CN104307570B - A kind of platinum allyl polyether composition catalyst and its preparation method and application - Google Patents
A kind of platinum allyl polyether composition catalyst and its preparation method and application Download PDFInfo
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- CN104307570B CN104307570B CN201410453676.6A CN201410453676A CN104307570B CN 104307570 B CN104307570 B CN 104307570B CN 201410453676 A CN201410453676 A CN 201410453676A CN 104307570 B CN104307570 B CN 104307570B
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Abstract
The invention discloses a kind of platinum allyl polyether composition catalyst and its preparation method and application, under nitrogen atmosphere, by allyl polyether in 120 DEG C of dewater treatment 30min, then 30~105 DEG C are cooled the temperature to, the aqueous isopropanol of chloroplatinic acid is added, under agitation, in 0.5~3.5h of reaction at 30~125 DEG C, 40~50 DEG C of vacuum distillations remove isopropanol, that is, obtain platinum allyl polyether composition catalyst.The excellent catalytic effect of catalyst of the present invention, the catalyst of stable in catalytic performance, it is adaptable to the hydrosilylation of allyl polyether and containing hydrogen silicone oil.The catalyst is applied to the hydrosilylation of allyl polyether and containing hydrogen silicone oil, is compared with traditional chloroplatinic acid catalyst, its high catalytic efficiency, reaction condition are gentle, product clarification, close to water white transparency.
Description
Technical field
The present invention relates to a kind of preparation method of platinum catalyst, specially field of organic silicon in field of organic silicon, silicon hydrogen adds
The preparation method of platinum complex catalyst into reaction.
Background technology
In organo-silicon compound and its study on the synthesis field of polymer, silicon hydrogen catalysis addition reaction is that complex functionality has
The important channel of organic silicon compound and its polymer.Silicon hydrogen catalysis addition reaction catalyst experienced a very long history and become
Change, early in nineteen forty-seven, people have done substantial amounts of research to transiting state metal catalyzing addition reaction of silicon with hydrogen, while also achieving very big
Progress.But it is this kind of that polymerisation occurs because catalytic selectivity is not high, be difficult to avoid that unsaturated compound, it is limited in city
Application on field.At present, catalyst for addition reaction of hydrogen and silicon uses platinum catalyst mostly, and it is also to study the deepest so far
The catalyst for addition reaction of hydrogen and silicon enter, being most widely used.Hydrosilylation on the market uses chloroplatinic acid-isopropyl mostly
Alcohol as catalyst, but this kind of catalyst due to the consumption of catalyst it is big, reaction temperature is high, and hydrosilylation product is carried
Certain yellow.
Chinese patent CN101434615A is prepared for a kind of activated catalyst, and its specific procedure is by chloroplatinic acid weight 2~6
Times and 2~10 times add DHF and acetic acid acetyl triethyls, stir, be warming up to 60 DEG C reaction 1h, and then
Temperature is risen into 100 DEG C to steam low-boiling-point substance, the catalyst of activation process is obtained.Apply it to allyl polyether and Silicon Containing Hydrogen
The hydrosilylation of oil, 1~10h is reacted at 110 DEG C~180 DEG C, obtains polyether modified silicon oil.Wherein catalyst chloroplatinic acid with
Pt meters press the 1 × 10 of Methyl Hydrogen Polysiloxane Fluid weight-6~10 × 10-6Ratio is added.Using the catalyst can cause that this is polyether-modified
Silicone oil obtains lower surface tension.But its reaction temperature is high, the reaction time is long, and the activating treatment agent for being used has 2,3- dihydros
Furans and acetic acid acetyl triethyl, wherein acetic acid acetyl triethyl are harmful to the health of human body, while activating treatment agent and catalyst
Separation increases production cost.
Chinese patent CN101322946A discloses a kind of preparation method of catalyst for addition reaction of hydrogen and silicon, by chloroplatinic acid and
The amino-compound of carboxyl group n (Pt) in molar ratio:N (- COOH)=1：1~20 is added in there-necked flask, with tetrahydrochysene furan
Mutter as solvent, reaction temperature is 80~120 DEG C.Reaction time is 2~24h, and heating in vacuum removes solvent, in vacuum drying chamber
In dry at 60 DEG C, obtained a kind of catalyst for addition reaction of hydrogen and silicon.It is applied in hydrosilylation, the end-product warp for obtaining
GC-MS detects that it is excellent that detection obtains the hydrosilylation catalyst catalytic performance.But this reaction response overlong time, production is thrown
Enter big；To human health, soakage can excessively cause hepatosis to the tetrahydrofuran for being used.
The content of the invention
Problem solved by the invention there is provided a kind of platinum-allyl polyether composition catalyst and preparation method thereof,
The catalyst is applied to the hydrosilylation of allyl polyether and containing hydrogen silicone oil.The high catalytic efficiency of the catalyst, reaction bar
Part is gentle, preparation-obtained polyether modified silicon oil is clear, near colorless.
The object of the invention is achieved through the following technical solutions：
A kind of preparation method of platinum-allyl polyether composition catalyst, under nitrogen atmosphere, allyl polyether is existed
120 DEG C of dewater treatment 30min, then cool the temperature to 30~105 DEG C, the aqueous isopropanol of chloroplatinic acid are added, in stirring condition
Under, in 0.5~3.5h is reacted at 30~125 DEG C, 40~50 DEG C of vacuum distillations remove isopropanol, that is, obtain platinum-allyl polyether
Composition catalyst；It is 1 × 10 that wherein chloroplatinic acid is counted with the mass ratio of allyl polyether with Pt-6~10000 × 10-6。
Being configured to 1g chloroplatinic acid isopropanol constant volumes to 100ml for the aqueous isopropanol of the chloroplatinic acid, shakes up.
The molecular formula of the allyl polyether is：
H2C=CH-CH2O-[CH2CH2O]m-[CHCH3CH2O]n-R
M, n are 0 or positive integer；R is H, methyl or butyl.
The reaction temperature is 60~85 DEG C, and the reaction time is 0.5~1.5h.
It is 500 × 10 that the chloroplatinic acid is counted with the mass ratio of allyl polyether with Pt-6~10000 × 10-6。
The condition of the vacuum distillation is pressure -0.096MPa.
The catalyst is used for the hydrosilylation of allyl polyether and containing hydrogen silicone oil.Wherein, described Silicon Containing Hydrogen
The hydrogen content of oil is 0.05%~0.80%.
The hydrogen content of described containing hydrogen silicone oil is 0.05%~0.65%.
Catalyst amount accounts for the 1 × 10 of reaction gross mass in the hydrosilylation-6~50 × 10-6, reaction temperature is
80~145 DEG C, 3~4h of reaction time.
Relative to prior art, advantages of the present invention is as follows：
(1) catalyst that the catalyst prepared by the present invention coordinates for allyl polyether with chloroplatinic acid, complex pi-allyl
Simultaneously as the reaction raw materials in silicon hydrogen catalysis addition reaction, the addition of complex will not cause the hair of other side reactions to polyethers
It is raw, and reaction raw materials will not be polluted.
(2) catalyst prepared by the present invention has excellent catalytic effect to hydrosilylation, it is adaptable to pi-allyl
The hydrosilylation of polyethers and containing hydrogen silicone oil.
(3) catalyst prepared by the present invention is applied to the hydrosilylation of allyl polyether and containing hydrogen silicone oil.Catalysis
Gentle, the resulting polyether modified silicon oil of efficiency high, reaction condition is clear, of light color, near colorless.
(4) platinum-allyl polyether composition catalyst prepared by the present invention, is carried out with traditional chloroplatinic acid catalyst
Contrast, it is found that the catalytic performance of prepared platinum-allyl complex catalyst is better than traditional chloroplatinic acid catalyst.
(5) method for preparing catalyst provided by the present invention is easy, and reappearance is good, and reaction condition is gentle, with preferable
Economic benefit.
Specific embodiment
Below in conjunction with specific embodiment, the invention will be further described, but scope of the present invention is not
It is confined to the involved scope of embodiment.
Embodiment 1
Step 1) 30.00g polyethers F6 is added in there-necked flask, under nitrogen atmosphere, dewater treatment 30min at 120 DEG C,
Temperature is reduced to 60 DEG C, is added thereto to be dissolved in platinum acid chloride solution (the 1g chloroplatinic acid catalyst isopropanol constant volumes of isopropanol
To 100ml) 6.33g, stir-activating treatment 60min at 60 DEG C.Aqueous isopropanol is removed in -0.096MPa/45 DEG C of vacuum distillation.
Obtain the catalyst that polyethers F6 coordinates with platinum.
Step 2) 99.68g polyethers F6 is added in there-necked flask, under nitrogen atmosphere, 120 DEG C of dewater treatment 30min will
Temperature is reduced to 100 DEG C, is added thereto to the containing hydrogen silicone oil 26.38g that hydrogen content is 0.197%, and then adds step 1) system
The catalyst 0.474g for obtaining.Wherein catalyst (in terms of Pt) accounts for the 3.75 × 10 of reactant gross mass-6.Logical nitrogen is stirred at 100 DEG C
Four hours of solid/liquid/gas reactions, obtain the polyether modified silicon oil of clear, near colorless.Conversion ratio is 95.18%.
Embodiment 2
1) 30.00g polyethers F6 is added in there-necked flask, under nitrogen atmosphere, dewater treatment 30min at 120 DEG C, by temperature
Degree is reduced to 75 DEG C, and (1g chloroplatinic acid catalyst isopropanol constant volumes are arrived to be added thereto to be dissolved in the platinum acid chloride solution of isopropanol
100ml) 3.16g, stir-activating treatment 30min at 75 DEG C.Aqueous isopropanol is removed in -0.096MPa/45 DEG C of vacuum distillation.
To the catalyst that polyethers F6 and platinum coordinate.
2) 99.05g polyethers F6 is added in there-necked flask, under nitrogen atmosphere, 120 DEG C of dewater treatment 30min, by temperature
100 DEG C are reduced to, the containing hydrogen silicone oil 26.38g that hydrogen content is 0.197% is added thereto to, step 1 is and then added) it is obtained
Catalyst 0.948g.Wherein catalyst (in terms of Pt) accounts for the 3.75 × 10 of reactant gross mass-6.Logical nitrogen is stirred at 100 DEG C anti-
Four hours are answered, the polyether modified silicon oil of clear, near colorless is obtained.Conversion ratio is 94.24%.
Embodiment 3
Step 1) molecular formula of polyethers is：
H2C=CH-CH2O-[CH2CH2O]4-[CHCH3CH2O]12-H
This kind of polyethers of 30.00g is added in there-necked flask, under nitrogen atmosphere, dewater treatment 30min at 120 DEG C, by temperature
Degree is reduced to 60 DEG C, and (1g chloroplatinic acid catalyst isopropanol constant volumes are arrived to be added thereto to be dissolved in the platinum acid chloride solution of isopropanol
100ml) 6.33g, stir-activating treatment 30min at 60 DEG C.Aqueous isopropanol is removed in -0.096MPa/45 DEG C of vacuum distillation, is obtained
To the catalyst that polyethers and platinum coordinate.
Step 2) this kind of polyethers of 99.48g is added in there-necked flask, under nitrogen atmosphere, 120 DEG C of dewater treatment 30min,
Temperature is reduced to 95 DEG C, the containing hydrogen silicone oil 29.36g that hydrogen content is 0.308% is added thereto to, step 1 is and then added) system
The catalyst 0.52g for obtaining, wherein catalyst (in terms of Pt) accounts for the 4 × 10 of reactant gross mass-6.Logical nitrogen reaction is stirred at 95 DEG C
Four hours, obtain polyether modified silicon oil.Its product appearance is clear, near colorless, and conversion ratio is 99.59%.
Embodiment 4
Step 1) 30.00g polyethers F6 is added in there-necked flask, under nitrogen atmosphere, dewater treatment 30min at 120 DEG C,
Temperature is reduced to 75 DEG C, (1g chloroplatinic acid catalysts isopropanol is determined to be added thereto to be dissolved in the chloroplatinic acid catalyst of isopropanol
Hold 100ml) 6.33g, stir-activating treatment 50min at 75 DEG C.- 0.096MPa/45 DEG C of vacuum distillation removes aqueous isopropanol.
Obtain the catalyst that polyethers F6 coordinates with platinum.
Step 2) 49.60g polyethers F6 is added in there-necked flask, under nitrogen atmosphere, 120 DEG C of dewater treatment 30min will
Temperature is reduced to 90 DEG C, is added thereto to the containing hydrogen silicone oil 51.96g that hydrogen content is 0.05%, and then adds step 1) it is obtained
Catalyst 0.762g, wherein catalyst (in terms of Pt) accounts for the 7.5 × 10 of reactant gross mass-6.Logical nitrogen is stirred at 90 DEG C anti-
Four hours are answered, the polyether modified silicon oil of clear, near colorless is obtained.Conversion ratio is 95.48%.
Embodiment 5
Step 1) molecular formula of butyl end-capping polyethers is：
H2C=CH-CH2O-[CH2CH2O]10-[CHCH3CH20]6-CH2CH2CH2CH3
By 30.00g, the polyethers is added in there-necked flask, under nitrogen atmosphere, dewater treatment 30min at 120 DEG C, by temperature
60 DEG C are reduced to, are added thereto to be dissolved in the platinum acid chloride solution 6.33g of isopropanol, stir-activating treatment 30min at 60 DEG C.-
0.096MPa/45 DEG C of vacuum distillation removes aqueous isopropanol.Obtain the catalyst that butyl end-capping polyethers coordinates with platinum.
Step 2) the above-mentioned polyethers of 99.60g is added in there-necked flask, under nitrogen atmosphere, 120 DEG C of dewater treatment 30min,
Temperature is reduced to 110 DEG C, the containing hydrogen silicone oil 14.31g that hydrogen content is 0.65% is added thereto to, step 1 is and then added) system
The catalyst 0.400g for obtaining, wherein catalyst (in terms of Pt) accounts for the 3.5 × 10 of reactant gross mass-6.Logical nitrogen is stirred at 110 DEG C
Three hours of reaction, obtain the polyether modified silicon oil of clear, near colorless.Conversion ratio is 96.18%.
Embodiment 6
Step 1) addition method of traditional polyethers and containing hydrogen silicone oil is：The polyethers F6 of 100g, hydrogen content are 0.197%
Containing hydrogen silicone oil 26.38g, be dissolved in isopropanol chloroplatinic acid solution (chloroplatinic acid of 1g isopropanol constant volume to 100ml) 268uL,
(wherein catalyst chloroplatinic acid accounts for the 8 × 10 of reaction gross mass in terms of platinum-6) be together added in there-necked flask, in 120 DEG C of logical nitrogen
Stirring reaction 4h under gas.Polyether modified silicon oil is obtained, its conversion ratio is 90.05%
Contrast is carried out with embodiment 1 and compares to obtain：
Result shows the catalyst of platinum-polyethers cooperation in terms of catalyst amount, reaction temperature, product appearance, conversion ratio
It is superior to traditional chloroplatinic acid catalyst.
Claims (10)
1. the preparation method of a kind of platinum-allyl polyether composition catalyst, it is characterised in that
Under nitrogen atmosphere, 30~105 DEG C are then cooled the temperature to by allyl polyether in 120 DEG C of dewater treatment 30min, plus
Enter the aqueous isopropanol of chloroplatinic acid, under agitation, in 0.5~1.5h of reaction, 40~50 DEG C of vacuum distillations at 30~125 DEG C
Removal isopropanol, that is, obtain platinum-allyl polyether composition catalyst；Wherein chloroplatinic acid in terms of Pt with the quality of allyl polyether
Than being 1 × 10-6~10000 × 10-6。
2. method according to claim 1, it is characterised in that the molecular formula of the allyl polyether is：
H2C=CH-CH2O-[CH2CH2O]m-[CHCH3CH2O]n-R
M, n are 0 or positive integer；R is H, methyl or butyl.
3. method according to claim 1 and 2, it is characterised in that the reaction temperature is 60~85 DEG C.
4. method according to claim 3, it is characterised in that the chloroplatinic acid in terms of Pt with the mass ratio of allyl polyether
It is 500 × 10-6~10000 × 10-6。
5. method according to claim 4, it is characterised in that the condition of the vacuum distillation is pressure -0.096MPa.
6. the catalyst that prepared by Claims 1 to 5 any one methods described.
7. the application of catalyst described in claim 6, it is characterised in that the catalyst is used for allyl polyether and Silicon Containing Hydrogen
The hydrosilylation of oil.
8. application according to claim 7, it is characterised in that the hydrogen content of described containing hydrogen silicone oil be 0.05%~
0.80%.
9. application according to claim 8, it is characterised in that the hydrogen content of described containing hydrogen silicone oil be 0.05%~
0.65%.
10. the application according to claim 7 or 8 or 9, it is characterised in that catalyst amount in the hydrosilylation
Account for the 1 × 10 of reactant gross mass-6~50 × 10-6, reaction temperature is 80~145 DEG C, 3~4h of reaction time.
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| CN111849349A (en) * | 2020-08-04 | 2020-10-30 | 吴江南玻玻璃有限公司 | Antireflection coating liquid, preparation method thereof, antireflection coated glass and photovoltaic module |
| CN114471726B (en) * | 2022-01-26 | 2023-12-29 | 淮安晨化新材料有限公司 | Preparation method and application of efficient catalyst for hydrosilylation reaction |
| CN115845920B (en) * | 2022-12-20 | 2024-03-22 | 江西晨光新材料股份有限公司 | Preparation method of solid platinum catalyst and polyether modified methyldimethoxy silane |
| CN116003799A (en) * | 2023-01-06 | 2023-04-25 | 国科广化(南雄)新材料研究院有限公司 | Method for synthesizing hydroxyl hydrogen-containing silicone oil through hydrosilylation reaction |
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