CN107556483B - Linear amphoteric carboxyl-terminated polyether amino silicone oil, cross-linked amphoteric carboxyl-terminated polyether amino silicone emulsion softening agent prepared from same and preparation method - Google Patents
Linear amphoteric carboxyl-terminated polyether amino silicone oil, cross-linked amphoteric carboxyl-terminated polyether amino silicone emulsion softening agent prepared from same and preparation method Download PDFInfo
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Abstract
The invention discloses linear amphoteric carboxyl terminated polyether amino silicone oil which is prepared from a mixture containing amino terminated polyether silicone oil and dibasic acid anhydride; wherein, the amino terminated polyether silicone oil is prepared from a mixture containing epoxy terminated polyether silicone oil, polyether amine and isopropanol. The invention also discloses a cross-linking amphoteric carboxyl polyether amino silicon emulsion softening agent prepared based on the linear carboxyl-terminated polyether amino silicon oil and a preparation method thereof. The cross-linked amphoteric carboxyl polyether amino silicone oil is emulsified by the nonionic surfactant to prepare a silicone emulsion softener, and the silicone emulsion softener is used for fabric after-finishing, so that the soft hydrophilic performance and the hand feeling of the fabric can be improved, and the fabric can be endowed with good elastic stiffness and one-bath usability.
Description
Technical Field
The invention belongs to the technical field of textile finishing agents, and particularly relates to linear amphoteric carboxyl terminated polyether amino silicone oil, a cross-linked amphoteric carboxyl terminated polyether amino silicone emulsion softening agent prepared from the same and a preparation method of the cross-linked amphoteric carboxyl terminated polyether amino silicone emulsion softening agent.
Background
The polyether amino silicon has multiple excellent performances of a hydrophilic polyether group and amino silicone oil, is used for after-finishing of fiber fabrics, can obviously improve the softness, smoothness and hand feeling of the fiber fabrics, and can endow the fabrics with good moisture absorption, air permeability and antistatic performance, so that the polyether amino silicon is a most popular soft after-finishing auxiliary agent in recent years. However, limited by cationic character, polyether amino silicone is only suitable for cationic and nonionic systems; when used in an anionic system, the cationic polyether amino silicon has opposite electrical property with the system, so that the system is easy to demulsify, float oil or delaminate.
The carboxyl group is introduced into the structure of the polyether amino silicon, the amino group is converted into a zwitterionic group, and the application range of the polyether amino silicon can be expanded on the premise of not reducing or slightly reducing the flexibility, so that the polyether amino silicon can be used for a cationic non-ionic system, an anionic system such as shampoo, the preparation of acrylic resin coating and the like, and can be used together with an anionic resin auxiliary agent such as brightener VBL, dye and the like without emulsion breaking, precipitation or floating oil. If the linear structure of the amphoteric carboxyl polyether amino silicon can be further crosslinked and branched by using the reactant, the smooth and elastic properties of the amphoteric polyether amino silicon are improved, and meanwhile, the target silicone oil can generate comfortable and loose hand feeling.
In view of the above, the invention uses a two-step synthesis method, namely, firstly, linear amphoteric carboxyl-terminated polyether amino silicone oil is synthesized by chemical reaction, and then the carboxyl-terminated polyether amino silicone is modified by using the branched amphoteric polyether polyurethane prepolymer, so that the amphoteric carboxyl polyether amino silicone emulsion which has a cross-linking structure and can be used with anionic and cationic resins/auxiliaries in one bath is prepared, and the amphoteric carboxyl polyether amino silicone emulsion is used for the softening and after-finishing of fabrics, so that the fabrics can obtain expected anti-wrinkle and elastic effects under the premise of keeping good softness and instant hydrophilic performance of the fabrics.
Disclosure of Invention
The invention aims to disclose linear amphoteric carboxyl terminated polyether amino silicone oil, a cross-linked amphoteric carboxyl terminated polyether amino silicone emulsion softening agent prepared from the linear amphoteric carboxyl terminated polyether amino silicone oil and a preparation method of the cross-linked amphoteric carboxyl terminated polyether amino silicone emulsion softening agent. The silicone oil and the silicone emulsion prepared by the method are used for softening after-finishing of fabrics, not only can endow the fabrics with good softness, hydrophilicity and elastic stiffness, but also do not generate emulsion breaking and floating oil when used together with anionic and cationic resin assistants in one bath.
Therefore, the invention adopts the following technical scheme:
the invention utilizes aminolysis ring-opening reaction of epoxy-terminated polyether-based silicone oil and polyether amine to firstly synthesize an amino-terminated polyether silicone oil precursor, then the precursor reacts with aliphatic dicarboxylic anhydride, and firstly linear amphoteric carboxyl-terminated polyether amino silicone oil (alpha, omega-CPEAS) with molecular end groups simultaneously carrying functional groups such as polyether amino, carboxyl, carbon hydroxyl and the like is synthesized; secondly, diisocyanate, polyether polyol, triethanolamine-dimethylolpropionic acid and other mixtures in equal molar ratio are reacted in sequence to prepare branched amphoteric polyether polyurethane Prepolymer (PU), then alpha, omega-CPEAS and PU are reacted to prepare polyether polyurethane modified amphoteric carboxyl polyether amino silicone oil with a cross-linked structure, and the corresponding silicon emulsion softener can be obtained after emulsification.
(1) Preparation of solvent type linear amphoteric carboxyl terminated polyether amino silicone oil: sequentially weighing alpha, omega-EPS and PEA according to the molar ratio of the epoxy-terminated polyether-based silicone oil (alpha, omega-EPS) to the polyether amine (PEA) of 1:2, uniformly stirring, adding an Isopropanol (IPA) solvent accounting for 20-200% of the mass of the alpha, omega-EPS and PEA, stirring, heating to 80-85 ℃, continuously reacting for 4-24h, and then carrying out reduced pressure distillation to recover the IPA solvent to obtain an amino-terminated polyether silicone oil (alpha, omega-PEAS) precursor; stirring, adding 20-30% of polar alcohol ether solvent A according to the mass of precursor alpha, omega-PEAS, adjusting the reaction temperature to 70-125 ℃, then adding dibasic acid anhydride according to the molar ratio of the alpha, omega-PEAS to the dibasic acid anhydride of 1:2 to carry out carboxylation reaction for 1-4h, and obtaining slightly turbid to transparent liquid after the reaction is finished, namely the solvent type linear amphoteric carboxyl terminated polyether amino silicone oil (alpha, omega-CPEAS) with the silicone oil content of about 77.0-85.0%.
(2) Preparing a branched amphoteric polyether polyurethane prepolymer: adding Diisocyanate (DIC) into a drying reactor, stirring and heating to 35-80 ℃, dropwise adding polyether polyol and a non-reactive polar solvent B accounting for 20-50% of the mass of DIC and PEPO according to the molar ratio of diisocyanate to polyether polyol (PEPO) of 2:1-1.25:1, controlling the temperature to be 35-80 ℃ for reaction for 0.5-1h, then adding a mixture of triethanolamine and dimethylolpropionic acid accounting for 0.5-1% of the mass of DIC and PEPO in an equal molar ratio, controlling the temperature to be 35-80 ℃ and continuing to react for 0.5-2h to obtain a product, namely a branched amphoteric polyether polyurethane Prepolymer (PU).
(3) Preparing an amphoteric carboxyl polyether amino silicon emulsion softening agent with a cross-linked structure: mixing solvent type linear alpha, omega-CPEAS and branched amphoteric PU, controlling the dosage of the two so that the mass ratio of alpha, omega-CPEAS silicone oil to PU solid in the system is 1:1-0.3, stirring, controlling the temperature to be 30-70 ℃, and then carrying out reaction for 0.5-2h to obtain a product, namely, a crosslinking structure amphoteric carboxyl polyether amino silicone oil (PUCS) solution.
Taking the PUCS solution, adding 30-50% of fatty alcohol-polyoxyethylene ether emulsifier by mass of silicone oil into the PUCS solution according to the mass of the silicone oil, stirring and mixing the mixture for 30min, adding acetic acid (HAc) into the mixture to adjust the pH value of the system to be 5-6, and adding water into the mixture while stirring to emulsify the mixture to obtain semitransparent and transparent micro emulsion, namely the cross-linked structure amphoteric carboxyl polyether amino silicon emulsion softener with the solid content of about 15-30%.
The structure of the epoxy-terminated polyether silicone oil (alpha, omega-EPS) is shown as a formula (1), the main chain is polydimethylsiloxane, and the end group is an epoxy polyether group:
in the formula (1), n is the polymerization degree of dimethyl siloxane chain units, and the value range is 25-270; a. b is the polymerization degree of oxyethylene and oxypropylene chain units, a and b range from 0 to 30, and a + b range from 3 to 30.
The polyether amine is aliphatic binary organic amine with two molecular ends connected with aliphatic primary amino and a polyoxyethylene polyoxypropylene ether chain segment in the middle, and has the structure as follows:
H2N(C3H6O)x(C2H4O)y(C3H6O)zC3H6NH2 (2)
wherein x, y, and z are positive numbers, x + z is in the range of 2.5-33.1, y is in the range of 0-39, the polyetheramine has a number average molecular weight (Mn) of 230-.
The dibasic acid anhydride is aliphatic dibasic acid anhydride, and is one of maleic anhydride, succinic anhydride, methylene succinic anhydride, adipic anhydride, glutaric anhydride and the like.
The epoxy terminated polyether silicone oil and the polyether amine are reacted, the molar ratio of alpha, omega-EPS to PEA is 1:2, the reaction temperature is 80-85 ℃, the reaction time is 4-24h, and the obtained product is a precursor, namely amino terminated polyether silicone oil (alpha, omega-PEAS); the alpha, omega-PEAS and the dibasic acid anhydride are subjected to carboxylation reaction, the molar ratio of the alpha, omega-PEAS to the dibasic acid anhydride is 1:2 (the molar ratio of polyetheramine to the dibasic acid anhydride contained in the alpha, omega-PEAS is 1:1), the reaction temperature is 70-125 ℃, the reaction time is 1-4 hours, and the obtained product is amphoteric carboxyl terminated polyether amino silicone oil (alpha, omega-CPEAS) with a structure shown in a formula (3); the precursor product amino-terminated polyether silicone oil (alpha, omega-PEAS) has a structure shown in a formula (4):
in the formulas (3) and (4), pe1, pe2 and pe3 are polyether groups, pe1 is from raw materials of alpha, omega-EPS, pe2 and pe3 are from polyether amine, and pe2 and pe3 can be the same or different; in addition, in the formulas (3) and (4), the values of n, a and b are in the same range as that of the formula (1), and the values of x, y and z are in the same range as that of polyether amine.
The diisocyanate is mainly aliphatic or aromatic diisocyanate containing two NCO groups in a molecule, and one of Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), 4' -diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI) and the like is selected; the polyether polyol (PEPO) is one of polyethylene glycol (PEG) with the number average molecular weight of 200-2000, polytetrahydrofuran ether glycol (PTHG) and the like, and preferably one or a mixture of any two of polyethylene glycol with the average molecular weight of 200, 400, 600, 1000 and 2000, such as PEG-200, PEG-400, PEG-600, PEG-1000, PEG-2000 and the like.
The polar alcohol ether solvent A is generally an alcohol ether and ether ester compound which has good solubilizing effect on the precursor amino-terminated polyether silicone oil, aliphatic dicarboxylic anhydride and polyether polyurethane in the subsequent reaction and is easily soluble in water, one or a mixture of any two of ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether and ethylene glycol methyl ether acetate is preferably selected, and the dosage of the alcohol ether solvent A is generally 20-30% of the mass of the amino-terminated polyether silicone oil; the non-reactive solvent B and the polar alcohol ether solvent A can be the same or different, one or a mixture of any two of the alcohol ether solvent A, acetone or dioxane is selected, and the dosage is generally 20-50% of the mass of DIC + PEPO.
The cross-linked structure amphoteric carboxyl polyether amino silicone oil prepared by the reaction of alpha, omega-CPEAS and PU is easy to form an elastomer and cannot be used if the system is excessively cross-linked in the reaction process or the product is placed for a long time; in order to avoid the phenomenon, the emulsifier can be directly added into the system for emulsification after the reaction is finished (without removing the solvent), and the silicone oil can be converted into the stable silicon microemulsion for storage.
The cross-linked structure amphoteric carboxyl polyether amino silicon emulsion softener has the solid content of 15-30 percent, is diluted by water and used for fabric softening after-finishing by a dipping or one-dipping-one-rolling process, and is cured by baking, so that the treated fabric has excellent softening performance and hand feeling, the static water absorption time (represented by the time for 1 drop of water absorbed by the surface of the fabric) of the fabric can be shortened to several seconds (1.87s), and the elastic stiffness (represented by the warp and weft wrinkle recovery angle (measured by a fabric wrinkle elasticity meter) reaches 302 degrees.
The molecule of the amphoteric carboxyl polyether amino silicon emulsion softener with the cross-linked structure simultaneously carries carboxyl and amino amphoteric functional groups, so that the amphoteric carboxyl polyether amino silicon emulsion softener can stably exist in a wider pH value range (pH is 1-14), and can not generate emulsion breaking and floating oil when being used with anionic, cationic, nonionic and amphoteric ion resins or assistants in one bath.
The cross-linked amphoteric carboxyl polyether amino silicon emulsion softener is used together with anionic and cationic resin auxiliaries in a bath without emulsion breaking and floating oil, is used for after-finishing of fabrics, and can endow the fabrics with good softness, hydrophilicity and elastic stiffness.
The invention has the beneficial effects that:
the invention takes the terminal amino polyether silicone oil formed by the ring-opening reaction of the terminal epoxy polyether silicone oil and the polyether amine as a precursor raw material, the terminal amino polyether silicone oil reacts with aliphatic dicarboxylic anhydride, and the linear amphoteric terminal carboxyl polyether amino silicone oil (alpha, omega-CPEAS) with polyether amino, carboxyl alkyl and C-OH simultaneously connected in the molecule is firstly synthesized by utilizing the characteristic that the carboxyl can be released when the primary amino group reacts with the anhydride to form amide;
secondly, in order to achieve the effect of elasticity, diisocyanate and hydrophilic polyether polyol are reacted, and then the blend with the equal molar ratio of the latent amphoteric TEOA and dimethylolpropionic acid is used for chain extension and crosslinking, so that an NCO-terminated amphiphilic polyether polyurethane Prepolymer (PU) with multi-point branched and crosslinked intramolecular is synthesized; the carboxyl polyether amino silicon and the polyether polyurethane prepolymer which is elastically branched are chemically bonded together by taking the carboxyl polyether amino silicon as a macromolecular reactant and utilizing the characteristic that residual-NCO in PU can react when meeting amino and C-OH in alpha, omega-CPEAS, so that the carboxyl polyether amino silicon PUCS with a cross-linked structure, which has the properties of softness, hydrophilicity, elasticity and stiffness and polyurethane modification, is prepared;
in addition, under the action of the fatty alcohol-polyoxyethylene ether nonionic surfactant, the PUCS is emulsified into stable silicon emulsion for softening and after-finishing of fabrics, and the result shows that the PUCS emulsion can be used together with the anionic and cationic resin auxiliary agent in a bath, the static water absorption time of the fabric finished by the emulsion can be shortened to 1.87s, the warp and weft wrinkle recovery angle can reach 302 degrees, and the fabric has very good softening, hydrophilic and elastic and stiff effects.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
(1) Preparation of solvent type linear carboxyl-terminated polyether amino silicone oil: in a three-necked bottle provided with a thermometer, a reflux condenser tube and an electric stirrer, epoxy polyether silicone oil is added according to the proportion: 0.01mol (203.58g) of polyether amine with the molar ratio of 1:2 is weighed in sequence, and the structural formula is shown in formula (1), n is 270, and a is 3α, ω -EPS-1 with 0.02mol (4.6g) average molecular weight 230, x + z 2.5, y 0 structure H2NC3H6O(C3H6O)2.5C3H6NH2Uniformly stirring and mixing the polyether amine D230, adding 20 percent of isopropanol solvent accounting for the mass of alpha, omega-EPS-1 and D230 and about 41.64g of isopropanol solvent, stirring, heating to 80 ℃, continuously reacting for 4 hours, and then decompressing and recovering IPA solvent at 80 ℃ and 0.2MPa to obtain 0.01mol of amino-terminated polyether silicone oil (alpha, omega-PEAS-1) with the total amount of about 208.18 g; then, 20 percent and about 41.64g of ethylene glycol dibutyl ether solvent are added according to the mass of the alpha, omega-PEAS-1, the reaction temperature is adjusted to 70 ℃, the mixture is stirred, 0.02mol and about 1.96g of maleic anhydride (the molar ratio of the alpha, omega-PEAS-1 to the maleic anhydride is 1:2) are added in batches for carboxylation reaction for 1h, and light yellow transparent liquid is obtained after the reaction is finished, namely the solvent type amphoteric carboxyl terminated polyether amino silicone oil with the structure shown as (3-1), which is marked as alpha, omega-CPEAS-1, and the content of the silicone oil is about 83.46 percent.
(2) Preparing an amphoteric polyether polyurethane prepolymer PU-1: 0.03mol and 6.66g of isophorone diisocyanate (IPDI) are taken to be put into a dry three-necked bottle with a thermometer, a reflux condenser tube and an electric stirrer, stirred and heated to 80 ℃, then 0.015mol, namely 30g of dried polyethylene glycol PEG-2000 and 20 mass percent of IPDI + PEG-2000 and about 7.33g of diethylene glycol dimethyl ether solvent are added dropwise according to the molar ratio of IPDI to polyether polyol of 2:1, the temperature is controlled to react for 0.5h, then a mixture of 0.5 mass percent of IPDI + PEG-2000 and about 0.18g of TEOA and dimethylolpropionic acid is added dropwise, the temperature is controlled to be 35 ℃, and the reaction is continued for 2h, so that a total amount of about 43.99g of product, namely, the amphoteric polyether polyurethane prepolymer (PU-1) is obtained, and the solid content is about 83.74%.
(3) Preparing an amphoteric carboxyl polyether amino silicon emulsion softening agent with a cross-linked structure: 20g of 83.46 percent solvent type alpha, omega-CPEAS-1 (containing 16.69g of silicon oil) is mixed with 19.93g of PU-1 (containing 16.69g of solid) with the solid content of 83.74 percent, the mass ratio of the alpha, omega-CPEAS-1 silicon oil to the solid content of the PU-1 in the system is 1:1, the mixture is stirred, the temperature is controlled at 30 ℃, and then the mixture is reacted for 0.5h, the obtained product, namely the polyether polyurethane modified crosslinking structure amphoteric carboxyl polyether amino silicone oil (PUCS-1) solution has the silicone oil content of about 83.59 percent.
30g of PUCS-1 solution with the silicone oil content of 83.59 percent is taken, 30 percent of isomeric tridecanol polyoxyethylene ether 1350/1390 (mass ratio of 1:2) emulsifier which is calculated by the mass of the silicone oil and about 7.52g of isomeric tridecanol polyoxyethylene ether 1350/1390 are added, the mixture is mechanically stirred and mixed for 30min, HAc is added to adjust the pH value of the system to be 5-6, and then 71.14g of deionized water is added to emulsify while stirring, so that transparent micro emulsion, namely the cross-linked structure amphoteric carboxyl polyether amino silicon emulsion (PUCS-1) softener with the solid content of about 30 percent is obtained.
Example 2
(1) Preparation of carboxyl-terminated polyether amino silicone oil: 0.01mol (48.50g) of epoxy polyether group-terminated silicone oil (alpha, omega-EPS-2) with the structure shown in formula (1), n-25, a-30, b-0 and Mn of about 4850 and 0.02mol (40.00g) of epoxy polyether silicone oil (alpha, omega-EPS-2) with the average molecular weight of 2000, y-39, x + z-6 and the structure H are weighed in sequence according to the molar ratio of epoxy polyether group-terminated silicone oil to polyether amine of 1:2 in a three-necked bottle with a thermometer, a reflux condenser and an electric stirrer2NC3H6O(C3H6O)6(C2H4O)39C3H6NH2Uniformly stirring and mixing the polyether amine ED2003, adding about 177.0g of IPA solvent accounting for 200 mass percent of alpha, omega-EPS-2 + ED2003, stirring, heating to 85 ℃ for continuous reaction for 24h, and then removing the IPA solvent by evaporation under reduced pressure to obtain 0.01mol of amino-terminated polyether silicone oil (alpha, omega-PEAS-2) with the total amount of about 88.50 g; then, 30 percent and about 26.55g of diethylene glycol dibutyl ether solvent are added according to the mass of the alpha, omega-PEAS-2, the mixture is stirred, the reaction temperature is adjusted to 125 ℃, 0.02mol and about 2.0g of succinic anhydride (the molar ratio of the alpha, omega-PEAS-2 to the succinic anhydride is 1:2) are added in batches, the carboxylation reaction is carried out for 4 hours at 125 ℃, and the total amount of 117.05g of light yellow transparent liquid, namely the solvent type amphoteric carboxyl polyether amino silicone oil (alpha, omega-CPEAS-2) with the structure shown as (3-2) is obtained after the reaction is finished, wherein the silicone oil content is about 77.32 percent.
(2) Preparation of amphoteric polyether polyurethane prepolymer (PU-2): 0.05mol and 8.41g of Hexamethylene Diisocyanate (HDI) are taken to be put into a dry three-necked bottle with a thermometer, reflux condensation and an electric stirrer to be stirred and heated to 35 ℃, then 0.04mol, namely 8g of dried PEG-200(Mn200) and 50% by mass of HDI + PEG-200 and about 8.21g of non-reactive diethylene glycol dibutyl ether solvent are added dropwise according to the molar ratio of HDI to polyether polyol of 1.25:1, the temperature is controlled to be reacted for 1h, then a mixture of HDI + PEG-200 and 1% by mass of about 0.16g of TEOA and dimethylolpropionic acid is added dropwise, the temperature is controlled to be 80 ℃, the reaction is continued for 0.5h, and the total amount of about 24.78g of product, namely, amphoteric polyether polyurethane prepolymer (PU-2) with the solid content of 66.89% is obtained.
(3) Preparing a crosslinking modified amphoteric carboxyl polyether amino silicon emulsion softening agent: 30g of solvent type alpha, omega-CPEAS-2 with the solid content of about 77.32 percent is mixed with 10.40g of amphoteric polyether polyurethane prepolymer PU-2 with the solid content of about 66.89 percent, the mass ratio of the alpha, omega-CPEAS-2 silicone oil to PU-2 solid content in the system is 1:0.3, the mixture is stirred and evenly mixed, heated to 70 ℃ and then reacted for 2 hours to obtain 40.40g of product, namely polyether polyurethane modified amphoteric carboxyl polyether amino silicone oil (PUCS-2) solution with the cross-linked structure, and the solid content of the polyether polyurethane modified amphoteric carboxyl polyether amino silicone oil (PUCS-2) solution is about 74.62 percent.
20.0g of PUCS-2 solution (containing 14.92g of silicone oil) with the silicone oil content of 74.62 percent is taken, 50 percent of fatty alcohol-polyoxyethylene ether emulsifier AEO-3/AEO-9 (the mass ratio is 1:3) which is calculated by the mass of the silicone oil and about 7.46g of fatty alcohol-polyoxyethylene ether emulsifier are added, the mixture is stirred and mixed for 30min, HAc is added to adjust the pH value of the system to be 5-6, and 121.81g of deionized water is added while stirring to obtain transparent micro emulsion, namely the cross-linked structure amphoteric carboxyl polyether amino silicon emulsion (PUCS-2) softener with the solid content of about 15 percent.
Example 3
(1) Preparation of solvent type carboxyl-terminated polyether amino silicone oil: in a three-necked bottle provided with a thermometer, a reflux condenser tube and an electric stirrer, the epoxy polyether-based silicone oil is terminated according to the following steps: 0.02mol (211.4g) of epoxy terminated polyether silicone oil (alpha, omega-EPS-3) with the structure shown in formula (1), n-133, a-7, b-3 and Mn of about 10570 and 0.04mol (24.0g) of average are weighed in sequence at a polyether amine molar ratio of 1:2Molecular weight of 600, y 9, x + z 3.6, structure H2NC3H6O(C3H6O)3.6(C2H4O)9C3H6NH2Uniformly stirring and mixing the polyether amine ED600, adding about 141.24g of IPA solvent accounting for 60% of the mass of alpha, omega-EPS-3 + ED-600, heating to 80 ℃, continuously reacting for 8h, and then carrying out reduced pressure distillation to recover the solvent IPA, thereby obtaining 0.02mol of amino-terminated polyether silicone oil (alpha, omega-PEAS-3) with the total amount of about 235.4 g; then, 25 percent and about 58.85g of dipropylene glycol dimethyl ether solvent are added according to the mass of the alpha, omega-PEAS-3, the reaction temperature is adjusted to 75 ℃, 0.04mol and about 4.48g of methylene succinic anhydride (the molar ratio of the alpha, omega-PEAS-3 to the methylene succinic anhydride is 1:2) are added in batches, the temperature is controlled to 75 ℃ for carboxylation reaction for 2 hours, and the total amount of 298.75g of light yellow transparent liquid is obtained after the reaction is finished, namely the solvent type amphoteric carboxyl polyether amino silicone oil (alpha, omega-CPEAS-3) with the structure shown as (3-3) has the silicone oil content of about 80.29 percent.
(2) Preparation of amphoteric polyether polyurethane prepolymer (PU-3): 0.03mol and 7.51g of 4, 4' -diphenylmethane diisocyanate (MDI) are taken to be put into a dry three-necked bottle provided with a thermometer, a reflux condenser and an electric stirrer, stirred and heated to 60 ℃, then 0.02mol, namely 12g of dried PEG-600, 25 mass percent of MDI plus PEG-600 and 4.88g of dipropylene glycol dibutyl ether are added dropwise according to the molar ratio of MDI to polyether polyol of 1.5:1, the temperature is controlled to be 70 ℃ for reaction for 50min, then a mixture of 0.6 mass percent of MDI plus PEG-600 and 0.12g of TEOA-dimethylolpropionic acid is added dropwise, the temperature is controlled to be 60 ℃, and the reaction is continued for 1.5h, so that about 24.51g of products are obtained, namely, the amphoteric polyether polyurethane prepolymer (PU-3, the solid content is about 80.09%).
(3) Preparation of crosslinking modified amphoteric carboxyl polyether amino silicon emulsion softening agent
21.83g of solvent type alpha, omega-CPEAS-3 (containing 17.53g of silicon oil) with the silicone oil content of 80.29 percent is mixed with 10.94g of polyether polyurethane prepolymer PU-3 with the solid content of about 80.09 percent (containing 8.77g of solid), and the mass ratio of the alpha, omega-CPEAS-3 silicone oil to the PU-3 solid in the system is 1: 0.5, stirring and mixing evenly, heating to 40 ℃ for reaction for 2 hours to obtain a product with the total amount of about 32.77g, namely the polyether polyurethane modified cross-linked structure amphoteric carboxyl polyether amino silicone oil (PUCS-3) solution with the silicone oil content of about 80.26 percent.
20g of PUCS-3 (containing 16.05g of silicone oil) with the silicone oil content of about 80.26 percent is taken, 40 percent of isomeric dodecyl alcohol polyoxyethylene ether XP-30/XP-90 (the mass ratio is 1:2.5) emulsifier which is calculated by the mass of the silicone oil and about 6.42g of isomeric dodecyl alcohol polyoxyethylene ether XP-30/XP-90 are added, the mixture is stirred and mixed for 30min, HAc is added to adjust the pH value of the system to be 5-6, and 85.93g of deionized water is added while stirring to obtain transparent micro emulsion, namely the cross-linked amphoteric carboxyl polyether amino silicon emulsion (PUCS-3) softener with the solid content of about 20 percent.
Example 4
(1) Preparation of solvent type carboxyl-terminated polyether amino silicone oil: in a three-necked flask provided with a thermometer, a reflux condenser tube and an electric stirrer, the epoxy polyether-based silicone oil is terminated by the following steps: 0.005mol (39.5g) of epoxy terminated polyether silicone oil alpha, omega-EPS-4 with the structure shown in formula (1), n is 90, a is 10 and b is 0 and 0.01mol (9.0g) of epoxy terminated polyether silicone oil alpha, omega-EPS-4 with the average molecular weight of 900, y is 12.5 and x + z is 6 and the structure is H are weighed in sequence with the polyether amine molar ratio of 1:22NC3H6O(C3H6O)6(C2H4O)12.5C3H6NH2Adding 100 percent of IPA solvent accounting for the mass of alpha, omega-EPS-4 and PEA and about 48.5g of IPA solvent into the polyether amine ED900, uniformly stirring, heating to 82 ℃ for continuous reaction for 12 hours, and then decompressing and recovering the IPA solvent to obtain 0.005mol of amino-terminated polyether silicone oil (alpha, omega-PEAS-4) with the total amount of about 48.5 g; then, 20 percent and about 9.7g of solvent consisting of ethylene glycol dibutyl ether and ethylene glycol monobutyl ether acetate (mass ratio is 2:1) are added according to the mass of the alpha, omega-PEAS-4, the reaction temperature is adjusted to 70 ℃, 0.01mol and about 1.14g of glutaric anhydride (the molar ratio of the alpha, omega-PEAS-4 to the glutaric anhydride is 1:2) are added, the temperature is controlled at 70 ℃, the carboxylation reaction is carried out for 1.5h, and the total amount is 59.34g of colorless-light yellow transparent liquid, namely the solvent type amphoteric carboxyl polyether amino silicone oil (alpha, omega-CPEAS-4) with the structure shown as (3-4) is obtained after the reaction, and the silicone oil content is about 83.65 percent.
(2) Preparation of amphoteric polyether polyurethane prepolymer (PU-4): 0.04mol and 6.97g of Toluene Diisocyanate (TDI) are put into a dry three-necked bottle with a thermometer, a reflux condenser and an electric stirrer, stirred and heated to 60 ℃, then 0.0222mol and 22.22g of dried polyethylene glycol PEG-1000 and 28% of solvent consisting of dipropylene glycol dibutyl ether and dioxane (mass ratio of 1:1) are added according to the molar ratio of HDI to polyether polyol (1.8: 1) according to the mass of TDI + PEG-1000 (total amount of 29.19g), the temperature is controlled at 50 ℃, the reaction is carried out for 45min, then a mixture of 0.5% of TDI + PEG-1000 (mass of 29.19g) and 0.146g of TEOA and dimethylolpropionic acid in equal molar ratio is added dropwise, and the reaction is continued for 1h, and the obtained product, namely the amphoteric polyether polyurethane prepolymer (PU-4) has the solid content of about 77.23%.
(3) Preparation of crosslinking modified amphoteric carboxyl polyether amino silicon emulsion softening agent
21.83g of solvent type alpha, omega-CPEAS-4 (containing 18.26g of silicon oil) with the silicone oil content of 83.65 percent is mixed with 18.92g of polyether polyurethane prepolymer PU-4 with the solid content of about 77.23 percent (containing 14.61g of solid), and the mass ratio of the alpha, omega-CPEAS-4 silicone oil to the PU-4 solid in the system is 1: 0.8, stirring, controlling the temperature to be 40 ℃ and reacting for 2h to obtain a product with the total amount of about 40.75g, namely the product, namely the polyether polyurethane modified crosslinking structure amphoteric carboxyl polyether amino silicone oil (PUCS-4) solution, wherein the content of the silicone oil is about 80.66 percent.
20g of PUCS-3 solution (containing 16.13g of silicone oil) with the silicone oil content of about 80.66 percent is taken, 35 percent of isomeric dodecyl alcohol polyoxyethylene ether XL-40/XL90 (mass ratio of 1:3) emulsifier which is calculated by the mass of the silicone oil is added, the mixture is stirred and mixed for 30min, HAc is added to adjust the pH value of the system to be 5-6, 83.21g of deionized water is added while stirring, and transparent micro emulsion, namely the cross-linked amphoteric carboxyl polyether amino silicon soft emulsion (PUCS-4) soft agent with the solid content of about 20 percent is obtained.
Example 5
(1) Preparation of solvent type carboxyl-terminated polyether amino silicone oil: in a three-necked flask provided with a thermometer, a reflux condenser tube and an electric stirrer, the epoxy polyether-based silicone oil is terminated by the following steps:0.006mol (89.62g) of epoxy terminated polyether silicone oil alpha, omega-EPS-5 with the structure shown in formula (1), n-174, a-14 and b-6 and 0.006mol (2.4g) of average molecular weight 400, x-5.5, y-z-0 and H with the structure shown in formula (1) are weighed in sequence at a polyether amine molar ratio of 1:22NC3H6O(C3H6O)5.5C3H6NH2With 0.006mol (5.4g) of a polyetheramine D400 having an average molecular weight of 900, y equal to 12.5, x + z equal to 6 and a structure H2NC3H6O(C3H6O)6(C2H4O)12.5C3H6NH2Uniformly stirring and mixing the polyether amine ED900, then adding 75% of IPA solvent with the mass of alpha, omega-EPS-5 + D400+ ED900 and about 73.07g of IPA solvent, uniformly stirring and mixing, heating to 80 ℃, continuously reacting for 10 hours, and then decompressing and recovering the solvent IPA to obtain 0.06mol of amino-terminated polyether silicone oil (alpha, omega-PEAS-5) with the total amount of about 97.42 g; then, 23 percent and about 22.41g of diethylene glycol diethyl ether solvent are added according to the mass of the alpha and omega-PEAS-5 of the silicone oil, the reaction temperature is adjusted to 80 ℃, 0.012mol and about 1.54g of adipic anhydride (the molar ratio of the alpha and omega-PEAS-5 to the adipic anhydride is 1:2) are added, the temperature is controlled at 80 ℃ for carboxylation reaction for 1 hour, and the total amount of 121.37g of colorless-light yellow transparent liquid is obtained after the reaction, namely the solvent type amphoteric carboxyl terminated polyether amino silicone oil (alpha, omega-CPEAS-5) with the structure shown as (3-5) and the silicone oil content is about 81.54 percent.
(2) Preparation of amphoteric polyether polyurethane prepolymer (PU-5)
0.05mol and 11.11g of isophorone diisocyanate (IPDI) are taken to be put into a dry three-necked bottle provided with a thermometer, a reflux condenser and an electric stirrer, stirred and heated to 50 ℃, then 0.04mol and about 16.0g of dried PEG-400(Mn400) and 20% by mass of IPDI + PEG-400 and 5.42g of mixed solvent consisting of diethylene glycol diethyl ether and acetone (mass ratio of 1:2) are added according to the molar ratio of IPDI to polyether polyol, the temperature is controlled at 70 ℃ for reaction for 1h, then 0.8% by mass of IPDI + PEG-400 and about 0.22g of mixture of TEOA and dimethylolpropionic acid in equal molar ratio are added dropwise for reaction for 0.5h, and the total amount of the product, namely the amphoteric polyether polyurethane prepolymer (PU-5), is about 32.75g, and the solid content is 83.45%.
(3) Preparation of crosslinking modified amphoteric carboxyl polyether amino silicon softening agent
30.0g of solvent type alpha, omega-CPEAS-5 (containing 24.46g of silicone oil) with the silicone oil content of 81.54 percent is mixed with 19.05g of polyether polyurethane prepolymer PU-5 with the solid content of 83.45 percent (solid content of 15.89g), and the mass ratio of the alpha, omega-CPEAS-5 silicone oil to the PU-5 solid content in the system is 1: 0.65, stirring and mixing evenly, and then controlling the temperature to be 40 ℃ to react for 2 hours to obtain a product with the total amount of about 49.05g, namely the polyurethane modified cross-linked structure amphoteric carboxyl polyether amino silicone oil (PUCS-5) solution with the solid content of about 82.26 percent.
Taking 25g of a PUCS-5 solution with the silicone oil content of 82.26 percent, adding 35 percent of isomeric deca-alcohol polyoxyethylene ether XL-40/XL90 (mass ratio of 1:3) emulsifier which accounts for about 7.20g of the silicone oil mass, stirring and mixing for 30min, adding HAc to adjust the pH value of the system to be 5-6, and adding 88.54g of deionized water while stirring for emulsification to obtain transparent micro emulsion, namely the cross-linked amphoteric carboxyl polyether amino silicon emulsion (PUCS-5) softener with the solid content of about 23.0 percent.
Example 6
The PEG-1000 in example 4 was replaced with polytetrahydrofuran ether glycol PTHG-1000, the amount and process of the other raw materials were the same as in example 4, and the resulting translucent microemulsion, i.e., the amphoteric carboxy polyether amino silicone emulsion (PUCS-6) softener having a cross-linked structure, had a solid content of about 20%.
Example 7
Polytetrahydrofuran ether glycol PTHG-2000 is used to replace PEG-2000 in example 1, the rest of raw materials and the amount and the process are the same as those in example 1, and the finally obtained semitransparent microemulsion, namely amphoteric carboxyl polyether amino silicon emulsion (PUCS-7) softening agent, has the solid content of about 30 percent.
The cross-linked amphoteric carboxyl polyether amino silicon emulsion softener prepared in the examples 1-7 is converted into silicon microemulsion with the solid content of 30%, and then diluted according to the proportion of 1g of silicon microemulsion and 100g of water to prepare the working bath solution. Then, white cotton cloth (specification 21 × 21 × 108 × 98) with a warp × weft area of 16.3cm × 12.6cm was taken, dipped into a working bath solution, and finished by one dip and one roll with a laboratory mini-padder, wherein the pressure of the padder is about 0.4MPa, the rolling residue is about 70%, and then the fabric was dried at 100 ℃ for 5min, cured at 165 ℃ for 90s, and subjected to a performance test after being balanced at room temperature of 25 ± 2 ℃ and humidity of 48% for 24 h.
The flexibility is expressed by bending rigidity, and the bending rigidity is smaller, the flexibility of the fabric is better; the water absorption was expressed as the static water absorption time, and the time taken for the surface of the fabric to absorb 1 drop of water (25 drops to 1mL) was measured using a stopwatch; the elastic stiffness is expressed as [ warp (w) + weft (f) ] return angle to wrinkle and is measured by YG54 fabric wrinkle elasticity meter; one-bath usability measurement: taking the silicon milk of the examples 1-7, diluting the silicon milk with water to the solid content or the mass concentration which is the same as that of the test sample, then mixing the diluted silicon milk and the test sample in equal volume, standing the mixture, and observing whether the appearance form of the test sample is changed, wherein the reference is the amino terminated polyether silicon PEAS silicon milk of the examples, and the result is shown in tables 1-2. Wherein, the table 1 is the application performance of the cross-linked structure amphoteric carboxyl polyether amino silicon emulsion softener for treating the fabrics, and the table 2 is the result of the one-bath usability measurement of the PUCS and the anionic and cationic resin auxiliary agents.
TABLE 1
BR bending stiffness, WA crimp recovery angle
TABLE 2
Very good-no obvious change
As can be seen from tables 1-2, the amphoteric PUCS silicone emulsion does not produce demulsification and floating oil when being used together with anionic, cationic and nonionic resins/auxiliaries, and the fabric finished by the PUCS has good hydrophilicity, strong elastic stiffness and increased softness.
Claims (7)
1. A preparation method of amphoteric carboxyl polyether amino silicon emulsion softener with a cross-linked structure is characterized by comprising the following steps:
1) preparation of solvent type amphoteric carboxyl terminated polyether amino silicone oil: sequentially weighing alpha, omega-EPS and PEA according to the mol ratio of the alpha, omega-EPS and the PEA of the epoxy terminated polyether silicone oil of 1:2, uniformly stirring, adding an isopropanol IPA solvent accounting for 20-200% of the mass of the alpha, omega-EPS and the PEA, stirring, heating to 80-85 ℃ for reaction for 4-24h, and then decompressing and recovering the IPA solvent to obtain an amino terminated polyether silicone oil alpha, omega-PEAS precursor; stirring, adding 20-30% of polar alcohol ether solvent A according to the mass of the alpha, omega-PEAS, adjusting the reaction temperature to 70-125 ℃, then adding the dibasic acid anhydride according to the molar ratio of the alpha, omega-PEAS to the dibasic acid anhydride of 1:2, continuing the carboxylation reaction for 1-4h, and obtaining slightly turbid transparent liquid after the reaction is finished, namely the solvent type amphoteric carboxyl terminated polyether amino silicone oil alpha, omega-CPEAS, wherein the silicone oil content is 77.0-85.0%;
2) preparing a branched amphoteric polyether polyurethane prepolymer: taking diisocyanate DIC, stirring and heating to 35-80 ℃, dropwise adding polyether polyol and a non-reactive solvent B accounting for 20-50% of the mass of DIC and PEPO according to the molar ratio of the diisocyanate to the polyether polyol PEPO of 2:1-1.25:1, controlling the temperature to be 35-80 ℃, reacting for 0.5-1h, then adding a mixture of triethanolamine and dimethylolpropionic acid accounting for 0.5-1% of the mass of DIC and PEPO, controlling the temperature to be 35-80 ℃, and continuously reacting for 0.5-2h to obtain a product, namely a branched amphoteric polyether polyurethane prepolymer PU;
3) preparing an amphoteric carboxyl polyether amino silicon emulsion softening agent with a cross-linked structure: mixing solvent type alpha, omega-CPEAS with branched amphoteric polyether polyurethane prepolymer, controlling the dosage of the two so that the mass ratio of alpha, omega-CPEAS silicone oil to PU solid in the system is 1:1-0.3, stirring, controlling the temperature to be 30-70 ℃, and then carrying out reaction for 0.5-2h to obtain a product, namely a solution of cross-linked structure amphoteric carboxyl polyether amino silicone oil PUCS;
and (3) directly adding an emulsifier into the system for emulsification after the reaction is finished:
taking the PUCS solution, adding 30-50% of heterogeneous fatty alcohol-polyoxyethylene ether emulsifier by mass of silicone oil into the PUCS solution by mass of the contained silicone oil, stirring and mixing for 30min, adding acetic acid to adjust the pH of the system to be 5-6, and then adding water while stirring for emulsification to obtain semitransparent-transparent microemulsion, namely the amphoteric carboxyl polyether amino silicon emulsion softener with the cross-linked structure, wherein the solid content is 15-30%;
the polar alcohol ether solvent A is one or more of diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, ethylene glycol dibutyl ether and ethylene glycol methyl ether acetate;
the non-reactive solvent B is one or more of diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, ethylene glycol methyl ether acetate, acetone and dioxane.
2. The method of claim 1, wherein: the structure of the terminal epoxy polyether silicone oil alpha, omega-EPS is shown as the formula (1):
in the formula, the value range of n is 25-270, the value ranges of a and b are 0-30, and the value range of a + b is 3-30.
3. The method of claim 1, wherein: the structure of the polyether amine PEA is shown as the formula (2):
H2NC3H6O(C3H6O)x(C2H4O)y(C3H6O)zC3H6NH2 (2)
wherein x, y and z are positive numbers, the value range of x + z is 2.5-33.1, the value range of y is 0-39, the number average molecular weight of the polyetheramine is 230-2000, and the polyetheramine is one or more of D230, D400, D2000, ED600, ED900 and ED 2003.
4. The method of claim 1, wherein: the binary anhydride is aliphatic binary anhydride and is one or more of maleic anhydride, succinic anhydride, methylene succinic anhydride, glutaric anhydride and adipic anhydride.
5. The method according to any one of claims 2 to 4, wherein: the amphoteric carboxyl-terminated polyether amino silicone oil comprises the main components as shown in the formula (3):
in the formula, pe1From the raw material alpha, omega-EPS, pe2、pe3From polyetheramines PEA, pe2And pe3The same or different.
6. The method of claim 1, further comprising: the fatty alcohol-polyoxyethylene ether emulsifier is one or more of fatty alcohol-polyoxyethylene ether, isomeric tridecanol polyoxyethylene ether and isomeric tridecanol polyoxyethylene ether.
7. The method of claim 1, wherein: the amphoteric polyether polyurethane prepolymer PU is prepared from a mixture containing the following components:
the polyether polyol PEPO is polyethylene glycol PEG or polytetrahydrofuran ether glycol with the number average molecular weight of 200-2000;
the diisocyanate DIC is one or more of methylene diisocyanate, isophorone diisocyanate, 4' -diphenylmethane diisocyanate and toluene diisocyanate, and the non-reactive solvent B is one or more of diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, ethylene glycol methyl ether acetate, acetone and dioxane.
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