CN105854946A - Platiniferous hydrosilylation catalyst and preparation method thereof - Google Patents
Platiniferous hydrosilylation catalyst and preparation method thereof Download PDFInfo
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- CN105854946A CN105854946A CN201610221480.3A CN201610221480A CN105854946A CN 105854946 A CN105854946 A CN 105854946A CN 201610221480 A CN201610221480 A CN 201610221480A CN 105854946 A CN105854946 A CN 105854946A
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- hydrosilylation catalyst
- platiniferous
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- platiniferous hydrosilylation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/828—Platinum
Abstract
The invention belongs to the technical field of chemical synthesis, and in particular discloses a platiniferous hydrosilylation catalyst and a preparation method thereof. The platiniferous hydrosilylation catalyst is a platinum-organic complex generated from reaction of a platiniferous compound and organic ligand; and the organic ligand is a macrocyclic compound with unsaturated bonds. By adopting the platiniferous hydrosilylation catalyst disclosed by the invention, hydrosilylation reaction of a double-band containing organic silicon compound and a platiniferous organism can be effectively catalyzed, so that the problems that a conventional platiniferous hydrosilylation catalyst is not stable to store and easily losable in catalytic activity as the catalyst can easily react with metal ions and active compounds can be solved, and moreover, relatively high catalytic activity can be maintained while the problems are all solved.
Description
Technical field
The invention belongs to chemosynthesis technical field, be specifically related to a kind of platiniferous hydrosilylation catalyst and system thereof
Preparation Method.
Background technology
Hydrosilylation refers to be entered under certain condition with unsaturated compound by the silane compound of siliceous hydrogen
A kind of additive reaction of row, it has a wide range of applications and consequence in the middle of organosilicon chemistry, since
Since this reaction is found, in decades, experienced by the development in the most several stage, from initial simple
The condition using high temperature is reacted, and to introducing ultraviolet afterwards, peroxide, azo-compound etc. is commonly used
Catalyst is catalyzed, until Speier finds, is dissolved in isopropanol by chloroplatinic acid and can effectively be catalyzed silicon hydrogen
Additive reaction, is incorporated into platinum element in hydrosilylation for the first time.Hereafter Willing uses at Speier
Method on the basis of, chloroplatinic acid is reacted with the silicone compounds containing unsaturated bond, will reaction after formed
Compound, in hydrosilylation, can continue to improve the efficiency of Si-H addition reaction.Karstedt is at forefathers' base
On plinth, the method for Willing is further improved, use chloroplatinic acid or chloroplatinate in ethanol with carbon
Acid hydrogen sodium and vinylsiloxane reacting by heating, form the vinylsiloxane complex of platinum, and this kind eliminates
The catalyst of halogen, catalytic efficiency is compared with the vinylsiloxane complex of chloroplatinic acid before, and it is catalyzed
Efficiency has had a further raising, and this kind of catalyst today is still as the most frequently used urging in hydrosilylation
Agent is applied to the industrial numerous areas of organosilicon chemistry, although this kind of catalyst relatively before catalysis
Agent is compared, and has higher catalytic efficiency, but there is also simultaneously and deposit instability, easy and storage condition
In heavy metal ion and other active compounds produce reaction, form the platinum that new high-valence state is unstable
Compound, ultimately forms platinum black precipitation, loses catalysis activity.Therefore, develop one can with industrialized production,
Keep higher catalytic activity simultaneously, less sensitive to the active ion species in storage condition again, can be more
Under the conditions of the hydrosilylation catalyst of storage-stable be just particularly important.
Summary of the invention
In place of shortcoming and defect for solution prior art, the primary and foremost purpose of the present invention is to provide a kind of platiniferous
Hydrosilylation catalyst.
Another object of the present invention is to provide the preparation method of a kind of platiniferous hydrosilylation catalyst.
The object of the invention is achieved through the following technical solutions:
A kind of platiniferous hydrosilylation catalyst, this platiniferous hydrosilylation catalyst is by containing platinum compounds and organic
Metal platinum-organic complex that ligand reaction is formed；Described organic ligand is a kind of big cyclisation containing unsaturated bond
Compound, it possesses the structure shown in formula I and/or formula II:
The preparation method of a kind of platiniferous hydrosilylation catalyst, comprises the following steps:
(1) will be dissolved in organic solvent containing platinum compounds, macrocyclic compound containing unsaturated bond and acid binding agent,
Stir；
(2) mixture step (1) stirred reacts 1～8 in 50 DEG C～120 DEG C under stirring
Hour；Thing to be mixed stops heating and stirring, cooling after fully reacting；
(3) reactant liquor is transferred out from container, then acid binding agent is separated from reactant liquor；Will
The reactant liquor getting rid of acid binding agent is mixed homogeneously by a certain percentage with vinyl silicone oil, organic by mixed liquor
Solvent uses the method for decompression distillation to be totally separated out, obtains the ethylene containing metal platinum-organic ligand complex
Base silicon oil solution i.e. platiniferous hydrosilylation catalyst concentrated solution, can work as platiniferous silicon hydrogen after dilution by a certain percentage
Addition catalyst uses.
The described amount ratio containing platinum compounds with the material of the macrocyclic compound containing unsaturated bond of step (1) is
2:1～1:10；The described macrocyclic compound containing unsaturated bond both can be monocyclic compound, its structural formula such as formula
Shown in I；Can also be dicyclic compound, its structural formula be as shown in formula II；Can also be two kinds of compounds
Mixture.
Step (1) is described includes H containing platinum compounds2PtCl6、PtCl2、Pt(COD)2、Na2PtCl4、K2PtCl4
Deng.Preferably, H is used2PtCl6With Pt (COD)2In at least one.
Step (1) described organic solvent can select dichloromethane, chloroform, acetonitrile, oxolane,
In the conventional organic solvents such as N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone
At least one.Preferably, at least one in dichloromethane, chloroform is used.
Step (1) described acid binding agent can select sodium carbonate, sodium bicarbonate, pyridine, potassium carbonate, calcium carbonate,
At least one in the alkaline reagents such as sodium hydroxide, calcium hydroxide and various organic amine (such as triethylamine).
Preferably, at least one in sodium carbonate, potassium carbonate, sodium bicarbonate is used.
The ratio of the amount of step (1) described acid binding agent and the material containing platinum compounds is 1:1～8:1.
Step (2) described heat time heating time is preferably 3 hours, and heating-up temperature is preferably 70 DEG C～90 DEG C.
The methods such as in step (3), the method for separating reaction liquid and acid binding agent can filter with extraction, centrifugal.
If the acid binding agent used is the inorganic compound insoluble in organic solvent such as sodium bicarbonate, sodium carbonate, used
Acid binding agent is separated by filter or centrifugal method, if the acid binding agent used is the organic bases such as triethylamine, then makes
By the method for extraction, organic base is separated.
Step (3) described vinyl silicone oil may select the ethylene that contents of ethylene percentage by weight is 0.5%～5%
Radical siloxane, the addition of vinyl silicone oil is 30:1～150:1 with the mass ratio containing platinum compounds.
Step (3) described vinyl silicone oil may select contents of ethylene percentage by weight and is preferably 1%～2%
Vinylsiloxane, the addition of vinyl silicone oil is preferably 80:1～100:1 with the mass ratio containing platinum compounds.
Compared with prior art, the present invention has the following advantages and beneficial effect:
The platiniferous hydrosilylation catalyst that the present invention provides can effectively be catalyzed containing double bond organo-silicon compound and contain
Silicon hydrogen Organic substance carries out hydrosilylation, efficiently solves existing platiniferous hydrosilylation catalyst and stores not
Stable, easy reaction with metal ion and active compound loses the problem being catalyzed activity, and is solving
Higher catalysis activity can also be kept while problem above.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention do not limit
In this.
Embodiment 1
By monocyclic compound, the sodium bicarbonate of 0.3g and the three of 30mL shown in 1g chloroplatinic acid, 0.8g formula I
Chloromethanes joins in two mouthfuls of flasks of 50mL, and 80 DEG C of agitating heating are reacted 2 hours；After stopped reaction, treat
Reactant liquor natural cooling, then uses filter paper filtering to fall the sodium bicarbonate in reactant liquor.By contents of ethylene it is
The vinyl silicone oil 80g of 1% (percentage by weight) joins in filtrate, uses decompression distillation after mix homogeneously
Method be totally separated out by the chloroform in mixed liquor, obtain the concentrated solution of catalyst, use ethylene
Concentrated solution is diluted to finite concentration by base silicone oil, can be used as hydrosilylation catalyst and uses.
Embodiment 2
Tetrahydrochysene furan by dicyclic compound, the sodium carbonate of 0.4g and the 30mL shown in 1g chloroplatinic acid, 2g formula II
Muttering in the two mouthfuls of flasks joining 50mL, 60 DEG C of agitating heating are reacted 3 hours；After stopped reaction, question response
Liquid natural cooling, then uses centrifuge to separate the sodium carbonate in reactant liquor.It is 1% (weight by contents of ethylene
Amount percentage ratio) vinyl silicone oil 100g join in filtrate, after mix homogeneously use decompression distillation method
It is totally separated out by the oxolane in mixed liquor, obtains the concentrated solution of catalyst, use vinyl silicone oil
Concentrated solution is diluted to finite concentration, can be used as hydrosilylation catalyst and use.
Embodiment 3
By 1g Pt (COD)2, the monocyclic compound shown in 1g formula I, the dicyclic compound shown in 1g formula II,
The sodium carbonate of 0.6g and the chloroform of 30mL join in two mouthfuls of flasks of 50mL, and 70 DEG C of agitating heating are anti-
Answer 3 hours；After stopped reaction, question response liquid natural cooling, then use filter paper filtering to fall in reactant liquor
Sodium carbonate.The vinyl silicone oil 100g that contents of ethylene is 2% (percentage by weight) is joined in filtrate,
Oxolane in mixed liquor is totally separated out by the method using decompression distillation after mix homogeneously, is urged
The concentrated solution of agent, uses vinyl silicone oil that concentrated solution is diluted to finite concentration, can be used as Si-H addition reaction
Catalyst uses.
Embodiment 4
By the monocyclic compound shown in 1g chloroplatinic acid, 0.5g formula I, the dicyclic compound shown in 2g formula II,
The potassium carbonate of 0.5g and the chloroform of 30mL join in two mouthfuls of flasks of 50mL, and 80 DEG C of agitating heating are anti-
Answer 4 hours；After stopped reaction, question response liquid natural cooling, then use centrifuge to isolate in reactant liquor
Sodium carbonate.The vinyl silicone oil 90g that contents of ethylene is 1.5% (percentage by weight) is joined filtrate
In, use the method for decompression distillation to be totally separated out by the oxolane in mixed liquor after mix homogeneously,
To the concentrated solution of catalyst, use vinyl silicone oil that concentrated solution is diluted to finite concentration, can be used as silicon hydrogen
Addition catalyst uses.
Will the catalyst of preparation in embodiment 1-4, join silicone oil that hydrogen content is 1% and double bond content be 2%
Vinyl silicone oil in, test different temperatures under hardening time, under the same conditions, add same amount of
Catalyst, the hardening time of catalyst prepared by embodiment 1-4 is all short than traditional Karstedt catalyst,
Concrete data are as shown in table 1 to table 4:
Catalyst prepared by table 1 embodiment 1-4 and the hardening time of Karstedt catalyst
Catalyst prepared by table 2 embodiment 1-4 and the hardening time of Karstedt catalyst
Catalyst prepared by table 3 embodiment 1-4 and the hardening time of Karstedt catalyst
Catalyst prepared by table 4 embodiment 1-4 and the hardening time of Karstedt catalyst
The catalyst prepared in embodiment 1-4 and Karstedt catalyst are all used the percentage by weight of vinyl
The vinyl silicone oil of 1% is diluted to 3000ppm, places in a reservoir, and add 30ppm easily makes catalyst
The compound of poisoning, observes the storage time, occurs that platinum black is as the criterion in catalyst, it is possible to find, embodiment 1-4
Catalyst under the same conditions, the stabilization time of storage is considerably longer than Karstedt catalyst, concrete such as table 5
Shown in.
Catalyst prepared by table 5 embodiment 1-4 and the storage time of Karstedt catalyst
| Karstedt | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Iron chloride | 3 days | ＞ 30 days | ＞ 30 days | ＞ 30 days | ＞ 30 days |
| Copper chloride | 5 days | ＞ 30 days | ＞ 30 days | ＞ 30 days | ＞ 30 days |
| Stannic chloride | 1 day | 6 days | 6 days | 8 days | 8 days |
| Stearylmercaptan | 1 day | 7 days | 7 days | 10 days | 12 days |
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-mentioned reality
Execute the restriction of example, the change made under other any spirit without departing from the present invention and principle, modification,
Substitute, combine, simplify, all should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (10)
1. a platiniferous hydrosilylation catalyst, it is characterised in that this platiniferous hydrosilylation catalyst is by containing
Metal platinum-organic complex that platinum compounds and organic ligand reaction are formed；Described organic ligand is for containing unsaturation
The macrocyclic compound of key, it possesses the structure shown in formula I and/or formula II:
2. the preparation method of the platiniferous hydrosilylation catalyst described in claim 1, it is characterised in that include
Following steps:
(1) will be dissolved in organic solvent containing platinum compounds, macrocyclic compound containing unsaturated bond and acid binding agent,
Stir；
(2) mixture step (1) stirred reacts 1～8 in 50 DEG C～120 DEG C under stirring
Hour；Thing to be mixed stops heating and stirring, cooling after fully reacting；
(3) reactant liquor is transferred out from container, is then peeled off reactant liquor and acid binding agent；To get rid of and tie up
The reactant liquor of acid agent is mixed homogeneously by a certain percentage with vinyl silicone oil, then distillation of reducing pressure, and obtains platiniferous silicon hydrogen
The concentrated solution of addition catalyst.
The preparation method of platiniferous hydrosilylation catalyst the most according to claim 2, it is characterised in that
The described amount ratio containing platinum compounds with the material of the macrocyclic compound containing unsaturated bond of step (1) is 2:1～1:
10；The described macrocyclic compound containing unsaturated bond is the monocyclic compound shown in formula I, or shown in formula II
Dicyclic compound, or the mixture of two kinds of compounds.
The preparation method of platiniferous hydrosilylation catalyst the most according to claim 2, it is characterised in that
Step (1) is described includes H containing platinum compounds2PtCl6、PtCl2、Pt(COD)2、Na2PtCl4、K2PtCl4
In at least one.
The preparation method of platiniferous hydrosilylation catalyst the most according to claim 2, it is characterised in that
Step (1) described organic solvent is dichloromethane, chloroform, acetonitrile, oxolane, N, N-dimethyl
At least one in Methanamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone.
The preparation method of platiniferous hydrosilylation catalyst the most according to claim 2, it is characterised in that
Step (1) described acid binding agent be sodium carbonate, sodium bicarbonate, pyridine, potassium carbonate, calcium carbonate, sodium hydroxide,
At least one in calcium hydroxide and various organic amine.
The preparation method of platiniferous hydrosilylation catalyst the most according to claim 2, it is characterised in that
The ratio of the amount of step (1) described acid binding agent and the material containing platinum compounds is 1:1～8:1.
The preparation method of platiniferous hydrosilylation catalyst the most according to claim 2, it is characterised in that
Response time described in step (2) is 3 hours, and the temperature of reaction is 70 DEG C～90 DEG C.
The preparation method of platiniferous hydrosilylation catalyst the most according to claim 2, it is characterised in that
Step (3) described vinyl silicone oil be contents of ethylene percentage by weight be the vinylsiloxane of 0.5%～5%,
The addition of vinyl silicone oil is 30:1～150:1 with the mass ratio containing platinum compounds.
The preparation method of platiniferous hydrosilylation catalyst the most according to claim 2, it is characterised in that
Step (3) described vinyl silicone oil be contents of ethylene percentage by weight be the vinylsiloxane of 1%～2%,
The addition of vinyl silicone oil is 80:1～100:1 with the mass ratio containing platinum compounds.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109111573A (en) * | 2018-07-20 | 2019-01-01 | 清华大学深圳研究生院 | Organic-silicon-modified fullerene of a kind of platinum load and its preparation method and application |
| CN110252411A (en) * | 2019-06-26 | 2019-09-20 | 江西蓝星星火有机硅有限公司 | A kind of end epoxy silicon oil production solvay-type platinum catalyst and its preparation method and application |
| US11322750B2 (en) | 2019-04-24 | 2022-05-03 | Toyota Motor Engineering & Manufacturing North America, Inc. | Surface modified platinum or platinum alloy catalyst for oxygen reduction reaction |
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| US3775452A (en) * | 1971-04-28 | 1973-11-27 | Gen Electric | Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes |
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Non-Patent Citations (3)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109111573A (en) * | 2018-07-20 | 2019-01-01 | 清华大学深圳研究生院 | Organic-silicon-modified fullerene of a kind of platinum load and its preparation method and application |
| CN109111573B (en) * | 2018-07-20 | 2021-01-29 | 清华大学深圳研究生院 | Platinum-loaded organic silicon modified fullerene and preparation method and application thereof |
| US11322750B2 (en) | 2019-04-24 | 2022-05-03 | Toyota Motor Engineering & Manufacturing North America, Inc. | Surface modified platinum or platinum alloy catalyst for oxygen reduction reaction |
| CN110252411A (en) * | 2019-06-26 | 2019-09-20 | 江西蓝星星火有机硅有限公司 | A kind of end epoxy silicon oil production solvay-type platinum catalyst and its preparation method and application |
| CN110252411B (en) * | 2019-06-26 | 2022-02-08 | 江西蓝星星火有机硅有限公司 | Complex platinum catalyst for producing epoxy-terminated silicone oil and preparation method and application thereof |
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Effective date of registration: 20221212 Address after: 512400 No.3 complex building, Ping'an 1st Road, Dongguan Dalingshan (Nanxiong) industrial transfer industrial park, Nanxiong City, Shaoguan City, Guangdong Province Patentee after: Guoke Guanghua (Nanxiong) New Materials Research Institute Co.,Ltd. Patentee after: GUANGZHOU CHEMISTRY Co.,Ltd. CHINESE ACADEMY OF SCIENCES Patentee after: GUANGDONG GUANHAO HIGH-TECH CO.,LTD. Address before: 512400 Zhuji Industrial Park, Nanxiong City, Shaoguan City, Guangdong Province (Nanxiong Fine Chemical Base, Guangdong Province) Patentee before: NANXIONG MATERIAL PRODUCTION BASE OF CHINESE ACADEMY OF SCIENCES GUANGZHOU CHEMICAL Co.,Ltd. Patentee before: GUANGZHOU CHEMISTRY Co.,Ltd. CHINESE ACADEMY OF SCIENCES Patentee before: GUANGDONG GUANHAO HIGH-TECH CO.,LTD. |