CN101792592A - Room-temperature self-crosslinked aqueous polyurethane-polyacrylate containing fluoroalkyl groups in lateral chains and preparation method thereof - Google Patents
Room-temperature self-crosslinked aqueous polyurethane-polyacrylate containing fluoroalkyl groups in lateral chains and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a room-temperature self-crosslinked aqueous polyurethane-polyacrylate containing fluoroalkyl groups in lateral chains and a preparation method thereof. The preparation method comprises following steps: vacuum-dehydrating polyether glycol containing fluorine, and reacting with polyisocyanate to obtain FPU prepolymer containing -NCO end groups; chain-extending with dimethylolpropionic acid to obtain FPU prepolymer containing carboxyl groups; neutralizing with triethylamine to obtain hydrophilic FPU prepolymer, adding water, stirring, and dispersing at high speed to obtain an emulsion; adding a water solution containing a chain extender ADH to obtain chain-extended FPU; orderly adding diacetone acrylamide and vinyl monomer, and initiating by stirring to obtain the PUA copolymerized emulsion; and finally, uniformly mixing the chain-extended FPU with the PUA copolymerized emulsion, coating the mixture on a teflon plate, and drying and crosslinking at room temperature to form the film. The invention can be widely used for surface protection for plastics, rubber, leather, fabrics, ceramics, glass, high-rise building external walls, solar batteries and other materials and devices.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of room-temperature self crosslinking type side chain and contain waterborne polyurethane-polyacrylate (SC-FPUA) of fluoroalkyl and preparation method thereof.
Background technology
General waterborne polyurethane resin is compared with solvent type, has that film formation time is long, gloss is low, a shortcoming such as water-fast, solvent and chemical corrosion resistance difference and hardness are low.For overcoming its applied defect, need be to its modification, main path is by forming stable crosslinking structure, realizing its hydrophilic modifying with the acrylate resin polymerization.The polyurethane-polyacrylate of Water-borne modification (PUA) resin is because of containing carbamate and acrylate simultaneously in its molecular structure, its film-forming thing has high scuff resistance, wear resistance, snappiness, high-tear strength, high tensile, high impact strength and the low-temperature performance etc. of urethane and polyacrylic ester concurrently and remarkable optical property, sticking power and the weathering resistance of giving.
The early-stage Study result of this seminar shows and [sees Chinese invention patent " side chain contains waterborne polyurethane-polyacrylate of fluoroalkyl and preparation method thereof ", the patent No.: 201010108129.6], aqueous fluorine-containing urethane is after acrylate is compound, it is aqueous fluorine-containing polyurethane-polyacrylate (FPUA) emulsion, its cured article has not only kept its inherent excellent properties, and also the existence because of the C-F key has remarkable more low surface energy, UV resistant and nuclear radiation and overlength weathering resistance etc.Be expected to fields such as widespread use Yu Haiyang, aerospace, coastal structures, urban infrastructure construction, petrochemical complex, the energy, maritime facilities, traffic, plastics, rubber, leather, fabric, pottery, glass, food and medicine.Generally, the aqueous fluorine-containing polyurethane-polyacrylate can be under room temperature film-forming (～7 days), the quality that the very big degree influence of environmental factorss such as weather, atmospheric moisture is filmed makes the film performance instability.This obviously is unfavorable for its large-area construction.
Based on above background, press for development a kind of be suitable for industrialized, can be under room temperature fast self-crosslinking, side chain contains waterborne polyurethane-polyacrylate resin emulsion of fluoroalkyl and preparation method thereof, its cured article has good mechanical property, chemicals-resistant corrosive nature and low surface energy etc.
Summary of the invention
Problem to be solved by this invention provide a kind of can large-scale production, high performance, room-temperature self crosslinking type side chain contains waterborne polyurethane-polyacrylate of fluoroalkyl and preparation method thereof.
Know-why of the present invention
Introduce stable self-cross linking type structure in the FPUA structure, promptly form the FPUA emulsion (SC-FPUA) of self-crosslinking, its cured article will have excellent more water-fast, acid and alkali-resistance, antipollution and good mechanical property.The self-crosslinking structure forms under room temperature fast, and not only convenient construction has also shortened construction period, has reduced cost, greatly widens its range of application.
The technical solution used in the present invention
A kind of room-temperature self crosslinking type side chain contains the preparation method of the waterborne polyurethane-polyacrylate of fluoroalkyl
A kind of room-temperature self crosslinking type side chain contains the preparation method of the waterborne polyurethane-polyacrylate of fluoroalkyl, may further comprise the steps:
(1), contains-preparation of NCO end group fluorochemical urethane (FPU) performed polymer
With the fluorochemical polyether polyol resin of 0.2mol processed 1.0～2.0h under 110～120 ℃, vacuum tightness 0.08MPa; the polyisocyanates that adds 0.22～0.30mol again; and feeding nitrogen protection; in 60～80 ℃ of following stirring reaction 1～3h; contained-NCO end group FPU performed polymer, its reaction process is as follows:
a?OCN-R
1-NCO+bHO-R
2-OH→OCN-S-NCO
S represents
Wherein a is 3～10, and b is 1～2;
R wherein
1Be vulcabond, be 4,4 '-diphenylmethanediisocyanate (MDI), 2,4-or 2,6-tolylene diisocyanate (TDI), 1,4-phenylene diisocyanate, 1,5-naphthalene diisocyanate, xylylene vulcabond (XDI), tetramethylxylylene diisocyanate (TMXDI), 1, hexamethylene-diisocyanate (HDI), isophorone diisocyanate (IPDI) or 4,4 '-dicyclohexyl methane diisocyanate (HMDI) removes the last structure of two terminal isocyanate groups;
R wherein
2As follows:
R
2For
M is 0～1 in the said structure formula, and n is 0～3; W is 0～1, and t is 0～3; S is 1～100, and x is 1～100, and z is 1～100, and y is 1～100; R ' representation hydrocarbyl; It is 1～20 fluoroalkyl that RF represents carbon atom;
The described polyisocyanates of step (1) is 4,4 '-diphenylmethanediisocyanate (MDI), 2,4-or 2,6-tolylene diisocyanate (TDI), 1,4-phenylene diisocyanate, 1,5-naphthalene diisocyanate, xylylene vulcabond (XDI), tetramethylxylylene diisocyanate (TMXDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) or 4,4 '-a kind of in the dicyclohexyl methane diisocyanate (HMDI);
The described fluorochemical polyether polyol resin of step (1) is a kind of among molecular weight 1000～10000g/mol;
(2), the preparation of carboxylic hydrophilic FPU performed polymer
To step (1) gained contain-add the wetting ability chainextender dimethylol propionic acid (DMPA) be equivalent to prepolymer quality 6%～10% in NCO end group fluorochemical urethane (FPU) performed polymer, in 80 ℃ of following isothermal reaction 1～3h, obtain carboxylic hydrophilic FPU performed polymer, its reaction formula is as follows:
X wherein
1Be 1～1000;
Wherein s is
B is 1～2, R
1R described in the same step (1)
1
(3), the preparation of salifiable wetting ability FPU prepolymer
The carboxylic hydrophilic FPU of step (2) gained performed polymer is cooled to 10～40 ℃; according to step (2) in the ratio of the mol ratios such as DMPA that added triethylamine (TEA) is added in the reactor; and feeding nitrogen protection; stir 5～30min down in normal pressure, 100～500rpm rotating speed; obtain salifiable wetting ability FPU prepolymer, its reaction equation is as follows:
X wherein
1Be 1～1000;
Wherein s is
B is 1～2, R
1R described in the same step (1)
1
(4), the preparation of emulsification FPU
The salifiable wetting ability FPU prepolymer discharging of step (3) gained in dispersion tank, is placed on the high speed dispersor, and to the distilled water that wherein adds 80mL, vigorous stirring under the dispersion rotating speed of 1000～4000rpm promptly gets emulsification FPU;
(5), the preparation of chain extension type FPU
In the emulsification FPU of step (4) gained, add adipic dihydrazide (ADH) chainextender, stir 5min down, promptly arrive chain extension type FPU in normal pressure, 100～500rpm rotating speed;
Use S
1Expression
Above-mentioned s
1X in the structural formula
1Be 1～1000;
Above-mentioned s
1S is in the structural formula
B is 1～2, R
1R described in the same step (1)
1
Wherein the add-on of chainextender ADH is calculated by itself and emulsification FPU volume ratio, i.e. chainextender ADH: emulsification FPU is 1～5: 100;
(6), the preparation of PUA copolymer emulsion
In the four-hole boiling flask of band stirring arm, thermometer, reflux exchanger and dropping funnel, drip diacetone acrylamide (DAAM) and vinyl monomer mixing solutions, stir down and heat up, and the initiator acetone soln of dropping concentration 1%, 70 ℃ are incubated 0.5h down, are incubated 3～4h again under 75 ℃, reach 97% transformation efficiency to monomer, promptly get the PUA copolymer emulsion, its signal process is as follows:
R
3Be alkyl or alkyl ester structure;
Described vinyl monomer is one or both in the just own ester of vinylformic acid, methacrylic acid, methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, isopropyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, lauryl methacrylate, methacrylic acid, the glycidyl methacrylate etc.;
The add-on of diacetone acrylamide (DAAM) and vinyl monomer mixing solutions is by to wherein adding the vinyl monomer be equivalent to salifiable wetting ability FPU prepolymer quality 5%～30%;
DAAM and vinyl monomer mol ratio are DAAM in DAAM and the vinyl monomer mixing solutions: vinyl monomer is 1～5: 100;
Described initiator is a kind of in Diisopropyl azodicarboxylate (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile), the benzoyl peroxide;
The add-on of initiator acetone soln is 1%～3% of a vinyl monomer quality;
(7), the preparation of FPUA self-crosslinking film under the room temperature
Under the room temperature, with step (5) and (6) made FPU and PUA copolymer emulsion by mass ratio 5～6: 1 mix after, be coated on the polyfluortetraethylene plate, natural drying at room temperature 16～24h, make the thick organic film of about 1mm, this solidification process is at room temperature comparatively fast finished, and ketone hydrazine crosslinking reaction wherein mainly takes place, and equation is as follows:
PU
1Expression
PA
1Expression
S wherein
1For
Above-mentioned s
1X in the structural formula
1Be 1～1000;
Above-mentioned s
1S is in the structural formula
B is 1～2, R
1In the same step (1)
Described R
1
A kind of room-temperature self crosslinking type side chain contains the waterborne polyurethane-polyacrylate of fluoroalkyl
A kind of room-temperature self crosslinking type side chain of preparation method's gained that above-mentioned a kind of room-temperature self crosslinking type side chain contains the waterborne polyurethane-polyacrylate of fluoroalkyl contains the waterborne polyurethane-polyacrylate of fluoroalkyl, its soft segment is the polyether polyol resin structure that contains fluoroalkyl on the side chain, wherein the molecular weight of the polyether polyol resin that contains fluoroalkyl of soft segment is 1000～10000g/mol, and the waterborne polyurethane-polyacrylate emulsion solid content that the room-temperature self crosslinking type side chain of gained of the present invention contains fluoroalkyl is 25%～35%; Its film is 60 °～109 ° to the contact angle of water, and tensile strength is 11.5～17.3MPa, and elongation at break is 100%～300%.
Useful achievement of the present invention
The method that the present invention adopts soft segment lateral chain to introduce fluorin radical is prepared the waterborne polyurethane-polyacrylate that room-temperature self crosslinking type side chain contains fluoroalkyl.Soft segment lateral chain is fluorine-containing is convenient to fluorine-containing groups towards the aligning and enrichment of surface, and the waterborne polyurethane-polyacrylate that made room-temperature self crosslinking type side chain contains fluoroalkyl has characteristics such as excellent heat-resisting, good mechanical property of chemicals-resistant burn into and utmost point low surface energy.The patent No.: 201010108129.6 is film forming set time in about 1 week among the preparation method of the side chain waterborne polyurethane-polyacrylate that contains fluoroalkyl, and film forming curing of the present invention only needs 16～24h, therefore construction period significantly shortens, and has advantage simple to operate, efficient energy-saving.And the fluorine-containing side chain chain length that the prepared room-temperature self crosslinking type side chain of the present invention contains the waterborne polyurethane-polyacrylate of fluoroalkyl is easily controlled, the main chain chemical structure can be regulated according to needs, and water-based emulsion safety, environmental protection, ambient temperature curable have been saved the energy.The coating that adopts this room-temperature self crosslinking type side chain to contain the waterborne polyurethane-polyacrylate of fluoroalkyl will surpass the water-based PUA coating that uses in this Application Areas at present at hardness, aspect such as heat-resisting, weather-proof.Because product of the present invention has cross-linked network structure system is played static stabilization, thereby make the stability of product and obviously be better than the waterborne polyurethane-polyacrylate that uncrosslinked type side chain contains fluoroalkyl work-ing life, thereby can more be widely used for the anticorrosion and antifouling of field surfacings such as ocean, aerospace, coastal structures, urban infrastructure construction, petrochemical complex, the energy, maritime facilities, traffic, plastics, rubber, leather, fabric, pottery, glass, food and medicine, give its automatic cleaning action simultaneously.
Embodiment
Below by embodiment the present invention is described in further detail, but do not limit the present invention.
Embodiment 1
(1) be that the fluorochemical polyether polyol resin of 2000g/mol is in 110 ℃ with the molecular weight of 0.2mol; processed 1.5h under the vacuum tightness 0.08MPa condition adds the MDI of 0.22mol again, and nitrogen protection is stirred down; in 60 ℃ of following isothermal reaction 2h, must contain-NCO end group FPU performed polymer.
(2) the wetting ability chainextender dimethylol propionic acid (DMPA) of adding prepolymer 6% in the performed polymer of made step (1) in 80 ℃ of following isothermal reaction 3h, gets carboxylic hydrophilic FPU performed polymer.
(3) the carboxylic hydrophilic FPU of step (2) gained performed polymer is cooled to 40 ℃; according to ratio triethylamine (TEA) is added in the reactor with mol ratios such as DMPA; and feeding nitrogen protection; stir 15min down fast in normal pressure, 400rpm rotating speed, fully obtain salifiable wetting ability FPU prepolymer after the reaction.
(4) with the discharging of the salifiable wetting ability FPU prepolymer of step (3) in dispersion tank, place on the high speed dispersor, vigorous stirring under the dispersion rotating speed of 1000rpm simultaneously in the distilled water adding system with 80mL, makes it to disperse to form emulsion.
(5) in step (4) dispersion system, add the ADH chainextender that is equivalent to emulsification FPU volume percent 3%; Stir 5min down fast in normal pressure, 500rpm rotating speed, promptly arrive chain extension type FPU-M.
(6) in the four-hole boiling flask of band stirring arm, thermometer, reflux exchanger and dropping funnel, drip the methyl methacrylate (MMA) of 0.6mol and be equivalent to the DAAM mixing solutions of monomer total mass 2%, stir down and heat up, and the solution of the 1%AIBN of dropping monomer total mass, 70 ℃ are incubated 0.5h down, again in 75 ℃ of following insulation 3h, meet the requirements of transformation efficiency to monomer, promptly get the PUA copolymer emulsion.
(7) FPU that step (5) and (6) are made and PUA copolymer emulsion press 6: 1 mixed of mass ratio evenly after, be coated on the polyfluortetraethylene plate, the self-vulcanizing time is 20h, makes the thick organic film of about 1mm.
The solid content that room-temperature self crosslinking type side chain contains the waterborne polyurethane-polyacrylate emulsion of fluoroalkyl is 27%, and its film forming matter is 109 ° to the contact angle of water, and tensile strength is 13.8MPa, and elongation at break is 230%.
Embodiment 2
In the step (1), the molecular weight that will contain the polyether polyol resin of fluoroalkyl changes 1000g/mol into by 2000g/mol, changes dehydration treatment time into 2h by 1.5h, changes the MDI of 0.22mol the HMDI of 0.30mol into, and other step is all identical with embodiment 1.
The solid content that side chain contains the aqueous polyurethane emulsion of fluoroalkyl is 31%, and its film forming matter is 107 ° to the contact angle of water, and tensile strength is 17.3MPa, and elongation at break is 100%.
Embodiment 3
In the step (1), the molecular weight that will contain the polyether polyol resin of fluoroalkyl changes 10000g/mol into by 2000g/mol, change dehydration treatment time into 1h by 1.5h, change treatment temp into 120 ℃ by 110 ℃, change 60 ℃ of following isothermal reaction 2h into 80 ℃ of isothermal reaction 1h, in the step (5), change ADH chainextender add-on into 1% by being equivalent to emulsification FPU volume percent 3%, other step is all identical with embodiment 1.
The solid content that side chain contains the aqueous polyurethane emulsion of fluoroalkyl is 26%, and its film forming matter is 79 ° to the contact angle of water, and tensile strength is 11.5MPa, and elongation at break is 300%.
Embodiment 4
In the step (1), change 60 ℃ of following isothermal reaction 2h into 80 ℃ of isothermal reaction 3h; In the step (2), change wetting ability chainextender dimethylol propionic acid (DMPA) 10% of adding prepolymer into by 6% of adding prepolymer, change 80 ℃ of following isothermal reaction times into 1h by 3h, other step is all identical with embodiment 1.
The solid content that side chain contains the aqueous polyurethane emulsion of fluoroalkyl is 35%, and its film forming matter is 105 ° to the contact angle of water, and tensile strength is 17.8MPa, and elongation at break is 113%.
Embodiment 5
In the step (3), the carboxylic hydrophilic FPU of step (2) gained performed polymer is reduced to temperature change 10 ℃ into by 40 ℃, the 400rpm rotating speed is stirred 15min down fast change the quick 30min of stirring under the 100rpm rotating speed into, in the step (5), to add the ADH chainextender and change 5% into by being equivalent to emulsification FPU volume percent 3%, other step is all identical with embodiment 1.
The solid content that side chain contains the aqueous polyurethane emulsion of fluoroalkyl is 30%, and its film forming matter is 105 ° to the contact angle of water, and tensile strength is 15.5MPa, and elongation at break is 155%.
Embodiment 6
In the step (3), the 400rpm rotating speed is stirred 15min down fast change the quick 5min of stirring under the 500rpm rotating speed into; In the step (4), will disperse rotating speed to change 4000rpm into by 1000rpm, other step is all identical with embodiment 1.
The solid content that side chain contains the aqueous polyurethane emulsion of fluoroalkyl is 29%, and its film forming matter is 96 ° to the contact angle of water, and tensile strength is 14.9MPa, and elongation at break is 125%.
Embodiment 7
In the step (5), the 500rpm rotating speed is stirred 5min down fast change the quick 30min of stirring under the 100rpm rotating speed into; In the step (6), change the add-on of DAAM into 5% by being equivalent to monomer total mass 2%, change the add-on of the solution of AIBN 3% of monomer total mass into by 1% of monomer total mass; In the step (7), changed the mass ratio of FPU and PUA copolymer emulsion into 5: 1 by 6: 1, the self-vulcanizing time changes 16h into by 20h, and other step is all identical with embodiment 1.
The solid content that side chain contains the aqueous polyurethane emulsion of fluoroalkyl is 27%, and its film forming matter is 89 ° to the contact angle of water, and tensile strength is 15.5MPa, and elongation at break is 150%.
Embodiment 8
In the step (6), change methyl methacrylate into butyl methacrylate, change the reaction times into 4h by 3h, IBN changes BPO into initiator A, changes the add-on of DAAM into 1% by being equivalent to monomer total mass 2%; In the step (7), the self-vulcanizing time, other step was all identical with embodiment 1 in order to change 24h into by 20h.
The solid content that side chain contains the aqueous polyurethane emulsion of fluoroalkyl is 23%, and its film forming matter is 60 ° to the contact angle of water, and tensile strength is 15.7MPa, and elongation at break is 180%.
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (5)
1. a room-temperature self crosslinking type side chain contains waterborne polyurethane-polyacrylate of fluoroalkyl and preparation method thereof, it is characterized in that comprising the following steps:
(1), contains-preparation of NCO end group fluorochemical urethane (FPU) performed polymer
With the fluorochemical polyether polyol resin of 0.2mol processed 1.0～2.0h under 110～120 ℃, vacuum tightness 0.08MPa; the polyisocyanates that adds 0.22～0.30mol again; and feeding nitrogen protection; in 60～80 ℃ of following stirring reaction 1～3h; contained-NCO end group FPU performed polymer, its reaction process is as follows:
aOCN-R
1-NCO+bHO-R
2-OH→OCN-S-NCO
Wherein a is 3～10, and b is 1～2;
R wherein
1Be vulcabond, be 4,4 '-diphenylmethanediisocyanate (MDI), 2,4-or 2,6-tolylene diisocyanate (TDI), 1,4-phenylene diisocyanate, 1,5-naphthalene diisocyanate, xylylene vulcabond (XDI), tetramethylxylylene diisocyanate (TMXDI), 1, hexamethylene-diisocyanate (HDI), isophorone diisocyanate (IPDI) or 4,4 '-dicyclohexyl methane diisocyanate (HMDI) removes the last structure of two terminal isocyanate groups;
R wherein
2As follows:
M is 0～1 in the said structure formula, and n is 0～3; W is 0～1, and t is 0～3; S is 1～100, and x is 1～100, and z is 1～100, and y is 1～100; R ' representation hydrocarbyl; It is 1～20 fluoroalkyl that RF represents carbon atom;
The described polyisocyanates of step (1) is 4,4 '-diphenylmethanediisocyanate (MDI), 2,4-or 2,6-tolylene diisocyanate (TDI), 1,4-phenylene diisocyanate, 1,5-naphthalene diisocyanate, xylylene vulcabond (XDI), tetramethylxylylene diisocyanate (TMXDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) or 4,4 '-a kind of in the dicyclohexyl methane diisocyanate (HMDI);
The described fluorochemical polyether polyol resin of step (1) is a kind of among molecular weight 1000～10000g/mol;
(2), the preparation of carboxylic hydrophilic FPU performed polymer
In step (1) gained contain-NCO end group fluorochemical urethane (FPU) performed polymer in, add the wetting ability chainextender dimethylol propionic acid (DMPA) that is equivalent to prepolymer quality 6%～10%, in 80 ℃ of following isothermal reaction 1～3h, obtain carboxylic hydrophilic FPU performed polymer, its reaction formula is as follows:
X wherein
1Be 1～1000;
Wherein s is
B is 1～2, R
1R described in the same step (1)
1
(3), the preparation of salifiable wetting ability FPU prepolymer
The carboxylic hydrophilic FPU of step (2) gained performed polymer is cooled to 10～40 ℃; according to step (2) in the ratio of the mol ratios such as DMPA that added triethylamine (TEA) is added in the reactor; and feeding nitrogen protection; stir 5～30min down in normal pressure, 100～500rpm rotating speed; obtain salifiable wetting ability FPU prepolymer, its reaction equation is as follows:
X wherein
1Be 1～1000;
Wherein s is
B is 1～2, R
1R described in the same step (1)
1
(4), the preparation of emulsification FPU
The salify wetting ability FPU prepolymer discharging of step (3) gained in dispersion tank, is placed on the high speed dispersor, and to the distilled water that wherein adds 80mL, vigorous stirring under the dispersion rotating speed of 1000～4000rpm promptly gets emulsification FPU;
(5), the preparation of chain extension type FPU
In the emulsification FPU of step (4) gained, add adipic dihydrazide (ADH) chainextender, stir 5min down, obtain chain extension type FPU in normal pressure, 100～500rpm rotating speed;
Above-mentioned s
1X in the structural formula
1Be 1～1000;
Above-mentioned s
1S is in the structural formula
B is 1～2, R
1In the same step (1)
Described R
1
Wherein the add-on of chainextender ADH is calculated by itself and emulsification FPU volume ratio, i.e. chainextender ADH: emulsification FPU is 1～5: 100;
(6), the preparation of PUA copolymer emulsion
In the four-hole boiling flask of band stirring arm, thermometer, reflux exchanger and dropping funnel, drip diacetone acrylamide (DAAM) and vinyl monomer mixing solutions, stir down and heat up, and the initiator acetone soln of dropping concentration 1%, 70 ℃ are incubated 0.5h down, are incubated 3～4h again under 75 ℃, reach 97% transformation efficiency to monomer, promptly get the PUA copolymer emulsion, its signal process is as follows:
R
3Be alkyl or alkyl ester structure;
Described vinyl monomer is one or both in the just own ester of vinylformic acid, methacrylic acid, methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, isopropyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, lauryl methacrylate, methacrylic acid, the glycidyl methacrylate etc.;
The add-on of diacetone acrylamide (DAAM) and vinyl monomer mixing solutions is by the vinyl monomer to the quality 5%～30% that wherein adds the salifiable wetting ability FPU prepolymer be equivalent to step (3) gained;
DAAM and vinyl monomer mol ratio, i.e. DAAM in DAAM and the vinyl monomer mixing solutions: vinyl monomer is 1～5: 100;
Described initiator is a kind of in Diisopropyl azodicarboxylate (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile), the benzoyl peroxide;
The add-on of the acetone soln of initiator is 1%～3% of a vinyl monomer quality;
(7), the preparation of FPUA self-crosslinking film under the room temperature
Under the room temperature, FPU that step (5) and (6) are made and PUA copolymer emulsion are by mass ratio 5～6: 1 mix after, be coated on the polyfluortetraethylene plate, natural drying at room temperature 16～24h, make the thick organic film of about 1mm, this solidification process is finished under room temperature, and ketone hydrazine crosslinking reaction wherein mainly takes place, and equation is as follows:
S wherein
1For
Above-mentioned s
1X in the structural formula
1Be 1～1000;
Above-mentioned s
1S is in the structural formula
B is 1～2, R
1R described in the same step (1)
1
2. an a kind of room-temperature self crosslinking type side chain as claimed in claim 1 room-temperature self crosslinking type side chain that contains the waterborne polyurethane-polyacrylate preparation method gained of fluoroalkyl contains the waterborne polyurethane-polyacrylate of fluoroalkyl, and the waterborne polyurethane-polyacrylate soft segment that the room-temperature self crosslinking type side chain that it is characterized in that gained contains fluoroalkyl is the polyether glycol structure that contains fluoroalkyl on the side chain.
3. an a kind of room-temperature self crosslinking type side chain as claimed in claim 1 room-temperature self crosslinking type side chain that contains the waterborne polyurethane-polyacrylate preparation method gained of fluoroalkyl contains the waterborne polyurethane-polyacrylate of fluoroalkyl, and the waterborne polyurethane-polyacrylate that the side chain that it is characterized in that gained contains fluoroalkyl is the self-vulcanizing self-cross linking type.
4. the room-temperature self crosslinking type side chain that a kind of room-temperature self crosslinking type side chain according to claim 2 contains the waterborne polyurethane-polyacrylate preparation method gained of fluoroalkyl contains the waterborne polyurethane-polyacrylate of fluoroalkyl, and it is 1000～10000g/mol that the room-temperature self crosslinking type side chain that it is characterized in that gained contains the molecular weight that contains the polyether polyol resin of fluoroalkyl on the side chain of waterborne polyurethane-polyacrylate of fluoroalkyl.
5. an a kind of room-temperature self crosslinking type side chain as claimed in claim 1 room-temperature self crosslinking type side chain that contains the waterborne polyurethane-polyacrylate preparation method gained of fluoroalkyl contains the waterborne polyurethane-polyacrylate emulsion of fluoroalkyl, the waterborne polyurethane-polyacrylate emulsion solid content that the room-temperature self crosslinking type side chain that it is characterized in that gained contains fluoroalkyl is 25%～35%, its film is 60 °～109 ° to the contact angle of water, tensile strength is 11.5～17.3MPa, and elongation at break is 100%～300%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010115802 CN101792592A (en) | 2010-03-02 | 2010-03-02 | Room-temperature self-crosslinked aqueous polyurethane-polyacrylate containing fluoroalkyl groups in lateral chains and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010115802 CN101792592A (en) | 2010-03-02 | 2010-03-02 | Room-temperature self-crosslinked aqueous polyurethane-polyacrylate containing fluoroalkyl groups in lateral chains and preparation method thereof |
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| CN101792592A true CN101792592A (en) | 2010-08-04 |
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| CN 201010115802 Pending CN101792592A (en) | 2010-03-02 | 2010-03-02 | Room-temperature self-crosslinked aqueous polyurethane-polyacrylate containing fluoroalkyl groups in lateral chains and preparation method thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757546A (en) * | 2012-07-30 | 2012-10-31 | 富思特新材料科技有限公司 | Preparation method of self-crosslinking aqueous polyurethane for terrace |
| CN103668957A (en) * | 2012-09-17 | 2014-03-26 | 湖北中科博策新材料研究院 | Crosslinked curing agent for improving washing resistance of three-proofing finishing agent of fabric |
| CN103772692A (en) * | 2013-12-27 | 2014-05-07 | 南京信息工程大学 | Copolymerized glycol of perfluoroalkyl glycidyl ethers and cyclic ether and preparation method of copolymerized glycol |
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| CN109439264A (en) * | 2018-12-04 | 2019-03-08 | 顺德职业技术学院 | Response type fluorine richness flame retardant polyurethane hot melt adhesive and preparation method thereof |
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| CN113801366A (en) * | 2020-06-12 | 2021-12-17 | 万华化学集团股份有限公司 | Thermal expansion microsphere and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6423809B1 (en) * | 1999-04-01 | 2002-07-23 | Alcatel | Polyurethane acrylate or vinyl type polymeric material for coating optical fibers based on a fluorinated diol |
| CN1995087A (en) * | 2006-12-27 | 2007-07-11 | 武汉工程大学 | High solid share fluorine-containing polyurethane preparation method |
| CN101220192A (en) * | 2007-09-30 | 2008-07-16 | 安徽大学 | Synthesis of fluoridation aquosity polyurethane-polyacrylate composite emulsion |
| CN101230120A (en) * | 2008-01-10 | 2008-07-30 | 安徽大学 | Radiation polymerization method for aqueous polyurethane-fluorine containing acrylic ester emulsion |
| CN101519479A (en) * | 2009-01-22 | 2009-09-02 | 广东天银化工实业有限公司 | Method for preparing self-cross linking type water-based fluorine-contained acrylic resin and polyurethane hybrid |
-
2010
- 2010-03-02 CN CN 201010115802 patent/CN101792592A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6423809B1 (en) * | 1999-04-01 | 2002-07-23 | Alcatel | Polyurethane acrylate or vinyl type polymeric material for coating optical fibers based on a fluorinated diol |
| CN1995087A (en) * | 2006-12-27 | 2007-07-11 | 武汉工程大学 | High solid share fluorine-containing polyurethane preparation method |
| CN101220192A (en) * | 2007-09-30 | 2008-07-16 | 安徽大学 | Synthesis of fluoridation aquosity polyurethane-polyacrylate composite emulsion |
| CN101230120A (en) * | 2008-01-10 | 2008-07-30 | 安徽大学 | Radiation polymerization method for aqueous polyurethane-fluorine containing acrylic ester emulsion |
| CN101519479A (en) * | 2009-01-22 | 2009-09-02 | 广东天银化工实业有限公司 | Method for preparing self-cross linking type water-based fluorine-contained acrylic resin and polyurethane hybrid |
Non-Patent Citations (2)
| Title |
|---|
| 《安徽大学学报(自然科学版)》 200907 吴庆云,杨建军,王小君,张建安,吴明元,瞿贤超,崔国庭 酮肼交联型聚氨酯-氟化聚丙烯酸酯乳液的制备 75-80 1-5 第33卷, 第4期 2 * |
| 《涂料工业》 200704 王小君,杨建军,吴庆云,张建安,吴明元 氟化聚氨酯-丙烯酸酯乳液研究进展 55-58 1-5 第37卷, 第4期 2 * |
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| CN107760144A (en) * | 2017-10-24 | 2018-03-06 | 上海应用技术大学 | A kind of antibiosis and self-cleaning type aqueous fluorine-containing polyurethane coating and preparation method thereof |
| CN109337429A (en) * | 2018-08-03 | 2019-02-15 | 广东中星科技股份有限公司 | A kind of aqueous mallear stria agent and the aqueous polyurethane paint using mallear stria agent |
| CN109439264A (en) * | 2018-12-04 | 2019-03-08 | 顺德职业技术学院 | Response type fluorine richness flame retardant polyurethane hot melt adhesive and preparation method thereof |
| CN110982418A (en) * | 2019-12-24 | 2020-04-10 | Ppg涂料(天津)有限公司 | Aqueous pigmented paint coating compositions with color stability |
| CN113801366A (en) * | 2020-06-12 | 2021-12-17 | 万华化学集团股份有限公司 | Thermal expansion microsphere and preparation method thereof |
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| CN115417972A (en) * | 2022-10-09 | 2022-12-02 | 安徽圣达生物药业有限公司 | Aromatic waterborne polyurethane resin and preparation method thereof |
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