CN106065054B - Brominated block copolymer as fire retardant and preparation method thereof - Google Patents
Brominated block copolymer as fire retardant and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to brominated block copolymers, are formula S before bromination1‑IS1‑I1‑BI1‑B‑BI2‑I2‑IS2‑S2Base block copolymer, wherein S1And S2Represent styrene block, IS1And IS2Represent the trapezoidal copolymerized block of isoprene and styrene, I1And I2Represent isoprene block, BI1And BI2Representing the trapezoidal copolymerized block of butadiene and isoprene, B represents butadiene block, after bromination, at least 40 moles of % of the unsaturated carbon-carbon double bond contained by isoprene monomer unit, and at most 95 moles of % are brominated；At least 5 moles of % of unsaturated carbon-carbon double bond contained by butadiene monomer unit, and at most 40 moles of % are brominated.The invention further relates to the method for preparing the brominated block copolymer, the solution including making base block copolymer is reacted with bromating agent.The brominated block copolymer of the present invention has excellent thermal stability, good compatibility and good processing performance.The method of the present invention can realize the preference bromination to the isoprene monomer unit in base block copolymer.
Description
Technical field
The present invention relates to the block copolymers and its system as the brominated styrene of fire retardant, butadiene and isoprene
Preparation Method.
Background technology
Bromide such as hexabromo dodecane, deca-BDE, tetrabromobisphenol A etc. are often used as the fire retardant of polymer.However,
For the worry to these small molecule bromide potential hazard environment and biology health, occur limiting them or even
Forbid the requirement used.It is contemplated that within following a period of time, bromide flame retardant can not possibly also be complete
Forbid, especially the application field in electric equipment products.
Macromolecular bromide flame retardant is to substitute small molecule bromide to biological health hazard smaller to more environment-friendly
A kind of selection of fire retardant.
The block copolymer of conjugated diene and styrene generally includes Styrene-Butadiene-Styrene Block Copolymer
(SBS) and styrene-isoprene-styrene block copolymer (SIS) etc..This based block copolymer be commonly used as adhesive,
Plastic modifier and asphalt modifier etc..Since in practical applications, SBS is heated and is easily crosslinked and increases melt viscosity, and SIS is then
Easily reduce viscosity due to degradation, thus develop in recent years the block copolymer of styrene, butadiene and isoprene with gram
Take SBS and the SIS problem in the application.
The content of the invention
In view of above-mentioned condition of the prior art, present inventor has carried out depth in macromolecular bromide flame retardant field
Enter and widely study, to find a kind of brominated styrene, butadiene and the block copolymer of isoprene, not only
Because effective bromination has been obtained there is excellent thermal stability, and gather during processed and applied with good with other
The compatibility of object is closed, while its processing performance will not be influenced because viscosity change is too big.It turns out that by by styrene,
Isoprene monomer unit preference bromination products therefrom in the block copolymer of butadiene and isoprene can be real
Existing above-mentioned purpose.The present inventor is based on above-mentioned discovery and completes the present invention.
Therefore, it is preferentially brominated by selectivity it is an object of the present invention to provide a kind of wherein isoprene monomer unit
The block copolymer of styrene, butadiene and isoprene.
Another object of the present invention is to provide a kind of method for preparing the brominated block copolymer.
The technical solution for realizing above-mentioned purpose of the present invention can be summarized as follows：
1. a kind of brominated block copolymer, the brominated block copolymer is formula S before bromination1-IS1-I1-BI1-
B-BI2-I2-IS2-S2Base block copolymer, wherein S1And S2Each independently represent styrene block, IS1And IS2Each
Independently represent the trapezoidal copolymerized block of isoprene and styrene, I1And I2Each independently represent isoprene block, BI1
And BI2The trapezoidal copolymerized block of butadiene and isoprene is each independently represented, B represents butadiene block, basis is embedding
After section copolymer bromination, trapezoidal copolymerized block IS1And IS2, isoprene block I1And I2And trapezoidal copolymerized block BI1And BI2
At least 40 moles of % of unsaturated carbon-carbon double bond contained by middle isoprene monomer unit, preferably at least 50 moles of %, more preferably
At least 60 moles of %, and at most 95 moles of % are brominated；Trapezoidal copolymerized block BI1And BI2And fourth two in butadiene block B
At least 5 moles of % of unsaturated carbon-carbon double bond contained by alkene monomer unit, and at most 40 moles of % are brominated.
2. according to the brominated block copolymer of the 1st, wherein before bromination, the number-average molecular weight of base block copolymer
For 5 × 104-50×104G/mol, preferably 5 × 104-30×104g/mol。
3. according to the brominated block copolymer of the 1st or 2, wherein before bromination, based on the total of base block copolymer
Weight, styrenic monomer units are 10-50 weight %, and butadiene monomer unit is 5-30 weight % and isoprene monomer list
Member is 20-85 weight %；Optimization styrene monomeric unit is 10-40 weight %, butadiene monomer unit for 5-20 weight % and
Isoprene monomer unit is 40-85 weight %；More preferable styrenic monomer units are 10-40 weight %, divinylic monomer list
Member is 5-15 weight % and isoprene monomer unit is 45-85 weight %.
4. according to the brominated block copolymer of any one of 1-3, wherein S1And S2Represent identical styrene block,
And/or IS1And IS2Represent the trapezoidal copolymerized block and/or I of identical isoprene and styrene1And I2Represent identical different
Pentadiene block and/or BI1And BI2Represent the trapezoidal copolymerized block of identical butadiene and isoprene.
5. a kind of method for preparing the brominated block copolymer according to any one of 1-4, the described method includes formulas
S1-IS1-I1-BI1-B-BI2-I2-IS2-S2Solution and the bromating agent of base block copolymer react.
6. according to the method for the 5th, the dosage of wherein bromating agent so that bromating agent is copolymerized with base block in terms of molecular bromine
The molar ratio of unsaturated carbon-carbon double bond in object contained by all isoprene monomer units is 0.5-2.0, preferably 0.8-1.5.
7. according to the method for the 5th or 6, the solution solvent for use of wherein base block copolymer includes but not limited to ether
Class, such as tetrahydrofuran and Isosorbide-5-Nitrae-dioxane；Hydro carbons, such as pentane, hexane, hexamethylene, benzene and toluene；Halogenated hydrocarbons, such as
Monochloro methane, dichloromethane, chloroform and carbon tetrachloride；Halogenated aryl hydrocarbon, such as chlorobenzene and bromobenzene；And above-mentioned solvent is mixed
Close object.
8. according to the method for any one of 5-7, wherein bromating agent is bromine.
9. according to the method for any one of 5-7, wherein bromating agent is bromine solutions, preferably bromine solutions use and base block
The identical solvent of the solution of copolymer.
10. according to the method for any one of 5-9, the method is additionally included in after the completion of bromination reaction, is mixed to reaction
Reducing agent and neutralizer are added in object.
11. according to the method for the 10th, wherein reducing agent and neutralization are added in into reaction mixture in form of an aqueous solutions
Agent.
12. according to the method for the 10th or 11, wherein reducing agent be selected from sulphite for example sodium sulfite, sodium hydrogensulfite,
Sodium pyrosulfite or nitrite such as sodium nitrite.
13. according to the method for the 10th or 11, wherein neutralizer is the hydrogen of alkaline matter, preferred as alkali or alkaline-earth metal
Oxide, such as sodium hydroxide and potassium hydroxide, especially sodium hydroxide；The salt of weak acid of alkali or alkaline earth metal, such as carbon
Sour hydrogen sodium, saleratus, sodium carbonate, potassium carbonate and calcium carbonate.
The brominated block copolymer of the present invention not only has excellent thermal stability, but also has during processed and applied
The good compatibility with other polymer, while show good processing performance due to viscosity change is little.Present invention side
Method can be realized to formula S1-IS1-I1-BI1-B-BI2-I2-IS2-S2Base block copolymer in isoprene monomer unit
Preference bromination.
These and other purposes, features and advantages of the present invention are readily able to after integrally the present invention is considered as ordinary skill
Personnel understand.
Specific embodiment
According to an aspect of the invention, there is provided a kind of brominated block copolymer, the brominated block copolymer
It is formula S before bromination1-IS1-I1-BI1-B-BI2-I2-IS2-S2Base block copolymer, wherein S1And S2Table independently
Show styrene block (being referred to as styrene block S), IS1And IS2Each independently represent the trapezoidal common of isoprene and styrene
Poly block (is referred to as trapezoidal copolymerized block IS), I1And I2It each independently represents isoprene block and (it is embedding to be referred to as isoprene
Section I), BI1And BI2The trapezoidal copolymerized block for each independently representing butadiene and isoprene (is referred to as trapezoidal copolymerized block
BI), B represent butadiene block, after by base block copolymer bromination, trapezoidal copolymerized block IS, isoprene block I and
At least 40 moles of %, such as 40-80 of unsaturated carbon-carbon double bond in trapezoidal copolymerized block BI contained by isoprene monomer unit
Butadiene monomer unit institute in mole %, and at most 95 moles of % are brominated, trapezoidal copolymerized block BI and butadiene block B
At least 5 moles of % of the unsaturated carbon-carbon double bond contained, and at most 40 moles of % are brominated.
Before bromination, formula S1-IS1-I1-BI1-B-BI2-I2-IS2-S2Base block copolymer include nine blocks,
Middle butadiene block B is located at centre, and both ends are connected to the trapezoidal copolymerized block (BI of butadiene and isoprene1With
BI2), the two trapezoidal copolymerized block both ends are connected to isoprene block (I1And I2), isoprene block both ends difference
It is connected with the trapezoidal copolymerized block (IS of isoprene and styrene1And IS2), the two trapezoidal copolymerized block both ends connect respectively again
It is connected to styrene block (S1And S2)。
Although S1And S2Represent the styrene block being connected with trapezoidal copolymerized block IS, but the two blocks are in chain length
On there may be difference.In other words, the length of the two blocks may be the same or different.It is preferred that they are with identical
Chain length.
Although IS1And IS2Represent the trapezoidal copolymerized block for the isoprene and styrene being connected with isoprene block,
But the two blocks may have difference in chain length.In other words, the length of the two blocks can be identical, can not also
Together.It is preferred that they have identical chain length.
Although I1And I2Represent the isoprene block being connected with trapezoidal copolymerized block BI, but the two blocks are in chain
There may be difference in length.In other words, the length of the two blocks may be the same or different.It is preferred that they have phase
Same chain length.
Although BI1And BI2Represent the trapezoidal copolymerized block for the butadiene and isoprene being connected with butadiene block, but
It is that the two blocks there may be difference in chain length.In other words, the length of the two blocks can be identical, can not also
Together.It is preferred that they have identical chain length.
In a preferred embodiment of the invention, before bromination, the total weight based on base block copolymer, styrene list
Body unit is 10-50 weight %, and butadiene monomer unit is 5-30 weight % and isoprene monomer unit is 20-85 weights
Measure %.
In the more preferred of the present invention, before bromination, the total weight based on base block copolymer, styrene
Monomeric unit is 10-40 weight %, and butadiene monomer unit is 5-20 weight % and isoprene monomer unit is 40-85 weights
Measure %.
In present invention further optimization embodiment, before bromination, the total weight based on base block copolymer, benzene
Ethylene monomer unit is 10-40 weight %, and butadiene monomer unit is 5-15 weight % and isoprene monomer unit is 45-
85 weight %.
In a preferred embodiment of the invention, before bromination, 1, the 2- butadiene structure lists in base block copolymer
Content of the member in butadiene monomer unit is no more than 15 weight %.
In a preferred embodiment of the invention, before bromination, 3, the 4- isoprene structures in base block copolymer
Content of the unit in isoprene monomer unit is no more than 15 weight %.
In a preferred embodiment of the invention, number-average molecular weight of the base block copolymer before bromination is 5 × 104-
50×104G/mol, preferably 5 × 104-30×104g/mol。
In a preferred embodiment of the invention, after by base block copolymer bromination, isoprene monomer unit institute
At least 50 moles of % of the unsaturated carbon-carbon double bond contained, such as 50-85 moles of % are brominated.
In the more preferred of the present invention, after by base block copolymer bromination, isoprene monomer unit
At least 60 moles of % of contained unsaturated carbon-carbon double bond, such as 60-95 moles of % are brominated.
The brominated block copolymer of the present invention has excellent thermal stability, this is helped to ensure that will be described brominated embedding
Section copolymer will not bring adverse effect due to thermal stability difference when being used as fire retardant to using its product.Thermal stability is general
It is characterized with 5% weightless temperature.5% weightless temperature refers to temperature during 5 weight % of loss.The brominated block copolymer of the present invention
5% weightless temperature is generally higher than 200 DEG C.
The brominated block copolymer of the present invention because having styrenic monomer units, butadiene monomer unit and isoamyl two simultaneously
Alkene monomer unit and there are the good compatibilities with other polymer during processed and applied, simultaneously as there are still contain
There are the butadiene and isoprene monomer unit of unsaturated carbon-carbon double bond, therefore be unlikely in process because of viscosity change too
Influence its processing performance greatly.Under given melting temperature, the melt viscosity of the brominated block copolymer is started with melting
When viscosity for radix, in the case of 15 minutes, melt viscosity relative value is 0.80-1.25.
According to another aspect of the present invention, a kind of method for preparing brominated block copolymer, the method bag are provided
Include formula S1-IS1-I1-BI1-B-BI2-I2-IS2-S2Solution and the bromating agent of base block copolymer react.
Present inventor is had found the isoprene monomer in the block copolymer of styrene, butadiene and isoprene
Unit preference bromination is to prepare a kind of effective way of macromolecular bromide flame retardant.Specifically, by formula S1-
IS1-I1-BI1-B-BI2-I2-IS2-S2Base block copolymer it is brominated during, bromination reaction is preferentially happened at trapezoidal common
On isoprene monomer unit in poly block IS, isoprene block I and trapezoidal copolymerized block BI, it can avoid or at least portion
Divide and avoid the butadiene monomer unit bromination in trapezoidal copolymerized block BI and butadiene block B.
As brominated base block copolymer is treated, it can be prepared by a conventional method, specifically refer to anionic polymerisation
Theory and application；Xue Lianbao, Golden Customs are safe；China Friendship Publishing Co.；December nineteen ninety.
In the present invention, base block copolymer can be prepared as follows：Add in butadiene list in a solvent first
Body, isoprene monomer, styrene monomer and structure regulator if necessary, add in after system temperature reaches design temperature
After bifunctional polymerization initiator, fully reaction, it is eventually adding terminator and terminates reaction.As solvent, usually using nonpolar molten
Agent includes but not limited to (ring) alkanes, such as pentane, hexane, heptane, hexamethylene or its mixture or aromatic hydrocarbons, such as
Benzene or alkylbenzene.As bifunctional polymerization initiator, usually using difunctional alkyl's lithium initiator, include but not limited to two lithium fourths
Alkane and Chinese patent application disclose difunctional alkyl's lithium described in 1145367 A of CN, are incorporated into herein by quoting herein
In.It as terminator, can be used alcohols material, such as methanol and isopropanol or water be directly used as terminator.Butadiene and
The microstructure of isoprene monomer unit, i.e. 1,2- structural units and the respective relative scale of 3,4- structural unit, can pass through
Structure regulator is adjusted.Structure regulator be selected generally from it is oxygen-containing, nitrogenous, containing Phosphorus polar compound and metal alkoxides chemical combination
One or more in object, for example, tetrahydrofuran, ether, glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether,
Diethylene glycol diethyl ether, crown ether, triethylamine, N, N- tetramethylethylenediamines, dipiperidinoethane, hexamethylphosphoramide, the tert-butyl alcohol
Potassium etc..Solvent, bifunctional polymerization initiator, the dosage of structure regulator and terminator are conventional, and can be by art technology
Personnel are readily determined.Polymerization initiating temperature is generally 0-120 DEG C.
In embodiments of the invention, the total weight based on base block copolymer, the benzene in base block copolymer
Ethylene monomer unit is 10-50 weight %, preferably 10-40 weight %.In embodiments of the invention, it is total to based on base block
The total weight of polymers, the butadiene monomer unit in base block copolymer are 5-30 weight %, preferably 5-20 weight %, more excellent
Select 5-15 weight %.In embodiments of the invention, the total weight based on base block copolymer, in base block copolymer
Isoprene monomer unit for 20-85 weight %, preferably 40-85 weight %, more preferable 45-85 weight %.Have to the present invention
Sharp, content of 1, the 2- butadiene structural units in butadiene monomer unit does not surpass generally in gained base block copolymer
15 weight % are crossed, content of 3, the 4- isoprene structures units in isoprene monomer unit is usually no more than 15 weight %.
Advantageously, the number-average molecular weight of base block copolymer is 5 × 104-50×104G/mol, preferably 5 × 104-30
×104g/mol。
As the solvent that base block copolymer is dissolved before bromination, include but not limited to ethers, such as tetrahydrofuran and 1,
4- dioxane；Hydro carbons, such as pentane, hexane, hexamethylene, benzene and toluene；Halogenated hydrocarbons, such as monochloro methane, dichloromethane, three
Chloromethanes and carbon tetrachloride；Halogenated aryl hydrocarbon, such as chlorobenzene and bromobenzene；And the mixture of above-mentioned solvent.The dosage of the solvent
It is conventional in this field.
As bromating agent, it is preferable to use bromine or bromine solutions, especially bromine solutions, because bromine is relatively close at 20 DEG C
It spends for 3.119g/mL, and the density of the solution of base block copolymer is generally 1.0g/mL or so, the two density difference is too big
So that it is unfavorable for the mixing of reactant and disperses.Bromine solutions include bromine water and bromine in other solvents such as carbon tetrachloride in addition to water
In solution.It is preferred that the solvent is identical with dissolving base block copolymer solvent for use.The concentration of bromine solutions is generally 1-50
Weight %, preferably 5-30 weight %.The concentration of bromine solutions is too low can be so that reactant concentration final in reaction system be too low, no
Beneficial to the progress of reaction, but also the increase of solvent recovery cost can be caused；Concentration is too high, is likely to cause bromine solutions layering.
In order to obtain the brominated block copolymer of the present invention, it is advantageous to which the dosage of bromating agent should cause in terms of molecular bromine
The molar ratio of unsaturated carbon-carbon double bond of the bromating agent contained by with all isoprene monomer units in base block copolymer is
0.5-2.0, preferably 0.8-1.5.
The reaction temperature of solution and bromating agent to base block copolymer is not particularly limited, but usually unsuitable excessively high,
And it is advisable with 0-60 DEG C.Bromination temperature is too low, and reaction mixture viscosity is too big, and energy consumption increases, and mixing difficulty also increases；Bromination temperature
Du Taigao, side reaction substantially increase.
With the increase of bromination reaction degree, in some cases, bromination reaction product may gradually be precipitated.This
In the case of, it is necessary to continuously stir.If stirring is insufficient, product local excessive bromination will be caused, and then causes final product
Heat resistance and processed and applied performance be substantially deteriorated.
After the completion of bromination reaction, reducing agent and neutralizer are added in into reaction mixture.Reducing agent is used for remaining bromine
Agent reduces, and may be selected from sulphite such as sodium sulfite, sodium hydrogensulfite, sodium pyrosulfite or nitrite such as nitrous acid
Sodium.The dosage of reducing agent is generally calculated as bromating agent molal quantity usually it is ensured that remaining bromating agent is completely reduced with molecular bromine
0.1-1.5 times.The addition of reducing agent is very little, and reduction is incomplete, and product is apt to deteriorate after the drying；Reducing agent adds in too many
It will cause wastes, are unfavorable for cost control and wastewater treatment.Neutralizer is generally alkaline matter, preferred as alkali or alkaline earth gold
The hydroxide of category, such as sodium hydroxide and potassium hydroxide etc., especially sodium hydroxide.Neutralizer can also be alkali metal or alkali
The salt of weak acid of earth metal, such as sodium acid carbonate, saleratus, sodium carbonate, potassium carbonate and calcium carbonate etc..The dosage of neutralizer is usual
It is ensured that the hydrogen bromide that reduction generates is fully neutralized, 0.1-1.5 times of bromating agent molal quantity is generally calculated as with molecular bromine.It neutralizes
The addition of agent is very little, neutralizes not exclusively, product is apt to deteriorate after the drying；Neutralizer addition can then generate waste too much, no
Beneficial to cost control and wastewater treatment.Reducing agent and neutralizer usually add in form of an aqueous solutions.The dosage of water in aqueous solution
For the 10-30 weight % of reaction mixture.The addition of water is very little, and reduction and neutralization are incomplete, and product easily becomes after the drying
Matter；Water addition is then unfavorable for wastewater treatment too much.In addition, for solvent miscible with water such as tetrahydrofuran or Isosorbide-5-Nitrae-dioxy six
Ring, water, which adds in, is excessively easy to cause block copolymer precipitation, causes to reduce and neutralize not exclusively, product easily becomes in drying
Matter.
It is reducing with after the completion of neutralization reaction, water phase can be removed by settling, then washed repeatedly using deionized water
Final aqueous pH values are 7, to avoid the influence of remaining reducing agent and neutralizer to properties of product.After the completion of washing, antioxygen is added in
The auxiliary agents such as agent and stabilizer.Antioxidant is, for example, the common hindered phenol anti-oxidants of rubber industry, such as Irganox
1010th, Irganox 1076 and Irganox 1330.Stabilizer is, for example, epoxidized vegetable oil and stearate, such as epoxy soybean
Oil and calcium stearate.The dosage of antioxidant and stabilizer can according to actual needs be determined by those skilled in the art.Then take off
Except solvent and the brominated block copolymer of the dry acquisition present invention.
Controlled by the ratio to brominated isoprene monomer unit and butadiene monomer unit, for example, by the former
It is at least 40 moles of %, such as 40-80 moles of % to control, preferably at least 50 moles of %, such as 50-85 moles of %, more preferably extremely
The latter's control is at least 5 moles of %, and at most by few 60 moles of %, such as 60-95 moles of %, and at most 95 moles of %
40 moles of %, the brominated block copolymer of gained not only have excellent thermal stability and good compatible with other polymer
Property, and during processed and applied good processing performance is being shown due to its viscosity change is little.
Embodiment
The present invention is specifically described below with reference to embodiment, but the embodiment is not to scope of the invention structure
Into any restrictions.
Number-average molecular weight is measured by gel permeation chromatography.
Base block copolymer and brominated block are total to using Bruker AVANCE 400MHz nuclear magnetic resonances instrument
The structure of polymers is characterized.9.40 tesla of magnetic field intensity, sample pipe diameter 5mm, sample are molten with deuterochloroform at normal temperatures
Solution is configured to the solution of 2 weight %, using TMS as internal standard, tests at room temperature.
5% weightless temperature is measured using METTLER TG/DSC1.Specific procedure is：100 DEG C are warming up to first, and constant temperature 5 divides
Then clock is warming up to 600 DEG C in a nitrogen atmosphere with 10 DEG C/min of rate.
Using high temperature viscosity measuring instrument SNB-AI, (Shanghai Ni Run intelligence science and technology has the melt viscosity of brominated block copolymer
Limit company) it measures, wherein test temperature is 180 DEG C, viscosity based on melt viscosity during by 0 minute, with 5 minutes, 10 points
Clock and melt viscosity relative value at 15 minutes change to characterize melt viscosity variation.Melt viscosity and basis in the stipulated time
The ratio of viscosity shows that the viscosity change of melt is smaller closer to 1.
Embodiment 1
In 5L glass kettles, solvent hexamethylene 2000mL and butadiene 10g, isoprene 170g and styrene are added in
20g makes reaction system be warming up to 50 DEG C using water bath with thermostatic control, adds in the two lithium butane Li that active lithium concentration is 1.0mol/L afterwards
(CH2)4Li initiator 2.2mL keep 50 DEG C of water bath with thermostatic control to react 100 minutes, then add in methanol 0.1mL.It is obtained after removing solvent
Base block copolymer is obtained, number-average molecular weight is 9.8 × 104G/mol, 1,2- butadiene structural units account for divinylic monomer list
10.0 weight % of first total amount, 3,4- isoprene structures units account for 9.8 weight % of isoprene monomer unit total amount.
In the 10L stainless steel cauldrons for scribbling polytetrafluoroethyllining lining, gained base block copolymer is re-dissolved
The solution that concentration is 10 weight % is obtained in methylene chloride, is added dropwise (is equivalent to institute comprising bromine 400.0g under high velocity agitation
With 1.0 times of isoprene monomer molal quantity) dichloromethane solution 2000g, make reaction using water bath with thermostatic control during dropwise addition
System temperature is maintained at 10 DEG C, continues to stir the progress that reacts fully in 20 minutes after being added dropwise to complete.Then add in by deionized water
The aqueous solution that 600g, sodium hydroxide 63.8g and sodium sulfite 82.5g are configured to is sufficiently stirred 20 minutes.Reaction mixture sat
Sedimentation, is separated off water phase and solid residue, the solution of the brominated block copolymer of gained is washed with deionized water repeatedly to
PH is neutrality, adds in calcium stearate 7.8g, 1010 0.8g of epoxidized soybean oil 7.8g and Irganox, finally removes solvent and does
It is dry, obtain the brominated block copolymer of required product.
Nuclear magnetic resonance result shows that 10.9 moles of % butadiene monomer units are brominated in product, 80.2 moles of % isoamyls
Diene monomer unit is brominated；5% weightless temperature of brominated product is 215.0 DEG C.The relative viscosity of product changes such as 1 institute of table
Show.
Embodiment 2
In 5L glass kettles, solvent hexamethylene 2000mL and butadiene 20g, isoprene 160g and styrene are added in
20g makes reaction system be warming up to 50 DEG C using water bath with thermostatic control, adds in the two lithium butane Li that active lithium concentration is 1.0mol/L afterwards
(CH2)4Li initiator 4.2mL keep 50 DEG C of water bath with thermostatic control to react 100 minutes, then add in methanol 0.1mL.It is obtained after removing solvent
Base block copolymer is obtained, number-average molecular weight is 5.2 × 104G/mol, 1,2- butadiene structural units account for divinylic monomer list
9.7 weight % of first total amount, 3,4- isoprene structures units account for 9.1 weight % of isoprene monomer unit total amount.
In the 10L stainless steel cauldrons for scribbling polytetrafluoroethyllining lining, gained base block copolymer is re-dissolved
The solution that concentration is 10 weight % is obtained in chloroform, is added dropwise (is equivalent to institute comprising bromine 564.7g under high velocity agitation
With 1.5 times of isoprene monomer molal quantity) chloroform soln 3000g, make reaction using water bath with thermostatic control during dropwise addition
System temperature is maintained at 10 DEG C, continues to stir the progress that reacts fully in 20 minutes after being added dropwise to complete.Then add in by deionized water
The aqueous solution that 1000g, sodium hydroxide 129.7g and sodium sulfite 215.3g are configured to is sufficiently stirred 20 minutes.Reaction is mixed
Object standing sedimentation is separated off water phase and solid residue, by the solution of the brominated block copolymer of gained with deionized water repeatedly
Washing is neutrality to pH, adds in calcium stearate 8.4g, 1010 0.8g of epoxidized soybean oil 8.4g and Irganox, finally removes molten
Agent and drying obtain the brominated block copolymer of required product.
Nuclear magnetic resonance result shows that 33.3 moles of % butadiene monomer units are brominated in product, 92.1 moles of % isoamyls
Diene monomer unit is brominated；5% weightless temperature of brominated product is 209.7 DEG C.The relative viscosity of product changes such as 1 institute of table
Show.
Embodiment 3
In 5L glass kettles, solvent hexamethylene 2000mL and butadiene 30g, isoprene 140g and styrene are added in
30g makes system be warming up to 50 DEG C using water bath with thermostatic control, adds in the two lithium butane Li that active lithium concentration is 1.0mol/L afterwards
(CH2)4Li initiator 1.2mL keep 50 DEG C of water bath with thermostatic control to react 100 minutes, add in methanol 0.1mL afterwards.It is obtained after removing solvent
Base block copolymer is obtained, number-average molecular weight is 20.3 × 104G/mol, 1,2- butadiene structural units account for divinylic monomer
9.2 weight % of unit total amount, 3,4- isoprene structures units account for 9.6 weight % of isoprene monomer unit total amount.
In the 10L stainless steel cauldrons for scribbling polytetrafluoroethyllining lining, gained base block copolymer is re-dissolved
The solution that concentration is 10 weight % is obtained in tetrahydrofuran, is added dropwise (is equivalent to institute comprising bromine 395.3g under high velocity agitation
With 1.2 times of isoprene monomer molal quantity) tetrahydrofuran solution 3000g, make reaction using water bath with thermostatic control during dropwise addition
System temperature is maintained at 10 DEG C, continues to stir the progress that reacts fully in 20 minutes after being added dropwise to complete.Then add in by deionized water
The aqueous solution that 600g, sodium hydroxide 65.7g and sodium hydrogensulfite 93.9g are configured to is sufficiently stirred 20 minutes.By reaction mixture
Standing sedimentation is separated off water phase and solid residue, and the solution of the brominated block copolymer of gained is washed repeatedly with deionized water
It is neutrality to wash to pH, adds in calcium stearate 7.5g, 1010 0.8g of epoxidized soybean oil 7.5g and Irganox, finally removes solvent
And drying, obtain the brominated block copolymer of required product.
Nuclear magnetic resonance result shows that 22.1 moles of % butadiene monomer units are brominated in product, 87.8 moles of % isoamyls
Diene monomer unit is brominated；5% weightless temperature of brominated product is 221.3 DEG C.The relative viscosity of product changes such as 1 institute of table
Show.
Embodiment 4
In 5L glass kettles, solvent hexamethylene 2000mL and butadiene 10g, isoprene 130g and styrene are added in
60g makes system be warming up to 50 DEG C using water bath with thermostatic control, adds in the two lithium butane Li that active lithium concentration is 1.0mol/L afterwards
(CH2)4Li initiator 2.2mL keep 50 DEG C of water bath with thermostatic control to react 100 minutes, add in methanol 0.1mL afterwards.It is obtained after removing solvent
Base block copolymer is obtained, number-average molecular weight is 9.5 × 104G/mol, 1,2- butadiene structural units account for divinylic monomer list
10.2 weight % of first total amount, 3,4- isoprene structures units account for 9.3 weight % of isoprene monomer unit total amount.
In the 10L stainless steel cauldrons for scribbling polytetrafluoroethyllining lining, gained base block copolymer is re-dissolved
The solution that concentration is 10 weight % is obtained in Isosorbide-5-Nitrae-dioxane, is added dropwise under high velocity agitation comprising bromine 244.7g (quite
In 0.8 times of isoprene monomer molal quantity used) Isosorbide-5-Nitrae-dioxane solution 2000g, be added dropwise during utilize thermostatted water
Bath makes temperature of reaction system be maintained at 10 DEG C, continues to stir the progress that reacts fully in 20 minutes after being added dropwise to complete.Then add in by
The aqueous solution that deionized water 600g, sodium hydroxide 35.2g and sodium hydrogensulfite 36.3g are configured to is sufficiently stirred 20 minutes.It will be anti-
Mixture standing sedimentation is answered, is separated off water phase and solid residue, by the solution deionization of the brominated block copolymer of gained
It is neutrality that water, which is washed repeatedly to pH, adds in calcium stearate 5.8g, 1010 0.6g of epoxidized soybean oil 5.8g and Irganox, finally
Solvent and drying are removed, obtains the brominated block copolymer of required product.
Nuclear magnetic resonance result shows that 6.9 moles of % butadiene monomer units are brominated in product, 68.4 moles of % isoamyls two
Alkene monomer unit is brominated；5% weightless temperature of brominated product is 242.2 DEG C.The relative viscosity variation of product is as shown in table 1.
Embodiment 5
In 5L glass kettles, solvent hexamethylene 2000mL and butadiene 10g, isoprene 130g and styrene are added in
60g makes system be warming up to 50 DEG C using water bath with thermostatic control, adds in the two lithium butane Li that active lithium concentration is 1.0mol/L afterwards
(CH2)4Li initiator 2.2mL keep 50 DEG C of water bath with thermostatic control to react 100 minutes, add in methanol 0.1mL afterwards.It is obtained after removing solvent
Base block copolymer is obtained, number-average molecular weight is 9.8 × 104G/mol, 1,2- butadiene structural units account for divinylic monomer list
9.2 weight % of first total amount, 3,4- isoprene structures units account for 10.3 weight % of isoprene monomer unit total amount.
In the 10L stainless steel cauldrons for scribbling polytetrafluoroethyllining lining, gained base block copolymer is re-dissolved
The solution that concentration is 10 weight % is obtained in hexamethylene, is added dropwise (is equivalent to used comprising bromine 305.9g under high velocity agitation
1.0 times of isoprene monomer molal quantity) cyclohexane solution 2000g, make reaction system using water bath with thermostatic control during dropwise addition
Temperature is maintained at 10 DEG C, continues to stir the progress that reacts fully in 20 minutes after being added dropwise to complete.Then add in by deionized water 600g,
The aqueous solution that sodium hydroxide 41.2g and sodium hydrogensulfite 48.1g are configured to is sufficiently stirred 20 minutes.By reaction mixture sat
Sedimentation, is separated off water phase and solid residue, the solution of the brominated block copolymer of gained is washed with deionized water repeatedly to
PH is neutrality, adds in calcium stearate 5.8g, 1010 0.6g of epoxidized soybean oil 5.8g and Irganox, finally removes solvent and does
It is dry, obtain the brominated block copolymer of required product.
Nuclear magnetic resonance result shows that 15.7 moles of % butadiene monomer units are brominated in product, 84.0 moles of % isoamyls
Diene monomer unit is brominated；5% weightless temperature of brominated product is 223.5 DEG C.The relative viscosity of product changes such as 1 institute of table
Show.
Comparative example 1
In 5L glass kettles, solvent hexamethylene 2000mL and butadiene 10g, isoprene 170g and styrene are added in
20g makes reaction system be warming up to 50 DEG C using water bath with thermostatic control, adds in the two lithium butane Li that active lithium concentration is 1.0mol/L afterwards
(CH2)4Li initiator 2.2mL keep 50 DEG C of water bath with thermostatic control to react 100 minutes, add in methanol 0.1mL afterwards.It is obtained after removing solvent
Base block copolymer is obtained, number-average molecular weight is 9.8 × 104G/mol, 1,2- butadiene structural units account for divinylic monomer list
10.3 weight % of first total amount, 3,4- isoprene structures units account for 10.1 weight % of isoprene monomer unit total amount.
In the 10L stainless steel cauldrons for scribbling polytetrafluoroethyllining lining, gained base block copolymer is re-dissolved
The solution that concentration is 10 weight % is obtained in methylene chloride, is added dropwise (is equivalent to institute comprising bromine 160.0g under high velocity agitation
With 0.4 times of isoprene monomer molal quantity) dichloromethane solution 1000g, make reaction using water bath with thermostatic control during dropwise addition
System temperature is maintained at 10 DEG C, continues to stir the progress that reacts fully in 20 minutes after being added dropwise to complete.Then add in by deionized water
The aqueous solution that 600g, sodium hydroxide 24.1g and sodium sulfite 21.0g are configured to is sufficiently stirred 20 minutes.Reaction mixture sat
Sedimentation, is separated off water phase and solid residue, the solution of the brominated block copolymer of gained is washed with deionized water repeatedly to
PH is neutrality, adds in calcium stearate 7.8g, 1010 0.8g of epoxidized soybean oil 7.8g and Irganox, finally removes solvent and does
It is dry, obtain the brominated block copolymer of required product.
Nuclear magnetic resonance result shows that 2.4 moles of % butadiene monomer units are brominated in product, 38.9 moles of % isoamyls two
Alkene monomer unit is brominated；5% weightless temperature of brominated product is 238.6 DEG C.The relative viscosity variation of product is as shown in table 1.
Comparative example 2
In 5L glass kettles, solvent hexamethylene 2000mL and butadiene 100g, isoprene 60g and styrene are added in
40g makes reaction system be warming up to 50 DEG C using water bath with thermostatic control, adds in the two lithium butane Li that active lithium concentration is 1.0mol/L afterwards
(CH2)4Li initiator 2.2mL keep 50 DEG C of water bath with thermostatic control to react 100 minutes, add in methanol 0.1mL afterwards.It is obtained after removing solvent
Base block copolymer is obtained, number-average molecular weight is 9.7 × 104G/mol, 1,2- butadiene structural units account for divinylic monomer list
9.7 weight % of first total amount, 3,4- isoprene structures units account for 9.8 weight % of isoprene monomer unit total amount.
In the 10L stainless steel cauldrons for scribbling polytetrafluoroethyllining lining, gained base block copolymer is re-dissolved
The solution that concentration is 10 weight % is obtained in methylene chloride, is added dropwise (is equivalent to institute comprising bromine 141.2g under high velocity agitation
With 1.0 times of isoprene monomer molal quantity) dichloromethane solution 1000g, make reaction using water bath with thermostatic control during dropwise addition
System temperature is maintained at 10 DEG C, continues to stir the progress that reacts fully in 20 minutes after being added dropwise to complete.Then add in by deionized water
The aqueous solution that 600g, sodium hydroxide 10.6g and sodium sulfite 28.5g are configured to is sufficiently stirred 20 minutes.Reaction mixture sat
Sedimentation, is separated off water phase and solid residue, the solution of the brominated block copolymer of gained is washed with deionized water repeatedly to
PH is neutrality, adds in calcium stearate 7.8g, 1010 0.8g of epoxidized soybean oil 7.8g and Irganox, finally removes solvent and does
It is dry, obtain the brominated block copolymer of required product.
Nuclear magnetic resonance result shows that 12.1 moles of % butadiene monomer units are brominated in product, 70.9 moles of % isoamyls
Diene monomer unit is brominated；5% weightless temperature of brominated product is 239.2 DEG C.The relative viscosity of product changes such as 1 institute of table
Show.
The structure composition of block copolymer and melt viscosity variation before and after 1. bromination of table
Claims (23)
1. a kind of brominated block copolymer, the brominated block copolymer is formula S before bromination1-IS1-I1-BI1-B-BI2-
I2-IS2-S2Base block copolymer, wherein S1And S2Each independently represent styrene block, IS1And IS2Independently
Represent the trapezoidal copolymerized block of isoprene and styrene, I1And I2Each independently represent isoprene block, BI1And BI2Respectively
From the trapezoidal copolymerized block for independently representing butadiene and isoprene, B represents butadiene block, by base block copolymer
After bromination, trapezoidal copolymerized block IS1And IS2, isoprene block I1And I2And trapezoidal copolymerized block BI1And BI2Middle isoamyl two
At least 40 moles of % of unsaturated carbon-carbon double bond contained by alkene monomer unit, and at most 95 moles of % are brominated；Trapezoidal copolymerization
B block I1And BI2And at least 5 moles of % of the unsaturated carbon-carbon double bond in butadiene block B contained by butadiene monomer unit,
And at most 40 moles of % are brominated,
Wherein before bromination, the total weight based on base block copolymer, styrenic monomer units be 10-40 weight %, fourth two
Alkene monomer unit is 5-20 weight % and isoprene monomer unit is 40-85 weight %.
2. brominated block copolymer according to claim 1, wherein after by base block copolymer bromination, trapezoidal copolymerization is embedding
Section IS1And IS2, isoprene block I1And I2And trapezoidal copolymerized block BI1And BI2Contained by middle isoprene monomer unit not
At least 50 moles of % of saturation carbon-carbon double bond and at most 95 moles of % are brominated.
3. brominated block copolymer according to claim 1, wherein after by base block copolymer bromination, trapezoidal copolymerization is embedding
Section IS1And IS2, isoprene block I1And I2And trapezoidal copolymerized block BI1And BI2Contained by middle isoprene monomer unit not
At least 60 moles of % of saturation carbon-carbon double bond and at most 95 moles of % are brominated.
4. brominated block copolymer according to claim 1, wherein before bromination, the number-average molecular weight of base block copolymer
For 5 × 104-50×104g/mol。
5. brominated block copolymer according to claim 4, wherein before bromination, the number-average molecular weight of base block copolymer
For 5 × 104-30×104g/mol。
6. brominated block copolymer as claimed in one of claims 1-5 wherein before bromination, is copolymerized based on base block
The total weight of object, styrenic monomer units are 10-40 weight %, and butadiene monomer unit is 5-15 weight % and isoprene
Monomeric unit is 45-85 weight %.
7. brominated block copolymer as claimed in one of claims 1-5, wherein S1And S2Represent that identical styrene is embedding
Section and/or IS1And IS2Represent the trapezoidal copolymerized block and/or I of identical isoprene and styrene1And I2Represent identical
Isoprene block and/or BI1And BI2Represent the trapezoidal copolymerized block of identical butadiene and isoprene.
8. brominated block copolymer according to claim 6, wherein S1And S2Represent identical styrene block and/or IS1
And IS2Represent the trapezoidal copolymerized block and/or I of identical isoprene and styrene1And I2Represent that identical isoprene is embedding
Section and/or BI1And BI2Represent the trapezoidal copolymerized block of identical butadiene and isoprene.
9. a kind of method for preparing brominated block copolymer as claimed in one of claims 1-8, the described method includes make
Formula S1-IS1-I1-BI1-B-BI2-I2-IS2-S2Solution and the bromating agent of base block copolymer react.
10. the dosage of method according to claim 9, wherein bromating agent so that bromating agent is copolymerized with base block in terms of molecular bromine
The molar ratio of unsaturated carbon-carbon double bond in object contained by all isoprene monomer units is 0.5-2.0.
11. the dosage of method according to claim 10, wherein bromating agent so that bromating agent is total to base block in terms of molecular bromine
The molar ratio of unsaturated carbon-carbon double bond in polymers contained by all isoprene monomer units is 0.8-1.5.
12. according to the method for any one of claim 9-11, the solution solvent for use of wherein base block copolymer include but
It is not limited to ethers；Hydro carbons；Halogenated hydrocarbons；Halogenated aryl hydrocarbon；And the mixture of above-mentioned solvent.
13. method according to claim 12, wherein the ethers is tetrahydrofuran and Isosorbide-5-Nitrae-dioxane；The hydro carbons is penta
Alkane, hexane, hexamethylene, benzene and toluene；The halogenated hydrocarbons is monochloro methane, dichloromethane, chloroform and carbon tetrachloride；It is described
Halogenated aryl hydrocarbon is chlorobenzene and bromobenzene.
14. according to the method for any one of claim 9-11, wherein bromating agent is bromine.
15. according to the method for any one of claim 9-11, wherein bromating agent is bromine solutions.
16. method according to claim 15, wherein the bromine solutions use it is identical with the solution of base block copolymer molten
Agent.
17. according to the method for any one of claim 9-11, the method is additionally included in after the completion of bromination reaction, mixed to reaction
It closes and reducing agent and neutralizer is added in object.
18. method according to claim 17, wherein adding in reducing agent and neutralization into reaction mixture in form of an aqueous solutions
Agent.
19. method according to claim 17, wherein reducing agent are selected from sulphite or nitrite.
20. method according to claim 19, wherein the sulphite is sodium sulfite, sodium hydrogensulfite and pyrosulfurous acid
Sodium, the nitrite are sodium nitrite.
21. method according to claim 17, wherein neutralizer are alkaline matter.
22. method according to claim 21, wherein hydroxide, alkali gold of the alkaline matter for alkali or alkaline earth metal
The salt of weak acid of category or alkaline-earth metal.
23. method according to claim 22, wherein alkali metal hydroxide are sodium hydroxide and potassium hydroxide；Alkali metal or alkali
Earth metal salt of weak acid is sodium acid carbonate, saleratus, sodium carbonate, potassium carbonate and calcium carbonate.
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| 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 |
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| 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 |
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| CN1242382A (en) * | 1999-07-28 | 2000-01-26 | 北京燕山石油化工公司研究院 | Nine block copolymer of butadiene, isoprene and styrene, and method for prepn. of same |
| US6518368B2 (en) * | 1996-06-14 | 2003-02-11 | Albemarle Corporation | Brominated polystyrene having improved thermal stability and color and process for the preparation thereof |
| CN101501076A (en) * | 2006-08-16 | 2009-08-05 | 陶氏环球技术公司 | Process for brominating butadiene/vinyl aromatic copolymers |
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| JPH03227370A (en) * | 1990-01-31 | 1991-10-08 | Dainippon Ink & Chem Inc | Flame-retardant masterbatch |
| US6518368B2 (en) * | 1996-06-14 | 2003-02-11 | Albemarle Corporation | Brominated polystyrene having improved thermal stability and color and process for the preparation thereof |
| CN1242382A (en) * | 1999-07-28 | 2000-01-26 | 北京燕山石油化工公司研究院 | Nine block copolymer of butadiene, isoprene and styrene, and method for prepn. of same |
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