CN108727683A - A kind of preparation method of polypropene composition - Google Patents
A kind of preparation method of polypropene composition Download PDFInfo
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- CN108727683A CN108727683A CN201710260083.1A CN201710260083A CN108727683A CN 108727683 A CN108727683 A CN 108727683A CN 201710260083 A CN201710260083 A CN 201710260083A CN 108727683 A CN108727683 A CN 108727683A
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- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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Abstract
The invention discloses a kind of preparation methods of polypropene composition, belong to field of material technology, the present invention is including at least 100 parts of polypropylene, 0.05~0.15 part of primary antioxidant, 0.1~0.3 part of auxiliary anti-oxidant, 0.05~0.2 part of halogen-absorber, it assists squeezing out using supercritical carbon dioxide, it restrained effectively polyacrylic heat and oxygen degradation in extrusion, greatly accelerate the dissolution of small molecule volatile matter simultaneously, and before extruding dies by way of pressure release extraction by small molecule volatile matter removing.Simple for process using the method for the present invention, applied widely, production cost is low.
Description
Technical field
The invention belongs to field of material technology, and in particular to a kind of preparation method of low smell prolylene polymer composition.
Background technology
Polypropylene (PP) is the high-molecular compound obtained from propylene polymerization.Due to its abundant raw material, synthesis technology ratio
Relatively simple, compared with other general-purpose thermoplastic plastics, PP has that relative density is small, price is low, and has proof stress outstanding, cracking
Property and wearability, are fastest-rising kinds in general-purpose thermoplastic plastic, the status in economic construction and people's lives is increasingly
It is important, become the kind that increase of production is most fast in plastics, is widely used in the various fields such as automobile, household electrical appliances, daily necessities and packaging.
But polypropylene itself and various additives would generally bring larger smell into, limit its application in certain fields, and
With the development and the improvement of people's living standards of national economy, the odor profiles requirement of polypropylene material is also increasingly improved.For
It is used for a long time and expands application range, how to obtain the polypropylene material of low smell, also have attracted increasing attention.
Chinese patent mandate CN102952341 discloses a kind of high strong and unyielding low-odor polypropylene ene compositions and its preparation side
Method is matrix by selecting low smell impact polypropylene, using addition high-melting-point, the antioxidant 3114 and 330 of low-volatile
Composite antioxidant and white carbon be odor suppressing agents, be granulated and obtained by mixed at high speed melting extrusion.
Chinese patent mandate CN102482458 discloses a kind of polypropylene-talc composite that smell mitigates, by adding
Add pyrrolotriazine derivatives as smell scavenger, obtains the PP composite material for automotive upholstery.
Chinese patent mandate CN102757597 discloses high-strength and high ductility low-odor polypropylene ene compositions and preparation method thereof,
Oder levels can be reduced to 3~3.5 by it by adding the organophilic inorganic powder W1000 of multi-cellular structure from 5.
Chinese patent mandate CN103044793 can be by polystyrene by the way that 0.5%~29% steam stripping agent master batch is added
The oder levels of composition have 6 to be reduced to 3~4.
Chinese patent discloses CN102532929 and discloses a kind of odor suppressing agents suitable for high molecular synthetic material product
Composition comprising plant polyphenol kind compound, convex-concave stick, diatomite and boiling water mixture, according to 0.5~3.0% weight
Than being added in high molecular synthetic material product, 1~2 grade of oder levels can be reduced.
Chinese granted patent CN103044776 discloses a kind of low smell color inhibition polypropene composition, passes through addition
0.5~2 parts by weight of eliminating smell agent can control the oder levels of composition below 4.
It can be seen that mainly using chelating agent or physics to inhale in terms of reducing PP composite material smell at present
Attached dose reduces the smell of material.Chelating agent can reduce the smell of PP, mainly since these chemistry eliminating smell agents can be with
It is reacted with the small molecule for releasing smell or other harmful VOC, so that it is generated, relative molecular mass is larger, Bu Huicong
Another compound evaporated in material, to achieve the effect that eliminate peculiar smell.Reaction involved by this method is extremely
Complexity, but it is with strong points, it is suitable for the specific product of VOC types.Physical absorbent can be adsorbed in the form of physical absorption
Odorous small-molecule substance can theoretically adsorb any smell or VOC to reduce the smell of PP.Current suction
Attached dose of system includes the mineral soil body such as activated carbon system, silica gel system, attapulgite system, molecular sieve system etc..But in reality
In process, it is also desirable to consider the aperture of odor adsorption agent, pore size distribution, the influence of pore structure, desorption temperature, often
It is difficult to fully meet needs.
Invention content
To solve the above-mentioned problems, the present invention provides a kind of preparation method of low-odor polypropylene ene compositions, energy of the present invention
It is enough effectively to reduce PP and its composite material smell, while there is the method for broad applicability, to meet the smell to PP compositions
The requirement of aspect.
The technical scheme is that：A kind of polypropene composition, it is characterised in that include following components：
Isotactic homopolymerization or the copolymerized type propene polymer grain that the polypropylene is 0.1~120g/10min of melt flow rate (MFR)
Material, or mixtures thereof powder.
The primary antioxidant, preferably hindered phenol compound, more preferable β-(4 hydroxyl -3,5- di-tert-butyl-phenyl) propionic acid
Positive octadecanol ester (article number：Antioxidant 1076), four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters
(article number：Antioxidant 1010), 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid (trade names：Antioxidant
3114) or combinations thereof, most preferably β-(4- hydroxyls -3,5- di-tert-butyl-phenyl) propionic acid n-octadecyl alcohol ester (article number：Antioxidant
1076)。
The auxiliary anti-oxidant, preferably (2,4- di-tert-butyl-phenyl) tris phosphite (article number：Irgasfos 168), season penta
Tetrol bis-phosphite two (2,4- di-tert-butyl phenyl) ester (antioxidant 626) or combinations thereof.
The halogen-absorber can be selected from the one or more of calcium stearate, zinc stearate and hydrated magnesium silicate, preferably
Calcium stearate.
The eliminating smell agent, can be selected from medical stone, Bio-sil, molecular sieve etc. it is one or more.
The smell chelating agent is selected from zinc ricinoleate.
Primary antioxidant, auxiliary anti-oxidant and the halogen-absorber can be added with pure form, can also masterbatch or
Compound additive form is added.
The polymers compositions is selected from polypropylene powder, primary antioxidant is selected from four [β-(3,5- di-t-butyl -4- hydroxyls
Phenyl) propionic acid] pentaerythritol ester, auxiliary anti-oxidant be selected from (2,4- di-tert-butyl-phenyl) tris phosphite, halogen-absorber and be selected from
Calcium stearate, eliminating smell agent are selected from medical stone, smell chelating agent is selected from zinc ricinoleate, talcum powder.
The polymers compositions is selected from polypropylene powder, primary antioxidant is selected from β-(4 hydroxyl -3,5- di-tert-butyl-phenyl)
Propionic acid n-octadecyl alcohol ester, auxiliary anti-oxidant are selected from (2,4- di-tert-butyl-phenyl) tris phosphite, halogen-absorber is selected from tristearin
Sour calcium, eliminating smell agent are selected from medical stone, smell chelating agent is selected from zinc ricinoleate, talcum powder.
The polymers compositions is selected from polypropylene powder, primary antioxidant is selected from β-(4 hydroxyl -3,5- di-tert-butyl-phenyl)
Propionic acid n-octadecyl alcohol ester, auxiliary anti-oxidant are selected from (2,4- di-tert-butyl-phenyl) tris phosphite, halogen-absorber is selected from tristearin
Sour calcium, eliminating smell agent are selected from medical stone, smell chelating agent is selected from zinc ricinoleate, talcum powder.
The polymers compositions is selected from polypropylene powder, primary antioxidant is selected from 1,3,5- tri- (3,5- di-t-butyl -4- hydroxyls
Base benzyl) isocyanuric acid, auxiliary anti-oxidant be selected from pentaerythritol bis-phosphite two (2,4- di-tert-butyl phenyl) ester, halogen absorb
Agent is selected from calcium stearate, eliminating smell agent is selected from medical stone, smell chelating agent is selected from zinc ricinoleate, talcum powder.
The polymers compositions is selected from polypropylene powder, and primary antioxidant is selected from four [β-(3,5- di-t-butyl -4- hydroxyls
Phenyl) propionic acid] pentaerythritol ester, auxiliary anti-oxidant be selected from (2,4- di-tert-butyl-phenyl) tris phosphite, halogen-absorber and be selected from
Calcium stearate, eliminating smell agent are selected from medical stone and Bio-sil, and smell chelating agent is selected from zinc ricinoleate and talcum powder.
The polymers compositions is selected from polypropylene powder, and primary antioxidant is selected from four [β-(3,5- di-t-butyl -4- hydroxyls
Phenyl) propionic acid] pentaerythritol ester, auxiliary anti-oxidant be selected from (2,4- di-tert-butyl-phenyl) tris phosphite, halogen-absorber and be selected from
Calcium stearate, eliminating smell agent is selected from Bio-sil, smell chelating agent is selected from zinc ricinoleate and talcum powder.
The polymers compositions is selected from impact copolymer polypropylene powder, and primary antioxidant is selected from four [β-(3,5- bis- tertiary fourths
Base -4- hydroxy phenyls) propionic acid] pentaerythritol ester and β-(4 hydroxyl -3,5- di-tert-butyl-phenyl) propionic acid n-octadecyl alcohol ester (press
According to 1: 1 ratio), auxiliary anti-oxidant be selected from (2,4- di-tert-butyl-phenyl) tris phosphite and pentaerythritol bis-phosphite two (2,
4- di-tert-butyls phenyl) ester (according to 1: 1 ratio), halogen-absorber be selected from zinc stearate, eliminating smell agent be selected from molecular sieve, smell chela
Mixture is selected from zinc ricinoleate and talcum powder.
A kind of polypropene composition, it is characterised in that include following components：
Isotactic homopolymerization or the copolymerized type propene polymer grain that the polypropylene is 0.1~200g/10min of melt flow rate (MFR)
Material, or mixtures thereof powder.
The primary antioxidant, preferably hindered phenol compound, more preferable β-(4 hydroxyl -3,5- di-tert-butyl-phenyl) propionic acid
Positive octadecanol ester (article number：Antioxidant 1076), four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters
(article number：Antioxidant 1010), 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid (trade names：Antioxidant
3114) or combinations thereof, most preferably β-(4- hydroxyls -3,5- di-tert-butyl-phenyl) propionic acid n-octadecyl alcohol ester article number：Antioxidant
1076)。
The auxiliary anti-oxidant, preferably (2,4- di-tert-butyl-phenyl) tris phosphite (article number：Irgasfos 168), season penta
Tetrol bis-phosphite two (2,4- di-tert-butyl phenyl) ester (antioxidant 626) or combinations thereof.
The halogen-absorber can be selected from the one or more of calcium stearate, zinc stearate and hydrated magnesium silicate, preferably
Calcium stearate.
The polymers compositions is selected from polypropylene powder (melt flow rate (MFR) 100g/10min), and primary antioxidant is selected from four
[β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, auxiliary anti-oxidant are selected from (2,4- di-tert-butyl-phenyl) Asia
Phosphotriester, halogen-absorber are selected from zinc stearate.
Primary antioxidant, auxiliary anti-oxidant and the halogen-absorber can be added with pure form, can also masterbatch or
Compound additive form is added.
A method of polypropene composition is prepared, is included the following steps：
(1) each raw material of formula is weighed in proportion, and super mixer is added and is uniformly mixed；
(2) each component mixture of step (1) formula is added from the first heating zone of double screw extruder, and faced super
Boundary's CO 2 fluid is added twin-screw extrude from third heating zone or the second heating zone, supercritical carbon dioxide fluid
Quality accounts for the 2~30% of extrudate gross mass.50 revs/min~500 revs/min of extruder driving screw rotating speed, extrusion temperature 150~
It is 240 DEG C, one or many before extruding dies to vacuumize devolatilization, it squeezes out water cooled material strip, granulation and drying and obtains.
Tc=31 DEG C, Pc=7.4MPa of supercritical carbon dioxide, as long as meeting higher than above-mentioned critical-temperature and facing simultaneously
Boundary's pressure, carbon dioxide, that is, in a supercritical state.
Advantageous effect：
The present invention is squeezed out using supercritical carbon dioxide auxiliary, restrained effectively polyacrylic heat and oxygen in extrusion
Degradation, while greatly accelerating the dissolution of small molecule volatile matter, and before extruding dies by way of pressure release extraction by small point
Sub- volatile matter removing.Simple for process using the method for the present invention, applied widely, production cost is low, is conducive to promote and apply；It is made
Standby polypropene composition have it is functional, the low feature of smell can effectively avoid the health to air environment and people
Have an adverse effect；Composition can be used for the higher occasion of odor dispersion performance requirement, such as automotive upholstery, various packing timbers
The processing and application of material and regenerating polypropylene material.
The present invention is comprehensive
Falling a part by supercritical carbon dioxide extracting when modified has the small molecule of larger smell, in addition again by adding in formula
Add the auxiliary agent for having absorption and chelation to smell, final to realize the purpose for reducing polymer smell, effect is better than existing
The simple scheme using formula adjustment.(this it is different with the supercritical carbon dioxide ancillary technique of existing high molecular material it
It is in existing high molecular material supercritical carbon dioxide ancillary technique is assisted reactant by supercritical carbon dioxide
Or small molecule is disperseed/is diffused into high molecular material)
Specific implementation mode
Illustrate the present invention in further detail with reference to embodiments, but the present invention is not limited to these Examples.
Polypropene composition tests its correlated performance using following methods：
(1) measurement of odor standard：By Volkswagen's VW ' s PV3900E standards, evaluated using 1~6 grade, grade
Not higher, smell is bigger.Concrete regulation such as following table
| Rank | Description |
| 1 | It is imperceptible |
| 2 | It can feel, not disturb people |
| 3 | It can be clearly felt that but not disturb people also |
| 4 | Disturb people |
| 5 | Strong dislike |
| 6 | It is difficult to tolerate |
Embodiment 1
Weigh 50kg polypropylene powders (melt flow rate (MFR) 0.2g/10min), 25g antioxidant 1010s, 50g antioxidant
168,25g halogen-absorbers calcium stearate, 500 grams of medical stones (2500 mesh of granularity), 500 grams of zinc ricinoleates and 5kg talcum powder,
It is agitated be sufficiently mixed after, the double screw extruder that draw ratio L/D is 48: 1, rate of feeding 50g/min, screw speed is added
100 revs/min；Supercritical carbon dioxide fluid is added to extruder, overcritical dioxy from the second heating zone of double screw extruder
The quality for changing carbon flow body is the 20% of polypropylene quality, and addition speed is 10g/min.Double screw extruder is divided into 10 heating
Area, wherein the first Heating Zone Temperature is 180 DEG C, other Heating Zone Temperatures are 160 DEG C~220 DEG C.Devolatilization is vacuumized in the 8th area,
The water cooled pelletizing of extruding pelletization material strip obtains product.
Embodiment 2
Weigh 50kg polypropylene powders (melt flow rate (MFR) 0.5g/10min), 50g antioxidant 1010s, 100g antioxidant
168,25g halogen-absorbers calcium stearate, 1500 grams of medical stones (2500 mesh of granularity), 250 grams of zinc ricinoleates and 7.5kg talcums
Powder, it is agitated be sufficiently mixed after, the double screw extruder that draw ratio L/D is 48: 1, rate of feeding 50g/min, screw rod is added
100 revs/min of rotating speed；Supercritical carbon dioxide fluid is added to extruder from the second heating zone of double screw extruder, overcritical
The quality of CO 2 fluid is the 10% of polypropylene quality, and addition speed is 5g/min.Double screw extruder is divided into 10
Heating zone, wherein the first Heating Zone Temperature is 180 DEG C, other Heating Zone Temperatures are 160 DEG C~220 DEG C.It is taken out in the 8th heating zone true
Empty devolatilization, the water cooled pelletizing of extruding pelletization material strip obtain product.
Embodiment 3
Weigh 50kg polypropylene powders (melt flow rate (MFR) 2.5g/10min), 75g antioxidant 1076s, 100g antioxidant
168,50g halogen-absorbers calcium stearate, 2500 grams of medical stones (2500 mesh of granularity), 350 grams of zinc ricinoleates and 10kg talcums
Powder, it is agitated be sufficiently mixed after, the double screw extruder that draw ratio L/D is 48: 1, rate of feeding 50g/min, screw rod is added
100 revs/min of rotating speed；Supercritical carbon dioxide fluid is added to extruder from the second heating zone of double screw extruder, overcritical
The quality of CO 2 fluid is the 30% of polypropylene quality, and addition speed is 15g/min.Double screw extruder is divided into 10
Heating zone, wherein the first Heating Zone Temperature is 180 DEG C, other Heating Zone Temperatures are 160 DEG C~220 DEG C.It is taken out in the 8th heating zone true
Empty devolatilization, the water cooled pelletizing of extruding pelletization material strip obtain product.
Embodiment 4
Weigh 50kg polypropylene powders (melt flow rate (MFR) 10g/10min), 50g antioxidant 3114s, 100g antioxidant
626,50g halogen-absorbers zinc stearate, 1000 grams of medical stones (2500 mesh of granularity), 150 grams of zinc ricinoleates and 15kg talcums
Powder, it is agitated be sufficiently mixed after, the double screw extruder that draw ratio L/D is 48: 1, rate of feeding 50g/min, screw rod is added
100 revs/min of rotating speed；Supercritical carbon dioxide fluid is added to extruder from the second heating zone of double screw extruder, overcritical
The quality of CO 2 fluid is the 30% of polypropylene quality, and addition speed is 15g/min.Double screw extruder is divided into 10
Heating zone, wherein the first Heating Zone Temperature is 180 DEG C, other Heating Zone Temperatures are 160 DEG C~220 DEG C.It is taken out in the 8th heating zone true
Empty devolatilization, the water cooled pelletizing of extruding pelletization material strip obtain product.
Embodiment 5
Weigh 50kg polypropylene powders (melt flow rate (MFR) 20g/10min), 50g antioxidant 1010s, 50g irgasfos 168s,
25g halogen-absorber calcium stearates, 500 grams of medical stones (2500 mesh of granularity), 1000 grams of Bio-sils, 50 grams of zinc ricinoleates and
20kg talcum powder, it is agitated be sufficiently mixed after, the double screw extruder that draw ratio L/D is 48: 1, rate of feeding 50g/ is added
Min, 100 revs/min of screw speed；Supercritical carbon dioxide fluid is added to extrusion from the second heating zone of double screw extruder
Machine, the quality of supercritical carbon dioxide fluid are the 15% of polypropylene quality, and addition speed is 7.5g/min.Double screw extruder
10 heating zones are divided into, wherein the first Heating Zone Temperature is 180 DEG C, other Heating Zone Temperatures are 160 DEG C~220 DEG C.The 8th
Heating zone vacuumizes devolatilization, and the water cooled pelletizing of extruding pelletization material strip obtains product.
Embodiment 6
Weigh 50kg polypropylene powders (melt flow rate (MFR) 60g/10min), 50g antioxidant 1010s, 50g irgasfos 168s,
25g halogen-absorber calcium stearates, 1000 grams of Bio-sils, 50 grams of zinc ricinoleates and 5kg talcum powder are agitated to be sufficiently mixed
Afterwards, the double screw extruder that draw ratio L/D is 48: 1, rate of feeding 50g/min, 100 revs/min of screw speed is added；It is super to face
Boundary's CO 2 fluid is added to extruder, the quality of supercritical carbon dioxide fluid from the second heating zone of double screw extruder
It is the 2% of polypropylene quality, addition speed is 1g/min.Double screw extruder is divided into 10 heating zones, wherein the first heating
Area's temperature is 180 DEG C, and other Heating Zone Temperatures are 160 DEG C~220 DEG C.Devolatilization, extruding pelletization material strip are vacuumized in the 8th heating zone
Water cooled pelletizing obtains product.
Embodiment 7
Weigh 50kg polypropylene powders (melt flow rate (MFR) 100g/10min), 25g antioxidant 1010s, 50g antioxidant
168,100g halogen-absorbers zinc stearate, it is agitated be sufficiently mixed after, the twin-screw extrusion that draw ratio L/D is 48: 1 is added
Machine, rate of feeding 50g/min, 100 revs/min of screw speed；Supercritical carbon dioxide fluid from double screw extruder second
Heating zone is added to extruder, and the quality of supercritical carbon dioxide fluid is the 30% of polypropylene quality, and addition speed is 15g/
min.Double screw extruder is divided into 10 heating zones, wherein the first Heating Zone Temperature is 180 DEG C, other Heating Zone Temperatures are
160 DEG C~220 DEG C.Devolatilization is vacuumized in the 8th heating zone, the water cooled pelletizing of extruding pelletization material strip obtains product.
Embodiment 8
Weigh 50kg polypropylene powders (melt flow rate (MFR) 120g/10min), 75g antioxidant 1010s, 150g antioxidant
168,25g halogen-absorbers zinc stearate, it is agitated be sufficiently mixed after, the double screw extruder that draw ratio L/D is 48: 1 is added,
Rate of feeding is 50g/min, 100 revs/min of screw speed；Second heating of the supercritical carbon dioxide fluid from double screw extruder
Area is added to extruder, and the quality of supercritical carbon dioxide fluid is the 30% of polypropylene quality, and addition speed is 15g/min.
Double screw extruder is divided into 10 heating zones, wherein the first Heating Zone Temperature is 180 DEG C, other Heating Zone Temperatures are 160 DEG C
~220 DEG C.Devolatilization is vacuumized in the 8th heating zone, the water cooled pelletizing of extruding pelletization material strip obtains product.
Comparative example 1
Weigh 50kg polypropylene powders (melt flow rate (MFR) 2.5g/10min), 50g antioxidant 1010s, 50g antioxidant
168,50g halogen-absorbers zinc stearate, it is agitated be sufficiently mixed after, the double screw extruder that draw ratio L/D is 48: 1 is added,
Rate of feeding is 50g/min, 100 revs/min of screw speed；Double screw extruder is divided into 10 heating zones, wherein the first heating
Area's temperature is 180 DEG C, and other Heating Zone Temperatures are 160 DEG C~220 DEG C.Devolatilization, extruding pelletization material strip are vacuumized in the 8th heating zone
Water cooled pelletizing obtains product.
Comparative example 2
Weigh 50kg polypropylene powders (melt flow rate (MFR) 60g/10min), 50g antioxidant 1010s, 50g irgasfos 168s,
50g halogen-absorber zinc stearates, it is agitated be sufficiently mixed after, the double screw extruder that draw ratio L/D is 48: 1, feeding is added
Speed is 50g/min, 100 revs/min of screw speed；Double screw extruder is divided into 10 heating zones, wherein the first heating zone temperature
Degree is 180 DEG C, and other Heating Zone Temperatures are 160 DEG C~220 DEG C.Devolatilization is vacuumized in the 8th heating zone, extruding pelletization material strip is through water
Cold palletizing obtains product.
The performance of 1. polypropene composition of table
Method using the present invention is plus addition eliminating smell agent, Ke Yiyou it can be seen from embodiment 1-6 and comparative example comparison
By the various volatile small molecules and organic compound in composition, polypropene composition prepared by the present invention has low gas on effect ground
Taste feature.
By embodiment 7 and embodiment 8 with from the point of view of the comparison of comparative example 1 and comparative example 2, overcritical dioxy using the present invention
Change carbon extracting method can effectively by polymer volatile small molecule and organic compound dissolution extracting, more significantly
Reduce the oder levels of polypropene composition.
Claims (10)
1. a kind of preparation method of polypropene composition, it is characterized in that including the following steps：
(1) each raw material of formula is weighed in following ratios, super mixer is added and is uniformly mixed；
The polypropene composition includes following components：
Isotactic homopolymerization or the copolymerized type propene polymer pellet that the polypropylene is 0.1~120g/10min of melt flow rate (MFR), powder
Or mixtures thereof end；The primary antioxidant is hindered phenol compound；
(2) each component mixture of step (1) formula is added from the first heating zone of double screw extruder, and by overcritical two
Carbon oxide fluid is added twin-screw extrude from third heating zone or the second heating zone, the quality of supercritical carbon dioxide fluid
Account for the 2~30% of extrudate gross mass, 50 revs/min~500 revs/min of extruder driving screw rotating speed, 150~240 DEG C of extrusion temperature,
Devolatilization is vacuumized in extruding dies, water cooled material strip, granulation and drying is squeezed out and obtains.
2. a kind of preparation method of polypropene composition, it is characterized in that including the following steps：
(1) each raw material of formula is weighed in following ratios, super mixer is added and is uniformly mixed；
The polypropene composition includes following components：
Isotactic homopolymerization or the copolymerized type propene polymer pellet that the polypropylene is 0.1~200g/10min of melt flow rate (MFR), powder
Or mixtures thereof end；The primary antioxidant is hindered phenol compound；
(2) each component mixture of step (1) formula is added from the first heating zone of double screw extruder, and by overcritical two
Carbon oxide fluid is added twin-screw extrude from third heating zone or the second heating zone, the quality of supercritical carbon dioxide fluid
Account for the 2~30% of extrudate gross mass, 50 revs/min~500 revs/min of extruder driving screw rotating speed, 150~240 DEG C of extrusion temperature,
Devolatilization is vacuumized before extruding dies, is squeezed out water cooled material strip, granulation and drying and is obtained.
3. preparation method according to claim 1 or 2, it is characterised in that：The primary antioxidant be selected from β-(4 hydroxyl -3,
5- di-tert-butyl-phenyls) propionic acid n-octadecyl alcohol ester, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythrites
Ester, 1, one kind or combinations thereof in 3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) isocyanuric acids.
4. preparation method according to claim 1 or 2, it is characterised in that：The auxiliary anti-oxidant is selected from (2,4- bis- tertiary fourths
Base phenyl) tris phosphite, one kind or combinations thereof in pentaerythritol bis-phosphite two (2,4- di-tert-butyl phenyl) ester.
5. preparation method according to claim 1 or 2, it is characterised in that：The halogen-absorber be selected from calcium stearate,
Zinc stearate and hydrated magnesium silicate it is one or more.
6. preparation method according to claim 1, it is characterised in that：The eliminating smell agent is selected from medical stone, Bio-sil,
Molecular sieve etc. it is one or more.
7. preparation method according to claim 1, it is characterised in that：The smell chelating agent is zinc ricinoleate.
8. preparation method according to claim 1, it is characterised in that：The polymers compositions is selected from polypropylene, master resists
Oxygen agent is selected from four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, auxiliary anti-oxidant is selected from (2,4- bis- tertiary fourths
Base phenyl) tris phosphite, halogen-absorber be selected from calcium stearate, eliminating smell agent be selected from medical stone, smell chelating agent be selected from castor-oil plant
Alkyd zinc, talcum powder；
Or the polymers compositions is selected from polypropylene, primary antioxidant is selected from β-(4 hydroxyl -3,5- di-tert-butyl-phenyl) propionic acid
Positive octadecanol ester, auxiliary anti-oxidant are selected from (2,4- di-tert-butyl-phenyl) tris phosphite, halogen-absorber is selected from calcium stearate,
Eliminating smell agent is selected from medical stone, smell chelating agent is selected from zinc ricinoleate, talcum powder；
Or the polymers compositions is selected from polypropylene, primary antioxidant is selected from β-(4 hydroxyl -3,5- di-tert-butyl-phenyl) propionic acid
Positive octadecanol ester, auxiliary anti-oxidant are selected from (2,4- di-tert-butyl-phenyl) tris phosphite, halogen-absorber is selected from calcium stearate,
Eliminating smell agent is selected from medical stone, smell chelating agent is selected from zinc ricinoleate, talcum powder；
Or the polymers compositions is selected from polypropylene, primary antioxidant is selected from 1,3,5- tri- (3,5- di-t-butyl -4- hydroxyl benzyls
Base) isocyanuric acid, auxiliary anti-oxidant be selected from pentaerythritol bis-phosphite two (2,4- di-tert-butyl phenyl) ester, halogen-absorber select
From calcium stearate, eliminating smell agent are selected from medical stone, smell chelating agent is selected from zinc ricinoleate, talcum powder；
Or the polymers compositions is selected from polypropylene, primary antioxidant is selected from four [β-(3,5- di-tert-butyl-hydroxy phenyl)
Propionic acid] pentaerythritol ester, auxiliary anti-oxidant be selected from (2,4- di-tert-butyl-phenyl) tris phosphite, halogen-absorber be selected from stearic acid
Calcium, eliminating smell agent are selected from medical stone and Bio-sil, and smell chelating agent is selected from zinc ricinoleate, talcum powder；
Or the polymers compositions is selected from polypropylene, primary antioxidant is selected from four [β-(3,5- di-tert-butyl-hydroxy phenyl)
Propionic acid] pentaerythritol ester, auxiliary anti-oxidant be selected from (2,4- di-tert-butyl-phenyl) tris phosphite, halogen-absorber be selected from stearic acid
Calcium, eliminating smell agent is selected from Bio-sil, smell chelating agent is selected from zinc ricinoleate, talcum powder.
9. preparation method according to claim 2, it is characterised in that：The polymers compositions is selected from polypropylene powder,
Primary antioxidant is selected from four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, auxiliary anti-oxidant is selected from (2,4- bis-
Tert-butyl-phenyl) tris phosphite, halogen-absorber be selected from zinc stearate.
10. preparation method according to claim 1 or 2, it is characterised in that：Primary antioxidant, auxiliary anti-oxidant and the halogen
Plain absorbent is added by pure form or is added in the form of masterbatch or compound additive.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535568A (en) * | 2018-12-19 | 2019-03-29 | 上海睿聚环保科技有限公司 | A kind of low VOC regenerating polypropylene material and its preparation process |
| CN109957172A (en) * | 2019-04-03 | 2019-07-02 | 金旸（厦门）新材料科技有限公司 | A kind of eliminating smell agent, it is low distribute, automobile interior decoration polypropylene material resistant to high temperature and preparation method thereof |
| CN110183780A (en) * | 2019-06-14 | 2019-08-30 | 国家能源投资集团有限责任公司 | Polypropylene wiredrawing material, its PP Pipe Compound and BOPP film product |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0367396A2 (en) * | 1988-09-19 | 1990-05-09 | Sumitomo Chemical Company, Limited | Polypropylene molded article |
| CN102837408A (en) * | 2012-09-18 | 2012-12-26 | 贵州凯科特材料有限公司 | Double screw extruder and method for using same to prepare light-smell polypropylene |
| CN103044770A (en) * | 2012-12-17 | 2013-04-17 | 上海普利特复合材料股份有限公司 | Long glass fiber reinforced polypropylene material with low smell and high performance and manufacturing method thereof |
| CN103254499A (en) * | 2013-03-06 | 2013-08-21 | 苏州旭光聚合物有限公司 | Low-smell vehicle polypropylene composite material and its preparation method |
| US20160257609A1 (en) * | 2013-10-15 | 2016-09-08 | Athanasios KARALIS | Expanded, micronized surface treated aluminosilicate volcanic glass as lamellar functional filler for plastics and special coatings |
| CN106243483A (en) * | 2016-08-29 | 2016-12-21 | 合肥会通新材料有限公司 | A kind of zero VOC polypropylene material and preparation technology thereof |
| CN106317743A (en) * | 2016-09-19 | 2017-01-11 | 南京德尔隆工程塑料有限公司 | High-mobility low-odor scratch-resistant automobile trim polypropylene material and preparation method thereof |
| CN106479162A (en) * | 2015-08-27 | 2017-03-08 | 合肥杰事杰新材料股份有限公司 | A kind of low abnormal smells from the patient, low distribute, halogen-free flameproof PA6/PP alloy and preparation method thereof |
-
2017
- 2017-04-20 CN CN201710260083.1A patent/CN108727683A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0367396A2 (en) * | 1988-09-19 | 1990-05-09 | Sumitomo Chemical Company, Limited | Polypropylene molded article |
| CN102837408A (en) * | 2012-09-18 | 2012-12-26 | 贵州凯科特材料有限公司 | Double screw extruder and method for using same to prepare light-smell polypropylene |
| CN103044770A (en) * | 2012-12-17 | 2013-04-17 | 上海普利特复合材料股份有限公司 | Long glass fiber reinforced polypropylene material with low smell and high performance and manufacturing method thereof |
| CN103254499A (en) * | 2013-03-06 | 2013-08-21 | 苏州旭光聚合物有限公司 | Low-smell vehicle polypropylene composite material and its preparation method |
| US20160257609A1 (en) * | 2013-10-15 | 2016-09-08 | Athanasios KARALIS | Expanded, micronized surface treated aluminosilicate volcanic glass as lamellar functional filler for plastics and special coatings |
| CN106479162A (en) * | 2015-08-27 | 2017-03-08 | 合肥杰事杰新材料股份有限公司 | A kind of low abnormal smells from the patient, low distribute, halogen-free flameproof PA6/PP alloy and preparation method thereof |
| CN106243483A (en) * | 2016-08-29 | 2016-12-21 | 合肥会通新材料有限公司 | A kind of zero VOC polypropylene material and preparation technology thereof |
| CN106317743A (en) * | 2016-09-19 | 2017-01-11 | 南京德尔隆工程塑料有限公司 | High-mobility low-odor scratch-resistant automobile trim polypropylene material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 徐国平: "低气味聚丙烯改性料的研制", 《工程塑料应用》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535568A (en) * | 2018-12-19 | 2019-03-29 | 上海睿聚环保科技有限公司 | A kind of low VOC regenerating polypropylene material and its preparation process |
| CN109535568B (en) * | 2018-12-19 | 2021-06-25 | 上海睿聚环保科技有限公司 | Low-VOC (volatile organic compound) regenerated polypropylene material and preparation process thereof |
| CN109957172A (en) * | 2019-04-03 | 2019-07-02 | 金旸（厦门）新材料科技有限公司 | A kind of eliminating smell agent, it is low distribute, automobile interior decoration polypropylene material resistant to high temperature and preparation method thereof |
| CN110183780A (en) * | 2019-06-14 | 2019-08-30 | 国家能源投资集团有限责任公司 | Polypropylene wiredrawing material, its PP Pipe Compound and BOPP film product |
| CN111548554A (en) * | 2020-04-27 | 2020-08-18 | 中国神华煤制油化工有限公司 | Adhesive tape film material composition, application thereof and adhesive tape film material |
| CN113754953A (en) * | 2021-08-11 | 2021-12-07 | 江苏中科聚合新材料产业技术研究院有限公司 | Preparation method and application of clean and odorless polypropylene |
| CN113754953B (en) * | 2021-08-11 | 2023-10-13 | 常州福隆科技新材料有限公司 | Preparation method and application of clean and odorless polypropylene |
| CN113881138A (en) * | 2021-09-30 | 2022-01-04 | 中国石油化工股份有限公司 | Preparation method of low-odor ultrahigh-fluidity polypropylene |
| WO2024012475A1 (en) * | 2022-07-13 | 2024-01-18 | 上海睿聚环保科技有限公司 | Odorless environmentally friendly recycled polypropylene plastic and preparation method therefor |
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Application publication date: 20181102 |