A type of nickel complex and its application in the preparation of polyether organosilicon copolymers

Abstract

The present invention belongs to the field of chemical industry, and specifically relates to a type of nickel complex containing a long alkyl chain, and its application in the preparation of polyether silicone copolymers. This type of new complex is convenient to source and low in cost, and its price is one percent of that of a general platinum / palladium catalyst; in addition, since this type of complex contains a longer alkyl chain, it has good fat solubility and can be fully miscible with hydrogen-containing polysiloxane and allyl polyether, thereby efficiently catalyzing the reaction of the two to prepare polyether silicone copolymers. 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.

Description

Technical Field

[0001] The invention belongs to the field of chemical industry, and specifically relates to a type of 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 type of nickel complex containing a long alkyl chain, and the application of the same in preparing a polyether organosilicon copolymer.

[0005] First, the long alkyl chain ligand L and the nickel salt are hydrothermally reacted to generate a nickel complex M containing a long alkyl chain. The specific reaction formula is as follows:

[0006]

[0007] Where R 1 is a substituent of the pyridine ring, which can be at any reasonable position on the pyridine ring and is selected from hydrogen, alkyl, halogen, alkoxy, amino or trifluoromethyl; R 2 is selected from an alkyl group containing 5-20 carbon atoms; X is a counter anion of the nickel ion selected from chloride, bromine, iodine, acetate, trifluoroacetate, perchlorate, hexafluorophosphate, and the like.

[0008] The alkyl group is preferably a C1-6 alkyl group, and the alkoxy group is preferably a C1-6 alkoxy group.

[0009] Further, representative nickel complexes M1 to M4 containing long alkyl chains are as follows:

[0010]

[0011] On the other hand, a polyether silicone copolymer is prepared by using a nickel complex containing a long alkyl chain as a catalyst, and a hydrogen-containing polysiloxane and an allyl polyether are weighed at a molar ratio of 1.0:(1.0-1.1), and then the above-mentioned 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 the allyl polyether are reacted by a hydrosilylation reaction under the catalysis of the nickel complex to prepare a polyether silicone copolymer.

[0012] Wherein, the allyl polyether is selected from allyl polyethers with a molecular weight of 500 to 2400.

[0013] Furthermore, the allyl polyether is selected from the allyl polyethers with molecular weights of 580, 700, 800, 900, 1000, 2000 and 2400.

[0014] The beneficial effects of the present invention are:

[0015] The present invention provides a method for preparing a type of nickel complex containing a long alkyl chain. This type of new complex is convenient to source and low in cost, and its price is one percent of that of a general platinum / palladium catalyst. In addition, since this type of complex contains a relatively long alkyl chain, it has good fat solubility and can be fully miscible with hydrogen-containing polysiloxane and allyl polyether, thereby efficiently catalyzing the reaction of the two to prepare a polyether organosilicon copolymer. 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. DETAILED DESCRIPTION

[0016] Preparation of nickel complexes containing long alkyl chains (general step 1):

[0017] Hydrazide can be prepared by reacting the corresponding carboxylic acid methyl ester or ethyl ester with an excess of hydrazine hydrate, and the process steps are known from the open literature.

[0018]

[0019] In the first step, long-chain hydrazide (10 mmol), pyridine carboxaldehyde (10 mmol) and solvent ethanol (20 mL) were added to the reaction bottle, and refluxed for 10 hours under stirring. After the reaction was completed, it was extracted three times with water and dichloromethane. The water layer was removed, and the organic layer was dried with anhydrous sodium sulfate, filtered, concentrated, and recrystallized with 20 mL of ethanol to obtain the long alkyl chain ligand L.

[0020] In the second step, long alkyl chain ligand L (10 mmol), nickel salt (11 mmol) and water (20 mL) were added to a high-pressure reactor, and the temperature was raised to 150 degrees for reaction for 10 hours under stirring. After the reaction was completed, the temperature was lowered and filtered. The filter cake was washed once with 10 mL of water and once with 10 mL of methanol, and then vacuum dried to obtain a nickel complex M containing a long alkyl chain.

[0021] Preparation of polyether silicone copolymer by reaction of hydrogen-containing polysiloxane and allyl polyether (general step 2):

[0022] In a reaction kettle, hydrogen-containing polysiloxane and allyl polyether are added in a molar ratio of 1:1, and then 1 mol% of the above nickel complex M is added, and the temperature is raised to 100-110° C. and reacted for 8-10 hours to obtain a polyether silicone copolymer.

[0023] Example 1 Preparation of Nickel Complex M1

[0024]

[0025] According to general step 1, the hydrazide is selected as n-hexylhydrazide, the pyridinecarboxaldehyde is selected as 5-methoxypyridine-2-carboxaldehyde, and the nickel salt is selected as nickel bromide to prepare the nickel complex M1 with a yield of 84%.

[0026] Example 2 Preparation of Nickel Complex M2

[0027]

[0028] According to general step 1, the hydrazide is selected as lauryl hydrazide, the pyridine carboxaldehyde is selected as 3-methylpyridine-2-carboxaldehyde, and the nickel salt is selected as nickel acetate to prepare the nickel complex M2 with a yield of 81%.

[0029] Example 3 Preparation of Nickel Complex M3

[0030]

[0031] According to general step 1, the hydrazide is palmitoyl hydrazide, the pyridine carboxaldehyde is 4-bromopyridine-2-carboxaldehyde, and the nickel salt is nickel hexafluorophosphate to prepare the nickel complex M3 with a yield of 85%.

[0032] Example 4 Preparation of Nickel Complex M4

[0033]

[0034] According to general step 1, the hydrazide is stearyl hydrazide, the pyridinecarboxaldehyde is pyridine-2-carboxaldehyde, and the nickel salt is nickel perchlorate to prepare nickel complex M4 with a yield of 88%.

[0035] Example 5 Reaction of hydrogen-containing polysiloxane and allyl polyether with molecular weight 580

[0036] 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 M1 to prepare the corresponding polyether silicone copolymer.

[0037] Example 6 Reaction of hydrogen-containing polysiloxane and allyl polyether with a molecular weight of 700

[0038] 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 M3 to prepare the corresponding polyether silicone copolymer.

[0039] Example 7 Reaction of hydrogen-containing polysiloxane and allyl polyether with a molecular weight of 800

[0040] 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 M1 to prepare the corresponding polyether silicone copolymer.

[0041] Example 8 Reaction of hydrogen-containing polysiloxane and allyl polyether with a molecular weight of 900

[0042] 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 M2 to prepare the corresponding polyether silicone copolymer.

[0043] Example 9 Reaction of hydrogen-containing polysiloxane and allyl polyether with a molecular weight of 1000

[0044] 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 M4 to prepare the corresponding polyether silicone copolymer.

[0045] Example 10 Reaction of hydrogen-containing polysiloxane and allyl polyether with a molecular weight of 2000

[0046] 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 M3 to prepare the corresponding polyether silicone copolymer.

[0047] Example 11 Reaction of hydrogen-containing polysiloxane and allyl polyether with a molecular weight of 2400

[0048] 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 M2 to prepare the corresponding polyether silicone copolymer.

Claims

1. A method for preparing a nickel complex containing a long alkyl chain, characterized in that: Using a long alkyl chain ligand L and a nickel salt as raw materials, a nickel complex M containing a long alkyl chain is generated by a hydrothermal reaction. The specific reaction formula is as follows: ， Wherein, the long alkyl chain ligand L is selected from: , and ; The nickel complex M is selected from: , and .

2. A method for preparing a polyether silicone copolymer, characterized in that: Hydrogen-containing polysiloxane and allyl polyether are used as raw materials, and the nickel complex containing a long alkyl chain as claimed in claim 1 is added to obtain a polyether silicone copolymer.

3. The method according to claim 2, characterized in that: The molar ratio of the hydrogen-containing polysiloxane to the allyl polyether is 1.0:(1.0-1.1).

4. The method according to claim 2, characterized in that: The amount of the nickel complex is 1-5% of the hydrogen-containing polysiloxane.

5. The method according to claim 2, characterized in that: The molecular weight of the allyl polyether is 500-2400.

6. The method according to claim 2, characterized in that The molecular weight of the allyl polyether is 580, 700, 800, 900, 1000, 2000 or 2400.

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