CN101497685A - Production of rosin based aqueous polyurethanes - Google Patents
Production of rosin based aqueous polyurethanes Download PDFInfo
- Publication number
- CN101497685A CN101497685A CNA2009100244537A CN200910024453A CN101497685A CN 101497685 A CN101497685 A CN 101497685A CN A2009100244537 A CNA2009100244537 A CN A2009100244537A CN 200910024453 A CN200910024453 A CN 200910024453A CN 101497685 A CN101497685 A CN 101497685A
- Authority
- CN
- China
- Prior art keywords
- acid
- preparation
- based aqueous
- rosin
- glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method of rosin-based waterborne polyurethane, which is characterized in that only rosin-based polyester polyol or the compounded rosin-based polyester polyol and regular olyether or polyester polyol is dehydrated in a vacuum way for 2-3 hours at the temperature of 100-120 DEG C, vulcabond and catalyst are added after cooling to react for 1-3 hour(s) at the temperature of 60-90 DEG C, hydrophilic monomer is added to react for 1-2 hours at the temperature of 60-90 DEG C, organic solvent and micromolecule chain extendor are added to react for 3-6 hours at the temperature of 0-70 DEG C, and salt forming agent is added after cooling, is dispersed in water after being stirred dramatically, and finally the solvent is removed in a vacuum way to obtain the rosin-based waterborne polyurethane. The invention has the advantages of high glossiness, big hardness, good heat and water resisting properties, and the like.
Description
Technical field
The present invention relates to a kind of Synthesis of Waterborne Polyurethane method, the preparation that relates in particular to a kind of rosin based aqueous polyurethanes is by method.
Background technology
The feature of urethane be on high molecular main chain, contain multiple amino-formate bond structural unit-NHCOO-, be polymerized by step-reaction polymerization by binary or multicomponent isocyanate and polyether glycol or polyester polyol usually.Except generating carbamate groups, also generate groups such as urea, biuret, so the bonding strength of polyurethane material, toughness, wear resistance, chemical-resistant and weather resistance etc. are all very excellent.Aqueous polyurethane is that urethane is dissolved or dispersed in the binary colloidal state system that forms in the water, the reservation that it is more complete the characteristics of solvent borne polyurethane, simultaneously because its external phase is water, environmentally safe, safety is easily taken care of and stored, and is easy to use.So the development of aqueous polyurethane and production more and more are subjected to the attention of countries in the world.
Also there are some shortcomings in aqueous polyurethane.Itself does not have wetting ability urethane, to be dispersed in it in the water, will on its molecular chain, introduce the ionic group that hydrophilic link or side are hung, and this also causes the poor water resistance of aqueous polyurethane: isocyanate material, polymer polyatomic alcohol, the chainextender of preparation aqueous polyurethane mostly are two functionality materials greatly, so the molecular chain of aqueous polyurethane is based on linearity, this just makes that the resistance toheat of aqueous polyurethane is not enough.
Patent CN1611522 adopts fluorinated acrylate and the silane coupler modified aqueous polyurethane of acrylate, obtained good water-repellancy and solvent resistance, but preparation cost is too high, and economic and practical is not strong.Patent CN1144827C adopts plant oil modified polyester polyol to prepare aqueous polyurethane dispersion, has obtained water tolerance and alcohol resistance preferably, but plant oil modified aqueous polyurethane coating softness, hardness is low, jaundice and Color are poor.Patent CN 101265318A adopts the polymer polyatomic alcohol that contains ring texture can improve over-all propertieies such as aqueous polyurethane dispersion water tolerance, alcohol resistance, thermotolerance and hardness preferably, but the thermotolerance raising is limited.
Summary of the invention
The aqueous polyurethane glossiness that prior art exists is low, hardness is little in order to solve, the shortcoming of heat-resisting, poor water resistance, the invention provides a kind of preparation method of rosin based aqueous polyurethanes, the aqueous polyurethane of preparation has glossiness height, the good characteristics of big, the heat-resisting water resistance of hardness.
Technical scheme of the present invention is: a kind of preparation method of rosin based aqueous polyurethanes, and step is:
The first step, preparation rosinyl polyester polyol: with the modified rosin polyprotonic acid separately or with carbonatoms be that 3～6 diprotic acid is arbitrarily than composite back and small molecules polyvalent alcohol, acid-alcohol ratio is 1:1.1-1:1.6, and the number-average molecular weight that makes through dehydration condensation under 150-270 ℃ of condition is the rosinyl polyester polyol of 500-3000;
Second step, the preparation rosin based aqueous polyurethanes: the rosinyl polyester polyol that the first step is obtained separately or with polyether glycol or polyester polyol arbitrarily than composite, at 100～120 ℃ of following vacuum hydro-extraction 2-3 hours, the cooling back adds vulcabond and catalyzer reacted 1～3 hour in 60～90 ℃, add hydrophilic monomer then in 60～90 ℃ of reactions 1～2 hour, then add organic solvent and small molecule chain extender in 0～70 ℃ of reaction 3～6 hours, the cold back of going adds salt forming agent, be dispersed in the water under the vigorous stirring, last vacuum desolventizing makes rosin based aqueous polyurethanes.The isocyanate index R of the total material of building-up process wherein
(NCO/OH)Be 1.1-1.5; The consumption of hydrophilic chain extender is the 3%-5% of material total mass; The consumption of salt forming agent is determined according to the excessive consumption of hydrophilic chain extender, keeps degree of neutralization at 70%-100%; The 10-40% that solvent is pressed total mass according to the viscosity material of reaction system adds, and catalyst consumption is the 0.05%-0.2% of material total mass.
Wherein the modified rosin polyprotonic acid be in rosin acrylic acid, maleopimaric acid, the fumaropimaric acid one or more arbitrarily than mixture.Described carbonatoms be 3～6 diprotic acid be in propanedioic acid, Succinic Acid, pentanedioic acid, the hexanodioic acid one or more arbitrarily than mixture.The small molecules polyvalent alcohol be in ethylene glycol, propylene glycol, butyleneglycol, neopentyl glycol, glycol ether, triglycol, the polyoxyethylene glycol one or more arbitrarily than mixture.
The used vulcabond of the present invention is to choose any one kind of them among tolylene diisocyanate TDI, isophorone diisocyanate IPDI, hexamethylene diisocyanate HDI, '-diphenylmethane diisocyanate MDI, xylylene diisocyanate XDI, tetramethylxylylene diisocyanate TMXDI, two cyclic group methane diisocyanate HMDI, trimethylammonium hexamethylene diisocyanate TMDI, the hexahydrotoluene vulcabond HTDI or the mixture of several any ratios.
The used polyether glycol of the present invention is that number-average molecular weight is the mixture of one or more any ratios of 1000～3000 polyoxypropyleneglycol, polytetrahydrofuran diol, tetrahydrofuran (THF)-propylene oxide copolymerization glycol etc.
The used normal polyester polyvalent alcohol of the present invention is that number-average molecular weight is 1000～3000 polyethylene glycol adipate, poly-hexanodioic acid glycol ether ester, poly-hexanodioic acid-1, the mixture of any ratio of one or more in 4-butanediol ester, the polyneopentyl glycol adipate.The used catalyzer of the present invention is the mixture of one or more any ratios in dibutyl tin laurate, stannous octoate, tetramethyl butane diamine, triethylenediamine, the triethylene diamine.
The used hydrophilic monomer of the present invention is dimethylol propionic acid, dimethylolpropionic acid, dihydroxyl half ester, second diamino sulfonic acid sodium, any one in the methyldiethanolamine.
The used small molecule chain extender of the present invention is an ethylene glycol, 1,4-butyleneglycol, glycol ether, quadrol, diethylenetriamine, one or more in triethylene tetramine, the TriMethylolPropane(TMP) arbitrarily than mixture.In the used solvent acetone of the present invention, butanone, methylethylketone, the pimelinketone any one.
The used salt forming agent of the present invention is any one of triethylamine, ammoniacal liquor, sodium hydroxide, potassium hydroxide, hydrochloric acid, acetic acid.
Beneficial effect: the rosin based aqueous polyurethanes of method preparation of the present invention has good thermotolerance, water tolerance, glossiness and hardness, specular gloss reaches 120, pendulum-rocker hardness〉0.55, impact strength〉80kgcm, 1 grade of sticking power, snappiness 0.5mm, thermogravimetric analysis 5% decomposition temperature〉250 ℃, water tolerance is qualified.Specular gloss adopts GB/T1743-1979 to measure; Pendulum-rocker hardness adopts GB/T1930-2007 to measure; Impact strength adopts GB/T1729-1993 to measure; Sticking power adopts GB/T1720-1979 to measure; Snappiness adopts GB/T1731-1993 to measure; Water tolerance adopts GB/T1733-1993 to measure; Thermogravimetric analysis adopts 409PC type simultaneous thermal analysis instrument to measure, and characterizes the thermotolerance of aqueous polyurethane with the temperature of sample weightlessness 5%.
Description of drawings
Fig. 1 is the infrared spectra of rosinyl polyester polyol.
Embodiment
The present invention illustrates it especially exemplified by example for better implement, but is not limitation of the present invention.
A kind of preparation method of rosin based aqueous polyurethanes, step is:
The first step, preparation rosinyl polyester polyol: with the modified rosin polyprotonic acid separately or with carbonatoms be that 3～6 diprotic acid is arbitrarily than composite back and small molecules polyvalent alcohol, acid-alcohol ratio is 1:1.1-1:1.6, and the number-average molecular weight that makes through dehydration condensation under 150-270 ℃ of condition is the rosinyl polyester polyol of 500-3000;
Second step, the preparation rosin based aqueous polyurethanes: the rosinyl polyester polyol that the first step is obtained separately or with polyether glycol or polyester polyol arbitrarily than composite, at 100～120 ℃ of following vacuum hydro-extraction 2-3 hours, the cooling back adds vulcabond and catalyzer reacted 1～3 hour in 60～90 ℃, add hydrophilic monomer then in 60～90 ℃ of reactions 1～2 hour, then add organic solvent and small molecule chain extender in 0～70 ℃ of reaction 3～6 hours, the cold back of going adds salt forming agent, vigorous stirring, be dispersed in the water under the 500-1500rpm rotating speed, last vacuum desolventizing makes rosin based aqueous polyurethanes.The isocyanate index R of the total material of building-up process wherein
(NCO/OH)Be 1.1-1.5; The consumption of hydrophilic chain extender is the 3%-5% of material total mass; The consumption of salt forming agent is determined according to the excessive consumption of hydrophilic chain extender, keeps degree of neutralization at 70%-100%; The 10-40% that solvent is pressed total mass according to the viscosity material of reaction system adds, and catalyst consumption is the 0.05%-0.2% of material total mass.
Wherein the modified rosin polyprotonic acid is one or more in rosin acrylic acid, maleopimaric acid, the fumaropimaric acid.Conventional polyprotonic acid is one or more in propanedioic acid, Succinic Acid, pentanedioic acid, the hexanodioic acid.The small molecules polyvalent alcohol is one or more in ethylene glycol, propylene glycol, butyleneglycol, neopentyl glycol, glycol ether, triglycol, the polyoxyethylene glycol.
The used vulcabond of the present invention is to choose any one kind of them among tolylene diisocyanate TDI, isophorone diisocyanate IPDI, hexamethylene diisocyanate HDI, '-diphenylmethane diisocyanate MDI, xylylene diisocyanate XDI, tetramethylxylylene diisocyanate TMXDI, two cyclic group methane diisocyanate HMDI, trimethylammonium hexamethylene diisocyanate TMDI, the hexahydrotoluene vulcabond HTDI or the mixture of several any ratios.
The used polyether glycol of the present invention is that number-average molecular weight is the mixture of one or more any ratios of 1000～3000 polyoxypropyleneglycol, polytetrahydrofuran diol, tetrahydrofuran (THF)-propylene oxide copolymerization glycol etc.
The used normal polyester polyvalent alcohol of the present invention is that number-average molecular weight is 1000～3000 polyethylene glycol adipate, poly-hexanodioic acid glycol ether ester, poly-hexanodioic acid-1, the mixture of any ratio of one or more in 4-butanediol ester, the polyneopentyl glycol adipate.The used catalyzer of the present invention is the mixture of one or more any ratios in dibutyl tin laurate, stannous octoate, tetramethyl butane diamine, triethylenediamine, the triethylene diamine.
The used hydrophilic monomer of the present invention is dimethylol propionic acid, dimethylolpropionic acid, dihydroxyl half ester, second diamino sulfonic acid sodium, any one in the methyldiethanolamine.
The used small molecule chain extender of the present invention is an ethylene glycol, 1,4-butyleneglycol, glycol ether, quadrol, diethylenetriamine, one or more in triethylene tetramine, the TriMethylolPropane(TMP) arbitrarily than mixture.In the used solvent acetone of the present invention, butanone, methylethylketone, the pimelinketone any one.
The used salt forming agent of the present invention is any one of triethylamine, ammoniacal liquor, sodium hydroxide, potassium hydroxide, hydrochloric acid, acetic acid.
In the flask of the 500ml that is equipped with thermometer, agitator, airway, still head, add rosin acrylic acid 74.8g, 1,4-butyleneglycol 27g, 220 ℃ are reacted to the system acid number and drop to 40mg/g, being reacted to the system acid number then under the vacuum condition reduces to below the 3mg/g, cool to 160 ℃ of dischargings, obtaining hydroxyl value is the rosinyl polyester polyol of 95.44mg/g.As seen from Figure 1, at 3438.35cm
-1The hydroxyl charateristic avsorption band is contained at the place, at 1728.87cm
-1The ester carbonyl group charateristic avsorption band is contained at the place, illustrates that product is polyester polyol really.
Get above-mentioned rosinyl polyester polyol 10g, polyethers N-210 15g, at 120 ℃ of following vacuum hydro-extraction 2-3 hours, the cooling back adds tolylene diisocyanate 16g and dibutyl tin laurate 0.02g, in 85 ℃ of reactions 1.5 hours, add dimethylol propionic acid 2.3g again, 85 ℃ were reacted 1 hour, add 4.3g glycol ether and 11g acetone at last, 60 ℃ were reacted 4～5 hours, the cooling back adds the triethylamine neutralization, be dispersed in the 90g water under the violent stirring of 600rpm, acetone is sloughed in decompression, solid content is 34% white emulsion.Specular gloss 131.6, pendulum-rocker hardness 0.82, impact strength〉80kgcm, 1 grade of sticking power, snappiness 0.5mm, 260.3 ℃ of thermogravimetric analysis 5% decomposition temperatures, water tolerance is qualified.
Comparing embodiment:
Get polyethers N-210 25g, at 100～120 ℃ of following vacuum hydro-extraction 2-3 hours, the cooling back added tolylene diisocyanate 16g and dibutyl tin laurate 0.02g, in 85 ℃ of reactions 1.5 hours, add dimethylol propionic acid 2.3g again, 85 ℃ were reacted 1 hour, and added 4.3g glycol ether and 11g acetone at last, 60 ℃ were reacted 4～5 hours, the cooling back adds the triethylamine neutralization, and violent stirring is dispersed under the rotating speed 600rpm in the 100g water, acetone is sloughed in decompression, gets the white emulsion of solid content 28%.Specular gloss 126, pendulum-rocker hardness 0.2, impact strength〉120kgcm, 1 grade of sticking power, snappiness 0.5mm, 188.8 ℃ of thermogravimetric analysis 5% decomposition temperatures, water tolerance is defective.
By embodiment 1 and comparing embodiment as can be seen, the rosin based aqueous polyurethanes with method preparation of the present invention has good thermotolerance, water tolerance, glossiness and hardness.
Embodiment 2
In the flask of the 500ml that is equipped with thermometer, agitator, airway, still head, add rosin acrylic acid 74.8g, glycol ether 42.4g, 220 ℃ are reacted to the system acid number and drop to 40mg/g, react under the vacuum condition then to the system acid number and drop to below the 3mg/g, cool to 160 ℃ of dischargings, obtaining hydroxyl value is the rosinyl polyester polyol of 195.37mg/g.
Get above-mentioned rosinyl polyester polyol 5g, polyethers N-210 15g, at 100～120 ℃ of following vacuum hydro-extraction 2-3 hours, the cooling back adds tolylene diisocyanate 16g and dibutyl tin laurate 0.02g, in 85 ℃ of reactions 1.5 hours, add dimethylol propionic acid 2.3g again, 85 ℃ were reacted 1 hour, add 4.3g glycol ether and 12g acetone at last, 60 ℃ were reacted 4～5 hours, the cooling back adds the triethylamine neutralization, and violent stirring is dispersed under the rotating speed 600rpm in the 100g water, acetone is sloughed in decompression, gets the white emulsion of solid content 28%.Specular gloss 134.6, pendulum-rocker hardness 0.66, impact strength〉90kgcm, 1 grade of sticking power, snappiness 0.5mm, 251.9 ℃ of water tolerance of thermogravimetric analysis 5% decomposition temperature are qualified.
Embodiment 3
Get rosinyl polyester polyol 7.5g among the embodiment 1, number-average molecular weight is 1000 poly-hexanodioic acids-1,4-butanediol ester 17.5g, at 100～120 ℃ of following vacuum hydro-extraction 2-3 hours, the cooling back adds tolylene diisocyanate 16g and dibutyl tin laurate 0.02g, in 85 ℃ of reactions 1.5 hours, add dimethylol propionic acid 2.3g again, 85 ℃ were reacted 1 hour, add 4.3g glycol ether and 10g acetone at last, 60 ℃ were reacted 4～5 hours, and the cooling back adds the triethylamine neutralization, and dispersed with stirring is in 100g water under the rotating speed 600rpm, acetone is sloughed in decompression, gets the white emulsion of solid content 28%.Specular gloss 132.1, pendulum-rocker hardness 0.68, impact strength〉90kgcm, 1 grade of sticking power, snappiness 0.5mm, 252.8 ℃ of thermogravimetric analysis 5% decomposition temperatures, water tolerance is qualified.
Embodiment 4
In the flask of the 500ml that is equipped with thermometer, agitator, airway, still head, add maleopimaric acid 40g, hexanodioic acid 29.2g, 1,4-butyleneglycol 36g, 220 ℃ are reacted to the system acid number and drop to 40mg/g, being reacted to the system acid number then under the vacuum condition reduces to below the 3mg/g, cool to 160 ℃ of dischargings, obtaining hydroxyl value is 108.44mg/g rosinyl polyester polyol.
Get above-mentioned rosinyl polyester polyol 5g, polyethers N-210 20g, at 120 ℃ of following vacuum hydro-extraction 2-3 hours, the cooling back adds Xylene Diisocyanate 16g and tetramethyl butane diamine 0.03g, in 85 ℃ of reactions 1.5 hours, add dimethylolpropionic acid 2.3g again, 85 ℃ were reacted 1 hour, add 2.7g ethylene glycol and 11g acetone at last, 60 ℃ were reacted 4～5 hours, the cooling back adds the ammoniacal liquor neutralization, dispersed with stirring is in 110g water under the speed of rotating speed 600rpm, acetone is sloughed in decompression, solid content is 31% white emulsion.Specular gloss 120.6, pendulum-rocker hardness 0.51, impact strength〉120kgcm, 1 grade of sticking power, snappiness 0.5mm, 257.1 ℃ of thermogravimetric analysis 5% decomposition temperatures, water tolerance is qualified.
Claims (10)
1, a kind of preparation method of rosin based aqueous polyurethanes is characterized in that, step is:
The first step, preparation rosinyl polyester polyol: in acid-alcohol ratio is the ratio of 1:1.1～1:1.6, with the modified rosin polyprotonic acid separately or with carbonatoms be that 3～6 diprotic acid is the rosinyl polyester polyol of 500-3000 through the number-average molecular weight that dehydration condensation makes than composite back and small molecules polyvalent alcohol under 150-270 ℃ of condition arbitrarily;
Second step, the preparation rosin based aqueous polyurethanes: the rosinyl polyester polyol that the first step is obtained separately or with polyether glycol or polyester polyol arbitrarily than composite, 100～120 ℃ of following vacuum hydro-extractions 2～3 hours, the cooling back adds vulcabond and catalyzer reacted 1～3 hour in 60～90 ℃, add hydrophilic monomer then in 60～90 ℃ of reactions 1～2 hour, then add organic solvent and small molecule chain extender in 0～70 ℃ of reaction 3～6 hours, the cold back of going adds salt forming agent, be dispersed in the water under the vigorous stirring, last vacuum desolventizing makes rosin based aqueous polyurethanes.
2, the preparation method of a kind of rosin based aqueous polyurethanes according to claim 1, it is characterized in that described modified rosin polyprotonic acid be in rosin acrylic acid, maleopimaric acid, the fumaropimaric acid one or more arbitrarily than mixture, described carbonatoms be 3～6 diprotic acid be in propanedioic acid, Succinic Acid, pentanedioic acid, the hexanodioic acid one or more arbitrarily than mixture, the small molecules polyvalent alcohol be in ethylene glycol, propylene glycol, butyleneglycol, neopentyl glycol, glycol ether, triglycol, the polyoxyethylene glycol one or more arbitrarily than mixture.
3, the preparation method of a kind of rosin based aqueous polyurethanes according to claim 1, it is characterized in that, described vulcabond be in tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, '-diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, two cyclic group methane diisocyanates, trimethylammonium hexamethylene diisocyanate, the hexahydrotoluene vulcabond any one or a few arbitrarily than mixture.
4, the preparation method of a kind of rosin based aqueous polyurethanes according to claim 1, it is characterized in that, described polyether glycol be number-average molecular weight be in 1000～3000 polyoxypropyleneglycol, polytetrahydrofuran diol, the tetrahydrofuran (THF)-propylene oxide copolymerization glycol one or more arbitrarily than mixture.
5, the preparation method of a kind of rosin based aqueous polyurethanes according to claim 1, it is characterized in that described polyester polyol is that number-average molecular weight is 1000～3000 polyethylene glycol adipate, poly-hexanodioic acid glycol ether ester, poly-hexanodioic acid-1, one or more in 4-butanediol ester, the polyneopentyl glycol adipate arbitrarily than mixture.
6, the preparation method of a kind of rosin based aqueous polyurethanes according to claim 1, it is characterized in that, described catalyzer be in dibutyl tin laurate, stannous octoate, tetramethyl butane diamine, triethylenediamine, the triethylene diamine one or more arbitrarily than mixture.
7, the preparation method of a kind of rosin based aqueous polyurethanes according to claim 1, it is characterized in that, described hydrophilic monomer be dimethylol propionic acid,, in the dimethylolpropionic acid, dihydroxyl half ester, second diamino sulfonic acid sodium, methyldiethanolamine any one.
8, the preparation method of a kind of rosin based aqueous polyurethanes according to claim 1, it is characterized in that, described small molecule chain extender is an ethylene glycol, 1,4-butyleneglycol, glycol ether, quadrol, diethylenetriamine, one or more in triethylene tetramine, the TriMethylolPropane(TMP) arbitrarily than mixture.
9, the preparation method of a kind of rosin based aqueous polyurethanes according to claim 1 is characterized in that, described organic solvent is any one in acetone, butanone, methylethylketone, the pimelinketone.
10, the preparation method of a kind of rosin based aqueous polyurethanes according to claim 1 is characterized in that, described salt forming agent is any one in triethylamine, ammoniacal liquor, sodium hydroxide, potassium hydroxide, hydrochloric acid, the acetic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100244537A CN101497685A (en) | 2009-02-23 | 2009-02-23 | Production of rosin based aqueous polyurethanes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100244537A CN101497685A (en) | 2009-02-23 | 2009-02-23 | Production of rosin based aqueous polyurethanes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101497685A true CN101497685A (en) | 2009-08-05 |
Family
ID=40944968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009100244537A Pending CN101497685A (en) | 2009-02-23 | 2009-02-23 | Production of rosin based aqueous polyurethanes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101497685A (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880373A (en) * | 2010-07-15 | 2010-11-10 | 中国林业科学研究院林产化学工业研究所 | Rosin polyisocyanate for rigid polyurethane foam, preparation method and application |
| CN102918075A (en) * | 2010-05-28 | 2013-02-06 | 日本优必佳株式会社 | Alcohol compound, polyester resin, unsaturated polyester resin, resin particle and electrophotography toner |
| CN103113552A (en) * | 2013-01-22 | 2013-05-22 | 中国科学院宁波材料技术与工程研究所 | Rosin-based chain extender and preparation method thereof |
| CN104045805A (en) * | 2013-03-11 | 2014-09-17 | 广东彩格科技有限公司 | Novel printing material for replacing acidic printing and dyeing material and manufacturing method thereof |
| CN104725592A (en) * | 2015-03-24 | 2015-06-24 | 中国林业科学研究院林产化学工业研究所 | Preparation method of maleopimaric double-component waterborne polyurethane |
| CN104829804A (en) * | 2015-04-15 | 2015-08-12 | 南昌航空大学 | Neutral imitating low-foam rosin sizing agent preparation method |
| CN104893539A (en) * | 2015-06-18 | 2015-09-09 | 西安科技大学 | Preparation method of hydrophobic and flame-retardant PU (polyurethane) coating |
| CN105504216A (en) * | 2015-12-21 | 2016-04-20 | 桂林市和鑫防水装饰材料有限公司 | Preparation method of rosin-based waterborne polyurethane waterproof material |
| CN105646838A (en) * | 2016-03-13 | 2016-06-08 | 桂林理工大学 | Preparation method of polymerized rosin-based polyurethane prepolymer |
| CN105646831A (en) * | 2016-03-13 | 2016-06-08 | 桂林理工大学 | Method for preparing rosin-based aliphatic polyurethane prepolymers |
| CN105646822A (en) * | 2016-03-13 | 2016-06-08 | 桂林理工大学 | Method for preparing rosin-based IPDI (isophorone diisocyanate)-type polyurethane prepolymers |
| CN105669944A (en) * | 2016-03-13 | 2016-06-15 | 桂林理工大学 | Method for preparing rosinyl MDI type polyurethane prepolymer |
| CN105778028A (en) * | 2016-03-13 | 2016-07-20 | 桂林理工大学 | Method for preparing rosin-based TDI type polyurethane prepolymer |
| CN106118443A (en) * | 2016-07-13 | 2016-11-16 | 蚌埠市正园电子科技有限公司 | A kind of weather resistant waterborne polyester coating and preparation method thereof |
| CN107383323A (en) * | 2017-08-12 | 2017-11-24 | 桂林理工大学 | The preparation method of abietyl aromatic type aqueous polyurethane |
| CN109468845A (en) * | 2018-10-23 | 2019-03-15 | 温州东泰树脂有限责任公司 | A kind of use for synthetic leather aqueous surface-treating agent and preparation method thereof |
| CN110343503A (en) * | 2019-06-21 | 2019-10-18 | 佛山市顺德区蓝德堡实业有限公司 | A kind of hot melt polyurethane adhesive and preparation method thereof for cellular board fitting |
| CN110835398A (en) * | 2019-11-06 | 2020-02-25 | 桂林理工大学 | Preparation method of rosin-based waterborne polyurethane emulsion |
| CN113105850A (en) * | 2021-03-12 | 2021-07-13 | 华南理工大学 | Waterborne polyurethane-acrylate-epoxidized soybean oil label adhesive and preparation method thereof |
-
2009
- 2009-02-23 CN CNA2009100244537A patent/CN101497685A/en active Pending
Cited By (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102918075B (en) * | 2010-05-28 | 2016-08-17 | 日本优必佳株式会社 | Alcoholic compound, polyester resin, unsaturated polyester resin, resin particle and electrophotography powdered ink |
| CN102918075A (en) * | 2010-05-28 | 2013-02-06 | 日本优必佳株式会社 | Alcohol compound, polyester resin, unsaturated polyester resin, resin particle and electrophotography toner |
| CN101880373B (en) * | 2010-07-15 | 2012-10-24 | 中国林业科学研究院林产化学工业研究所 | Rosin polyisocyanate for rigid polyurethane foam, preparation method and application |
| CN101880373A (en) * | 2010-07-15 | 2010-11-10 | 中国林业科学研究院林产化学工业研究所 | Rosin polyisocyanate for rigid polyurethane foam, preparation method and application |
| CN103113552A (en) * | 2013-01-22 | 2013-05-22 | 中国科学院宁波材料技术与工程研究所 | Rosin-based chain extender and preparation method thereof |
| CN104045805A (en) * | 2013-03-11 | 2014-09-17 | 广东彩格科技有限公司 | Novel printing material for replacing acidic printing and dyeing material and manufacturing method thereof |
| CN104725592A (en) * | 2015-03-24 | 2015-06-24 | 中国林业科学研究院林产化学工业研究所 | Preparation method of maleopimaric double-component waterborne polyurethane |
| CN104725592B (en) * | 2015-03-24 | 2018-04-27 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of maleopimaric acid dual-component aqueous polyurethane |
| CN104829804A (en) * | 2015-04-15 | 2015-08-12 | 南昌航空大学 | Neutral imitating low-foam rosin sizing agent preparation method |
| CN104829804B (en) * | 2015-04-15 | 2017-10-27 | 南昌航空大学 | A kind of preparation method of the low bubble rosin sizing agent of imitative neutrality |
| CN104893539A (en) * | 2015-06-18 | 2015-09-09 | 西安科技大学 | Preparation method of hydrophobic and flame-retardant PU (polyurethane) coating |
| CN105504216A (en) * | 2015-12-21 | 2016-04-20 | 桂林市和鑫防水装饰材料有限公司 | Preparation method of rosin-based waterborne polyurethane waterproof material |
| CN105669944B (en) * | 2016-03-13 | 2018-07-06 | 桂林理工大学 | A kind of preparation method of abietyl MDI Type Polyurethane Prepolymers |
| CN105646822A (en) * | 2016-03-13 | 2016-06-08 | 桂林理工大学 | Method for preparing rosin-based IPDI (isophorone diisocyanate)-type polyurethane prepolymers |
| CN105646822B (en) * | 2016-03-13 | 2018-07-03 | 桂林理工大学 | A kind of preparation method of abietyl IPDI Type Polyurethane Prepolymers |
| CN105646831B (en) * | 2016-03-13 | 2018-07-06 | 桂林理工大学 | A kind of preparation method of abietyl aliphatic polyurethane performed polymer |
| CN105778028A (en) * | 2016-03-13 | 2016-07-20 | 桂林理工大学 | Method for preparing rosin-based TDI type polyurethane prepolymer |
| CN105669944A (en) * | 2016-03-13 | 2016-06-15 | 桂林理工大学 | Method for preparing rosinyl MDI type polyurethane prepolymer |
| CN105778028B (en) * | 2016-03-13 | 2018-07-06 | 桂林理工大学 | A kind of preparation method of abietyl TDI Type Polyurethane Prepolymers |
| CN105646831A (en) * | 2016-03-13 | 2016-06-08 | 桂林理工大学 | Method for preparing rosin-based aliphatic polyurethane prepolymers |
| CN105646838A (en) * | 2016-03-13 | 2016-06-08 | 桂林理工大学 | Preparation method of polymerized rosin-based polyurethane prepolymer |
| CN105646838B (en) * | 2016-03-13 | 2018-07-03 | 桂林理工大学 | A kind of preparation method of newtrex based polyurethanes performed polymer |
| CN106118443A (en) * | 2016-07-13 | 2016-11-16 | 蚌埠市正园电子科技有限公司 | A kind of weather resistant waterborne polyester coating and preparation method thereof |
| CN107383323A (en) * | 2017-08-12 | 2017-11-24 | 桂林理工大学 | The preparation method of abietyl aromatic type aqueous polyurethane |
| CN109468845A (en) * | 2018-10-23 | 2019-03-15 | 温州东泰树脂有限责任公司 | A kind of use for synthetic leather aqueous surface-treating agent and preparation method thereof |
| CN110343503A (en) * | 2019-06-21 | 2019-10-18 | 佛山市顺德区蓝德堡实业有限公司 | A kind of hot melt polyurethane adhesive and preparation method thereof for cellular board fitting |
| CN110835398A (en) * | 2019-11-06 | 2020-02-25 | 桂林理工大学 | Preparation method of rosin-based waterborne polyurethane emulsion |
| CN113105850A (en) * | 2021-03-12 | 2021-07-13 | 华南理工大学 | Waterborne polyurethane-acrylate-epoxidized soybean oil label adhesive and preparation method thereof |
| CN113105850B (en) * | 2021-03-12 | 2022-07-12 | 华南理工大学 | Waterborne polyurethane-acrylate-epoxidized soybean oil label adhesive and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101497685A (en) | Production of rosin based aqueous polyurethanes | |
| CN106496485B (en) | A kind of epoxy-modified yin/non-ionic water polyurethane resin and preparation method thereof | |
| CN103881049B (en) | The preparation method of eleostearic acid monoglyceride modified aqueous polyurethane emulsion | |
| CN101649036B (en) | polyisocyanate curing agent and preparation method thereof | |
| CN101235129B (en) | Method for preparing polybutadiene-base water polyurethane and modified emulsion thereof | |
| CN103709361B (en) | A kind of aqueous polyurethane and its production and use | |
| CN105111412B (en) | A kind of compound polyether-type of soft hydrolysis is high to peel off wet polyurethane resin and preparation method thereof | |
| CN104995242B (en) | Pass through the polyurethane foam of reaction injection molding(RIM) | |
| CN100497426C (en) | High solid content water polyurethane adhesive for non-absorbability base material and preparing method | |
| CN110835401B (en) | Waterborne polyurethane surface layer resin and preparation method thereof | |
| CN106674996A (en) | Self-repaired graphene oxide/polyurethane composite material and preparation method thereof | |
| CN101235130B (en) | Cation water polyurethane emulsion and preparation method thereof | |
| CN102766246B (en) | Waterborne polyurethane resin for shoe material ink | |
| US20160009852A1 (en) | Vegetable Oil-Modified, Hydrophobic Polyurethane Dispersions | |
| CN100460434C (en) | Self-emulsifying water-thinned anion polyurethane emulsion and its prepn process | |
| CN102167795A (en) | Amino silicone modified waterborne polyurethane and preparation method thereof | |
| CN102408525B (en) | Acrylate modified maleopimaric acid aqueous polyurethane emulsion and preparation method thereof | |
| CN102241956A (en) | Poly(propylene carbonate)-based water-borne polyurethane adhesive and preparation method thereof | |
| CN102532463A (en) | Aqueous polyurethane and preparation method thereof | |
| CN109898342B (en) | Preparation method of scratch-resistant synthetic leather based on high-resilience waterborne polyurethane | |
| CN103408715A (en) | Internal crosslinking polypropylene carbonate waterborne polyurethane emulsion and preparation method and application thereof | |
| CN102898609A (en) | Waxy-luster polyurethane resin used in synthetic leather surface treatment, and preparation method thereof | |
| CN108546323A (en) | Cation is from matting resin and its preparation method and application | |
| CN101280050A (en) | Method for preparing waterborne polyurethane from reproducible polylol | |
| CN104371085B (en) | A kind of preparation method of amphion aqueous polyurethane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20090805 |