CN101607212A - Binary alkyl benzene sulfonic acid rare earth catalyst and method for making and application - Google Patents
Binary alkyl benzene sulfonic acid rare earth catalyst and method for making and application Download PDFInfo
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Abstract
The present invention relates to binary alkyl benzene sulfonic acid rare earth catalyst and method for making and application.This catalyst is made up of alkyl benzene sulfonic acid rare earth compound and alkyl aluminum; Utilize the reaction of alkyl benzene sulphonate and rare earth oxide to make the alkyl benzene sulfonic acid rare earth compound; again under nitrogen protection; in the catalyst preparation device that drying is handled; add alkyl benzene sulfonic acid rare earth compound and alkyl aluminum by proportioning; add hexane solution again, obtain binary alkyl benzene sulfonic acid rare earth catalyst.Described catalyst is used for isoprene polymerization; Under nitrogen protection, in the polymerizer of anhydrous and oxygen-free, add isoprene monomer, then add catalyst, all can be aggregated under the condition of no solvent, obtain monomer conversion＞90%, weight average molecular weight is the polyisoprene rubber of 5000-100000.This catalyst has increased a new kind again for existing rare-earth catalysis system, has increased a catalyst system and catalyzing again for producing the synthetic rubber field.
Description
Technical field
The present invention relates to binary alkyl benzene sulfonic acid rare earth catalyst and method for making and application.
Background technology
As far back as the early sixties in last century, Changchun Applied Chemistry Research Inst., Chinese Academy of Sciences has utilized the rare earth resources of China Feng Zang, has carried out research (Shen Zhiquan, Gong Zhongyuan, the Zhong Chongqi etc. of rare earth catalyst stereospecfic polymerization diolefin, Science Bulletin, 1964,4:335), but catalytic activity is not high.Since rare earth catalyst was found, the rare earth catalyst that is used for the diene polymerization was updated and is perfect, and now existing polytype catalyst system and catalyzing is used for the homopolymerization and the copolymerization of diene.According to the composition of rare earth catalyst, can be divided into binary and ternary system (an aromatic plant metioned in ancient books in Huang Baotong, Shen etc., " alkene diolefin coordination polymerization progress " Science Press, 1998,203-219).Early stage binary rare earth chloride catalyst is used for the low (Chinese science of catalysis diene polymerization activity, 1980, (2): 127-135), afterwards through process modification (comprising preparation rare earth chloride alcohol adduct and rare earth chloride phosphoric acid ester complex compound), though polymerization activity is improved, (Die AngewandteMakromolekulare Chemie 249 (1997) 59-77 (Nr.4335), operating procedure is loaded down with trivial details, complicated, time-consuming shortcoming (CN 1861649A) but still there is the preparation condition harshness.
It's synthesizing and sign there is to past bibliographical information about the organic sulfonic acid rare earth compound, but only be confined to sign and explanation, do not relate to the research of organic sulfoacid rare earth application of compound particularly about being applied to the information of isoprene polymerization aspect to compound structure and building-up process.(polyhedron?Vol：17，No.8.1381-1385.1998；Z.Anorg，Allg.Chem.2001.627，1675-1681；New?J.Chem，2007，31，634-645；Inorganic?Chemistry，Vol.43，No.18，2004，5630-5634)。
And the report of relevant sulfonic acid class rare earth catalyst relates generally to reaction (applied chemistry, 2006.Vol.23 No.2, the 212-214 of the esterification of perfluoro octyl sulfonic acid rare earth metal salt catalysis fluorine two-phase; Organic chemistry, 2005, Vol.25,1434～1436), and utilize TFMS rare earth catalyst caprolactone ring-opening polymerization (SCI 2007, Vol.28No.6.1186～1188).
And the domestic and international patent of relevant rare earth sulfoacid compound aspect then is mainly used in the following aspects, as: the rare earth sulfonate compound is as solid acid catalyst catalysis Friedel-Crafts reaction (JP2004337819-A); Rare earth sulfonate and derivative thereof and 2,3,6-pseudocuminol prepared in reaction vitamin E (WO2004063182-A1; US2006052618-A1;
JP2006514959-W); And the alkyl sulfonic acid compound that utilizes fluorine-containing replacement is applied to the nitration reaction (CN1730463-A of trimethylbenzene; CN100378067-C).Be used for isoprene polymerization with the alkyl benzene sulfonic acid rare earth compound as catalyst and yet there are no patent or bibliographical information.
Summary of the invention
The invention provides binary alkyl benzene sulfonic acid rare earth catalyst and method for making and application.
Binary alkyl benzene sulfonic acid rare earth catalyst provided by the present invention is made up of alkyl benzene sulfonic acid rare earth compound and alkyl aluminum, and the rare earth neodymium of described alkyl aluminum and alkyl benzene sulfonic acid rare earth compound or the mol ratio of praseodymium are 20～60: 1;
The chemical formula of described alkyl benzene sulfonic acid rare earth compound is: Ln (CH
3(CH
2)
nRSO
3)
3, in the formula, Ln is neodymium or praseodymium, R is a phenyl, n=7～15;
Described alkyl aluminum is: trialkylaluminium or alkyl-al hydride, preferred triisobutyl aluminium, diisobutyl aluminium hydride or ADEH.
The method for making of binary alkyl benzene sulfonic acid rare earth catalyst provided by the present invention is characterized in that step and condition are as follows:
Under 70 ℃ of heating, 300 rev/mins of stirring condition, rare earth neodymium or praseodymium oxide are joined in the benzene sulfonamide acid solution, wherein, the mol ratio of rare earth neodymium or praseodymium oxide and alkyl benzene sulphonate is 10: 1, reacts after 2 hours, filter, the unreacted rare earth oxide is removed, obtained the alkyl benzene sulfonic acid rare earth compound water solution, revolve steaming with Rotary Evaporators and dewater, drying obtains the alkyl benzene sulfonic acid rare earth compound;
Under nitrogen protection; in the catalyst preparation device of drying; add alkyl benzene sulfonic acid rare earth compound and alkyl aluminum by described proportioning, the volume ml ratio of adding mol number that hexane solution makes alkyl benzene sulfonic acid rare earth compound middle rare earth neodymium or praseodymium and the hexane solution of alkyl aluminum again is 2.5 * 10
-5～5.0 * 10
-5: 1, in-20～80 ℃ of following ageings 60 minutes～48 hours, obtain binary alkyl benzene sulfonic acid rare earth catalyst.
Binary alkyl benzene sulfonic acid rare earth catalyst provided by the present invention is used for the catalysis isoprene polymerization.
Binary alkyl benzene sulfonic acid rare earth catalyst provided by the present invention is used for the method for isoprene polymerization, it is characterized in that step and condition are as follows:
Under nitrogen protection, in the polymerizer of anhydrous and oxygen-free, add isoprene monomer, then add catalyst, the mol number of the rare earth of catalyst and the quality g proportioning of isoprene monomer are 0.92 * 10
-6～1.7 * 10
-5: 1, all can be aggregated under solvent or the condition of no solvent, under 20 ℃～60 ℃ temperature, reacted 20～48 hours; After reaction finishes, with contain mass fraction be 1% 2, the ethanolic solution of 6-di-tert-butyl methyl phenol stops, after the washing extruding, vacuum drying is 24 hours under 40 ℃ of temperature, obtains polyisoprene rubber again.The monomer conversion of this polyisoprene rubber＞90%, weight average molecular weight are 5000-100000.
Beneficial effect: binary alkyl benzene sulfonic acid rare earth catalyst provided by the present invention is used for isoprene polymerization, and catalyst system is formed fairly simple, and compound method is easy, and has advantages of high catalytic activity, has been aggregated under the condition of no solvent all can carry out.Can obtain the polyisoprene rubber of monomer conversion＞90%, molecular weight (weight average)=5000-100000 through polymerization.
The characteristics that are used for the polymerization of catalysis diene with binary rare earth chloride catalyst are compared with condition, and this alkyl benzene sulfonic acid rare earth compound provided by the present invention can be exempted the harsh conditions of preparation anhydrous chlorides of rase earth elements and complex compound thereof as catalyst.And compare with the carboxylic acid rare-earth catalysis system, need not add the 3rd component in this catalyst preparation process, simplified process; Reduced preparation cost; And exempted the corrosion that bring to production equipment as the 3rd component in the chlorine source; Therefore, except that catalyst system and catalyzings such as existing rare earth chloride, carboxylic acid rare earth, rare-earth phosphorate are used for the polymerization of catalysis diene, utilize the alkyl benzene sulfonic acid rare earth compound to be used for isoprene polymerization as catalyst, we can say to existing rare-earth catalysis system has increased a new kind again, for rare-earth catalysis system preparation, production synthetic rubber field have increased a catalyst system and catalyzing again.
The specific embodiment
Embodiment 1:
Binary eight alkyl benzene sulphonate neodymium Nd (C
14H
21SO
3)
3Catalyst and method for making and be applied to isoprene polymerization, its concrete steps and condition are as follows: (one) binary eight alkyl benzene sulphonate neodymium catalyst and method for makings: under 70 ℃ of heating, 300 rev/mins of stirring condition, with 0.1mol neodymia Nd
2O
3Join in the 0.01mol eight benzene sulfonamide acid solutions, react after 2 hours, filter, unreacted neodymia Nd
2O
3Remove, the gained eight alkyl benzene sulphonate neodymium compound aqueous solution are revolved steaming with Rotary Evaporators dewater, drying obtains eight alkyl benzene sulphonate neodymium compound 3.3mmol; Under nitrogen protection, in the catalyst preparation device that drying is handled, add the eight alkyl benzene sulphonate neodymium compounds of 0.25mmol successively, the 5mmol triisobutyl aluminium is added the 3.71ml hexane solution again, and being mixed with concentration is 2.5 * 10
-5The binary eight alkyl benzene sulphonate neodymium rare earth catalysts of mol/ml.The mol ratio of triisobutyl aluminium and Nd is 20 between the component, after 24 hours, obtains being used for the binary eight alkyl benzene sulphonate neodymium catalysts of isoprene polymerization in-20 ℃ of following ageings.(2) to be applied to the step and the condition of isoprene polymerization as follows for binary eight alkyl benzene sulphonate neodymium catalysts: under nitrogen protection; in the polymerizer of anhydrous and oxygen-free, add the 13.6g isoprene monomer; then add the above-mentioned catalyst of 0.5ml, the molal quantity mol of catalyst middle rare earth and the quality g proportioning of isoprene monomer are 0.92 * 10
-6, polymerization is 20 hours under 60 ℃ of temperature; After reaction finishes, with contain weight ratio be 1% 2, the ethanolic solution of 6-di-tert-butyl methyl phenol stops.After the washing extruding, vacuum drying is 24 hours under 40 ℃ of temperature, and obtaining monomer conversion is that 93% (12.65g polyisoprene rubber), weight average molecular weight are 80000 polyisoprene rubber.
Comparative example 1:
Tetraalkyl benzene sulfonic acid neodymium Nd (C
10H
13SO
3)
3Catalyst and preparation and be applied to isoprene polymerization, tetraalkyl benzene sulfonic acid neodymium catalyst and preparation and be applied to the isoprene polymerization step with embodiment 1, obtaining monomer conversion through polymerization is that 16% (2.18g polyisoprene rubber), weight average molecular weight are 20000 polyisoprene rubber.
Embodiment 2:
Binary DBSA neodymium Nd (C
18H
29SO
3)
3Catalyst and preparation and be applied to isoprene polymerization, concrete steps are as follows: (one) DBSA neodymium catalyst and preparation: the preparation method of DBSA neodymium compound and step are with embodiment 1, just alkyl benzene sulphonate changes to DBSA by eight alkyl benzene sulphonates, gets required DBSA neodymium compound 3.3mmol.Add the DBSA neodymium compound of 0.25mmol under nitrogen protection in the catalyst preparation device that drying is handled successively, the 7.5mmol triisobutyl aluminium is added the 3.07ml hexane solution again, and being mixed with concentration is 5.0 * 10
-5The binary DBSA neodymium rare earth catalyst of mol/ml.The mol ratio of triisobutyl aluminium and Nd is 30 between the component, after 24 hours, obtains being used for the DBSA neodymium catalyst of isoprene polymerization in 50 ℃ of following ageings.(2) binary DBSA neodymium catalyst is applied to isoprene polymerization: under nitrogen protection; in the polymerizer of anhydrous and oxygen-free, add the 3g isoprene monomer; add the 17ml hexane again; then add the above-mentioned catalyst of 1.0ml, the molal quantity mol of catalyst middle rare earth and the quality g proportioning of isoprene monomer are 1.7 * 10
-5, polymerization is 48 hours under 50 ℃ of temperature; After reaction finishes, with contain 1% (weight ratio) 2, the ethanolic solution of 6-di-tert-butyl methyl phenol stops.After the washing extruding, vacuum drying is 24 hours under 40 ℃ of temperature, and obtaining monomer conversion is that 95% (2.85g polyisoprene rubber), weight average molecular weight are 100000 polyisoprene rubber.
Comparative example 2:
Tetraalkyl benzene sulfonic acid neodymium Nd (C
10H
13SO
3)
3Catalyst and preparation and be applied to isoprene polymerization, the preparation process of tetraalkyl benzene sulfonic acid neodymium rare earth compound and rare earth catalyst is with embodiment 2, and obtaining monomer conversion is that 28% (0.84g polyisoprene rubber), weight average molecular weight are 70000 polyisoprene rubber.
Embodiment 3:
Binary DBSA neodymium Nd (C
18H
29SO
3)
3Catalyst and preparation and be applied to isoprene polymerization, concrete method for preparing catalyst and be applied to the isoprene polymerization step with embodiment 2, just used alkyl aluminum changes to diisobutyl aluminium hydride by triisobutyl aluminium in the catalyst preparation process; The hexane solution additional amount becomes 3.66ml, and the isoprene polymerization temperature becomes 20 ℃, and polymerization time changes 20 hours into; Obtaining monomer conversion is that 94% (2.82g polyisoprene rubber), weight average molecular weight are 5000 polyisoprene rubber.
Embodiment 4:
Binary DBSA neodymium Nd (C
18H
29SO
3)
3Catalyst and preparation and be applied to isoprene polymerization, concrete method for preparing catalyst and be applied to the isoprene polymerization step with embodiment 1, just alkyl aluminum changes to ADEH by triisobutyl aluminium in the catalyst preparation process; The addition of ADEH is 15mmol, the mol ratio of ADEH and Nd was 60 between the component, and the hexane solution additional amount becomes 3.37ml, and catalyst ageing condition changes to: in 80 ℃ of following ageings 60 minutes, the isoprene polymerization temperature becomes 50 ℃, and polymerization time changes 24 hours into; Obtaining monomer conversion is that 91.5% (2.745g polyisoprene rubber), weight average molecular weight are 20000 polyisoprene rubber.
Embodiment 5:
Binary cetyl benzene sulfonic acid praseodymium Pr (C
22H
37SO
3)
3Catalyst and method for making and be applied to isoprene polymerization, its concrete steps and condition are as follows: (one) binary cetyl benzene sulfonic acid praseodymium catalyst and method for making: under 70 ℃ of heating, 300 rev/mins of stirring condition, with 0.1mol praseodymium oxide Pr
2O
3Join in the 0.01mol cetyl benzene sulfonic acid solution, react after 2 hours, filter, unreacted praseodymium oxide Pr
2O
3Remove, the gained cetyl benzene sulfonic acid praseodymium compound aqueous solution is revolved steaming with Rotary Evaporators dewater, drying obtains cetyl benzene sulfonic acid praseodymium compound 3.3mmol; Under nitrogen protection, in the catalyst preparation device that drying is handled, add the cetyl benzene sulfonic acid praseodymium compound of 0.25mmol successively, the 5mmol triisobutyl aluminium is added the 3.71ml hexane solution again, and being mixed with concentration is 2.5 * 10
-5The binary cetyl benzene sulfonic acid praseodymium rare earth catalyst of mol/ml.In-20 ℃ of following ageings 48 hours, obtain being used for the binary cetyl benzene sulfonic acid praseodymium catalyst of isoprene polymerization.(2) to be applied to the step and the condition of isoprene polymerization as follows for binary cetyl benzene sulfonic acid praseodymium catalyst: under nitrogen protection; in the polymerizer of anhydrous and oxygen-free, add the 13.6g isoprene monomer; then add the above-mentioned catalyst of 2.72ml, the molal quantity mol of catalyst middle rare earth praseodymium and the quality g proportioning of isoprene monomer are 0.92 * 10
-6, polymerization is 20 hours under 60 ℃ of temperature; After reaction finishes, with contain weight ratio be 1% 2, the ethanolic solution of 6-di-tert-butyl methyl phenol stops.After the washing extruding, vacuum drying is 24 hours under 40 ℃ of temperature, and obtaining monomer conversion is that 93% (12.65g polyisoprene rubber), weight average molecular weight are 85000 polyisoprene rubber.
Claims (5)
1, binary alkyl benzene sulfonic acid rare earth catalyst is characterized in that, described catalyst is made up of alkyl benzene sulfonic acid rare earth compound and alkyl aluminum, and the rare earth neodymium of described alkyl aluminum and alkyl benzene sulfonic acid rare earth compound or the mol ratio of praseodymium are 20～60: 1;
The chemical formula of described alkyl benzene sulfonic acid rare earth compound is: Ln (CH
3(CH
2)
nRSO
3)
3, in the formula, Ln is neodymium or praseodymium, R is a phenyl, n=7～15;
Described alkyl aluminum is: trialkylaluminium or alkyl-al hydride.
2, binary alkyl benzene sulfonic acid rare earth catalyst as claimed in claim 1 is characterized in that described alkyl aluminum is triisobutyl aluminium, diisobutyl aluminium hydride or ADEH.
3, the method for making of binary alkyl benzene sulfonic acid rare earth catalyst as claimed in claim 1 is characterized in that step and condition are as follows:
Under 70 ℃ of heating, 300 rev/mins of stirring condition, rare earth neodymium or praseodymium oxide are joined in the benzene sulfonamide acid solution, wherein, the mol ratio of rare earth neodymium or praseodymium oxide and alkyl benzene sulphonate is 10: 1, reacts after 2 hours, filter, the unreacted rare earth oxide is removed, obtained the alkyl benzene sulfonic acid rare earth compound water solution, revolve steaming with Rotary Evaporators and dewater, drying obtains the alkyl benzene sulfonic acid rare earth compound;
Under nitrogen protection; in the catalyst preparation device of drying; add alkyl benzene sulfonic acid rare earth compound and alkyl aluminum by described proportioning, the volume ml ratio of adding mol number that hexane solution makes alkyl benzene sulfonic acid rare earth compound middle rare earth neodymium or praseodymium and the hexane solution of alkyl aluminum again is 2.5 * 10
-5～5.0 * 10
-5: 1, in-20～80 ℃ of following ageings 60 minutes～48 hours, obtain binary alkyl benzene sulfonic acid rare earth catalyst.
4, the application of binary alkyl benzene sulfonic acid rare earth catalyst as claimed in claim 1 is characterized in that, it is used for the catalysis isoprene polymerization.
5, the method for the catalysis isoprene polymerization of binary alkyl benzene sulfonic acid rare earth catalyst as claimed in claim 4; it is characterized in that step and condition are as follows: under nitrogen protection; in the polymerizer of anhydrous and oxygen-free, add isoprene monomer; then add catalyst, the mol number of the rare earth of catalyst and the quality g proportioning of isoprene monomer are 0.92 * 10
-6～1.7 * 10
-5: 1, all can be aggregated under solvent or the condition of no solvent, under 20 ℃～60 ℃ temperature, reacted 20～48 hours; After reaction finishes, with contain mass fraction be 1% 2, the ethanolic solution of 6-di-tert-butyl methyl phenol stops, after the washing extruding, vacuum drying is 24 hours under 40 ℃ of temperature, obtains polyisoprene rubber again.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059053A (en) * | 2013-01-28 | 2013-04-24 | 中国科学院长春应用化学研究所 | Rare earth complex and preparation method thereof, rare earth catalyst system and preparation method of butadiene-isoprene copolymer |
| CN104140451A (en) * | 2013-05-08 | 2014-11-12 | 中国石油化工股份有限公司 | Rare earth complex and preparation method thereof, catalyst and application thereof, and preparation method of rare earth isoprene rubber |
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| US6018007A (en) * | 1997-09-22 | 2000-01-25 | Bridgestone Corporation | Synthesis of 1,4-trans-polybutadiene using a lanthanide organic acid salt catalyst |
| CN1834121B (en) * | 2006-03-24 | 2012-07-11 | 中国科学院长春应用化学研究所 | Rare-earth catalyst for diolefin polymerization and its prepn. |
| CN101323652B (en) * | 2008-03-07 | 2011-04-20 | 上海生大医保股份有限公司 | Preparing methods of polyisoprene emulsion and rubber thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059053A (en) * | 2013-01-28 | 2013-04-24 | 中国科学院长春应用化学研究所 | Rare earth complex and preparation method thereof, rare earth catalyst system and preparation method of butadiene-isoprene copolymer |
| CN103059053B (en) * | 2013-01-28 | 2015-11-18 | 中国科学院长春应用化学研究所 | The preparation method of rare earth compounding and preparation method thereof, rare earth catalyst system and butadiene isoprene copolymer |
| CN104140451A (en) * | 2013-05-08 | 2014-11-12 | 中国石油化工股份有限公司 | Rare earth complex and preparation method thereof, catalyst and application thereof, and preparation method of rare earth isoprene rubber |
| CN104140451B (en) * | 2013-05-08 | 2016-12-07 | 中国石油化工股份有限公司 | Rare earth compounding and preparation method thereof and catalyst and its application and the preparation method of rare-earth isoprene rubber |
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