CN105646739A - Method used for preparing hydroxylation modified butyl rubber, and applications thereof - Google Patents
Method used for preparing hydroxylation modified butyl rubber, and applications thereof Download PDFInfo
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Abstract
The invention discloses a method used for preparing hydroxylation modified butyl rubber. The method comprises following steps: under the action of a phase transfer catalyst, contact reaction of an organic solvent solution of halogenated butyl rubber with an aqueous solution of a carboxylate is carried out so as to generate butyl rubber containing ester groups, and then butyl rubber containing hydroxyl is obtained via hydrolysis. The hydroxylation modified butyl polymer prepared using the method possesses the excellent performance of butyl rubber and improved polarity; the method is simple; and production is convenient.
Description
Technical field
The present invention relates to a kind of rubber materials, say further, relate to a kind of method preparing hydroxylation modified butyl rubber. The present invention also relates to the application of hydroxylation modified butyl rubber prepared by aforesaid method.
Background technology
Isoprene-isobutylene rubber (IIR) is the rubbery copolymer become with a small amount of isoprene random copolymerization by iso-butylene, has good chemical stability, thermostability, ozone resistants and gratifying damping and amortization. But, the isoprene-isobutylene rubber of commercial grade has the unsaturated level of about 2mol%, and degree of unsaturation is directly proportional to the stability of material, limit the solidification reactivity of these polymkeric substance, and its polarity is more weak, causing the consistency of itself and other polymkeric substance poor, hydrophilicity is poor. For this reason, it is necessary to isoprene-isobutylene rubber is carried out modification, as isoprene-isobutylene rubber is carried out halogenation modification, reduce degree of unsaturation, it is to increase with the consistency of other polymkeric substance and wetting ability etc., it is possible to expand its range of application. Isoprene-isobutylene rubber carrying out halogenation modification and has become a kind of comparatively ripe isoprene-isobutylene rubber modification technology, its main products has chlorinated butyl rubber (CIIR) and brominated butyl rubber (BIIR). But, halogenated butyl rubber has certain defect, namely when halogenated butyl rubber is carried out burning disposal, can produce the toxic gas of Halogen, cause environmental pollution.
Isoprene-isobutylene rubber is carried out the polymkeric substance that the method for modification is exactly synthesis hydroxyl by another kind; as first synthesis contains the monomer of blocking group; then the polymkeric substance of blocking group is contained by controlled/active sun (the moon) ionic polymerization synthesis side base; the polymkeric substance that last polymkeric substance obtains side base contain hydroxyl by being hydrolyzed further, it is possible to improve the hydrophilicity of polymkeric substance well. As the people such as Faust report the monomer of the carried out controllable cationic polymerization containing saturated group, such as tertiary butyl dimethyl Si base vinylbenzene, to tert-Butyl vinyl ether. But, the monomer of synthesis containing blocking group is cumbersome, complex process, it is difficult to apply.
The present invention provides a kind of method preparing hydroxylation isoprene-isobutylene rubber, and its technique is simple, and flow process is short, it is possible to effectively improve the hydrophilicity of polymkeric substance, improves consistency, adhesive property etc.
Summary of the invention
For deficiency of the prior art, it provides a kind of method preparing hydroxylation isoprene-isobutylene rubber, technical process is short, and technique is simple to operation, it is possible to improve the hydrophilicity of polymkeric substance, improves consistency, adhesive property etc.
According to an aspect of the present invention, provide a kind of method preparing hydroxylation isoprene-isobutylene rubber, comprise: under the effect of phase-transfer catalyst, the organic solvent solution of halogenated butyl rubber contacts with the aqueous solution of carboxylate salt and reacts, generating the isoprene-isobutylene rubber containing ester group, then hydrolysis obtains the isoprene-isobutylene rubber of hydroxyl.
Superpolymer (halogenated butyl rubber, group containing electrophilic) and nucleophilic reagent solubleness difference very greatly different, in these two phase reactions, often to be used phase-transfer catalyst, mainly in order to promote the generation of nucleophilic substitution reaction on two-phase interface, or the nucleophilic reagent in superpolymer is changed into electrophilic reagent. In a specific examples, described phase-transfer catalyst comprises quaternary ammonium salts phase-transfer catalyst, it is preferable that comprise in Tetrabutyl amonium bromide, TBAH, triethyl benzyl ammonia chloride and cetyl trimethylammonium bromide one or more. In a preferred application examples, the mol ratio of described phase-transfer catalyst and carboxylate salt is 0.1:1-5:1, it is preferable that 0.5:1-2.5:1.
According to the present invention, described carboxylate salt is anionic nucleophile. In a specific embodiment, described carboxylate salt is that carboxylic acid and an alkali metal salt generate. In a specific embodiment, described carboxylate salt can represent by the form of carboxylic acid/an alkali metal salt. In a specific embodiment according to the method for the invention, described carboxylate salt and halogenated butyl rubber, the mol ratio of halogen is 1:2-30:1, it is preferable that 1:1-20:1, it is more preferable to 1:5-1:20, such as 1:5-1:10, such as 1:10-1:20. According to a preferred embodiment of the present invention, described an alkali metal salt is Na or the K salt of hydroxyl, such as sodium hydroxide or potassium hydroxide. Described carboxylic acid structure formula is R-COOH, and wherein, R can select from the group of H, aryl and alkyl composition, it is preferable that from H, C1-C20Alkyl (such as C1-C18Alkyl), C2-C20Alkene base (such as C2-C10Alkene base) and C6-C15Containing aryl group. Described carboxylic acid is preferably from formic acid, acetic acid, propionic acid, vinylformic acid, butyric acid, stearic acid, styracin, methacrylic acid.
Another specific embodiment according to the method for the invention, the temperature of reaction is 20-200 DEG C, it is preferable that 40-120 DEG C, it is more preferable to 60-90 DEG C. The time of described reaction is 0.1-24h, it is preferable that 0.1-8h, it is more preferable to 0.5-8h, it is most preferred that 2-4h. In above-mentioned temperature of reaction and/or in the time, be conducive to the carrying out of nucleophilic substitution reaction, avoid the variable color etc. of rubber.
According to method of the present invention, described hydrolysis can any can be hydrolyzed when carry out, as carried out in acid condition, it is possible to carry out in the basic conditions. In a specific examples, described hydrolysis carries out in the basic conditions, carry out in the basic conditions being conducive to hydrolysis reaction carries out more thoroughly, more abundant. In one embodiment of the invention, described alkaline condition realizes by adding pH adjusting agent in solution. In a preferred application examples, by adding, alkali lye realizes described alkaline condition. Alkali in described alkali lye can to form carboxylate salt alkali used identical or different. When it is identical, it is possible to the alkali lye needed for required for the hydrolysis alkali lye that uses and formation carboxylate salt is together added.
In a specific examples, described alkaline condition refers to that the pH value of solution is for being greater than 7. In the preferred case, alkaline condition refers to that pH value is 8-14, it is more preferable to pH value 12-14; Also namely preferably it is hydrolyzed under strongly alkaline conditions, is conducive to the carrying out of hydrolysis reaction.
Another specific embodiment according to the method for the invention, the temperature of described hydrolysis is 20-200 DEG C, it is preferable that 40-120 DEG C, it is more preferable to 60-90 DEG C. The time of hydrolysis is 0.1-24h, it is preferable that 0.1-8h, it is more preferable to 0.5-8h, it is most preferred that 2-4h. Under described hydrolysising condition, be conducive to the carrying out of hydrolysis reaction.
According to the present invention, described halogenated butyl polymer comprises at least one in polymer bromobutyl and chlorinated butyl polymkeric substance.
A specific embodiment according to the method for the invention, described organic solvent can comprise any organic solvent that can be dissolved by halogenated butyl rubber, it is selected from toluene, N, one or more in dinethylformamide, tetrahydrofuran (THF) and dimethylbenzene as comprised.
According to another one aspect of the present invention, it provides the isoprene-isobutylene rubber of hydroxyl prepared by a kind of described method is in the application increased in tough, pressure buffer material. Isoprene-isobutylene rubber according to hydroxyl provided by the invention, owing to effectively improving the hydrophilicity of rubber, consistency, adhesive property etc., has broad application prospect increasing in the fields such as tough, pressure buffer material.
According to the present invention, take halogenated butyl polymer as matrix, under phase-transfer catalyst effect, carry out nucleophilic substitution reaction, obtain the butyl polymer containing ester group, then under alkalescence effect, be hydrolyzed into the butyl polymer of hydroxyl.
According to method provided by the invention, utilize phase-transfer catalyst, the hydroxylation butyl polymer prepared by nucleophilic substitution reaction and hydrolysis reaction in a mild condition, not only there is the excellent properties of isoprene-isobutylene rubber, and enhance the polarity of itself, effectively improve the hydrophilicity of polymkeric substance, improve consistency, adhesive property, and have technique simple, be easy to the advantages such as production.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described, but does not form any limitation of the invention.
Testing method:
Infrared analysis: the Avatar360FTIR infrared spectrometer of Nicolet company of the U.S., test condition: within the scope of wave band 500-4000cm-1, with KBr pressed disc method sample preparation, the infrared spectra of BIIR before and after test reaction.
Nuclear magnetic resonance spectroscopy: adopting Switzerland's BrukerAVANCE400 nuclear magnetic resonance analyser (400Hz), magneticstrength 9.40 tesla, with CDC13Making solvent, TMS is interior mark, and room temperature is tested.
BIIR used in embodiment (brominated butyl rubber, 2222, commercially available), containing bromine 1.8mmol in 5gBIIR. Hydroxyl Replacement rate described in embodiment refers to the ratio that ester group is optionally substituted by a hydroxyl group.
Embodiment 1 (contrast)
Under nitrogen atmosphere, being dissolved in toluene (80ml) by BIIR (2222, commercially available, 5g), acetic acid (0.11g, 1.8mmol) is dissolved in potassium hydroxide (0.1g, 1.8mmol) solution. In the there-necked flask that agitator, reflux condensing tube, thermometer are housed, add the toluene solution of BIIR, start stirring so that it is dissolve completely. Slowly add the aqueous sodium hydroxide solution (50ml) of acetic acid, after stirring 10min, it is warmed up to 60 DEG C. After reaction 6h, mixing solutions is poured into separating funnel leaves standstill cooling, isolate organic phase (toluene solution), by the product methanol extraction in organic phase, then with, after soda lye wash, going out with acetone precipitation, after repeatable operation 3 times, sample is put into vacuum drying oven and is dried to constant weight. Product is analyzed from infrared spectrum: at 2952cm-1There is the stretching vibration absorption peak of methyl methylene radical at place, 1576cm-1And 1540cm-1There is double bond charateristic avsorption band at place, 1471cm-1Place is the formation vibration absorption peak of methylene radical, 1389cm-1And 1365cm-1Place is methyl formation vibration absorption peak, 1229cm-1Place is C-C skeleton stretching vibration absorption peak, 761cm-1Place is the charateristic avsorption band of C-Br, and these are all the charateristic avsorption bands of brominated butyl rubber, and the Infrared spectroscopy of reaction product shows do not having substitution reaction.
Embodiment 2
Under nitrogen atmosphere, being dissolved in toluene (80ml) by BIIR (5g), acetic acid (0.11g, 1.8mmol) is dissolved in potassium hydroxide (0.1g, 1.8mmol) solution (50ml). In the there-necked flask that agitator, reflux condensing tube, thermometer are housed, add toluene solution and phase-transfer catalyst benzyltriethylammoinium chloride (0.5g, 2mmol) of BIIR, start stirring so that it is dissolve completely. Slowly add acetic acid/potassium hydroxide aqueous solution, after stirring 10min, it is warmed up to 60 DEG C, after reaction 2h, takes out part mixing solutions (about 1/5) and pour standing cooling in separating funnel into, isolate organic phase (toluene solution), by the product methanol extraction in organic phase, then with, after soda lye wash, going out with acetone precipitation, after repeatable operation 3 times, sample is put into vacuum drying oven and is dried to constant weight. The bromine Replacement rate of intermediate product (isoprene-isobutylene rubber containing ester group) is 30%, analyzes from infrared spectrum: except the charateristic avsorption band of brominated butyl rubber, at 1737cm-1For the characteristic peak of carbonyl absorption, the Infrared spectroscopy of reaction product shows the ester grafting success of isoprene-isobutylene rubber.
In remaining mixing solutions, add the sodium hydroxide solution aqueous solution (0.05mol/L), make pH be 12, then at 60 DEG C, react 4h, then pour into and separating funnel leaves standstill cooling, isolate organic phase (toluene solution). By the product methanol extraction in organic phase, then with, after soda lye wash, going out with acetone precipitation, after repeatable operation 3 times, sample is put into vacuum drying oven and is dried to constant weight. The hydroxyl Replacement rate of final product is 95%. Analyze from infrared spectrum: except the charateristic avsorption band of brominated butyl rubber, 3600cm-1For the characteristic peak of hydroxyl group absorption, the Infrared spectroscopy of reaction product shows the hydroxylation grafting success of isoprene-isobutylene rubber.
Embodiment 3
With embodiment 2, but phase-transfer catalyst kind is different, and phase-transfer catalyst is cetyl trimethylammonium bromide, and consumption is 0.7g, 2mmol. The bromine Replacement rate of intermediate product is 45%. The hydroxyl Replacement rate of final product is 94%.
Embodiment 4
With embodiment 2, but phase-transfer catalyst kind is different, and phase-transfer catalyst is TBAH, and consumption is 0.6g, 2mmol. The bromine Replacement rate of intermediate product is 72%. The hydroxyl Replacement rate of final product is 96%.
Embodiment 5
With embodiment 2, but phase-transfer catalyst kind is different with consumption, and phase-transfer catalyst is Tetrabutyl amonium bromide, and consumption is 0.32g, 1mmol. Intermediate product bromine Replacement rate is 48%. The hydroxyl Replacement rate of final product is 93%.
Embodiment 6
With embodiment 5, only phase-transfer catalyst consumption is different, and phase-transfer catalyst Tetrabutyl amonium bromide, consumption is 0.645g, 2mmol. Intermediate product bromine Replacement rate is 75%. The hydroxyl Replacement rate of final product is 94%.
Embodiment 7
With embodiment 5, only phase-transfer catalyst consumption is different, and phase-transfer catalyst Tetrabutyl amonium bromide consumption is 1.612g, 5mmol. The bromine Replacement rate of intermediate product is 61%. The hydroxyl Replacement rate of final product is 94%.
Nucleophilic substitution reaction all can be made to occur from embodiment 2-7 it can be seen that belong to quaternary ammonium salts phase-transfer catalyst benzyltriethylammoinium chloride, cetyl trimethylammonium bromide, TBAH, Tetrabutyl amonium bromide. Phase-transfer catalyst is comparatively more suitable than controlling in the scope of 0.5:1-2.5:1 with the mol of acetic acid.
Embodiment 8
Under nitrogen atmosphere, being dissolved in toluene (80ml) by BIIR (2222, commercially available, 5g), styracin (0.3g, 2mmol) solution is in sodium hydroxide (0.08g, 2mmol) solution (50ml). In the there-necked flask that agitator, reflux condensing tube, thermometer are housed, add toluene solution and the Tetrabutyl amonium bromide (0.645g, 2mmol) of BIIR, start stirring so that it is dissolve completely. Slowly add the aqueous sodium hydroxide solution of styracin, after stirring 10min, it is warmed up to 40 DEG C. After reaction 4h, take out a small amount of solution (about 1/5) and pour standing cooling in separating funnel into, isolate intermediate product methanol extraction, then with after soda lye wash, go out with acetone precipitation, after repeatable operation 3 times, sample is put into vacuum drying oven and is dried to constant weight. The bromine Replacement rate of intermediate product is 38%, analyzes from infrared spectrum: except the charateristic avsorption band of brominated butyl rubber, at 1737cm-1For the characteristic peak of carbonyl absorption, the Infrared spectroscopy of reaction product shows the ester grafting success of isoprene-isobutylene rubber.
In remaining solution, add ammoniacal liquor, make solution ph be 10, then stir 1h at 90 DEG C. Pour into and separating funnel leaves standstill cooling, isolate product methanol extraction, then with, after soda lye wash, going out with acetone precipitation, after repeatable operation 3 times, sample is put into vacuum drying oven and is dried to constant weight. The hydroxyl Replacement rate of product is 90%. Analyze from infrared spectrum: except the charateristic avsorption band of brominated butyl rubber, 3600cm-1For the characteristic peak of hydroxyl group absorption, the Infrared spectroscopy of reaction product shows the hydroxylation grafting success of isoprene-isobutylene rubber.
Embodiment 9
With embodiment 8, difference is: the difference of temperature of reaction, temperature of reaction 60 DEG C, and the bromine Replacement rate of intermediate product is 43%; Adding potassium hydroxide aqueous solution, to be adjusted to pH value be 13, and the hydroxyl Replacement rate of final product is 95%.
Embodiment 10
With embodiment 9, difference is: the difference of temperature of reaction, and temperature of reaction is 90 DEG C, and intermediate product bromine Replacement rate is 73%.
Embodiment 11
With embodiment 9, difference is: the difference of temperature of reaction, and temperature of reaction is 120 DEG C. Intermediate product bromine Replacement rate is 30%.
From embodiment 8-11 it can be seen that along with the rising of temperature of reaction, Br Replacement rate increases gradually, but when temperature of reaction is too high, aqueous phase evaporation aggravation, is unfavorable for the generation of substitution reaction on the contrary. It is thus preferred that the scope of temperature is 20-200 DEG C, it is more preferable to 40-120 DEG C, it is most preferred that 60-90 DEG C.
Embodiment 12
Under nitrogen atmosphere, being dissolved in toluene (80ml) by BIIR (5g), stearic acid (0.57g, 2mmol) solution is in sodium hydroxide (0.08g, 2mmol) solution (50ml). In the there-necked flask that agitator, reflux condensing tube, thermometer are housed, add toluene solution and the Tetrabutyl amonium bromide (0.6g, 2mmol) of BIIR, start stirring so that it is dissolve completely. Slowly add the aqueous sodium hydroxide solution of stearic acid, after stirring 10min, it is warmed up to 70 DEG C, reacts 0.1 hour. Then a small amount of mixing solutions (about 1/5) is poured into and separating funnel leaves standstill cooling, isolate organic phase product methanol extraction, then with, after soda lye wash, going out with acetone precipitation, after repeatable operation 3 times, sample is put into vacuum drying oven and is dried to constant weight. Intermediate product bromine Replacement rate is 15%, analyzes from infrared spectrum: except the charateristic avsorption band of brominated butyl rubber, at 1737cm-1For the characteristic peak of carbonyl absorption, the Infrared spectroscopy of reaction product shows the ester grafting success of isoprene-isobutylene rubber.
The sodium hydroxide solution aqueous solution (0.05mol/L) is added in remaining mixing solutions, the pH making mixing solutions is 13.5, then at 70 DEG C, it is hydrolyzed 2h, then pours into and separating funnel leaves standstill cooling, isolate organic phase (toluene solution). By the product methanol extraction in organic phase, then with, after soda lye wash, going out with acetone precipitation, after repeatable operation 3 times, sample is put into vacuum drying oven and is dried to constant weight. The hydroxyl Replacement rate of final product is 95%. Analyze from infrared spectrum: except the charateristic avsorption band of brominated butyl rubber, 3600cm-1For the characteristic peak of hydroxyl group absorption, the Infrared spectroscopy of reaction product shows the hydroxylation grafting success of isoprene-isobutylene rubber.
Embodiment 13
With embodiment 12, difference is: the difference in reaction times, and the reaction times is 4h, and intermediate product bromine Replacement rate is 71%; Hydrolysis time is 1h, and the hydroxyl Replacement rate of final product is 94%.
Embodiment 14
With embodiment 13, difference is: the difference in reaction times, and the reaction times is 8h, and intermediate product bromine Replacement rate is 65%.
From embodiment 12-14 it can be seen that along with the prolongation in reaction times, when the reaction time is too long, it is easy to cause BIIR degraded or variable color. Therefore, the reaction times is 0.1-24h, it is preferable that 0.1-8h, it is more preferable to 0.5-8h, it is most preferred that 2-4h.
Embodiment 15
Under nitrogen atmosphere, being dissolved in toluene (80ml) by BIIR (5g), methacrylic acid (0.155g, 1.8mmol) is dissolved in sodium hydroxide (0.07g, 1.8mmol) solution (50ml). In the there-necked flask that agitator, reflux condensing tube, thermometer are housed, add toluene solution and the Tetrabutyl amonium bromide (0.6g, 2mmol) of BIIR, start stirring so that it is dissolve completely. Slowly add the aqueous sodium hydroxide solution of methacrylic acid, after stirring 10min, it is warmed up to 70 DEG C, reacts 4 hours. A part (about 1/5) for the mixing solutions obtained is poured into separating funnel leaves standstill cooling, isolate product methanol extraction, then with, after soda lye wash, going out with acetone precipitation, after repeatable operation 3 times, sample is put into vacuum drying oven and is dried to constant weight. Product bromine Replacement rate is 32%, analyzes from infrared spectrum: at 1737cm-1For the characteristic peak of carbonyl absorption, show the ester grafting success of isoprene-isobutylene rubber.
Then in remaining mixing solutions, pH value regulator is added, solution ph is made to be 12, after reacting 2h at 70 DEG C, pour into and separating funnel leaves standstill cooling, isolate product methanol extraction, then with, after soda lye wash, going out with acetone precipitation, after repeatable operation 3 times, sample is put into vacuum drying oven and is dried to constant weight. Product hydroxyl Replacement rate is 94%. Analyze from infrared spectrum: except the charateristic avsorption band of brominated butyl rubber, 3600cm-1For the characteristic peak of hydroxyl group absorption, the Infrared spectroscopy of reaction product shows the hydroxylation grafting success of isoprene-isobutylene rubber.
Embodiment 16
With embodiment 15, difference is: the difference of nucleophilic reagent consumption, is 1.55g, 18mmol, and intermediate product bromine Replacement rate is 75%.
Embodiment 17
With embodiment 15, difference is: the difference of nucleophilic reagent consumption, is 3.1g, 36mmol. Intermediate product bromine Replacement rate is 63%.
Can learning from embodiment 15-17, nucleophilic substitution reaction is had important impact by the amount of the nucleophilic reagent added. In optimization acid's salt and halogenated butyl rubber, the mol ratio of halogen is 1:1-20:1, it is more preferable to 1:5-1:20, such as 1:10-1:20.
Embodiment 18
Under nitrogen atmosphere, by BIIR (2222, commercially available, 5g) it is dissolved in toluene (80ml), methacrylic acid (1.55g, 0.018mol) is dissolved in sodium hydroxide (1.2g, 0.03mol) solution (50ml). In the there-necked flask that agitator, reflux condensing tube, thermometer are housed, add toluene solution and the Tetrabutyl amonium bromide (5.8g, 0.018mol) of BIIR, start stirring so that it is dissolve completely. Slowly add the aqueous sodium hydroxide solution of methacrylic acid, after stirring 10min, it is warmed up to 70 DEG C. React to be poured into by mixing solutions after 4 hours and separating funnel leaves standstill cooling, isolate product methanol extraction, then with, after soda lye wash, going out with acetone precipitation, after repeatable operation 3 times, sample is put into vacuum drying oven and is dried to constant weight. Analyze from infrared spectrum: except the charateristic avsorption band of brominated butyl rubber, 3600cm-1For the characteristic peak of carbonyl absorption, the Infrared spectroscopy of reaction product shows the hydroxylation grafting success of isoprene-isobutylene rubber.
As seen from the above embodiment: alkali used for hydrolysis is added together with forming the alkali needed for nucleophilic reagent, and the ester group being obtained by reacting continues to be hydrolyzed to hydroxyl again, obtains the polymkeric substance of hydroxyl.
It is noted that above-described embodiment is only for explaining the present invention, do not form any limitation of the invention. By referring to exemplary embodiments, invention has been described, it should be understood that for word wherein used is descriptive and explanatory vocabulary, instead of limited vocabulary. By being defined in the scope of the claims in the present invention, the present invention can be modified, and in the scope and spirit not deviating from the present invention, the present invention be revised. Although the present invention wherein described relates to specific method, material and embodiment, but and do not mean that the present invention is limited to particular case disclosed in it, on the contrary, the present invention can expand to other all methods and applications with identical function.
Claims (10)
1. prepare the method for hydroxylation isoprene-isobutylene rubber for one kind, comprise: under the effect of phase-transfer catalyst, the organic solvent solution of halogenated butyl rubber contacts with the aqueous solution of carboxylate salt and reacts, and generates the isoprene-isobutylene rubber containing ester group, and then hydrolysis obtains the isoprene-isobutylene rubber of hydroxyl.
2. method according to claim 1, it is characterised in that, in described carboxylate salt and halogenated butyl rubber, the mol ratio of halogen is 1:2-30:1, it is preferable that 1:1-20:1, it is more preferable to 1:5-1:20.
3. method according to claim 1 and 2, it is characterised in that, the mol ratio of described phase-transfer catalyst and carboxylate salt is 0.1:1-5:1, it is preferable that 0.5:1-2.5:1.
4. according to method described in any one in claim 1-3, it is characterised in that, the temperature of reaction is 20-200 DEG C, it is preferable that 40-120 DEG C, it is more preferable to 60-90 DEG C; The time of described reaction is 0.1-24h, it is preferable that 0.1-8h, it is more preferable to 0.5-8h, it is most preferred that 2-4h.
5. according to method described in any one in claim 1-4, it is characterised in that, described hydrolysis carries out in the basic conditions; Preferred described alkaline condition refers to that the pH value of solution is for being greater than 7, it is more preferable to be 8-14, it is most preferred that 12-14.
6. according to method described in any one in claim 1-5, it is characterised in that, the temperature of described hydrolysis is 20-200 DEG C, it is preferable that 40-120 DEG C, it is more preferable to 60-90 DEG C; And/or the time of hydrolysis is 0.1-24h, it is preferable that 0.1-8h, it is more preferable to 0.5-8h, it is most preferred that 2-4h.
7. according to method described in any one in claim 1-6, it is characterized in that, described phase-transfer catalyst comprises quaternary ammonium salts phase-transfer catalyst, it is preferable that comprise one or more that be selected from Tetrabutyl amonium bromide, TBAH, triethyl benzyl ammonia chloride and cetyl trimethylammonium bromide.
8. according to method described in any one in claim 1-7, it is characterised in that, described halogenated butyl polymer comprises at least one in polymer bromobutyl and chlorinated butyl polymkeric substance.
9. according to method described in any one in claim 1-8, it is characterised in that, described carboxylate salt is the anionic nucleophile that carboxylic acid and an alkali metal salt generate; Wherein, it is preferable that described an alkali metal salt is Na or the K salt of hydroxyl, and/or preferred described carboxylic acid structure formula be R-COOH, R can be H, alkyl or aryl, it is preferable that from H, C1-C20Alkyl, C2-C20Alkene and C6-C15Containing aryl group; More preferably described carboxylic acid is selected from formic acid, acetic acid, propionic acid, vinylformic acid, butyric acid, styracin, stearic acid, methacrylic acid.
10. the isoprene-isobutylene rubber of the hydroxyl prepared according to method described in any one in claim 1-9 is in the application increased in tough, pressure buffer material.
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