CN104017158A - Preparation method of organic silicon modified amphiprotic polyurethane aqueous dispersion - Google Patents

Preparation method of organic silicon modified amphiprotic polyurethane aqueous dispersion Download PDF

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CN104017158A
CN104017158A CN201410253158.XA CN201410253158A CN104017158A CN 104017158 A CN104017158 A CN 104017158A CN 201410253158 A CN201410253158 A CN 201410253158A CN 104017158 A CN104017158 A CN 104017158A
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silicon
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CN104017158B (en
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邬元娟
张萌
张树秋
郭栋梁
郭长英
梁京芸
邓立刚
李腾
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Institute of Agricultural Quality Standards and Testing Technology of Shandong Academy of Agricultural Sciences
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
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    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Abstract

The invention discloses a preparation method of organic silicon modified amphiprotic polyurethane aqueous dispersion. The method comprises the following steps of: performing reaction on dihydroxyl alkyl-terminated organic silicon containing a tert-sulfonium group and polyisocyanates to introduce cationic organic silicon into a polyurethane structure; performing reaction on a hydrophilic chain extender, a general chain extender and the organic silicon modified polyurethane prepolymer to introduce an anionic group into the polyurethane structure; finally, dispersing the reaction type organic silicon modified polyurethane prepolymer into water by an acetone method through self-emulsification. The compounded organic silicon modified amphiprotic polyurethane aqueous dispersion molecule contains the hydrophilic cation tert-sulfonium group and the hydrophilic anionic carboxyl group, so that stable dispersion of the final product can be formed in an acid or alkali medium, and the application range of polyurethane aqueous dispersion is widened.

Description

The preparation method of organic-silicon-modified amphotenic polkyurethanes water dispersion
Technical field
The present invention relates to a kind of preparation method of organic-silicon-modified amphotenic polkyurethanes water dispersion, specifically one both had polysiloxane block or (with) graft modification structure, there is again the preparation method of the amphotenic polkyurethanes water dispersion of cationic hydrophilic group and anionic hydrophilic group simultaneously.
Background technology
Due to environmentally friendly, aqueous polyurethane has obtained significant progress in association area since coming out, and is widely used in medical material, electronic material and chemical materials, but has also run into a difficult problem that restricts its application.Because synthetic aqueous polyurethane is mostly line style dispersion product, add the existence of hydrophilic radical in molecule segment, make the poor water resistance of aqueous polyurethane film.Research data shows, organosilicon is linked to the water tolerance that can greatly improve polyurethane coating film in polyurethane molecular.
At present, the polyurethane aqueous dispersion body system of research and application is only confined to the polyurethane aqueous dispersion body of single yin, yang ionic, and it is also in the majority with the research report of anionic for organic-silicon-modified aqueous polyurethane, these systems in use have larger limitation, especially the pH sensitivity to applied environment.
Summary of the invention
In order to improve the water resistance of aqueous polyurethane film, reduce the susceptibility of polyurethane aqueous dispersion body to applicating medium pH, the invention provides a kind of preparation method of organic-silicon-modified amphotenic polkyurethanes water dispersion, specifically one both had polysiloxane block or (with) graft modification structure, there is again the preparation method of the amphotenic polkyurethanes water dispersion of cationic hydrophilic group and anionic hydrophilic group simultaneously.First it select the two hydroxyl alkyl blocking silicones that contain tertiary sulfonium group to react with polyisocyanates, and cation type organic silicon is incorporated in polyurethane structural; Then, then hydrophilic chain extender and general chainextender are reacted with above-mentioned organic silicon modified polyurethane prepolymer, anionic group is incorporated in polyurethane structural; Finally, adopt acetone method that base polyurethane prepolymer for use as organic-silicon-modified response type is distributed in water by self-emulsifying.
Technical characterictic of the present invention is: taking the cation type organic silicon of two hydroxyl alkyl end-blockings of containing tertiary sulfonium group, polyisocyanates, polymer polyatomic alcohol, hydrophilic chain extender, general chainextender, organic amine neutralizing agent, dispersion chainextender as raw material, by prepolymerization reaction, salt-forming reaction and dispersion chain extending reaction, obtain organic-silicon-modified amphotenic polkyurethanes water dispersion.
The molecular formula of cation type organic silicon has states two kinds of structures (double ended type and single-ended):
Wherein, R 1that carbon atom is any one of 1～12 alkyl, aliphatics alkoxyl group, alicyclic alkoxyl group and aromatic series alkoxyl group; R 2and R 3can be identical group, can be also different groups, R 2and R 3that carbon atom is any one of 1～12 alkyl and alkylene; R 4that hydrogen atom and carbon atom are any one of 1～12 alkyl and aryl; R 5that carbon atom is 1～12 alkyl; R 6and R 7can be identical group, can be also different groups, R 6and R 7that carbon atom is any one of 1～12 alkyl, aliphatics alkoxyl group, alicyclic alkoxyl group and aromatic series alkoxyl group; In said structure formula, m>1, n>1; Participate in reaction process, double ended type and single-ended can use separately and participate in reaction, also can use simultaneously and participate in reaction; In the time that both use simultaneously, the mass ratio of double ended type and single-ended is 1:9～9:1.
The hydroxyl alkyl blocking silicone that above-mentioned double ended type and single-ended contain tertiary sulfonium group can obtain by ion reaction, taking double ended type monocycle oxygen blocking silicone and single-ended bis-epoxy blocking silicone as raw material, carry out ion reaction with thioether and monobasic organic acid respectively.The synthetic equation of the hydroxyl alkyl blocking silicone that double ended type and single-ended contain tertiary sulfonium group is as follows, and the structural formula of the hydroxyl alkyl blocking silicone that wherein double ended type involved in the present invention and single-ended contain tertiary sulfonium group is also not only confined to structural formula mentioned in equation.
Wherein, the hydroxyl alkyl blocking silicone that double ended type contains tertiary sulfonium group is with α, and ω-bis-epoxy terminated polysiloxane, dialkyl sulfide and monoprotic acid are starting raw material, obtains through epoxy addition reaction; Wherein: α, the existing play-by-play in existing document of the synthetic method of ω-bis-epoxy terminated polysiloxane (refers to: " Journal of Functional Polymers ", 1996, the 9th volume, the 3rd phase, 475-479 page), and carrying out the synthetic method of ring-opening reaction, epoxide group and sulfide compound in foreign language document, also have similar relevant report (to refer to: " Langmuir ", 2000 years, the 16th volume, 3214-3220 page), their synthetic method is incorporated to this patent by reference.
Wherein, the hydroxyl alkyl blocking silicone that single-ended contains tertiary sulfonium group is taking single end-blocking bis-epoxy polysiloxane, dialkyl sulfide and monoprotic acid as starting raw material, obtains through epoxy addition reaction, wherein: single end-blocking bis-epoxy polysiloxane can obtain by addition reaction of silicon with hydrogen taking Platinic chloride as catalyzer by single silicon hydrogen terminated polysiloxane and unsaturated diepoxides, the former synthetic method is at CN101274984, CN101508778 and CN101580589 disclose, latter can prepare by unsaturated dihydroxyl compound and epoxy chloropropane under alkali effect, the synthetic method of unsaturated dihydroxyl compound is at CN101274984, CN101508778 and CN101580589 also disclose, and carrying out the synthetic method of ring-opening reaction, epoxide group and sulfide compound in foreign language document, also have similar relevant report (to refer to: " Langmuir ", 2000, the 16th volume), their synthetic method is incorporated to this patent by reference.
Polyisocyanates is any one or any two kinds and the two or more mixture in tolylene diisocyanate, '-diphenylmethane diisocyanate, polymethylene polyphenyl vulcabond, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, trimethyl hexamethylene diisocyanate and hydrogenated tolylene diisocyanate.
Polymer polyatomic alcohol is any one or any two kinds and the two or more mixture in polyether Glycols, polyester diol and PCDL; Wherein: 1) polyether Glycols is any one or any two kinds and the two or more mixture in polytetrahydrofuran dibasic alcohol, polyoxyethylene glycol, Polyoxypropylene diol, or tetrahydrofuran (THF), ethylene oxide, propylene oxide any one in both copolymerization dibasic alcohol or any two kinds and two or more mixtures arbitrarily, or tetrahydrofuran (THF), ethylene oxide, propylene oxide three copolymerization dibasic alcohol; 2) polyester diol is any one or any two kinds and the two or more mixture in poly-hexanodioic acid hexylene glycol ester, poly adipate succinic acid ester, polyethylene glycol adipate, polyneopentyl glycol adipate, poly-phthalic acid hexylene glycol ester, or the polyester diol being formed by diprotic acid and dibasic alcohol condensation, or the polyester diol being formed by lactone ring opening polymerization; 3) PCDL is the oligopolymer containing two or more terminal hydroxy group carbonate-containing structures, is to be obtained by transesterify by carbonic diester and dibasic alcohol.
Hydrophilic chain extender is any one or any two kinds and the two or more mixture in dimethylol propionic acid, dimethylolpropionic acid and quadrol base ethyl sulfonic acid sodium (CAS:34730-59-1).
General chainextender is for having HOR 8r 9oH and R 10hNR 8r 9nHR 11any one in structural formula compound or any two kinds and two or more mixtures, wherein R 8and R 9can be identical group, can be also different groups, R 8and R 9that carbon atom is any one of 1～12 alkyl and alkylene; R 10and R 11can be identical group, can be also different groups, R 10and R 11be that hydrogen atom and carbon atom are any one of 1～12 alkyl, typical general chainextender comprises ethylene glycol, propylene glycol, butyleneglycol, Diethylene Glycol, triethylene glycol, quadrol, butanediamine and hexanediamine etc.
Organic amine neutralizing agent is for having NR 12r 13r 14any one in structural formula compound or any two kinds and two or more mixtures, wherein R 12, R 13and R 14can be identical group, can be also different groups, R 12, R 13and R 14group is that carbon atom is any one in 2～12 alkyl, and typical organic amine compound comprises triethylamine, tripropyl amine, Tributylamine and triisopropylamine etc.
Disperseing chainextender is any one or any two kinds and the two or more mixtures with three or three above amine compound, primary alconol compound and alcohol amine compounds containing active hydrogen functional group, typically disperses chainextender to comprise diethylenetriamine, triethylene tetramine, diethanolamine, trolamine and serinol etc.
The principal reaction of synthetic method of the present invention is as follows:
Prepolymerization reaction: add polyisocyanates and cation type organic silicon in reaction vessel, react 0.5～6h after being warming up to 50～80 DEG C; Then add polymer polyatomic alcohol, at same temperature, continue reaction 0.5～6h; Hydrophilic chain extender is joined in reaction system, at 50～80 DEG C, react after 0.5～6h; Then add at 50～80 DEG C of general chainextenders and react isocyanato content in 0.5～6h post analysis prepolymer, when isocyanato (NCO) content reaches theoretical value, termination reaction, obtains the polynary block prepolymer of main chain containing tertiary sulfonium base, ether, urethano, carboxyl and polysiloxane segment; Wherein, isocyanato content in prepolymer=(polyisocyanates amount of substance-oxy-compound reacting with isocyanato and total amount of substance of amino-complex) * 2* isocyanato molecular weight/total solids quality.Remarks: amido is the same with hydroxyl, can react with isocyanato, and both are equal in amount, and an amido is equal to a hydroxyl.
Salt-forming reaction: prepolymer is down to room temperature, adds acetone to reduce viscosity, under room temperature, stir until prepolymer dissolves, obtain homogeneous phase solution, then add in organic amine neutralizing agent and molecular chain in carboxylic acid and/or sulfonic acid;
Disperse chain extending reaction: above-mentioned product brute force is scattered in the deionized water that disperses chainextender and makes its emulsification chain extension; After emulsification chain extension finishes, acetone and part deionized water are removed in underpressure distillation, obtain solid content and be 20%～40% organic-silicon-modified amphotenic polkyurethanes water dispersion.
Wherein, hydroxyl in described raw material polyisocyanates in isocyanato and raw material cation type organic silicon, polymer polyatomic alcohol, hydrophilic chain extender and general chainextender and the mol ratio of amido summation are 2～10:1, the mol ratio of described hydrophilic chain extender and organic amine neutralizing agent is 1:1, and in described the first step prepolymerization reaction, isocyanato (NCO) content theoretical value is 0.1%～20%; When in described dispersion chainextender, active group (active hydrogen) finishes with prepolymerization reaction, in prepolymer, the mol ratio of isocyanato is 0.1～1:1; .
Wherein, cation type organic silicon content range is: 1%～30%, and described polymer polyatomic alcohol content range is: 10%～54%, described hydrophilic radical carboxylic acid group and/or sulfonic group (COO-and/or SO 3-) content range is: 1%～4%; Described cation type organic silicon, polymer polyatomic alcohol and hydrophilic radical carboxylic acid group and/or sulfonic content are respectively cation type organic silicon, polymer polyatomic alcohol and hydrophilic radical carboxylic acid group and/or sulfonic quality and account for the per-cent of total solids quality; Described total solids quality is the total mass (not comprising the quality of disperseing chainextender) of cation type organic silicon, polyisocyanates, polymer polyatomic alcohol, hydrophilic chain extender, general chainextender and organic amine neutralizing agent.
Beneficial effect of the present invention is:
1, select double ended type or (with) the single-ended hydroxyl alkyl blocking silicone that contains tertiary sulfonium group carries out modification to urethane: 1) if while use separately, the former obtains organic block modified structure, the latter obtains organosilicon grafted and modified structure, 2) if while use simultaneously, obtain on molecular backbone chain He on side chain and contain organosilyl urethane simultaneously, and the organosilyl water tolerance that can greatly improve urethane that adds.
2, in synthetic organic silicon polyurethane water dispersion molecule, both contained the tertiary sulfonium group of hydrophilic positively charged ion, contain again hydrophilic negatively charged ion carboxylic group, make final product in acidity or alkaline medium, all can form stabilising dispersions, increase the range of application of polyurethane aqueous dispersion body.
3, in traditional amphotenic polkyurethanes building-up process, conventionally by use two hydroxyl tertiary amine compounds to make to have in polyurethane molecular cationically group, but can be used as catalyzer, tertiary amine accelerates reacting of isocyanate group and hydroxyl, make reaction system heat release violent, in the present invention, take tertiary sulfonium cation to substitute amino positively charged ion, can avoid the very exothermic phenomenon in polyurethane production process, thereby make production technique be more prone to control.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of the amphotenic polkyurethanes water dispersion prepared of the embodiment of the present invention 1.
Embodiment
Embodiment 1 (cation type organic silicon content=14.1%, COOH%=1.3%, NCO/OH=2.86:1)
1, cation type organic silicon is synthetic:
Balanced reaction: taking trifluoromethane sulfonic acid as catalyzer, by tetramethyl-two hydrogen siloxanes and octamethylcyclotetrasiloxane (D 4) carry out polyreaction, in reaction process, to protect with nitrogen, temperature of reaction is: 65 DEG C, the reaction times is: 20h, obtains α, ω-bis-silicon hydrogen terminated polysiloxanes.In described balanced reaction, the molar ratio of above-mentioned 2 kinds of reactants is depending on the size of final product molecular weight or the number of silicon hydrogen richness.According to above-mentioned reaction formula, molecular weight design formula (taking tetramethyl-two hydrogen siloxanes as end-capping reagent, consumption is that 1mol is example) is as follows, molecular weight (the 134)+D of the design molecular weight=end-capping reagent of polysiloxane 4molecular weight (296) × D 4amount of substance, i.e. the design molecular weight=134+74m of polysiloxane, if design molecular weight is 1000, in above-mentioned reaction formula, m is about 12, prepares molecular weight and be 1000 polysiloxane, approximately needs the end-capping reagent of 1mol and the D of 3mol 4.
Silicon hydrogen addition: taking Platinic chloride as catalyzer; by α; ω-bis-silicon hydrogen terminated polysiloxanes are added drop-wise in glycidyl allyl ether toluene solution; in reaction process, protect with nitrogen, temperature of reaction is: 80～110 DEG C, the reaction times is: 8～12h; obtain α; ω-bis-epoxy terminated polysiloxane, described addition reaction of silicon with hydrogen molar ratio is: glycidyl allyl ether: α, ω-bis-silicon hydrogen terminated polysiloxanes: Platinic chloride=2～3:1:3.1 × 10 -4.
Ring-opening reaction: by α, ω-bis-epoxy terminated polysiloxane, propyl thioether and acetic acid join in reaction flask and stir, temperature of reaction is: 70～80 DEG C, reaction times is: 4～12h, in the time that reaction system acid number is less than 5, stopped reaction, obtains the hydroxyl alkyl blocking silicone that double ended type contains tertiary sulfonium group, described ring-opening reaction molar ratio is: α, ω-bis-silicon hydrogen terminated polysiloxanes: propyl thioether: acetic acid=1:2～2.2:2.
Below in conjunction with concrete synthetic method, the cation type organic silicon in embodiments of the invention 1 is described further.
Balanced reaction (mol ratio tetramethyl-two hydrogen siloxanes: D 4=1:1.25)
In 2L three-necked bottle, add successively 268g tetramethyl-two hydrogen siloxanes and 740g D 4pass into after nitrogen 20min, reaction system is warming up to 65 DEG C and add 60 μ L trifluoromethane sulfonic acids, at this temperature, react 20h, then neutralize with potassium hydroxide-methanol solution of 1.0mL1mol/L, excessive potassium hydroxide neutralizes with hydrochloric acid-methanol solution of 0.40mL1mol/L again.Low-boiling-point substance is removed in underpressure distillation, obtains α, ω-bis-silicon hydrogen terminated polysiloxane 1000g, yield 99.2%.
The addition of silicon hydrogen (mol ratio glycidyl allyl ether: α, ω-bis-silicon hydrogen terminated polysiloxanes: Platinic chloride=2:1:3.1 × 10 -4)
In 1L four-necked bottle, add successively 268g glycidyl allyl ether, 50mL toluene and contain Platinic chloride 3.1 × 10 -4the aqueous isopropanol of mol, passes into after nitrogen 20min, and reaction system is warming up to 100 DEG C, drips 500g α at this temperature, ω-bis-silicon hydrogen terminated polysiloxanes, termination reaction after reaction 8h.Low-boiling-point substance is removed in underpressure distillation, obtains α, ω-bis-epoxy terminated polysiloxane 745g, yield 97.0%.
Ring-opening reaction (mol ratio α, ω-bis-silicon hydrogen terminated polysiloxanes: propyl thioether: acetic acid=1:2:2)
In 1L four-necked bottle, add successively 384g α, ω-bis-epoxy terminated polysiloxane, 59g propyl thioether and 60g acetic acid, be warming up to 70 DEG C by reaction system, and now system heat release is obvious, if temperature of reaction system exceedes 80 DEG C, should lower the temperature with ice bath in time; After heat release finishes, at this temperature, react 8h, termination reaction in the time that reaction system acid number is less than 5, obtains the hydroxyl alkyl blocking silicone (M that double ended type contains tertiary sulfonium group n=1000) 496g, yield 98.6%.
2, product is synthetic
Prepolymerization reaction: being equipped with in the there-necked flask of agitator and thermometer, add the cation type organic silicon (M of 174g tolylene diisocyanate and 50g structure as implied above n=1000), react 1h after being warming up to 70 DEG C; Then add 100g polyether Glycols (M n=1000), at same temperature, continue reaction 1h.13.4g dimethylol propionic acid is joined in reaction system, at 70 DEG C, react after 0.5h, then add at 70 DEG C of 6.2g ethylene glycol, to react after 0.5h and analyze isocyanato content in prepolymer by standard Di-n-Butyl Amine back titration method, in the time that isocyanato content reaches theoretical value 15.9%, termination reaction, obtains the polynary block prepolymer of main chain containing tertiary sulfonium base, ether, urethano, carboxyl and polysiloxane segment.
Salt-forming reaction
Prepolymer is down to room temperature, adds 100g acetone viscosity reduction, under room temperature, stir until prepolymer dissolves, obtain homogeneous phase solution, then add in 10.1g triethylamine and molecular chain in carboxylic acid.
Disperse chain extending reaction
Base polyurethane prepolymer for use as brute force is scattered in and in the 2400g deionized water containing 22.3g diethylenetriamine, makes its emulsification chain extension.After emulsification chain extension finishes, acetone is removed in underpressure distillation, and the further water of underpressure distillation remove portion, obtains solid content and be 20.4% organic block modification by copolymerization amphotenic polkyurethanes water dispersion.
This water dispersion is characterized with infrared spectra, obtain infrared spectrum as shown in drawings.3300cm – 1the symmetrical stretching vibration absorption peak of the ammonia ester bond N-H of place key, 1728cm – 1the vibration absorption peak of the ammonia ester bond C=O of place, 2870-2970cm – 1the CH of place 2and CH 3vibration absorption peak and 1103cm – 1the absorption peak of the C-O-C of place, these characteristic peaks show that urethane is successfully synthesized.1017cm in figure – 1the vibration absorption peak of the Si-O of place key, 805cm – 1the Si-CH of place 3the vibration absorption peak of key shows that organosilicon has successfully been connected in polyurethane molecular.To sum up analyze, cation type organic silicon modified polyurethane aqueous dispersion body is successfully preparation.
Table 1 water dispersion performance comparison data
? Pure urethane Embodiment 1 sample
Stability (pH scope) 6～8 4～10
Table 2 film performance correlation data
? Pure urethane Embodiment 1 sample
Water-intake rate (%) 74.31 64.32
Inhale toluene rate (%) 82.77 74.68
Can be found out by table 1 data, due to adding of tertiary sulfonium cation, make urethane moisture body after modification can the scope that be 4～10 in pH value in stable existence, but the pH value use range of traditional anion polyurethane moisture body is only 6～8; In the time that polymkeric substance exists with sulfonium salt form, can be by it compared with good dissolving or be dispersed in water so that in the even film forming of body surface, after film forming in the situation that of light or heating sulfonium base with the volatilization of thioether form, thereby make water-solubility membrane become hydrophobic membrane; In addition, the organosilyl water tolerance (referring to table 2 data) that also can greatly improve urethane moisture body that adds.
Embodiment 2 (cation type organic silicon content=21.3%, COOH%=1.44%, NCO/OH=2.5:1)
1, cation type organic silicon is synthetic:
Hydroxyl protection: under room temperature; first hexamethyldisilazane is added drop-wise in glycerine; reaction system is warming up to 90～120 DEG C; and 4～8h hour is reacted in continuation at this temperature; stopped reaction, excessive hexamethyldisilazane is removed in underpressure distillation, obtains 1; 3-bis-(trimethyl silicane) oxygen base-2-propyl alcohol, in described hydroxyl protection reaction process, molar ratio is: glycerine: hexamethyldisilazane=1:1～1.1.
Alkylated reaction: under room temperature, 1,3-bis-(trimethyl silicane) oxygen base-2-propyl alcohol is slowly added drop-wise in the tetrahydrofuran solution that contains sodium hydride, starts and stir and be slowly warming up to 40～60 DEG C of reaction 2h and produce to no hydrogen; Reaction system is cooled to after 0 DEG C, start and stir and slowly drip allyl bromide 98, after dropwising, be warming up to 40～60 DEG C reaction 6h after stopped reaction, remove by filter Sodium Bromide precipitation, and tetrahydrofuran (THF) and excessive allyl bromide 98 are removed in underpressure distillation, obtain 1,3-bis-(trimethyl silicane) oxygen base-2-allyloxy propane, in described alkylation process, molar ratio is: 1,3-bis-(trimethyl silicane) oxygen base-2-propyl alcohol: sodium hydride: allyl bromide 98=1:1:1～1.1.
Alcoholysis reaction: taking acetic acid as catalyzer, by 1,3-bis-(trimethyl silicane) oxygen base-2-allyloxy propane joins in methanol solution, temperature of reaction is: 65 DEG C, and reaction 6～12h, methyl alcohol and low-boiling-point substance are removed in underpressure distillation, obtain 2-allyloxy-1,3 propylene glycol, described alcoholysis reaction molar ratio is: 1,3-bis-(trimethyl silicane) oxygen base-2-allyloxy propane: methyl alcohol: acetic acid=1:20～100:0.4～1.3.
Secondary alkylated reaction: by 2-allyloxy-1, be warming up to 60～80 DEG C after 3 propylene glycol and epoxy chloropropane mix, and drip the aqueous solution of sodium hydroxide at this temperature.After dropwising, stopped reaction after continuation reaction 4～10h at 60～80 DEG C.In the time that temperature of reaction system is cooled to room temperature, in reaction flask, add distilled water and toluene.After fully stirring, leave standstill and isolate moisture with separating funnel, then with distilled water wash for several times, until water is neutrality and without chlorion.The organic layer separating, subtract air distillation and remove most toluene, water and unreacted epoxy chloropropane, obtain 2-allyloxy-1, ammediol diglycidylether, described secondary alkylated reaction molar ratio is: 2-allyloxy-1,3 propylene glycol: sodium hydroxide: epoxy chloropropane=1:2:2～2.2.
Anionic ring-opening polymerization reaction: by hexamethyl cyclotrisiloxane (D 3) prepare with initiator ring-opening polymerization in organic solvent the polysiloxane that single-ended hydrosilyl group-containing is rolled into a ball.Feeding mode is first by D 3be dissolved in non-polar organic solvent, join in anhydrous and oxygen-free reaction flask after treatment, inject initiator and promotor, temperature of reaction: 0～30 DEG C, reaction times: 4～12h, finally injects dimethyl hydrogen one chlorosilane termination reaction with syringe.Reaction soln is filtered, and low-boiling-point substance is removed in underpressure distillation, obtains the polysiloxane that single-ended hydrosilyl group-containing is rolled into a ball.Above-mentioned non-polar organic solvent refers to any one in benzene, toluene, normal hexane, hexanaphthene, initiator refers to any one in n-Butyl Lithium, s-butyl lithium, trimethylsiloxy group lithium, and promotor refers to any one in tetrahydrofuran (THF), methyl-sulphoxide, hexamethylphosphoramide.D 3with the ratio of initiator depending on molecular weight.According to above-mentioned reaction formula, molecular weight design formula (taking n-Butyl Lithium as initiator, consumption is that 1mol is example) is as follows, molecular weight (the 57)+D of the design molecular weight=normal-butyl of polysiloxane 3molecular weight (222) × D 3amount of substance+(CH 3) 2the molecular weight (59) of SiH, i.e. the design molecular weight=57+74n+59 of polysiloxane, if design molecular weight is 1000, in above-mentioned reaction formula, n is about 12, prepares molecular weight and be 1000 polysiloxane, approximately needs the initiator of 1mol, the D of 3mol 3encapsulant with 1mol.
Addition reaction of silicon with hydrogen: taking Platinic chloride as catalyzer, the polysiloxane that single-ended hydrosilyl group-containing is rolled into a ball is added drop-wise in the toluene solution of 2-allyloxy-1,3-PD diglycidylether, protects in reaction process with nitrogen.Molar ratio is: the polysiloxane that single-ended hydrosilyl group-containing is rolled into a ball: 2-allyloxy-1,3-PD diglycidylether: Platinic chloride=1:1～1.1:3.1 × 10 -4, temperature of reaction is: 80～110 DEG C, the reaction times is: 8～12h, obtains α-butyl, ω-bis-epoxy base terminated polysiloxane.
Ring-opening reaction: by α-butyl, ω-bis-epoxy base terminated polysiloxane, propyl thioether and acetic acid join in reaction flask and stir, temperature of reaction is: 70～80 DEG C, reaction times is: 4～12h, in the time that reaction system acid number is less than 5, stopped reaction, obtains the hydroxyl alkyl blocking silicone that single-ended contains tertiary sulfonium group, described ring-opening reaction molar ratio is: α-butyl, ω-bis-epoxy base terminated polysiloxane: propyl thioether: acetic acid=1:2～2.2:2.
Below in conjunction with concrete synthetic method, the cation type organic silicon in embodiments of the invention 1 is described further.
Hydroxyl protection (mol ratio glycerine: hexamethyldisilazane=1:1)
In 2L three-necked bottle, add 460g glycerine, under room temperature, slowly drip 805g hexamethyldisilazane, after dropwising, reaction system is warming up to 100 DEG C, and in this temperature, continues reaction 8 hours, stopped reaction.Underpressure distillation is removed after low-boiling-point substance, obtains 1121g1,3-bis-(trimethyl silicane) oxygen base-2-propyl alcohol, yield 95.0%.
Alkylated reaction (mol ratio 1,3-bis-(trimethyl silicane) oxygen base-2-propyl alcohol: sodium hydride: allyl bromide 98=1:1:1)
Under room temperature, by 472g1,3-bis-(trimethyl silicane) oxygen base-2-propyl alcohol is slowly added drop-wise in the 2L reaction flask of the tetrahydrofuran solution that contains 48g sodium hydride, starts to stir and be slowly warming up to 40 DEG C of reaction 2h and produce to no hydrogen; Reaction system is cooled to after 0 DEG C, start and stir and slowly drip 264g allyl bromide 98, after dropwising, be warming up to 60 DEG C reaction 6h after stopped reaction, remove by filter Sodium Bromide precipitation, and tetrahydrofuran (THF) and excessive allyl bromide 98 are removed in underpressure distillation, obtain 541g1,3-bis-(trimethyl silicane) oxygen base-2-allyloxy propane, yield 98.0%.
Alcoholysis reaction (mol ratio 1,3-bis-(trimethyl silicane) oxygen base-2-allyloxy propane: methyl alcohol: acetic acid=1:20:0.4)
In 2L three-necked bottle, add successively 552g1,3-bis-(trimethyl silicane) oxygen base-2-allyloxy propane, 1280g methyl alcohol and 48g acetic acid.Under reflux condition, react stopped reaction after 8 hours.Acetic acid, excessive methyl alcohol and low-boiling-point substance are removed in underpressure distillation, obtain 252g2-allyloxy-1,3 propylene glycol, yield 95.5%.
Secondary alkylated reaction (mol ratio 2-allyloxy-1,3 propylene glycol: epoxy chloropropane: sodium hydroxide=1:2.2:2)
Add 132g2-allyloxy-1,3 propylene glycol and 203.5g epoxy chloropropane to being equipped with in the 2L three-necked bottle of agitator, reflux condensing tube and thermometer.Start and stir and reaction system is heated to 75 DEG C, at this temperature, drip 320g mass percent concentration and be 25% aqueous sodium hydroxide solution, dropwise rear continuation and at this temperature, react 8h, stopped reaction.When temperature is cooled to after room temperature, in reaction flask, add toluene, after fully stirring, leave standstill and isolate moisture with separating funnel, then with distilled water wash for several times, until water is neutrality and without chlorion.The organic layer separating, most benzene is removed in air distillation, and then residual solvent, water and unreacted epoxy chloropropane are removed in underpressure distillation, obtain 241g2-allyloxy-1,3-PD diglycidylether, yield 98%.
Anionic ring-opening polymerization reaction (mol ratio n-Butyl Lithium: D 3=1:6.3)
Through in anhydrous and oxygen-free 2L reaction flask after treatment, add successively the n-Butyl Lithium, 300mL of 0.5mol containing 700g D with syringe 3benzole soln and 400ml tetrahydrofuran (THF), at 25 DEG C after stirring reaction 8h, add dimethyl hydrogen one chlorosilane termination reaction with syringe.Reacting liquid filtering is removed to the lithium chloride of generation, underpressure distillation is removed after low-boiling-point substance, obtains the polysiloxane (Mn=1500) of the single-ended hydrosilyl group-containing of 730g colourless transparent liquid group, yield 96.3%.
Addition reaction of silicon with hydrogen (mol ratio 2-allyloxy-1,3-PD diglycidylether: the polysiloxane that single-ended hydrosilyl group-containing is rolled into a ball: Platinic chloride=1:1:3.1 × 10 -4)
In 1L four-necked bottle, add successively 73.8g2-allyloxy-1,3-PD diglycidylether, 50mL toluene and contain Platinic chloride 0.93 × 10 -4the aqueous isopropanol of mol, passes into after nitrogen 20min, and reaction system is warming up to 100 DEG C, drips the polysiloxane (Mn=1500) of 450g hydrosilyl group-containing group at this temperature, termination reaction after reaction 8h.Low-boiling-point substance is removed in underpressure distillation, obtains 495g α-butyl, ω-bis-epoxy base terminated polysiloxane, yield 94.5%.
Ring-opening reaction (mol ratio α-butyl, ω-bis-epoxy base terminated polysiloxane: propyl thioether: acetic acid=1:2:2)
In 1L four-necked bottle, add successively 384g α-butyl, ω-bis-epoxy terminated polysiloxane, 59g propyl thioether and 60g acetic acid, reaction system is warming up to 70 DEG C, now system heat release is obvious, if temperature of reaction system exceedes 80 DEG C, should lower the temperature with ice bath in time; After heat release finishes, at this temperature, react 8h, termination reaction in the time that reaction system acid number is less than 5, obtains the hydroxyl alkyl blocking silicone (M that double ended type contains tertiary sulfonium group n=1000) 496g, yield 98.6%.
2, product is synthetic
Prepolymerization reaction: being equipped with in the there-necked flask of agitator and thermometer, add 222g isophorone dicyanate and the 100g cation type organic silicon (M of structure as shown above n=2000), react 1.5h after being warming up to 70 DEG C; Then add 100g polyether Glycols (M n=1000), at same temperature, continue reaction 1.5h.22.2g dimethylolpropionic acid is joined in reaction system, at 70 DEG C, react after 1h, then add at 70 DEG C of 9.08g butyleneglycols, to react after 1h and analyze isocyanato content in prepolymer by standard Di-n-Butyl Amine back titration method, in the time that isocyanato content reaches theoretical value 11.1%, termination reaction, obtains the multi-grafted prepolymer that main chain contains polysiloxane segment containing tertiary sulfonium base, ether, urethano, carboxyl and side chain.
Salt-forming reaction: prepolymer is down to room temperature, adds 150g acetone viscosity reduction, under room temperature, stir until prepolymer dissolves, obtain homogeneous phase solution, then add in 15.15g triethylamine and molecular chain in carboxylic acid group.
Disperse chain extending reaction: base polyurethane prepolymer for use as brute force is scattered in and in the 2400g deionized water containing 28.84g diethylenetriamine, makes its emulsification chain extension.After emulsification chain extension finishes, acetone is removed in underpressure distillation, and the further water of underpressure distillation remove portion, obtains solid content and be 21.8% graft copolymerization by organic silicon amphotenic polkyurethanes water dispersion.
Embodiment 3 (cation type organic silicon content=24.4%, COOH%=1.34%, NCO/OH=2.5:1)
Prepolymerization reaction: being equipped with in the there-necked flask of agitator and thermometer, add the cation type organic silicon (M of 250g diphenylmethanediisocyanate, 75g structure (I) n=1500) and the cation type organic silicon (M of 50g structure (II) n=1000), react 1.2h after being warming up to 70 DEG C; Then add 100g polyether Glycols (M n=2000), at same temperature, continue reaction 1.5h.22.2g dimethylolpropionic acid is joined in reaction system, at 70 DEG C, react after 1h, then add at 70 DEG C of 6.20g ethylene glycol, to react after 1h and analyze isocyanato content in prepolymer by standard Di-n-Butyl Amine back titration method, in the time that isocyanato content reaches theoretical value 11.83%, termination reaction, obtain main chain containing tertiary sulfonium base, ether, urethano, carboxyl and polysiloxane segment, the polynary block that side chain contains polysiloxane segment and grafting prepolymer.
Salt-forming reaction: prepolymer is down to room temperature, adds 150g acetone viscosity reduction, under room temperature, stir until prepolymer dissolves, obtain homogeneous phase solution, then add in 15.15g triethylamine and molecular chain in carboxylic acid group.
Disperse chain extending reaction: base polyurethane prepolymer for use as brute force is scattered in and in the 2600g deionized water containing 43.26g diethylenetriamine, makes its emulsification chain extension.After emulsification chain extension finishes, acetone is removed in underpressure distillation, and the further water of underpressure distillation remove portion, obtains solid content and be 29.72% organic block and grafting modification by copolymerization amphotenic polkyurethanes water dispersion simultaneously.
Embodiment 4
Tolylene diisocyanate in embodiment 1 is changed to dicyclohexyl methane diisocyanate, polyether Glycols is changed to the mixture (three's mass ratio is 1:1:1) of polyether Glycols, polyester diol and PCDL, N dimethylol propionic acid is changed to N-sulfonic acid ethylethylenediamine, other reaction conditionss as described in example 1 above, the organic-silicon-modified amphotenic polkyurethanes water dispersion that the solid content that obtains being different from embodiment 1 is 24.3%.
Embodiment 5
Tolylene diisocyanate in embodiment 1 is changed to the mixture of methyl hexamethylene diisocyanate and hydrogenated tolylene diisocyanate, cation type organic silicon is changed to two kinds of organosilyl mixtures of different structure positively charged ion (both mass ratioes are: 3:4) in embodiment 1 and embodiment 2, other reaction conditionss as described in example 1 above, the organic-silicon-modified amphotenic polkyurethanes water dispersion that the solid content that obtains being different from embodiment 1 is 23.8%.
Embodiment 6
Diphenylmethanediisocyanate in embodiment 3 is changed to the mixture of tolylene diisocyanate and hydrogenated tolylene diisocyanate, disperse chainextender to be changed to the mixture of triethylene tetramine and diethanolamine by diethylenetriamine, other reaction conditionss as described in example 3 above, the organic-silicon-modified amphotenic polkyurethanes water dispersion that the solid content that obtains being different from embodiment 3 is 25.7%.

Claims (10)

1. the preparation method of an organic-silicon-modified amphotenic polkyurethanes water dispersion, it is characterized in that, taking cation type organic silicon, polyisocyanates, polymer polyatomic alcohol, hydrophilic chain extender, general chainextender, the organic amine neutralizing agent of two hydroxyl alkyl end-blockings of containing tertiary sulfonium group with disperse chainextender as raw material, by prepolymerization reaction, salt-forming reaction and dispersion chain extending reaction, obtain organic-silicon-modified amphotenic polkyurethanes water dispersion.
2. the preparation method of a kind of organic-silicon-modified amphotenic polkyurethanes water dispersion as claimed in claim 1, is characterized in that,
Described prepolymerization reaction: add the cation type organic silicon of polyisocyanates and two hydroxyl alkyl end-blockings of containing tertiary sulfonium group in reaction vessel, react 0.5～6h after being warming up to 50～80 DEG C; Then add polymer polyatomic alcohol, continue reaction 0.5～6h at 50～80 DEG C; Hydrophilic chain extender is joined in reaction system, at 50～80 DEG C, react after 0.5～6h; Then add at 50～80 DEG C of general chainextenders and react isocyanato content in 0.5～6h post analysis prepolymer, when isocyanato content reaches theoretical value, termination reaction, obtains the polynary block prepolymer of main chain containing tertiary sulfonium base, ether, urethano, carboxyl and polysiloxane segment; Hydroxyl in described raw material polyisocyanates in isocyanato and raw material cation type organic silicon, polymer polyatomic alcohol, hydrophilic chain extender and general chainextender and the mol ratio of amido summation are 2～10:1; Described hydrophilic chain extender is any one or any two kinds and the two or more mixture in dimethylol propionic acid, dimethylolpropionic acid and quadrol base ethyl sulfonic acid sodium;
Described salt-forming reaction: prepolymer is down to room temperature, adds acetone, under room temperature, stir until prepolymer dissolves, obtain homogeneous phase solution, then add in organic amine neutralizing agent and molecular chain in carboxylic acid and/or sulfonic acid;
Described dispersion chain extending reaction: the product brute force after salify is scattered in the deionized water that disperses chainextender and makes its emulsification chain extension; After emulsification chain extension finishes, acetone and part deionized water are removed in underpressure distillation, obtain solid content and be 20%～40% organic-silicon-modified amphotenic polkyurethanes water dispersion; When in described dispersion chainextender, active group and prepolymerization reaction finish, in prepolymer, the mol ratio of isocyanato is 0.1～1:1;
The cation type organic silicon of the described two hydroxyl alkyl end-blockings that contain tertiary sulfonium group is double ended type and/or single-ended;
Described double ended type structure is as follows:
Described single-ended structure is as follows:
Wherein, R 1that carbon atom is any one of 1～12 alkyl, aliphatics alkoxyl group, alicyclic alkoxyl group and aromatic series alkoxyl group; R 2and R 3for identical or different groups, R 2and R 3that carbon atom is any one of 1～12 alkyl and alkylene; R 4that hydrogen atom and carbon atom are any one of 1～12 alkyl and aryl; R 5that carbon atom is 1～12 alkyl; R 6and R 7for identical or different groups, R 6and R 7that carbon atom is any one of 1～12 alkyl, aliphatics alkoxyl group, alicyclic alkoxyl group and aromatic series alkoxyl group; In said structure formula, m>1, n>1.
3. the preparation method of a kind of organic-silicon-modified amphotenic polkyurethanes water dispersion as claimed in claim 2, it is characterized in that, described cation type organic silicon content range is: 1%～30%, described polymer polyatomic alcohol content range is: 10%～54%, and described hydrophilic radical carboxylic acid group and/or sulfonic group content range are: 1%～4%; Described cation type organic silicon, polymer polyatomic alcohol and hydrophilic radical carboxylic acid group and/or sulfonic content are respectively cation type organic silicon, polymer polyatomic alcohol and hydrophilic radical carboxylic acid group and/or sulfonic quality and account for the per-cent of total solids quality; Described total solids quality is the total mass of cation type organic silicon, polyisocyanates, polymer polyatomic alcohol, hydrophilic chain extender, general chainextender and organic amine neutralizing agent.
4. the preparation method of a kind of organic-silicon-modified amphotenic polkyurethanes water dispersion as claimed in claim 2, is characterized in that, in described prepolymerization reaction, isocyanato content theoretical value is 0.1%～20%.
5. the preparation method of a kind of organic-silicon-modified amphotenic polkyurethanes water dispersion as claimed in claim 2, is characterized in that, described double ended type and single-ended use simultaneously, and the mass ratio of described double ended type and single-ended is 1:9～9:1.
6. the preparation method of a kind of organic-silicon-modified amphotenic polkyurethanes water dispersion as described in any one in claim 1-5, it is characterized in that, described polyisocyanates is any one or any two kinds and the two or more mixture in tolylene diisocyanate, '-diphenylmethane diisocyanate, polymethylene polyphenyl vulcabond, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, trimethyl hexamethylene diisocyanate and hydrogenated tolylene diisocyanate.
7. the preparation method of a kind of organic-silicon-modified amphotenic polkyurethanes water dispersion as described in any one in claim 1-5, it is characterized in that, described polymer polyatomic alcohol is any one or any two kinds and the two or more mixture in polyether Glycols, polyester diol and PCDL.
8. the preparation method of a kind of organic-silicon-modified amphotenic polkyurethanes water dispersion as claimed in claim 7, is characterized in that,
Described polyether Glycols is any one or any two kinds and the two or more mixture in polytetrahydrofuran dibasic alcohol, polyoxyethylene glycol, Polyoxypropylene diol, or tetrahydrofuran (THF), ethylene oxide, propylene oxide any one in both copolymerization dibasic alcohol or any two kinds and two or more mixtures arbitrarily, or tetrahydrofuran (THF), ethylene oxide, propylene oxide three copolymerization dibasic alcohol;
Described polyester diol is any one or any two kinds and the two or more mixture in poly-hexanodioic acid hexylene glycol ester, poly adipate succinic acid ester, polyethylene glycol adipate, polyneopentyl glycol adipate, poly-phthalic acid hexylene glycol ester, or the polyester diol being formed by diprotic acid and dibasic alcohol condensation, or the polyester diol being formed by lactone ring opening polymerization;
Described PCDL is the oligopolymer containing two or more terminal hydroxy group carbonate-containing structures.
9. the preparation method of a kind of organic-silicon-modified amphotenic polkyurethanes water dispersion as described in any one in claim 1-5, is characterized in that,
Described general chainextender is for having HOR 8r 9oH and R 10hNR 8r 9nHR 11any one in structural formula compound or any two kinds and two or more mixtures, wherein R 8and R 9for identical or different group, R 8and R 9that carbon atom is any one of 1～12 alkyl and alkylene; R 10and R 11for identical or different group, R 10and R 11that hydrogen atom and carbon atom are any one of 1～12 alkyl;
Described organic amine neutralizing agent is for having NR 12r 13r 14any one in structural formula compound or any two kinds and two or more mixtures, wherein R 12, R 13and R 14for identical or different group, R 12, R 13and R 14group is that carbon atom is any one in 2～12 alkyl;
Described dispersion chainextender is any one or any two kinds and the two or more mixture with three or three above amine compound, primary alconol compound and alcohol amine compounds containing active hydrogen functional group.
10. the preparation method of a kind of organic-silicon-modified amphotenic polkyurethanes water dispersion as claimed in claim 9, is characterized in that,
Described general chainextender is any one or any two kinds and the two or more mixture in ethylene glycol, propylene glycol, butyleneglycol, Diethylene Glycol, triethylene glycol, quadrol, butanediamine and hexanediamine;
Described organic amine neutralizing agent is any one or any two kinds and the two or more mixture in triethylamine, tripropyl amine, Tributylamine and triisopropylamine;
Described dispersion chainextender is any one or any two kinds and the two or more mixture in diethylenetriamine, triethylene tetramine, diethanolamine, trolamine and serinol.
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