High internal phase emulsion

Abstract

The invention specifically discloses a high internal phase emulsion. The high internal phase emulsion comprises an oil phase raw material and a water phase raw material, the oil-phase raw materials comprise an acrylate monomer, a cross-linking agent, an emulsifier and a photoinitiator; the acrylate monomer is selected from one or a composition of more than one of ethyl heptyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl methacrylate and dodecyl methacrylate. The high internal phase emulsion with the composition disclosed by the invention has relatively short light curing time; therefore, when the high internal phase emulsion is used for preparing the water absorbing material, the production efficiency can be improved.

Description

Technical Field

[0001] The invention relates to the technical field of chemical material preparation, and specifically discloses a high internal phase emulsion. Background Art

[0002] High internal phase emulsion, also known as super concentrated emulsion or gel emulsion, is a type of emulsion with a dispersed phase volume fraction of more than 74.05%. The porous functional materials prepared by it have the advantages of high specific surface area, high porosity and light weight, and are currently widely used in the production of water-absorbing materials.

[0003] For example, U.S. Patent No. 010752710B2 discloses a method for polymerizing open-cell foam, which includes preparing a high internal phase emulsion, curing the high internal phase emulsion, and drying the emulsion. The curing is completed by a multi-layer curing furnace, which is composed of different components. The emulsion containing a photoinitiator is exposed to an ultraviolet light source to partially polymerize the top surface of the emulsion, which can reduce the adhesion of the top surface of the HIPE. Subsequently, the partially polymerized emulsion is moved to a second polymerization stage through a mold or a scraper to enter thermal curing. When the HIPE reaches the desired dryness, it can be cut or sliced ​​into a shape suitable for the intended application.

[0004] Chinese invention patent CN 118027258 A discloses a high internal phase emulsion and a preparation method thereof. The preparation method of the high internal phase emulsion comprises the following steps: (1) adding the aqueous phase raw material and the oil phase raw material into a first emulsification reaction device for preliminary emulsification to obtain a premixed emulsion; (2) transferring the premixed emulsion into a second emulsification reaction device for emulsification to obtain a second emulsified material; (3) transferring the second emulsified material into a third emulsification reaction device, and then adding an initiator for emulsification reaction to obtain a high internal phase emulsion. The present invention provides a new preparation method of a high internal phase emulsion. The method of the present invention can make the oil phase and the aqueous phase fully dispersed and emulsified, thereby obtaining a high internal phase emulsion with good stability.

[0005] Although various high internal phase emulsions are disclosed in the prior art, the inventors found in the actual production process that the high internal phase emulsions in the prior art have a long solidification time when used to prepare water-absorbing materials, which leads to relatively low production efficiency in the subsequent preparation of water-absorbing materials; further improvement is needed. Summary of the invention

[0006] In order to overcome at least one of the technical problems existing in the prior art, the present invention first provides a high internal phase emulsion.

[0007] The technical solution of the present invention is as follows:

[0008] The present invention first provides a high internal phase emulsion, comprising an oil phase raw material and a water phase raw material; the oil phase raw material comprises an acrylate monomer, a crosslinking agent, an emulsifier and a photoinitiator;

[0009] The acrylic acid ester monomer is selected from one or a combination of more than one of ethyl heptyl acrylate, isooctyl acrylate, 2-ethylhexyl methacrylate, benzyl methacrylate and dodecyl methacrylate.

[0010] The inventors found in their research that the selection of the specific type of acrylate monomer plays an important role in the curing speed of the high internal phase emulsion. The research shows that the high internal phase emulsion using the above acrylate monomer has a shorter UV curing time.

[0011] Preferably, the acrylic acid ester monomer is selected from isooctyl acrylate, 2-ethylhexyl methacrylate and dodecyl methacrylate.

[0012] Preferably, the mass ratio of isooctyl acrylate, 2-ethylhexyl methacrylate and dodecyl methacrylate is 2-5:1-3:1-3.

[0013] The inventors found in further research that the acrylate monomer is selected from a combination of isooctyl acrylate, 2-ethylhexyl methacrylate and dodecyl methacrylate; compared with other combinations, it can significantly shorten the UV curing time of the high internal phase emulsion.

[0014] Preferably, the crosslinking agent is selected from one or a combination of triethylene glycol dimethacrylate, ethylene glycol dimethacrylate and trimethylolpropane triacrylate.

[0015] Preferably, the emulsifier is selected from one or a combination of glyceryl stearate, glyceryl caprylate, glyceryl sebacate, glyceryl oleate, glyceryl linolenate, glyceryl palmitate, glyceryl laurate, glyceryl caprate, glyceryl dodecanoate, glyceryl linolenate and glyceryl octadecanoate.

[0016] Preferably, the photoinitiator is selected from one or a combination of 1-hydroxycyclohexyl phenyl ketone, triphenylacetonitrile, triphenylphosphine and methyl benzoate.

[0017] Preferably, the photoinitiator is selected from a combination of 1-hydroxycyclohexyl phenyl ketone and triphenylphosphine.

[0018] Preferably, the mass ratio of 1-hydroxycyclohexyl phenyl ketone to triphenylphosphine is 1-2:1-2.

[0019] Most preferably, the mass ratio of 1-hydroxycyclohexyl phenyl ketone to triphenylphosphine is 1:1.

[0020] The inventors found in further research that the choice of photoinitiator has a decisive influence on the UV curing time of the high internal phase emulsion; the study shows that when the acrylate monomer of the high internal phase emulsion is selected from the combination of isooctyl acrylate, 2-ethylhexyl methacrylate and dodecyl methacrylate, the UV curing time of the high internal phase emulsion is much shorter than that of the high internal phase emulsion using a single 1-hydroxycyclohexyl phenone or a single triphenylphosphine as a photoinitiator; and it is also much shorter than that of the high internal phase emulsion using other initiator combinations. The selection of an initiator composed of 1-hydroxycyclohexyl phenone and triphenylphosphine can synergistically shorten the UV curing time of the high internal phase emulsion whose acrylate monomer is selected from the combination of isooctyl acrylate, 2-ethylhexyl methacrylate and dodecyl methacrylate.

[0021] Preferably, the aqueous phase raw material is selected from one or a combination of more than one of sodium chloride solution, calcium chloride solution, magnesium sulfate solution, sodium citrate solution and sodium lactate solution.

[0022] Preferably, the mass fraction of the solute in the aqueous phase raw material is 0.1 to 10%;

[0023] More preferably, the mass fraction of the solute in the aqueous phase raw material is 3-6%.

[0024] Preferably, the weight of the water phase raw material accounts for 1-20% of the weight of the oil phase raw material.

[0025] Preferably, the mass ratio of the acrylic ester monomer, the crosslinking agent, the emulsifier and the photoinitiator in the oil phase is 100:5-15:1-5:1-3.

[0026] Most preferably, the mass ratio of the acrylic ester monomer, the crosslinking agent, the emulsifier and the photoinitiator in the oil phase is 100:10:3:1.

[0027] Beneficial effects: The present invention provides a new high internal phase emulsion. Studies have shown that the high internal phase emulsion of the present invention has a shorter photocuring time. Therefore, the use of the high internal phase emulsion of the present invention for preparing water-absorbing materials helps to improve production efficiency. DETAILED DESCRIPTION

[0028] The present invention is further explained below in conjunction with specific examples, but the examples do not limit the present invention in any form.

[0029] Example 1 Preparation of high internal phase emulsion

[0030] The oil phase raw material and the water phase raw material are mixed and emulsified uniformly to obtain the high internal phase emulsion;

[0031] Wherein, the weight of the water phase raw material accounts for 5% of the weight of the oil phase raw material;

[0032] The aqueous phase is a 5% sodium chloride aqueous solution;

[0033] The oil phase raw material is composed of acrylic ester monomer, crosslinking agent, emulsifier and photoinitiator in a mass ratio of 100:10:3:1;

[0034] The acrylic acid ester monomers are composed of isooctyl acrylate, 2-ethylhexyl methacrylate and dodecyl methacrylate in a mass ratio of 4:2:1;

[0035] The crosslinker is selected from triethylene glycol dimethacrylate; the emulsifier is selected from glyceryl stearate;

[0036] The photoinitiator is composed of 1-hydroxycyclohexyl phenyl ketone and triphenylphosphine in a mass ratio of 1:1.

[0037] Example 2 Preparation of high internal phase emulsion

[0038] The oil phase raw material and the water phase raw material are mixed and emulsified uniformly to obtain the high internal phase emulsion;

[0039] Wherein, the weight of the water phase raw material accounts for 5% of the weight of the oil phase raw material;

[0040] The aqueous phase is a 5% sodium chloride aqueous solution;

[0041] The oil phase raw material is composed of acrylic ester monomer, crosslinking agent, emulsifier and photoinitiator in a mass ratio of 100:10:3:1;

[0042] The acrylic acid ester monomers are composed of ethyl heptyl acrylate, isooctyl acrylate and dodecyl methacrylate in a mass ratio of 4:2:1;

[0043] The crosslinker is selected from triethylene glycol dimethacrylate; the emulsifier is selected from glyceryl stearate;

[0044] The photoinitiator is composed of 1-hydroxycyclohexyl phenyl ketone and triphenylphosphine in a mass ratio of 1:1.

[0045] Example 3 Preparation of high internal phase emulsion

[0046] The oil phase raw material and the water phase raw material are mixed and emulsified uniformly to obtain the high internal phase emulsion;

[0047] Wherein, the weight of the water phase raw material accounts for 5% of the weight of the oil phase raw material;

[0048] The aqueous phase is a 5% sodium chloride aqueous solution;

[0049] The oil phase raw material is composed of acrylic ester monomer, crosslinking agent, emulsifier and photoinitiator in a mass ratio of 100:10:3:1;

[0050] The acrylic acid ester monomer is composed of ethyl heptyl acrylate, benzyl methacrylate and dodecyl methacrylate in a mass ratio of 4:2:1;

[0051] The crosslinker is selected from triethylene glycol dimethacrylate; the emulsifier is selected from glyceryl stearate;

[0052] The photoinitiator is composed of 1-hydroxycyclohexyl phenyl ketone and triphenylphosphine in a mass ratio of 1:1.

[0053] Example 4 Preparation of high internal phase emulsion

[0054] The oil phase raw material and the water phase raw material are mixed and emulsified uniformly to obtain the high internal phase emulsion;

[0055] Wherein, the weight of the water phase raw material accounts for 5% of the weight of the oil phase raw material;

[0056] The aqueous phase is a 5% sodium chloride aqueous solution;

[0057] The oil phase raw material is composed of acrylic ester monomer, crosslinking agent, emulsifier and photoinitiator in a mass ratio of 100:10:3:1;

[0058] The acrylic acid ester monomer is composed of isooctyl acrylate, benzyl methacrylate and dodecyl methacrylate in a mass ratio of 4:2:1;

[0059] The crosslinker is selected from triethylene glycol dimethacrylate; the emulsifier is selected from glyceryl stearate;

[0060] The photoinitiator is composed of 1-hydroxycyclohexyl phenyl ketone and triphenylphosphine in a mass ratio of 1:1.

[0061] Example 5 Preparation of high internal phase emulsion

[0062] The oil phase raw material and the water phase raw material are mixed and emulsified uniformly to obtain the high internal phase emulsion;

[0063] Wherein, the weight of the water phase raw material accounts for 5% of the weight of the oil phase raw material;

[0064] The aqueous phase is a 5% sodium chloride aqueous solution;

[0065] The oil phase raw material is composed of acrylic ester monomer, crosslinking agent, emulsifier and photoinitiator in a mass ratio of 100:10:3:1;

[0066] The acrylic acid ester monomers are composed of isooctyl acrylate, 2-ethylhexyl methacrylate and dodecyl methacrylate in a mass ratio of 4:2:1;

[0067] The crosslinker is selected from triethylene glycol dimethacrylate; the emulsifier is selected from glyceryl stearate;

[0068] The photoinitiator is 1-hydroxycyclohexyl phenyl ketone.

[0069] Example 6 Preparation of high internal phase emulsion

[0070] The oil phase raw material and the water phase raw material are mixed and emulsified uniformly to obtain the high internal phase emulsion;

[0071] Wherein, the weight of the water phase raw material accounts for 5% of the weight of the oil phase raw material;

[0072] The aqueous phase is a 5% sodium chloride aqueous solution;

[0073] The oil phase raw material is composed of acrylic ester monomer, crosslinking agent, emulsifier and photoinitiator in a mass ratio of 100:10:3:1;

[0074] The acrylic acid ester monomers are composed of isooctyl acrylate, 2-ethylhexyl methacrylate and dodecyl methacrylate in a mass ratio of 4:2:1;

[0075] The crosslinker is selected from triethylene glycol dimethacrylate; the emulsifier is selected from glyceryl stearate;

[0076] The photoinitiator is triphenylphosphine.

[0077] Example 7 Preparation of high internal phase emulsion

[0078] The oil phase raw material and the water phase raw material are mixed and emulsified uniformly to obtain the high internal phase emulsion;

[0079] Wherein, the weight of the water phase raw material accounts for 5% of the weight of the oil phase raw material;

[0080] The aqueous phase is a 5% sodium chloride aqueous solution;

[0081] The oil phase raw material is composed of acrylic ester monomer, crosslinking agent, emulsifier and photoinitiator in a mass ratio of 100:10:3:1;

[0082] The acrylic acid ester monomers are composed of isooctyl acrylate, 2-ethylhexyl methacrylate and dodecyl methacrylate in a mass ratio of 4:2:1;

[0083] The crosslinker is selected from triethylene glycol dimethacrylate; the emulsifier is selected from glyceryl stearate;

[0084] The photoinitiator is composed of 1-hydroxycyclohexyl phenyl ketone and methyl benzoyl ether in a mass ratio of 1:1.

[0085] Example 8 Preparation of high internal phase emulsion

[0086] The oil phase raw material and the water phase raw material are mixed and emulsified uniformly to obtain the high internal phase emulsion;

[0087] Wherein, the weight of the water phase raw material accounts for 5% of the weight of the oil phase raw material;

[0088] The aqueous phase is a 5% sodium chloride aqueous solution;

[0089] The oil phase raw material is composed of acrylic ester monomer, crosslinking agent, emulsifier and photoinitiator in a mass ratio of 100:10:3:1;

[0090] The acrylic acid ester monomers are composed of isooctyl acrylate, 2-ethylhexyl methacrylate and dodecyl methacrylate in a mass ratio of 4:2:1;

[0091] The crosslinker is selected from triethylene glycol dimethacrylate; the emulsifier is selected from glyceryl stearate;

[0092] The photoinitiator consists of triphenylphosphine and methyl benzoyl ether in a mass ratio of 1:1.

[0093] Take the high internal phase emulsion described in any one of Examples 1 to 8, pour it into a mold of 100 mm×50 mm×1 mm, put it under a UV lamp for curing test, and record the curing time; the results are shown in Table 1.

[0094] Table 1. Curing time of high internal phase emulsion

[0095]

[0096]

[0097] It can be seen from the experimental results in Table 1 that the UV curing time of the high internal phase emulsion in Example 1 is significantly shorter than that of the high internal phase emulsions described in Examples 2 to 4; this indicates that the acrylate monomer is selected from a combination of isooctyl acrylate, 2-ethylhexyl methacrylate and dodecyl methacrylate; compared with other combinations, it can significantly shorten the UV curing time of the high internal phase emulsion.

[0098] It can be seen from the experimental results in Table 1 that the UV curing time of the high internal phase emulsion in Example 1 is much shorter than that of the high internal phase emulsions described in Examples 5 and 6; this indicates that the selection of the photoinitiator has a decisive influence on the UV curing time of the high internal phase emulsion; when the acrylate monomer of the high internal phase emulsion is selected from a combination of isooctyl acrylate, 2-ethylhexyl methacrylate and dodecyl methacrylate, the UV curing time of the high internal phase emulsion is much shorter than that of the high internal phase emulsion using a single 1-hydroxycyclohexyl phenone or a single triphenylphosphine as the photoinitiator; the use of an initiator composed of 1-hydroxycyclohexyl phenone and triphenylphosphine can synergistically shorten the UV curing time of the high internal phase emulsion in which the acrylate monomer is selected from a combination of isooctyl acrylate, 2-ethylhexyl methacrylate and dodecyl methacrylate.

[0099] It can be seen from the experimental results in Table 1 that the UV curing time of the high internal phase emulsion in Example 1 is much shorter than that of the high internal phase emulsions described in Examples 7 and 8; this indicates that the selection of the photoinitiator has a decisive influence on the UV curing time of the high internal phase emulsion; when the acrylate monomer of the high internal phase emulsion is selected from a combination of isooctyl acrylate, 2-ethylhexyl methacrylate and dodecyl methacrylate, the initiator composed of 1-hydroxycyclohexyl phenyl ketone and triphenylphosphine is selected, and its UV curing time is much shorter than that of the high internal phase emulsion using other combinations of photoinitiators; the selection of other combinations of photoinitiators cannot synergistically shorten the UV curing time of the high internal phase emulsion in which the acrylate monomer is selected from a combination of isooctyl acrylate, 2-ethylhexyl methacrylate and dodecyl methacrylate.

Claims

1. A high internal phase emulsion, comprising an oil phase raw material and a water phase raw material; the oil phase raw material comprises an acrylate monomer, a crosslinking agent, an emulsifier and a photoinitiator; It is characterized in that The acrylic acid ester monomer is selected from one or a combination of more than one of ethyl heptyl acrylate, isooctyl acrylate, 2-ethylhexyl methacrylate, benzyl methacrylate and dodecyl methacrylate.

2. The high internal phase emulsion according to claim 1, characterized in that The acrylic acid ester monomer is selected from isooctyl acrylate, 2-ethylhexyl methacrylate and dodecyl methacrylate.

3. The high internal phase emulsion according to claim 1, characterized in that The mass ratio of isooctyl acrylate, 2-ethylhexyl methacrylate and dodecyl methacrylate is 2-5:1-3:1-3.

4. The high internal phase emulsion according to claim 1, characterized in that The crosslinking agent is selected from one or a combination of triethylene glycol dimethacrylate, ethylene glycol dimethacrylate and trimethylolpropane triacrylate.

5. The high internal phase emulsion according to claim 1, characterized in that The emulsifier is selected from one or a combination of glyceryl stearate, glyceryl caprylate, glyceryl sebacate, glyceryl oleate, glyceryl linolenate, glyceryl palmitate, glyceryl laurate, glyceryl caprate, glyceryl dodecanoate, glyceryl linolenate and glyceryl octadecanoate.

6. The high internal phase emulsion according to claim 1, characterized in that The photoinitiator is selected from one or a combination of 1-hydroxycyclohexyl phenyl ketone, triphenylphosphine and methyl benzoyl ether.

7. The high internal phase emulsion according to claim 1, characterized in that The aqueous phase raw material is selected from one or a combination of sodium chloride solution, calcium chloride solution, magnesium sulfate solution, sodium citrate solution and sodium lactate solution.

8. The high internal phase emulsion according to claim 1, characterized in that The mass fraction of the solute in the aqueous phase raw material is 0.1 to 10%; More preferably, the mass fraction of the solute in the aqueous phase raw material is 3-6%.

9. The high internal phase emulsion according to claim 1, characterized in that The weight of the water phase raw material accounts for 1 to 20% of the weight of the oil phase raw material.

10. The high internal phase emulsion according to any one of claims 1 to 9, characterized in that: The mass ratio of the acrylic ester monomer, the crosslinking agent, the emulsifier and the photoinitiator in the oil phase is 100:5-15:1-5:1-3.

Images