CN105646739B - A kind of method and application thereof for preparing hydroxylated modified butyl rubber - Google Patents

Abstract

The invention discloses a method for preparing hydroxylated butyl rubber, which comprises the following steps: under the action of phase transfer catalyst, organic solvent solution of halogenated butyl rubber is contacted with water solution of carboxylate and reacted to produce butyl rubber containing ester group, and the butyl rubber containing hydroxyl group is hydrolyzed. The hydroxylated butyl polymer prepared by the method provided by the invention not only has the excellent performance of butyl rubber, but also enhances the polarity of the hydroxylated butyl polymer, and has the advantages of simple process and easy production.

Description

A kind of method and application thereof for preparing hydroxylated modified butyl rubber

technical field

The invention relates to the field of rubber, in particular to a method for preparing hydroxylated modified butyl rubber. The present invention also relates to the application of the hydroxylated modified butyl rubber prepared by the above method.

Background technique

Butyl rubber (IIR) is a rubber copolymer obtained by random copolymerization of isobutylene and a small amount of isoprene. It has good chemical stability, thermal stability, ozone resistance and satisfactory damping properties. However, commercial grades of butyl rubber have an unsaturation level of approximately 2 mol%, which is directly proportional to the stability of the material, limiting the cure reactivity of these polymers, and is relatively weak in polarity, making it difficult to compare with other The polymer has poor compatibility and poor hydrophilicity. For this reason, it is necessary to modify butyl rubber, such as halogenation modification of butyl rubber, to reduce unsaturation, improve compatibility and hydrophilicity with other polymers, etc., which can expand its application range. Halogenation modification of butyl rubber has become a relatively mature butyl rubber modification technology, and its main products are chlorinated butyl rubber (CIIR) and brominated butyl rubber (BIIR). However, the halogenated butyl rubber has certain defects, that is, when the halogenated butyl rubber is incinerated, it will produce toxic gas containing halogen, which will cause environmental pollution.

Another way to modify butyl rubber is to synthesize hydroxyl-containing polymers, such as synthesizing monomers containing protective groups first, and then synthesizing side groups containing protective groups through controlled/living cationic (anion) polymerization Finally, the polymer is further hydrolyzed to obtain a polymer with side groups containing hydroxyl groups, which can improve the hydrophilic properties of the polymer. For example, Faust et al. reported monomers containing saturated groups that can undergo controlled cationic polymerization, such as tert-butyldimethylsiloxystyrene and p-tert-butyl vinyl ether. However, the synthesis of monomers containing protective groups is cumbersome and complicated, making it difficult to popularize and apply.

The invention provides a method for preparing hydroxylated butyl rubber, which has a simple process and a short process, and can effectively improve the hydrophilic property of the polymer, and improve the compatibility, bonding performance and the like.

Contents of the invention

Aiming at the deficiencies in the prior art, a method for preparing hydroxylated butyl rubber is provided, the process flow is short, the process is simple and easy to operate, the hydrophilic property of the polymer can be improved, the compatibility, the bonding performance and the like can be improved.

According to one aspect of the present invention, there is provided a method for preparing hydroxylated butyl rubber, comprising: under the action of a phase transfer catalyst, an organic solvent solution of halogenated butyl rubber contacts and reacts with an aqueous solution of carboxylate to generate The ester-based butyl rubber is then hydrolyzed to obtain hydroxyl-containing butyl rubber.

The solubilities of polymers (halogenated butyl rubber, containing electrophilic groups) and nucleophiles are very different. In these two-phase reactions, phase transfer catalysts are often used, mainly to promote the two-phase interface. A nucleophilic substitution reaction occurs, or the conversion of a nucleophile in a polymer to an electrophile. In a specific example, the phase transfer catalyst includes a quaternary ammonium salt phase transfer catalyst, preferably including tetrabutylammonium bromide, tetrabutylammonium hydroxide, triethylbenzylammonium chloride and cetyltrimethyl One or more of ammonium bromide. In a preferred application example, the molar ratio of the phase transfer catalyst to the carboxylate is 0.1:1-5:1, preferably 0.5:1-2.5:1.

According to the invention, the carboxylate is an anionic nucleophile. In a specific embodiment, the carboxylate is produced from a carboxylic acid and an alkali metal salt. In a specific embodiment, the carboxylate may be expressed in the form of a carboxylic acid/alkali metal salt. According to a specific embodiment of the method of the present invention, the molar ratio of the carboxylate to the halogen in the halogenated butyl rubber is 1:2-30:1, preferably 1:1-20:1, more preferably 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, the alkali metal salt is Na or K salt of hydroxyl, such as sodium hydroxide or potassium hydroxide. The structural formula of the carboxylic acid is R-COOH, wherein R can be selected from groups consisting of H, aryl and alkyl, preferably selected from H, C ₁ -C ₂₀ alkyl (such as C ₁ -C ₁₈ alkane group), C ₂ -C ₂₀ alkenyl group (such as C ₂ -C ₁₀ alkenyl group) and C ₆ -C ₁₅ aryl-containing group. The carboxylic acid is preferably selected from formic acid, acetic acid, propionic acid, acrylic acid, butyric acid, stearic acid, cinnamic acid, methacrylic acid.

According to another specific embodiment of the method of the present invention, the reaction temperature is 20-200°C, preferably 40-120°C, more preferably 60-90°C. The reaction time is 0.1-24h, preferably 0.1-8h, more preferably 0.5-8h, most preferably 2-4h. At the above reaction temperature and/or time, it is beneficial to carry out the nucleophilic substitution reaction and avoid discoloration of the rubber.

According to the method of the present invention, the hydrolysis can be carried out under any conditions capable of hydrolysis, for example, it can be carried out under acidic conditions, or it can be carried out under alkaline conditions. In a specific example, the hydrolysis is carried out under alkaline conditions, which is conducive to a more thorough and complete hydrolysis reaction. In one embodiment of the present invention, the alkaline condition can be achieved by adding a pH regulator to the solution. In a preferred application example, the alkaline condition can be realized by adding lye. The base in the lye may be the same or different from the base used to form the carboxylate. When they are the same, the lye required for hydrolysis may also be added together with the lye required for carboxylate formation.

In a specific example, the alkaline condition means that the pH of the solution is greater than 7. In a preferred case, the alkaline condition refers to a pH value of 8-14, more preferably a pH value of 12-14; that is, the hydrolysis is preferably carried out under strongly alkaline conditions, which is conducive to the progress of the hydrolysis reaction.

According to another specific embodiment of the method of the present invention, the temperature of the hydrolysis is 20-200°C, preferably 40-120°C, more preferably 60-90°C. The hydrolysis time is 0.1-24h, preferably 0.1-8h, more preferably 0.5-8h, most preferably 2-4h. Under the hydrolysis conditions, it is favorable for the hydrolysis reaction to proceed.

According to the present invention, the halogenated butyl polymer includes at least one of brominated butyl polymer and chlorinated butyl polymer.

According to a specific embodiment of the method of the present invention, the organic solvent may include any organic solvent capable of dissolving halogenated butyl rubber, such as may include an organic solvent selected from toluene, N, N-dimethylformamide, tetrahydrofuran and dihydrofuran. One or more of toluene.

According to another aspect of the present invention, an application of the hydroxyl-containing butyl rubber prepared by the method in toughening and pressure buffering materials is provided. The hydroxyl-containing butyl rubber provided by the present invention has broad application prospects in the fields of toughening and pressure buffering materials due to effectively improving the hydrophilic properties, compatibility, bonding properties and the like of the rubber.

According to the present invention, the halogenated butyl polymer is used as the substrate, and a nucleophilic substitution reaction is carried out under the action of a phase transfer catalyst to obtain a butyl polymer containing an ester group, which is then hydrolyzed into a butyl polymer containing a hydroxyl group under the action of alkalinity. things.

According to the method provided by the present invention, using a phase transfer catalyst, the hydroxylated butyl polymer prepared by nucleophilic substitution reaction and hydrolysis reaction under mild conditions not only has the excellent properties of butyl rubber, but also enhances its own polarity , effectively improve the hydrophilic properties of polymers, improve compatibility and bonding performance, and have the advantages of simple process and easy production.

Detailed ways

The present invention will be further described below in conjunction with specific examples, but this does not constitute any limitation to the present invention.

testing method:

Infrared analysis: Avatar 360FTIR infrared spectrometer from Nicolet Company of the United States, test conditions: in the range of 500-4000cm-1, the sample was prepared by KBr tablet method, and the infrared spectrum of BIIR before and after the reaction was tested.

Nuclear Magnetic Resonance Analysis: A Swiss Bruker AVANCE400 nuclear magnetic resonance instrument (400Hz) was used with a magnetic field strength of 9.40 Tesla, CDC1 ₃ was used as a solvent, TMS was used as an internal standard, and the test was performed at room temperature.

BIIR (bromobutyl rubber, 2222, commercially available) used in the examples contains 1.8 mmol of bromine in 5 g of BIIR. The hydroxyl substitution ratio described in the examples refers to the ratio of ester groups replaced by hydroxyl groups.

Embodiment 1 (comparison)

Under nitrogen atmosphere, BIIR (2222, commercially available, 5 g) was dissolved in toluene (80 ml), acetic acid (0.11 g, 1.8 mmol) was dissolved in potassium hydroxide (0.1 g, 1.8 mmol) solution. In a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, add the toluene solution of BIIR, and start stirring to make it completely dissolve. Aqueous sodium hydroxide aqueous solution (50ml) of acetic acid was slowly added, and after stirring for 10min, the temperature was raised to 60°C. After reacting for 6 hours, pour the mixed solution into a separatory funnel and let it stand for cooling, separate the organic phase (toluene solution), and precipitate the product in the organic phase with methanol, then wash it with alkaline water, then precipitate it with acetone, and repeat the operation After 3 times, put the sample into a vacuum drying oven to dry to constant weight. The product can be seen from the infrared spectrogram analysis: there is a stretching vibration absorption peak of methyl methylene at 2952cm ^-1 , there are double bond characteristic absorption peaks at 1576cm ^-1 and 1540cm ^-1 , and the deformation of methylene at 1471cm ^-1 Vibration absorption peaks, methyl deformation vibration absorption peaks at 1389cm ^-1 and 1365cm ^-1 , CC skeleton stretching vibration absorption peaks at 1229cm ^-1 , and characteristic absorption peaks of C-Br at 761cm ^-1 , all of which are brominated The characteristic absorption peak of butyl rubber, the infrared spectrum analysis of the reaction product shows that there is no substitution reaction.

Example 2

Under nitrogen atmosphere, BIIR (5 g) was dissolved in toluene (80 ml), acetic acid (0.11 g, 1.8 mmol) was dissolved in potassium hydroxide (0.1 g, 1.8 mmol) solution (50 ml). In a three-neck flask equipped with a stirrer, a reflux condenser, and a thermometer, add the toluene solution of BIIR and the phase transfer catalyst benzyltriethylammonium chloride (0.5g, 2mmol), and start stirring to completely dissolve it. Slowly add acetic acid/potassium hydroxide aqueous solution, stir for 10 minutes, heat up to 60°C, and react for 2 hours, take out part of the mixed solution (about 1/5) and pour it into a separatory funnel for cooling, and separate the organic phase (toluene solution) , the product in the organic phase was precipitated with methanol, then washed with alkaline water, and then precipitated with acetone. After repeated operations 3 times, the sample was placed in a vacuum drying oven and dried to constant weight. The bromine substitution ratio of intermediate product (the butyl rubber containing ester group) is 30%, can know by infrared spectrogram analysis: except the characteristic absorption peak of bromobutyl rubber, be the characteristic peak of carbonyl absorption at 1737cm ^-1 , reaction The infrared spectrum analysis of the product indicated that the esterification grafting of butyl rubber was successful.

Add sodium hydroxide solution aqueous solution (0.05mol/L) in remaining mixed solution, make pH be 12, then react 4h at 60 ℃, then pour into the separatory funnel and leave to cool, separate the organic phase (toluene solution). The product in the organic phase was precipitated with methanol, washed with alkaline water, and precipitated with acetone. After repeated operations for 3 times, the sample was dried in a vacuum drying oven to constant weight. The hydroxyl substitution rate of the final product was 95%. From the analysis of infrared spectrum, it can be seen that in addition to the characteristic absorption peak of bromobutyl rubber, 3600cm ^-1 is the characteristic peak of hydroxyl absorption. The infrared spectrum analysis of the reaction product shows that the hydroxylation grafting of butyl rubber is successful.

Example 3

Same as Example 2, but the type of phase transfer catalyst is different, the phase transfer catalyst is cetyltrimethylammonium bromide, the dosage is 0.7g, 2mmol. The bromine substitution ratio of the intermediate product was 45%. The hydroxyl substitution rate of the final product was 94%.

Example 4

Same as Example 2, but the type of phase transfer catalyst is different, the phase transfer catalyst is tetrabutylammonium hydroxide, and the consumption is 0.6g, 2mmol. The bromine substitution rate of the intermediate product was 72%. The hydroxyl substitution rate of the final product was 96%.

Example 5

Same as Example 2, but the type and amount of the phase transfer catalyst are different, the phase transfer catalyst is tetrabutylammonium bromide, and the amount is 0.32g, 1mmol. The bromine substitution rate of the intermediate product is 48%. The hydroxyl substitution rate of the final product was 93%.

Example 6

Same as Example 5, only the amount of phase transfer catalyst is different, the amount of phase transfer catalyst tetrabutylammonium bromide is 0.645g, 2mmol. The bromine substitution rate of the intermediate product is 75%. The hydroxyl substitution rate of the final product was 94%.

Example 7

Same as Example 5, only the amount of phase transfer catalyst is different, the amount of phase transfer catalyst tetrabutylammonium bromide is 1.612g, 5mmol. The bromine substitution rate of the intermediate product was 61%. The hydroxyl substitution rate of the final product was 94%.

Can find out from embodiment 2-7: belong to quaternary ammonium salt class phase transfer catalyst benzyl triethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, tetrabutyl ammonium hydroxide, tetrabutyl ammonium bromide all Allows nucleophilic substitution reactions to occur. It is more appropriate to control the molar ratio of phase transfer catalyst to acetic acid in the range of 0.5:1-2.5:1.

Example 8

Under nitrogen atmosphere, BIIR (2222, commercially available, 5 g) was dissolved in toluene (80 ml), and cinnamic acid (0.3 g, 2 mmol) was dissolved in sodium hydroxide (0.08 g, 2 mmol) solution (50 ml). In a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, add the toluene solution of BIIR and tetrabutylammonium bromide (0.645 g, 2 mmol), and start stirring to dissolve it completely. Slowly add the aqueous sodium hydroxide solution of cinnamic acid, stir for 10 min, then raise the temperature to 40°C. After reacting for 4 hours, take out a small amount of solution (about 1/5) and pour it into a separatory funnel and let it stand for cooling. The intermediate product is separated and precipitated with methanol, then washed with alkaline water, and precipitated with acetone. After repeated operations 3 times, The samples were dried in a vacuum oven until constant weight. The bromine substitution rate of the intermediate product is 38%. From the analysis of the infrared spectrum, it can be seen that in addition to the characteristic absorption peak of bromobutyl rubber, it is the characteristic peak of the carbonyl absorption at 1737cm ^-1 . The infrared spectrum analysis of the reaction product shows that the butyl rubber The esterification grafting was successful.

Aqueous ammonia was added to the remaining solution to make the pH of the solution 10, and then stirred at 90° C. for 1 h. Pour it into a separatory funnel and let it stand for cooling. The isolated product was precipitated with methanol, washed with alkaline water, and precipitated with acetone. After repeated operations for 3 times, the sample was dried in a vacuum drying oven to constant weight. The hydroxyl substitution rate of the product is 90%. From the analysis of infrared spectrum, it can be seen that in addition to the characteristic absorption peak of bromobutyl rubber, 3600cm ^-1 is the characteristic peak of hydroxyl absorption. The infrared spectrum analysis of the reaction product shows that the hydroxylation grafting of butyl rubber is successful.

Example 9

Same as Example 8, the difference is that the reaction temperature is different, the reaction temperature is 60°C, the bromine substitution rate of the intermediate product is 43%; the pH value is adjusted to 13 by adding potassium hydroxide aqueous solution, and the hydroxyl substitution rate of the final product is 95%.

Example 10

Same as Example 9, the difference is that the reaction temperature is different, the reaction temperature is 90° C., and the bromine substitution rate of the intermediate product is 73%.

Example 11

Same as Example 9, the difference is: the reaction temperature is different, and the reaction temperature is 120°C. The bromine substitution rate of the intermediate product is 30%.

It can be seen from Examples 8-11 that as the reaction temperature increases, the Br substitution rate gradually increases, but when the reaction temperature is too high, the evaporation of the water phase intensifies, which is not conducive to the occurrence of the substitution reaction. Therefore, the preferred temperature range is 20-200°C, more preferably 40-120°C, most preferably 60-90°C.

Example 12

Under nitrogen atmosphere, BIIR (5g) was dissolved in toluene (80ml), and stearic acid (0.57g, 2mmol) was dissolved in sodium hydroxide (0.08g, 2mmol) solution (50ml). In a three-neck flask equipped with a stirrer, a reflux condenser, and a thermometer, add the toluene solution of BIIR and tetrabutylammonium bromide (0.6 g, 2 mmol), and start stirring to dissolve it completely. Add stearic acid aqueous sodium hydroxide solution slowly, stir for 10 minutes, then raise the temperature to 70°C, and react for 0.1 hour. Then pour a small amount of mixed solution (about 1/5) into the separatory funnel and let it stand to cool, separate the organic phase product and precipitate it with methanol, then wash it with alkaline water, and precipitate it with acetone. After repeated operations 3 times, the test The samples were dried in a vacuum oven until constant weight. The bromine substitution rate of the intermediate product is 15%. From the analysis of the infrared spectrum, it can be seen that except the characteristic absorption peak of bromobutyl rubber, it is the characteristic peak of the carbonyl absorption at 1737cm ^-1 . The infrared spectrum analysis of the reaction product shows that the butyl rubber has Esterification grafting was successful.

Add aqueous sodium hydroxide solution (0.05mol/L) to the remaining mixed solution to make the pH of the mixed solution 13.5, then hydrolyze it at 70°C for 2h, then pour it into a separatory funnel and let it stand for cooling to separate the organic phase (toluene solution). The product in the organic phase was precipitated with methanol, washed with alkaline water, and precipitated with acetone. After repeated operations for 3 times, the sample was dried in a vacuum drying oven to constant weight. The hydroxyl substitution rate of the final product was 95%. From the analysis of infrared spectrum, it can be seen that in addition to the characteristic absorption peak of bromobutyl rubber, 3600cm ^-1 is the characteristic peak of hydroxyl absorption. The infrared spectrum analysis of the reaction product shows that the hydroxylation grafting of butyl rubber is successful.

Example 13

Same as Example 12, the difference is: the difference in reaction time, the reaction time is 4h, the bromine substitution rate of the intermediate product is 71%; the hydrolysis time is 1h, the hydroxyl substitution rate of the final product is 94%.

Example 14

Same as Example 13, the difference is that the reaction time is different, the reaction time is 8h, and the bromine substitution rate of the intermediate product is 65%.

It can be seen from Examples 12-14 that: with the prolongation of the reaction time, when the reaction time is too long, it is easy to cause degradation or discoloration of BIIR. Therefore, the reaction time is 0.1-24h, preferably 0.1-8h, more preferably 0.5-8h, most preferably 2-4h.

Example 15

Under nitrogen atmosphere, BIIR (5 g) was dissolved in toluene (80 ml), methacrylic acid (0.155 g, 1.8 mmol) was dissolved in sodium hydroxide (0.07 g, 1.8 mmol) solution (50 ml). In a three-neck flask equipped with a stirrer, a reflux condenser, and a thermometer, add the toluene solution of BIIR and tetrabutylammonium bromide (0.6 g, 2 mmol), and start stirring to dissolve it completely. Add sodium hydroxide aqueous solution of methacrylic acid slowly, stir for 10 minutes, then raise the temperature to 70°C, and react for 4 hours. Pour a part (about 1/5) of the resulting mixed solution into a separatory funnel and let it stand for cooling. The separated product is precipitated with methanol, washed with alkaline water, and precipitated with acetone. After repeated operations 3 times, the test The samples were dried in a vacuum oven until constant weight. The bromine substitution rate of the product is 32%. According to the infrared spectrum analysis, the characteristic peak of carbonyl absorption is at 1737cm ^-1 , indicating that the esterification grafting of butyl rubber is successful.

Then add a pH regulator to the remaining mixed solution to make the pH of the solution 12. After reacting at 70°C for 2 hours, pour it into a separatory funnel and let it cool down. The separated product is precipitated with methanol, and then washed with alkaline water. After washing, it was precipitated with acetone, and after repeated operation 3 times, the sample was dried in a vacuum drying oven to constant weight. The hydroxyl substitution rate of the product is 94%. From the analysis of infrared spectrum, it can be seen that in addition to the characteristic absorption peak of bromobutyl rubber, 3600cm ^-1 is the characteristic peak of hydroxyl absorption. The infrared spectrum analysis of the reaction product shows that the hydroxylation grafting of butyl rubber is successful.

Example 16

Same as Example 15, the difference is that the amount of nucleophile used is 1.55 g, 18 mmol, and the bromine substitution rate of the intermediate product is 75%.

Example 17

Same as Example 15, the difference is that the amount of nucleophile used is 3.1 g, 36 mmol. The bromine substitution rate of the intermediate product is 63%.

As can be seen from Examples 15-17, the amount of nucleophile added has an important effect on the nucleophilic substitution reaction. Preferably the molar ratio of carboxylate to halogen in the halobutyl rubber is 1:1-20:1, more preferably 1:5-1:20, such as 1:10-1:20.

Example 18

Under nitrogen atmosphere, BIIR (2222, commercially available, 5g) was dissolved in toluene (80ml), methacrylic acid (1.55g, 0.018mol) was dissolved in sodium hydroxide (1.2g, 0.03mol) solution (50ml) . In a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, add the toluene solution of BIIR and tetrabutylammonium bromide (5.8 g, 0.018 mol), and start stirring to dissolve it completely. Add sodium hydroxide aqueous solution of methacrylic acid slowly, stir for 10 minutes, and then raise the temperature to 70°C. After reacting for 4 hours, pour the mixed solution into a separatory funnel and let it stand for cooling. The separated product is precipitated with methanol, washed with alkaline water, and precipitated with acetone. After repeated operations for 3 times, the sample is placed in a vacuum drying oven. Dry to constant weight. From the analysis of infrared spectrum, it can be seen that in addition to the characteristic absorption peak of bromobutyl rubber, 3600cm ^-1 is the characteristic peak of carbonyl absorption. The infrared spectrum analysis of the reaction product shows that the hydroxylation grafting of butyl rubber is successful.

It can be seen from the above examples that the base used for hydrolysis and the base required for forming the nucleophile are added together, and the ester group obtained by the reaction is further hydrolyzed into a hydroxyl group to obtain a hydroxyl-containing polymer.

It should be noted that the above-mentioned embodiments are only used to explain the present invention, and do not constitute any limitation to the present invention. The invention has been described with reference to typical embodiments, but the words which have been used therein are words of description and explanation rather than words of limitation. The present invention can be modified within the scope of the claims of the present invention as prescribed, and the present invention can be revised without departing from the scope and spirit of the present invention. Although the invention described therein refers to specific methods, materials and examples, it is not intended that the invention be limited to the specific examples disclosed therein, but rather, the invention extends to all other methods and applications having the same function.

Claims (31)

1. a kind of method for preparing hydroxylating butyl rubber, including：Under the action of phase transfer catalyst, halogenated butyl rubber Organic solvent solution is contacted and reacted with the aqueous solution of carboxylate, generates the butyl rubber containing ester group, and then hydrolysis obtains containing hydroxyl The butyl rubber of base.

2. according to the method described in claim 1, it is characterized in that, in the carboxylate and halogenated butyl rubber halogen mole Than for 1:2-30:1.

3. according to the method described in claim 1, it is characterized in that, in the carboxylate and halogenated butyl rubber halogen mole Than for 1:1-20:1.

4. according to the method described in claim 1, it is characterized in that, in the carboxylate and halogenated butyl rubber halogen mole Than for 10:1-20:1.

5. according to the method described in claim 1, it is characterized in that, the molar ratio of the phase transfer catalyst and carboxylate is 0.1:1-5:1。

6. according to the method described in claim 5, it is characterized in that, the molar ratio of the phase transfer catalyst and carboxylate is 0.5:1-2.5:1。

7. according to the method described in any one in claim 1-6, it is characterised in that the temperature of the reaction is 20-200 ℃；The time of the reaction is 0.1-24h.

8. the method according to the description of claim 7 is characterized in that the temperature of the reaction is 40-120 DEG C；The reaction Time is 0.1-8h.

9. the method according to the description of claim 7 is characterized in that the temperature of the reaction is 60-90 DEG C；The reaction when Between be 0.5-8h.

10. the method according to the description of claim 7 is characterized in that the time of the reaction is 2-4h.

11. according to the method described in any one in claim 1-6, it is characterised in that it is described hydrolysis in alkaline conditions into OK.

12. according to the method for claim 11, it is characterised in that the pH value that the alkaline condition refers to solution is more than 7.

13. according to the method for claim 11, it is characterised in that the pH value that the alkaline condition refers to solution is 8-14.

14. according to the method for claim 11, it is characterised in that the pH value that the alkaline condition refers to solution is 12-14.

15. according to the method described in any one in claim 1-6, it is characterised in that the temperature of the hydrolysis is 20-200 ℃。

16. according to the method for claim 15, it is characterised in that the temperature of the hydrolysis is 40-120 DEG C.

17. according to the method for claim 15, it is characterised in that the temperature of the hydrolysis is 60-90 DEG C.

18. according to the method described in any one in claim 1-6, it is characterised in that the time of the hydrolysis is 0.1- 24h。

19. according to the method for claim 18, it is characterised in that the time of the hydrolysis is 0.1-8h.

20. according to the method for claim 18, it is characterised in that the time of the hydrolysis is 0.5-8h.

21. according to the method for claim 18, it is characterised in that the time of the hydrolysis is 2-4h.

22. according to the method described in any one in claim 1-6, it is characterised in that the phase transfer catalyst includes season Ammonium salt class phase transfer catalyst.

23. according to the method for claim 22, it is characterised in that the phase transfer catalyst includes being selected from tetrabutyl phosphonium bromide One or more in ammonium, tetrabutylammonium hydroxide, triethyl benzyl ammonia chloride and cetyl trimethylammonium bromide.

24. according to the method described in any one in claim 1-6, it is characterised in that the halogenated butyl rubber includes bromine Change at least one of butyl rubber and chlorinated scoline.

25. according to the method described in any one in claim 1-6, it is characterised in that the carboxylate is carboxylic acid and alkali gold Belong to the anionic nucleophile of salt generation.

26. according to the method for claim 25, it is characterised in that the alkali metal salt is Na the or K salt of hydroxyl.

27. according to the method for claim 25, it is characterised in that the structural formula of the carboxylic acid is R-COOH, and R is H, alkyl Or aryl.

28. according to the method for claim 27, it is characterised in that R is selected from H, C₁-C₂₀Alkyl and C₆-C₁₅Contain aryl Group.

29. according to the method for claim 25, it is characterised in that the structural formula of the carboxylic acid is R-COOH, and R is C₂-C₂₀ Alkylene.

30. according to the method for claim 25, it is characterised in that the carboxylic acid be selected from formic acid, acetic acid, propionic acid, acrylic acid, Butyric acid, cinnamic acid, stearic acid and methacrylic acid.

31. the butyl rubber of the hydroxyl prepared according to any one the method in claim 1-30 delays in toughness reinforcing, pressure Rush the application in material.