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A method for continuous production of amino-terminated polyether

A technology of primary amino-terminated polyether and hydroxyl polyether, which is applied in the low-pressure hydrogenation of low-molecular-weight hydroxyl-terminated polyether to prepare amino-terminated polyether and its catalyst, and can solve the problems of low liquid space velocity, high pressure and temperature, Low catalytic activity and other problems, to achieve the effect of low volatility, high primary amine selectivity, high conversion rate

Inactive Publication Date: 2018-11-20
南京莱克施德药业有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The catalyst is generally Ni-Cu-Cr-M type, and its activity is generally relatively low. According to foreign literature reports, the production conditions of amino-terminated polyether (especially its molecular weight is 200-300) are at a temperature of 200-260 ° C, pressure 3.5-20MPa, therefore, this method of reductive amination requires relatively high pressure and temperature. Generally, the reaction temperature is required to be around 200°C, and the reaction pressure is 3.5-34.5MPa, which requires high requirements for production equipment.
[0005] In recent years, a method of producing amino-terminated polyether using a fixed-bed reactor has appeared in China, but because of its low catalytic activity, its reaction pressure is generally 4.0 MPa or above, and the polyether liquid space velocity is extremely low, and the catalyst is generally For Ni-Cu-Cr-M type, generally 0.01h -1 , coupled with poor stability of middle and low molecular weight hydroxyl-terminated polyether, so the actual yield is low

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] Preparation of Ni-Cu-Cr-La-Al by coprecipitation method 2 o 3 Catalyst: Co-precipitate the nitrate of nickel, copper, chromium, lanthanum and sodium carbonate at a certain temperature to prepare the catalyst. Adopt to add metal content (reduction state) to be: nickel 50%, copper 30%, lanthanum 1.00%, metal nitrate solution concentration is 0.5mol / L, precipitant Na 2 CO 3 0.5mol / L, co-precipitation reaction occurs at 40°C, aged at 60°C for 30 minutes, suction filtration and washing are performed in sequence, and the carrier Al is selected 2 o 3 The amount is 14%, dried for 10 hours after suction filtration, through grinding and granulation, and roasted at 350 ° C for 2 hours, and finally the catalyst after the roasting is added to the catalyst matrix with 1% weight of oxalic acid and other auxiliary agents to mix and compress tablets to obtain Columnar catalyst 1 with a specific surface area of ​​168.58m 2 / g, the pore volume is 0.30ml / g.

Embodiment 2

[0020] Preparation of Ni-Cu-Cr-Pd-Al by Co-precipitation 2 o 3 Catalyst: Co-precipitate nickel, copper, chromium, palladium nitrate and potassium bicarbonate at a certain temperature to prepare a catalyst for Ni-Cu-Cr-Pd-Al 2 o 3 Catalyst preparation. Adopt to add the metal content (reduced state) to be: nickel 80%, copper 5%, palladium 0.005%, metal nitrate solution concentration is 1mol / L, precipitant K 2 CO 3 1mol / L, the precipitation temperature is 60°C, aging at 70°C for 30min, suction filtration and washing in sequence, and the carrier SiO 2 The content is 10%, dried for 10 hours after suction filtration, after grinding and granulating, roasting at 300°C for 2 hours, and finally adding 5.0% citric acid as the parent material to the calcined catalyst for tableting to obtain columnar catalyst 2. Surface area is 157.64m 2 / g, the pore volume is 0.35ml / g.

Embodiment 3

[0022] Preparation of Ni-Cu-Cr-La-SiO by Co-precipitation 2 / Catalyst: Co-precipitate the chloride of elements such as nickel and potassium carbonate at a certain temperature to prepare the catalyst. Adopting to add metal content (reduced state) is: nickel 20%, copper 20%, lanthanum 10%, metal nitrate solution concentration is 2mol / L, precipitating agent Na 2 CO 32mol / L, co-precipitation reaction occurs at 80°C, aged at 80°C for 30min, suction filtration and washing are performed in sequence, and the carrier is selected as Al 2 o 3 and SiO 2 The amount of the mixture (each accounting for 50% (weight), its addition is 50%, dried for 10 hours after suction filtration, through grinding and granulation, roasted at 400 ° C for 2 hours, and finally added the precursor 3.0% lemon to the catalyst after roasting Acid and oxalic acid mixture (respectively accounting for 50% (weight) carry out tabletting, obtain columnar catalyst 3, and this catalyst specific surface area is 165.31m ...

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Abstract

The invention discloses a method for continuously producing an amine-terminated polyether. The method comprises the steps of adopting a hydroxyl-terminated polyether as a polyether material, wherein the molecular weight of polyether is low molecular weight 200-2,000, the polyether polyol contains 1-3 hydroxy; mixing a polyether polyol material with liquid ammonia, wherein the volume velocity of the polyether polyol material is 0.01-0.1h<-1> and the volume velocity of the liquid ammonia is 0.05-3.0h<-1>; and carrying out heating in a preheating furnace until the reaction temperature is 180-260 DEG C, controlling the reaction pressure to be 0.05-2.5MPa and carrying out continuous production under the action of a catalyst to obtain the amine-terminated polyether. The problem that the quality of the produced small-molecular amine-terminated polyether product cannot reach the requirements is solved, the method has relatively high conversion rate and primary amine selectivity; the reaction conversion rate is greater than or equal to 95.0%; and the primary amine selectivity is greater than or equal to 95.0%.

Description

technical field [0001] The invention belongs to the technical field of chemical synthesis, and in particular relates to the preparation of amino-terminated polyether by low-pressure hydrogenation of low-molecular-weight hydroxyl-terminated polyether and its catalyst method. Background technique [0002] Amino-terminated polyether is a kind of polyalkylene oxide compound terminated by primary amino group or primary amino group. It can be divided into various series of products according to molecular weight and number of functional groups. Because the terminal amino group of its molecular chain contains active hydrogen, which can interact with various reactive groups, it is widely used as a synthetic raw material for polyurethane (polyurea) materials and as a curing agent for epoxy resins. In addition, it can also be used in engine fuel oil Used as anti-turbidity and anti-sedimentation additives. Medium and low molecular weight amino-terminated polyethers can be used in the f...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G65/325C07C213/02C07C217/08B01J23/86B01J23/89
CPCB01J23/868B01J23/8993C07C213/02C08G65/3255C08G2650/50C07C217/08
Inventor 吴永忠丁志平张云龙
Owner 南京莱克施德药业有限公司