TWI805177B - Multi-branched surfactant and method for producing the same - Google Patents

Abstract

The present invention relates to a multi-branched surfactant, and a method for producing the same. The multi-branched surfactant is produced by performing a ring-opening reaction to a mixture. The mixture comprises a core reactant and a branched reactant. The core reactant includes a polyol compound and a polyamines compound, and the branched reactant includes a compound having an epoxy group. The multi-branched surfactant of the present application has excellent surface properties and compatibility.

Description

Multi-branched surfactant and preparation method thereof

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

By adjusting the hydrophilic-lipophilic balance, 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-based 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 compatibility, and then precipitates over time. The end 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 starting Applications where the foam is milder and it is not easy to eliminate dense foam. Furthermore, general non-silicon type 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 conventional surfactants, its preparation method and the solution containing it. The defect of the interface active solution.

Therefore, one aspect of the present invention is to provide a kind of multi-branched surfactant, which has a specific multi-branched structure, and has better interfacial activity effect and compatibility, and this multi-branched surfactant has the ability to Modified terminal 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 methylene alkyl ether with a carbon number of 1 to 20, a carbon number Methyl aryl ether with 6 to 25 carbons, methyl alkenyl ether with 2 to 4 carbons, alkylphenol group, aryl phenol group, or alkene group with 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 aspect of the present invention, a method for preparing a hyperbranched surfactant is proposed. The preparation method is to carry out ring-opening reaction on the mixture to prepare 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 with 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 an epoxy group has a 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 methylated alkyl ether with a carbon number of 1 to 20, a methylated aryl ether with a carbon number of 6 to 25, Methylenyl ether, alkylphenol group, arylphenol group with 2 to 4 carbons, or alkene group with 1 to 20 carbons.

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

，且「*」代表與R'鍵結之位置；R"係與X₁之二級胺的氮原子鍵結；R'與R"分別獨立地代表如下式(III-1)所示之結構；n代表不小於2之整數，當n1與n2獨立地代表不小於2之整數時，複數個R"係相同或不相同，且複數個-X₂-R'係相同或不相同。 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 an integer from 0 to n, and n 1 and n 2 The sum is n; X ₂ stands for -O-* or

, and "*" represents the bonded position with R';R" is bonded with 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, the plurality of R" are the same or different, and the plurality of -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, a carbon number Methyl aryl ethers with 6 to 25 carbons, methyl alkenyl ethers with 2 to 4 carbons, alkylphenol groups, aryl phenol groups, or alkene groups with 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 manufacturing method can selectively perform an addition reaction on the nuclear reactant and the epoxy compound having 2 or 3 carbon atoms.

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

Using the multi-branched surfactant of the present invention, its production method and the surfactant solution containing it, it can easily form the core structure of the multi-branched surfactant and the number of bonds bonded to the core structure through the ring-opening reaction. a branch 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 branch structure and the length of the chain segment, the prepared multi-branched surfactant can be an amphiphilic molecule with an appropriate hydrophilic-lipophilic balance value and good interfacial properties.

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 examples discussed are for description, not intended to limit the scope of the present invention.

The multi-branched 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 carbon numbers of 2 to 20. 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 having 2 to 20 carbon atoms 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. Understandably, 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 the compatibility when it is used 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, but X ₂₁ is bonded to the carbon atom of X ₁ . Understandably, 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 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 _X21 (i.e., the value of n1) can be greater than or equal to 2, And the maximum is (2N _C +2), wherein, based on the theoretical knowledge of synthetic reactions such as the bonding angle of the chain segment, the electron distribution of the bond, the reactivity of the compound and the steric barrier of the functional group, those with ordinary knowledge can understand that X ₂₁ is in the The actual bonding situation 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 can be n2, and the sum of n1 and n2 can 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, pentanediol, 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-di(3-aminopropyl) dodecylamine, N-oleyl-dipropylene Triamine, N,N-bis(3-aminopropyl) tallow amine, N'-(3-aminopropyl)-N,N-dimethyl-1,3-propanediamine, tri Propylenetetramine, N-tallow-tripropylenetetramine, N-oleyl-tripropylenetetramine, tetraethylenepentamine, monoisopropanolamine, diisopropanolamine, 2-(isopropylamino)ethanol , N-isopropyldiethanolamine, amine ethylethanolamine, other appropriate polyol compounds or polyamine compounds, or any mixture of the above compounds.

Branching reactants may include 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 methylated alkyl ether with a carbon number of 1 to 20, a methylated aryl ether with a carbon number of 6 to 25, Methylenyl ether, alkylphenol group, arylphenol group with 2 to 4 carbons, or alkene group with 1 to 20 carbons.

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-epoxydodeca 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, glycidyl pentyl ether, glycidyl hexyl ether, glycidyl heptyl ether, glycidyl octyl ether, 2-ethylhexyl glycidyl ether, glycidyl nonyl ether, glycidyl decyl ether Ether, 3-Propylheptyl glycidyl ether, Undecyl glycidyl ether, Dodecyl glycidyl ether, Tridecyl glycidyl ether, Myristyl glycidyl ether, Pentadecyl glycidyl ether Ether, Hexadecyl Glycidyl Ether, Heptadecyl Glycidyl Ether, Stearyl Glycidyl Ether, Phenyl Glycidyl Ether, Cresyl Glycidyl Ether, Styrenated Phenyl Glycidyl Ether, Benzyl Glycidyl Ether Glyceryl ether, tert-butylphenyl glycidyl ether, cardanol glycidyl ether, allyl glycidyl ether, other appropriate 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 nuclear reactants is n, the amount of branched reactants is preferably from n moles to 90n moles, more preferably from 2n moles to 40n moles, and preferably 3n moles to 10n moles. When the amount of branched reactant is the aforementioned range, the prepared multi-branched surfactant can have at least two branched structures, and each branched structure has a suitable molecular length, and has good interfacial properties (such 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 common knowledge can use the appropriate catalyst type and adjust its dosage, 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, chloride Aluminum, boron trifluoride, tin tetraisopropoxide, zinc perchlorate, other appropriate 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 reactants can also be bonded to each other to form the following formula (III) The multi-branched surfactant of the present invention. Understandably, 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.

，且「*」代表與R'鍵結之位置；R"係與X₁之二級胺的氮原子鍵結；R'與R"分別獨立地代表如下式(III-1)所示之結構；n代表不小於2之整數。當n1與n2獨立地代表不小於2之整數時，複數個R"係相同或不相同，且複數個-X₂-R'係相同或不相同。 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 an integer from 0 to n, and n 1 and n 2 The sum is n; X ₂ stands for -O-* or

, and "*" represents the bonded position with R';R" is bonded with 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, the plurality of R" are the same or different, and the plurality of -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, a carbon number Methyl aryl ethers of 6 to 25, methyl alkenyl ethers of 2 to 4 carbons, alkylphenol groups, aryl phenol groups, or alkene groups of 1 to 20 carbons, among which 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 position of the bond.

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 can have better interfacial properties. The sum of a, b and c can 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 multi-branched surfactant can have an appropriate molecular length, so that the multi-branched surfactant can have better interfacial properties. 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. Understandably, when the molecular structure of each branch structure of the multi-branched surfactant is the same, the multi-branched surfactant can be prepared by 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 in the aforementioned range, the core structure of the multi-branched surfactant can 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 be by ring-opening reaction, further react with branched compound to form multi-branched interfacial activity of the present invention as shown in aforementioned formula (III) agent. 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 2 or 3 carbons may be the same as or different from that of the branched compound. During the addition reaction, the epoxy group of the epoxy compound with 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 of 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 Better interface characteristics. In some embodiments, in the addition reaction, the epoxy compound with a carbon number of 2 or 3 reacts with a part of the hydroxyl group or amine group of the core reactant, so that each branch of the prepared multi-branched surfactant The structure has a different chain segment structure, thereby improving its interface properties.

In some embodiments, 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 multi-branched surfactant prepared by the present invention has lipophilic groups from lower alcohols to higher alcohols, and can be adjusted by alkyl carbon chains or epoxy compounds with 2 or 3 carbons Hydrophilic and 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 conventional 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 multi-branched surfactant of the present invention can be combined with Other ingredients (such as: different surfactants and/or solvents) are mixed 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. Anyone skilled in this art can 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 a catalytic amount of tetra-n-butylammonium bromide were added to 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 for ring-opening reaction at 100°C Should, after 8 hours, can react and obtain the intermediate product of embodiment 2.

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, which can be obtained as follows The multi-branched surfactant of embodiment 2 shown in formula (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 reactants. 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 compound of Example 3 shown in the following formula (V-3) can be obtained after 5 hours. Multi-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 triphenyl Phosphine was added into the reactor and heated to 120° C. to carry out the ring-opening reaction. After 8 hours, the multi-branched surfactant of Example 4 represented by the following formula (V-4) could be prepared. Among them, 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, so that the temperature is between 130 ° C and 140 ° C. The addition reaction is carried out at ℃ 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 it to 120°C to carry out the ring-opening reaction. After 4 hours, the following formula (V-5) can be obtained The hyperbranched surfactant of Example 5 is shown.

Example 6

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

Then, add the modified nuclear reactant, 18 moles of butyl glycidyl ether and boron trifluoride to the reaction kettle, and heat to 70°C to 80°C to carry out the ring-opening reaction for 1 hour to 2 hours The multi-branched 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. Among them, the surfactant of Comparative Example 1 is manufactured by Sino-Japanese Synthetic, and the product model is TL-260; the surfactant of Comparative Example 2 is manufactured by Sino-Japanese Synthetic, and the product model is PE81; the surfactant of Comparative Example 3 is The agent is produced by Sino-Japanese Synthesis, and the product model is GL-F50.

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 embodiment 1 and embodiment 3 To embodiment 6 (the terminal structure of branched structure contains butyl ether, dodecyl ether or tetradecyl ether), because the terminal structure of the branched structure of the multi-branched surfactant of embodiment 2 is ethylene oxide The alkane segment, 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 slower, 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 branch structures, and can be further improved by using the terminal groups of the branch structure. quality 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 and changes without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be defined by the scope of the appended patent application.

(none)

Claims (7)

A multi-branched surfactant has a structure shown in the following formula (I):

In formula (I), X represents a polyol group or a polyamine group with a carbon number of 2 to 20, 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 methylene alkyl ether with a carbon number of 1 to 20, a carbon number It is a methyl aryl ether of 6 to 25, a methyl alkenyl ether of 2 to 4 carbons, an alkylphenol group, an aryl phenol group, or an alkene group of 1 to 20 carbons, and R ₁ , R ₂ and R ₃ are different from each other; x, y and z independently represent 0 to 30, and the sum of x, y and z is 2 to 90; "*" represents formula (I-1) and the polyol The position where the oxygen atom of the polyamine group or the nitrogen atom of the polyamine group is bonded. The multi-branched surfactant as claimed in claim 1, wherein the polyhydric alcohol group or the polyamine group has 2 to 10 hydroxyl groups and/or amine groups, and q represents an integer of 2 to 10. The multi-branched surfactant as claimed in claim 2, wherein the amine groups comprise primary amines and/or secondary amines. A method for preparing a multi-branched surfactant, comprising: performing a ring-opening reaction on a mixture to obtain the multi-branched surfactant, wherein the mixture includes: a nuclear reactant, including a carbon number of 2 to 20 A polyol compound or a polyamine compound; and a branched reactant, comprising a compound with an epoxy group, and wherein the hyperbranched 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 an integer from 0 to n, and n 1 and n 2 The sum is n; X ₂ stands for -O-* or

, and "*" represents the bonded position with R';R" is bonded to the nitrogen atom of each secondary amine in _X1 ; R' and R" independently represent the following formula (III-1) structure; n represents an integer not less than 2, when n1 and n2 independently represent an integer not less than 2, the plural R" are the same or different, and the plural -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, a carbon number It is a methyl aryl ether with 6 to 25 carbons, a methyl alkenyl ether with 2 to 4 carbons, an alkylphenol group, an aryl phenol group, or an alkene group with a carbon number of 1 to 20, and Y ₁ , Y ₂ and Y ₃ are different from each other; a, b and c independently represent 0 to 30, and the sum of a, b and c is 2 to 90; "*" represents the position of the bond. The method for preparing a multi-branched surfactant according to claim 4, wherein the amount of the branched reactant is at least 2 moles based on the amount of the nuclear reactant being 1 mole. The preparation method of multi-branched surfactant as described in claim item 4, wherein the compound with an 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 methylated alkyl ether with a carbon number of 1 to 20, a methylated aryl ether with a carbon number of 6 to 25, Methylenyl ether, alkylphenol group, arylphenol group with 2 to 4 carbons, or alkene group with 1 to 20 carbons. As the preparation method of the multi-branched surfactant described in claim 4, before performing the ring-opening reaction, the preparation method further includes: adding an epoxy compound with 2 or 3 carbons to the nuclear reactant reaction.