Propylene glycol monovinyl ether and its synthesis method and application

Abstract

The embodiment of the present invention discloses a propylene glycol monovinyl ether and a synthesis method and application thereof. The propylene glycol monovinyl ether provided by the present invention contains a three-carbon structure in the molecule, which enhances the adsorption of the ethylene end and increases the anchoring force with the adsorbate. The polycarboxylic acid water reducer synthesized by using the propylene glycol monovinyl ether as an initiator to prepare a macromonomer has stronger adsorption to cement particles, and can improve the water reduction and plasticity of the water reducer. The synthesis method and application of the improved propylene glycol monovinyl ether of the present invention expand the channels and varieties of preferred polyether monomer initiators, and have broad application prospects.

Description

Technical Field

[0001] The embodiments of the present invention relate to the technical field of organic synthesis, and specifically to propylene glycol monovinyl ether and a synthesis method and application thereof. Background Art

[0002] Propylene glycol monovinyl ether is a small molecule ether compound with unsaturated double bonds. Because it has an alcoholic hydroxyl group, it can be used as an initiator to make polyether macromonomers through ring-opening polymerization with ethylene oxide / propylene oxide to produce polycarboxylic acid water reducers.

[0003] At present, there have been reports on the preparation of ethylene glycol monovinyl ether. Propylene glycol monovinyl ether has a three-carbon chain structure in its molecular structure, which enhances the adsorption of the ethylene end, thereby increasing the anchoring force with cement particles. The performance of the polycarboxylic acid water reducer made from it has obvious advantages over the double-carbon chain structure of ethylene glycol monovinyl ether.

[0004] There are no public reports on the synthesis method and application of propylene glycol monovinyl ether. Summary of the invention

[0005] To this end, an embodiment of the present invention provides propylene glycol monovinyl ether and a synthesis method and application thereof.

[0006] In order to achieve the above purpose, the embodiment of the present invention provides the following technical solutions:

[0007] According to a first aspect of an embodiment of the present invention, the present invention provides propylene glycol monovinyl ether, whose structure is shown in (I) or (II):

[0008]

[0009] According to a second aspect of an embodiment of the present invention, the present invention provides a method for synthesizing propylene glycol monovinyl ether as described above, comprising the following steps:

[0010] 1) The reactor and pipelines are subjected to anhydrous treatment, vacuumization and nitrogen purging in turn;

[0011] 2) dissolving the catalyst in propylene glycol, then adding it into the reaction kettle, stirring and heating to 140-190° C.;

[0012] 3) Pass acetylene into the reaction kettle to make the pressure inside the kettle reach 0.15-0.4Mpa;

[0013] 4) Acetylene and propylene glycol react under the action of a catalyst, and the reaction product is continuously taken out from the reactor through reflux, and is successively subjected to distillation, condensation, separation, and rectification to obtain propylene glycol monovinyl ether;

[0014] 5) Continuously add acetylene and propylene glycol into the kettle to replenish the materials consumed by the reaction, and the reaction cycle continues.

[0015] In some specific embodiments, the catalyst is selected from any one of potassium hydroxide, sodium hydroxide, potassium oxide, sodium oxide, potassium ethoxide, and sodium ethoxide.

[0016] In some specific embodiments, in step 2), the amount of the catalyst used is 2.5-7% of the mass of propylene glycol.

[0017] According to a third aspect of the embodiments of the present invention, the present invention provides the use of the propylene glycol monovinyl ether as described above in preparing a polycarboxylate water-reducing agent.

[0018] According to a fourth aspect of an embodiment of the present invention, the present invention provides a polycarboxylate water reducer, wherein the preparation method thereof comprises:

[0019] The propylene glycol monovinyl ether as mentioned above is used as an initiator, and is subjected to ring-opening polymerization with alkylene oxide to prepare polyoxyethylene polyether, which is then copolymerized with acrylic acid to prepare a polycarboxylic acid water reducer.

[0020] In some specific embodiments, the alkylene oxide is ethylene oxide or propylene oxide.

[0021] In some specific embodiments, the polyoxyethylene ether is propylene glycol monovinyl polyoxyethylene ether or propylene glycol monovinyl polyoxyethylene block polyoxypropylene ether.

[0022] In some specific embodiments, the molecular weight of the polyoxyethylene polyether is 2000-6500.

[0023] The embodiments of the present invention have the following advantages:

[0024] The propylene glycol monovinyl ether molecule provided by the present invention contains a three-carbon structure, which enhances the adsorption of the ethylene end and increases the anchoring force with the adsorbate. The macromonomer prepared by using the propylene glycol monovinyl ether as the initiator and then synthesized polycarboxylic acid water reducer has stronger adsorption to cement particles, and can improve the water reduction and plasticity of the water reducer. The synthesis method and application of the improved propylene glycol monovinyl ether of the present invention expand the channels and varieties of preferred polyether monomer initiators, and have broad application prospects. DETAILED DESCRIPTION

[0025] The following is a description of the implementation of the present invention by specific embodiments. People familiar with the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0026] Example 1

[0027] Dissolve 25g of potassium hydroxide in 1000g of 1,3-propylene glycol, mix and add to a 5L reactor, replace the air in the reactor with nitrogen, preheat to 130°C, introduce acetylene, and then continue to heat to 190°C. Use acetylene to adjust the pressure in the reactor to 0.2MPa. The reaction product propylene glycol monovinyl ether mixture (mixed with propylene glycol, acetylene, etc.) is continuously taken out of the reactor. During the process, 1,3-propylene glycol is continuously added to the reactor to maintain the reaction liquid in the reactor (controlled by liquid level). The mixed product is distilled and condensed to obtain a crude mixture of propylene glycol monovinyl ether, and the final product propylene glycol monovinyl ether, i.e. 1,3-propylene glycol monovinyl ether, is obtained after rectification.

[0028] Example 2

[0029] 70g of sodium hydroxide was dissolved in 1000g of 1,3-propylene glycol, mixed and added to a 5L reactor, the air in the reactor was replaced with nitrogen, the temperature was pre-raised to 130°C, acetylene was introduced, and the temperature was further raised to 160°C. The pressure in the reactor was adjusted to 0.3MPa with acetylene, and the reaction product propylene glycol monovinyl ether mixture (mixed with propylene glycol, acetylene, etc.) was continuously taken out of the reactor. During the process, 1,3-propylene glycol was continuously added to the reactor to maintain the reaction liquid in the reactor (liquid level control). The mixed product was distilled and condensed to obtain a crude mixture of propylene glycol monovinyl ether, and the final product propylene glycol monovinyl ether, i.e. 1,3-propylene glycol monovinyl ether, was obtained after rectification.

[0030] Example 3

[0031] Dissolve 45g of sodium oxide in 1000g of 1,3-propylene glycol, mix and add to a 5L reactor, replace the air in the reactor with nitrogen, preheat to 130°C, introduce acetylene, and then continue to heat to 170°C. Use acetylene to adjust the pressure in the reactor to 0.3MPa. The reaction product propylene glycol monovinyl ether mixture (mixed with propylene glycol, acetylene, etc.) is continuously taken out of the reactor. During the process, 1,3-propylene glycol is continuously added to the reactor to maintain the reaction liquid in the reactor (liquid level control). The mixed product is distilled and condensed to obtain a crude mixture of propylene glycol monovinyl ether, and the final product propylene glycol monovinyl ether, i.e. 1,3-propylene glycol monovinyl ether, is obtained after rectification.

[0032] Example 4

[0033] Dissolve 30g of potassium oxide in 1000g of 1,3-propylene glycol, mix and add to a 5L reactor, replace the air in the reactor with nitrogen, preheat to 130°C, introduce acetylene, and then continue to heat to 140°C. Use acetylene to adjust the pressure in the reactor to 0.4MPa. The reaction product propylene glycol monovinyl ether mixture (mixed with propylene glycol, acetylene, etc.) is continuously taken out of the reactor. During the process, 1,3-propylene glycol is continuously added to the reactor to maintain the reaction liquid in the reactor (liquid level control). The mixed product is distilled and condensed to obtain a crude mixture of propylene glycol monovinyl ether, and the final product propylene glycol monovinyl ether, i.e. 1,3-propylene glycol monovinyl ether, is obtained after rectification.

[0034] Example 5

[0035] Dissolve 40g of sodium ethoxide in 1000g of 1,3-propylene glycol, mix and add to a 5L reactor, replace the air in the reactor with nitrogen, preheat to 130°C, introduce acetylene, and then continue to heat to 180°C. Use acetylene to adjust the pressure in the reactor to 0.25MPa. The reaction product propylene glycol monovinyl ether mixture (mixed with propylene glycol, acetylene, etc.) is continuously taken out of the reactor. During the process, 1,3-propylene glycol is continuously added to the reactor to maintain the reaction liquid in the reactor (liquid level control). The mixed product is distilled and condensed to obtain a crude mixture of propylene glycol monovinyl ether, and the final product propylene glycol monovinyl ether, i.e. 1,3-propylene glycol monovinyl ether, is obtained after rectification.

[0036] Example 6

[0037] Dissolve 40g of potassium ethoxide in 1000g of 1,3-propylene glycol, mix and add to a 5L reactor, replace the air in the reactor with nitrogen, preheat to 130°C, introduce acetylene, and then continue to heat to 170°C. Use acetylene to adjust the pressure in the reactor to 0.15MPa. The reaction product propylene glycol monovinyl ether mixture (mixed with propylene glycol, acetylene, etc.) is continuously taken out of the reactor. During the process, 1,3-propylene glycol is continuously added to the reactor to maintain the reaction liquid in the reactor (liquid level control). The mixed product is distilled and condensed to obtain a crude mixture of propylene glycol monovinyl ether, and the final product propylene glycol monovinyl ether, i.e. 1,3-propylene glycol monovinyl ether, is obtained after rectification.

[0038] Example 7

[0039] 40g of potassium hydroxide was dissolved in 1000g of 1,2-propylene glycol, mixed and added to a 5L reactor, the air in the reactor was replaced with nitrogen, the temperature was pre-raised to 130°C, acetylene was introduced, and the temperature was further raised to 190°C. The pressure in the reactor was adjusted to 0.25MPa with acetylene, and the reaction product propylene glycol monovinyl ether mixture (mixed with propylene glycol, acetylene, etc.) was continuously taken out of the reactor. During the process, 1,2-propylene glycol was continuously added to the reactor to maintain the reaction liquid in the reactor (liquid level control). The mixed product was distilled and condensed to obtain a crude mixture of propylene glycol monovinyl ether, and the final product propylene glycol monovinyl ether, i.e. 1,2-propylene glycol monovinyl ether, was obtained after rectification.

[0040] Comparative Example 1

[0041] Ethylene glycol monovinyl ether (produced by Anlu Xinjing Chemical Co., Ltd.) was purchased.

[0042] Test Case

[0043] Propylene glycol monovinyl ether synthesized by the methods of Examples 1 to 7 and ethylene glycol monovinyl ether of Comparative Example 1 were used as initiators, respectively, and polyoxyethylene polyether (prepared according to the same molecular weight) was prepared in the same way, and then copolymerized with acrylic acid small monomers to prepare polycarboxylic acid water reducer.

[0044] Preparation of polyether monomers:

[0045] Nitrogen is introduced into a synthesis reactor to purge and exclude air, a pre-mixed initiator (propylene glycol monovinyl ether or ethylene glycol monovinyl ether) and a sodium hydrogen alkaline catalyst are added into the reactor, the reactor is heated to 120° C., ethylene oxide is gradually introduced, and the pressure is controlled at 0.2 MPa. After the amount of ethylene oxide reaches a predetermined molecular weight design value, a polyether macromonomer is obtained, which is put into a post-treatment reactor, cooled, and glacial acetic acid is added to neutralize to alkalinity to obtain propylene glycol monovinyl polyoxyethylene ether or ethylene glycol monovinyl polyoxyethylene ether monomer.

[0046] Preparation of polycarboxylate water reducer:

[0047] 360g of propylene glycol monovinyl polyoxyethylene ether or ethylene glycol monovinyl polyoxyethylene ether monomer is placed in the bottom of a kettle, 300g of water and 3.5g of hydrogen peroxide are added, and material A (a mixture of 30g of acrylic acid and 20g of water) and material B (a mixture of 1.2g of mercaptoethanol, 0.5g of reducing agent E51 and 20g of water) are added dropwise at the same time. The dropping time of material A and material B is controlled within 60min. After the dropping is completed, water is added and liquid alkali is added for neutralization, and the solid content is adjusted to 40%, thereby obtaining a polycarboxylic acid water reducer.

[0048] The prepared polycarboxylate water reducer was subjected to concrete tests under the same conditions. The water reduction rate was measured according to the water reduction rate determination method in 5.5.1 of GB8076-1997 Concrete Admixtures. The initial (0h) slump and 1h slump were measured according to the slump test in 3.1 of GB-T50080-2002 Test Methods for Performance of Ordinary Concrete Mixtures.

[0049] The concrete mix ratio is as follows: 170kg water, 210kg cement, 70kg fly ash, 90kg mineral powder, 820kg medium sand, 1000kg crushed stone, and 1.4kg water reducer (40%).

[0050] The results of the parallel tests on concrete are shown in Table 1 below.

[0051] Table 1

[0052]

[0053]

[0054] As can be seen from Table 1, the polycarboxylate water-reducing agent prepared by using propylene glycol monovinyl ether provided in the embodiment of the present invention as the initiator is superior to the polycarboxylate water-reducing agent prepared by using ethylene glycol monovinyl polyether in various properties such as water reduction rate, slump loss and workability of concrete.

[0055] Although the present invention has been described in detail above by general description and specific embodiments, it is obvious to those skilled in the art that some modifications or improvements can be made to the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all belong to the scope of protection claimed by the present invention.

Claims

1. Propylene glycol monovinyl ether is used to prepare polycarboxylate water-reducing agent, characterized in that: The structure of propylene glycol monovinyl ether is shown in formula (I) or (II): H2C=CH-O-CH2-CH2-CH2-OH (I) The preparation method of the polycarboxylate water reducer comprises: The propylene glycol monovinyl ether is used as an initiator, and is subjected to ring-opening polymerization with alkylene oxide to prepare polyoxyethylene polyether, which is then copolymerized with acrylic acid to prepare a polycarboxylic acid water reducer.

2. The polycarboxylate water-reducing agent according to claim 1, characterized in that: The alkylene oxide is ethylene oxide or propylene oxide.

3. The polycarboxylate water reducer according to claim 1, characterized in that: The polyoxyethylene polyether is propylene glycol monovinyl polyoxyethylene ether or propylene glycol monovinyl polyoxyethylene block polyoxypropylene ether.

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