CN103980450B - The preparation method of organic-silicon-modified cation aqueous polyurethane - Google Patents

The preparation method of organic-silicon-modified cation aqueous polyurethane Download PDF

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CN103980450B
CN103980450B CN201410254854.2A CN201410254854A CN103980450B CN 103980450 B CN103980450 B CN 103980450B CN 201410254854 A CN201410254854 A CN 201410254854A CN 103980450 B CN103980450 B CN 103980450B
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silicon
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CN103980450A (en
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邬元娟
张萌
张树秋
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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Abstract

The invention discloses a kind of preparation method of organic-silicon-modified cation aqueous polyurethane.It first selects two ends to contain hydroxyl alkyl and side base reacts containing the organosilicon of epoxide group and polyisocyanates, is incorporated into by silicone backbone in polyurethane structural; Again general chainextender and monohydroxy glycidyl ether (or mixture of monohydroxy glycidyl ester or two kinds of arbitrary proportions) are reacted with above-mentioned organic silicon modified polyurethane prepolymer; Then select organic amine compound (or organo phosphorous compounds, organosulfur compound) and organic acid to join in the organic silicon modified polyurethane after with butanone dilution, carry out ion reaction; Finally be distributed in water by the organic silicon modified polyurethane after ionization by self-emulsifying, underpressure distillation obtains organic-silicon-modified cation aqueous polyurethane after removing butanone.

Description

The preparation method of organic-silicon-modified cation aqueous polyurethane
Technical field
The present invention relates to a kind of preparation method of organic-silicon-modified cation aqueous polyurethane, a kind of cationic hydrophilic group is as the preparation method of the organic silicon modified aqueous polyurethane of polysiloxane segment pendant group specifically.
Background technology
Due to environmentally friendly, aqueous polyurethane has obtained significant progress in association area since appearance, is widely used in medical material, electronic material and chemical materials, but also encounters a difficult problem for its application of restriction.Because the aqueous polyurethane of synthesis is mostly line style dispersion product, adds the existence of hydrophilic radical in molecule segment, make the poor water resistance of aqueous polyurethane film.Research data shows, polysiloxane segment is linked to the water tolerance that greatly can improve polyurethane coating film in polyurethane molecular.
Organic silicon modified aqueous polyurethane can according in preparation process adopt the kind of salt forming agent different, be divided into anion aqueous polyurethane and cation aqueous polyurethane.At present, the research report of polysiloxane segment modified anion aqueous polyurethane is a lot, and the type product achieves industrialization, and relatively less about the Product Report of polysiloxane segment modified cation aqueous polyurethane.Compared with anion-type water-thinned polyurethane, cation aqueous polyurethane due to its ion that formed be quaternary ammonium salt, particle is positively charged, with dust in air with electric charge identical, there is certain dustproof effect; Hydrogen bond can be formed with the hydroxyl in xylon for the amino group in timber positively charged ion, to hydrophobic polyester, propenyl kind fabric fiber, there is good wetting property; The adhesive property of cation aqueous polyurethane is also better, can be used as the tackiness agent of some base materials; In addition cation aqueous polyurethane also has certain germicidal action, can be widely used as fabric finishing agent.In addition, cation aqueous polyurethane is insensitive to water hardness, and can use in acid condition.
But the cation-type water-thinned polyurethane of non-modified, its glued membrane is poor performance in thermotolerance, water tolerance, tensile strength etc., needs its modification, to improve the partial properties of cation aqueous polyurethane, widens its practical application area.Existing cation aqueous polyurethane product is generally quaternary ammonium type, and tertiary amine group is incorporated on polyurethane molecular main chain as chainextender by the main N methyldiethanol amine that uses, and re-uses alkylating reagent and carries out quaterisation.The people such as Shen Yiding have prepared a kind of cationic silicones urethane self-crossing emulsion.This emulsion with polyethers and tolylene diisocyanate for raw material, after small molecule chain extender chain extension, add hydroxy silicon oil carry out modification, add the obtained performed polymer containing tertiary amine groups of N methyldiethanol amine reaction again, finally to add in organic acid and salify emulsion obtains the milky white sub-translucent emulsion (" modern chemical industry " of blue light, 2003, the 23rd volume supplementary issue).The people such as the Yi Yunhong organic silicon modified aqueous cation polyurethane that also adopted similar method to synthesize, uniquely the silane coupling agent containing ammonia alkyl is selected to substitute hydroxy silicon oil (" Chinese coating " unlike them, 2006,21st volume, 8th phase and " coatings industry ", 2008, the 38th volume, the 1st phase).In the preparation method of above-mentioned organic-silicon-modified cation aqueous polyurethane, N methyldiethanol amine and isocyanic ester radical reaction is all used to prepare the performed polymer containing tertiary amine groups, but tertiary amine group can be used as in the process preparing aqueous polyurethane the reaction that catalyzer accelerates isocyanato and hydroxyl, make system very exothermic in reaction process, synthesis technique is wayward.Therefore by cation aqueous polyurethane prepared by this route, technics comparing is complicated, and sometimes emulsifying product is stable not, so bring difficulty to suitability for industrialized production.
Summary of the invention
In order to improve the water resistance of aqueous polyurethane film, the invention provides a kind of preparation method of organic-silicon-modified cation aqueous polyurethane, a kind of cationic hydrophilic group is as the preparation method of the organic silicon modified aqueous polyurethane of polysiloxane segment pendant group specifically.
Technical characteristic of the present invention is: first select two ends to contain hydroxyl alkyl and side base reacts containing the organosilicon of epoxide group and polyisocyanates, is incorporated into by silicone backbone in polyurethane structural; Again chainextender and monohydroxy glycidyl ether (or mixture of monohydroxy glycidyl ester or two kinds of arbitrary proportion mixing) are carried out chain extension and end capping with above-mentioned organic silicon modified polyurethane prepolymer; Then select organic amine compound (or organo phosphorous compounds or organosulfur compound) and organic acid to join in the organic silicon modified polyurethane after with butanone dilution, carry out ion reaction; Finally be distributed in water by the organic silicon modified polyurethane after ionization by self-emulsifying, underpressure distillation obtains organic-silicon-modified cation aqueous polyurethane after removing butanone.
Two ends are containing hydroxyl alkyl and the organosilicon that side base contains epoxide group is with unsaturated monohydroxy compound, hexamethyldisilazane, tetramethyl disiloxane, D h 4(tetramethyl-ring tetrasiloxane), D 4(octamethylcyclotetrasiloxane) and unsaturated epoxy compound are starting raw material, obtain two ends containing hydroxyl alkyl and the side base organosilicon containing epoxide group through hydroxyl protection, Si―H addition reaction, equilibrium polymerization, secondary Si―H addition reaction and alcoholysis reaction.The synthesis equation of final product is as follows:
Hydroxyl protection
CH 2＝CHCH 2OH+(CH 3) 3SiNHSi(CH 3) 3→CH 2＝CHCH 2OSi(CH 3) 3
Secondary Si―H addition reaction
Alcoholysis reaction
R:CH 2CH 2CH 2OSi(CH 3) 3R 1:CH 2CH 2CH 2OHR 2:CH 2CH 2CH 2CH(O)CH 2
Structural formula involved in the present invention is also not only confined to structural formula mentioned in equation, and final two ends are containing hydroxyl alkyl and the organosilicon that side base contains epoxide group has having structure:
In structure above, m>1, n>1; Wherein R 1for any one in following structure:
A 1)CH 2CH 2CH 2OHA 2)CH 2CH 2CH 2CH 2OHA 3)CH 2CH 2CH 2CH 2CH 2OH
A 4)CH 2CH 2CH 2CH 2CH 2CH 2OHA 5)CH 2CH 2CH 2OCH 2CH(OH)CH 2OCH 3
Wherein R 2for any one in following structure:
With two ends containing hydroxyl alkyl and the side base organosilicon (R containing epoxide group 1=A 1, R 2=B 1, m=5, n=8, M n=2000) synthesize example, its technological line is specific as follows:
Hydroxyl protection
Under room temperature; first hexamethyldisilazane is added drop-wise in vinyl carbinol; reaction system is warming up to 90 ~ 120 DEG C; and continue reaction 4 ~ 8h hour at this temperature; stopped reaction; normal pressure collects the cut of 98 ~ 100 DEG C, and obtain allyloxy trimethyl silane, in described hydroxyl protection reaction process, molar ratio is: vinyl carbinol: hexamethyldisilazane=2:1 ~ 2:1.1.
Addition reaction of silicon with hydrogen
Take Platinic chloride as catalyzer; tetramethyl disiloxane is added drop-wise in allyloxy trimethyl silane toluene solution; protect with nitrogen in reaction process; temperature of reaction is: 80 ~ 110 DEG C; reaction times is: 8 ~ 12h; obtain two (trimethylsiloxy group) disiloxane of 1,3-, described addition reaction of silicon with hydrogen molar ratio is: allyloxy trimethyl silane: tetramethyl disiloxane: Platinic chloride=2.4:1:3.1 × 10 -4~ 3:1:3.1 × 10 -4.
Balanced reaction
Take trifluoromethane sulfonic acid as catalyzer, by two for 1,3-(trimethylsiloxy group) disiloxane, D 4(octamethylcyclotetrasiloxane) and D h 4(tetramethyl-ring tetrasiloxane) carries out polyreaction, protects in reaction process with nitrogen, and temperature of reaction is: 65 DEG C, and the reaction times is: 20h, obtains two (trimethylsiloxy group) propyl group terminated polysiloxanes of side base hydrosilyl group-containing.The size of molar ratio depending on final product molecular weight of above-mentioned 3 kinds of reactants and the number of silicon hydrogen richness in described balanced reaction.According to above-mentioned reaction formula, molecular weight design formula is (with 1, two (trimethylsiloxy group) disiloxane of 3-is end-capping reagent, and consumption is 1mol is example) as follows, molecular weight (the 394)+D of the design molecular weight=end-capping reagent of polysiloxane h 4molecular weight (240) × D h 4amount of substance (x=n/4)+D 4molecular weight (296) × D 4amount of substance (y=m/4), the i.e. design molecular weight=60n+74m+394 of polysiloxane, if design molecular weight is 1200, in above-mentioned reaction formula, n and m is respectively 8 and 5, then x and y is about 2 and 1.25 respectively, namely prepare the polysiloxane that molecular weight is 1200, about need the end-capping reagent of 1mol, the D of 2mol h 4with the D of 1.25mol 4.
Secondary addition reaction of silicon with hydrogen
Take Platinic chloride as catalyzer; by two (trimethylsiloxy group) propyl group terminated polysiloxanes of side base hydrosilyl group-containing in the toluene solution of glycidyl allyl ether; protect with nitrogen in reaction process; temperature of reaction is: 80 ~ 110 DEG C; reaction times is: 8 ~ 12h; obtain two (trimethylsiloxy group) propyl group terminated polysiloxanes of side base containing epoxy group(ing), described addition reaction of silicon with hydrogen molar ratio is: two (trimethylsiloxy group) propyl group terminated polysiloxanes of side base hydrosilyl group-containing: glycidyl allyl ether: Platinic chloride=1:n:3.1 × 10 -4~ 1:1.1n:3.1 × 10 -4, n is (CH 3) 2the number of repeat unit of SiH.
Alcoholysis reaction
Take acetic acid as catalyzer, two (trimethylsiloxy group) propyl group terminated polysiloxanes of side base hydrosilyl group-containing are joined in methanol solution, temperature of reaction is: 65 DEG C, reaction 6 ~ 12h, methyl alcohol and low-boiling-point substance are removed in underpressure distillation, namely obtain target compound two ends containing hydroxyl alkyl and the side base organosilicon containing epoxide group, described alcoholysis reaction molar ratio is: two ends containing hydroxyl alkyl and side base containing the organosilicon of epoxide group: methyl alcohol: acetic acid=1:150:0.8 ~ 1:250:1.3.
Polyisocyanates is the mixture of any one or the two or more arbitrary proportion mixing in tolylene diisocyanate, '-diphenylmethane diisocyanate, polymethylene polyphenyl vulcabond, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexyl methyl hydride isocyanic ester, trimethyl hexamethylene diisocyanate and hydrogenated tolylene diisocyanate.
Polymer polyatomic alcohol is the mixture of any one or the two or more arbitrary proportion mixing in polyether glycol, polyester polyol and polycarbonate polyol; Wherein: 1) polyether glycol is the mixture of any one or the two or more arbitrary proportion mixing in polytetrahydrofuran polyol, polyoxyethylated polyols, polyoxypropylene polyol, or tetrahydrofuran (THF), ethylene oxide, any one or the two or more arbitrary proportion mixing of propylene oxide arbitrarily in both polyol mixture, or tetrahydrofuran (THF), ethylene oxide, propylene oxide three polyol; 2) polyester polyol is the mixture of any one or the mixing of two or more arbitrary proportion 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 by the polyester polyol of diprotic acid and dibasic alcohol condensation, or by the polyester polyol of lactone ring opening polymerization; 3) polycarbonate polyol is the oligopolymer containing two or more terminal hydroxy group carbonate-containing structures, is obtained by transesterify by carbonic diester and dibasic alcohol.
Chainextender is general chainextender, for having HOR 3r 4the mixture of any one or the two or more arbitrary proportion mixing in OH structural formula compound, wherein R 3and R 4can be identical group, also can be different groups, R 3and R 4to be carbon atom be 1 ~ 12 alkyl and any one of alkylene, typical general chainextender comprises ethylene glycol, propylene glycol, butyleneglycol, Diethylene Glycol and triethylene glycol etc.
Monohydroxy glycidyl ether is have the mixture that in following structural compound, any one or two or more arbitrary proportion mix:
Wherein, R 5hydrogen atom, carbon atom be 1 ~ 12 hydroxyl alkyl and hydroxyl alkylene in any one;
Monohydroxy glycidyl ester is have the mixture that in following structural compound, any one or two or more arbitrary proportion mix:
Wherein, R 6to be carbon atom be 1 ~ 12 hydroxyl alkyl and hydroxyl alkylene in any one.
Organic amine compound is for having NR 7r 8r 9the mixture of any one or the two or more arbitrary proportion mixing in structural formula compound, wherein R 7, R 8and R 9can be identical group, also can be different groups, R 7, R 8and R 9group to be carbon atom be 2 ~ 12 alkyl, any one in hydroxyl alkyl and hydroxyl alkylene, typical organic amine compound comprises triethylamine, tripropyl amine, Tributylamine, trolamine, triisopropylamine and N, N-dimethylethanolamine etc.; Organo phosphorous compounds is for having PR 10r 11r 12the mixture of any one or the two or more arbitrary proportion mixing in structural formula compound, wherein R 10, R 11and R 12can be identical group, also can be different groups, R 10, R 11and R 12group to be carbon atom be 2 ~ 12 alkyl, any one in hydroxyl alkyl and hydroxyl alkylene, typical organo phosphorous compounds comprises triethyl phosphine, tripropyl phosphorus, tributyl phosphorus, trihydroxyethyl phosphorus and three hydroxypropyl phosphorus etc.; Organosulfur compound is for having SR 13r 14the mixture of any one or the two or more arbitrary proportion mixing in structural formula compound, wherein R 13and R 14can be identical group, also can be different groups, R 13and R 14group to be carbon atom be 2 ~ 12 alkyl, any one in hydroxyl alkyl and hydroxyl alkylene, typical organosulfur compound comprises diethyl thioether, dipropyl thioether, butyl sulfide, diphenylsulfide, ethylphenyl thioether and 1-hydroxyethyl sulfydryl-2, ammediol etc.
Organic acid is the mixture of any one or the mixing of two or more arbitrary proportion in the aliphatics containing 1 ~ 20 carbon atom, alicyclic, aromatic series or heterocycle monoprotic acid, and typical organic acid comprises formic acid, acetic acid, propionic acid, butyric acid and lactic acid etc.
The principal reaction of the preparation method of the organic-silicon-modified cation aqueous polyurethane of the present invention is as follows:
Prepolymerization reaction: add in reaction vessel polyisocyanates and two ends containing hydroxyl alkyl and side base containing the organosilicon of epoxide group, react 0.5 ~ 4h after being warming up to 50 ~ 80 DEG C; Then add polymer polyatomic alcohol, at same temperature, continue reaction 0.5 ~ 4h.
Chain extension and end capping: chainextender is joined in reaction system, isocyanato content in 0.5 ~ 4h post analysis prepolymer is reacted at 50 ~ 80 DEG C, when isocyanato content reaches theoretical value, at adding monohydroxy glycidyl ether (or mixture of monohydroxy glycidyl ester or two kinds of arbitrary proportion mixing) 50 ~ 80 DEG C, reaction 0.5 ~ 4h carries out end-blocking, obtain main chain ether-containing key, ammonia ester bond and silicone segments, side chain is containing epoxide group, and two ends are the organic silicon modified polyurethane of epoxide group; Wherein, isocyanato content in prepolymer=(the total amount of substance of amount-oxy-compound of polyisocyanate species) × 2 × isocyanato molecular weight/total solids quality, described total solids quality be two ends contain hydroxyl alkyl and side base containing the total mass of the organosilicon of epoxide group, polyisocyanates, polymer polyatomic alcohol and chainextender.
Ion reaction: organic amine compound, organo phosphorous compounds or organosulfur compound and organic acid are joined in the above-mentioned organic silicon modified polyurethane after with butanone dilution, at 50 ~ 80 DEG C, react 1-6h carry out ion reaction, obtain the organic silicon modified polyurethane of molecule cation group; Wherein, ionization process epoxy group group, machine amine compound and organic acid mol ratio are: 1:1:1 ~ 1:1.2:1; Epoxide group, organo phosphorous compounds or organosulfur compound and organic acid mol ratio are: 1:1:1 ~ 1:1.5:1.
Dispersion and emulsion: above-mentioned product high force dispersion is made its emulsification 0.5 ~ 1h in deionized water, after emulsification terminates, butanone is removed in underpressure distillation.
Wherein, in described raw material polyisocyanates isocyanate group and two ends containing hydroxyl alkyl and side base is 10:1 ~ 2:1 containing the mol ratio of the hydroxyl summation in the organosilicon of epoxide group, polymer polyatomic alcohol and chainextender; Solid content (content of the non-volatile matter after the dispersion and emulsion) scope of described product is 20% ~ 40%, and described silicone content scope is 1% ~ 30%; Described polymer polyatomic alcohol content range is 10% ~ 50%, and described hydrophilic radical cations scope is 1% ~ 20%; The cationic content of described organosilicon, polymer polyatomic alcohol and hydrophilic radical is respectively two ends account for total solids quality containing the organosilicon of epoxide group, polymer polyatomic alcohol and the cationic quality of hydrophilic radical per-cent containing hydroxyl alkyl and side base; Described total solids quality be two ends contain hydroxyl alkyl and side base containing the organosilicon of epoxide group, polyisocyanates, polymer polyatomic alcohol, chainextender, monohydroxy glycidyl ether (or mixture of monohydroxy glycidyl ester or two kinds of arbitrary proportion mixing), machine amine compound (or organo phosphorous compounds or organosulfur compound) and organic acid total mass.
Reaction principle of the present invention is: first select two ends to contain hydroxyl alkyl and side base reacts containing the organosilicon of epoxide group and polyisocyanates, is incorporated into by silicone backbone in polyurethane structural; Again chainextender and monohydroxy glycidyl ether (or mixture of monohydroxy glycidyl ester or two kinds of arbitrary proportion mixing) are carried out chain extension and end capping with above-mentioned organic silicon modified polyurethane prepolymer; Then select organic amine compound (or organo phosphorous compounds or organosulfur compound) and organic acid to join in the organic silicon modified polyurethane after with butanone dilution, carry out ion reaction; Finally be distributed in water by the organic silicon modified polyurethane after ionization by self-emulsifying, underpressure distillation obtains organic-silicon-modified cation aqueous polyurethane after removing butanone.
Compared with synthetic method of the prior art, beneficial effect of the present invention is:
1, two ends are selected to contain hydroxyl alkyl and side base carries out modification containing the Organo-silicon on Polyurethane of epoxide group, obtain the block modified structure of polysiloxane segment, namely on polyurethane molecular main chain containing polysiloxane segment, and organosilylly add the water tolerance that greatly can improve urethane.
2, the use hydroxy silicon oil had in prior art and isocyanate reaction, the unstable facile hydrolysis of the Si-O-C key generated after reaction, thus cause the storage stability of emulsion poor, and the organosilicon selected self had is just containing multiple Si-O-C key, therefore also there is the problem of emulsion storage stability difference.Use hydroxyl alkyl polysiloxane and isocyanate reaction in the present invention, generate Si-C key that is stable and not facile hydrolysis after reaction, thus the organic-silicon-modified cation aqueous polyurethane emulsion good stability prepared of technique, water tolerance is high.
3, in building-up process of the present invention, epoxide group is linked on polyurethane molecular, then by epoxy addition ionization, hydrophilic radical is incorporated on polyurethane molecular.Because tertiary amine group can be used as in the process preparing aqueous polyurethane the reaction that catalyzer accelerates isocyanate group and hydroxyl, make system very exothermic in reaction process, therefore preparation method involved in the present invention is adopted, can before isocyanate group completely consumed, any material containing tertiary amine and isocyanic ester is not used to react, thus avoid prior art in building-up process, use N methyldiethanol amine to carry out chain extension, reduce technology difficulty.
4, two hydroxyl epoxy compounds and two hydroxyl alkyl blocking silicone are designed into a molecule to get on, thus it is single-component modified to make two-pack modification become, decrease the charging times in building-up process, simplify production process, shorten the reaction times, improve production efficiency.
5, when the hydrophilic radical in polyurethane aqueous dispersion body exists with quaternary ammonium salt, quaternary alkylphosphonium salt or tertiary sulfonium salts, it better can be dissolved or dispersed in water, so that at body surface homogeneous film formation; And hydrophilic radical after film forming in molecule issues solution estranged in the situation of illumination or heating and transfers not hydrophilic group to, such as: tertiary sulfonium base with the volatilization of thioether form, thus makes water-solubility membrane become hydrophobic membrane, improve the water tolerance of film further.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of organic-silicon-modified polyurethane/cationic ester aqueous dispersion prepared by the embodiment of the present invention 2.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is further illustrated.
Embodiment 1
Two ends are containing hydroxyl alkyl and the side base organosilicon (R containing epoxide group 1=A 1, R 2=B 1, m=5, n=8, M n=2000) synthetic technology route:
Hydroxyl protection reaction (mol ratio vinyl carbinol: hexamethyldisilazane=2:1.1)
In 1L three-necked bottle, under room temperature, 355.2g hexamethyldisilazane is slowly added drop-wise in 232.3g vinyl carbinol, after dropwising, reaction system is warming up to 100 DEG C, and in this temperature, continue reaction 6 hours, stopped reaction.The cut of 98-100 DEG C is collected in air distillation, obtains allyloxy trimethyl silane 447.5g, yield 86%.
Addition reaction of silicon with hydrogen (mol ratio allyloxy trimethyl silane: tetramethyl disiloxane: Platinic chloride=2.4:1:3.1 × 10 -4)
In 1L four-necked bottle, add allyloxy trimethyl silane 312.5g, 50mL toluene successively and contain Platinic chloride 3.1 × 10 -4the aqueous isopropanol of mol, after passing into nitrogen 20min, is warming up to 100 DEG C by reaction system, drip 134.1g tetramethyl disiloxane at this temperature, termination reaction after reaction 8h.122-124 DEG C (0.27KPa) is collected in underpressure distillation, obtains two (trimethylsiloxy group) disiloxane 353.6g of 1,3-, yield 90%.
Balanced reaction (mol ratio D h 4: two (trimethylsiloxy group) disiloxane: the D of 1,3- 4=2:1:1.25)
In 5L three-necked bottle, add 960gD successively h 4, two (trimethylsiloxy group) disiloxane of 788g1,3-and 740gD 4after passing into nitrogen 20min, reaction system be warming up to 65 DEG C and add 120 μ L trifluoromethane sulfonic acids, reacting 20h at this temperature, then neutralize with the potassium hydroxide-methanol solution of 2mL1mol/L, excessive potassium hydroxide neutralizes with the hydrochloric acid-methanol solution of 0.80mL1mol/L again.Low-boiling-point substance is removed in underpressure distillation, obtains two (trimethylsiloxy group) propyl group terminated polysiloxane 2315g (Mn=1244, n=8, m=5) of side base hydrosilyl group-containing, yield 93%.
Secondary addition reaction of silicon with hydrogen (two (trimethylsiloxy group) propyl group terminated polysiloxanes of mol ratio side base hydrosilyl group-containing: glycidyl allyl ether: Platinic chloride=1:8:3.1 × 10 -4)
In 5L four-necked bottle, add 912g glycidyl allyl ether, 100mL toluene successively and contain Platinic chloride 3.1 × 10 - 4the aqueous isopropanol of mol, after passing into nitrogen 20min, is warming up to 100 DEG C by reaction system, drip two (trimethylsiloxy group) propyl group terminated polysiloxanes of 1244g side base hydrosilyl group-containing at this temperature, termination reaction after reaction 8h.Low-boiling-point substance is removed in underpressure distillation, obtains two (trimethylsiloxy group) propyl group terminated polysiloxanes of 2058g side base containing epoxy group(ing), yield 95%.
Alcoholysis reaction (mol ratio side base is containing two (trimethylsiloxy group) propyl group terminated polysiloxanes of epoxy group(ing): methyl alcohol: acetic acid=1:150:0.89)
In 2L three-necked bottle, add the acetic acid of 539g side base containing two (trimethylsiloxy group) propyl group terminated polysiloxane, 1200g methyl alcohol and the 26.7g of epoxy group(ing) successively.Under heated reflux condition, temperature of reaction is: 65 DEG C, reacts stopped reaction after 8 hours.Acetic acid, excessive methyl alcohol and low-boiling-point substance are removed in underpressure distillation, obtain two ends containing hydroxyl alkyl and the side base organosilicon 485g containing epoxide group, yield 95%.
The preparation method of embodiment 2 one kinds of organic-silicon-modified cation aqueous polyurethanes
Prepolymerization reaction
In the reaction flask that agitator and thermometer are housed, add 174g tolylene diisocyanate and 100g two ends containing hydroxyl alkyl and side base containing the organosilicon (R of epoxide group 1=A 1, R 2=B 1, m=5, n=8, M n=2000) 0.5h is reacted after, being warming up to 70 DEG C; Then 200g polyether Glycols (M is added n=800), reaction 0.5h is continued at same temperature.
Chain extension and end capping
12.4g ethylene glycol is joined in reaction system, analyzes isocyanato content in prepolymer with standard Di-n-Butyl Amine back titration method react 0.5h at 70 DEG C after, when isocyanato content reaches theoretical value 8.63%, add 74g monohydroxy glycidyl ether (R 5=H, M n=74) termination reaction, obtains main chain ether-containing key, ammonia ester bond and polysiloxane segment, and side chain is containing epoxide group, and two ends are the organic silicon modified polyurethane of epoxide group.
Ion reaction
Above-mentioned modified polyurethane is down to room temperature, adds 200g butanone viscosity reduction and stir until room-temperature dissolution, obtaining homogeneous phase solution, then add 124.6gN, at N-dimethylethanolamine and 84g acetic acid 80 DEG C, react 4h, after acid value is less than 5, stopped reaction.
Dispersion and emulsion
When the temperature of ionization post-modification polyurethane system is down to 50 DEG C, add 2500g deionized water and strong stirring 30min, then the water of butanone and part is deviate from underpressure distillation, obtains the organic-silicon-modified cation aqueous polyurethane that solid content is 23.4%.
With infrared spectra, this water dispersion is characterized, obtain infrared spectrum as shown in drawings.3300cm -1the symmetrical stretching vibration absorption peak of place ammonia ester bond N-H key, 1728cm -1the vibration absorption peak of place ammonia ester bond C=O, 2870-2970cm -1place CH 2and CH 3vibration absorption peak and 1103cm -1the absorption peak of place C-O-C, these characteristic peaks show that urethane is successfully synthesized.1017cm in figure -1the vibration absorption peak of place Si-O key, 805cm -1place Si-CH 3the vibration absorption peak of key shows that polysiloxane segment has successfully been connected in polyurethane molecular.To sum up analyze, organic-silicon-modified cation aqueous polyurethane is successfully prepared.
The preparation method of embodiment 3 one kinds of organic-silicon-modified cation aqueous polyurethanes
Prepolymerization reaction
In the reaction flask that agitator and thermometer are housed, add 222g isophorone diisocyanate and 150g two ends containing hydroxyl alkyl and side base containing the organosilicon (R of epoxide group 1=A 1, R 2=B 8, m=9, n=2, M n=1500) 0.5h is reacted after, being warming up to 70 DEG C; Then 250g polyether Glycols (M is added n=1000), reaction 0.5h is continued at same temperature.
Chain extension and end capping
6.2g ethylene glycol is joined in reaction system, isocyanato content in prepolymer is analyzed with standard Di-n-Butyl Amine back titration method react 0.5h at 70 DEG C after, when isocyanato content reaches theoretical value 7.35%, add 114.4g monohydroxy glycidyl ether (R 5=OHCH 2, M n=104) termination reaction, obtains main chain ether-containing key, ammonia ester bond and polysiloxane segment, and side chain is containing epoxide group, and two ends are the organic silicon modified polyurethane of epoxide group.
Ion reaction
Above-mentioned modified polyurethane is down to room temperature, adds 400g butanone viscosity reduction and stir until room-temperature dissolution, obtaining homogeneous phase solution, then react 4h at adding 135g diethyl thioether and 201g dimethylol propionic acid 80 DEG C, after acid value is less than 4, stopped reaction.
Dispersion and emulsion
When the temperature of ionization post-modification polyurethane system is down to 50 DEG C, add 5000g deionized water and strong stirring 30min, then the water of butanone and part is deviate from underpressure distillation, obtains the organic-silicon-modified cation aqueous polyurethane that solid content is 18.9%.
The preparation method of embodiment 4 one kinds of organic-silicon-modified cation aqueous polyurethanes
Prepolymerization reaction
In the reaction flask that agitator and thermometer are housed, add 168g hexamethylene diisocyanate and 100g two ends containing hydroxyl alkyl and side base containing the organosilicon (R of epoxide group 1=A 1, R 2=B 9, m=3, n=2, M n=1000) 0.5h is reacted after, being warming up to 70 DEG C; Then 300g polyether Glycols (M is added n=2000), reaction 0.5h is continued at same temperature.
Chain extension and end capping
6.2g ethylene glycol is joined in reaction system, isocyanato content in prepolymer is analyzed with standard Di-n-Butyl Amine back titration method react 0.5h at 70 DEG C after, when isocyanato content reaches theoretical value 8.73%, add 141.6g monohydroxy glycidyl ether (R 5=HOCH 2cH 2, M n=118) termination reaction, obtains main chain ether-containing key, ammonia ester bond and polysiloxane segment, and side chain is containing epoxide group, and two ends are the organic silicon modified polyurethane of epoxide group.
Ion reaction
Above-mentioned modified polyurethane is down to room temperature, adds 200g butanone viscosity reduction and stir until room-temperature dissolution, obtaining homogeneous phase solution, then react 4h at adding 195.2g thiodiglycol and 96g acetic acid 80 DEG C, after acid value is less than 5, stopped reaction.
Dispersion and emulsion
When the temperature of ionization post-modification polyurethane system is down to 50 DEG C, add 4000g deionized water and strong stirring 30min, then the water of butanone and part is deviate from underpressure distillation, obtains the organic-silicon-modified cation aqueous polyurethane that solid content is 25.7%.
The preparation method of embodiment 5 one kinds of organic-silicon-modified cation aqueous polyurethanes
Tolylene diisocyanate in embodiment 1 is changed to dicyclohexyl methyl hydride isocyanic ester, polyether Glycols is changed to the mixture (three's mass ratio is 1:1:1) of polyether Glycols, polyester diol and PCDL, N, N-dimethylethanolamine is changed to tributylphosphine, acetic acid is changed to the mixture of phenylformic acid and butyric acid, as described in example 1 above, the solid content obtaining being different from embodiment 1 is the organic-silicon-modified cation aqueous polyurethane of 28.3% to other reaction conditionss.
The preparation method of embodiment 6 one kinds of organic-silicon-modified cation aqueous polyurethanes
Isophorone diisocyanate in embodiment 2 is changed to the mixture of methyl hexamethylene diisocyanate and hydrogenated tolylene diisocyanate, there is R 1=A 1and R 2=B 8the organosilicon of structural formula is changed to has R 1=A 2and R 2=B 3the organosilicon of structural formula, as described in example 1 above, the solid content obtaining being different from embodiment 1 is the organic-silicon-modified cation aqueous polyurethane of 25.1% to other reaction conditionss.
The preparation method of embodiment 7 one kinds of organic-silicon-modified cation aqueous polyurethanes
By the monohydroxy glycidyl ether (R in embodiment 3 5=HOCH 2cH 2) be changed to monohydroxy glycidyl ester (R 5=OHCH 2), other reaction conditionss as described in example 3 above, obtain the organic-silicon-modified cation aqueous polyurethane being different from embodiment 3.
The preparation method of embodiment 8 one kinds of organic-silicon-modified cation aqueous polyurethanes
By the monohydroxy glycidyl ether (R in embodiment 1 5=H) be changed to monohydroxy glycidyl ether (R 5=HOCH 2cH 2) and monohydroxy glycidyl ester (R 5=OHCH 2) mixture of mass ratio 1:2, other reaction conditionss as described in example 1 above, obtain the organic-silicon-modified cation aqueous polyurethane being different from embodiment 1.

Claims (8)

1. a preparation method for organic-silicon-modified cation aqueous polyurethane, is characterized in that, first selects two ends to contain hydroxyl alkyl and side base carries out prepolymerization reaction containing the organosilicon of epoxide group and polyisocyanates, is incorporated into by silicone backbone in polyurethane structural; Again the mixture of chainextender and monohydroxy glycidyl ether or monohydroxy glycidyl ester or two kinds of arbitrary proportion mixing and above-mentioned organic silicon modified polyurethane prepolymer are carried out chain extension and end capping; Then select organic amine compound or organo phosphorous compounds or organosulfur compound, and organic acid joins in the organic silicon modified polyurethane after with butanone dilution, carries out ion reaction; Finally be distributed in water by the organic silicon modified polyurethane after ionization by self-emulsifying, underpressure distillation obtains organic-silicon-modified cation aqueous polyurethane after removing butanone;
Described prepolymerization reaction is: add in reaction vessel polyisocyanates and two ends containing hydroxyl alkyl and side base containing the organosilicon of epoxide group, react 0.5 ~ 4h after being warming up to 50 ~ 80 DEG C; Then add polymer polyatomic alcohol, at same temperature, continue reaction 0.5 ~ 4h;
Described chain extension and end capping are: joined by chainextender in reaction system, isocyanato content in 0.5 ~ 4h post analysis prepolymer is reacted at 50 ~ 80 DEG C, when isocyanato content reaches theoretical value, at adding 50 ~ 80 DEG C, the mixture of monohydroxy glycidyl ether or monohydroxy glycidyl ester or two kinds of arbitrary proportion mixing, reaction 0.5 ~ 4h carries out end-blocking, obtain main chain ether-containing key, ammonia ester bond and silicone segments, side chain is containing epoxide group, and two ends are the organic silicon modified polyurethane of epoxide group; Wherein, isocyanato content in prepolymer=(the total amount of substance of amount-oxy-compound of polyisocyanate species) × 2 × isocyanato molecular weight/total solids quality, described total solids quality be two ends contain hydroxyl alkyl and side base containing the total mass of the organosilicon of epoxide group, polyisocyanates, polymer polyatomic alcohol and chainextender;
Described ion reaction is: by organic amine compound or organo phosphorous compounds or organosulfur compound, join in the above-mentioned organic silicon modified polyurethane after with butanone dilution with organic acid, at 50 ~ 80 DEG C, react 1-6h carry out ion reaction, obtain the organic silicon modified polyurethane of molecule cation group; Wherein, ionization process epoxy group group, organic amine compound and organic acid mol ratio are 1:1:1 ~ 1:1.2:1; Epoxide group, organo phosphorous compounds or organosulfur compound and organic acid mol ratio are 1:1:1 ~ 1:1.5:1;
Described dispersion and emulsion is: above-mentioned product high force dispersion is made its emulsification 0.5 ~ 1h in deionized water, and after emulsification terminates, butanone is removed in underpressure distillation;
Wherein, in described raw material polyisocyanates isocyanate group and two ends containing hydroxyl alkyl and side base is 10:1 ~ 2:1 containing the mol ratio of the hydroxyl summation in the organosilicon of epoxide group, polymer polyatomic alcohol and chainextender; The range of solid content of described product is 20% ~ 40%, and described silicone content scope is 1% ~ 30%; Described polymer polyatomic alcohol content range is 10% ~ 50%, and described hydrophilic radical cations scope is 1% ~ 20%; The cationic content of described organosilicon, polymer polyatomic alcohol and hydrophilic radical is respectively two ends account for total solids quality containing the organosilicon of epoxide group, polymer polyatomic alcohol and the cationic quality of hydrophilic radical per-cent containing hydroxyl alkyl and side base; Described total solids quality be two ends contain hydroxyl alkyl and side base containing the organosilicon of epoxide group, polyisocyanates, polymer polyatomic alcohol, chainextender, monohydroxy glycidyl ether or monohydroxy glycidyl ester, organic amine compound or organo phosphorous compounds or organosulfur compound and organic acid total mass.
2. the preparation method of organic-silicon-modified cation aqueous polyurethane according to claim 1, is characterized in that,
Described two ends are containing hydroxyl alkyl and the organosilicon that side base contains epoxide group has having structure:
In structure above, m>1, n>1; Wherein R 1for following A 1-A 7any one in structure:
A 1)CH 2CH 2CH 2OHA 2)CH 2CH 2CH 2CH 2OHA 3)CH 2CH 2CH 2CH 2CH 2OH
A 4)CH 2CH 2CH 2CH 2CH 2CH 2OHA 5)CH 2CH 2CH 2OCH 2CH(OH)CH 2OCH 3
Wherein R 2for following B 1-B 11any one in structure:
3. the preparation method of organic-silicon-modified cation aqueous polyurethane according to claim 1, it is characterized in that, described polyisocyanates is the mixture of any one or the two or more arbitrary proportion mixing in tolylene diisocyanate, '-diphenylmethane diisocyanate, polymethylene polyphenyl vulcabond, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexyl methyl hydride isocyanic ester, trimethyl hexamethylene diisocyanate and hydrogenated tolylene diisocyanate.
4. the preparation method of organic-silicon-modified cation aqueous polyurethane according to claim 1, it is characterized in that, described polymer polyatomic alcohol is the mixture of any one or the two or more arbitrary proportion mixing in polyether glycol, polyester polyol and polycarbonate polyol; Wherein: described polyether glycol is the mixture of any one or the two or more arbitrary proportion mixing in polytetrahydrofuran polyol, polyoxyethylated polyols, polyoxypropylene polyol, or tetrahydrofuran (THF), ethylene oxide, any one or the two or more arbitrary proportion mixing of propylene oxide arbitrarily in both polyol mixture, or tetrahydrofuran (THF), ethylene oxide, propylene oxide three polyol; Described polyester polyol is the mixture of any one or the mixing of two or more arbitrary proportion 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 by the polyester polyol of lactone ring opening polymerization; Described polycarbonate polyol is the oligopolymer containing two or more terminal hydroxy group carbonate-containing structures, is obtained by transesterify by carbonic diester and dibasic alcohol.
5. the preparation method of organic-silicon-modified cation aqueous polyurethane according to claim 1, is characterized in that, described chainextender is for having HOR 3r 4the mixture of any one or the two or more arbitrary proportion mixing in OH structural formula compound, wherein R 3and R 4can be identical group, also can be different groups, R 3and R 4to be carbon atom be 1 ~ 12 alkyl and any one of alkylene.
6. the preparation method of organic-silicon-modified cation aqueous polyurethane according to claim 1, is characterized in that, described monohydroxy glycidyl ether is have the mixture that in following structural compound, any one or two or more arbitrary proportion mix:
Wherein, R 5hydrogen atom, carbon atom be 1 ~ 12 hydroxyl alkyl and hydroxyl alkylene in any one;
Described monohydroxy glycidyl ester is have the mixture that in following structural compound, any one or two or more arbitrary proportion mix:
Wherein, R 6to be carbon atom be 1 ~ 12 hydroxyl alkyl and hydroxyl alkylene in any one.
7. the preparation method of organic-silicon-modified cation aqueous polyurethane according to claim 1, is characterized in that, described organic amine compound is for having NR 7r 8r 9the mixture of any one or the two or more arbitrary proportion mixing in structural formula compound, wherein R 7, R 8and R 9can be identical group, also can be different groups, R 7, R 8and R 9group to be carbon atom be 2 ~ 12 alkyl, any one in hydroxyl alkyl and hydroxyl alkylene; Described organo phosphorous compounds is for having PR 10r 11r 12the mixture of any one or the two or more arbitrary proportion mixing in structural formula compound, wherein R 10, R 11and R 12can be identical group, also can be different groups, R 10, R 11and R 12group to be carbon atom be 2 ~ 12 alkyl, any one in hydroxyl alkyl and hydroxyl alkylene; Described organosulfur compound is for having SR 13r 14the mixture of any one or the two or more arbitrary proportion mixing in structural formula compound, wherein R 13and R 14can be identical group, also can be different groups, R 13and R 14group to be carbon atom be 2 ~ 12 alkyl, any one in hydroxyl alkyl and hydroxyl alkylene.
8. the preparation method of organic-silicon-modified cation aqueous polyurethane according to claim 1, it is characterized in that, described organic acid is the mixture of any one or the mixing of two or more arbitrary proportion in the aliphatics containing 1 ~ 20 carbon atom, alicyclic, aromatic series or heterocycle monoprotic acid.
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