CN106565875B - A method of continuously preparing molecular weight-controllable brominated polystyrene master batch - Google Patents
A method of continuously preparing molecular weight-controllable brominated polystyrene master batch Download PDFInfo
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- CN106565875B CN106565875B CN201610930107.5A CN201610930107A CN106565875B CN 106565875 B CN106565875 B CN 106565875B CN 201610930107 A CN201610930107 A CN 201610930107A CN 106565875 B CN106565875 B CN 106565875B
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- 239000004793 Polystyrene Substances 0.000 title claims abstract description 92
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 92
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000005893 bromination reaction Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 18
- 230000031709 bromination Effects 0.000 claims abstract description 15
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 12
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 10
- 238000004064 recycling Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 7
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- 235000013312 flour Nutrition 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000003801 milling Methods 0.000 claims description 5
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 5
- 235000012424 soybean oil Nutrition 0.000 claims description 5
- 239000003549 soybean oil Substances 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 4
- -1 polyphenylene Polymers 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 3
- 235000013339 cereals Nutrition 0.000 claims description 3
- 238000002845 discoloration Methods 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 238000005453 pelletization Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- DGZQEAKNZXNTNL-UHFFFAOYSA-N 1-bromo-4-butan-2-ylbenzene Chemical class CCC(C)C1=CC=C(Br)C=C1 DGZQEAKNZXNTNL-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000129 anionic group Chemical group 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 238000012805 post-processing Methods 0.000 abstract 1
- 239000003063 flame retardant Substances 0.000 description 10
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920006389 polyphenyl polymer Polymers 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- BBCAQPYJVYMQFB-UHFFFAOYSA-N sodium;2-methylpropane Chemical compound [Na+].C[C-](C)C BBCAQPYJVYMQFB-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
-
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a kind of methods for preparing molecular weight-controllable brominated polystyrene master batch, the reaction of body anionic extruding polymerization is carried out including causing styrene using butyl lithium, dissolved polystyrene simultaneously carries out bromination and prepares brominated Polystyrene, brominated Polystyrene solution neutralizes, after washing and separation, obtains molecular weight and the controllable brominated Polystyrene master batch of bromine content by double screw extruder removing and recycling design, devolatilization and discharging pelletizing.Use the above method can be using styrene as raw material; it is continuously available brominated Polystyrene master batch by polymerization, bromination, post-processing and master batch, production procedure can be reduced, reduces production cost; pollution is reduced, is the method for resource-conserving manufacture brominated Polystyrene master batch of new generation.
Description
Technical field
The invention belongs to chemical fields, in particular to a kind of environmental-friendly and energy-saving safe continuously to prepare controllable molecular weight
The method of brominated Polystyrene master batch.
Technical background
Brominated Polystyrene (BPS) is a kind of novel addition type high molecular weight flame retardant, and heat-resist, no blooming does not move
The features such as shifting, resistance to precipitation.Low toxicity, environmental protection are BPS biggest advantages, are to commonly use fire retardant polybrominated biphenyls and polybrominated diphenyl ethers most
Good substitute products.
It is generally used for thermostability engineering plastic such as PA, PET, PBT, syndiotactic polytyrene, cyclohexanedimethanol's alkene two
Methylene base ester etc. it is fire-retardant, apply in household electrical appliance, chemicals or grain containers.
The molecular weight of brominated Polystyrene greatly influences the processing performance of fire retardant and the compatibility performance with matrix resin.
Brominated Polystyrene is usually to be made by polystyrene through bromination, so the size of BPS molecular weight is entirely by polystyrene original
What the molecular weight of material determined.By controlling the degree of polymerization, the molecular weight of oligomer can be effectively controlled, being formed has different softening temperatures
Oligomer, adapt to the demand of different substrate materials.
Domestic present brominated polystyrenic product is mostly the polyphenyl using high molecular weight (molecular weight is 200,000 or more)
The direct bromination of ethylene forms, so obtained molecular weight product is also very high, processing temperature is excessively high, and by fire-retardant matrix resin
Compatibility is bad, the strong influence mechanical performance of resin, and product quality is also unstable.
In Chinese Patent Application No. 200710037339.9, low molecular weight polycaprolactone styrene is prepared for using ATRP catalysis technique
As raw material, low molecule brominated Polystyrene is obtained as bromination under catalysts conditions in alchlor.
In Chinese patent CN1122046C, lewis acid is used as catalyst, using bromine chloride or bromine as bromine
Agent is prepared for brominated Polystyrene as raw material using the polystyrene of ten thousand molecular weight of 500-150.
In Chinese patent CN101824113B, using styrene as raw material, benzene second is passed through as catalyst using tert-butyl sodium
The controllable polymerization of alkene reacts, and prepares polystyrene under solution state；Polystyrene in solution state is subjected to bromination system
Standby brominated Polystyrene, and by extracting brominated Polystyrene after precipitating or solvent distillation.
Fire-retardant master granule is to make on the basis of fire retardant by the combination of a variety of fire-retardant compositions, modification and synergistic
With adding certain plastic carrier, and pass through double screw extruder by a kind of graininess prepared by being kneaded, squeeze out, being granulated
Product.Fire-retardant master granule is high, easy to use with flame retarding efficiency and resin compatible is good, reduces cost, improves product added value etc.
Advantage, the advantage of all various aspects make it have become effective substitute of conventional flame retardant and be largely applied to making for plastics
The various aspects such as grain, extrusion, injection molding.
Chinese patent CN102627812R discloses a kind of brominated Polystyrene master batch and preparation method thereof, effectively prevents
The situation that powder and pellet mixing unevenly cause quality of materials unstable.
Brominated Polystyrene master batch is prepared using above method, needs first to extract polystyrene, then carries out bromination, is extracted
Brominated Polystyrene, then brominated Polystyrene master batch is prepared, production procedure is complicated, and at high cost, energy consumption is high, production process controllability
It is bad.
Summary of the invention
It is an object of the invention to overcome above-mentioned the deficiencies in the prior art, through inventor's long campaigns polymer work
The developmental research of journey, provides that a kind of molecular weight is controllable, reduces production procedure, reduces production cost, economizes on resources, production process can
The method for continuously preparing the controllable brominated Polystyrene master batch of molecular weight of control.
A kind of method continuously preparing the controllable brominated Polystyrene master batch of molecular weight provided by the invention, including following step
It is rapid:
1), styrene ontology extruding polymerization
The pretreatment of double screw extruder
Before styrene ontology extruding polymerization, the screw rod and barrel of double screw extruder are cleaned, and under preheating, taken out true
Empty, rear logical nitrogen is for several times；The temperature of the screw zones are as follows: first segment is the metering conveying section of styrene, temperature 20-50
℃；；Second segment and third section are that initiator butyl lithium is metered and polymerization reaction zone, temperature are 30-120 DEG C；4th section and
5th section of mainly melt conveying zone, temperature is 120-180 DEG C；6th section is mouth mold section, and temperature is 150-200 DEG C.Polymerization is anti-
Answer the too low then rate of polymerization of temperature too low, conversion ratio is insufficient, and the mechanical shearing of polymer is easily caused to degrade.Polymeric reaction temperature
Excessively high, rate of polymerization is too fast, and heat dissipation is insufficient, will cause thermal degradation.Therefore, polymeric reaction temperature is distributed trapezoidal accurate control.
Material controls between 3-20 minutes in the mean residence time in double screw extruder.Residence time is lower than 3 points
Zhong Shi, polymerisation conversion is too low, and molecular weight distribution is too wide: when the residence time is more than 20 minutes, thermal oxidative degradation can occur for material,
It has been greatly reduced production efficiency.The slewing rate of screw rod controls between 20-200rpm.When revolving speed is lower than 20rpm, object is caused
The residence time of material is too long, mixing is uneven and production efficiency is low: when revolving speed is higher than 200rpm, can make polystyrene shearing drop
Solution and residence time are insufficient, therefore cannot obtain high conversion polystyrene.Styrene ontology extruding polymerization monomer of the present invention turns
Rate is close to 100%.
In the melt conveying zone of polystyrene, by terminator and antioxidant from the side of double screw extruder to addition.In this way,
Not only thermal oxidative reaction can be prevented, but also can be directly entered in bromination reaction kettle after the extrusion and dissolve bromination.
2), polystyrene catalytic bromination
(1), polystyrene dissolves
By above-mentioned steps 1), that the polystyrene in bulk state is directly dissolved in the dichloroethanes in bromination reaction kettle is molten
It in agent, stirs to dissolve, forms the solution of the 5-15wt% containing polystyrene.
(2), catalytic bromination
The antimony trichloride catalyst for being equivalent to polystyrene weight 5-13wt% is added into above-mentioned polystyrene solution, stirs
It mixes and makes it dissolve, control solution temperature under the conditions of 10 DEG C -25 DEG C, slowly into the solution of above-mentioned addition antimony trichloride catalyst
Bromine chloride is added, bromine chloride and polystyrene monomers molar ratio are 3.5: 1-3.8: 1, after charging, keep temperature to continue anti-
It answers 3-4 hours.
(3), washing, separation are neutralized and is stablized
5wt% sodium sulfite is added in polystyrene reactant liquid after catalytic bromination or aqueous solution of sodium bisulfite terminates
Reaction, removes the hydrochloric acid of excessive bromine chloride and generation, the sodium sulfite or sodium hydrogensulfite of addition, until reaction residual liquor is from red
Until discoloration is white or faint yellow no longer discoloration, 5wt% sodium hydroxide solution is added, until solution is in neutrality, is washed with water,
Isolate brominated Polystyrene solution.With brominated Polystyrene quality for 100, add respectively into brominated Polystyrene solution respectively
Enter 0.5-1.5 parts of epoxidized soybean oils, 2264 stabilizer of 0.1-1.0 part and 0.5-5.0 parts of blended wax.
3) brominated Polystyrene master batch, is prepared
(1), solvent recovery
Step 2), brominated Polystyrene solution are injected into the solvent recovery section of double screw extruder, institute with metering pump
State the reversed extruder of twin-screw that double screw extruder is diameter phi 25- φ 100mm, L/D=20-55, the twin-screw extrusion
The engine speed 50-500r/min of machine, collet have heat or cool, heating make brominated Polystyrene solution keep compared with
High-temperature excludes to recycle most of solvent, first row outlet pressure 100KPa-50KPa, temperature is before entering devolatilization section
80~120 DEG C, second exhaust port pressure 50KPa-20KPa, temperature is 120~150 DEG C, to ensure the removing of a large amount of solvents and return
It receives.
(2), devolatilization
The inert gases such as nitrogen or carbon dioxide are added from devolatilization auxiliary agent mouth, the pressure of nitrogen or carbon dioxide is 0.3~
1.0MPa, this exhaust port pressure are 50-10KPa, and temperature is 120~180 DEG C, to ensure all low-boiling-point substances in brominated Polystyrene
Removing.
(3), it is granulated
By brominated Polystyrene after above-mentioned devolatilization, from double screw extruder, (automatically cleaning that can be used for middle and high viscous systems is double
Screw extruder (Chinese patent CN03131140.7)) in squeezed out through die head, brominated polyphenylene then is made through air-cooled flour milling pelletizing
Ethylene master batch, the molecular weight 20,000-20 ten thousand of products obtained therefrom, bromine mass content 60-69% in product brominated Polystyrene.
The present invention provides a kind of the characteristics of continuously preparing molecular weight-controllable brominated polystyrene master batch method are as follows: this method is logical
It crosses styrene ontology extruding polymerization and can be continuously available molecular weight-controllable brominated polystyrene, realize that the controllable ontology of styrene is poly-
It closes, styrene extruding polymerization reaction monomers high conversion rate, close to 100%.
Polystyrene master batch high production efficiency reduces production procedure, reduces production cost, economizes on resources, and reduces pollution, is
Resource-conserving of new generation, environmental-friendly and energy-saving safe the method for preparing molecular weight-controllable brominated polystyrene master batch, can
Thoroughly change the looks of traditional brominated Polystyrene agglomerate preparation method.
Specific embodiment
The present invention is further illustrated by the following Examples in the present invention, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
By the polymer grade styrene of purification, under the conveying of metering pump, with n-butyl lithium initiator in diameter 25mm (L/D
=46) reaction of styrene ontology extruding polymerization is carried out in parallel dual-screw extruding machine, and the polyphenyl that weight average molecular weight is 5.2 ten thousand is made
Ethylene product.
Process conditions are provided that
Screw zones temperature: 30/50/100/120/130/150 DEG C
Monomer mass flow: 6 kgs/hour
Initiator and monomer mass flow-rate ratio: 1.48 × 10-3
Screw speed: 100rpm.
Bromination reaction kettle is added in above-mentioned polystyrene, 10.5kg polystyrene is dissolved in 125L dichloroethane solvent,
After stirring and dissolving, antimony trichloride 9g is added, after stirring and dissolving, polystyrene solution is cooled to 10 DEG C, is measured with advection
Pump is slowly added to 415g bromine chloride, and charging process is passed through cooling medium to reacting kettle jacketing, and control temperature maintains 10-12 DEG C,
Charging in 2.5 hours finishes.Kept for 12 DEG C of reacting liquid temperature continue stirring 3 hours.5wt% sodium hydrogensulfite 540mL is added to stop
Reaction, and extra bromine chloride is removed, 150mL5wt% sodium hydroxide solution is added and neutralizes, washes twice.After water oil layer,
0.2 part of epoxidized soybean oil, 0.1 part of 2264 stabilizer and 0.5 part of blended wax are separately added into lower layer's oil phase.
Above-mentioned brominated Polystyrene solution is injected into the solvent recovery section of double screw extruder, double spiral shells with metering charge pump
Bar extruder is diameter phi 25mm, the reversed extruder of the twin-screw of L/D=36, the engine speed 200r/ of double screw extruder
Min, first row outlet pressure 50KPa or so, 100~120 DEG C of temperature adjustings, second exhaust port pressure 20KPa or so, temperature exists
120~150 DEG C of adjustings, to ensure the removing and recycling of a large amount of solvents.Nitrogen is added from devolatilization auxiliary agent mouth, the pressure of nitrogen maintains
In 0.5MPa, exhaust port pressure 20KPa or so, temperature is adjusted at 120~180 DEG C, by brominated Polystyrene after above-mentioned devolatilization from
It is squeezed out in double screw extruder through die head, brominated Polystyrene master batch, bromine in products obtained therefrom then is made through air-cooled flour milling pelletizing
Mass content 66.8%.
Embodiment 2
By the polymer grade styrene of purification, under the conveying of metering pump, with n-butyl lithium initiator in the double of upper embodiment 1
It carries out carrying out styrene extrusion bulk polymerization reaction in screw extruder, obtains the polyphenyl second that weight average molecular weight is 2.8 ten thousand
Alkene product.
Process conditions are provided that
Screw zones temperature: 30/48/100/120/140/160 DEG C
Monomer mass flow: 5 kgs/hour
Initiator and monomer mass flow-rate ratio: 2.6 × 10-3
Screw speed: 90rpm.
Bromination reaction kettle is added in above-mentioned polystyrene, 20.8kg polystyrene is taken to be dissolved in 250L dichloroethane solvent
In, after dissolution, antimony trichloride 21g is added, stirring is allowed to dissolve.Polystyrene solution is cooled to 15 DEG C, is pumped into 850g
Bromine chloride maintains the temperature at 14-16 DEG C during charging, and charging in 3 hours finishes.It is kept for 14-16 DEG C of reacting liquid temperature to continue to stir
It mixes 3 hours.5wt% sodium hydrogensulfite 1.08L stopped reaction is added, and removes extra bromine chloride, 310mL5wt% hydrogen is added
Sodium hydroxide solution neutralizes, and washes twice.After water oil layer, 1 part of epoxidized soybean oil, 0.5 part are separately added into lower layer's oil phase
2264 stabilizers and 1.5 parts of blended wax.
Above-mentioned brominated Polystyrene solution is injected into the solvent recovery section of double screw extruder, double spiral shells with metering charge pump
Bar extruder is diameter phi 36mm, the reversed extruder of the twin-screw of L/D=30, the engine speed 180r/ of double screw extruder
Min, first row outlet pressure 45KPa or so, 100~120 DEG C of temperature adjustings, second exhaust port pressure 20KPa or so, temperature exists
120~140 DEG C of adjustings, to ensure the removing and recycling of a large amount of solvents.Nitrogen is added from devolatilization auxiliary agent mouth, the pressure of nitrogen maintains
In 0.3MPa, exhaust port pressure 10KPa or so, temperature is adjusted at 140~200 DEG C, by brominated Polystyrene after above-mentioned devolatilization from
It is squeezed out in double screw extruder, brominated Polystyrene master batch then is made through air-cooled flour milling pelletizing, bromine quality contains in products obtained therefrom
Amount 63.6%.
Embodiment 3
By the polymer grade styrene of purification, under the conveying of metering pump, with n-butyl lithium initiator in double screw extruder
It is interior to carry out the reaction of styrene ontology extruding polymerization according to following process conditions.
Process conditions are provided that
Screw zones temperature: 40/68/90/110/130/150 DEG C
Monomer mass flow: 3 kgs/hour
Initiator and monomer mass flow-rate ratio: 2.5 × 10-4
Screw speed: 80rpm.
Obtain the polystyrene products that weight average molecular weight is 2.8 ten thousand.
Bromination reaction kettle is added in above-mentioned polystyrene, 20.8Kg polystyrene is taken to be dissolved in 250L dichloroethane solvent
In, after dissolution, antimony trichloride 21g is added, stirring is allowed to dissolve.Polystyrene solution is cooled to 15 DEG C, with advection meter
850g bromine chloride is added with 4.7g/ points in amount pump, maintains the temperature at 14-16 DEG C during charging, is added dropwise within 3 hours.Keep anti-
14-16 DEG C of liquid temperature is answered to continue stirring 3 hours.5wt% sodium hydrogensulfite 1.08L stopped reaction is added, and removes extra chlorine
Change bromine, 310mL 5wt% sodium hydroxide solution is added and neutralizes, washes twice.After water oil layer, it is separately added into lower layer's oil phase
1 part of epoxidized soybean oil, 0.5 part of 2264 stabilizer and 1.5 parts of blended wax.
Above-mentioned brominated Polystyrene solution is injected into the solvent recovery section of double screw extruder, double spiral shells with metering charge pump
Bar extruder is diameter phi 60mm, the reversed intermeshing extruder of the twin-screw of L/D=24, the engine speed of double screw extruder
150r/min, first row outlet pressure 45KPa or so, 100~120 DEG C of temperature adjustings, second exhaust port pressure 20KPa or so,
Temperature is adjusted at 120~160 DEG C, to ensure the removing and recycling of a large amount of solvents.Nitrogen, the pressure of nitrogen is added from devolatilization auxiliary agent mouth
Power maintains 0.3MPa, exhaust port pressure 10KPa or so, and temperature is adjusted at 160~180 DEG C, by brominated polyphenylene after above-mentioned devolatilization
Ethylene is squeezed out from double screw extruder, and brominated Polystyrene master batch, bromine in products obtained therefrom then is made through air-cooled flour milling pelletizing
Mass content 63.6%.
Claims (1)
1. a kind of method for the brominated Polystyrene master batch for continuously preparing controllable molecular weight, including the following steps:
1), styrene ontology extruding polymerization
The pretreatment of double screw extruder
Before styrene ontology extruding polymerization, clean the screw rod and barrel of double screw extruder, and under preheating, vacuumize, after
Logical nitrogen is for several times；The temperature of the screw zones are as follows: first segment is the metering conveying section of styrene, and temperature is 20-50 DEG C；Second
Section and third section are that initiator butyl lithium is metered and polymerization reaction zone, temperature are 30-120 DEG C；4th section and the 5th section of master
If melt conveying zone, temperature is 120-180 DEG C；6th section is mouth mold section, and temperature is 150-200 DEG C, polymeric reaction temperature point
The trapezoidal accurate control of cloth,
Material controls between 3-20 minutes in the mean residence time in double screw extruder, and the slewing rate of screw rod is 20-
200rpm, obtain monomer conversion close to 100% conversion ratio polystyrene；
In the melt conveying zone of polystyrene, by terminator and antioxidant from the side of double screw extruder to addition, after the extrusion,
It is directly entered in bromination reaction kettle and dissolves bromination；
2), polystyrene catalytic bromination
(1), polystyrene dissolves
By above-mentioned steps 1), the polystyrene in bulk state be directly dissolved in the dichloroethane solvent in bromination reaction kettle
In, it stirs to dissolve, forms the solution of the 5-15wt% containing polystyrene；
(2), catalytic bromination
The antimony trichloride catalyst for being equivalent to polystyrene weight 5-13wt% is added into above-mentioned polystyrene solution, stirring makes
It is dissolved, and is controlled solution temperature under the conditions of 10 DEG C -25 DEG C, is slowly added into the solution of above-mentioned addition antimony trichloride catalyst
Bromine chloride, bromine chloride and polystyrene monomers molar ratio are 3.5: 1-3.8: 1, after charging, keep temperature the reaction was continued 3-4
Hour；The bromine mass content 60-69% of gained brominated Polystyrene
(3), washing, separation are neutralized and is stablized
5wt% sodium sulfite is added in polystyrene reactant liquid after catalytic bromination or aqueous solution of sodium bisulfite terminates instead
It answers, removes the hydrochloric acid of excessive bromine chloride and generation, the sodium sulfite or sodium hydrogensulfite of addition, until reaction residual liquor is from red
Until becoming white or faint yellow no longer discoloration, 5wt% sodium hydroxide solution is added, until solution is in neutrality, is washed with water, point
Brominated Polystyrene solution is separated out, with brominated Polystyrene quality for 100, is separately added into respectively into brominated Polystyrene solution
0.5-1.5 parts of epoxidized soybean oils, 2264 stabilizer of 0.1-1.0 part and 0.5-5.0 parts of blended wax；
3) brominated Polystyrene master batch, is prepared
(1), solvent recovery
Step 2), brominated Polystyrene solution are injected into the solvent recovery section of double screw extruder with metering pump, it is described double
Screw extruder is the reversed extruder of twin-screw of diameter phi 25- φ 100mm, L/D=20-55, the double screw extruder
Engine speed 50-500r/min, collet have heat or cool, and heating makes brominated Polystyrene solution keep higher temperatures
Degree excludes to recycle most of solvent, first row outlet pressure 100KPa-50KPa before entering devolatilization section, and temperature is 80~
120 DEG C, second exhaust port pressure 50KPa-20KPa, temperature is 120~150 DEG C, with removing and recycling design；
(2), devolatilization
From devolatilization auxiliary agent mouth addition nitrogen or carbon dioxide inert gas, the pressure of nitrogen or carbon dioxide is 0.3~1.0MPa,
This exhaust port pressure is 50-10KPa, and temperature is 120~180 DEG C, to remove the low-boiling-point substance in brominated Polystyrene；
(3), it is granulated
Brominated Polystyrene after above-mentioned devolatilization is squeezed out from automatically cleaning double screw extruder through die head, is then cut through air-cooled flour milling
Brominated Polystyrene master batch is made in grain, and the molecular weight of products obtained therefrom brominated Polystyrene master batch is 20,000-20 ten thousand, brominated polyphenylene second
Bromine mass content 60-69% in alkene.
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| JPH06322023A (en) * | 1993-05-14 | 1994-11-22 | Manac Inc | Production of brominated polystyrene from recovered polystyrene foam |
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