CN108816285A - The controllable epoxidized SBS of epoxy rate, peroxidating phosphorus heteropoly tungstic acid phase transfer catalyst and preparation method thereof - Google Patents
The controllable epoxidized SBS of epoxy rate, peroxidating phosphorus heteropoly tungstic acid phase transfer catalyst and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/08—Epoxidation
Abstract
The present invention discloses a kind of preparation method of peroxidating phosphorus heteropoly tungstic acid phase transfer catalyst, is reacted under heating with hydrogen peroxide, wolframic acid, and phosphoric acid is added, and C is added dropwise into filtrate for filteringnH2n+4NCl solution, stirring, stratification take lower layer's solution, filter after being dried over anhydrous sodium sulfate, and catalyst, the C are obtained after vacuum distillationnH2n+ 438 >=n >=16 in NCl.The present invention discloses a kind of peroxidating phosphorus heteropoly tungstic acid phase transfer catalyst.In addition, a kind of preparation method of the epoxidized SBS that epoxy rate is controllable (eSBS), with the mixed solvent of one or more of dichloroethanes, toluene, hexamethylene, ethyl acetate, using hydrogen peroxide as oxygen source, used oxidation phosphorus heteropoly tungstic acid phase transfer catalyst, catalytic oxidation, it is alternately washed with n-hexane and methanol, after anhydrous magnesium sulfate is dry, vacuum drying obtains epoxidized SBS (eSBS).The present invention discloses a kind of epoxidized SBS that epoxy rate is controllable (eSBS).
Description
Technical field
The invention belongs to chemical processing fields, and in particular to the controllable epoxidized SBS of epoxy rate, peroxidating phosphorus tungsten are miscellaneous more
Sour phase transfer catalyst and preparation method thereof.
Background technique
SBS has extensive purposes in fields such as adhesive, sealant, coating, shoes, asphalt modification and polymer modifications,
It has the double grading of thermoplastic and vulcanized rubber, is the current maximum thermoplastic elastomer (TPE) of yield in the world.But SBS
Polybutadiene (PB) section on there are a large amount of double bond functional groups, loss of properties on aging, oil resistivity and mechanical strength are insufficient, affect
The application of SBS in all respects.In recent years, epoxidized SBS is main chemical modification method, i.e., by from oxygen source to polybutadiene
(PB) double bond in section introduces oxygen atom to reduce double bond content, not only increases polarity and resistance to ag(e)ing, and improve SBS's
Mechanical property.There is researcher to use fatty acid organic solvent using hydrogen peroxide as oxygen source epoxidized SBS, this method exists secondary anti-
It answers, is unfavorable for the control of epoxidation level.Chinese patent CN102675569A uses formic acid/hexamethylene/phase transfer reagent system
Using hydrogen peroxide as oxygen source, epoxidation modification has been carried out to SBS, the epoxidized SBS (ESBS) that epoxide number is 1-10% can be made, mention
The high performance of various aspects, this method, which whether there is side reaction and have no, to be discussed in detail.Chinese patent CN 105949353A is used
Double octadecyldimethylamine/the organic solvents of formic acid/bromination are prepared for epoxide number and exist using tert-butyl hydroperoxide as oxygen source
The epoxidized SBS of 0.14-0.22mol/100g, but not yet mention the dissolubility of different epoxide number SBS.Therefore, it is necessary to further
Further investigation SBS epoxy rate is controllable and meets effective method of modifying of Green Chemistry.
Summary of the invention
The purpose of the present invention is to provide the controllable epoxidized SBSs and preparation method thereof of epoxy rate, another object is that mentioning
For a kind of peroxidating phosphorus heteropoly tungstic acid phase transfer catalyst and preparation method thereof.
In order to achieve the above object of the invention, the technical scheme is that：
A kind of preparation method of peroxidating phosphorus heteropoly tungstic acid phase transfer catalyst, is reacted under heating with hydrogen peroxide, wolframic acid,
Filtering, is added phosphoric acid, and C is added dropwise into filtrate for stirringnH2n+4NCl solution, stirring, stratification takes lower layer's solution, through anhydrous sulphur
It is filtered after sour sodium is dry, catalyst, the C is obtained after vacuum distillationnH2n+438 >=n >=16 in NCl.
Preferably, the concentration of the hydrogen peroxide is 20wt%~50wt%；The temperature of the reaction is 40 DEG C~80 DEG C；Institute
The time for stating reaction is 3 hours~12 hours；The concentration of the phosphoric acid is 30w/v%~85w/v%.
Preferably, the temperature of the reaction is 50 DEG C~70 DEG C；The time of the reaction is 4 hours~10 hours；It is described
The concentration of phosphoric acid is 30w/v%~60w/v%.
Preferably, the CnH2n+4NCl solution using chlorohydrocarbon as solvent, the chlorohydrocarbon be methylene chloride, dichloroethanes,
One or both of chloroform, the CnH2n+4NCl solution is quaternary ammonium salt solution, and the quaternary ammonium salt solution is tetrabutyl chlorine
Change one or both of ammonium, methyl tricapryl ammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride
More than.
A kind of peroxidating phosphorus heteropoly tungstic acid phase transfer catalyst, the catalyst are prepared by above-mentioned steps.
A kind of preparation method for the epoxidized SBS that epoxy rate is controllable, with dichloroethanes, toluene, hexamethylene, ethyl acetate
One or more of mixed solvent, using hydrogen peroxide as oxygen source, used oxidation phosphorus heteropoly tungstic acid phase transfer catalyst, with
SBS is raw material, carries out catalytic oxidation；It with n-hexane extraction catalytic oxidation product, stands, recycles upper layer product, use
Alternately washing upper layer product is dried in vacuo after anhydrous magnesium sulfate drying, obtains epoxidized SBS for n-hexane and methanol.
Preferably, the catalytic oxidation temperature is 40 DEG C~90 DEG C, and the reaction time is 0.5 hour~5 hours；Institute
The concentration for stating hydrogen peroxide is 20wt%~50wt%.
Preferably, the catalytic oxidation temperature is 50 DEG C~80 DEG C, and the reaction time is 2 hours~4 hours.
A kind of epoxidized SBS that epoxy rate is controllable, polystyrene and polybutadiene mass ratio are in the epoxidized SBS
More than or equal to 1:4, concentration of the epoxidized SBS in organic phase is 2wt%~10wt%, double in the epoxidized SBS
The concentration of oxygen water is the wt% of 0.5wt%~8.
Preferably, concentration of the epoxidized SBS in organic phase is 3wt%~7wt%, double in the epoxidized SBS
The concentration of oxygen water is 0.85wt%~5.5wt%.
The present invention has compared with prior art such as following advantages：
1, the catalytic activity of peroxidating phosphorus heteropoly tungstic acid phase transfer catalyst is high, and using hydrogen peroxide as oxygen source, selectivity is high, nothing
Side reaction can be recycled and recycle, meets the requirement of circular economy.
2, reaction system is homogeneous during the reaction, and meeting AUTOMATIC ZONING becomes two-phase after reaction, after reaction
Handle fairly simple, the purification of product easy to accomplish and the recycling of solvent.
3, epoxidization reaction process is simple, mild condition, easy to control, and product yield is high.The epoxidised extent of reaction is easy to
It is precisely controlled, is conducive to the design of macromolecular structure.
4, the different solubility properties and application performance for determining epoxidized SBS (eSBS) of epoxy rate, are conducive to establish knot
Relationship between structure and application realizes the regulation to the solubility property of epoxidized SBS (eSBS).
5, eSBS of the present invention, polystyrene (PS) are more than or equal to 1 than polybutadiene (PB) mass ratio:4, such as
Middle petrochemical industry SBS792, LG SBS501.
Detailed description of the invention
Fig. 1 is that eSBS46 is dissolved in CDCl3In1H-NMR spectrum.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
The characterization of the epoxy rate of epoxidized SBS (eSBS)：A small amount of freshly prepd epoxidized SBS (eSBS) is taken to be dissolved in
CDCl3In, then utilize1H NMR calculates the epoxy rate of double bond, i.e. the hydrogen integral area of epoxidation double bond accounts for total double bond hydrogen product
The percentage of facet product, circular refer to [Elena Serrano, Maider Larranaga, Pedro
M.Remiro, Inaki Mondragon,Pedro M.Carrasco,Jose A.Pomposo,David Mecerreyes
Macromol.Chem.Phys.2004,205,987–996]。
The meaning of epoxy rate of the present invention is：Epoxidation double bond mole accounts for the percentage of total PB (polybutadiene) section mole
Than.
Raw material LG SBS501 in the following example is produced by LG chemical company of South Korea.
The preparation of 1 peroxidating phosphorus heteropoly tungstic acid phase transfer catalyst of embodiment
In 250ml three-necked flask, hydrogen peroxide (concentration 30wt%) 35ml, wolframic acid 7.56g is added, magneton installs cold
It after solidifying pipe, is stirred 4 hours at 65 DEG C, is reacted until yellow becomes colourless stopping, after filtering, 1.9ml is added into filtrate
The dichloro of 132 grams of methyl tricapryl ammonium chlorides (concentration 5wt%) is added dropwise after stirring 15 minutes in phosphoric acid (concentration 40w/v%) solution
Dichloromethane, after stirring 15 minutes, stratification takes lower layer's solution that anhydrous sodium sulfate 5g after magnetic stirring for 10 minutes mistake is added
Filter, takes filtrate to be evaporated under reduced pressure at 45 DEG C, obtains peroxidating phosphorus heteropoly tungstic acid phase transfer catalyst, (C8H17)3NCH3]+ 3[PO4
[W(O)(O)2]4]3-(PWC), colorless and transparent viscous body.
The preparation of 2 peroxidating phosphorus heteropoly tungstic acid phase transfer catalyst of embodiment
In 250ml three-necked flask, hydrogen peroxide (concentration 30wt%) 55ml, wolframic acid 7.56g is added, magneton installs cold
It after solidifying pipe, is stirred 5 hours at 70 DEG C, is reacted until yellow becomes colourless stopping, after filtering, 1.9ml is added into filtrate
The dichloro of 132 grams of methyl tricapryl ammonium chlorides (concentration 5wt%) is added dropwise after stirring 15 minutes in phosphoric acid (concentration 40w/v%) solution
Dichloromethane, after stirring 15 minutes, stratification takes lower layer's Solutions Solution that anhydrous sodium sulfate 5g after magnetic stirring for 10 minutes are added
Filtering, takes filtrate to be evaporated under reduced pressure at 45 DEG C, obtains peroxidating phosphorus heteropoly tungstic acid phase transfer catalyst (PWC), molecular formula is
[(C8H17)3NCH3]+ 3[PO4[W(O)(O)2]4]3-, colorless and transparent viscous body.
The preparation of 3 epoxidized SBS of embodiment (eSBS)
In 250ml three-necked flask, it is added and passes through 6.7 grams of the processed LG SBS501 of acetone extraction, dichloroethanes
125.7 grams, 4 milliliters of hydrogen peroxide (concentration 30wt%), 0.67 gram of peroxidating phosphorus heteropoly tungstic acid phase transfer catalyst (PWC), go from
21 milliliters of sub- water is warming up to 70 DEG C, 3 hours of catalytic oxidation, then pours into reactant in a large amount of n-hexane, stands
After be separately recovered upper layer product and lower catalyst agent, upper layer product is after n-hexane and methanol alternately wash, anhydrous magnesium sulfate
After drying, after vacuum drying, 6.5 grams of epoxidized SBS are obtained.
Epoxidized product SBS yield is up to 97%, epoxy rate 32.6%.Lower layer's reaction liquid passes through ethyl acetate extraction and recovery
Obtain 0.61 gram of PWC catalyst, the rate of recovery 91.4%.Obtain eSBS32.6.Polystyrene and polybutadiene in epoxidized SBS
Alkene mass ratio is greater than 1:4.Concentration of the epoxidized SBS in organic phase is 5wt%, and hydrogen peroxide is dense in the epoxidized SBS
Degree is 3.8wt%.
The preparation of 4 epoxidized SBS of embodiment (eSBS)
In 250ml three-necked flask, it is added and passes through 6.7 grams of the processed LG SBS501 of acetone extraction, dichloroethanes
125.7 grams, 0.67 gram of peroxidating phosphorus heteropoly tungstic acid phase transfer catalyst PWC, 10 milliliters of hydrogen peroxide (concentration 30wt%), go from
15 milliliters of sub- water stirs 170 minutes at 70 DEG C, then pours into a large amount of n-hexane reactant, be separately recovered after standing
Upper layer product and lower catalyst agent, for upper layer product after a large amount of n-hexane and methanol alternately wash, anhydrous magnesium sulfate is dry
Afterwards, after vacuum drying, 6.6 grams of epoxidized SBS are obtained.
Epoxidized SBS product yield is up to 98.5%, epoxy rate 38%.Lower layer's reaction liquid passes through ethyl acetate extraction and recovery
Obtain 0.58 gram of PWC catalyst, the rate of recovery 86.5%.Obtain eSBS38.Polystyrene and polybutadiene in epoxidized SBS
Mass ratio is greater than 1:4.Concentration of the epoxidized SBS in organic phase is 6wt%, the concentration of hydrogen peroxide in the epoxidized SBS
It is 5wt%.
The preparation of 5 epoxidized SBS of embodiment (eSBS)
In 250ml three-necked flask, it is added and passes through 6.7 grams of the processed LG SBS501 of acetone extraction, dichloroethanes
125.7 grams, 0.67 gram of peroxidating phosphorus heteropoly tungstic acid phase transfer catalyst PWC, 15 milliliters of hydrogen peroxide (concentration 30wt%), go from
10 milliliters of sub- water stirs 170 minutes at 70 DEG C, then pours into a large amount of n-hexane reactant, be separately recovered after standing
Upper layer product and lower catalyst agent, for upper layer product after a large amount of n-hexane and methanol alternately wash, anhydrous magnesium sulfate is dry
Afterwards, after vacuum drying, 6.7 grams of epoxidized SBS (eSBS) is obtained.
Epoxidized SBS (eSBS) product yield is up to 100%, epoxy rate 39%.Lower layer's reaction liquid extracts by ethyl acetate
It fetches receipts and obtains 0.60 gram of PWC catalyst, the rate of recovery 89.5%.Obtain eSBS39.Polystyrene and poly- fourth in epoxidized SBS
Diene mass ratio is greater than 1:4.Concentration of the epoxidized SBS in organic phase is 5wt%, hydrogen peroxide in the epoxidized SBS
Concentration is 5wt%.
The preparation of 6 epoxidized SBS of embodiment (eSBS)
In 250ml three-necked flask, it is added and passes through 6.7 grams of the processed LG SBS501 of acetone extraction, dichloroethanes
125.7 grams, 0.67 gram of peroxidating phosphorus heteropoly tungstic acid phase transfer catalyst PWC, 20 milliliters of hydrogen peroxide (concentration 30wt%), go from
5 milliliters of sub- water stirs 170 minutes at 65 DEG C, then pours into a large amount of n-hexane reactant, be separately recovered after standing
Upper layer product and lower catalyst agent, for upper layer product after a large amount of n-hexane and methanol alternately wash, anhydrous magnesium sulfate is dry
Afterwards, after vacuum drying, 6.7 grams of epoxidized SBS (eSBS) is obtained.
Epoxidized SBS (eSBS) product yield is up to 100%, epoxy rate 46%.Lower layer's reaction liquid extracts by ethyl acetate
It fetches receipts and obtains 0.60 gram of PWC catalyst, the rate of recovery 89.5%.Obtain eSBS46.Polystyrene and poly- fourth in epoxidized SBS
Diene mass ratio is greater than 1:4.Concentration of the epoxidized SBS in organic phase is 2wt%~10wt%, in the epoxidized SBS
The concentration of hydrogen peroxide is 4.5wt%.
The preparation of 7 epoxidized SBS of embodiment (eSBS)
In 250ml three-necked flask, it is added and passes through 6.7 grams of the processed LG SBS501 of acetone extraction, dichloroethanes
125.7 grams, 0.67 gram of peroxidating phosphorus heteropoly tungstic acid phase transfer catalyst PWC, 25 milliliters of hydrogen peroxide (concentration 30wt%), 65
It stirs 170 minutes at DEG C, then pours into reactant in a large amount of n-hexane, upper layer product is separately recovered after standing and lower layer urges
Agent, upper layer product after anhydrous magnesium sulfate is dry, after vacuum drying, obtain after a large amount of n-hexane and methanol alternately wash
To 6.7 grams of epoxidized SBS (eSBS).
Epoxidized SBS (eSBS) product yield is up to 100%, epoxy rate 55%.Lower layer's reaction liquid extracts by ethyl acetate
It fetches receipts and obtains 0.60 gram of PWC catalyst, the rate of recovery 89.5%.Obtain eSBS55.Polystyrene and poly- fourth in epoxidized SBS
Diene mass ratio is greater than 1:4.Concentration of the epoxidized SBS in organic phase is 2wt%, hydrogen peroxide in the epoxidized SBS
Concentration is 5wt%.
The preparation of 8 epoxidized SBS of embodiment (eSBS)
In 250ml three-necked flask, it is added by 6.7 grams of the processed LG SBS501 of acetone extraction, 100 milli of toluene
It rises, 0.7 gram of peroxidating phosphorus heteropoly tungstic acid phase transfer catalyst PWC, 9.1 milliliters of hydrogen peroxide (concentration 30wt%), deionized water
It 15.9 milliliters, is stirred 70 minutes at 60 DEG C, then reactant is poured into a large amount of n-hexane, is separately recovered after standing
Layer product and lower catalyst agent, upper layer product is after a large amount of n-hexane and methanol alternately wash, after anhydrous magnesium sulfate is dry,
After vacuum drying, 6.7 grams of epoxidized SBS (eSBS) is obtained.
Epoxidized SBS (eSBS) product yield is up to 100%, epoxy rate 73%.Lower layer's reaction liquid extracts by ethyl acetate
It fetches receipts and obtains 0.56 gram of PWC catalyst, the rate of recovery 80%.Obtain eSBS73.Polystyrene and polybutadiene in epoxidized SBS
Alkene mass ratio is greater than 1:4.Concentration of the epoxidized SBS in organic phase is 2wt%, and hydrogen peroxide is dense in the epoxidized SBS
Degree is 6wt%.
The preparation of 9 epoxidized SBS of embodiment (eSBS)
In 250ml three-necked flask, it is added by 6.7 grams of the processed LG SBS501 of acetone extraction, 100 milli of toluene
It rises, 0.7 gram of peroxidating phosphorus heteropoly tungstic acid phase transfer catalyst PWC, 9.1 milliliters of hydrogen peroxide (concentration 30wt%), deionized water
It 15.9 milliliters, is stirred 110 minutes at 60 DEG C, then reactant is poured into a large amount of n-hexane, is separately recovered after standing
Layer product and lower catalyst agent, upper layer product is after a large amount of n-hexane and methanol alternately wash, after anhydrous magnesium sulfate is dry,
After vacuum drying, 6.7 grams of epoxidized SBS (eSBS) is obtained.
Epoxidized SBS (eSBS) product yield is up to 100%, epoxy rate 75%.Lower layer's reaction liquid extracts by ethyl acetate
It fetches receipts and obtains 0.60 gram of PWC catalyst, the rate of recovery 85.7%.Obtain eSBS75.Polystyrene and poly- fourth in epoxidized SBS
Diene mass ratio is greater than 1:4.Concentration of the epoxidized SBS in organic phase is 2wt%, hydrogen peroxide in the epoxidized SBS
Concentration is 8wt%.
Dissolution situation of the eSBS of the different epoxy rates of table 1 in common solvents
Note：1. eSBS32.7 indicates that the epoxy rate of epoxidation eSBS is 32.7%；
2. above-mentioned mass percentage concentration is that 2%, √ indicates dissolution, zero is insoluble, △ heating；
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of peroxidating phosphorus heteropoly tungstic acid phase transfer catalyst, which is characterized in that added with hydrogen peroxide, wolframic acid
Phosphoric acid is added in the lower reaction of heat, filtering, and C is added dropwise into filtrate for stirringnH2n+4NCl solution, stirring, stratification take lower layer's solution,
It is filtered after being dried over anhydrous sodium sulfate, catalyst, the C is obtained after vacuum distillationnH2n+438 >=n >=16 in NCl.
2. preparation method according to claim 1, which is characterized in that the concentration of the hydrogen peroxide be 20wt%~
50wt%；The temperature of the reaction is 40 DEG C~80 DEG C；The time of the reaction is 3 hours~12 hours；The phosphoric acid it is dense
Degree is 30w/v%~85w/v%.
3. preparation method according to claim 2, which is characterized in that the temperature of the reaction is 50 DEG C~70 DEG C；It is described
The time of reaction is 4 hours~10 hours；The concentration of the phosphoric acid is 30w/v%~60w/v%.
4. preparation method according to claim 1, which is characterized in that the CnH2n+4NCl solution using chlorohydrocarbon as solvent,
The chlorohydrocarbon is one or both of methylene chloride, dichloroethanes, chloroform, the CnH2n+4NCl solution is quaternary ammonium salt
Solution, the quaternary ammonium salt solution are tetrabutylammonium chloride, methyl tricapryl ammonium chloride, hexadecyltrimethylammonium chloride, 18
One or more of alkyl trimethyl ammonium chloride.
5. a kind of peroxidating phosphorus heteropoly tungstic acid phase transfer catalyst, which is characterized in that the catalyst is appointed by Claims 1 to 4
One is prepared.
6. a kind of preparation method for the epoxidized SBS that epoxy rate is controllable, which is characterized in that with dichloroethanes, toluene, hexamethylene
The mixed solvent of one or more of alkane, ethyl acetate, using hydrogen peroxide as oxygen source, used oxidation phosphorus heteropoly tungstic acid phase turns
Shifting catalyst carries out catalytic oxidation using SBS as raw material；It with n-hexane extraction catalytic oxidation product, stands, recycling
Upper layer product, with n-hexane and methanol, alternately washing upper layer product is dried in vacuo after anhydrous magnesium sulfate drying, obtains epoxidation
SBS。
7. preparation method according to claim 6, which is characterized in that the catalytic oxidation temperature is 40 DEG C~90
DEG C, the reaction time is 0.5 hour~5 hours；The concentration of the hydrogen peroxide is 20wt%~50wt%.
8. preparation method according to claim 7, which is characterized in that the catalytic oxidation temperature is 50 DEG C~80
DEG C, the reaction time is 2 hours~4 hours.
9. a kind of epoxidized SBS that epoxy rate is controllable, which is characterized in that polystyrene and polybutadiene in the epoxidized SBS
Alkene mass ratio is more than or equal to 1:4, concentration of the epoxidized SBS in organic phase is 2wt%~10wt%, the epoxy
The concentration of hydrogen peroxide is 0.5wt%~8wt% in SBS.
10. epoxidized SBS according to claim 9, which is characterized in that concentration of the epoxidized SBS in organic phase
It is 3wt%~7wt%, the concentration of hydrogen peroxide is 0.85wt%~5.5wt% in the epoxidized SBS.
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| CN112250776A (en) * | 2020-08-13 | 2021-01-22 | 沧州信联化工有限公司 | Tetramethyl ammonium hydroxide catalytic thermoplastic material and preparation method thereof |
| CN112250776B (en) * | 2020-08-13 | 2022-07-22 | 沧州信联化工有限公司 | Tetramethyl ammonium hydroxide catalytic thermoplastic material and preparation method thereof |
| CN114591268A (en) * | 2022-04-01 | 2022-06-07 | 福州大学 | Method for synthesizing alpha-epoxy pinane by epoxidation of alpha-pinene |
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Application publication date: 20181116 |