CN104448059B - High-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber and preparation method thereof - Google Patents
High-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber and preparation method thereof. The method comprises: (1) prepares epoxidation butadiene rubber by butadiene rubber; (2 prepare high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber; (3) one kettle way is prepared high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber; (4) high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber is prepared in reduction. The present invention prepares high-cis-1 by butadiene rubber, 4 content epoxy terminal hydroxyl polybutadiene liquid rubbers, cis-1,4 content can reach 70.0-98.0%, epoxy rate can regulate between 1-30%, number-average molecular weight can regulate between 2000-13000g/mol, and molecular weight distribution is between 1.2-3.0, and degree of functionality is between 1.9-2.2. Under the butadiene rubber rubber background that supply exceed demand and petroleum resources day is becoming tight, prepare high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber by butadiene rubber oxicracking method, thereby be of great practical significance.
Description
Technical field
The present invention relates to one and prepare high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxy polybutadiene liquid rubber by butadiene rubberThe method of glue, relates in particular to one and prepares high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber by one kettle wayMethod, and then prepare high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber.
Background technology
The polymerization methods of 1,3-butadiene has Isosorbide-5-Nitrae-polymerization and 1,2-polymerization, generates respectively cis-Isosorbide-5-Nitrae, anti-form-1,4 or1,2-vinyl polybutadiene (PBDs), its performance depends primarily on the microstructure of polymer. At these different isomersIn, high-cis-Isosorbide-5-Nitrae polybutadiene becomes important industrial products, i.e. butadiene rubber with its excellent rubber performance. High-cis 1,4-polybutadiene rubber (butadiene rubber, BR) has excellent especially cold resistance, wearability and elasticity, also has preferably resistance to oldVoltinism energy; With natural rubber, neoprene and acrylonitrile-butadiene rubber etc. use, in tire, impact modification, cold-resistant goods, bufferingIn the production of the rubbers such as material, adhesive tape and rubber overshoes, having a wide range of applications, is that current production rate is only second to butadiene-styrene rubberSecond-biggest-in-the-world general purpose synthetic rubber. In addition, in butadiene rubber, cis-Isosorbide-5-Nitrae content is higher, and its glass transition temperature is lower,Resistance to low temperature is better.
But due to the characteristic of the full carbochain of polybutadiene self, its strand polarity is low, is difficult to and other polar material phasesHold to reach performance synergy. Therefore, the polybutadiene of modification is also widely studied. Wherein, at polybutadiene molecule last-in-chain(LIC)End is introduced polar group as hydroxyl, carboxyl etc., thus reach to increase polarity of chain the object that expands its range of application. ItsIn hydroxy-end capped terminated polybutadiene liquid rubber due to the characteristics such as its low-molecular-weight, linear molecule chain make it have workability,The features such as high adaptability to changes, macromolecular chain flexibility, thereby at space flight and aviation, coating, Embedding Material, encapsulant, membrane material, materialAll there is very important application the aspects such as material modification. Epoxidation end hydroxy butadiene is at end hydroxy butadiene macromolecular chainUpper introducing epoxide group, the not only macromolecular polarity of effective raising, and the epoxide group of introducing, can as reactive functional groupsWith with urethane crosslinks solidification process in the amino that produces occur further crosslinkedly, improve the mechanical property, sticky of polyurethane materialClose intensity and heat resistance. Therefore, epoxidation end hydroxy butadiene is for end hydroxy butadiene, and strand has moreHigh polarity, epoxide group is as reactive functional groups, at the aspect such as modified epoxy, modified polyurethane elastomer tool simultaneouslyThere is application widely.
At present, commercial epoxidation end hydroxy butadiene is all to draw on the macromolecular basis of end hydroxy butadieneEnter epoxide group, therefore the microstructure of its main chain depends primarily on the preparation technology of end hydroxy butadiene. Generally speaking, endThe preparation of hydroxyl polybutadiene is generally to cause butadiene radical polymerization or anionic polymerisation by bifunctional initiator,Hydrolysis obtains end hydroxy butadiene eventually. But, the end hydroxyl obtaining by traditional radical polymerization or anionic polymerisation modeBase polybutadiene, its microstructure generally: anti-form-1,4/ cis-Isosorbide-5-Nitrae/1, the ratio of 2-vinyl is 0.6/0.2/0.2,Depend primarily on reaction dissolvent and reaction temperature, be difficult to reach the microstructure (Journal of accurate control end hydroxy butadieneofMacromolecularScience,PartA:PureandAppliedChemistry2013,50,128–138)。Therefore, cannot prepare high-cis-Isosorbide-5-Nitrae content end hydroxy butadiene by traditional radical polymerization or anionic polymerisation, withTime also cannot prepare high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, provide a kind of high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxy group poly-Butadiene liquid rubber and preparation method thereof.
The method of preparing high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber comprises the steps:
1) butadiene rubber epoxidation reaction is prepared epoxidation butadiene rubber
It is anti-that mass concentration is that the butadiene rubber of 10g/L-100g/L and epoxidation reagent carry out epoxidation in reaction mediumShould prepare epoxidation butadiene rubber;
In described epoxidation reagent and butadiene rubber, the mol ratio of butadiene structure unit is 1%-30%; Described is anti-Answering temperature is between 0 DEG C to 80 DEG C; The described reaction time is between 30 minutes to 12 hours;
2) epoxidation butadiene rubber oxidative cracking reaction is prepared high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group polybutadiene liquidBody rubber
Epoxidation butadiene rubber reacts and obtains high-cis-Isosorbide-5-Nitrae content under the effect of oxicracking reagent in reaction mediumEpoxidation terminal aldehyde group terminated polybutadiene liquid rubber;
Described epoxidation butadiene rubber concentration is 10g/L-100g/L, and epoxidation butadiene rubber epoxy rate is 1-30%;Described reaction temperature is between 10 DEG C to 60 DEG C, and the described reaction time is between 10 minutes to 3 hours;
3) high-cis-Isosorbide-5-Nitrae content ring is prepared in the reduction of high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubberOxidation terminal hydroxyl polybutadiene liquid rubber;
High-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber is gone back under reaction medium and reducing agent existenceFormer high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber for preparing;
The number-average molecular weight of described high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber is 2000-13000g/mol, molecular weight distribution is 1.2-3.0, degree of functionality is 1.9-2.2; Described reaction temperature is between 0 DEG C to 80 DEG C;The described reaction time is between 1 hour to 12 hours.
Described step 1) in butadiene rubber be that nickel polymerized BR, cobalt are butadiene rubber or Rare Earth butadiene rubber; InstituteThe reaction medium of stating is carrene, chloroform, and C6-C8 alkane, cyclohexane, raffinates oil, benzene, toluene, the one in oxolaneOr multiple; Described epoxidation reagent is peroxy acid, metal onidiges catalyst/oxidant or metal complex catalysts/oxidationAgent, wherein said peroxy acid is peroxyformic acid, Peracetic acid, trifluoro Peracetic acid, benzoyl hydroperoxide, metachloroperbenzoic acidOr monoperphthalic acid, described metal oxide catalyst is methyl three oxygen rheniums, molybdenum trioxide or acetylacetone,2,4-pentanedione vanadyl,Described metal complex catalysts is (1S, 2S)-(+)-[1,2-cyclohexane diamine nitrogen-N, two (3,5-di-t-butyl Asias of N'-Salicyl)] manganese chloride (III), described oxidant is hydrogen peroxide, TBHP, iodosobenzene or clorox.
Described step 2) in reaction medium be carrene, chloroform, C6-C8 alkane, cyclohexane, raffinates oil, benzene, firstBenzene, one or more in oxolane; Described oxicracking reagent is perchloric acid, hyperbromic acid, periodic acid or sodium metaperiodate.
Described step 3) in reaction medium be carrene, chloroform, C6-C8 alkane, cyclohexane, raffinates oil, benzene, firstBenzene, one or more in oxolane; Described reducing agent is sodium borohydride, two (2-methoxyethoxy) sodium aluminate or the hydrogen of dihydroChange aluminium lithium.
The method of preparing high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber comprises the steps:
1) butadiene rubber one pot reaction is prepared high-cis-Isosorbide-5-Nitrae content terminal aldehyde group terminated polybutadiene liquid rubber
Epoxidation butadiene rubber and epoxidation reagent, oxicracking reagent one pot reaction in reaction medium are prepared Gao ShunFormula-Isosorbide-5-Nitrae content terminal aldehyde group terminated polybutadiene liquid rubber;
Described butadiene rubber concentration is 10g/L-100g/L; Reaction medium is carrene, chloroform, C6-C8 alkane, ringHexane, raffinates oil, benzene, toluene, one or more in oxolane; Reaction temperature is between 0 DEG C to 80 DEG C; Reaction time isBetween 1 hour to 12 hours;
2) high-cis-Isosorbide-5-Nitrae content ring is prepared in the reduction of high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubberOxidation terminal hydroxyl polybutadiene liquid rubber;
High-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber is gone back under reaction medium and reducing agent existenceFormer high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber for preparing;
Described step 3) in reaction medium be carrene, chloroform, C6-C8 alkane, cyclohexane, raffinates oil, benzene, firstBenzene, one or more in oxolane; Described reducing agent is sodium borohydride, two (2-methoxyethoxy) sodium aluminate or the hydrogen of dihydroChange aluminium lithium; The number-average molecular weight of described high-cis-Isosorbide-5-Nitrae content terminal aldehyde group terminated polybutadiene liquid rubber is 2000-13000g/Mol, molecular weight distribution is 1.2-3.0, degree of functionality is 1.9-2.2; Described reaction temperature is between 0 DEG C to 80 DEG C; DescribedReaction time is between 1 hour to 12 hours.
Described step 1) in butadiene rubber be that nickel polymerized BR, cobalt are butadiene rubber or Rare Earth butadiene rubber; InstituteStating epoxidation reagent is peroxy acid, metal onidiges catalyst/oxidant or metal complex catalysts/oxidant, Qi ZhongsuoThe peroxy acid of stating is peroxyformic acid, Peracetic acid, trifluoro Peracetic acid, benzoyl hydroperoxide, metachloroperbenzoic acid or single peroxidePhthalic acid, described metal oxide catalyst is methyl three oxygen rheniums, molybdenum trioxide or acetylacetone,2,4-pentanedione vanadyl, described goldMetal complex catalyst is (1S, 2S)-(+)-[1,2-cyclohexane diamine nitrogen-N, N'-two (3,5-di-t-butyl salicylidene)]Manganese chloride (III), described oxidant is hydrogen peroxide, TBHP, iodosobenzene or clorox, described oxygenChange lytic reagent is perchloric acid, hyperbromic acid, periodic acid or sodium metaperiodate, described oxicracking reagent and epoxide group mol ratioFor 1:2～1:31.
Described epoxidation medium comprises carrene, chloroform, and C6-C8 alkane, cyclohexane, raffinates oil, benzene, firstBenzene, the one in oxolane or mixed solvent. Described epoxidation medium is preferably carrene, n-hexane, hexamethyleneAlkane, oxolane, toluene, raffinates oil. Described butadiene rubber concentration is 10g/L-100g/L. Described butadiene rubber concentration is excellentElect 30g/L-80g/L as. Described epoxidation reagent comprises peroxy acid, metal onidiges catalyst/oxidant, metal complexCatalyst/oxidant. Described epoxidation reagent is preferably metachloroperbenzoic acid, molybdenum trioxide/TBHP,(1S, 2S)-(+)-[1,2-cyclohexane diamine nitrogen-N, N'-two (3,5-di-t-butyl salicylidene)] manganese chloride (III)/idousAcyl benzene. Described reaction temperature is between 0 DEG C to 80 DEG C. Described reaction temperature is preferably between 20 DEG C to 50 DEG C. DescribedReaction time is between 1 hour to 12 hours. The described reaction time is preferably between 1 hour to 3 hours.
Described cracking reaction medium comprises carrene, chloroform, and C6-C8 alkane, cyclohexane, raffinates oil, benzene, toluene,One in oxolane or mixed solvent. Described cracking reaction medium is preferably carrene, n-hexane, cyclohexane, fourHydrogen furans, toluene, raffinates oil. Described epoxidation butadiene rubber concentration is 10g/L-100g/L. Described epoxidation is along fourth rubberGum concentration is preferably 30g/L-80g/L. Described oxicracking reagent comprises perchloric acid, hyperbromic acid, periodic acid, sodium metaperiodate.Described oxicracking reagent is preferably periodic acid, and described oxicracking reagent and epoxide group mol ratio are 1:2～1:31.Described reaction temperature is between 0 DEG C to 80 DEG C. Described reaction temperature is preferably between 20 DEG C to 50 DEG C. When described reactionBetween be between 10 minutes to 3 hours. The described reaction time was preferably between half an hour to 2 hour.
One kettle way is prepared high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber, comprises butadiene rubber epoxyChange reaction and epoxidation butadiene rubber oxidative cracking reaction. Butadiene rubber dissolves completely in reaction medium, at a certain temperature,Add epoxidation reagent to carry out epoxidation reaction, in the time that epoxidation reaction finishes, add oxicracking reagent to carry out in-situ oxidationCracking reaction, original position obtains high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber. Described reaction medium bagDraw together carrene, chloroform, C6-C8 alkane, cyclohexane, raffinates oil, benzene, toluene, oxolane, a kind of in ethanol or mix moltenAgent. Described reaction medium is preferably carrene, n-hexane, and cyclohexane, oxolane, toluene, raffinates oil. Described suitable fourthRubber concentrations is 10g/L-100g/L. Described butadiene rubber concentration is preferably 30g/L-80g/L. Described epoxidation reagent bagDraw together peroxy acid, metal onidiges catalyst/oxidant, metal complex catalysts/oxidant. Described epoxidation reagent is preferredFor metachloroperbenzoic acid, molybdenum trioxide/TBHP, (1S, 2S)-(+)-[1,2-cyclohexane diamine nitrogen-N, N'-Two (3,5-di-t-butyl salicylidenes)] manganese chloride (III)/iodosobenzene. Described oxicracking reagent comprises perchloric acid, heightBromic acid, periodic acid, sodium metaperiodate. Described oxicracking reagent is preferably periodic acid, described oxicracking reagent and epoxyGroup molar ratio is 1:2～1:31. Described reaction temperature is between 0 DEG C to 80 DEG C. Described reaction temperature is preferably 20 DEG CBetween 50 DEG C. Described total reaction time is between 1 hour to 12 hours.
Described total reaction time is preferably between 1 hour to 3 hours.
High-cis-Isosorbide-5-Nitrae content epoxy is prepared in the reduction of high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubberChange terminal hydroxyl polybutadiene liquid rubber, high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group polybutadiene liquid is complete in reaction mediumCL, at a certain temperature, adds reducing agent to carry out reduction reaction. Described reaction medium comprises carrene, chloroform,C6-C8 alkane, cyclohexane, raffinates oil, benzene, toluene, the one in oxolane or mixed solvent. Described reaction medium is preferredFor carrene, n-hexane, cyclohexane, oxolane, toluene, raffinates oil. Described reducing agent comprises sodium borohydride, and dihydro is two(2-methoxyethoxy) sodium aluminate, lithium aluminium hydride reduction. Described reducing agent is preferably sodium borohydride. Described reaction temperature is 0 DEG CBetween 80 DEG C. Described reaction temperature is preferably between 20 DEG C to 60 DEG C. The described reaction time be 1 hour to 12 hours itBetween. The described reaction time is preferably between 2 hours to 5 hours.
The present invention is under the butadiene rubber rubber background that supply exceed demand and petroleum resources day is becoming tight, by butadiene rubber oxygenChange cleavage method and prepare high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber, thereby there is very important showingSincere justice, the method for preparing high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber has very high reaction effectRate has been introduced epoxide group and chain end aldehyde radical in chain in butadiene rubber oxicracking process simultaneously, and chain end aldehyde radical is through going backAfter former, can obtain high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber, technique is simply efficient, has widelyProspects for commercial application.
Brief description of the drawings
Fig. 1 is raw material butadiene rubber, intermediate products epoxidation terminal aldehyde group polybutadiene and final products epoxidation terminal hydroxy groupThe nucleus magnetic hydrogen spectrum figure of polybutadiene.
Detailed description of the invention
The present invention relates to prepare high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber by butadiene rubberMethod, comprises that butadiene rubber epoxidation reaction prepares epoxidation butadiene rubber, the preparation of epoxidation butadiene rubber oxidative cracking reactionThe poly-fourth two of high-cis-Isosorbide-5-Nitrae content end ring oxidation aldehyde radical terminated polybutadiene liquid rubber and high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde groupHigh-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber is prepared in the reduction of alkene liquid rubber. Can according to following two kinds notCarry out with flow process: three-step approach and two-step method.
Three-step approach is prepared high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber
Two-step method is prepared high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber
(1) the concrete preparation process of three-step approach is as follows:
1), in the situation that stirring, butadiene rubber dissolves completely in reaction medium, and constant temperature at a certain temperature, addsEpoxidation reagent, reacts certain hour under constant temperature, and reaction finishes afterproduct and precipitates with a large amount of ethanol, and 40 DEG C of vacuum drying 24 are littleTime, prepare epoxidation butadiene rubber.
2) by step 1) the epoxidation butadiene rubber of gained is dissolved in reaction medium completely, constant temperature at a certain temperature,Add oxicracking reagent, under constant temperature, react certain hour, product isolated by filtration, 40 DEG C of vacuum drying 24 hours, prepareHigh-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber.
3) by step 2) high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber of obtaining is at reaction mediumIn dissolve completely, and constant temperature at a certain temperature adds reducing agent in the situation that stirring, and after isothermal reaction certain hour, addsEnter a small amount of deionized water, product isolated by filtration, 40 DEG C of vacuum drying 24 hours, prepare high-cis-Isosorbide-5-Nitrae content epoxy endHydroxyl terminated polybutadiene liquid rubber.
(2) the concrete preparation process of two-step method is as follows:
1), in the situation that stirring, butadiene rubber dissolves completely in reaction medium, and constant temperature at a certain temperature, addsEpoxidation reagent, reacts certain hour under constant temperature, and original position adds oxicracking reagent subsequently, and at same temperature, reaction is certainTime, product isolated by filtration, 40 DEG C of vacuum drying 24 hours, prepare the poly-fourth two of high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde groupAlkene liquid rubber.
2) by step 1) high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber of obtaining is at reaction mediumIn dissolve completely, and constant temperature at a certain temperature adds reducing agent in the situation that stirring, and after isothermal reaction certain hour, addsEnter a small amount of deionized water, product isolated by filtration, 40 DEG C of vacuum drying 24 hours, prepare high-cis-Isosorbide-5-Nitrae content epoxy endHydroxyl terminated polybutadiene liquid rubber.
What the present invention relates to prepares high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber by butadiene rubberMethod, comprise that butadiene rubber epoxidation reaction prepares epoxidation butadiene rubber, epoxidation butadiene rubber oxidative cracking reaction systemThe poly-fourth of standby high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber and high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde groupHigh-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber is prepared in the reduction of diene liquid rubber.
Prepare epoxidation butadiene rubber for above-mentioned butadiene rubber epoxidation reaction, preferred butadiene rubber concentration is30g/L-80g/L, preferred reaction medium is carrene, cyclohexane, oxolane, toluene, preferred epoxidation reagent isPeroxyformic acid, metachloroperbenzoic acid, preferred reaction temperature is 20-50 DEG C, the preferred reaction time is 1 hour to 3 hours.Above-mentioned epoxidation butadiene rubber oxidative cracking reaction is prepared high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group polybutadiene liquid rubberGlue, preferred epoxidation butadiene rubber concentration is 30g/L-80g/L, preferred reaction medium is carrene, cyclohexane, tetrahydrochyseneFurans, toluene, preferred oxicracking reagent is periodic acid, and preferred reaction temperature is 20-50 DEG C, and the preferred reaction time isHalf an hour to 2 hour; Above-mentioned one kettle way is prepared high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber, preferablyButadiene rubber concentration be 30g/L-80g/L, preferred reaction medium is carrene, cyclohexane, oxolane, toluene, excellentThe epoxidation reagent of choosing is peroxyformic acid, metachloroperbenzoic acid, and preferred oxicracking reagent is periodic acid, preferably reactionTemperature is between 20 DEG C to 50 DEG C, and preferred total reaction time is between 1 hour to 3 hours. Above-mentioned is contained by high-cis-Isosorbide-5-NitraeAmount epoxidation terminal aldehyde group terminated polybutadiene liquid rubber is prepared high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber,Preferred reaction medium is carrene, toluene, oxolane, and preferably going back original reagent is sodium borohydride, preferred reaction temperatureDegree is 20-60 DEG C, and the preferred reaction time is 2 hours to 5 hours.
Describe the present invention with specific embodiment below and prepare high-cis-Isosorbide-5-Nitrae content epoxy end hydroxyl by butadiene rubberThe process of base terminated polybutadiene liquid rubber, but they should not be considered as limiting scope of the present invention.
Embodiment 1
Get nickel polymerized BR (BR9000) 5.00g, be dissolved in completely in 100mL oxolane, rubber concentrations is 50g/L, constant temperature to 30 DEG C, adds metachloroperbenzoic acid under vigorous stirring, and metachloroperbenzoic acid consumption is nickel polymerized BR (BR9000) 2% of middle butadiene structure unit, the reaction time is 6 hours, a large amount of ethanol precipitations vacuum drying for product. ProductWarp1HNMR characterizes to such an extent that epoxy rate is 2.0%.
Get above-mentioned epoxidation butadiene rubber 4.00g, be dissolved in completely in 100mL oxolane, rubber concentrations is 40g/L,Constant temperature to 30 DEG C, adds periodic acid under vigorous stirring, and periodic acid and epoxide group mol ratio are 1:2, reacts 30 minutes. Product mistakeFilter can obtain high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber, product warp1HNMR characterizes to such an extent that epoxy rate is1.0％。
Get above-mentioned high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber 3.00g, be dissolved in tetrahydrochysene completelyIn furans, constant temperature to 30 DEG C, adds 0.11g sodium borohydride, reacts 8 hours, adds a small amount of water. Product filter can obtain high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber, characterizes to such an extent that number-average molecular weight is 12000g/mol through GPC, molecular weightBe distributed as 1.80, warp1HNMR and13CNMR characterizes to such an extent that microstructure is cis-Isosorbide-5-Nitrae/anti-form-1,4/1,2-vinyl=95.2%/1.4%/2.4%, hydroxy functionality is 2.01, and epoxy rate is 1.0%.
Embodiment 2
Getting cobalt is butadiene rubber (Taipol) 5.00g, is dissolved in completely in 200mL cyclohexane, and rubber concentrations is 25g/L,Constant temperature to 50 DEG C, adds metachloroperbenzoic acid under vigorous stirring, and metachloroperbenzoic acid consumption is that cobalt is butadiene rubber(Taipol) 4% of middle butadiene structure unit, the reaction time is 4 hours, a large amount of ethanol precipitations vacuum drying for product. ProduceThing warp1HNMR characterizes to such an extent that epoxy rate is 4.0%.
Get above-mentioned epoxidation butadiene rubber 4.00g, be dissolved in completely in 100mL cyclohexane, rubber concentrations is 40g/L, perseveranceTemperature, to 50 DEG C, adds periodic acid under vigorous stirring, and periodic acid and epoxide group mol ratio are 1:4, react 40 minutes. Product filtersCan obtain high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber, epoxy rate is 3.0%
Get above-mentioned high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber 3.00g, be dissolved in hexamethylene completelyIn alkane, constant temperature to 50 DEG C, adds 0.14g sodium borohydride, reacts 12 hours, adds a small amount of water. Product filters can obtain high-cis-1,4 content epoxy terminal hydroxyl polybutadiene liquid rubbers, characterize to such an extent that number-average molecular weight is 11800g/mol through GPC, and molecular weight dividesCloth is 1.87, warp1HNMR and13CNMR characterizes to such an extent that microstructure is cis-Isosorbide-5-Nitrae/anti-form-1,4/1,2-vinyl=93.2%/1.4%/2.4%, hydroxy functionality is 2.00, and epoxy rate is 3.0%.
Embodiment 3
Getting neodymium is butadiene rubber (BR9100) 5.00g, is dissolved in completely in 100mL toluene, and rubber concentrations is 50g/L, perseveranceTemperature, to 70 DEG C, adds under vigorous stirring (1S, 2S)-(+)-[1,2-cyclohexane diamine nitrogen-N, two (sub-water of 3,5-di-t-butyl of N'-Yankee)] manganese chloride (III) 0.005g, clorox consumption is that neodymium is butadiene structure unit in butadiene rubber (BR9100)8%, the reaction time is 2 hours, a large amount of ethanol precipitations vacuum drying for product. Product warp1HNMR characterizes to such an extent that epoxy rate is8.0％。
Get above-mentioned epoxidation butadiene rubber 4.00g, be dissolved in completely in 100mL toluene, rubber concentrations is 40g/L, constant temperatureTo 50 DEG C, under vigorous stirring, add periodic acid, periodic acid and epoxide group mol ratio are 1:8, react 50 minutes. Product filters canObtain high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber.
Get above-mentioned high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber 3.00g, be dissolved in toluene completelyIn, constant temperature to 80 DEG C, adds 0.23g sodium borohydride, reacts 3 hours, adds a small amount of water. Product filtration can obtain high-cis-Isosorbide-5-Nitrae and containAmount epoxidation terminal hydroxyl polybutadiene liquid rubber, characterizes to such an extent that number-average molecular weight is 12000g/mol through GPC, and molecular weight distribution is2.01, warp1HNMR and13CNMR characterizes to such an extent that microstructure is cis-Isosorbide-5-Nitrae/anti-form-1,4/1,2-vinyl=91.6%/0.3%/1.1%, hydroxy functionality is 1.99, and epoxy rate is 7.0%.
Embodiment 4
Get nickel polymerized BR (BR9000) 5.00g, be dissolved in completely in 100mL n-hexane, rubber concentrations is 50g/L,Constant temperature to 30 DEG C, adds benzoyl hydroperoxide under vigorous stirring, and benzoyl hydroperoxide consumption is fourth in nickel polymerized BR (BR9000)15% of diene structure unit, the reaction time is 6 hours, a large amount of ethanol precipitations vacuum drying for product. Product warp1HNMRCharacterize to such an extent that epoxy rate is 15.0%.
Get above-mentioned epoxidation butadiene rubber 4.00g, be dissolved in completely in 50mL n-hexane, rubber concentrations is 80g/L, constant temperatureTo 30 DEG C, under vigorous stirring, add periodic acid, periodic acid and epoxide group mol ratio are 1:15, react 30 minutes. Product filtersCan obtain high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber.
Get above-mentioned high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber 3.00g, be dissolved in tetrahydrochysene completelyIn furans, constant temperature to 30 DEG C, adds 0.11g sodium borohydride, reacts 8 hours, adds a small amount of water. Product filter can obtain high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber, characterizes to such an extent that number-average molecular weight is 11500g/mol through GPC, molecular weightBe distributed as 2.00, warp1HNMR and13CNMR characterizes to such an extent that microstructure is cis-Isosorbide-5-Nitrae/anti-form-1,4/1,2-vinyl=82.2%/1.4%/2.4%, hydroxy functionality is 2.01, and epoxy rate is 14.0%.
Embodiment 5
Get nickel polymerized BR (BR9000) 5.00g, be dissolved in completely in 500mL carrene, rubber concentrations is 10g/L, constant temperature to 0 DEG C, adds peroxyformic acid under vigorous stirring, and peroxyformic acid consumption is fourth two in nickel polymerized BR (BR9000)35% of alkene construction unit, the reaction time is 12 hours, a large amount of ethanol precipitations vacuum drying for product. Product warp1HNMR tableObtaining epoxy rate is 31.0%.
Get above-mentioned epoxidation butadiene rubber 4.00g, be dissolved in completely in 50mL carrene, rubber concentrations is 80g/L, perseveranceTemperature, to 10 DEG C, adds periodic acid under vigorous stirring, and periodic acid and epoxide group mol ratio are 1:31, react 1 hour. Product filtersCan obtain high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber.
Get above-mentioned high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber 3.00g, be dissolved in toluene completelyIn, constant temperature to 30 DEG C, adds two (2-methoxyethoxy) sodium aluminates of 0.5g dihydro, reacts 8 hours, adds a small amount of water. Product mistakeFilter can obtain high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber, characterizes to such an extent that number-average molecular weight is through GPC13000g/mol, molecular weight distribution is 1.90, warp1HNMR and13CNMR characterizes to such an extent that microstructure is cis-Isosorbide-5-Nitrae/anti-form-1,4/1,2-vinyl=66.2%/1.4%/2.4%, hydroxy functionality is 2.05, epoxy rate is 30.0%.
Embodiment 6
Get nickel polymerized BR (BR9000) 5.00g, be dissolved in completely in 50mL chloroform, rubber concentrations is 100g/L, constant temperature to 10 DEG C, adds metachloroperbenzoic acid under vigorous stirring, and metachloroperbenzoic acid consumption is nickel polymerized BR (BR9000) 8% of middle butadiene structure unit, the reaction time is 1 hour, a large amount of ethanol precipitations vacuum drying for product. ProductWarp1HNMR characterizes to such an extent that epoxy rate is 8.0%.
Get above-mentioned epoxidation butadiene rubber 4.00g, be dissolved in completely in 40mL chloroform, rubber concentrations is 100g/L,Constant temperature to 20 DEG C, adds periodic acid under vigorous stirring, and periodic acid and epoxide group mol ratio are 1:4, reacts 1 hour. Product mistakeFilter can obtain high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber.
Get above-mentioned high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber 3.00g, be dissolved in hexamethylene completelyIn alkane, constant temperature to 80 DEG C, adds 0.23g sodium borohydride, reacts 12 hours, adds a small amount of water. Product filters can obtain high-cis-1,4 content epoxy terminal hydroxyl polybutadiene liquid rubbers, characterize to such an extent that number-average molecular weight is 7000g/mol through GPC, molecular weight distributionBe 1.60, warp1HNMR and13CNMR characterizes to such an extent that microstructure is cis-Isosorbide-5-Nitrae/anti-form-1,4/1,2-vinyl=90.5%/1.1%/2.4%, hydroxy functionality is 2.10, and epoxy rate is 6.0%.
Embodiment 7
Get nickel polymerized BR (BR9000) 5.00g, be dissolved in completely in 100mL chloroform, rubber concentrations is 50g/L, constant temperature to 30 DEG C, adds methyl three oxygen rhenium 0.005g under vigorous stirring, and hydrogen peroxide (30% aqueous solution) consumption is that nickel system is along fourth15% of the middle butadiene structure of rubber (BR9000) unit, the reaction time is 3 hours, a large amount of ethanol precipitations vacuum for productDry. Product warp1HNMR characterizes to such an extent that epoxy rate is 15.0%.
Get above-mentioned epoxidation butadiene rubber 4.00g, be dissolved in completely in 100mL chloroform, rubber concentrations is 40g/L,Constant temperature to 10 DEG C, adds perchloric acid under vigorous stirring, and perchloric acid and epoxide group mol ratio are that 2:15 answers 3 hours. Product filtersCan obtain high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber.
Get above-mentioned high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber 3.00g, be dissolved in toluene completelyIn, constant temperature to 30 DEG C, adds 0.23g lithium aluminium hydride reduction, reacts 12 hours, adds a small amount of water. Product filters can obtain high-cis-Isosorbide-5-NitraeContent epoxy terminal hydroxyl polybutadiene liquid rubber, characterizes to such an extent that number-average molecular weight is 7000g/mol through GPC, molecular weight distributionBe 1.95, warp1HNMR and13CNMR characterizes to such an extent that microstructure is cis-Isosorbide-5-Nitrae/anti-form-1,4/1,2-vinyl=83.5%/1.1%/2.4%, degree of functionality is 2.20, and epoxy rate is 13.0%.
Embodiment 8
Get nickel polymerized BR (BR9000) 5.00g, be dissolved in completely during 100mL raffinates oil, rubber concentrations is 50g/L,Constant temperature to 30 DEG C, adds molybdenum trioxide 0.05g under vigorous stirring, TBHP (70% aqueous solution) consumption is that nickel is suitable33% of the middle butadiene structure of fourth rubber (BR9000) unit, the reaction time is 2 hours, a large amount of ethanol precipitations true for productEmpty dry. Product warp1HNMR characterizes to such an extent that epoxy rate is 32.0%.
Get above-mentioned epoxidation butadiene rubber 4.00g, be dissolved in completely during 100mL raffinates oil, rubber concentrations is 40g/L, perseveranceTemperature, to 10 DEG C, adds perchloric acid under vigorous stirring, and perchloric acid and epoxide group mol ratio are 2:32, react 3 hours. Product filtersCan obtain high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber.
Get above-mentioned high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber 3.00g, more than being dissolved in taking out completelyIn oil, constant temperature to 30 DEG C, adds 0.23g lithium aluminium hydride reduction, reacts 12 hours, adds a small amount of water. Product filters can obtain high-cis-1,4 content terminal hydroxyl polybutadiene liquid rubbers, characterize to such an extent that number-average molecular weight is 7300g/mol through GPC, and molecular weight distribution is1.45, warp1HNMR and13CNMR characterizes to such an extent that microstructure is cis-Isosorbide-5-Nitrae/anti-form-1,4/1,2-vinyl=66.5%/1.1%/2.4%, hydroxy functionality is 2.20, and epoxy rate is 30%.
Embodiment 9
Get nickel polymerized BR (BR9000) 5.00g, be dissolved in completely in 100mL toluene, rubber concentrations is 50g/L, perseveranceTemperature, to 80 DEG C, adds Peracetic acid under vigorous stirring, and Peracetic acid consumption is butadiene knot in nickel polymerized BR (BR9000)15% of structure unit, the reaction time is 12 hours, a large amount of ethanol precipitations vacuum drying for product. Product warp1HNMR characterizesEpoxy rate is 12.0%.
Get above-mentioned epoxidation butadiene rubber 4.00g, be dissolved in completely in 100mL toluene, rubber concentrations is 40g/L, constant temperatureTo 40 DEG C, under vigorous stirring, add hyperbromic acid, hyperbromic acid and epoxide group mol ratio are 1:3, react 3 hours. Product filters canObtain high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber.
Get above-mentioned high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber 3.00g, be dissolved in toluene completelyIn, constant temperature to 30 DEG C, adds 0.46g lithium aluminium hydride reduction, reacts 6 hours, adds a small amount of water. Product filtration can obtain high-cis-Isosorbide-5-Nitrae and containAmount epoxidation terminal hydroxyl polybutadiene liquid rubber, characterizes to such an extent that number-average molecular weight is 5000g/mol through GPC, and molecular weight distribution is2.00, warp1HNMR and13CNMR characterizes to such an extent that microstructure is cis-Isosorbide-5-Nitrae/anti-form-1,4/1,2-vinyl=88.2%/1.4%/2.4%, hydroxy functionality is 2.10, and epoxy rate is 8.0%.
Embodiment 10
Get nickel polymerized BR (BR9000) 5.00g, be dissolved in completely in 100mL carrene, rubber concentrations is 50g/L, constant temperature to 0 DEG C, adds peroxyformic acid under vigorous stirring, and peroxyformic acid consumption is fourth two in nickel polymerized BR (BR9000)10% of alkene construction unit, the reaction time is 12 hours, product warp1HNMR characterizes to such an extent that epoxy rate is 8.0%. Original position adds saltAcid and sodium metaperiodate, hydrochloric acid consumption ensures that reacting system PH value is less than 7, periodic acid and epoxide group mol ratio are 1:2, reaction 2Hour. Product filters can obtain high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber.
Get above-mentioned high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber 3.00g, be dissolved in dichloro completelyIn methane, constant temperature to 20 DEG C, adds 0.2g sodium borohydride, reacts 4 hours, adds a small amount of water. Product filters can obtain high-cis-1,4 content epoxy terminal hydroxyl polybutadiene liquid rubbers, characterize to such an extent that number-average molecular weight is 5500g/mol through GPC, molecular weight distributionBe 2.51, warp1HNMR and13CNMR characterizes to such an extent that microstructure is cis-Isosorbide-5-Nitrae/anti-form-1,4/1,2-vinyl=96.5%/1.1%/2.4%, hydroxy functionality is 1.93, and epoxy rate is 4.0%.
Embodiment 11
Get nickel polymerized BR (BR9000) 5.00g, be dissolved in completely in 100mL carrene, rubber concentrations is 50g/L, constant temperature to 10 DEG C, adds trifluoro Peracetic acid under vigorous stirring, and trifluoro Peracetic acid consumption is nickel polymerized BR (BR9000) 20% of middle butadiene structure unit, the reaction time is 2 hours, product warp1HNMR characterizes to such an extent that epoxy rate is 20.0%.Original position adds perchloric acid, and perchloric acid and epoxide group mol ratio are 1:5, reacts 2 hours. Product filtration can obtain high-cis-Isosorbide-5-Nitrae and containAmount epoxidation terminal aldehyde group terminated polybutadiene liquid rubber.
Get above-mentioned high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber 3.00g, be dissolved in tetrahydrochysene completelyIn furans, constant temperature to 30 DEG C, adds 0.1g lithium aluminium hydride reduction, reacts 6 hours, adds a small amount of water. Product filters can obtain high-cis-1,4 content epoxy terminal hydroxyl polybutadiene liquid rubbers, characterize to such an extent that number-average molecular weight is 5600g/mol through GPC, molecular weight distributionBe 1.58, warp1HNMR and13CNMR characterizes to such an extent that microstructure is cis-Isosorbide-5-Nitrae/anti-form-1,4/1,2-vinyl=81.5%/1.1%/2.4%, hydroxy functionality is 2.05, and epoxy rate is 15.0%.
Embodiment 12
Getting cobalt is butadiene rubber (Taipol) 5.00g, is dissolved in completely during 100mL raffinates oil, and rubber concentrations is 50g/L,Constant temperature to 20 DEG C, adds benzoyl hydroperoxide under vigorous stirring, and benzoyl hydroperoxide consumption is that cobalt is fourth in butadiene rubber (Taipol)34% of diene structure unit, the reaction time is 6 hours, product warp1HNMR characterizes to such an extent that epoxy rate is 34%. Original position adds heightAcid iodide, periodic acid and epoxide group mol ratio are 2:17, react 1 hour. Product filters can obtain high-cis-Isosorbide-5-Nitrae content epoxyTerminal aldehyde group terminated polybutadiene liquid rubber.
Get above-mentioned high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber 3.00g, be dissolved in tetrahydrochysene completelyIn furans, constant temperature to 30 DEG C, adds 0.14g sodium borohydride, reacts 4 hours, adds a small amount of water. Product filter can obtain high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber, characterizes to such an extent that number-average molecular weight is 5700g/mol through GPC, and molecular weight dividesCloth is 2.82, warp1HNMR and13CNMR characterizes to such an extent that microstructure is cis-Isosorbide-5-Nitrae/anti-form-1,4/1,2-vinyl=66.2%/1.4%/2.4%, hydroxy functionality is 2.02, and epoxy rate is 30%.
Embodiment 13
Getting cobalt is butadiene rubber (Taipol) 5.00g, is dissolved in completely in 100mL oxolane, and rubber concentrations is 50g/L, constant temperature to 0 DEG C, adds monoperphthalic acid under vigorous stirring, and monoperphthalic acid consumption is that cobalt is butadiene rubber(Taipol) 20% of middle butadiene structure unit, the reaction time is 12 hours, product warp1HNMR characterizes to such an extent that epoxy rate is20.0%. Original position adds hyperbromic acid, and hyperbromic acid and epoxide group mol ratio are 1:2, reacts 3 hours. Product filters can obtain Gao ShunFormula-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber.
Get above-mentioned high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber 3.00g, be dissolved in dichloro completelyIn methane, constant temperature to 20 DEG C, adds 0.11g sodium borohydride, reacts 10 hours, adds a small amount of water. Product filter can obtain high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber, characterizes to such an extent that number-average molecular weight is 2000g/mol through GPC, and molecular weight dividesCloth is 1.89, warp1HNMR and13CNMR characterizes to such an extent that microstructure is cis-Isosorbide-5-Nitrae/anti-form-1,4/1,2-vinyl=86.2%/1.4%/2.4%, degree of functionality is 2.01, and epoxy rate is 10.0%.
Embodiment 14
Getting cobalt is butadiene rubber (Taipol) 5.00g, is dissolved in completely during 100mL raffinates oil, and rubber concentrations is 50g/L,Constant temperature to 20 DEG C, adds under vigorous stirring (1S, 2S)-(+)-[1,2-cyclohexane diamine nitrogen-N, two (3,5-di-t-butyl Asias of N'-Salicyl)] manganese chloride (III) 0.005g, iodosobenzene consumption is that cobalt is butadiene structure unit in butadiene rubber (Taipol)40%, the reaction time is 1 hour, product warp1HNMR characterizes to such an extent that epoxy rate is 40%. Original position adds periodic acid, periodic acid withEpoxide group mol ratio is 1:4, reacts 3 hours. Product filters can obtain high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group polybutadieneLiquid rubber.
Get above-mentioned high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber 3.00g, more than being dissolved in taking out completelyIn oil, constant temperature to 20 DEG C, adds two (2-methoxyethoxy) sodium aluminates of 0.5g dihydro, reacts 8 hours, adds a small amount of water. ProductFiltration can obtain high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber, characterizes to such an extent that number-average molecular weight is through GPC3000g/mol, molecular weight distribution is 2.12, warp1HNMR and13CNMR characterizes to such an extent that microstructure is cis-Isosorbide-5-Nitrae/anti-form-1, and 4/1,2-vinyl=66.3%/1.3%/2.4%, hydroxy functionality is 1.98, epoxy rate is 30%.
Embodiment 15
Getting neodymium is butadiene rubber (BR9100) 5.00g, is dissolved in completely in 100mL cyclohexane, and rubber concentrations is 50g/L,Constant temperature to 20 DEG C, adds molybdenum trioxide 0.005g under vigorous stirring, TBHP (70% aqueous solution) consumption is neodymium systemButadiene structure unit 2% in butadiene rubber (BR9100), the reaction time is 8 hours, product warp1HNMR characterizes to obtain epoxy rateBe 2.0%. Original position adds hydrochloric acid and sodium metaperiodate, and hydrochloric acid consumption ensures that reacting system PH value is less than 7, sodium metaperiodate and epoxy radicalsGroup's mol ratio is 1:2, reacts 3 hours. Product filters can obtain high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group polybutadiene liquid rubberGlue.
Get above-mentioned high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber 3.00g, more than being dissolved in taking out completelyIn oil, constant temperature to 0 DEG C, adds 0.18g sodium borohydride, reacts 12 hours, adds a small amount of water. Product filters can obtain high-cis-Isosorbide-5-NitraeContent epoxy terminal hydroxyl polybutadiene liquid rubber, characterizes to such an extent that number-average molecular weight is 12000g/mol through GPC, molecular weight distributionBe 2.76, warp1HNMR and13CNMR characterizes to such an extent that microstructure is cis-Isosorbide-5-Nitrae/trans Isosorbide-5-Nitrae/1,2-vinyl=97.6%/0.3%/1.1%, hydroxy functionality is 1.98, and epoxy rate is 1.0%.
Embodiment 16
Getting neodymium is butadiene rubber (BR9100) 5.00g, is dissolved in completely in 100mL cyclohexane, and rubber concentrations is 50g/L,Constant temperature to 30 DEG C, adds metachloroperbenzoic acid under vigorous stirring, and metachloroperbenzoic acid consumption is that neodymium is butadiene rubber (BR9100) 10% of middle butadiene structure unit, the reaction time is 6 hours, product warp1HNMR characterizes to such an extent that epoxy rate is 10.0%.Original position adds periodic acid, and periodic acid and epoxide group mol ratio are 1:5, reacts 2 hours. Product filtration can obtain high-cis-Isosorbide-5-Nitrae and containAmount epoxidation terminal aldehyde group terminated polybutadiene liquid rubber.
Get above-mentioned high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber 3.00g, be dissolved in toluene completelyIn, constant temperature to 40 DEG C, adds 0.23g sodium borohydride, reacts 3 hours, adds a small amount of water. Product filtration can obtain high-cis-Isosorbide-5-Nitrae and containAmount epoxidation terminal hydroxyl polybutadiene liquid rubber, characterizes to such an extent that number-average molecular weight is 7000g/mol through GPC, and molecular weight distribution is1.86, warp1HNMR and13CNMR characterizes to such an extent that microstructure is cis-Isosorbide-5-Nitrae/anti-form-1,4/1,2-vinyl=90.6%/0.3%/1.1%, hydroxy functionality is 2.00, and epoxy rate is 8.0%.
Embodiment 17
Getting neodymium is butadiene rubber (BR9100) 5.00g, is dissolved in completely in 100mL toluene, and rubber concentrations is 50g/L, perseveranceTemperature, to 50 DEG C, adds metachloroperbenzoic acid under vigorous stirring, and metachloroperbenzoic acid consumption is that neodymium is butadiene rubber (BR9100) 20% of middle butadiene structure unit, the reaction time is 2 hours, product warp1HNMR characterizes to such an extent that epoxy rate is 20.0%.Original position adds periodic acid, and periodic acid and epoxide group mol ratio are 1:5, reacts 1 hour. Product filtration can obtain high-cis-Isosorbide-5-Nitrae and containAmount epoxidation terminal aldehyde group terminated polybutadiene liquid rubber.
Get above-mentioned high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber 3.00g, be dissolved in hexamethylene completelyIn alkane, constant temperature to 0 DEG C, adds 0.30g sodium borohydride, reacts 12 hours, adds a small amount of water. Product filters can obtain high-cis-Isosorbide-5-NitraeContent epoxy terminal hydroxyl polybutadiene liquid rubber, characterizes to such an extent that number-average molecular weight is 5500g/mol through GPC, molecular weight distributionBe 1.92, warp1HNMR and13CNMR characterizes to such an extent that microstructure is cis-Isosorbide-5-Nitrae/anti-form-1,4/1,2-vinyl=83.6%/0.3%/1.1%, hydroxy functionality is 2.01, and epoxy rate is 15.0%.
Embodiment 18
Getting neodymium is butadiene rubber (BR9100) 5.00g, is dissolved in completely in 100mL toluene, and rubber concentrations is 50g/L, perseveranceTemperature, to 80 DEG C, adds acetylacetone,2,4-pentanedione vanadyl 0.005g under vigorous stirring, TBHP (70% aqueous solution) consumption is neodymiumBe 40% of the middle butadiene structure of butadiene rubber (BR9100) unit, the reaction time is half an hour, product warp1HNMR characterizesEpoxy rate is 40.0%. Original position adds periodic acid, and periodic acid and epoxide group mol ratio are 1:4, reacts 10 minutes. Product filtersCan obtain high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber.
Get above-mentioned high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber 3.00g, be dissolved in toluene completelyIn, constant temperature to 80 DEG C, adds 0.30g sodium borohydride, reacts 1 hour, adds a small amount of water. Product filtration can obtain high-cis-Isosorbide-5-Nitrae and containAmount epoxidation terminal hydroxyl polybutadiene liquid rubber, characterizes to such an extent that number-average molecular weight is 3000g/mol through GPC, and molecular weight distribution is2.48, warp1HNMR and13CNMR characterizes to such an extent that microstructure is cis-Isosorbide-5-Nitrae/anti-form-1,4/1,2-vinyl=68.6%/0.3%/1.1%, hydroxy functionality is 2.01, and epoxy rate is 30.0%.
Claims (7)
1. a method of preparing high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber, is characterized in that, bagDraw together following steps:
1) butadiene rubber epoxidation reaction is prepared epoxidation butadiene rubber
Mass concentration is that butadiene rubber and the epoxidation reagent epoxidation reaction in reaction medium of 10g/L-100g/L is prepared intoTo epoxidation butadiene rubber;
In described epoxidation reagent and butadiene rubber, butadiene structure unit mol ratio is 1%-30%; Described reaction temperature isBetween 0 DEG C to 80 DEG C; The described reaction time is between 30 minutes to 12 hours;
2) epoxidation butadiene rubber oxidative cracking reaction is prepared high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group polybutadiene liquid rubberGlue
Epoxidation butadiene rubber reacts and obtains high-cis-Isosorbide-5-Nitrae content epoxy under the effect of oxicracking reagent in reaction mediumChange terminal aldehyde group terminated polybutadiene liquid rubber; Described oxicracking reagent and epoxide group mol ratio are 1:2 ~ 1:31;
Described epoxidation butadiene rubber concentration is 10g/L-100g/L, and epoxidation butadiene rubber epoxy rate is 1-30%; DescribedReaction temperature be between 10 DEG C to 60 DEG C, the described reaction time is between 10 minutes to 3 hours;
3) high-cis-Isosorbide-5-Nitrae content epoxy is prepared in the reduction of high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubberTerminal hydroxyl polybutadiene liquid rubber;
High-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber is reduction system under reaction medium and reducing agent existenceStandby high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber that obtains;
The number-average molecular weight of described high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber is 2000-13000g/mol, molecular weight distribution is 1.2-3.0, degree of functionality is 1.9-2.2; Described reaction temperature is between 0 DEG C to 80 DEG C;The described reaction time is between 1 hour to 12 hours.
2. side of preparing high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber according to claim 1Method, is characterized in that, the butadiene rubber in described step 1) is that nickel polymerized BR, cobalt are that butadiene rubber or Rare Earth are along fourth rubberGlue; Described reaction medium is carrene, chloroform, C6-C8 alkane, cyclohexane, raffinate oil, in benzene, toluene, oxolaneOne or more; Described epoxidation reagent be peroxy acid, metal oxide catalyst/oxidant or metal complex catalysts/Oxidant, wherein said peroxy acid is peroxyformic acid, Peracetic acid, trifluoro Peracetic acid, benzoyl hydroperoxide, m-chloro peroxide benzeneFormic acid or monoperphthalic acid, described metal oxide catalyst is methyl three oxygen rheniums, molybdenum trioxide or acetylacetone,2,4-pentanedioneVanadyl, described metal complex catalysts is (1S, 2S)-(+)-[1,2-cyclohexane diamine nitrogen-N, two (3,5-, bis-uncles of N'-Butyl salicylidene)] manganese chloride (III), described oxidant is hydrogen peroxide, TBHP, iodosobenzene or inferiorSodium chlorate.
3. side of preparing high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber according to claim 1Method, is characterized in that, described step 2) in reaction medium be carrene, chloroform, C6-C8 alkane, cyclohexane, raffinates oil,Benzene, toluene, one or more in oxolane; Described oxicracking reagent is perchloric acid, hyperbromic acid, periodic acid or high iodineAcid sodium.
4. side of preparing high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber according to claim 1Method, is characterized in that, the reaction medium in described step 3) is carrene, chloroform, and C6-C8 alkane, cyclohexane, raffinates oil,Benzene, toluene, one or more in oxolane; Described reducing agent is sodium borohydride, two (2-methoxyethoxy) aluminic acids of dihydroSodium or lithium aluminium hydride reduction.
5. a method of preparing high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber, is characterized in that, bagDraw together following steps
1) butadiene rubber one pot reaction is prepared high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber
Butadiene rubber and epoxidation reagent, oxicracking reagent one pot reaction in reaction medium are prepared high-cis-Isosorbide-5-Nitrae contentEpoxidation terminal aldehyde group terminated polybutadiene liquid rubber;
Described butadiene rubber concentration is 10g/L-100g/L; Reaction medium is carrene, chloroform, C6-C8 alkane, hexamethyleneAlkane, raffinates oil, benzene, toluene, one or more in oxolane; Reaction temperature is between 0 DEG C to 80 DEG C; Reaction time is 1Hour between 12 hours;
Described oxicracking reagent and epoxide group mol ratio are 1:2 ~ 1:31;
2) high-cis-Isosorbide-5-Nitrae content epoxy is prepared in the reduction of high-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubberTerminal hydroxyl polybutadiene liquid rubber;
High-cis-Isosorbide-5-Nitrae content epoxy terminal aldehyde group terminated polybutadiene liquid rubber is reduction system under reaction medium and reducing agent existenceStandby high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber that obtains;
Described step 2) in reaction medium be carrene, chloroform, C6-C8 alkane, cyclohexane, raffinates oil, benzene, toluene, fourOne or more in hydrogen furans; Described reducing agent is sodium borohydride, two (2-methoxyethoxy) sodium aluminate or the aluminum hydride of dihydroLithium; The number-average molecular weight of described high-cis-Isosorbide-5-Nitrae content terminal aldehyde group terminated polybutadiene liquid rubber is 2000-13000g/mol, suitableFormula-Isosorbide-5-Nitrae content can reach 70.0-98.0%, and epoxy rate can regulate between 1-30%, and molecular weight distribution is 1.2-3.0, and degree of functionality is1.9-2.2; Described reaction temperature is between 0 DEG C to 80 DEG C; The described reaction time is between 1 hour to 12 hours.
6. side of preparing high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber according to claim 5Method, is characterized in that, the butadiene rubber in described step 1) is that nickel polymerized BR, cobalt are that butadiene rubber or Rare Earth are along fourth rubberGlue; Described epoxidation reagent is peroxy acid, metal onidiges catalyst/oxidant or metal complex catalysts/oxidant, itsDescribed in peroxy acid be peroxyformic acid, Peracetic acid, trifluoro Peracetic acid, benzoyl hydroperoxide, metachloroperbenzoic acid or listPeroxide phthalic acid, described metal oxide catalyst is methyl three oxygen rheniums, molybdenum trioxide or acetylacetone,2,4-pentanedione vanadyl, described inMetal complex catalysts be (1S, 2S)-(+)-[1,2-cyclohexane diamine nitrogen-N, two (sub-bigcatkin willows of 3,5-di-t-butyl of N'-Base)] manganese chloride (III), described oxidant is hydrogen peroxide, TBHP, iodosobenzene or clorox, described inOxicracking reagent be perchloric acid, hyperbromic acid, periodic acid or sodium metaperiodate.
7. high-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxy polybutadiene liquid that as described in claim 1 or 5 prepared by methodRubber, is characterized in that, cis-Isosorbide-5-Nitrae content is 70.0-98.0%, and epoxy rate is between 1-30%, and number-average molecular weight is 2000G/mol is between 13000g/mol, and molecular weight distribution is between 1.2-3.0, and degree of functionality is between 1.9-2.2.
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