CN107556452B - Castor oil-based hydrophilic chain extender and preparation method and application thereof - Google Patents
Castor oil-based hydrophilic chain extender and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a castor oil based hydrophilic chain extender and a preparation method and application thereof. The invention starts from castor oil which is one of renewable resources, hydroxyl is introduced by utilizing sulfydryl-alkene light click reaction to obtain an intermediate, then carboxyl is generated by ester group hydrolysis reaction (or ricinoleic acid is generated by ester group hydrolysis reaction of castor oil, and hydroxyl is introduced by utilizing sulfydryl-alkene light click reaction), the hydrophilic chain extender containing at least two hydroxyl and one carboxyl is prepared, and the hydrophilic chain extender is applied to the preparation of the anionic waterborne polyurethane emulsion. The castor oil is applied to the hydrophilic chain extender raw material, has positive reference value for widening the application of natural oil products and improving the added value of the natural oil products, and plays a positive role in reducing or replacing the environmental problems caused by the use of petroleum non-renewable resources. The castor oil-based hydrophilic chain extender prepared by the invention is liquid at normal temperature, has larger contact area with other raw materials during reaction, is more uniformly mixed and has higher reaction speed.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a castor oil based hydrophilic chain extender and a preparation method and application thereof.
Background
Because of its outstanding properties, polyurethanes are widely used in many areas of national economy, such as paints, foams, adhesives, etc. The solvent polyurethane generates a large amount of VOC (volatile organic compounds) including toluene, butanone and the like in the using process, and causes great damage to the environment and construction personnel, so that the development of the aqueous polyurethane emulsion is imperative. The waterborne polyurethane is generally prepared from raw materials of polyol, isocyanate and a hydrophilic chain extender, the types of the polyol and the isocyanate are very many, and the hydrophilic chain extender which is one of key monomers for preparing the waterborne polyurethane emulsion only comprises a plurality of dimethylolbutyric acid (DMBA), 2-dimethylolpropionic acid (DMPA) and the like. The petrochemical-based hydrophilic chain extenders such as DMPA and DMBA have low solubility in acetone and high melting temperature, so that the uniformity and volatility of the waterborne polyurethane are extremely high, the preparation process greatly depends on the experience of operators, and the stable production of the waterborne polyurethane is seriously influenced. On the other hand, as petrochemical resources are increasingly exhausted and the price of the petrochemical resources is influenced by external factors such as politics, the fluctuation is large, and the urgent need of modern life for environmental protection is met, the development of renewable resources as substitutes of the petrochemical resources to prepare green polyurethane products becomes a great trend in domestic and foreign scientific research and industry.
As a typical renewable biomass resource, the vegetable oil has a simple structure (mainly triglyceride), wide sources and low price. And the vegetable oil resources in China are very rich, and the method has great advantages in the aspect of developing biomass materials. Many vegetable oils structurally contain 1-7 unsaturated double bonds and 3 ester bonds, and contain more active reaction groups such as hydroxyl groups and the like, so that chemical modification and synthesis are facilitated, and theoretically, the vegetable oils have a structural basis for constructing a high-molecular monomer and a material system thereof. The units such as Pittsburgh State University, Iowa State University, French institute Charles Gerhardt Montpellier and China southern China University in China do a lot of work on the efficient conversion of high value-added chemical products and high molecular materials (coatings, lubricating oil, adhesives, plasticizers and the like) thereof from vegetable oil.
The renewable content of the waterborne polyurethane can be further improved by preparing the hydrophilic chain extender from the vegetable oil, and the prepared hydrophilic chain extender is liquid at normal temperature due to the low melting point of the vegetable oil, so that the performance of the waterborne polyurethane is expected to be further improved. Such as Ruqi Chen (2014), etc., successfully prepares the anionic polyhydroxy fatty acid hydrophilic chain extender capable of replacing DMPA, DMBA, etc. by using the epoxy linseed oil. The novel hydrophilic chain extender is synthesized by utilizing a sulfydryl-alkene click reaction and reacting castor oil with 3-mercaptopropionic acid, such as Devzechnological university Devzechtung, etc.: ricinoleic acid based polycarboxylic acid (MCO).
At present, few patents for preparing novel hydrophilic chain extenders exist, and renewable materials are not used as matrixes, for example, a Chinese patent with publication number CN104356330A discloses a carboxylic acid type waterborne polyurethane chain extender and a preparation method thereof, and a Chinese patent with publication number CN106046288A discloses a hydrophilic chain extender and a preparation method and application thereof, and although the two patents successfully prepare the chain extender with more excellent performance, the chain extender is expected to replace the traditional chain extender, but the chain extender is made of petroleum-based materials.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide the castor oil-based hydrophilic chain extender.
The invention also aims to provide a preparation method of the castor oil based hydrophilic chain extender.
The invention further aims to provide application of the castor oil-based hydrophilic chain extender in waterborne polyurethane.
The purpose of the invention is realized by the following technical scheme:
a castor oil based hydrophilic chain extender has a structural formula shown in formula (1):
wherein n is a natural number of 1-5, and R is an alkyl group having a main chain of less than or equal to 10 carbons; preferably, n is 1 or 2, and R is a linear alkyl group having 2 to 10 carbons in length.
The preparation method of the castor oil based hydrophilic chain extender comprises the following steps:
(1) sequentially adding a metered photoinitiator, castor oil and mercaptan, and reacting for 1-5 hours under magnetic stirring and ultraviolet light; washing a reaction product for 3-5 times by using a water-insoluble organic solvent as a solvent, discarding a water phase, dehydrating by using a drying agent, carrying out suction filtration, and carrying out rotary evaporation to obtain an intermediate product, namely a light yellow viscous liquid castor oil-based polyol (CO-SH or CO-TG), and finishing the first-step reaction;
(2) putting the intermediate product prepared in the step (1) into a temperature of 60-80 ℃, and drying for 0-14 h; taking a proper amount of intermediate product, adding a proper amount of alkali under magnetic stirring at the temperature of 60-80 ℃, reacting for 1-10 h, and adding acid to adjust the reaction system to be acidic; and (3) washing the reaction product for 3-5 times by using a water-insoluble organic solvent as a solvent, discarding the water phase, dewatering by using a drying agent, performing suction filtration, and performing rotary evaporation to obtain the hydrophilic chain extender, namely the castor oil-based hydrophilic chain extender.
Alternatively, the first and second electrodes may be,
(A) taking castor oil, adding a proper amount of alkali under magnetic stirring at 60-80 ℃, reacting for 1-10 h, and adding acid to adjust the reaction system to be acidic; washing a reaction product for 3-5 times by using a water-insoluble organic solvent as a solvent, discarding a water phase, dewatering by using a drying agent, performing suction filtration, and performing rotary evaporation to obtain an intermediate product ricinoleic acid;
(B) sequentially adding a photoinitiator, ricinoleic acid serving as an intermediate product prepared in the step (A) and mercaptan, and reacting for 1-5 hours under magnetic stirring and ultraviolet light; and (3) washing the reaction product for 3-5 times by using a water-insoluble organic solvent as a solvent, discarding the water phase, dewatering by using a drying agent, performing suction filtration, and performing rotary evaporation to obtain the hydrophilic chain extender, namely the castor oil-based hydrophilic chain extender.
The preparation method of the castor oil-based hydrophilic chain extender further comprises the step (2) of using castor oil, and the step (1) of replacing the castor oil with the obtained intermediate product, namely the step (A) and the step (B).
The dosage of the photoinitiator in the step (1) is (mass of castor oil + mass of mercaptan) multiplied by 2% to (mass of castor oil + mass of mercaptan) multiplied by 3%.
The molar ratio of the double bond in the castor oil to the sulfydryl in the mercaptan in the step (1) is 1: 1.5-1: 5.5.
The molar ratio of the ester group of the intermediate product in the step (2) to the alkali is 1: 1-1: 3.
The molar ratio of the ester group to the alkali in the castor oil in the step (A) is 1: 1-1: 3.
The amount of the photoinitiator used in the step (B) is (the mass of the intermediate product ricinoleic acid + the mass of the mercaptan) × 2% to (the mass of the intermediate product ricinoleic acid + the mass of the mercaptan) × 3%.
The molar ratio of the double bond of the intermediate product ricinoleic acid in the step (B) to the sulfydryl in the mercaptan is 1: 1.5-1: 5.5.
The photoinitiator in the steps (1) and (B) refers to a compound capable of initiating monomer polymerization, crosslinking and curing under ultraviolet light, and includes photoinitiator 1173 (2-hydroxy-2-methyl-1-phenyl-1-acetone, abbreviated as HMPP), 184, 907, 369, 1490, 1700, BP, 261, NS-1, NS-2, PBCP, CCP, NCP, BCP, CS-1, CS-2, photobase generators ketoxime ester, cobalt-amine complex, formamide, quaternary ammonium salt, alkali breeder benzenesulfonyl carbamate, 9-fluorene carbamate, 3-nitropentyl carbamate, and the like, preferably photoinitiator 1173 (2-hydroxy-2-methyl-1-phenyl-1-acetone, abbreviated as HMPP);
the thiol in the steps (1) and (B) refers to a monohydric thiol containing one or more hydroxyl groups, including mercaptoethanol, thioglycerol, 1-mercapto-2-propanol, 2-mercapto-3-butanol, 6-mercaptohexanol, etc., preferably mercaptoethanol or thioglycerol;
the water-insoluble organic solvent in the steps (1), (2), (A) and (B) comprises ethyl acetate, dichloromethane, petroleum ether, diethyl ether, carbon tetrachloride and the like, and preferably ethyl acetate;
the drying agent in the steps (1), (2), (A) and (B) comprises anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous calcium chloride and the like, and preferably anhydrous magnesium sulfate;
the acid in the step (2) and the step (A) comprises hydrochloric acid, sulfuric acid, acetic acid, nitric acid, carbonic acid, phosphoric acid and the like, and is preferably hydrochloric acid;
the alkali in the steps (2) and (A) comprises sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium bisulfite, potassium carbonate and the like, and preferably sodium hydroxide;
the castor oil based hydrophilic chain extender is applied to the preparation of waterborne polyurethane.
An anionic waterborne polyurethane emulsion comprises the following components in parts by mass:
20-130 parts of castor oil based hydrophilic chain extender, 100 parts of polyol, 40-210 parts of diisocyanate, 0.25-3.4 parts of catalyst, 125-680 parts of organic solvent, 250-1700 parts of water and 4-40 parts of neutralizer.
The polyol comprises polyester polyol, polyether polyol and natural oil polyol; the polyester polyol comprises polycarbonate diol (PCDL), dimer acid Polyester Diol (PDFA), phthalic acid polyester diol (PPA), poly adipic acid-1, 4-butanediol ester diol (PBA), polycaprolactone diol (PCL), poly adipic acid-1, 6-hexanediol ester diol (PHA) and the like; polyether polyols include polytetrahydrofuran ether glycol (PTMG), polypropylene glycol (PPG), polyethylene glycol (PEG), and the like; the natural oil polyol includes castor oil and vegetable oil-based polyols, wherein the vegetable oil-based polyols include linseed oil-based polyols, soybean oil-based polyols, corn oil-based polyols, coconut oil-based polyols, cauliflower oil-based polyols, and the like, preferably castor oil among the natural oil polyols;
the diisocyanate comprises isophorone diisocyanate (IPDI), Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (HMDI), Lysine Diisocyanate (LDI), 1, 6-Hexamethylene Diisocyanate (HDI) and the like, and is preferably isophorone diisocyanate (IPDI);
the catalyst comprises dibutyltin dilaurate (DBTDL), stannous octoate, triethylenediamine, N-ethyl morpholine, triethylenediamine, N-dimethyl cyclohexylamine and the like, preferably dibutyltin dilaurate (DBTDL);
the organic solvent comprises butanone, acetone, toluene, xylene, butyl acetate, cyclohexanone and the like, and is preferably butanone;
the neutralizer comprises Triethylamine (TEA), Dimethylethanolamine (DMEA), ammonia water, sodium hydroxide, potassium hydroxide, sodium bicarbonate, triethanolamine and the like, and preferably Triethylamine (TEA).
The preparation method of the anionic waterborne polyurethane emulsion comprises the following steps:
taking the castor oil based hydrophilic chain extender, the polyol and the diisocyanate, stirring for 5-20 min at 100-300 r/min in an oil bath at 50-80 ℃, adding the catalyst, and continuing stirring for reaction at 60-80 ℃ in the oil bath; when the viscosity of the solution is increased to almost no flow, adding an organic solvent, continuously stirring for 1-7 hours at 60-80 ℃, stopping heating when the reaction system becomes clear and transparent, adding a neutralizer after the solution is cooled to room temperature, continuously stirring, adding water for emulsification after the rotation speed is adjusted to 300-500 r/min, and continuously stirring for 1-4 hours; and (3) carrying out rotary evaporation on the product at the temperature of 40-60 ℃ for 30 min-1 h to obtain the anionic waterborne polyurethane emulsion.
The preparation principle of the castor oil-based hydrophilic chain extender comprises the following chemical reactions:
the preparation principle of the castor oil-based hydrophilic chain extender also comprises the steps of hydrolyzing ester groups in the castor oil, and then grafting sulfhydryl groups
Mercaptoethanol in principle (3) can be replaced by thioglycerol.
The mechanism of the invention is as follows:
according to the preparation method, a typical renewable resource, namely castor oil, is used, hydroxyl is introduced by utilizing a sulfydryl-alkene light click reaction to obtain an intermediate, carboxyl is generated by an ester group hydrolysis reaction (or ricinoleic acid is generated by the ester group hydrolysis reaction of the castor oil, and hydroxyl is introduced by utilizing the sulfydryl-alkene light click reaction), a hydrophilic chain extender containing at least two hydroxyl groups and one carboxyl group is prepared, the hydrophilic chain extender is applied to the preparation of an anionic waterborne polyurethane emulsion, and the performance of the prepared waterborne polyurethane coating material is characterized. Meanwhile, the influence of the illumination intensity, the reaction charge ratio and the illumination time on the structure of the mercapto-alkene light click product is explored, and the conversion rate of double bonds is fully improved.
Compared with the prior art, the invention has the following advantages and effects:
(1) the castor oil is applied to the hydrophilic chain extender raw material, has positive reference value for widening the application of natural oil products and improving the added value of the natural oil products, and plays a positive role in reducing or replacing the environmental problems caused by the use of petroleum non-renewable resources.
(2) The hydrophilic chain extenders COFA-SH and COFA-TG prepared by the invention are liquid at normal temperature, and have larger contact area with other raw materials, more uniform mixing and faster reaction speed in reaction compared with DMPA and DMBA which are solid at normal temperature.
Drawings
FIG. 1 is a GPC chart of Castor oil based hydrophilic chain extender (COFA-SH), intermediate Castor oil based polyol (CO-SH), and Castor oil (Castor oil) of example 1.
FIG. 2 is a GPC chart of castor oil-based hydrophilic chain extender (COFA-TG) of example 2, castor oil-based hydrophilic chain extender (COFA-SH) of example 1 and Castor Oil (CO).
FIG. 3 is a graph of castor oil-based hydrophilic chain extender COFA-SH (c) of example 1 and its intermediate castor oil-based polyol CO-SH (b), castor oil-based hydrophilic chain extender COFA-TG (d) of example 2, and castor oil (a)1H-NMR chart.
FIG. 4 is a particle size diagram of the aqueous polyurethane emulsion prepared from the castor oil based hydrophilic chain extender (COFA-SH) of example 1 and the castor oil based hydrophilic chain extender (COFA-TG) of example 2.
FIG. 5 is a coating stress-strain curve of a part of the aqueous polyurethane emulsion prepared in test example 1; wherein, (a) the COFA-SH of example 1 is used as a hydrophilic chain extender; (b) the COFA-TG of example 2 was used as a hydrophilic chain extender.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
(1) The measured photoinitiator 1173, castor oil and mercaptoethanol (the molar ratio of double bonds to mercapto groups is 1: 4.5; the dosage of the photoinitiator is (oil mass + mercaptoethanol mass) × 2%) are sequentially added into a test tube, and the reaction is carried out for 4.5h under the conditions of magnetic stirring and ultraviolet light. And (3) washing the reaction product for 5 times by using ethyl acetate as a solvent and brine, removing the water phase, removing water by using anhydrous magnesium sulfate, performing suction filtration and rotary evaporation to obtain a light yellow viscous liquid castor oil-based polyol CO-SH, and finishing the reaction in the first step.
(2) And (2) putting the intermediate product prepared in the step (1) into a 60 ℃ oven, and baking for 12 h. Taking a proper amount of intermediate product CO-SH in a single-mouth bottle, adding a proper amount of NaOH (the molar ratio of ester group to NaOH is 1:2) under the magnetic stirring at the temperature of 80 ℃, reacting for 5 hours, and adding HCl to adjust the reaction system to acidity. And (3) washing the reaction product for 5 times by using ethyl acetate as a solvent and brine, removing the water phase, removing water by using anhydrous magnesium sulfate, performing suction filtration, and performing rotary evaporation to obtain the COFA-SH hydrophilic chain extender.
And (3) performing Gel Permeation Chromatography (GPC) test, wherein polystyrene is used as a standard sample, Tetrahydrofuran (THF) is used as a mobile phase, the flow rate is 0.5mL/min, the test temperature is 35 ℃, and a 2414 differential refractometer is used as a detection instrument for determination.
FIG. 1 shows GPC charts of Castor Oil (CO), castor oil-based polyol (CO-SH), and hydrophilic chain extender (COFA-SH), wherein the shorter the leaching time of the polymer is, the larger the molecular weight is, and 3 polymers are shown in FIG. 1, the largest molecular weight is CO-SH, and the second is castor oil, which shows that mercaptoethanol has reacted with double bonds to be successfully introduced into castor oil molecules. The molecular weight of the COFA-SH is the smallest, which indicates that the ester group in the CO-SH is hydrolyzed.
NMR analysis by NMR with a Bruker Avance 600 NMR spectrometer with CDCl3Is a solvent.
FIG. 3 shows castor oil (a), castor oil-based polyol CO-SH (b), and hydrophilic chain extender COFA-SH (c)1In the H-NMR chart, (a) shows that the shift of hydrogen (-CH ═ CH-) on the unsaturated double bond in castor oil around 5.43ppm has completely disappeared in (b) and (c), indicating that the double bond is completely involved in the reaction. and-CH is present at 2.6ppm in (b)2The hydrogen proton peak of S-indicates the successful introduction of mercaptoethanol molecules.Comparing the shifts of hydrogen on 5.27 ppm-COO-CH-with 4.31ppm and 4.15 ppm-COO-CH in (b), (c) and (b) of FIG. 32The hydrogen-up shifts are completely disappeared in (c), which indicates that all three ester groups on the molecular chain of the intermediate product CO-SH are hydrolyzed to generate the target product COFA-SH.
Example 2
(1) The measured photoinitiator 1173, castor oil and thioglycerol (the molar ratio of double bonds to sulfydryl is 1: 4.5; the dosage of the photoinitiator is (the mass of oil plus the mass of thioglycerol) × 2%) are sequentially added into a test tube, and the reaction is carried out for 4.5 hours under the conditions of magnetic stirring and ultraviolet light. And (3) washing the reaction product for 5 times by using ethyl acetate as a solvent and brine, discarding the water phase, removing water by using anhydrous magnesium sulfate, performing suction filtration and rotary evaporation to obtain a light yellow viscous liquid castor oil-based polyol CO-TG, and finishing the reaction in the first step.
(2) And (2) putting the intermediate product prepared in the step (1) into a 60 ℃ oven, and baking for 12 h. Taking a proper amount of intermediate product CO-TG into a single-mouth bottle, adding a proper amount of NaOH (the molar ratio of ester group to NaOH is 1:2) under the magnetic stirring at the temperature of 80 ℃, reacting for 5 hours, and adding HCl to adjust the reaction system to acidity. And (3) washing the reaction product for 5 times by using ethyl acetate as a solvent and brine, removing the water phase, removing water by using anhydrous magnesium sulfate, performing suction filtration, and performing rotary evaporation to obtain the COFA-TG hydrophilic chain extender.
FIG. 2 is a GPC spectrogram of Castor Oil (CO), a hydrophilic chain extender COFA-SH and a hydrophilic chain extender COFA-TG measured by 2414 differential refractometer, and it can be known that the molecular weight of the hydrophilic chain extender COFA-TG is larger than that of the hydrophilic chain extender COFA-SH, which is caused by the fact that the molecular weight of thioglycerol is larger than that of mercaptoethanol, which indicates that the COFA-TG has successfully introduced thioglycerol into a molecular chain, and the molecular weight of the hydrophilic chain extender COFA-TG is smaller than that of castor oil, which indicates that an ester group in the CO-TG has been hydrolyzed.
FIG. 3 (d) is a nuclear magnetic hydrogen spectrum of COFA-TG as a hydrophilic chain extender measured by Bruker Avance 600 NMR, and the shift of hydrogen (-CH ═ CH-) on the unsaturated double bond in castor oil of 5.43ppm in (a) is completely disappeared in (d), indicating that the double bond is completely involved in the reaction. and-CH is present at 2.6ppm in (d)2The hydrogen proton peak of S-indicates the successful introduction of mercaptoethanol molecules. At the same time as 5.27 ppm-COO-CH-in (a)Hydrogen shift and 4.15ppm of-COO-CH2The hydrogen shift on the-chain has completely disappeared in (d), which indicates that all three ester groups on the molecular chain of the intermediate product CO-TG have been hydrolyzed to generate the target product COFA-TG.
Example 3
(1) The measured photoinitiator 1173, castor oil and mercaptoethanol (the molar ratio of double bonds to mercapto groups is 1: 1.5; the dosage of the photoinitiator is (oil mass + mercaptoethanol mass) × 2%) are sequentially added into a test tube, and the reaction is carried out for 5 hours under the conditions of magnetic stirring and ultraviolet light. And (3) washing the reaction product for 3 times by using ethyl acetate as a solvent and brine, removing the water phase, removing water by using anhydrous magnesium sulfate, performing suction filtration and rotary evaporation to obtain a light yellow viscous liquid castor oil-based polyol CO-SH, and finishing the reaction in the first step.
(2) Taking a proper amount of the intermediate product CO-SH prepared in the step (1) into a single-mouth bottle, adding a proper amount of NaOH (the molar ratio of ester group to NaOH is 1:1) under the magnetic stirring at 60 ℃, reacting for 1h, and adding HCl to adjust the reaction system to be acidic. And (3) washing the reaction product for 3 times by using ethyl acetate as a solvent and brine, removing the water phase, removing water by using anhydrous magnesium sulfate, performing suction filtration, and performing rotary evaporation to obtain the COFA-SH hydrophilic chain extender.
The GPC chart of the hydrophilic chain extender measured by a 2414 differential refractometer and the nuclear magnetic hydrogen spectrum of the hydrophilic chain extender measured by a Bruker Avance 600 nuclear magnetic resonance spectrometer both obtained characteristic peaks are the same as those in example 1.
Example 4
(1) The method comprises the steps of sequentially adding metered photoinitiator 1173, castor oil and thioglycerol (the molar ratio of double bonds to sulfydryl is 1: 1.5; the dosage of the photoinitiator is (the mass of oil plus the mass of thioglycerol) × 3%) into a test tube, and reacting for 1 hour under magnetic stirring and ultraviolet light. And (3) washing the reaction product for 3 times by using ethyl acetate as a solvent and brine, discarding the water phase, removing water by using anhydrous magnesium sulfate, performing suction filtration and rotary evaporation to obtain a light yellow viscous liquid castor oil-based polyol CO-TG, and finishing the reaction in the first step.
(2) And (2) putting the intermediate product prepared in the step (1) into an oven at 80 ℃ and baking for 14 h. Taking a proper amount of intermediate product CO-TG into a single-mouth bottle, adding a proper amount of NaOH (the molar ratio of ester group to NaOH is 1:3) under the magnetic stirring at 60 ℃, reacting for 10 hours, and adding HCl to adjust the reaction system to acidity. And washing the reaction product for 3 times by using ethyl acetate as a solvent and brine, removing a water phase, removing water by using anhydrous magnesium sulfate, performing suction filtration, and performing rotary evaporation to obtain the COFA-TG hydrophilic chain extender.
The GPC chart of the hydrophilic chain extender measured by a 2414 differential refractometer and the nuclear magnetic hydrogen spectrum of the hydrophilic chain extender measured by a Bruker Avance 600 nuclear magnetic resonance spectrometer both obtained characteristic peaks of the results are the same as those of example 2.
Example 5
(1) The method comprises the steps of sequentially adding metered photoinitiator 1173, castor oil and mercaptoethanol (the molar ratio of double bonds to mercapto groups is 1: 2.5; the dosage of the photoinitiator is (the mass of oil plus the mass of mercaptoethanol) × 3%) into a test tube, and reacting for 5 hours under the conditions of magnetic stirring and ultraviolet light. And (3) washing the reaction product for 3 times by using ethyl acetate as a solvent and brine, removing the water phase, removing water by using anhydrous magnesium sulfate, performing suction filtration and rotary evaporation to obtain a light yellow viscous liquid castor oil-based polyol CO-SH, and finishing the reaction in the first step.
(2) And (2) putting the intermediate product prepared in the step (1) into an oven at 80 ℃ and baking for 12 hours. Taking a proper amount of intermediate product CO-SH in a single-mouth bottle, adding a proper amount of NaOH (the molar ratio of ester group to NaOH is 1:1.5) under the magnetic stirring at 60 ℃, reacting for 1h, and adding HCl to adjust the reaction system to acidity. And (3) washing the reaction product for 3 times by using ethyl acetate as a solvent and brine, removing the water phase, removing water by using anhydrous magnesium sulfate, performing suction filtration, and performing rotary evaporation to obtain the COFA-SH hydrophilic chain extender.
The GPC chart of the hydrophilic chain extender measured by a 2414 differential refractometer and the nuclear magnetic hydrogen spectrum of the hydrophilic chain extender measured by a Bruker Avance 600 nuclear magnetic resonance spectrometer both obtained characteristic peaks are the same as those in example 1.
Example 6
(1) The method comprises the steps of sequentially adding metered photoinitiator 1173, castor oil and thioglycerol (the molar ratio of double bonds to sulfydryl is 1: 5.5; the dosage of the photoinitiator is (the mass of oil plus the mass of thioglycerol) × 2%) into a test tube, and reacting for 5 hours under magnetic stirring and ultraviolet light. And (3) washing the reaction product for 3 times by using ethyl acetate as a solvent and brine, discarding the water phase, removing water by using anhydrous magnesium sulfate, performing suction filtration and rotary evaporation to obtain a light yellow viscous liquid castor oil-based polyol CO-TG, and finishing the reaction in the first step.
(2) And (2) putting the intermediate product prepared in the step (1) into an oven at 80 ℃ and baking for 12 hours. Taking a proper amount of intermediate product CO-TG into a single-mouth bottle, adding a proper amount of NaOH (the molar ratio of ester group to NaOH is 1:1.5) under the magnetic stirring at 60 ℃, reacting for 1h, and adding HCl to adjust the reaction system to acidity. And washing the reaction product for 3 times by using ethyl acetate as a solvent and brine, removing a water phase, removing water by using anhydrous magnesium sulfate, performing suction filtration, and performing rotary evaporation to obtain the COFA-TG hydrophilic chain extender.
The GPC chart of the hydrophilic chain extender measured by a 2414 differential refractometer and the nuclear magnetic hydrogen spectrum of the hydrophilic chain extender measured by a Bruker Avance 600 nuclear magnetic resonance spectrometer both obtained characteristic peaks of the results are the same as those of example 2.
Example 7
(1) Taking a proper amount of castor oil in a single-mouth bottle, adding a proper amount of NaOH (the molar ratio of ester group to NaOH is 1:2.5) under the magnetic stirring at the temperature of 80 ℃, reacting for 1h, and adding HCl to adjust the reaction system to acidity. And (3) washing the reaction product for 5 times by using ethyl acetate as a solvent and brine, removing the water phase, removing water by using anhydrous magnesium sulfate, performing suction filtration and rotary evaporation to obtain an intermediate product ricinoleic acid, and finishing the reaction in the first step.
(2) And (2) sequentially adding a metered photoinitiator 1173 and the ricinoleic acid and mercaptoethanol prepared in the step (1) (the molar ratio of double bonds to mercapto groups is 1: 5.5; and the dosage of the photoinitiator is (the mass of the ricinoleic acid and the mass of the mercaptoethanol) × 3%) into a test tube, and reacting for 4.5 hours under magnetic stirring and ultraviolet light. And (3) washing the reaction product for 5 times by using ethyl acetate as a solvent and brine, removing the water phase, removing water by using anhydrous magnesium sulfate, performing suction filtration, and performing rotary evaporation to obtain the COFA-SH hydrophilic chain extender.
The GPC chart of the hydrophilic chain extender measured by a 2414 differential refractometer and the nuclear magnetic hydrogen spectrum of the hydrophilic chain extender measured by a Bruker Avance 600 nuclear magnetic resonance spectrometer both obtained characteristic peaks are the same as those in example 1.
Example 8
(1) Taking a proper amount of castor oil in a single-mouth bottle, adding a proper amount of NaOH (the molar ratio of ester group to NaOH is 1:1) under the magnetic stirring at the temperature of 80 ℃, reacting for 5 hours, and adding HCl to adjust the reaction system to be acidic. And (3) washing the reaction product for 5 times by using ethyl acetate as a solvent and brine, removing the water phase, removing water by using anhydrous magnesium sulfate, performing suction filtration and rotary evaporation to obtain an intermediate product ricinoleic acid, and finishing the reaction in the first step.
(2) And (2) sequentially adding a metered photoinitiator 1173 and the ricinoleic acid and the thioglycerol prepared in the step (1) (the molar ratio of double bonds to sulfydryl is 1: 4.5; and the dosage of the photoinitiator is (the mass of the ricinoleic acid plus the mass of the thioglycerol) multiplied by 3%) into a test tube, and reacting for 4.5 hours under magnetic stirring and ultraviolet light. And (3) washing the reaction product for 5 times by using ethyl acetate as a solvent and brine, removing the water phase, removing water by using anhydrous magnesium sulfate, performing suction filtration, and performing rotary evaporation to obtain the COFA-TG hydrophilic chain extender.
The GPC chart of the hydrophilic chain extender measured by a 2414 differential refractometer and the nuclear magnetic hydrogen spectrum of the hydrophilic chain extender measured by a Bruker Avance 600 nuclear magnetic resonance spectrometer both obtained characteristic peaks of the results are the same as those of example 2.
Example 9
(1) Taking a proper amount of castor oil in a single-mouth bottle, adding a proper amount of NaOH (the molar ratio of ester group to NaOH is 1:3) under the magnetic stirring at the temperature of 80 ℃, reacting for 10 hours, and adding HCl to adjust the reaction system to be acidic. And (3) washing the reaction product for 4 times by using ethyl acetate as a solvent and brine, discarding the water phase, removing water by using anhydrous magnesium sulfate, performing suction filtration and rotary evaporation to obtain an intermediate product ricinoleic acid, and finishing the reaction in the first step.
(2) And (2) sequentially adding a metered photoinitiator 1173 and the ricinoleic acid and mercaptoethanol prepared in the step (1) (the molar ratio of double bonds to mercapto groups is 1: 5.5; and the dosage of the photoinitiator is (the mass of the ricinoleic acid and the mass of the mercaptoethanol) × 2%) into a test tube, and reacting for 3 hours under magnetic stirring and ultraviolet light. And (3) washing the reaction product for 4 times by using ethyl acetate as a solvent and brine, removing the water phase, removing water by using anhydrous magnesium sulfate, performing suction filtration, and performing rotary evaporation to obtain the COFA-SH hydrophilic chain extender.
The GPC chart of the hydrophilic chain extender measured by a 2414 differential refractometer and the nuclear magnetic hydrogen spectrum of the hydrophilic chain extender measured by a Bruker Avance 600 nuclear magnetic resonance spectrometer both obtained characteristic peaks are the same as those in example 1.
Test example 1: comprehensive performance test of products of various embodiments
Water-based polyurethane emulsion prepared from castor oil-based hydrophilic chain extender prepared in each embodiment
Taking a proper amount of castor oil-based hydrophilic chain extender prepared in each example, diisocyanate and 6g of polyol, putting the castor oil-based hydrophilic chain extender, the diisocyanate and the polyol into a double-neck round-bottom flask, and stirring the castor oil-based hydrophilic chain extender, the diisocyanate and the polyol for 5 to 20 minutes by using an electric stirrer (the rotating speed is 100 to 300r/min) at 50 to 80 ℃ in an oil bath. Adding 1-6 drops of catalyst, and continuously stirring in an oil bath at 60-80 ℃ for reaction. When the viscosity of the solution is increased to almost no flow, 10-50 mL of organic solvent is added, and the stirring is continued for 1-7 h at 60-80 ℃, so that the reaction system becomes clear and transparent. Stopping heating, adding appropriate amount of neutralizer after the solution is cooled to room temperature, and continuing stirring for 30 min. After the rotating speed is adjusted to 300-500 r/min, 20-90 mL of deionized water is added for emulsification, and stirring is continued for 1-4 h. Transferring the product to a single-mouth round-bottom flask, and carrying out rotary evaporation at 40-60 ℃ for 30 min-1 h to obtain the anionic waterborne polyurethane emulsion with the solid content of 10.68-57.8 wt%.
The molar ratio of hydroxyl in the polyol, isocyanate group of diisocyanate and hydroxyl in the hydrophilic chain extender in the above step is 1: (1.5-3): (0.49-1.99).
The neutralization degree of the neutralizer in the steps is 85-110%.
The polyols described in the above steps include polyester polyol, polyether polyol and natural oil polyol, and the polyester polyol includes polycarbonate diol (PCDL), dimer acid Polyester Diol (PDFA), phthalic acid polyester diol (PPA), poly-1, 4-butylene glycol adipate diol (PBA), polycaprolactone diol (PCL), poly-1, 6-hexanediol adipate diol (PHA), etc.; polyether polyols include polytetrahydrofuran ether glycol (PTMG), polypropylene glycol (PPG), polyethylene glycol (PEG), and the like; the natural oil polyol includes castor oil and vegetable oil-based polyols, wherein the vegetable oil-based polyols include linseed oil-based polyols, soybean oil-based polyols, corn oil-based polyols, coconut oil-based polyols, cauliflower oil-based polyols, and the like, preferably castor oil among the natural oil polyols;
the diisocyanate described in the above step includes isophorone diisocyanate (IPDI), Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (HMDI), Lysine Diisocyanate (LDI), 1, 6-Hexamethylene Diisocyanate (HDI), etc., preferably isophorone diisocyanate (IPDI);
the catalyst described in the above step includes dibutyltin dilaurate (DBTDL), stannous octoate, triethylenediamine, N-ethyl morpholine, triethylenediamine, N-dimethylcyclohexylamine, etc., preferably dibutyltin dilaurate (DBTDL);
the organic solvent comprises butanone, acetone, toluene, xylene, butyl acetate, cyclohexanone and the like, and is preferably butanone;
the neutralizing agent used in the above step includes Triethylamine (TEA), Dimethylethanolamine (DMEA), ammonia, sodium hydroxide, potassium hydroxide, sodium bicarbonate, triethanolamine, etc., preferably Triethylamine (TEA).
And (3) testing the particle size and the Zeta potential of the aqueous polyurethane emulsion, diluting the emulsion to 0.01%, respectively placing samples in a cuvette and a potential cell at room temperature, and measuring the particle size and the Zeta potential of the aqueous polyurethane emulsion by using a Malvern nanometer particle size analyzer. The test results are shown in FIG. 4 and Table 1.
From table 1, it can be seen that the aqueous polyurethane emulsion prepared by the novel hydrophilic chain extender has small average particle size, high Zeta potential absolute value and excellent emulsion stability. The average particle size of the aqueous polyurethane emulsion prepared by using the COFA-SH as a hydrophilic chain extender is 40-154 nm, and the absolute value of the Zeta potential is more than 38.2 mV; the average particle size of the aqueous polyurethane emulsion prepared by using the COFA-TG as a hydrophilic chain extender is 87-150 nm, and the absolute value of the Zeta potential is more than 37 mV. FIG. 4 is a particle size diagram of the aqueous polyurethane emulsion prepared from the castor oil based hydrophilic chain extender (COFA-SH) of example 1 and the castor oil based hydrophilic chain extender (COFA-TG) of example 2, and it can be seen that the particle size distribution of the emulsion is concentrated and the dispersibility is good.
TABLE 1 Performance test results for various examples
Test example 2
The aqueous polyurethane emulsion prepared from the castor oil-based hydrophilic chain extender of each example prepared in test example 1 was cast into a silica gel mold, baked at 80 ℃ for 48 hours, and the resulting coating film was dried in an oven at 60 ℃ for 24 hours. And obtaining the aqueous polyurethane emulsion coating film prepared by the castor oil-based hydrophilic chain extender in each embodiment.
Tensile strength analysis of the coating film, mechanical properties of the photocurable film were measured according to GB13022-91 using a UTM4204 type universal electronic tester, the thickness of the sample was 1mm, the width was 10mm, and the tensile rate was 100 mm/min. The test results are shown in FIG. 5 and Table 1.
From table 1, it can be seen that the aqueous polyurethane coating film prepared by the novel hydrophilic chain extender has good tensile strength and excellent elongation at break. The tensile strength of the aqueous polyurethane coating film prepared by using the COFA-SH as a hydrophilic chain extender is more than 0.59MPa, and the elongation at break is more than 310%; the tensile strength of the aqueous polyurethane coating film prepared by using the COFA-TG as the hydrophilic chain extender is more than 3.35MPa, and the elongation at break is more than 80%.
Fig. 5(a) is a stress-strain curve of an aqueous polyurethane coating film prepared using the hydrophilic chain extender obtained in example 1, and fig. 5(b) is a stress-strain curve of an aqueous polyurethane coating film prepared using the hydrophilic chain extender obtained in example 2. As can be seen, the waterborne polyurethane coating film prepared by taking the COFA-SH as the hydrophilic chain extender has excellent ductility and can be used for the aspects of equipment protective films, rubber mats and the like; the waterborne polyurethane coating film prepared by taking the COFA-TG as the hydrophilic chain extender has excellent tensile strength, good ductility and wider application range. The waterborne polyurethane coating prepared by the novel hydrophilic chain extender has excellent mechanical property and can completely meet the requirement of practical application.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (4)
1. A preparation method of a castor oil based hydrophilic chain extender is characterized by comprising the following steps:
(1) sequentially adding a metered photoinitiator, castor oil and mercaptan, and reacting for 1-5 hours under magnetic stirring and ultraviolet light; washing the reaction product with saline water for 3-5 times by using ethyl acetate as a solvent, discarding a water phase, dehydrating with a drying agent, carrying out suction filtration and rotary evaporation to obtain an intermediate product, namely a faint yellow viscous liquid castor oil-based polyol, and finishing the reaction in the first step; the dosage of the photoinitiator is (the mass of the castor oil plus the mass of the mercaptan) multiplied by 2% to (the mass of the castor oil plus the mass of the mercaptan) multiplied by 3%; the thiol refers to a monohydric thiol containing one or more hydroxyl groups; the molar ratio of double bonds in the castor oil to sulfydryl in the mercaptan is 1: 1.5-1: 5.5;
(2) putting the intermediate product prepared in the step (1) into a temperature of 60-80 ℃, and drying for 0-14 h; taking a proper amount of intermediate product, adding a proper amount of alkali under magnetic stirring at the temperature of 60-80 ℃, reacting for 1-10 h, and adding acid to adjust the reaction system to be acidic; washing a reaction product for 3-5 times by using ethyl acetate as a solvent and brine, discarding a water phase, dewatering by using a drying agent, performing suction filtration, and performing rotary evaporation to obtain a hydrophilic chain extender, namely the castor oil-based hydrophilic chain extender; the molar ratio of ester groups of the intermediate product to alkali is 1: 1-1: 3;
the structural formula of the castor oil-based hydrophilic chain extender is shown as the formula (1):
formula (1)
Wherein n = a natural number of 1-5, and R is an alkyl group having a main chain of 10 or less carbons.
2. A preparation method of a castor oil based hydrophilic chain extender is characterized by comprising the following steps:
(A) taking castor oil, adding a proper amount of alkali under magnetic stirring at 60-80 ℃, reacting for 1-10 h, and adding acid to adjust the reaction system to be acidic; washing a reaction product for 3-5 times by using ethyl acetate as a solvent and brine, discarding a water phase, dewatering by using a drying agent, performing suction filtration, and performing rotary evaporation to obtain an intermediate product ricinoleic acid; the molar ratio of ester groups to alkali in the castor oil is 1: 1-1: 3;
(B) sequentially adding a photoinitiator, ricinoleic acid serving as an intermediate product prepared in the step (A) and mercaptan, and reacting for 1-5 hours under magnetic stirring and ultraviolet light; washing a reaction product for 3-5 times by using ethyl acetate as a solvent and brine, discarding a water phase, dewatering by using a drying agent, performing suction filtration, and performing rotary evaporation to obtain a hydrophilic chain extender, namely the castor oil-based hydrophilic chain extender; the dosage of the photoinitiator is (the mass of the intermediate product ricinoleic acid plus the mass of the mercaptan) multiplied by 2% to (the mass of the intermediate product ricinoleic acid plus the mass of the mercaptan) multiplied by 3%; the thiol refers to a monohydric thiol containing one or more hydroxyl groups; the molar ratio of the double bond of the intermediate product ricinoleic acid to the sulfydryl in the mercaptan is 1: 1.5-1: 5.5;
the structural formula of the castor oil-based hydrophilic chain extender is shown as the formula (1):
formula (1)
Wherein n = a natural number of 1-5, and R is an alkyl group having a main chain of 10 or less carbons.
3. The method for preparing the castor oil-based hydrophilic chain extender according to claim 1 or 2, wherein the castor oil-based hydrophilic chain extender comprises the following steps:
the photoinitiator is a photoinitiator 1173;
the mercaptan includes mercaptoethanol, thioglycerol, 1-mercapto-2-propanol, 2-mercapto-3-butanol and 6-mercaptohexanol.
4. The method for preparing the castor oil-based hydrophilic chain extender according to claim 1 or 2, wherein the castor oil-based hydrophilic chain extender comprises the following steps:
the drying agent comprises anhydrous magnesium sulfate, anhydrous sodium sulfate and anhydrous calcium chloride;
the acid comprises hydrochloric acid, sulfuric acid, acetic acid, nitric acid, carbonic acid and phosphoric acid;
the alkali comprises sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium bisulfite and potassium carbonate.
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