CN106700224A - Polypropylene composition and preparation method thereof - Google Patents
Polypropylene composition and preparation method thereof Download PDFInfo
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- CN106700224A CN106700224A CN201510439721.7A CN201510439721A CN106700224A CN 106700224 A CN106700224 A CN 106700224A CN 201510439721 A CN201510439721 A CN 201510439721A CN 106700224 A CN106700224 A CN 106700224A
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Abstract
The invention discloses a polypropylene composition. The polypropylene composition consists of the following components: 100 parts of a propylene polymer, 0.05 to 0.15 part of a main antioxidant, 0.1 to 0.3 part of an auxiliary antioxidant, 0.01 to 0.05 part of a halogen absorbing agent and 0.05 to 0.3 part of a beta crystal nucleating agent. The invention also discloses a preparation method of the propylene polymer. The preparation method is simple and suitable for large-scale production; a polypropylene microporous film is prepared through melt drawing formation of the polypropylene composition provided by the invention, the microporous film has excellent formation processing performance and mechanical performance, and the film has few crystal points and defects, so that the strict requirements of the film comprising a lithium battery diaphragm can be met; the polypropylene composition can be applied to the polypropylene microporous film manufactured through dry double-drawing pore forming, and the film can be applied in the fields of artificial kidney dialysis membranes, artificial lung membranes, sterile filtering and sterile packaging membranes, lithium battery diaphragms, air purifying membranes, films for water treatment, films for gas separation, food preservative films and the like.
Description
Technical field
The invention belongs to field of new, and in particular to a kind of polypropene composition and preparation method thereof.
Background technology
Microporous polypropylene membrane is that, with polypropylene as raw material, the average pore size obtained by special molding mode is at 0.01~10 micron
Between microporous barrier, microporous polypropylene membrane due to having the excellent mechanical property for efficiently separating ability and plastic sheeting of functional membrane concurrently simultaneously,
The dust of the various bacteriums and 0.1 more than μ more than 0.2~0.5 μ can completely be intercepted, it might even be possible to intercept the larger virus in part,
Therefore it is used widely in medicine, battery, purification of air, food industry or even the medium field of daily life.
At present, the preparation method of microporous polypropylene membrane is mainly molded using dry process, and dry process can be further divided into unidirectionally again
Drawing process and stretch processes.Wherein stretch processes pore-forming principle can be sketched and be：Stretching beta crystal content is higher to be gathered
Polypropylene sheet, by the defect inside the difference and diaphragm of β and α crystal densities, micro-interface or gap is internally formed in diaphragm
To obtain microporous barrier.Because dry method fusion drawn method does not include phase separation, its technique is relatively easy, without dirt in production process
One of dye, therefore the main forming method as microporous barriers such as domestic lithium ion battery separators.
Chinese patent application 201180050627 discloses a kind of using two esters internal electron donors, in being produced by Gas-phase reactor
The method of equimolecular quantity distribution, high-crystallinity and low-ash high-purity propylene polymer, but resin is not directed in micro-pore septum
The application in field.Korean Patent KR101300346 discloses a kind of high purity polypropylene tree with low inorganic compound content
The preparation method of fat, includes solid titanium compound primary catalysts, co-catalyst and external electron donor, and carry out by using catalyst
The acrylic polymers that the reaction of refined propylene monomer and hydrogen is obtained.But because employing external electron donor, its overall ash content is still inclined
Height, and it is not directed to application of the resin in microporous membrane field.
Chinese patent application 201210105083.1 discloses a kind of polyethylene composition for manufacturing strength battery diaphragm, passes through
The common polyvinyl resin with super-high molecular weight of selection, the polyvinyl resin with super-high molecular weight of HMW and high density polyethylene (HDPE) tree
Fat, adds diluent and mixes polyethylene composition, it is adaptable to make the lithium battery of anti-puncture intensity high and high anti-tearing strength
Barrier film.Chinese patent application 201310303894.7 discloses microporous barrier high-density polyethylene resin composition includes following components,
By weight percentage：Polyethylene powder 17wt%~50wt%, antioxidant 0.1wt%~1wt%, diluent 50wt%~
83wt%.Microporous barrier high-density polyethylene resin composition of the present invention is a kind of suitable industrialized production, can be well molten
Mixed homogeneous system, is particularly useful as the polyethylene composition raw material of wet processing lithium ion battery micro-pore septum.But the two
It is applied to wet moulding lithium battery diaphragm.
The first step that dry method stretch processes prepare microporous polypropylene membrane is to select or prepare Suitable propylene polymer raw material, to carry
For shaped micro-cavity film good processing characteristics and mechanical property, while needing to ensure good pore-creating character.It is poly- using traditional propylene
, used as raw material, because its ash content and metal ion content are high, the surface spherulite or defect for easily causing barrier film are excessive and put certainly for compound
The phenomenons such as electricity, badly influence battery capacity, endurance and batch production.Therefore, current present situation is, it is still desirable to carry
For a kind of PP raw materials, it has low ash content (impurity) content, good micropore pore-creating character, at the same provide good tensile property,
Paracentesis resistance energy and less surface spherulite defect, to meet the application as filter membrane or lithium battery diaphragm etc..
The content of the invention
Goal of the invention：Cannot meet filter membrane or lithium battery the invention aims to solve acrylic polymers of the prior art
Application in barrier film, there is provided one kind has low ash content (impurity) content, good micropore pore-creating character, while providing good drawing
Performance, paracentesis resistance energy and less polypropene composition of surface spherulite defect and preparation method thereof are stretched, to meet as filtering
The application of film or lithium battery diaphragm etc..
Technical scheme：
A kind of polypropene composition, it is according to the mass fraction, composed of the following components：
Wherein, acrylic polymers is HOPP or linear propylene/random copolymer of hexene -1, and primary antioxidant is Hinered phenols
Compound, auxiliary anti-oxidant is (2,4- di-tert-butyl-phenyl) tris phosphite or (2, the 4- di-t-butylbenzenes of pentaerythritol bis-phosphite two
Base) ester, β crystalline substance nucleators are condensed-nuclei aromatics nucleator, organic carboxyl acid and its esters nucleator, aromatic amides class nucleator or rare earth
One kind in class nucleator；
The HOPP has following characteristic：
(1) melt flow rate (MFR) is 1.0~8g/10min；
Under (2) 10 kilograms of loads under melt flow rate (MFR) and 2.16 kilograms of loads melt flow rate (MFR) ratio between 18~30；
(3) isotactic index is between 96%~99%；
(4) xylene soluble content is no more than 5.0%；
(5) composition total ash≤70ppm；
The linear propylene/random copolymer of hexene -1 has following characteristic：
(1) melt flow rate (MFR) is 1.0~8g/10min；
Under (2) 10 kilograms of loads under melt flow rate (MFR) and 2.16 kilograms of loads melt flow rate (MFR) ratio between 18~30；
(3) content of comonomer hexene -1 is in 0.5~2.5wt%, preferably 0.5~2.0wt%；
(4) xylene soluble content is no more than 4.0%；
(5) with being respectively greater than and two different fusing points less than 160 DEG C or melting peak wide.
Further, the primary antioxidant is β-positive octadecanol ester of (4 hydroxyl -3,5- di-tert-butyl-phenyls) propionic acid or four [β-(3,5-
Di-tert-butyl-hydroxy phenyl) propionic acid] one or two in pentaerythritol ester.
Further, the β crystalline substances nucleator is N ' N- dicyclohexyl terephthalamides, the Cyclohexamide of naphthalene two, the formyl of equal benzene three
- three (2,3- dimethyl cyclohexyl amines), (N-2,2,6,6- tetramethyl-piperidyls) the naphthalene diamides of 2,6- bis- or the organic cooperation of rare earth
One kind in thing.
Further, the halogen-absorber is one or more of calcium stearate, zinc stearate and hydrated magnesium silicate.
Described primary antioxidant, auxiliary anti-oxidant and β crystalline substance nucleator can be added with pure form, it is also possible to which masterbatch or be combined adds
Plus dosage form formula is added.
A kind of preparation method of polypropene composition, including following several steps：
Acrylic polymers powder is added in super mixer, and primary antioxidant, auxiliary anti-oxidant, halogen-absorber and β is brilliant
After nucleator is mutually mixed, stirring mixing in super mixer is added to, is discharged after the completion of mixing, immediately add the premix
Melt mixed extruding pelletization being carried out in the double screw extruder for set temperature and being obtained, double screw extruder design temperature is
160~240 DEG C.
The preparation method of prolylene polymer composition of the present invention can also be：By two kinds of polypropylene resin components and known
Additive carries out melt mixed and obtains in being added to Banbury blender.
The preparation method of the acrylic polymers is：
The liquid propene of 2L is injected in the autoclave that hot nitrogen purges more than 3 times, the second of co-catalyst three of 6ml is added
Base aluminium, starts stirring, reinjects 2L liquid propenes；The HA catalyst of 8-12mg and the hydrogen of 30-320g are added, finally
The liquid propene of 1L is injected, catalyst is all flushed into reactor, close charging valve；By high pressure in 15~20 minutes
Polymerization reaction kettle be warmed up to 70 DEG C after timing, reaction 1-2 hour after emit residual gas, discharge, obtain white acrylic be polymerized
Thing powder.
The preparation method of the acrylic polymers can also be：
The liquid propene of 2L is injected in the autoclave that hot nitrogen purges more than 3 times, the second of co-catalyst three of 6ml is added
Base aluminium and 1ml external electron donor D-donor, start stirring, reinject 2L liquid propenes；The ND catalyst of 60mg is added,
The hydrogen of 30-410g and hexene -1 of 25-150ml, finally inject the liquid propene of 1L, and catalyst is all flushed into reactor
It is interior, close charging valve；Timing after high pressure polymerisation reactor is warmed up into 70 DEG C in 15~20 minutes, reacts 1 hour heel row
Residual gas is bled off, is discharged, obtain white acrylic polymer powders.
The polypropene composition production microporous polypropylene membrane provided using the present invention can be molded by biaxial tension method.Beta crystal phase
There is lower crystal density, melt temperature and melting enthalpy than alpha-crystal form.Using these physical properties of beta crystal and alpha-crystal form
Difference, use special crystallization condition or add β crystalline substance nucleator so that polypropylene preferentially generates beta crystal, and will extrude beta crystal
Crystal formation is biaxial stretch-formed or successively and multi-drawing simultaneously for sheet material, and polyacrylic beta crystal changes to alpha-crystal form in drawing process, close
Degree increase causes film to form microcellular structure, so as to microporous polypropylene membrane is obtained.
Beneficial effect：Polypropene composition of the present invention, method is simple, is suitable to large-scale production；There is provided using the present invention
Polypropene composition prepares microporous polypropylene membrane by melt drawn shaping, the moulding processability and good mechanical performance of microporous barrier,
The fisheye and defect of film are few, such that it is able to meet the rigors including lithium battery diaphragm；Can be used to the double holes that pull into of dry method manufacture
Microporous polypropylene membrane, its film can be used for artificial kidney dialysis membrane, artificial lung film, be sterile filtered and aseptic packaging film, lithium electricity
The fields such as pond barrier film, purification of air film, water process film, gas separation film and food fresh keeping membrane.
Specific embodiment
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, and these embodiments are only used
In the present invention is explained, it is not intended to limit the scope of the present invention..
Microporous polypropylene membrane described in following examples is molded using following methods：Polypropene composition is added to first
In 100 × 100 × 5mm is framed, suppressed 10 minutes under 220 DEG C, 10MPa, be then cooled to 120 DEG C with 40 DEG C/min,
And 5 minutes are incubated, and room temperature then is cooled to 15 DEG C/min, obtain containing β brilliant polypropylene screen base.Then sample is put into just
Hand in cupping machine, after being heated 5 minutes at 90 DEG C, carry out longitudinal stretching, draw ratio is 4, then raises temperature to 140 DEG C
After carrying out 5.5 times of cross directional stretch, annealing obtains microporous polypropylene membrane in 5 minutes at 115 DEG C.
The measure of performance in following examples：
According to ASTM D726 measure, (when determining pressure 2.3cmHg, 10ml gases flow through microporous barrier Gurley air penetrabilities
6.452cm2The time required to film surface area (sec)).
The stretching strength determination of film is carried out with reference to GB/T 13022-1991.
The puncture strength of microporous barrier is determined and carried out with reference to GB/T10004-2008, and the test piece of a diameter of 100mm is arranged on into sample film
On clamping ring, diameter 1.0mm is then used, diameter tip radius are the draw point of 0.5mm, with the speed of (50 ± 5) mm/min
Degree goes to top to pierce, and reads the peak load that draw point penetrates test piece.
Film surface defects detection method：Area 50cm × 50cm barrier films are extracted to be flattened on the white lamp box of equal area size,
The number of the artificial abnormal bright spot of statistics, and take 5 averages of sample.
Double screw extruder is Haake double screw extruder；
HA catalyst and ND catalyst described in following examples originate from China PetroChemical Corporation；
Four { β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid } pentaerythritol ester (article numbers：Antioxidant 1010), (2,4- bis- tertiary fourths
Base phenyl) tris phosphite (article number：Irgasfos 168), β-(4- hydroxyl -3,5- di-tert-butyl-phenyls) positive octadecanol ester of propionic acid
(article number：Antioxidant 1076), pentaerythritol bis-phosphite two (2,4- di-tert-butyl phenyl) ester (article number：Antioxidant 626).
Embodiment 1
The preparation of HOPP：
Polymerisation is carried out in 10L autoclaves (polymerisation in bulk)：Noted in the autoclave that hot nitrogen purges more than 3 times
Enter the liquid propene of 2L, add the co-catalyst triethyl aluminum of 6ml, start stirring, reinject 2L liquid propenes；Add 11mg
HA catalyst and 30g hydrogen, finally inject 1L liquid propene, catalyst is all flushed into reactor, close plus
Material valve.Timing after high pressure polymerisation reactor is warmed up into 70 DEG C in 15~20 minutes, reaction emits residual gas after 2 hours
Body, discharging, obtains white homo-polypropylene powder.Homo-polypropylene powder weighs the gross weight of polymer after fully drying
1040 grams, it is 9.5 ten thousand times to calculate catalyst efficiency.
The preparation of polypropene composition：
According to the mass fraction, 100 parts of homo-polypropylene powder is added in super mixer, and by 0.1 part of primary antioxidant
Four { β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid } pentaerythritol esters, 0.2 part of auxiliary anti-oxidant (2,4- di-tert-butyl-phenyls) are sub-
Phosphotriester, 0.05 part of halogen-absorber calcium stearate and 0.1 part of β crystalline substances nucleant agent N ' N- dicyclohexyl terephthalamides
After being mutually mixed, stirring mixing in super mixer is added to, speed of agitator is 400 revs/min, and stirring incorporation time is 10
Minute.Discharged after the completion of mixing, be immediately added to the premix carries out melt and mix in the double screw extruder for set temperature
Close extruding pelletization and obtain polypropene composition, 160~240 DEG C of double screw extruder design temperature.
Micropore film properties are shown in Table 3.
Embodiment 2
The preparation of HOPP：
Polymerisation is carried out in 10L autoclaves (polymerisation in bulk)：Noted in the autoclave that hot nitrogen purges more than 3 times
Enter the liquid propene of 2L, add the co-catalyst triethyl aluminum of 6ml, start stirring, reinject 2L liquid propenes；Add 10mg
HA catalyst and 70g hydrogen, finally inject 1L liquid propene, catalyst is all flushed into reactor, close plus
Material valve.Timing after high pressure polymerisation reactor is warmed up into 70 DEG C in 15~20 minutes, reaction emits residual gas after 2 hours
Body, discharging, obtains white homo-polypropylene powder.Homo-polypropylene powder weighs the gross weight of polymer after fully drying
1180 grams, it is 11.8 ten thousand times to calculate catalyst efficiency.
The preparation of polypropene composition：
According to the mass fraction, 100 parts of homo-polypropylene powders are added in super mixer, and by 0.05 part of β-(4- hydroxyls
Base -3,5- di-tert-butyl-phenyls) the positive octadecanol ester of propionic acid, 0.3 part of auxiliary anti-oxidant (2,4- di-tert-butyl-phenyls) phosphorous acid three
After ester, 0.04 part of halogen-absorber zinc stearate and the Cyclohexamide of 0.3 part of β crystalline substance nucleators naphthalene two are mutually mixed, it is added to
Mixing is stirred in super mixer, speed of agitator is 400 revs/min, and stirring incorporation time is 10 minutes.Go out after the completion of mixing
Material, being immediately added to the premix in the Kazakhstan double screw extruder for set temperature carries out melt mixed extruding pelletization and is gathered
Propylene compositions, 160~240 DEG C of double screw extruder design temperature.
Embodiment 3
The preparation of HOPP：
Polymerisation is carried out in 10L autoclaves (polymerisation in bulk)：Noted in the autoclave that hot nitrogen purges more than 3 times
Enter the liquid propene of 2L, add the co-catalyst triethyl aluminum of 6ml, start stirring, reinject 2L liquid propenes；Add 8mg
HA catalyst and 150g hydrogen, finally inject 1L liquid propene, catalyst is all flushed into reactor, close
Charging valve.Timing after high pressure polymerisation reactor is warmed up into 70 DEG C in 15~20 minutes, reaction emits remnants after 2 hours
Gas, discharging, obtains white homo-polypropylene powder.Homo-polypropylene powder weighs the gross weight of polymer after fully drying
790 grams of amount, it is 9.9 ten thousand times to calculate catalyst efficiency.
The preparation of polypropene composition：
According to the mass fraction, 100 parts of homo-polypropylene powders are added in super mixer, and by 0.15 part of primary antioxidant four
{ β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid } pentaerythritol ester, 0.3 part of auxiliary anti-oxidant pentaerythritol bis-phosphite two
(2,4- di-tert-butyls phenyl) ester, 0.04 part of halogen-absorber calcium stearate and 0.2 part of β crystalline substances nucleant agent N ' N- dicyclohexyls pair
After benzenedicarboxamide is mutually mixed, stirring mixing in super mixer is added to, speed of agitator is 400 revs/min, stirring mixing
Time is 10 minutes.Discharged after the completion of mixing, be added in the double screw extruder for set temperature by the premix immediately
Row melt mixed extruding pelletization obtains polypropene composition, 160~240 DEG C of double screw extruder design temperature.
Micropore film properties are shown in Table 3.
Embodiment 4
The preparation of HOPP：
Polymerisation is carried out in 10L autoclaves (polymerisation in bulk)：Noted in the autoclave that hot nitrogen purges more than 3 times
Enter the liquid propene of 2L, add the co-catalyst triethyl aluminum of 6ml, start stirring, reinject 2L liquid propenes；Add 9mg
HA catalyst and 320g hydrogen, finally inject 1L liquid propene, catalyst is all flushed into reactor, close
Charging valve.Timing after high pressure polymerisation reactor is warmed up into 70 DEG C in 15~20 minutes, reaction emits remnants after 1 hour
Gas, discharging, obtains white homo-polypropylene powder.Homo-polypropylene powder weighs the gross weight of polymer after fully drying
980 grams of amount, it is 10.9 ten thousand times to calculate catalyst efficiency.
The preparation of polypropene composition：
According to the mass fraction, 100 parts of homo-polypropylene powders are added in super mixer, and by 0.05 part of primary antioxidant four
{ β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid } pentaerythritol ester, 0.15 part of auxiliary anti-oxidant (2,4- di-tert-butyl-phenyls) phosphorous
Sour three esters, 0.02 part of halogen-absorber calcium stearate and 0.1 part of β crystalline substances nucleant agent N ' N- dicyclohexyl terephthalamide phases
Mutually after mixing, stirring mixing in super mixer is added to, speed of agitator is 400 revs/min, and stirring incorporation time is 10 points
Clock.Discharged after the completion of mixing, the premix is added in the double screw extruder for set temperature carries out melt mixed immediately
Extruding pelletization obtains polypropene composition, 160~240 DEG C of double screw extruder design temperature.
Embodiment 5
The preparation of linear propylene/random copolymer of hexene -1：
Polymerisation is carried out in 10L autoclaves (polymerisation in bulk)：Noted in the autoclave that hot nitrogen purges more than 3 times
Enter the liquid propene of 2L, add the co-catalyst triethyl aluminum and 1ml external electron donor D-donor of 6ml, start stirring, then
Injection 2L liquid propenes；ND catalyst, 30g hydrogen and 26ml hexene -1 of 60mg are added, the liquid of 1L is finally injected
Propylene, catalyst is all flushed into reactor, closes charging valve.By high pressure polymerisation reactor liter in 15~20 minutes
Temperature emits residual gas to timing after 70 DEG C after reacting 1 hour, discharges, and obtains white linear propylene/random copolymerization of hexene -1
Thing powder.Linear propylene/the random copolymer of hexene -1 powder weighs 1260 grams of the gross weight of polymer, meter after fully drying
It is 2.1 ten thousand times to calculate catalyst efficiency.
The preparation of polypropene composition：
According to the mass fraction, 100 parts of linear propylenes/random copolymer powder of hexene -1 is added in super mixer, and by 0.05
Part primary antioxidant four { β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid } pentaerythritol ester, 0.2 part of the auxiliary anti-oxidant (uncles of 2,4- bis-
Butyl phenyl) tris phosphite, 0.05 part of halogen-absorber (calcium stearate) and 0.05 part of β crystalline substances nucleant agent N ' rings of N- bis-
After hexyl terephthalamide is mutually mixed, stirring mixing in super mixer is added to, speed of agitator is 400 revs/min, is stirred
Incorporation time is mixed for 10 minutes.Discharged after the completion of mixing, the premix is added to the twin-screw extrusion for having set temperature immediately
Melt mixed extruding pelletization is carried out in machine and obtains polypropene composition, 160~240 DEG C of double screw extruder design temperature.
Embodiment 6
The preparation of linear propylene/random copolymer of hexene -1：
Polymerisation is carried out in 10L autoclaves (polymerisation in bulk)：Noted in the autoclave that hot nitrogen purges more than 3 times
Enter the liquid propene of 2L, add the co-catalyst triethyl aluminum and 1ml external electron donor D-donor of 6ml, start stirring, then
Injection 2L liquid propenes；The ND catalyst of 60mg, 80g hydrogen and 50ml hexene -1 are added, the liquid of 1L is finally injected
Propylene, catalyst is all flushed into reactor, closes charging valve.By high pressure polymerisation reactor liter in 15~20 minutes
Temperature emits residual gas to timing after 70 DEG C after reacting 1 hour, discharges, and obtains white linear propylene/random copolymerization of hexene -1
Thing powder.Linear propylene/the random copolymer of hexene -1 powder weighs 1380 grams of the gross weight of polymer, meter after fully drying
It is 2.3 ten thousand times to calculate catalyst efficiency.
The preparation of polypropene composition：
According to the mass fraction, 100 parts of linear propylenes/random copolymer powder of hexene -1 is added in super mixer, and by 0.1
Primary antioxidant β-(4- hydroxyl -3,5- di-tert-butyl-phenyls) the positive octadecanol ester of propionic acid, 0.3 part of auxiliary anti-oxidant (2,4- of part
Di-tert-butyl-phenyl) tris phosphite, the β crystalline substance nucleator rare earths of 0.1 part of halogen-absorber calcium stearate and 0.15 part organic match somebody with somebody
After compound is mutually mixed, stirring mixing in super mixer is added to, speed of agitator is 400 revs/min, stirring incorporation time is
10 minutes.Discharged after the completion of mixing, the premix is added in the double screw extruder for set temperature carries out melt immediately
Mixing extruding pelletization obtains polypropene composition, 160~240 DEG C of double screw extruder design temperature.
Embodiment 7
The preparation of linear propylene/random copolymer of hexene -1：
Polymerisation is carried out in 10L autoclaves (polymerisation in bulk)：Noted in the autoclave that hot nitrogen purges more than 3 times
Enter the liquid propene of 2L, add the co-catalyst triethyl aluminum and 1ml external electron donor D-donor of 6ml, start stirring, then
Injection 2L liquid propenes；ND catalyst, 200g hydrogen and 80ml hexene -1 of 60mg are added, the liquid of 1L is finally injected
Propylene, catalyst is all flushed into reactor, closes charging valve.By high pressure polymerisation reactor liter in 15~20 minutes
Temperature emits residual gas to timing after 70 DEG C after reacting 1 hour, discharges, and obtains white linear propylene/random copolymerization of hexene -1
Thing powder, the linear propylene/random copolymer of hexene -1 powder weighs 1130 grams of the gross weight of polymer, meter after fully drying
It is 1.9 ten thousand times to calculate catalyst efficiency.
The preparation of polypropene composition：
According to the mass fraction, 100 parts of linear propylenes/random copolymer powder of hexene -1 is added in super mixer, and by 0.15
Part primary antioxidant four { β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid } pentaerythritol ester, 0.1 part of auxiliary anti-oxidant pentaerythrite are double
Phosphite ester two (2,4- di-tert-butyls phenyl) ester, 0.05 part of halogen-absorber calcium stearate and 0.3 part of β crystalline substances nucleant agent N ' N-
After dicyclohexyl terephthalamide is mutually mixed, stirring mixing in super mixer is added to, speed of agitator is 400 revs/min,
Stirring incorporation time is 10 minutes.Discharged after the completion of mixing, the premix is added to immediately has been set the twin-screw of temperature and is squeezed
Go out in machine to carry out melt mixed extruding pelletization to obtain polypropene composition.160~240 DEG C of double screw extruder design temperature.
Embodiment 8
The preparation of linear propylene/random copolymer of hexene -1：
Polymerisation is carried out in 10L autoclaves (polymerisation in bulk)：Noted in the autoclave that hot nitrogen purges more than 3 times
Enter the liquid propene of 2L, add the co-catalyst triethyl aluminum and 1ml external electron donor D-donor of 6ml, start stirring, then
Injection 2L liquid propenes；ND catalyst, 410g hydrogen and 150ml hexene -1 of 60mg are added, the liquid of 1L is finally injected
Body propylene, catalyst is all flushed into reactor, closes charging valve.By high pressure polymerisation reactor in 15~20 minutes
Timing after being warmed up to 70 DEG C, reaction emits residual gas after 1 hour, discharges, and obtains white linear propylene/hexene -1 randomly altogether
Polymers powder.Linear propylene/the random copolymer of hexene -1 powder weighs 1300 grams of the gross weight of polymer after fully drying,
It is 2.2 ten thousand times to calculate catalyst efficiency.
The preparation of polypropene composition：
According to the mass fraction, 100 parts of linear propylenes/random copolymer powder of hexene -1 is added in super mixer, and by 0.1
Part primary antioxidant four { β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid } pentaerythritol ester, 0.2 part of (2,4- di-tert-butyl-phenyls)
Tris phosphite (article number：168), 0.05 part of halogen-absorber calcium stearate and 0.1 part of β crystalline substances nucleant agent N ' rings of N- bis-
After hexyl terephthalamide is mutually mixed, stirring mixing in super mixer is added to, speed of agitator is 400 revs/min, is stirred
Incorporation time is mixed for 10 minutes.Discharged after the completion of mixing, the premix is added to the twin-screw extrusion for having set temperature immediately
Melt mixed extruding pelletization is carried out in machine and obtains polypropene composition, 160~240 DEG C of double screw extruder design temperature.
Comparative example 1
According to the mass fraction, 100 parts of polypropylene (F1002B, Sinopec Yangzi Petrochemical Co) powder is added
To in super mixer, and by 0.1 part of primary antioxidant four { β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid } pentaerythritol ester, 0.2
Part (2,4- di-tert-butyl-phenyls) tris phosphite, the β crystalline substance nucleators of 0.05 part of halogen-absorber calcium stearate and 0.1 part
After N ' N- dicyclohexyl terephthalamides are mutually mixed, it is added to and mixing is stirred in super mixer, speed of agitator is 400 turns/
Minute, stirring incorporation time is 10 minutes.Discharged after the completion of mixing, the premix is added to has set the double of temperature immediately
Melt mixed extruding pelletization is carried out in screw extruder and obtains polypropene composition, 160~240 DEG C of double screw extruder design temperature.
Acrylic polymers, linear propylene/random copolymer of hexene -1, the performance of polypropene composition are shown in Table 1- tables 3.
The HOPP performance of table 1
2 linear propylenes of the table/random copolymerization physical performance of hexene -1
The micropore film properties of table 3
The above embodiments merely illustrate the technical concept and features of the present invention, its object is to allow person skilled in the art's energy
Solution present disclosure much of that is simultaneously implemented according to this, and it is not intended to limit the scope of the present invention, all according to spirit of the invention
The equivalent change or modification that essence is made, should all be included within the scope of the present invention.
Claims (7)
1. a kind of polypropene composition, it is characterised in that according to the mass fraction, composed of the following components：
Wherein, acrylic polymers is HOPP or linear propylene/random copolymer of hexene -1, and primary antioxidant is Hinered phenols
Compound, auxiliary anti-oxidant is (2,4- di-tert-butyl-phenyl) tris phosphite or (2, the 4- di-tert-butyls of pentaerythritol bis-phosphite two
Phenyl) ester, β crystalline substance nucleator be condensed-nuclei aromatics nucleator, organic carboxyl acid and its esters nucleator, aromatic amides class nucleator or
One kind in terres rares nucleator；
The HOPP has following characteristic：
(1) melt flow rate (MFR) is 1.0~8g/10min；
Under (2) 10 kilograms of loads under melt flow rate (MFR) and 2.16 kilograms of loads melt flow rate (MFR) ratio between 18~30；
(3) isotactic index is between 96%~99%；
(4) xylene soluble content is no more than 5.0%；
(5) composition total ash≤70ppm；
The linear propylene/random copolymer of hexene -1 has following characteristic：
(1) melt flow rate (MFR) is 1.0~8g/10min；
Under (2) 10 kilograms of loads under melt flow rate (MFR) and 2.16 kilograms of loads melt flow rate (MFR) ratio between 18~30；
(3) content of comonomer hexene -1 is in 0.5~2.5wt%, preferably 0.5~2.0wt%；
(4) xylene soluble content is no more than 4.0%；
(5) with being respectively greater than and two different fusing points less than 160 DEG C or melting peak wide.
2. polypropene composition according to claim 1, it is characterised in that the primary antioxidant is β-(4 hydroxyl -3,5-
Di-tert-butyl-phenyl) in the positive octadecanol ester of propionic acid or four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters one
Plant or two kinds.
3. polypropene composition according to claim 1, it is characterised in that the β crystalline substances nucleator is the hexamethylenes of N ' N- bis-
Base terephthalamide, the Cyclohexamide of naphthalene two, the formyl-three (2,3- dimethyl cyclohexyl amine) of equal benzene three, 2,6- bis- (N-2,2,
6,6- tetramethyl-piperidyls) one kind in naphthalene diamides or rare earth organic complex.
4. polypropene composition according to claim 1, it is characterised in that the halogen-absorber be calcium stearate,
One or more of zinc stearate and hydrated magnesium silicate.
5. a kind of preparation method of polypropene composition, it is characterised in that including following several steps：
Acrylic polymers powder is added in super mixer, and by primary antioxidant, auxiliary anti-oxidant, halogen-absorber and β
After brilliant nucleator is mutually mixed, stirring mixing in super mixer is added to, is discharged after the completion of mixing, immediately by the premix
Being added in the double screw extruder for set temperature carries out melt mixed extruding pelletization and obtains, double screw extruder setting
Temperature is 160~240 DEG C.
6. the preparation method of polypropene composition according to claim 5, it is characterised in that the system of the acrylic polymers
Preparation Method is：
The liquid propene of 2L is injected in the autoclave that hot nitrogen purges more than 3 times, the second of co-catalyst three of 6ml is added
Base aluminium, starts stirring, reinjects 2L liquid propenes；The HA catalyst of 8-12mg and the hydrogen of 30-320g are added, most
The liquid propene of 1L is injected afterwards, catalyst is all flushed into reactor, close charging valve；Will in 15~20 minutes
High pressure polymerisation reactor be warmed up to 70 DEG C after timing, reaction emits residual gas, discharges after 1-2 hour, obtains white third
Alkene polymer powder.
7. the preparation method of polypropene composition according to claim 5, it is characterised in that the acrylic polymers
Preparation method is：
The liquid propene of 2L is injected in the autoclave that hot nitrogen purges more than 3 times, the second of co-catalyst three of 6ml is added
Base aluminium and 1ml external electron donor D-donor, start stirring, reinject 2L liquid propenes；Add the ND catalysis of 60mg
Agent, the hydrogen of 30-410g and hexene -1 of 25-150ml, finally inject the liquid propene of 1L, and catalyst is all flushed into
In reactor, charging valve is closed；Timing after high pressure polymerisation reactor is warmed up into 70 DEG C in 15~20 minutes, reaction 1
Residual gas is emitted after hour, is discharged, obtain white acrylic polymer powders.
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