CN108250375A - Two one-step preparation method of intermediate molecular weight bromination segmented copolymer fire retardant and its lotion - Google Patents
Two one-step preparation method of intermediate molecular weight bromination segmented copolymer fire retardant and its lotion Download PDFInfo
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Abstract
The invention discloses a kind of two one-step preparing methods of lotion of intermediate molecular weight (degree of polymerization is 150~790) bromination segmented copolymer fire retardant：It is prepared using Invertible ideal method, using styrene and diolefin as polymerized monomer, azo-compound or organic peroxide are initiator, three thioes derivatives polymerize to obtain medium molecule weight phenylethylene diolefin styrene triblock copolymer by two step method as chain-transferring agent；Copolymer obtains intermediate molecular weight bromination segmented copolymer fire retardant after brominating agent, that is, intermediate molecular weight brominated styrene diolefin styrene triblock copolymer bromide fire retardant.The fire retardant bromine content is high, good flame retardation effect.
Description
Technical field
The present invention relates to polymer flame retardant field more particularly to a kind of bromination medium molecule weight phenylethylene-diolefin-benzene
Ethylene 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 polyphenylene second
Alkene-butadiene-styrene copolymer Br-SBS, bromine content are higher for PBS and Br-SBS.Rigid aromatic radical in wherein PBS
Segment makes it when being compounded with base material so that toughness of material reduce, and in Br-SBS linear butadiene segment introducing, can make
The toughness of material increases.But presently commercially available Br-SBS flame retardant molecules amount is generally more than 100,000, be using anionic polymerisation and
The upper brominations of high molecular weight SBS and obtain, this so that it is not easy to disperse in high molecular material, and bromination reaction difficulty, causes
Bromine content 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 contents (bromine content about 70.2~74.8wt%), medium
Brominated styrene-diolefin-styrene triblock copolymer fire retardant of molecular weight and preparation method thereof.
In order to solve the above technical problem, the present invention provides a kind of intermediate molecular weight (degree of polymerization is 150~790) bromination is more
Two one-step preparation method of lotion of block copolymer fire retardant：It is prepared using reversible addion-fragmentation chain transfer (RAFT) polymerization, with
Styrene and diolefin are polymerized monomer, and azo-compound or organic peroxide are initiator, and three thioes derivatives are as chain
Transfer agent polymerize to obtain medium molecule weight phenylethylene-diolefin-styrene triblock copolymer by two step method；Copolymer passes through
After brominating agent, intermediate molecular weight (degree of polymerization is 150~790) bromination segmented copolymer fire retardant is obtained, that is, middle decile
Son amount brominated styrene-diolefin-styrene triblock copolymer bromide fire retardant.
The improvement of two one-step preparation method of lotion of intermediate molecular weight bromination segmented copolymer fire retardant as the present invention：Institute
Two step method is stated to be polymerized to follow the steps below successively：
It 1), will be as the H of solvent2O, 0.8~6.4 part of emulsifier, 10~100 parts of diolefins, 0.5~1.0 part be used as chain
After three thioes derivatives of transfer agent stir evenly, under inert gas (nitrogen) protection, 50~80 DEG C are warming up to, adds in 0.01
After~0.02 part of 2~10h of azo-compound or organic peroxide insulation reaction as initiator, diolefin homopolymerization is obtained
Object；
2) 10~60 parts of styrene, are added under inert gas shielding in the reaction kettle after step 1), in 50~
2~10h is reacted at 80 DEG C；Obtain medium molecule weight phenylethylene-diolefin-styrene triblock copolymer；
Above-mentioned part is mass parts.
In the step 1), the dosage of water is 100~200 parts.
As the present invention intermediate molecular weight bromination segmented copolymer fire retardant two one-step preparation method of lotion it is further
It improves：
The diolefin is 1,4- butadiene, one kind in isoprene.
As the present invention intermediate molecular weight bromination segmented copolymer fire retardant two one-step preparation method of lotion 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 for dibenzoyl peroxide (BPO), the benzoyl peroxide tert-butyl ester,
Ammonium persulfate (APS), potassium peroxydisulfate (KPS)；
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 intermediate molecular weight bromination segmented copolymer fire retardant two one-step preparation method of lotion it is further
It improves：
The emulsifier is lauryl sodium sulfate, neopelex, polyoxyethylene sorbitan aliphatic acid
At least one of ester T-80, OP-10.
As the present invention intermediate molecular weight bromination segmented copolymer fire retardant two one-step preparation method of lotion it is further
It improves：
In the step 2), after reaction (cooling terminates reaction), product is freeze-dried to constant weight, obtains middle decile
Sub- weight phenylethylene-diolefin-styrene triblock copolymer.
As the present invention intermediate molecular weight bromination segmented copolymer fire retardant two one-step preparation method of lotion it is further
It improves, the bromination process is：
Copolymer 5~10 mass times is added in medium molecule weight phenylethylene-diolefin-styrene triblock copolymer
Isobutanol, which is warming up to 30~70 DEG C, dissolves copolymer, and the bromating agent stirring of the mass times of copolymer 1~15 is added under heat-retaining condition
1~15h is reacted, with 500 parts of methanol extractions and is filtered after reaction, is dried under vacuum to constant weight, obtains intermediate molecular weight bromination
Segmented copolymer fire retardant.
As the present invention intermediate molecular weight bromination segmented copolymer fire retardant two one-step preparation method of lotion it is further
It improves：The bromating agent is bromine chloride or tetraethylammonium bromide.
The present invention also provides simultaneously to be hindered using the intermediate molecular weight bromination segmented copolymer that the above method is prepared
Agent is fired, between 150~790, molecular weight is easy to add by monomer (styrene, Isosorbide-5-Nitrae-butadiene/isoprene) degree of polymerization
Dosage is regulated and controled.
The improvement of intermediate molecular weight bromination segmented copolymer fire retardant as the present invention：Bromine content for 70.2~
74.8wt%, bromine content can be adjusted by bromating agent dosage.
In the present invention, using reversible addion-fragmentation chain transfer (RAFT) polymerization side in activity/controllable free-radical polymerisation
Method using styrene, Isosorbide-5-Nitrae-butadiene/isoprene as polymerized monomer, by point two batches of charging technologies, prepares intermediate molecular weight
Styrene-diolefin-styrene triblock copolymer.
Styrene-diolefin-styrene triblock copolymer of the present invention can pass through control using RAFT polymerizations
The degree of polymerization, regulation and control form the product of different intermediate molecular weights, enhance and resin matrix compatibility.In addition, it is provided in the present invention
Bromination process so that the bromo element of high-content, the flame retarding efficiency of unit mass fire retardant have been chemically combined in three block structure
It will be enhanced.
The present invention combines the advantages of RAFT polymerizations and bromination technique, is prepared for medium molecule weight phenylethylene-diolefin-benzene second
Alkene triblock copolymer fire retardant controls the quality of monomer and bromating agent, can obtain different intermediate molecular weights, different three block knots
The bromide fire retardant product of structure, different bromine contents.
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 the present invention selects intermediate molecular weight and more block structures to solve
The problem.
The fire retardants such as the brominated Polystyrene relative to existing intermediate molecular weight, triblock copolymer of the invention use
Monomer carries out living polymerization, while keeping intermediate molecular weight, increases the soft segment of butadiene/isoprene, becomes more blocks
Structure, suitable for different systems, and good flame retardation effect；Relative to the bromination PS of high molecular weight, bromination SBS, of the invention three is embedding
Section copolymer bromide fire retardant molecular weight is slightly lower, is easy to regulate and control uniformly dispersing in different matrix, is not easy to be precipitated, and bromine content
Height, good flame retardation effect.
The triblock copolymer fire retardant of the present invention has the characteristics that intermediate molecular weight, bromine content height, 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 bromine content is high,
It is easily dispersed；Compared with the PS of existing intermediate molecular weight, the present invention has the characteristics that more block structures.
In conclusion the present invention azo-compound or has using styrene, Isosorbide-5-Nitrae-butadiene/isoprene as polymerized monomer
Machine peroxide is initiator, and three thioes derivatives are polymerize as chain-transferring agent using reversible addion-fragmentation chain transfer (RAFT)
Method prepares the controllable styrene-diolefin-styrene triblock copolymer of molecular weight by emulsion polymerization.The copolymer
By obtaining the efficient flame-retarding agent that a kind of brominated amount is high, stability is good after brominating agent, polystyrene can be used as, polyester, gathered
The fire retardant of amide etc. is good with the compatibility of base material.The quality of control monomer and bromating agent can obtain different molecular weight, different bromines
The bromine based polymer fire retardant of content.
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 intermediate molecular weight bromine based polymer fire retardant：
First, using styrene, Isosorbide-5-Nitrae-butadiene as polymerized monomer, azodiisobutyronitrile (AIBN) be initiator, three thio carbon
Bis- (α, the α '-dimethyl-α "-acetic acid) esters of acid are chain-transferring agent, and lauryl sodium sulfate is emulsifier, is polymerize by two step method
To intermediate molecular weight styrene-butadiene-styrene triblock copolymer, step is as follows：
(1), by 150 grams of H2O and 0.88 gram of lauryl sodium sulfate is added in reaction kettle, is stirring evenly and then adding into 10 gram 1,
4- butadiene, bis- (α, the α '-dimethyl-α "-acetic acid) esters of 0.5 gram of trithiocarbonic acid, under nitrogen protection, is warming up to 60 DEG C, adds
After entering 0.01 gram of azodiisobutyronitrile (AIBN) insulation reaction 2h, the dienite that the degree of polymerization is 96 is obtained, molecular weight is
5184=96*54；
(2), under nitrogen protection, 12 grams of styrene is added in aforesaid reaction vessel, react 2h at 60 DEG C；Reaction time
After arrival, cooling terminates reaction, and chilled (- 30 DEG C) dryings of product to constant weight obtain styrene-fourth two that the degree of polymerization is 156
Alkene-styrene triblock copolymer, molecular weight 11424=96*54+30*2*104.
2nd, bromide fire retardant is made in gained copolymer after brominating agent, and step is as follows：
Above-mentioned obtained styrene-butadiene-styrene triblock copolymer is added in reaction vessel, with 5 mass
Isobutanol rising temperature for dissolving again, temperature are maintained at 40 DEG C, and the bromine chloride for adding in 2 mass times is stirred to react 2h, uses after reaction
500mL methanol extractions simultaneously filter, and 40 DEG C of vacuum drying oven dryings of gained filter cake to constant weight obtain bromide fire retardant, fired by oxygen bottle
After burning through ion chromatography bromine content be 70.2%.
Embodiment 2, a kind of preparation method of intermediate molecular weight bromine based polymer fire retardant：
First, using styrene, isoprene as polymerized monomer, two isobutyl imidazoline hydrochloride (AIBI) of azo is initiator,
Bis- (α, the α '-dimethyl-α "-acetic acid) esters of trithiocarbonic acid are chain-transferring agent, and neopelex is emulsifier, passes through two
Footwork polymerize to obtain intermediate molecular weight styrene-isoprene-styrene triblock copolymer, and step is as follows：
(1), by 150 grams of H2O and 2.6 gram of neopelex is added in reaction kettle, is stirring evenly and then adding into 35 grams
Isoprene, bis- (α, the α '-dimethyl-α "-acetic acid) esters of 0.8 gram of trithiocarbonic acid, under nitrogen protection, is warming up to 65 DEG C, adds
After entering 0.016 gram of two isobutyl imidazoline hydrochloride (AIBI) insulation reaction 4h of azo, it is equal to obtain the isoprene that the degree of polymerization is 167
Polymers, molecular weight 11356；
(2), under nitrogen protection, 30 grams of styrene is added in aforesaid reaction vessel, react 4h at 65 DEG C；Reaction time
After arrival, cooling terminates reaction, and product is freeze-dried to constant weight, obtains styrene-isoprene-benzene that the degree of polymerization is 261
Ethylene triblock copolymer, molecular weight 21132.
2nd, bromide fire retardant is made in gained copolymer after brominating agent, and step is as follows：
Above-mentioned obtained styrene-isoprene-styrene triblock copolymer is added in reaction vessel, with 6 matter
The isobutanol rising temperature for dissolving of amount times, temperature are maintained at 45 DEG C, and the tetraethylammonium bromide for adding in 4 mass times is stirred to react 4h, react
After with 500mL methanol extractions and filter, the 45 DEG C of vacuum drying oven dryings of gained filter cake obtain bromide fire retardant, bromine to constant weight
Content is 71.1%.
Embodiment 3, a kind of preparation method of intermediate molecular weight bromine based polymer fire retardant：
First, using styrene, isoprene as polymerized monomer, azo isobutyl cyano formamide (V30) is initiator, and three is thio
Bis- (α, the α '-dimethyl-α "-valeric acid) esters of carbonic acid are chain-transferring agent, and polyoxyethylene sorbitan fatty acid ester T-80 is emulsification
Agent polymerize to obtain intermediate molecular weight styrene-isoprene-styrene triblock copolymer by two step method, and step is as follows：
(1), by 150 grams of H2O and 6.4 gram of polyoxyethylene sorbitan fatty acid ester T-80 is added in reaction kettle, stirring
100 grams of isoprene, bis- (α, the α '-dimethyl-α "-valeric acid) esters of 1.0 grams of trithiocarbonic acids, in nitrogen protection are added in after uniformly
Under, 70 DEG C are warming up to, after adding in 0.02 gram of azo isobutyl cyano formamide (V30) insulation reaction 6h, it is 382 to obtain the degree of polymerization
Isoprene homopolymer, molecular weight 25976；
(2), under nitrogen protection, 60 grams of styrene is added in aforesaid reaction vessel, react 6h at 70 DEG C；Reaction time
After arrival, cooling terminates reaction, and product is freeze-dried to constant weight, obtains styrene-isoprene-benzene that the degree of polymerization is 532
Ethylene triblock copolymer, molecular weight 41576.
2nd, bromide fire retardant is made in gained copolymer after brominating agent, and step is as follows：
Above-mentioned obtained styrene-isoprene-styrene triblock copolymer is added in reaction vessel, with 7 matter
The isobutanol rising temperature for dissolving of amount times, temperature are maintained at 50 DEG C, and the bromine chloride for adding in 6 mass times is stirred to react 6h, after reaction
It with 500mL methanol extractions and filters, 50 DEG C of vacuum drying oven dryings of gained filter cake to constant weight obtain bromide fire retardant, bromine content is
72.5%.
Embodiment 4, a kind of preparation method of intermediate molecular weight bromine based polymer fire retardant：
First, using styrene, Isosorbide-5-Nitrae-butadiene as polymerized monomer, dibenzoyl peroxide (BPO) be initiator, three thio carbon
Bis- (α, the α '-dimethyl-α "-valeric acid) esters of acid are chain-transferring agent, and OP-10 is emulsifier, polymerize to obtain middle decile by two step method
Sub- weight phenylethylene-butadiene-styrene triblock copolymer, step are as follows：
(1), by 150 grams of H2O and 6.4 gram of OP-10 is added in reaction kettle, is stirring evenly and then adding into 100 grams of Isosorbide-5-Nitrae-butadiene,
Bis- (α, the α '-dimethyl-α "-valeric acid) esters of 0.8 gram of trithiocarbonic acid, under nitrogen protection, are warming up to 75 DEG C, add in 0.016 gram
After dibenzoyl peroxide (BPO) insulation reaction 8h, the dienite that the degree of polymerization is 602, molecular weight 32508 are obtained；
(2), under nitrogen protection, 60 grams of styrene is added in aforesaid reaction vessel, react 8h at 75 DEG C；Reaction time
After arrival, cooling terminates reaction, and product is freeze-dried to constant weight, obtains styrene-butadiene-benzene second that the degree of polymerization is 789
Alkene triblock copolymer, molecular weight 52060.
2nd, bromide fire retardant is made in gained copolymer after brominating agent, and step is as follows：
Above-mentioned obtained styrene-butadiene-styrene triblock copolymer is added in reaction vessel, with 8 mass
Isobutanol rising temperature for dissolving again, temperature are maintained at 55 DEG C, and the tetraethylammonium bromide for adding in 8 mass times is stirred to react 8h, reaction knot
Shu Houyong 500mL methanol extractions simultaneously filter, and 55 DEG C of vacuum drying oven dryings of gained filter cake to constant weight obtain bromide fire retardant, bromine contains
Measure is 73.6%.
Embodiment 5, a kind of preparation method of intermediate molecular weight bromine based polymer fire retardant：
First, using styrene, Isosorbide-5-Nitrae-butadiene as polymerized monomer, potassium peroxydisulfate (KPS) is initiator, and trithiocarbonic acid is double
(α, α '-diethyl-α "-acetic acid) ester is chain-transferring agent, and lauryl sodium sulfate is emulsifier, is polymerize in obtaining by two step method
Equimolecular quantity styrene-butadiene-styrene triblock copolymer, step are as follows：
(1), by 150 grams of H2O and 3.00 gram of lauryl sodium sulfate is added in reaction kettle, is stirring evenly and then adding into 55 gram 1,
4- butadiene, bis- (α, the α '-diethyl-α "-acetic acid) esters of 0.6 gram of trithiocarbonic acid, under nitrogen protection, is warming up to 80 DEG C, adds
After entering 0.012 gram of potassium peroxydisulfate (KPS) insulation reaction 10h, the dienite that the degree of polymerization is 441 is obtained, molecular weight is
23814；
(2), under nitrogen protection, 20 grams of styrene is added in aforesaid reaction vessel, react 10h at 80 DEG C；During reaction
Between reach after, cooling terminates reaction, and product is freeze-dried to constant weight, obtains styrene-butadiene-benzene that the degree of polymerization is 525
Ethylene triblock copolymer, molecular weight 32550.
2nd, bromide fire retardant is made in gained copolymer after brominating agent, and step is as follows：
Above-mentioned obtained styrene-butadiene-styrene triblock copolymer is added in reaction vessel, with 10 times of matter
The isobutanol rising temperature for dissolving of amount, temperature are maintained at 60 DEG C, and the bromine chloride for adding in 10 times of quality is stirred to react 10h, after reaction
It with 500mL methanol extractions and filters, 60 DEG C of vacuum drying oven dryings of gained filter cake to constant weight obtain bromide fire retardant, bromine content is
74.8%.
Being summarized as follows for the technological parameter of 1~embodiment of above-described embodiment 5 is stated 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), Br-SBS fire retardants (Great Lakes, Emerald 3000, molecular weight 10 ten thousand), bromination PS fire retardants (bromination PS, it is beautiful
Ferro companies of state, model PB68, molecular weight 15000), (ten thousand) ICL, FR122P, molecular weight 10 are compared Br-SBS fire retardants
Compared with 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,
The fire retardant of 17 parts of Examples 1 to 5,4.5 parts Sb2O3 and 78.5 part of ABS are compounded, according to standard ASTM
D256 tests 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
| Fire retardant | Chalpy impact/(J/m) |
| Embodiment 1 | 201 |
| Embodiment 2 | 191 |
| Embodiment 3 | 188 |
| Embodiment 4 | 203 |
| Embodiment 5 | 197 |
| ABS | 140 |
| CN103923239A:Br-PS | 100.3 |
It is provided by the invention fire-retardant by compared with the brominated Polystyrene Br-PS of single structure (comparison result is shown in Table 3)
Agent has more block structures so that the toughness increase of material.
Comparative example 1-1,
Make the potassium peroxydisulfate (KPS) in 5 step 1) of embodiment into 0.0024 gram by 0.012 gram, trithiocarbonic acid is double
The amount of (α, α '-diethyl-α "-acetic acid) ester makes 0.12 gram by 0.6 gram, reaction time 12h；Remaining is equal to embodiment 1.
The degree of polymerization of gained copolymer is 2625.Molecular weight is 162750.
Comparative example 1-2,
Make the potassium peroxydisulfate (KPS) in 5 step 1) of embodiment into 0.0012 gram by 0.012 gram, trithiocarbonic acid is double
The amount of (α, α '-diethyl-α "-acetic acid) ester makes 0.06 gram by 0.6 gram, reaction time 20h；Remaining is equal to embodiment 1.
The degree of polymerization of gained copolymer is 5250.Molecular weight is 325500.
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)
1. two one-step preparation method of lotion of intermediate molecular weight bromination segmented copolymer fire retardant, it is characterised in that：Added using reversible
Into-fracture chain transfer polymerization method preparation, using styrene and diolefin as polymerized monomer, azo-compound or organic peroxide
For initiator, three thioes derivatives polymerize to obtain medium molecule weight phenylethylene-diolefin-by two step method as chain-transferring agent
Styrene triblock copolymer；Copolymer obtains intermediate molecular weight bromination segmented copolymer fire retardant after brominating agent.
2. two one-step preparation method of lotion of intermediate molecular weight bromination segmented copolymer fire retardant according to claim 1,
It is characterized in that：The two step method is polymerized to follow the steps below successively：
It 1), will be as the H of solvent2O, 0.8~6.4 part of emulsifier, 10~100 parts of diolefins, 0.5~1.0 part be used as chain-transferring agent
Three thioes derivatives stir evenly after, under inert gas shielding, be warming up to 50~80 DEG C, add in 0.01~0.02 part of conduct
After 2~10h of azo-compound or organic peroxide insulation reaction of initiator, diolefin homopolymer is obtained；
2) 10~60 parts of styrene, are added under inert gas shielding in the reaction kettle after step 1), in 50~80 DEG C
2~10h of lower reaction；Obtain medium molecule weight phenylethylene-diolefin-styrene triblock copolymer；
Above-mentioned part is mass parts.
3. two one-step preparation method of lotion of intermediate molecular weight bromination segmented copolymer fire retardant according to claim 2,
It is characterized in that：
The diolefin is 1,4- butadiene, one kind in isoprene.
4. two one-step preparation method of lotion of intermediate molecular weight bromination segmented copolymer fire retardant 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 for dibenzoyl peroxide, the benzoyl peroxide tert-butyl ester, ammonium persulfate,
Potassium peroxydisulfate；
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 lotion of intermediate molecular weight bromination segmented copolymer fire retardant according to claim 4,
It is characterized in that：
The emulsifier is lauryl sodium sulfate, neopelex, polyoxyethylene sorbitan fatty acid ester T-
80th, at least one of OP-10.
6. two one-step preparation method of lotion of intermediate molecular weight bromination segmented copolymer fire retardant according to claim 2,
It is characterized in that：
In the step 2), after reaction, product is freeze-dried to constant weight, obtains medium molecule weight phenylethylene-diolefin-
Styrene triblock copolymer.
7. according to the two step system of lotion of any intermediate molecular weight bromination segmented copolymer fire retardant of claim 1~6
Standby method, which is characterized in that the bromination process is：
The isobutyl of copolymer 5~10 mass times is added in medium molecule weight phenylethylene-diolefin-styrene triblock copolymer
Alcohol, which is warming up to 30~70 DEG C, dissolves copolymer, and the bromating agent that the mass times of copolymer 1~15 is added under heat-retaining condition is stirred to react 1
~15h with 500 parts of methanol extractions and is filtered, is dried under vacuum to constant weight, obtains the more blocks of intermediate molecular weight bromination after reaction
Copolymer fire retardant.
8. two one-step preparation method of lotion of intermediate molecular weight bromination segmented copolymer fire retardant according to claim 7,
It is characterized in that：The bromating agent is bromine chloride or tetraethylammonium bromide.
9. the intermediate molecular weight bromination segmented copolymer fire retardant being prepared using claim 1~8 either method, special
Sign is：The degree of polymerization is between 150~790.
10. intermediate molecular weight bromination segmented copolymer fire retardant according to claim 9, it is characterised in that：Bromine content
For 70.2~74.8wt%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111393555A (en) * | 2019-01-02 | 2020-07-10 | 北京化工大学 | Method for preparing liquid polyisoprene rubber based on reversible addition-fragmentation chain transfer free radical polymerization and rubber material |
| 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 |
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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111393555A (en) * | 2019-01-02 | 2020-07-10 | 北京化工大学 | Method for preparing liquid polyisoprene rubber based on reversible addition-fragmentation chain transfer free radical polymerization and rubber material |
| 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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