CN107141385A - A kind of preparation method of low molecular weight brominated polystyrene - Google Patents
A kind of preparation method of low molecular weight brominated polystyrene Download PDFInfo
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- 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
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- 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
- C08F8/24—Haloalkylation
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
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Abstract
A kind of preparation method of low molecular weight brominated polystyrene, including：(1) first styrene, RAFT agent and initiator are mixed, the controllable low-molecular-weight polystyrene of molecular weight is prepared using activity/controllable free-radical polymerisation mode, i.e. RAFT polymerizations；(2) polystyrene, lewis acid catalyst, halogenated hydrocarbon solvent and bromide reagent are mixed, the brominated Polystyrene of specific low molecule amount is made in heating response.The present invention reacted with styrene monomer and RAFT agent, react (1) in can by body or polymerisation in solution, can also carry out emulsion polymerization and suspension polymerisation；It can be triggered using the mode such as thermal initiation, γ radiation, UV radiation, plasma and obtain that molecular weight is controllable and polystyrene of narrow molecular weight distribution.Obtained low-molecular-weight polystyrene is using lewis acid as catalyst, and as solvent, with bromide reagent bromination reaction, which occurs, for halogenated hydrocarbons can prepare the brominated polystyrenic product of specific low molecule amount.
Description
Technical field
RAFT polymerizations are utilized the present invention relates to a kind of preparation method of low molecular weight brominated polystyrene, more particularly to one kind
The method for preparing the controllable low molecular weight brominated polystyrene of molecular weight, belongs to the preparing technical field of fire retardant.
Background technology
Brominated Polystyrene (BPS) belongs to addition type macromolecule brominated flame retardant, and brominated amount is high, low, heat-resisting with toxicity
Property good, resistance to punching, the features such as frost resistance is superior.It is that performance is excellent available for the fire retardant processing of the fire resistant resins such as nylon, polyester, ABS
Different environment-friendly type halogen flame.
Brominated Polystyrene is that the product after parental materials i.e. bromination occurs on polystyrene (PS) phenyl ring.Its structural formula
It is as follows：
Domestic many bromide fire retardant manufacturers study and produced to brominated Polystyrene, but result needs
Improve.General Purpose Polystyrenre more than current domestic enterprise using relative molecular mass more than 200,000 is as raw material, obtained bromine
Change polystyrene relative molecular mass typically between 18-40 ten thousand, the excessive dispersiveness for causing brominated Polystyrene of molecular weight is not
Good, the poor compatibility with base material greatly compromises the mechanical performance of resin；On the other hand, the average molecular matter of polystyrene
Amount distribution is wide, causes that chain rupture occurs in brominated Polystyrene process is prepared, degree of polymerization reduction, gained brominated Polystyrene
Decomposition temperature is low, easily decompose in process, strong influence properties of product.
In the research that catalytic bromination polystyrene synthesizes Brominated Polystyrene through bromination, we do not solve two thoroughly also
Individual problem, one is to prevent crosslinking, and two be to prevent the hydrogen on fatty carbon chain from being replaced by bromine.High molecular weight polystyrene goes out in the reaction
Now crosslinking can form netted or build high polymer, and basic change can occur for its physics and chemical property, and they are not dissolved, and losing can
Plasticity.The polystyrene of low molecule amount is crosslinked during the course of the reaction, its physics and chemical property will not occurs basic
Change.After hydrogen on fatty carbon chain is replaced by bromine, the heat endurance reduction of molecule, in the processing and forming of high polymer material, meeting
Pernicious gas hydrogen bromide is released, while promoting macromolecular to disintegrate, the anti-flammability and mechanical strength of high polymer material is influenceed.
In contrast, low molecule brominated Polystyrene possesses fabulous heat resistance and mobile performance, and it is to matrix tree
The influence of the mechanical performances such as impact resistance, the tensile resistance of fat is small.Research finds that the molecular weight of brominated Polystyrene can be very big
Influence fire retardant processing characteristics and compatibility with matrix resin.And brominated Polystyrene it is general by polystyrene through bromination
Obtain, therefore the preparation of controllable suitable molecular weight polystyrene raw material will determine the performance of final brominated polystyrenic product.
US5328983 proposes polystyrene bromination product and is dispersed in pressure cooking in concentrated ammonia liquor, can both eliminate bromination and gather
α-bromine atoms in styrene product, can remove the free bromine of brominated polystyrene product entrainment again, improve polystyrene
The heat endurance and whiteness of brominated product.US5726252 is used before polystyrene bromination, the main chain added into reaction system
Halogenated alkyl inhibitor, can effectively reduce main chain substitution, improve the heat endurance of product.Japan Patent 2008133484
Disclose the preparation method for the brominated Polystyrene that heat endurance and color have clear improvement.It is used as main chain by adding TiCl4
Replace inhibitor, obtain bromine content more than 66%, main chain substitution is less than 750ppm.CN200710022496 is proposed commercially available bromine
Change polystyrene to be dissolved in the tetrahydrofuran of sufficient amount, the reducing agent such as addition Zn, Al or Na makes in brominated polystyrene product
α-bromine atoms depart from brominated Polystyrene.CN101497673 proposes to add sulphur into reaction, and sulphur is used as polystyrene parent
In electric bromination reaction system in the scavenger of micro-moisture and the electrophilic bromination reaction of polystyrene free radical quencher.
Liu Lin et al. described inside patent CN101240046 it is a kind of using ATRP (ATRP) or
Reverse atom transfer radical polymerization (FATRP) obtains to prepare the low molecular weight polycaprolactone styrene that molecular weight is controllable, then through bromination reaction
To polystyrene.The brominated Polystyrene bromine content prepared by the method is high, good with substrate compatibility.But, ATRP polymerization
Itself have the shortcomings that some are difficult to overcome, harsh such as is required to polymerizing condition (anhydrous and oxygen-free) condition, metal is urged after reaction
Agent is difficult to remove, and alkyl halide species initiator has larger injury to human body.And equally it is used as the reversible of radical polymerization
Addition-fracture chain transfer polymerization (abbreviation RAFT polymerizations) then solves these problems well.
RAFT polymerization be a kind of new controllable free radical polymerization process, can to the sequential structure of polymer, molecular weight and its
Distribution etc. is regulated and controled, and has the advantages that its is unique compared with conventional free radical polymerize：
1st, monomer is applied widely, in addition to common monomer, the list with specific functional groups such as carboxyl, hydroxyl, di alkylamino groups
Body can also be smoothed out polymerization.
2nd, polymerizing condition is gentle, can be carried out under the conditions of traditional radical polymerization, Applicable temperature wider range (- 20-
200 DEG C), typically at 40-160 DEG C, course of reaction is without protection；
3rd, the reagent (mistake in ATRP for using some expensive reagents (TEMPO) or being difficult to remove from polymerizate is avoided
Cross metal ion, bipyridyl etc.)；
4th, polymerization implementation is various, and not only available ontologies or solution polymerization process are carried out, can also carry out emulsion polymerization and
Suspension polymerisation；Not only can thermal initiation, can also be triggered using the mode such as γ-radiation, UV- radiation, plasma.
RAFT polymerizations implementation almost polymerize with conventional free radical, while having other " activity " concurrently again.Free radical
It polymerize controllability good, the problem of also removing residual metal ions in the absence of ATRP, it is considered to be most industrialize so far
" activity "/controllable free radical polymerization process of application prospect.
Method made above so that the product bromine content of brominated Polystyrene is high, heat endurance is good, but low molecular weight brominated
The research of polystyrene is also fewer, and the controllable low molecular weight brominated polyphenyl second of molecular weight is prepared in particular by RAFT polymerizations
Alkene.
The content of the invention
The present invention is in view of the deficienciess of the prior art, providing a kind of utilization RAFT polymerizations prepares controllable low point of molecular weight
The method of son amount brominated Polystyrene.Brominated Polystyrene bromine content, reduction are improved it is a further object of the present invention to provide one kind
The method that hydrogen on fatty carbon chain is replaced by bromine.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：A kind of preparation side of low molecular weight brominated polystyrene
Method, step is as follows：
(1) first styrene, RAFT agent and initiator are mixed and carries out RAFT polymerizations, using activity/controllable free
Base polymerization methodses, you can inverse addition-fracture chain transfer polymerization (RAFT) prepares the controllable low-molecular-weight polystyrene of molecular weight；
(2) polystyrene, lewis acid catalyst, halogenated hydrocarbon solvent and bromide reagent are mixed, spy is made in heating response
Determine the brominated Polystyrene of low molecule amount.
The present invention is reacted with styrene monomer and RAFT agent, and body or solution can be passed through in reaction (1)
It polymerize, can also carries out emulsion polymerization and suspension polymerisation；It can use the modes such as thermal initiation, γ-radiation, UV- radiation, plasma
Initiation obtains that molecular weight is controllable and polystyrene of narrow molecular weight distribution.Obtained low-molecular-weight polystyrene using lewis acid as
Catalyst, as solvent, with bromide reagent bromination reaction, which occurs, for halogenated hydrocarbons can prepare the brominated Polystyrene of specific low molecule amount
Product.
The present invention is further arranged to, in (1), and styrene, RAFT agent and initiator are stirred under nitrogen protection
Mix to reaction and terminate, reacted mixture is added drop-wise in anhydrous lower aliphatic alcohols, settle, filter, dry, obtain polyphenyl second
Alkene.
The present invention is further arranged to, and the mol ratio of the styrene, RAFT agent and initiator is 100-1000:
1-20:1-10, controls the mol ratio of each reactant added, can obtain the polystyrene of target low molecule amount.
The present invention is further arranged to, and the RAFT agent is the monothioester chain-transferring agent of two sulphur/tri-.For example, can be with
It is two thio β-naphthoic acid isobutyronitrile ester, dithiobenzoic acid -1- phenethyls -ester, double thio -1- naphthoic acids isobutyronitrile esters, three
One or more in sulfocarbonate, two thio phenylacetic acid -1- phenethyl -ester.
The present invention is further arranged to, and the initiator is thermal initiator or light trigger.Thermal initiator such as metering system
Sour methyl esters peroxide, methyl methacrylate, light trigger such as dibenzoyl peroxide, azodiisobutyronitrile etc..
The present invention is further arranged to, and utilizes polystyrene, lewis acid catalyst, halogenated hydrocarbon solvent and bromide reagent system
The step of brominated Polystyrene of standby specific low molecule amount is：
(1) polystyrene is added in halogenated hydrocarbon solvent, heating stirring dissolves it；
(2) lewis acid catalyst is added into the solution of (1), the 1%-10% of polystyrene quality is respectively accounted for, stirring is equal
Bromide reagent is at the uniform velocity added dropwise after even and carries out bromination reaction；
(3) after bromination is complete, sodium hydrogensulfite or sodium hydrate aqueous solution are slowly added dropwise into solution, will be organic after washing
Mutually it is poured slowly into lower aliphatic alcoholic solution, stirs, filter, dries, obtain low molecular weight brominated polystyrene.
By above-mentioned technical proposal, sodium hydrogensulfite, sodium hydroxide or other alkaline reagents are added, can be removed unreacted
Bromide reagent.
Wherein, bromide reagent can be bromine, BrCl or other reagents.Optimal conditions when bromide reagent is added dropwise are set to temperature
It is maintained at 0-50 DEG C.After completion of dropping, insulation a period of time, make bromination complete.
The present invention is further arranged to, the halogenated hydrocarbons comprising carbon tetrachloride, dichloromethane, dichloroethanes, trichloroethanes,
One or more in tetrachloroethanes.
By above-mentioned technical proposal, bromination reaction is carried out preferably in dichloroethane solvent.
The present invention is further arranged to, the catalyst comprising alchlor, alchlor, ferric trichloride, ferric bromide,
One or more in trichloride antimony, zinc dichloride, antimony oxide.
By above-mentioned technical proposal, the catalyst of selection can be weaker lewis acid, to prevent from being catalyzed polystyrene
Occur Friedel-Crafts alkylated reactions with halogenated hydrocarbons, it is to avoid the generation of cross-linking reaction.Except selecting weaker Louis
Sour outer, we can also be by " strong-weak " lewis acidic collocation, to regulate and control the power of catalyst.
The present invention is further arranged to, in (2), is added before bromide reagent, is additionally added secondary solvent, main chain protective agent
Or nucleopilic reagent, secondary solvent, main chain protective agent or nucleopilic reagent respectively account for the 1%-10% of polystyrene quality.
The present invention is further arranged to, and the secondary solvent includes the one or more in carbon tetrachloride, carbon disulfide.
By above-mentioned technical proposal, experiment finds that lewis acid catalyst is slightly soluble in halogenated hydrocarbon solvent, causes the effect of catalysis
Rate is not high.Must just heterogeneous catalysis system be changed into homogeneous catalysis system by improving catalytic efficiency, improve catalyst in solvent
In solubility.Therefore select and both dissolved each other with halogenated hydrocarbons, and have the solvent of larger solubility as auxiliary with lewis acid catalyst
Solvent.Secondary solvent makes bromination reaction be changed into homogeneous reaction, greatly improves the catalytic efficiency of catalyst.
The present invention is further arranged to, and the main chain protective agent includes one in titanium tetrachloride, tin trichloride, boron chloride
Plant or a variety of.
By above-mentioned technical proposal, main chain protective agent effectively prevents the hydrogen on fatty carbon chain from being replaced by bromine, improves product heat
Stability.But require that added protective agent should play a part of destroying free radical, do not influence to replace instead on phenyl ring again
That answers is normally carried out.Research finds that titanium tetrachloride, tin trichloride, boron chloride can destroy free radical, so as to prevent main chain alkyl
The substitution reaction of upper hydrogen.
The present invention is further arranged to, the nucleopilic reagent comprising water, hydrogen sulfide, ammonia, phosphorus trichloride, sulfur dioxide,
One or more in fatty alcohol.
By above-mentioned technical proposal, the power of catalyst is regulated and controled by adding nucleopilic reagent.Such as general bromination reaction
Carry out, because water can cause lewis acid catalyst to lose activity, but it was found that, protected in solvent in anhydrous conditions
Catalyst structure can be made by holding appropriate moisture, and the friendship of polystyrene during bromination reaction can be prevented if control is proper
Connection.
In summary, the invention has the advantages that：
(1) present invention opens the new way of a preparation low molecular weight brominated polystyrene, by controlling to add monomer
Relative molecular mass can obtain different low-molecular-weight polystyrenes.
(2) selection to catalyst, the compounding of catalyst, nucleopilic reagent selection, catalyst secondary solvent and fat are passed through
Fat carbochain is protectant to be added, and is prepared for the high low-molecular-weight polystyrene of bromine content.
(3) products obtained therefrom heat endurance of the present invention is good, and mobility is favourable, when with engineering plastics melt blending, with phase
Capacitive is good, applied widely, low toxin.
(4) it is not only that bromide fire retardant provides more wide thinking, can also fills the domestic gaps, enrich domestic resistance
Agent species is fired, is conducive to the upgrading of downstream Related product, with great practical significance.
Brief description of the drawings
Fig. 1 is the GPC figures of product in embodiment 4.
Embodiment
The technical scheme in the embodiment of the present invention is clearly and completely described below, it is clear that described embodiment
Only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, the common skill in this area
The every other embodiment that art personnel are obtained under the premise of creative work is not made, belongs to the model that the present invention is protected
Enclose.
Embodiment 1：
The preparation of low-molecular-weight polystyrene：Under nitrogen protection, by styrene 50g, 2- (dodecyl trithiocarbonates
Base) -2 Methylpropionic acid 0.25g, benzoyl peroxide 0.06g 30 DEG C mixing, high-pressure sodium lamp radiation, filter out 320nm with
Under short-wave ultraviolet radiation, obtain long-wave ultraviolet radiation source, reaction uses benzoquinone's terminating reaction after terminating, by reactant mixture
It is added drop-wise in ethanol and settles, filters and dried after the PS powder separated out.
The preparation of brominated Polystyrene：By polystyrene 30g, dissolved with 300g dichloromethane, add appropriate nucleophilic examination
Agent ethanol, main chain protective agent titanium tetrachloride, at 25 DEG C, 138g is slowly added dropwise in 0.1g ferric trichlorides, secondary solvent carbon tetrachloride
Bromine, after insulation reaction is complete, is added dropwise aqueous solution of sodium bisulfite, stirring makes solution colour become faint yellow or colourless by rufous
Untill, remove unreacted BrCl.By mixture point liquid, organic phase, regulation to neutrality are isolated.Washing 3 times, organic phase is delayed
Slow to import in ethanol solution, agitating solution, BPS crystallizations are separated out, and are dried after filtering.
It is 9324 (molecular weight that gained low-molecular-weight polystyrene determines weight average molecular weight through gel permeation chromatograph (GPC)
It is distributed as 1.1), it is 67% to measure brominated amount through elementary analysis.
Embodiment 2：
The preparation of low-molecular-weight polystyrene：By 50g styrene, 0.35g azodiisobutyronitriles, 0.89g β-naphthoic acid
Isobutyronitrile ester is well mixed, and logical nitrogen protection is reacted, after reaction terminates, cooling, adds appropriate tetrahydrofuran dissolving polymerization
Thing, polymer solution is added drop-wise in a large amount of methanol solutions, separates out polymer, and suction filtration after deionized water cyclic washing, is dried
To constant weight.
The preparation of brominated Polystyrene：By polystyrene 30g, dissolved with 400g trichloroethanes, add appropriate nucleophilic examination
Agent ammoniacal liquor, main chain protective agent tin trichloride, secondary solvent carbon tetrachloride, carbon disulfide, 0.1g alchlors, under 20 DEG C of constant temperature
157g bromines are slowly added dropwise, after insulation reaction is complete, quality aqueous solution of sodium bisulfite are slowly added dropwise, stirring makes solution colour by red
Untill brown becomes faint yellow or colourless, unreacted BrCl is removed.By mixture point liquid, organic phase is isolated, is adjusted into
Property.Washing 3 times, organic phase is slowly imported in methanol solution, agitating solution, and BPS crystallizations are separated out, and are dried after filtering.
It is 14231 (molecular weight that gained low-molecular-weight polystyrene determines weight average molecular weight through gel permeation chromatograph (GPC)
It is distributed as 1.21).It is 68.5% to measure brominated amount through elementary analysis.
Embodiment 3：
The preparation of low-molecular-weight polystyrene：By 50g styrene, using 180g water and 2g hexadecanes as solvent, 1.25g bis-
After thiobenzoate -1- phenethyls -ester is well mixed, in the aqueous solution for pouring into emulsifier sodium lauryl sulfate, stirring mixing
Polymer is uniformly dispersed, under nitrogen protection, reacted at 75 DEG C, add initiator potassium persulfate, trigger polymerization.Instead
After should terminating, slowly poured under stirring in propyl alcohol, collect the polymer that precipitation is washed out, dried after washing.
The preparation of brominated Polystyrene：By polystyrene 30g, dissolved with 600g tetrachloroethanes, main chain protective agent tri-chlorination
Tin, secondary solvent carbon disulfide, catalyst use the composite catalyst of alchlor and antimony oxide, at 20 DEG C, slowly
160g bromines are added dropwise, after insulation reaction is complete, aqueous solution of sodium bisulfite are slowly added dropwise into reaction flask, stirring makes solution colour
Untill becoming faint yellow or colourless by rufous, unreacted BrCl is removed.By mixture point liquid, organic phase is isolated, is adjusted
To neutrality.Washing 3 times, organic phase is slowly imported in propanol solution, agitating solution, and BPS crystallizations are separated out, and are dried after filtering.
It is 9849 (molecular weight that gained low-molecular-weight polystyrene determines weight average molecular weight through gel permeation chromatograph (GPC)
It is distributed as 1.21).It is 67.7% to measure brominated amount through elementary analysis.
Embodiment 4：
The preparation of low-molecular-weight polystyrene：By 50g styrene, 150g ethylene glycol, S-1- dodecyls-S'- (α, α '-
Dimethyl-α "-acetic acid) trithiocarbonate mixing, under nitrogen protection, reacted in 70 DEG C, add initiator A IBN, draw
Hair polymerization.After reaction terminates, slowly poured under stirring in methanol, collect the polymer that precipitation is washed out, then spent glycol
Dried after washing.
The preparation of brominated Polystyrene：By polystyrene 30g, dissolved with 500g dichloroethanes, main chain protective agent tri-chlorination
Boron, secondary solvent carbon disulfide, catalyst uses zinc dichloride, and 160g bromines are slowly added dropwise at 25 DEG C, after insulation reaction is complete, delays
Slow to be added dropwise aqueous solution of sodium bisulfite, stirring makes untill solution colour becomes faint yellow or colourless by rufous, to remove unreacted
BrCl.By mixture point liquid, organic phase, regulation to neutrality are isolated.Washing 3 times, organic phase is slowly imported ethylene glycol molten
In liquid, agitating solution, BPS crystallizations are separated out, and are dried after filtering.
It is 9849 (molecular weight that gained low-molecular-weight polystyrene determines weight average molecular weight through gel permeation chromatograph (GPC)
It is distributed as 1.11).It is 69.5% to measure brominated amount through elementary analysis.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc. should be included in the scope of the protection.
Claims (10)
1. a kind of preparation method of low molecular weight brominated polystyrene, it is characterised in that step is：
(1) first styrene, RAFT agent and initiator are mixed and carries out RAFT polymerizations, polystyrene is made；
(2) polystyrene, lewis acid catalyst, halogenated hydrocarbon solvent and bromide reagent are mixed, heating response is made specific low
The brominated Polystyrene of molecular weight.
2. the preparation method of a kind of low molecular weight brominated polystyrene according to claim 1, it is characterised in that in (1)
In, styrene, RAFT agent and initiator are stirred to reaction under nitrogen protection to be terminated, and reacted mixture is added drop-wise to
In anhydrous lower aliphatic alcohols, settle, filter, dry, obtain polystyrene.
3. a kind of preparation method of low molecular weight brominated polystyrene according to claim 1, it is characterised in that the benzene
The mol ratio of ethene, RAFT agent and initiator is 100-1000:1-20:1-10.
4. according to a kind of preparation method of any described low molecular weight brominated polystyrene of claim 1-3, it is characterised in that
The RAFT agent is the monothioester chain-transferring agent of two sulphur/tri-.
5. according to a kind of preparation method of any described low molecular weight brominated polystyrene of claim 1-3, it is characterised in that
The initiator is thermal initiator or light trigger.
6. the preparation method of a kind of low molecular weight brominated polystyrene according to claim 1, it is characterised in that utilize poly-
Styrene, lewis acid catalyst, halogenated hydrocarbon solvent and bromide reagent prepare the step of the brominated Polystyrene of specific low molecule amount
Suddenly it is：
(1) polystyrene is added in halogenated hydrocarbon solvent, heating stirring dissolves it；
(2) lewis acid catalyst is added into the solution of (1), accounts for the 1%-10% of polystyrene quality, it is even after stirring
Speed is added dropwise bromide reagent and carries out bromination reaction；
(3) after bromination is complete, sodium hydrogensulfite or sodium hydrate aqueous solution is slowly added dropwise into solution, delays organic phase after washing
Slowly pour into lower aliphatic alcoholic solution, stir, filter, dry, obtain low molecular weight brominated polystyrene.
7. the preparation method of a kind of low molecular weight brominated polystyrene according to claim 6, it is characterised in that in (2)
In, add before bromide reagent, be additionally added secondary solvent, main chain protective agent or nucleopilic reagent, secondary solvent, main chain protective agent or
Nucleopilic reagent respectively accounts for the 1%-10% of polystyrene quality.
8. the preparation method of a kind of low molecular weight brominated polystyrene according to claim 7, it is characterised in that described auxiliary
Cosolvent includes the one or more in carbon tetrachloride, carbon disulfide.
9. a kind of preparation method of low molecular weight brominated polystyrene according to claim 7, it is characterised in that the master
Chain protective agent includes the one or more in titanium tetrachloride, tin trichloride, boron chloride.
10. the preparation method of a kind of low molecular weight brominated polystyrene according to claim 7, it is characterised in that described
Nucleopilic reagent includes the one or more in water, hydrogen sulfide, ammonia, phosphorus trichloride, sulfur dioxide, fatty alcohol.
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| CN108102053A (en) * | 2017-12-12 | 2018-06-01 | 浙江大学 | The brominated segmented copolymer fire retardant of intermediate molecular weight and its two one-step preparation method of lotion |
| CN108129621A (en) * | 2017-12-12 | 2018-06-08 | 浙江大学 | Three one-step preparation method of intermediate molecular weight bromination segmented copolymer fire retardant and its lotion |
| CN108129588A (en) * | 2017-12-12 | 2018-06-08 | 浙江大学 | The brominated segmented copolymer fire retardant of middle low molecular weight and its two one-step preparation method of solution |
| CN108129619A (en) * | 2017-12-12 | 2018-06-08 | 浙江大学 | Two one-step preparation method of middle low molecular weight brominated segmented copolymer fire retardant and its solution |
| CN108250374A (en) * | 2017-12-12 | 2018-07-06 | 浙江大学 | Three one-step preparation method of middle low molecular weight brominated segmented copolymer fire retardant and its solution |
| CN108250375A (en) * | 2017-12-12 | 2018-07-06 | 浙江大学 | Two one-step preparation method of intermediate molecular weight bromination segmented copolymer fire retardant and its lotion |
| CN109762087A (en) * | 2018-12-27 | 2019-05-17 | 山东旭锐新材有限公司 | Low molecular weight PS product and preparation method thereof |
| CN109865522A (en) * | 2017-12-03 | 2019-06-11 | 潍坊双丰化工有限公司 | A kind of brominated Polystyrene catalyst for preparing |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109865522A (en) * | 2017-12-03 | 2019-06-11 | 潍坊双丰化工有限公司 | A kind of brominated Polystyrene catalyst for preparing |
| CN108047401A (en) * | 2017-12-12 | 2018-05-18 | 浙江大学 | The brominated segmented copolymer fire retardant of intermediate molecular weight and its three one-step preparation method of lotion |
| CN108102053A (en) * | 2017-12-12 | 2018-06-01 | 浙江大学 | The brominated segmented copolymer fire retardant of intermediate molecular weight and its two one-step preparation method of lotion |
| CN108129621A (en) * | 2017-12-12 | 2018-06-08 | 浙江大学 | Three one-step preparation method of intermediate molecular weight bromination segmented copolymer fire retardant and its lotion |
| CN108129588A (en) * | 2017-12-12 | 2018-06-08 | 浙江大学 | The brominated segmented copolymer fire retardant of middle low molecular weight and its two one-step preparation method of solution |
| CN108129619A (en) * | 2017-12-12 | 2018-06-08 | 浙江大学 | Two one-step preparation method of middle low molecular weight brominated segmented copolymer fire retardant and its solution |
| CN108250374A (en) * | 2017-12-12 | 2018-07-06 | 浙江大学 | Three one-step preparation method of middle low molecular weight brominated segmented copolymer fire retardant and its solution |
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| CN109762087A (en) * | 2018-12-27 | 2019-05-17 | 山东旭锐新材有限公司 | Low molecular weight PS product and preparation method thereof |
| CN109762087B (en) * | 2018-12-27 | 2021-07-30 | 山东旭锐新材有限公司 | Low molecular weight PS product and preparation method thereof |
| CN116535553A (en) * | 2023-07-04 | 2023-08-04 | 潍坊双丰化工有限公司 | Preparation method of high-thermal-stability brominated polystyrene |
| CN116535553B (en) * | 2023-07-04 | 2023-09-26 | 潍坊双丰化工有限公司 | Preparation method of high-thermal-stability brominated polystyrene |
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