CN103772708A - Glycosyl modified polysiloxane organic silicone softener and preparation method thereof - Google Patents
Glycosyl modified polysiloxane organic silicone softener and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a glycosyl modified polysiloxane organic silicone softener and a preparation method thereof. The preparation method comprises the steps of enabling gamma-glycidoxy propyl methyl dialkoxy silane and octamethyl cyclotetrasiloxane with the mole rate of 1: (2.5-50) to react in an alkyl polyglucoside surfactant and basic catalyst water solution at the temperature of 60-100 DEG C to obtain a semitransparent alkoxy modified polysiloxane intermediate emulsion; regulating the pH value of the alkoxy modified polysiloxane intermediate emulsion in the step (1) to 0.5-6, adding N, N-dimethyl-N'-glycosylacyl-1, 3-propane diamine, and enabling N, N-dimethyl-N'-glycosylacyl-1, 3-propane diamine and gamma-glycidoxy propyl methyl dialkoxy silane in the step (1) to react at the temperature of 70-95 DEG C to obtain a semitransparent glycosyl modified polysiloxane emulsion, wherein the mole ratio of N, N-dimethyl-N'-glycosylacyl-1, 3-propane diamine to gamma-glycidoxy propyl methyl dialkoxy silane is (0.3-0.8):1. The softener disclosed by the invention has the super softness of amino silicon oil and the solidifying and finishing effects of epoxy modified silicon oil, and can be used for effectively improving the washing fastness and the smoothness.
Description
Technical field
The present invention relates to a kind of glycosyl modified polyorganosiloxane fabric of organosilicon softening agent and preparation method thereof.
Background technology:
Modified organic silicon softening agent is called as third generation silicone softening agent, this series products is by various active groups such as amino, polyethers, epoxy group(ing), hydroxyls in siloxane chain or on macromolecular main chain, forms the segmented copolymer of polysiloxane and other modified group, greatly improve washing fastness, shrink resistance, wetting ability of fabric etc., and rely on different groups to give fabric different styles.People mainly concentrate on third generation organosilicon product the research of silicone softening agent at present.Wherein, amido silicon oil product is one of product with fastest developing speed in silicone softening agent, it can give the slipperiness, flexibility, fullness of fabric uniqueness, very may just as well, the performance such as drape, and the fabric after arranging also has good washing fastness, can be widely used in the softening of all kinds of textiless, often be called as " king of softening agent ".Amido silicon oil class softening agent accounts for 90% of organosilicon series softening agent at present, has become fabric indispensable finishing composition before finished product.
The amino silicones fabric post-treatment agent of industrial a large amount of uses is take amino silicon oil emulsion or microemulsion as main, and its main ingredient is amido silicon oil, is secondly emulsifying agent and water.From molecular structure, at present, exceeding 90% commercial amino-modified silicone softening agent is the sub-aminopropylpolysiloxane of aminoethyl, this diamine type structure is under heating or UV-irradiation condition, while there is oxygenizement, there is synergistic effect, can promote chromophoric formation, finally cause finish fabric yellowing; Conventionally ammonia value is higher, and xanthochromia is more serious, falls low amonia value, and xanthochromia can be alleviated to some extent, but can reduce the flexibility of finish fabric.This problem can be by becoming secondary amine for the primary amine group of modification or tertiary amine group improves.But along with the minimizing of hydrogen on nitrogen-atoms, this hydrophobicity just with strong hydrophobic amido silicon oil is stronger, make all to decline to some extent usually used as preparation, stability in storage, transportation stability and the application stability of the amino silicon oil emulsion of emulsion formulation or the sale of microemulsion formulation, higher to emulsifier content and performance requriements in its emulsion.
Aspect preparation technology, the conventional preparation method of amino silicon oil emulsion has two kinds, and one is first to prepare after amido silicon oil polymkeric substance, adopts machinery emulsification method, amido silicon oil is added in the water that is dissolved with a large amount of emulsifying agents, adopts homogenizing emulsifying equipment to carry out emulsification.In U.S. Pat 4620878, Gee etc. carry out emulsification by amido silicon oil with tensio-active agent and prepare silicone oil emulsion, and using alkylphenol series non-ionic surfactants as preferred surfactant.In " a kind of multi-functional softening agent and preparation method thereof " of announcing in Chinese patent CN103321053A, amido silicon oil is added and is equivalent in compound soft dose of amido silicon oil massfraction 20%～80%, add again water-soluble chitosan and water, 30～70 ℃ of temperature, under 5000～10000 revs/min of velocity of shear, add water, emulsification 30～150 minutes, regulate after pH, obtain multi-functional emulsifier product.The main component of its compound emulsifying agent is polyoxyethylene nonylphenol ether and alkylphenol polyoxyethylene, also has fatty alcohol-polyoxyethylene ether and other amphoterics, and wherein induced by alkyl hydroxybenzene has reached 40%～60% of emulsifying agent total mass.In Chinese patent CN103061146A " preparation method of composite antibacterial softening agent ", first prepare mixed emulsion: the ACRYLIC EMULSION of 10～30 weight parts, the emulsifying agent of 10～15 parts, the solubilizing agent of 12～20 parts are mixed in the water of 300 parts, under 30～40 ℃, the rotating speed of 900～1100r/min, add the amido silicon oil composition of 50～200 parts, stir 250～260min, add 700 parts of deionized waters, under above-mentioned rotating speed, continue to stir 55～65min, obtain mixed emulsion.Its emulsifying agent is one or the composition in fatty alcohol-polyoxyethylene ether, anhydrous sorbitol lipid acid, polyoxyethylene nonylphenol ether.Thisly adopt machinery emulsification to prepare the method pair and the amido silicon oil with higher molecular weight and high amine value of amino silicon oil emulsion amido silicon oil, because the viscosity of silicone oil product is excessive, be difficult for emulsification.Due to the requirement to higher shear effect, the emulsification times often needing is longer, and the use of some homogenizer has increased industrialization cost or has been difficult for realizing at industrially scalable.As the preferred surfactant kind alkylphenol polyoxyethylene ether (APEO) of silicone oil emulsification agent although series of surfactants itself do not there is carinogenicity and cause variability, but its biological degradation is slow, the APEO and the alkylphenol (AP) that in degraded after product, contain less oxyethyl group, and produce biological degradation meta-bolites nonyl phenol (NP) and octyl phenol (OP).NP, OP, NPEO and OPEO belong to environmental hormone chemical substance, invade the effect after human body with similar female hormone, i.e. so-called " female effect " and the reproduction property that distorts has become the natural enemy of all organic sphere including the mankind.If the APEO in the 2003/53/EC of European Union instruction restriction chemical and prepared product thereof and AP content are higher than 0.1% (100mg/kg, weight percent), this chemical and prepared product thereof can not be used for the formula of textiles and leathers processing, pulp production and paper, makeup, sterilant and biocide.Therefore, use APEO series of surfactants cannot export European market as the softening agent product of emulsifying agent.Although China does not also have clear and definite decree to limit its scope of application, along with the reinforcement day by day of people's environmental consciousness, APEO will be eliminated by market gradually.Fatty alcohol-polyoxyethylene ether series of surfactants (AEO) is not although there is no the shortcoming of alkylphenol series at aspects such as bio-toxicities, but the physico-chemical property of this series of surfactants itself determines its appearance of gelatin phenomenon under certain mass concentration in the aqueous solution, while forming solution, must stride across gel district, cause dissolving slower, this brings considerable influence to product configuration process, in addition, be applicable to fabric softener and prepare the AEO product of required hydrophile-lipophile balance value scope due to the existence of its cloud point, application of temperature is had to great restriction, once temperature reaches or approaches its cloud point, emulsion is just by breakdown of emulsion.
The another kind of method of preparing amino silicon oil emulsion is to adopt to contain amino organosilane monomer and other monomer or small molecules amount siloxanes and carry out emulsion and telomerize, obtain emulsion form product, judge whether as required to add the emulsifying agent of certain mass mark, preparation becomes comparatively stable product emulsion again.In U.S. Pat 6071975, disclose organosilane monomer has been distributed to first by tensio-active agent, in the alcohols of cosurfactant, solution that water forms, prepared and become emulsion, caused afterwards letex polymerization, prepared the method for amino silicon oil emulsion.(the Meng Qingfei such as Meng Qingfei, Liu Guochao. Synthesis of Amino Modified Silicone Micro-emulsion by One-Step [J]. organosilicon material, 2002,16 (4): 16-17.) first cyclotetrasiloxane D4, surfactant A EO9, water are mixed into pre-emulsion under 2000r/min, afterwards pre-emulsion are slowly added dropwise in the aqueous solution that is mixed with cats product and alkali and prepare amino silicon oil emulsion; Or pre-emulsion is added dropwise in the aqueous solution that is mixed with anion surfactant, then is added dropwise to by the emulsion of nonionic AEO tensio-active agent and silane coupling agent and reacts.Processing condition complexity, the dropwise reaction time is long, and rate of addition is wayward, is unfavorable for suitability for industrialized production.
In order to improve the wetting ability of amino polysiloxane soft agent, the general employing of existing method carried out polyether-modified to amino silicones.In silicone macromolecule, introduce Soxylat A 25-7 or polyoxyethylene poly-oxygen propylene aether block segments improves its wetting ability.U.S. Pat 5891977 adopts addition reaction of silicon with hydrogen, using Platinic chloride as catalyzer, will hold the poly-alkoxyl group segment of thiazolinyl and glycidyl allyl ether to introduce polysiloxane macromole with side chain form and form Siloxane-Oxyalkylene Copolymers intermediate.Take Virahol as solvent, N-METHYL-ALPHA-L-GLUCOSAMINE being introduced to macromole by epoxide group ring-opening reaction afterwards carries out amino modified.The intermediate in reaction process, the first step being obtained is added dropwise in the N-METHYL-ALPHA-L-GLUCOSAMINE solution under reflux temperature, after reacting certain hour under reflux temperature, add again isopropanol solvent continuation reaction, obtain osamine base Siloxane-Oxyalkylene Copolymers aqueous isopropanol product.This process using addition reaction of silicon with hydrogen mode, chloroplatinic acid catalyst high expensive, must be via filtering and remove from system after reaction terminating, unreacted glycidyl allyl ether can be removed by underpressure distillation, and unreacted end thiazolinyl alkoxy polyether cannot be removed from reaction system.The preparation method of the polyether modified amino silicone oil of all the other bibliographical informations, no matter be amino silicones macromole itself to be accessed to polyether segment again carry out modification, still first prepare two ends be respectively amino-terminated and polysiloxane segment active epoxy group polyethers end-blocking react again obtain block polyether modified amino silicon oil (Cheng Jinfang. synthesizing and applied research [D] of polyether-modified amido silicon oil. Institutes Of Technology Of Zhejiang, 2013.03. tutor: Wu Minghua .), all increase reaction difficulty.Although in addition polyether segment add the wetting ability that can effectively improve modified amino silicon oil, then by the composite stability that can effectively improve softening agent emulsion or microemulsion product of tensio-active agent.But the size of polyether segment and the position of introducing in polysiloxane molecule structure thereof all can affect wetting ability and the flexibility of modified silicon oil finish fabric.In the macromolecular main chain of block polyether amino-modified silicone oil, polysiloxane chain and polyoxyethylene segment coexist, although this molecular structure has effectively improved the wetting ability of silicone softening agent, but because the massfraction of PolydimethylsiloxaneChain Chain section in macromole in whole macromole declines, polyether block has isolated the absorption continuity of polysiloxane segment at fabric face, can cause the smooth and soft effect of fabric to decline to some extent.In the aqueous solution time, due to hydrophobic interaction, may there is hydrophilic polyether segment and wrap up hydrophobic polysiloxane segment in the polyether-modified amido silicon oil of side chain, affect the absorption of organosilicon segment on fabric fibre, affects soft effect and washing fastness.
Summary of the invention
The object of the invention is the shortcoming for prior art, provide a kind of glycosyl modified polyorganosiloxane fabric of organosilicon softening agent and preparation method thereof, particularly a kind of microemulsion-type polysiloxane fabric sofetening softening agent with sugared amide group and quaternary ammonium salt cationic diamine structure side chain and epoxy group(ing) side chain and preparation method thereof.Softening agent prepared by the present invention, when softening agent excellent hydrophilic is provided, keeps soft effect unaffected, not yellowing, and there is the finishing effect weather resistance of alkoxy-modified amido silicon oil simultaneously.
Microemulsion-type glycosyl modified polyorganosiloxane silicone softening agent of the present invention, the main activeconstituents glycosyl of softening agent modified polyorganosiloxane is shown below:
Wherein, mean polymerisation degree M
n20,000～1,000,000, and x:y:z=0.7～0.2:2.5～50:0.3～0.8, GA group is to have quaternary ammonium salt cationic structure-N, N-dimethyl-N[3-(sugared acyl group)] propyl ammonium.
The present invention also provides a kind of preparation method of microemulsion-type glycosyl modified polyorganosiloxane silicone softening agent, comprise: the preparation of (1) epoxy group(ing) modified polyorganosiloxane intermediate: in the aqueous solution of alkyl glucoside surfactant and basic catalyst, molar ratio is that γ-glycidyl ether oxygen propyl methyl dialkoxy silicane of 1:2.5～50 reacts at 60～100 ℃ with octamethylcyclotetrasiloxane, obtains the alkoxy-modified polysiloxane intermediate emulsion of translucent emulsion form; (2) preparation of emulsion-type glycosyl modified polyorganosiloxane: the pH value of the alkoxy-modified polysiloxane intermediate emulsion obtaining in (1) step is adjusted to 0.5～6; add N; N-dimethyl-N '-sugared acyl group-1; 3-propylene diamine; in itself and step (1), the mol ratio of γ-glycidyl ether oxygen propyl methyl dialkoxy silicane used is 0.3～0.8:1; 70～95 ℃ of reactions, obtain translucent emulsion form glycosyl modified polyorganosiloxane emulsion.
The preferred preparation method according to the present invention, wherein, in step (1), the alkyl glucoside surfactant of described alkyl carbon chain is the combination of the alkyl glucoside surfactant of two or more C6～C18 alkyl chains; And/or the basic metal that described basic catalyst is solubility or alkaline earth metal oxide or oxyhydroxide, alkali metal alcoholates, alkaline carbonate and supercarbonate or Tetramethylammonium hydroxide; And/or described γ-glycidyl ether oxygen propyl methyl dialkoxy silicane is γ-glycidyl ether oxygen propyl methyl dimethoxy oxygen base silicon or γ-glycidyl ether oxygen propyl methyldiethoxysilane.
The preferred preparation method according to the present invention, wherein, in step (2), the described pH value of described alkoxy-modified polysiloxane intermediate emulsion is adjusted to 0.5～4; And/or described N, N-dimethyl-N '-sugared acyl group-1,3-propylene diamine is N, N-dimethyl-N '-glucose acyl group-1,3-propylene diamine or N, N-dimethyl-N '-lactose acyl group-1, the one in 3-propylene diamine; And/or temperature of reaction is 80～90 ℃, 4～6 hours reaction times.
The present invention is a kind of microemulsion-type glycosyl modified polyorganosiloxane silicone softening agent prepared according to the methods of the invention on the other hand.
The present invention is by N; N-dimethyl-N '-sugared acyl group-1; 3-propylene diamine is by introducing polysiloxane macromole with the ring-opening reaction of epoxide group; in introducing sugared amide group, form quaternary ammonium salt cationic structure; in guaranteeing the ultra-flexible that amido brings; good stability, not flavescence, the while has been improved the wetting ability of polysiloxane macromonomer greatly.N, N-dimethyl amine structure is reacted with epoxide group and can under gentle reaction conditions, be carried out fast under solutions of weak acidity, and reaction is thoroughly.In addition, in the polysiloxane macromole in the present invention, lead to and go back retained part epoxide group, when making this softening agent there is amido silicon oil ultra-flexible, also there is solidification effect and the finishing effect of epoxide modified silicone oil, effectively improve washing fastness and smoothness.
The microemulsion-type glycosyl modified polysiloxane softening agent the present invention relates to, reaction conditions gentleness, technological operation is simple, and equipment requirements is low, is convenient to suitability for industrialized production.Microemulsion system good stability, can adapt to wider accumulating temperature range and temperature limit, can better adapt to the requirement of dyeing and finishing with bath process.
Compared with the technology of preparing amido silicon oil or epoxy silicon oil with existing letex polymerization, alkyl glycoside APG series of surfactants as emulsifying agent of the present invention is the nonionogenic tenside of being made up of renewable plant material, good with skin-friendliness, nontoxic non-stimulated, biological degradability is splendid, can quick and complete biological degradation, its intermediates has no adverse effects to environment and ecology.And APG series of surfactants is different from fatty alcohol-polyoxyethylene ether nonionogenic tenside, APG does not have cloud point in the aqueous solution, the temperature range that softening agent can be tolerated in the time of fabric postprocessing working procedures is wider, there will not be AEO series and nonyl phenol series nonionic such, in the time that temperature connects or reach its cloud point, because the water-soluble and surfactivity variation of AEO tensio-active agent causes the phenomenon of silicone oil emulsion breakdown of emulsion floating oil.APG series of surfactants has excellent acidproof, alkaline-resisting and electrolyte-resistant characteristic, and under the environment of high potential of hydrogen and high salinity, its solvability and surfactivity can not be subject to remarkably influenced, can effectively guarantee the stability of silicone oil emulsion in dyeing and finishing process.When short carbon chain and branched-chain alkyl APG have extremely low foam, under high alkalinity and polyelectrolyte condition, perviousness and wettability are significantly increased on the contrary, can help silicone oil emulsion in fiber and fabric face wetting and infiltration fast and effectively, improve finishing effect.In addition APG series of surfactants does not have gel district in the aqueous solution, dissolves rapidly, and technological operation is more simply saved time; Composite use by APG tensio-active agent brings efficient emulsifying property, does not need harsh pre-emulsification process, does not need special homogenizer, is conducive to suitability for industrialized production.
Accompanying drawing explanation
The infrared spectrum of the glycosyl modified polysiloxane softening agent that Fig. 1 embodiment 1 obtains.
Embodiment
Content of the present invention can be achieved through the following technical solutions: a kind of microemulsion-type glycosyl modified polyorganosiloxane silicone softening agent, is characterized in that as the general structure of the glycosyl modified polyorganosiloxane of the main activeconstituents of softening agent as shown below:
Wherein, mean polymerisation degree M
n20,000～1,000,000, and x:y:z=0.7～0.2:2.5～50:0.3～0.8, GA group is to have quaternary ammonium salt cationic structure-N, N-dimethyl-N[3-(sugared acyl group)] propyl ammonium.
Wherein sugared acyl group can be selected from glucose acyl group or lactose acyl group.
The preparation method of microemulsion-type glycosyl modified polysiloxane softening agent of the present invention comprises the following steps:
(1) preparation of epoxy group(ing) modified polyorganosiloxane intermediate
Being provided with in the four-hole boiling flask of mechanical stirring device, condensation reflux unit, add a certain amount of water and a certain amount of non-ionic surfactant composition, stirring at room temperature forms transparent aqueous solution; Add basic catalyst to stir and become transparent aqueous solution; Under the stir speed (S.S.) of 400～600rpm/min, a certain amount of γ-glycidyl ether oxygen propyl methyl dialkoxy silicane and octamethylcyclotetrasiloxane (D4) are successively added in four-hole bottle; Under the stir speed (S.S.) of 600～800rpm/min, stir 10～60min, obtain translucent emulsion system.
Above-mentioned emulsion system is warming up to 60～100 ℃, is cooled to room temperature react 2～8h under the stir speed (S.S.) of 600～800rpm/min after, obtain the alkoxy-modified polysiloxane intermediate emulsion of translucent emulsion form.
(2) preparation of emulsion-type glycosyl modified polysiloxane softening agent
The pH value of the alkoxy-modified polysiloxane intermediate emulsion obtaining in (1) step is adjusted to 0.5～6 scope with acid; under the stir speed (S.S.) of 600～800rpm/min by a certain amount of N; N-dimethyl-N '-sugared acyl group-1; 3-propylene diamine adds in flask, obtains translucent emulsion system.
Above-mentioned emulsion system is warming up to 70～95 ℃, under the stir speed (S.S.) of 600～800rpm/min, reacts after 4～8h, be cooled to room temperature, obtain translucent emulsion form glycosyl modified polyorganosiloxane emulsion.
(3) microemulsion-type glycosyl modified polysiloxane softening agent product configuration
In the translucent emulsion form glycosyl modified polyorganosiloxane emulsion obtaining at second step, add deionized water, regulating the massfraction of polysiloxane in product is 15～40%, add alkali to regulate product pH 6～7, obtain translucent to transparent, the slightly microemulsion-type glycosyl modified polysiloxane softening agent product of blue light.
Non-ionic surfactant composition is the composition with two or more the composite formation in the alkyl glycoside series of surfactants (APG) of different carbon number alkyl carbon chains in described step (1), is specially two or more the composition in the alkyl glycoside class tensio-active agent that alkyl chain is distributed in C6～C18.(APG06, as the GreenAPG IC of Shanghai Fakai Chemical Co., Ltd. to be specially hexyl glycoside
06), (APG08, as the GreenAPG PC of Shanghai Fakai Chemical Co., Ltd. for OG
8), (APGi8, as the GreenAPG IC of Shanghai Fakai Chemical Co., Ltd. for iso-octyl glucosides
08), (APG0810, as the GreenAPG PC of Shanghai Fakai Chemical Co., Ltd. for octyl group/Decyl Polyglucoside
0810), (APG1214, as the GreenAPG PC of Shanghai Fakai Chemical Co., Ltd. for Plantacare APG 1200G
1214), (APG1618, as the GreenAPG PC of Shanghai Fakai Chemical Co., Ltd. for hexadecyl glucosides
1618) composition of two or more in proportionlity each other does not clearly define, according to the particular case difference of system stability after the monomer concentration of emulsification system, polyreaction, the proportioning composition of required surfactant compound emulsifying agent is also different, be determined on a case-by-case basis.
The basic metal that described step (1) neutral and alkali catalyzer is solubility or alkaline earth metal oxide or oxyhydroxide, alkali metal alcoholates, alkaline carbonate and supercarbonate, Tetramethylammonium hydroxide etc. are inorganic and organic alkali source.Be preferably potassium hydroxide, potassium ethylate, sodium hydroxide, sodium ethylate.
In described step (1), γ-glycidyl ether oxygen propyl methyl dialkoxy silicane is the one in γ-glycidyl ether oxygen propyl methyl dimethoxy oxygen base silicon or γ-glycidyl ether oxygen propyl methyldiethoxysilane.
In described step (1), it is 15～40% that organosilane monomer (comprising D4 and γ-glycidyl ether oxygen propyl methyl dialkoxy silicane) accounts for water, APG surfactant composition, organosilane monomer three total mass umber, preferably 20～35%.It is 3～20% that APG surfactant composition accounts for total mass mark, is preferably 5～15%.APG series of surfactants commodity are generally solution-type product, and the product weight of add-on take active matter content as 50% massfraction calculates.
In described step (1), the molar ratio of γ-glycidyl ether oxygen propyl methyl dialkoxy silicane and D4 is 1:50～2:5, is preferably 1:30～3:10.
Described step (1) neutral and alkali catalyzer accounts for 0.2～5% of step (1) reaction system total mass, is preferably 0.5～2%.
Described step adds after flask at total overall reaction material in (1), preferably 20～30min of churning time under the stir speed (S.S.) of 600～800rpm/min.
Preferably 70～95 ℃ of temperature of reaction in described step (1), the reaction times is 4～8h preferably.
In described step (2), can be organic or inorganic acid in order to the acid that regulates pH value of reaction system, be preferably hydrochloric acid, citric acid, acetic acid, Phenylsulfonic acid.
In described step (2), regulate after pH value of reaction system with acid, the preferred pH of reaction system is 0.5～4.
N in described step (2), N-dimethyl-N '-sugared acyl group-1,3-propylene diamine is N, N-dimethyl-N '-glucose acyl group-1,3-propylene diamine or N, N-dimethyl-N '-lactose acyl group-1, the one in 3-propylene diamine.
Described step adds N in (2), N-dimethyl-N '-sugared acyl group-1, and the mol ratio of the γ-glycidyl ether oxygen propyl methyl dialkoxy silicane dropping in the amount of 3-propylene diamine and step (1) is 0.3～0.8:1.
Preferably 80～90 ℃ of temperature of reaction in described step (2), the reaction times is 4～6h preferably.
In described step (3), be alkali-metal oxyphie compound, carbonate, supercarbonate and ammonia in order to regulate the alkali of product pH, be preferably KOH, NaOH, Na
2cO
3, diethanolamine.
(1) preparation of epoxy group(ing) modified polyorganosiloxane intermediate
In the 2000ml four-hole boiling flask that mechanical stirring device, condensation reflux unit are installed, add the composition (wherein APG121439.5g, APG161813.2g, APGi824.8g, APG0621.5g) of 198g water, 99gAPG, stirring at room temperature forms transparent aqueous solution; Add catalyzer KOH24.75g to stir and become transparent aqueous solution; Under the stir speed (S.S.) of 600rpm/min, γ-glycidyl ether oxygen propyl methyl diethoxy silicon 49.7g, octamethylcyclotetrasiloxane D4198.0g are successively added in four-hole bottle; Under the stir speed (S.S.) of 800rpm/min, stir 60min, obtain emulsion system.
Above-mentioned emulsion system is warming up to 95 ℃, under the stir speed (S.S.) of 800rpm/min, reacts after 8h, be cooled to room temperature, obtain alkoxy-modified polysiloxane intermediate emulsion.
(2) preparation of glycosyl modified polysiloxane softening agent
The pH value of the alkoxy-modified polysiloxane intermediate emulsion obtaining in (1) step is adjusted to 0.5 with hydrochloric acid; under the stir speed (S.S.) of 800rpm/min by N; N-dimethyl-N '-glucose acyl group-1,3-propylene diamine 44.8g adds in flask, obtains emulsion system.
Above-mentioned emulsion system is warming up to 90 ℃, under the stir speed (S.S.) of 800rpm/min, reacts after 6h, be cooled to room temperature, obtain translucent emulsion form glycosyl modified polyorganosiloxane emulsion.
(3) microemulsion-type glycosyl modified polysiloxane softening agent product configuration
In the translucent emulsion form glycosyl modified polyorganosiloxane emulsion obtaining in (2) step, add deionized water 656.5g, the massfraction of polysiloxane is adjusted to 40%, add KOH to regulate product pH 6～7; Obtain translucent to transparent, the slightly microemulsion-type glycosyl modified polysiloxane softening agent product of blue light.
Shown in the glycosyl modified polyorganosiloxane macromolecular structure following formula that embodiment 1 obtains, wherein x:y:z=0.20:2.68:0.79, can according to hydrogen nuclear magnetic resonance spectrogram (
1h NMR) in group characteristic peak calculate; Mean polymerisation degree Mn is 20,500, can be obtained by gel permeation chromatography.
Accompanying drawing 1 is shown in by the FT-IR collection of illustrative plates of the glycosyl modified polysiloxane softening agent that embodiment 1 obtains.
FT-IT:3368.2cm-
1(-OH),3048.6cm-
1(C-H?in?epoxy),2941.2-2819.6cm-
1(-CH
2-,-CH
3),1651.3cm-
1(C=O?in?amine),1464.7cm-
1(-CH
2-),1261.1cm-
1(Si-CH
3),1093.6cm-
1(Si-O-Si),1091.5-1036.7cm-
1(O-H),799.5cm-
1(Si-CH
3).
1H?NMR(CDCl
3,400MHz):δ:0.09(Si-CH
3),0.51(Si-CH
2),2.5&2.7(CH
2in?epoxy),3.11(CH?in?epoxy),3.39(N
+-CH
2-CH2-),3.84(HO-CH),4.1～5.5(6H?of?sugar),8.08(CO-NH-).
Embodiment 2
(1) preparation of epoxy group(ing) modified polyorganosiloxane intermediate
In the 3000ml four-hole boiling flask that mechanical stirring device, condensation reflux unit are installed, add the composition (wherein APG0812.2g, APG121432.9g) of 1191.3g water, 45.1gAPG, stirring at room temperature forms transparent aqueous solution; Add catalyzer C
2h
5oK7.7g stirs becomes transparent aqueous solution; Under the stir speed (S.S.) of 600rpm/min, γ-glycidyl ether oxygen propyl methyl dimethoxy oxygen base silicon 5.0g, octamethylcyclotetrasiloxane D4296.6g are successively added in four-hole bottle; Under the stir speed (S.S.) of 800rpm/min, stir 20min, obtain translucent emulsion system.
Above-mentioned emulsion system is warming up to 90 ℃, under the stir speed (S.S.) of 800rpm/min, reacts after 4h, be cooled to room temperature, obtain the translucent emulsion of alkoxy-modified polysiloxane intermediate.
(2) preparation of glycosyl modified polysiloxane softening agent
The pH value of the alkoxy-modified polysiloxane intermediate emulsion obtaining in (1) step is adjusted to 2.0 with Phenylsulfonic acid; under the stir speed (S.S.) of 600rpm/min by N; N-dimethyl-N '-lactose acyl group-1,3-propylene diamine 5.6g adds in flask, obtains translucent emulsion system.
Above-mentioned emulsion system is warming up to 80 ℃, under the stir speed (S.S.) of 600rpm/min, reacts after 4h, be cooled to room temperature, obtain translucent emulsion form glycosyl modified polyorganosiloxane emulsion.
(3) microemulsion-type glycosyl modified polysiloxane softening agent product configuration
In the translucent emulsion form glycosyl modified polyorganosiloxane emulsion obtaining in (2) step, adding NaOH to regulate product pH is 6～7; Obtain the microemulsion-type glycosyl modified polysiloxane softening agent product of translucent slightly blue light.
The glycosyl modified polyorganosiloxane macromole x:y:z=0.50:51.30:0.49 that embodiment 2 obtains; Mean polymerisation degree M
nbe 980,500.
FT-IT:3368.3cm-
1(-OH),3048.7cm-
1(C-H?in?epoxy),2941.3-2819.4cm-
1(-CH
2-,-CH
3),1651.2cm-
1(C=O?in?amine),1464.6cm-
1(-CH
2-),1261.3cm-
1(Si-CH
3),1093.4cm-
1(Si-O-Si),1091.4-1036.5cm-
1(O-H),799.6cm-
1(Si-CH
3).
1H?NMR(CDCl
3,400MHz):δ:0.09(Si-CH
3),0.50(Si-CH
2),2.5&2.7(CH
2in?epoxy),3.12(CH?in?epoxy),3.38(N
+-CH
2-CH2-),3.82(HO-CH),4.1～5.5(6H?of?sugar),8.09(CO-NH-).
Embodiment 3
(1) preparation of epoxy group(ing) modified polyorganosiloxane intermediate
In the 3000ml four-hole boiling flask that mechanical stirring device, condensation reflux unit are installed, add the composition (wherein APG0613.2g, APG081042.5g, APG16188.6g) of 964.2g water, 64.3gAPG, stirring at room temperature forms transparent aqueous solution; Add catalyst n aOH51.4g to stir and become transparent aqueous solution; Under the stir speed (S.S.) of 700rpm/min, γ-glycidyl ether oxygen propyl methyl diethoxy silicon 24.8g, octamethylcyclotetrasiloxane D4296.6g are successively added in four-hole bottle; Under the stir speed (S.S.) of 800rpm/min, stir 30min, obtain emulsion system.
Above-mentioned emulsion system is warming up to 70 ℃, under the stir speed (S.S.) of 800rpm/min, reacts after 8h, be cooled to room temperature, obtain alkoxy-modified polysiloxane intermediate emulsion.
(2) preparation of glycosyl modified polysiloxane softening agent
The pH value of the alkoxy-modified polysiloxane intermediate emulsion obtaining in (1) step is adjusted to 4.0 with acetic acid; under the stir speed (S.S.) of 600rpm/min by N; N-dimethyl-N '-glucose acyl group-1,3-propylene diamine 16.8g adds in flask, obtains translucent emulsion system.
Above-mentioned emulsion system is warming up to 70 ℃, under the stir speed (S.S.) of 800rpm/min, reacts after 8h, be cooled to room temperature, obtain translucent emulsion form glycosyl modified polyorganosiloxane emulsion.
(3) microemulsion-type glycosyl modified polysiloxane softening agent product configuration
In the translucent emulsion form glycosyl modified polyorganosiloxane emulsion obtaining in (2) step, adding diethanolamine to regulate product pH is 6～7; Obtain the microemulsion-type glycosyl modified polysiloxane softening agent product of translucent slightly blue light.
The glycosyl modified polyorganosiloxane macromole x:y:z=0.39:10.07:0.59 that embodiment 3 obtains; Mean polymerisation degree M
nbe 254,800.
FT-IT:3368.4cm-
1(-OH),3048.6cm-
1(C-H?in?epoxy),2941.4-2819.5cm-
1(-CH
2-,-CH
3),1651.3cm-
1(C=O?in?amine),1464.5cm-
1(-CH
2-),1261.4cm-
1(Si-CH
3),1093.5cm-
1(Si-O-Si),1091.3-1036.5cm-
1(O-H),799.8cm-
1(Si-CH
3).
1H?NMR(CDCl
3,400MHz):δ:0.09(Si-CH
3),0.51(Si-CH
2),2.5&2.7(CH
2in?epoxy),3.14(CH?in?epoxy),3.39(N
+-CH
2-CH2-),3.82(HO-CH),4.1～5.5(6H?of?sugar),8.08(CO-NH-).
Embodiment 4
(1) preparation of epoxy group(ing) modified polyorganosiloxane intermediate
In the 3000ml four-hole boiling flask that mechanical stirring device, condensation reflux unit are installed, add the composition (wherein APG0618.0g, APGi842.5g, APG121428.6g) of 946.1g water, 89.1gAPG, stirring at room temperature forms transparent aqueous solution; Add catalyzer sodium ethylate 2.3g to stir and become transparent aqueous solution; Under the stir speed (S.S.) of 700rpm/min, γ-glycidyl ether oxygen propyl methyl diethoxy silicon 18.7g, octamethylcyclotetrasiloxane D4148.3g are successively added in four-hole bottle; Under the stir speed (S.S.) of 600rpm/min, stir 20min, obtain emulsion system.
Above-mentioned emulsion system is warming up to 85 ℃, under the stir speed (S.S.) of 800rpm/min, reacts after 6h, be cooled to room temperature, obtain alkoxy-modified polysiloxane intermediate emulsion.
(2) preparation of glycosyl modified polysiloxane softening agent
The pH value of the alkoxy-modified polysiloxane intermediate emulsion obtaining in (1) step is adjusted to 6.0 with citric acid; under the stir speed (S.S.) of 700rpm/min by N; N-dimethyl-N '-glucose acyl group-1,3-propylene diamine 6.3g adds in flask, obtains emulsion system.
Above-mentioned emulsion system is warming up to 90 ℃, under the stir speed (S.S.) of 700rpm/min, reacts after 6h, be cooled to room temperature, obtain translucent emulsion form glycosyl modified polyorganosiloxane emulsion.
(3) microemulsion-type glycosyl modified polysiloxane softening agent product configuration
In the translucent emulsion form glycosyl modified polyorganosiloxane emulsion obtaining in (2) step, adding diethanolamine to regulate product pH is 6～7; Obtain the microemulsion-type glycosyl modified polysiloxane softening agent product of translucent slightly blue light.
The glycosyl modified polyorganosiloxane macromole x:y:z=0.69:6.82:0.30 that embodiment 4 obtains, mean polymerisation degree M
nbe 389,600.
FT-IT:3368.3cm-
1(-OH),3048.6cm-
1(C-H?in?epoxy),2941.4-2819.4cm-
1(-CH
2-,-CH
3),1651.5cm-
1(C=O?in?amine),1464.6cm-
1(-CH
2-),1261.4cm-
1(Si-CH
3),1093.5cm-
1(Si-O-Si),1091.3-1036.5cm-
1(O-H),799.8cm-
1(Si-CH
3).
1H?NMR(CDCl
3,400MHz):δ:0.09(Si-CH
3),0.51(Si-CH
2),2.5&2.7(CH
2in?epoxy),3.11(CH?in?epoxy),3.39(N
+-CH
2-CH2-),3.82(HO-CH),4.1～5.5(6H?of?sugar),8.08(CO-NH-).
Embodiment 5
(1) preparation of epoxy group(ing) modified polyorganosiloxane intermediate
In the 2000ml four-hole boiling flask that mechanical stirring device, condensation reflux unit are installed, add the composition (wherein APG066.2g, APGi84.0g, APG16188.4g) of 433g water, 18.6gAPG, stirring at room temperature forms transparent aqueous solution; Add catalyzer KOH6.2g to stir and become transparent aqueous solution; Under the stir speed (S.S.) of 800rpm/min, γ-glycidyl ether oxygen propyl methyl diethoxy silicon 37.3g, octamethylcyclotetrasiloxane D4148.3g are successively added in four-hole bottle; Under the stir speed (S.S.) of 800rpm/min, stir 30min, obtain emulsion system.
Above-mentioned emulsion system is warming up to 95 ℃, under the stir speed (S.S.) of 800rpm/min, reacts after 7h, be cooled to room temperature, obtain alkoxy-modified polysiloxane intermediate emulsion.
(2) preparation of glycosyl modified polysiloxane softening agent
The pH value of the alkoxy-modified polysiloxane intermediate emulsion obtaining in (1) step is adjusted to 1.5 with hydrochloric acid; under the stir speed (S.S.) of 800rpm/min by N; N-dimethyl-N '-glucose acyl group-1,3-propylene diamine 33.6g adds in flask, obtains emulsion system.
Above-mentioned emulsion system is warming up to 90 ℃, under the stir speed (S.S.) of 800rpm/min, reacts after 7h, be cooled to room temperature, obtain translucent emulsion form glycosyl modified polyorganosiloxane emulsion.
(3) microemulsion-type glycosyl modified polysiloxane softening agent product configuration
In the translucent emulsion form glycosyl modified polyorganosiloxane emulsion obtaining in (2) step, adding sodium carbonate to regulate product pH is 6～7; Obtain the microemulsion-type glycosyl modified polysiloxane softening agent product of translucent slightly blue light.
The glycosyl modified polyorganosiloxane macromole x:y:z=0.21:3.41:0.78 that embodiment 5 obtains, mean polymerisation degree M
nbe 298,300.
FT-IT:3368.2cm-
1(-OH),3048.6cm-
1(C-H?in?epoxy),2941.2-2819.6cm-
1(-CH
2-,-CH
3),1651.3cm-
1(C=O?in?amine),1464.7cm-
1(-CH
2-),1261.1cm-
1(Si-CH
3),1093.6cm-
1(Si-O-Si),1091.5-1036.7cm-
1(O-H),799.5cm-
1(Si-CH
3).
1H?NMR(CDCl
3,400MHz):δ:0.09(Si-CH
3),0.51(Si-CH
2),2.5&2.7(CH
2in?epoxy),3.12(CH?in?epoxy),3.38(N
+-CH
2-CH2-),3.84(HO-CH),4.1～5.5(6H?of?sugar),8.08(CO-NH-).
Embodiment 6
(1) preparation of epoxy group(ing) modified polyorganosiloxane intermediate
In the 3000ml four-hole boiling flask that mechanical stirring device, condensation reflux unit are installed, add the composition (wherein APG0624.9g, APG0818.7g, APG121468.5g) of 711.4g water, 112.1gAPG, stirring at room temperature forms transparent aqueous solution; Add catalyzer potassium ethylate 12.2g to stir and become transparent aqueous solution; Under the stir speed (S.S.) of 800rpm/min, γ-glycidyl ether oxygen propyl methyl diethoxy silicon 8.3g, octamethylcyclotetrasiloxane D4296.6g are successively added in four-hole bottle; Under the stir speed (S.S.) of 800rpm/min, stir 10min, obtain translucent emulsion system.
Above-mentioned emulsion system is warming up to 90 ℃, under the stir speed (S.S.) of 800rpm/min, reacts after 7h, be cooled to room temperature, obtain the translucent emulsion of alkoxy-modified polysiloxane intermediate.
(2) preparation of glycosyl modified polysiloxane softening agent
The pH value of the alkoxy-modified polysiloxane intermediate emulsion obtaining in (1) step is adjusted to 2 with Phenylsulfonic acid; under the stir speed (S.S.) of 600rpm/min by N; N-dimethyl-N '-glucose acyl group-1,3-propylene diamine 6.5g adds in flask, obtains emulsion system.
Above-mentioned emulsion system is warming up to 90 ℃, under the stir speed (S.S.) of 800rpm/min, reacts after 6h, be cooled to room temperature, obtain translucent emulsion form glycosyl modified polyorganosiloxane emulsion.
(3) microemulsion-type glycosyl modified polysiloxane softening agent product configuration
In the translucent emulsion form glycosyl modified polyorganosiloxane emulsion obtaining in (2) step, adding diethanolamine to regulate product pH is 6～7; Obtain the microemulsion-type glycosyl modified polysiloxane softening agent product of translucent slightly blue light.
The glycosyl modified polyorganosiloxane macromole x:y:z=0.31:30.6:0.69 that embodiment 6 obtains, mean polymerisation degree M
nbe 427,900.
FT-IT:3368.3cm-
1(-OH),3048.7cm-
1(C-H?in?epoxy),2941.2-2819.4cm-
1(-CH
2-,-CH
3),1651.3cm-
1(C=O?in?amine),1464.7cm-
1(-CH
2-),1261.1cm-
1(Si-CH
3),1093.6cm-
1(Si-O-Si),1091.5-1036.7cm-
1(O-H),799.6cm-
1(Si-CH
3).
1H?NMR(CDCl
3,400MHz):δ:0.09(Si-CH
3),0.50(Si-CH
2),2.5&2.7(CH
2in?epoxy),3.11(CH?in?epoxy),3.39(N
+-CH
2-CH2-),3.82(HO-CH),4.1～5.5(6H?of?sugar),8.08(CO-NH-).
Comparative example 1
The epoxidized polyether modified polysiloxane softening agent contrast sample that this comparative example obtains is according to the 1 method preparation of embodiment in patent CN101565896B.This softening agent is the polysiloxane fabric softener kind with cationic quaternary ammonium group.
Comparative example 2
The amino-polyether modified polysiloxane soft agent sample of this comparative example is commercially available import MAGNASOFT450 softening agent product.This softening agent is hydrophilic polyether modified amino polysiloxane soft agent kind.
Comparative example 3
The epoxide modified silicone oil softener of this comparative example contrast sample according to document " the synthetic and application [J] of epoxide modified silicone oil (and Liu Ruiyun. dyeing and finishing technique .2009,31 (8): 34-6. " described method preparation.
Comparative example 4
Common commercially available amino-silicone oil softening agent, model JF-8026.Compound method: 30% solid content, amido silicon oil JF-8026:20 part, emulsifying agent JF-T10:10 part, glacial acetic acid: 0.6 part; 10 parts of JF-T2 emulsifying agents and 20 parts of high-speed stirring of JF-8026 amido silicon oil are stirred evenly for 5 minutes; Under agitation condition, slowly add 70 parts, water, high-speed stirring 10 minutes, stirs; Under stirring state, be warming up to 80 ℃, continue to stir 1h.
The following describes the character of embodiment 1-6 gained softening agent and comparative example 1-3 gained softening agent and Performance Ratio.
The centrifugal stability experiment comparing result of the softening agent product of embodiment 1-6 and comparative example 1-4 is shown in as table 1.Stability test method: add 40ml softening agent product in 50ml centrifuge tube, put into supercentrifuge, with 5000rpm/min rotating speed, centrifugal 30min, takes out and observe, and as not stratified, floating oil not, shows good emulsion stability.
The anti-shear stability experiment comparing result of the softening agent product of embodiment 1-6 and comparative example 1-4 is shown in as table 1.Anti-shear stability testing method: softening agent product is diluted to 100g/L, and high speed shear 1h under the rotating speed of 1000rmp/min, observes after standing 24h, without becoming the phenomenons such as muddiness, layering, floating oil, shows that anti-shear stability is good.
The environmental resistance of the softening agent product of embodiment 1-6 and comparative example 1-4, comprising: acidproof, alkaline-resisting, salt tolerant, heatproof stability experiment comparing result are shown in as table 1.Stability test method: 1. acid resistance: softening agent product is diluted to 100g/L, in 500ml beaker, adds 200ml softening agent diluent, the concentrated hydrochloric acid condition pH that is 36～38% with massfraction, the system pH of making is 3; 2. softening agent product is diluted to 100g/L, adds 200ml softening agent diluent in 500ml beaker, with the aqueous sodium hydroxide solution condition pH of mass concentration 32%, the system pH of making is 12; 3. with the sodium chloride solution of 10% massfraction, softening agent product is diluted to 100g/L, in 500ml beaker, adds 200ml softening agent diluent.By above-mentioned diluent high speed shear 1h under the rotating speed of 1000rmp/min, after standing 24h, observe, without becoming muddiness, layering, the appearance of floating oil phenomenon, show acidproof, alkaline-resisting or good salt tolerance.Heat resistance testing method: softening agent product is diluted to 100g/L, preserves respectively 48h at-4 ℃ and 60 ℃, afterwards at room temperature through 24h recovery temperature, observe and whether have muddiness, demixing phenomenon.
The application performance comparing result of the softening agent product of embodiment 1-6 and comparative example 1-4 is in table 2.Effect test condition: fabric: pure-cotton woven fabric; Working fluid softening agent product concentration: 50g/L; Finishing technique: pad technique, working fluid softening agent product consumption 50g/L(pick-up 75%) → dehydration → dry (110 ℃, 90s) → bake (180 ℃, 60s).Whiteness: utilize ZDG type whiteness instrument to measure.Flexibility, elasticity, fullness ratio, smoothness evaluation: many staff touch rating method, point 1-5 level, 1 grade is the poorest, and 5 grades are best; Get the mean value of many people's marking.
The wetting ability comparing result of the softening agent product of embodiment 1-6 and comparative example 1-4 is in table 3.Wetting ability adopts water droplet osmose process, water gaging drip off full penetration time (unit: s).
Claims (9)
1. a microemulsion-type glycosyl modified polyorganosiloxane silicone softening agent, is characterized in that, the main activeconstituents glycosyl of softening agent modified polyorganosiloxane is shown below:
Wherein, mean polymerisation degree M
n20,000～1,000,000, and x:y:z=0.7～0.2:2.5～50:0.3～0.8, GA group is to have quaternary ammonium salt cationic structure-N, N-dimethyl-N[3-(sugared acyl group)] propyl ammonium.
2. a preparation method for microemulsion-type glycosyl modified polyorganosiloxane silicone softening agent, comprising:
(1) preparation of epoxy group(ing) modified polyorganosiloxane intermediate
In the aqueous solution of alkyl glucoside surfactant and basic catalyst, molar ratio is that γ-glycidyl ether oxygen propyl methyl dialkoxy silicane of 1:2.5～50 reacts at 60～100 ℃ with octamethylcyclotetrasiloxane, obtains the alkoxy-modified polysiloxane intermediate emulsion of translucent emulsion form;
(2) preparation of emulsion-type glycosyl modified polyorganosiloxane
The pH value of the alkoxy-modified polysiloxane intermediate emulsion obtaining in (1) step is adjusted to 0.5～6; add N; N-dimethyl-N '-sugared acyl group-1; 3-propylene diamine; in itself and step (1), the mol ratio of γ-glycidyl ether oxygen propyl methyl dialkoxy silicane used is 0.3～0.8:1; 70～95 ℃ of reactions, obtain translucent emulsion form glycosyl modified polyorganosiloxane emulsion.
3. according to the preparation method of claim 2, also comprise,
(3) allotment of softening agent product
The microemulsion-type glycosyl modified polyorganosiloxane silicone softening agent product that the massfraction that the translucent emulsion form glycosyl modified polyorganosiloxane emulsion obtaining in (2) is deployed into polysiloxane is 15～40%, pH is 6～7.
4. according to the preparation method of claim 2, wherein, in step (1), the alkyl glucoside surfactant of described alkyl carbon chain is the combination of the alkyl glucoside surfactant of two or more C6～C18 alkyl chains; And/or the basic metal that described basic catalyst is solubility or alkaline earth metal oxide or oxyhydroxide, alkali metal alcoholates, alkaline carbonate and supercarbonate or Tetramethylammonium hydroxide; And/or described γ-glycidyl ether oxygen propyl methyl dialkoxy silicane is γ-glycidyl ether oxygen propyl methyl dimethoxy oxygen base silicon or γ-glycidyl ether oxygen propyl methyldiethoxysilane.
5. according to the preparation method of claim 2, wherein in the reaction system of step (1), the total mass umber of γ-glycidyl ether oxygen propyl methyl dialkoxy silicane and octamethylcyclotetrasiloxane is 15～40%, the massfraction of alkyl glucoside surfactant is 3～20%, and the massfraction of basic catalyst is 0.2～5%.
6. according to the preparation method of claim 5, wherein in the reaction system of step (1), the mol ratio of γ-glycidyl ether oxygen propyl methyl dialkoxy silicane and octamethylcyclotetrasiloxane is that 3:10 to 1:30 and both total mass umbers are 20～35%, the massfraction of alkyl glucoside surfactant is 5～15%, the massfraction of basic catalyst is 0.5～2%, temperature of reaction is 70～95 ℃, 4～8 hours reaction times.
7. according to the preparation method of claim 2, wherein, in step (2), the described pH value of described alkoxy-modified polysiloxane intermediate emulsion is adjusted to 0.5～4; And/or described N, N-dimethyl-N '-sugared acyl group-1,3-propylene diamine is N, N-dimethyl-N '-glucose acyl group-1,3-propylene diamine or N, N-dimethyl-N '-lactose acyl group-1, the one in 3-propylene diamine; And/or temperature of reaction is 80～90 ℃, 4～6 hours reaction times.
8. a microemulsion-type glycosyl modified polyorganosiloxane silicone softening agent, is characterized in that, according to the method preparation of any one in claim 2-7.
9. softening agent according to claim 8, wherein glycosyl modified polyorganosiloxane is shown below:
Wherein, mean polymerisation degree M
n20,000～1,000,000, and x:y:z=0.7～0.2:2.5～50:0.3～0.8, GA group is to have quaternary ammonium salt cationic structure-N, N-dimethyl-N[3-(sugared acyl group)] propyl ammonium.
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