Nickel catalyst and use thereof in preparation of polyether organosilicon copolymer

Abstract

Disclosed are a nickel complex containing a long alkyl chain, and the use thereof in the preparation of a polyether organosilicon copolymer. The catalyst comprises a silyl structure, and the organosilicon copolymer prepared thereby is particularly suitable for foam stabilizers for polyurethane foams, especially foam stabilizers for foaming achieved by mechanical stirring of polyurethane.

Description

Nickel catalyst and its use in the preparation of polyether silicone copolymers TECHNICAL FIELD

[0001] The present invention belongs to the field of chemical industry, and particularly relates to a nickel complex containing long alkyl chain and its use in the preparation of polyether silicone copolymers. BACKGROUND

[0002] Polyether silicone copolymer is a new type of surfactant with unique molecular structure containing both polysiloxane and polyether. The polysiloxane part endows the surfactant with low surface tension, antistatic and physiological inertness, etc. By adjusting the polymerization degree and ratio of ethylene oxide (EO) and propylene oxide (PO) of polyether, and the ratio of polyether and polysiloxane, different performance and purpose of silicone surfactants can be obtained, which can be widely applied in the industries of coating, polyurethane, pesticide and daily chemical, etc.

[0003] The key reaction in the preparation of polyether silicone copolymer is the addition reaction of hydrogen-containing polysiloxane and allyl polyether. Generally, inorganic platinum salt catalyst is used in the reaction. Such catalyst has poor liposolubility, and the contact with hydrogen-containing polysiloxane is often not sufficient enough, which affects the reaction efficiency. In addition, platinum catalyst is relatively expensive, which greatly increases the production cost.

[0004] SUMMARY

[0005] In order to overcome the defects of the prior art, the present invention provides a preparation method of nickel catalyst and its use in the preparation of polyether silicone copolymer.

[0006] Firstly, polyether, tetraethyl orthosilicate and carboxyethyl silanetriol sodium salt are chemically reacted to obtain a catalyst intermediate, which is then washed with acid; and the intermediate is reacted with nickel salt to obtain the corresponding nickel complex catalyst.

[0007] The polyether is selected from polyethylene oxide, polypropylene oxide and copolymer thereof with a molecular weight of 2000-6000; and the nickel salt is selected from nickel chloride, nickel nitrate, nickel bromide, etc.

[0008] On the other hand, the above-mentioned nickel catalyst is used to prepare polyether silicone copolymer. Hydrogen-containing polysiloxane and allyl polyether are weighed, and the molar ratio thereof is 1.0: (1.0-1.1); then the above-mentioned nickel complex containing long alkyl chain is added, and the amount of substance of the nickel complex is 1-5% of the hydrogen-containing polysiloxane. Finally, the hydrogen-containing polysiloxane and the allyl polyether are prepared into polyether silicone copolymer through silicon-hydrogen addition reaction under the catalysis of the nickel complex.

[0009] The allyl polyether is selected from allyl polyether with a molecular weight of 500-2400.

[0010] Further, the allyl polyether is selected from allyl polyether with molecular weight of 580, 700, 800, 900, 1000, 2000, 2400.

[0011] The beneficial effects of the present application are:

[0012] The present application provides a preparation method of a nickel complex catalyst. The new catalyst is convenient to obtain, low in cost, and one hundredth of the price of general platinum / palladium catalysts. In addition, the catalyst contains a silicon-based structure, has good compatibility with hydrogen-containing polysiloxane, can fully contact with hydrogen-containing polysiloxane and allyl polyether, and thus efficiently catalyzes the reaction of the two to prepare polyether silicone copolymer. The prepared silicone copolymer is particularly suitable for foam stabilizer of polyurethane foam, especially foam stabilizer of mechanically whipped polyurethane. In summary, the method is low in reagent cost, simple in formula, and convenient to operate, and is green, safe, efficient, and environmentally friendly, and is suitable for industrial production. BRIEF DESCRIPTION OF DRAWINGS

[0013] FIG. 1 is a high-resolution XPS diagram of catalysts C2 and C8. DETAILED DESCRIPTION

[0014] Preparation of a nickel complex catalyst (general step one):

[0015] In the first step, 2 grams of polyether were dissolved in 60 grams of 2 mol / L hydrochloric acid, and the obtained solution was stirred at 50 degrees for 4 hours, and then a solution containing 24 grams of carboxyethyl silanetriol sodium salt and 96 grams of tetraethyl orthosilicate was added dropwise. After the dropwise addition was completed, the solution was continuously stirred at 50 degrees for 12 hours. The obtained white suspension was aged at 100 degrees for 24 hours, filtered, and the filter cake was washed with deionized water and dried to obtain a white solid.

[0016] In the second step, 1 gram of the white solid obtained in the above step was dispersed in 250 milliliters of 48 wt% sulfuric acid, and the obtained mixed system was stirred and reacted at 100 degrees for 24 hours. After filtration, the filter cake was washed with deionized water and dried to obtain a catalyst intermediate.

[0017] In the third step, 0.5 grams of the catalyst intermediate obtained in the above step were dispersed in 50 milliliters of a 0.05M nickel salt solution, and a 0.1M sodium hydroxide solution was added dropwise to the mixture under continuous stirring until the pH value reached 9. At this time, a light green solid was precipitated, which was filtered and washed with deionized water and dried to obtain a light green solid. Further, the solid was calcined at 600 degrees under an atmosphere of a mixture of argon and hydrogen (95:5) for 8 hours, cooled, and the target catalyst was obtained and stored in a vacuum drying box.

[0018] Preparation of polyether silicone copolymer by reaction of hydrogen-containing polysiloxane and allyl polyether (general step two):

[0019] In a reaction vessel, hydrogen-containing polysiloxane (silicon hydrogen content 0.18%, viscosity 10-20 cp) and allyl polyether were added in a molar ratio of 1:1, 1 wt% of the above nickel complex M was added, and the temperature was raised to 80-100°C for 6-8h to produce a polyether organosilicon copolymer.

[0020] Example 1 Preparation of nickel complex C1

[0021] According to the general procedure I, the polyether was selected from polyethylene oxide with a molecular weight of 2000, and the nickel salt was selected from nickel bromide, to produce 0.694g of nickel complex C1 with a yield of 82%.

[0022] Example 2 Preparation of nickel complex C2

[0023] According to the general procedure I, the polyether was selected from polyethylene oxide with a molecular weight of 4000, and the nickel salt was selected from nickel chloride, to produce 0.625g of nickel complex C2 with a yield of 85%. The characterization data is shown in Figure 1.

[0024] Example 3 Preparation of nickel complex C3

[0025] According to the general procedure I, the polyether was selected from polyethylene oxide with a molecular weight of 6000, and the nickel salt was selected from nickel nitrate, to produce 0.698g of nickel complex C3 with a yield of 87%.

[0026] Example 4 Preparation of nickel catalyst C4

[0027] According to the general procedure I, the polyether was selected from polypropylene oxide with a molecular weight of 2000, and the nickel salt was selected from nickel bromide, to produce 0.728g of nickel complex C4 with a yield of 86%.

[0028] Example 5 Preparation of nickel complex C5

[0029] According to the general procedure I, the polyether was selected from polypropylene oxide with a molecular weight of 4000, and the nickel salt was selected from nickel chloride, to produce 0.596g of nickel complex C5 with a yield of 81%.

[0030] Example 6 Preparation of nickel complex C6

[0031] According to the general procedure I, the polyether was selected from polypropylene oxide with a molecular weight of 6000, and the nickel salt was selected from nickel nitrate, to produce 0.665g of nickel complex C6 with a yield of 83%.

[0032] Example 7 Preparation of nickel catalyst C7

[0033] According to the general procedure I, the polyether was selected from polypropylene oxide with a molecular weight of 6000, and the nickel salt was selected from nickel nitrate, to produce 0.665g of nickel complex C6 with a yield of 83%.

[0034] Example 8 Preparation of nickel complex C8

[0035] According to general procedure I, the polyether was chosen as a polyether of ethylene oxide propylene oxide copolymer with a molecular weight of 4000 and the nickel salt was chosen as nickel chloride, to give 0.603 g of nickel complex C8 with a yield of 82%. The characterization data are shown in Figure 1.

[0036] Example 9 Preparation of nickel complex C9

[0037] According to general procedure I, the polyether was chosen as a polyether of ethylene oxide propylene oxide copolymer with a molecular weight of 6000 and the nickel salt was chosen as nickel nitrate, to give 0.705 g of nickel complex C9 with a yield of 88%.

[0038] Example 10 Reaction of hydrogen-containing polysiloxane and allyl polyether with a molecular weight of 580

[0039] According to general procedure II, the allyl polyether was chosen as an allyl polyether with a molecular weight of 580 and the catalyst was chosen as complex CI, to give the corresponding polyether organosilicon copolymer PI.

[0040] Example 11 Reaction of hydrogen-containing polysiloxane and allyl polyether with a molecular weight of 700

[0041] According to general procedure II, the allyl polyether was chosen as an allyl polyether with a molecular weight of 700 and the catalyst was chosen as complex C2, to give the corresponding polyether organosilicon copolymer P2.

[0042] Example 12 Reaction of hydrogen-containing polysiloxane and allyl polyether with a molecular weight of 800

[0043] According to general procedure II, the allyl polyether was chosen as an allyl polyether with a molecular weight of 800 and the catalyst was chosen as complex C3, to give the corresponding polyether organosilicon copolymer P3.

[0044] Example 13 Reaction of hydrogen-containing polysiloxane and allyl polyether with a molecular weight of 900

[0045] According to general procedure II, the allyl polyether was chosen as an allyl polyether with a molecular weight of 900 and the catalyst was chosen as complex C4, to give the corresponding polyether organosilicon copolymer P4.

[0046] Example 14 Reaction of hydrogen-containing polysiloxane and allyl polyether with a molecular weight of 1000

[0047] According to general procedure II, the allyl polyether was chosen as an allyl polyether with a molecular weight of 1000 and the catalyst was chosen as complex C5, to give the corresponding polyether organosilicon copolymer P5.

[0048] Example 15 Reaction of hydrogen-containing polysiloxane and allyl polyether with a molecular weight of 2000

[0049] Following General Procedure Two, the allyl polyether was selected to be allyl polyether with a molecular weight of 2000 and the catalyst was selected to be Complex C6 to produce polyether silicone copolymer P6.

[0050] Example 16 Reaction of hydrogen-containing polysiloxane and allyl polyether with a molecular weight of 2400

[0051] Following General Procedure Two, the allyl polyether was selected to be allyl polyether with a molecular weight of 2400 and the catalyst was selected to be Complex C7 to produce polyether silicone copolymer P7.

[0052] Example 17 Reaction of hydrogen-containing polysiloxane and allyl polyether with a molecular weight of 2400

[0053] Following General Procedure Two, the allyl polyether was selected to be allyl polyether with a molecular weight of 2400 and the catalyst was selected to be Complex C8 to produce polyether silicone copolymer P8.

[0054] Example 18 Reaction of hydrogen-containing polysiloxane and allyl polyether with a molecular weight of 2400

[0055] Following General Procedure Two, the allyl polyether was selected to be allyl polyether with a molecular weight of 2400 and the catalyst was selected to be Complex C9 to produce polyether silicone copolymer P9.

[0056] Example 19 Reaction of hydrogen-containing polysiloxane and allyl polyether with a molecular weight of 700

[0057] Following General Procedure Two, the allyl polyether was selected to be allyl polyether with a molecular weight of 700 and the catalyst was selected to be Complex C5 to produce polyether silicone copolymer P10.

[0058] Example 20 Reaction of hydrogen-containing polysiloxane and allyl polyether with a molecular weight of 700

[0059] Following General Procedure Two, the allyl polyether was selected to be allyl polyether with a molecular weight of 700 and the catalyst was selected to be Complex C8 to produce polyether silicone copolymer P11.

[0060] The polyether silicone copolymers P2, P10, P11 produced using catalysts C2, C5, C8 were tested for physical properties. The control was a silicone copolymer produced following General Procedure Two using allyl polyether with a molecular weight of 700 and using acetylacetone nickel as the catalyst. The results are shown in Table 1.

[0061] Table 1

[0062] From the above test results, it can be seen that the catalyst of the present application has faster reaction, the raw materials can be completely converted in a shorter time, and the key performance of the polyether organosilicon copolymer can be greatly improved, fully demonstrating the superiority of the nickel catalyst.

[0063] In addition, it is also found that the polyether organosilicon copolymer prepared by the catalyst of the present application has excellent cell stability and less catalyst dosage when used in a polyurethane system with air whipping.

[0064] In Example 21, 5 parts of the organosilicon copolymer P7 were added to a combined material of 100 parts of polyether polyol A (trifunctional, hydroxyl value 35) and 10 parts of dipropylene glycol, 2 parts of an acetylacetone nickel solution (concentration 10%) were added as a catalyst, and 25 parts of crude MDI were used for crosslinking. After air whipping for 5 minutes, the overall density can be reduced to 620 g / L. The room temperature operation time of the system is 2 hours, and the curing time at 120 degrees Celsius is 5 minutes.

[0065] In Example 22, 5 parts of the organosilicon copolymer P8 were added to a combined material of 100 parts of polyether polyol A (trifunctional, hydroxyl value 35) and 10 parts of dipropylene glycol, 2 parts of an acetylacetone nickel solution (concentration 10%) were added as a catalyst, and 25 parts of crude MDI were used for crosslinking. After air whipping for 5 minutes, the overall density can be reduced to 610 g / L. The room temperature operation time of the system is 2 hours, and the curing time at 120 degrees Celsius is 5 minutes.

[0066] In Example 23, 2.5 parts of the organosilicon copolymer P8 and 2.5 parts of a macromolecular organosilicon block copolymer (Menhover S-9164) were added to a combined material of 100 parts of polyether polyol A (trifunctional, hydroxyl value 35) and 10 parts of dipropylene glycol, 2 parts of an acetylacetone nickel solution (concentration 10%) were added as a catalyst, and 25 parts of crude MDI were used for crosslinking. After air whipping for 5 minutes, the overall density can be reduced to 480 g / L. The room temperature operation time of the system is 2.5 hours, and the curing time at 120 degrees Celsius is 7 minutes.

[0067] In Comparative Example 1, 5 parts of the organosilicon copolymer Menhover S-193 were added to a combined material of 100 parts of polyether polyol A (trifunctional, hydroxyl value 35) and 10 parts of dipropylene glycol, 2 parts of an acetylacetone nickel solution (concentration 10%) were added as a catalyst, and 25 parts of crude MDI were used for crosslinking. After air whipping for 5 minutes, the overall density can be reduced to 980 g / L. The room temperature operation time of the system is 3 hours, and the curing time at 120 degrees Celsius is 10 minutes.

Claims

1. A process for the preparation of a nickel complex catalyst, characterized in that, First, polyether, tetraethyl orthosilicate and sodium carboxyethyl silanetriol salt are chemically reacted to obtain a catalyst intermediate; the intermediate is reacted with a nickel salt to obtain a corresponding nickel catalyst.

2. The process for the preparation of a nickel complex catalyst according to claim 1, characterized in that, The polyether is selected from polyethylene oxide, polypropylene oxide or a copolymer of both with a molecular weight of 2000-6000.

3. The process for the preparation of 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 of making a polyether siloxane copolymer characterized by, The nickel complex of any one of claims 1-3 is used as a catalyst, and the steps include weighing hydrogen-containing polysiloxane and allyl polyether with a molar ratio of 1.0:(1.0-1.1), then adding the nickel complex, and the amount of the nickel complex is 1-5% of the hydrogen-containing polysiloxane; finally, the hydrogen-containing polysiloxane and the allyl polyether are prepared into a polyether organosilicon copolymer through a silicon-hydrogen addition reaction under the catalysis of the nickel complex.

5. The method of claim 4, wherein, The allyl polyether is selected from allyl polyether with a molecular weight of 500-2400.

6. The method of claim 4, wherein, The allyl polyether is selected from allyl polyether with a molecular weight of 580, 700, 800, 900, 1000, 2000 or 2400.

7. The polyether organosilicon copolymer prepared according to the method of any one of claims 4-6 is used as a foaming stabilizer in polyurethane foaming.

8. The use of claim 7, wherein the foaming stabilizer is used in mechanically whipped polyurethane foaming.

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