CN105348476B - A kind of organic silicon modified aqueous polyurethane emulsion and preparation method thereof - Google Patents

A kind of organic silicon modified aqueous polyurethane emulsion and preparation method thereof Download PDF

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CN105348476B
CN105348476B CN201510824293.XA CN201510824293A CN105348476B CN 105348476 B CN105348476 B CN 105348476B CN 201510824293 A CN201510824293 A CN 201510824293A CN 105348476 B CN105348476 B CN 105348476B
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organic silicon
silicon modified
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CN105348476A (en
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洪杰
王艳
林伟
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Anhui sanjeshu coating Co.,Ltd.
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Skshu Paint Co Ltd
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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Abstract

The present invention relates to a kind of organic silicon modified aqueous polyurethane emulsion and preparation method thereof, it is formulated by following components：PEPA, isoflurane chalcone diisocyanate, diluent, hydrophilic chain extender, bis-hydroxypropyl terminated polysiloxane, dihydric alcohol, dibutyl tin laurate, nertralizer, water, ethylenediamine.The present invention has the following advantages：Avoid water resistance caused by additional emulsifying agent and decline problem；The polysiloxanes and polyurethane copolymerization that the present invention blocks hydroxyalkyl, substantially improve water resistance, mechanical property, hot property of waterborne polyurethane paint film etc..

Description

A kind of organic silicon modified aqueous polyurethane emulsion and preparation method thereof
Technical field
The present invention relates to technical field of aqueous paint, and in particular to a kind of organic-silicon-modified poly- ammonia emulsion and its preparation side Method.
Background technology
With the increasingly reinforcement of countries in the world environmental consciousness, some environmental regulations have been formulated in succession both at home and abroad to limit volatilization Property organic compound (VOC) to air discharge, high-performance, environmental protection turn into paint development direction.The conjunction of polyurethane resin Into by traditional solvent-borne type hydrotropism polyurethane transformation.
Aqueous polyurethane is nonflammable because its is nontoxic, environmentally friendly, and cost is low, is readily cleaned, excellent lower temperature resistance And the concern of people can be enjoyed the advantages that feel.But compared with solvent type polyurethane, the solid content of aqueous polyurethane is smaller, Film formation time is grown, due to the PEPA facile hydrolysis used in synthesis of polyurethane, therefore the problem of go back existence and stability difference.And water Property polyurethane resin because structure in contain hydrophilic group, the shortcomings of water resistance and glossiness difference of paint film also be present.
To meet people to the requirement on aqueous polyurethane application performance, it is poly- with labyrinth that researcher starts synthesis Urethane, it is desirable to which it has performance excellent as conventional urethane.Although the interior method for being crosslinked or adding outside cross-linking agent can be passed through Improved, but receive the limitation of emulsifying technology.For single-component system, interior crosslinking degree is too big, then emulsion is unstable, only The water resistance that can not make film by interior crosslinking is greatly improved.
Polysiloxanes has that low-temperature flexibility is good, surface tension is low, heat endurance is high, weatherability and water-tolerant etc. are excellent Performance, polysiloxanes is used to the material that excellent performance is can obtain in the modification of polyurethane.But due to polysiloxanes and polyurethane Solubility parameters differs greatly, and the result of simple blend is unsatisfactory.Can only be modification by copolymerization for this.It is total to for polyurethane Gather in modified polysiloxanes, the hydroxy silicon oil that Many researchers all use.- OH is directly connected with Si, in polymerization temperature condition Under, cyclization easily occurs and loses degree of functionality and reactivity, what is formed after reaction is Si-O-C structures, and its hydrolytic resistance is poor, It is unstable, it is very difficult to form substantial combination.According to the polysiloxanes of hydroxyalkyl end-blocking, that formed after copolymerization is Si-C-O Key, hydrolytic stability can be improved.
The content of the invention
The invention provides a kind of organic-silicon-modified poly- ammonia emulsion and preparation method thereof, it is resistance to that it solves aqueous polyurethane The technical problems such as water-based poor, poor solvent resistance and stability be bad, the present invention are used as from newborn using intermediate product polyurethane prepolymer Agent, avoid water resistance caused by additional emulsifying agent and decline problem；The polysiloxanes and polyurethane copolymerization blocked with hydroxyalkyl, Substantially improve water resistance, mechanical property, hot property of waterborne polyurethane paint film etc..
Technical solution of the present invention is as follows：
One) scheme one：
A kind of organic silicon modified polyurethane emulsion, it is characterised in that：It is prepared by following components by following ratio of weight and number Form：
Further, described bis-hydroxypropyl terminated polysiloxane was prepared according to following the step of sequentially carrying out 's：
1) 2- allyloxy trimethyl silanes, hereinafter referred to as ATMS are synthesized
In reactor A, 20.0-22.0 part propenyls are added, in the case where room temperature and stir speed (S.S.) are 300-500rmp, slowly 41.6-44.0 part HMDSs are added dropwise, after being added dropwise, reaction system is warming up to 96-104 DEG C, and in this temperature Continue to react 3-4 hour, stop reaction, collect the cut between 91-99 DEG C；Reaction equation such as formula one；
Formula one
2) double (the silyloxy propyl group of the 3- tri-) tetramethyl disiloxanes, hereinafter referred to as TDMS of 1,3- are synthesized
In reactor B, at room temperature, the 2- allyloxy trimethyls that 30.0-33.0 part steps 1) are prepared are added Silane and the chloroplatinic acid/aqueous isopropanol of 0.2-0.25 parts, after being warming up to 90-95 DEG C, are slowly added dropwise tetramethyl disiloxane 13.4-15.5 parts, and in said temperature insulation reaction 3-4h, then heat to 110-120 DEG C of reaction 2-3h, be evaporated under reduced pressure and collect 144-146 DEG C/cut l.067KPa, obtain light yellow transparent liquid；Described chloroplatinic acid/aqueous isopropanol is chloroplatinic acid Mass fraction is 2-3% aqueous isopropanol；
Reaction equation such as formula two；
Formula two
3) 1,3- bis-hydroxypropyl tetramethyl disiloxanes, hereinafter referred to as DS are synthesized
In reactor C, at room temperature, double (the 3- front three silica of 1,3- that 11.5-12.5 part steps 2) are prepared are added Base propyl group) after tetramethyl disiloxane, 0.3-0.5 parts acetic acid and 115-120 part methanol, it is warming up at 66-68 DEG C, back flow reaction 7-8h, excessive methanol, acetic acid then are steamed with circulating water type vacuum pump pressure, finally collect evaporating for 98-99 DEG C/3.2KPa Point, obtain light yellow transparent liquid；
Reaction equation such as formula three；
Formula three
4) bis-hydroxypropyl terminated polysiloxane is prepared
In the reactor, at room temperature, the silicon of 1,3- bis-hydroxypropyls tetramethyl two that 4.2-5.2 part steps 3) are prepared into is added Oxygen alkane and 4.3-5.3 part octamethylcy-clotetrasiloxanes, then heat to after 80-85 DEG C and add the fluoroform of 0.015-0.017 parts Base sulfonic acid, and continue reaction 24-25h at 80-85 DEG C, then add 0.4-0.5 parts potassium hydroxide/methanol solution and neutralize, afterwards 0.3-0.4 parts hydrochloric acid/methanol solution reaction 1-2h is added, decompression steams low-boiling-point substance, obtains light yellow transparent liquid；Described Potassium hydroxide/methanol solution is that the substance withdrawl syndrome of potassium hydroxide is 1-2mol/L methanol solution；Described hydrochloric acid/methanol Solution is that the substance withdrawl syndrome of hydrochloric acid is 1-2mol/L methanol solution.
Formula four
Further, the PEPA is the PEPA that molecular weight is 1000-2000.
Further, the retarder thinner uses one kind in acetone, butanone or 1-METHYLPYRROLIDONE.
Further, described dihydric alcohol be ethylene glycol, propane diols, BDO, pentanediol, diglycol or One kind in neopentyl glycol.
Further, described hydrophilic chain extender is 2,2- dihydromethyl propionic acids；Described nertralizer is triethylamine.
Two) scheme two：A kind of organic silicon modified polyurethane emulsion, it is characterised in that：Described organic silicon modified polyurethane Emulsion is according to following the step of sequentially carrying out preparation：
1) preparation of polyurethane prepolymer：
PEPA 24.00-26.00 parts and isoflurane chalcone diisocyanate 25.36-30.18 are added in the reactor Part, 80-85 DEG C is heated under 300-500rpm speeds of agitator and nitrogen protection, reacts to measured-NCO content and reaches reason By value；
2) preparation of organic silicon modified polyurethane prepolymer：
Then, above-mentioned rotating speed and temperature are kept, adds the diluent regulation system viscosity of 42.00-46.00 parts, is then added Enter the dibutyl tin laurate of the hydrophilic chain extender of 4.00-5.00 parts, the organosilicon of 1.00-8.00 parts and 0.04-0.08 parts, Start measure-NCO content afterwards, when-NCO content reaches theoretical value, the binary of 2.66-3.27 parts is added into reactor Alcohol, then start measure-NCO content, when-NCO content reaches theoretical value, you can organic silicon modified polyurethane prepolymer；
3) neutralization of organic silicon modified polyurethane prepolymer, emulsification, aqueous phase chain extension：
Then above-mentioned rotating speed is kept, reaction system made from step 2) is cooled to 30-40 DEG C, adds 2.73-3.78 parts Nertralizer, neutralize 3-5min；97.98-117.20 part water is subsequently added into, improves rotating speed afterwards to 1000-1500rpm, dilution Emulsify 15-20min；Then speed of agitator is reduced to 300-500rpm, and the ethylenediamine of 1.00-2.00 parts is dissolved into 24.00- In 26.00 parts of water, ethylenediamine solution is added drop-wise in reaction system with 10-15 minutes, in aqueous phase chain extending reaction 1-2 hours, Then butanone is evaporated under reduced pressure out, obtains the aqueous polyurethane emulsion of organic siliconresin modification.
Further, the assay method of described-NCO content is di-n-butylamine back titration method.
The inventive principle of the present invention is as follows：
This research uses method prepared by carboxylic acid type anion, is hydrophilic chain extender from dihydromethyl propionic acid (DMPA), Carboxyl is introduced in polyurethane structural, neutralizes carboxyl, adds water emulsification to form polyurethane aqueous and dissipates, introduced in polyurethane prepolymer Organosiloxane resins, utilize silicone resin excellent low-temperature flexibility energy, low surface tension, high thermal stability, excellent Weatherability and water resistance.The polysiloxanes and polyurethane copolymerization of hydroxyalkyl end-blocking, substantially improve the resistance to of waterborne polyurethane paint film Water-based, mechanical property, hot property etc..
The present invention compared with prior art, has the following advantages：
1) this preparation method is avoided additional emulsifying agent and caused using intermediate product polyurethane prepolymer as self-emulsifier Water resistance decline problem；
2) present invention introduces organosiloxane resins in polyurethane prepolymer, utilizes the low temperature that silicone resin is excellent Submissive performance, low surface tension, high thermal stability, excellent weatherability and water resistance.The polysiloxanes of hydroxyalkyl end-blocking is with gathering Urethane is copolymerized, and substantially improves water resistance, mechanical property, hot property of waterborne polyurethane paint film etc..
Embodiment
Present invention is described in detail with reference to embodiment, embodiment：
(1) embodiment
A kind of organic silicon modified polyurethane emulsion, it is characterised in that：It is prepared by following components by following ratio of weight and number Form：
A kind of organic silicon modified polyurethane emulsion, it is characterised in that：Described organic silicon modified polyurethane emulsion according to Under the step of sequentially carrying out preparation：
1) preparation of polyurethane prepolymer：
PEPA 24.00-26.00 parts and isoflurane chalcone diisocyanate 25.36-30.18 are added in the reactor Part, 80-85 DEG C is heated under 300-500rpm speeds of agitator and nitrogen protection, reacts to measured-NCO content and reaches reason By value；
2) preparation of organic silicon modified polyurethane prepolymer：
Then, above-mentioned rotating speed and temperature are kept, adds the diluent regulation system viscosity of 42.00-46.00 parts, is then added Enter the dibutyl tin laurate of the hydrophilic chain extender of 4.00-5.00 parts, the organosilicon of 1.00-8.00 parts and 0.04-0.08 parts, Start measure-NCO content afterwards, when-NCO content reaches theoretical value, the binary of 2.66-3.27 parts is added into reactor Alcohol, then start measure-NCO content, when-NCO content reaches theoretical value, you can organic silicon modified polyurethane prepolymer；
3) neutralization of organic silicon modified polyurethane prepolymer, emulsification, aqueous phase chain extension：
Then above-mentioned rotating speed is kept, reaction system made from step 2) is cooled to 30-40 DEG C, adds 2.73-3.78 parts Nertralizer, neutralize 3-5min；97.98-117.20 part water is subsequently added into, improves rotating speed afterwards to 1000-1500rpm, dilution Emulsify 15-20min；Then speed of agitator is reduced to 300-500rpm, and the ethylenediamine of 1.00-2.00 parts is dissolved into 24.00- In 26.00 parts of water, ethylenediamine solution is added drop-wise in reaction system with 10-15 minutes, in aqueous phase chain extending reaction 1-2 hours, Then butanone is evaporated under reduced pressure out, obtains the aqueous polyurethane emulsion of organic siliconresin modification.
The assay method of described-NCO content is di-n-butylamine back titration method.
(2) embodiment：
Embodiment 1
A kind of organic silicon modified aqueous polyurethane emulsion, it is formulated by following components by following ratio of weight and number：
A kind of preparation of organic silicon modified aqueous polyurethane emulsion, it by following weight match raw material according to it is following sequentially The step of progress, is prepared：
1) preparation of polyurethane prepolymer：
Equipped with agitator, thermometer, condenser pipe 500mL four-hole boiling flasks in, add 24.00 parts of PEPA and different 25.36 parts of fluorine that ketone diisocyanate, 80 DEG C are heated under 300rpm speeds of agitator and nitrogen protection, is reacted to measured - NCO content reaches theoretical value (15.33%).
2) preparation of organic silicon modified polyurethane prepolymer：
42 parts of diluent regulation system viscosity is added in above-mentioned reaction system, then adds 4 parts of hydrophilic chain extender 2,2- dihydromethyl propionic acids (DMPA), 1 part of bis-hydroxypropyl terminated polysiloxane and 0.04 part of dibutyl tin laurate (T- 12) when NCO content reaches theoretical value (5.21%), the dihydric alcohol of 2.66 parts of reaction is added into reactor, in 85 DEG C of bar Reacted under part, with di-n-butylamine back titration method measure-NCO content, when reaching theoretical value (2.57%), next step can be entered Reaction.
3) neutralization of polyurethane prepolymer, emulsification, aqueous phase chain extension：
System made from step 2) is cooled to 30 DEG C, adds 2.73 parts of nertralizer triethylamine, after neutralizing 5min, is added 97.98 parts of water dilution emulsifications, improve rotating speed to 1000rpm, emulsify 20min.Speed of agitator is reduced to 300rpm, by 1.46 parts Ethylenediamine was dissolved into 24 parts of water, is added drop-wise in reaction system, is added dropwise 10 minutes, in aqueous phase chain extending reaction 1 hour.Emulsify Cheng Hou, butanone is evaporated under reduced pressure out, obtains organic-silicon-modified aqueous polyurethane emulsion.
Embodiment 2
A kind of organic silicon modified aqueous polyurethane emulsion, it is formulated by following components by following ratio of weight and number：
A kind of preparation of organic silicon modified aqueous polyurethane emulsion, it by following weight match raw material according to it is following sequentially The step of progress, is prepared：
1) preparation of polyurethane prepolymer：
Equipped with agitator, thermometer, condenser pipe 500mL four-hole boiling flasks in, add 26 parts of PEPA and different fluorine 30.18 parts of your ketone diisocyanate, 85 DEG C are heated under 500rpm speeds of agitator and nitrogen protection, react to it is measured- NCO content reaches theoretical value (16.41%).
2) organic silicon modified polyurethane prepolymer：
46 parts of diluent regulation system viscosity is added in reaction system, then adds 5 parts of hydrophilic chain extender 2,2- Dihydromethyl propionic acid (DMPA), 3 parts of bis-hydroxypropyl terminated polysiloxane and 0.08 part of dibutyl tin laurate (T-12), When NCO content reaches theoretical value (5.41%), the dihydric alcohol of 3.27 parts of reaction is added into reactor, under conditions of 85 DEG C Reaction, with di-n-butylamine back titration method measure-NCO content, when reaching theoretical value (2.55%), the anti-of next step can be entered Should.
3) neutralization of polyurethane prepolymer, emulsification, aqueous phase chain extension：
System made from step 2) is cooled to 40 DEG C, adds 3.78 parts of nertralizer triethylamine, after neutralizing 5min, is added 121.20 parts of water dilution emulsifications, improve rotating speed to 1500rpm, emulsify 20min.Speed of agitator is reduced to 500rpm, by 1.66 parts Ethylenediamine be dissolved into 26.00 parts of water, be added drop-wise to 10 minutes in reaction system, in aqueous phase chain extending reaction 1 hour.Emulsification After the completion of, butanone is evaporated under reduced pressure out, obtains organic-silicon-modified aqueous polyurethane emulsion.
Embodiment 3
A kind of organic-silicon-modified aqueous polyurethane emulsion, it is formulated by following components by following ratio of weight and number：
A kind of preparation of organic-silicon-modified aqueous polyurethane emulsion, it by following weight match raw material according to below according to The step of sequence is carried out is prepared：
1) preparation of polyurethane prepolymer：
Equipped with agitator, thermometer, condenser pipe 500mL four-hole boiling flasks in, add 25 parts of PEPA and different fluorine 30.18 parts of your ketone diisocyanate, 85 DEG C are heated under 500rpm speeds of agitator and nitrogen protection, react to it is measured- NCO content reaches theoretical value (16.86%).
2) organic silicon modified polyurethane prepolymer：
44 parts of diluent regulation system viscosity is added in reaction system, then adds 5 parts of hydrophilic chain extender 2,2- Dihydromethyl propionic acid (DMPA), 5 parts of bis-hydroxypropyl terminated polysiloxane and 0.06 part of dibutyl tin laurate (T-12), When NCO content reaches theoretical value (5.46%), the dihydric alcohol of 2.66 parts of reaction is added into reactor, under conditions of 85 DEG C Reaction, with di-n-butylamine back titration method measure-NCO content, when reaching theoretical value (3.11%), the anti-of next step can be entered Should.
3) neutralization of polyurethane prepolymer, emulsification, aqueous phase chain extension：
System made from step 2) is cooled to 40 DEG C, adds 3.78 parts of nertralizer triethylamine, after neutralizing 5min, is added 117.20 parts of water dilution emulsifications, improve rotating speed to 1500rpm, emulsify 20min.Speed of agitator is reduced to 500rpm, by 1.99 parts Ethylenediamine be dissolved into 25 parts of water, be added drop-wise in reaction system, be added dropwise 10 minutes, in aqueous phase chain extending reaction 1 hour, then Butanone is evaporated under reduced pressure out, obtains organic-silicon-modified aqueous polyurethane emulsion.
Embodiment 4
A kind of organic-silicon-modified aqueous polyurethane emulsion, it is formulated by following components by following ratio of weight and number：
A kind of preparation of organic-silicon-modified aqueous polyurethane emulsion, it by following weight match raw material according to below according to The step of sequence is carried out is prepared：
1) preparation of polyurethane prepolymer：
Equipped with agitator, thermometer, condenser pipe 500mL four-hole boiling flasks in, add 25 parts of PEPA and different fluorine 27.17 parts of your ketone diisocyanate, speed of agitator are heated to 85 DEG C in 500rpm under nitrogen protection, react to it is measured- NCO content reaches theoretical value (15.66%).
2) organic silicon modified polyurethane prepolymer：
44 parts of diluent regulation system viscosity is added in reaction system, then adds 4 parts of hydrophilic chain extender 2,2- Dihydromethyl propionic acid (DMPA), 8 parts of bis-hydroxypropyl terminated polysiloxane and 0.06 part of dibutyl tin laurate (T-12), When NCO content reaches theoretical value (4.92%), the dihydric alcohol of 3.27 parts of reaction is added into reactor, under conditions of 85 DEG C Reaction, with di-n-butylamine back titration method measure-NCO content, when reaching theoretical value (2.56%), the anti-of next step can be entered Should.
3) neutralization of polyurethane prepolymer, emulsification, aqueous phase chain extension：
System made from step 2) is cooled to 40 DEG C, adds 3.78 parts of nertralizer triethylamine, after neutralizing 5min, is added 102.80 parts of water dilution emulsifications, improve rotating speed to 1500rpm, emulsify 20min.Speed of agitator is reduced to 500rpm, by 1.63 parts Ethylenediamine be dissolved into 25 parts of water, be added drop-wise in reaction system, be added dropwise 10 minutes, in aqueous phase chain extending reaction 2 hours, then Butanone is evaporated under reduced pressure out, obtains organic-silicon-modified aqueous polyurethane emulsion.
Embodiment 5
A kind of organic-silicon-modified aqueous polyurethane emulsion, it is formulated by following components by following ratio of weight and number：
A kind of preparation of organic-silicon-modified aqueous polyurethane emulsion, it by following weight match raw material according to below according to The step of sequence is carried out is prepared：
1) preparation of polyurethane prepolymer：
Equipped with agitator, thermometer, condenser pipe 500mL four-hole boiling flasks in, add 25 parts of PEPA and different fluorine 27.17 parts of your ketone diisocyanate, 85 DEG C are heated under 500rpm speeds of agitator and nitrogen protection, react to it is measured- NCO content reaches theoretical value (15.66%).
2) organic silicon modified polyurethane prepolymer：
44 parts of diluent regulation system viscosity is added in above-mentioned reaction system, then adds 5 parts of hydrophilic chain extender 2,2- dihydromethyl propionic acids (DMPA), 5 parts of bis-hydroxypropyl terminated polysiloxane and 0.06 part of dibutyl tin laurate (T- 12), when NCO content reaches theoretical value (4.55%), the dihydric alcohol of 3.16 parts of reaction is added into reaction system, at 85 DEG C Under the conditions of react, with di-n-butylamine back titration method measure-NCO content, when reaching theoretical value (1.72%), can enter in next step Reaction.
3) neutralization of polyurethane prepolymer, emulsification, aqueous phase chain extension：
System made from step 2) is cooled to 40 DEG C, adds 3.78 parts of nertralizer triethylamine, after neutralizing 5min, is added 102.80 parts of water, rotating speed is improved to 1500rpm, dilution emulsification 20min.Speed of agitator is reduced to 500rpm, by 1.08 parts of second Diamines is dissolved into 25 parts of water, is added drop-wise in reaction system, is added dropwise 10 minutes, in aqueous phase chain extending reaction 1 hour, is then depressurized Butanone is distilled out, obtains organic-silicon-modified aqueous polyurethane emulsion.
Embodiment 6-8 is the preparation method of bis-hydroxypropyl terminated polysiloxane
Embodiment 6
Bis-hydroxypropyl terminated polysiloxane is prepared according to following the step of sequentially carrying out：
1) 2- allyloxy trimethyl silanes are synthesized
In reactor A, 20.0g propenyls are added, in the case where room temperature and stir speed (S.S.) are 300rmp, 41.6g is slowly added dropwise HMDS, after being added dropwise, reaction system is warming up to 96 DEG C, and continue to react 3 hours in this temperature, stopping Reaction, collect the cut between 91 DEG C；
2) double (the silyloxy propyl group of the 3- tri-) tetramethyl disiloxanes of 1,3- are synthesized
In reactor B, at room temperature, 30.0g 2- allyloxys trimethyl silanes and 0.2g chloroplatinic acid/different is added Propyl alcohol, after being warming up to 90 DEG C, it is slowly added dropwise tetramethyl disiloxane 13.4g, and in said temperature insulation reaction 3h, then heats up To 110 DEG C of reaction 2h, it is evaporated under reduced pressure and collects 144 DEG C/cut l.067KPa, obtain light yellow transparent liquid；
3) 1,3- bis-hydroxypropyl tetramethyl disiloxanes are synthesized
In reactor C, at room temperature, double (the silyloxy propyl group of the 3- tri-) tetramethyl disiloxanes of addition 11.5g1,3-, After 0.3g acetic acid and 115ml methanol, it is warming up at 66 DEG C, back flow reaction 7h, was then steamed with circulating water type vacuum pump pressure Methanol, the acetic acid of amount, 98- DEG C/3.2KPa cut is finally collected, obtains light yellow transparent liquid；
4) bis-hydroxypropyl terminated polysiloxane is prepared
In the reactor, at room temperature, the 4.2g1 that step 3) is prepared into, 3- bis-hydroxypropyl tetramethyl disiloxanes are added With 4.3g octamethylcy-clotetrasiloxanes, then heat to after 80 DEG C and add 0.015mL trifluoromethane sulfonic acid, and in 80 DEG C of continuation 24h is reacted, 0.4ml potassium hydroxide/methanol solution is then added and neutralizes, adds 0.3ml hydrochloric acid/methanol solution reaction afterwards 1h, decompression steam low-boiling-point substance, obtain light yellow transparent liquid；Described hydrochloric acid/concentration of methanol solution is 1mol/L.
Embodiment 7
Bis-hydroxypropyl terminated polysiloxane is prepared according to following the step of sequentially carrying out：
1) 2- allyloxy trimethyl silanes are synthesized
In reactor A, 22.0g propenyls are added, in the case where room temperature and stir speed (S.S.) are 500rmp, 44.0g is slowly added dropwise HMDS, after being added dropwise, reaction system is warming up to 104 DEG C, and continues 4 hours of reaction in this temperature, stopped Only react, collect the cut between 99 DEG C；
2) double (the silyloxy propyl group of the 3- tri-) tetramethyl disiloxanes of 1,3- are synthesized
In reactor B, at room temperature, 33.0g 2- allyloxys trimethyl silanes and 0.25g chloroplatinic acid/different is added Propyl alcohol, after being warming up to 95 DEG C, it is slowly added dropwise tetramethyl disiloxane 15.5g, and in said temperature insulation reaction 4h, then heats up To 120 DEG C of reaction 3h, it is evaporated under reduced pressure and collects 146 DEG C/cut l.067KPa, obtain light yellow transparent liquid；
3) 1,3- bis-hydroxypropyl tetramethyl disiloxanes are synthesized
In reactor C, at room temperature, double (the silyloxy propyl group of the 3- tri-) tetramethyl disiloxanes of addition 12.5g1,3-, After 0.5g acetic acid and 120ml methanol, it is warming up at 68 DEG C, back flow reaction 8h, was then steamed with circulating water type vacuum pump pressure Methanol, the acetic acid of amount, 99 DEG C/3.2KPa cut is finally collected, obtains light yellow transparent liquid；
4) bis-hydroxypropyl terminated polysiloxane is prepared
In the reactor, at room temperature, the 5.2g1 that step 3) is prepared into, 3- bis-hydroxypropyl tetramethyl disiloxanes are added With 5.3g octamethylcy-clotetrasiloxanes, then heat to after 85 DEG C and add 0.017mL trifluoromethane sulfonic acid, and in 85 DEG C of continuation 25h is reacted, 0.5ml potassium hydroxide/methanol solution is then added and neutralizes, adds 0.4ml hydrochloric acid/methanol solution reaction afterwards 2h, decompression steam low-boiling-point substance, obtain light yellow transparent liquid；Described hydrochloric acid/concentration of methanol solution is 2mol/L.
Embodiment 8
Bis-hydroxypropyl terminated polysiloxane is prepared according to following the step of sequentially carrying out：
1) 2- allyloxy trimethyl silanes are synthesized
In reactor A, 21.0g propenyls are added, in the case where room temperature and stir speed (S.S.) are 400rmp, 43.0g is slowly added dropwise HMDS, after being added dropwise, reaction system is warming up to 102 DEG C, and continues 3.5 hours of reaction in this temperature, Stop reaction, collect the cut between 95 DEG C；
2) double (the silyloxy propyl group of the 3- tri-) tetramethyl disiloxanes of 1,3- are synthesized
In reactor B, at room temperature, 32.0g 2- allyloxys trimethyl silanes and 0.21g chloroplatinic acid/different is added Propyl alcohol, after being warming up to 92 DEG C, it is slowly added dropwise tetramethyl disiloxane 15g, and in said temperature insulation reaction 3.5h, then heats up To 115 DEG C of reaction 2.2h, it is evaporated under reduced pressure and collects 145 DEG C/cut l.067KPa, obtain light yellow transparent liquid；
3) 1,3- bis-hydroxypropyl tetramethyl disiloxanes are synthesized
In reactor C, at room temperature, double (the silyloxy propyl group of the 3- tri-) tetramethyl disiloxanes of addition 12g1,3-, After 0.4g acetic acid and 117ml methanol, it is warming up at 67 DEG C, back flow reaction 7h, was then steamed with circulating water type vacuum pump pressure Methanol, the acetic acid of amount, 98 DEG C/3.2KPa cut is finally collected, obtains light yellow transparent liquid；
4) bis-hydroxypropyl terminated polysiloxane is prepared
In the reactor, at room temperature, the 4.7g1 that step 3) is prepared into, 3- bis-hydroxypropyl tetramethyl disiloxanes are added With 4.8g octamethylcy-clotetrasiloxanes, then heat to after 82 DEG C and add 0.016mL trifluoromethane sulfonic acid, and in 82 DEG C of continuation 24h is reacted, 0.4ml potassium hydroxide/methanol solution is then added and neutralizes, adds 0.3ml hydrochloric acid/methanol solution reaction afterwards 1h, decompression steam low-boiling-point substance, obtain light yellow transparent liquid；Described hydrochloric acid/concentration of methanol solution is 2mol/L.
Individual raw material in various embodiments above is commercially available product, except bis-hydroxypropyl terminated polysiloxane be according to It is prepared by embodiment 6-8 productions.
The CMA-44 of the preferred Hua Da chemistry of described PEPA；
Described isoflurane chalcone diisocyanate is preferably the IPDI of Bayer production；
Described 2,2- dihydromethyl propionic acids, 1,4- butanediols, azodiisobutyronitrile, butanone, ethylenediamine are preferably me Fourth reagent.
Described dibutyl tin laurate is preferably the product of the triumphant auspicious chemical Science and Technology Ltd. in Changzhou.
Organic-silicon-modified aqueous polyurethane emulsion is carried out particle size, hardness, film-forming temperature, water resistance, resistance to vinegar, The performance tests such as alcohol resistance.
Grain size analysis：Emulsion particle diameter is tested using Malvern company 3000SHA type nano-particle size analysis instrument.
Gloss (60 DEG C)：Provide to test according to GB/T 9754.
Hardness：Tested according to the regulations of GB/T 6739.
Adhesive force：Tested according to GB/T 9286-1998 regulations, draw compartment away from for 2mm.
Water resistance：Tested according to GB/T 4893.1-2005 regulations.Water-fast 24 hours, whether paint film there is exception.
Alcohol resistance：Method of testing is identical with water resistance, and test solution is the ethanol solution of 50% (volume fraction), and experimental period is 1h, after testing 1 hour, whether observation paint film is normal.
Resistance to vinegar：From making vinegar, after testing 1 hour, whether observation paint film is normal.
Film-forming temperature：Using RHOPOINT companies of Britain MFFT Bar-60 minimum film forming temperature testers, emulsion is tested MFT.
By the test to each embodiment, the detection data for the aqueous polyurethane emulsion that organic siliconresin of the invention is modified As a result as shown in following table：
The experimental data of each embodiment test of the organic siliconresin modified aqueous polyurethane emulsion of table one
From table one, it is apparent that various embodiments of the present invention be respectively provided with difficult environmental conditions it is good water-fast Property, alcohol resistance and stain resistance, particle diameter distribution there is very high adhesive force and hardness in 100nm or so, well should have With value.
In summary, the organic-silicon-modified aqueous polyurethane emulsion of various embodiments of the present invention have very high hardness and Adhesive force, there is good water resistance, alcohol resistance and stain resistance.
Simply technical scheme is explained in detail for above-mentioned embodiment, the present invention not only only office Be limited to above-described embodiment, it will be understood by those skilled in the art that it is every according to above-mentioned principle and spirit on the basis of the present invention Improve, substitute, all should be within protection scope of the present invention.

Claims (7)

  1. A kind of 1. organic silicon modified aqueous polyurethane emulsion, it is characterised in that：It is matched somebody with somebody by following components by following ratio of weight and number System forms：
    Described bis-hydroxypropyl terminated polysiloxane is prepared according to following the step of sequentially carrying out：
    1) 2- allyloxy trimethyl silanes are synthesized
    In reactor A, 20.0-22.0 part propenyls are added, in the case where room temperature and stir speed (S.S.) are 300-500rmp, are slowly added dropwise 41.6-44.0 part HMDSs, after being added dropwise, reaction system is warming up to 96-104 DEG C, and continue in this temperature 3-4 hour is reacted, stops reaction, collects the cut between 91-99 DEG C；
    2) double (the silyloxy propyl group of the 3- tri-) tetramethyl disiloxanes of 1,3- are synthesized
    In reactor B, at room temperature, the 2- allyloxy trimethyl silanes that 30.0-33.0 part steps 1) are prepared are added With the chloroplatinic acid/aqueous isopropanol of 0.2-0.25 parts, after being warming up to 90-95 DEG C, tetramethyl disiloxane 13.4- is slowly added dropwise 15.5 parts, and in said temperature insulation reaction 3-4h, then heat to 110-120 DEG C of reaction 2-3h, be evaporated under reduced pressure and collect 144- 146 DEG C/cut l.067KPa, obtain light yellow transparent liquid；
    Described chloroplatinic acid/aqueous isopropanol is that the mass fraction of chloroplatinic acid is 2-3% aqueous isopropanol；
    3) 1,3- bis-hydroxypropyl tetramethyl disiloxanes are synthesized
    In reactor C, at room temperature, the double (silyloxies third of 3- tri- of 1,3- that 11.5-12.5 part steps 2) are prepared are added Base) after tetramethyl disiloxane, 0.3-0.5 parts acetic acid and 115-120 part methanol, it is warming up at 66-68 DEG C, back flow reaction 7- 8h, excessive methanol, acetic acid then are steamed with circulating water type vacuum pump pressure, finally collect 98-99 DEG C/3.2KPa cut, Obtain light yellow transparent liquid；
    4) bis-hydroxypropyl terminated polysiloxane is prepared
    In reactor D, at room temperature, the silica of 1,3- bis-hydroxypropyls tetramethyl two that 4.2-5.2 part steps 3) are prepared into is added Alkane and 4.3-5.3 part octamethylcy-clotetrasiloxanes, then heat to after 80-85 DEG C and add the trifluoromethyl of 0.015-0.017 parts Sulfonic acid, and continue reaction 24-25h at 80-85 DEG C, then add 0.4-0.5 parts potassium hydroxide/methanol solution and neutralize, Zhi Houzai 0.3-0.4 parts hydrochloric acid/methanol solution reaction 1-2h is added, decompression steams low-boiling-point substance, obtains light yellow transparent liquid；
    Described potassium hydroxide/methanol solution is that the substance withdrawl syndrome of potassium hydroxide is 1-2mol/L methanol solution；It is described Hydrochloric acid/methanol solution be hydrochloric acid substance withdrawl syndrome be 1-2mol/L methanol solution.
  2. A kind of 2. organic silicon modified aqueous polyurethane emulsion according to claim 1, it is characterised in that：The polyester polyols Alcohol is the PEPA that molecular weight is 1000-2000.
  3. A kind of 3. organic silicon modified aqueous polyurethane emulsion according to claim 1, it is characterised in that：The diluent is One kind in acetone, butanone or 1-METHYLPYRROLIDONE.
  4. A kind of 4. organic silicon modified aqueous polyurethane emulsion according to claim 1, it is characterised in that：Described dihydric alcohol For one kind in ethylene glycol, propane diols, 1,4- butanediols, pentanediol, diglycol or neopentyl glycol.
  5. A kind of 5. organic silicon modified aqueous polyurethane emulsion according to claim 1, it is characterised in that：Described hydrophilic expansion Chain agent is 2,2- dihydromethyl propionic acids；Described nertralizer is triethylamine.
  6. A kind of 6. preparation method of organic silicon modified aqueous polyurethane emulsion, it is characterised in that：Described is organic silicon modified aqueous Polyaminoester emulsion is by following content of component according to following the step of sequentially carrying out preparation：
    1) preparation of polyurethane prepolymer：
    PEPA 24.00-26.00 parts and isoflurane chalcone diisocyanate 25.36-30.18 parts are added in the reactor, 80-85 DEG C is heated under 300-500rpm speeds of agitator and nitrogen protection, reacts to measured-NCO content and reaches theoretical value；
    2) preparation of organic silicon modified polyurethane prepolymer：
    Then, above-mentioned rotating speed and temperature are kept, the diluent regulation system viscosity of 42.00-46.00 parts is added, is subsequently added into The February of the hydrophilic chain extender of 4.00-5.00 parts, the bis-hydroxypropyl terminated polysiloxane of 1.00-8.00 parts and 0.04-0.08 parts Dilaurylate, start measure-NCO content afterwards, when-NCO content reaches theoretical value, 2.66- is added into reactor 3.27 parts of dihydric alcohol, then start measure-NCO content, when-NCO content reaches theoretical value, that is, obtain organic-silicon-modified poly- Urethane prepolymer；
    3) neutralization of organic silicon modified polyurethane prepolymer, emulsification, aqueous phase chain extension：
    Then above-mentioned rotating speed is kept, reaction system made from step 2) is cooled to 30-40 DEG C, added in 2.73-3.78 parts And agent, neutralize 3-5min；97.98-117.20 part water is subsequently added into, improves rotating speed afterwards to 1000-1500rpm, dilution emulsification 15-20min；Then speed of agitator is reduced to 300-500rpm, and the ethylenediamine of 1.00-2.00 parts is dissolved into 24.00-26.00 In the water of part, ethylenediamine solution is added drop-wise in reaction system with 10-15 minutes, in aqueous phase chain extending reaction 1-2 hours, then subtracted Pressure distills out diluent, obtains organic-silicon-modified aqueous polyurethane emulsion.
  7. A kind of 7. preparation method of organic silicon modified aqueous polyurethane emulsion according to claim 6, it is characterised in that：Institute State-assay method of NCO content is di-n-butylamine back titration method.
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CN107522864B (en) * 2017-08-23 2020-12-08 江西蓝星星火有机硅有限公司 Silane modified polymer and preparation method thereof
CN108840987B (en) * 2018-06-28 2022-02-15 优美特（北京）环境材料科技股份公司 Organosilicon polyol modified waterborne polyurethane emulsion and preparation method thereof
CN109369862A (en) * 2018-09-28 2019-02-22 合众（佛山）化工有限公司 A kind of fluorine-silicon polyurethane modified acroleic acid water-base resin and preparation method thereof
CN109679327B (en) * 2018-12-26 2021-03-23 浙江东进新材料有限公司 Nano organic silicon composite polyurethane waterproof emulsion
CN110452361B (en) * 2019-07-09 2021-09-21 广东德美精细化工集团股份有限公司 Synthetic method of polyurethane acrylic acid modified organic silicon fluoride-free waterproof agent and waterproof agent
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