CN115945217B - A kind of solid-supported platinum catalyst, polyether-modified siloxane and preparation method - Google Patents
A kind of solid-supported platinum catalyst, polyether-modified siloxane and preparation method Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 201
- 239000003054 catalyst Substances 0.000 title claims abstract description 138
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 100
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 22
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 95
- 229920000570 polyether Polymers 0.000 claims description 95
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 35
- 239000001257 hydrogen Substances 0.000 claims description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims description 35
- 238000010438 heat treatment Methods 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000007480 spreading Effects 0.000 abstract description 5
- 238000003892 spreading Methods 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 2
- 239000002815 homogeneous catalyst Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 61
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 24
- 238000003756 stirring Methods 0.000 description 19
- 239000000047 product Substances 0.000 description 15
- 230000004913 activation Effects 0.000 description 14
- 208000012839 conversion disease Diseases 0.000 description 14
- 238000001914 filtration Methods 0.000 description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 13
- 230000003100 immobilizing effect Effects 0.000 description 13
- 229910000077 silane Inorganic materials 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000004321 preservation Methods 0.000 description 12
- 238000006459 hydrosilylation reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- -1 siloxanes Chemical class 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 description 5
- 239000008139 complexing agent Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QJTAAHJJXWYZSK-UHFFFAOYSA-N [Br].CC(O)=O Chemical compound [Br].CC(O)=O QJTAAHJJXWYZSK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000003622 immobilized catalyst Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Silicon Polymers (AREA)
- Catalysts (AREA)
Abstract
本发明实施例公开了一种固载化配合铂催化剂、聚醚改性硅氧烷及制备方法。一种固载化配合铂催化剂的制备方法，包括：将聚乙二醇、铂源溶于乙醇中，得混合溶液；加入载体，浸渍，烘干，得所述固载化配合铂催化剂；其中，所述铂源为氯铂酸‑异丙醇溶液，所述混合溶液中铂元素的摩尔浓度为0.01～0.04mol/L。本发明提供的固载化配合铂催化剂制备方法简单易操作，且其较均相催化剂催化活性更高，易回收可重复利用，能有效降低生产成本，对环境友好。利用上述固载化配合铂催化剂合成聚醚改性硅氧烷，副反应物少，产物外观清澈透亮且具有极低的表面张力和突出的铺展性能。The embodiments of the present invention disclose a kind of immobilized platinum catalyst, polyether-modified siloxane and preparation method. A kind of preparation method of immobilized platinum catalyst, comprising: dissolving polyethylene glycol and platinum source in ethanol to obtain a mixed solution; adding a carrier, impregnating, drying, and obtaining the immobilized platinum catalyst; wherein, the platinum source is chloroplatinic acid-isopropanol solution, and the molar concentration of platinum element in the mixed solution is 0.01-0.04mol/L. The preparation method of immobilized platinum catalyst provided by the present invention is simple and easy to operate, and its catalytic activity is higher than that of homogeneous catalysts, it is easy to recover and reuse, can effectively reduce production costs, and is environmentally friendly. The above-mentioned immobilized platinum catalyst is used to synthesize polyether-modified siloxane, with few side reactions, and the product appearance is clear and transparent and has extremely low surface tension and outstanding spreading performance.
Description
Technical Field
The invention belongs to the technical field of platinum catalysts, and particularly relates to an immobilized matched platinum catalyst, polyether modified siloxane and a preparation method thereof.
Background
Polyether modified siloxanes can be classified into hydrolysis type and non-hydrolysis type according to the connection form of the silicon atom on the siloxane segment and the polyether segment, wherein the connection by Si-O-C bond is called hydrolysis type, the structure is unstable and easy to hydrolyze, and the connection by Si-C bond is called non-hydrolysis type, the structure is stable and difficult to hydrolyze. The special structural performance of the non-hydrolytic polyether modified siloxane becomes a variety with the largest yield in the modified siloxane product, and has wide application prospect in a plurality of fields such as textile, light industry, medical treatment, coating and the like.
At present, the synthetic polyether modified siloxane mainly utilizes hydrosilylation reaction between siloxane and polyether, and the reaction can be performed under the action of a catalyst. On the one hand, the reaction can be catalyzed by ultraviolet light, peroxides, azo compounds or heating, but the reaction is greatly limited due to poor selectivity and the difficulty in avoiding side reactions such as polymerization of unsaturated bonds in some systems. On the other hand, transition metals like platinum, palladium, germanium can be used as catalysts for the reaction.
The catalyst for synthesizing polyether modified siloxane is mainly a homogeneous platinum catalyst, and when in use, the catalyst needs to react with an organic solvent firstly and then coexist with a reactant in a liquid phase to carry out hydrosilylation reaction. However, the used catalyst is difficult to separate and recycle from the system, so that the noble metal platinum is wasted, meanwhile, the catalyst residues exist in the product, a metal container is easy to erode, the color appearance of the product is also influenced, and the product has the defect of low catalytic activity for certain reactions, so that the quality of the final product is poor.
In view of the above, it is important to find a green, economical and easy-to-prepare catalyst which is applied to a hydrosilylation reaction system to prepare polyether-modified siloxane with excellent performance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an immobilized matched platinum catalyst, polyether modified siloxane and a preparation method thereof.
In order to achieve the above object, the embodiment of the present invention provides the following technical solutions:
according to a first aspect of an embodiment of the present invention, the present invention provides a method for preparing an immobilized complex platinum catalyst, including:
dissolving polyethylene glycol and a platinum source in ethanol to obtain a mixed solution;
Adding a carrier, dipping and drying to obtain the immobilized complex platinum catalyst;
The platinum source is chloroplatinic acid-isopropanol solution, and the molar concentration of platinum element in the mixed solution is 0.01-0.04 mol/L.
According to the invention, when the immobilized platinum catalyst is prepared by an impregnation method, the polyethylene glycol is used, so that the loading capacity of the impregnation liquid on the carrier can be obviously improved, and the activity of the obtained catalyst is further improved.
Further, the polyethylene glycol is used as a complexing agent, and the mass volume ratio of the polyethylene glycol to the ethanol is 1.5-2.5 g:15mL.
Further, the carrier is silica gel, al 2O3 or active carbon, and the mass ratio of the carrier to the polyethylene glycol is 4.0-6.0:1.5-2.5.
Further, the soaking time is 24-36 h, and the drying temperature is 80-100 ℃.
According to a second aspect of embodiments of the present invention, there is provided an immobilized complex platinum catalyst made by the method as described in any one of the preceding claims.
According to a third aspect of embodiments of the present invention, the present invention provides a method for preparing polyether modified siloxane, comprising the steps of:
Polyether and the immobilized platinum catalyst are heated for 30-60 min at 75-80 ℃, siloxane is added, the temperature is raised to 120-140 ℃ and the heat preservation reaction is carried out for 5-8 h, wherein the molecular weight of the siloxane is 250-20000, and the hydrogen content is 0.2% -1.0%.
Further, the molar ratio of the siloxane to the polyether is 1.0:1.0-1.5, and the dosage of the immobilized complex platinum catalyst is 10-35 mug/g based on the total mass of the siloxane and the polyether.
In some specific embodiments, the preparation method of the polyether modified siloxane comprises the steps of adding polyether and the synthesized immobilized platinum catalyst into a four-neck flask with a reflux condenser, a thermometer and a stirrer, stirring the polyether and the platinum catalyst uniformly without introducing nitrogen, heating to 75-80 ℃ for catalyst activation for 30-60 min, adding the siloxane into the system, heating to 120-140 ℃ for heat preservation reaction for 5-8 h. The molar ratio of the added siloxane to the polyether is 1.0:1.0-1.5, the dosage of the immobilized complex platinum catalyst is 10-35 mug/g, and finally the reaction conversion rate of the siloxane in the reaction is determined by measuring the hydrogen content. And after the reaction is finished, filtering, separating and immobilizing to match with a platinum catalyst to obtain polyether modified siloxane.
The polyether has the structural formula:
Wherein n=2-7, -R is-H, -CH 3 or-CH 2CH3.
The siloxane has the structural formula:
wherein x, y=1, 2,3, the molecular weight is 250-20000, and the hydrogen content is 0.2% -1.0%.
The hydrosilylation reaction formula is:
wherein x, y=1, 2,3, n=an integer from 2 to 7,
-R is-H, -CH 3 or-CH 2CH3.
According to a fourth aspect of embodiments of the present invention, there is provided a polyether modified siloxane made by the method as described in any one of the above.
The embodiment of the invention has the following advantages:
1. The preparation method of the immobilized complex platinum catalyst provided by the invention is simple and feasible, can be recycled after being recovered, has higher activity after being used for four times, greatly reduces the production cost and is environment-friendly;
2. Compared with the traditional homogeneous platinum catalyst and the common immobilized catalyst, the immobilized complex platinum catalyst provided by the invention has the advantages of strong loading and high catalytic activity;
3. The preparation method of the polyether modified siloxane is simple, the catalyst usage amount is small, no catalyst residue exists in the product, and the product has clear and transparent appearance, extremely low surface tension and outstanding spreadability.
Detailed Description
Other advantages and advantages of the present invention will become apparent to those skilled in the art from the following detailed description, which, by way of illustration, is to be read in connection with certain specific embodiments, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Chloroplatinic acid-isopropanol solution available from Nanjing chemical reagents, inc.
Example 1
(1) The preparation of the immobilized complex platinum catalyst comprises the steps of dissolving 2.0g of polyethylene glycol (PEG) in 15mL of ethanol, adding 4mL of chloroplatinic acid-isopropanol solution, uniformly stirring, adding 4.0g of silica gel, soaking for 24 hours, and drying at 80 ℃ to finally prepare the immobilized complex platinum catalyst.
(2) The preparation of polyether modified siloxane comprises the steps of adding 274.37g of allyl polyether and 0.01g of synthesized immobilized platinum catalyst into a four-neck flask with a reflux condenser, a thermometer and a stirrer, stirring the allyl polyether and the platinum catalyst uniformly without introducing nitrogen, heating to 75-80 ℃ for catalyst activation for 30min, adding 225.63g of siloxane with molecular weight of 250 and hydrogen content of 0.5% into the system, heating to 120 ℃, and reacting for 6h in a heat-preserving way. Wherein the mol ratio of the added siloxane to the polyether is 1.0:1.0, the catalyst dosage is 20 mug/g, and finally the reaction conversion rate of the silane in the reaction is determined by measuring the hydrogen content. And after the reaction is finished, filtering, separating and immobilizing to match with a platinum catalyst to obtain polyether modified siloxane.
Example 2
(1) The preparation of the immobilized complex platinum catalyst comprises the steps of dissolving 2.0g of PEG in 15mL of ethanol, adding 4mL of chloroplatinic acid-isopropanol solution, uniformly stirring, adding 4.0g of silica gel, soaking for 24 hours, and drying at 90 ℃ to finally prepare the immobilized complex platinum catalyst.
(2) The preparation of polyether modified siloxane comprises the steps of adding 210.92g of allyl polyether and 0.01g of immobilized platinum catalyst into a flask, stirring the allyl polyether and the platinum catalyst uniformly without introducing nitrogen, heating to 75-80 ℃ for catalyst activation for 30min, adding 289.08g of siloxane with molecular weight of 500 and hydrogen content of 0.5% into the system, heating to 130 ℃ for heat preservation reaction for 6h. Wherein the mol ratio of the added siloxane to the polyether is 1.0:1.2, the catalyst dosage is 20 mug/g, and finally the reaction conversion rate of the silane in the reaction is determined by measuring the hydrogen content. And after the reaction is finished, filtering, separating and immobilizing to match with a platinum catalyst to obtain polyether modified siloxane.
Example 3
(1) The preparation of the immobilized complex platinum catalyst comprises the steps of dissolving 2.5g of PEG in 15mL of ethanol, adding 4mL of chloroplatinic acid-isopropanol solution, uniformly stirring, adding 4.0g of aluminum oxide, soaking for 36h, and drying at 90 ℃ to obtain the immobilized complex platinum catalyst.
(2) The preparation of polyether modified siloxane comprises the steps of adding 296.68g of allyl polyether and 0.01g of immobilized platinum catalyst into a flask, stirring the allyl polyether and the platinum catalyst uniformly without introducing nitrogen, heating to 75-80 ℃ for catalyst activation for 30min, adding 203.32g of siloxane with molecular weight of 250 and hydrogen content of 0.7% into the system, heating to 130 ℃ for heat preservation reaction for 7h. Wherein the mol ratio of the added siloxane to the polyether is 1.0:1.2, the catalyst dosage is 20 mug/g, and finally the reaction conversion rate of the silane in the reaction is determined by measuring the hydrogen content. And after the reaction is finished, filtering, separating and immobilizing to match with a platinum catalyst to obtain polyether modified siloxane.
Example 4
(1) The preparation of the immobilized complex platinum catalyst comprises the steps of dissolving 2.5g of PEG in 15mL of ethanol, adding 4mL of chloroplatinic acid-isopropanol solution, uniformly stirring, adding 4.0g of activated carbon, soaking for 36h, and drying at 80 ℃ to obtain the immobilized complex platinum catalyst.
(2) The preparation of polyether modified siloxane comprises adding 189.05g allyl polyether and 0.0075g immobilized platinum catalyst into a flask, stirring them uniformly without introducing nitrogen gas, heating to 75-80deg.C for catalyst activation for 30min, adding 310.95g siloxane with molecular weight of 500 and hydrogen content of 0.7% into the above system, heating to 130deg.C, and reacting for 7 hr. Wherein the mol ratio of the added siloxane to the polyether is 1.0:1.0, the catalyst dosage is 15 mug/g, and finally the reaction conversion rate of the silane in the reaction is determined by measuring the hydrogen content. And after the reaction is finished, filtering, separating and immobilizing to match with a platinum catalyst to obtain polyether modified siloxane.
Example 5
(1) The preparation of the immobilized complex platinum catalyst comprises the steps of dissolving 2.5g of PEG in 15mL of ethanol, adding 4mL of chloroplatinic acid-isopropanol solution, uniformly stirring, adding 5.0g of aluminum oxide, soaking for 36h, and drying at 90 ℃ to obtain the immobilized complex platinum catalyst.
(2) The preparation of polyether modified siloxane comprises adding 163.62g allyl polyether and 0.0075g immobilized platinum catalyst into a flask, stirring them uniformly without introducing nitrogen gas, heating to 75-80deg.C for catalyst activation for 30min, adding 336.38g siloxane with molecular weight of 750 and hydrogen content of 0.5% into the above system, heating to 120deg.C, and reacting for 8 hr. Wherein the mol ratio of the added siloxane to the polyether is 1.0:1.2, the catalyst dosage is 15 mug/g, and finally the reaction conversion rate of the silane in the reaction is determined by measuring the hydrogen content. And after the reaction is finished, filtering, separating and immobilizing to match with a platinum catalyst to obtain polyether modified siloxane.
Example 6
(1) The preparation of the immobilized complex platinum catalyst comprises the steps of dissolving 2.5g of PEG in 15mL of ethanol, adding 4mL of chloroplatinic acid-isopropanol solution, uniformly stirring, adding 5.0g of activated carbon, soaking for 36h, and drying at 90 ℃ to obtain the immobilized complex platinum catalyst.
(2) The preparation of polyether modified siloxane comprises the steps of adding 189.05g of allyl polyether and 0.005g of immobilized platinum catalyst into a flask, stirring the allyl polyether and the platinum catalyst uniformly without introducing nitrogen, heating to 75-80 ℃ for catalyst activation for 30min, adding 310.95g of siloxane with molecular weight of 500 and hydrogen content of 0.5% into the system, heating to 120 ℃ for heat preservation reaction for 8h. Wherein the mol ratio of the added siloxane to the polyether is 1.0:1.0, the catalyst dosage is 10 mug/g, and finally the reaction conversion rate of the silane in the reaction is determined by measuring the hydrogen content. And after the reaction is finished, filtering, separating and immobilizing to match with a platinum catalyst to obtain polyether modified siloxane.
Example 7
(1) The preparation of the immobilized complex platinum catalyst comprises the steps of dissolving 2.5g of PEG in 15mL of ethanol, adding 4mL of chloroplatinic acid-isopropanol solution, uniformly stirring, adding 5.0g of activated carbon, soaking for 36h, and drying at 90 ℃ to obtain the immobilized complex platinum catalyst.
(2) The preparation of polyether modified siloxane comprises adding 9.27g allyl polyether and 0.005g immobilized platinum catalyst into a flask, stirring the allyl polyether and the platinum catalyst uniformly without introducing nitrogen, heating to 75-80 ℃ for catalyst activation for 30min, adding 490.73g siloxane with molecular weight of 19306 and hydrogen content of 0.2% into the system, heating to 130 ℃ for heat preservation reaction for 8h. Wherein the mol ratio of the added siloxane to the polyether is 1.0:1.2, the catalyst dosage is 10 mug/g, and finally the reaction conversion rate of the silane in the reaction is determined by measuring the hydrogen content. And after the reaction is finished, filtering, separating and immobilizing to match with a platinum catalyst to obtain polyether modified siloxane.
Comparative example 1
274.37G of allyl polyether and 1.22mL of chloroplatinic acid-isopropanol solution are added into a flask together, nitrogen is not required to be introduced into the flask, the allyl polyether and the solution are stirred uniformly, the temperature is raised to 75-80 ℃ for catalyst activation for 30min, 225.63g of siloxane with the molecular weight of 250 and the hydrogen content of 0.5% are added into the system, and the temperature is raised to 120 ℃ for heat preservation reaction for 6h. Wherein the mol ratio of the added siloxane to the polyether is 1.0:1.0, the catalyst dosage is 20 mug/g, the mol concentration of platinum element in chloroplatinic acid-isopropanol solution is 0.02mol/L, and finally the reaction conversion rate of silane in the reaction is determined by measuring the hydrogen content. And after the reaction is finished, filtering, separating and immobilizing to match with a platinum catalyst to obtain polyether modified siloxane.
Comparative example 2
210.92G of allyl polyether and 1.22mL of chloroplatinic acid-isopropanol solution are added into a flask together, nitrogen is not required to be introduced into the flask, the allyl polyether and the solution are stirred uniformly, the temperature is raised to 75-80 ℃ for catalyst activation for 30min, 289.08g of siloxane with molecular weight of 500 and hydrogen content of 0.5% are added into the system, and the temperature is raised to 130 ℃ for heat preservation reaction for 6h. Wherein the mol ratio of the added siloxane to the polyether is 1.0:1.2, the catalyst dosage is 20 mug/g, the mol concentration of platinum element in chloroplatinic acid-isopropanol solution is 0.02mol/L, and finally the reaction conversion rate of silane in the reaction is determined by measuring the hydrogen content. And after the reaction is finished, filtering, separating and immobilizing to match with a platinum catalyst to obtain polyether modified siloxane.
Comparative example 3
163.62G of allyl polyether and 1.22mL of chloroplatinic acid-isopropanol solution are added into a flask together, nitrogen is not required to be introduced into the flask, the allyl polyether and the solution are stirred uniformly, the temperature is raised to 75-80 ℃ for catalyst activation for 30min, 336.38g of siloxane with molecular weight of 750 and hydrogen content of 0.5% are added into the system, and the temperature is raised to 120 ℃ for heat preservation reaction for 8h. Wherein the mol ratio of the added siloxane to the polyether is 1.0:1.2, the catalyst dosage is 20 mug/g, the mol concentration of platinum element in chloroplatinic acid-isopropanol solution is 0.02mol/L, and finally the reaction conversion rate of silane in the reaction is determined by measuring the hydrogen content. And after the reaction is finished, filtering, separating and immobilizing to match with a platinum catalyst to obtain polyether modified siloxane.
Comparative example 4
9.27G of allyl polyether and 1.22mL of chloroplatinic acid-isopropanol solution are added into a flask together, the allyl polyether and the solution are stirred uniformly without introducing nitrogen, the temperature is raised to 75-80 ℃ for catalyst activation for 30min, then 490.73g of siloxane with molecular weight of 19306 and hydrogen content of 0.2% are added into the system, and the temperature is raised to 130 ℃ for heat preservation reaction for 8h. Wherein the mol ratio of the added siloxane to the polyether is 1.0:1.2, the catalyst dosage is 20 mug/g, and finally the reaction conversion rate of the silane in the reaction is determined by measuring the hydrogen content, so as to obtain the polyether modified siloxane.
The catalyst used in comparative examples 1 to 4 was an isopropyl alcohol solution of chloroplatinic acid, and it was difficult to recycle the catalyst after the completion of the reaction, which greatly increased the production cost and caused waste of resources. In addition, the conversion of the reaction product is low, and the product is yellow and unstable in performance. The immobilized platinum catalyst in the embodiment 7 can not only solve the defect that the catalyst cannot be recovered after reaction by simple filtration, but also improve the conversion rate of the product, and the obtained product has clear and transparent appearance and stable performance, and the catalyst can be recovered and recycled for 4 times, so that the production cost is greatly reduced, and the method accords with the strategy of sustainable development.
Comparative example 5
(1) The preparation of the immobilized complex platinum catalyst comprises the steps of adding 15mL of ethanol into 4mL of chloroplatinic acid-isopropanol solution, uniformly stirring, adding 5.0g of activated carbon, soaking for 36h, and drying at 90 ℃ to finally prepare the immobilized complex platinum catalyst.
(2) The preparation of polyether modified siloxane comprises adding 9.27g allyl polyether and 0.01g immobilized platinum catalyst into a flask, stirring the allyl polyether and the platinum catalyst uniformly without introducing nitrogen, heating to 75-80 ℃ for catalyst activation for 30min, adding 490.73g siloxane with molecular weight of 19306 and hydrogen content of 0.2% into the system, heating to 130 ℃ for heat preservation reaction for 8h. Wherein the mol ratio of the added siloxane to the polyether is 1.0:1.2, the catalyst dosage is 20 mug/g, and finally the reaction conversion rate of the silane in the reaction is determined by measuring the hydrogen content. And after the reaction is finished, filtering, separating and immobilizing to match with a platinum catalyst to obtain polyether modified siloxane.
Comparative example 6
(1) The preparation of the immobilized complex platinum catalyst comprises the steps of taking 4mL of chloroplatinic acid-isopropanol solution, adding 15mL of ethanol, uniformly stirring, adding 5.0g of aluminum oxide, soaking for 36h, and drying at 90 ℃ to finally prepare the immobilized complex platinum catalyst.
(2) The preparation of polyether modified siloxane comprises the steps of adding 163.62g of allyl polyether and 0.01g of immobilized platinum catalyst into a flask, stirring the allyl polyether and the platinum catalyst uniformly without introducing nitrogen, heating to 75-80 ℃ for catalyst activation for 30min, adding 336.38g of siloxane with molecular weight of 750 and hydrogen content of 0.5% into the system, heating to 120 ℃ for heat preservation reaction for 8h. Wherein the mol ratio of the added siloxane to the polyether is 1.0:1.2, the catalyst dosage is 20 mug/g, and finally the reaction conversion rate of the silane in the reaction is determined by measuring the hydrogen content. And after the reaction is finished, filtering, separating and immobilizing to match with a platinum catalyst to obtain polyether modified siloxane.
The catalysts described in comparative examples 5 to 6 were impregnated with a carrier with a chloroplatinic acid solution alone, whereas the immobilized complex platinum catalysts of examples 1 to 7 were prepared by adding polyethylene glycol as a complexing agent to the impregnation solution. The use of polyethylene glycol can make the impregnating solution be better loaded on the carrier, so as to raise the catalyst content on the carrier.
Test example 1
Determination of Properties of polyether modified siloxanes
(1) The determination of the hydrogen content is carried out by a sodium thiosulfate titration method, about 0.1g of the polyether modified siloxane samples prepared in the examples 1-7 and the comparative examples 1-6 are taken and placed in a 250mL iodometric bottle, 20mL of carbon tetrachloride is taken to dissolve the polyether modified siloxane samples, 10mL of bromine-acetic acid solution with the concentration of 0.2mol/L and 0.5mL of water are added to the polyether modified siloxane samples, shaking is carried out, liquid sealing is carried out by deionized water, the mixture is placed in a dark place to react for 30min, 25mL of KI solution with the mass fraction of 10% is added, the bottle mouth is washed by deionized water, the starch solution with the mass fraction of 1% is dropwise added as an indicator, titration is carried out by 0.1mol/L of sodium thiosulfate solution, and when the solution is converted from blue to colorless, the end point is obtained, and a blank test is carried out. The calculation formula is as follows:
w=M(V0-V1)*0.5/(G*1000)*100%
wherein w is the mass fraction (%) of active hydrogen in the sample;
M is the molar concentration (mol/L) of the standard solution of sodium thiosulfate
V 0 is the volume of blank consumed sodium thiosulfate solution (mL);
V 1 is the volume of sample consumed sodium thiosulfate solution (mL);
g is the sample mass (G).
After the mass fraction of active hydrogen is calculated, the conversion of Si-H can be calculated as follows:
Si-H conversion= (w 0-w1)/w0 x 100%
Wherein w 0 is the mass fraction (%) of active hydrogen before reaction;
w 1 is the mass fraction (%) of active hydrogen after the reaction.
The conversion of polyether-modified siloxane and the measurement result of the color state of the product are shown in Table 1.
TABLE 1
| Conversion (%) | Product color status | |
| Example 1 | 88.3 | Transparent and transparent |
| Example 2 | 86.5 | Transparent and transparent |
| Example 3 | 88.4 | Transparent and transparent |
| Example 4 | 89.7 | Transparent and transparent |
| Example 5 | 90.2 | Transparent and transparent |
| Example 6 | 93.5 | Transparent and transparent |
| Example 7 | 96.8 | Transparent and transparent |
| Comparative example 1 | 87.0 | Pale yellow |
| Comparative example 2 | 86.0 | Pale yellow |
| Comparative example 3 | 89.4 | Pale yellow |
| Comparative example 4 | 87.9 | Pale yellow |
| Comparative example 5 | 90.3 | Transparent and transparent |
| Comparative example 6 | 87.2 | Transparent and transparent |
As can be seen from Table 1, the polyether modified siloxanes prepared in examples 1-7 using the catalyst of the immobilized platinum catalyst were clear and transparent in color and had higher conversion in the same synthesis process. In comparative examples 1 to 4, the product was pale yellow in color and the conversion was relatively low when the catalyst used for the hydrosilylation reaction was an isopropanol solution of chloroplatinic acid. The catalyst used in comparative examples 5-6 is an immobilized complex platinum catalyst prepared without adding complexing agent polyethylene glycol, and the synthesis process is the same as that of the catalyst prepared by adding complexing agent polyethylene glycol for impregnation in comparative example 7 and comparative example 5 and comparative example 6, so that the catalyst dosage is less, the conversion rate of catalytic polyether modified siloxane is higher, and the immobilized complex platinum catalyst provided by the invention has higher catalytic activity, and the loading of platinum in the carrier is improved by adding polyethylene glycol.
(2) Determination of HLB value Using the modified titration method of Green's, 0.2g of the polyether-modified siloxane samples prepared in examples 1 to 7 and comparative examples 1 to 6 described above were dissolved in 20mL of dioxane/benzene (90% by volume/4% by volume), and then titrated with distilled water to a clear visible turbidity. The number of milliliters of water used is referred to as the water value V. The HLB value is calculated by using the water value V, and the calculation formula is as follows:
HLB=23.6lgV-10.6
The measurement results are shown in Table 2.
TABLE 2
As can be seen from Table 2, the HLB values of the polyether-modified siloxanes in examples 1 to 7 are close to those of comparative examples 1 to 6, indicating that the products obtained by the preparation method of the polyether-modified siloxanes catalyzed by the immobilized platinum catalyst provided by the invention are more suitable for wetting and permeation.
(3) And (3) measuring the surface tension, namely preparing a polyether modified siloxane sample into a solution with the mass fraction of 0.1% by using a full-automatic interfacial tension meter, controlling the temperature of the solution to be 25 ℃, measuring the corresponding aqueous solutions of the polyether modified siloxanes prepared in the examples 1-7 and the comparative examples 1-6 by using a platinum ring method, and repeating the steps for three times to obtain an average value.
The measurement results are shown in Table 3.
TABLE 3 Table 3
As can be seen from Table 3, the surface tension of the product obtained by the synthetic process for preparing polyether-modified siloxane according to the present invention is generally lower, and the surface tension of the product of example 7, which is the immobilized platinum catalyst according to the present invention, is only 19.5mN/m.
(4) Measurement of spreading area 10. Mu.L of the test solution was taken with a pipette and dropped onto a plastic sheet labeled with cells, and after 120 seconds, the spreading area was obtained by the number of cells, and the average was taken three times. The spreading area of the aqueous solution of the polyether-modified siloxane prepared in examples 1 to 7 and comparative examples 1 to 6, respectively, was determined by the above-described method to be 0.1% by mass.
The measurement results are shown in Table 4.
TABLE 4 Table 4
As can be seen from Table 4, the aqueous solution of the polyether-modified siloxane prepared by the immobilization of the example and the catalysis of the platinum catalyst has a larger spreading area, and particularly, the polyether-modified siloxane prepared by the example 7 has excellent wettability.
Test example 2
(1) Catalyst recycling performance test
The immobilized complex platinum catalyst provided by the invention is filtered, separated and dried after once hydrosilylation, and is reused, and the catalyst reuse performance is tested by repeatedly carrying out hydrosilylation reaction in example 7 and recording the siloxane conversion rate.
The measurement results are shown in Table 5.
TABLE 5
| Number of repetitions | 1 | 2 | 3 | 4 |
| Conversion (%) | 96.3 | 95.6 | 94.2 | 92.7 |
As shown in Table 5, the polyether modified siloxane prepared by the immobilized platinum catalyst of the embodiment of the invention after being repeatedly used for 4 times has a conversion rate of 92.7%, and the conversion rate can be maintained higher, which indicates that the catalyst provided by the invention can be recycled.
In conclusion, the immobilized complex platinum catalyst prepared by the invention can not only improve the catalytic activity of the catalyst, but also ensure that the obtained polyether modified siloxane has excellent wettability, clear and transparent appearance, and the catalyst can be recycled, thereby greatly reducing the production cost and being beneficial to sustainable development.
While the invention has been described in detail in the foregoing general description and specific examples, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (2)
1. The preparation method of the polyether modified siloxane is characterized by comprising the following steps:
Heating polyether and an immobilized platinum catalyst at 75-80 ℃ for 30-60 min, adding siloxane, heating to 120-140 ℃, and reacting for 5-8 h at a temperature maintained, wherein the molecular weight of the siloxane is 250-20000, and the hydrogen content is 0.2% -1.0%;
the preparation method of the immobilized complex platinum catalyst comprises the following steps:
dissolving polyethylene glycol and a platinum source in ethanol to obtain a mixed solution;
Adding a carrier, dipping and drying to obtain the immobilized complex platinum catalyst;
Wherein the platinum source is chloroplatinic acid-isopropanol solution, and the molar concentration of platinum element in the mixed solution is 0.02mol/L;
the mass volume ratio of the polyethylene glycol to the ethanol is 2.5g to 15mL;
the carrier is activated carbon, and the mass ratio of the carrier to the polyethylene glycol is 5.0:2.5;
The soaking time is 36 hours, and the drying temperature is 90 ℃;
The mol ratio of the siloxane to the polyether is 1.0:1.2, and the dosage of the immobilized complex platinum catalyst is 10 mug/g based on the total mass of the siloxane and the polyether.
2. Polyether modified siloxane, characterized in that it is produced by the process according to claim 1.
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| CN109957104A (en) * | 2019-04-03 | 2019-07-02 | 杭州硅途新材料科技有限公司 | A method of using the modified trisiloxanes of solid-borne platinum catalyst synthesizing polyether |
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