CN101805426B - Modified butyl rubber - Google Patents

Modified butyl rubber Download PDF

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Publication number
CN101805426B
CN101805426B CN2010101559039A CN201010155903A CN101805426B CN 101805426 B CN101805426 B CN 101805426B CN 2010101559039 A CN2010101559039 A CN 2010101559039A CN 201010155903 A CN201010155903 A CN 201010155903A CN 101805426 B CN101805426 B CN 101805426B
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parts
weight
butyl rubber
rubber
modified butyl
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CN101805426A (en
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刘峰
熊磊
缪可存
丁婉
袁荞龙
刘青
倪萍
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JIANGSU SHENGJIE INDUSTRY Co Ltd
East China University of Science and Technology
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JIANGSU SHENGJIE INDUSTRY Co Ltd
East China University of Science and Technology
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Abstract

The present invention relates to modified butyl rubber. The modified butyl rubber is prepared by reacting the following components at 50-140 DEG C for 1-6 hours in parts by weight: 100 parts of butyl rubber, 1-30 parts of maleic anhydride, 1-50 parts of sulfonyl chloride and 100-1,000 parts of organic solvent. The modified butyl rubber not only has the excellent specific properties of chlorobutyl rubber (CIIR), but also overcomes the property deficiency of the traditional CIIR. In addition, the method for preparing the modified butyl rubber has the advantages of simple process, moderate reaction condition, convenient mass production, and the like.

Description

Modified butyl rubber
Technical field
The present invention relates to a kind of modified butyl rubber, specifically, relate to a kind of through MALEIC ANHYDRIDE (maleic anhydride) and halogen modified isoprene-isobutylene rubber.
Background technology
Isoprene-isobutylene rubber (butyl rubber) is the rubbery copolymer that formed by iso-butylene and a small amount of hydrocarbon olefin-copolymerization of conjugation (typical case as: the rubber copolymerized product of iso-butylene and isoprene, the content of isoprene is generally 2.0%～4.5%).Though isoprene-isobutylene rubber has good chemical stability, thermostability, resistance to air loss, watertightness and electrical insulating property etc. (the most outstanding is resistance to air loss and watertightness), but it is defectiveness also: since the polarity of isoprene-isobutylene rubber a little less than, cause the consistency of itself and other polymkeric substance relatively poor (for example poor, as can't to obtain the ideal toughening effect) with the consistency of nylon and the strong resin of vibrin isopolarity.For this reason, need carry out modification, expand its range of application isoprene-isobutylene rubber.
Isoprene-isobutylene rubber is carried out the halogenation modification become a kind of comparatively sophisticated isoprene-isobutylene rubber modification technology.Its main products has chlorinated butyl rubber (CIIR) and brominated butyl rubber (BIIR).Chlorinated butyl rubber is except that low ventilative, the damping that has kept conventional butyl rubbers, anti-ozone and chemical mediator-resitant property, also increased the not available characteristic of conventional butyl rubbers, fast as vulcanization rate, make moderate progress with natural rubber, styrene-butadiene rubber(SBR) consistency and binding property, can better thermotolerance etc. be arranged separately with the zinc oxide sulfuration.
But since the polarity of chlorinated butyl rubber still a little less than, it is (for example poor with the consistency of nylon and the strong resin of vibrin isopolarity to cause the consistency of itself and polar polymer relatively poor, can't obtain the ideal toughening effect), simultaneously chlorinated butyl rubber and polar material (as stainless steel etc.) interfacial adhesion strength is still unsatisfactory.
Given this, the novel modified butyl rubber of development just becomes the technical issues that need to address of the present invention.
Summary of the invention
The objective of the invention is to, a kind of novel modified butyl rubber is provided, overcome the defective that exists in existing isoprene-isobutylene rubber or the chloro modified butyl rubber, satisfy the demand of related industries department.
The said modified butyl rubber of the present invention, it is characterized in that said modified butyl rubber was mainly made in 50 ℃～140 ℃ (preferred 80 ℃～120 ℃) reaction by the isoprene-isobutylene rubber of 100 parts by weight, the MALEIC ANHYDRIDE (claiming maleic anhydride again) of 1 parts by weight～30 parts by weight, the SULPHURYL CHLORIDE of 1 parts by weight～50 parts by weight and the organic solvent of 300 parts by weight～1000 parts by weight in 0.1 hour～6 hours.
Wherein: the consumption of maleic anhydride, SULPHURYL CHLORIDE and organic solvent is that the isoprene-isobutylene rubber with 100 parts by weight serves as to calculate benchmark to get;
Said organic solvent is selected from: by C 1～C 3Alkyl substituted benzene, halogenated C 1～C 4Alkane, C 1～C 6A kind of, two or more mixture in alkane, 5-6 unit's naphthenic hydrocarbon or the tetrahydrofuran (THF);
Preferred organic is: the C of chloro 1～C 4Alkane [as (but being not limited to): methylene dichloride, trichloromethane, vinyl trichloride or tetrachloroethane etc.], by C 1～C 3Alkyl substituted benzene [as (but being not limited to): toluene, ethylbenzene, isopropyl benzene, trimethylbenzene or dimethylbenzene etc.], C 1～C 6Alkane is or/and 5-6 unit naphthenic hydrocarbon.
Said isoprene-isobutylene rubber is meant among the present invention: by the rubbery copolymer that iso-butylene and a small amount of hydrocarbon olefin-copolymerization of conjugation form, wherein the hydrocarbon olefin ratios of iso-butylene and conjugation is 75: 25～98: 2.
Embodiment
Rubber copolymerized product with iso-butylene and isoprene is an example below, specifically sets forth the preparation method of the said modified butyl rubber of the present invention.
Said preparation method's key step is: the isoprene-isobutylene rubber (the rubber copolymerized product of iso-butylene and isoprene) and the organic solvent of 300 parts by weight～1000 parts by weight of 100 parts by weight are placed reactor, heat is warming up to 50 ℃～140 ℃ (preferred 80 ℃～120 ℃) under the rare gas element existence condition having, the maleic anhydride that in this reaction, adds 1 parts by weight～30 parts by weight, the initiator of the SULPHURYL CHLORIDE of 1 parts by weight～50 parts by weight and 0.01 parts by weight～10 parts by weight, reinforced finishing, keep (reaction) 0.1 hour～6 hours at this state, drive remaining sour gas away with rare gas element, then the material in the reactor is poured in the precipitation agent, stirred 1 hour～5 hours, successively after filtration, get target compound (modified butyl rubber) after extracting and the drying;
Said organic solvent is: the C of chloro 1～C 4Alkane, by C 1～C 3Alkyl substituted benzene, C 1～C 6Alkane is or/and 5-6 unit naphthenic hydrocarbon, and preferred organic solvent is that methylene dichloride, trichloromethane, vinyl trichloride, sym.-tetrachloroethane, toluene, ethylbenzene, isopropyl benzene, trimethylbenzene, dimethylbenzene, normal hexane are or/and hexanaphthene;
Said initiator is selected from: a kind of in Diisopropyl azodicarboxylate, dibenzoyl peroxide, di-isopropyl peroxydicarbonate, tert-butyl peroxy acetate, peroxidized t-butyl perbenzoate or the dicumyl peroxide, two or more mixture;
Said precipitation agent is acetone and/or ethanol, and its consumption is 3 times～10 times of volume of material (preferred 5 times～10 times) in the reactor;
In said extraction steps, used extract (solvent) is acetone and/or ethanol;
In said drying step, its drying temperature should be controlled at 40 ℃～100 ℃, and be 5 hours～40 hours time of drying.
Modified butyl rubber provided by the present invention, it not only has the peculiar excellent properties of chlorinated butyl rubber (CIIR), and has overcome the performance deficiency (as having improved the interfacial adhesion strength with stainless steel isopolarity material) of existing CIIR.In addition, the method for preparing modified chlorinated isoprene-isobutylene rubber of the present invention has that technology is simple, reaction conditions is gentle and be convenient to advantages such as scale production.
The present invention is further elaborated below by embodiment, and its purpose only is better to understand content of the present invention.Therefore the cited case does not limit protection scope of the present invention.
Embodiment one
With 12g isoprene-isobutylene rubber (1751, Beijing yanshan petrochemical company limited, down together), the 55ml tetrachloroethane adds in the 250ml there-necked flask, under argon gas atmosphere, fully stir, oil bath is heated to and adds the 1.2g maleic anhydride about 110 ℃, after treating that material dissolves fully, add the 1.5g SULPHURYL CHLORIDE, and the 0.4g dicumyl peroxide is dissolved in the 10ml tetrachloroethane, dropwise add above-mentioned system, drip off in 30 minutes, stop heating after 2 hours, stopped reaction is driven remaining sour gas away with argon gas, pour product into 10 times and in the acetone of its volume, precipitate, and with the solid that obtains with acetone again extracting after 24 hours in vacuum drying oven after the oven dry target compound (modified butyl rubber).Promptly obtaining cl content is that 1.43wt%, percentage of grafting are the maleic anhydride graft chlorinated butyl rubber of 1.12wt%.
The gained target compound is carried out infrared analysis, by infared spectrum as can be known: at 2953cm -1There are the stretching vibration absorption peak of methyl methylene radical, 1473cm in the place -1The place is the scissoring vibration absorption peak of methylene radical, 1390cm -1With 1366cm -1The place is the flexural vibration absorption peak of methyl, 1228cm -1Be C-C stretching vibration absorption peak, 1647cm -1The place is the C=C charateristic avsorption band of isoprene-isobutylene rubber, more than all be the charateristic avsorption band of isoprene-isobutylene rubber.In addition, at 752cm -1The place is the charateristic avsorption band of C-Cl, 1721cm -1The place is that the C=O stretching vibration absorption peak of acid anhydrides, the Infrared spectroscopy of reaction product show the chlorination and the grafting success of isoprene-isobutylene rubber.
Press GB 7139-86, adopt " Fo Erhadefa " to measure the cl content of chlorination situ-formed graft product.Concrete grammar is: take by weighing a certain amount of sample, with the filter paper parcel, it is enclosed within the Aze: add 100ml 2%NaOH solution and be full of oxygen in Molotov cocktail, make sample perfect combustion in Molotov cocktail then; Leave standstill 30min, after the gas that burning is produced is absorbed fully, make indicator, be neutralized to colourlessly with 2mol/L nitric acid, and guarantee its sour environment with phenolphthalein; Adding excessive concentration is N 1AgNO 3Standardized solution drips 2～3 ammonium ferric sulfate solutions as indicator, is N with concentration 2The Silver Nitrate of ammonium thiocyanate solution overtitration, titration to solution become blush and shake gently after do not disappear yet and be terminal point.Cl content by formula (A) calculation sample:
Cl % = ( N 1 V 1 - N 2 V 2 ) × 35.46 1000 G × 100 % - - - ( A )
(A) in the formula: N 1-AgNO 3The concentration of solution ((mol/L);
N 2-NH 4The concentration of SCN solution (mol/L);
V 1-adding AgNO 3The volume of solution (mL);
V 2-titration consumes NH 4The volume of SCN solution (mL);
The quality of G-sample (g);
Adopt the chemical titration percentage of grafting:
Concrete grammar is: accurately takes by weighing sample (being accurate to 0.001g) behind the 1.0g purifying, is dissolved in an amount of toluene, and heating for dissolving, the NaOH-methanol solution that the cooling back adds 0.05mol/L carries out saponification backflow 1h, drips 1～2 phenolphthalein indicator then.With the HCl-Virahol standard solution titration of 0.05mol/L to terminal.
The percentage of grafting G of product YImplication: the percentage ratio that contains maleic anhydride monomer in the graft product.It calculates by formula (B):
G Y ( % ) = N 1 V 1 - N 2 V 2 2 W × 98 × 10 - 3 × 100 % - - - ( B )
(B) in the formula, N 1, N 2Be respectively the concentration of the used HCl-aqueous isopropanol of used NaOH-methanol solution of titration and back titration, mol/L; V 1, V 2Be respectively the volume of the used HCl-aqueous isopropanol of used NaOH-methanol solution of titration and back titration, mL; W is the quality that takes by weighing sample behind the purifying, g; After maleic anhydride open loop of 2 expressions two carboxyls are arranged.
In following examples two to embodiment six, except that specifying, the structural characterization of gained target compound all adopts infrared spectra.Because the data of infrared spectra are very similar, so give unnecessary details no longer one by one.
In addition, among the embodiment two to embodiment six, cl content in the target compound and percentage of grafting all calculate and get by formula (A) and formula (B).
Comparative example one
12g isoprene-isobutylene rubber, 55ml tetrachloroethane are added in the 250ml there-necked flask, under argon gas atmosphere, fully stir, oil bath is heated to and adds the 1.2g SULPHURYL CHLORIDE about 110 ℃, stop heating after 30 minutes, finish reaction, drive remaining sour gas away, pour product into 10 times and in the acetone of its volume, precipitate with argon gas, and with the solid that obtains with acetone again extracting in vacuum drying oven, dry after 24 hours, promptly obtain the chlorinated butyl rubber that cl content is 1.38%wt.
The self-control glue that the common chlorinated butyl rubber that maleic anhydride graft chlorinated butyl rubber that comparing embodiment one obtains and comparative example one obtain is formed is to the adhesiveproperties of chlorinated butyl rubber test specimen and stainless steel test specimen, press the GB/T15254 standard and make rubber test specimen and stainless steel test specimen, earlier sandblasting is carried out on stainless steel test specimen surface, then with ethyl acetate cleaning stainless steel test specimen and rubber test specimen surface.Carry out the test of stripping strength by GB/T 2790 standards again, the stripping strength that obtains common chlorinated butyl rubber is 1.78kN/m, and the stripping strength of maleic anhydride graft chlorinated butyl rubber can reach 4.26k N/m.
Embodiment two
With the 12g isoprene-isobutylene rubber, the 65ml trichloroethane adds in the 250ml there-necked flask, under argon gas atmosphere, fully stir, oil bath is heated to and adds the 1.2g maleic anhydride about 100 ℃, after treating that material dissolves fully, beginning dropwise adds the 6g SULPHURYL CHLORIDE, drip off in 1 hour, and the 0.012g dicumyl peroxide is dissolved in the 10ml trichloroethane, dropwise add above-mentioned system, drip off in 30 minutes, stop heating after 3 hours, stopped reaction is driven remaining sour gas away with argon gas, pours product into 10 times and precipitates in the acetone of its volume, and with the solid that obtains with acetone again extracting in vacuum drying oven, dry after 24 hours, promptly obtaining cl content is 8.23wt%, percentage of grafting be 0.48wt% (chlorination maleic anhydride graft isoprene-isobutylene rubber.Obtaining stripping strength according to comparative example one identical test method is 2.92k N/m.
Embodiment three
With the 10g isoprene-isobutylene rubber, 20g hexanaphthene and 80g toluene, add in the 250ml there-necked flask, under argon gas atmosphere, fully stir, oil bath is heated to and adds the 3.0g maleic anhydride about 70 ℃, after treating that material dissolves fully, and 0.05g Diisopropyl azodicarboxylate and 0.05g dibenzoyl peroxide be dissolved in 10ml toluene, dropwise add above-mentioned system, drip off in 30 minutes, begin dropwise to add the 0.1g SULPHURYL CHLORIDE again, 0.1 drip off in hour, stop heating after 6 hours, stopped reaction is driven remaining sour gas away with argon gas, pours product into 10 times and precipitates in the acetone of its volume, and with the solid that obtains with acetone again extracting in vacuum drying oven, dry after 24 hours, promptly obtaining cl content is 0.25wt%, percentage of grafting is the chlorination maleic anhydride graft isoprene-isobutylene rubber of 1.02wt%.Obtaining stripping strength according to comparative example one identical test method is 3.46k N/m.
Embodiment four
With the 100g isoprene-isobutylene rubber, 150g tetrachloroethane and 150g trimethylbenzene, add in the 1000ml there-necked flask, under argon gas atmosphere, fully stir, oil bath is heated to 140 ℃ and adds the 1.0g maleic anhydride, after treating that material dissolves fully, and 0.005g di-isopropyl peroxydicarbonate and 0.025g tert-butyl peroxy acetate and 0.025g peroxidized t-butyl perbenzoate be dissolved in 10ml dimethylbenzene, dropwise add above-mentioned system, after dripping off in 30 minutes, add the 10g SULPHURYL CHLORIDE, react again and stop heating after 0.1 hour, stopped reaction, drive remaining sour gas away with argon gas, pour product into 10 times and in the acetone of its volume, precipitate, and with the solid that obtains with acetone again extracting in vacuum drying oven, dry after 24 hours, promptly obtaining cl content is 1.02wt%, percentage of grafting is the chlorination maleic anhydride graft isoprene-isobutylene rubber of 0.25wt%.Obtaining stripping strength according to comparative example one identical test method is 2.58k N/m.
Embodiment five
With the 100g isoprene-isobutylene rubber, 300g normal hexane and 600g trichloromethane and 200g methylene dichloride and 100g tetrahydrofuran (THF), add in the 1500ml there-necked flask, under argon gas atmosphere, fully stir, oil bath is heated to and adds the 10.2g maleic anhydride about 50 ℃, after treating that material dissolves fully, and the 1.2g dibenzoyl peroxide is dissolved in the 10ml trichloromethane, dropwise add above-mentioned system, drip off in 30 minutes, beginning dropwise adds the 10g SULPHURYL CHLORIDE, drip off in 1 hour, stop heating after 6 hours, stopped reaction is driven remaining sour gas away with argon gas, pours product into 10 times and precipitates in the acetone of its volume, and with the solid that obtains with acetone again extracting in vacuum drying oven, dry after 24 hours, promptly obtaining cl content is 0.93wt%, percentage of grafting is the chlorination maleic anhydride graft isoprene-isobutylene rubber of 0.68wt%.Obtaining stripping strength according to comparative example one identical test method is 3.12k N/m.
Embodiment six
100g isoprene-isobutylene rubber and 800g dimethylbenzene are added in the 1500ml there-necked flask, under argon gas atmosphere, fully stir, oil bath is heated to and adds the 20.5g maleic anhydride about 120 ℃, after treating that material dissolves fully, and the 3.2g dicumyl peroxide is dissolved in 30ml dimethylbenzene, dropwise add above-mentioned system, drip off in 60 minutes, beginning dropwise adds the 10g SULPHURYL CHLORIDE, 0.5 drip off in hour, stop heating after 2 hours, stopped reaction is driven remaining sour gas away with argon gas, pours product into 10 times and precipitates in the acetone of its volume, and with the solid that obtains with acetone again extracting in vacuum drying oven, dry after 24 hours, promptly obtaining cl content is 1.13wt%, percentage of grafting is the chlorination maleic anhydride graft isoprene-isobutylene rubber of 1.18wt%.Obtaining stripping strength according to comparative example one identical test method is 3.92k N/m.

Claims (7)

1. modified butyl rubber, it is characterized in that said modified butyl rubber was mainly made in 50 ℃～140 ℃ reactions by the isoprene-isobutylene rubber of 100 parts by weight, the MALEIC ANHYDRIDE of 1 parts by weight～30 parts by weight, the SULPHURYL CHLORIDE of 1 parts by weight～50 parts by weight and the organic solvent of 300 parts by weight～1000 parts by weight in 0.1 hour～6 hours;
Said organic solvent is selected from: by C 1～C 3Alkyl substituted benzene, halogenated C 1～C 4Alkane, C 1～C 6The mixture of one or two or more kinds in alkane, 5-6 unit's naphthenic hydrocarbon or the tetrahydrofuran (THF).
2. modified butyl rubber as claimed in claim 1 is characterized in that, wherein said isoprene-isobutylene rubber is the rubber copolymerized product of iso-butylene and isoprene.
3. modified butyl rubber as claimed in claim 1 is characterized in that, wherein said organic solvent is: the C of chloro 1～C 4Alkane, by C 1～C 3Alkyl substituted benzene, C 1～C 6Alkane is or/and 5-6 unit naphthenic hydrocarbon.
4. as any described modified butyl rubber in the claim 1～3, it is characterized in that, described modified butyl rubber mainly by: the isoprene-isobutylene rubber of 100 parts by weight and the organic solvent of 300 parts by weight～1000 parts by weight are placed reactor, heat is warming up to 50 ℃～140 ℃ under the rare gas element existence condition having, the maleic anhydride that in this reaction, adds 1 parts by weight～30 parts by weight, the initiator of the SULPHURYL CHLORIDE of 1 parts by weight～50 parts by weight and 0.01 parts by weight～10 parts by weight, reinforced finishing, kept 0.1 hour～6 hours at this state, drive remaining sour gas away with rare gas element, then the material in the reactor is poured in the precipitation agent, stirred 1 hour～5 hours, successively after filtration, obtain after extracting and the drying;
Wherein said organic solvent is: methylene dichloride, trichloromethane, vinyl trichloride, sym.-tetrachloroethane, toluene, ethylbenzene, isopropyl benzene, trimethylbenzene, dimethylbenzene, normal hexane are or/and hexanaphthene;
Said initiator is: Diisopropyl azodicarboxylate, dibenzoyl peroxide, di-isopropyl peroxydicarbonate, tert-butyl peroxy acetate, peroxidized t-butyl perbenzoate and/or dicumyl peroxide; Said precipitation agent is acetone and/or ethanol.
5. modified butyl rubber as claimed in claim 4 is characterized in that, wherein the precipitation agent consumption is 3 times～10 times of volume of material in the reactor.
6. modified butyl rubber as claimed in claim 4 is characterized in that, in the said therein extraction steps, used extract is acetone and/or ethanol.
7. modified butyl rubber as claimed in claim 4 is characterized in that, in the said therein drying step, drying temperature is 40 ℃～100 ℃, and be 5 hours～40 hours time of drying.
CN2010101559039A 2010-04-23 2010-04-23 Modified butyl rubber Expired - Fee Related CN101805426B (en)

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CN102432952B (en) * 2010-09-29 2013-10-30 中国石油化工股份有限公司 Quickly vulcanized butyl rubber and preparation method and application thereof
CN102432724A (en) * 2010-09-29 2012-05-02 中国石油化工股份有限公司 Carboxylate butyl rubber and preparation method thereof
CN103289019A (en) * 2013-06-26 2013-09-11 金轮橡胶（海门）有限公司 Modified butyl rubber
CN104390973A (en) * 2014-11-28 2015-03-04 苏州佑君环境科技有限公司 Reagent for detecting trichloromethane and preparation method of reagent
CN105778000B (en) * 2014-12-16 2019-02-15 中国石油天然气股份有限公司 A kind of isoprene rubber grafted maleic anhydride and preparation method thereof
CN107778671A (en) * 2016-08-30 2018-03-09 孙剑钊 A kind of formula and preparation technology of Butyl Rubber Closure in Medical Field material

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