CN108727660A - A kind of preparation method of low smell polyethylene composition - Google Patents
A kind of preparation method of low smell polyethylene composition Download PDFInfo
- Publication number
- CN108727660A CN108727660A CN201710260081.2A CN201710260081A CN108727660A CN 108727660 A CN108727660 A CN 108727660A CN 201710260081 A CN201710260081 A CN 201710260081A CN 108727660 A CN108727660 A CN 108727660A
- Authority
- CN
- China
- Prior art keywords
- polyethylene
- butyl
- phenyl
- tert
- smell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a kind of preparation methods of low smell polyethylene composition, belong to field of material technology, including at least 100 parts of polyethylene, 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 the heat of polyethylene 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, is conducive to promote and apply.
Description
Technical field
The present invention relates to a kind of preparation methods being used to prepare ethylene polymer composition.
Background technology
Polyethylene (PE) is the high-molecular compound obtained from vinyl polymerization.Due to its abundant raw material, synthesis technology ratio
Relatively simple, compared with other general-purpose thermoplastic plastics, PE has price low, and has proof stress, cracking behavior and wearability outstanding,
It is fastest-rising kind in general-purpose thermoplastic plastic, the status in economic construction and people's lives becomes more and more important, and becomes modeling
The most fast kind of increase of production in material, can use blowing, squeeze out, injection moulding the methods of processing, be widely used in manufacture film, in
Empty product, fiber and daily use Sundry goods etc..But polyethylene itself and various additives would generally bring larger smell into, limitation
Its certain fields application, and with the development and the improvement of people's living standards of national economy, to polythene material
Odor profiles requirement also increasingly improve.In order to be used for a long time and expand application range, the polythene material of low smell how is obtained,
Also it has 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.
Patent application CN201110198093 discloses a kind of low odor polyethylene plastic hose, by:High density is linear
Polyethylene 70~80%, age resister 2~3%, silicone oil 1~2%, modifying agent 13.5~26.5%, antioxidant 0.1~0.5%,
BX molecular sieves 0.2~0.5%, activated alumina 0.2~0.5%.It mainly passes through BX molecular sieve of the addition containing a large amount of holes
Plastics smell is reduced with volatile matter that activated alumina comes in adsorption plastic.
It can be seen that chelating agent or object are mainly used in terms of reducing polyethylene or polypropylene material smell at present
Adsorbent is managed to reduce the smell of material.Chelating agent can reduce the smell of PE, mainly due to these chemistry eliminating smell agents
It can be reacted with the small molecule for releasing smell or other harmful VOC, so that it is generated relative molecular mass larger, no
Another compound that can be evaporated from material, to achieve the effect that eliminate peculiar smell.Reaction involved by this method
It is extremely complex, but it is with strong points, it is suitable for the specific product of VOC types.Physical absorbent can be in the form of physical absorption
Odorous small-molecule substance is adsorbed to reduce the smell of PE, any smell or VOC can theoretically be adsorbed.At present
Sorbent systems include the mineral soil body such as activated carbon system, silica gel system, attapulgite system, molecular sieve system etc..But
During actual processing, it is also desirable to consider the aperture of odor adsorption agent, pore size distribution, the influence of pore structure, desorption temperature,
It is often difficult to fully meet needs.
Invention content
To solve the above-mentioned problems, the present invention provides a kind of preparation method of low smell polyethylene composition, party's legal system
PE and its composite material smell can be effectively reduced for the polyethylene composition gone out, while there is good mechanical property.
The technical scheme is that:
A kind of preparation method of polyethylene composition, includes the following steps:
(1) each raw material of formula is weighed in proportion, and super mixer is added and is uniformly mixed;
The polyethylene composition includes following components:
(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.
The polyethylene is 0.1~120g/10min of melt flow rate (MFR), 0.912~0.965g/cm of density3Homopolymerization
Or copoly type polyethylene pellet, 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, one or more, the preferred medical stone of molecular sieve etc..
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 polyethylene composition group is divided into:Polyethylene, primary antioxidant are 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 smell chelating agent is selected from zinc ricinoleate.
The polyethylene composition group is divided into:Polyethylene, primary antioxidant are selected from β-(4 hydroxyl -3,5- di-tert-butyls
Base) propionic acid n-octadecyl alcohol ester, auxiliary anti-oxidant be selected from (2,4- di-tert-butyl-phenyl) tris phosphite, halogen-absorber be selected from it is hard
Resin acid calcium, eliminating smell agent are selected from medical stone, and smell chelating agent is selected from zinc ricinoleate.
The polyethylene composition group is divided into:Polyethylene, primary antioxidant are selected from 1,3,5- tri- (3,5- di-t-butyl -4-
Hydroxybenzyl) isocyanuric acid, auxiliary anti-oxidant be selected from pentaerythritol bis-phosphite two (2,4- di-tert-butyl phenyl) ester, halogen inhale
It receives agent and is selected from calcium stearate, eliminating smell agent is selected from medical stone, and smell chelating agent is selected from zinc ricinoleate.
The polyethylene composition group is divided into:Polyethylene, primary antioxidant are 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.
The polyethylene composition group is divided into:Polyethylene, primary antioxidant are 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 Bio-sil, and smell chelating agent is selected from zinc ricinoleate.
The polyethylene composition group is divided into:Polyethylene, primary antioxidant are selected from four [β-(3,5- di-t-butyl -4- hydroxyls
Phenyl) propionic acid] pentaerythritol ester and β-(4 hydroxyl -3,5- di-tert-butyl-phenyl) propionic acid n-octadecyl alcohol ester (article number:Antioxygen
Agent 1076) (in 1: 1 ratio), auxiliary anti-oxidant be selected from (2,4- di-tert-butyl-phenyl) tris phosphite and pentaerythrite diphosphite
Ester two (2,4- di-tert-butyl phenyl) ester (antioxidant 626) (in 1: 1 ratio), halogen-absorber are selected from calcium stearate, eliminating smell agent
Selected from medical stone and Bio-sil, smell chelating agent is selected from zinc ricinoleate.
A kind of polyethylene composition can also include following components:
The polyethylene is 0.1~200g/10min of melt flow rate (MFR), 0.912~0.965g/cm of density3Homopolymerization
Or copoly type polyethylene pellet, 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.
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 polyethylene composition group is divided into:Polyethylene, primary antioxidant are 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
Zinc stearate.
Advantageous effect:
The present invention is squeezed out using supercritical carbon dioxide auxiliary, restrained effectively the heat and oxygen of polyethylene 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 polyethylene 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 food product packing film, various beverages
With the processing and application of drug packing material and regenerated polythene material.
The present invention is comprehensive
Falling a part by supercritical carbon dioxide extracting when modified has small molecule (this and the existing macromolecule material of larger smell
The supercritical carbon dioxide ancillary technique of material the difference is that, existing high molecular material supercritical carbon dioxide ancillary technique
It is by supercritical carbon dioxide to assist that reactant or small molecule are disperseed/be diffused into high molecular material), in addition pass through again
Addition has smell the auxiliary agent of absorption and chelation in formula, final to realize that the purpose for reducing polymer smell, effect are wanted
Better than the existing simple scheme using formula adjustment.
Specific implementation mode
Illustrate the present invention in further detail with reference to embodiments, but the present invention is not limited to these Examples.
Polyethylene 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 polyethylene 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 are agitated abundant
After mixing, 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;
Supercritical carbon dioxide fluid is added to extruder from the second heating zone of double screw extruder, supercritical carbon dioxide fluid
Quality is the 20% of polyethylene quality, and addition speed is 10g/min.Double screw extruder is divided into 10 heating zones, wherein the
One Heating Zone Temperature is 180 DEG C, and other Heating Zone Temperatures are 160 DEG C~220 DEG C.Devolatilization, extruding pelletization material are vacuumized in the 8th area
The water cooled pelletizing of item obtains product.
Embodiment 2
Weigh 50kg polyethylene 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 are agitated abundant
After mixing, 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;
Supercritical carbon dioxide fluid is added to extruder from the second heating zone of double screw extruder, supercritical carbon dioxide fluid
Quality is the 10% of polyethylene quality, and addition speed is 5g/min.Double screw extruder is divided into 10 heating zones, wherein first
Heating Zone Temperature 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
The water cooled pelletizing of material strip obtains product.
Embodiment 3
Weigh 50kg polyethylene 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 are agitated abundant
After mixing, 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;
Supercritical carbon dioxide fluid is added to extruder from the second heating zone of double screw extruder, supercritical carbon dioxide fluid
Quality is the 30% of polyethylene quality, and addition speed is 15g/min.Double screw extruder is divided into 10 heating zones, wherein the
One Heating Zone Temperature is 180 DEG C, and other Heating Zone Temperatures are 160 DEG C~220 DEG C.Devolatilization is vacuumized in the 8th heating zone, extrusion is made
The water cooled pelletizing of pellet item obtains product.
Embodiment 4
Weigh 50kg polyethylene 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 are agitated abundant
After mixing, 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;
Supercritical carbon dioxide fluid is added to extruder from the second heating zone of double screw extruder, supercritical carbon dioxide fluid
Quality is the 30% of polyethylene quality, and addition speed is 15g/min.Double screw extruder is divided into 10 heating zones, wherein the
One Heating Zone Temperature is 180 DEG C, and other Heating Zone Temperatures are 160 DEG C~220 DEG C.Devolatilization is vacuumized in the 8th heating zone, extrusion is made
The water cooled pelletizing of pellet item obtains product.
Embodiment 5
Weigh 50kg polyethylene 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,
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 15% of polyethylene quality, and addition speed is 7.5g/min.Double screw extruder is divided into 10 and adds
Hot-zone, wherein the first Heating Zone Temperature is 180 DEG C, other Heating Zone Temperatures are 160 DEG C~220 DEG C.It is vacuumized in the 8th heating zone
Devolatilization, the water cooled pelletizing of extruding pelletization material strip obtain product.
Embodiment 6
Weigh 50kg polyethylene 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, it is agitated be sufficiently mixed after, be added major diameter
Than the double screw extruder that L/D is 48: 1, rate of feeding 50g/min, 100 revs/min of screw speed;Stream of supercritical carbon dioxide
Body is added to extruder from the second heating zone of double screw extruder, and the quality of supercritical carbon dioxide fluid is polyethylene quality
2%, addition speed be 1g/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, the water cooled pelletizing of extruding pelletization material strip are vacuumized in the 8th heating zone
Obtain product.
Embodiment 7
Weigh 50kg polyethylene 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 polyethylene 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 polyethylene 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 polyethylene 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 polyethylene 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 polyethylene 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. polyethylene 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, polyethylene 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 polyethylene composition.
Claims (9)
1. a kind of preparation method of low smell polyethylene composition, it is characterised in that include the following steps:
(1) each raw material of formula is weighed in proportion, and super mixer is added and is uniformly mixed;
The polyethylene is 0.1~120g/10min of melt flow rate (MFR), 0.912~0.965g/cm of density3Homopolymerization or altogether
Poly- type polyethylene pellet, or mixtures thereof powder, the primary antioxidant are selected from 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.
2. a kind of preparation method of low smell polyethylene composition, it is characterised in that include the following steps:
(1) each raw material of formula is weighed in proportion, and super mixer is added and is uniformly mixed;
The polyethylene composition includes following components:
The polyethylene is 0.1~200g/10min of melt flow rate (MFR), 0.912~0.965g/cm of density3Homopolymerization or altogether
Poly- type polyethylene pellet, or mixtures thereof powder;The primary antioxidant is selected from 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 is selected from β-(4 hydroxyls -3,5-
Di-tert-butyl-phenyl) propionic acid n-octadecyl alcohol ester, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters,
1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid or combinations thereof.
4. preparation method according to claim 1 or 2, it is characterised in that:The auxiliary anti-oxidant is selected from (2,4- di-t-butyls
Phenyl) tris phosphite, pentaerythritol bis-phosphite two (2,4- di-tert-butyl phenyl) ester or combinations thereof.
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 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 polyethylene composition group is divided into:Polyethylene, primary antioxidant are selected from four [β-(3,5- di-t-butyl -4- hydroxy benzenes
Base) propionic acid] pentaerythritol ester, auxiliary anti-oxidant be selected from (2,4- di-tert-butyl-phenyl) tris phosphite, halogen-absorber be selected from it is hard
Resin acid calcium, eliminating smell agent are selected from medical stone, and smell chelating agent is selected from zinc ricinoleate;
Or the polyethylene composition group is divided into:Polyethylene, primary antioxidant are selected from β-(4- hydroxyl -3,5- di-tert-butyls
Base) propionic acid n-octadecyl alcohol ester, auxiliary anti-oxidant be selected from (2,4- di-tert-butyl-phenyl) tris phosphite, halogen-absorber be selected from it is hard
Resin acid calcium, eliminating smell agent are selected from medical stone, and smell chelating agent is selected from zinc ricinoleate;
Or the polyethylene composition group is divided into:Polyethylene, primary antioxidant are selected from 1,3,5- tri- (3,5- di-t-butyl -4-
Hydroxybenzyl) isocyanuric acid, auxiliary anti-oxidant be selected from pentaerythritol bis-phosphite two (2,4- di-tert-butyl phenyl) ester, halogen inhale
It receives agent and is selected from calcium stearate, eliminating smell agent is selected from medical stone, and smell chelating agent is selected from zinc ricinoleate;
Or the polyethylene composition group is divided into:Polyethylene, primary antioxidant are 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;
Or the polyethylene composition group is divided into:Polyethylene, primary antioxidant are 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 Bio-sil, and smell chelating agent is selected from zinc ricinoleate.
9. preparation method according to claim 2, it is characterised in that:The polyethylene composition group is divided into:Polyethylene,
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.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710260081.2A CN108727660A (en) | 2017-04-20 | 2017-04-20 | A kind of preparation method of low smell polyethylene composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710260081.2A CN108727660A (en) | 2017-04-20 | 2017-04-20 | A kind of preparation method of low smell polyethylene composition |
Publications (1)
Publication Number | Publication Date |
---|---|
CN108727660A true CN108727660A (en) | 2018-11-02 |
Family
ID=63933323
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710260081.2A Pending CN108727660A (en) | 2017-04-20 | 2017-04-20 | A kind of preparation method of low smell polyethylene composition |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108727660A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111607022A (en) * | 2020-06-11 | 2020-09-01 | 黄河三角洲京博化工研究院有限公司 | Devolatilization method of trans-butyl amyl rubber |
CN114585676A (en) * | 2019-10-15 | 2022-06-03 | Sabic环球技术有限责任公司 | Polyethylene compositions for use with recycled polyethylene |
CN114716792A (en) * | 2021-01-06 | 2022-07-08 | 合肥杰事杰新材料股份有限公司 | Low-odor PET composite material with good physical properties and preparation method thereof |
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 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005264111A (en) * | 2004-03-22 | 2005-09-29 | Hitachi Chemical Filtec Inc | Wrap film for food packaging having degradability in natural environment |
US20080011709A1 (en) * | 2006-07-14 | 2008-01-17 | Japan Polyethylene Corporation | Polyethylene-based resin molding material |
CN102585324A (en) * | 2011-01-17 | 2012-07-18 | 中国石油化工股份有限公司 | Polyethylene composition for improving yellow index and lustrousness and preparation method thereof |
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 |
CN102875864A (en) * | 2011-07-15 | 2013-01-16 | 薛申生 | Low-odor polyethylene plastic hose and preparation method thereof |
CN103804745A (en) * | 2012-11-14 | 2014-05-21 | 中国石油天然气股份有限公司 | Polyethylene resin composition with improved appearance and odor |
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 |
-
2017
- 2017-04-20 CN CN201710260081.2A patent/CN108727660A/en active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005264111A (en) * | 2004-03-22 | 2005-09-29 | Hitachi Chemical Filtec Inc | Wrap film for food packaging having degradability in natural environment |
US20080011709A1 (en) * | 2006-07-14 | 2008-01-17 | Japan Polyethylene Corporation | Polyethylene-based resin molding material |
CN102585324A (en) * | 2011-01-17 | 2012-07-18 | 中国石油化工股份有限公司 | Polyethylene composition for improving yellow index and lustrousness and preparation method thereof |
CN102875864A (en) * | 2011-07-15 | 2013-01-16 | 薛申生 | Low-odor polyethylene plastic hose and preparation method thereof |
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 |
CN103804745A (en) * | 2012-11-14 | 2014-05-21 | 中国石油天然气股份有限公司 | Polyethylene resin composition with improved appearance and odor |
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 |
Non-Patent Citations (1)
Title |
---|
季孟渊: "一种耐刮擦、低气味、低VOC聚乙烯复合材料的研究", 《汽车零部件》 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114585676A (en) * | 2019-10-15 | 2022-06-03 | Sabic环球技术有限责任公司 | Polyethylene compositions for use with recycled polyethylene |
CN114585676B (en) * | 2019-10-15 | 2023-09-29 | Sabic环球技术有限责任公司 | Polyethylene composition for use with recycled polyethylene |
CN111607022A (en) * | 2020-06-11 | 2020-09-01 | 黄河三角洲京博化工研究院有限公司 | Devolatilization method of trans-butyl amyl rubber |
CN111607022B (en) * | 2020-06-11 | 2022-08-02 | 黄河三角洲京博化工研究院有限公司 | Devolatilization method of trans-butyl amyl rubber |
CN114716792A (en) * | 2021-01-06 | 2022-07-08 | 合肥杰事杰新材料股份有限公司 | Low-odor PET composite material with good physical properties and preparation method thereof |
CN114716792B (en) * | 2021-01-06 | 2024-02-20 | 合肥杰事杰新材料股份有限公司 | PET composite material with low odor and good physical properties and preparation method thereof |
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 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108727683A (en) | A kind of preparation method of polypropene composition | |
CN108727660A (en) | A kind of preparation method of low smell polyethylene composition | |
CN108727661A (en) | A kind of preparation method of bottle cap polyethylene composition | |
CN104830010A (en) | Hardened scratch-resistant antibacterial polypropylene master batch material for household electrical appliances and preparation method of polypropylene master batch material | |
CN108148276A (en) | A kind of low smell, low VOC PP composite material preparation method | |
EP2976384A2 (en) | "thermoplastic polymer formulation containing recycled polyolefins and method of preparing" | |
CN104277278A (en) | Efficient and lasting smell removal agent master batch, and preparation method and application thereof | |
CN103739944A (en) | Low-odour glass-fiber-enhanced polypropylene composite material and preparation method thereof | |
CN107903492A (en) | One kind is low to distribute low smell filling functional agglomerate and preparation method thereof | |
CN109608809B (en) | Low-odor polypropylene composite material and preparation method thereof | |
US20030092793A1 (en) | Process for the preparation of biodegradable resin | |
KR102509689B1 (en) | Thermoplastic compositions having improved toughness, articles therefrom and methods thereof | |
CN108178878A (en) | A kind of odor adsorption type functional agglomerate and preparation method and the automotive trim PP composite material being made from it | |
CN106380699A (en) | Polypropylene composition with low VOC (Volatile Organic Compound) and low odor and preparation method of polypropylene composition | |
CN108794847A (en) | Rotational moulding polyolefin composition and preparation method thereof | |
CN106479162A (en) | A kind of low abnormal smells from the patient, low distribute, halogen-free flameproof PA6/PP alloy and preparation method thereof | |
CN110872418A (en) | Polypropylene composition and preparation method thereof | |
CN1131277C (en) | Radiation cross-linked and foamed polypropylene material and its preparing process | |
CN109694523A (en) | A kind of low VOC Low-odor polypropylene resin composition and preparation method thereof | |
CN109852076A (en) | A kind of low smell, modified thermoplastic elastomer material of low VOC and preparation method thereof | |
CN1517398A (en) | Thermal oxidative degradation-promoting mother particle used for plastics and its preparation method | |
CN109694521A (en) | A kind of low VOC Low-odor polypropylene resin composition and preparation method thereof | |
CN107964173A (en) | A kind of EPDM sulfuration thermoplastic elastomers of ultra-low-smell and preparation method thereof | |
CN108102327A (en) | A kind of low smell PC/ABS wear resistant alloy materials and preparation method thereof | |
CN105017597B (en) | It is a kind of to improve composite assistant, its preparation method and its application of the polyolefin transparency |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181102 |
|
RJ01 | Rejection of invention patent application after publication |