CN101468302A - Quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent and active organosilicon end capping polypropylene oxide cationoid emulsion - Google Patents
Quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent and active organosilicon end capping polypropylene oxide cationoid emulsion Download PDFInfo
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Abstract
The invention relates to a method for preparing active organosilicon end capping polypropylene oxide cationoid emulsion, which comprises the following steps: using hydrogen-containing polysiloxane, unsaturated polyether and epoxy-containing unsaturated compounds as main raw materials to prepare epoxy-containing polyether-polysiloxane by adopting two steps of silicon-hydrogen addition reaction and then prepare a series of quaternary ammonium salt type polyether-polysiloxane nonionic cationic surfactants with different molecular weights and different hydrophilic and oleophilic values through quaterisation, and then using the obtained surfactant to emulsify active organosilicon end capping polypropylene oxide (SPPO), so as to obtain the active organosilicon end capping polypropylene oxide cationoid emulsion containing no organic solvent and having good storage stability and freeze-thaw stability through phase inversion emulsifying process. The method has the advantages of little equipment investment, simple process, easy operation and low production cost; and the obtained active organosilicon end capping polypropylene oxide cationoid emulsion can be used as a basic material for producing environment-friendly water-based polymer products such as paint, adhesive and sealant.
Description
Technical field
The invention belongs to macromolecule and fine chemical technology field, more specifically, the present invention relates to a kind of quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent and preparation method thereof, and utilize active organosilicon end capping polypropylene oxide cationoid emulsion of described quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent acquisition and preparation method thereof.
Background technology
As a kind of important base polymer, active organosilicon oxygen alkane end capping polypropylene oxide (SPPO) has obtained people's extensive concern in recent years, has obtained fast development in fields such as building, sealings.
Because SPPO molecule hydrophobicity is extremely strong, and contain the hydrolyzable crosslinked active organosilicon alcoxyl end group of water electrode for sensitivity, its Water-borne modification difficulty is very big, does not also see the report of relevant SPPO Water-borne modification at present.The Water-borne modification of SPPO not only can reduce environmental pollution, can also reduce product cost easily greatly, enlarges product purpose.Therefore, prepare the SPPO aqueous emulsion of excellent performance, can widen the application of SPPO greatly, have important practice significance and very big commercial value.
The approach that will have polymer waterborneization at present now mainly comprises two kinds of direct emulsion process and phase reversal emulsion processes, wherein directly emulsion process often needs to use a large amount of surfactants and powerful for a long time the stirring, and the macromolecule that only possesses special nature could be by directly emulsification, and it is of limited application; Compare with direct emulsification, the phase reversal emulsion process need not powerful the stirring just can directly be emulsified into aqueous emulsion with many macromolecules, and the latex particle size of gained emulsion is little, good stability.
For the stable active organosilicon end capping polypropylene oxide aqueous emulsion of processability, must use special surfactant.
Organic silicon surfactant is a kind of new surface active agents that grows up along with the organosilicon new material, except that having excellent wetting capacity, defoaming and low bubble property, also have excellent properties such as heatproof, weatherability variation, the corrosion of nontoxic nothing and physiology inertia, so organic silicon surfactant there is application comparatively widely in fields such as weaving, papermaking, petrochemical industry, cosmetics, water treatment, environmental improvement, material surface modifyings.
According to the design feature of SPPO, the present invention at first designs and has prepared a class quaternary organic silicon surfactant, and it successfully is used for the emulsification of SPPO, has prepared the SPPO aqueous emulsion of stable performance by the phase reversal emulsifying technology.
Need not to add a large amount of surfactants and other auxiliary agent among the active organosilicon end capping polypropylene oxide cationoid emulsion preparation method provided by the invention, need not powerful the stirring, technology is simple.
And, this active organosilicon end capping polypropylene oxide cationoid emulsion product of the present invention have cost low, do not fire, advantage such as safe in utilization, can be used as the base stock of friendly waterborne polymeric product of production environment such as coating, binder, sealant.
Summary of the invention
The present invention is at first with hydrogen containing siloxane and unsaturated polyether and to contain the epoxy radicals unsaturated compound be that raw material is by hydrosilylation and quaterisation, prepare quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent, use this surfactant to prepare the one pack system active organosilicon end capping polypropylene oxide cationoid emulsion of the stable performance that does not contain any organic solvent by the phase reversal emulsifying technology then.
Particularly, the invention provides a kind of quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent, its molecular weight is 3000-250000, preferred 4000-200000, most preferably 5000-100000 and have following schematic general formula:
Wherein, x is the integer of 0-1000, and y is the integer of 5-1000, and z is the integer of 5-1000, and m is the integer of 0-1000, and n is the integer of 0-1000, and condition is that m, n are not 0 simultaneously, R
1Be H, CH
3, C
2H
5Or OCCH
3, R
2Be H or CH
3, G is CH
2Or C=0, R
3For containing the alkyl of 1-6 carbon atom, R
4For benzyl or contain the alkyl of 1-6 carbon atom, and in this general formula, when the X of mark existed, it was a halogen, and when the X of mark did not exist, the H on the hydroxyl of institute's mark left away.
According to the present invention, the molecular weight of described quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent and hydrophilic and oleophilic value are controlled, and have that raw material sources are wide, production cost is low, productive rate is high and advantage such as surface-active is strong.Particularly, the critical micelle concentration CMC of described quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent can be very low, for example is lower than 1200mg/l, is preferably 300-1000mg/l.
Particularly, the present invention also provides the preparation method of described quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent, and it comprises the steps:
A. in the presence of the platinum compounds catalyst, make hydrogen containing siloxane and unsaturated polyether and contain the epoxy radicals unsaturated compound and carry out hydrosilylation in proper order, obtain thick product;
B. remove the excessive epoxy radicals unsaturated compound that contains, obtain containing the epoxy radicals polyether-polysiloxane;
C. in the presence of organic solvent, make to contain the epoxy radicals polyether-polysiloxane and the reaction of excessive quaternizing agent obtains thick product; With
D. remove and desolvate and excessive quaternizing agent, obtain quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent at last.
In the method for preparing quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent of the present invention, wherein in step a, described hydrogen containing siloxane is selected from hydrogen containing polysiloxane (PDMHS) and polymethyl hydrogen siloxane (PMHS), wherein the molecular weight of hydrogen containing polysiloxane (PDMHS) is 300-100000, preferred 600-50000,800-20000 most preferably, with hydrogen content Hwt% be 0.05-1.67wt%, preferred 0.1-1.4wt%, 0.2-1.25wt% most preferably, wherein the molecular weight of polymethyl hydrogen siloxane (PMHS) is 400-100000, preferred 600-50000, most preferably 800-20000.
In the method for preparing quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent of the present invention, wherein in step a, described unsaturated polyether is selected from the allyl capped polyethers, the molecular weight of preferred allyl capped polyethers is 250-40000, more preferably 300-15000,350-10000 most preferably, it has following schematic general formula:
Wherein, m is the integer of 0-1000, and n is the integer of 0-1000, condition be m, n be not simultaneously 0 and R be H, CH
3, C
2H
5Or OCCH
3And in the present invention, the preparation of the method for described unsaturated polyether list of references (Cai Zhenyun etc., organosilicon material, 2005,19 (4): 20-22)
In the method for preparing quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent of the present invention, wherein the described epoxy radicals unsaturated compound that contains of step a is selected from allyl glycidyl ether (AGE), GMA (GMA) and glycidyl acrylate (GA).
In the method for preparing quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent of the present invention, wherein in step a, when in atent solvent, carrying out, described atent solvent reply reactionlessness, promptly do not participate in reaction, and should have suitable boiling point, making described solvent be suitable for being retained in the reaction system neutralization under reaction condition is easy to remove from reaction system after reaction, particularly, described atent solvent is selected from aliphatic hydrocarbon, aromatic hydrocarbon, dioxane and oxolane, preferred toluene and cyclohexane are also removed atent solvent this moment in step b, preferably by distillation, more preferably remove by decompression distillation; When carrying out in inert atmosphere, described inert atmosphere specifically is selected from nitrogen, helium and argon gas, and preferred nitrogen usually, should add catalyst after 5-10 minute at the formation inert atmosphere; Wherein employed catalyst is the platinum compounds catalyst, is designated as [Pt] catalyst, and its concentration in system is 1-100ppmw, preferred 5-50ppmw, and most preferably 10-30ppmw and this platinum compounds catalyst can be chloroplatinic acid (H
2PtCl
6), inferior chloroplatinic acid (H
2PtCl
4) or their solution of salt, this moment, solution solvent was selected from isopropyl alcohol, dicyclopentadiene and 1,1,2,2-tetramethyl-1,2-divinyl disiloxane etc.
In the method for preparing quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent of the present invention, wherein in step a, the rate of charge of employed raw material is as follows: the mol ratio r of unsaturated polyether and Si-H group
mBe 0.05-0.95, preferred 0.1-0.9, most preferably 0.15-0.85 and contain the epoxy radicals unsaturated compound and the mol ratio of Si-H group is (1-r
m) 1-3.5 doubly, preferred 1.1-2.5 doubly, most preferably 1.1-2 is doubly.
In the method for preparing quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent of the present invention, wherein in step a, 40-110 ℃, preferred 60-110 ℃, most preferably under 70-110 ℃ the reaction temperature, make hydrogen containing siloxane and unsaturated polyether hydrosilylation 1-24 hour, preferred 1.5-18 hour, most preferably 2-12 hour, add then and contain the epoxy radicals unsaturated compound, continued hydrosilylation 1-24 hour, preferred 1.5-18 hour, most preferably 2-12 hour, therefore, what carry out in the present invention was two step hydrosilylations.
In the method for preparing quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent of the present invention, wherein in step a, can use
1H NMR detects the degree of carrying out of hydrosilylation, specifically can use
1H NMR detects the extent of reaction of unsaturated polyether and Si-H group and contains epoxy compounds and the extent of reaction of Si-H group.
In the method for preparing quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent of the present invention, wherein in step b, remove the excessive epoxy radicals unsaturated compound that contains by distillation, preferred decompression distillation, obtain containing the epoxy radicals polyether-polysiloxane.
In the method for preparing quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent of the present invention, wherein in step c, described organic solvent is a polar organic solvent, it is responsible for dissolving and contains epoxy radicals polyether-polysiloxane and quaternizing agent, be preferably lower alcohol, more preferably methyl alcohol or ethanol, with described quaternizing agent be tertiary amine, preferred trimethylamine and triethylamine, perhaps be the combination of secondary amine and halogenated hydrocarbons, preferred dimethylamine or diethylamine and halogenation benzyl or contain the halogenated alkane of 1-6 carbon atom.
In the method for preparing quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent of the present invention, wherein in step c: the reaction temperature that contains epoxy radicals polyether-polysiloxane and tertiary amine is 20-90 ℃, preferred 30-80 ℃, most preferably 40-65 ℃, the reaction time is 1-12 hour; The reaction temperature that contains epoxy radicals polyether-polysiloxane and secondary amine is 20-70 ℃, and preferred 30-65 ℃, most preferably 40-60 ℃, the reaction time is 1-12 hour; With the reaction temperature that contains epoxy radicals polyether-polysiloxane and halogenated hydrocarbons be 20-100 ℃, preferred 30-90 ℃, most preferably 40-80 ℃, the reaction time is 1-12 hour; Making itself and the mol ratio that contains epoxy radicals in the epoxy radicals polyether-polysiloxane with the consumption of each quaternizing agent such as tertiary amine, secondary amine and halogenated hydrocarbons is 1-6, preferred 1.5-4, most preferably 2-3.
In the method for preparing quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent of the present invention, wherein in steps d, remove and desolvate and excessive quaternizing agent by distillation, preferred decompression distillation, obtain described quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent at last.
According to the preferred embodiments of the invention, prepare described quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent as follows:
In toluene or cyclohexane, add PDMHS, unsaturated polyether, be heated to 40-110 ℃ under the blanket of nitrogen, preferred 60-110 ℃, most preferably 70-110 ℃, add [Pt] catalyst, its concentration in system is 1-100ppmw, preferred 5-50ppmw, most preferably 10-30ppmw reacted 1-24 hour, preferred 1.5-18 hour, most preferably 2-12 hour, add afterwards and contain the epoxy radicals unsaturated compound, continue isothermal reaction 1-24 hour, preferred 1.5-18 hour, most preferably 2-12 hour;
Decompression steams solvent and the excessive epoxy radicals unsaturated compound that contains, and obtains containing the epoxy radicals polyether-polysiloxane;
Then can be by following prepared in one of two ways quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent:
A: with methyl alcohol or ethanol is solvent, 20-90 ℃, preferred 30-80 ℃, most preferably under 40-65 ℃, make and contain the epoxy radicals polyether-polysiloxane and cross quantity tertiary amine stirring reaction 1-12 hour, decompression steams solvent and excessive tertiary amine then, obtains quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent; Perhaps
B: with methyl alcohol or ethanol is solvent, 20-70 ℃, preferred 30-65 ℃, most preferably under 40-60 ℃, make to contain epoxy radicals polyether-polysiloxane and excessive secondary amine stirring reaction 1-12 hour, reduce pressure then and steam solvent and excessive secondary amine; Be solvent with methyl alcohol or ethanol again, 20-100 ℃, preferred 30-90 ℃, most preferably under 40-80 ℃, make above-mentioned product and excessive halogenated hydrocarbons stirring reaction 1-12 hour, decompression steams solvent and excessive halogenated hydrocarbons then, obtains quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent.
According to the present invention, the molecular weight of described quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent can recently be controlled by the feeding intake of hydrogen content, pfpe molecule amount and raw material of regulating hydrogen containing siloxane.
In addition, the present invention also provides a kind of solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion, it is included in active organosilicon end capping polypropylene oxide and the emulsifying agent that disperses in the water, the weight average molecular weight of wherein said active organosilicon end capping polypropylene oxide is 1500-150000, preferred 2000-100000,3000-80000 most preferably, it has following schematic general formula:
Wherein, n is 0 or 1, and m is the integer of 0-10, and x is the integer of 1-50, and y is the integer of 15-2000, R
1Be methyl or ethyl, R
2Be methyl or ethyl, R
3For methylene or-(CH
2)
3-, R
4Be H or phenyl, R
5Or/and H, G is for methyl
R wherein
6For-(CH
2)
6-,
And/or
In the present invention, described active organosilicon end capping polypropylene oxide can be according to for example U.S.Patent Nos.5,300,608; 3,971,751; 4,374,237; 6,803,412; Disclosed conventional method preparation in 5,986,014 and 6,420,492.
According to the present invention, the solid content of described solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion reaches as high as 80wt%, preferably between 45-70wt%.
According to the present invention, the latex particle size of described solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion is very little, for example can be preferably 2-8 μ m less than 10 μ m.
Therefore, the solid content height of solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion product of the present invention, latex particle size is little, have good bin stability and freeze-thaw stability thus, wherein for bin stability, it at room temperature can be stablized and stores more than 180 days and can stablize storage 50 ℃ under more than 50 days.
Further, the present invention also provides the method for the described solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion of preparation, and this method adopts the phase reversal emulsifying process under the organic solvent-free existence to carry out, and comprises the steps:
A1. in reactor, add active organosilicon end capping polypropylene oxide and emulsifying agent, fully mix, described emulsifying agent is the mixture of quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent of the present invention or quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent of the present invention and non-ionic surface active agent;
B1. in mixed system, drip water, continue to mix; With
C1. dropwise the back and continue to stir a period of time, thereby obtain the solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion.
In the method for the described solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion of preparation of the present invention, raw materials used active organosilicon end capping polypropylene oxide (SPPO), emulsifying agent and the water of comprising, wherein in 100 parts of described active organosilicon end capping polypropylene oxides, the consumption of described emulsifying agent is 2-20 part, preferred 4-16 part, most preferably 4-14 part, with the consumption of water be 20-200 part, preferred 30-150 part, 40-120 part most preferably, all umbers are all in weight portion.
In the method for the described solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion of preparation of the present invention, wherein the temperature among the step a1 is 0-90 ℃, preferred 5-50 ℃, most preferably 10-40 ℃, with the time that mixes be 10-240 minute, preferred 30-120 minute, most preferably 30-100 minute.
In the method for the described solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion of preparation of the present invention, wherein the stir speed (S.S.) among the step b1 is controlled at 50-3000rpm, preferred 100-2000rpm, most preferably 200-1500rpm and wherein add entry in the mode that at the uniform velocity drips.
In the method for the described solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion of preparation of the present invention, wherein the stirring among the step c1 continues 10-240 minute, and preferred 20-180 minute, most preferably 30-120 minute.
In the method for the described solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion of preparation of the present invention, be under the situation of mixture wherein at described emulsifying agent, weight ratio in the mixture between non-ionic surface active agent and the quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent is 0.5-10, preferred 1-7.5, most preferably 1-5.
Particularly, described non-ionic surface active agent is selected from following material: fatty glyceride, as glycerine monofatty ester etc.; Sorbitan fatty acid ester is as sorbierite monopalmitate (Span-40) etc.; Polysorbate is as polyoxyethylene (20) anhydrous sorbitol monopalmitate (Tween-40) etc.; Polyoxyethylene fatty acid ester is as polyoxyethylene (40) stearate etc.; APEO is as NPE (OP-10), NPE (OP-3) etc.
More specifically, solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion of the present invention can prepare as follows:
In reactor, add SPPO and emulsifying agent, 0-90 ℃, preferred 5-50 ℃, most preferably under 10-40 ℃, fully mixed 10-240 minute, preferred 30-120 minute, most preferably 30-100 minute;
At the uniform velocity drip water then in above-mentioned system, stir speed (S.S.) is controlled at 50-3000rpm, preferred 100-2000rpm, most preferably 200-1500rpm; With
Dropwise the back and continue to stir 10-240 minute, preferred 20-180 minute, most preferably 30-120 minute, obtain the SPPO emulsion at last.
According to the present invention, utilizing the phase reversal emulsifying process to prepare in the process of SPPO emulsion, need not use any auxiliary agent, also need not carry out powerful for a long time the stirring, therefore, production technology is simple, product meets environmental requirement, have cost low, do not fire, advantage such as safe in utilization, and prepared SPPO emulsion solid content height, and had good storing stability (room temperature:〉180 days; 50 ℃:〉50 days) and freeze-thaw stability.
The specific embodiment
Below by embodiment, the present invention is described in further detail, described embodiment only is to describe the present invention rather than restriction the present invention.
Raw material SPPO is provided by Henke1 company (Dusseldorfer, Germany), and for example referring to U.S. Patent No. 5,300,608, concrete parameter is as shown in table 1:
The concrete parameter of several SPPO of table 1
In following all embodiment:
By
1H NMR (600MHz, Bruker, Switzerland) and IR (Nicolet 560, Nicolet, the U.S.) detect the extent of reaction of unsaturated polyether and Si-H group and contain epoxy compounds and the extent of reaction of Si-H group; The DCAT21 type surface tension instrument of the German Dataphysics of the surface tension of organic silicon surfactant and critical micelle concentration (CMC) use company is at room temperature measured; The emulsion solid content gravimetric detemination; Latex particle size is measured down in 25 ℃ on the MicroPlus Mastersizer of Britain Malvern company laser particle size analyzer; The freeze-thaw stability of emulsion is measured by State Standard of the People's Republic of China GB9268-88 method; Adopt static method in climatic chamber, to measure with the bin stability of emulsion under room temperature and 50 ℃.
In addition, in the following example, at first prepared quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent of the present invention, utilized this surfactant to prepare solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion of the present invention then as emulsifying agent.
Used umber is parts by weight in following examples.
Embodiment 1
(1) preparation of quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent
Adding 4.5g PDMHS in 50ml toluene (chemical pure, Hwt%=0.44, Mn=1950, Si-H:0.02mol) (in its schematic general formula: m=12, n=0 and R are OCCH for 0.01mol, Mn=660 with 6.6g allyl capped polyethers
3), mix, be warming up to 90 ℃, feed nitrogen after 10 minutes, adding 0.08 ml concn is [Pt] catalyst (aqueous isopropanols of six hydration chloroplatinic acids) of 2wt%, isothermal reaction 5 hours; Add 1.26gAGE (0.012mol analyzes pure) afterwards, continue isothermal reaction 6 hours, remove solvent and excessive AGE then under reduced pressure, obtain containing the epoxy radicals polyether-polysiloxane.
The said goods is dissolved in 20ml ethanol, is warming up to 55 ℃, add 1.83g diethylamine (0.025mol analyzes pure), react after 6 hours, remove solvent and excessive diethylamine under reduced pressure; Products therefrom is dissolved in 30ml ethanol, be warming up to 75 ℃, add 2.53g benzyl chloride (0.02mol, analyze pure), react after 7 hours, remove solvent and excessive benzyl chloride under reduced pressure, obtain quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent, its productive rate is 96.5%, and CMC is 970mg/l.
(2) preparation of solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion
In a column type Flat bottom container, add 100 parts of STPEMO2-120,10 parts of 0P-10 and 3 parts of quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agents, under 40 ℃, fully mixed 25 minutes; Add 90 parts of deionized waters again in mixture, stir speed (S.S.) is controlled at about 400rpm; Dropwise the back and continue to stir 30 minutes, obtain the SPPO emulsion.
The gained emulsion property: latex particle size is 3.64 μ m, and solid content is 55.29wt%, and the bin stability under 50 ℃ surpasses 50 days, and the bin stability under the normal temperature was greater than 180 days, and freeze-thaw stability is fine.
Embodiment 2
(1) preparation of quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent
Adding 5.3g PDMHS in the 50ml cyclohexane (chemical pure, Hwt%=0.38, Mn=2100, Si-H:0.02mol) (in its schematic general formula: m=12, n=0 and R are OCCH for 0.01mol, Mn=660 with 6.6g allyl capped polyethers
3), mix, be warming up to 80 ℃, adding 0.08 ml concn is [Pt] catalyst (1,1,2 of six hydration chloroplatinic acids of 2wt%, 2-tetramethyl-1,2-divinyl disiloxane solution), isothermal reaction added 1.37gAGE (0.013mol after 5 hours, analyze pure), continue isothermal reaction after 7 hours, remove solvent and excessive AGE under reduced pressure, obtain containing the epoxy radicals polyether-polysiloxane.
Product is dissolved in 25ml ethanol, is warming up to 55 ℃, add the dimethylamine (0.03mol analyzes pure) of 1.32g, react after 6 hours, remove solvent and excessive dimethylamine under reduced pressure; Products therefrom is dissolved in 30ml ethanol, warming-in-water to 75 ℃, benzyl chloride (the 0.03mol that adds 3.80g, analyze pure), react after 6 hours, remove ethanol and excessive benzyl chloride under reduced pressure, obtain quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent, its productive rate is 95.2%, and CMC is 830mg/l.
(2) preparation of solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion
In a column type Flat bottom container, add 100 parts of STPEMO2-35,9.6 parts of 0P-3 and 2.4 parts of quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agents, under 40 ℃, fully mixed 20 minutes; Add 80 parts of deionized waters again in mixture, stir speed (S.S.) is controlled at about 300rpm; Dropwise the back and continue to stir 30 minutes, obtain the SPPO emulsion.
The gained emulsion property: latex particle size is 2.33 μ m, and solid content is 56.80wt%, can surpass 50 days 50 ℃ of stable down preservations, and normal temperature is next greater than 150 days, and freeze-thaw stability is fine.
Embodiment 3
(1) preparation of quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent
With 6.1g PDMHS (chemical pure, Hwt%=0.33, Mn=1800, Si-H:0.02mol) (in its schematic general formula: m=20, n=4 and R are CH for 0.01mol, Mn=1200 with 12g allyl capped polyethers
3) mix, be warming up to 90 ℃, feed nitrogen after 10 minutes, adding 0.08 ml concn is [Pt] catalyst (aqueous isopropanol of potassium chloroplatinate) of 2wt%, isothermal reaction 6 hours; The AGE (0.013mol analyzes pure) that adds 1.37g afterwards continued isothermal reaction after 6 hours, removed excessive AGE under reduced pressure, obtained containing the epoxy radicals polyether-polysiloxane.
Above-mentioned product is dissolved in the 25ml methyl alcohol, is warming up to 55 ℃, add 2.19g diethylamine (0.03mol analyzes pure) reaction 6 hours, remove solvent and excessive diethylamine then under reduced pressure; Products therefrom is dissolved in 30ml methyl alcohol, be warming up to 65 ℃, add the positive NBB (0.02mol of 2.74g, analyze pure), react after 6 hours, remove solvent and excessive positive NBB under reduced pressure, obtain quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent, its productive rate is 95.0%, and CMC is 610mg/l.
(2) preparation of solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion
BAC-LA-8872-85,12 parts of OP-10 and 4 parts of quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agents of adding 100 parts in a column type Flat bottom container fully mixed under 45 ℃ 20 minutes; Add 100 parts of deionized waters again in mixture, stir speed (S.S.) is controlled at about 500rpm; Dropwise the back and continue to stir 30 minutes, obtain the SPPO emulsion.
The gained emulsion property: latex particle size is 4.1 μ m, and solid content is 52.83wt%, and the bin stability under 50 ℃ surpasses 50 days, and then greater than 180 days, freeze-thaw stability was fine for the bin stability under the normal temperature.
Embodiment 4
(1) preparation of quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent
Adding 5.3g PDMHS in 50ml toluene (chemical pure, Hwt%=0.38, Mn=2100, Si-H:0.02mol) (in its schematic general formula: m=0, n=10 and R are OCCH for 0.01mol, Mn=660 with 6.6g allyl capped polyethers
3), mix, be warming up to 90 ℃, feed nitrogen after 10 minutes, adding 0.08 ml concn is [Pt] catalyst (aqueous isopropanol of potassium chloroplatinate) of 2wt%, isothermal reaction 5 hours; Add 1.85g GMA (0.013mol analyzes pure) afterwards, continue isothermal reaction after 7 hours, remove solvent and excessive GMA under reduced pressure, obtain containing the epoxy radicals polyether-polysiloxane.
Product is dissolved in 25ml methyl alcohol, be warming up to 60 ℃, triethylamine (the 0.03mol that adds 3.03g, analyze pure), react after 7 hours, remove solvent and excessive triethylamine under reduced pressure, obtain quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent, its productive rate is 96.4%, and CMC is 1070mg/l.
(2) preparation of solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion
In a column type Flat bottom container, add 100 parts of STPEMO2-35,9.6 parts of 0P-10 and 2.4 parts of quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agents, under 40 ℃, fully mixed 20 minutes; Add 90 parts of deionized waters again in mixture, stir speed (S.S.) is controlled at about 400rpm; Dropwise the back and continue to stir 30 minutes, obtain the SPPO emulsion.
The gained emulsion property: latex particle size is 3.95 μ m, and solid content is 54.37wt%, can surpass 50 days 50 ℃ of stable down preservations, and normal temperature is next greater than 150 days, and freeze-thaw stability is fine.
Embodiment 5
The preparation of solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion
In a column type Flat bottom container, add the prepared quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent of 100 parts of STPEMO2-35,8 parts of embodiment 1, under 40 ℃, fully mixed 30 minutes; Add 105 parts of deionized waters again in mixture, stir speed (S.S.) is controlled at about 400rpm; Dropwise the back and continue to stir 30 minutes, obtain the SPPO emulsion.
The gained emulsion property: latex particle size is 6.15 μ m, and solid content is 50.12wt%, and the bin stability under 50 ℃ surpasses 50 days, and the bin stability under the normal temperature was greater than 180 days, and freeze-thaw stability is fine.
By the result of the foregoing description as can be seen, the present invention can prepare quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent with very high productive rate, and prepared quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent has very low critical micelle concentration; In addition, utilize quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent of the present invention, can obtain that solid content is higher, latex particle size is less and stable good solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion.
Claims (31)
1. quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent, its molecular weight is 3000-250000, preferred 4000-200000, most preferably 5000-100000 and have following schematic general formula:
Wherein, x is the integer of 0-1000, and y is the integer of 5-1000, and z is the integer of 5-1000, and m is the integer of 0-1000, and n is the integer of 0-1000, and condition is that m, n are not 0 simultaneously, R
1Be H, CH
3, C
2H
5Or OCCH
3, R
2Be H or CH
3, G is CH
2Or C=0, R
3For containing the alkyl of 1-6 carbon atom, R
4For benzyl or contain the alkyl of 1-6 carbon atom, and in this general formula, when the X of mark existed, it was a halogen, and when the X of mark did not exist, the H on the hydroxyl of institute's mark left away.
2. the quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent of claim 1, its critical micelle concentration CMC is lower than 1200mg/l.
3. the quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent of claim 2, its critical micelle concentration CMC is 300-1000mg/l.
4. each the preparation method of quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent of claim 1-3, it comprises the steps:
A. in the presence of the platinum compounds catalyst, make hydrogen containing siloxane and unsaturated polyether and contain the epoxy radicals unsaturated compound and carry out hydrosilylation in proper order, obtain thick product;
B. remove the excessive epoxy radicals unsaturated compound that contains, obtain containing the epoxy radicals polyether-polysiloxane;
C. in the presence of organic solvent, make to contain the epoxy radicals polyether-polysiloxane and the reaction of excessive quaternizing agent obtains thick product; With
D. remove and desolvate and excessive quaternizing agent, obtain quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent at last.
5. the method for claim 4, wherein said hydrogeneous polysiloxane is selected from hydrogen containing polysiloxane and polymethyl hydrogen siloxane, the molecular weight of preferred hydrogen containing polysiloxane is 300-100000, preferred 600-50000, most preferably 800-20000, with hydrogen content Hwt% be 0.05-1.67wt%, preferred 0.1-1.4wt%, most preferably the molecular weight of 0.2-1.25wt% and preferred polymethyl hydrogen siloxane is 400-100000, preferred 600-50000, most preferably 800-20000.
6. claim 4 or 5 method, wherein said unsaturated polyether is selected from the allyl capped polyethers, and the molecular weight of preferred allyl capped polyethers is 250-40000, more preferably 300-15000,350-10000 most preferably, it has following schematic general formula:
Wherein, m is the integer of 0-1000, and n is the integer of 0-1000, condition be m, n be not simultaneously 0 and R be H, CH
3, C
2H
5Or OCCH
3
7. each method of claim 4-6, the wherein said epoxy radicals unsaturated compound that contains is selected from allyl glycidyl ether, GMA and glycidyl acrylate.
8. each method of claim 4-7, wherein step a carries out in atent solvent, this atent solvent is selected from aliphatic hydrocarbon, aromatic hydrocarbon, dioxane and oxolane, preferred toluene and cyclohexane, in step b, also remove atent solvent this moment, preferably by distilling, more preferably removing by decompression distillation; Carry out under inert atmosphere with step a, this inert gas is selected from nitrogen, helium and argon gas, preferred nitrogen.
9. each method of claim 4-8, wherein the platinum compounds catalyst concentration among the step a is 1-100ppmw, preferred 5-50ppmw, most preferably 10-30ppmw and this platinum compounds catalyst are the solution of chloroplatinic acid, inferior chloroplatinic acid or their salt, and its solvent is selected from isopropyl alcohol, dicyclopentadiene and 1,1,2,2-tetramethyl-1,2-divinyl disiloxane.
10. each method of claim 4-10, wherein the mol ratio r of unsaturated polyether among the step a and Si-H group
mBe 0.05-0.95, preferred 0.1-0.9, most preferably 0.15-0.85 and contain the epoxy radicals unsaturated compound and the mol ratio of Si-H group is (1-r
m) 1-3.5 doubly, preferred 1.1-2.5 doubly, most preferably 1.1-2 is doubly.
11. each method of claim 4-11, wherein in step a, 40-110 ℃, preferred 60-110 ℃, most preferably under 70-110 ℃ the reaction temperature, make hydrogen containing siloxane and unsaturated polyether hydrosilylation 1-24 hour, preferred 1.5-18 hour, most preferably 2-12 hour, add then and contain the epoxy radicals unsaturated compound, continued hydrosilylation 1-24 hour, preferred 1.5-18 hour, most preferably 2-12 hour.
12. each method of claim 4-11 is wherein removed the excessive epoxy radicals unsaturated compound that contains by distillation, preferred decompression distillation among the step b.
13. each method of claim 4-12, wherein the organic solvent among the step c is a polar organic solvent, preferred lower alcohol, most preferably methyl alcohol and ethanol, quaternizing agent is a tertiary amine, preferred trimethylamine and triethylamine, perhaps be the combination of secondary amine and halogenated hydrocarbons, preferred dimethylamine, diethylamine, halogenation benzyl and contain the halogenated alkane of 1-6 carbon atom and mol ratio that the consumption of each quaternizing agent makes it and contains epoxy radicals in the epoxy radicals polyether-polysiloxane is 1-6, preferred 1.5-4, most preferably 2-3.
14. each method of claim 4-13, wherein among the step c: the reaction temperature that contains epoxy radicals polyether-polysiloxane and tertiary amine is 20-90 ℃, and preferred 30-80 ℃, most preferably 40-65 ℃, the reaction time is 1-12 hour; The reaction temperature that contains epoxy radicals polyether-polysiloxane and secondary amine is 20-70 ℃, and preferred 30-65 ℃, most preferably 40-60 ℃, the reaction time is 1-12 hour; With the reaction temperature that contains epoxy radicals polyether-polysiloxane and halogenated hydrocarbons be 20-100 ℃, preferred 30-90 ℃, most preferably 40-80 ℃, the reaction time is 1-12 hour.
15. each method of claim 4-14 is wherein removed and is desolvated and excessive quaternizing agent by distillation, preferred decompression distillation in the steps d.
16. solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion, it is included in active organosilicon end capping polypropylene oxide and the emulsifying agent that disperses in the water, the weight average molecular weight of wherein said active organosilicon end capping polypropylene oxide is 1500-150000, preferred 2000-100000,3000-80000 most preferably, it has following schematic general formula:
Wherein, n is 0 or 1, and m is the integer of 0-10, and x is the integer of 1-50, and y is the integer of 15-2000, R
1Be methyl or ethyl, R
2Be methyl or ethyl, R
3For methylene or-(CH
2)
3-, R
4Be H or phenyl, R
5Or/and H, G is for methyl
, R wherein
6For-(CH
2)
6-,
And/or
17. the solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion of claim 16 is characterized in that the solid content of described emulsion reaches as high as 80wt%.
18. the solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion of claim 16 or 17, the solid content that it is characterized in that described emulsion is between 45-70wt%.
19. each solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion of claim 16-18, the latex particle size of wherein said emulsion is less than 10 μ m.
20. each solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion of claim 16-19, the latex particle size of wherein said emulsion is 2-8 μ m.
21. each solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion of claim 16-20, wherein in 100 parts of described active organosilicon end capping polypropylene oxides, the content of described emulsifying agent is 2-20 part, preferred 4-16 part, most preferably the content of 4-14 part and water is 20-200 part, preferred 30-150 part, 40-120 part most preferably, all umbers are all in weight portion.
22. each solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion of claim 16-21, wherein said emulsifying agent be claim 1-3 each quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent or claim 4-15 each the quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent of method preparation or the mixture of this quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent and non-ionic surface active agent, with be under the situation of mixture at described emulsifying agent, weight ratio in the mixture between non-ionic surface active agent and the quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent is 0.5-10, preferred 1-7.5, most preferably 1-5.
23. the solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion of claim 22, wherein said non-ionic surface active agent is selected from fatty glyceride, sorbitan fatty acid ester, polysorbate, polyoxyethylene fatty acid ester and APEO.
24. the preparation method of a solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion, the weight average molecular weight of wherein said active organosilicon end capping polypropylene oxide is 1500-150000, preferred 2000-100000,3000-80000 most preferably, it has following schematic general formula:
Wherein, n is 0 or 1, and m is the integer of 0-10, and x is the integer of 1-50, and y is the integer of 15-2000, R
1Be methyl or ethyl, R
2Be methyl or ethyl, R
3For methylene or-(CH
2)
3-, R
4Be H or phenyl, R
5Or/and H, G is for methyl
R wherein
6For-(CH
2)
6-,
And/or
This method adopts the phase reversal emulsifying process under the organic solvent-free existence to carry out, and comprises the steps:
A1. in reactor, add described active organosilicon end capping polypropylene oxide and emulsifying agent, fully mix, described emulsifying agent be claim 1-3 each quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent or claim 4-15 each the quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent of method preparation or the mixture of this quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent and non-ionic surface active agent;
B1. in mixed system, drip water, continue to mix; With
C1. dropwise the back and continue to stir a period of time, thereby obtain the solvent-free active organosilicon end capping polypropylene oxide cationoid emulsion.
25. the method for claim 24, wherein in 100 parts of described active organosilicon end capping polypropylene oxides, the consumption of described emulsifying agent is 2-20 part, preferred 4-16 part, most preferably the consumption of 4-14 part and water is 20-200 part, preferred 30-150 part, 40-120 part most preferably, all umbers are all in weight portion.
26. the method for claim 24 or 25, wherein the temperature among the step a1 is 0-90 ℃, and preferred 5-50 ℃, most preferably 10-40 ℃ and time of mixing are 10-240 minute, preferred 30-120 minute, and most preferably 30-100 minute.
27. each method of claim 24-26, wherein the stir speed (S.S.) among the step b1 is controlled at 50-3000rpm, preferred 100-2000rpm, most preferably 200-1500rpm.
28. each method of claim 24-27, wherein the stirring among the step c1 continues 10-240 minute, preferred 20-180 minute, and most preferably 30-120 minute.
29. each method of claim 24-28, be under the situation of mixture wherein at described emulsifying agent, weight ratio in the mixture between non-ionic surface active agent and the quaternary ammonium salt type polyether-polysiloxane non-ionic cation surface active agent is 0.5-10, preferred 1-7.5, most preferably 1-5.
30. each method of claim 24-29, wherein said non-ionic surface active agent is selected from fatty glyceride, sorbitan fatty acid ester, polysorbate, polyoxyethylene fatty acid ester and APEO.
31. each method of claim 24-30 wherein adds entry in the mode that at the uniform velocity drips among the step b1.
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Application publication date: 20090701 |