CN102675569A - Epoxydized SBS (styrene-butadiene-styrene) and epoxydized SBS polymer - Google Patents
Epoxydized SBS (styrene-butadiene-styrene) and epoxydized SBS polymer Download PDFInfo
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- CN102675569A CN102675569A CN2012101300199A CN201210130019A CN102675569A CN 102675569 A CN102675569 A CN 102675569A CN 2012101300199 A CN2012101300199 A CN 2012101300199A CN 201210130019 A CN201210130019 A CN 201210130019A CN 102675569 A CN102675569 A CN 102675569A
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Abstract
The invention discloses epoxydized SBS (styrene-butadiene-styrene) and an epoxydized SBS polymer. The performances of all aspects are improved by utilizing epoxidized modification carried out on SBS, and the modified SBS polymer is prepared through the epoxidized modification. A novel high-molecular composite material is prepared under the situations of ionization and neutralization. The performance of the material is greatly improved through the modified polymer. The epoxydized SBS (styrene-butadiene-styrene) and the epoxydized SBS polymer have the benefits that through the modification on the SBS and the development of a new process, the production technology is optimized, the energy consumption and the material consumption are reduced, and the application field of the SBS is burdened; and epoxy modified products and other high-end products satisfy the domestic demands, and the quality of an SBS product is improved.
Description
Technical field
The present invention relates to a kind of epoxidized SBS (PS-butadiene-styrene) and utilize the epoxidized SBS ionic polymer of this epoxidized SBS, belong to field of polymer technology for feedstock production.
Background technology
SBS has a lot of premium propertiess, and Application Areas is also very extensive, but also there are some defectives in himself.Just at present; The existing greatest problem of SBS is that ageing-resistant performance is relatively poor; Effect to light, heat, oxygen is responsive; Especially under UV-irradiation, can take place xanthochromia, crosslinked, sclerosis is rotten and can't process problem such as use, this mainly is owing to have a large amount of double bond functional groups on the PB section in the SBS structure.In addition, because SBS polarity is little, make its oil-proofness and solvent resistance relatively poor, these deficiencies have all limited SBS use in every respect.
Summary of the invention
To the objective of the invention is the defective that exists in the prior art in order solving, a kind of anti-dissolubility is high, over-all properties is high epoxidized SBS and epoxidized SBS ionic polymer to be provided.
In order to achieve the above object; The invention provides a kind of epoxidized SBS; Prepare through following steps: SBS is dissolved in the organic solvent, stirs 10-30 min, obtaining SBS quality percentage composition is the solution of 1%-30%; In this solution, adding concentration subsequently is that 20%-95% formic acid solution, concentration are 10%-30% aqueous hydrogen peroxide solution and phase-transfer catalyst, mixes the back and reacts 1-10 hour down at 20-70 ℃; After reaction is accomplished, in solution, add 95% ethanol or the acetone of 3-5 times of volume, deposition, after the filtration with washing of precipitate 5-10 time to pH be 6.5-7, after vacuum drier 3-8 hour, obtain epoxidised SBS; Wherein, organic solvent is hexanaphthene, toluene or chloroform; The weight of hydrogen peroxide is the 0.1-5% of SBS weight; The mol ratio of formic acid and hydrogen peroxide is 1-3:1; Phase-transfer catalyst is a hydrophilic polymer, preferred polyoxyethylene glycol, polytetramethylene glycol or Z 150PH, and consumption is the 0.1-5 % of SBS weight.The oxirane value of the epoxidized SBS for preparing is 1-10%
The present invention also provides a kind of epoxidized SBS ionic polymer; This ionic polymer is a feedstock production with above-mentioned epoxidized SBS; May further comprise the steps: said epoxidized SBS is dissolved in the organic solvent, obtains the solution that epoxidized SBS concentration is 0.02-0.27g/mL, in solution, add phase-transfer catalyst and ring opening catalyst; Add the aqueous potassium hydrogen sulfate that concentration is 0.036%-4.86% then, at 30-85 ℃ of following stirring reaction 3-10 hour; After reaction is accomplished, in solution, add alkali and stirred 5-30 minute, the mixed solution that obtains precipitates in the acetone of 3-5 times of volume, will be deposited in the acetone repetitive scrubbing three times after the filtration after, vacuum-drying obtains the epoxidized SBS ionic polymer; Wherein, organic solvent is hexanaphthene, toluene or chloroform; The preferred tetraethylammonium bromide of phase-transfer catalyst, 4-butyl ammonium hydrogen sulfate, Tetrabutyl amonium bromide or tetrabutylammonium chloride, consumption are the weight 1-15% of epoxidized SBS; The preferred N of ring opening catalyst, accelerine, N-N dimethyl benzylamine, triethylamine, 1,4-diazabicyclo [2.2.2]-octane or triphenylphosphine, consumption are the 1-15% of epoxidized SBS weight; The mol ratio of epoxide group is 0.6-1.8:1 in sal enixum and the epoxidized SBS; The preferred NaOH of alkali, KOH, LiOH, Pb (OH)
2, Zn (OH)
2, Mg (OH)
2Or Ca (OH)
2, wherein the mol ratio of hydroxide radical and sal enixum is 1-1.2:1.
The present invention compares prior art and has the following advantages: the present invention utilizes the two keys that contain on the PB section in the SBS molecular structure, and it is carried out epoxidation modification, and the epoxidized SBS that makes (ESBS) force of cohesion increases; Elasticity reduces; In solvent, be easier to dissolving, soltion viscosity is little, and the transparency is high.Utilize ESBS to prepare ionic polymer simultaneously, improved the performance of SBS each side: strengthened the polarity of SBS, in the time of can expanding SBS as pressure sensitive adhesive by the scope of sticky object, like the base material of bonded metal, leather isopolarity; Simultaneously, strengthened the effect of SBS, promoted the tensile strength of SBS as expanding material.
Description of drawings
Fig. 1 is the infrared spectrogram of ESBS of the present invention.
Embodiment
Below in conjunction with accompanying drawing and concrete embodiment the present invention is further described.
Embodiment 1
ESBS prepares embodiment
SBS is dissolved in the hexanaphthene; Stir 10 min; Obtain SBS content and be 5% solution; In this solution, adding the concentration that accounts for SBS weight 1% subsequently is that 60% formic acid solution, concentration are that 10% aqueous hydrogen peroxide solution and the polyoxyethylene glycol that accounts for SBS weight 0.5% are phase-transfer catalyst, mixes back 35 ℃ of following reacting by heating 2 hours.95% ethanol or the acetone precipitation that add 3 times of volumes wash 5 times until neutral (pH is 6.5-7), and vacuum drier obtains epoxidised SBS (being designated as ESBS) after 3 hours.
Embodiment 2
ESBS prepares embodiment
SBS is dissolved in the chloroform; Stir 20 min; Obtain SBS content and be 15% solution; In this solution, adding the concentration that accounts for SBS 0.5wt% subsequently is that 75% formic acid solution, concentration are that 20% aqueous hydrogen peroxide solution and the polytetramethylene glycol that accounts for SBS 1wt% are phase-transfer catalyst, mixes back 60 ℃ of following reacting by heating 3 hours.95% ethanol or the acetone precipitation that add 4 times of volumes wash 7 times until neutral (pH is 6.5-7), and vacuum drier obtained ESBS after 5 hours.
Embodiment 3
ESBS prepares embodiment
SBS is dissolved in the toluene; Stir 30 min; Obtain SBS content and be 20% solution; In this solution, adding the concentration that accounts for SBS 2wt% subsequently is that 88% formic acid solution, concentration are that 30% aqueous hydrogen peroxide solution and the Z 150PH that accounts for SBS 1.5wt% are phase-transfer catalyst, mixes back 70 ℃ of following reacting by heating 4 hours.95% ethanol or the acetone precipitation that add 5 times of volumes wash 7 times until neutral (pH is 6.5-7), and vacuum drier obtained ESBS after 8 hours.
IR spectroscopy: Fourier transform infrared spectroscopy (FTIR) is analyzed and will be purified after also exsiccant ESBS is dissolved in toluene; Film on the Potassium Bromide wafer; The Equinox 55 type FTIR that produce with German Bruker company characterize sweep limit 400～4 000 cm
-1
Fig. 1 is the infrared spectrogram of ESBS.Show absorption peak 910 cm that have two keys on the polyhutadiene by figure
-1, 968 cm
-1, 730cm
-1With at 699 cm
-1With 1450 cm
-1The absorption peak of the phenyl group at place is at 3450 cm
-1Have the general peak of an OH group to absorb, wherein the OH group is at epoxide group and KHSO
4The ring-opening reaction process in form simultaneously; 810 cm
-1With 880 cm
-1The existence of place's absorption peak is owing to there is unreacted epoxy groups group; 1219 cm
-1With 1448 cm
-1The existence of place's absorption peak is that infrared spectrogram has shown the functional group that has ESBS owing to the S=O in the sulfate group on the main chain.
Embodiment 4
The epoxidized SBS ionic polymer prepares embodiment
Be that raw material carries out following reaction with the ESBS for preparing among the embodiment 1 to 3 respectively:
ESBS is dissolved in (strength of solution is 0.05 g/mL) in the hexanaphthene; Adding the 4-butyl ammonium hydrogen sulfate (TBAB) account for ESBS1wt% is ring opening catalyst for the N-N dimethyl benzylamine of phase-transfer catalyst and 1wt%; The sal enixum that to add concentration then be 0.036%, account for ESBS 3wt% was 30 ℃ of following stirring reactions 10 hours.The equimolar NaOH of adding and sal enixum stirs stopped reaction after 30 minutes.Mixed solution precipitates in the acetone of 5 times of volumes, obtains Powdered deposition behind the filtration washing 3 times, obtains epoxidized SBS sodium ion polymkeric substance after the vacuum-drying.
Embodiment 5
The epoxidized SBS ionic polymer prepares embodiment
Be that raw material carries out following reaction with the ESBS for preparing among the embodiment 1 to 3 respectively:
ESBS is dissolved in (strength of solution is 0.1 g/mL) in the toluene; Adding the Tetrabutyl amonium bromide that accounts for ESBS5wt% is the triethylamine ring opening catalyst of phase-transfer catalyst and 5wt%; The sal enixum that to add concentration then be 1.5%, account for ESBS 5wt% was 60 ℃ of following stirring reactions 8 hours.The equimolar KOH of adding and sal enixum stirs stopped reaction after 30 minutes.Mixed solution precipitates in the acetone of 4 times of volumes, obtains Powdered deposition behind the filtration washing 3 times, obtains epoxidized SBS potassium ion polymkeric substance after the vacuum-drying.
Embodiment 6
The epoxidized SBS ionic polymer prepares embodiment
Be that raw material carries out following reaction with the ESBS for preparing among the embodiment 1 to 3 respectively:
ESBS is dissolved in (strength of solution is 0.15 g/mL) in the chloroform; Adding the tetraethylammonium bromide (TEAB) that accounts for ESBS8wt% is the N of phase-transfer catalyst and 8wt%; Accelerine (DMA) ring opening catalyst; The sal enixum that to add concentration then be 4.5%, account for ESBS 7wt% was 75 ℃ of following stirring reactions 7 hours.The Ca (OH) that adds 1/2 mole of sal enixum
2Stir stopped reaction after 30 minutes.Mixed solution precipitates in the acetone of 3 times of volumes, obtains Powdered deposition behind the filtration washing 3 times, obtains epoxidized SBS calcium ion polymkeric substance after the vacuum-drying.
Claims (7)
1. epoxidized SBS; It is characterized in that: prepare: SBS is dissolved in the organic solvent through following steps; Stir 10-30 min; Obtain the solution that the SBS mass percentage concentration is 1%-30%, in this solution, adding concentration subsequently is that 20%-95% formic acid solution, concentration are 10%-30% aqueous hydrogen peroxide solution and phase-transfer catalyst, mixes the back and reacts 1-10 hour down at 20-70 ℃; After reaction is accomplished, in solution, add 95% ethanol or the acetone of 3-5 times of volume, deposition, after the filtration with washing of precipitate 5-10 time to pH be 6.5-7, after vacuum drier 3-8 hour, obtain epoxidised SBS; Said organic solvent is hexanaphthene, toluene or chloroform; The weight of said hydrogen peroxide is the 0.1-5% of SBS weight; The mol ratio of formic acid and hydrogen peroxide is 1-3:1; Said phase-transfer catalyst is a hydrophilic polymer, and consumption is the 0.1-5 % of SBS weight.
2. epoxidized SBS according to claim 1 is characterized in that: said phase-transfer catalyst is polyoxyethylene glycol, polytetramethylene glycol or Z 150PH.
3. epoxidized SBS according to claim 1 is characterized in that: the oxirane value of said epoxidized SBS is 1-10%.
4. epoxidized SBS ionic polymer; With the said epoxidized SBS of claim 1 is feedstock production; It is characterized in that: prepare: said epoxidized SBS is dissolved in the organic solvent, obtains the solution that epoxidized SBS concentration is 0.02-0.27g/mL, in solution, add phase-transfer catalyst and ring opening catalyst through following steps; Add the aqueous potassium hydrogen sulfate that concentration is 0.036%-4.86% then, at 30-85 ℃ of following stirring reaction 3-10 hour; After reaction is accomplished, in solution, add alkali and stirred 5-30 minute, the mixed solution that obtains precipitates in the acetone of 3-5 times of volume, will be deposited in the acetone repetitive scrubbing three times after the filtration after, vacuum-drying obtains the epoxidized SBS ionic polymer; Said organic solvent is hexanaphthene, toluene or chloroform; The weight 1-15 % that said phase-transfer catalyst consumption is an epoxidized SBS; Said ring opening catalyst consumption is the 1-15% of epoxidized SBS weight; The mol ratio of epoxide group is 0.6-1.8:1 in said sal enixum and the epoxidized SBS; The mol ratio of hydroxide radical and sal enixum is 1-1.2:1 in the said alkali.
5. epoxidized SBS ionic polymer according to claim 4 is characterized in that; Said phase-transfer catalyst is tetraethylammonium bromide, 4-butyl ammonium hydrogen sulfate, Tetrabutyl amonium bromide or tetrabutylammonium chloride.
6. epoxidized SBS ionic polymer according to claim 4 is characterized in that: said ring opening catalyst is N, accelerine, N-N dimethyl benzylamine, triethylamine, 1,4-diazabicyclo [2.2.2]-octane or triphenylphosphine.
7. epoxidized SBS ionic polymer according to claim 4 is characterized in that: said alkali is NaOH, KOH, LiOH, Pb (OH)
2, Zn (OH)
2, Mg (OH)
2Or Ca (OH)
2
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| CN2012101300199A CN102675569A (en) | 2012-04-28 | 2012-04-28 | Epoxydized SBS (styrene-butadiene-styrene) and epoxydized SBS polymer |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104479590A (en) * | 2014-12-23 | 2015-04-01 | 兰州理工大学 | Preparation method of epoxidized SSBR (solution polymerized butadiene styrene rubber) adhesive |
| CN105505266A (en) * | 2016-01-15 | 2016-04-20 | 上海嘉好胶粘制品有限公司 | Infusion plaster glue and preparing method thereof |
| CN105505267A (en) * | 2016-01-15 | 2016-04-20 | 上海嘉好胶粘制品有限公司 | Movable label adhesive and preparation method thereof |
| CN105949353A (en) * | 2016-05-25 | 2016-09-21 | 付文 | Method for preparing epoxidized SBS (styrene butadiene styrene) |
| CN107189323A (en) * | 2017-07-07 | 2017-09-22 | 广西师范学院 | A kind of high abrasion sisal fiber modified SBS composite and preparation method thereof |
| CN107200990A (en) * | 2017-07-07 | 2017-09-26 | 广西师范学院 | A kind of ageing-resistant sisal fiber modified SBS composite |
| CN107216591A (en) * | 2017-07-07 | 2017-09-29 | 广西师范学院 | A kind of high heat-resisting sisal fiber modified SBS composite and preparation method thereof |
| CN108559011A (en) * | 2018-04-13 | 2018-09-21 | 中科广化（重庆）新材料研究院有限公司 | A kind of epoxy resin composite material and preparation method thereof |
| CN114789586A (en) * | 2022-05-25 | 2022-07-26 | 三维控股集团股份有限公司 | Ceramic composite rubber conveyer belt covering layer and wear-resistant impact-resistant rubber conveyer belt |
| CN117384556A (en) * | 2023-10-13 | 2024-01-12 | 东莞市欣美电子材料有限公司 | High-temperature-resistant rubber type adhesive tape for lithium battery and preparation method thereof |
| CN118388852A (en) * | 2024-06-19 | 2024-07-26 | 广东万瑞通电缆实业有限公司 | Wear-resistant stretch-resistant cable and preparation method thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104479590A (en) * | 2014-12-23 | 2015-04-01 | 兰州理工大学 | Preparation method of epoxidized SSBR (solution polymerized butadiene styrene rubber) adhesive |
| CN105505266A (en) * | 2016-01-15 | 2016-04-20 | 上海嘉好胶粘制品有限公司 | Infusion plaster glue and preparing method thereof |
| CN105505267A (en) * | 2016-01-15 | 2016-04-20 | 上海嘉好胶粘制品有限公司 | Movable label adhesive and preparation method thereof |
| CN105949353A (en) * | 2016-05-25 | 2016-09-21 | 付文 | Method for preparing epoxidized SBS (styrene butadiene styrene) |
| CN107189323A (en) * | 2017-07-07 | 2017-09-22 | 广西师范学院 | A kind of high abrasion sisal fiber modified SBS composite and preparation method thereof |
| CN107200990A (en) * | 2017-07-07 | 2017-09-26 | 广西师范学院 | A kind of ageing-resistant sisal fiber modified SBS composite |
| CN107216591A (en) * | 2017-07-07 | 2017-09-29 | 广西师范学院 | A kind of high heat-resisting sisal fiber modified SBS composite and preparation method thereof |
| CN108559011A (en) * | 2018-04-13 | 2018-09-21 | 中科广化（重庆）新材料研究院有限公司 | A kind of epoxy resin composite material and preparation method thereof |
| CN114789586A (en) * | 2022-05-25 | 2022-07-26 | 三维控股集团股份有限公司 | Ceramic composite rubber conveyer belt covering layer and wear-resistant impact-resistant rubber conveyer belt |
| CN117384556A (en) * | 2023-10-13 | 2024-01-12 | 东莞市欣美电子材料有限公司 | High-temperature-resistant rubber type adhesive tape for lithium battery and preparation method thereof |
| CN118388852A (en) * | 2024-06-19 | 2024-07-26 | 广东万瑞通电缆实业有限公司 | Wear-resistant stretch-resistant cable and preparation method thereof |
| CN118388852B (en) * | 2024-06-19 | 2024-08-20 | 广东万瑞通电缆实业有限公司 | Wear-resistant stretch-resistant cable and preparation method thereof |
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Application publication date: 20120919 |