CN102580774A - Unsaturated polymer hydrogenation catalyst and preparation method thereof - Google Patents
Unsaturated polymer hydrogenation catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention provides an unsaturated polymer hydrogenation catalyst and a preparation method thereof. The unsaturated polymer hydrogenation catalyst is formed by reacting metal organic compounds of IA, IIA and IIIA groups with a nickel/cobalt metal inorganic salt, wherein the metal mol ratio of organic metal to inorganic metal is (1-10): 1. The hydrogenation effect of the catalyst on a homopolymer of conjugated diene or a copolymer of the conjugated diene and vinyl arene is obvious, the hydrogenation selectivity of the catalyst is high and the catalyst is not easily remained in the polymer after a hydrogenation reaction and can be washed by water, so that the catalyst is good for improving the purity and the quality of the polymer.
Description
Technical field
The present invention relates to a kind of unsaturated polymer hydrogenation catalyst and preparation method thereof.
Background technology
Some polymer; Like the homopolymers of conjugated diene or the copolymer of conjugated diene and vinyl-arene; In molecular structure, there is unsaturated double-bond; Unsaturated bond in the polymer has intolerance to environmental factors such as light, oxygen, ozone, heat; Scission of link or oxidation caused that polymer is aging to quicken gradually when promptly in use unsaturated double-bond received Effect of Environmental such as light, oxygen, ozone, heat; Have influence on the service life of polymer product, had numerous inventors to develop some fruitful polymer hydrogenating catalysts for this reason, particularly the copolymer of the homopolymers of conjugated diene or conjugated diene and vinyl-arene is implemented catalyst and the hydrogenation technique and the method for hydrogenation.
Hydrogenation catalyst is divided into two kinds of heterogeneous catalysis and homogeneous catalysts.
What use as far back as the hydrogenation of polymer field is heterogeneous catalysis with low cost, and the catalyst metals that is about to high dispersive is carried on the carriers such as active carbon, diatomite, alundum (Al, barium sulfate polymer solution or dispersion liquid are reacted hydrogenation.The shortcoming one of such catalyst is that the polymolecularity of catalyst metals on activity of such catalysts and the carrier is closely related, and therefore has influence on the speed of catalytic hydrogenation reaction, and in general the hydrogenation efficiency of heterogeneous catalysis is lower; The 2nd, relatively harsher to the conditional request of catalytic hydrogenation reaction, the reaction condition of HTHP certainly will cause the decomposition of polymer and the generation of polymerization-filling thing gel, influences performance; The 3rd, the use amount of catalyst is higher; The 4th, the selectivity of hydrogenation reaction is lower, and the benzene ring structure of polymer can be difficult to complete maintenance, thereby has influence on polymer properties behind the hydrogenation.
The homogeneous hydrogenation catalyst generally is made up of one or more VIII family's metallic compounds and one or more reducing agents; The reducing agent multiselect is from metal alkyls, metal alkoxide or the hydroxide of IA, IIA, IIIA family; Can overcome the shortcoming of heterogeneous catalysis well, thereby obtain very big development.The hydrogenation catalyst of being introduced like U.S.3700 633 and U.S.3 465 063 is the product that organic acid nickel and alkyl aluminum react; The hydrogenation catalyst that U.S.4 980 331 introduces is made up of the product of isooctyl acid nickel and triethyl aluminum, MAO, and the hydrogenation activity of hydrogenation catalyst can be regulated; EP 0 360 356 report be a kind of organic nickel with (or) catalyst of cobalt, reducing agent is alkyl aluminum commonly used, different is organic nickel with (or) cobalt combines prior to a spot of water with the alkyl aluminum reaction before, subsequently again with alkyl aluminum prepared in reaction catalyst; The catalyst that uses among the U.S.3595 942 is the product of nickel acetylacetonate and triethyl aluminum; The hydrogenation catalyst of PCT WO 98/55516 report is that organic nickel/aluminium cooperates system, and different is in order to improve the hydrogenation of polymer degree, to reduce the catalyst addition, before hydrogenation of polymer, with dry ice polymer solution (or dispersion liquid) being handled; 02/34799 of PCT WO selects the organic titanium metallic catalyst that unsaturated polymer is carried out hydrogenation, can accomplish that to the butadiene in the SB 1 2-addition structure is carried out selective hydrogenation; U.S.5925717 also is that selection organic titanium metal is a major catalyst, and the employing Ester is a metallic reducing agent.All these catalyst all are to adopt the organic nickel compound; After the hydrogenation of polymer reaction is accomplished; For guaranteeing the quality of polymer product; Must take various effective methods to remove catalyst metals, the organic acid that combines with nickel in the catalyst then left behind in polymer, has influenced the purity and the quality of polymer.
For this reason; The present invention adopts the inorganic salts of nickel/cobalt metal that the metallic element in the catalyst is provided; The alkylates or the alkoxide that are aided with aluminium/magnesium/lithium are that reducing agent is processed hydrogenation catalyst, remain in inorganic ions or acid ion in the polymer after hydrogenation reaction is accomplished and can be easy to washing and remove.
Summary of the invention
At first; Of the present invention a kind of can be that metallo-organic compound and nickel/cobalt metal inorganic reactant salt by IA, IIA, IIIA family generates to the catalyst that unsaturated polymer carries out high-selective and hydrogenating, the metal molar ratio of organic metal/inorganic metal is 1～10: 1.
The metallo-organic compound of IA, IIA, IIIA family is metal alkyls, metal alkoxide; Preferred trialkylaluminium, tri-alkoxy aluminium, monoalkoxy-aluminum dialkyl, dialkyl magnesium, alkoxyl magnesium, monoalkyl lithium; More preferably triisobutyl aluminium, triethyl aluminum, aluminium ethoxide, methoxyl group-diethyl aluminum, dibutylmagnesium, butyl lithium.
Nickel/preferred nickel chloride/the cobalt of cobalt metal inorganic salt, nickelous sulfate/cobalt, nickel nitrate/cobalt, nickel phosphate/cobalt, more preferably nickel chloride, cobalt chloride, nickelous sulfate, cobaltous sulfate.
Hydrogenation catalyst of the present invention is applicable to the selective hydrogenation of the selective hydrogenation to unsaturated polymer, particularly styrene-butadiene/isoprene copolymer or butadiene/isoprene homopolymer, also comprises the occasion of other type unsaturated polymer hydrogenation.
Selective hydrogenation of the present invention refers to styrene-butadiene/isoprene copolymer; Hydrogenation reaction only occurs in polybutadiene block/isoprene block; And do not take place or seldom occur in polystyrene block, in general, the hydrogenation reaction that takes place at polystyrene block should be less than 5%; Otherwise polymer performance is had bigger change, and influence is used.Behind catalyst to catalyzing hydrogenating of the present invention; The polystyrene block benzene ring hydrogenation degree of styrene-butadiene/isoprene copolymer is less than 5%; And the degree of hydrogenation of polybutadiene/isoprene block can reach more than 99%; Therefore, catalyst of the present invention is a kind of high selectivity, hydrogenation catalyst efficiently.
Unsaturated polymer hydrogenization catalyst preparation method provided by the invention:
(1) nickel/cobalt metal inorganic salt is baked and banked up with earth, remove the moisture of combination;
(2) in atent solvent, nickel/cobalt metal inorganic salt is disperseed to form suspension fully, the concentration of suspension is 1～50g/l;
(3) metallo-organic compound of IA, IIA, IIIA family is diluted to solution in atent solvent, and solution concentration is 1～250g/l;
(4) with the suspension of nickeliferous/cobalt metal inorganic salt and the metal-organic solution that contains IA, IIA, IIIA family by: the metal molar ratio of organic metal/inorganic metal is 1～10: 1, fully mixes, in temperature: 0～150 ℃ of reaction down.
In method for preparing catalyst of the present invention, the nickel that is adopted/cobalt metal inorganic salt at first must be handled through removal of impurities, mainly is the moisture of removing wherein.Inorganic nickel compound has a certain proportion of crystallization water usually and presents various in various degree blue or green, cures to handle through high temperature to present yellow after losing the crystallization water; The color of inorganic cobalt compound also is that CoCL2 is a pink and different along with the quantity that contains the crystallization water in the compound is different, and four water cobalt chlorides are bluish violet, and waterless cobaltous chloride then is blue.Nickel/the cobalt compound that loses the crystallization water is formed bulk easily, so will pass through milled processed, being ground into tiny particle could use, otherwise particle is thick influential to the catalyst synthetic reaction.
In the method for preparing catalyst of the present invention; Treated nickel/cobalt metal inorganic salt needs in atent solvent, fully to disperse; Employed atent solvent can be the alkane of cyclohexane, n-hexane class, the aromatic hydrocarbons of benzene, toluene class, the polar solvent of chloroform, dichloromethane alkanes.The dispersion of inorganic salts in atent solvent can take magnetic stirring apparatus to carry out, to form suspension.
In the method for preparing catalyst of the present invention; From security consideration; The inorganic salts of employed IA, IIA, IIIA family metallo-organic compound and nickel/cobalt metal need in above-mentioned atent solvent, to be diluted to weak solution; Otherwise heat release is violent when these two component hybrid reactions, in very short time, sharply discharges a large amount of gases, and is very dangerous.And consider from economic angle; Compound concentration again can not be too low, otherwise the required catalyst volume of hydrogenation reaction is too big, and the reaction temperature to polymeric system when getting into polymeric system has considerable influence; The Macrodilution solvent brings a large amount of impurity simultaneously, can influence the quality of catalyst.For well, preferred solution concentration is 10～100g/l to the concentration of weak solution at 1～250g/l.
In the method for preparing catalyst of the present invention, the mol ratio of metal is 1～10: 1 in employed metallo-organic compound and the metal inorganic salt.If reaction ratio is excessive, can cause cost to improve, unnecessary reducing agent can hinder the carrying out of hydrogenation reaction in system, influence the hydrogenation effect; When the metal proportioning is too small in metallo-organic compound and the metal inorganic salt; Reducing power is not enough, and catalyst nickel/cobalt metal can not effectively be participated in hydrogenation reaction, influences the hydrogenation effect; Therefore, the preferred molar ratio of metal is 3～8: 1 in metallo-organic compound and the metal inorganic salt.
In the method for preparing catalyst of the present invention, range of reaction temperature depends primarily on the employed retarder thinner type of component of participating in reaction at 0～150 ℃; When employed retarder thinner boiling point is higher; Reaction temperature can be higher, when the boiling point of retarder thinner hangs down, and the corresponding reduction of reaction temperature.
The present invention has following beneficial effect:
Beneficial effect one of the present invention, the catalyst of preparation is remarkable to the copolymer hydrogenating effect of the homopolymers of conjugated diene or conjugated diene and vinyl-arene.
Beneficial effect two of the present invention, the catalyst of preparation is high to the hydrogenation selectivity of polymer.
Beneficial effect three of the present invention, catalyst of the present invention is difficult for remaining in the polymer after accomplishing hydrogenation reaction, can wash and remove, and helps to improve the purity and the quality of polymer.
The specific embodiment
According to specific embodiment the present invention is described further below:
Embodiment 1: the preparation of nickel metal inorganic salt suspension
Get about nickel chloride 90g; Put into Muffle furnace and carried out roasting two hours for inherent 350 ℃, treat to represent when nickel chloride transfers yellow to that the crystallization water wherein loses fully, the nickel chloride that cures is changed in the drying basin; And take by weighing 64.5 the gram; Quick mechanical disruption powdered, and be scattered in rapidly in 1 liter of n-hexane solvent with magnetic stirring apparatus, forming concentration is the nickel chloride/n-hexane suspension of 64.5 grams per liters.
Embodiment 2: the preparation of cobalt metal inorganic salt suspension
Get about cobaltous sulfate 100g; Put into Muffle furnace and carried out roasting two hours for inherent 350 ℃, treat to represent when nickelous sulfate transfers yellow to that the crystallization water wherein loses fully, the nickelous sulfate that cures is changed in the drying basin; And take by weighing 77.5 the gram; Quick mechanical disruption powdered, and be scattered in rapidly in 1 liter of cyclohexane solvent with magnetic stirring apparatus, forming concentration is the nickelous sulfate/cyclohexane suspension of 77.5 grams per liters.
Embodiment 3: the preparation of reducing agent
Get reducing agent triisobutyl aluminium, triethyl aluminum, dibutylmagnesium, butyl lithium and methoxyl group-diethyl aluminum and in the solvent cyclohexane, be made into certain density solution respectively, list in table one
| Reducing agent | Triisobutyl aluminium | Triethyl aluminum | Dibutylmagnesium | Butyl lithium | Methoxyl group-diethyl aluminum |
| Concentration, grams per liter | 99 | 57 | 69 | 64 | 87 |
Embodiment 4: in the four-hole boiling flask of clean band stirring, reflux condenser, thermometer, feeder, add 16 milliliters of homodisperse nickel chloride suspensions, 56 milliliters of rare triisobutyl aluminum solutions that adding while stirring prepares; The electricity consumption heating jacket heats up or cold water is removed heat, keeps reaction temperature at 30-45 ℃, after reaction is kept 2 hours; Naturally cool to room temperature; Product is transferred to rapidly in the little wide-mouth bottle, and the sealing secluding air is preserved, and is for use.
Embodiment 5: in the four-hole boiling flask of clean band stirring, reflux condenser, thermometer, feeder, add 10 milliliters of homodisperse nickel chloride suspensions, 5 milliliters of homodisperse cobaltous sulfate suspensions; 40 milliliters of rare triethyl aluminium solution that adding while stirring prepares; The electricity consumption heating jacket heats up or cold water is removed heat, keeps reaction temperature at 50-65 ℃, after reaction is kept 2 hours; Naturally cool to room temperature; Product is transferred to rapidly in the little wide-mouth bottle, and the sealing secluding air is preserved, and is for use.
Embodiment 6: in the four-hole boiling flask of clean band stirring, reflux condenser, thermometer, feeder, add 5 milliliters of homodisperse nickel chloride suspensions, 5 milliliters of homodisperse cobaltous sulfate suspensions; 30 milliliters of rare triethyl aluminium solution that adding while stirring prepares, 20 milliliters of rare dibutylmagnesium solution, the electricity consumption heating jacket heats up or cold water is removed heat; Keep reaction temperature at 50-65 ℃; After reaction is kept 2 hours, cool to room temperature naturally, product is transferred to rapidly in the little wide-mouth bottle; The sealing secluding air is preserved, and is for use.
Embodiment 7: in the four-hole boiling flask of clean band stirring, reflux condenser, thermometer, feeder, add 5 milliliters of homodisperse nickel chloride suspensions, 15 milliliters of rare triethyl aluminium solution that adding while stirring prepares; 2.5 milliliters of rare butyl lithium solutions, the electricity consumption heating jacket heats up or cold water is removed heat, keeps reaction temperature at 40-50 ℃; After reaction is kept 2 hours, cool to room temperature naturally, product is transferred to rapidly in the little wide-mouth bottle; The sealing secluding air is preserved, and is for use.
Embodiment 8: in the four-hole boiling flask of clean band stirring, reflux condenser, thermometer, feeder, add 4 milliliters of homodisperse nickel chloride suspensions, 4 milliliters of homodisperse cobalt sulfate solutions; 15 milliliters of rare triisobutyl aluminum solutions that adding while stirring prepares, 5 milliliters of methoxyl group-diethyl aluminums, the electricity consumption heating jacket heats up or cold water is removed heat; Keep reaction temperature at 45-60 ℃; After reaction is kept 2 hours, cool to room temperature naturally, product is transferred to rapidly in the little wide-mouth bottle; The sealing secluding air is preserved, and is for use.
Embodiment 9: styrene-butadiene/isoprene copolymer synthetic
In handling clean polymeric kettle, add 2500 milliliters of reaction dissolvent cyclohexanes, add 60 milliliters of styrene, conditioning agent is a small amount of; 10 milliliters of initators (0.4M); 60-70 ℃ of polymeric kettle temperature reacted after 40 minutes and to be added 250 milliliters of isoprene, react to add styrene after 40 minutes and continue for 60 milliliters to react 40 minutes; Add the terminator cessation reaction, form polymer A and treat hydrogenation usefulness.
Embodiment 10: butadiene/isoprene homopolymer is synthetic
In handling clean polymeric kettle, add 2500 milliliters of reaction dissolvent cyclohexanes, the adding conditioning agent is an amount of, 10 milliliters of initators (0.4M); 60-70 ℃ of polymeric kettle temperature adds 300 milliliters of butadiene, reacts after 1 hour; Add the terminator cessation reaction, form polymer B and treat hydrogenation usefulness.
Embodiment 11: hydrogenation reaction
Polymer A, polymer B are imported respectively in the clean hydrogenation reaction kettle of processing; Fed hydrogen reaction 30 minutes; Add the catalyst of embodiment 4-8, catalyst amount is in table two, at temperature 60-150 ℃; Carried out under the Hydrogen Vapor Pressure 1.2-8.5Mpa condition hydrogenation reaction 2-8 hour, and reacted the degree of hydrogenation of specimen.The hydrogenation of polymer degree is meant the degree of hydrogenation of polyisoprene blocks in the polymer; The selectivity of polymer samples hydrogenation is meant the size of polymer benzene ring hydrogenation degree; According to the application performance requirement of polymer, the benzene ring hydrogenation degree must be less than 5%, and the degree of hydrogenation of polyisoprene blocks should be greater than 98%.
Table two catalyst type, consumption and catalytic hydrogenation result
| Catalyst type | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Type of polymer | ?A | ?B | ?A | ?A | ?B |
| Consumption, ml | ?35 | ?12 | ?10 | ?28 | ?20 |
| Degree of hydrogenation, % | ?98.0 | ?95.6 | ?98.3 | ?99.2 | ?94.9 |
| The benzene ring hydrogenation degree, % | ?3.55 | ?2.68 | ?4.96 | ?3.66 | ?4.83 |
Comparative Examples 1-2 is respectively and adopts this catalyst and other organic nickel catalyst unsaturated polymer hydrogenation after washing to be removed the situation of the metal impurities in the glue.
Glue oxidation in the presence of oxygen or air or other oxidant that Comparative Examples 1 is accomplished embodiment 6 hydrogenation; The water that adds glue total amount 10-20%; Stir washing; Get rid of the waste water that contains the water-soluble metal ion that washing generates, pure glue adopts atomic absorption method test metal ion content wherein through cohesion, drying.
Comparative Examples 2 is processed polymer A with organic nickel (nickel naphthenate) and triethyl aluminum catalyst to catalyzing hydrogenating; Hydrogenation technique is identical with embodiment 6; Glue warp behind the hydrogenation is washed with Comparative Examples 1 identical technology; Pure glue adopts atomic absorption method test metal ion content wherein through cohesion, drying.
The washing result of Comparative Examples 1-2 sees table three
Table three hydrogenation glue tenor in the glue after washing
| Kish ion concentration in the glue, ppm | Nickel | Aluminium | Lithium |
| Comparative Examples 1 | 9.3 | 13.6 | 0.3 |
| Comparative Examples 2 | 863 | 1295 | 165 |
Claims (7)
1. unsaturated polymer hydrogenation catalyst is characterized in that: metallo-organic compound and nickel/cobalt metal inorganic reactant salt by IA, IIA, IIIA family generate, and the metal molar ratio of organic metal/inorganic metal is 1～10: 1.
2. catalyst according to claim 1; It is characterized in that: the metallo-organic compound of IA, IIA, IIIA family is trialkylaluminium, tri-alkoxy aluminium, monoalkoxy-aluminum dialkyl, dialkyl magnesium, alkoxyl magnesium, monoalkyl lithium, and nickel/cobalt metal inorganic salt is nickel chloride/cobalt, nickelous sulfate/cobalt, nickel nitrate/cobalt, nickel phosphate/cobalt.
3. catalyst according to claim 1; It is characterized in that: the metallo-organic compound of IA, IIA, IIIA family is triisobutyl aluminium, triethyl aluminum, aluminium ethoxide, methoxyl group-diethyl aluminum, dibutylmagnesium, butyl lithium, and nickel/cobalt metal inorganic salt is nickel chloride, cobalt chloride, nickelous sulfate, cobaltous sulfate.
4. a unsaturated polymer hydrogenization catalyst preparation method is characterized in that: comprise the steps:
(1) nickel/cobalt metal inorganic salt is baked and banked up with earth, remove the moisture of combination;
(2) in atent solvent, nickel/cobalt metal inorganic salt is disperseed to form suspension fully, the concentration of suspension is 1～50g/l;
(3) metallo-organic compound of IA, IIA, IIIA family is diluted to solution in atent solvent, and solution concentration is 1～250g/l;
(4) with the suspension of nickeliferous/cobalt metal inorganic salt and the metal-organic solution that contains IA, IIA, IIIA family by: the metal molar ratio of organic metal/inorganic metal is 1～10: 1, fully mixes, in temperature: 0～150 ℃ of reaction down.
5. method according to claim 4 is characterized in that: atent solvent is selected from cyclohexane, n-hexane, benzene, toluene, chloroform, carrene.
6. method according to claim 4 is characterized in that: the metallo-organic compound solution concentration is 10～100g/l.
7. method according to claim 4 is characterized in that: the metal molar ratio of organic metal/inorganic metal is 3～8: 1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106563503A (en) * | 2016-10-25 | 2017-04-19 | 山东聚圣科技有限公司 | Ternary catalysis system used for selective hydrogenation of conjugated diene containing polymer and application thereof |
| CN107597189A (en) * | 2017-06-27 | 2018-01-19 | 苏州双湖化工技术有限公司 | Hydrogenation catalyst for unsaturated bond polymer and its preparation method and application |
| CN108404916A (en) * | 2018-05-04 | 2018-08-17 | 河南科技学院 | A kind of preparation method of metal Co catalysts and its application in Butadiene hydrogenation reaction |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106563503A (en) * | 2016-10-25 | 2017-04-19 | 山东聚圣科技有限公司 | Ternary catalysis system used for selective hydrogenation of conjugated diene containing polymer and application thereof |
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| CN108404916B (en) * | 2018-05-04 | 2020-09-11 | 河南科技学院 | Preparation method of metal cobalt catalyst and application of metal cobalt catalyst in catalyzing butadiene hydrogenation reaction |
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Application publication date: 20120718 |