CN103421162B - 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 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 take water as dispersion medium, and compared to solvent type urethane, it has the characteristic such as environmental friendliness, construction safety convenience.Become the study hotspot of coating in recent years and sizing agent industry.But up to now, the raw material producing aqueous polyurethane is petroleum chemicals, along with the exhaustion day by day of petroleum resources, its sustainable developability is tested.Natural renewable resources such as Vegetable oil lipoprotein etc. is adopted to replace petroleum chemicals to be a kind of well solutions gradually.
Vegetables oil has recyclability, resource distribution scope is wide, cheap, from structure analysis, there is abundant application possibility, but due to directly can carry out the double bond density of being polymerized in vegetables oil and activity lower, its homopolymer can only obtain the lower polymkeric substance of molecular weight, wearing quality is poor, so pure plant oil fluoropolymer resin is less, comonomer is generally it can be used as to participate in polyreaction, prepare the renewable carbon restricted levels of the polymer materials of gained, nonetheless, the reaction system that vegetables oil participates in polymerization mostly is solvent system, the preparation of the plant oil based resin of water-based of high content of vegetable oil is less sees report.Based on the consideration of environmental protection and the direct utilising efficiency of renewable resources, studying with vegetables oil is that the waterborne polyurethane resin of starting raw material is significant.
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, design and synthesis has the Rap Oil-based monomer of secondary reaction activity, and monomer obtains a kind of full Rap Oil-based waterborne polyurethane resin after polyreaction.
Concrete technical scheme is: with rapeseed oil and compounds containing thiol groups for raw material, under ultra violet lamp, by controlling the ratio of double bond and sulfydryl in vegetables oil, reacting from 3-thiohydracrylic acid and mercaptoethanol respectively and generating the different Rap Oil-based polycarboxylic acid of double bond substitution value and Rap Oil-based polyvalent alcohol; Gained Rap Oil-based polycarboxylic acid is on the one hand by chloride and curtius' rearrangement synthesis Rap Oil-based isocyanic ester, and the Rap Oil-based polycarboxylic acid that double bond substitution value is low on the other hand and mercaptoethanol continue to react to prepare Rap Oil-based carboxylic acid type hydrophilic chain extender.The Rap Oil-based isocyanic ester more than final utilization prepared, Rap Oil-based polyvalent alcohol, Rap Oil-based hydrophilic chain extender prepare full Rap Oil-based waterborne polyurethane resin.Concrete steps are as follows:
Be that Material synthesis prepares the route of waterborne polyurethane resin as shown in Figure 1 with rapeseed oil.
A preparation method for 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 DEG C of whipped state, ultra violet lamp 6 ~ 8 hours, deionized water wash solution is used to remove excessive 3-thiohydracrylic acid, organic layer uses anhydrous magnesium sulfate drying, revolve and steam the rapeseed oil that removing methylene dichloride obtains 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, at temperature is 35 ~ 50 DEG C, stir 5 ~ 6 hours, revolve and steam removing methylene dichloride and sulfur oxychloride, obtain Rap Oil-based acyl chlorides, in the rapeseed oil of wherein 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 dripping Rap Oil-based acyl chlorides; add extraction into ethyl acetate 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.Added by organic layer in reaction flask, at 60 ~ 80 DEG C, return stirring 2h, obtains 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 DEG C of whipped state, ultra violet lamp 3 ~ 8 hours, deionized water wash solution is used to remove excessive mercaptoethanol, organic layer uses anhydrous magnesium sulfate drying, revolve steaming removing methylene dichloride and obtain 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 DEG C of whipped state, ultra violet lamp 3 ~ 8 hours, use deionized water wash solution to remove excessive mercaptoethanol, organic layer uses anhydrous magnesium sulfate drying, revolve and steam removing methylene dichloride and obtain 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 Rap Oil-based isocyanic ester, Rap Oil-based polyvalent alcohol and acetone add in reaction flask, and react under the effect of organotin catalysts and generate prepolymer in 3 ~ 4 hours, temperature of reaction is 70 ~ 80 DEG C, and isocyanic ester is 1.6:1 ~ 2:1 based on the ratio of hydroxyl.
(5) preparation of polyurethane aqueous dispersion body:
In above-mentioned prepolymer, add Rap Oil-based carboxylic acid type hydrophilic chain extender carry out chain extending reaction 3 ~ 4 hours, temperature of reaction is 70 ~ 80 DEG C.Add salt-forming reagent neutralization, react 0.5 hour, temperature of reaction is 50 ~ 60 DEG C.Above-mentioned polymkeric substance is added in deionized water, uses 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, all monomers all adopt rapeseed oil to be Material synthesis, and are liquid under synthesized hydrophilic monomer normal temperature, need not dissolve by additional high boiling solvent in reaction process.Obtained polyaminoester emulsion has very high Bio-based content.Its theoretical biorenewable carbon content (%BRC) is more than 90%, and obtained Rap Oil-based waterborne polyurethane resin has good visco-elasticity, can be used for coating and sizing agent.
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 DEG C of whipped states, use 1.8mw cm
2ultra violet lamp 8 hours, use deionized water wash solution to remove excessive 3-thiohydracrylic acid, organic layer uses anhydrous magnesium sulfate drying, revolves and steams the rapeseed oil 16.43g that removing methylene dichloride obtains carboxyl graft modification; To be combined with acid number titration by NMR technology and determine the reaction number of double bond, 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.By rapeseed oil 8.00g, N of carboxyl graft modification, dinethylformamide 6, methylene dichloride 20ml, and sulfur oxychloride 20.00g is added in reaction flask, at temperature is 45 DEG C, stir 5 hours, revolve and steam removing methylene dichloride and sulfur oxychloride, obtain Rap Oil-based acyl chlorides, in the rapeseed oil of wherein carboxyl graft modification, the mol ratio of carboxyl and sulfur oxychloride is 10:1.Sodiumazide 1.79g and deionized water 19.45g is joined in reaction flask; ice bath; the tetrahydrofuran solution being dissolved with Rap Oil-based acyl chlorides is under agitation dripped in 30 minutes; dropwise rear continuation reaction 2 hours; add extraction into ethyl acetate organic layer again, 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, stirring and refluxing 2h at 70 DEG C, revolve and steam except desolventizing, obtain object product 5.89g(with carboxy-modified rapeseed oil for starting raw material calculates, 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 alcohol:
Rapeseed oil 12g, mercaptoethanol 15.94g, light trigger (UV1173) 0.414g and methylene dichloride 30ml are added in reaction flask, under 20 DEG C of whipped states, ultra violet lamp 3 hours, deionized water wash solution is used to remove excessive mercaptoethanol, organic layer uses anhydrous magnesium sulfate drying, revolve steaming removing methylene dichloride and obtain 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 extender:
By carboxy-modified rapeseed oil 12g, mercaptoethanol 15.94g, light trigger (UV1173) 0.414g and methylene dichloride 30ml adds in reaction flask, under 25 DEG C of whipped states, ultra violet lamp 6 hours, deionized water wash solution is used to remove excessive mercaptoethanol, organic layer uses anhydrous magnesium sulfate drying, revolve steaming removing methylene dichloride and obtain 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 resin
(1) add in reaction flask by Rap Oil-based isocyanic ester 2.0g, Rap Oil-based polyvalent alcohol 1.14g and acetone 15ml, react under the effect of organotin catalysts and generate prepolymer in 3 ~ 4 hours, the temperature of reaction of prepolymerization reaction is 70 ~ 80 DEG C.
(2) preparation of polyurethane aqueous dispersion body:
In above-mentioned prepolymer, add Rap Oil-based carboxylic acid type hydrophilic chain extender 1.4g carry out chain extending reaction 3 ~ 4 hours, temperature of reaction is 70 ~ 80 DEG C.
Add salt-forming reagent triethylamine 0.363g to neutralize, react 0.5 hour, temperature of reaction is 50 ~ 60 DEG C.
Above-mentioned polymkeric substance is added in 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 (7)
1. the preparation method of a pure rapeseed oil base water polyurethane resin, it is characterized in that the preparation comprising the steps: (1) Rap Oil-based isocyanic ester: by rapeseed oil, 3-thiohydracrylic acid, light trigger and methylene dichloride add in reaction flask, under 18-40 DEG C of whipped state, ultra violet lamp 6 ~ 8 hours, deionized water wash solution is used to remove excessive 3-thiohydracrylic acid, organic layer uses anhydrous magnesium sulfate drying, revolve and steam the rapeseed oil that removing methylene dichloride obtains 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, at temperature is 35 ~ 50 DEG C, stir 5 ~ 6 hours, revolve and steam removing methylene dichloride and sulfur oxychloride, obtain Rap Oil-based acyl chlorides, in the rapeseed oil of wherein 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 dripping Rap Oil-based acyl chlorides, add extraction into ethyl acetate 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, added by organic layer in reaction flask, at 60 ~ 80 DEG C, return stirring 2h, obtains 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 DEG C of whipped state, ultra violet lamp 3 ~ 8 hours, deionized water wash solution is used to remove excessive mercaptoethanol, organic layer uses anhydrous magnesium sulfate drying, revolve steaming removing methylene dichloride and obtain 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 lower for double bond substitution value, mercaptoethanol, light trigger and methylene dichloride add in reaction flask, under 18-40 DEG C of whipped state, ultra violet lamp 3 ~ 8 hours, deionized water wash solution is used to remove excessive mercaptoethanol, organic layer uses anhydrous magnesium sulfate drying, revolve and steam removing methylene dichloride and obtain 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 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, the temperature of reaction of prepolymerization reaction is 70 ~ 80 DEG C, and the ratio of isocyanate group and hydroxyl is 1.6:1 ~ 2:1, (5) preparation of pure rapeseed oil base water polyurethane resin: add Rap Oil-based hydrophilic chain extender and carry out chain extending reaction 3 ~ 4 hours in above-mentioned prepolymer, temperature of reaction is 70 ~ 80 DEG C, add salt-forming reagent neutralization, react 0.5 hour, temperature of reaction is 50 ~ 60 DEG C, above-mentioned polymkeric substance is added in deionized water, uses 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, one or more mixture in 2-diethoxy acetophenone.
3. preparation method according to claim 1, is characterized in that adding acetone in each step of step (4) step (5) or arbitrary step reduces viscosity.
4. preparation method according to claim 1, is characterized in that described organotin catalysts is dibutyl tin laurate or stannous octoate.
5. preparation method according to claim 4, is characterized in that described organotin catalysts is dibutyl tin laurate.
6. preparation method according to claim 1, is characterized in that described salt-forming reagent is triethylamine, sodium hydroxide, potassium hydroxide or ammoniacal liquor.
7. preparation method according to claim 6, is characterized in that described salt-forming reagent is triethylamine.
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| CN104086743B (en) * | 2014-06-30 | 2016-04-06 | 江西科技师范大学 | The preparation method of cardanol polylol and urethane 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 |
| CN107556452B (en) * | 2017-09-15 | 2020-11-13 | 华南农业大学 | Castor oil-based hydrophilic chain extender and preparation method and application thereof |
| 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 |
| CN112028801B (en) * | 2020-07-24 | 2021-07-09 | 华南农业大学 | Chain extender and preparation method and application thereof |
| CN114703600B (en) * | 2022-04-11 | 2023-02-07 | 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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