CN103421162A - Preparation method for pure rapeseed oil-based waterborne polyurethane resin - Google Patents
Preparation method for pure rapeseed oil-based waterborne polyurethane resin Download PDFInfo
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Abstract
The invention discloses a method for preparing pure rapeseed oil-based waterborne polyurethane resin by taking rapeseed oil as an initial raw material. Monomers for preparing polyurethane comprise rapeseed oil-based isocyanate, rapeseed oil-based polyalcohol and a rapeseed oil-based hydrophilic chain extender which are all prepared by thiol-ene click reaction of the rapeseed oil with sulfydryl-containing compounds. Finally, the prepared rapeseed oil-based isocyanate, rapeseed oil-based polyalcohol and rapeseed oil-based hydrophilic chain extender are subjected to copolymerization reaction to prepare the pure rapeseed oil-based waterborne polyurethane resin.
Description
Technical field
The present invention relates to the urethane resin field, be specifically related to a kind of preparation method of pure rapeseed oil base water polyurethane resin desired raw material and the technology of preparing of pure plant oil based waterborne polyurethane resin.
Background technology
Aqueous polyurethane be take water as dispersion medium, and than solvent type urethane, it has the characteristics such as environmental friendliness, construction safety convenience.Become coating in recent years and the study hotspot of sizing agent industry.But up to now, the raw material of producing aqueous polyurethane is petroleum chemicals, along with the exhaustion day by day of petroleum resources, its sustainable developability is tested.Adopting natural renewable resources is a kind of good solutions as Vegetable oil lipoprotein etc. replaces petroleum chemicals gradually.
Vegetables oil has recyclability, the resource distribution scope is wide, cheap, there is abundant application possibility from structure analysis, but because two key density and the activity that can directly carry out polymerization in vegetables oil are lower, its homopolymer can only obtain the polymkeric substance that molecular weight is lower, wearing quality is poor, so pure plant oil fluoropolymer resin is less, generally it is participated in to polyreaction as comonomer, the renewable carbon content of polymer materials for preparing gained is limited, nonetheless, the reaction system that vegetables oil participates in polymerization mostly is solvent system, the less report that sees of the preparation of the plant oil based resin of water-based of high content of vegetable oil.Consideration based on environmental protection and the direct utilising efficiency of renewable resources, it is significant that the waterborne polyurethane resin that vegetables oil is starting raw material is take in research.
Summary of the invention
The object of the invention is to utilize the advantage that sulfydryl-alkene click-reaction molecular designing ability is strong and reaction is efficient, suitable monomers is wide, the synthetic Rap Oil-based monomer with secondary reaction activity of design, monomer obtains a kind of full Rap Oil-based waterborne polyurethane resin after polyreaction.
Concrete technical scheme is: take rapeseed oil and compounds containing thiol groups as raw material, under ultra violet lamp, by the ratio of two keys and sulfydryl in the control vegetables oil, generate two key substitution values different Rap Oil-based polycarboxylic acid and Rap Oil-based polyvalent alcohol from 3-thiohydracrylic acid and mercaptoethanol reaction respectively; Gained Rap Oil-based polycarboxylic acid on the one hand can be by chloride and the synthetic Rap Oil-based isocyanic ester of curtius' rearrangement, and the Rap Oil-based polycarboxylic acid that two key substitution values are low on the other hand continues to react to prepare Rap Oil-based carboxylic acid type hydrophilic chain extender with mercaptoethanol.Final Rap Oil-based isocyanic ester, Rap Oil-based polyvalent alcohol, the Rap Oil-based hydrophilic chain extender of above preparation of using prepares full Rap Oil-based waterborne polyurethane resin.Concrete steps are as follows:
The route that the rapeseed oil of take prepares waterborne polyurethane resin as raw material synthesizes as shown in Figure 1.
A kind of preparation method of pure rapeseed oil base water polyurethane resin comprises the following steps:
(1) preparation of Rap Oil-based isocyanic ester:
Rapeseed oil, 3-thiohydracrylic acid, light trigger and methylene dichloride are added in reaction flask, under 18-40 ℃ of whipped state, ultra violet lamp 6 ~ 8 hours, use deionized water wash solution to remove excessive 3-thiohydracrylic acid, organic layer is used anhydrous magnesium sulfate drying, revolve to steam and remove the rapeseed oil that methylene dichloride obtains the carboxyl graft modification, wherein the mol ratio of 3-thiohydracrylic acid and rapeseed oil is defined as 1.2:1 ~ 3:1 according to the content of unsaturated double-bond in rapeseed oil.By the rapeseed oil of carboxyl graft modification, N, dinethylformamide, methylene dichloride and sulfur oxychloride are added in reaction flask, in temperature, be under 35 ~ 50 ℃, stir 5 ~ 6 hours, revolve to steam and remove methylene dichloride and sulfur oxychloride, obtain the Rap Oil-based acyl chlorides, wherein in the rapeseed oil of carboxyl graft modification, the mol ratio of carboxyl and sulfur oxychloride is 7:1 ~ 10:1.Sodiumazide and deionized water are joined in reaction flask; ice bath; stir the lower tetrahydrofuran solution that drips the Rap Oil-based acyl chlorides; add ethyl acetate extraction organic layer; stratification; separate organic layer and use anhydrous magnesium sulfate drying, obtain the solution of rapeseed oil acyl azide, wherein the mol ratio of Rap Oil-based acyl chlorides and sodiumazide is 1:1.5.Organic layer is added in reaction flask, and 60 ~ 80 ℃ of lower return stirring 2h, obtain target product.
(2) preparation of Rap Oil-based polyvalent alcohol:
Rapeseed oil, mercaptoethanol, light trigger and methylene dichloride are added in reaction flask, under 18-40 ℃ of whipped state, ultra violet lamp 3 ~ 8 hours, use deionized water wash solution to remove excessive mercaptoethanol, organic layer is used anhydrous magnesium sulfate drying, revolve to steam and remove methylene dichloride and obtain the Rap Oil-based polyvalent alcohol, wherein the mol ratio of mercaptoethanol and rapeseed oil is defined as 3:1 ~ 5:1 according to the content of unsaturated double-bond in rapeseed oil.
(3) preparation of Rap Oil-based hydrophilic chain extender:
By carboxy-modified rapeseed oil, mercaptoethanol, light trigger and methylene dichloride add in reaction flask, under 18-40 ℃ of whipped state, ultra violet lamp 3 ~ 8 hours, used deionized water wash solution to remove excessive mercaptoethanol, and organic layer is used anhydrous magnesium sulfate drying, revolve to steam and remove methylene dichloride and obtain the Rap Oil-based hydrophilic chain extender, wherein mercaptoethanol and carboxy-modified rapeseed oil mol ratio be defined as 3:1 ~ 5:1 according to the content of unsaturated double-bond in carboxy-modified rapeseed oil.
(4) preparation of polyurethane prepolymer:
By the Rap Oil-based isocyanic ester, Rap Oil-based polyvalent alcohol and acetone add in reaction flask, react under the effect of organotin catalysts and generate prepolymer in 3 ~ 4 hours, and temperature of reaction is 70 ~ 80 ℃, and the ratio of isocyanic ester based on hydroxyl is 1.6:1 ~ 2:1.
(5) preparation of polyurethane aqueous dispersion body:
In above-mentioned prepolymer, add Rap Oil-based carboxylic acid type hydrophilic chain extender to carry out chain extending reaction 3 ~ 4 hours, temperature of reaction is 70 ~ 80 ℃.Add the salt-forming reagent neutralization, react 0.5 hour, temperature of reaction is 50 ~ 60 ℃.Above-mentioned polymkeric substance is added in deionized water, use high speed dispersor to carry out emulsion dispersion, vacuumize de-acetone, obtain pure rapeseed oil base water polyurethane resin.
Compared with prior art, the present invention has following beneficial effect: of the present invention containing full Rap Oil-based aqueous polyurethane emulsion, it is that raw material is synthetic that all monomers all adopt rapeseed oil, and under synthesized hydrophilic monomer normal temperature, is liquid, in reaction process, need not be dissolved by additional high boiling solvent.Prepared polyaminoester emulsion has very high bio-based content.Its theoretical biological renewable carbon content (%BRC) is more than 90%, and prepared Rap Oil-based waterborne polyurethane resin has good visco-elasticity, can be used for coating and sizing agent.
The accompanying drawing explanation
The synthetic technology route of Fig. 1 pure rapeseed oil base water polyurethane of the present invention resin raw materials.
Embodiment
The preparation of embodiment 1 Rap Oil-based isocyanic ester:
Rapeseed oil 15.00g, 3-thiohydracrylic acid 11.20g, light trigger (UV1173) 0.393g and methylene dichloride 30ml are added in reaction flask, under 18 ℃ of whipped states, use 1.8mw cm
2Ultra violet lamp 8 hours, used deionized water wash solution to remove excessive 3-thiohydracrylic acid, and organic layer is used anhydrous magnesium sulfate drying, revolves to steam and remove the rapeseed oil 16.43g that methylene dichloride obtains the carboxyl graft modification; Combine with acid number titration by the NMR technology and determine the reaction number of two keys, wherein the mol ratio of 3-thiohydracrylic acid and rapeseed oil is defined as 1.74:1 according to the content of unsaturated double-bond in rapeseed oil.Rapeseed oil 8.00g, N by the carboxyl graft modification, 6 of dinethylformamides, methylene dichloride 20ml, and sulfur oxychloride 20.00g is added in reaction flask, in temperature, be under 45 ℃, stir 5 hours, revolve to steam and remove methylene dichloride and sulfur oxychloride, obtain the Rap Oil-based acyl chlorides, wherein in the rapeseed oil of carboxyl graft modification, the mol ratio of carboxyl and sulfur oxychloride is 10:1.Sodiumazide 1.79g and deionized water 19.45g are joined in reaction flask; ice bath; under agitation drip the tetrahydrofuran solution that is dissolved with the Rap Oil-based acyl chlorides in 30 minutes; dropwise rear continuation reaction 2 hours; add ethyl acetate extraction organic layer, stratification, separate organic layer and use anhydrous magnesium sulfate drying again; obtain the solution of rapeseed oil acyl azide, wherein the mol ratio of Rap Oil-based acyl chlorides and sodiumazide is 1:1.5.Organic layer is added in reaction flask, and 70 ℃ of lower stirring and refluxing 2h, revolve and steam except desolventizing, obtains purpose product 5.89g(and take carboxy-modified rapeseed oil as starting raw material calculating, productive rate 73.6%).
Structural Identification:
FT-IR (pressing potassium bromide troche, cm
-1): 2924,2854,2360,2263,2155,1745,1679.
1HNMR(400MHZ，CDCl
3，δ?ppm)：?5.53-5.27?(m,?3H),?5.26?(d,?
J?=?16.3?Hz,?1H),?4.27?(dd,?
J?=?11.8,?3.9?Hz,?2H),?4.12?(dd,?
J?=?11.8,?5.9?Hz,?2H),?3.72?(t,?
J?=?6.3?Hz,?2H),?3.40?(t,?
J?=?6.6?Hz,?3H),?2.83?–?2.65?(m,?3H),?2.65?–?2.49?(m,?2H),?2.28?(dd,?
J?=?15.1,?8.1?Hz,?7H),?1.92?(t,?
J?=?15.1?Hz,?5H),?1.64?–?1.12?(m,?73H),?0.84?(dd,?J?=?17.2,?10.5?Hz,?9H)。
13C?NMR?(100MHZ，CDCl
3，δ?ppm)：173.13（C=O）,?172.72?(C=O),?130.41?(C=C),?130.11?(C=C),?123.77?(N=C=O),?68.87?(CH),?67.87?(CH
2),?62.03?(CH
2),?46.33?(CH),?43.05?(CH
2),?34.98?(CH
2),?34.91?(CH
2),?34.11?(CH
2),?33.96?(CH
2),?32.54?(CH
2),?32.49?(CH
2),?32.24?(CH
2),?31.84?(CH
2),?29.63?(CH
2),?29.60?(CH
2),?29.56?(CH
2),?29.52?(CH
2),?29.42?(CH
2),?29.29?(CH
2),?29.25?(CH
2),?29.21?(CH
2),?29.12?(CH
2),?29.05?(CH
2),?29.01?(CH
2),?28.89?(CH
2),?26.70?(CH
2),?25.56?(CH
2),?24.79?(CH
2),?22.61?(CH
2),?14.03?(CH
3)。
The preparation of embodiment 2 Rap Oil-based polyvalent alcohols:
Rapeseed oil 12g, mercaptoethanol 15.94g, light trigger (UV1173) 0.414g and methylene dichloride 30ml are added in reaction flask, under 20 ℃ of whipped states, ultra violet lamp 3 hours, use deionized water wash solution to remove excessive mercaptoethanol, organic layer is used anhydrous magnesium sulfate drying, revolve to steam and remove methylene dichloride and obtain the Rap Oil-based polyvalent alcohol, wherein the mol ratio of mercaptoethanol and rapeseed oil is defined as 4.25:1 according to the content of unsaturated double-bond in rapeseed oil.
Structural Identification:
FT-IR (pressing potassium bromide troche, cm
-1): 3622-3155,2926,2854,1745,1465,1379,1164,1099,1043,968,723.
1HNMR?(400MHZ，CDCl
3，δ?ppm)：?5.55-5.18?(m,?4H),?4.27?(dd,?
J?=?11.8,?4.2?Hz,?2H),?4.12?(dd,?
J?=?11.8,?5.8?Hz,?2H),?3.76?–?3.60?(m,?4H),?2.69?(t,?
J?=?6.0?Hz,?4H),?2.57?(dd,?
J?=?12.7,?6.4?Hz,?2H),?2.28?(dd,?
J?=?16.5,?9.4?Hz,?7H),?1.94?(s,?5H),?1.66-1.14?(m,?68H),?0.86?(t,?
J?=?6.3?Hz,?9H).
13C?NMR?(100MHZ，CDCl
3，δ?ppm)：173.18?(COO),?172.76?(COO),?130.40?(C=C),?130.10?(C=C),?68.86?(CH),?62.04?(CH
2),,?60.83?(CH
2),?45.82?(CH),?34.92?(CH
2),?34.12?(CH
2),?33.96?(CH
2),?33.66?(CH
2),?32.54?(CH
2),?32.49?(CH
2),?31.84?(CH
2),?29.64?(CH
2),?29.59?(CH
2),?29.53?(CH
2),?29.48?(CH
2),?29.43?(CH
2),?29.25?(CH
2),?29.12?(CH
2),?29.05?(CH
2),?29.01?(CH
2),?28.97?(CH
2),?28.89?(CH
2),?26.74?(CH
2),?26.68?(CH
2),?24.79?(CH
2),?22.62?(CH
2),?14.05?(CH
3)。
The preparation of embodiment 3 Rap Oil-based hydrophilic chain extenders:
By carboxy-modified rapeseed oil 12g, mercaptoethanol 15.94g, light trigger (UV1173) 0.414g and methylene dichloride 30ml add in reaction flask, under 25 ℃ of whipped states, ultra violet lamp 6 hours, use deionized water wash solution to remove excessive mercaptoethanol, organic layer is used anhydrous magnesium sulfate drying, revolve to steam and remove methylene dichloride and obtain the Rap Oil-based hydrophilic chain extender, wherein the mol ratio of mercaptoethanol and carboxy-modified rapeseed oil is defined as 4.25:1 according to the content of unsaturated double-bond in carboxy-modified rapeseed oil.
Structural Identification:
FT-IR (pressing potassium bromide troche, cm
-1): 3643-2412,3475,2925,2852,1743,1712,1465,1373,1246,1167,1053,910,723.
1HNMR(400MHZ，CDCl
3，δ?ppm)：5.24?(s,?1H),?4.27?(d,?
J?=?11.9?Hz,?2H),?4.12?(dd,?
J?=?11.8,?5.8?Hz,?2H),?3.70?(dt,?
J?=?11.6,?6.1?Hz,?8H),?2.69?(dt,?
J?=?17.5,?9.1?Hz,?7H),?2.64-2.51?(m,?7H),?2.29?(t,?
J?=?7.1?Hz,?6H),?1.89-1.76?(m,?5H),?1.71-1.14?(m,?78H),?0.85?(t,?
J?=?6.4?Hz,?9H).
13C?NMR?(100MHZ，CDCl
3，δ?ppm)：176.50?(COOH),?173.27?(COO),?172.73?(COO),?68.89?(CH),?62.06?(CH
2),?60.90?(CH
2),?46.23?(CH),?34.85?(CH
2),?34.10?(CH
2),?33.94?(CH
2),?31.81?(CH
2),?29.61?(CH
2),?29.56?(CH
2),?29.51?(CH
2),?29.46?(CH
2),?29.27?(CH
2),?29.23?(CH
2),?29.21?(CH
2),?29.11?(CH
2),?28.95?(CH
2),?26.71?(CH
2),?26.65?(CH
2),?24.99?(CH
2),?24.75?(CH
2),?22.59?(CH
2),?14.02?(CH
3)。
The preparation of embodiment 4 pure rapeseed oil base water polyurethane resins
(1) by Rap Oil-based isocyanic ester 2.0g, Rap Oil-based polyvalent alcohol 1.14g and acetone 15ml add in reaction flask, react under the effect of organotin catalysts and generate prepolymer in 3 ~ 4 hours, and the temperature of reaction of prepolymerization reaction is 70 ~ 80 ℃.
(2) preparation of polyurethane aqueous dispersion body:
In above-mentioned prepolymer, add Rap Oil-based carboxylic acid type hydrophilic chain extender 1.4g to carry out chain extending reaction 3 ~ 4 hours, temperature of reaction is 70 ~ 80 ℃.
Add salt-forming reagent triethylamine 0.363g neutralization, react 0.5 hour, temperature of reaction is 50 ~ 60 ℃.
Above-mentioned polymkeric substance is added in the 11.3g deionized water, use high speed dispersor to carry out emulsion dispersion, vacuumize de-acetone, obtain pure rapeseed oil base water polyurethane resin.
Claims (5)
1. the preparation method of a pure rapeseed oil base water polyurethane resin, it is characterized in that comprising the steps: the preparation of (1) Rap Oil-based isocyanic ester: by rapeseed oil, the 3-thiohydracrylic acid, light trigger and methylene dichloride add in reaction flask, under 18-40 ℃ of whipped state, ultra violet lamp 6 ~ 8 hours, use deionized water wash solution to remove excessive 3-thiohydracrylic acid, organic layer is used anhydrous magnesium sulfate drying, revolve to steam and remove the rapeseed oil that methylene dichloride obtains the carboxyl graft modification, wherein the mol ratio of 3-thiohydracrylic acid and rapeseed oil is defined as 1.2:1 ~ 3:1 according to the content of unsaturated double-bond in rapeseed oil, by the rapeseed oil of carboxyl graft modification, N, dinethylformamide, methylene dichloride and sulfur oxychloride are added in reaction flask, in temperature, be under 35 ~ 50 ℃, stir 5 ~ 6 hours, revolve to steam and remove methylene dichloride and sulfur oxychloride, obtain the Rap Oil-based acyl chlorides, wherein in the rapeseed oil of carboxyl graft modification, the mol ratio of carboxyl and sulfur oxychloride is 7:1 ~ 10:1, sodiumazide and deionized water are joined in reaction flask, ice bath, stir the lower tetrahydrofuran solution that drips the Rap Oil-based acyl chlorides, add ethyl acetate extraction organic layer, stratification, separate organic layer and use anhydrous magnesium sulfate drying, obtain the solution of rapeseed oil acyl azide, wherein the mol ratio of Rap Oil-based acyl chlorides and sodiumazide is 1:1.5, organic layer is added in reaction flask, and 60 ~ 80 ℃ of lower return stirring 2h, obtain target product, (2) preparation of Rap Oil-based polyvalent alcohol: rapeseed oil, mercaptoethanol, light trigger and methylene dichloride are added in reaction flask, under 18-40 ℃ of whipped state, ultra violet lamp 3 ~ 8 hours, use deionized water wash solution to remove excessive mercaptoethanol, organic layer is used anhydrous magnesium sulfate drying, revolve to steam and remove methylene dichloride and obtain the Rap Oil-based polyvalent alcohol, wherein the mol ratio of mercaptoethanol and rapeseed oil is defined as 3:1 ~ 5:1 according to the content of unsaturated double-bond in rapeseed oil, (3) preparation of Rap Oil-based hydrophilic chain extender: the lower carboxy-modified rapeseed oil by two key substitution values, mercaptoethanol, light trigger and methylene dichloride add in reaction flask, under 18-40 ℃ of whipped state, ultra violet lamp 3 ~ 8 hours, use deionized water wash solution to remove excessive mercaptoethanol, organic layer is used anhydrous magnesium sulfate drying, revolve to steam and remove methylene dichloride and obtain the Rap Oil-based hydrophilic chain extender, wherein mercaptoethanol and carboxy-modified rapeseed oil mol ratio be defined as 3:1 ~ 5:1 according to the content of unsaturated double-bond in carboxy-modified rapeseed oil, (4) preparation of polyurethane prepolymer: by the Rap Oil-based isocyanic ester, Rap Oil-based polyvalent alcohol and acetone add in reaction flask, react under the effect of organotin catalysts and within 3 ~ 4 hours, generate prepolymer, the temperature of reaction of prepolymerization reaction is 70 ~ 80 ℃, and the ratio of isocyanate group and hydroxyl is 1.6:1 ~ 2:1, (5) preparation of pure rapeseed oil base water polyurethane resin: in above-mentioned prepolymer, add Rap Oil-based carboxylic acid type hydrophilic chain extender to carry out chain extending reaction 3 ~ 4 hours, temperature of reaction is 70 ~ 80 ℃, add the salt-forming reagent neutralization, react 0.5 hour, temperature of reaction is 50 ~ 60 ℃, above-mentioned polymkeric substance is added in deionized water, use high speed dispersor to carry out emulsion dispersion, vacuumize de-acetone, obtain pure rapeseed oil base water polyurethane resin.
2. preparation method according to claim 1, is characterized in that described light trigger comprises: st-yrax photoinitiator, 2-dihydroxy benaophenonel, 2,2-dimethyl benzil ketals, 2, the mixture of one or more in the 2-diethoxy acetophenone.
3. preparation method according to claim 1, is characterized in that in each step of step (4) step (5) or arbitrary step adding acetone to reduce viscosity.
4. preparation method according to claim 1, is characterized in that described organotin catalysts is dibutyl tin laurate or stannous octoate; Be preferably dibutyl tin laurate.
5. preparation method according to claim 1, is characterized in that described salt-forming reagent is triethylamine, sodium hydroxide, potassium hydroxide or ammoniacal liquor; Be preferably triethylamine.
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| CN104086743A (en) * | 2014-06-30 | 2014-10-08 | 江西科技师范大学 | Preparation method of cardanol-base polyalcohols and polyurethanes thereof |
| CN104804496A (en) * | 2015-04-28 | 2015-07-29 | 中科院广州化学有限公司南雄材料生产基地 | Low-surface-energy polyurethane photocureable coating and preparation method thereof |
| CN104804496B (en) * | 2015-04-28 | 2017-10-03 | 中科院广州化学有限公司南雄材料生产基地 | A kind of low-surface-energy polyurethane photocureable coating and preparation method thereof |
| CN107556452A (en) * | 2017-09-15 | 2018-01-09 | 华南农业大学 | A kind of castor oil-base hydrophilic chain extender and its preparation method and application |
| CN109824814A (en) * | 2019-01-29 | 2019-05-31 | 中国林业科学研究院林产化学工业研究所 | Compound super-hydrophobic coat solution of vegetable oil/inorganic nano-particle and its preparation method and application |
| CN109824814B (en) * | 2019-01-29 | 2021-02-19 | 中国林业科学研究院林产化学工业研究所 | Vegetable oil/inorganic nanoparticle composite super-hydrophobic coating solution and preparation method and application thereof |
| CN110790882A (en) * | 2019-11-13 | 2020-02-14 | 浩力森涂料（上海）有限公司 | Organic silicon modified cardanol-based waterborne polyurethane and preparation method thereof |
| CN112028801A (en) * | 2020-07-24 | 2020-12-04 | 华南农业大学 | Chain extender and preparation method and application thereof |
| CN112028801B (en) * | 2020-07-24 | 2021-07-09 | 华南农业大学 | Chain extender and preparation method and application thereof |
| CN114703600A (en) * | 2022-04-11 | 2022-07-05 | 江苏伊贝实业股份有限公司 | Preparation method of waterproof breathable polyurethane bootie lining film |
| CN116731432A (en) * | 2023-07-13 | 2023-09-12 | 深圳市好年璟科技有限公司 | Heat-conducting rubber-plastic composite material and preparation method thereof |
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