Nothing Special   »   [go: up one dir, main page]

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

Multi-branched surfactant and preparation method thereof Download PDF

Info

Publication number
CN116444354A
CN116444354A CN202211330784.5A CN202211330784A CN116444354A CN 116444354 A CN116444354 A CN 116444354A CN 202211330784 A CN202211330784 A CN 202211330784A CN 116444354 A CN116444354 A CN 116444354A
Authority
CN
China
Prior art keywords
group
carbon atoms
branched
branched surfactant
methylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202211330784.5A
Other languages
Chinese (zh)
Inventor
邱柏豪
林雅慧
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sino Japan Chemical Co ltd
Original Assignee
Sino Japan Chemical Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sino Japan Chemical Co ltd filed Critical Sino Japan Chemical Co ltd
Publication of CN116444354A publication Critical patent/CN116444354A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/13—Saturated ethers containing hydroxy or O-metal groups
    • C07C43/135—Saturated ethers containing hydroxy or O-metal groups having more than one ether bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/02—Foam dispersion or prevention
    • B01D19/04—Foam dispersion or prevention by addition of chemical substances
    • B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/02—Foam dispersion or prevention
    • B01D19/04—Foam dispersion or prevention by addition of chemical substances
    • B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
    • B01D19/0413—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing N-atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
    • C07C217/08—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/10—Saturated ethers of polyhydroxy compounds
    • C07C43/11—Polyethers containing —O—(C—C—O—)n units with ≤ 2 n≤ 10

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Abstract

The invention relates to a multi-branched surfactant and a preparation method thereof. The multi-branched surfactant is prepared by subjecting a mixture to a ring-opening reaction. The mixture includes a core reactant and a branching reactant, wherein the core reactant includes a polyol compound and a polyamine compound, and the branching reactant includes a compound having an epoxy group. The prepared multi-branched surfactant has good interface characteristics 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 a multi-branched surfactant with a multi-branched structure and a preparation method thereof.
Background
By adjusting the hydrophilic-lipophilic balance, the surfactant can have good interfacial properties. Among them, surfactants having a specific structure or functional group in part are effective in eliminating foam, so they are often added to a solution to suppress the formation of foam. Surfactants that are generally used as defoamers can be classified into silicon-type defoamers containing siloxane bonds, and non-silicon-type defoamers such as polyethers, alcohols, or fatty acid esters.
Wherein, compared with the non-silicon type defoamer, the silicon type defoamer has better defoaming property. However, when a silicon-type defoaming agent is used, the dispersion stability of the groups in water is easily damaged in a high-temperature environment, so that the silicon-type surfactant is easily migrated and layered to reduce the compatibility and then is precipitated with time, and a terminal product containing the silicon-type surfactant is easily provided with surface defects such as blurred appearance, fish eyes or oil spots.
Although the non-silicon type antifoaming agent is not easily precipitated, the non-silicon type antifoaming agent generally lacks siloxane bond, so it has poor antifoaming property, but is applicable only to application fields where foamability is mild, and it is not easy to eliminate dense foam. Furthermore, typical non-silicon defoamers have poor acid and alkali resistance, low temperature flow and cold resistance. Accordingly, the application field of general non-silicon type defoamers is limited.
In view of the foregoing, it is desirable to provide a multi-branched surfactant, a method for preparing the same and a surfactant solution containing the same, so as to further improve the interfacial properties of the surfactant and solve the drawbacks of the conventional surfactant, the method for preparing the same and the surfactant solution containing the same.
Disclosure of Invention
Therefore, an aspect of the present invention is to provide a multi-branched surfactant having a specific multi-branched structure, which has a better interfacial activity effect and compatibility, and which has a modifiable terminal group, thereby improving 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, there is provided a multi-branched surfactant having 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 a polyol group or a nitrogen atom of a polyamine group.
According to some embodiments of the invention, the aforementioned polyol or polyamine groups have 2 to 10 hydroxyl or amine groups, and q represents an integer from 2 to 10.
According to some embodiments of the invention, the amine group comprises a primary amine and/or a secondary amine.
According to some embodiments of the invention, the aforementioned R 1 、R 2 And R is R 3 Are different from each other.
According to another aspect of the present invention, a method for producing a multi-branched surfactant is provided. The preparation method is to carry out ring opening reaction on the mixture to obtain the multi-branched surfactant. Wherein the mixture comprises a nuclear reactant and a branching reactant. The core reactant comprises a polyol compound or polyamine compound having a carbon number of 2 to 20, and the branching reactant comprises a compound having one epoxy group.
According to some embodiments of the invention, the branching reactant is used in an amount of at least 2 moles based on 1 mole of the aforementioned nuclear reactant.
According to some embodiments of the invention, the aforementioned 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.
According to some embodiments of the invention, the aforementioned 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 the 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 aryl 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 olefin having 1 to 20 carbon atomsA base; 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.
According to some embodiments of the invention, the foregoing Y 1 、Y 2 And Y is equal to 3 Are different from each other.
According to some embodiments of the present invention, the preparation method may selectively perform an addition reaction between the nuclear reactant and the epoxy compound having 2 or 3 carbon atoms before performing the ring-opening reaction.
According to yet another aspect of the present invention, a surfactant solution is presented. The surfactant solution comprises a multi-branched surfactant, and the multi-branched surfactant is prepared by the method.
The multi-branched surfactant, the method for producing the same and the surfactant solution containing the same can be used for forming a core structure of the multi-branched surfactant and a plurality of branch structures bonded to the core structure simply by ring-opening reaction. The branched structure of the multi-branched surfactant can effectively improve the interface characteristic of the surfactant, and the terminal group of the multi-branched surfactant can be further used for modifying resin, paint or polymer materials. Furthermore, the multi-branched surfactant prepared by adjusting the bonding number of the branched structure and the chain segment length thereof can be amphiphilic molecules, has proper hydrophilic-lipophilic balance value and has good interface characteristics.
Detailed Description
The making and using of the embodiments of the present invention are discussed in detail below. However, it is to be understood that the embodiments provide many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The particular embodiments discussed are merely illustrative and are not meant to limit the scope of the invention.
The multi-branched surfactant of the present invention is produced by subjecting the reaction mixture to a ring-opening reaction. The multi-branched surfactant is divided into a core structure and a plurality of branched structures bonded to the core structure according to the structure thereof, so that the reaction mixture correspondingly comprises a core reactant and a branched reactant.
The core reactant comprises a polyol compound having a carbon number of 2 to 20 and a polyamine compound. The polyol compound or polyamine compound may have a structure shown by the following formula (IV).
In formula (IV), X 1 Represents a group having 2 to 20 carbon atoms, and X 1 May or may not have a secondary amine; x is X 21 Represents hydroxy (-OH) or primary amine (-NH) 2 ) The method comprises the steps of carrying out a first treatment on the surface of the And n1 represents an integer of not less than 2.
The aforementioned group having 2 to 20 carbon atoms may be, for example, a linear alkyl group, a linear alkenyl group, a branched alkyl group, a branched alkenyl group, an aromatic alkyl group, a cycloalkyl group, a cycloalkenyl group, a heterocycloalkyl group, a heterocycloalkenyl group, the aforementioned group having an ether group, and/or other suitable groups. It will be appreciated that in the foregoing examples, when X 1 With a secondary amine (-NH-) the secondary amine is bonded between two carbon atoms. If X 1 If the carbon number is more than 20, the compatibility of the defoaming agent is reduced due to the excessively long carbon chain, and the defoaming agent is not easy to uniformly disperse. Preferably X 1 May represent a group having 2 to 10 carbon atoms. In formula (IV), X 21 Bonded to X 1 The position of (2) is not particularly limited as long as X 21 Is with X 1 Is bonded to the carbon atoms of the group (C). It will be appreciated that X, to facilitate bonding of subsequent branched structures 21 The bonding position of (2) does not affect the bonding of subsequent reactions. In other embodiments, at X 1 And X 21 Each carbon atom bound thereto being bound only to one X 21 。
In formula (IV), it is understood that X 21 The number of bonds of (2) is the number of n1, so according to X 1 X is a structure of (1) 21 The number of bonds (i.e., the range of n1 values) is contemplated. For example, when X 1 Represents a carbon number of N C Based on the carbon chain structure of the linear alkyl group, X can be understood 21 The number of bonds (i.e., N1 value) may be greater than or equal to 2 and a maximum of (2N) C +2) wherein the bonding angle based on the segment,The theoretical knowledge of the bond electron distribution, the reactivity of the compound, the steric hindrance of the functional group, and the like, has the general knowledge that X can be understood 21 The actual bonding on the carbon chain can be used to confirm the range of n1 values. In some embodiments, n1 may preferably represent an integer from 2 to 10, more preferably an integer from 2 to 8, and even more preferably an integer from 3 to 6. Next, when X 1 With 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 from 3 to 8.
In some embodiments, the nuclear reactant may include, but is not limited to, ethylene glycol, 2-propylene glycol, 1, 3-propylene glycol, butylene glycol, pentylene glycol, neopentyl glycol, hexylene glycol, heptylene glycol, octylene glycol, nonylene glycol, decylene glycol, glycerol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, polyglycerol, sorbitol, alkyl glucosides, sugar alcohols, cyclic alcohols, ethylenediamine, propylenediamine, decylenediamine, dodecylenediamine, tetradecyl-1, 3-propylenediamine, N-cocoyl-1, 3-propylenediamine, N-tallow-1, 3-propylenediamine, N-stearyl-1, 3-propylenediamine, N-oil-1, 3-propylenediamine, diethylenetriamine, dipropylenetriamine, N-tallow-dipropylenetriamine, N, N-di (3-aminopropyl) dodecylamine, N-oleyl-dipropylenetriamine, N-di (3-aminopropyl) tallow amine, N' - (3-aminopropyl) -N, N-dimethyl-1, 3-propylenediamine, tripropylenetetramine, N-tallow-tripropylenetetramine, N-oleyl-tripropylenetetramine, tetraethylenepentamine, monoisopropanolamine, diisopropanolamine, 2- (isopropylamino) ethanol, N-isopropyldiethanolamine, aminoethylethanolamine, other suitable polyol compounds or polyamine compounds, or any combination of the above.
The branched reactant may comprise a compound having one epoxide group. In some embodiments, the branched reactant may have a structure as shown in formula (II) below.
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.
In some embodiments, the branching reactants may include, but are not limited to, ethylene oxide, propylene oxide, butylene oxide, 1, 2-epoxypentane, 1, 2-epoxyhexane, 1, 2-epoxyheptane, 1, 2-epoxyoctane, 1, 2-epoxynonane, 1, 2-epoxydecane, 1, 2-epoxyundecane, 1, 2-epoxydodecane, 1, 2-epoxytridecane, 1, 2-epoxytetradecane, 1, 2-epoxypentadecane, 1, 2-epoxyhexadecane, 1, 2-epoxyheptadecane, 1, 2-epoxyoctadecane, phenyl ethylene oxide, tolyl ethylene oxide, styrenated phenyl ethylene oxide, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, amyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, 2-ethylhexyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, 3-propyl heptyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, pentadecyl glycidyl ether, tetradecyl glycidyl ether, phenyl glycidyl ether, hexadecyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, or any combination of the above.
The amount of the branched reactant is preferably n to 90n moles, more preferably 2n to 40n moles, and particularly preferably 3n to 10n moles based on 1 mole of hydroxyl groups and amine groups (including primary amine and secondary amine) of the nuclear reactant. When the amount of the branched reactant is in the aforementioned range, the multi-branched surfactant may have at least two branched structures each having an appropriate molecular length and having good interface characteristics (e.g., defoaming property, emulsifying property, dispersibility, wettability, acid-alkali resistance, etc.).
To enhance the reactivity, the reaction mixture may optionally contain a catalyst. According to the reaction mechanism of the nuclear reactant and the branched reactant, a person having ordinary skill can use a proper catalyst and adjust the amount thereof, so that the description is omitted here. In some embodiments, the catalyst may comprise an acid catalyst or a base catalyst. In some embodiments, the catalyst may include, but is not limited to, triphenylphosphine, triethylamine, benzyltriethylammonium chloride, tetra-n-butylammonium bromide, sodium hydroxide, potassium hydroxide, aluminum chloride, boron trifluoride, tetraisopropoxysin, zinc perchlorate, other suitable catalyst materials, or any mixture of the foregoing.
In the reaction, the epoxy groups of the branched reactants may undergo a ring-opening reaction to react with the hydroxyl groups or the amine groups of the core reactants, and the branched reactants may also be bonded to each other, thereby forming the multi-branched surfactant of the present invention as shown in the following formula (III). It is understood that the branched reactant after the ring-opening reaction is not limited to the terminal primary amine (-NH) that is only available for the nuclear reactant 2 ) Is bonded by reaction with nitrogen atoms. When the nuclear reactant comprises a secondary amine (-NH-), the epoxide group of the branched reactant may also be reactive bonded with the nitrogen atom of the secondary amine.
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 the secondary amine; r 'and R' each independently representA structure represented by the formula (III-1); n represents an integer of not less than 2. When n1 and n2 independently represent an integer 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 aryl 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, wherein the methylene alkyl ether, the methylene aryl ether, and the methylene of the methylene alkenyl ether are each bonded between the carbon chains of the ether group and the ethoxy group; 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.
It will be appreciated that the foregoing X 1 The n value of the represented n-valent group is defined by the structure of the nuclear reactant represented by the aforementioned formula (IV). The related descriptions are detailed before, so they are not repeated here.
In some embodiments, Y 1 、Y 2 And Y is equal to 3 Are different from each other. When Y is 1 、Y 2 And Y is equal to 3 When different from each other, these different branched groups can impart better interfacial properties to the resulting multi-branched surfactants. Preferably Y 1 、Y 2 And Y is equal to 3 Can independently represent a hydrogen atom, methyl, ethyl, propyl, butyl, dodecyl, tetradecyl, methylethyl, methylpropyl, methylbutyl, 2-ethylhexyl, dodecyl, tetradecyl, methylphenyl, styrenated, benzyl, tert-butylphenyl, cardanol, allyl, etc. In some embodiments, Y 1 、Y 2 And Y is equal to 3 At least one of (2)Not a hydrogen atom, methyl or ethyl. When Y is 1 、Y 2 And Y is equal to 3 When at least one of them is not a hydrogen atom, a methyl group or an ethyl group, the resulting multi-branched surfactant may have better interface characteristics. a. The sum of b and c may be from 2 to 40, and particularly preferably from 3 to 10. Wherein, when the sum of a, b and c is in the aforementioned range, each branched structure of the multi-branched surfactant may have an appropriate molecular length, and the multi-branched surfactant may have a preferable interface characteristic. In some embodiments, at least two of a, b and c are not 0, and the sum of a, b and c may be 2 to 90, where the sum of a, b and c is preferably 2 to 40, and may be 3 to 10. In these embodiments, Y 1 、Y 2 And Y is equal to 3 May be the same or different from each other. In some embodiments, in the prepared multi-branched surfactant, the molecular structures of each branched structure may be the same or different from each other, and the molecular lengths of each branched structure may be the same or different from each other. It is understood that when the molecular structures of each branched structure of the multi-branched surfactant are identical to each other, the multi-branched surfactant can be prepared by one-step reaction (i.e., ring-opening reaction). In some embodiments, the terminal group of the branched structure of the multi-branched surfactant of the present invention may preferably not be an ethylene oxide segment to have better defoaming property. If each branched structure has a different segment structure, the defoaming property of the multi-branched surfactant is improved as the number of branched structures with ethylene oxide segments at the end is reduced.
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 even more preferably from 3 to 8. When n is in the aforementioned range, the core structure of the multi-branched surfactant may have an appropriate valence for bonding of the branched structure, thereby improving the interfacial properties of the multi-branched surfactant.
The nuclear reactant of formula (IV) (i.e., a polyol compound or a polyamine compound) may be optionally subjected to an addition reaction with an epoxy compound having 2 or 3 carbon atoms (e.g., ethylene oxide and/or propylene oxide) to form a modified nuclear reactant, and then may be further reacted with a branched compound by a ring-opening reaction to form the multi-branched surfactant of the present invention as shown in formula (III) above, before the ring-opening reaction. In some embodiments, the epoxy compound having 2 or 3 carbon atoms is used in an amount of preferably 2 to 3n moles, and more preferably n to 3n moles, based on 1 mole of hydroxyl or amine groups of the nuclear reactant. In some embodiments, the amount of the epoxy compound having 2 or 3 carbon atoms may be the same as or different from the amount of the branched compound. In the addition reaction, the epoxy group of the epoxy compound having 2 or 3 carbon atoms reacts with the hydroxyl group or amine group of the nuclear reactant through a ring-opening reaction to form a modified nuclear reactant. The branched reactant can be more easily bonded to the end of the extension chain segment by the extension chain segment formed by the epoxy compound with 2 or 3 carbon numbers, so that the multi-branched surfactant prepared later can have better interface characteristics. In some embodiments, in the addition reaction, an epoxy compound having 2 or 3 carbon atoms reacts with a part of hydroxyl groups or amine groups of the core reactant, so that each branched structure of the prepared multi-branched surfactant has a different segment structure, thereby improving the interface characteristics thereof.
In some embodiments, the multi-branched surfactants of the present invention may be, for example, but not limited to, comb (comb) compounds, star compounds, dendrimer compounds, and/or other suitable forms of compounds. Preferably, the multi-branched surfactant may be a star compound or a dendrimer compound.
The multi-branched surfactant prepared by the invention has lipophilic groups from low alcohol to high alcohol, and can adjust the hydrophilic-lipophilic balance through an alkyl carbon chain or an epoxy compound with 2 or 3 carbon numbers, thereby having good interfacial characteristics such as emulsifying property, dispersity, solubilizing property, wettability, lubricity and the like. In addition, the multi-branched surfactant has a plurality of branched structures, so that compared with common non-silicon surfactants such as polyether, alcohols or fatty acid esters, the multi-branched surfactant has better defoaming property, acid and alkali resistance, compatibility, cold resistance and low-temperature fluidity, and the high-branched structure is favorable for inhibiting precipitation defects caused by siloxane bonds in the traditional defoaming agent. In addition, the amphiphilic structure and the terminal functional group of the branched structure of the multi-branched surfactant can be further modified, so the multi-branched surfactant can be used for modifying resin materials, coatings and high polymer materials.
In some embodiments, the multi-branched surfactants of the present invention may be mixed with other ingredients (e.g., different surfactants and/or solvents) to formulate a surfactant solution.
The following examples are set forth to illustrate the practice of the invention and are not intended to limit the invention thereto, as various modifications and variations may be made by those skilled in the art without departing from the spirit and scope of the invention.
Preparation of Multi-branched surfactants
Example 1
1 mole of trimethylolpropane (trimethyl propane) was added to the reaction flask and heated to 50 ℃. Then, 6 moles of butyl glycidyl ether (butyl glycidyl ether) and a catalytic amount of tetra-n-butyl ammonium bromide were added to the reaction flask and heated to 100 ℃ to perform a ring opening reaction. After 8 hours of reaction, the multi-branched surfactant of example 1 represented by the following formula (V-1) was obtained.
Example 2
1 mole of trimethylolpropane is added to the reaction flask and heated to 50 ℃. Then, 15 moles of butyl glycidyl ether and a catalytic amount of benzyl triethyl ammonium chloride were added to the reaction flask to perform a ring-opening reaction at 100℃for 8 hours, thereby obtaining an intermediate product of example 2.
Then, the above intermediate, 6 moles of ethylene oxide and a catalytic amount of potassium hydroxide were added to a high temperature high pressure reaction vessel and heated to 150 to 160 ℃ to perform a ring opening reaction, thereby obtaining the multi-branched surfactant of example 2 represented by the following formula (V-2).
Example 3
1 mole of pentaerythritol (pentaerythritol) was added to a high temperature, high pressure autoclave, and 4 moles of ethylene oxide was added with a catalytic amount of potassium hydroxide to perform an addition reaction at 150 to 160 c to form a modified nuclear reactant. Then, 8 moles of butyl glycidyl ether was added to the reaction vessel and heated to 120℃to perform a ring-opening reaction, and the multi-branched surfactant of example 3 represented by the following formula (V-3) was obtained over 5 hours.
Example 4
1 mole of pentaerythritol (pentaerythritol) was added to a high temperature and high pressure reaction vessel, and 4 moles of branched reactant (containing dodecyl glycidyl ether and tetradecyl glycidyl ether) and a catalytic amount of triphenylphosphine were added to the reaction vessel, and heated to 120℃to perform a ring-opening reaction, thereby obtaining the multi-branched surfactant of example 4 represented by the following formula (V-4) over 8 hours. Wherein R' "represents dodecyl or tetradecyl.
Example 5
1 mole of ethylenediamine (ethylenediamine) was added to a high temperature high pressure reactor, and 8 moles of ethylene oxide, 20 moles of propylene oxide, and a catalytic amount of potassium hydroxide were added to perform an addition reaction at 130 to 140 c to form a modified nuclear reactant.
Then, the modified nuclear reactant and 10 moles of butyl glycidyl ether were added to a reaction vessel and heated to 120℃to perform a ring-opening reaction, and the multi-branched surfactant of example 5 shown by the following formula (V-5) was prepared over 4 hours.
Example 6
1 mole of sorbitol (sorbitol) was added to a high temperature, high pressure autoclave, and 25 moles of ethylene oxide was added with a catalytic amount of potassium hydroxide to perform an addition reaction at 150 to 160 c to form a modified nuclear reactant.
Then, the modified nuclear reactant, 18 moles of butyl glycidyl ether and boron trifluoride were added to a reaction vessel and heated to 70 to 80℃to perform a ring-opening reaction, and the multi-branched surfactant of example 6 represented by the following formula (V-6) was prepared over 1 to 2 hours.
Evaluation method-defoaming Property
An aqueous solution of octylphenyl polyoxyethylene ether (octyl phenol ethoxylate; triton X-100) was prepared, and 1wt% of the surfactant of the example or comparative example was added based on 100wt% of the aqueous solution. Then, the defoaming property of the surfactant was evaluated by the Rose-Miles method at 25℃and the evaluation results are shown in Table 1. The surfactant of comparative example 1 is a commercial product of model TL-260, which is prepared by middle day synthesis; the surfactant of comparative example 2 was a commercial product of PE81, which was produced synthetically on the middle day; the surfactant of comparative example 3 was a commercial product of GL-F50, which was produced synthetically on a medium day.
TABLE 1
From the results in Table 1, it is found that the multi-branched surfactant of the present invention has good defoaming property. Among them, since the branched structures of the multi-branched surfactants of example 2 each have an ethylene oxide segment as compared with examples 1 and 3 to 6 (the branched structures each have butyl ether, dodecyl ether or tetradecyl ether), example 2 has relatively low defoaming property, but it is understood that example 2 is still effective in eliminating foam as compared with comparative examples.
In addition, comparative example 3 was effective in eliminating foam, but it was slower in defoaming speed and inferior in defoaming property to examples 1 to 6. Therefore, the surfactant of comparative example 3 still has the disadvantage of a general non-silicon defoamer, but cannot meet the application requirements.
Accordingly, the multi-branched surfactant and the surfactant solution containing the multi-branched surfactant of the invention can have good interface characteristics through a specific core structure and a plurality of branch structures, and can further modify resin, paint or polymer materials by utilizing the terminal groups of the branch structures. In addition, the multi-branched surfactant of the invention can be simply prepared through ring opening reaction, and the process cost can be effectively reduced.
While the present invention has been described with reference to the embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention, and it is intended that the invention be limited only 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.
CN202211330784.5A 2022-01-07 2022-10-27 Multi-branched surfactant and preparation method thereof Pending CN116444354A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TW111100836 2022-01-07
TW111100836A TWI805177B (en) 2022-01-07 2022-01-07 Multi-branched surfactant and method for producing the same

Publications (1)

Publication Number Publication Date
CN116444354A true CN116444354A (en) 2023-07-18

Family

ID=87129042

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211330784.5A Pending CN116444354A (en) 2022-01-07 2022-10-27 Multi-branched surfactant and preparation method thereof

Country Status (2)

Country Link
CN (1) CN116444354A (en)
TW (1) TWI805177B (en)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1398657A (en) * 2001-07-20 2003-02-26 气体产品与化学公司 Alkyl glycidyl ether capped polyamine foam controlling agent
CN1435454A (en) * 2002-02-01 2003-08-13 气体产品与化学公司 Alkyl glycidyl ether end-capped diamine compound foam control agent
CN1535952A (en) * 2003-03-13 2004-10-13 �����Ʒ�뻯ѧ��˾ Double structure glycidyl ether addition compound of polyhydroxy alkylalkylidine diamine
CN1902353A (en) * 2003-11-03 2007-01-24 西巴特殊化学制品控股公司 Stabilized body care products, household products, textiles and fabrics
CN101104674A (en) * 2006-07-13 2008-01-16 气体产品与化学公司 N,N,N'-trimethyl-bis-(aminoethyl) ether and its derviatives as catalysts for polyurethanes
CN101799625A (en) * 2009-12-18 2010-08-11 湛江师范学院 Hyperbranched polyester micro-optical photoresist
JP2011111582A (en) * 2009-11-30 2011-06-09 Nippon Shokubai Co Ltd Polyalkylene glycol-based compound, method for producing the same and application thereof
CN108373420A (en) * 2016-11-28 2018-08-07 中日合成化学股份有限公司 Cationic surfactant, preparation method and application thereof
CN109303051A (en) * 2018-11-19 2019-02-05 江苏钟山化工有限公司 It is a kind of for glufosinate-ammonium and the thickener composition of bispyribac-sodium and its preparation method and application
JP2020139261A (en) * 2019-02-22 2020-09-03 三洋化成工業株式会社 Fiber sizing agent

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1398657A (en) * 2001-07-20 2003-02-26 气体产品与化学公司 Alkyl glycidyl ether capped polyamine foam controlling agent
CN1435454A (en) * 2002-02-01 2003-08-13 气体产品与化学公司 Alkyl glycidyl ether end-capped diamine compound foam control agent
CN1535952A (en) * 2003-03-13 2004-10-13 �����Ʒ�뻯ѧ��˾ Double structure glycidyl ether addition compound of polyhydroxy alkylalkylidine diamine
CN1902353A (en) * 2003-11-03 2007-01-24 西巴特殊化学制品控股公司 Stabilized body care products, household products, textiles and fabrics
CN101104674A (en) * 2006-07-13 2008-01-16 气体产品与化学公司 N,N,N'-trimethyl-bis-(aminoethyl) ether and its derviatives as catalysts for polyurethanes
JP2011111582A (en) * 2009-11-30 2011-06-09 Nippon Shokubai Co Ltd Polyalkylene glycol-based compound, method for producing the same and application thereof
CN101799625A (en) * 2009-12-18 2010-08-11 湛江师范学院 Hyperbranched polyester micro-optical photoresist
CN108373420A (en) * 2016-11-28 2018-08-07 中日合成化学股份有限公司 Cationic surfactant, preparation method and application thereof
CN109303051A (en) * 2018-11-19 2019-02-05 江苏钟山化工有限公司 It is a kind of for glufosinate-ammonium and the thickener composition of bispyribac-sodium and its preparation method and application
JP2020139261A (en) * 2019-02-22 2020-09-03 三洋化成工業株式会社 Fiber sizing agent

Also Published As

Publication number Publication date
TW202328422A (en) 2023-07-16
TWI805177B (en) 2023-06-11

Similar Documents

Publication Publication Date Title
US5075403A (en) Amino/polyoxyalkylenated polydioganosiloxanes
US9399011B2 (en) Low viscosity polyorganosiloxanes comprising quaternary ammonium groups, methods for the production and the use thereof
US6987157B2 (en) Certain silicone polyethers, methods for making them and uses
CN105315437B (en) A kind of self-emulsifying aqueous epoxy hardener of nonionic and preparation method thereof
US9512275B2 (en) Low viscosity polyorganosiloxanes comprising quaternary ammonium groups, methods for the production and the use thereof (II)
CA2670305C (en) Novel polyether siloxane-containing alkoxylation products by direct alkoxylation of organomodified .alpha, omega-dihydroxysiloxanes over double metal cyanide (dmc) catalysts, and also process for producing them
JPS61137844A (en) Carbonate treatment dispersant and lubricating oil composition containing same
US20090075851A1 (en) Novel siloxane containing block copolymers, process for their preparation and their use for lubricants
CA2627140A1 (en) Polysiloxane and textile auxiliary containing a polysiloxane
CA2854915A1 (en) Block aba silicon polyalkylene oxide copolymers, methods of preparation, and applications for employing the same
EP3409745A1 (en) Engine coolant composition for automobiles and engine concentrated coolant composition for automobiles
US20010027227A1 (en) Branched polymeric surfactant reaction products, methods for their preparation, and uses therefor
CN112194797B (en) High-flash-point quaternized polyether block silicone oil and preparation method thereof
KR102628912B1 (en) Organosilicone emulsion composition
CN116444354A (en) Multi-branched surfactant and preparation method thereof
AU620661B2 (en) Water based functional fluids
CA1100245A (en) Polyether polyols and method of preparing same
US20130280201A1 (en) Fully acylated amino-functional organopolysiloxanes
EP0423696A2 (en) Betaine-containing siloxane compounds and method for making
CN101125922A (en) Process for preparing polyoxyalkylene glycol ethers using alkoxylated oligo- or polyethyleneimines as demulsifiers
CN115975204B (en) Oligosiloxane sulfonate surfactant and preparation method thereof
WO1998037126A1 (en) Method for producing organofunctional siloxanes and use of same
US7074950B2 (en) Process for preparing organosilicon compounds
JP3063498B2 (en) Polyether-siloxane copolymer and method for producing the same
CN116457408A (en) Oil compound for silicone defoamer, method for producing same, and defoamer comprising oil compound for silicone defoamer

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination