CN106243250A - Control method of solution method butyl rubber bromination structure - Google Patents
Control method of solution method butyl rubber bromination structure Download PDFInfo
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- CN106243250A CN106243250A CN201510303041.2A CN201510303041A CN106243250A CN 106243250 A CN106243250 A CN 106243250A CN 201510303041 A CN201510303041 A CN 201510303041A CN 106243250 A CN106243250 A CN 106243250A
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- China
- Prior art keywords
- butyl rubber
- bromo
- solution
- bromine
- control method
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Links
- 238000000034 method Methods 0.000 title claims abstract description 90
- 229920005549 butyl rubber Polymers 0.000 title claims abstract description 69
- 238000005893 bromination reaction Methods 0.000 title claims abstract description 29
- 230000031709 bromination Effects 0.000 title abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 61
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 57
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 56
- 239000003292 glue Substances 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000001590 oxidative effect Effects 0.000 claims abstract description 14
- 239000003381 stabilizer Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 230000007935 neutral effect Effects 0.000 claims abstract description 11
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 8
- 238000002347 injection Methods 0.000 claims abstract description 8
- 239000007924 injection Substances 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 5
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 4
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 4
- 125000001246 bromo group Chemical group Br* 0.000 claims description 69
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 16
- 239000012046 mixed solvent Substances 0.000 claims description 15
- 238000009835 boiling Methods 0.000 claims description 11
- 230000018044 dehydration Effects 0.000 claims description 11
- 238000006297 dehydration reaction Methods 0.000 claims description 11
- 230000003472 neutralizing effect Effects 0.000 claims description 11
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical group [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims description 8
- ISSUNVDQFLJNRZ-UHFFFAOYSA-N CCCCCC.[Br] Chemical compound CCCCCC.[Br] ISSUNVDQFLJNRZ-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 235000019359 magnesium stearate Nutrition 0.000 claims description 3
- 235000012424 soybean oil Nutrition 0.000 claims description 3
- 239000003549 soybean oil Substances 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 claims description 2
- 238000007701 flash-distillation Methods 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- XIVNZHXRIPJOIZ-UHFFFAOYSA-N octadecanoic acid;zinc Chemical compound [Zn].CCCCCCCCCCCCCCCCCC(O)=O XIVNZHXRIPJOIZ-UHFFFAOYSA-N 0.000 claims 1
- NRTLTGGGUQIRRT-UHFFFAOYSA-N triethylazanium;bromide Chemical compound [Br-].CC[NH+](CC)CC NRTLTGGGUQIRRT-UHFFFAOYSA-N 0.000 claims 1
- 239000012752 auxiliary agent Substances 0.000 abstract description 9
- 229920001971 elastomer Polymers 0.000 abstract description 7
- 238000005406 washing Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract description 3
- -1 liquid bromine alkane Chemical class 0.000 abstract description 3
- 238000007865 diluting Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 239000006184 cosolvent Substances 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 73
- 125000000746 allylic group Chemical group 0.000 description 25
- 238000003860 storage Methods 0.000 description 18
- 238000005516 engineering process Methods 0.000 description 12
- 108010010803 Gelatin Proteins 0.000 description 11
- 229920000159 gelatin Polymers 0.000 description 11
- 239000008273 gelatin Substances 0.000 description 11
- 235000019322 gelatine Nutrition 0.000 description 11
- 235000011852 gelatine desserts Nutrition 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 8
- 230000004044 response Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 6
- 235000013539 calcium stearate Nutrition 0.000 description 6
- 239000008116 calcium stearate Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 230000001186 cumulative effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 description 3
- 229920005557 bromobutyl Polymers 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 235000003642 hunger Nutrition 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000010092 rubber production Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for effectively controlling bromination substitution position of solution-process butyl rubber, which comprises the steps of firstly removing unreacted monomers in a butyl rubber glue solution synthesized by a solution process, adding a cosolvent consisting of alkane and an electrophilic reagent in a certain proportion, diluting the butyl rubber glue solution to a certain concentration, adding a strong oxidizing reagent solution, uniformly mixing, then adding a liquid bromine alkane solution into a reaction kettle by a multipoint injection method for bromination reaction, adding alkali liquor after the reaction is finished, stopping, and washing with water to be neutral; adding a brominated structure regulator to adjust three microstructures; and finally, adding auxiliary agents such as a structural stabilizer, an antioxidant, a deacidification agent and the like, and performing post-treatment to obtain a product, wherein the relative content of the brominated secondary allyl structure is more than 70%, the content of the brominated primary allyl structure is less than 20%, and various performances such as bromine content, unsaturation degree, Mooney viscosity and the like meet the use requirements of an inner tube air-tight layer of an automobile tire, a medical rubber plug and the like.
Description
Technical field
The present invention relates to a kind of solwution method brombutyl and replace the control method of position, the method can effectively be controlled
The relative scale of three kinds of microstructures in brombutyl processed.
Background technology
Along with domestic tire meridian, tubeless and the butylated fast development of medical rubber stopper, China is to bromine
Change the demand sustainable growth of butyl rubber.The Apparent con-sumption of China's brombutyl in 2007 is only
12.50 ten thousand t, increase to 17.51 ten thousand t for 2011, within 2012 and 2013, increase respectively to 18.82 further
Ten thousand t and 20.15 ten thousand t.Within 2013, Chinese brombutyl import volume increases about 59% in relatively 2007,
Average annual amplification is about 8%.The corresponding product degree of self-sufficiency is developed into 2013 by the import that is completely dependent on of 2007
About the 7% of year, the product degree of self-sufficiency is relatively low.
Within 2013, China's brombutyl is in the Supply Structure of low and middle-end field and high-end field, the Yanshan Mountain
Petrochemical industry and Zhejiang mail transfer company occupy the supply ratio in low and middle-end field 47%, and contour at curing bag
End application is substantially by occupied by external bright Sheng and Exxon Corporation.Therefore, novel bromination fourth is developed
Base rubber production technology, produces high-quality brombutyl, fills up domestic market blank, reduces abroad
The dependence of imported product, the popularization and application to domestic brombutyl is following have important practical significance.
The bromination reaction of butyl rubber is mainly carried out by ion-type substitution reaction course, and first molecular bromine is by alkene
Double bond polarization on hydrocarbon forms positive and negative ion, and the double bond of the butyl rubber of Bromonium ion attack afterwards forms transition
State bromide ion.Owing to the steric hindrance of methyl makes bromine anion stalled offence on side chain, cause transition state
Lose H+Generate, form bromo secondary position allylic structure, generate little molecule hydrogen bromide simultaneously.Owing to bromo is secondary
Position allylic structure is unstable, it is easy to occur rearrangement reaction to be transformed into bromo uncle position allylic structure.Bromination fourth
Base rubber exists non-bromination, bromo uncle's position pi-allyl and the three kinds of microstructures of pi-allyl of bromo secondary position.Due to
The brombutyl that bromo uncle position allylic structure relative amount is high has vulcanization reaction speed faster, but
Also reduce the mooney scorch safety of rubber simultaneously, and bromo secondary position allylic structure is the most in contrast.
Therefore, commercial production needs strictly control the relative scale of three kinds of microstructures in brombutyl, from
And prepare high performance brombutyl product.
Summary of the invention
In order to develop novel brombutyl production technology, produce high-quality brombutyl, to fill out
Mending the dependence that domestic market is blank, minimizing is to external imported product, the present invention proposes a kind of effective solution
The control method of method butyl rubber bromo structure, can realize continuous, efficient and stable preparing three kinds of microcosmic
The brombutyl product that structure proportion is the most qualified.
The present invention provides the control method of a kind of solwution method butyl rubber bromo structure, comprises the following steps:
A () synthesizes butyl rubber glue, heated and stirred in 40～80 DEG C of waters bath with thermostatic control by solwution method
0.5～6h, unreacted monomer in removing glue；
B () adds electrophilicity reagent in the synthesis butyl rubber glue remove unreacted monomer, afterwards
Add strong oxidizing property reagent；
C () adds the alkane solution of bromine in reactor and carries out bromination reaction；
D () bromination reaction terminates after, the NaOH solution adding mass fraction 1.0～20wt% terminates reaction,
Stop stirring after neutralizing reaction 5～30min, glue is washed with distilled water to pH value close to neutral；
E () adds structure regulator in the glue that step (d) obtains；
F () adds bromo structural stabilizing agent, antioxidant and deacidification agent in the glue that step (e) obtains；
G () adds boiling water in the glue that step (f) obtains, solvent flash distillation removed subsequently, and gained produces
The post-treated dehydration of thing, be dried and extruding in bulk after obtain product.
The control method of solwution method butyl rubber bromo structure of the present invention, wherein, in step (b)
The concentration synthesizing butyl rubber glue with mixed solvent after diluting is preferably 10～40wt%.
The control method of solwution method butyl rubber bromo structure of the present invention, wherein, in step (b),
Electrophilicity reagent contained by mixed solvent accounts for the ratio of total solvent volume and is preferably not greater than 50% and is not
0。
The control method of solwution method butyl rubber bromo structure of the present invention, wherein, in step (b),
Electrophilicity reagent is preferably dichloromethane, dichloroethanes, oxirane, pyridine or N, N-dimethyl formyl
Amine.
The control method of solwution method butyl rubber bromo structure of the present invention, wherein, in step (b),
The strong oxidizing property reagent added in synthesis butyl rubber glue, its consumption is preferably the 0.1～5 of bromine molal quantity
Times.
The control method of solwution method butyl rubber bromo structure of the present invention, wherein, in step (b),
Strong oxidizing property reagent is preferably potassium dichromate, sodium metaperiodate, potassium permanganate or hydrogen peroxide.
The control method of solwution method butyl rubber bromo structure of the present invention, wherein, in step (c),
The alkane solution of bromine is preferably the bromine hexane solution of 0.1～3mol/L.
The control method of solwution method butyl rubber bromo structure of the present invention, wherein, in step (c),
Bromine solution is preferably added by multiple spot injection method under the conditions of normal pressure lucifuge.
The control method of solwution method butyl rubber bromo structure of the present invention, wherein, in step (e),
The consumption of structure regulator preferably accounts for the mass percent 0.5～3% of brombutyl, after addition
10～90 DEG C of stirring reactions 5～30min.
The control method of solwution method butyl rubber bromo structure of the present invention, wherein, in step (e),
Structure regulator is preferably tetrabutyl ammonium bromide, tetraethylammonium bromide, benzyl triethyl ammonium bromide or triphenyl
Phosphine.
The control method of solwution method butyl rubber bromo structure of the present invention, wherein, in step (f),
Bromo structural stabilizing agent adds in the glue that step (e) obtains after being dissolved in mineral oil, bromo Stability Analysis of Structures
The consumption of agent preferably accounts for the mass percent 0.1～3.0% of brombutyl.
The control method of solwution method butyl rubber bromo structure of the present invention, wherein, in step (f),
Bromo structural stabilizing agent be preferably dibutyl tin laurate, zinc stearate, magnesium stearate, iron naphthenate or
Epoxy soybean oil.
There is advantages that
(1) the present invention relates to one and prepare bromination by solwution method synthesis butyl rubber glue direct bromination
The method of butyl rubber, it is to avoid what slurry processes technology prepares the solvent switching needed for brombutyl and sizing material
Dissolution process, simplify bromination reaction technique, reduce production cost；
(2) reaction dissolvent involved in the present invention adds a certain amount of electrophilicity reagent, accelerate bromination
Reaction rate, shortens the bromination reaction time, improves production efficiency；
(3) the invention discloses a kind of method that effective control solwution method butyl rubber bromination replaces position, with
Suppression bromo structure has secondary position to change to uncle position, efficiently, continuously and stably prepares the brominated butyl of high-quality
Rubber.
Detailed description of the invention
Hereinafter embodiments of the invention are elaborated: the present embodiment is premised on technical solution of the present invention
Under implement, give detailed embodiment and process, but protection scope of the present invention be not limited to following
Embodiment, the experimental technique of unreceipted actual conditions in the following example, generally according to normal condition.
The concentration of synthesis butyl rubber glue after dilution:
In the present invention, the concentration synthesizing butyl rubber glue after dilution is not particularly limited, generally with mixed
Bonding solvent will synthesize the concentration dilution of butyl rubber glue to 10～40wt%: if the synthesis fourth after Xi Shi
Base rubber gelatin concentration is less than 10wt%, owing to gelatin concentration is too low, easily causes and causes bromination after reaction
Butyl rubber Mooney viscosity reduces；If the synthesis butyl rubber gelatin concentration after Xi Shi is higher than 40wt%,
Owing to gelatin concentration is too high, viscosity is excessive, cause bromine and glue course of reaction mix uneven, synthesis
Bromine content of brominated butyl rubber on the low side, and structure proportion is defective.
Electrophilicity reagent accounts for the ratio of mixed solvent cumulative volume:
In the present invention, the ratio that electrophilicity reagent used is accounted for mixed solvent cumulative volume is not particularly limited,
Generally electrophilicity reagent accounts for the ratio of mixed solvent cumulative volume is 0～50%: if electrophilicity reagent accounts for mixing
The ratio of total solvent volume is 0, owing to not having electrophilicity reagent, easily causes bromo secondary position allyl
Based structures content reduces；If the ratio that electrophilicity reagent accounts for mixed solvent cumulative volume is more than 50%, due to
In solvent, electrophilicity ratio of reagents is too high, causes bromobutyl rubber structure ratio defective.
The consumption of strong oxidizing property reagent:
In the present invention, being not particularly limited the consumption of strong oxidizing property reagent used, usual strong oxidizing property is tried
The consumption of agent is 0.1～5 times of bromine molal quantity: if the consumption of strong oxidizing property reagent is less than bromine mole
0.1 times of number, owing to the consumption of strong oxidizing property reagent is very few, easily causes the unsaturation of brombutyl
Spend and increase along with the response time and reduce always；If the consumption of strong oxidizing property reagent is higher than bromine molal quantity
5 times, owing to the consumption of strong oxidizing property reagent is too much, after causing reaction, in glue, strong oxidizer remains more difficulty
In removing.
The concentration of bromine hexane solution:
In the present invention, being not particularly limited the concentration of bromine hexane solution used, usual bromine is just own
The concentration of alkane solution is 0.1～3mol/L: if the concentration of bromine hexane solution is less than 0.1mol/L, by
Too low in concentration, after easily causing bromination, bromine content of brominated butyl rubber is on the low side；If bromine hexane solution
Concentration higher than 3mol/L, due to excessive concentration, cause brombutyl degree of unsaturation to reduce, structure
Ratio is defective.
The consumption of structure regulator:
In the present invention, the consumption of structure regulator used is not particularly limited, usual structure regulator
It is 0.5～3% that consumption accounts for the mass percent of brombutyl: if the consumption of structure regulator accounts for bromination
The mass percent of butyl rubber is less than 0.5%, owing to the consumption of structure regulator is very few, easily causes tune
Joint structural response is insufficient, does not reaches the purpose of effective adjustment structure；If the consumption of structure regulator accounts for bromine
The mass percent changing butyl rubber is higher than 3%, owing to the consumption of structure regulator is too much, causes and produces into
This rising, and easily affect the performance of final products.
Temperature when structure regulator adds:
In the present invention, temperature when adding structure regulator is not particularly limited, usual structure regulator
Temperature during interpolation is 10～90 DEG C: if temperature is less than 10 DEG C, owing to reaction temperature is relatively low, easily make
Become adjustment structure reaction rate relatively low, add the time cost of reaction；If temperature is higher than 90 DEG C, by
Too high in reaction temperature, cause by bromo secondary position allylic structure to the transformation of bromo uncle position allylic structure.
The response time of adjustment structure:
In the present invention, the response time of adjustment structure is not particularly limited, the reaction of usual adjustment structure
Time is 5～30min: if the response time of adjustment structure is less than 5min, owing to the response time is too short,
Easily cause adjustment structure reaction insufficient, do not reach the purpose of effective adjustment structure；If adjustment structure
Response time is more than 30min, owing to the response time is long, causes the rising of time cost, and there is no other
Beneficial effect.
The consumption of bromo structural stabilizing agent:
In the present invention, the consumption of bromo structural stabilizing agent used is not particularly limited, usual bromo structure
It is 0.1～3% that the consumption of stabilizer accounts for the mass percent of brombutyl: if bromo structural stabilizing agent
Consumption account for the mass percent of brombutyl less than 0.1%, owing to the consumption of structure regulator is very few,
Do not reach the purpose of the bromo structure of substantially stabilized final products；If the consumption of bromo structural stabilizing agent accounts for bromine
The mass percent changing butyl rubber is more than 3%, owing to the consumption of bromo structural stabilizing agent is too much, causes life
Produce the rising of cost, and easily affect the performance of final products.
7 embodiments being set forth below, is further illustrated with the present invention, it is real that the present invention is not limited solely to these
Execute example.
Embodiment 1:
Butyl rubber glue 2000mL solwution method synthesized adds in reactor, add normal hexane with
The mixed solvent of dichloroethanes composition, is diluted to 15% by gelatin concentration, and wherein to account for solution total for dichloroethanes
The 30% of volume, adds the potassium dichromate aqueous solution 100mL of 27.59g/L, the insatiable hunger of butyl rubber afterwards
It is 1.9% with degree；By the hexane solution 20mL (normal hexane is 25:1 with the volume ratio of bromine) of bromine
Add in storage tank；Temperature of charge in reactor is heated to 45 DEG C, is injected by multiple spot in reactor
Method adds the hexane solution of bromine in storage tank, after bromination reaction 2min, adds 400mL mass fraction
The NaOH solution of 1.5wt% terminates, and stops stirring after neutralizing reaction 15min；By glue distillation washing
Wash to pH value close to neutral, add the tetrabutyl ammonium bromide solution water solution 100mL of mass fraction 0.5%,
At 30 DEG C of stirring reaction 10min, it is eventually adding dibutyl tin laurate (2.0wt%), antioxidant 1010
(1.0wt%) and the auxiliary agents such as auxiliary agent such as deacidification agent calcium stearate (1.5wt%), add boiling water and flash off molten
Agent, after dehydration, being dried and extrude the aftertreatment technologys such as in bulk, bromine in the brombutyl product obtained
The relative amount of Dai Zhongwei allylic structure is 72%, and the relative amount of bromo uncle position allylic configuration is
16%, bromine content is 2.1wt%, degree of unsaturation 1.5%.
Embodiment 2:
Butyl rubber glue 3000mL solwution method synthesized adds in reactor, adds normal hexane and two
The mixed solvent of chloromethanes composition, is diluted to 10% by gelatin concentration, and wherein dichloromethane accounts for overall solution
Long-pending 50%, adds the potassium permanganate solution 150mL of 41.39g/L, the unsaturation of butyl rubber afterwards
Degree is 2.0%；The hexane solution 30mL (normal hexane is 20:1 with the volume ratio of bromine) of bromine is added
In storage tank；Temperature of charge in reactor is heated to 50 DEG C, is added by multiple spot injection method in reactor
Enter the hexane solution of bromine in storage tank, after bromination reaction 2.5min, add 400mL mass fraction
The NaOH solution of 2.0wt% terminates, and stops stirring after neutralizing reaction 20min；By glue distillation washing
Wash to pH value close to neutral, add the benzyl triethyl ammonium bromide aqueous solution 150mL of mass fraction 1.0%,
At 50 DEG C of stirring reaction 15min, it is eventually adding iron naphthenate (1.5wt%), antioxidant 1010 (1.0wt%)
With the auxiliary agent such as deacidification agent calcium stearate (1.5wt%), add boiling water and flash off solvent, through dehydration, be dried
And after extruding the aftertreatment technologys such as in bulk, bromo secondary position allylic structure in the brombutyl product obtained
Relative amount be 74%, bromo uncle position allylic configuration relative amount be 15%, bromine content is
2.2wt%, degree of unsaturation 1.6%.
Embodiment 3:
Butyl rubber glue 5000mL solwution method synthesized adds in reactor, add normal hexane with
The mixed solvent of dichloromethane composition, is diluted to 13% by gelatin concentration, and wherein to account for solution total for dichloromethane
The 40% of volume, adds the sodium metaperiodate aqueous solution 200mL of 38.79g/L, the insatiable hunger of butyl rubber afterwards
It is 1.8% with degree；The hexane solution 40mL (normal hexane is 19:1 with the volume ratio of bromine) of bromine is added
Enter in storage tank；Temperature of charge in reactor is heated to 40 DEG C, by multiple spot injection method in reactor
Add the alkane solution of bromine in storage tank, after bromination reaction 1.5min, add 400mL mass fraction
The NaOH solution of 2.5wt% terminates, and stops stirring after neutralizing reaction 10min；By glue distillation washing
Wash to pH value close to neutral, add the hexane solution 200mL of the triphenylphosphine of mass fraction 2.0%,
40 DEG C of stirring reaction 5min, are eventually adding magnesium stearate (2.0wt%), antioxidant 1010 (1.0wt%)
With the auxiliary agent such as deacidification agent calcium stearate (1.5wt%), add boiling water and flash off solvent, through dehydration, be dried
And after extruding the aftertreatment technologys such as in bulk, bromo secondary position allylic structure in the brombutyl product obtained
Relative amount be 71%, bromo uncle position allylic configuration relative amount be 14%, bromine content is
2.0wt%, degree of unsaturation 1.7%.
Embodiment 4:
Butyl rubber glue 5000mL solwution method synthesized adds in reactor, adds normal hexane and two
The mixed solvent of chloromethanes composition, is diluted to 17% by gelatin concentration, and wherein dichloromethane accounts for overall solution
Long-pending 40%, adds the hydrogen peroxide 20mL of concentration 30% afterwards, and the degree of unsaturation of butyl rubber is 1.8%；
The hexane solution 40mL (normal hexane is 19:1 with the volume ratio of bromine) of bromine is added in storage tank；Will
Temperature of charge in reactor is heated to 40 DEG C, adds liquid in storage tank by multiple spot injection method in reactor
The alkane solution of bromine, after bromination reaction 1.5min, adds the NaOH of 400mL mass fraction 2.5wt%
Solution (asking supplemental amount) terminates, and stops stirring after neutralizing reaction 10min；By glue distillation washing
Wash to pH value close to neutral, add the tetraethylammonium bromide aqueous solution 400mL of mass fraction 3.0%,
50 DEG C of stirring reaction 25min, are eventually adding zinc stearate (2.0wt%), antioxidant 1010 (1.0wt%)
With the auxiliary agent such as deacidification agent calcium stearate (1.5wt%), add boiling water and flash off solvent, through dehydration, be dried
And after extruding the aftertreatment technologys such as in bulk, bromo secondary position allylic structure in the brombutyl product obtained
Relative amount be 71%, bromo uncle position allylic configuration relative amount be 14%, bromine content is
1.9wt%, degree of unsaturation 1.65%.
Embodiment 5:
Butyl rubber glue 3000mL solwution method synthesized adds in reactor, add normal hexane with
The mixed solvent of oxirane composition, is diluted to 20% by gelatin concentration, and it is total that its ethylene oxide accounts for solution
The 30% of volume, adds the sodium metaperiodate aqueous solution 100mL of 21.39g/L, the insatiable hunger of butyl rubber afterwards
It is 2.0% with degree；By the hexane solution 100mL (normal hexane is 20:1 with the volume ratio of bromine) of bromine
Add in storage tank；Temperature of charge in reactor is heated to 50 DEG C, is injected by multiple spot in reactor
Method adds the hexane solution of bromine in storage tank, after bromination reaction 2.5min, adds 200mL mass fraction
The NaOH solution of 2.0wt% terminates, and stops stirring after neutralizing reaction 20min；By glue distillation washing
Wash to pH value close to neutral, add the benzyl triethyl ammonium bromide aqueous solution 150mL of mass fraction 1.0%,
At 10 DEG C of stirring reaction 15min, it is eventually adding epoxy soybean oil (3.0wt%), antioxidant 1010 (1.0wt%)
With the auxiliary agent such as deacidification agent calcium stearate (1.5wt%), add boiling water and flash off solvent, through dehydration, be dried
And after extruding the aftertreatment technologys such as in bulk, bromo secondary position allylic structure in the brombutyl product obtained
Relative amount be 74%, bromo uncle position allylic configuration relative amount be 15%, bromine content is
2.2wt%, degree of unsaturation 1.6%.
Embodiment 6:
Butyl rubber glue 3000mL solwution method synthesized adds in reactor, add normal hexane with
The mixed solvent of pyridine composition, is diluted to 40% by gelatin concentration, and wherein pyridine accounts for the 40% of overall solution volume,
Adding the potassium dichromate aqueous solution 500mL of 68.63g/L afterwards, the degree of unsaturation of butyl rubber is 2.0%；
The hexane solution 5mL (normal hexane is 16:7 with the volume ratio of bromine) of bromine is added in storage tank；Will
Temperature of charge in reactor is heated to 50 DEG C, adds liquid in storage tank by multiple spot injection method in reactor
The hexane solution of bromine, after bromination reaction 2.5min, adds the NaOH of 500mL mass fraction 2.0wt%
Solution terminates, and stops stirring after neutralizing reaction 20min；Glue is washed with distilled water to pH value close in
Property, add the tetrabutyl phosphonium bromide aqueous ammonium 150mL of mass fraction 1.0%, 90 DEG C of stirring reactions
15min, is eventually adding iron naphthenate (0.1wt%), antioxidant 1010 (1.0wt%) and deacidification agent stearic
The auxiliary agents such as acid calcium (1.5wt%), add boiling water and flash off solvent, through dehydration, are dried and extrude in bulk etc.
After aftertreatment technology, in the brombutyl product obtained, the relative amount of bromo secondary position allylic structure is
74%, the relative amount of bromo uncle position allylic configuration is 15%, and bromine content is 2.2wt%, degree of unsaturation
1.6%.
Embodiment 7:
Butyl rubber glue 3000mL solwution method synthesized adds in reactor, add normal hexane with
The mixed solvent of DMF composition, is diluted to 40% by gelatin concentration, wherein N, N-diformazan
Base Methanamide accounts for the 50% of overall solution volume, adds the potassium permanganate solution 300mL of 35.85g/L afterwards,
The degree of unsaturation of butyl rubber is 2.0%；By hexane solution 20mL (normal hexane and the body of bromine of bromine
Long-pending ratio is 13:8) add in storage tank；Temperature of charge in reactor is heated to 50 DEG C, in reactor
Add the hexane solution of bromine in storage tank by multiple spot injection method, after bromination reaction 2.5min, add 700
The NaOH solution of mL mass fraction 2.0wt% terminates, and stops stirring after neutralizing reaction 20min；By glue
It is close neutral that liquid is washed with distilled water to pH value, and the tetraethylammonium bromide adding mass fraction 1.0% is water-soluble
Liquid 150mL, at 70 DEG C of stirring reaction 15min, is eventually adding iron naphthenate (1.5wt%), antioxidant
The auxiliary agents such as 1010 (1.0wt%) and deacidification agent calcium stearate (1.5wt%), add boiling water and flash off solvent,
After dehydration, being dried and extrude the aftertreatment technologys such as in bulk, in the brombutyl product obtained, bromo is secondary
The relative amount of position allylic structure is 74%, and the relative amount of bromo uncle position allylic configuration is 15%,
Bromine content is 2.2wt%, degree of unsaturation 1.6%.
Comparative example 1:
Butyl rubber glue 2000mL solwution method synthesized adds in reactor, adds hexane by glue
Concentration dilution is to 15%, and the degree of unsaturation of butyl rubber is 1.9%；By the hexane solution 20mL of bromine
(normal hexane is 25:1 with the volume ratio of bromine) adds in storage tank；Temperature of charge in reactor is heated
To 45 DEG C, in reactor, add the hexane solution of bromine in storage tank, after bromination reaction 2min, add
The NaOH solution of 400mL mass fraction 1.5wt% terminates, and stops stirring after neutralizing reaction 15min；Will
Glue is washed with distilled water to pH value close to neutral, adds boiling water and flashes off solvent, through dehydration, be dried and
After the aftertreatment technologys such as extruding in bulk, bromo secondary position allylic structure in the brombutyl product obtained
Relative amount is 46%, and the relative amount of bromo uncle position allylic configuration is 28%, and bromine content is 1.7wt%,
Degree of unsaturation 1.3%.
Comparative example 2:
Butyl rubber glue 2000mL solwution method synthesized adds in reactor, adds hexane by glue
Concentration dilution, to 15%, adds the potassium dichromate aqueous solution 100mL of 27.59g/L afterwards, butyl rubber
Degree of unsaturation is 1.9%；By the hexane solution 20mL (normal hexane is 25:1 with the volume ratio of bromine) of bromine
Add in storage tank；Temperature of charge in reactor is heated to 45 DEG C, is injected by multiple spot in reactor
Method adds the hexane solution of bromine in storage tank, after bromination reaction 2min, adds 400mL mass fraction
The NaOH solution of 1.5wt% terminates, and stops stirring after neutralizing reaction 15min；By glue distillation washing
Wash to pH value close to neutral, add boiling water and flash off solvent, through dehydration, be dried and locate after extruding in bulk etc.
After science and engineering skill, in the brombutyl product obtained, the relative amount of bromo secondary position allylic structure is
52%, the relative amount of bromo uncle position allylic configuration is 36%, and bromine content is 2.0wt%, degree of unsaturation
1.2%.
Claims (12)
1. the control method of a solwution method butyl rubber bromo structure, it is characterised in that include following step
Rapid:
A () synthesizes butyl rubber glue, heated and stirred in 40～80 DEG C of waters bath with thermostatic control by solwution method
0.5～6h, unreacted monomer in removing glue；
B () adds electrophilicity reagent in the synthesis butyl rubber glue remove unreacted monomer, afterwards
Add strong oxidizing property reagent；
C () adds the alkane solution of bromine in reactor and carries out bromination reaction；
D () bromination reaction terminates after, the NaOH solution adding mass fraction 1.0～20wt% terminates reaction,
Stop stirring after neutralizing reaction 5～30min, glue is washed with distilled water to pH value close to neutral；
E () adds structure regulator in the glue that step (d) obtains；
F () adds bromo structural stabilizing agent, antioxidant and deacidification agent in the glue that step (e) obtains；
G () adds boiling water in the glue that step (f) obtains, solvent flash distillation removed subsequently, and gained produces
The post-treated dehydration of thing, be dried and extruding in bulk after obtain product.
2. the control method of solwution method butyl rubber bromo structure as claimed in claim 1, its feature exists
In, in step (b), it is 10～40wt% that described synthesis butyl rubber glue mixed solvent is diluted to concentration.
3. the control method of solwution method butyl rubber bromo structure as claimed in claim 2, its feature exists
In, in step (b), described mixed solvent contains and accounts for total solvent volume no more than 50% and be not 0.
4. the control method of solwution method butyl rubber bromo structure as claimed in claim 3, its feature exists
In, in step (b), described electrophilicity reagent is dichloromethane, dichloroethanes, oxirane, pyridine
Or N,N-dimethylformamide.
5. the control method of solwution method butyl rubber bromo structure as claimed in claim 1, its feature exists
In, in step (b), consumption is bromine molal quantity 0.1～5 times of described strong oxidizing property reagent.
6. the control method of the solwution method butyl rubber bromo structure as described in claim 1 or 5, it is special
Levying and be, in step (b), described strong oxidizing property reagent is potassium dichromate, sodium metaperiodate, potassium permanganate
Or hydrogen peroxide.
7. the control method of solwution method butyl rubber bromo structure as claimed in claim 1, its feature exists
In, in step (c), the alkane solution of described bromine is the bromine hexane solution of 0.1～3mol/L.
8. the control method of the solwution method butyl rubber bromo structure as described in claim 1 or 7, it is special
Levying and be, in step (c), described bromine solution is added by multiple spot injection method under the conditions of normal pressure lucifuge.
9. the control method of solwution method butyl rubber bromo structure as claimed in claim 1, its feature exists
In, in step (e), the consumption of described structure regulator account for the mass percent of brombutyl be 0.5～
3%, 10～90 DEG C of stirring reactions 5～30min after addition.
10. the control method of the solwution method butyl rubber bromo structure as described in claim 1 or 8, it is special
Levying and be, in step (e), described structure regulator is tetrabutyl ammonium bromide, tetraethylammonium bromide, benzyl
Base triethylammonium bromide or triphenylphosphine.
The control method of 11. solwution method butyl rubber bromo structures as claimed in claim 1, its feature exists
In, in step (f), described bromo structural stabilizing agent adds what step (e) obtained after being dissolved in mineral oil
In glue, the consumption of described bromo structural stabilizing agent account for the percent of brombutyl quality be 0.1～
3.0%.
The control method of the 12. solwution method butyl rubber bromo structures as described in claim 1 or 10, its
Being characterised by, in step (f), described bromo structural stabilizing agent is dibutyl tin laurate, stearic acid
Zinc, magnesium stearate, iron naphthenate or epoxy soybean oil.
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| CN106749816A (en) * | 2016-11-30 | 2017-05-31 | 黄河三角洲京博化工研究院有限公司 | A kind of preparation method of brombutyl |
| CN110642965A (en) * | 2019-10-30 | 2020-01-03 | 山东京博中聚新材料有限公司 | Preparation method of brominated butyl rubber |
| CN112142884A (en) * | 2020-09-01 | 2020-12-29 | 中北大学 | Brominated butyl rubber synthesis device and process |
| CN114426688A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing rubber aid dispersion liquid, brominated butyl rubber and preparation method thereof |
| CN115232238A (en) * | 2022-09-21 | 2022-10-25 | 山东海化集团有限公司 | Method for preparing brominated butyl rubber by using microchannel reactor |
| CN115947881A (en) * | 2023-03-15 | 2023-04-11 | 山东润科化工股份有限公司 | Synthesis method of brominated ethylene propylene diene monomer |
| CN114790256B (en) * | 2022-04-28 | 2023-12-01 | 山东京博中聚新材料有限公司 | Preparation method of brominated butyl rubber under action of phase transfer agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106749816A (en) * | 2016-11-30 | 2017-05-31 | 黄河三角洲京博化工研究院有限公司 | A kind of preparation method of brombutyl |
| CN106749816B (en) * | 2016-11-30 | 2020-05-12 | 黄河三角洲京博化工研究院有限公司 | Preparation method of brominated butyl rubber |
| CN110642965A (en) * | 2019-10-30 | 2020-01-03 | 山东京博中聚新材料有限公司 | Preparation method of brominated butyl rubber |
| CN112142884A (en) * | 2020-09-01 | 2020-12-29 | 中北大学 | Brominated butyl rubber synthesis device and process |
| CN112142884B (en) * | 2020-09-01 | 2023-06-09 | 中北大学 | Brominated butyl rubber synthesis device and process |
| CN114426688A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing rubber aid dispersion liquid, brominated butyl rubber and preparation method thereof |
| CN114790256B (en) * | 2022-04-28 | 2023-12-01 | 山东京博中聚新材料有限公司 | Preparation method of brominated butyl rubber under action of phase transfer agent |
| CN115232238A (en) * | 2022-09-21 | 2022-10-25 | 山东海化集团有限公司 | Method for preparing brominated butyl rubber by using microchannel reactor |
| CN115947881A (en) * | 2023-03-15 | 2023-04-11 | 山东润科化工股份有限公司 | Synthesis method of brominated ethylene propylene diene monomer |
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