CN109467623A - A kind of epoxidizing method of high molecular weight conjugated diene polymer - Google Patents
A kind of epoxidizing method of high molecular weight conjugated diene polymer Download PDFInfo
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Abstract
The invention discloses a kind of epoxidizing methods of high molecular weight conjugated diene polymer, belong to high molecular polymer technical field of modification.Using phosphotungstic acid quaternary as catalyst, in organic solvent, epoxidation is carried out to the partial double bond in high molecular weight conjugated diene polymer with hydrogen peroxide.After the reaction was completed, catalyst is present in reaction solution in solid form, recycles catalyst through being separated by solid-liquid separation, and reuses after washing is dry.Hydrogen peroxide conversion in reaction process in hydrogen peroxide is up to 100%, the epoxy rate of carbon-carbon double bond is adjustable between 0.08~50mol% in high molecular weight conjugated diene polymer, and catalyst still reaches the 70~100% of fresh catalyst using rear catalytic efficiency three times.Compared with the conventional method, the advantages that this method has easy to operate, and reaction efficiency is high, and oxidant cleaning is cheap, catalyst recoverable.
Description
Technical field
The invention belongs to the modification fields of heavy polymer, and in particular to a kind of pair of high molecular weight conjugated diene is poly-
Close the method that object carries out catalysis epoxidation.
Background technique
Conjugated diene is common one kind monomer in high polymer synthesis industry, mainly includes 1,3-butadiene and isoamyl two
Alkene can be copolymerized to obtain structure different polymer, i.e. conjugate diene polymerization by itself homopolymerization or with other type monomers
Object.The conjugated diene polymer of high molecular weight includes, such as butadiene rubber, solution polymerized butadiene styrene rubber, emulsion polymerized styrene butadiene rubber, isoamyl rubber
Glue, SBS, SIS thermoplastic elastomer (TPE), K resin, HIPS, ABS thermoplastic etc..In the conjugated diene of these high molecular weight
In polymer, a C=C double bond is still had after conjugated diene monomer is aggregated, makes polymer that there is unsaturated characteristic, has
The advantage of further chemical modification, but the disadvantages of also make polymer poor there are weatherability.In addition, most conjugated dienes
Hydrocarbon polymer is free of polar monomer unit, is difficult to because of poor compatibility filling-modified to its with polarity inorganic, or uses polarity
Polymer is to its blending and modifying.Thus, the saturation of conjugated diene polymer is modified and polarityization is modified to have become to improve and be somebody's turn to do
Quasi polymer performance, an important research field for expanding their application ranges.
Epoxidation is carried out to the carbon-carbon double bond in conjugated diene polymer, on the one hand can make the carbon-carbon double bond in polymer
On the other hand saturation can increase the polarity of polymer, and the further modified offer for existing for polymer of epoxy group
Effective active site.Therefore, epoxidation conjugated diene polymer is in coating, composite material, sealing material, automobile work
Industry, national defense industry etc. are widely used in.
Currently, the technique of large-scale production epoxidation conjugated diene polymer was acid system (" Advances in
Polymer Science",2015,269:163–202；"RSC Advances",2014,4:31249-31260；
" Cellulose ", 2017,24:2849-2860), i.e., with the acid peroxide such as Peracetic acid, peroxyformic acid, metachloroperbenzoic acid
Compound is the epoxidation that oxygen source carries out double bond.Not only the price of oxygen source is high, is easy to happen the side reactions such as epoxy bond open loop, and anti-
Should during can generate acid, corrosion to equipment and larger to the pollution of environment, the post-processing of reaction product is also difficult.
Also there are document (" Journal of Organometallic Chemistry ", 2014,45:25-32 in the recent period；
"Advances in Organometallic Chemistry",2015,64:1-39；"Journal of Polymer
Science ", 2003,29:547-553) report, with transition-metal catalyst Catalytic Wet Peroxide Oxidation conjugate diene polymerization
Object.This method avoid the uses of caustic acid, and side reaction is few, and the introducing of catalyst is but also product is easily purified.Main body
System has: methyl rhenium trioxide-hydrogen peroxide system, molybdenum trioxide-tert-butyl hydroperoxide system etc..But such reaction is still deposited
Catalyst it is expensive, reaction after catalysis be difficult to the disadvantages of recycling.
Summary of the invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of economy, efficiently prepare epoxidation conjugation two
The method of olefin polymer.This method is easy to operate, and reaction condition is mild, and the reaction time is shorter, and oxidant cleaning is cheap, catalysis
Agent is recyclable to be recycled, and recovery method is simple.
Specific technical solution used by the invention is as follows:
A kind of epoxidizing method of high molecular weight conjugated diene polymer:
Under the effect of the catalyst, using hydrogen peroxide as oxygen source, in organic solvent to high molecular weight conjugate diene polymerization
Double bond in object carries out epoxidation, to produce epoxidised high molecular weight conjugated diene polymer.When reaction, by macromolecule
Amount conjugated diene polymer is dissolved in the first organic solvent, is made into the homogeneous phase solution that solid content is 10g/L~100g/L.Again
It is added into the mixture being made of hydrogen peroxide, the second organic solvent and catalyst and reacts.The wherein peroxidating in hydrogen peroxide
Hydrogen is 0.1~62.5mol% relative to the equivalent of double bond in high molecular weight conjugated diene polymer, and catalyst is relative to high score
The dosage of son amount conjugated diene polymer is 1~10wt%.The reaction temperature of reaction is 20~80 DEG C, and the reaction time is 10 points
Clock~4 hour.After the reaction was completed, be separated by solid-liquid separation solid powder and granule shape catalyst and epoxidation high molecular weight conjugated diene are poly-
Polymer solution.The solvent in epoxidation high molecular weight conjugated diene polymer solution is removed, epoxidised high molecular weight is obtained
Conjugated diene polymer.
Reaction catalyst used is the compound that cetyl pyriudinium cations and phosphotungstic anion form, molecular formula
For [π-C5H5NC16H33]3[PW4O16], structural formula is as follows:
In reaction process, hydrogen peroxide, the second organic solvent and catalyst should mix well to form mixing at 20~80 DEG C
Object.After reaction, should be 5~40 minutes cooling at 0~10 DEG C by reaction solution, it is then centrifuged for, filter residue is obtained by filtration, use is organic
Solvent washs filter residue for several times, is dried under vacuum to constant weight to get the catalyst of recycling.Again filtrate is passed through to flash distillation again and removes solvent,
Obtain epoxidised conjugated diene polymer.
The catalyst uses the mistake of cleaning green to the epoxidation of conjugated diene polymer catalytic activity with higher
Hydrogen oxide is oxidant, can be efficiently by the part carbon-carbon double bond epoxidation in a variety of conjugated diene polymers.It reacted
For the conversion ratio of hydrogen peroxide up to 100%, the epoxy rate of conjugated diene polymer is controllable between 0.08~50mol% in journey.
In reaction process, when reaction system contains hydrogen peroxide, whole system is homogeneous system, but when reaction terminates (i.e. peroxide
Change hydrogen to exhaust) after, the catalyst insoluble in reaction solution is then precipitated in the reaction system.Pass through what is be centrifuged, be filtered, washed, dry
Method can be such that catalyst recycles.Therefore, epoxidation conjugated diene polymer obtained is with high purity in this approach.
Preferably, high molecular weight conjugated diene polymer be it is obtained by conjugated diene monomer homopolymerization or copolymerization,
Weight average molecular weight range existsBetween polymer.Conjugated diene monomer is 1,3- butadiene or different
Pentadiene.High molecular weight conjugated diene polymer specifically includes butadiene rubber, solution polymerized butadiene styrene rubber, emulsion polymerized styrene butadiene rubber, different
Penta rubber, SBS, SIS thermoplastic elastomer (TPE), K resin, HIPS, ABS thermoplastic etc..
Preferably, the first organic solvent is 1,2- dichloroethanes, C6~C8 linear paraffin or cycloalkane, raffinates oil, first
The mixture of one of benzene, tetrahydrofuran, butyl acetate or a variety of compositions.
Preferably, the second organic solvent be one of methylene chloride, 1,2- dichloroethanes, toluene, tetrahydrofuran or
The mixture of a variety of compositions.
Preferably, the second organic solvent is 10:1~1:10 relative to the volume ratio of the first consumption of organic solvent.
Preferably, the hydrogen peroxide mass concentration in hydrogen peroxide is 20~99.9wt%.
Preferably, the epoxy rate of obtained epoxidised high molecular weight conjugated diene polymer be 0.08~
50mol%；And it can be by the additional amount of hydrogen peroxide come the epoxy rate of quantitatively regulating and controlling product；If the additional amount of hydrogen peroxide is opposite
The mole fraction of double bond is x in conjugated diene polymer, wherein 0.1 < x < 62.5%, then the ring of conjugated diene polymer
Oxygen rate is between 0.8x and 1.2x.
Preferably, catalyst is reusable catalyst；Described being separated by solid-liquid separation after the reaction was completed is resulting
Still has catalytic activity after solid powder and granule shape catalyst is dry.The epoxidised high molecular weight conjugation two that reuse of catalyst catalysis generates
The yield of olefin polymer still can reach the 70~100% of fresh catalyst.
Raw material used in the present invention is only conjugated diene polymer, hydrogen peroxide, catalysts and solvents, oxygen used
Source --- hydrogen peroxide economy, environmental protection, the conversion ratio of hydrogen peroxide is up to 100%, and without side reaction.Used catalyst is hexadecane
The compound of pyridinium cations and phosphotungstic anion composition, it is inexpensive, be easy to get, Yi Huishou, it may be reused.With existing side
Method is compared, this method have it is easy to operate, reaction condition is mild, to equipment corrode it is small, oxygen source is economic and environment-friendly, and product epoxy rate can
The features such as tune, has extensive prospects for commercial application.
Detailed description of the invention
Fig. 1 be solution polymerized butadiene styrene rubber (SSBR), epoxidation solution polymerized butadiene styrene rubber (ESSBR) nucleus magnetic hydrogen spectrum (1H NMR)
Figure.
Fig. 2 is the infrared spectrogram of original catalyst and first, second, and third reuse of catalyst.
Specific embodiment
Embodiment 1
Butadiene rubber (BR 9000) 4.00g is taken, is dissolved completely in 100mL 1, in 2- dichloroethanes, rubber concentrations are
40g/L, constant temperature is to 60 DEG C.Hydrogen peroxide, 20mL 1,2- dichloroethanes, 0.08g catalyst that 160 μ L concentration are 30wt% are existed
It is uniformly mixed, and is slowly dropped in rubber solutions at 60 DEG C, reacted 2 hours at 60 DEG C.Hydrogen peroxide use is butadiene rubber
The 2mol% of middle butadiene structural units, catalyst amount are the 2wt% of butadiene rubber quality.It after reaction will be anti-at 5 DEG C
Answer liquid cooling but 15 minutes, after centrifugation, filtering for several times with a small amount of 1,2- dichloroethanes washing solids, eluate is incorporated to liquid, Gu
It is used as the catalyst of lower secondary response after body object is dry.The solvent in liquid is evaporated up to epoxidation butadiene rubber, warp1H NMR table
Sign, measuring epoxy rate is 1.9mol%, and practical epoxy rate is 0.95 times of theoretical epoxy rate.
Embodiment 2
Butadiene rubber (BR 9000) 4.00g is taken, is dissolved completely in 100mL 1, in 2- dichloroethanes, rubber concentrations are
40g/L, constant temperature is to 60 DEG C.Hydrogen peroxide, 20mL 1,2- dichloroethanes, 0.20g catalyst that 3200 μ L concentration are 30wt% are existed
It is uniformly mixed at 60 DEG C, is slowly dropped in rubber solutions, is reacted 2 hours at 60 DEG C.Hydrogen peroxide use is in butadiene rubber
The 40mol% of butadiene structural units, catalyst amount are the 5wt% of butadiene rubber quality.It after reaction will reaction at 5 DEG C
Liquid cooling but 15 minutes, after centrifugation, filtering for several times with a small amount of 1,2- dichloroethanes washing solids, eluate was incorporated to liquid, solid
It is used as the catalyst of lower secondary response after object is dry.The solvent in liquid is evaporated up to epoxidation butadiene rubber, warp1H NMR characterization,
Measuring epoxy rate is 41.7mol%, and practical epoxy rate is 1.04 times of theoretical epoxy rate.
Embodiment 3
Butadiene rubber (BR 9000) 4.00g is taken, is dissolved completely in 200mL tetrahydrofuran, rubber concentrations 20g/L, it is permanent
Temperature is to 80 DEG C.Hydrogen peroxide, 20mL 1,2- dichloroethanes, 0.20g catalyst that 800 μ L concentration are 30wt% are mixed at 60 DEG C
It closes uniformly, is slowly dropped in rubber solutions, is reacted 3 hours at 80 DEG C.Hydrogen peroxide use is butadiene knot in butadiene rubber
The 10mol% of structure unit, catalyst amount are the 5wt% of butadiene rubber quality.After reaction by reaction solution cooling 30 at 5 DEG C
Minute, after centrifugation, filtering for several times with a small amount of 1,2- dichloroethanes washing solids, eluate is incorporated to liquid, after solids is dry
Catalyst as lower secondary response.The solvent in liquid is evaporated up to epoxidation butadiene rubber, warp1H NMR characterization, measures epoxy
Rate is 11.0mol%, and practical epoxy rate is 1.10 times of theoretical epoxy rate.
Embodiment 4
Take butadiene rubber (BR 9000) 4.00g, be dissolved completely in 40mL 1,2- dichloroethanes and 60mL hexamethylene it is mixed
In bonding solvent, rubber concentrations 40g/L, constant temperature is to 60 DEG C.Hydrogen peroxide, the 20mL 1,2- dichloro for being 30wt% by 800 μ L concentration
Ethane, 0.20g catalyst are uniformly mixed at 60 DEG C, are slowly dropped in rubber solutions, are reacted 1 hour at 60 DEG C.Peroxidating
Hydrogen dosage is the 10mol% of butadiene structural units in butadiene rubber, and catalyst amount is the 5wt% of butadiene rubber quality.Instead
It is at 5 DEG C that reaction solution is 15 minutes cooling after answering, after centrifugation, filtering for several times with a small amount of 1,2- dichloroethanes washing solids,
Eluate is incorporated to liquid, and the catalyst of lower secondary response is used as after solids is dry.The solvent being evaporated in liquid is suitable up to epoxidation
Buna, warp1H NMR characterization, measuring epoxy rate is 10.5mol%, and practical epoxy rate is 1.05 times of theoretical epoxy rate.
Embodiment 5
Butadiene rubber (BR 9000) 4.00g is taken, is dissolved completely in 50mL toluene, rubber concentrations 80g/L, constant temperature is extremely
80℃.Hydrogen peroxide, 20mL 1,2- dichloroethanes, 0.20g catalyst that 800 μ L concentration are 30wt% are mixed at 60 DEG C
It is even, it is slowly dropped in rubber solutions, is reacted 3 hours at 80 DEG C.Hydrogen peroxide use is butadiene structure list in butadiene rubber
The 10mol% of member, catalyst amount are the 5wt% of butadiene rubber quality.It is reaction solution is 30 points cooling at 5 DEG C after reaction
Clock, after centrifugation, filtering for several times with a small amount of 1,2- dichloroethanes washing solids, eluate is incorporated to liquid, uses after solids is dry
Make the catalyst of lower secondary response.The solvent in liquid is evaporated up to epoxidation butadiene rubber, warp1H NMR characterization, measures epoxy rate
For 9.5mol%, practical epoxy rate is 0.95 times of theoretical epoxy rate.
Embodiment 6
Solution polymerized butadiene styrene rubber 4.00g is taken, is dissolved completely in 100mL 1, in 2- dichloroethanes, rubber concentrations 40g/L is permanent
Temperature is to 60 DEG C.Hydrogen peroxide, 20mL 1,2- dichloroethanes, 0.20g catalyst that 610 μ L concentration are 30wt% are mixed at 60 DEG C
It closes uniformly, is slowly dropped in rubber solutions, is reacted 1 hour at 60 DEG C.Hydrogen peroxide use is fourth two in solution polymerized butadiene styrene rubber
The 10mol% of alkene structural unit, catalyst amount are the 5wt% of solution polymerized butadiene styrene rubber quality.It after reaction will reaction at 5 DEG C
Liquid cooling but 15 minutes, after centrifugation, filtering for several times with a small amount of 1,2- dichloroethanes washing solids, eluate was incorporated to liquid, solid
It is used as the catalyst of lower secondary response after object is dry.The solvent in liquid is evaporated up to epoxidation solution polymerized butadiene styrene rubber, warp1H NMR
Characterize epoxy rate is 10.9mol%, practical epoxy rate is 1.09 times of theoretical epoxy rate.Solution polymerized butadiene styrene rubber (SSBR) and ring
Aoxidize solution polymerized butadiene styrene rubber (ESSBR)1H NMR spectra is as shown in Figure 1.Original catalyst is red with recycling drying rear catalyst
Outer spectrogram is respectively as shown in " fresh " and " first " in Fig. 2, it is seen that is not become substantially using the structure of a rear catalyst
Change.
Embodiment 7
Solution polymerized butadiene styrene rubber 4.00g is taken, 100mL 1, the mixed solvent of 2- dichloroethanes and 60mL toluene are dissolved completely in
In, rubber concentrations 25g/L, constant temperature is to 80 DEG C.By 1220 μ L concentration be the hydrogen peroxide of 30wt%, 20mL 1,2- dichloroethanes,
0.20g catalyst is uniformly mixed at 80 DEG C, is slowly dropped in rubber solutions, is reacted 4 hours at 80 DEG C.Hydrogen peroxide use
For the 20mol% of butadiene structural units in solution polymerized butadiene styrene rubber, catalyst amount is the 5wt% of solution polymerized butadiene styrene rubber quality.
It is reaction solution is 15 minutes cooling at 5 DEG C after reaction, with a small amount of 1,2- dichloroethanes washing solids number after centrifugation, filtering
Secondary, eluate is incorporated to liquid, and the catalyst of lower secondary response is used as after solids is dry.The solvent in liquid is evaporated up to epoxidation
Solution polymerized butadiene styrene rubber, warp1H NMR characterize epoxy rate is 21.5mol%, practical epoxy rate is 1.08 times of theoretical epoxy rate.
Catalytic agent reuse experiment:
Embodiment 8
Solution polymerized butadiene styrene rubber 4.00g is taken, is dissolved completely in 100mL 1, in 2- dichloroethanes, rubber concentrations 40g/L is permanent
Temperature is to 60 DEG C.Hydrogen peroxide, 20mL 1,2- dichloroethanes, 0.20g catalyst that 610 μ L concentration are 30wt% are mixed at 60 DEG C
It closes uniformly, is slowly dropped in rubber solutions, is reacted 2 hours at 60 DEG C.Wherein used catalyst is the catalysis that embodiment 6 recycles
Agent, hydrogen peroxide use are the 10mol% of butadiene structural units in solution polymerized butadiene styrene rubber, and catalyst amount is solution polymerized butylbenzene rubber
The 5wt% of colloid amount.It is reaction solution is 15 minutes cooling at 5 DEG C after reaction, with a small amount of 1,2- dichloroethanes after centrifugation, filtering
Wash solids for several times, eluate is incorporated to liquid, and the catalyst of lower secondary response is used as after solids is dry.It is evaporated molten in liquid
Agent is up to epoxidation solution polymerized butadiene styrene rubber, warp1H NMR characterize epoxy rate be 10.6mol%, practical epoxy rate be theoretical epoxy
1.06 times of rate.It recycles shown in " second " of the infrared spectrum of dry rear catalyst such as in Fig. 2, it is seen that using being catalyzed afterwards twice
The structure of agent does not change substantially.
Embodiment 9
Solution polymerized butadiene styrene rubber 2.00g is taken, is dissolved completely in 50mL 1, in 2- dichloroethanes, rubber concentrations 40g/L is permanent
Temperature is to 60 DEG C.Hydrogen peroxide, 10mL 1,2- dichloroethanes, 0.10g catalyst that 305 μ L concentration are 30wt% are mixed at 60 DEG C
It closes uniformly, is slowly dropped in rubber solutions, is reacted 2 hours at 60 DEG C.Wherein used catalyst is the catalysis that embodiment 8 recycles
Agent, hydrogen peroxide use are the 10mol% of butadiene structural units in solution polymerized butadiene styrene rubber, and catalyst amount is solution polymerized butylbenzene rubber
The 5wt% of colloid amount.It is reaction solution is 15 minutes cooling at 5 DEG C after reaction, with a small amount of 1,2- dichloroethanes after centrifugation, filtering
Wash solids for several times, eluate is incorporated to liquid, and the catalyst of lower secondary response is used as after solids is dry.It is evaporated molten in liquid
Agent is up to epoxidation solution polymerized butadiene styrene rubber, warp1H NMR characterize epoxy rate be 9.7mol%, practical epoxy rate be theoretical epoxy
0.97 times of rate.It recycles shown in " third " of the infrared spectrum of dry rear catalyst such as in Fig. 2, it is seen that using being catalyzed afterwards three times
The structure of agent does not change substantially.
Claims (8)
1. a kind of epoxidizing method of high molecular weight conjugated diene polymer, which is characterized in that under the effect of the catalyst, with
Hydrogen peroxide is oxygen source, epoxidation is carried out to the double bond in high molecular weight conjugated diene polymer in organic solvent, to make
Take epoxidised high molecular weight conjugated diene polymer；When reaction, high molecular weight conjugated diene polymer is dissolved in
In one organic solvent, be made into solid content be 10g/L~100g/L homogeneous phase solution, be added by hydrogen peroxide, the second organic solvent and
In the mixture of catalyst composition, wherein the hydrogen peroxide in hydrogen peroxide is relative to double in high molecular weight conjugated diene polymer
The equivalent of key be 0.1~62.5mol%, catalyst relative to high molecular weight conjugated diene polymer dosage be 1~
10wt%, reaction temperature are 20~80 DEG C, and the reaction time is 10 minutes~4 hours；After the reaction was completed, it is separated by solid-liquid separation to obtain solid
Granular catalyst and epoxidation high molecular weight conjugated diene polymer solution；Solvent is removed, epoxidised macromolecule is obtained
Measure conjugated diene polymer；
The catalyst is the compound that cetyl pyriudinium cations and phosphotungstic anion form, and molecular formula is [π-
C5H5NC16H33]3[PW4O16], structural formula is as follows:
2. epoxidizing method as described in claim 1, which is characterized in that the high molecular weight conjugated diene polymer is
By conjugated diene monomer homopolymerization or copolymerization, obtained, weight average molecular weight range existsBetween polymerization
Object；The conjugated diene monomer is 1,3- butadiene or isoprene.
3. epoxidizing method as described in claim 1, which is characterized in that first organic solvent is 1,2-, bis- chloroethene
Alkane, C6~C8 linear paraffin or cycloalkane, raffinate oil, one of toluene, tetrahydrofuran, butyl acetate or a variety of compositions it is mixed
Close object.
4. epoxidizing method as described in claim 1, which is characterized in that second organic solvent be methylene chloride, 1,
The mixture of one of 2- dichloroethanes, toluene, tetrahydrofuran or a variety of compositions.
5. epoxidizing method as described in claim 1, which is characterized in that second organic solvent is organic relative to first
The volume ratio of solvent usage is 10:1~1:10.
6. epoxidizing method as described in claim 1, which is characterized in that the hydrogen peroxide mass concentration in the hydrogen peroxide is
20~99.9wt%.
7. epoxidizing method as described in claim 1, which is characterized in that the obtained epoxidised high molecular weight is total
The epoxy rate of yoke diene polymer is 0.08~50mol%；And the additional amount by controlling hydrogen peroxide is come quantitatively regulating and controlling production
The epoxy rate of object；If the additional amount of hydrogen peroxide is x relative to the mole fraction of double bond in conjugated diene polymer, wherein
0.1 < x < 62.5%, then the epoxy rate of conjugated diene polymer is between 0.8x and 1.2x.
8. epoxidizing method as described in claim 1, which is characterized in that the catalyst is reusable catalysis
Agent；Described still has catalytic activity after the resulting solid powder and granule shape catalyst of separation of solid and liquid is dry after the reaction was completed.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113893875A (en) * | 2021-11-12 | 2022-01-07 | 泉州师范学院 | Preparation method of double-bond epoxidation phase transfer catalyst with high recovery rate |
| CN114174374A (en) * | 2019-07-30 | 2022-03-11 | 住友化学株式会社 | Method for producing pi-conjugated polymer |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1323739A3 (en) * | 2001-12-22 | 2004-01-28 | Degussa AG | Preparation of epoxidized polyalkenylenes |
| CN101613424A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of method for preparing polybutadiene epoxy resin |
| CN103172777A (en) * | 2011-12-22 | 2013-06-26 | 中国科学院大连化学物理研究所 | Method for preparing polybutadiene epoxy resin |
| CN104998689A (en) * | 2015-06-29 | 2015-10-28 | 湖北大学 | Anion resin-carried peroxyphosphotungstic acid, its preparation method and use, and epoxycycloparaffin synthesis method |
| CN105693887A (en) * | 2016-03-08 | 2016-06-22 | 华南理工大学 | Preparation method of epoxidised polybutadiene |
| CN107459591A (en) * | 2016-06-06 | 2017-12-12 | 中国石油化工股份有限公司 | High vinyl polybutadiene rubber and its preparation method and application in a kind of epoxidation |
| CN108395492A (en) * | 2018-02-07 | 2018-08-14 | 浙江大学 | - 1,4 content carboxyl-terminated polybutadiene liquid rubber of high-cis and end carboxyl polyethylene and preparation method thereof |
| CN108530564A (en) * | 2018-04-17 | 2018-09-14 | 中科广化（重庆）新材料研究院有限公司 | It a kind of epoxidized SBS, block macromolecular reactive amines toughener and its prepares and application in the epoxy |
-
2018
- 2018-10-29 CN CN201811266898.1A patent/CN109467623B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1323739A3 (en) * | 2001-12-22 | 2004-01-28 | Degussa AG | Preparation of epoxidized polyalkenylenes |
| CN101613424A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of method for preparing polybutadiene epoxy resin |
| CN103172777A (en) * | 2011-12-22 | 2013-06-26 | 中国科学院大连化学物理研究所 | Method for preparing polybutadiene epoxy resin |
| CN104998689A (en) * | 2015-06-29 | 2015-10-28 | 湖北大学 | Anion resin-carried peroxyphosphotungstic acid, its preparation method and use, and epoxycycloparaffin synthesis method |
| CN105693887A (en) * | 2016-03-08 | 2016-06-22 | 华南理工大学 | Preparation method of epoxidised polybutadiene |
| CN107459591A (en) * | 2016-06-06 | 2017-12-12 | 中国石油化工股份有限公司 | High vinyl polybutadiene rubber and its preparation method and application in a kind of epoxidation |
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| CN114174374B (en) * | 2019-07-30 | 2024-04-26 | 住友化学株式会社 | Method for producing pi-conjugated polymer |
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