CN105646739B - A kind of method and its application for preparing hydroxylating modified butyl rubber - Google Patents
A kind of method and its application for preparing hydroxylating modified butyl rubber Download PDFInfo
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Abstract
The invention discloses a kind of method for preparing hydroxylating butyl rubber, including：Under the action of phase transfer catalyst, the organic solvent solution of halogenated butyl rubber is contacted and reacted with the aqueous solution of carboxylate, generates the butyl rubber containing ester group, and then hydrolysis obtains the butyl rubber of hydroxyl.Hydroxylating butyl polymer prepared by the method provided according to the present invention, the not only excellent properties with butyl rubber, but also enhance the polarity of itself, technique is simple, is readily produced.
Description
Technical field
The present invention relates to a kind of rubber materials, further say, be related to and a kind of prepare hydroxylating modified butyl rubber
Method.The application of the hydroxylating modified butyl rubber prepared the invention further relates to the above method.
Background technology
Butyl rubber (IIR) is the rubbery copolymer formed by isobutene and a small amount of isoprene random copolymerization, is had good
Good chemical stability, heat endurance, ozone resistants and gratifying damping and amortization.However, the butyl rubber of commerical grade has
The unsaturation of about 2mol% is horizontal, and degree of unsaturation is directly proportional to the stability of material, limits the curing of these polymer
Reactivity, and its polarity is weaker, causes it poor with the compatibility of other polymers, hydrophilicity is poor.For this reason, it may be necessary to butyl
Rubber is modified, and such as carries out halogenation modification to butyl rubber, reduces degree of unsaturation, improve with the compatibilities of other polymers and
Hydrophily etc., can expand its application range.Carry out halogenation modification to butyl rubber becomes a kind of more mature butyl rubber
Glue modification technology, its major product have chlorinated scoline (CIIR) and brombutyl (BIIR).However, halobutyl rubber
Glue has the defects of certain, i.e., when carrying out burning disposal to halogenated butyl rubber, can produce halogen toxic gas, cause ring
Pollute in border.
Another kind is exactly to synthesize the polymer of hydroxyl to the method that butyl rubber is modified, and such as first synthesis contains protection
The monomer of group, the polymer of blocking group is then contained by positive (the moon) ionic polymerization synthesis side base of controllable/activity, is finally gathered
Compound further by hydrolyzing the polymer for obtaining side base and containing hydroxyl, can improve the hydrophilicity of polymer well.Such as
Faust et al. reports the monomer for carrying out controllable cationic polymerization containing saturated group, such as tertiary butyl dimethyl Si base
Styrene, to tert-Butyl vinyl ether.However, monomer of the synthesis containing blocking group is cumbersome, complex process, it is difficult to push away
Wide application.
The present invention provides a kind of method for preparing hydroxylating butyl rubber, its technique is simple, and flow is short, can be effectively
Improve the hydrophilicity of polymer, improve compatibility, adhesive property etc..
The content of the invention
For deficiency of the prior art, there is provided a kind of method for preparing hydroxylating butyl rubber, technological process is short, work
Skill is simple to operation, can improve the hydrophilicity of polymer, improves compatibility, adhesive property etc..
According to an aspect of the invention, there is provided a kind of method for preparing hydroxylating butyl rubber, including：In phase transfer
Under the action of catalyst, the organic solvent solution of halogenated butyl rubber is contacted and reacted with the aqueous solution of carboxylate, and generation is ester-containing
The butyl rubber of base, then hydrolysis obtain the butyl rubber of hydroxyl.
The solubility of high polymer (halogenated butyl rubber, containing electrophilic group) and nucleopilic reagent differs very greatly different,
In these two phase reactions, often to use and arrive phase transfer catalyst, primarily to promoting nucleophilic displacement of fluorine anti-on two-phase interface
The generation answered, or the nucleopilic reagent in high polymer is changed into electrophilic reagent.In an instantiation, the phase transfer
Catalyst includes quaternary ammonium salts phase transfer catalyst, preferably includes tetrabutylammonium bromide, tetrabutylammonium hydroxide, triethylbenzyl
One or more in ammonium chloride and cetyl trimethylammonium bromide.In a preferable application examples, the phase transfer is urged
Agent and the molar ratio of carboxylate are 0.1:1-5:1, preferably 0.5:1-2.5:1.
According to the present invention, the carboxylate is anionic nucleophile.In a specific embodiment, the carboxylate is carboxylic
Acid is generated with alkali metal salt.In a specific embodiment, the carboxylate can use the form table of carboxylic acid/alkali metal salt
Show.A specific embodiment of the method according to the present invention, the molar ratio of halogen in the carboxylate and halogenated butyl rubber
For 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 the present invention one
A preferred embodiment, the alkali metal salt is Na the or K salt of hydroxyl, such as sodium hydroxide or potassium hydroxide.The carboxylic acid structure formula
For R-COOH, wherein, R can be selected from the group that H, aryl and alkyl form, and preferably be selected from H, C1-C20Alkyl (such as C1-
C18Alkyl), C2-C20Alkenyl (such as C2-C10Alkenyl) and C6-C15Group containing aryl.The carboxylic acid preferably is selected from formic acid, second
Acid, propionic acid, acrylic acid, butyric acid, stearic acid, cinnamic acid, methacrylic acid.
Another specific embodiment of the method according to the present invention, the temperature of reaction is 20-200 DEG C, preferably 40-120
DEG C, more preferably 60-90 DEG C.The time of the reaction is 0.1-24h, preferably 0.1-8h, more preferably 0.5-8h, most preferably 2-4h.
In above-mentioned reaction temperature and/or in the time, be conducive to the progress of nucleophilic substitution, avoid discoloration of rubber etc..
Method according to the present invention, the hydrolysis can it is any can be hydrolyzed under conditions of carry out, such as can be
Carry out under acid condition, can also carry out in alkaline conditions.In an instantiation, it is described hydrolysis in alkaline conditions into
OK, carry out being conducive to the more thorough, more abundant of hydrolysis progress in alkaline conditions.In one embodiment of the invention,
The alkaline condition can be realized by adding pH adjusting agent into solution.In a preferable application examples, the alkalescence bar
Part can be realized by adding lye.Alkali in the lye can be identical or different with the alkali used in formation carboxylate.When its phase
Meanwhile also the lye used needed for hydrolysis can together be added with forming the lye needed for carboxylate.
In an instantiation, the pH value that the alkaline condition refers to solution is more than 7.It is in situations where it is preferred, alkaline
It is 8-14, more preferably pH value 12-14 that condition, which refers to pH value,；Namely be preferably hydrolyzed under strongly alkaline conditions, it is anti-to be conducive to hydrolysis
The progress answered.
Another specific embodiment of the method according to the present invention, the temperature of the hydrolysis is 20-200 DEG C, preferably 40-
120 DEG C, more preferably 60-90 DEG C.The time of hydrolysis is 0.1-24h, preferably 0.1-8h, more preferably 0.5-8h, most preferably 2-4h.
Under the hydrolysising condition, be conducive to the progress of hydrolysis.
According to the present invention, the halogenated butyl polymer is included in polymer bromobutyl and chlorinated butyl polymer extremely
Few one kind.
A specific embodiment of the method according to the present invention, the organic solvent can include it is any can be by halogenation
The organic solvent of butyl rubber dissolving, as may include in toluene, n,N-Dimethylformamide, tetrahydrofuran and dimethylbenzene
It is one or more.
Another aspect according to the present invention, there is provided a kind of butyl rubber of hydroxyl prepared by the method is increasing
Application in tough, pressure buffer material.The butyl rubber of the hydroxyl provided according to the present invention, due to effectively improving rubber
Hydrophilicity, compatibility, adhesive property etc., there is broad application prospect in the fields such as toughness reinforcing, pressure buffer material.
According to the present invention, using halogenated butyl polymer as matrix, progress nucleophilic displacement of fluorine is anti-under phase transfer catalyst effect
Should, the butyl polymer containing ester group is obtained, then in the case where alkalescence acts on, is hydrolyzed into the butyl polymer of hydroxyl.
The method provided according to the present invention, using phase transfer catalyst, in a mild condition by nucleophilic substitution and
Hydroxylating butyl polymer prepared by hydrolysis, the not only excellent properties with butyl rubber, but also enhance itself
Polarity, effectively improves the hydrophilicity of polymer, improves compatibility, adhesive property, and with technique it is simple, be readily produced
Advantage.
Embodiment
The present invention is further described with reference to specific embodiment, but does not form any limitation of the invention.
Test method：
Infrared analysis：The Avatar 360FTIR infrared spectrometers of Nicolet companies of the U.S., test condition：In wave band
In the range of 500-4000cm-1, with KBr pressed disc method sample preparations, the infrared spectrum of BIIR before and after test reaction.
Nuclear magnetic resonance spectroscopy：It is special using Switzerland's Bruker AVANCE400 Nuclear Magnetic Resonance (400Hz), magnetic field intensity 9.40
Si La, with CDC13Make solvent, TMS is internal standard, and room temperature is tested.
Brominated 1.8mmol in BIIR used in embodiment (brombutyl, 2222, commercially available), 5gBIIR.Embodiment
Described in hydroxyl Replacement rate refer to the ratio that ester group is optionally substituted by a hydroxyl group.
Embodiment 1 (contrast)
Under nitrogen atmosphere, BIIR (2222, commercially available, 5g) is dissolved in toluene (80ml), acetic acid (0.11g,
1.8mmol) it is dissolved in potassium hydroxide (0.1g, 1.8mmol) solution.Equipped with blender, reflux condensing tube, thermometer three
In mouth flask, the toluene solution of BIIR is added, stirring is started, is completely dissolved it.The sodium hydroxide for being slowly added to acetic acid is water-soluble
Liquid (50ml), after stirring 10min, is warming up to 60 DEG C.After reacting 6h, mixed solution is poured into cooling is stood in separatory funnel, point
Organic phase (toluene solution) is separated out, by the product methanol extraction in organic phase, then with after soda lye wash, uses acetone precipitation
Go out, after operating 3 times repeatedly, sample is put into vacuum drying chamber and is dried to constant weight.Product is analyzed from infrared spectrum：
2952cm-1There are the stretching vibration absworption peak of methylmethylene, 1576cm in place-1And 1540cm-1There is double bond characteristic absorption peak at place,
1471cm-1Locate the deformation vibration the absworption peak for methylene, 1389cm-1And 1365cm-1Locate as methyl deformation vibration the absworption peak,
1229cm-1Locate as C-C skeleton stretching vibration absworption peaks, 761cm-1Locate the characteristic absorption peak for C-Br, these are all brominated butyls
The characteristic absorption peak of rubber, the infrared spectrum analysis of reaction product show in no substitution reaction.
Embodiment 2
Under nitrogen atmosphere, BIIR (5g) is dissolved in toluene (80ml), acetic acid (0.11g, 1.8mmol) is dissolved in hydrogen
In potassium oxide (0.1g, 1.8mmol) solution (50ml).Equipped with blender, reflux condensing tube, thermometer three-necked flask in,
The toluene solution and phase transfer catalyst benzyltriethylammoinium chloride (0.5g, 2mmol) of BIIR is added, stirring is started, makes its complete
Fully dissolved.Acetic acid/potassium hydroxide aqueous solution is slowly added to, after stirring 10min, is warming up to 60 DEG C, after reacting 2h, it is mixed to take out part
Close solution (about 1/5) and pour into standing cooling in separatory funnel, isolate organic phase (toluene solution), the product in organic phase is used
Methanol extraction, then with after soda lye wash, is gone out with acetone precipitation, after operating 3 times repeatedly, sample is put into vacuum drying chamber and is done
It is dry to constant weight.The bromine Replacement rate of intermediate product (butyl rubber containing ester group) is 30%, is analyzed from infrared spectrum：Except bromine
Outside the characteristic absorption peak for changing butyl rubber, in 1737cm-1For the characteristic peak of carbonyl absorption, the infrared spectrum analysis table of reaction product
The ester grafting success of bright butyl rubber.
Sodium hydroxide solution aqueous solution (0.05mol/L) is added into remaining mixed solution, it is 12 to make pH, then 60
4h is reacted at DEG C, is subsequently poured into separatory funnel and stands cooling, isolate organic phase (toluene solution).By the product in organic phase
With methanol extraction, then with after soda lye wash, gone out with acetone precipitation, after operating 3 times repeatedly, sample is put into vacuum drying chamber
Dry to constant weight.The hydroxyl Replacement rate of final product is 95%.Analyzed from infrared spectrum：Except the spy of brombutyl
Levy outside absworption peak, 3600cm-1For the characteristic peak of hydroxyl group absorption, the infrared spectrum analysis of reaction product shows the hydroxyl of butyl rubber
Change is grafted successfully.
Embodiment 3
With embodiment 2, but phase transfer catalyst species is different, and phase transfer catalyst is cetyl trimethylammonium bromide,
Dosage 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 species is different, and phase transfer catalyst is tetrabutylammonium hydroxide, and dosage 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 species is different with dosage, and phase transfer catalyst is tetrabutylammonium bromide, is used
Measure as 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 dosage is different, phase transfer catalyst tetrabutylammonium bromide, and dosage 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 dosage is different, and phase transfer catalyst tetrabutylammonium bromide dosage is
1.612g 5mmol.The bromine Replacement rate of intermediate product is 61%.The hydroxyl Replacement rate of final product is 94%.
It can be seen that from embodiment 2-7：Belong to quaternary ammonium salts phase transfer catalyst benzyltriethylammoinium chloride, cetyl
Trimethylammonium bromide, tetrabutylammonium hydroxide, tetrabutylammonium bromide can make nucleophilic substitution.Phase transfer catalyst with
The mol of acetic acid is than control 0.5:1-2.5：It is more suitable in the range of 1.
Embodiment 8
Under nitrogen atmosphere, BIIR (2222, commercially available, 5g) is dissolved in toluene (80ml), cinnamic acid (0.3g,
2mmol) solution is in sodium hydroxide (0.08g, 2mmol) solution (50ml).Equipped with blender, reflux condensing tube, thermometer
In three-necked flask, the toluene solution and tetrabutylammonium bromide (0.645g, 2mmol) of BIIR are added, starts stirring, make it completely molten
Solution.The sodium hydrate aqueous solution of cinnamic acid is slowly added to, after stirring 10min, is warming up to 40 DEG C.After reacting 4h, take out a small amount of
Solution (about 1/5), which pours into, stands cooling in separatory funnel, isolate intermediate product methanol extraction, then with after soda lye wash,
Gone out with acetone precipitation, after operating 3 times repeatedly, sample is put into vacuum drying chamber and is dried to constant weight.The bromine substitution of intermediate product
Rate is 38%, is analyzed from infrared spectrum：In addition to the characteristic absorption peak of brombutyl, in 1737cm-1Inhaled for carbonyl
The characteristic peak of receipts, the infrared spectrum analysis of reaction product show the ester grafting success of butyl rubber.
Ammonium hydroxide is added into remaining solution, it is 10 to make solution ph, then stirs 1h at 90 DEG C.Pour into separatory funnel
Cooling is stood, product methanol extraction is isolated, then with after soda lye wash, is gone out with acetone precipitation, will after operating 3 times repeatedly
Sample is put into vacuum drying chamber and dries to constant weight.The hydroxyl Replacement rate of product is 90%.Analyzed from infrared spectrum：Except
Outside the characteristic absorption peak of brombutyl, 3600cm-1For the characteristic peak of hydroxyl group absorption, the infrared spectrum analysis table of reaction product
The hydroxylating of bright butyl rubber is grafted successfully.
Embodiment 9
With embodiment 8, difference lies in：The difference of reaction temperature, 60 DEG C of reaction temperature, the bromine Replacement rate of intermediate product are
43%；It is 13 to add potassium hydroxide aqueous solution and adjust to pH value, and the hydroxyl Replacement rate of final product is 95%.
Embodiment 10
With embodiment 9, difference lies in：The difference of reaction temperature, reaction temperature are 90 DEG C, and intermediate product bromine Replacement rate is
73%.
Embodiment 11
With embodiment 9, difference lies in：The difference of reaction temperature, reaction temperature are 120 DEG C.Intermediate product bromine Replacement rate is
30%.
It can be seen that from embodiment 8-11：With the rise of reaction temperature, Br Replacement rates gradually increase, but work as reaction temperature
When excessive, water mutually evaporates aggravation, is unfavorable for the generation of substitution reaction on the contrary.It is therefore preferable that the scope of temperature is 20-200 DEG C, more
It is preferred that 40-120 DEG C, most preferably 60-90 DEG C is most.
Embodiment 12
Under nitrogen atmosphere, BIIR (5g) is dissolved in toluene (80ml), stearic acid (0.57g, 2mmol) solution is in hydrogen-oxygen
Change in sodium (0.08g, 2mmol) solution (50ml).Equipped with blender, reflux condensing tube, thermometer three-necked flask in, add
The toluene solution and tetrabutylammonium bromide (0.6g, 2mmol) of BIIR, starts stirring, is completely dissolved it.It is slowly added to stearic acid
Sodium hydrate aqueous solution, after stirring 10min, 70 DEG C are warming up to, when reaction 0.1 is small.Then by a small amount of mixed solution (about 1/5)
Pour into and cooling is stood in separatory funnel, isolate organic phase product methanol extraction, then with after soda lye wash, use acetone precipitation
Go out, after operating 3 times repeatedly, sample is put into vacuum drying chamber and is dried to constant weight.Intermediate product bromine Replacement rate is 15%, by red
Outer spectrum analysis are understood：In addition to the characteristic absorption peak of brombutyl, in 1737cm-1For the characteristic peak of carbonyl absorption, instead
The infrared spectrum analysis of product is answered to show the ester grafting success of butyl rubber.
Sodium hydroxide solution aqueous solution (0.05mol/L) is added into remaining mixed solution, the pH for making mixed solution is
13.5,2h then is hydrolyzed at 70 DEG C, is subsequently poured into separatory funnel and stands cooling, isolate organic phase (toluene solution).Will
Product methanol extraction in organic phase, then with after soda lye wash, is gone out with acetone precipitation, and after operating 3 times repeatedly, sample is put
Enter in vacuum drying chamber and dry to constant weight.The hydroxyl Replacement rate of final product is 95%.Analyzed from infrared spectrum：Except bromine
Outside the characteristic absorption peak for changing butyl rubber, 3600cm-1For the characteristic peak of hydroxyl group absorption, the infrared spectrum analysis of reaction product shows
The hydroxylating of butyl rubber is grafted successfully.
Embodiment 13
With embodiment 12, difference lies in：The difference in reaction time, reaction time 4h, intermediate product bromine Replacement rate are
71%；Hydrolysis time is 1h, and the hydroxyl Replacement rate of final product is 94%.
Embodiment 14
With embodiment 13, difference lies in：The difference in reaction time, reaction time 8h, intermediate product bromine Replacement rate are
65%.
It can be seen that from embodiment 12-14：With the extension in reaction time, when the reaction time is too long, it is easy to cause
BIIR degrades or discoloration.Therefore, reaction time 0.1-24h, preferably 0.1-8h, more preferably 0.5-8h, most preferably 2-4h.
Embodiment 15
Under nitrogen atmosphere, BIIR (5g) is dissolved in toluene (80ml), methacrylic acid (0.155g, 1.8mmol)
It is dissolved in sodium hydroxide (0.07g, 1.8mmol) solution (50ml).Equipped with blender, reflux condensing tube, thermometer three
In mouth flask, the toluene solution and tetrabutylammonium bromide (0.6g, 2mmol) of BIIR are added, stirring is started, is completely dissolved it.
The sodium hydrate aqueous solution of methacrylic acid is slowly added to, after stirring 10min, is warming up to 70 DEG C, when reaction 4 is small.By what is obtained
A part (about 1/5) for mixed solution, which is poured into, stands cooling in separatory funnel, isolate product methanol extraction, then use buck
After washing, gone out with acetone precipitation, after operating 3 times repeatedly, sample is put into vacuum drying chamber and is dried to constant weight.Product bromine substitutes
Rate is 32%, is analyzed from infrared spectrum：In 1737cm-1For the characteristic peak of carbonyl absorption, show the ester of butyl rubber
It is grafted successfully.
Then pH adjusting agent is added into remaining mixed solution, it is 12 to make solution ph, after reacting 2h at 70 DEG C,
Pour into and cooling is stood in separatory funnel, isolate product methanol extraction, then with after soda lye wash, gone out with acetone precipitation, instead
After operating 3 times again, sample is put into vacuum drying chamber and is dried to constant weight.Product hydroxy Replacement rate is 94%.By infrared spectrum
Analysis is understood：In addition to the characteristic absorption peak of brombutyl, 3600cm-1For the characteristic peak of hydroxyl group absorption, reaction product
Infrared spectrum analysis shows that the hydroxylating of butyl rubber is grafted successfully.
Embodiment 16
With embodiment 15, difference lies in：The difference of nucleopilic reagent dosage, is 1.55g, 18mmol, the substitution of intermediate product bromine
Rate is 75%.
Embodiment 17
With embodiment 15, difference lies in：The difference of nucleopilic reagent dosage, is 3.1g, 36mmol.Intermediate product bromine Replacement rate
For 63%.
From embodiment 15-17 it is known that the amount of the nucleopilic reagent added has important influence to nucleophilic substitution.
It is preferred that the molar ratio of halogen is 1 in carboxylate and halogenated butyl rubber:1-20:1, more preferably 1:5-1:20, such as 1:10-1:20.
Embodiment 18
Under nitrogen atmosphere, BIIR (2222, commercially available, 5g) is dissolved in toluene (80ml), methacrylic acid (1.55g,
0.018mol) it is dissolved in sodium hydroxide (1.2g, 0.03mol) solution (50ml).Equipped with blender, reflux condensing tube, temperature
Spend in the three-necked flask of meter, add the toluene solution and tetrabutylammonium bromide (5.8g, 0.018mol) of BIIR, start stirring, make
It is completely dissolved.The sodium hydrate aqueous solution of methacrylic acid is slowly added to, after stirring 10min, is warming up to 70 DEG C.It is small to react 4
When after mixed solution poured into stand in separatory funnel cool down, isolate product methanol extraction, then with after soda lye wash, use
Acetone precipitation goes out, and after operating 3 times repeatedly, sample is put into vacuum drying chamber and is dried to constant weight.Analyzed from infrared spectrum：
In addition to the characteristic absorption peak of brombutyl, 3600cm-1For the characteristic peak of carbonyl absorption, the infrared spectrum point of reaction product
Analysis shows that the hydroxylating of butyl rubber is grafted successfully.
As seen from the above embodiment：Hydrolysis alkali used is added with being formed together with the alkali needed for nucleopilic reagent, is reacted
To ester group be further continued for being hydrolyzed to hydroxyl, obtained the polymer of hydroxyl.
It should be noted that embodiment described above is only used for explaining the present invention, do not form to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, on the contrary, this hair
It is bright to can be extended to other all methods and applications with identical 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.
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| CN101003603A (en) * | 2005-08-26 | 2007-07-25 | 兰科瑟斯有限公司 | Novel methods for the preparation of butyl graft copolymers |
| CN101233186A (en) * | 2005-08-05 | 2008-07-30 | 朗盛公司 | Halobutyl elastomers |
| CN103443166A (en) * | 2010-08-13 | 2013-12-11 | 朗盛公司 | Method of preparing novel graft copolymers |
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| CN101233186A (en) * | 2005-08-05 | 2008-07-30 | 朗盛公司 | Halobutyl elastomers |
| CN101003603A (en) * | 2005-08-26 | 2007-07-25 | 兰科瑟斯有限公司 | Novel methods for the preparation of butyl graft copolymers |
| CN103443166A (en) * | 2010-08-13 | 2013-12-11 | 朗盛公司 | Method of preparing novel graft copolymers |
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