A nonionic polyether polymer surfactant and its preparation method and application

Abstract

The present invention discloses a nonionic polyether type polymer surfactant and a preparation method and application thereof. The nonionic polyether type polymer surfactant is obtained by esterification modification or etherification modification of the secondary hydroxyl group of the chain polyether type polymer surfactant and is used as a soaping agent for cotton fabrics. The nonionic polyether type polymer surfactant prepared by the present invention has strong adsorption performance, complexing ability and colloid protection performance, etc., can have a strong binding ability with dyes during soaping, has a strong removal effect on floating color on the surface of fabrics, makes the washed dyes stably exist in the washing liquid, no longer stains the fabrics, and effectively avoids the occurrence of flocculation and precipitation.

Description

Technical Field

[0001] The present invention relates to the technical field of surfactant preparation, in particular to a nonionic polyether type polymer surfactant and a preparation method and application thereof. Background Art

[0002] The application ratio of reactive dyes in cellulose fiber dyeing is constantly expanding, but after reactive dye dyeing, some dyes do not react with fibers to form covalent bonds, but are stained on the surface of fabrics after hydrolysis to form floating colors, which affects the fastness of dyed fabrics. Therefore, fabrics generally need to be soaped after dyeing. Soaping is a process in which the unfixed dyes, auxiliary dyes used, printing pastes, etc. on the surface of fiber fabrics are washed under near-boiling conditions with soap or detergent solutions to improve their color fastness and brightness after printing and dyeing. During the soaping process, the unfixed dyes are gradually transferred from the fabric to the washing bath, forming a dyeing bath condition with a certain dye concentration, temperature and time, causing the dyes to transfer to each other between different dyed parts of the washed fabric through the washing bath, especially the color transfer from the colored part to the colorless part, resulting in white ground contamination. Therefore, soaping agents need to have the functions of both washing and preventing white ground contamination.

[0003] Currently, the soap detergents for cotton fabrics on the market are generally polyacrylates or maleic acid / acrylic acid copolymers, which have good chelating, dispersing and solubilizing effects and can effectively chelate Ca 2+ Mg 2+ , can form complexes with dyes to prevent washed dyes from re-staining fabrics. However, polyacrylic acid salts or maleic / acrylic acid copolymers do not have degreasing and decontamination properties. When cotton fabrics are contaminated and dirty, they need to be compounded with low-molecular surfactants. At the same time, polyacrylic acid salts or maleic / acrylic acid copolymers are a type of polycarboxylate surfactant. When encountering cationic quaternary ammonium salts, especially quaternary ammonium salt polymers, flocculation and precipitation are likely to occur. Summary of the invention

[0004] The main technical problem solved by the present invention is to provide a nonionic polyether type macromolecular surfactant and a preparation method thereof.

[0005] In order to solve the above technical problems, the present invention provides a nonionic polyether polymer surfactant, which at least comprises the following structural formula:

[0006] ,

[0007] Wherein, the (D)- is a substituent of the monofunctional compound (D)-H;

[0008] The structure of -(AO)- is , where R a , Rb and R c are the same or different alkylene groups; n1 and n2 are both integers of 0 to 100, n3 and n4 are both integers of 1 to 100; and n1+n2+n3+n4≥10;

[0009] The -(M)- is , wherein -(W)- is a diphenol compound H-(W)-H with two phenolic hydroxyl hydrogen substituents removed; m is an integer from 1 to 21; R is -C 1-21 H 3-43 or ;

[0010] The -(N)- is a substituent of the bifunctional compound H-(N)-H;

[0011] The x is an integer of 0-20.

[0012] Furthermore, the R a , R b and R c are the same or different alkylene groups, the alkylene groups include any one or any two of -CH2-CH2-, -CH(CH3)-CH2-, -CH2-CH(CH3)-, -CH(CH2CH3)-CH2- or -CH2-CH(CH2CH3)-; and when the R a is -CH2-CH2-, and the R b and R c When it is not -CH2-CH2-, n1+n4≥n2+n3; the R b is -CH2-CH2-, and the R a and R c When it is not -CH2-CH2-, n2+n4≥n1+n3; the R c is -CH2-CH2-, and the R a and R b When it is not -CH2-CH2-, n3+n4≥n1+n2.

[0013] In order to solve the above technical problems, the present invention provides a method for preparing a nonionic polyether-type polymer surfactant, which uses a compound of structural formula (1) as a raw material, and esterifies or etherifies its secondary hydroxyl group to obtain the nonionic polyether-type polymer surfactant;

[0014] (1)

[0015] Furthermore, the esterification modification method is:

[0016] Add C2 to C 22 Fatty acid and catalyst III, esterification reaction is carried out at 80-180°C by vacuum dehydration or azeotropic dehydration;

[0017] Furthermore, the C2 to C 22 The amount of fatty acid added is 1.0 to 1.2 times the molar amount of the secondary hydroxyl group of the compound of formula (1); the amount of catalyst III added is 22 The added mass of fatty acid is 0.1-1.0%; the catalyst III includes at least one of a non-oxidizing organic acid, a reducing inorganic acid or a solid superacid.

[0018] Furthermore, the esterification modification method is: adding fatty acid C1-C4 low-carbon alcohol ester and catalyst IV to a reaction kettle containing the compound of the structural formula (1), vacuuming at 60-130°C to remove C1-C4 alcohol for esterification reaction; the C2-C 22 The added amount of fatty acid C1~C4 low-carbon alcohol ester is 1.0~1.1 times the molar amount of secondary hydroxyl group of the polyether-type polymer surfactant; the added amount of the catalyst IV is 0.2~2.0% of the added mass of the fatty acid C1~C4 low-carbon alcohol ester; the catalyst IV includes at least one of alkali metal, alkali metal alkoxide, alkaline earth metal, alkaline earth metal alkoxide, alkali metal oxide, alkali metal hydroxide or alkaline earth metal hydroxide.

[0019] Furthermore, the esterification modification method is: adding C1-C4 fatty acid anhydride to a reaction kettle containing the compound of the structural formula (1), keeping the temperature at 60-160°C for 2-6 hours to carry out esterification reaction, and then vacuuming at 60-160°C to remove C1-C4 low-carbon fatty acids and unreacted C1-C4 fatty acid anhydride.

[0020] Furthermore, the etherification modification method is: firstly add alkali metal, alkaline earth metal, alkali metal hydroxide, alkali metal oxide, alkali metal hydride, alkaline earth metal hydride, or C1-C4 alcohol alkali metal salt into a reaction kettle containing the compound of the structural formula (1), remove the generated small molecular substances at 40-160°C, and then add halogenated C1-C 21 The alkane is subjected to a nucleophilic substitution reaction at 60 to 120° C., and the salt is filtered to remove the salt, thereby obtaining the nonionic polyether-type polymer surfactant; the amount of the alkali metal, alkaline earth metal, alkali metal hydroxide, alkali metal oxide, alkali metal hydride, alkaline earth metal hydride or C1 to C4 alcohol alkali metal salt added is 1.0 to 3.0 times the molar amount of the secondary hydroxyl group of the compound of the structural formula (1); the halogenated C1 to C 21 The amount of alkane added is 1.0 to 1.5 times the molar amount of the secondary hydroxyl group of the compound of the structural formula (1).

[0021] In order to solve the above technical problems, the present invention provides an application of a nonionic polyether type polymer surfactant, wherein the nonionic polyether type polymer surfactant is used as a soaping agent for cotton fabrics.

[0022] The beneficial effects of the present invention are as follows: the present invention provides a nonionic polyether type polymer surfactant and a preparation method and application thereof; the prepared nonionic polyether type polymer surfactant has strong adsorption performance, complexing ability and colloid protection performance, etc., can have a strong binding ability with dyes during soap washing, has a strong removal effect on floating colors on the surface of fabrics, and can make the washed dyes stably exist in the washing liquid and no longer stain the fabrics, effectively avoiding the occurrence of flocculation and precipitation; the present invention is nonionic, not limited by ionicity, stable to anionic and cationic compounds in aqueous solution, and can be mixed with other nonionic, anionic or cationic products for use.

[0023] Polyacrylate or maleic / acrylic acid copolymer is a polycarboxylate surfactant. When it encounters cationic quaternary ammonium salt, especially quaternary ammonium salt polymer, it is easy to flocculate and precipitate. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is an infrared spectrum of a nonionic polyether polymer surfactant prepared in Example 1 of the present invention;

[0025] Figure 2 It is a comparison chart of the soaping effects of a nonionic polyether polymer surfactant prepared in Examples 1, 2, 3, and 4 of the present invention as a soaping agent. DETAILED DESCRIPTION

[0026] The preferred embodiments of the present invention are described in detail below in conjunction with the accompanying drawings so that the advantages and features of the present invention can be more easily understood by those skilled in the art, thereby making a clearer and more definite definition of the protection scope of the present invention.

[0027] A nonionic polyether polymer surfactant, comprising the following structural formula:

[0028] ,

[0029] Wherein, the (D)- is a substituent of a monofunctional compound (D)-H; the (D)-H has a single active hydrogen and can react with a 1,2-epoxyalkyl compound (such as ethylene oxide, 1,2-epoxypropylene, 1,2-epoxybutylene, etc.), including natural monophenol compounds, aliphatic alcohol compounds or fatty amide compounds; the natural monophenol compounds include one or more of 3-pentadecylphenol, 3-(8-pentadecenyl)phenol, 3-(8,11-pentadecadienyl)phenol, and 3-(8,11,14-pentadecatrienyl)phenol;

[0030] The structure of -(AO)- is , where R a , R b and R c are the same or different alkylene groups, the alkylene groups include any one or two of -CH2-CH2-, -CH(CH3)-CH2-, -CH2-CH(CH3)-, -CH(CH2CH3)-CH2- or -CH2-CH(CH2CH3)-; and when the R a is -CH2-CH2-, and the R b and R c When it is not -CH2-CH2-, n1+n4≥n2+n3; the R b is -CH2-CH2-, and said R a and R c When it is not -CH2-CH2-, n2+n4≥n1+n3; the R c is -CH2-CH2-, and the R a and R b When it is not -CH2-CH2-, n3+n4≥n1+n2; n1 and n2 are both integers of 0 to 100, n3 and n4 are both integers of 1 to 100; and n1+n2+n3+n4≥10;

[0031] The structural formula of -(M)- is , wherein the R is -C 1- 21 H 3-43 or , the -(W)- is a diphenol compound H-(W)-H with two phenolic hydroxyl hydrogen substituents removed; the m is an integer of 1 to 21;

[0032] The diphenol compound H-(W)-H comprises:

[0033] Refined cardols, such as 5-pentadecyl-1,3-benzenediol, 5-(8-pentadecenyl)-1,3-benzenediol, and 5-(8,11-pentadecenyl)-1,3-benzenediol;

[0034] Refined 2-methyl cardol, such as 2-methyl-5-pentadecyl-1,3-benzenediol, 2-methyl-5-(8-pentadecenyl)-1,3-benzenediol, 2-methyl-5-(8,11-pentadecenyl)-1,3-benzenediol;

[0035] Alkylene-linked cardanol dimer ( , wherein the alkylene group is located at the para and ortho positions of the phenolic hydroxyl group, and n is 0, 1 or 2);

[0036] Resorcinol;

[0037] Alkyl-substituted resorcinol or halogenated resorcinol ( );

[0038] Hydroquinone;

[0039] Alkyl-substituted hydroquinone or halogenated hydroquinone ( );

[0040] Alkyl substituted catechol dihalogenated catechol ( );

[0041] 1,3-naphthalenediol, 2,3-naphthalenediol, 1,4-naphthalenediol, (including alkyl-substituted 1,3-naphthalenediol, halogenated 1,3-naphthalenediol, alkyl-substituted 2,3-naphthalenediol, halogenated 2,3-naphthalenediol, alkyl-substituted 1,4-naphthalenediol, halogenated 1,4-naphthalenediol);

[0042] 1,5-naphthalenediol, 1,6-naphthalenediol, 1,7-naphthalenediol, 1,8-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, (including: alkyl-substituted 1,5-naphthalenediol, halogenated 1,5-naphthalenediol, alkyl-substituted 1,6-naphthalenediol, halogenated 1,6-naphthalenediol, alkyl-substituted 1,7-naphthalenediol, halogenated 1,7-naphthalenediol, alkyl-substituted 1,8-naphthalenediol, halogenated 1,8-naphthalenediol, alkyl-substituted 2,6-naphthalenediol, halogenated 2,6-naphthalenediol, alkyl-substituted 2,7-naphthalenediol, halogenated 2,7-naphthalenediol);

[0043] (including 2,2-bis(4-hydroxyphenyl)propane, 4,4'-dihydroxydiphenylmethane, 3,3',5,5'-tetrachlorobisphenol A, 3,3',5,5'-tetrabromobisphenol A);

[0044] 4,4'-Thiodiphenol; 4,4'-Sulfonyldiphenol; 2,2'-Sulfonyldiphenol; 4,4'-Dihydroxybenzophenone; 3,3'-Dimethoxybisphenol A; 4,4'-Dihydroxybiphenyl; 3,3',5,5'-Tetramethyl-4,4'-dihydroxybiphenyl; 4,4'-Dihydroxy-α-methylstilbene; 4,4'-Dihydroxybenzanilide; 4,4'-Dihydroxystilbene; 4,4'-Dihydroxy-α-cyanostilbene; 1,4-Dihydroxy-3,6-dimethoxybenzene; 1,3-Dihydroxy-4-nitrophenol; 1,3-Dihydroxy-4-cyanophenol; 4,4'-Dihydroxydiphenyloxyether;

[0045] Alkyl-substituted dihydroxy-p-diphenyl ether or halogen-substituted p-phenol ether ( );

[0046] 1,1'-Bis(4-hydroxyphenyl)-1-phenylethane ( , bisphenol AP);

[0047] 1,1'-Bis(4-hydroxyphenyl)-diphenylmethane ( , bisphenol BP);

[0048] Bisphenol E ( );

[0049] 4,4′-(1,3-phenylene diisopropylidene) diphenol (bisphenol M);

[0050] 4,4′-(1,4-phenylenediisopropylidene)diphenol ( , bisphenol P);

[0051] Bisphenol S ( );

[0052] 1,1-Bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane ( , bisphenol TMC); 1,1-bis(4-hydroxyphenyl)cyclohexane ( , bisphenol Z).

[0053] In the above formulas, R1, R2, R3, R4, R5, and R6 are H, C1 to C 20 A straight or branched alkyl or halogen; wherein the halogen is fluorine, chlorine, bromine or iodine;

[0054] The -(N)- is a substituent of a bifunctional compound H-(N)-H having two active hydrogen atoms; the x is an integer of 0 to 20; further, the H-(N)-H has two active hydrogen atoms and can undergo an alkoxylation reaction with a 1,2-epoxyalkyl compound (such as ethylene oxide, 1,2-epoxypropylene, 1,2-epoxybutylene, etc.), including diphenol compounds H-(W)-H, C6 to C36 Alkyl glycol; C6~C 36 Alkenyl diol; butynediol; dimethyloctyne diol; tetramethyldecynediol; alkyl alcohol ether diol; azelaic acid; sebacic acid; undecanedioic acid; dodecanedioic acid; dimer fatty acid; dodecylamine; octadecylamine, etc.

[0055] The preparation method of the above nonionic polyether polymer surfactant comprises the following steps:

[0056] A. Prepare a compound of the following structural formula (1);

[0057] (1)

[0058] (1) Alkoxylation reaction: add the above-mentioned monofunctional compound, difunctional compound and catalyst I accounting for 0.02-1% of the total mass of the monofunctional compound and difunctional compound in a molar ratio of 1:0.5-10 into a reactor, stir at 70-130°C for 30 minutes, vacuum remove water and replace with nitrogen, so that the water content in the reaction system is less than 0.1% of the mass of the raw materials and the oxygen content is less than 500 ppm; then add a quantitative 1,2-epoxyalkyl compound, react at 80-180°C and -0.1-0.6MPa for 0.4-4h, and after the reaction is completed, remove non-condensable gas and a trace amount of unreacted epoxyalkyl compound, then add an acidic neutralizer (such as an inorganic acid, an organic acid or an acidic compound) to neutralize the catalyst I, and separate to obtain (D)-(AO)-H and H-(AO)-(N)-(AO)H;

[0059] The catalyst I is one or more basic catalysts, including alkali metals, alkaline earth metals, alkali metal alkoxides, alkaline earth metal alkoxides, alkali metal oxides, alkali metal hydrides, alkali metal hydroxides, alkaline alkali metal or alkaline earth metal strong base weak acid salts or tertiary amines;

[0060] (2) Ring-opening polymerization reaction: Add the prepared (D)-(AO)-H, H-(AO)-(N)-(AO)H and the di-epoxy aromatic compound diluted with an alcohol ether inert solvent into the ring-opening polymerization reactor. and catalyst II, and carry out a ring-opening polymerization reaction at 40 to 140° C. for 0.5 to 6 hours. After the reaction, add a base to adjust the pH value of the reaction solution to 5.0 to 9.0 to deactivate catalyst II, thereby obtaining the compound of structural formula (1);

[0061] The alcohol ether inert solvent has a boiling point of 80-200° C. and is a compound containing no active hydrogen and having hydroxyl hydrogens in the molecule completely terminated by alkyl groups, including aliphatic ether solvents, alicyclic ether solvents, aromatic ether solvents, crown ether solvents or polyether solvents;

[0062] The amount of the diepoxy aromatic compound is 0.33 to 0.5 times the molar amount of the total active hydrogen in the compounds (D)-(AO)-H and H-(AO)-(N)-(AO)H;

[0063] The amount of the alcohol ether inert solvent is 0.05 to 5.0 times the mass of the diepoxy aromatic compound;

[0064] The amount of the catalyst II is 0.001 to 0.3 times the molar amount of the diepoxy aromatic compound;

[0065] The catalyst II includes at least one of fluorides, chlorides, bromides of boron, aluminum, iron, tin, titanium in Lewis acid and complexes of the fluorides, chlorides, bromides and alkyl ethers.

[0066] The bicyclic aromatic compound , which is a copolymer of a diphenol compound H-(W)-H and chloromethyl oxirane reacted under alkaline conditions.

[0067] The preparation method of the above structural formula (1) uses a monofunctional polyether as a capping agent, which can not only adjust the molecular weight of the entire structural formula as needed, but also reduce the risk of explosion during the reaction. By using a completely capped alcohol ether inert solvent to form a complex with the Lewis acid catalyst, on the one hand, the concentration of catalyst II is diluted, the volatility of catalyst II is reduced, and the reaction activity of catalyst II is stabilized; on the other hand, the viscosity of the entire reaction system is greatly reduced, which is convenient for removing the reaction heat and is conducive to the effective control of the temperature of the entire reaction system.

[0068] B. Esterification or etherification to prepare nonionic polyether polymer surfactant, the structural formula of which is as follows;

[0069]

[0070] The method comprises: esterifying or etherifying the secondary hydroxyl group of the compound of structural formula (1);

[0071] (1)

[0072] (3) There are three esterification methods, as follows:

[0073] Esterification method 1 is:

[0074] Add C2 to C3 into the reaction kettle containing the compound of formula (1). 22The fatty acid and the catalyst III are heated to 80-180°C, vacuum dehydrated for 3-8 hours, or azeotropic dehydration is performed for 3-8 hours by adding azeotropic agents such as chloroform, toluene, xylene or dichloroethane, and finally the residual azeotropic agent is removed under reduced pressure at 80-150°C to obtain the nonionic polyether polymer surfactant.

[0075] C2~C 22 Fatty acids include C2~C 22 Saturated fatty acids or C2~C 22 The unsaturated fatty acid is added in an amount of 1.0 to 1.2 times the molar amount of the secondary hydroxyl group of the compound of the structural formula (1).

[0076] The amount of catalyst III added is 22 The added mass of fatty acid is 0.1-1.0%. The catalyst III includes at least one of a non-oxidizing organic acid, a reducing inorganic acid or a solid superacid. Among them, the non-oxidizing organic acid includes: methanesulfonic acid, ethylsulfonic acid, propylsulfonic acid, butylsulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, 2,4-dimethylbenzenesulfonic acid, 2,4,5-trimethylbenzenesulfonic acid, 4-isopropylbenzenesulfonic acid, dodecylbenzenesulfonic acid, etc. The reducing inorganic acid includes hypophosphorous acid, phosphorous acid, sulfurous acid, etc. The solid superacid is SO4 2- / M x O y Type solid superacid.

[0077] Esterification method 2 is:

[0078] Add fatty acid C1-C4 low-carbon alcohol ester and catalyst IV to a reaction kettle containing the compound of the structural formula (1), remove the C1-C4 alcohol by vacuum at 60-130°C to carry out esterification reaction, and obtain the nonionic polyether polymer surfactant.

[0079] The fatty acid C1-C4 low carbon alcohol ester is a saturated fatty acid C1-C4 low carbon alcohol ester or an unsaturated fatty acid C1-C4 low carbon alcohol ester, and its added amount is 1.0 to 1.1 times the molar amount of the secondary hydroxyl group of the compound of the structural formula (1).

[0080] The added amount of the catalyst IV is 0.2-2.0% of the added mass of the fatty acid C1-C4 low-carbon alcohol ester; the catalyst IV includes at least one of alkali metals, alkali metal alcoholates (such as sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium tert-butoxide, potassium tert-butoxide, etc.), alkaline earth metals, alkaline earth metal alcoholates, alkali metal oxides, alkaline earth metal oxides, alkali metal hydroxides or alkaline earth metal hydroxides (such as KOH, NaOH, Mg(OH)2, etc.), and alkaline alkali metals or alkaline earth metal strong base weak acid salts (such as sodium carbonate, potassium acetate, calcium acetate, etc.).

[0081] Esterification method three is:

[0082] Add C1-C4 fatty acid anhydride to a reaction kettle containing the compound of the structural formula (1), keep the temperature at 60-160°C for 2-6 hours to carry out esterification reaction, and then vacuum remove C1-C4 low-carbon fatty acid and unreacted C1-C4 fatty acid anhydride at 60-160°C to obtain the nonionic polyether polymer surfactant.

[0083] Wherein, the amount of C1-C4 fatty acid anhydride added is 1.0-2.0 times the molar amount of secondary hydroxyl groups in the compound of the structural formula (1).

[0084] (4) The etherification modification method is: firstly add alkali metal, alkali metal hydroxide, alkali metal oxide or C1-C4 alcohol alkali metal salt into a reaction kettle containing the compound of the structural formula (1), remove small molecular substances (such as water, alcohol, hydrogen, etc.) at 40-160°C under normal pressure or reduced pressure, and then add halogenated C1-C 21 The alkane is reacted at 60-120° C., and after the reaction, the salt is removed by filtration to obtain the nonionic polyether polymer surfactant;

[0085] The amount of the alkali metal, alkali metal hydroxide, alkali metal oxide or C1-C4 alcohol alkali metal salt added is 1.0 to 3.0 times the molar amount of the secondary hydroxyl group of the compound of the structural formula (1); 21 The amount of alkane added is 1.0 to 1.5 times the molar amount of secondary hydroxyl groups in the compound of the structural formula (1).

[0086] The invention also provides an application of a nonionic polyether type high molecular surfactant used as a soaping agent for cotton fabrics.

[0087] Example 1

[0088] 150 g of a mixture of 3-(8-pentadecenyl)-phenol, 3-(8,11-pentadecadienyl)-phenol, and 3-pentadecanylphenol (about 0.5 mol), 142 g of a mixture of 5-(8-pentadecenyl)-1,3-benzenediol, 5-(8,11-pentadecadienyl)-1,3-benzenediol, and 5-pentadecanyl-1,3-benzenediol (about 0.5 mol), 16.5 g of 2- A mixture of methyl-5-(8-pentadecanyl)-1,3-benzenephenol, 2-methyl-5-(8,11-pentadecanyl)-1,3-benzenephenol, and 2-methyl-5-pentadecanyl-1,3-benzenephenol (about 0.05 mol) was put into a high-pressure reactor, and then 4.9 g of 30% sodium methoxide methanol solution was added. The temperature was raised to 100°C to remove methanol for 60 minutes, and the moisture content of the material was sampled and tested to be less than 0.1%. After nitrogen was replaced and the oxygen content in the reactor was less than 500 ppm, 4950 g (about 112.5 mol) of ethylene oxide was continuously introduced, and the reaction temperature was controlled at 155-165°C. After the ethylene oxide was introduced, the temperature was kept at 120-165°C and matured for 30 minutes until the pressure in the reactor no longer changed, that is, the unreacted ethylene oxide was basically exhausted. The temperature was lowered to 100°C, and the unreacted ethylene oxide and other non-condensable gases were removed by vacuum degassing for 0.5 hours. The temperature was lowered to 80°C, 1.63 g of acetic acid was added, and the mixture was stirred for 30 minutes.

[0089] Transfer the above reaction product to the etherification kettle, add 8.8g of boron trifluoride ether and 25.4g of diethylene glycol dimethyl ether mixed solution, then drip 255g (about 0.75 mol) of 2,2-bis(4-hydroxyphenyl)propane diglycidyl ether and 255g of diethylene glycol dimethyl ether mixed solution, control the dripping to be completed in 1.5 hours, control the reaction temperature to 80-90℃ during the whole process of adding materials, after adding, keep the reactor at 90℃ for 60 minutes; heat to 100℃ for 120 minutes. Add 5.0g of 50% sodium hydroxide solution and stir for 30 minutes, heat to 150-160℃, and remove the diethylene glycol dimethyl ether solvent by vacuuming.

[0090] The above reaction product was transferred to an esterification reaction kettle, 423 g (1.5 mol) oleic acid and 3.5 g p-toluenesulfonic acid were added, the temperature was raised to 150-160°C, and vacuum dehydration was started for 6 hours until the acid value of the reaction material no longer decreased to obtain the final product.

[0091] Appearance (25℃) Light yellow solid Solid content (wt%, 110℃) 99.7 Viscosity (mPa·s, 50°C) 7300 pH value (1% aqueous solution) 5.7

[0092] Example 2

[0093] A mixture of 150 g of 3-(8-pentadecenyl)-phenol, 3-(8,11-pentadecadienyl)-phenol, and 3-pentadecanylphenol (about 0.5 mol), a mixture of 142 g of 5-(8-pentadecenyl)-1,3-benzenediol, 5-(8,11-pentadecadienyl)-1,3-benzenediol, and 5-pentadecanyl-1,3-benzenediol (about 0.5 mol), and a mixture of 16.5 g of 2-methyl-5-(8-pentadecenyl)-1,3-benzenediol, 2-methyl-5-(8,11-pentadecadienyl)-1,3-benzenediol, and 2-methyl-5-pentadecanyl-1,3-benzenediol (about 0.05 mol) were put into a high-pressure reactor, and 1.54 g of potassium hydroxide powder was added. The temperature was raised to 110°C for dehydration for 60 minutes, and the moisture content of the material was sampled and tested to be less than 0.1%. After replacing nitrogen and the oxygen content in the kettle is lower than 500ppm, continue to introduce 264g (about 6 moles) of ethylene oxide, control the reaction temperature at 155-165℃, and complete the introduction of ethylene oxide; then introduce 261g (about 4.5 moles) of propylene oxide, control the reaction temperature at 125-135℃, and complete the introduction of propylene oxide; then introduce 1320g (about 30 moles) of ethylene oxide, control the reaction temperature at 155-165℃, and after the addition of ethylene oxide, keep the temperature at 120-165℃ and mature for 2 hours to basically consume the unreacted ethylene oxide and propylene oxide. Cool down to 100℃, vacuum degas for 0.5 hours to remove unreacted ethylene oxide, propylene oxide and other non-condensable gases. Cool down to 80℃, add 1.65g of acetic acid, and stir for 30 minutes.

[0094] The above reaction product was transferred to an etherification kettle, and a mixed solution of 7.6 g of boron trifluoride ether and 22.8 g of ethylene glycol diethyl ether was added, stirred for 20 minutes, and a mixed solution of 167 g (about 0.75 mole) of resorcinol diglycidyl ether and 166 g of ethylene glycol diethyl ether was continuously added dropwise. The reaction temperature was controlled to be 80-90°C during the addition process. After the addition, the reactor was kept at 90°C for 60 minutes; the temperature was raised to 100°C for 120 minutes. 3.5 g of sodium hydroxide was added and stirred for 30 minutes, and the temperature was raised to 110-120°C, and the ethylene glycol diethyl ether solvent was removed by vacuum.

[0095] The above reaction product was transferred to an esterification reaction kettle, 321 g (about 1.5 mol) of methyl laurate and 3.2 g of 30% sodium methoxide methanol solution were added, the temperature was raised to 100-110°C, and the methanol was removed by vacuum until the methanol in the reaction material was completely removed to obtain the final product.

[0096] Appearance (25℃) Light yellow solid Solid content (wt%, 110℃) 99.7 Viscosity (mPa·s, 50°C) 5100 pH value (1% aqueous solution) 8.7

[0097] Example 3

[0098] A mixture of 75 g (about 0.25 mol) of 3-pentadecylphenol, 3-(8-pentadecenyl)-phenol, and 3-(8,11-pentadecadienyl)-phenol, 142 g (about 0.45 mol) of 5-pentadecyl-1,3-benzenediol, 5-(8-pentadecenyl)-1,3-benzenediol, and 16.5 g (about 0.25 mol) of 5-pentadecyl-1,3-benzenediol, 5-(8,11-pentadecadienyl)-1,3-benzenediol, A mixture of 2-methyl-5-pentadecyl-1,3-benzenephenol (2.05 mol), 2-methyl-5-(8-pentadecanyl)-1,3-benzenephenol, and 2-methyl-5-(8,11-pentadecanyl)-1,3-benzenephenol was placed in a high-pressure reactor, and 7.2 g of 30% potassium methoxide methanol solution was added. The temperature was raised to 100°C and the methanol was removed by vacuum for 60 minutes. The moisture content of the material was sampled and tested to be less than 0.1%. After nitrogen was replaced and the oxygen content in the reactor was lower than 500 ppm, 3960 g (about 90 mol) of ethylene oxide was continuously introduced, and the reaction temperature was controlled at 155-165°C. After the introduction of ethylene oxide was completed, the reaction was aged for 0.5 hour to exhaust the unreacted ethylene oxide. The temperature was lowered to 100°C, and the unreacted ethylene oxide and other non-condensable gases were removed by vacuum degassing for 0.5 hour. The temperature was lowered to 80°C, 1.85 g of acetic acid was added, and the mixture was stirred for 30 minutes.

[0099] Transfer the above reaction product to the etherification kettle, add 21.3 g of boron trifluoride ether and 21.3 g of ethylene glycol diethyl ether mixed solution, stir for 20 minutes, continuously drop 138 g (about 0.625 mole) of resorcinol diglycidyl ether and 138 g of ethylene glycol diethyl ether mixed solution, control the reaction temperature to 80-90°C during the dropwise addition, after the addition, keep the reactor at 90°C for 60 minutes; heat to 100°C for 120 minutes. Cool down to 90°C, add 12 g of 50% sodium hydroxide solution and stir for 30 minutes. Heat to 110-130°C, vacuum and reduce pressure distillation to recover ethylene glycol diethyl ether.

[0100] Add 247.5 g (about 1.375 mol) of 30% sodium methoxide methanol solution to the above reaction product, raise the temperature to 110-120°C, vacuum remove methanol until no methanol is removed, cool to 80°C, add 158 g (about 1.25 mol) of benzyl chloride, react at 80-90°C for 2 hours, finally add 12.5 g (about 0.125 mol) of 36.5% hydrochloric acid to adjust the pH to neutral, filter and remove salt to obtain the final product.

[0101] Appearance (25℃) Yellow brown solid Solid content (wt%, 110℃) 99.8 Viscosity (mPa·s, 50°C) 6200 pH value (1% aqueous solution) 8.7

[0102] Example 4

[0103] A mixture of 75 g (about 0.25 mol) of 3-pentadecylphenol, 3-(8-pentadecenyl)-phenol, and 3-(8,11-pentadecadienyl)-phenol, 142 g (about 0.45 mol) of 5-pentadecyl-1,3-benzenediol, 5-(8-pentadecenyl)-1,3-benzenediol, and 16.5 g (about 0.25 mol) of 5-pentadecyl-1,3-benzenediol, 5-(8,11-pentadecadienyl)-1,3-benzenediol, A mixture of 2-methyl-5-pentadecyl-1,3-benzenephenol (2.05 mol), 2-methyl-5-(8-pentadecanyl)-1,3-benzenephenol, and 2-methyl-5-(8,11-pentadecanyl)-1,3-benzenephenol was placed in a high-pressure reactor, and 7.2 g of 30% potassium methoxide methanol solution was added. The temperature was raised to 100°C and the methanol was removed by vacuum for 60 minutes. The moisture content of the material was sampled and tested to be less than 0.1%. After nitrogen was replaced and the oxygen content in the reactor was lower than 500 ppm, 3300 g (about 75 mol) of ethylene oxide was continuously introduced, and the reaction temperature was controlled at 155-165°C. After the introduction of ethylene oxide was completed, the reaction was aged for 0.5 hour to exhaust the unreacted ethylene oxide. The temperature was lowered to 100°C, and the unreacted ethylene oxide and other non-condensable gases were removed by vacuum degassing for 0.5 hour. The temperature was lowered to 80°C, 1.85 g of acetic acid was added, and the mixture was stirred for 30 minutes.

[0104] Transfer the above reaction product to the etherification kettle, add 21.3 grams of boron trifluoride ether and 21.3 grams of ethylene glycol diethyl ether mixed solution, stir for 20 minutes, continuously drop 212 grams (about 0.625 moles) of bis[4-(2,3-epoxypropoxy)]phenylpropane and 212 grams of ethylene glycol diethyl ether mixed solution, control the reaction temperature to 80-90°C during the dropwise addition, and after the addition, keep the reactor at 90°C for 60 minutes; heat to 100°C and keep the reaction for 120 minutes. Cool down to 90°C, add 12 grams of 50% sodium hydroxide solution and stir for 30 minutes. Heat to 110-130°C, and vacuum distill to recover ethylene glycol diethyl ether.

[0105] The above reaction product was transferred to an esterification reaction kettle, 166 g (about 1.625 mol) of acetic anhydride was added, the temperature was raised to 120-125°C and refluxed for reaction for 3 hours, the temperature was raised to 135-145°C and vacuumed to remove acetic acid and excess unreacted acetic anhydride until acetic acid and acetic anhydride in the reaction material were completely removed to obtain the final product.

[0106] Appearance (25℃) Yellow brown solid Solid content (wt%, 110℃) 99.9 Viscosity (mPa·s, 50°C) 6800 pH value (1% aqueous solution) 4.9

[0107] The soaping test method of the Ministry of Industry and Information Technology on "HG / T 4660-2014 Determination of the Soaping Effect of Soaping Agents for Cotton in Textile Dyeing and Finishing Auxiliary Agents" was adopted, and the nonionic polyether polymer surfactant prepared in Examples 1, 2, 3, and 4 was used as a soaping agent to perform a soaping experiment on cotton fabrics. At the same time, a blank comparison test without adding a soaping agent was performed. The experimental conditions are as follows:

[0108] Pure cotton fabric: colored cloth (bright red) 7.5g + white cloth 2.5g;

[0109] Soaping process: soaping agent 1.5g / L, condition 95℃×20min, bath ratio 1:10;

[0110] The soaped fabric was washed three times with room temperature water at a bath ratio of 1:30, each time for 5 minutes, dehydrated, dried in an oven at 100°C for 5 minutes, cooled, and tested for soaping effect. Figure 2 As shown;

[0111] Example 1 Example 2 Example 3 Example 4 Blank K / S value 0.368 0.367 0.365 0.366 0.381

[0112] Test the K / S value, and the results are shown in the table above.

[0113] From the data in the above table, it can be seen that the use of the polyether nonionic comb-type polymer surfactants prepared in Examples 1, 2, 3 and 4 of the present invention as soaping agents can significantly reduce the K / S value of pure cotton fabrics. This shows that the polyether nonionic comb-type polymer surfactants prepared in the present invention have excellent soaping performance.

[0114] The nonionic polyether type high molecular surfactant prepared by the present invention is nonionic, not limited by ionicity, stable to anionic and cationic compounds in aqueous solution, and can be mixed with other nonionic, anionic or cationic products for use; and has strong adsorption performance, complexing ability and colloid protection performance, etc., can have strong binding ability with dyes in the soap washing process, has strong removal effect on floating color on the surface of fabrics, and can make the washed dyes stably exist in the washing liquid and no longer stain the fabrics, effectively avoiding the flocculation and precipitation phenomenon existing when using polyacrylate or maleic / acrylic acid copolymer which has no decontamination and degreasing ability as a surfactant.

[0115] The foregoing description of specific exemplary embodiments of the present invention is for the purpose of illustration and demonstration. These descriptions are not intended to limit the present invention to the precise form disclosed, and it is clear that many changes and variations can be made based on the above teachings. The purpose of selecting and describing the exemplary embodiments is to explain the specific principles of the present invention and its practical application, so that those skilled in the art can realize and utilize various different exemplary embodiments of the present invention and various different selections and changes. The scope of the present invention is intended to be limited by the claims and their equivalents.

Claims

1. A nonionic polyether polymer surfactant, characterized in that: At least the following structural formula: Wherein, the (D)- is a substituent of a monofunctional natural monophenol compound (D)-H; The structure of -(AO)- is wherein Ra, Rb and Rc are the same or different alkylene groups; n1 and n2 are both integers of 0 to 100, n3 and n4 are both integers of 1 to 100; and n1+n2+n3+n4≥10; Ra, Rb and Rc are the same or different alkylene groups, and the alkylene groups include -CH2-CH2-, -CH(CH3)-CH2-, -CH2-CH(CH3)-, -CH(CH2CH3)-CH2- or -CH2-CH(CH H2CH3)-; and when Ra is -CH2-CH2-, and Rb and Rc are not -CH2-CH2-, n1+n4≥n2+n3; when Rb is -CH2-CH2-, and Ra and Rc are not -CH2-CH2-, n2+n4≥n1+n3; when Rc is -CH2-CH2-, and Ra and Rb are not -CH2-CH2-, n3+n4≥n1+n2; The -(W)- is a diphenol compound H-(W)-H with two phenolic hydroxyl hydrogen substituents removed, and the m is an integer of 1 to 21; The R is -C 1-21 H 3-43 or The -(N)- is a substituent of the diphenol compound H-(N)-H; The x is an integer from 1 to 20; The preparation method of the nonionic polyether type polymer surfactant is to use the compound of structural formula (1) as a raw material, and to perform esterification modification or etherification modification on the secondary hydroxyl group thereof to obtain the nonionic polyether type polymer surfactant; The method for preparing the compound of structural formula (1) comprises the following steps: (1) Alkoxylation reaction: adding the above-mentioned monofunctional compound, difunctional compound and catalyst I accounting for 0.02-1% of the total mass of the monofunctional compound and difunctional compound in a molar ratio of 1:0.5-10 to a reactor, stirring at 70-130° C. for 30 min, vacuuming to remove water and replacing with nitrogen, so that the water content in the reaction system is less than 0.1% of the mass of the raw materials and the oxygen content is less than 500 ppm; then adding a certain amount of 1,2-epoxyalkyl compound, reacting at 80-180° C. and -0.1-0.6 MPa for 0.4-4 h, after the reaction is completed, removing non-condensable gas and a trace amount of unreacted epoxyalkyl compound, and then adding an acidic neutralizer to neutralize catalyst I, and separating to obtain (D)-(AO)-H and H-(AO)-(N)-(AO)H; (2) Ring-opening polymerization: Add the prepared (D)-(AO)-H, H-(AO)-(N)-(AO)H, and the di-epoxy aromatic compound diluted with an alcohol ether inert solvent into the ring-opening polymerization reactor. and catalyst II, and carry out a ring-opening polymerization reaction at 40 to 140° C. for 0.5 to 6 hours. After the reaction, add a base to adjust the pH value of the reaction solution to 5.0 to 9.0 to deactivate catalyst II, thereby obtaining the compound of structural formula (1); The alcohol ether inert solvent has a boiling point of 80-200° C. and is a compound containing no active hydrogen and having hydroxyl hydrogens in the molecule completely terminated by alkyl groups, and is a fatty ether solvent, alicyclic ether solvent, aromatic ether solvent, crown ether solvent or polyether solvent; The catalyst II is at least one of fluorides, chlorides, bromides of boron, aluminum, iron, tin, titanium in Lewis acid and complexes of the fluorides, chlorides, bromides and alkyl ethers.

2. A nonionic polyether polymer surfactant according to claim 1, characterized in that: The esterification modification method is: adding C2 to C 22 Fatty acid and catalyst III are subjected to esterification reaction at 80-180°C by vacuum dehydration or azeotropic dehydration.

3. A nonionic polyether polymer surfactant according to claim 1, characterized in that: C2~C 22 The amount of fatty acid added is 1.0 to 1.2 times the molar amount of the secondary hydroxyl group of the compound of formula (1); the amount of catalyst III added is 1.0 to 1.2 times the molar amount of the secondary hydroxyl group of the compound of formula (1); 22 The added mass of fatty acid is 0.1 to 1.0%.

4. A nonionic polyether polymer surfactant according to claim 3, characterized in that: The catalyst III is at least one of a non-oxidizing organic acid, a reducing inorganic acid or a solid superacid.

5. A nonionic polyether polymer surfactant according to claim 1, characterized in that: The esterification modification method is: adding C2 to C 22 Fatty acid C1~C4 low-carbon alcohol ester and catalyst IV are vacuumed at 60~130℃ to remove C1~C4 low-carbon alcohol for esterification reaction.

6. A nonionic polyether polymer surfactant according to claim 5, characterized in that: The amount of the C2-C22 fatty acid C1-C4 low-carbon alcohol ester added is 1.0-1.1 times the molar amount of the secondary hydroxyl group of the compound of the structural formula (1); the amount of the catalyst IV added is 22 The added mass of fatty acid C1~C4 low carbon alcohol ester is 0.2~2.0%.

7. A nonionic polyether polymer surfactant according to claim 6, characterized in that: The catalyst IV is at least one of an alkali metal, an alkali metal alkoxide, an alkaline earth metal, an alkaline earth metal alkoxide, an alkali metal oxide, an alkali metal hydroxide or an alkaline earth metal hydroxide.

8. A nonionic polyether polymer surfactant according to claim 1, characterized in that: The esterification modification method is: adding C1-C4 fatty acid anhydride to a reaction kettle containing the compound of the structural formula (1), keeping the temperature at 60-160°C for 2-6 hours to carry out esterification reaction, and then vacuuming at 60-160°C to remove C1-C4 low-carbon fatty acids and unreacted C1-C4 fatty acid anhydride.

9. A nonionic polyether polymer surfactant according to claim 2, characterized in that: The etherification modification method comprises: firstly adding alkali metal, alkali metal hydroxide, alkali metal oxide or C1-C4 alcohol alkali metal salt into a reaction kettle containing the compound of the structural formula (1), removing the generated small molecular substances under vacuum at 40-160° C., and then adding halogenated C1-C 21 The alkane is subjected to etherification reaction, filtered and desalted to obtain the nonionic polyether type polymer surfactant.

10. A nonionic polyether polymer surfactant according to claim 9, characterized in that: The amount of the alkali metal, alkali metal hydroxide, alkali metal oxide or C1-C4 alcohol alkali metal salt added is 1.0-3.0 times the molar amount of the secondary hydroxyl group of the compound of the structural formula (1); 21 The amount of alkane added is 1.0 to 1.5 times the molar amount of the secondary hydroxyl group of the compound of the structural formula (1).

11. A use of the nonionic polyether polymer surfactant as claimed in claim 1, characterized in that: The nonionic polyether type high molecular surfactant is used as a soaping agent for cotton fabrics.

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