CN105854946B - A kind of platiniferous hydrosilylation catalyst and preparation method thereof - Google Patents
A kind of platiniferous hydrosilylation catalyst and preparation method thereof Download PDFInfo
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- CN105854946B CN105854946B CN201610221480.3A CN201610221480A CN105854946B CN 105854946 B CN105854946 B CN 105854946B CN 201610221480 A CN201610221480 A CN 201610221480A CN 105854946 B CN105854946 B CN 105854946B
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- hydrosilylation catalyst
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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 chemosynthesis technical fields, specifically disclose a kind of platiniferous hydrosilylation catalyst and preparation method thereof.The platiniferous hydrosilylation catalyst is that the metal platinum organic complex formed is reacted by compound containing platinum and organic ligand；The organic ligand is a kind of macrocyclic compound containing unsaturated bond.Platiniferous hydrosilylation catalyst provided by the invention can effectively be catalyzed organo-silicon compound containing double bond and siliceous hydrogen organic matter carries out hydrosilylation, it solve thes problems, such as that the storage of existing platiniferous hydrosilylation catalyst is unstable, easily reacted with metal ion and active compound and lose catalytic activity, and higher catalytic activity can also be kept while solving problem above.
Description
Technical field
The invention belongs to chemosynthesis technical fields, and in particular to a kind of platiniferous hydrosilylation catalyst and its preparation side
Method.
Background technology
Hydrosilylation refers to what is carried out under certain condition with unsaturated compound by the silane compound of siliceous hydrogen
A kind of addition reaction, has a wide range of applications and consequence in organosilicon chemistry, since the reaction be found with
Come, in decades, experienced the development in faster several stages, reacted, arrived from the initial simple condition for using high temperature
It introduces the custom catalysts such as ultraviolet light, peroxide, azo-compound later to be catalyzed, until Speier discoveries, by chlorine platinum
Acid be dissolved in isopropanol can effective catalyzing addition reaction of silicon with hydrogen, platinum element is introduced into hydrosilylation for the first time.This
On the basis of the method that Willing is used in Speier afterwards, chloroplatinic acid is reacted with silicone compounds containing unsaturated bond, it will be anti-
The compound that should be formed afterwards is used in hydrosilylation, can continue to improve the efficiency of Si―H addition reaction.Karstedt is in forefathers
On the basis of, the method for Willing is further improved, using chloroplatinic acid or chloroplatinate in ethanol with sodium bicarbonate and
Vinylsiloxane heating reaction forms the vinylsiloxane complex compound of platinum, such catalyst for eliminating halogen, catalysis effect
For rate compared with the vinylsiloxane complex compound of chloroplatinic acid before, catalytic efficiency has further raising, such catalysis
Agent is still applied to organosilicon chemistry industrial many necks today as most common catalyst in hydrosilylation
Domain, although such catalyst relatively before catalyst compare, have higher catalytic efficiency, however, there are also storage is unstable
It is fixed, it is easily reacted with the heavy metal ion in storage condition and other active compound generations, it is unstable to form new high-valence state
Fixed platinum compounds ultimately forms platinum black precipitation, loses catalytic activity.Therefore, one kind is developed to keep with industrialized production
Higher catalytic activity is simultaneously, and less sensitive to the active ion species in storage condition, can under the conditions of more storage-stable
Hydrosilylation catalyst be just particularly important.
Invention content
To solve the disadvantage that the prior art and shortcoming, primary and foremost purpose of the invention is that providing a kind of platiniferous silicon hydrogen adds
Into catalyst.
Another object of the present invention is to provide a kind of preparation method of platiniferous hydrosilylation catalyst.
The object of the invention is achieved through the following technical solutions：
A kind of platiniferous hydrosilylation catalyst, the platiniferous hydrosilylation catalyst are anti-by compound containing platinum and organic ligand
Metal platinum-the organic complex that should be formed；The organic ligand is a kind of macrocyclic compound containing unsaturated bond, has formula I
And/or the structure shown in formula II：
A kind of preparation method of platiniferous hydrosilylation catalyst, includes the following steps：
(1) compound containing platinum, the macrocyclic compound containing unsaturated bond and acid binding agent are dissolved in organic solvent, are sufficiently stirred
Uniformly；
(2) mixture for stirring evenly step (1) reacts 1~8 hour under stirring in 50 DEG C~120 DEG C；It treats
Mixture stops heating and stirring, cooling after fully reacting；
(3) reaction solution is transferred out from container, then acid binding agent is separated from reaction solution；It will get rid of and tie up
The reaction solution of sour agent is mixed in a certain ratio uniformly with vinyl silicone oil, and the organic solvent in mixed liquor is used vacuum distillation
Method is totally separated out, obtains the i.e. platiniferous Si―H addition reaction of vinyl silicone oil solution containing metal platinum-organic ligand complex compound and urges
Agent concentrate can work as platiniferous hydrosilylation catalyst and use after diluting by a certain percentage.
The amount ratio of step (1) compound containing platinum and the substance of the macrocyclic compound containing unsaturated bond is 2:1~1：
10；The macrocyclic compound containing unsaturated bond is either monocyclic compound, and structural formula is as shown in formula I；Can also be double
Cycle compound, structural formula is as shown in formula II；It can also be the mixture of two kinds of compounds.
Step (1) described compound containing platinum includes H2PtCl6、PtCl2、Pt(COD)2、Na2PtCl4、K2PtCl4Deng.It is preferred that
Ground uses H2PtCl6With Pt (COD)2At least one of.
Step (1) described organic solvent can select dichloromethane, chloroform, acetonitrile, tetrahydrofuran, N, N- dimethyl
At least one of common organic solvent such as formamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone.Preferably, it uses
At least one of dichloromethane, chloroform.
Step (1) described acid binding agent can select sodium carbonate, sodium bicarbonate, pyridine, potassium carbonate, calcium carbonate, sodium hydroxide,
At least one of calcium hydroxide and various organic amines (such as triethylamine) alkaline reagent.Preferably, using sodium carbonate, carbonic acid
At least one of potassium, sodium bicarbonate.
The ratio of the amount of the substance of step (1) acid binding agent and compound containing platinum is 1:1~8:1.
Step (2) heating time is preferably 3 hours, and heating temperature is preferably 70 DEG C~90 DEG C.
The methods of method of separation reaction solution and acid binding agent can use extraction in step (3), filter, centrifugation.If it uses
Acid binding agent is the inorganic compound insoluble in organic solvent such as sodium bicarbonate, sodium carbonate, will be tied up using the method for filtering or centrifugation
Sour agent is separated, if the acid binding agent used is the organic bases such as triethylamine, is separated organic base using the method for extraction.
The vinyl silicon that contents of ethylene weight percent is 0.5%~5% may be selected in step (3) described vinyl silicone oil
Oxygen alkane, the additive amount of vinyl silicone oil and the mass ratio of compound containing platinum are 30:1~150:1.
The vinyl that contents of ethylene weight percent is preferably 1%~2% may be selected in step (3) described vinyl silicone oil
Siloxanes, the additive amount of vinyl silicone oil and the mass ratio of compound containing platinum are preferably 80:1~100:1.
Compared with prior art, the present invention has the following advantages and beneficial effects：
Platiniferous hydrosilylation catalyst provided by the invention can effectively be catalyzed organo-silicon compound containing double bond and siliceous hydrogen
Organic matter carries out hydrosilylation, efficiently solve the storage of existing platiniferous hydrosilylation catalyst it is unstable, easy with it is golden
Belong to ion and active compound reacts the problem of losing catalytic activity, and can also be kept while solving problem above
Higher catalytic activity.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1
Monocyclic compound, the chloroform of the sodium bicarbonate of 0.3g and 30mL shown in 1g chloroplatinic acids, 0.8g formulas I is added in
Into the two mouth flask of 50mL, 80 DEG C of agitating and heatings are reacted 2 hours；After stopping reaction, treat reaction solution natural cooling, then use
Filter paper filters out the sodium bicarbonate in reaction solution.Vinyl silicone oil 80g of the contents of ethylene for 1% (weight percent) is added in
Into filtrate, after mixing the chloroform in mixed liquor is totally separated out using the method for vacuum distillation, be urged
Concentrate is diluted to a certain concentration, you can use as hydrosilylation catalyst by the concentrate of agent using vinyl silicone oil.
Embodiment 2
Dicyclic compound, the sodium carbonate of 0.4g and the tetrahydrofuran of 30mL shown in 1g chloroplatinic acids, 2g formulas II is added to
In the two mouth flask of 50mL, 60 DEG C of agitating and heatings are reacted 3 hours；Stop reaction after, treat reaction solution natural cooling, then use from
Scheming separates the sodium carbonate in reaction solution.Vinyl silicone oil 100g of the contents of ethylene for 1% (weight percent) is added in
Into filtrate, after mixing the tetrahydrofuran in mixed liquor is totally separated out using the method for vacuum distillation, be urged
Concentrate is diluted to a certain concentration, you can use as hydrosilylation catalyst by the concentrate of agent using vinyl silicone oil.
Embodiment 3
By 1g Pt (COD)2, the monocyclic compound shown in 1g formulas I, the dicyclic compound shown in 1g formulas II, 0.6g carbonic acid
The chloroform of sodium and 30mL are added in the two mouth flask of 50mL, and 70 DEG C of agitating and heatings are reacted 3 hours；After stopping reaction, treat
Then reaction solution natural cooling filters out the sodium carbonate in reaction solution using filter paper.It is 2% (weight percent by contents of ethylene
Than) vinyl silicone oil 100g be added in filtrate, after mixing using the method for vacuum distillation by the tetrahydrochysene in mixed liquor
Furans is totally separated out, obtains the concentrate of catalyst, and concentrate is diluted to a certain concentration using vinyl silicone oil, you can
It is used as hydrosilylation catalyst.
Embodiment 4
By the monocyclic compound shown in 1g chloroplatinic acids, 0.5g formulas I, the dicyclic compound shown in 2g formulas II, 0.5g carbonic acid
Potassium and the chloroform of 30mL are added in the two mouth flask of 50mL, and 80 DEG C of agitating and heatings are reacted 4 hours；After stopping reaction, treat
Then reaction solution natural cooling isolates the sodium carbonate in reaction solution using centrifuge.It is 1.5% (weight by contents of ethylene
Percentage) vinyl silicone oil 90g be added in filtrate, after mixing using the method for vacuum distillation by four in mixed liquor
Hydrogen furans is totally separated out, obtains the concentrate of catalyst, concentrate is diluted to a certain concentration using vinyl silicone oil, i.e.,
It can be used as hydrosilylation catalyst.
The catalyst that will be prepared in embodiment 1-4 is added to the silicone oil that hydrogen content is 1% and the second that double bond content is 2%
In alkenyl silicone oil, the hardening time under different temperatures is tested, under the same conditions, adds in same amount of catalyst, embodiment 1-4
The hardening time of the catalyst of preparation is shorter than traditional Karstedt catalyst, and specific data are as shown in table 1 to table 4：
Catalyst and the hardening time of Karstedt catalyst prepared by 1 embodiment 1-4 of table
Catalyst and the hardening time of Karstedt catalyst prepared by 2 embodiment 1-4 of table
Catalyst and the hardening time of Karstedt catalyst prepared by 3 embodiment 1-4 of table
Catalyst and the hardening time of Karstedt catalyst prepared by 4 embodiment 1-4 of table
The catalyst prepared in embodiment 1-4 and Karstedt catalyst are used to the weight percent 1% of vinyl
Vinyl silicone oil be diluted to 3000ppm, place in a reservoir, add in the compound for easily making catalyst poisoning of 30ppm, see
Examine storage time, occur subject to platinum black in catalyst, it is possible to find, the catalyst of embodiment 1-4 under the same conditions, storage it is steady
It fixes time and is considerably longer than Karstedt catalyst, it is specific as shown in table 5.
Catalyst and the storage time of Karstedt catalyst prepared by 5 embodiment 1-4 of table
| 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 preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (9)
1. a kind of platiniferous hydrosilylation catalyst, which is characterized in that the platiniferous hydrosilylation catalyst be by compound containing platinum and
Organic ligand reacts the metal platinum-organic complex to be formed；The organic ligand is the macrocyclic compound containing unsaturated bond, is had
Structure shown in standby formula I and/or formula II：
The preparation process of the platiniferous hydrosilylation catalyst includes：
(1) compound containing platinum, the macrocyclic compound containing unsaturated bond and acid binding agent are dissolved in organic solvent, are sufficiently stirred
It is even；
(2) mixture for stirring evenly step (1) reacts 1~8 hour under stirring in 50 DEG C~120 DEG C；It is to be mixed
Object stops heating and stirring, cooling after fully reacting；
(3) reaction solution is transferred out from container, then detaches reaction solution and acid binding agent；The reaction solution of acid binding agent will be got rid of
It is mixed in a certain ratio uniformly, then is evaporated under reduced pressure with vinyl silicone oil, obtain the concentrate of platiniferous hydrosilylation catalyst.
2. platiniferous hydrosilylation catalyst according to claim 1, which is characterized in that step (1) described compound containing platinum
Amount ratio with the substance of the macrocyclic compound containing unsaturated bond is 2:1~1：10；The macrocyclic compound containing unsaturated bond
It is the monocyclic compound shown in formula I or the dicyclic compound shown in formula II or the mixture of two kinds of compounds.
3. platiniferous hydrosilylation catalyst according to claim 1, which is characterized in that step (1) described compound containing platinum
Including H2PtCl6、PtCl2、Pt(COD)2、Na2PtCl4、K2PtCl4At least one of.
4. platiniferous hydrosilylation catalyst according to claim 1, which is characterized in that step (1) described organic solvent is
Dichloromethane, chloroform, acetonitrile, tetrahydrofuran, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- methylpyrroles
At least one of alkanone.
5. platiniferous hydrosilylation catalyst according to claim 1, which is characterized in that step (1) described acid binding agent is carbon
At least one of sour sodium, sodium bicarbonate, pyridine, potassium carbonate, calcium carbonate, sodium hydroxide, calcium hydroxide and various organic amines.
6. platiniferous hydrosilylation catalyst according to claim 1, which is characterized in that step (1) acid binding agent and contain
The ratio of the amount of the substance of platinum compounds is 1:1~8:1.
7. platiniferous hydrosilylation catalyst according to claim 1, which is characterized in that the reaction time described in step (2)
It it is 3 hours, the temperature of reaction is 70 DEG C~90 DEG C.
8. platiniferous hydrosilylation catalyst according to claim 1, which is characterized in that step (3) described vinyl silicone oil
It is the vinylsiloxane that contents of ethylene weight percent is 0.5%~5%, the additive amount of vinyl silicone oil and platiniferous chemical combination
The mass ratio of object is 30:1~150:1.
9. platiniferous hydrosilylation catalyst according to claim 1, which is characterized in that step (3) described vinyl silicone oil
Be contents of ethylene weight percent be 1%~2% vinylsiloxane, the additive amount and compound containing platinum of vinyl silicone oil
Mass ratio be 80:1~100:1.
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| 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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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. |