Amino resin and preparation method thereof, and preparation method of allyl glycidyl ether

Abstract

The invention provides amino resin as well as a preparation method and application thereof in the preparation process of allyl glycidyl ether. The amino resin comprises a styrene skeleton and an amino terminal, chloromethylated polystyrene is swelled and then reacts with an amine compound, the amino resin is used for replacing alkali liquor to serve as an acid-binding agent for a ring-closure reaction of an allyl alcohol chlorohydrin ether intermediate in the preparation process of allyl glycidyl ether, chlorine salt is not generated, and the reaction time is shortened. The three-waste treatment cost is greatly reduced, and meanwhile, the prepared amino resin can be regenerated through heating and can be repeatedly used.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of catalyst, in particular to a catalytic system of allyl glycidyl ether, and a preparation method of allyl glycidyl ether. BACKGROUND

[0002] Allyl glycidyl ether (AGE) is an important organic chemical raw material, which is widely used in epoxy resin, silane coupling agent.

[0003] There are two kinds of industrialized preparation methods of allyl glycidyl ether (AGE), which are ring-opening ring-closing process and phase transfer catalysis process. The ring-opening ring-closing process is to take allyl alcohol and epichlorohydrin as raw materials, and first perform ring-opening reaction under the catalysis of Lewis acid (sulfuric acid, tin tetrachloride, boron trifluoride ether, etc.) to obtain allyl chlorohydrin intermediate (1-chloro-2-hydroxy-3-allyloxy propane), and then perform ring-closing under alkaline condition (generally sodium hydroxide) to obtain the product, but a large amount of sodium chloride solid waste is generated in the second step of ring-closing reaction. The phase transfer catalysis process is to take allyl alcohol and epichlorohydrin as raw materials, and directly react under the action of base (generally sodium hydroxide) and phase transfer catalyst to produce AGE, and a large amount of sodium chloride solid waste is also generated, which increases the production cost.

[0004] Therefore, in the production process of allyl glycidyl ether, whether the ring-opening ring-closing process or the phase transfer catalysis process is selected, a large amount of sodium chloride solid waste will be inevitably generated, and the treatment cost is increased.

[0005] In order to overcome the shortcomings of the prior art, it is necessary to design a kind of acid-binding agent which can replace sodium hydroxide, and the acid-binding agent can be regenerated and reused. SUMMARY

[0006] In view of the above problems existing in the prior art, the present application provides an amino resin and a preparation method thereof, which can be used as an acid-binding agent for preparing allyl glycidyl ether, can realize the ring-closing reaction of intermediate 1-chloro-2-hydroxy-3-allyloxy propane, thereby preparing allyl glycidyl ether, and the amino resin can be regenerated at high temperature and can be reused.

[0007] In order to achieve the purpose of the present application, the present application adopts the following technical solutions:

[0008] On the one hand, the present application provides a preparation method of amino resin, comprising the following steps:

[0009] (a) adding an organic solvent to swell the chloromethyl polystyrene beads;

[0010] (b) adding an amine compound and stirring to react;

[0011] (c) After the reaction is completed, the amino resin is obtained by filtering, washing and drying.

[0012] Preferably, the organic solvent in step (a) is selected from one or more of anhydrous methanol, anhydrous ethanol, n-hexane, dichloromethane, toluene, etc., preferably toluene.

[0013] Preferably, in step (a), the amount of the organic solvent is 0.1-0.3 g / ml, for example 0.1 g / ml, 0.2 g / ml, 0.3 g / ml, in terms of the concentration of the chloromethyl polystyrene beads therein.

[0014] Preferably, in step (a), the chloromethyl polystyrene (chloromethylated styrene-divinylbenzene copolymer) beads have a particle size of 50-200 um.

[0015] Preferably, in step (a), the swelling can be carried out at room temperature, and the swelling time can be 4-8 h, so as to fully swell the beads.

[0016] Preferably, in step (b), the amine compound is selected from ethylenediamine, 1,2-propanediamine, 1,4-butanediamine, and the amount of the amine compound added is 5-10 times the mass of the chloromethyl polystyrene beads.

[0017] Preferably, the reaction in step (b) is carried out at 50-80℃ under stirring and condensation reflux for 4-36 h, and the reaction formula is as follows:

[0018]

[0019] The obtained amino resin comprises a styrene skeleton and an amino terminal, and the structural formula is as follows:

[0020]

[0021] Preferably, after the reaction in step (b) is completed, the amino resin is first obtained by filtering, then washed with water, ethanol and water in sequence, until the pH of the effluent is 6-8, and then dried at 80-100℃ in vacuum for 5-10 h, to obtain the amino resin.

[0022] In a second aspect, the present application further provides the use of the amino resin in the preparation of allyl glycidyl ether. Specifically, a preparation method of allyl glycidyl ether comprises the following steps:

[0023] (1) An acidic catalyst is added to allyl alcohol to obtain raw material 1; epichlorohydrin is added to the raw material 1 and an opening ring reaction is carried out at 30-50℃ for 3-8 h, to obtain an allyl chlorohydrin ether intermediate;

[0024] (2) The fixed bed reactor is filled with the amino resin prepared in the preceding step, and the allyl chlorohydrin ether intermediate obtained in step (1) is introduced into the fixed bed reactor to perform a ring closure reaction, thereby obtaining a crude product of allyl glycidyl ether;

[0025] (3) The crude product of allyl glycidyl ether is introduced into a rectifying column to perform rectification, thereby obtaining a finished product.

[0026] In one specific embodiment of the present application, the structure of the allyl glycidyl ether is shown in formula (1):

[0027]

[0028] In one specific embodiment of the present application, the molar ratio of the allyl alcohol to the epichlorohydrin in step (1) is 3-5:1, for example, 3:1, 4:1, 5:1, and preferably 3:1.

[0029] In one specific embodiment of the present application, the acid catalyst in step (1) is preferably a Lewis acid catalyst, and more preferably one or more of sulfuric acid, tin tetrachloride, boron trifluoride ether, etc.; the addition amount of the acid catalyst is 500-5000 ppm.

[0030] In one specific embodiment of the present application, the fixed bed reactor in step (2) is filled with the amino resin prepared in the preceding step.

[0031] In one specific embodiment of the present application, the residence time of the allyl chlorohydrin ether intermediate introduced into the fixed bed reactor in step (2) is 3-5 h.

[0032] In one specific embodiment of the present application, the ring closure reaction temperature in step (2) is 50-80℃, for example, 50℃, 60℃, 80℃.

[0033] In one specific embodiment of the present application, the used amino resin can release hydrogen chloride by heating, thereby being regenerated and reused, and the released hydrogen chloride can be used as a chemical raw material.

[0034] Compared with the prior art, the present application has the following advantages:

[0035] In the present application, the amino resin is used instead of lye as an acid-binding agent for the ring closure reaction of allyl alcohol chlorohydrin ether, and the advantage is that the preparation process of the allyl glycidyl ether in the present application does not produce chlorine salts, greatly reducing the treatment cost of the three wastes in the production process of the allyl glycidyl ether. At the same time, the amino resin in the present application can be regenerated by heating, and the produced hydrogen chloride gas can be recycled as a chemical raw material. DETAILED DESCRIPTION

[0036] The present invention will be further illustrated below with specific embodiments. These embodiments are merely illustrative and do not limit the scope of the invention.

[0037] The testing instruments used for the prepared amino resin in this embodiment of the invention are as follows:

[0038] Vario MICRO elemental analyzer, Elementar GmbH, Germany;

[0039] The instruments used for analyzing the reaction solutions of the closed-loop reaction in the embodiments and comparative examples of this invention are as follows:

[0040] Gas chromatography using Agilent 8890 and Wax column;

[0041] The main raw materials used in the embodiments and comparative examples of this invention are as follows:

[0042] Ethylenediamine: Inokai reagent;

[0043] 1,2-Propanediamine: Inokai reagent;

[0044] 1,4-Butanediamine: Inokai reagent;

[0045] Chloromethyl polystyrene resin: Inokai reagent, particle size 100-200 mesh, catalog number P-72017.

[0046] Example 1

[0047] In a 500 mL three-necked flask, 20.0 g of chloromethyl polystyrene beads were added and swollen in 100 mL of toluene at room temperature for 4 hours. Then, 150 g of ethylenediamine was added, and the mixture was stirred and refluxed at 80 °C for 10 hours. After the reaction was completed, the resin was filtered off and washed successively with water, ethanol, and water until the pH of the effluent was 6-8. The effluent was then dried under vacuum at 80 °C for 5 hours to obtain amino resin A.

[0048] Example 2

[0049] In a 500 mL three-necked flask, 20.0 g of chloromethyl polystyrene beads were added and swollen in 100 mL of anhydrous ethanol at room temperature for 8 hours. Then, 100 g of 1,2-propanediamine was added, and the mixture was stirred and refluxed at 80 °C for 36 hours. After the reaction was completed, the resin was filtered off and washed successively with water, ethanol, and water until the pH of the effluent was 6-8. The effluent was then dried under vacuum at 100 °C for 10 hours to obtain amino resin B.

[0050] Example 3

[0051] In a 500 mL three-necked flask, 20.0 g of chloromethyl polystyrene beads were added and swollen in 100 mL of dichloromethane at room temperature for 6 hours. Then, 200 g of 1,4-butanediamine was added, and the mixture was stirred and refluxed at 80 °C for 24 hours. After the reaction was completed, the resin was filtered off and washed successively with water, ethanol, and water until the pH of the effluent was 6-8. The effluent was then dried under vacuum at 90 °C for 8 hours to obtain amino resin C.

[0052] The elemental analysis results of the amino resin are as follows:

[0053] Resin C(％) N(％) H(％) O(％) Cl(％) Polystyrene 70.42 0 6.33 4.1 19.15 Amino resin A 74.42 11.64 8.73 4.86 0.35 Amino resin B 76.54 6.83 11.33 4.92 0.38 Amino resin C 77.84 4.33 12.54 4.89 0.40

[0054] Example 4

[0055] The preparation of the allyl chlorohydrin ether intermediate involves the following steps:

[0056] 3000g of allyl alcohol and 6g of SnCl4 were added to a 10L reactor and heated to a reaction temperature of 50℃. 4784g of epichlorohydrin was continuously and uniformly fed into the reactor via a pump. The reactor was subjected to a ring-opening reaction at 50℃ for 3 hours and an aging time of 1 hour to obtain an allyl chlorohydrin ether intermediate.

[0057] NMR results showed that the epichlorohydrin conversion rate was approximately 99%, with allyl chlorohydrin ether intermediates accounting for 95%.

[0058] A small-scale fixed-bed reactor was prepared using amino resin A. 1 kg of the aforementioned allyl chlorohydrin ether intermediate was fed into the fixed-bed reactor. The reaction temperature was 80°C. When the residence time was 5 h, the conversion rate of allyl chlorohydrin ether was 55%.

[0059] The crude allyl glycidyl ether product is fed into a distillation column for distillation to obtain the final product.

[0060] Example 5

[0061] A small-scale fixed-bed reactor of the same scale as in Example 4 was made using amino resin B. 1 kg of the allyl chlorohydrin intermediate prepared in Example 4 was fed into the fixed-bed reactor. The reaction temperature was 50°C. When the residence time was 3 h, the conversion rate of allyl chlorohydrin was 47%.

[0062] Example 6

[0063] A small-scale fixed-bed reactor of the same scale as in Example 4 was made using amino resin C. 1 kg of the allyl chlorohydrin ether intermediate prepared in Example 4 was fed into the fixed-bed reactor. The reaction temperature was 60°C and the residence time was 4 h. The conversion rate of allyl chlorohydrin ether was 42%.

[0064] Example 7

[0065] Amino resin A was reused 10 times, with the same ring-closing reaction conditions as in Example 4 each time. The residence time was set to 5 hours, and the conversion rate of amino resin A after 10 reuses was measured.

[0066] Number of times Allyl chlorohydrin ether conversion rate 1 55％ 2 53％ 3 50％ 4 48％ 5 45％ 6 40％ 7 32％ 8 23％ 9 10％ 10 5％

[0067] Example 8

[0068] After each 10 uses of amino resin A, it was regenerated by heating at 200°C for 2 hours, and then regenerated again at 200°C for 2 hours after another 10 uses. This process was repeated 5 times, with the remaining reaction conditions the same as in Example 4, and the residence time set to 5 hours. The results are shown in the table below.

[0069] Number of times of regeneration (after regeneration) Allyl chlorohydrin ether conversion rate 1 54％ 2 52％ 3 50％ 4 50％ 5 48％

Claims

1. A method for preparing an amino resin, characterized in that, Includes the following steps: (a) Swelling of chloromethyl polystyrene microspheres by adding an organic solvent; (b) Add an amine compound and stir to react; (c) After the reaction is complete, filter, wash and dry to obtain amino resin.

2. The preparation method according to claim 1, characterized in that, The organic solvent mentioned in step (a) is selected from one or more of anhydrous methanol, anhydrous ethanol, n-hexane, dichloromethane, and toluene, with toluene being preferred.

3. The preparation method according to claim 1, characterized in that, The amount of organic solvent used in step (a), in terms of the concentration of chloromethyl polystyrene microspheres therein, is 0.1-0.3 g / ml.

4. The preparation method according to claim 1, characterized in that, The swelling time in step (a) is 4-8 hours.

5. The preparation method according to claim 1, characterized in that, In step (b), the amine compound is selected from ethylenediamine, 1,2-propanediamine, and 1,4-butanediamine; the amount of amine compound added is 5-10 times the mass of the chloromethyl polystyrene microspheres.

6. The preparation method according to claim 1, characterized in that, Step (b) involves stirring and refluxing at 50-80°C for 4-36 hours.

7. The preparation method according to claim 1, characterized in that, Step (c) is as follows: first, the amino resin is obtained by filtration, then washed with water, ethanol and water in sequence until the pH of the effluent is 6-8, then the washing is completed, and then vacuum dried to obtain the amino resin.

8. An amino resin prepared by the preparation method according to any one of claims 1-7, characterized in that, The structure includes a styrene skeleton and amino terminals, and is shown in the following diagram:

9. A method for preparing allyl glycidyl ether, characterized in that, Includes the following steps: (1) An acidic catalyst was added to allyl alcohol to obtain raw material 1; sufficient epichlorohydrin was added to raw material 1 and a ring-opening reaction was carried out to obtain allyl chlorohydrin ether intermediate; (2) Fill a fixed-bed reactor with the amino resin prepared by any one of the preparation methods of claims 1-7 or the amino resin of claim 8, and pass the allyl chlorohydrin ether intermediate obtained in step (1) into the fixed-bed reactor to carry out a closed-ring reaction to obtain the crude product of allyl glycidyl ether. (3) The crude allyl glycidyl ether product is distilled to obtain the finished product.

10. The preparation method according to claim 9, characterized in that, In step (2), the residence time in the fixed-bed reactor is 3-5 hours, and the reaction temperature is 50-80℃.

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