CN116444354A - Multi-branched surfactant and preparation method thereof - Google Patents

Abstract

The invention relates to a multi-branched surfactant and a preparation method thereof. The multi-branched surfactant is prepared by subjecting the mixture to a ring-opening reaction. The mixture includes a core reactant and a branch reactant, wherein the core reactant includes a polyol compound and a polyamine compound, and the branch reactant includes a compound having an epoxy group. The prepared multi-branched surfactant has good interfacial properties and compatibility, and is not easy to separate out.

Description

Multi-branched surfactant and preparation method thereof

technical field

The invention relates to a surfactant, in particular to provide a multi-branched surfactant with a multi-branch structure and a preparation method thereof.

Background technique

By adjusting the hydrophilic-lipophilic balance value, the surfactant can have good interfacial properties. Among them, some surfactants with special structures or functional groups can effectively eliminate foam, so they are often added to the solution to inhibit the formation of foam. Surfactants generally used as defoamers can be divided into silicon-type defoamers containing siloxane bonds, and non-silicon-type defoamers such as polyethers, alcohols or fatty acid esters.

Among them, compared with non-silicon-type defoamers, silicon-type defoamers have better defoaming properties. However, when using a silicon-based defoamer, because the high-temperature environment is likely to destroy the dispersion stability of the group in water, the silicon-based surfactant is easy to migrate and delaminate, thereby reducing the compatibility, and then precipitates over time, so it contains The end products of these products are prone to surface defects such as blurred appearance, fish eyes or oil spots.

Although non-silicon-type defoamers are not easy to precipitate, but generally non-silicon-type defoamers lack siloxane bonds, so they have poor defoaming properties, and are only suitable for applications with milder foaming properties. It is not easy to remove dense foam. Furthermore, general non-silicon defoamers have poor acid and alkali resistance, low temperature fluidity and cold resistance. Accordingly, the application fields of general non-silicon type defoamers are relatively limited.

In view of this, there is an urgent need to provide a multi-branched surfactant, its preparation method and a surfactant solution containing it, so as to further improve the interfacial properties of the surfactant, and solve the problem of traditional surfactants, its preparation method and the solution containing it. Defects of the interface active solution.

Contents of the invention

Therefore, one aspect of the present invention is to provide a kind of multi-branched surfactant, it has specific multi-branched structure, and has better interfacial active effect and compatibility, and this multi-branched surfactant has Modified end groups to improve its applicability.

Another aspect of the present invention is to provide a method for preparing a multi-branched surfactant, which is prepared by reacting a mixture.

According to one aspect of the present invention, a multi-branched surfactant is proposed, which has the structure shown in the following formula (I).

In formula (I), X represents a polyhydric alcohol group or polyamine group having 2 to 20 carbon atoms, R represents the structure shown in the following formula (I-1), and q represents an integer not less than 2.

In formula (I-1), R ₁ , R ₂ and R ₃ independently represent a hydrogen atom, an alkyl group with a carbon number of 1 to 20, a methylidene alkyl ether with a carbon number of 1 to 20, a carbon number Methylene aryl ethers of 6 to 25, methylene alkenyl ethers of 2 to 4 carbons, alkylphenol groups, aryl phenol groups, or alkene groups of 1 to 20 carbons; x, y and z independently represent 0 to 30, and the sum of x, y and z is 1 to 90; "*" represents formula (I-1) bonded to the oxygen atom of the polyol group or the nitrogen atom of the polyamine group Location.

According to some embodiments of the present invention, the aforementioned polyol group or polyamine group has 2 to 10 hydroxyl groups or amine groups, and q represents an integer of 2 to 10.

According to some embodiments of the present invention, the aforementioned amine groups include primary amines and/or secondary amines.

According to some embodiments of the present invention, the aforementioned R ₁ , R ₂ and R ₃ are different from each other.

According to another invention of the present invention, a kind of preparation method of multi-branched surfactant is proposed. The preparation method is to carry out a ring-opening reaction on the mixture to prepare the multi-branched surfactant. Wherein, the mixture includes a nuclear reactant and a branched reactant. The core reactants include polyol compounds or polyamine compounds with carbon numbers of 2 to 20, and the branch reactants include compounds having one epoxy group.

According to some embodiments of the present invention, based on the aforementioned nuclear reactant being used in an amount of 1 mole, the branching reactant is used in an amount of at least 2 moles.

According to some embodiments of the present invention, the aforementioned compound having one epoxy group has the structure shown in the following formula (II).

In formula (II), Y represents a hydrogen atom, an alkyl group with a carbon number of 1 to 20, a methylidene alkyl ether with a carbon number of 1 to 20, a methylidene aryl ether with a carbon number of 6 to 25, A methylenyl ether group having 2 to 4 carbon atoms, an alkylphenol group, an arylphenol group, or an alkene group having 1 to 20 carbon atoms.

According to some embodiments of the present invention, the aforementioned hyper-branched surfactant has a structure shown in the following formula (III).

In formula (III), X ₁ represents an n-valent group with a carbon number of 2 to 20, and X ₁ has n 2 secondary amines, wherein n 1 and n 2 independently represent integers from 0 to n, and n 1 and n 2 The sum of is n; X ₂ stands for -O-* or And "*" represents the position bonded to R; R "bonds to the nitrogen atom of the secondary amine of _X1 ; R' and R" independently represent the structure shown in the following formula (III-1); n represents An integer not less than 2, when n1 and n2 independently represent an integer not less than 2, multiple R" are the same or different, and multiple -X ₂ -R' are the same or different.

In formula (III-1), Y ₁ , Y ₂ and Y ₃ independently represent a hydrogen atom, an alkyl group with a carbon number of 1 to 20, a methylidene alkyl ether with a carbon number of 1 to 20, and a carbon number Methylene aryl ethers of 6 to 25, methylene alkenyl ethers of 2 to 4 carbons, alkylphenol groups, aryl phenol groups, or alkene groups of 1 to 20 carbons; a, b and c independently represent 0 to 30, and the sum of a, b and c is 1 to 90; "*" represents the bonding position.

According to some embodiments of the present invention, the aforementioned Y ₁ , Y ₂ and Y ₃ are different from each other.

According to some embodiments of the present invention, before performing the aforementioned ring-opening reaction, the production method may selectively perform an addition reaction on the nuclear reactant and the epoxy compound having 2 or 3 carbons.

According to yet another aspect of the present invention, a surface active solution is provided. The surfactant solution includes a multi-branched surfactant, and the multi-branched surfactant is prepared by the aforementioned method.

Applying the multi-branched surfactant of the present invention, its preparation method and the interfacial active solution containing it, the core structure of the multi-branched surfactant and the multiple branches bonded to the core structure can be easily formed through a ring-opening reaction. structure. Among them, the branched structure of the multi-branched surfactant can effectively improve the interfacial properties of the surfactant, and its terminal groups can be further used to modify resins, coatings or polymer materials. Furthermore, by adjusting the number of bonds in the branched structure and the length of its chain segments, the prepared hyperbranched surfactant can be an amphiphilic molecule with an appropriate hydrophilic-lipophilic balance and good interfacial properties.

Detailed ways

The making and using of embodiments of the invention are discussed in detail below. It should be appreciated, however, that the embodiments provide many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed are illustrative only, and do not limit the scope of the invention.

The hyperbranched surfactant of the present invention is prepared by performing a ring-opening reaction on the reaction mixture. Wherein, according to the structure of the multi-branched surfactant, it can be divided into a core structure and a plurality of branch structures bonded to the core structure, so the reaction mixture correspondingly includes the core reactant and the branch reactant.

The nuclear reactants include polyalcohol compounds and polyamine compounds with 2 to 20 carbon atoms. The polyol compound or the polyamine compound may have a structure represented by the following formula (IV).

In formula (IV), X ₁ represents a group with a carbon number of 2 to 20, and X ₁ may have a secondary amine or not have a secondary amine; X ₂₁ represents a hydroxyl group (-OH) or a primary amine (-NH ₂ ); and n1 represents an integer not less than 2.

The aforementioned group with a carbon number of 2 to 20 can be, for example, a straight-chain alkyl group, a straight-chain alkenyl group, a branched chain alkyl group, a branched chain alkenyl group, an aralkyl group, a cycloalkyl group, a cycloalkenyl group, a heterocycloalkyl group, A heterocycloalkenyl group, the aforementioned group having an ether group, and/or other appropriate groups. It can be understood that, in the aforementioned examples, when X ₁ has a secondary amine (-NH-), the secondary amine is bonded between two carbon atoms. If the carbon number of X ₁ is greater than 20, the too long carbon chain will reduce its compatibility as a defoamer, making it difficult to uniformly disperse. Preferably, X ₁ may represent a group with 2 to 10 carbon atoms. In formula (IV), the position where X ₂₁ is bonded to X ₁ is not particularly limited, as long as X ₂₁ is bonded to the carbon atom of X ₁ . It can be understood that, in order to facilitate the bonding of subsequent branch structures, the bonding position of X ₂₁ does not affect the bonding of subsequent reactions. In other embodiments, in X ₁ , only one X ₂₁ is bonded to each carbon atom bonded to X ₂₁ .

In formula (IV), it can be understood that the number of bonds of X ₂₁ is the value of n1, so according to the structure of X ₁ , the number of bonds of X ₂₁ (ie the range of the value of n1) is predictable. For example, when X ₁ represents a straight-chain alkyl group with a carbon number of N _C , based on the carbon chain structure of the straight-chain alkyl group, it can be understood that the number of bonds of X ₂₁ (i.e. n1 value) can be greater than or equal to 2, And the maximum is (2N _C +2), where based on the theoretical knowledge of synthetic reactions such as the bonding angle of the chain segment, the electronic distribution of the bond, the reactivity of the compound and the steric barrier of the functional group, those with ordinary knowledge can understand X The actual bonding situation of ₂₁ on the carbon chain can further confirm the range of n1 value. In some embodiments, n1 preferably represents an integer of 2 to 10, more preferably an integer of 2 to 8, and most preferably an integer of 3 to 6. Secondly, when _X1 has secondary amines, the number of secondary amines may be n2, and the sum of n1 and n2 may be 2 to n, and preferably 3 to 8. Wherein, n is greater than 2, preferably greater than 2 and less than or equal to 12, more preferably greater than 2 and less than or equal to 10, and particularly preferably 3-8.

In some embodiments, nuclear reactants may include, but are not limited to, ethylene glycol, 2-propanediol, 1,3-propanediol, butylene glycol, pentylene glycol, neopentyl glycol, hexanediol, heptanediol, octanediol Alcohol, Nonanediol, Decanediol, Glycerin, Trimethylolpropane, Pentaerythritol, Ditrimethylolpropane, Dipentaerythritol, Polyglycerol, Sorbitol, Alkyl Glucoside, Sugar Alcohol, Cycloalcohol, Ethanol Diamine, propylenediamine, decyldiamine, dodecyldiamine, tetradecyldiamine, dodecyl-1,3-propylenediamine, tetradecyl-1,3-propylenediamine, N-coco Oleyl-1,3-propylenediamine, N-tallow-1,3-propylenediamine, N-stearyl-1,3-propylenediamine, N-oleyl-1,3-propylenediamine , diethylenetriamine, dipropylenetriamine, N-tallow-dipropylenetriamine, N, N-bis(3-aminopropyl) dodecylamine, N-oleyl-dipropylenetriamine, N,N-bis(3-aminopropyl) tallow amine, N'-(3-aminopropyl)-N,N-dimethyl-1,3-propanediamine, tripropylenetetramine, N-Tallowyl-tripropylenetetramine, N-oleyl-tripropylenetetramine, tetraethylenepentamine, monoisopropanolamine, diisopropanolamine, 2-(isopropylamino)ethanol, N-isopropanolamine Propyldiethanolamine, amineethylethanolamine, other suitable polyol compounds or polyamine compounds, or any mixture of the above compounds.

Branching reactants may comprise compounds with one epoxy group. In some embodiments, the branched reactant can have the structure shown in the following formula (II).

In formula (II), Y represents a hydrogen atom, an alkyl group with a carbon number of 1 to 20, a methylidene alkyl ether with a carbon number of 1 to 20, a methylidene aryl ether with a carbon number of 6 to 25, A methylenyl ether group having 2 to 4 carbon atoms, an alkylphenol group, an arylphenol group, or an alkene group having 1 to 20 carbon atoms.

In some embodiments, branched reactants may include, but are not limited to, ethylene oxide, propylene oxide, butylene oxide, 1,2-pentene oxide, 1,2-hexane oxide, 1,2- Epoxyheptane, 1,2-epoxyoctane, 1,2-epoxynonane, 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane Alkane, 1,2-epoxytridecane, 1,2-epoxytetradecane, 1,2-epoxypentadecane, 1,2-epoxyhexadecane, 1,2-epoxyheptadecane alkanes, 1,2-epoxyoctadecane, phenyloxirane, tolyloxirane, styrenated phenyloxirane, propyl glycidyl ether, isopropyl glycidyl ether, butyl Glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, 2-ethylhexyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, 3 -Propylheptyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, Hexaalkyl glycidyl ether, heptadecyl glycidyl ether, octadecyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, styrenated phenyl glycidyl ether, benzyl glycidyl ether, tert-butylphenyl glycidyl ether, cardanol glycidyl ether, allyl glycidyl ether, other suitable compounds with epoxy groups, or any mixture of the above compounds.

Based on the number of hydroxyl groups and amine groups (including primary amines and secondary amines) in 1 mole of the nuclear reactant is n, the amount of the branched reactant is preferably n moles to 90n moles, more preferably 2n moles to 40n moles, And more preferably, it can be 3n moles to 10n moles. When the consumption of branch reactant is aforesaid range, the multi-branched surfactant that makes can have at least two branch structures, and each branch structure has suitable molecular length, and has good interfacial property (as: defoaming, emulsifying, dispersing, wettability and acid and alkali resistance, etc.).

To enhance reactivity, the reaction mixture may optionally contain a catalyst. According to the reaction mechanism of the nuclear reactant and the branched reactant, those with ordinary knowledge can use the appropriate catalyst type and adjust the amount, so no further details are given here. In some embodiments, the catalyst may comprise an acid catalyst or a base catalyst. In some specific examples, the catalyst may include, but not limited to, triphenylphosphine, triethylamine, benzyltriethylammonium chloride, tetra-n-butylammonium bromide, sodium hydroxide, potassium hydroxide, aluminum chloride , boron trifluoride, tin tetraisopropoxide, zinc perchlorate, other suitable catalyst materials, or any mixture of the above materials.

During the reaction, the epoxy group of the branched reactant can undergo a ring-opening reaction, and react with the hydroxyl or amine group of the nuclear reactant to bond, and the branched reactant can also be bonded to each other, and then form the following formula (III) The multi-branched surfactant of the present invention. It can be understood that the branched reactant after the ring-opening reaction is not limited to react with the nitrogen atom of the terminal primary amine (—NH ₂ ) of the nuclear reactant. When the core reactant contains a secondary amine (-NH-), the epoxy group of the branched reactant can also react with the nitrogen atom of the secondary amine to bond.

In formula (III), X ₁ represents an n-valent group with a carbon number of 2 to 20, and X ₁ has n 2 secondary amines, wherein n 1 and n 2 independently represent integers from 0 to n, and n 1 and n 2 The sum of is n; X ₂ stands for -O-* or And "*" represents the position bonded to R; R "bonds to the nitrogen atom of the secondary amine of _X1 ; R' and R" independently represent the structure shown in the following formula (III-1); n represents An integer not less than 2. When n1 and n2 independently represent an integer of not less than 2, a plurality of R" is the same or different, and a plurality of -X ₂ -R' is the same or different.

In formula (III-1), Y ₁ , Y ₂ and Y ₃ independently represent a hydrogen atom, an alkyl group with a carbon number of 1 to 20, a methylidene alkyl ether with a carbon number of 1 to 20, and a carbon number Methylene aryl ethers of 6 to 25, methylene alkenyl ethers of 2 to 4 carbons, alkylphenol groups, aryl phenol groups, or alkene groups of 1 to 20 carbons, wherein methylene The methylene groups of base alkyl ethers, methylene aryl ethers and methylene alkenyl ethers are all bonded between the carbon chains of ether groups and ethoxy groups; a, b and c independently represent 0 to 30 , and the sum of a, b and c is 1 to 90; "*" represents the bonding position.

It can be understood that the n value of the n-valent group represented by the aforementioned X ₁ is defined by the structure of the nuclear reactant shown in the aforementioned formula (IV). Relevant descriptions have been described in detail above, so details are not repeated here.

In some embodiments, Y ₁ , Y ₂ and Y ₃ are different from each other. When Y ₁ , Y ₂ and Y ₃ are different from each other, these different branched chain groups can endow the prepared hyper-branched surfactant with better interfacial properties. Preferably, Y ₁ , Y ₂ and Y ₃ can independently represent a hydrogen atom, methyl, ethyl, propyl, butyl, dodecyl, tetradecyl, methyl ethyl ether, methylene methyl propyl ether, methyl butyl ether, methyl 2-ethylhexyl ether, methyl dodecyl ether, methyl tetradecyl ether, methyl phenyl ether, methyl Cresyl ether, methylene styrenated phenyl ether, methylene benzyl ether, methylene tert-butyl phenyl ether, methylene cardanol ether, methylene allyl ether, and the like. In some embodiments, at least one of Y ₁ , Y ₂ and Y ₃ is not a hydrogen atom, methyl or ethyl. When at least one of Y ₁ , Y ₂ and Y ₃ is not a hydrogen atom, a methyl group or an ethyl group, the prepared multi-branched surfactant may have better interfacial properties. The sum of a, b and c may be 2 to 40, and more preferably 3 to 10. Wherein, when the sum of a, b and c is within the aforementioned range, each branch structure of the hyper-branched surfactant can have an appropriate molecular length, so that the multi-branched surfactant can have better interfacial properties. In some embodiments, at least two of a, b and c are not 0, and the sum of a, b and c can be 2 to 90, wherein the sum of a, b and c is preferably 2 to 40, and especially The best is 3 to 10. In these embodiments, Y ₁ , Y ₂ and Y ₃ may or may not be the same as each other. In some embodiments, in the prepared hyper-branched surfactant, the molecular structure of each branch structure may be the same or different from each other, and the molecular length of each branch structure may also be the same or different from each other. It can be understood that when the molecular structure of each branch structure of the multi-branched surfactant is identical to each other, the multi-branched surfactant can be prepared through a one-step reaction (ie, ring-opening reaction). In some embodiments, the terminal group of the branched structure of the hyper-branched surfactant of the present invention is preferably not an ethylene oxide segment, so as to have better defoaming properties. Wherein, if each branch structure has a different segment structure, as the number of branch structures whose ends are ethylene oxide segments decreases, the defoaming property of the multi-branched surfactant increases accordingly.

In some embodiments, n is preferably greater than 2 and less than or equal to 12, more preferably greater than 2 and less than or equal to 10, and most preferably 3-8. When n is within the aforementioned range, the core structure of the multi-branched surfactant may have an appropriate valence for the bonding of the branched structure, thereby improving the interfacial properties of the multi-branched surfactant.

Before carrying out the aforementioned ring-opening reaction, the nuclear reactant (i.e. polyol compound or polyamine compound) of formula (IV) can optionally be first with carbon number be 2 or 3 epoxy compounds (such as: oxirane and (or propylene oxide) carry out addition reaction, and form the core reactant of modification, then can pass through ring-opening reaction, further react with branched compound to form multi-branched surfactant of the present invention as shown in aforementioned formula (III) . In some embodiments, the number of hydroxyl or amino groups based on 1 mole of the nuclear reactant is n, and the amount of the epoxy compound with 2 or 3 carbons is preferably 2 moles to 3n moles, and more preferably n moles to 3n moles. In some embodiments, the amount of the epoxy compound with a carbon number of 2 or 3 may be the same as or different from that of the branched compound. During the addition reaction, the epoxy group of the epoxy compound having 2 or 3 carbons will react with the hydroxyl group or amine group of the nuclear reactant through a ring-opening reaction to form a modified nuclear reactant. By the extended chain segment formed by the epoxy compound with carbon number 2 or 3, the branched reactant can be more easily bonded to the end of the extended chain segment, so that the subsequent prepared multi-branched surfactant can have a relatively Good interface characteristics. In some embodiments, in the addition reaction, the epoxy compound with carbon number of 2 or 3 reacts with some hydroxyl groups or amine groups of the core reactant, so that each branch structure of the prepared multi-branched surfactant It has a different segment structure, thereby improving its interface properties.

In some specific examples, the hyperbranched surfactant of the present invention may be, for example, but not limited to, comb compounds, star compounds, dendrimer compounds and/or other suitable types of compounds. Preferably, the multi-branched surfactant can be a star compound or a dendritic compound.

The prepared multi-branched surfactant of the present invention has the lipophilic group of low carbon alcohol (lower alcohol) to high carbon alcohol, and can be adjusted by the epoxy compound that alkyl carbon chain or carbon number are 2 or 3 Water-lipophilic balance, and has good interfacial properties such as emulsification, dispersibility, solubilization, wetting and lubricity. Secondly, the multi-branched surfactant of the present invention has multiple branch structures, so compared with non-silicon type surfactants such as general polyethers, alcohols or fatty acid esters, the multi-branched surfactant of the present invention has relatively Excellent defoaming properties, acid and alkali resistance, compatibility, cold resistance and low temperature fluidity, and its highly branched structure helps to suppress the precipitation defects caused by siloxane bonds in traditional defoamers. In addition, the amphiphilic structure and terminal functional groups of the branched structure of the multi-branched surfactant of the present invention can be further modified, so it can be used to modify resin materials, coatings and polymer materials.

In some application examples, the hyperbranched surfactant of the present invention can be mixed with other components (such as: different surfactants and/or solvents) to prepare a surfactant solution.

The following examples are used to illustrate the application of the present invention, but they are not intended to limit the present invention. Any person skilled in the art may make various changes and modifications without departing from the spirit and scope of the present invention.

Preparation of hyperbranched surfactants

Example 1

Add 1 mole of trimethyl propane to the reaction flask and heat to 50°C. Then, 6 moles of butyl glycidyl ether and catalytic amount of tetra-n-butylammonium bromide were added into the reaction flask, and heated to 100° C. to perform ring-opening reaction. After reacting for 8 hours, the hyperbranched surfactant of Example 1 shown in the following formula (V-1) can be prepared.

Example 2

Add 1 mole of trimethylolpropane to the reaction flask and heat to 50°C. Then, add 15 moles of butyl glycidyl ether and a catalytic amount of benzyltriethylammonium chloride to the reaction flask to carry out a ring-opening reaction at 100°C. After 8 hours, the reaction can obtain the mid product.

Then, add the above-mentioned intermediate product, 6 moles of ethylene oxide and a catalytic amount of potassium hydroxide into a high-temperature and high-pressure reactor, and heat it to 150°C to 160°C to carry out a ring-opening reaction, and the following formula can be obtained: The multi-branched surfactant of Example 2 shown in (V-2).

Example 3

Add 1 mole of pentaerythritol (pentaerythritol) to a high-temperature and high-pressure reactor, and add 4 moles of ethylene oxide and a catalytic amount of potassium hydroxide to perform an addition reaction at 150°C to 160°C to form a modified nuclear reaction things. Next, add 8 moles of butyl glycidyl ether into the reaction kettle, heat to 120°C to carry out the ring-opening reaction, and the polyol of Example 3 shown in the following formula (V-3) can be obtained after 5 hours. branched surfactants.

Example 4

Add 1 mole of pentaerythritol (pentaerythritol) to the high temperature and high pressure reactor, and add 4 moles of branched reactants (containing dodecyl glycidyl ether and tetradecyl glycidyl ether) and a catalytic amount of triphenylphosphine to Reactor, and heated to 120 ℃, to carry out the ring-opening reaction, after 8 hours, the multi-branched surfactant of Example 4 shown in the following formula (V-4) can be obtained. Wherein, R"' represents dodecyl or tetradecyl.

Example 5

Add 1 mole of ethylenediamine (ethylenediamine) to the high-temperature and high-pressure reactor, and add 8 moles of ethylene oxide, 20 moles of propylene oxide and a catalytic amount of potassium hydroxide to carry out the addition at 130°C to 140°C into a reaction to form a modified nuclear reactant.

Then, add the modified nuclear reactant and 10 moles of butyl glycidyl ether into the reaction kettle, and heat to 120°C to carry out the ring-opening reaction. After 4 hours, the following formula (V-5) can be obtained. The multi-branched surfactant of the embodiment 5 shown.

Example 6

Add 1 mole of sorbitol to the high-temperature and high-pressure reactor, and add 25 moles of ethylene oxide and a catalytic amount of potassium hydroxide to perform an addition reaction at 150°C to 160°C to form a modified nuclear reactants.

Then, the modified nuclear reactant, 18 moles of butyl glycidyl ether and boron trifluoride are added to the reaction kettle, and heated to 70°C to 80°C to carry out the ring-opening reaction, and the reaction time is 1 hour to 2 hours. The hyperbranched surfactant of Example 6 shown in the following formula (V-6) can be obtained.

Evaluation Method - Defoaming

An aqueous solution of octyl phenyl polyoxyethylene ether (octyl phenol ethoxylate; Triton X-100) was prepared, and based on the weight of the aqueous solution as 100 wt%, 1 wt% of the surfactant of the embodiment or comparative example was added. Then, at 25° C., the defoaming property of the surfactant was evaluated by the Rose-Miles method, and the evaluation results are shown in Table 1. Wherein, the surfactant of comparative example 1 is made by Sino-Japanese Synthetic, and the commodity of model is TL-260; The surfactant of comparative example 2 is manufactured by Sino-Japanese Synthetic, and the commodity of model is PE81; The agent is manufactured by Sino-Nippon Synthesis, and the product model is GL-F50.

Table 1

According to the results in Table 1, it can be seen that the hyperbranched surfactant of the present invention has good defoaming properties. Wherein, compared with Example 1 and Example 3 to Example 6 (the terminal structure of the branch structure contains butyl ether, dodecyl ether or myristyl ether), due to the multi-branched interface activity of Example 2 The terminal structures of the branched structure of the agent are all ethylene oxide segments, so Example 2 has a relatively low defoaming property, but it is understandable that compared with the comparative example, Example 2 can still effectively eliminate foam.

In addition, although Comparative Example 3 can effectively eliminate foam, its defoaming speed is relatively slow, and its defoaming performance is worse than that of Examples 1 to 6. Therefore, the surfactant of Comparative Example 3 still has the defects of general non-silicon type defoamers, and cannot meet the application requirements.

Accordingly, the multi-branched surfactant of the present invention and the surfactant solution containing it can have good interfacial properties through a specific core structure and multiple branched structures, and can be further modified by using the terminal groups of the branched structure Resins, coatings or polymer materials. In addition, the multi-branched surfactant of the present invention can be easily prepared through the ring-opening reaction, which can effectively reduce the process cost.

Although the present invention has been disclosed above in terms of implementation, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field of the present invention can make various modifications without departing from the spirit and scope of the present invention. Changes and modifications, so the protection scope of the present invention shall prevail as defined by the appended claims.

Claims (10)

1. A multi-branched surfactant, characterized in that the multi-branched surfactant has a structure represented by the following formula (I):

in the formula (I), X represents a polyhydric alcohol group or a polyhydric amine group having 2 to 20 carbon atoms, R represents a structure represented by the following formula (I-1), and q represents an integer of not less than 2;

in formula (I-1), R ₁ 、R ₂ And R is R ₃ Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a methylene alkyl ether having 1 to 20 carbon atoms, a methylene aromatic ether having 6 to 25 carbon atoms, a methylene alkenyl ether having 2 to 4 carbon atoms, an alkylphenol group, an arylphenol group, or an alkylene group having 1 to 20 carbon atoms; x, y and z each independently represent 0 to 30, and the sum of x, y and z is 1 to 90; ", represents the position of formula (I-1) bonded to an oxygen atom of the polyol group or a nitrogen atom of the polyamine group.

2. The multi-branched surfactant of claim 1, wherein the polyol group or the polyamine group has 2 to 10 hydroxyl groups and/or amine groups, and q represents an integer of 2 to 10.

3. The multi-branched surfactant of claim 2, wherein the amine groups comprise primary amines and/or secondary amines.

4. The multi-branched surfactant of claim 1, wherein R ₁ 、R ₂ And R is R ₃ Are different from each other.

5. A method for producing a multi-branched surfactant, the method comprising:

the multi-branched surfactant is prepared by subjecting a mixture to a ring opening reaction, wherein the mixture comprises:

a core reactant comprising a polyol compound or a polyamine compound having a carbon number of 2 to 20; and

a branched reactant comprising a compound having one epoxide group.

6. The method of producing a multi-branched surfactant according to claim 5, wherein the amount of the branched reactant is at least 2 moles based on 1 mole of the amount of the core reactant.

7. The method for producing a multi-branched surfactant according to claim 5, wherein the compound having one epoxy group has a structure represented by the following formula (II):

in the formula (II), Y represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a methylene alkyl ether having 1 to 20 carbon atoms, a methylene aromatic ether having 6 to 25 carbon atoms, a methylene alkenyl ether having 2 to 4 carbon atoms, an alkylphenol group, an arylphenol group, or an alkylene group having 1 to 20 carbon atoms.

8. The method for producing a multi-branched surfactant according to claim 7, wherein the multi-branched surfactant has a structure represented by the following formula (III):

in formula (III), X ₁ Represents an n-valent group having 2 to 20 carbon atoms, and X ₁ Having n2 secondary amines, wherein n1 and n2 each independently represent an integer of 0 to n, and the sum of n1 and n2 is n; x is X ₂ represents-O- & ltwbr/& gtorAnd "×" represents the position of the bond to R; r' and X ₁ Is bonded to the nitrogen atom of each secondary amine; r 'and R' each independently represent a structure represented by the following formula (III-1); n represents an integer of not less than 2, when n1 and n2 independently represent integers of not less than 2, a plurality of R's are the same or different, and a plurality of-X' s ₂ -R' are identical or different:

in formula (III-1), Y ₁ 、Y ₂ And Y is equal to ₃ Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a methylene alkyl ether having 1 to 20 carbon atoms, a methylene aromatic ether having 6 to 25 carbon atoms, a methylene alkenyl ether having 2 to 4 carbon atoms, an alkylphenol group, an arylphenol group, or an alkylene group having 1 to 20 carbon atoms; a. b and c each independently represent 0 to 30, and the sum of a, b and c is 1 to 90; ", represents the position of the bond.

9. The method for producing a multi-branched surfactant according to claim 8, wherein Y ₁ 、Y ₂ And Y is equal to ₃ Are different from each other.

10. The method of producing a multi-branched surfactant according to claim 5, further comprising, before the ring-opening reaction:

and carrying out addition reaction on the nuclear reactant and an epoxy compound with 2 or 3 carbon atoms.