CN107540952A - A kind of preparation method of transparent atactic copolymerized polypropene composition - Google Patents
A kind of preparation method of transparent atactic copolymerized polypropene composition Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of transparent atactic copolymerized polypropene composition, belong to new material technology field, including (1) in the presence of Titanium series catalyst, co-catalyst and electron donor, melt pelletization after (2) mix the impact polypropylene that step (1) preparation is drawn with other adjuvant components is obtained through two-stage polymerization mode using liquid-phase bulk polymerization kettle and obtained.Using transparent polypropylene composition preparation method provided by the present invention, there is resulting polypropene composition good rigid toughness balance quality, the preferably transparency, mist degree to be at maximum up to 7% or so simultaneously, be especially suitable for high transparency packaging material application.
Description
Technical field
The present invention relates to a kind of preparation method of transparent atactic copolymerized polypropene composition, belong to new material technology field.
Background technology
Transparent PP it is excellent the transparency and surface gloss can with typical transparent material, as makrolon, polyester (PET),
Polystyrene etc. compares favourably, thus can be widely applied to household supplies and packaging field.The heat resistance of transparent PP is than general PP
Height, utensil that is high and using or sterilize at high temperature is required especially suitable for the transparency, as injector for medical purpose, micro-wave oven cook ware,
Baby bottles, disposable fast food apparatus etc..With the fast development of China PP industry, transparent PP turns into speedup in PP products
One of most fast kind.
Improving the PP transparencys typically has three kinds of approach:(1) nucleator is added, i.e., is gathered by adding different types of nucleator and improving
The crystalline rate of compound, crystallization temperature, refinement spherocrystal change crystal formation, so improve the transparency of product, surface gloss,
Rigidity, heat distortion temperature, impact strength and shortening molding cycle;(2) be polymerization process production random copolymerization product [4-7], i.e., it is logical
Cross and use the Natta of forth generation Ziegler one (Z/N) catalyst or metallocene catalyst, directly produce binary on device or ternary is random
Copolymer, improve PP crystal property;(3) it is that blending is anti-reflection, i.e., is blended in process by several raw materials, changes PP
Crystallization behavior, reduce spherulite size.Since the 1990s, with the improvement of PP catalyst and polymerization technique technology,
A variety of transparent PPs with high added value are developed, they are widely used in by rigidity/toughness/transparent sexual balance
Packaging waits key areas with medical, has widened PP application significantly.
Chinese patent application 200780030588.3 discloses a kind of polypropene composition and its product, by the way that fusing point is less than
160 DEG C, propylene copolymer of the bending modulus less than 1000MPa and ethylene-propylene rubber are blended to obtain, and said composition has machinery
The optimum balance of performance and transparency.But the rigidity of the material is poor.
Chinese patent application 200610051053.1 is disclosed one kind and answered with Nano silica sol and organic phosphoric acid salt form polypropylene nucleater
With the method for preparing transparent polypropylene.It is high using transparent polypropylene bending modulus made from this method, but material is transparent relatively low,
Mist degree is higher, and impact strength is low.
Chinese patent application 02104405.8 discloses a kind of preparation method of transparent polypropylene, transparent by being added in polypropylene
Agent and dyes of anthraquinone, the clear acrylic with good appearance form and aspect is obtained after melting extrusion, can effectively solved transparent
Polypropylene articles yellowing phenomenon.But it is still a kind of conventional anti-reflection method.
Chinese Patent Application No. 200710202436.9 discloses a kind of preparation method of nontoxic colored transparent polypropylene, and it will be nontoxic
Coloured silicasol is added to melt pelletization in polypropylene and obtained as transparent nucleater and colouring agent.But due to being nucleated anti-reflection effect
Fruit is limited, and the combination property of material is still undesirable.
Chinese Patent Application No. 200710084361.9 discloses a kind of transparent polypropylene sheet shaping group with radiation resistant
Compound, its by 100 parts by weight of polypropylene homopolymers, ethylene contents be 5% or less Propylene-ethylene random copolymer or they
Resin compound, the phosphorus antioxidants of 0.01~0.125 parts by weight, the hindered amine compound of 0.01~0.1 parts by weight and
The calcium stearate composition of 0.01~0.1 parts by weight.Composition is similar to conventional addition nucleating agent compositions, increase only anti-ray spoke
Formed according to antioxidant system.
According to the current main stream approach for improving polypropylene transparent, for existing HOPP, atactic copolymerized polypropene and resist
Polypropylene is rushed to be modified.In three kinds of materials, HOPP is rigidly optimal, the transparency between it is other therebetween, but toughness
It is minimum;The atactic copolymerized polypropene transparency is optimal, toughness between it is other therebetween, but rigidity is minimum;Impact polypropylene toughness
Most preferably, rigidity between it is other therebetween, but the transparency it is worst.There is presently no a kind of method obtain with balance rigidity,
The polypropylene material of toughness and the transparency.Therefore, current present situation is, it is still desirable to a kind of clear acrylic is provided, its
While with good transparency, the rigidity and toughness that also balance, particularly low-temperature flexibility, for low temperature packaging material
Deng field.
The content of the invention
In order to solve the above problems, the present invention provides a kind of system of the transparent polypropylene composition with good low temperature shock resistance
Preparation Method, the polypropene composition has higher rigidity and low-temperature flexibility, while is also equipped with the good transparency.
A kind of preparation method of transparent atactic copolymerized polypropene composition, its step are as follows:
(1) in the presence of Titanium series catalyst, co-catalyst and electron donor, gathered using liquid-phase bulk polymerization kettle through two steps
Conjunction mode obtains:Wherein the first step is first to prepare propylene/ethylene binary atactic copolymerized polypropene;Second step is to add butene-1 to carry out
After polymerization obtains atactic copolymerized polypropene powder;Or the first step is first to prepare the binary random copolymerization poly- third of propene/but-1-ene -1
Alkene;Second step is to add ethene progress after polymerization to obtain atactic copolymerized polypropene powder;
(2) step (1) is prepared to melt pelletization after the impact polypropylene drawn mixes with other adjuvant components and obtained, it is described
The step of (1) prepare the impact polypropylene that draws and the ratio of other adjuvant components is as follows:
Described atactic copolymerized polypropene is the ethylene random COPP of propene/but-1-ene -1/, and melt flow rate (MFR) is 0.1~100
G/10min, the content of comonomer is 4-8wt%.
Described co-catalyst preferred triethyl aluminum, trimethyl aluminium, MAO, triisobutyl alumina alkane or its arbitrary combination,
Further preferably selected from MAO, triethyl aluminum or its arbitrary combination, most preferably triethyl aluminum.
The electron donor may be selected from alkylalkoxy silane, arylalkoxysilicane, cycloalkyl alkoxy silane or tetraalkoxy
One or more in the group of silane composition.
Specifically, alkylalkoxy silane can be selected from dicyclopentyl dimethoxyl silane, bicyclopentyl diethoxy silane and
Diisopropyl dimethoxy silane, n-propyl trimethoxy silane, n-propyl triethoxysilane, isopropyltri-methoxysilane,
Isopro-pyltriethoxysilane, tert-butyl trimethoxy silane or t-butyltriethoxysilane etc.;
Arylalkoxysilicane can be selected from phenyltrimethoxysila,e or phenyl triethoxysilane etc.;
Cycloalkyl alkoxy silane can be selected from cyclopentyl-trimethoxy-silane, cyclopenta triethoxysilane, cyclohexyl trimethoxy
Base silane or cyclohexyltriethyloxysilane etc.;
Tetraalkoxysilane can be selected from tetramethoxy-silicane or tetraethoxysilane etc..
It is preferred that dicyclopentyl dimethoxyl silane, bicyclopentyl diethoxy silane.
Described Titanium series catalyst is Ziegler-Natta catalyst, described Ziegler-Natta catalyst model NA, ND,
TK260。
Described primary antioxidant may be selected from β-positive octadecanol ester of (4- hydroxyls -3,5- di-tert-butyl-phenyl) propionic acid, four [β-(3,5- bis- uncles
Butyl -4- hydroxy phenyls) propionic acid] pentaerythritol ester.
Described auxiliary anti-oxidant may be selected from (2,4- di-tert-butyl-phenyl) tris phosphite, and (2,4- bis- is special for pentaerythritol bis-phosphite two
Butyl phenyl) ester.
Described halogen-absorber may be selected from the one or more of calcium stearate, zinc stearate and hydrated magnesium silicate, preferably stearic acid
Calcium.
Described nucleator may be selected from Sorbitol Nucleator agent (DBS classes), if dibenzal sorbitol (DBS), two are (to second
The benzal of base two) sorbierite, two (to the benzal of methyl two) sorbierites (MDBS) and two (benzal of 3,4- dimethyl two) sorbs
Alcohol etc.;Carboxylic acid and its esters nucleator such as two rings [2,2,1] heptane dicarboxylate salts (HPN-68) and two rings [2,2,1] heptane-
2,3- dicarboxylic acids sodium salts (HPN-68L);Nucleator in organic phosphate class such as NA-10, NA-11, NA-21 etc..It is preferred that sorb
Alcohols nucleator.
Described primary antioxidant, auxiliary anti-oxidant, halogen-absorber and nucleator etc. can be added in the form of pure substance, can also be female
Material or compound additive form add.
The preparation method of the acrylic polymers is:
The liquid propene that 2L is injected in the 10L autoclaves of more than 3 times is purged in hot nitrogen, adds 6ml co-catalyst
Triethyl aluminum, start stirring, reinject 2L liquid propenes;Add 8-12mg HA catalyst, 30-320g hydrogen and
15~500g ethene, 1L liquid propene is finally injected, catalyst is all flushed into reactor, close charging valve;
Timing after high pressure polymerisation reactor is warming up into 70 DEG C in 15~20 minutes, after reacting 0.5~1 hour, add 20-200ml fourth
Alkene -1, after continuing reaction 0.5~1 hour, residual gas is discharged, discharge, obtain white acrylic polymer powders.
The preparation method of the acrylic polymers can also be:
The liquid propene that 2L is injected in the autoclave of more than 3 times is purged in hot nitrogen, adds the 6ml second of co-catalyst three
Base aluminium and 1ml external electron donor D-donor, start stirring, reinject 2L liquid propenes;60mg ND catalyst is added,
30-410g hydrogen and 20~200ml butene-1,1L liquid propene is finally injected, catalyst is all flushed into reactor
It is interior, close charging valve;Timing after high pressure polymerisation reactor is warming up into 70 DEG C in 15~20 minutes, react 0.5~1 hour
Afterwards, 15~500g ethene is added, after continuing reaction 0.5~1 hour, discharges residual gas, is discharged, is obtained white acrylic and gather
Compound powder.
General polypropene composition is typically atactic copolymerized polypropene, HOPP and impact copolymer polypropylene, these three materials
Material is often difficult to reach balanced in rigidity-toughness-transparency.Using the method for the present invention, butene-1 is generated in first step polymerization
There is the low copolymerization amount atactic copolymerized polypropene of high transparency or random copolymerization poly- third that ethene is comonomer for comonomer
Alkene, and the ternary polymerized polypropylene of propylene/ethylene/butene -1 is generated in second step polymerization, by controlling two sections of co-monomer contents,
The atactic copolymerized polypropene composition that the transparency greatly improves is obtained, and polypropene composition has oligomer (n-hexane
Extract) it is low, tacky, the features such as modulus is high is not easy in polymerization process.In other words, can be respectively adopted using this method
Different comonomers polymerize to obtain matrix phase, and by controlling co-monomer content, to it is traditional only with ethene be copolymerization
The polyacrylic rigidity of COPP and the transparency of monomer have obvious improvement.
Beneficial effect
It is a discovery of the invention that using the manufacture method of transparent polypropylene composition provided by the present invention, using through special process condition
The acrylic polymers of polymerization is base-material, and compared with the third second combined polymerization, not tacky with polymerization process, the modulus of polymer is higher,
The good transparency and toughness are kept simultaneously, and polymerizate passes through the design of auxiliary formula, through simple continuous extrusion blend method
Obtain, prepare simply, manufactured suitable for industrial-scale.Moreover, compared with other normal transparent polypropene compositions, use
Transparent polypropylene composition preparation method provided by the present invention, resulting polypropene composition have good rigidity-toughness simultaneously
Balance quality, the preferably transparency, mist degree are at maximum up to 7% or so, are especially suitable for high transparency packaging material application.
Embodiment
With reference to specific embodiment, the present invention will be described in detail.Protection scope of the present invention not using embodiment as
Limit, but be defined in the claims.
Explanation is of the invention in further detail with reference to embodiments, but the invention is not restricted to these embodiments.
Melt flow rate (MFR) (MFR) measure reference standard GB/T 3682-2008 are carried out, and condition determination is that 230 DEG C and 2.16 are public
Jin load;Tensile property is tested by GB/T1040-2006, draw speed 50mm/min;Impact property presses GB/T
1843-2008 is tested;Bending property is tested by GB/T 9341-2008, and mist degree is tested according to GB/T2410-2008.
Ethylene contents determine:
Using the IFS 66/S Fourier transformation infrared spectrometers of Bruke companies in 758~679cm-1In the range of absorption area make
For the location parameter of ethene.The quantitative equation of Ethylene mass percentage composition is:142.69 × (A (758~679) cm-1/A(4482
~3950) cm-1)-0.15
The butene-1 copolymerization amount measure of copolymer:With copolymer infrared spectrum wave number 767cm-1Intensity of the place with characteristic peak is with gathering
The characteristic peak of propylene is (in wave number 806cm-1Place) intensity ratio (i.e. 767/806) can calculate the random copolymerization of propene/but-1-ene -1
The mass fraction of butene-1 in thing.
N-hexane extract presses GB/T9693-1988《Food packaging acrylic resin sanitary standard》Test.
Embodiment 1
Polyacrylic preparation:
Polymerisation is carried out in 10L autoclaves (polymerisation in bulk):Purge in the autoclave of more than 3 times and note in hot nitrogen
Enter 2L liquid propene, add 6ml co-catalyst triethyl aluminum, start stirring, reinject 2L liquid propenes;Add 11mg
HA catalyst, 30g hydrogen and 500g ethene, finally inject 1L liquid propene, catalyst is all flushed into reaction
In kettle, charging valve is closed.Timing after high pressure polymerisation reactor is warming up into 70 DEG C in 15~20 minutes, after reacting 1 hour,
20ml butene-1 is added, continues reaction 1 hour, discharges residual gas, discharges, obtains white homo-polypropylene powder.
Polypropylene powder weighs 1110 grams of the gross weight of polymer after fully drying, and it is 9.8 ten thousand times to calculate catalyst efficiency.
The preparation of polypropene composition:
According to the mass fraction, 100 parts of above-mentioned polypropylene powder is added in super mixer, and by 0.05 part of primary antioxidant
β-positive octadecanol the ester of (4- hydroxyls -3,5- di-tert-butyl-phenyl) propionic acid, 0.1 part of auxiliary anti-oxidant (2,4- di-tert-butyl-phenyl)
Tris phosphite, 0.05 part of halogen-absorber calcium stearate and 0.05 part of nucleator dibenzal sorbitol (DBS) are mutually mixed
Afterwards, it is added in super mixer and is stirred, speed of agitator is 400 revs/min, is stirred the time as 10 minutes.It is mixed
Discharged after the completion of conjunction, the premix is added into progress melt mixed extrusion in the double screw extruder for set temperature immediately makes
Grain obtains polypropene composition, 160~240 DEG C of double screw extruder design temperature.
Embodiment 2
Polyacrylic preparation:
Polymerisation is carried out in 10L autoclaves (polymerisation in bulk):Purge in the autoclave of more than 3 times and note in hot nitrogen
Enter 2L liquid propene, add 6ml co-catalyst triethyl aluminum and 1ml external electron donor D-donor, start stirring, then
Inject 2L liquid propenes;60mg ND catalyst, 410g hydrogen and 300g ethene is added, finally injects 1L liquid
Propylene, catalyst is all flushed into reactor, closes charging valve.By high pressure polymerisation reactor liter in 15~20 minutes
Temperature after reaction 1 hour, adds 200ml butene-1s, after continuing polymerization 1 hour, discharges residual gas to timing after 70 DEG C,
Discharging, obtains white random copolymer powder.Random copolymer powder weighs the gross weight 1200 of polymer after fully drying
Gram, it is 2.0 ten thousand times to calculate catalyst efficiency.
The preparation of polypropene composition:
According to the mass fraction, 100 parts of above-mentioned random copolymer powders are added in super mixer, and by 0.1 part of main antioxygen
Agent β-positive octadecanol the ester of (4- hydroxyls -3,5- di-tert-butyl-phenyl) propionic acid, 0.2 part of pentaerythritol bis-phosphite two (2,4-
Di-tert-butyl phenyl) ester, 0.1 part of halogen-absorber zinc stearate and 0.2 part of nucleator two (to the benzal of ethyl two) sorbierite
After being mutually mixed, it is added in super mixer and is stirred, speed of agitator is 400 revs/min, is stirred the time as 10
Minute.Discharged after the completion of mixing, the premix is added into progress melt in the double screw extruder for set temperature immediately mixes
Close extruding pelletization and obtain polypropene composition, 160~240 DEG C of double screw extruder design temperature.
Embodiment 3
Polyacrylic preparation:
Polymerisation is carried out in 10L autoclaves (polymerisation in bulk):Purge in the autoclave of more than 3 times and note in hot nitrogen
Enter 2L liquid propene, add 6ml co-catalyst triethyl aluminum, start stirring, reinject 2L liquid propenes;Add 8mg
HA catalyst, 150g hydrogen and 15g ethene, finally inject 1L liquid propene, catalyst is all flushed into reaction
In kettle, charging valve is closed.Timing after high pressure polymerisation reactor is warming up into 70 DEG C in 15~20 minutes, react 0.5 hour
Afterwards, 200ml butene-1s are added, after continuing reaction 1 hour, discharge residual gas, discharges, obtains white polypropylene powder.
Polypropylene powder weighs 980 grams of the gross weight of polymer after fully drying, and it is 12.2 ten thousand times to calculate catalyst efficiency.
The preparation of polypropene composition:
According to the mass fraction, 100 parts of above-mentioned polypropylene powders are added in super mixer, and by 0.15 part of primary antioxidant four
{ β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid } pentaerythritol ester, 0.3 part of auxiliary anti-oxidant (2,4- di-tert-butyl-phenyl) phosphorous acid
Three esters, 0.1 part of halogen-absorber DHT-4A and 0.5 part of nucleator two (to the benzal of methyl two) sorbierite (MDBS) phase
Mutually after mixing, it is added in super mixer and is stirred, speed of agitator is 400 revs/min, is stirred the time as 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 4
Polyacrylic preparation:
Polymerisation is carried out in 10L autoclaves (polymerisation in bulk):Purge in the autoclave of more than 3 times and note in hot nitrogen
Enter 2L liquid propene, add 6ml co-catalyst triethyl aluminum and 1ml external electron donor D-donor, start stirring, then
Inject 2L liquid propenes;60mg ND catalyst, 280g hydrogen and 280g ethene is added, finally injects 1L liquid
Propylene, catalyst is all flushed into reactor, closes charging valve.By high pressure polymerisation reactor liter in 15~20 minutes
Temperature after reacting 1 hour, adds 100ml butene-1s, after continuing polymerase 10 .5 hours, discharges residual gas to timing after 70 DEG C
Body, discharging, obtains white random copolymer powder.Random copolymer powder weighs the gross weight of polymer after fully drying
1350 grams, it is 2.25 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 0.10
Part primary antioxidant four { β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid } pentaerythritol ester, 0.2 part of auxiliary anti-oxidant pentaerythrite are double
Phosphite ester two (2,4- di-tert-butyl phenyl) ester, 0.3 part of halogen-absorber (calcium stearate) and 0.5 part of nucleator two (3,
The benzal of 4- dimethyl two) after sorbierite is mutually mixed, it is added in super mixer and is stirred, speed of agitator is 400 turns
/ minute, the time is stirred as 10 minutes.Discharged after the completion of mixing, the premix is added to has set temperature immediately
Melt mixed extruding pelletization is carried out in double screw extruder and obtains polypropene composition, double screw extruder design temperature
160~240 DEG C.
Embodiment 5
Polyacrylic preparation:
Polymerisation is carried out in 10L autoclaves (polymerisation in bulk):Purge in the autoclave of more than 3 times and note in hot nitrogen
Enter 2L liquid propene, add 6ml co-catalyst triethyl aluminum, start stirring, reinject 2L liquid propenes;Add 8mg
HA catalyst, 150g hydrogen and 200ml butene-1s, finally inject 1L liquid propene, catalyst is all flushed into
In reactor, charging valve is closed.Timing after high pressure polymerisation reactor is warming up into 70 DEG C in 15~20 minutes, reaction 0.5
After hour, 150g ethene is added, after continuing reaction 1 hour, discharges residual gas, discharges, obtains white polypropylene powder.
Polypropylene powder weighs 1120 grams of the gross weight of polymer after fully drying, and it is 140,000 times to calculate catalyst efficiency.
The preparation of polypropene composition:
According to the mass fraction, 100 parts of above-mentioned polypropylene powders are added in super mixer, and by 0.15 part of primary antioxidant four
{ β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid } pentaerythritol ester, 0.3 part of auxiliary anti-oxidant (2,4- di-tert-butyl-phenyl) phosphorous acid
Three esters, 0.1 part of halogen-absorber DHT-4A and 0.5 part of nucleator two (to the benzal of methyl two) sorbierite (MDBS) phase
Mutually after mixing, it is added in super mixer and is stirred, speed of agitator is 400 revs/min, is stirred the time as 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 6
Polyacrylic preparation:
Polymerisation is carried out in 10L autoclaves (polymerisation in bulk):Purge in the autoclave of more than 3 times and note in hot nitrogen
Enter 2L liquid propene, add 6ml co-catalyst triethyl aluminum and 1ml external electron donor D-donor, start stirring, then
Inject 2L liquid propenes;60mg ND catalyst, 280g hydrogen and 100ml butene-1s is added, finally injects 1L liquid
Body propylene, catalyst is all flushed into reactor, closes charging valve.By high pressure polymerisation reactor in 15~20 minutes
Timing after being warming up to 70 DEG C, after reacting 1 hour, 180g ethene is added, after continuing polymerase 10 .5 hours, discharges residual gas,
Discharging, obtains white random copolymer powder.Random copolymer powder weighs the gross weight 1460 of polymer after fully drying
Gram, it is 2.43 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 0.10
Part primary antioxidant four { β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid } pentaerythritol ester, 0.2 part of auxiliary anti-oxidant pentaerythrite are double
Phosphite ester two (2,4- di-tert-butyl phenyl) ester, 0.3 part of halogen-absorber (calcium stearate) and 0.5 part of nucleator two (3,
The benzal of 4- dimethyl two) after sorbierite is mutually mixed, it is added in super mixer and is stirred, speed of agitator is 400 turns
/ minute, the time is stirred as 10 minutes.Discharged after the completion of mixing, the premix is added to has set temperature immediately
Melt mixed extruding pelletization is carried out in double screw extruder and obtains polypropene composition, double screw extruder design temperature
160~240 DEG C.
Comparative example
The preparation of copolymer:
Polymerisation is carried out in 10L autoclaves (polymerisation in bulk):Purge in the autoclave of more than 3 times and note in hot nitrogen
Enter 2L liquid propene, add 6ml co-catalyst triethyl aluminum and 1ml external electron donor D-donor, start stirring, then
Inject 2L liquid propenes;60mg ND catalyst is added, 200g hydrogen, 1L liquid propene is finally injected, will be catalyzed
Agent is all flushed into reactor, closes charging valve.Counted after high pressure polymerisation reactor is warming up into 70 DEG C in 15~20 minutes
When, reaction discharges residual gas after 2 hours, discharges, obtains white polypropylene powder.Powder weighs after fully drying
1280 grams of the gross weight of polymer, it is 2.13 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-positive octadecanol the ester of (4- hydroxyls -3,5- di-tert-butyl-phenyl) propionic acid, 0.2 part of auxiliary anti-oxidant (2,4- of part
Di-tert-butyl-phenyl) tris phosphite, 0.1 part of halogen-absorber calcium stearate and 0.2 part of nucleator two (to the benzal of methyl two)
After sorbierite (MDBS) is mutually mixed, it is added in super mixer and is stirred, speed of agitator is 400 revs/min, stirring
Incorporation time is 10 minutes.Discharged after the completion of mixing, the premix is added to the double screw extruder for having set temperature immediately
Middle progress melt mixed extruding pelletization obtains polypropene composition, 160~240 DEG C of double screw extruder design temperature.
The performance of polypropene composition is shown in Table 1.
The Polypropylene compositions physical performance of table 1
As can be seen from Table 1, the polypropene composition prepared using the inventive method, compared with comparative example, has lower mist
Degree, the good transparency, low n-hexane extract, while normal temperature and low temperature notched impact strength also greatly improve, and can effectively open up
Open up the application of transparent polypropylene.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art can
Understand present disclosure and implement according to this, it is not intended to limit the scope of the present invention, all according to spirit of the invention
The equivalent change or modification made, it should all be included within the scope of the present invention.
Claims (8)
- A kind of 1. preparation method of transparent atactic copolymerized polypropene composition, it is characterised in that:(1) in the presence of Titanium series catalyst, co-catalyst and electron donor, gathered using liquid-phase bulk polymerization kettle through two steps Conjunction mode obtains:Wherein the first step is first to prepare propylene/ethylene binary atactic copolymerized polypropene;Second step is to add butene-1 to carry out After polymerization obtains atactic copolymerized polypropene powder;Or the first step is first to prepare the binary random copolymerization poly- third of propene/but-1-ene -1 Alkene;Second step is to add ethene progress after polymerization to obtain atactic copolymerized polypropene powder;(2) step (1) is prepared to melt pelletization after the impact polypropylene drawn mixes with other adjuvant components and obtained, it is described The step of (1) prepare the impact polypropylene that draws and the ratio of other adjuvant components is as follows:Described atactic copolymerized polypropene is the ethylene random COPP of propene/but-1-ene -1/, and melt flow rate (MFR) is 0.1~100 G/10min, the content of comonomer is 4-8wt%.
- 2. preparation method according to claim 1, it is characterised in that:Described co-catalyst is triethyl aluminum, trimethyl Aluminium, MAO, triisobutyl alumina alkane or its arbitrary combination.
- 3. preparation method according to claim 1, it is characterised in that:Described electron donor is selected from bicyclopentyl dimethoxy Base silane, bicyclopentyl diethoxy silane and diisopropyl dimethoxy silane, n-propyl trimethoxy silane, n-propyl three Ethoxysilane, isopropyltri-methoxysilane, isopro-pyltriethoxysilane, tert-butyl trimethoxy silane or the tert-butyl group three Ethoxysilane;Phenyltrimethoxysila,e or phenyl triethoxysilane;Cyclopentyl-trimethoxy-silane, the ethoxy of cyclopenta three Base silane, cyclohexyl trimethoxy silane or cyclohexyltriethyloxysilane;Tetramethoxy-silicane or tetraethoxysilane.
- 4. preparation method according to claim 1, it is characterised in that:Described Titanium series catalyst is ziegler-natta catalyzed Agent, described Ziegler-Natta catalyst are NA, ND, TK260.
- 5. preparation method according to claim 1, it is characterised in that:Described primary antioxidant is selected from β-(4 hydroxyls -3,5- Di-tert-butyl-phenyl) in the positive octadecanol ester of propionic acid or four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters one Kind or two kinds.
- 6. preparation method according to claim 1, it is characterised in that:Described auxiliary anti-oxidant is selected from (2,4- di-tert-butyls Base) tris phosphite, pentaerythritol bis-phosphite two (2,4- di-tert-butyl phenyl) ester.
- 7. preparation method according to claim 1, it is characterised in that:Described halogen-absorber is selected from calcium stearate, hard The one or more of resin acid zinc and hydrated magnesium silicate.
- 8. preparation method according to claim 1, it is characterised in that:Described nucleator is Sorbitol Nucleator or carboxylic Acid and its esters nucleator or nucleator in organic phosphate class;Described Sorbitol Nucleator is dibenzal sorbitol (DBS), two (to the benzal of ethyl two) sorbierites, two (to the benzal of methyl two) sorbierites (MDBS), two (3,4- bis- The benzal of methyl two) sorbierite;Described carboxylic acid and its esters nucleator be two rings [2,2,1] heptane dicarboxylate salts (HPN-68) and Two rings [2,2,1] heptane -2,3- dicarboxylic acids sodium salt (HPN-68L);Nucleator in organic phosphate class is NA-10, NA-11, NA-21。
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