carrying out melt mixing extrusion granulation to obtain the polypropylene composite material, wherein the set temperature of the double-screw extruder is 160-240 ℃.
The preparation method of the propylene polymer composition of the invention can also comprise the following steps: the two polypropylene resin components and the known additive are added into a Banbury mixer for melt mixing.
The preparation method of the propylene polymer comprises the following steps:
injecting 2L of liquid propylene into a high-pressure reaction kettle which is purged by hot nitrogen for more than 3 times, adding 6ml of cocatalyst triethyl aluminum, starting stirring, and then injecting 2L of liquid propylene; adding 8-12mg of HA catalyst and 30-320g of hydrogen, finally injecting 1L of liquid propylene, completely flushing the catalyst into the reaction kettle, and closing a feeding valve; heating the high-pressure polymerization reaction kettle to 70 ℃ within 15-20 minutes, timing, discharging residual gas after reacting for 1-2 hours, and discharging to obtain white propylene polymer powder.
The preparation method of the propylene polymer can also comprise the following steps:
injecting 2L of liquid propylene into a high-pressure reaction kettle which is purged by hot nitrogen for more than 3 times, adding 6ml of cocatalyst triethyl aluminum and 1ml of external electron donor D-donor, starting stirring, and then injecting 2L of liquid propylene; adding 60mg of ND catalyst, 30-410g of hydrogen and 25-150ml of hexene-1, finally injecting 1L of liquid propylene, completely flushing the catalyst into the reaction kettle, and closing a feeding valve; and (3) heating the high-pressure polymerization reaction kettle to 70 ℃ within 15-20 minutes, timing, reacting for 1 hour, discharging residual gas, and discharging to obtain the white propylene polymer powder.
The polypropylene microporous membrane produced by the polypropylene composition provided by the invention can be formed by a biaxial stretching method. The beta form has a lower crystalline density, melting temperature and enthalpy of fusion than the alpha form. The polypropylene is preferentially generated into beta crystal form by utilizing the difference of the physical properties of the beta crystal form and the alpha crystal form, and the extruded beta crystal form sheet is subjected to crystal form biaxial stretching or sequential and multiple stretching simultaneously, the beta crystal form of the polypropylene is converted into the alpha crystal form in the stretching process, and the density is increased to cause the film to form a microporous structure, thereby preparing the polypropylene microporous film.
Has the advantages that: the polypropylene composition is simple in method and suitable for large-scale production; the polypropylene microporous membrane prepared by melt stretch forming of the polypropylene composition provided by the invention has excellent forming and processing properties and mechanical properties, and few crystal points and defects of the membrane, so that the severe requirements of lithium battery diaphragms can be met; the polypropylene microporous membrane can be used for dry-method double-drawing pore-forming manufacturing, and the membrane can be used in the fields of artificial kidney dialysis membranes, artificial lung membranes, sterile filtration and packaging membranes, lithium battery membranes, air purification membranes, water treatment membranes, gas separation membranes, food preservative films and the like.
Detailed Description
In order to enhance the understanding of the present invention, the present invention will be further described with reference to the following examples, which are provided for illustration only and are not intended to limit the scope of the present invention.
The polypropylene microporous membranes described in the following examples were formed by the following method: firstly, adding the polypropylene composition into a die frame with the size of 100 multiplied by 5mm, pressing for 10 minutes at 220 ℃ and under 10MPa, then cooling to 120 ℃ at the speed of 40 ℃/minute, preserving the temperature for 5 minutes, and then cooling to room temperature at the speed of 15 ℃/minute to obtain a polypropylene film blank containing beta-crystals. Then the sample is put into an orthogonal tensile testing machine, heated at 90 ℃ for 5 minutes, longitudinally stretched at a stretch ratio of 4, heated to 140 ℃ for 5.5 times of transverse stretching, and annealed at 115 ℃ for 5 minutes to obtain the polypropylene microporous membrane.
Determination of the properties in the following examples:
the Gurley air permeability of the microporous membrane is determined according to ASTM D726 (determination of pressure 2.3cmHg, 10ml gas flow 6.452cm2Time required for membrane surface area (sec)).
Tensile strength of the films was determined with reference to GB/T13022-1991.
The puncture strength of the microporous membrane was measured with reference to GB/T10004-2008 by mounting a test piece having a diameter of 100mm on a sample membrane holding clamp, removing the top prick with a steel needle having a diameter of 1.0mm and a diameter tip radius of 0.5mm at a speed of (50. + -. 5) mm/min, and measuring the maximum load of the steel needle penetrating the test piece.
The detection method of the surface defects of the film comprises the following steps: a diaphragm with the area of 50cm multiplied by 50cm is drawn and flatly pasted on a white lamp box with the same area size, the number of abnormal bright spots is counted manually, and the average number of 5 samples is taken.
The double-screw extruder is a Haake double-screw extruder;
the HA catalyst and ND catalyst described in the following examples were both produced by petrochemical group of China;
pentaerythrityl tetrakis { beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate } (commercial product number: antioxidant 1010), triester of 2, 4-di-tert-butylphenyl) phosphite (commercial product number: antioxidant 168), n-octadecyl beta- (4-hydroxy-3, 5-di-tert-butylphenyl) propionate (commercial product number: antioxidant 1076), di (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (commercial product number: antioxidant 626).
Example 1
Preparation of homo-polypropylene:
the polymerization was carried out in a 10L autoclave (bulk polymerization): injecting 2L of liquid propylene into a high-pressure reaction kettle which is purged by hot nitrogen for more than 3 times, adding 6ml of cocatalyst triethyl aluminum, starting stirring, and then injecting 2L of liquid propylene; 11mg of HA catalyst and 30g of hydrogen were added and finally 1L of liquid propylene was injected, the catalyst was flushed completely into the reactor and the addition valve was closed. And (3) heating the high-pressure polymerization reaction kettle to 70 ℃ within 15-20 minutes, timing, reacting for 2 hours, discharging residual gas, and discharging to obtain white homo-polypropylene powder. After the homo-polypropylene powder was sufficiently dried, 1040 g of the total weight of the polymer was weighed, and the catalyst catalytic efficiency was calculated to be 9.5 ten thousand times.
Preparation of polypropylene composition:
adding 100 parts by mass of homopolymerized polypropylene powder into a high-speed mixer, mixing 0.1 part of main antioxidant namely tetra { beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid } pentaerythritol ester, 0.2 part of auxiliary antioxidant (2, 4-di-tert-butylphenyl) phosphite triester, 0.05 part of halogen absorbent calcium stearate and 0.1 part of beta crystal nucleating agent N' N-dicyclohexyl terephthalamide, adding the mixture into the high-speed mixer, stirring and mixing at the stirring speed of 400 revolutions per minute for 10 minutes. Discharging after mixing, immediately adding the premix into a double-screw extruder with a set temperature, and carrying out melt mixing extrusion granulation to obtain the polypropylene composition, wherein the set temperature of the double-screw extruder is 160-240 ℃.
The microporous membrane properties are shown in table 3.
Example 2
Preparation of homo-polypropylene:
the polymerization was carried out in a 10L autoclave (bulk polymerization): injecting 2L of liquid propylene into a high-pressure reaction kettle which is purged by hot nitrogen for more than 3 times, adding 6ml of cocatalyst triethyl aluminum, starting stirring, and then injecting 2L of liquid propylene; 10mg of HA catalyst and 70g of hydrogen are added, 1L of liquid propylene is finally injected, the catalyst is flushed completely into the reactor, and the feed valve is closed. And (3) heating the high-pressure polymerization reaction kettle to 70 ℃ within 15-20 minutes, timing, reacting for 2 hours, discharging residual gas, and discharging to obtain white homo-polypropylene powder. After the homo-polypropylene powder is fully dried, 1180 g of the total weight of the polymer is weighed, and the catalytic efficiency of the catalyst is calculated to be 11.8 ten thousand times.
Preparation of polypropylene composition:
adding 100 parts by mass of homopolymerized polypropylene powder into a high-speed mixer, mixing 0.05 part of beta- (4-hydroxy-3, 5-di-tert-butylphenyl) propionic acid n-octadecyl alcohol ester, 0.3 part of auxiliary antioxidant (2, 4-di-tert-butylphenyl) phosphite triester, 0.04 part of halogen absorbent zinc stearate and 0.3 part of beta crystal nucleating agent naphthalene dicyclohexylamide, and adding the mixture into the high-speed mixer to be stirred and mixed, wherein the stirring speed is 400 r/min, and the stirring and mixing time is 10 min. Discharging after mixing, immediately adding the premix into a Ha twin-screw extruder with a set temperature for melt mixing, extruding and granulating to obtain the polypropylene composition, wherein the set temperature of the twin-screw extruder is 160-240 ℃.
Example 3
Preparation of homo-polypropylene:
the polymerization was carried out in a 10L autoclave (bulk polymerization): injecting 2L of liquid propylene into a high-pressure reaction kettle which is purged by hot nitrogen for more than 3 times, adding 6ml of cocatalyst triethyl aluminum, starting stirring, and then injecting 2L of liquid propylene; 8mg of HA catalyst and 150g of hydrogen were added, 1L of liquid propylene was finally injected, the catalyst was flushed completely into the reactor, and the addition valve was closed. And (3) heating the high-pressure polymerization reaction kettle to 70 ℃ within 15-20 minutes, timing, reacting for 2 hours, discharging residual gas, and discharging to obtain white homo-polypropylene powder. After the homo-polypropylene powder is fully dried, 790 g of the total weight of the polymer is weighed, and the catalytic efficiency of the catalyst is calculated to be 9.9 ten thousand times.
Preparation of polypropylene composition:
adding 100 parts by mass of homopolymerized polypropylene powder into a high-speed mixer, mixing 0.15 part of main antioxidant tetra { beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid } pentaerythritol ester, 0.3 part of auxiliary antioxidant pentaerythritol diphosphite bis (2, 4-di-tert-butylphenyl) ester, 0.04 part of halogen absorbent calcium stearate and 0.2 part of beta crystal nucleating agent N' N-dicyclohexyl terephthalamide, adding into the high-speed mixer, stirring and mixing at the stirring speed of 400 revolutions per minute for 10 minutes. Discharging after mixing, immediately adding the premix into a double-screw extruder with a set temperature, and carrying out melt mixing extrusion granulation to obtain the polypropylene composition, wherein the set temperature of the double-screw extruder is 160-240 ℃.
The microporous membrane properties are shown in table 3.
Example 4
Preparation of homo-polypropylene:
the polymerization was carried out in a 10L autoclave (bulk polymerization): injecting 2L of liquid propylene into a high-pressure reaction kettle which is purged by hot nitrogen for more than 3 times, adding 6ml of cocatalyst triethyl aluminum, starting stirring, and then injecting 2L of liquid propylene; 9mg of HA catalyst and 320g of hydrogen were added, 1L of liquid propylene was finally injected, the catalyst was flushed completely into the reactor, and the addition valve was closed. And (3) heating the high-pressure polymerization reaction kettle to 70 ℃ within 15-20 minutes, timing, discharging residual gas after reacting for 1 hour, and discharging to obtain white homo-polypropylene powder. After the homo-polypropylene powder is fully dried, the total weight of the polymer is weighed to be 980 g, and the catalytic efficiency of the catalyst is calculated to be 10.9 ten thousand times.
Preparation of polypropylene composition:
adding 100 parts by mass of homopolymerized polypropylene powder into a high-speed mixer, mixing 0.05 part of main antioxidant namely tetra { beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid } pentaerythritol ester, 0.15 part of auxiliary antioxidant namely (2, 4-di-tert-butylphenyl) phosphite triester, 0.02 part of halogen absorbent calcium stearate and 0.1 part of beta crystal nucleating agent namely N' N-dicyclohexyl terephthalamide, adding the mixture into the high-speed mixer, stirring and mixing at the stirring speed of 400 r/min for 10 min. Discharging after mixing, immediately adding the premix into a double-screw extruder with a set temperature, and carrying out melt mixing extrusion granulation to obtain the polypropylene composition, wherein the set temperature of the double-screw extruder is 160-240 ℃.
Example 5
Preparation of a Linear propylene/hexene-1 random copolymer:
the polymerization was carried out in a 10L autoclave (bulk polymerization): injecting 2L of liquid propylene into a high-pressure reaction kettle which is purged by hot nitrogen for more than 3 times, adding 6ml of cocatalyst triethyl aluminum and 1ml of external electron donor D-donor, starting stirring, and then injecting 2L of liquid propylene; 60mg of ND catalyst, 30g of hydrogen and 26ml of hexene-1 are added, 1L of liquid propylene is finally injected, the catalyst is flushed completely into the reactor, and the addition valve is closed. Heating the high-pressure polymerization reaction kettle to 70 ℃ within 15-20 minutes, timing, discharging residual gas after reacting for 1 hour, and discharging to obtain white linear propylene/hexene-1 random copolymer powder. After the linear propylene/hexene-1 random copolymer powder was sufficiently dried, the total weight of the polymer was weighed to 1260 g, and the catalyst catalytic efficiency was calculated to be 2.1 ten thousand times.
Preparation of polypropylene composition:
according to the mass parts, 100 parts of linear propylene/hexene-1 random copolymer powder is added into a high-speed mixer, 0.05 part of a main antioxidant namely tetra { beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid } pentaerythritol ester, 0.2 part of an auxiliary antioxidant (2, 4-di-tert-butylphenyl) phosphite triester, 0.05 part of a halogen absorbent (calcium stearate) and 0.05 part of a beta crystal nucleating agent N' N-dicyclohexyl terephthalamide are mixed with each other, then the mixture is added into the high-speed mixer to be stirred and mixed, the stirring speed is 400 r/min, and the stirring and mixing time is 10 min. Discharging after mixing, immediately adding the premix into a double-screw extruder with a set temperature, and carrying out melt mixing extrusion granulation to obtain the polypropylene composition, wherein the set temperature of the double-screw extruder is 160-240 ℃.
Example 6
Preparation of a Linear propylene/hexene-1 random copolymer:
the polymerization was carried out in a 10L autoclave (bulk polymerization): injecting 2L of liquid propylene into a high-pressure reaction kettle which is purged by hot nitrogen for more than 3 times, adding 6ml of cocatalyst triethyl aluminum and 1ml of external electron donor D-donor, starting stirring, and then injecting 2L of liquid propylene; 60mg of ND catalyst, 80g of hydrogen and 50ml of hexene-1 are added, 1L of liquid propylene is finally injected, the catalyst is flushed completely into the reactor, and the addition valve is closed. Heating the high-pressure polymerization reaction kettle to 70 ℃ within 15-20 minutes, timing, discharging residual gas after reacting for 1 hour, and discharging to obtain white linear propylene/hexene-1 random copolymer powder. After the linear propylene/hexene-1 random copolymer powder was sufficiently dried, 1380 g of the total weight of the polymer was weighed, and the catalyst catalytic efficiency was calculated to be 2.3 ten thousand times.
Preparation of polypropylene composition:
adding 100 parts of linear propylene/hexene-1 random copolymer powder into a high-speed mixer, mixing 0.1 part of a main antioxidant beta- (4-hydroxy-3, 5-di-tert-butylphenyl) propionic acid n-octadecyl ester, 0.3 part of an auxiliary antioxidant (2, 4-di-tert-butylphenyl) phosphite triester, 0.1 part of a halogen absorbent calcium stearate and 0.15 part of a beta-crystal nucleating agent rare earth organic complex, adding the mixture into the high-speed mixer, stirring and mixing at the stirring speed of 400 revolutions per minute for 10 minutes. Discharging after mixing, immediately adding the premix into a double-screw extruder with a set temperature, and carrying out melt mixing extrusion granulation to obtain the polypropylene composition, wherein the set temperature of the double-screw extruder is 160-240 ℃.
Example 7
Preparation of a Linear propylene/hexene-1 random copolymer:
the polymerization was carried out in a 10L autoclave (bulk polymerization): injecting 2L of liquid propylene into a high-pressure reaction kettle which is purged by hot nitrogen for more than 3 times, adding 6ml of cocatalyst triethyl aluminum and 1ml of external electron donor D-donor, starting stirring, and then injecting 2L of liquid propylene; 60mg of ND catalyst, 200g of hydrogen and 80ml of hexene-1 are added, 1L of liquid propylene is finally injected, the catalyst is flushed completely into the reactor, and the addition valve is closed. Heating the high-pressure polymerization reaction kettle to 70 ℃ within 15-20 minutes, then timing, discharging residual gas after reacting for 1 hour, discharging to obtain white linear propylene/hexene-1 random copolymer powder, fully drying the linear propylene/hexene-1 random copolymer powder, weighing 1130 g of the total weight of the polymer, and calculating the catalytic efficiency of the catalyst to be 1.9 ten thousand times.
Preparation of polypropylene composition:
according to the mass parts, 100 parts of linear propylene/hexene-1 random copolymer powder is added into a high-speed mixer, 0.15 part of a main antioxidant, namely tetra { beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid } pentaerythritol ester, 0.1 part of an auxiliary antioxidant, namely pentaerythritol diphosphite bis (2, 4-di-tert-butylphenyl) ester, 0.05 part of a halogen absorbent, namely calcium stearate, and 0.3 part of a beta-crystal nucleating agent, namely N', N-dicyclohexyl terephthalamide, are mixed with each other, and then the mixture is added into the high-speed mixer to be stirred and mixed, wherein the stirring speed is 400 revolutions per minute, and the stirring and mixing time is 10 minutes. Discharging after mixing, immediately adding the premix into a double-screw extruder with a set temperature for melt mixing, extruding and granulating to obtain the polypropylene composition. The set temperature of the double-screw extruder is 160-240 ℃.
Example 8
Preparation of a Linear propylene/hexene-1 random copolymer:
the polymerization was carried out in a 10L autoclave (bulk polymerization): injecting 2L of liquid propylene into a high-pressure reaction kettle which is purged by hot nitrogen for more than 3 times, adding 6ml of cocatalyst triethyl aluminum and 1ml of external electron donor D-donor, starting stirring, and then injecting 2L of liquid propylene; 60mg of ND catalyst, 410g of hydrogen and 150ml of hexene-1 are added, 1L of liquid propylene is finally injected, the catalyst is flushed completely into the reactor, and the addition valve is closed. Heating the high-pressure polymerization reaction kettle to 70 ℃ within 15-20 minutes, timing, discharging residual gas after reacting for 1 hour, and discharging to obtain white linear propylene/hexene-1 random copolymer powder. After the linear propylene/hexene-1 random copolymer powder was sufficiently dried, the total weight of the polymer was weighed to 1300 g, and the catalyst catalytic efficiency was calculated to be 2.2 ten thousand times.
Preparation of polypropylene composition:
according to the mass parts, 100 parts of linear propylene/hexene-1 random copolymer powder is added into a high-speed mixer, and 0.1 part of main antioxidant namely tetra { beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid } pentaerythritol ester, 0.2 part of (2, 4-di-tert-butylphenyl) phosphite triester (trade name: 168), 0.05 part of halogen absorbent calcium stearate and 0.1 part of beta crystal nucleating agent N' N-dicyclohexyl terephthalamide are mixed with each other, added into the high-speed mixer and stirred for mixing, wherein the stirring speed is 400 r/min, and the stirring and mixing time is 10 min. Discharging after mixing, immediately adding the premix into a double-screw extruder with a set temperature, and carrying out melt mixing extrusion granulation to obtain the polypropylene composition, wherein the set temperature of the double-screw extruder is 160-240 ℃.
Comparative example 1
According to the mass parts, 100 parts of polypropylene (F1002B, China petrochemical Yangzi petrochemical company, Inc.) powder is added into a high-speed mixer, 0.1 part of a main antioxidant, namely tetra { beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid } pentaerythritol ester, 0.2 part of (2, 4-di-tert-butylphenyl) phosphite triester, 0.05 part of a halogen absorbent, namely calcium stearate, and 0.1 part of a beta crystal nucleating agent, namely N', N-dicyclohexylterephthalamide, are mixed with each other, then added into the high-speed mixer, and stirred and mixed, wherein the stirring speed is 400 r/min, and the stirring and mixing time is 10 min. Discharging after mixing, immediately adding the premix into a double-screw extruder with a set temperature, and carrying out melt mixing extrusion granulation to obtain the polypropylene composition, wherein the set temperature of the double-screw extruder is 160-240 ℃.
The properties of the propylene polymer, linear propylene/hexene-1 random copolymer, polypropylene composition are shown in tables 1 to 3.
TABLE 1 homo-polypropylene Properties
TABLE 2 Linear propylene/hexene-1 random copolymer Properties
TABLE 3 microporous Membrane Properties
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (7)
1. The polypropylene composition is characterized by comprising the following components in parts by weight:
wherein the propylene polymer is homo-polypropylene or linear propylene/hexene-1 random copolymer, the main antioxidant is hindered phenol compound, the auxiliary antioxidant is (2, 4-di-tert-butylphenyl) phosphite triester or pentaerythritol diphosphite di (2, 4-di-tert-butylphenyl) ester, the beta-crystal nucleating agent is one of polycyclic aromatic hydrocarbon nucleating agent, organic carboxylic acid and salt nucleating agent thereof, aromatic amide nucleating agent or rare earth nucleating agent;
the homo-polypropylene has the following characteristics:
(1) the melt flow rate is 1.0-8 g/10 min;
(2) the ratio of the melt flow rate under 10 kg load to the melt flow rate under 2.16 kg load is 18-30;
(3) the isotactic index is between 96 and 99 percent;
(4) the content of xylene solubles is not more than 5.0%;
(5)56ppm or less of total ash content of 70ppm or less;
the linear propylene/hexene-1 random copolymer has the following characteristics:
(1) the melt flow rate is 1.0-8 g/10 min;
(2) the ratio of the melt flow rate under 10 kg load to the melt flow rate under 2.16 kg load is 18-30;
(3) the content of the comonomer hexene-1 is 0.5-2.5 wt%;
(4) the content of xylene solubles is not more than 4.0%;
(5) having two different melting points greater and less than 160 c, respectively.
2. The polypropylene composition according to claim 1, wherein the primary antioxidant is one or both of n-octadecyl beta- (4-hydroxy-3, 5-di-tert-butylphenyl) propionate and pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
3. The polypropylene composition according to claim 1, wherein the beta crystal nucleating agent is one of N' N-dicyclohexylterephthalamide, naphthalene dicyclohexylamide, trimesoyl-tris (2, 3-dimethylcyclohexylamine), 2, 6-bis (N-2, 2, 6, 6-tetramethylpiperidyl) naphthalene diamide or a rare earth organic complex.
4. The polypropylene composition of claim 1, wherein the halogen absorber is one or more of calcium stearate, zinc stearate, and hydrous magnesium silicate.
5. A process for the preparation of a polypropylene composition according to any one of claims 1 to 4, comprising the steps of:
adding propylene polymer powder into a high-speed mixer, mixing a main antioxidant, an auxiliary antioxidant, a halogen absorbent and a beta crystal nucleating agent, adding the mixture into the high-speed mixer, stirring and mixing, discharging after mixing, immediately adding the premix into a double-screw extruder with a set temperature, and carrying out melt mixing extrusion granulation to obtain the polypropylene composite material, wherein the set temperature of the double-screw extruder is 160-240 ℃.
6. The method for preparing a polypropylene composition according to claim 5, wherein the propylene polymer is prepared by:
injecting 2L of liquid propylene into a high-pressure reaction kettle which is purged by hot nitrogen for more than 3 times, adding 6ml of cocatalyst triethyl aluminum, starting stirring, and then injecting 2L of liquid propylene; adding 8-12mg of HA catalyst and 30-320g of hydrogen, finally injecting 1L of liquid propylene, completely flushing the catalyst into the reaction kettle, and closing a feeding valve; heating the high-pressure polymerization reaction kettle to 70 ℃ within 15-20 minutes, timing, discharging residual gas after reacting for 1-2 hours, and discharging to obtain white propylene polymer powder.
7. The method for preparing a polypropylene composition according to claim 5, wherein the propylene polymer is prepared by:
injecting 2L of liquid propylene into a high-pressure reaction kettle which is purged by hot nitrogen for more than 3 times, adding 6ml of cocatalyst triethyl aluminum and 1ml of external electron donor D-donor, starting stirring, and then injecting 2L of liquid propylene; adding 60mg of ND catalyst, 30-410g of hydrogen and 25-150ml of hexene-1, finally injecting 1L of liquid propylene, completely flushing the catalyst into the reaction kettle, and closing a feeding valve; and (3) heating the high-pressure polymerization reaction kettle to 70 ℃ within 15-20 minutes, timing, reacting for 1 hour, discharging residual gas, and discharging to obtain the white propylene polymer powder.
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