CN107501506A - A kind of high-temperature resistant waterborne polyurethane and preparation method thereof - Google Patents
A kind of high-temperature resistant waterborne polyurethane and preparation method thereof Download PDFInfo
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- CN107501506A CN107501506A CN201710700297.6A CN201710700297A CN107501506A CN 107501506 A CN107501506 A CN 107501506A CN 201710700297 A CN201710700297 A CN 201710700297A CN 107501506 A CN107501506 A CN 107501506A
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- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
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- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
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- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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Abstract
The present invention relates to new material the field of chemical synthesis, discloses a kind of high-temperature resistant waterborne polyurethane and preparation method thereof, and the aqueous polyurethane includes：20 60 parts of aromatic polyester polyol, 10 20 parts of aromatic polyisocyanate, 28 parts of small molecule chain extender, 28 parts of hydrophilic chain extender, 0.01 0.05 parts of catalyst, 48 parts of the silanol-modified epoxy resin of diphenyl two, hydroxyalkyl 5 15 parts of methyl phenyl siloxane of end-blocking, 28 parts of nertralizer, 40 100 parts of deionized water.Preparation method is：（1）Aromatic polyester polyol, siloxane reactions, add aromatic polyisocyanate, catalyst reaction；（2）Add hydrophilic chain extender reaction；（3）Sequentially add epoxy resin, nertralizer, small molecule chain extender reaction.The aqueous polyurethane of the present invention obtains via the good Material synthesis of heat resistance, and substantially increases its heat-resisting quantity by epoxy resin and the dual modified of organosilicon.
Description
Technical field
The present invention relates to new material the field of chemical synthesis, more particularly to a kind of high-temperature resistant waterborne polyurethane and its preparation side
Method.
Background technology
Aqueous polyurethane is to replace organic solvent as the polyurethane system of decentralized medium using water, with solvent borne polyurethane phase
There is nontoxic, nonflammable, environmentally friendly, and the controllability of aqueous polyurethane structure-performance than, aqueous polyurethane
Make its property of flexible body and plastics and excellent wearability and adhesive force etc. simultaneously, thus in building, furniture, skin
The departments such as leather, weaving, automobile, printing use more and more common.
Contain the carbamate groups (- NHCOO-) construction unit repeated, amino first in the molecular backbone of aqueous polyurethane
The initial pyrolyzation temperature of acid esters key is relatively low, is 140-160 DEG C；Along with the molecular structure of aqueous polyurethane is mostly linear, compared with
Few crosslinking；Thus the heat-resisting quantity of aqueous polyurethane is generally poor at this stage.When temperature is at 80-90 DEG C, some weights of polyurethane
The mechanical property wanted, such as modulus, intensity, it can all be decreased obviously, if processing temperature is more than 200 DEG C, polyurethane will be sent out
Heat is degraded, and far from the requirement for meeting to have heat resistance demand material, this limits answering for aqueous polyurethane to a certain extent
Use field.
The heat resistance of aqueous polyurethane depends primarily on the state of aggregation of molecular chain structure and molecule, generally with softening temperature and
Heat decomposition temperature is weighed.Heat resistance influence of the species of isocyanates on aqueous polyurethane is very big, in general, isocyanic acid
Rigidity, regularity, the symmetry of ester are better, and the thermostabilization of water-base polyurethane material is higher.Diamine chain extenders can form urea bond,
Urea bond polarity and hydrogen bond action are more than ammonia ester bond, therefore heat resistance is better than glycol chain extender；In addition chain extender symmetry
Higher, heat resistance is better.For PAUR containing highly polar ester group, the polar group in soft segment can part and the pole in hard section
Property group formed hydrogen bond, make hard section mutually can be more evenly distributed in soft segment phase, play a part of resilient, crosslinked point, therefore polyester-type
The heat resistance of polyurethane, resistance to thermal degradation are better than polyether-type.
Except finding satisfactory synthesis material, it can also be modified by composite copolymerization and improve the hot steady of aqueous polyurethane
It is qualitative.The main method for improving aqueous polyurethane heat resistance at present is that aqueous polyurethane is changed using heat-resist composition
Property, such as silicate modified, acrylate modified, organobentonite is modified.
The content of the invention
In order to solve the above-mentioned technical problem, the invention provides a kind of high-temperature resistant waterborne polyurethane and preparation method thereof.This
The aqueous polyurethane of invention obtains via the good Material synthesis of heat resistance, and passes through the dual modified big of epoxy resin and organosilicon
Its heat-resisting quantity is improved greatly.
The present invention concrete technical scheme be：A kind of high-temperature resistant waterborne polyurethane, including the component of following parts by weight are made：
Aromatic polyester polyol 20-60 parts,
Aromatic polyisocyanate 10-20 parts,
Small molecule chain extender 2-8 parts,
Hydrophilic chain extender 2-8 parts,
Catalyst 0.01-0.05 parts,
The silanol-modified epoxy resin 4-8 parts of diphenyl two,
Hydroxyalkyl blocks methyl phenyl siloxane 5-15 parts,
Nertralizer 2-8 parts,
Deionized water 40-100 parts.
Epoxy resin is the high-molecular compound containing two or more epoxide groups in molecule.Except epoxy radicals with
Outside, hydroxyalkyl-functional is also contained in epoxy resin, can be with hydrotropism's polyurethane in the course of reaction with aqueous polyurethane
Introduce more branched structures in main chain, form partial mesh topology, so as to improve the tensile strength of aqueous polyurethane film, resistance to
Water-based, heat resistance, solvent resistance and chemical-resistant.In the presence of a catalyst, isocyanate groups (- NCO) meeting and epoxy radicals
Reaction generation oxazolidone ring, the polymer containing the structure is generally in high-fire resistance.
In addition the present invention is modified from modified epoxy resin as raw material to polyurethane, and diphenyl two is silanol-modified
Epoxy resin afterwards can further improve the heat resistance of product.
Organosilicon is the general designation of silane monomer and polysiloxanes, and polysiloxane is containing weight on a kind of strand main chain
Multiple Si-O keys, organic group are directly bonded to polymer on the silicon atoms.This special construction and composition of organosilicon, assign
It has the advantages that preferable high temperature resistant, water resistance, weatherability and excellent gas permeability and low-surface-energy, is modified with it water-based
Polyurethane must can greatly improve WPU temperature tolerance and water resistance.The mode of polymer modification is generally divided into blending and modifying and copolymerization
It is modified two kinds, but in organic silicon modified aqueous polyurethane, it is simple common because organosilicon and polyurethane solubility parameters differ greatly
Mixed, in-situ polymerization or the result for forming interpenetrating net polymer, it is all unsatisfactory；And by containing end hydroxyalkyl or end ammonia
The polysiloxanes of base carries out copolyreaction with diisocyanate or chain extender, is that organosilicon is modified more effective approach to WPU.
In addition the present invention is modified from modified organosilicon as raw material to polyurethane, modified siloxane molecule
Phenyl is connected with chain, can further improve resistance to elevated temperatures.
And because above-mentioned organosilicon and epoxy resin are pre- modifications, also overcome during modified polyurethane is prepared
Because the reaction time is shorter, technical problem that modifier can not be fully grafted.
The present invention it is dual modified by epoxy resin and organosilicon, can cooperate with enhancing aqueous polyurethane heat resistance, and
Realize and have complementary advantages in other performances.
Preferably, the aromatic polyester polyol is selected from benzoic anhydride polyester polyol, to benzene PEPA；The benzene
Acid anhydride PEPA, the molecular weight to benzene PEPA are 900-1100 or 1900-2100.
Preferably, the aromatic polyisocyanate is selected from PPDI, 1,5- naphthalene diisocyanates, diformazan
Base biphenyl diisocyanate, methyl diphenylene diisocyanate.
Preferably, the preparation method of the hydroxyalkyl end-blocking methyl phenyl siloxane is：
In the reaction bulb equipped with agitating device, reflux and thermometer, 45-55 mass parts hydroxyalkyls silicone oil, 45-55 are added
Mass parts 2,4,6- trimethyls -2,4,6- triphenyls cyclotrisiloxane, the ammoniacal liquor that 3-5 mass parts concentration is 23-27wt%, stirring
Under be warming up to 45-55 DEG C reaction 1.5-2.5 hours, then heat to 95-105 DEG C continue react 4-6 hours, be cooled to 45-55
DEG C, add 0.8-1.2 mass parts glacial acetic acid and neutralize, be evaporated under reduced pressure removing low-boiling-point substance and produce hydroxyalkyl end-blocking aminomethyl phenyl silica
Alkane.
Preferably, the hydroxyalkyl silicone oil is selected from hydroxypropyl silicone oil, hydroxyl butyl silicone oil, described hydroxypropyl silicone oil, hydroxyl
The molecular weight of butyl silicone oil is 1000-2000.
Preferably, the preparation method of the two silanol-modified epoxy resin of diphenyl is：
35-45 mass parts epoxy resin is well mixed with 0.08-0.12 mass parts stannous octoates, is slowly added to 8-12 mass parts
After the silanol of diphenyl two, it is passed through nitrogen and is warming up to 145-155 DEG C of reaction 1.5-2.5 hour to obtain diphenyl two silanol-modified
Epoxy resin.
Preferably, the epoxy resin is selected from epoxy resin E-20, E-44, E-51, E-54.
Preferably, the hydrophilic chain extender is selected from 2,2- dihydromethyl propionic acids, 2,2- dimethylolpropionic acids；It is described small
Molecule chain extender is selected from ethylenediamine, IPD, diethylenetriamine.
Preferably, the catalyst is selected from dibutyl tin laurate, stannous octoate.
Preferably, the solvent is selected from acetone, butanone, tetrahydrofuran；The nertralizer is selected from triethylamine, three ethanol
Amine, ammoniacal liquor.
A kind of preparation method of high-temperature resistant waterborne polyurethane, comprises the following steps：
(1) aromatic polyester polyol, hydroxyalkyl end-blocking methyl phenyl siloxane are added in reaction bulb, 95-105 DEG C of decompression is steamed
30-60 minutes are evaporated, until water content is less than 0.5%, 50-60 DEG C is cooled to, adds aromatic polyisocyanate, catalyst, rise
Warm to 70-90 DEG C reaction 2-4 hour.
(2) 50-60 DEG C is cooled to, adds hydrophilic chain extender, is warming up to 70-90 DEG C of reaction 2-4 hour, until NCO contains
Amount reaches theoretical value, obtains organic silicon modified aqueous polyurethane performed polymer.
(3) two silanol-modified epoxy resin of diphenyl is dissolved with solvent, it is pre- is added to organic silicon modified aqueous polyurethane
In aggressiveness, in 70-90 DEG C of insulation reaction 1-3 hour, 40-60 DEG C is cooled to, and with after solvent viscosity reduction, adds nertralizer, is reacted
15-30 minutes, the deionized water dissolved with small molecule chain extender is added, high-speed stirred, removing solvent is evaporated under reduced pressure and obtains asphalt mixtures modified by epoxy resin
Fat and the dual modified high-temperature resistant waterborne polyurethane of organosilicon.
Preferably, in step (3), the high-speed stirred rotating speed is 1800-2500rpm, and mixing time is 30-45 points
Clock.
It is compared with the prior art, the beneficial effects of the invention are as follows：
1st, the present invention selects a variety of different heat-resist copolymerization components, and by multiple elements design modified method, to water-based poly-
Urethane is modified, so as to improve the heat-resisting quantity of aqueous polyurethane.
2nd, the present invention is modified using hydroxyalkyl end-blocking methyl phenyl siloxane to aqueous polyurethane, anti-with isocyanates
The group that should be generated is Si-C-O- of bondings, and hydrolytic resistance is good, more suitable for the application environment that water-based system is complicated, this hair in addition
It is bright that polyurethane is modified as raw material from modified organosilicon, it is connected with phenyl, energy on modified siloxane molecule chain
It is enough further to improve resistance to elevated temperatures.And because organosilicon is pre- modification, also overcomes and preparing modified polyurethane process
In due to the reaction time it is shorter, the technical problem that modifier can not be fully grafted.
3rd, the present invention is changed using two silanol-modified epoxy resin of diphenyl by grafting copolymerization process to aqueous polyurethane
Property, so as to introduce epoxy construction, in film forming solidification process, epoxide group can be with raw into oxazolidone with NCO reaction
Ring, the heat resistance of aqueous polyurethane is further improved, the present invention selects modified epoxy resin as raw material to polyurethane in addition
It is modified, the epoxy resin after diphenyl two is silanol-modified can further improve the heat resistance of product.And due to epoxy
Resin is pre- modification, is also overcomed because the reaction time is shorter during modified polyurethane is prepared, modifier can not be filled
Tap the technical problem of branch.
4th, organic silicon modified aqueous polyurethane, which removes improved heat resistance, can also increase the flexibility and water resistance of aqueous polyurethane,
It is dual modified by epoxy resin and organosilicon and epoxy resin modification can strengthen the stability and adhesive force of aqueous polyurethane,
The heat resistance of enhancing aqueous polyurethane can be cooperateed with, and realizes and has complementary advantages in other performances.
5th, synthetic method of the invention it is simple, conveniently, be easy to industrialize, adhere to after obtained resin film forming with coating substrate
Power is good, can be used on a variety of surfaces such as glass, PVC board and sheet metal.
Embodiment
With reference to embodiment, the invention will be further described.
The preparation method of the high-temperature resistant waterborne polyurethane of the present invention, comprises the following steps：
(1) 20-60 parts (parts by weight, similarly hereinafter) aromatic polyester polyol, 5-15 parts hydroxyalkyl are blocked into aminomethyl phenyl silica
Alkane is added in reaction bulb, 100 DEG C of vacuum distillation 30-60 minutes, until water content is less than 0.5%, is cooled to 50-60 DEG C, is added
10-20 parts aromatic polyisocyanate, 0.01-0.05 part catalyst, it is warming up to 70-90 DEG C of reaction 2-4 hour；
(2) 50-60 DEG C is cooled to, adds 2-8 part hydrophilic chain extenders, is warming up to 70-90 DEG C of reaction 2-4 hour, until NCO contains
Amount reaches theoretical value, obtains organic silicon modified aqueous polyurethane performed polymer.
(3) two silanol-modified epoxy resin of 4-8 parts diphenyl 5-10 parts solvent is dissolved, is added to organic-silicon-modified water
In property base polyurethane prepolymer for use as, in 70-90 DEG C of insulation reaction 1-3 hour, 40-60 DEG C is cooled to, and with after 5-10 part solvent viscosity reductions,
2-8 part nertralizers are added, 15-30 minutes is reacted, adds 40-100 part deionized waters dissolved with 2-8 part small molecule chain extenders, it is high
Speed stirring (1800-2500rpm) 30-45 minutes, vacuum distillation removing solvent obtains epoxy resin and organosilicon is dual modified
High-temperature resistant waterborne polyurethane.
Wherein,
In preparation process, described aromatic polyester polyol is selected from benzoic anhydride polyester polyol, to benzene PEPA, described
Benzoic anhydride polyester polyol, the molecular weight to benzene PEPA are 900-1100 or 1900-2100；
In preparation process, described hydroxyalkyl end-blocking methyl phenyl siloxane is prepared by procedure below：
In the reaction bulb equipped with agitating device, reflux and thermometer, 50 mass parts hydroxyalkyl silicone oil, 50 mass parts are added
2,4,6- trimethyls -2,4,6- triphenyls cyclotrisiloxane, 4 mass parts ammoniacal liquor (25wt%), 50 DEG C of reactions 2 are warming up under stirring
Hour, then heat to 100 DEG C and continue reaction 5 hours, be cooled to 50 DEG C, add 1 mass parts glacial acetic acid and neutralize, vacuum distillation removes
Low-boiling-point substance is gone to produce hydroxyalkyl end-blocking methyl phenyl siloxane；
Described hydroxyalkyl silicone oil is selected from hydroxypropyl silicone oil, hydroxyl butyl silicone oil, described hydroxypropyl silicone oil, point of hydroxyl butyl silicone oil
Son amount is 1000-2000；
In preparation process, described aromatic polyisocyanate is selected from PPDI, 1,5- naphthalene diisocyanates, diformazan
Base biphenyl diisocyanate, methyl diphenylene diisocyanate；
In preparation process, described catalyst is selected from dibutyl tin laurate, stannous octoate；
In preparation process, described small molecule hydrophilic chain extender is selected from 2,2- dihydromethyl propionic acids, 2,2- dimethylolpropionic acids；
In preparation process, described two silanol-modified epoxy resin of diphenyl is prepared by procedure below：
40 mass parts epoxy resin are well mixed with 0.1 mass parts stannous octoate, are slowly added to the silicon of 10 mass parts diphenyl two
After alcohol, it is passed through nitrogen and is warming up to 150 DEG C of reactions and obtain two silanol-modified epoxy resin of diphenyl in 2 hours；
Described epoxy resin is selected from epoxy resin E-20, E-44, E-51, E-54；
In preparation process, described solvent is selected from acetone, butanone, tetrahydrofuran；
In preparation process, described nertralizer is selected from triethylamine, triethanolamine, ammoniacal liquor；
In preparation process, described small molecule chain extender is selected from ethylenediamine, IPD, diethylenetriamine；
Embodiment 1
(1) the hydroxypropyl silicon for being 1000 by benzoic anhydride polyester polyol that 20 parts of (parts by weight) molecular weight are 1000,5 parts of molecular weight
Oil sealing terminal methyl phenyl siloxane is added in reaction bulb, and 100 DEG C are evaporated under reduced pressure 30 minutes, until water content is less than 0.5%, cooling
To 50 DEG C, 10 parts of PPDIs, 0.01 part of dibutyl tin laurate are added, 70 DEG C is warming up to and reacts 4 hours；
(2) 50 DEG C are cooled to, adds 2 parts of 2,2- dihydromethyl propionic acids, 70 DEG C is warming up to and reacts 4 hours, measure NCO content and reach
Theoretical value, obtain organic silicon modified aqueous polyurethane performed polymer；
(3) by the silanol-modified epoxy resin E-20 of 4 parts of diphenyl two with 5 parts of acetone solutions, it is added to organic silicon modified aqueous poly-
In urethane performed polymer, in 70 DEG C of insulation reactions 3 hours, 40 DEG C are cooled to, and with after 5 parts of acetone viscosity reductions, adds 2 parts of triethylamines,
Reaction 30 minutes, adds 40 parts of deionized waters dissolved with 2 parts of ethylenediamines, high-speed stirred (1800rpm) 45 minutes, vacuum distillation removes
Solvent is gone to obtain epoxy resin and the dual modified high-temperature resistant waterborne polyurethane of organosilicon.
Embodiment 2
(1) the hydroxyl butyl silicone oil for being 1000 to benzene PEPA, 15 parts of molecular weight that 60 parts of molecular weight are 1000 is blocked into first
Base phenyl siloxane is added in reaction bulb, and 100 DEG C are evaporated under reduced pressure 60 minutes, until water content is less than 0.5%, are cooled to 60 DEG C,
20 parts of 1,5- naphthalene diisocyanates, 0.05 part of stannous octoate are added, 90 DEG C is warming up to and reacts 2 hours；
(2) 60 DEG C are cooled to, adds 8 parts of 2,2- dimethylolpropionic acids, 90 DEG C is warming up to and reacts 2 hours, measure NCO content and reach
Theoretical value, obtain organic silicon modified aqueous polyurethane performed polymer；
(3) 8 parts of two silanol-modified epoxy resin E-44s of diphenyl are dissolved with 10 parts of butanone, be added to organic silicon modified aqueous poly-
In urethane performed polymer, in 90 DEG C of insulation reactions 3 hours, 60 DEG C are cooled to, and with after 10 parts of butanone viscosity reductions, add 8 part of three ethanol
Amine, react 15 minutes, add 100 parts of deionized waters dissolved with 8 parts of IPDs, high-speed stirred (2500rpm) 30 minutes,
It is evaporated under reduced pressure and removes solvent and obtain epoxy resin and the dual modified high-temperature resistant waterborne polyurethane of organosilicon.
Embodiment 3
(1) the hydroxypropyl silicone oil that benzoic anhydride polyester polyol that 40 parts of molecular weight are 2000,10 parts of molecular weight are 2000 is blocked into first
Base phenyl siloxane is added in reaction bulb, and 100 DEG C are evaporated under reduced pressure 60 minutes, until water content is less than 0.5%, are cooled to 60 DEG C,
15 parts of dimethyl diphenyl diisocyanate, 0.02 part of dibutyl tin laurate are added, 80 DEG C is warming up to and reacts 3 hours；
(2) 60 DEG C are cooled to, adds 5 parts of 2,2- dihydromethyl propionic acids, 90 DEG C is warming up to and reacts 2 hours, measure NCO content and reach
Theoretical value, obtain organic silicon modified aqueous polyurethane performed polymer；
(3) the silanol-modified epoxy resin E-51 of 5 parts of diphenyl two is dissolved with 8 parts of tetrahydrofurans, is added to organic-silicon-modified water
Property base polyurethane prepolymer for use as in, in 90 DEG C of insulation reactions 2 hours, be cooled to 60 DEG C, and with after 8 parts of tetrahydrofuran viscosity reductions, add 5 parts
Ammoniacal liquor, react 20 minutes, add 60 parts of deionized waters dissolved with 5 parts of diethylenetriamines, high-speed stirred (2500rpm) 30 minutes,
It is evaporated under reduced pressure and removes solvent and obtain epoxy resin and the dual modified high-temperature resistant waterborne polyurethane of organosilicon.
Embodiment 4
(1) the hydroxyl butyl silicone oil for being 2000 to benzene PEPA, 15 parts of molecular weight that 60 parts of molecular weight are 2000 is blocked into first
Base phenyl siloxane is added in reaction bulb, and 100 DEG C are evaporated under reduced pressure 60 minutes, until water content is less than 0.5%, are cooled to 60 DEG C,
20 parts of methyl diphenylene diisocyanates, 0.05 part of dibutyl tin laurate are added, 90 DEG C is warming up to and reacts 2 hours；
(2) 60 DEG C are cooled to, adds 8 parts of 2,2- dimethylolpropionic acids, 90 DEG C is warming up to and reacts 2 hours, measure NCO content and reach
Theoretical value, obtain organic silicon modified aqueous polyurethane performed polymer；
(3) by the silanol-modified epoxy resin E-54 of 8 parts of diphenyl two with 10 parts of acetone solutions, it is added to organic silicon modified aqueous poly-
In urethane performed polymer, in 90 DEG C of insulation reactions 1 hour, 60 DEG C are cooled to, and with after 10 parts of acetone viscosity reductions, adds 8 parts of triethylamines,
Reaction 30 minutes, 100 parts of deionized waters dissolved with 8 parts of ethylenediamines are added, high-speed stirred (1800rpm) 45 minutes, are evaporated under reduced pressure
Remove solvent and obtain epoxy resin and the dual modified high-temperature resistant waterborne polyurethane of organosilicon.
Comparative example 1A-4A
For embodiment 1-4 except hydroxyalkyl end-blocking methyl phenyl siloxane is not added, other raw materials and step are identical.
Comparative example 1B-4B
For embodiment 1-4 except two silanol-modified epoxy resin of diphenyl is not added, other raw materials and step are identical.
Performance test：
The high-temperature resistant waterborne polyurethane that embodiment 1-4, comparative example 1A-4A and comparative example 1B-4B are obtained carries out thermogravimetric analysis, obtains
To initial pyrolyzation temperature.
Test result：High-temperature resistant waterborne polyurethane resistance to elevated temperatures test result such as table 1；
Table 1：High-temperature resistant waterborne polyurethane resistance to elevated temperatures test result
| Numbering | Initial pyrolyzation temperature/DEG C |
| Embodiment 1 | 292 |
| Comparative example 1A | 235 |
| Comparative example 1B | 244 |
| Embodiment 2 | 313 |
| Embodiment 2A | 250 |
| Embodiment 2B | 257 |
| Embodiment 3 | 298 |
| Embodiment 3A | 241 |
| Embodiment 3B | 250 |
| Embodiment 4 | 306 |
| Embodiment 4A | 251 |
| Embodiment 4B | 263 |
The initial pyrolyzation temperature of unmodified aqueous polyurethane is compared at 200 DEG C or so, embodiment 1-4 initial pyrolyzation temperature
Higher than 290 DEG C, more than 90 DEG C are improved, illustrates that the high-temperature resistant waterborne polyurethane of the present invention effectively improves heat-resisting quantity；Implement
Example 1-4 initial pyrolyzation temperature improves more than 55 DEG C than comparative example 1A-4A, improves more than 43 DEG C than comparative example 1B-4B, explanation
Epoxy resin and the dual modified heat resistance to aqueous polyurethane of organosilicon have chemiluminescence.
Raw materials used in the present invention, equipment, it is the conventional raw material, equipment of this area unless otherwise noted；In the present invention
Method therefor, it is the conventional method of this area unless otherwise noted.
It is described above, only it is presently preferred embodiments of the present invention, not the present invention is imposed any restrictions, it is every according to the present invention
Any simple modification, change and the equivalent transformation that technical spirit is made to above example, still fall within the technology of the present invention side
The protection domain of case.
Claims (10)
1. a kind of high-temperature resistant waterborne polyurethane, it is characterised in that the component including following parts by weight is made：
Aromatic polyester polyol 20-60 parts,
Aromatic polyisocyanate 10-20 parts,
Small molecule chain extender 2-8 parts,
Hydrophilic chain extender 2-8 parts,
Catalyst 0.01-0.05 parts,
The silanol-modified epoxy resin 4-8 parts of diphenyl two,
Hydroxyalkyl blocks methyl phenyl siloxane 5-15 parts,
Nertralizer 2-8 parts,
Deionized water 40-100 parts.
A kind of 2. high-temperature resistant waterborne polyurethane as claimed in claim 1, it is characterised in that the aromatic polyester polyol choosing
From benzoic anhydride polyester polyol, to benzene PEPA；The benzoic anhydride polyester polyol, the molecular weight to benzene PEPA are
900-1100 or 1900-2100.
A kind of 3. high-temperature resistant waterborne polyurethane as claimed in claim 1, it is characterised in that the aromatic polyisocyanate choosing
From PPDI, 1,5- naphthalene diisocyanates, dimethyl diphenyl diisocyanate, methyl diphenylene diisocyanate.
4. a kind of high-temperature resistant waterborne polyurethane as claimed in claim 1, it is characterised in that the hydroxyalkyl blocks aminomethyl phenyl
The preparation method of siloxanes is：
In the reaction bulb equipped with agitating device, reflux and thermometer, 45-55 mass parts hydroxyalkyls silicone oil, 45-55 are added
Mass parts 2,4,6- trimethyls -2,4,6- triphenyls cyclotrisiloxane, the ammoniacal liquor that 3-5 mass parts concentration is 23-27wt%, stirring
Under be warming up to 45-55 DEG C reaction 1.5-2.5 hours, then heat to 95-105 DEG C continue react 4-6 hours, be cooled to 45-55
DEG C, add 0.8-1.2 mass parts glacial acetic acid and neutralize, be evaporated under reduced pressure removing low-boiling-point substance and produce hydroxyalkyl end-blocking aminomethyl phenyl silica
Alkane；
The hydroxyalkyl silicone oil is selected from hydroxypropyl silicone oil, hydroxyl butyl silicone oil, described hydroxypropyl silicone oil, the molecule of hydroxyl butyl silicone oil
Measure as 1000-2000.
A kind of 5. high-temperature resistant waterborne polyurethane as claimed in claim 1, it is characterised in that the two silanol-modified ring of diphenyl
The preparation method of oxygen tree fat is：
35-45 mass parts epoxy resin is well mixed with 0.08-0.12 mass parts stannous octoates, is slowly added to 8-12 mass parts
After the silanol of diphenyl two, it is passed through nitrogen and is warming up to 145-155 DEG C of reaction 1.5-2.5 hour to obtain diphenyl two silanol-modified
Epoxy resin；
The epoxy resin is selected from epoxy resin E-20, E-44, E-51, E-54.
A kind of 6. high-temperature resistant waterborne polyurethane as claimed in claim 1, it is characterised in that the hydrophilic chain extender is selected from 2,
2- dihydromethyl propionic acids, 2,2- dimethylolpropionic acids；The small molecule chain extender is selected from ethylenediamine, IPD, diethyl
Alkene triamine.
7. a kind of high-temperature resistant waterborne polyurethane as claimed in claim 1, it is characterised in that the catalyst is selected from tin dilaurate
Dibutyl tin, stannous octoate.
A kind of 8. high-temperature resistant waterborne polyurethane as claimed in claim 1, it is characterised in that the solvent be selected from acetone, butanone,
Tetrahydrofuran；The nertralizer is selected from triethylamine, triethanolamine, ammoniacal liquor.
9. the preparation method of a kind of high-temperature resistant waterborne polyurethane as described in claim 1-8 is any, it is characterised in that including such as
Lower step：
（1）Aromatic polyester polyol, hydroxyalkyl end-blocking methyl phenyl siloxane are added in reaction bulb, 95-105 DEG C of decompression is steamed
30-60 minutes are evaporated, until water content is less than 0.5%, are cooled to 50-60 DEG C, add aromatic polyisocyanate, catalyst, heating
To 70-90 DEG C of reaction 2-4 hour；
（2）50-60 DEG C is cooled to, adds hydrophilic chain extender, is warming up to 70-90 DEG C of reaction 2-4 hour, until NCO content reaches
To theoretical value, organic silicon modified aqueous polyurethane performed polymer is obtained；
（3）Two silanol-modified epoxy resin of diphenyl is dissolved with solvent, is added to organic silicon modified aqueous polyurethane performed polymer
In, in 70-90 DEG C of insulation reaction 1-3 hour, 40-60 DEG C is cooled to, and with after solvent viscosity reduction, nertralizer is added, react 15-30
Minute, the deionized water dissolved with small molecule chain extender is added, high-speed stirred, removing solvent is evaporated under reduced pressure and obtains epoxy resin and have
The dual modified high-temperature resistant waterborne polyurethane of machine silicon.
A kind of 10. preparation method of high-temperature resistant waterborne polyurethane as claimed in claim 9, it is characterised in that step（3）In,
The high-speed stirred rotating speed is 1800-2500rpm, and mixing time is 30-45 minutes.
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| CN109371699A (en) * | 2018-09-12 | 2019-02-22 | 福建隆上超纤有限公司 | A kind of preparation method of high-temperature resistant waterborne polyurethane artificial leather |
| CN110129121A (en) * | 2019-05-31 | 2019-08-16 | 黄智翔 | Antirust corrosion-proof cutting fluid and preparation method thereof |
| CN110606929A (en) * | 2019-09-18 | 2019-12-24 | 牡丹江师范学院 | Epoxy modified waterborne polyurethane emulsion convenient to store and transport, preparation method and storage method |
| CN111378091A (en) * | 2018-12-28 | 2020-07-07 | 财团法人工业技术研究院 | Waterborne polyurethane and preparation method thereof |
| CN111748309A (en) * | 2020-07-09 | 2020-10-09 | 漳州市锐普化工有限公司 | High-temperature-and-humidity-resistant environment-friendly adhesive and preparation method thereof |
| CN114437661A (en) * | 2021-12-21 | 2022-05-06 | 江苏集萃先进高分子材料研究所有限公司 | High-temperature-resistant composite modified waterborne polyurethane adhesive and preparation method thereof |
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| CN109337354A (en) * | 2018-09-17 | 2019-02-15 | 诺弗斯绝热材料有限公司 | A kind of polyurethane adiabatic heat-insulation material |
| CN111378091A (en) * | 2018-12-28 | 2020-07-07 | 财团法人工业技术研究院 | Waterborne polyurethane and preparation method thereof |
| CN110129121A (en) * | 2019-05-31 | 2019-08-16 | 黄智翔 | Antirust corrosion-proof cutting fluid and preparation method thereof |
| CN110129121B (en) * | 2019-05-31 | 2022-04-05 | 黄智翔 | Antirust corrosion-resistant cutting fluid and preparation method thereof |
| CN110606929A (en) * | 2019-09-18 | 2019-12-24 | 牡丹江师范学院 | Epoxy modified waterborne polyurethane emulsion convenient to store and transport, preparation method and storage method |
| CN111748309A (en) * | 2020-07-09 | 2020-10-09 | 漳州市锐普化工有限公司 | High-temperature-and-humidity-resistant environment-friendly adhesive and preparation method thereof |
| CN111748309B (en) * | 2020-07-09 | 2021-11-26 | 漳州市锐普化工有限公司 | High-temperature-and-humidity-resistant environment-friendly adhesive and preparation method thereof |
| CN114437661A (en) * | 2021-12-21 | 2022-05-06 | 江苏集萃先进高分子材料研究所有限公司 | High-temperature-resistant composite modified waterborne polyurethane adhesive and preparation method thereof |
| CN115710339A (en) * | 2022-11-10 | 2023-02-24 | 江苏休伦新材料有限公司 | Bio-based waterborne polyurethane for clothing leather surface layer and preparation method thereof |
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