CN108129588A - The brominated segmented copolymer fire retardant of middle low molecular weight and its two one-step preparation method of solution - Google Patents
The brominated segmented copolymer fire retardant of middle low molecular weight and its two one-step preparation method of solution Download PDFInfo
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Abstract
The invention discloses a kind of two one-step preparing methods of solution of the brominated segmented copolymer fire retardant of middle low molecular weight (degree of polymerization is 7~80)：It is prepared using Reversible Addition Fragmentation Chain Transfer (RAFT) polymerization, to contain bromstyrol and/or brominated acrylate and diolefin as polymerized monomer, azo-compound or organic peroxide are initiator, three thioes derivatives polymerize to obtain middle low molecular weight brominated phenylethylene ethylene/propenoic acid ester diolefin brominated styrene/acrylate triblock copolymer by two step method as chain-transferring agent；Copolymer obtains the brominated segmented copolymer fire retardant of middle low molecular weight after brominating agent, that is, middle low molecular weight brominated phenylethylene ethylene/propenoic acid ester diolefin brominated styrene/acrylate triblock copolymer bromide fire retardant.
Description
Technical field
The present invention relates to low molecular weight phenylethylene/acrylate in polymer flame retardant field more particularly to a kind of bromination-
Diolefin-phenylethylene ethylene/propenoic acid ester triblock copolymer fire retardant and preparation method thereof.
Background technology
For bromide fire retardant due to good with fire-retardant high efficiency, thermal stability, can meet the fire-retardant of various high molecular materials will
It asks, and its sufficient raw, cheap, is that yield is maximum currently on the market, one of most widely used fire retardant.But
It is that usually there is easily from high score for currently used small molecule bromide fire retardant (molecular weight is less than 500, such as polybrominated diphenyl ethers)
The shortcomings that being precipitated in sub- material matrix, and it can generate the carcinogenic substances such as bioxin in burning, lead to environmental problem, and macromolecule
The backbone of bromide fire retardant makes it not easy to migrate, can be preferably applied to the fire-retardant and environmentally protective of high molecular material.
High molecular weight flame retardant effect is better than small molecule fire retardant, and currently used macromolecule bromide fire retardant mainly includes poly-
Brominated styrene PBS (or brominated Polystyrene BPS), brominated epoxy resin BEP, brominated polycarbonate BCO and brominated styrene-
Butadiene-styrene copolymer Br-SBS, bromine content are higher for PBS and Br-SBS.Rigid aromatic radical chain in wherein PBS
Section, make it when being compounded with base material so that toughness of material reduce, and in Br-SBS linear butadiene segment introducing, material can be made
The toughness of material increases.But presently commercially available Br-SBS flame retardant molecules amount is generally 100,000 or so, is to be made using anionic polymerisation
High molecular weight SBS again bromination and obtain, this so that it is not easy to disperse in high molecular material, and bromination reaction is difficult, and bromine is caused to contain
Amount is not high, and additive amount is big during use, influences flame retardant effect.
Patent CN104327214A reports a kind of side that bromide fire retardant is prepared using commercially available SBS products progress bromination
Method, bromine content are 65~70%, and the flame retardant molecule amount that the method obtains is higher (molecular weight is 100,000), is not easy in the base
Dispersion.
Patent CN102504067A is reported to be polymerize to obtain molecular weight to be respectively 10650 Hes using styrene conventional free radical
33500 polystyrene PS, then bromide fire retardant is obtained through bromination, bromine content is respectively 68.1% and 68.22%.
Patent CN101824113A, which is reported, uses anionic polymerisation to prepare molecular weight as 5000 polystyrene, then through bromine
Change and obtain the fire retardant that a kind of bromine content is 69%.
Patent CN103923239A, which is reported, uses anionic polymerisation to prepare molecular weight as 958~8100 polystyrene
PS, then obtain the fire retardant that bromine content is 68.3~78.7% through bromination.
The bromination PS of these above-mentioned high molecular weight and bromination SBS bromine contents are relatively low, and the bromination PS molecules of middle low molecular weight
Chain structure is single, without more block structures.
Invention content
The technical problem to be solved in the present invention is to provide a kind of high bromine content (bromine content about 70.2~74.8wt%), in it is low
Brominated styrene/acrylate-diolefin-phenylethylene ethylene/propenoic acid ester triblock copolymer fire retardant of molecular weight and its preparation
Method.
In order to solve the above technical problem, the present invention provides how embedding a kind of middle low molecular weight (degree of polymerization is 7~80) is brominated
Two one-step preparation method of solution of section copolymer fire retardant：It is prepared using reversible addion-fragmentation chain transfer (RAFT) polymerization, to contain
Bromstyrol and/or brominated acrylate and diolefin are polymerized monomer, azo-compound or organic peroxide to cause
Agent, three thioes derivatives as chain-transferring agent, by two step method polymerize to obtain middle low molecular weight brominated phenylethylene ethylene/propenoic acid ester-
Diolefin-brominated styrene/acrylate triblock copolymer；It is (poly- to obtain middle low molecular weight after brominating agent for copolymer
Right is 7~80) brominated segmented copolymer fire retardant, that is, middle low molecular weight brominated phenylethylene ethylene/propenoic acid ester-diolefin-bromine
Change phenylethylene ethylene/propenoic acid ester triblock copolymer bromide fire retardant.
The improvement of two one-step preparation method of solution of the brominated segmented copolymer fire retardant of middle low molecular weight as the present invention：Institute
Two step method is stated to be polymerized to follow the steps below successively：
1), by 5~100 parts of diolefins, 0.05~0.1 part of azo-compound or organic peroxide as initiator, 5
~10 parts of three thioes derivatives and solvent as chain-transferring agent are added in reaction kettle, under inert gas (nitrogen) protection,
2~10h is reacted at 50~150 DEG C, obtains diolefin homopolymer；
2) 40 are added under inert gas shielding, under inert gas shielding, in the reaction kettle after the step 1)~
150 parts contain bromstyrol and/or brominated acrylate, and 2~10h is reacted at 50~150 DEG C, obtains middle low molecular weight brominated benzene
Ethene/acrylic ester-diolefin-bromination brominated styrene/acrylate triblock copolymer；
Above-mentioned part is parts by weight.
Above-mentioned steps 1) in solvent about 150~250 parts by volume of dosage.
As the present invention the brominated segmented copolymer fire retardant of middle low molecular weight two one-step preparation method of solution it is further
It improves：The bromstyrol that contains is at least one of 2,4,6- phenylstilbene bromide, pentabromo- styrene；
The brominated acrylate is 2,4,6- tribromophenyl acrylates, 2,4,6- methacrylic acids tribromophenyl, propylene
At least one of sour pentabromo- benzyl ester；
The diolefin is 1,4- butadiene, one kind in isoprene.
As the present invention the brominated segmented copolymer fire retardant of middle low molecular weight two one-step preparation method of solution it is further
It improves：The azo-compound as initiator is azodiisobutyronitrile (AIBN), azobisisoheptonitrile (ABVN), azo two
NSC 18620 hydrochloride (AIBA), two isobutyl imidazoline hydrochloride (AIBI) of azo or azo isobutyl cyano formamide (V30)；
The organic peroxide as initiator is dibenzoyl peroxide (BPO) or the tertiary fourth of benzoyl peroxide
Ester；
Three thioes derivatives as chain-transferring agent are bis- (α, the α '-dimethyl-α "-acetic acid) esters of trithiocarbonic acid, trithio
For bis- (α, the α '-diethyl-α "-acetic acid) esters of bis- (α, the α '-dimethyl-α "-valeric acid) esters of carbonic acid, trithiocarbonic acid.
As the present invention the brominated segmented copolymer fire retardant of middle low molecular weight two one-step preparation method of solution it is further
It improves：Solvent in the step 1) is tetrahydrofuran (THF), toluene, dimethylbenzene, hexamethylene.
As the present invention the brominated segmented copolymer fire retardant of middle low molecular weight two one-step preparation method of solution it is further
It improves：
In the step 2) after reaction, under stirring, product is poured into being completely dissolved in solvent, then in first
Precipitation is (remove residual list) in alcohol；Above-mentioned dissolving and precipitation be repeatedly after 3 times, is placed in 30~100 DEG C of vacuum drying oven dryings to constant weight,
Obtain middle low molecular weight brominated phenylethylene ethylene/propenoic acid ester-diolefin-brominated styrene/acrylate triblock copolymer.
As the present invention the brominated segmented copolymer fire retardant of middle low molecular weight two one-step preparation method of solution it is further
It improves：The bromination process is：
In middle low molecular weight brominated phenylethylene ethylene/propenoic acid ester-diolefin-brominated styrene/acrylate triblock copolymer
The isobutanol of addition copolymer 5~10 mass times, which is warming up to 30~70 DEG C, in object dissolves copolymer, is added in altogether under heat-retaining condition
The bromating agent of polymers 1~15 mass times is stirred to react 1~15h, with methanol extraction and filters after reaction, is dried under vacuum to perseverance
Weight obtains middle low molecular weight (degree of polymerization is 7~80) brominated segmented copolymer fire retardant.
As the present invention the brominated segmented copolymer fire retardant of middle low molecular weight two one-step preparation method of solution it is further
It improves：The bromating agent is bromine chloride or tetraethylammonium bromide.
The present invention is also provided the brominated segmented copolymer of middle low molecular weight being prepared using the above method and hindered simultaneously
Fire agent：Between 7~80, molecular weight is easy to through monomer (containing bromstyrol, brominated acrylate, Isosorbide-5-Nitrae-fourth two degree of polymerization
Alkene/isoprene) additive amount regulated and controled.
The improvement of the brominated segmented copolymer fire retardant of middle low molecular weight as the present invention：Bromine content for 70.2~
74.8wt%, bromine content can be adjusted by polymerized monomer with when bromating agent dosage.
In the present invention, using reversible addion-fragmentation chain transfer (RAFT) polymerization side in activity/controllable free-radical polymerisation
Method to contain bromstyrol or brominated acrylate, Isosorbide-5-Nitrae-butadiene or isoprene as polymerized monomer, passes through point two batches of charging works
Skill, brominated styrene/acrylate-diolefin-brominated styrene/acrylate triblock copolymer of low molecular weight in preparation
Object.
Brominated styrene/acrylate-diolefin-brominated styrene/acrylate triblock copolymer bromine of the present invention
Based polymer fire retardant uses RAFT polymerizations, can be by controlling the degree of polymerization, and regulation and control form the production of low molecular weight in difference
Object enhances and resin matrix compatibility.In addition, the bromination process provided in the present invention so that chemistry knot in three block structure
The bromo element of high-content is closed, the flame retarding efficiency of unit mass fire retardant will be enhanced.
The present invention combines the advantages of RAFT polymerizations and bromination technique, is prepared for middle low molecular weight brominated styrene/acrylic
Ester-diolefin-brominated styrene/acrylate triblock copolymer fire retardant, controls the quality of brominated monomer and bromating agent, can
Obtain low molecular weight in difference, different three block structure, different bromine contents bromide fire retardant product.
In the present invention, because of the introducing of butadiene/isoprene segment, the scope of application of triblock copolymer compares bromination
PS is wider and can improve the mechanical property of material, so the present invention selects block structure；Since existing macromolecule bromine system is fire-retardant
Agent there are difficulties in dispersion, bromine content is not high enough the problem of, so low molecular weight and more block structures solve during the present invention selects
The problem.
Relative to fire retardants such as existing middle low molecular weight brominated polystyrene, triblock copolymer of the invention, which uses, to be contained
Bromine monomer carries out living polymerization, and low molecular weight and while compared with high bromine content in holding increases the soft of butadiene/isoprene
Section, becomes more block structures, suitable for different systems, dosage is few, good flame retardation effect and the mechanical property that can improve material；Relatively
Bromination PS, bromination SBS in high molecular weight, triblock copolymer bromide fire retardant molecular weight of the invention is relatively low, three sections of knots
Structure is adjustable, is easy to regulate and control uniformly dispersing in different matrix, is not easy to be precipitated, and bromine content is high, good flame retardation effect.
The triblock copolymer fire retardant of the present invention has the characteristics that middle low molecular weight, high bromine content, block structure；With showing
Some high molecular weight fire retardants (bromination PS, bromination SBS etc.) are compared, and the present invention has the characteristics that molecular weight is low and high bromine content,
It is easily dispersed；Compared with the PS of existing middle low molecular weight, the present invention has the characteristics that more block structures.
In conclusion the present invention is to contain bromstyrol or brominated acrylate, Isosorbide-5-Nitrae-butadiene or isoprene as polymerization
Monomer, azo-compound or organic peroxide are initiator, three thioes derivatives as chain-transferring agent, using reversible addition-
Be broken chain tra nsfer (RAFT) polymerization, by polymerisation in solution come prepare the controllable middle low molecular weight brominated styrene of molecular weight/
Acrylate-diolefin-phenylethylene ethylene/propenoic acid ester triblock copolymer.The copolymer is by can obtain one after brominating agent
The efficient flame-retarding agent that the brominated amount of kind is high, stability is good, can be as the fire retardant of polystyrene, polyester, polyamide etc., with base material
Compatibility is good.The quality of brominated monomer and bromating agent is controlled to can obtain the bromine based polymer resistance of different molecular weight, different bromine contents
Fire agent.
Present invention process is succinct, and products therefrom has symmetrical structure.
Specific embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This：
Embodiment 1, a kind of preparation method of middle low molecular weight bromine system segmented copolymer fire retardant：
First, with 2,4,6- phenylstilbene bromides, Isosorbide-5-Nitrae-butadiene, pentabromo- styrene for polymerized monomer, azodiisobutyronitrile
(AIBN) for initiator, bis- (α, the α '-dimethyl-α "-acetic acid) esters of trithiocarbonic acid are chain-transferring agent, are polymerize by two step method
To middle low molecular weight brominated styrene-butadiene-brominated styrene triblock copolymer, step is as follows：
(1), 65 grams of Isosorbide-5-Nitrae-butadiene, 0.05 gram of azodiisobutyronitrile (AIBN), bis- (α, the α '-diformazans of 5 grams of trithiocarbonic acids
Base-α "-acetic acid) ester, 200ml solvents tetrahydrofuranes (THF) add in reaction kettle in, under nitrogen protection, react 8h at 60 DEG C,
Obtain the dienite that the degree of polymerization is 63；
(2), in nitrogen protection under, by 50 grams of pentabromo- styrene, 80 gram 2,4,6- phenylstilbene bromides add in aforesaid reaction vessel
In, react 8h at 60 DEG C；Product is poured into 500ml tetrahydrofurans (THF) dissolving under stirring, in 500ml methanol
The residual list of precipitation removing, above-mentioned dissolving and precipitation after 3 times, are placed in 40 DEG C of vacuum drying oven dryings to constant weight, obtaining the degree of polymerization is repeatedly
80 brominated styrene-butadiene-brominated styrene triblock copolymer.Molecular weight is 9989.
2nd, a kind of bromide fire retardant is made in gained copolymer after brominating agent, and step is as follows：
Above-mentioned obtained brominated styrene-butadiene-brominated styrene triblock copolymer is added in reaction vessel,
With the isobutanol rising temperature for dissolving of 5 mass times, temperature is maintained at 40 DEG C, and the bromine chloride for adding in 2 mass times is stirred to react 2h, reaction knot
Shu Houyong 500mL methanol extractions simultaneously filter, and the 40 DEG C of vacuum drying oven dryings of gained filter cake obtain bromide fire retardant, pass through to constant weight
After Oxygen bottle combustion through ion chromatography bromine content be 71.7%.
Embodiment 2, a kind of preparation method of middle low molecular weight bromine based polymer fire retardant：
First, using pentabromobenzyl acrylate, isoprene as polymerized monomer, azo-bis-isobutyrate hydrochloride (AIBA) is causes
Agent, bis- (α, the α '-dimethyl-α "-acetic acid) esters of trithiocarbonic acid are chain-transferring agent, polymerize to obtain middle low molecular weight by two step method
Bromination acrylate-isoprene-bromination acrylate triblock copolymer, step are as follows：
(1), 95 grams of isoprene, 0.06 gram of azo-bis-isobutyrate hydrochloride (AIBA), 6 grams of trithiocarbonic acids it is bis- (α, α '-
Dimethyl-α "-acetic acid) ester, 200ml solvent toluenes add in reaction kettle in, under nitrogen protection, react 7h at 65 DEG C, obtain
The degree of polymerization is 61 isoprene homopolymer；
(2), under nitrogen protection, 92 grams of pentabromobenzyl acrylates is added in aforesaid reaction vessel, react 7h at 65 DEG C；
Product is poured into 500ml tetrahydrofurans (THF) dissolving under stirring, precipitation removes residual list in 500ml methanol, above-mentioned molten
Solution and precipitation be repeatedly after 3 times, is placed in 45 DEG C of vacuum drying oven dryings to constant weight, obtains bromination acrylate that the degree of polymerization is 68-different
Pentadiene-bromination acrylate triblock copolymer.Molecular weight is 8047.
2nd, a kind of bromide fire retardant is made in gained copolymer after brominating agent, and step is as follows：
Above-mentioned obtained bromination acrylate-isoprene-bromination acrylate triblock copolymer is added in into reaction
In container, with the isobutanol rising temperature for dissolving of 6 mass times, temperature is maintained at 45 DEG C, adds in the tetraethylammonium bromide stirring of 4 mass times
4h is reacted, with 500mL methanol extractions and is filtered after reaction, the 45 DEG C of vacuum drying oven dryings of gained filter cake obtain bromine to constant weight
Flame retardant, bromine content 70.2%.
Embodiment 3, a kind of preparation method of middle low molecular weight bromine based polymer fire retardant：
First, using pentabromobenzyl acrylate, Isosorbide-5-Nitrae-butadiene, pentabromo- styrene as polymerized monomer, two isobutyl imidazoline of azo
Hydrochloride (AIBI) is initiator, and bis- (α, the α '-dimethyl-α "-valeric acid) esters of trithiocarbonic acid are chain-transferring agent, pass through two step method
Polymerization obtains middle low molecular weight brominated styrene-butadiene-bromination acrylate triblock copolymer, and step is as follows：
(1), 45 grams of Isosorbide-5-Nitrae-butadiene, 0.065 gram of two isobutyl imidazoline hydrochloride (AIBI) of azo, 6.5 gram of three thio carbon
In bis- (α, the α '-dimethyl-α "-valeric acid) esters of acid, 200ml solvent xylenes addition reaction kettle, under nitrogen protection, at 70 DEG C
5h is reacted, obtains the dienite that the degree of polymerization is 33；
(2), under nitrogen protection, 45 grams of pentabromobenzyl acrylates, 40 grams of pentabromo- styrene are added in aforesaid reaction vessel,
5h is reacted at 70 DEG C；Product is poured into 500ml tetrahydrofurans (THF) dissolving under stirring, is precipitated in 500ml methanol
Remove residual list, above-mentioned dissolving and precipitation after 3 times, are placed in 50 DEG C of vacuum drying oven dryings to constant weight, it is 40 to obtain the degree of polymerization repeatedly
Brominated styrene-butadiene-bromination acrylate triblock copolymer.Molecular weight is 5507.
2nd, a kind of bromide fire retardant is made in gained copolymer after brominating agent, and step is as follows：
Above-mentioned obtained brominated styrene-butadiene-bromination acrylate triblock copolymer is added in into reaction vessel
In, with the isobutanol rising temperature for dissolving of 7 mass times, temperature is maintained at 50 DEG C, and the bromine chloride for adding in 6 mass times is stirred to react 6h, instead
Should after with 500mL methanol extractions and filter, 50 DEG C of vacuum drying oven dryings of gained filter cake to constant weight obtain bromide fire retardant,
Bromine content is 73.6%.
Embodiment 4, a kind of preparation method of middle low molecular weight bromine based polymer fire retardant：
First, with 2,4,6- phenylstilbene bromides, Isosorbide-5-Nitrae-butadiene, 2,4,6- methacrylic acid tribromophenyls for polymerized monomer,
Azo isobutyl cyano formamide (V30) is initiator, and bis- (α, the α '-dimethyl-α "-valeric acid) esters of trithiocarbonic acid are chain tra nsfer
Agent polymerize to obtain middle low molecular weight brominated acrylate-butadiene-brominated styrene triblock copolymer by two step method, step
It is rapid as follows：
(1), 85 grams of Isosorbide-5-Nitrae-butadiene, 0.07 gram of azo isobutyl cyano formamide (V30), 7 grams of trithiocarbonic acids it is bis- (α,
α '-dimethyl-α "-valeric acids) ester, 200ml solvents hexamethylene add in reaction kettle in, under nitrogen protection, react 6h at 75 DEG C,
Obtain the dienite that the degree of polymerization is 58；
(2), under nitrogen protection, by 30 gram 2,4,6- phenylstilbene bromides, 55 gram 2,4,6- methacrylic acid tribromophenyls
It adds in aforesaid reaction vessel, reacts 6h at 75 DEG C；Product is poured into 500ml tetrahydrofurans (THF) dissolving under stirring,
Precipitation removes residual list in 500ml methanol, and above-mentioned dissolving and precipitation be repeatedly after 3 times, is placed in 55 DEG C of vacuum drying oven dryings to constant weight,
Obtain bromination acrylate-butadiene-brominated styrene triblock copolymer that the degree of polymerization is 66.Molecular weight is 6150.
2nd, a kind of bromide fire retardant is made in gained copolymer after brominating agent, and step is as follows：
Above-mentioned obtained bromination acrylate-butadiene-brominated styrene triblock copolymer is added in into reaction vessel
In, with the isobutanol rising temperature for dissolving of 8 mass times, temperature is maintained at 55 DEG C, and the tetraethylammonium bromide for adding in 8 mass times is stirred to react
8h with 500mL methanol extractions and is filtered, 55 DEG C of vacuum drying oven dryings of gained filter cake to constant weight after reaction, obtains the resistance of bromine system
Fire agent, bromine content 72.5%.
Embodiment 5, a kind of preparation method of middle low molecular weight bromine based polymer fire retardant：
First, using isoprene, pentabromo- styrene as polymerized monomer, dibenzoyl peroxide (BPO) is initiator, and three is thio
Bis- (α, the α '-diethyl-α "-acetic acid) esters of carbonic acid are chain-transferring agent, polymerize to obtain middle low molecular weight brominated benzene second by two step method
Alkene-isoprene-brominated styrene triblock copolymer, step are as follows：
(1), 5 grams of isoprene, 0.08 gram of dibenzoyl peroxide (BPO), bis- (α, the α '-diethyls of 8 grams of trithiocarbonic acids
Base-α "-acetic acid) ester, 200ml solvent xylenes add in reaction kettle in, under nitrogen protection, react 4h at 80 DEG C, gathered
It is right be 2 isoprene homopolymer；
(2), under nitrogen protection, 97 grams of pentabromo- styrene is added in aforesaid reaction vessel, react 4h at 80 DEG C；It will production
Object pours into 500ml tetrahydrofurans (THF) dissolving under stirring, and precipitation removes residual list in 500ml methanol, above-mentioned dissolving and
Precipitation is repeatedly after 3 times, is placed in 60 DEG C of vacuum drying oven dryings to constant weight, obtain brominated styrene-isoprene that the degree of polymerization is 9-
Brominated styrene triblock copolymer.Molecular weight is 3130.
2nd, a kind of bromide fire retardant is made in gained copolymer after brominating agent, and step is as follows：
Above-mentioned obtained brominated styrene-isoprene-brominated styrene triblock copolymer is added in into reaction vessel
In, with the isobutanol rising temperature for dissolving of 10 mass times, temperature is maintained at 60 DEG C, and the bromine chloride for adding in 10 mass times is stirred to react 10h,
It with 500mL methanol extractions and filters after reaction, it is fire-retardant to obtain bromine system to constant weight for the 60 DEG C of vacuum drying oven dryings of gained filter cake
Agent, bromine content 74.8%.
Embodiment 6, a kind of preparation method of middle low molecular weight bromine based polymer fire retardant：
First, with Isosorbide-5-Nitrae-butadiene, 2,4,6- phenylstilbene bromides are polymerized monomer, and the benzoyl peroxide tert-butyl ester is causes
Agent, bis- (α, α '-diethyl-α "-acetic acid) the ester valeric acids of trithiocarbonic acid are chain-transferring agent, polymerize in obtaining low point by two step method
Son amount brominated styrene-butadiene-brominated styrene triblock copolymer, step are as follows：
(1), 6 grams of Isosorbide-5-Nitrae-butadiene, 0.09 gram of benzoyl peroxide tert-butyl ester, bis- (α, the α '-diethyls of 9 grams of trithiocarbonic acids
Base-α "-acetic acid) ester, 200ml solvents tetrahydrofuranes (THF) add in reaction kettle in, under nitrogen protection, react 3h at 85 DEG C,
Obtain the dienite that the degree of polymerization is 3；
(2), under nitrogen protection, by 48 gram 2,4,6- phenylstilbene bromides are added in aforesaid reaction vessel, are reacted at 85 DEG C
3h；Product is poured into 500ml tetrahydrofurans (THF) dissolving under stirring, precipitation removes residual list in 500ml methanol, on
Dissolving and precipitation are stated repeatedly after 3 times, 65 DEG C of vacuum drying oven dryings is placed in constant weight, obtains brominated styrene-fourth that the degree of polymerization is 7
Diene-brominated styrene triblock copolymer.Molecular weight is 1526.
2nd, a kind of bromide fire retardant is made in gained copolymer after brominating agent, and step is as follows：
Above-mentioned obtained brominated styrene-butadiene-brominated styrene triblock copolymer is added in reaction vessel,
With the isobutanol rising temperature for dissolving of 10 mass times, temperature is maintained at 40 DEG C, and the tetraethylammonium bromide for adding in 10 mass times is stirred to react
10h with 500mL methanol extractions and is filtered, 40 DEG C of vacuum drying oven dryings of gained filter cake to constant weight after reaction, obtains the resistance of bromine system
Fire agent, bromine content 71.1%.
The technological parameter of 1~embodiment of above-described embodiment 6 summarizes as shown in table 1.
Table 1
Experiment one,
The present invention is prepared to the bromide fire retardant of gained, is compounded with polystyrene (PS), polyester and polyamide substrate, according to
It reaches the minimum additive amount of V-0 to UL94 standard detections, and with bromination PS fire retardants (Albemarle, HP 7010, molecular weight 60
Ten thousand), bromination PS fire retardants (bromination PS, Ferro companies of the U.S., model PB68, molecular weight 15000), Br-SBS fire retardants
(Great Lakes, Emerald 3000, molecular weight 10 is ten thousand), (ten thousand) ICL, FR122P, molecular weight 10 carry out Br-SBS fire retardants
Compare, as a result such as the following table 2：
Table 2
By compared with commercially available macromolecule bromide fire retardant product (comparison result is shown in Table 2), fire retardant provided by the invention
Have the advantages that bromine content is high, additive amount is few.
Experiment two,
Any, 4.5 parts Sb2O3 and 78.5 part ABS in the fire retardant of 17 parts of Examples 1 to 6 is compounded, according to standard
ASTM D256 test its Izod notched impact performance, and with the brominated Polystyrene fire retardant of identical additive amount (Br-PS,
CN103923239A, molecular weight are 958~8100, and bromine content is 68.3~78.7%) compare, as a result such as the following table 3：
Table 3
By compared with the middle low molecular weight brominated polystyrene Br-PS of single structure (comparison result is shown in Table 3), the present invention
The fire retardant of offer has more block structures so that the toughness increase of material.
Comparative example 1-1,
Make the dibenzoyl peroxide (BPO) in 5 step 1) of embodiment into 0.008 gram by 0.08 gram, by three thio carbon
The amount of bis- (α, the α '-diethyl-α "-acetic acid) esters of acid makes 0.8 gram by 8 grams, reaction time 12h；Remaining is equal to embodiment
1。
The degree of polymerization of gained copolymer is 90.Molecular weight is 31980.
Comparative example 1-2,
Make the dibenzoyl peroxide (BPO) in 5 step 1) of embodiment into 0.002 gram by 0.08 gram, by three thio carbon
The amount of bis- (α, the α '-diethyl-α "-acetic acid) esters of acid makes 0.2 gram by 8 grams, reaction time 20h；Remaining is equal to embodiment
1。
The degree of polymerization of gained copolymer is 360.Molecular weight is 127920.
Above-mentioned all comparative examples are detected according to above-mentioned one the method for experiment, acquired results are as shown in table 4 below.
Table 4
Finally, it should also be noted that it is listed above be only the present invention several specific embodiments.Obviously, this hair
Bright to be not limited to above example, acceptable there are many deform.Those of ordinary skill in the art can be from present disclosure
All deformations for directly exporting or associating, are considered as protection scope of the present invention.
Claims (10)
- Two one-step preparation method of solution of the brominated segmented copolymer fire retardant of low molecular weight in 1., it is characterised in that：Added using reversible Into-preparation of chain transfer polymerization method is broken, to contain bromstyrol and/or brominated acrylate and diolefin as polymerized monomer, Azo-compound or organic peroxide are initiator, and three thioes derivatives polymerize to obtain as chain-transferring agent by two step method Middle low molecular weight brominated phenylethylene ethylene/propenoic acid ester-diolefin-brominated styrene/acrylate triblock copolymer；Copolymer passes through After brominating agent, the brominated segmented copolymer fire retardant of middle low molecular weight is obtained.
- 2. two one-step preparation method of solution of the brominated segmented copolymer fire retardant of middle low molecular weight according to claim 1, It is characterized in that：The two step method is polymerized to follow the steps below successively：1), by 5~100 parts of diolefins, 0.05~0.1 part of azo-compound or organic peroxide as initiator, 5~10 Part is added in as three thioes derivatives and solvent of chain-transferring agent in reaction kettle, under inert gas shielding, in 50~150 2~10h is reacted at DEG C, obtains diolefin homopolymer；2), under inert gas shielding, 40~150 parts are added in the reaction kettle after the step 1) under inert gas shielding Containing bromstyrol and/or brominated acrylate, 2~10h is reacted at 50~150 DEG C, obtain middle low molecular weight brominated styrene/ Acrylate-diolefin-bromination brominated styrene/acrylate triblock copolymer；Above-mentioned part is parts by weight.
- 3. two one-step preparation method of solution of the brominated segmented copolymer fire retardant of middle low molecular weight according to claim 2, It is characterized in that：The bromstyrol that contains is at least one of 2,4,6- phenylstilbene bromide, pentabromo- styrene；The brominated acrylate is 2,4,6- tribromophenyl acrylates, 2,4,6- methacrylic acids tribromophenyl, acrylic acid five At least one of bromobenzyl ester；The diolefin is 1,4- butadiene, one kind in isoprene.
- 4. two one-step preparation method of solution of the brominated segmented copolymer fire retardant of middle low molecular weight according to claim 3, It is characterized in that：The azo-compound as initiator is azodiisobutyronitrile, azobisisoheptonitrile, azo-bis-isobutyrate hydrochloride, Two isobutyl imidazoline hydrochloride of azo or azo isobutyl cyano formamide；The organic peroxide as initiator is dibenzoyl peroxide or the benzoyl peroxide tert-butyl ester；Three thioes derivatives as chain-transferring agent are bis- (α, the α '-dimethyl-α "-acetic acid) esters of trithiocarbonic acid, three thio carbon Bis- (α, the α '-diethyl-α "-acetic acid) esters of bis- (α, the α '-dimethyl-α "-valeric acid) esters of acid, trithiocarbonic acid.
- 5. two one-step preparation method of solution of the brominated segmented copolymer fire retardant of middle low molecular weight according to claim 4, It is characterized in that：Solvent in the step 1) is tetrahydrofuran, toluene, dimethylbenzene, hexamethylene.
- 6. according to the two step system of solution of any brominated segmented copolymer fire retardant of middle low molecular weight of Claims 1 to 5 Standby method, it is characterised in that：In the step 2) after reaction, under stirring, to being completely dissolved in solvent, then in methyl alcohol product pours into Precipitation；Above-mentioned dissolving and precipitation after 3 times, are placed in 30~100 DEG C of vacuum drying oven dryings to constant weight, obtain middle low molecular weight bromine repeatedly Change phenylethylene ethylene/propenoic acid ester-diolefin-brominated styrene/acrylate triblock copolymer.
- 7. according to the two step system of solution of any brominated segmented copolymer fire retardant of middle low molecular weight of claim 1~6 Standby method, which is characterized in that the bromination process is：In middle low molecular weight brominated phenylethylene ethylene/propenoic acid ester-diolefin-brominated styrene/acrylate triblock copolymer The isobutanol of addition copolymer 5~10 mass times, which is warming up to 30~70 DEG C, dissolves copolymer, and copolymer 1 is added under heat-retaining condition The bromating agent of~15 mass times is stirred to react 1~15h, with methanol extraction and filters after reaction, is dried under vacuum to constant weight, obtains To the brominated segmented copolymer fire retardant of middle low molecular weight.
- 8. two one-step preparation method of solution of the brominated segmented copolymer fire retardant of middle low molecular weight according to claim 7, It is characterized in that：The bromating agent is bromine chloride or tetraethylammonium bromide.
- It is 9. special using the brominated segmented copolymer fire retardant of middle low molecular weight that claim 1~8 either method is prepared Sign is：The degree of polymerization is between 7~80.
- 10. the brominated segmented copolymer fire retardant of middle low molecular weight according to claim 9, it is characterised in that：Bromine content For 70.2~74.8wt%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101240046A (en) * | 2007-02-09 | 2008-08-13 | 同济大学 | Method for preparing low molecular weight narrow distribution brominated polystyrene by active/controllable polymerization |
| CN106065054A (en) * | 2015-04-24 | 2016-11-02 | 中国石油化工股份有限公司 | Block copolymer of bromination as fire retardant and preparation method thereof |
| CN107141385A (en) * | 2017-06-02 | 2017-09-08 | 烟台新特路新材料科技有限公司 | A kind of preparation method of low molecular weight brominated polystyrene |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101240046A (en) * | 2007-02-09 | 2008-08-13 | 同济大学 | Method for preparing low molecular weight narrow distribution brominated polystyrene by active/controllable polymerization |
| CN106065054A (en) * | 2015-04-24 | 2016-11-02 | 中国石油化工股份有限公司 | Block copolymer of bromination as fire retardant and preparation method thereof |
| CN107141385A (en) * | 2017-06-02 | 2017-09-08 | 烟台新特路新材料科技有限公司 | A kind of preparation method of low molecular weight brominated polystyrene |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112831055A (en) * | 2021-01-13 | 2021-05-25 | 邱元栏 | Degradable flame-retardant polystyrene block copolymer and preparation method thereof |
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