Nickel catalyst and application thereof in preparation of polyether organosilicon copolymer
The nickel complex catalyst addresses inefficiencies in polyether silicone copolymer preparation by offering a cost-effective and efficient synthesis method, enhancing reaction compatibility and reducing production costs while producing suitable foam stabilizers for polyurethane foam.
Patent Information
- Application Number
- CN202411242226.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-05
- Publication Date
- 2024-12-13
AI Technical Summary
Existing methods for preparing polyether silicone copolymers using inorganic platinum salt catalysts face inefficiencies due to poor solubility and high costs, leading to incomplete reactions and increased production expenses.
A nickel complex catalyst is synthesized by reacting polyether with tetraethyl orthosilicate and a sodium salt of carboxyethylsilanetriol, followed by acid washing and reaction with a nickel salt, then used to catalyze the hydrosilylation of hydrogen-containing polysiloxane and allyl polyether with a molar ratio of 1:1.0-1.1, incorporating a long alkyl chain.
The nickel catalyst provides efficient, cost-effective, and environmentally friendly preparation of polyether organosilicon copolymers, suitable for foam stabilizers in polyurethane foam, with improved reaction compatibility and reduced material costs.
Smart Images
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Abstract
Description
Technical Field
[0001] The invention belongs to the field of chemical industry, and particularly relates to a nickel complex containing a long alkyl chain and application of the nickel complex in preparing a polyether organosilicon copolymer. Background Art
[0002] Polyether silicone copolymer is a new type of surfactant, which contains polysiloxane and polyether in its unique molecular structure. The polysiloxane part gives the surfactant the characteristics of low surface tension, antistatic and physiological inertness. By adjusting the polymerization degree and ratio of ethylene oxide (EO) and propylene oxide (PO) of polyether, as well as the ratio of polyether and polysiloxane, silicone surfactants with different properties and uses can be obtained. They can be widely used in coating industry, polyurethane, pesticide and daily chemical industry.
[0003] The key reaction in the preparation of polyether silicone copolymers is the addition reaction of hydrogen-containing polysiloxane and allyl polyether. This reaction generally uses an inorganic platinum salt catalyst, which has poor fat solubility and often does not contact the hydrogen-containing polysiloxane sufficiently during the reaction, affecting the reaction efficiency. In addition, platinum catalysts are relatively expensive, greatly increasing production costs. Summary of the invention
[0004] In order to overcome the defects of the prior art, the present invention provides a method for preparing a nickel catalyst and application of the nickel catalyst in preparing a polyether organosilicon copolymer.
[0005] Firstly, polyether, tetraethyl orthosilicate and sodium salt of carboxyethylsilanetriol are chemically reacted, and the obtained product is acid-washed to obtain a catalyst intermediate; the intermediate is then reacted with a nickel salt to obtain a corresponding nickel complex catalyst.
[0006] The polyether is selected from polyethylene oxide, polypropylene oxide and copolymers thereof with a molecular weight of 2000-6000; the nickel salt is selected from nickel chloride, nickel nitrate, nickel bromide and the like.
[0007] On the other hand, the polyether organosilicon copolymer is prepared by using the nickel catalyst, hydrogen-containing polysiloxane and allyl polyether are weighed, and the molar ratio thereof is 1.0:(1.0-1.1), and then the nickel complex containing a long alkyl chain is added, and the amount of the nickel complex is 1-5% of the hydrogen-containing polysiloxane. Finally, the hydrogen-containing polysiloxane and allyl polyether are reacted by hydrosilylation under the catalysis of the nickel complex to prepare the polyether organosilicon copolymer.
[0008] Wherein, the allyl polyether is selected from allyl polyethers with a molecular weight of 500-2400.
[0009] Furthermore, the allyl polyether is selected from the allyl polyethers with molecular weights of 580, 700, 800, 900, 1000, 2000 and 2400.
[0010] The beneficial effects of the present invention are:
[0011] The present invention provides a method for preparing a nickel complex catalyst. This new type of catalyst is convenient to source and low in cost, and its price is one percent of that of a general platinum / palladium catalyst. In addition, this type of catalyst contains a silicon-based structure, has good compatibility with hydrogen-containing polysiloxane, and can fully contact with hydrogen-containing polysiloxane and allyl polyether, thereby efficiently catalyzing the reaction of the two to prepare a polyether organosilicon copolymer. The organosilicon copolymer prepared by the method is particularly suitable for a foam stabilizer for polyurethane foam, especially a foam stabilizer for mechanical whipping foaming of polyurethane. In short, the method has cheap reagents, simpler formula, and more convenient operation. At the same time, it is green, safe, efficient, and environmentally friendly, and is suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS
[0012] Figure 1 High-resolution XPS images of catalysts C2 and C8. DETAILED DESCRIPTION
[0013] Preparation of nickel complex catalyst (general step 1):
[0014] In the first step, 2 grams of polyether is dissolved in 60 grams of 2 mol / L hydrochloric acid, and the resulting solution is stirred at 50 degrees for 4 hours, and then a solution containing 24 grams of carboxyethylsilanetriol sodium salt and 96 grams of ethyl orthosilicate is added dropwise thereto. After the addition is complete, the solution is stirred at 50 degrees for 12 hours. The resulting white suspension is aged at 100 degrees for 24 hours, filtered, and the filter cake is washed with deionized water and dried to obtain a white solid.
[0015] In the second step, 1 gram of the white solid obtained in the previous step was taken and dispersed in 250 ml of 48 wt% sulfuric acid. The resulting mixed system was stirred and reacted at 100 degrees for 24 hours, filtered, and the filter cake was washed with deionized water and dried to obtain a catalyst intermediate.
[0016] In the third step, 0.5 g of the catalyst intermediate obtained in the previous step was taken and dispersed in 50 ml of 0.05 M nickel salt solution. Under continuous stirring, 0.1 M sodium hydroxide solution was added dropwise to the solution to make the pH value reach 9. At this time, a light green solid was precipitated, filtered, and the filter cake was washed with deionized water and dried to obtain a light green solid. Further, the solid was calcined at 600 degrees in a mixed gas atmosphere of argon and hydrogen (95:5) for 8 hours, cooled to obtain the target catalyst, and stored in a vacuum drying oven.
[0017] Preparation of polyether silicone copolymer by reaction of hydrogen-containing polysiloxane and allyl polyether (general step 2):
[0018] In a reaction kettle, hydrogen-containing polysiloxane (silicon hydrogen content of 0.18%, viscosity of 10-20cp) and allyl polyether are added in a molar ratio of 1:1, and then 1wt% of the above nickel complex M is added, and the temperature is raised to 80-100°C for reaction for 6-8h to obtain a polyether silicone copolymer.
[0019] Example 1 Preparation of Nickel Complex C1
[0020] According to general step 1, the polyether is selected from polyethylene oxide with a molecular weight of 2000, and the nickel salt is selected from nickel bromide to obtain 0.694 g of nickel complex C1 with a yield of 82%.
[0021] Example 2 Preparation of Nickel Complex C2
[0022] According to general step 1, the polyether is selected from polyethylene oxide with a molecular weight of 4000, and the nickel salt is selected from nickel chloride to obtain 0.625g of nickel complex C2 with a yield of 85%. Characterization data are attached Figure 1 .
[0023] Example 3 Preparation of Nickel Complex C3
[0024] According to general step 1, the polyether is selected from polyethylene oxide with a molecular weight of 6000, and the nickel salt is selected from nickel nitrate to obtain 0.698 g of nickel complex C3 with a yield of 87%.
[0025] Example 4 Preparation of Nickel Catalyst C4
[0026] According to general step 1, the polyether is selected from polypropylene oxide with a molecular weight of 2000, and the nickel salt is selected from nickel bromide to obtain 0.728 g of nickel complex C4 with a yield of 86%.
[0027] Example 5 Preparation of Nickel Complex C5
[0028] According to general step 1, the polyether is selected from polypropylene oxide with a molecular weight of 4000, and the nickel salt is selected from nickel chloride to obtain 0.596 g of nickel complex C5 with a yield of 81%.
[0029] Example 6 Preparation of Nickel Complex C6
[0030] According to general step 1, the polyether is selected from polypropylene oxide with a molecular weight of 6000, and the nickel salt is selected from nickel nitrate to obtain 0.665 g of nickel complex C6 with a yield of 83%.
[0031] Example 7 Preparation of Nickel Catalyst C7
[0032] According to general step 1, the polyether is selected from ethylene oxide and propylene oxide copolymer with a molecular weight of 2000, and the nickel salt is selected from nickel bromide to obtain 0.677 g of nickel complex C7 with a yield of 80%.
[0033] Example 8 Preparation of Nickel Complex C8
[0034] According to the general step 1, the polyether is selected from ethylene oxide and propylene oxide copolymer with a molecular weight of 4000, and the nickel salt is selected from nickel chloride to obtain 0.603g of nickel complex C8 with a yield of 82%. Characterization data are attached Figure 1 .
[0035] Example 9 Preparation of Nickel Complex C9
[0036] According to general step 1, the polyether is selected from ethylene oxide and propylene oxide copolymer with a molecular weight of 6000, and the nickel salt is selected from nickel nitrate to obtain 0.705 g of nickel complex C9 with a yield of 88%.
[0037] Example 10 Reaction of hydrogen-containing polysiloxane and allyl polyether with a molecular weight of 580
[0038] According to general step 2, the allyl polyether is selected from the allyl polyether with a molecular weight of 580, and the catalyst is selected from the complex C1 to obtain the corresponding polyether silicone copolymer P1.
[0039] Example 11 Reaction of hydrogen-containing polysiloxane and allyl polyether with a molecular weight of 700
[0040] According to general step 2, the allyl polyether is selected from the allyl polyether with a molecular weight of 700, and the catalyst is selected from the complex C2 to obtain the corresponding polyether silicone copolymer P2.
[0041] Example 12 Reaction of hydrogen-containing polysiloxane and allyl polyether with a molecular weight of 800
[0042] According to general step 2, the allyl polyether is selected from the allyl polyether with a molecular weight of 800, and the catalyst is selected from the complex C3 to obtain the corresponding polyether silicone copolymer P3.
[0043] Example 13 Reaction of hydrogen-containing polysiloxane and allyl polyether with a molecular weight of 900
[0044] According to general step 2, the allyl polyether is selected from the allyl polyether with a molecular weight of 900, and the catalyst is selected from the complex C4 to obtain the corresponding polyether silicone copolymer P4.
[0045] Example 14 Reaction of hydrogen-containing polysiloxane and allyl polyether with a molecular weight of 1000
[0046] According to general step 2, the allyl polyether is selected from the allyl polyether with a molecular weight of 1000, and the catalyst is selected from the complex C5 to obtain the corresponding polyether silicone copolymer P5.
[0047] Example 15 Reaction of hydrogen-containing polysiloxane and allyl polyether with a molecular weight of 2000
[0048] According to general step 2, the allyl polyether is selected from the allyl polyether with a molecular weight of 2000, and the catalyst is selected from the complex C6 to obtain the corresponding polyether silicone copolymer P6.
[0049] Example 16 Reaction of hydrogen-containing polysiloxane and allyl polyether with a molecular weight of 2400
[0050] According to general step 2, the allyl polyether is selected from the allyl polyether with a molecular weight of 2400, and the catalyst is selected from the complex C7 to obtain the corresponding polyether silicone copolymer P7.
[0051] Example 17 Reaction of hydrogen-containing polysiloxane and allyl polyether with a molecular weight of 2400
[0052] According to general step 2, the allyl polyether is selected from the allyl polyether with a molecular weight of 2400, and the catalyst is selected from the complex C8 to obtain the corresponding polyether silicone copolymer P8.
[0053] Example 18 Reaction of hydrogen-containing polysiloxane and allyl polyether with a molecular weight of 2400
[0054] According to general step 2, the allyl polyether is selected from the allyl polyether with a molecular weight of 2400, and the catalyst is selected from the complex C9 to obtain the corresponding polyether silicone copolymer P9.
[0055] Example 19 Reaction of hydrogen-containing polysiloxane and allyl polyether with a molecular weight of 700
[0056] According to general step 2, the allyl polyether is selected from an allyl polyether with a molecular weight of 700, and the catalyst is selected from complex C5 to obtain the corresponding polyether silicone copolymer P10.
[0057] Example 20 Reaction of polysiloxane and allyl polyether with molecular weight 700
[0058] According to general step 2, the allyl polyether is selected from an allyl polyether with a molecular weight of 700, and the catalyst is selected from complex C8 to obtain the corresponding polyether silicone copolymer P11.
[0059] The physical properties of polyether silicone copolymers P2, P10, and P11 prepared using catalysts C2\C5\C8 were measured. The control group used nickel acetylacetonate as a catalyst and followed general step 2. Allyl polyether was selected from allyl polyethers with a molecular weight of 700 to prepare silicone copolymers. The test results are shown in Table 1:
[0060]
[0061]
[0062] Table 1
[0063] It can be seen from the above test results that the catalyst of the present invention has a faster reaction than ordinary nickel acetylacetonate, and the raw materials can be completely converted in a shorter time. At the same time, the key properties of the polyether silicone copolymer can be greatly improved, which fully demonstrates the superiority of this type of nickel catalyst.
[0064] In addition, it is found that the polyether silicone copolymer prepared by the catalyst of the present invention has excellent cell stability and less catalyst usage when using whipping air into the polyurethane system.
[0065] Example 21, 5 parts of organosilicon copolymer P7 are added to a combination of 100 parts of polyether polyol A (trifunctionality, hydroxyl value 35) and 10 parts of dipropylene glycol, 2 parts of nickel acetylacetonate solution (concentration 10%) are added as a catalyst, and 25 parts of crude MDI are used to crosslink it. After air whipping for 5 minutes, the overall density can be reduced to 620g / L. The system has a room temperature operation time of 2 hours and a curing time of 5 minutes at 120 degrees Celsius.
[0066] Example 22: 5 parts of organosilicon copolymer P8 are added to a combination of 100 parts of polyether polyol A (trifunctionality, hydroxyl value 35) and 10 parts of dipropylene glycol, 2 parts of nickel acetylacetonate solution (concentration 10%) are added as a catalyst, and 25 parts of crude MDI are used to crosslink it. After air whipping for 5 minutes, the overall density can be reduced to 610 g / L. The system has a room temperature operation time of 2 hours and a curing time of 5 minutes at 120 degrees Celsius.
[0067] Example 23, 2.5 parts of organosilicon copolymer P8; 2.5 parts of macromolecular organosilicon block copolymer (Menhover S-9164) were added to a combination of 100 parts of polyether polyol A (trifunctional, hydroxyl value 35) and 10 parts of dipropylene glycol, 2 parts of nickel acetylacetonate solution (concentration 10%) were added as a catalyst, and 25 parts of crude MDI were used to crosslink it. After air whipping for 5 minutes, the overall density can be reduced to 480g / L. The system has a room temperature operation time of 2.5 hours and a curing time of 7 minutes at 120 degrees Celsius.
[0068] Comparative Example 1: 5 parts of organosilicon copolymer Menhover S-193 were added to 100 parts of polyether polyol A (trifunctionality, hydroxyl value 35) and 10 parts of dipropylene glycol, 2 parts of nickel acetylacetonate solution (concentration 10%) were added as a catalyst, and 25 parts of crude MDI were used to crosslink it. After air whipping for 5 minutes, the overall density can be reduced to 980g / L. The system has a room temperature operation time of 3 hours and a curing time of 10 minutes at 120 degrees Celsius.
Claims
1. A method for preparing a nickel complex catalyst, characterized in that: Firstly, polyether, tetraethyl orthosilicate and sodium salt of carboxyethylsilanetriol are chemically reacted, and the obtained product is acid-washed to obtain a catalyst intermediate; the intermediate is then reacted with a nickel salt to obtain a corresponding nickel catalyst.
2. The method for preparing a nickel complex catalyst according to claim 1, characterized in that: The polyether is selected from polyethylene oxide, polypropylene oxide or a copolymer thereof with a molecular weight of 2000-6000.
3. The method for preparing a nickel complex catalyst according to claim 1, characterized in that: The nickel salt is selected from nickel chloride, nickel nitrate or nickel bromide.
4. A method for preparing a polyether silicone copolymer, characterized in that: The nickel complex described in any one of claims 1 to 3 is used as a catalyst, and the steps include weighing hydrogen-containing polysiloxane and allyl polyether in a molar ratio of 1.0:(1.0-1.1), and then adding the nickel complex, wherein the amount of the nickel complex is 1-5% of the hydrogen-containing polysiloxane; finally, the hydrogen-containing polysiloxane and the allyl polyether are reacted by a hydrosilylation reaction under the catalysis of the nickel complex to prepare a polyether silicone copolymer.
5. The method according to claim 4, characterized in that The allyl polyether is selected from allyl polyethers with a molecular weight of 500-2400.
6. The method according to claim 4, characterized in that The allyl polyether is selected from allyl polyethers with a molecular weight of 580, 700, 800, 900, 1000, 2000 or 2400.
7. The polyether silicone copolymer prepared according to the method according to any one of claims 4 to 6 is used as a foaming stabilizer in polyurethane foaming.
8. The use according to claim 7, wherein the foaming and stabilizing agent is used for mechanically whipping polyurethane foaming.