CN105348476A - Organosilicon modified waterborne polyurethane emulsion and preparation method thereof - Google Patents
Organosilicon modified waterborne polyurethane emulsion and preparation method thereof Download PDFInfo
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—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
- C08G18/753—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
- 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
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
Abstract
The invention relates to an organosilicon modified waterborne polyurethane emulsion and a preparation method thereof. The organosilicon modified waterborne polyurethane emulsion is prepared from the following components: polyester polyol, isophorone diisocyanate, a diluent, a hydrophilic chain extender, bis(hydroxypropyl)-terminiated polysiloxane, dihydric alcohol, dibutyltin dilaurate, a neutralizer, water and ethylene diamine. The invention has the following advantages: the problem of deterioration of water resistance caused by addition of an emulsifier is overcome; and copolymerization of hydroxyalkyl-terminiated polysiloxane and polyurethane substantially improves water resistance, mechanical properties, thermal behaviors and the like of a waterborne polyurethane film.
Description
Technical field
The present invention relates to technical field of aqueous paint, be specifically related to a kind of organic-silicon-modified poly-ammonia emulsion and preparation method thereof.
Background technology
Along with the reinforcement day by day of countries in the world environmental consciousness, in succession formulated some environmental regulations both at home and abroad to limit volatile organic compounds (VOC) to airborne release, high-performance, environmental protection have become the direction of paint development.The synthesis of urethane resin is changed by traditional solvent-borne type hydrotropisms urethane.
Aqueous polyurethane is nontoxic because of it, nonflammable, environmentally friendly, and cost is low, is easy to cleaning, advantages such as excellent resistance to low temperature and feel and enjoy the concern of people.But compared with solvent type urethane, the solid content of aqueous polyurethane is less, and film formation time is long, due to the polyester polyol facile hydrolysis that synthesis of polyurethane is used, therefore go back the problem of existence and stability difference.And waterborne polyurethane resin is because containing hydrophilic group in structure, also exist paint film water tolerance and the shortcoming such as glossiness difference.
For meeting people to the requirement on aqueous polyurethane application performance, investigator starts to synthesize the urethane with complex construction, wishes that it has excellent performance the same as conventional urethane.Although improved by interior method that is crosslinked or that add outside cross-linking agent, receive the restriction of emulsifying technology.For single-component system, interior crosslinking degree is too large, then emulsion is unstable, the water resistance of film can not be made to have greatly improved by means of only interior being cross-linked.
The excellent properties such as polysiloxane has that low-temperature flexibility is good, surface tension is low, thermostability is high, weathering resistance and water-tolerant, use the material that available in the modification of urethane can be excellent by polysiloxane.But because polysiloxane and urethane solubility parameters differ greatly, the result of simple blend is unsatisfactory.For this reason, can only be modification by copolymerization.In the polysiloxane for polyurethane copolymerization modification, the hydroxy silicon oil that Many researchers all adopts.-OH is directly connected with Si, and under conditions of polymerization temperature vary, easily cyclization occur and lose functionality and reactivity, what formed after reaction is Si-O-C structure, and its hydrolytic resistance is poor, unstable, is difficult to form substantial combination.According to the polysiloxane of hydroxyalkyl end-blocking, what formed after copolymerization is Si-C-O key, can improve stability to hydrolysis.
Summary of the invention
The invention provides a kind of organic-silicon-modified poly-ammonia emulsion and preparation method thereof, it solve the technical problems such as Water-resistance of Waterborne Polyurethane difference, poor solvent resistance and stability is bad, the present invention, using intermediate product polyurethane prepolymer as self-emulsifier, avoids the water tolerance decline problem that additional emulsifying agent causes; With polysiloxane and the polyurethane copolymerization of hydroxyalkyl end-blocking, greatly improve the water tolerance of waterborne polyurethane paint film, mechanical property, thermal characteristics etc.
Technical solution of the present invention is as follows:
One) scheme one:
A kind of organic silicon modified polyurethane emulsion, is characterized in that: it is formulated by following ratio of weight and number by following component:
Further, described bis-hydroxypropyl terminated polysiloxane is prepared from according to following step of sequentially carrying out:
1) 2-allyloxy trimethyl silane is synthesized, hereinafter referred to as ATMS
In reactor A, add 20.0-22.0 part vinylcarbinol, under room temperature and stir speed (S.S.) are 300-500rmp, slow dropping 41.6-44.0 part hexamethyldisilazane, after dropwising, reaction system is warmed up to 96-104 DEG C, and continues reaction 3-4 hour in this temperature, stopped reaction, the cut between collecting 91-99 DEG C; Reaction formula is such as formula one;
Formula one
2) two (the 3-tri-silyloxy propyl group) tetramethyl disiloxane of 1,3-is synthesized, hereinafter referred to as TDMS
In reactor B, at room temperature, add 30.0-33.0 part step 1) Platinic chloride/aqueous isopropanol of the 2-allyloxy trimethyl silane that is prepared from and 0.2-0.25 part, after being warmed up to 90-95 DEG C, slow dropping tetramethyl disiloxane 13.4-15.5 part, and at said temperature insulation reaction 3-4h, be then warming up to 110-120 DEG C of reaction 2-3h, 144-146 DEG C/cut is l.067KPa collected in underpressure distillation, obtains light yellow transparent liquid; Described Platinic chloride/aqueous isopropanol is the massfraction of Platinic chloride is the aqueous isopropanol of 2-3%;
Reaction formula is such as formula two;
Formula two
3) 1,3-bis-hydroxypropyl tetramethyl disiloxane is synthesized, hereinafter referred to as DS
In reactor C, at room temperature, add 11.5-12.5 part step 2) be prepared from 1, after two (3-tri-silyloxy propyl group) tetramethyl disiloxane, 0.3-0.5 part acetic acid and the 115-120 part methyl alcohol of 3-, at being warmed up to 66-68 DEG C, back flow reaction 7-8h, then steams excessive methyl alcohol, acetic acid with circulating water type vacuum pump pressure, finally collect the cut of 98-99 DEG C/3.2KPa, obtain light yellow transparent liquid;
Reaction formula is such as formula three;
Formula three
4) bis-hydroxypropyl terminated polysiloxane is prepared
In the reactor, at room temperature, add 4.2-5.2 part step 3) be prepared into 1,3-bis-hydroxypropyl tetramethyl disiloxane and 4.3-5.3 part octamethylcyclotetrasiloxane, add the trifluoromethane sulfonic acid of 0.015-0.017 part after being then warming up to 80-85 DEG C, and continue reaction 24-25h at 80-85 DEG C, then 0.4-0.5 part potassium hydroxide/methanol solution neutralization is added, add 0.3-0.4 part hydrochloric acid/methanol solution reaction 1-2h afterwards again, decompression steams low-boiling-point substance, obtains light yellow transparent liquid; Described potassium hydroxide/methanol solution is the substance withdrawl syndrome of potassium hydroxide is the methanol solution of 1-2mol/L; Described hydrochloric acid/methanol solution is the substance withdrawl syndrome of hydrochloric acid is the methanol solution of 1-2mol/L.
Formula four
Further, the polyester polyol of described polyester polyol to be molecular weight be 1000-2000.
Further, described diluting solvent adopts the one in acetone, butanone or N-Methyl pyrrolidone.
Further, described dibasic alcohol is the one in ethylene glycol, propylene glycol, BDO, pentanediol, glycol ether or neopentyl glycol.
Further, described hydrophilic chain extender is 2,2-dimethylol propionic acid; Described neutralizing agent is triethylamine.
Two) scheme two: a kind of organic silicon modified polyurethane emulsion, is characterized in that: described organic silicon modified polyurethane emulsion is according to the following step preparation sequentially carried out:
1) preparation of polyurethane prepolymer:
Add polyester polyol 24.00-26.00 part and isoflurane chalcone diisocyanate 25.36-30.18 part in the reactor, under 300-500rpm mixing speed and nitrogen protection, be heated to 80-85 DEG C, reaction to measured-NCO content reaches theoretical value;
2) preparation of organic silicon modified polyurethane prepolymer:
Then, keep above-mentioned rotating speed and temperature, add the thinner regulation system viscosity of 42.00-46.00 part, then add the hydrophilic chain extender of 4.00-5.00 part, the organosilicon of 1.00-8.00 part and the dibutyl tin laurate of 0.04-0.08 part, start afterwards to measure-NCO content, when-NCO content reaches theoretical value, the dibasic alcohol of 2.66-3.27 part is added in reactor, then start to measure-NCO content, when-NCO content reaches theoretical value, organic silicon modified polyurethane prepolymer;
3) neutralization of organic silicon modified polyurethane prepolymer, emulsification, aqueous phase chain extension:
Then keep above-mentioned rotating speed, by step 2) obtained reaction system cools to 30-40 DEG C, adds the neutralizing agent of 2.73-3.78 part, in and 3-5min; Then add 97.98-117.20 part water, improve rotating speed afterwards to 1000-1500rpm, dilution emulsification 15-20min; Then mixing speed is reduced to 300-500rpm, the quadrol of 1.00-2.00 part is dissolved in the water of 24.00-26.00 part, with 10-15 minute, ethylenediamine solution is added drop-wise in reaction system, at aqueous phase chain extending reaction 1-2 hour, then underpressure distillation goes out butanone, obtains the aqueous polyurethane emulsion of silicone resin modification.
Further, the measuring method of described-NCO content is Di-n-Butyl Amine back titration method.
Inventive principle of the present invention is as follows:
The method that this research adopts carboxylic acid type negatively charged ion to prepare, dimethylol propionic acid (DMPA) is selected to be hydrophilic chain extender, carboxyl is introduced in polyurethane structural, in and carboxyl, add emulsifying water formation polyurethane aqueous to fall apart, in polyurethane prepolymer, introduce organosiloxane resins, utilize the low-temperature flexibility energy of silicone resin excellence, low surface tension, high thermal stability, excellent weathering resistance and water tolerance.The polysiloxane of hydroxyalkyl end-blocking and polyurethane copolymerization, improve the water tolerance of waterborne polyurethane paint film, mechanical property, thermal characteristics etc. greatly.
The present invention compared with prior art, has the following advantages:
1) this preparation method is using intermediate product polyurethane prepolymer as self-emulsifier, avoids the water tolerance decline problem that additional emulsifying agent causes;
2) the present invention introduces organosiloxane resins in polyurethane prepolymer, utilizes the low-temperature flexibility energy of silicone resin excellence, low surface tension, high thermal stability, excellent weathering resistance and water tolerance.The polysiloxane of hydroxyalkyl end-blocking and polyurethane copolymerization, improve the water tolerance of waterborne polyurethane paint film, mechanical property, thermal characteristics etc. greatly.
Embodiment
Below in conjunction with embodiment, embodiment, content of the present invention is described in detail:
(1) embodiment
A kind of organic silicon modified polyurethane emulsion, is characterized in that: it is formulated by following ratio of weight and number by following component:
A kind of organic silicon modified polyurethane emulsion, is characterized in that: described organic silicon modified polyurethane emulsion is according to the following step preparation sequentially carried out:
1) preparation of polyurethane prepolymer:
Add polyester polyol 24.00-26.00 part and isoflurane chalcone diisocyanate 25.36-30.18 part in the reactor, under 300-500rpm mixing speed and nitrogen protection, be heated to 80-85 DEG C, reaction to measured-NCO content reaches theoretical value;
2) preparation of organic silicon modified polyurethane prepolymer:
Then, keep above-mentioned rotating speed and temperature, add the thinner regulation system viscosity of 42.00-46.00 part, then add the hydrophilic chain extender of 4.00-5.00 part, the organosilicon of 1.00-8.00 part and the dibutyl tin laurate of 0.04-0.08 part, start afterwards to measure-NCO content, when-NCO content reaches theoretical value, the dibasic alcohol of 2.66-3.27 part is added in reactor, then start to measure-NCO content, when-NCO content reaches theoretical value, organic silicon modified polyurethane prepolymer;
3) neutralization of organic silicon modified polyurethane prepolymer, emulsification, aqueous phase chain extension:
Then keep above-mentioned rotating speed, by step 2) obtained reaction system cools to 30-40 DEG C, adds the neutralizing agent of 2.73-3.78 part, in and 3-5min; Then add 97.98-117.20 part water, improve rotating speed afterwards to 1000-1500rpm, dilution emulsification 15-20min; Then mixing speed is reduced to 300-500rpm, the quadrol of 1.00-2.00 part is dissolved in the water of 24.00-26.00 part, with 10-15 minute, ethylenediamine solution is added drop-wise in reaction system, at aqueous phase chain extending reaction 1-2 hour, then underpressure distillation goes out butanone, obtains the aqueous polyurethane emulsion of silicone resin modification.
The measuring method of described-NCO content is Di-n-Butyl Amine back titration method.
(2) embodiment:
Embodiment 1
A kind of organic silicon modified aqueous polyurethane emulsion, it is formulated by following ratio of weight and number by following component:
A preparation for organic silicon modified aqueous polyurethane emulsion, it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) preparation of polyurethane prepolymer:
In the 500mL four-hole boiling flask that agitator, thermometer, prolong are housed; add polyester polyol 24.00 parts and isoflurane chalcone diisocyanate 25.36 parts; under 300rpm mixing speed and nitrogen protection, be heated to 80 DEG C, reaction to measured-NCO content reaches theoretical value (15.33%).
2) preparation of organic silicon modified polyurethane prepolymer:
The thinner regulation system viscosity of 42 parts is added in above-mentioned reaction system, add the hydrophilic chain extender 2 of 4 parts subsequently, the dibutyl tin laurate (T-12) of 2-dimethylol propionic acid (DMPA), the bis-hydroxypropyl terminated polysiloxane of 1 part and 0.04 part is when NCO content reaches theoretical value (5.21%), the dibasic alcohol of reaction 2.66 parts is added in reactor, react under the condition of 85 DEG C,-NCO content is measured with Di-n-Butyl Amine back titration method, when reaching theoretical value (2.57%), next step reaction can be entered.
3) neutralization of polyurethane prepolymer, emulsification, aqueous phase chain extension:
By step 2) obtained system cools to 30 DEG C, adds the neutralizing agent triethylamine of 2.73 parts, in and after 5min, add 97.98 parts of water dilution emulsifications, improve rotating speed to 1000rpm, emulsification 20min.Reduce mixing speed to 300rpm, the quadrol of 1.46 parts is dissolved in the water of 24 parts, is added drop-wise in reaction system, drip 10 minutes, aqueous phase chain extending reaction 1 hour.After emulsification completes, underpressure distillation goes out butanone, obtains organic-silicon-modified aqueous polyurethane emulsion.
Embodiment 2
A kind of organic silicon modified aqueous polyurethane emulsion, it is formulated by following ratio of weight and number by following component:
A preparation for organic silicon modified aqueous polyurethane emulsion, it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) preparation of polyurethane prepolymer:
In the 500mL four-hole boiling flask that agitator, thermometer, prolong are housed; add polyester polyol 26 parts and isoflurane chalcone diisocyanate 30.18 parts; under 500rpm mixing speed and nitrogen protection, be heated to 85 DEG C, reaction to measured-NCO content reaches theoretical value (16.41%).
2) organic silicon modified polyurethane prepolymer:
The thinner regulation system viscosity of 46 parts is added in reaction system, add the hydrophilic chain extender 2 of 5 parts subsequently, 2-dimethylol propionic acid (DMPA), the bis-hydroxypropyl terminated polysiloxane of 3 parts and the dibutyl tin laurate (T-12) of 0.08 part, when NCO content reaches theoretical value (5.41%), the dibasic alcohol of reaction 3.27 parts is added in reactor, react under the condition of 85 DEG C,-NCO content is measured with Di-n-Butyl Amine back titration method, when reaching theoretical value (2.55%), next step reaction can be entered.
3) neutralization of polyurethane prepolymer, emulsification, aqueous phase chain extension:
By step 2) obtained system cools to 40 DEG C, adds the neutralizing agent triethylamine of 3.78 parts, in and after 5min, add 121.20 parts of water dilution emulsifications, improve rotating speed to 1500rpm, emulsification 20min.Reduce mixing speed to 500rpm, the quadrol of 1.66 parts is dissolved in the water of 26.00 parts, was added drop-wise in reaction system with 10 minutes, aqueous phase chain extending reaction 1 hour.After emulsification completes, underpressure distillation goes out butanone, obtains organic-silicon-modified aqueous polyurethane emulsion.
Embodiment 3
An organic-silicon-modified aqueous polyurethane emulsion, it is formulated by following ratio of weight and number by following component:
A preparation for organic-silicon-modified aqueous polyurethane emulsion, it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) preparation of polyurethane prepolymer:
In the 500mL four-hole boiling flask that agitator, thermometer, prolong are housed; add polyester polyol 25 parts and isoflurane chalcone diisocyanate 30.18 parts; under 500rpm mixing speed and nitrogen protection, be heated to 85 DEG C, reaction to measured-NCO content reaches theoretical value (16.86%).
2) organic silicon modified polyurethane prepolymer:
The thinner regulation system viscosity of 44 parts is added in reaction system, add the hydrophilic chain extender 2 of 5 parts subsequently, 2-dimethylol propionic acid (DMPA), the bis-hydroxypropyl terminated polysiloxane of 5 parts and the dibutyl tin laurate (T-12) of 0.06 part, when NCO content reaches theoretical value (5.46%), the dibasic alcohol of reaction 2.66 parts is added in reactor, react under the condition of 85 DEG C,-NCO content is measured with Di-n-Butyl Amine back titration method, when reaching theoretical value (3.11%), next step reaction can be entered.
3) neutralization of polyurethane prepolymer, emulsification, aqueous phase chain extension:
By step 2) obtained system cools to 40 DEG C, adds the neutralizing agent triethylamine of 3.78 parts, in and after 5min, add 117.20 parts of water dilution emulsifications, improve rotating speed to 1500rpm, emulsification 20min.Reduce mixing speed to 500rpm, be dissolved into by the quadrol of 1.99 parts in the water of 25 parts, be added drop-wise in reaction system, drip 10 minutes, aqueous phase chain extending reaction 1 hour, then underpressure distillation went out butanone, obtains organic-silicon-modified aqueous polyurethane emulsion.
Embodiment 4
An organic-silicon-modified aqueous polyurethane emulsion, it is formulated by following ratio of weight and number by following component:
A preparation for organic-silicon-modified aqueous polyurethane emulsion, it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) preparation of polyurethane prepolymer:
In the 500mL four-hole boiling flask that agitator, thermometer, prolong are housed; add polyester polyol 25 parts and isoflurane chalcone diisocyanate 27.17 parts; mixing speed is at 500rpm; be heated to 85 DEG C under nitrogen protection, reaction to measured-NCO content reaches theoretical value (15.66%).
2) organic silicon modified polyurethane prepolymer:
The thinner regulation system viscosity of 44 parts is added in reaction system, add the hydrophilic chain extender 2 of 4 parts subsequently, 2-dimethylol propionic acid (DMPA), the bis-hydroxypropyl terminated polysiloxane of 8 parts and the dibutyl tin laurate (T-12) of 0.06 part, when NCO content reaches theoretical value (4.92%), the dibasic alcohol of reaction 3.27 parts is added in reactor, react under the condition of 85 DEG C,-NCO content is measured with Di-n-Butyl Amine back titration method, when reaching theoretical value (2.56%), next step reaction can be entered.
3) neutralization of polyurethane prepolymer, emulsification, aqueous phase chain extension:
By step 2) obtained system cools to 40 DEG C, adds the neutralizing agent triethylamine of 3.78 parts, in and after 5min, add 102.80 parts of water dilution emulsifications, improve rotating speed to 1500rpm, emulsification 20min.Reduce mixing speed to 500rpm, be dissolved into by the quadrol of 1.63 parts in the water of 25 parts, be added drop-wise in reaction system, drip 10 minutes, aqueous phase chain extending reaction 2 hours, then underpressure distillation went out butanone, obtains organic-silicon-modified aqueous polyurethane emulsion.
Embodiment 5
An organic-silicon-modified aqueous polyurethane emulsion, it is formulated by following ratio of weight and number by following component:
A preparation for organic-silicon-modified aqueous polyurethane emulsion, it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) preparation of polyurethane prepolymer:
In the 500mL four-hole boiling flask that agitator, thermometer, prolong are housed; add polyester polyol 25 parts and isoflurane chalcone diisocyanate 27.17 parts; under 500rpm mixing speed and nitrogen protection, be heated to 85 DEG C, reaction to measured-NCO content reaches theoretical value (15.66%).
2) organic silicon modified polyurethane prepolymer:
The thinner regulation system viscosity of 44 parts is added in above-mentioned reaction system, add the hydrophilic chain extender 2 of 5 parts subsequently, 2-dimethylol propionic acid (DMPA), the bis-hydroxypropyl terminated polysiloxane of 5 parts and the dibutyl tin laurate (T-12) of 0.06 part, when NCO content reaches theoretical value (4.55%), the dibasic alcohol of reaction 3.16 parts is added in reaction system, react under the condition of 85 DEG C,-NCO content is measured with Di-n-Butyl Amine back titration method, when reaching theoretical value (1.72%), next step reaction can be entered.
3) neutralization of polyurethane prepolymer, emulsification, aqueous phase chain extension:
By step 2) obtained system cools to 40 DEG C, adds the neutralizing agent triethylamine of 3.78 parts, in and after 5min, add 102.80 parts of water, improve rotating speed to 1500rpm, dilute emulsification 20min.Reduce mixing speed to 500rpm, be dissolved into by the quadrol of 1.08 parts in the water of 25 parts, be added drop-wise in reaction system, drip 10 minutes, aqueous phase chain extending reaction 1 hour, then underpressure distillation went out butanone, 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 from according to following step of sequentially carrying out:
1) 2-allyloxy trimethyl silane is synthesized
In reactor A, add 20.0g vinylcarbinol, under room temperature and stir speed (S.S.) are 300rmp, slow dropping 41.6g hexamethyldisilazane, after dropwising, is warmed up to 96 DEG C by reaction system, and continue reaction 3 hours in this temperature, stopped reaction, the cut between collecting 91 DEG C;
2) two (the 3-tri-silyloxy propyl group) tetramethyl disiloxane of 1,3-is synthesized
In reactor B, at room temperature, add the Platinic chloride/Virahol of 30.0g2-allyloxy trimethyl silane and 0.2g, after being warmed up to 90 DEG C, slow dropping tetramethyl disiloxane 13.4g, and at said temperature insulation reaction 3h, be then warming up to 110 DEG C of reaction 2h, 144 DEG C/cut is l.067KPa collected in underpressure distillation, obtains light yellow transparent liquid;
3) 1,3-bis-hydroxypropyl tetramethyl disiloxane is synthesized
In reactor C, at room temperature, add 11.5g1, after two (3-tri-silyloxy propyl group) tetramethyl disiloxane, 0.3g acetic acid and the 115ml methyl alcohol of 3-, at being warmed up to 66 DEG C, back flow reaction 7h, then steams excessive methyl alcohol, acetic acid with circulating water type vacuum pump pressure, finally collect the cut of 98-DEG C/3.2KPa, obtain light yellow transparent liquid;
4) bis-hydroxypropyl terminated polysiloxane is prepared
In the reactor, at room temperature, add step 3) 4.2g1 that is prepared into, 3-bis-hydroxypropyl tetramethyl disiloxane and 4.3g octamethylcyclotetrasiloxane, add the trifluoromethane sulfonic acid of 0.015mL after being then warming up to 80 DEG C, and continue reaction 24h at 80 DEG C, then 0.4ml potassium hydroxide/methanol solution neutralization is added, add 0.3ml hydrochloric acid/methanol solution reaction 1h afterwards again, decompression steams low-boiling-point substance, obtains light yellow transparent liquid; Described hydrochloric acid/concentration of methanol solution is 1mol/L.
Embodiment 7
Bis-hydroxypropyl terminated polysiloxane is prepared from according to following step of sequentially carrying out:
1) 2-allyloxy trimethyl silane is synthesized
In reactor A, add 22.0g vinylcarbinol, under room temperature and stir speed (S.S.) are 500rmp, slow dropping 44.0g hexamethyldisilazane, after dropwising, is warmed up to 104 DEG C by reaction system, and continue reaction 4 hours in this temperature, stopped reaction, the cut between collecting 99 DEG C;
2) two (the 3-tri-silyloxy propyl group) tetramethyl disiloxane of 1,3-is synthesized
In reactor B, at room temperature, add the Platinic chloride/Virahol of 33.0g2-allyloxy trimethyl silane and 0.25g, after being warmed up to 95 DEG C, slow dropping tetramethyl disiloxane 15.5g, and at said temperature insulation reaction 4h, be then warming up to 120 DEG C of reaction 3h, 146 DEG C/cut is l.067KPa collected in underpressure distillation, obtains light yellow transparent liquid;
3) 1,3-bis-hydroxypropyl tetramethyl disiloxane is synthesized
In reactor C, at room temperature, add 12.5g1, after two (3-tri-silyloxy propyl group) tetramethyl disiloxane, 0.5g acetic acid and the 120ml methyl alcohol of 3-, at being warmed up to 68 DEG C, back flow reaction 8h, then steams excessive methyl alcohol, acetic acid with circulating water type vacuum pump pressure, finally collect the cut of 99 DEG C/3.2KPa, obtain light yellow transparent liquid;
4) bis-hydroxypropyl terminated polysiloxane is prepared
In the reactor, at room temperature, add step 3) 5.2g1 that is prepared into, 3-bis-hydroxypropyl tetramethyl disiloxane and 5.3g octamethylcyclotetrasiloxane, add the trifluoromethane sulfonic acid of 0.017mL after being then warming up to 85 DEG C, and continue reaction 25h at 85 DEG C, then 0.5ml potassium hydroxide/methanol solution neutralization is added, add 0.4ml hydrochloric acid/methanol solution reaction 2h afterwards again, decompression steams low-boiling-point substance, obtains light yellow transparent liquid; Described hydrochloric acid/concentration of methanol solution is 2mol/L.
Embodiment 8
Bis-hydroxypropyl terminated polysiloxane is prepared from according to following step of sequentially carrying out:
1) 2-allyloxy trimethyl silane is synthesized
In reactor A, add 21.0g vinylcarbinol, under room temperature and stir speed (S.S.) are 400rmp, slow dropping 43.0g hexamethyldisilazane, after dropwising, is warmed up to 102 DEG C by reaction system, and continue reaction 3.5 hours in this temperature, stopped reaction, the cut between collecting 95 DEG C;
2) two (the 3-tri-silyloxy propyl group) tetramethyl disiloxane of 1,3-is synthesized
In reactor B, at room temperature, add the Platinic chloride/Virahol of 32.0g2-allyloxy trimethyl silane and 0.21g, after being warmed up to 92 DEG C, slow dropping tetramethyl disiloxane 15g, and at said temperature insulation reaction 3.5h, be then warming up to 115 DEG C of reaction 2.2h, 145 DEG C/cut is l.067KPa collected in underpressure distillation, obtains light yellow transparent liquid;
3) 1,3-bis-hydroxypropyl tetramethyl disiloxane is synthesized
In reactor C, at room temperature, add 12g1, after two (3-tri-silyloxy propyl group) tetramethyl disiloxane, 0.4g acetic acid and the 117ml methyl alcohol of 3-, at being warmed up to 67 DEG C, back flow reaction 7h, then steams excessive methyl alcohol, acetic acid with circulating water type vacuum pump pressure, finally collect the cut of 98 DEG C/3.2KPa, obtain light yellow transparent liquid;
4) bis-hydroxypropyl terminated polysiloxane is prepared
In the reactor, at room temperature, add step 3) 4.7g1 that is prepared into, 3-bis-hydroxypropyl tetramethyl disiloxane and 4.8g octamethylcyclotetrasiloxane, add the trifluoromethane sulfonic acid of 0.016mL after being then warming up to 82 DEG C, and continue reaction 24h at 82 DEG C, then 0.4ml potassium hydroxide/methanol solution neutralization is added, add 0.3ml hydrochloric acid/methanol solution reaction 1h afterwards again, decompression steams low-boiling-point substance, obtains light yellow transparent liquid; Described hydrochloric acid/concentration of methanol solution is 2mol/L.
Individual raw material in above each embodiment is all commercially available products, except bis-hydroxypropyl terminated polysiloxane is according to embodiment 6-8 manufacture.
The CMA-44 of the preferred Hua Da chemistry of described polyester polyol;
Described isoflurane chalcone diisocyanate is preferably the IPDI that Bayer is produced;
2,2-described dimethylol propionic acids, BDO, Diisopropyl azodicarboxylate, butanone, quadrol are preferably Aladdin 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 to the performance tests such as size, hardness, film-forming temperature, water tolerance, resistance to vinegar, alcohol resistance.
Sreen analysis: adopt Malvern company 3000SHA type nano-particle size analysis instrument test emulsion particle diameter.
Gloss (60 DEG C): according to the test of GB/T9754 regulation.
Hardness: test according to GB/T6739 regulation.
Sticking power: test according to GB/T9286-1998 regulation, drawing compartment distance is 2mm.
Water tolerance: test according to GB/T4893.1-2005 regulation.Water-fast 24 hours, whether paint film there is exception.
Alcohol resistance: testing method is identical with water tolerance, test solution is the ethanolic soln of 50% (volume fraction), and experimental period is 1h, tests after 1 hour, whether normally observes paint film.
Resistance to vinegar: select making vinegar, tested after 1 hour, whether normally observed paint film.
Film-forming temperature: adopt Britain RHOPOINT company MFFTBar-60 minimum film forming temperature tester, the minimum film-forming temperature of test emulsion.
Through the test to each embodiment, the detection data results of the aqueous polyurethane emulsion of silicone resin modification of the present invention is as shown in following table:
The experimental data of each embodiment test of table one silicone resin modified aqueous polyurethane emulsion
Can obviously find out from table one, various embodiments of the present invention all have good water tolerance, alcohol resistance and stain resistance under difficult environmental conditions, and size distribution, all at about 100nm, has very high sticking power and hardness, has good using value.
In sum, the organic-silicon-modified aqueous polyurethane emulsion of various embodiments of the present invention has very high hardness and sticking power, has good water tolerance, alcohol resistance and stain resistance.
Above-mentioned embodiment is just explained in detail technical scheme of the present invention; the present invention has more than and is only confined to above-described embodiment; those skilled in the art should be understood that; every improvement on basis of the present invention according to above-mentioned principle and spirit, substitute, all should within protection scope of the present invention.
Claims (8)
1. an organic silicon modified aqueous polyurethane emulsion, is characterized in that: it is formulated by following ratio of weight and number by following component:
2. a kind of organic silicon modified aqueous polyurethane emulsion according to claim 1, is characterized in that: described bis-hydroxypropyl terminated polysiloxane is prepared from according to following step of sequentially carrying out:
1) 2-allyloxy trimethyl silane is synthesized
In reactor A, add 20.0-22.0 part vinylcarbinol, under room temperature and stir speed (S.S.) are 300-500rmp, slow dropping 41.6-44.0 part hexamethyldisilazane, after dropwising, reaction system is warmed up to 96-104 DEG C, and continues reaction 3-4 hour in this temperature, stopped reaction, the cut between collecting 91-99 DEG C;
2) two (the 3-tri-silyloxy propyl group) tetramethyl disiloxane of 1,3-is synthesized
In reactor B, at room temperature, add 30.0-33.0 part step 1) Platinic chloride/aqueous isopropanol of the 2-allyloxy trimethyl silane that is prepared from and 0.2-0.25 part, after being warmed up to 90-95 DEG C, slow dropping tetramethyl disiloxane 13.4-15.5 part, and at said temperature insulation reaction 3-4h, be then warming up to 110-120 DEG C of reaction 2-3h, 144-146 DEG C/cut is l.067KPa collected in underpressure distillation, obtains light yellow transparent liquid;
Described Platinic chloride/aqueous isopropanol is the massfraction of Platinic chloride is the aqueous isopropanol of 2-3%;
3) 1,3-bis-hydroxypropyl tetramethyl disiloxane is synthesized
In reactor C, at room temperature, add 11.5-12.5 part step 2) be prepared from 1, after two (3-tri-silyloxy propyl group) tetramethyl disiloxane, 0.3-0.5 part acetic acid and the 115-120 part methyl alcohol of 3-, at being warmed up to 66-68 DEG C, back flow reaction 7-8h, then steams excessive methyl alcohol, acetic acid with circulating water type vacuum pump pressure, finally collect the cut of 98-99 DEG C/3.2KPa, obtain light yellow transparent liquid;
4) bis-hydroxypropyl terminated polysiloxane is prepared
In reactor D, at room temperature, add 4.2-5.2 part step 3) be prepared into 1,3-bis-hydroxypropyl tetramethyl disiloxane and 4.3-5.3 part octamethylcyclotetrasiloxane, add the trifluoromethane sulfonic acid of 0.015-0.017 part after being then warming up to 80-85 DEG C, and continue reaction 24-25h at 80-85 DEG C, then 0.4-0.5 part potassium hydroxide/methanol solution neutralization is added, add 0.3-0.4 part hydrochloric acid/methanol solution reaction 1-2h afterwards again, decompression steams low-boiling-point substance, obtains light yellow transparent liquid;
Described potassium hydroxide/methanol solution is the substance withdrawl syndrome of potassium hydroxide is the methanol solution of 1-2mol/L; Described hydrochloric acid/methanol solution is the substance withdrawl syndrome of hydrochloric acid is the methanol solution of 1-2mol/L.
3. a kind of organic silicon modified aqueous polyurethane emulsion according to claim 1, is characterized in that: the polyester polyol of described polyester polyol to be molecular weight be 1000-2000.
4. a kind of organic silicon modified aqueous polyurethane emulsion according to claim 1, is characterized in that: described diluting solvent is the one in acetone, butanone or N-Methyl pyrrolidone.
5. a kind of organic silicon modified aqueous polyurethane emulsion according to claim 1, is characterized in that: described dibasic alcohol is the one in ethylene glycol, propylene glycol, BDO, pentanediol, glycol ether or neopentyl glycol.
6. a kind of organic silicon modified aqueous polyurethane emulsion according to claim 1, is characterized in that: described hydrophilic chain extender is 2,2-dimethylol propionic acid; Described neutralizing agent is triethylamine.
7. an organic silicon modified aqueous polyurethane emulsion, is characterized in that: described organic silicon modified aqueous polyurethane emulsion is according to the following step preparation sequentially carried out:
1) preparation of polyurethane prepolymer:
Add polyester polyol 24.00-26.00 part and isoflurane chalcone diisocyanate 25.36-30.18 part in the reactor, under 300-500rpm mixing speed and nitrogen protection, be heated to 80-85 DEG C, reaction to measured-NCO content reaches theoretical value;
2) preparation of organic silicon modified polyurethane prepolymer:
Then, keep above-mentioned rotating speed and temperature, add the thinner regulation system viscosity of 42.00-46.00 part, then add the hydrophilic chain extender of 4.00-5.00 part, the organosilicon of 1.00-8.00 part and the dibutyl tin laurate of 0.04-0.08 part, start afterwards to measure-NCO content, when-NCO content reaches theoretical value, the dibasic alcohol of 2.66-3.27 part is added in reactor, then start to measure-NCO content, when-NCO content reaches theoretical value, namely obtain organic silicon modified polyurethane prepolymer;
3) neutralization of organic silicon modified polyurethane prepolymer, emulsification, aqueous phase chain extension:
Then keep above-mentioned rotating speed, by step 2) obtained reaction system cools to 30-40 DEG C, adds the neutralizing agent of 2.73-3.78 part, in and 3-5min; Then add 97.98-117.20 part water, improve rotating speed afterwards to 1000-1500rpm, dilution emulsification 15-20min; Then mixing speed is reduced to 300-500rpm, the quadrol of 1.00-2.00 part is dissolved in the water of 24.00-26.00 part, with 10-15 minute, ethylenediamine solution is added drop-wise in reaction system, at aqueous phase chain extending reaction 1-2 hour, then underpressure distillation goes out butanone, obtains organic-silicon-modified aqueous polyurethane emulsion.
8. the preparation of a kind of organic silicon modified polyurethane emulsion according to claim 1, is characterized in that: the measuring method of described-NCO content is Di-n-Butyl Amine back titration method.
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| 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 |
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