CN114591674B - Novel castor-based polyurethane coating material and preparation method thereof - Google Patents
Novel castor-based polyurethane coating material and preparation method thereof Download PDFInfo
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- CN114591674B CN114591674B CN202011413213.9A CN202011413213A CN114591674B CN 114591674 B CN114591674 B CN 114591674B CN 202011413213 A CN202011413213 A CN 202011413213A CN 114591674 B CN114591674 B CN 114591674B
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- 239000000463 material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 235000004443 Ricinus communis Nutrition 0.000 title claims abstract description 17
- 239000011527 polyurethane coating Substances 0.000 title claims abstract description 17
- 239000004814 polyurethane Substances 0.000 claims abstract description 106
- 229920002635 polyurethane Polymers 0.000 claims abstract description 106
- 239000002253 acid Substances 0.000 claims abstract description 89
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 59
- 239000002243 precursor Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 carboxyl methyl Chemical group 0.000 claims abstract description 19
- 150000005676 cyclic carbonates Chemical class 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 10
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 claims abstract description 8
- 229960003656 ricinoleic acid Drugs 0.000 claims abstract description 8
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 77
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 69
- 238000006243 chemical reaction Methods 0.000 claims description 65
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 40
- XKGDWZQXVZSXAO-UHFFFAOYSA-N ricinoleic acid methyl ester Natural products CCCCCCC(O)CC=CCCCCCCCC(=O)OC XKGDWZQXVZSXAO-UHFFFAOYSA-N 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 32
- XKGDWZQXVZSXAO-SFHVURJKSA-N Ricinolsaeure-methylester Natural products CCCCCC[C@H](O)CC=CCCCCCCCC(=O)OC XKGDWZQXVZSXAO-SFHVURJKSA-N 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 28
- 239000012074 organic phase Substances 0.000 claims description 23
- XKGDWZQXVZSXAO-ADYSOMBNSA-N Ricinoleic Acid methyl ester Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OC XKGDWZQXVZSXAO-ADYSOMBNSA-N 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 21
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 15
- 125000003367 polycyclic group Chemical group 0.000 claims description 15
- 238000006735 epoxidation reaction Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 12
- JBXYCUKPDAAYAS-UHFFFAOYSA-N methanol;trifluoroborane Chemical compound OC.FB(F)F JBXYCUKPDAAYAS-UHFFFAOYSA-N 0.000 claims description 12
- 150000004702 methyl esters Chemical class 0.000 claims description 12
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 9
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 6
- 150000004985 diamines Chemical class 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 238000006352 cycloaddition reaction Methods 0.000 abstract description 13
- 229940066675 ricinoleate Drugs 0.000 abstract description 11
- WBHHMMIMDMUBKC-QJWNTBNXSA-M ricinoleate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O WBHHMMIMDMUBKC-QJWNTBNXSA-M 0.000 abstract description 11
- 239000003513 alkali Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 7
- 229920000768 polyamine Polymers 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 5
- 239000004359 castor oil Substances 0.000 abstract description 4
- 235000019438 castor oil Nutrition 0.000 abstract description 4
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 abstract description 4
- 239000002028 Biomass Substances 0.000 abstract description 3
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- 150000002513 isocyanates Chemical class 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
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- 229920000647 polyepoxide Polymers 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000012216 screening Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
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- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 102100021202 Desmocollin-1 Human genes 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 101000968043 Homo sapiens Desmocollin-1 Proteins 0.000 description 1
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- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
- C08G71/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a novel castor-based polyurethane coating material and a preparation method thereof, wherein oligomeric ricinoleic acid with different acid values is taken as a raw material, and carboxyl methyl in the oligomeric ricinoleic acid is esterified to form methyl polyricinoleate; subsequently, epoxidizing the double bond in the methyl polyricinoleate molecule; the obtained epoxidized methyl polyricinoleate is further subjected to cycloaddition reaction with carbon dioxide, and the methyl polycyclocarbonate ricinoleate containing 3-8 cyclic carbonate structural units can be prepared and used as a polyurethane precursor. The polyurethane precursor reacts with polyamine to obtain polyurethane which has water resistance, acid and alkali resistance, is stable at 200 ℃, and can be used as a coating material. The process is clean and pollution-free, and the non-edible oil castor oil is used as a raw material, so that the development concept of biomass 'no competition with people' is met.
Description
Technical Field
The invention relates to a novel castor-based polyurethane coating material and a preparation method thereof, and belongs to the technical field of polyurethane preparation.
Background
Polyurethanes are currently the most common polymeric materials with excellent properties such as abrasion resistance, elasticity, durability and toughness. In view of their advantages in terms of overall properties, polyurethanes find wide application in many fields, such as foams, footwear, coatings and paints, industrial machinery, adhesives, packaging and medical devices. To meet the growing global market demand, optimizing product performance and preparation method becomes a research hotspot in the polyurethane field.
The polyurethane synthesis methods currently in widespread use rely mainly on polyaddition reactions between isocyanates and polyols. The key monomer isocyanate is mainly derived from fossil resources, so that the raw materials are nonrenewable; in addition, the industrial synthesis of isocyanate involves the toxic gas phosgene, which presents a potential hazard to the health and environment of operators. And isocyanate is unstable in the presence of water, so that the requirement on environmental conditions is high in the reaction process, and the reaction of isocyanate and water is prevented from being influenced by the formation of byproducts, the reaction of the isocyanate and alcohol is influenced, the residues of the byproducts in the material are caused, and the performance of the polyurethane material is further influenced. Since the 90 s of the last century, there has been an increasing shortage of fossil raw material supplies and an exacerbation of environmental problems, which has prompted researchers to develop new polyurethane materials based on renewable raw materials and green synthesis processes.
In the research of polyurethane synthesis technology, in order to avoid the use of toxic isocyanate in polyurethane synthesis, researchers successively develop four synthesis routes of polycondensation, rearrangement, ring-opening polymerization and polyaddition, and a plurality of non-isocyanate polyurethane materials are obtained. The synthesis of the relevant precursors of the "polycondensation route" requires the participation of phosgene or derivatives thereof, the "rearrangement route" is not separated from the use of harmful reactants such as acyl azide compounds, carboxamides and hydroxamate azide compounds, the "ring-opening polymerization route" requires the participation of phosgene precursors not only in the synthesis of cyclic carbamates, but also the aziridine, another raw material for the synthesis of cyclic carbamates, has relatively great toxicity. Thus, synthetic routes based on polyaddition of cyclic carbonates with polyamines have received great attention. The advantage of this route is that cyclic carbonates are widely available and non-toxic, they are relatively stable in the environment and are relatively safe to transport and store. Furthermore, the reaction between the cyclic carbonate and the amine is 100% an atomic economic reaction, without releasing any volatile organic compounds, which makes this route useful in the coating industry.
Routes based on polyaddition of cyclic carbonates and polyamines not only provide a green process for the preparation of polyurethanes, but also facilitate the use of renewable raw materials in the production of polyurethanes. The vegetable oil (triglyceride) has the advantages of being renewable, nontoxic, biodegradable, structurally modifiable and the like, and is the best substitute for synthesizing polyurethane by replacing fossil raw materials. Because the vegetable oil has double bonds in the molecular structure, the vegetable oil can be easily converted into epoxide and then is further combined with CO 2 The cycloaddition, the compound formed with two or more cyclic carbonate structural units, is a precursor for synthesizing polyurethane. At present, the preparation of novel bio-based polyurethane with wide structural and functional characteristics by using edible grease such as soybean oil, palm oil and the like is reported, but the preparation of castor-based polyurethane is limited, only the research of synthesizing polyurethane by adopting castor-based polyol through an isocyanate route is carried out at present, and the synthesis of polyurethane through a non-isocyanate route is not reported yet.
Because castor oil has a special structure and belongs to non-edible oil, the preparation of polyurethane precursors containing a plurality of cyclic carbonates by taking castor oil as a raw material is helpful for developing polyurethane materials with different structures and properties, and accords with the development concept of biomass 'no competition with people' in grain.
Disclosure of Invention
The invention aims to provide a novel castor-based polyurethane coating material for a non-isocyanate route and a preparation method thereof. By adopting polyricinoleic acid with adjustable acid value as raw material and utilizing the characteristic of double bond in the molecular structure, the polyricinoleic acid is subjected to esterification, epoxidation and CO 2 Cycloaddition to prepare the poly cyclic carbonate methyl ricinoleate containing 3-8 cyclic carbonate structures, taking the poly cyclic carbonate methyl ricinoleate as a precursor, and further reacting with polyamine to synthesize the polyurethane coating material, wherein the specific reaction process is shown in figure 1. The method has the advantages that the performance of the obtained polyurethane coating material can be regulated by the acid value of polyricinoleic acid and the type of diamine, and the obtained product has water resistance, acid and alkali resistance and thermal stability below 200 ℃; the preparation process is clean and pollution-free, and is environment-friendly, thereby being beneficial to industrial production.
The technical scheme of the invention is that the preparation steps of the novel castor-based polyurethane coating material are as follows:
1) Methyl polyricinoleate: and (3) carrying out reflux reaction on polyricinoleic acid, a catalyst boron trifluoride methanol complex and excessive methanol for a period of time at a certain temperature, distilling the excessive methanol under reduced pressure, and washing with water for three times to remove residual methanol and catalyst, thereby obtaining an organic phase, namely polyricinoleic acid methyl ester.
2) Epoxidation of methyl polyricinoleate: and (2) putting the methyl polyricinoleate obtained in the step (1) into a reaction bottle, then adding a certain amount of oxidizing agent m-chloroperoxybenzoic acid and solvent diethyl ether into the reaction bottle, reacting for a period of time at room temperature, and then washing with a certain amount of sodium thiosulfate, sodium bicarbonate and water for three times respectively to obtain the methyl polyricinoleate.
3) Polyepoxyricinoleic acid methyl ester and CO 2 Cycloaddition reaction: adding the polyepoxy ricinoleic acid methyl ester obtained in the step 2, a catalyst tetrabutylammonium bromide and a solvent N, N-dimethylformamide into a high-pressure reaction kettle, then introducing carbon dioxide with certain pressure into the high-pressure reaction kettle, heating to react, and washing with water for three times after the reaction is finished to remove the solvent and the catalyst, thereby obtaining the polycyclic carbonic ester ricinoleic acid methyl ester serving as a polyurethane precursor;
4) And (3) feeding the polyurethane precursor obtained in the step (3) and diamine according to a certain proportion, and reacting and curing for a certain time at a certain temperature to obtain the final product, namely the castor-based polyurethane.
The acid value of the raw material polyricinoleic acid used in the step 1 is 30-60 mg KOH/g, the dosage of the catalyst boron trifluoride methanol complex is 0.05-0.3 mL/g polyricinoleic acid, the dosage of the solvent methanol is 2-5 mL/g polyricinoleic acid, the reaction temperature is 70-100 ℃, and the reaction time is 6-16 h.
The molar ratio of the oxidizing agent m-chloroperoxybenzoic acid to the double bond in the polyricinoleic acid methyl ester structure in the step 2 is 1-1.5, the consumption of the solvent diethyl ether is 4-6 mL/g of polyricinoleic acid methyl ester, and the reaction time is 12-36 h.
The catalyst tetrabutylammonium bromide in the step 3The dosage is 3-5% of the mass of the poly epoxy methyl ricinoleate, the dosage of the solvent N, N-dimethylformamide is 2-4 mL/g of the poly epoxy methyl ricinoleate, and CO is generated in the reaction 2 The pressure range is 2-5 MPa, the reaction temperature is 120-160 ℃, and the reaction time is 18-36 h.
In the step 4, the molar ratio of the cyclic carbonate group in the poly cyclic carbonate methyl ricinoleate to the amine group in the diamine is 1:1, and the diamine selected comprises hexamethylenediamine and isophorone diamine, and the curing temperature is 60-120 ℃.
According to the operating conditions, the tensile strength of the polyurethane coating prepared by the invention is 0.6-2.4 MPa, the elongation at break is 75-255%, and the prepared polyurethane coating has water resistance and acid and alkali resistance and can be kept stable at 200 ℃.
In the course of the above reaction, the formation of methyl polyricinoleate, methyl polyepoxide ricinoleate and methyl polycyclocarbonate ricinoleate was verified by Nuclear Magnetic Resonance (NMR), infrared spectroscopy (FT-IR) and mass spectrometry for flight (MALDI-TOF), respectively (see fig. 2 to 5), and the obtained polyurethanes were characterized by infrared spectroscopy (see fig. 6, 7). According to the analysis result of the flight mass spectrum, when the acid value of the polyricinoleic acid is 60mgKOH/g, the distribution range of the polymerization degree is 3-8, and thus the obtained poly cyclic carbonate methyl ricinoleate molecule contains 3-8 cyclic carbonate structural units.
The invention has the following advantages and characteristics:
1, the acid value of the main raw material polyricinoleic acid is adjustable and is derived from renewable resources, the polyricinoleic acid can be obtained through castor oil hydrolysis and esterification polymerization, the acid value of the polyricinoleic acid can be adjusted and controlled through esterification polymerization time, and the polyricinoleic acid is a cheap and easily available renewable resource, is convenient to store and transport, and has obvious advantages in the aspect of industrial production;
2, the non-edible oil castor is used as a raw material, which accords with the development concept of biomass 'no grain competition with people';
3, adopting a non-isocyanate route, and solidifying the polyurethane precursor and the polyamine under the condition of no solvent and no catalyst to obtain polyurethane, thereby being green, environment-friendly and pollution-free;
the polyurethane obtained in step 4 has water resistance, acid and alkali resistance, can be kept stable at 200 ℃, can be widely used in the fields of coatings, textiles, elastomers and the like, and has industrial production prospects.
Drawings
FIG. 1 is a schematic illustration of a process for preparing a novel polyurethane coating material.
FIG. 2 is a schematic illustration of methyl polyricinoleate, methyl polyepoxide ricinoleate, and methyl polycyclocarbonate ricinoleate derived from polyricinoleic acid having an acid number of 60 1 H NMR spectrum.
FIG. 3 is a schematic illustration of methyl polyricinoleate, methyl polyepoxide ricinoleate, and methyl polycyclocarbonate ricinoleate derived from polyricinoleic acid having an acid number of 60 13 C NMR spectrum.
FIG. 4 is an FT-IR spectrum of methyl polyricinoleate, methyl polyepoxide ricinoleate, and methyl polycyclocarbonate ricinoleate obtained from polyricinoleic acid having an acid value of 60.
FIG. 5 is a MALDI TOF spectrum of methyl polyricinoleate, methyl polyepoxide ricinoleate, and methyl polycyclocarbonate ricinoleate obtained from polyricinoleic acid having an acid value of 60.
FIG. 6 is a FT-IR spectrum of a polyurethane prepared from a polyurethane precursor obtained by polyricinoleic acid having an acid value of 60 and hexamethylenediamine.
FIG. 7 is a FT-IR spectrum of a polyurethane prepared from a polyurethane precursor obtained by polyricinoleic acid having an acid value of 60 and isophorone diamine.
Detailed Description
The invention relates to a novel castor-based polyurethane coating material and a preparation method thereof. Polyricinoleic acid is used as raw material, and is esterified, epoxidized and mixed with CO 2 Cycloaddition to synthesize poly cyclic carbonate methyl ricinoleate containing 3-8 cyclic carbonate structures as polyurethane precursor, and further reacting with polyamine to synthesize polyurethane, wherein the properties of the obtained polyurethane can be adjusted by the polymerization degree of the oligomeric ricinoleic acid and the type of polyamine. The preparation process is clean and pollution-free, and is environment-friendly, so that the product has a wide application prospect.
EXAMPLE 1 screening of methyl polyricinoleate reaction conditions
Methyl esterification was carried out using polyricinoleic acid having an acid value of 60mg KOH/g as a raw material, and the optimum conditions for methyl esterification were examined. The method comprises the following specific steps:
10g of polyricinoleic acid having an acid value of 60mg KOH/g, 20 to 50mL of methanol and 0.5 to 3mL of boron trifluoride-methanol solution were added to a 50mL flask. After the reflux reaction for 6 to 16 hours, methanol was removed by a rotary evaporator. After further dilution with 30mL of diethyl ether, the mixture was transferred to a separatory funnel and washed 3 times with water. The solvent in the organic phase is removed to finally obtain the yellow oily liquid methyl polyricinoleate.
TABLE 1 screening of methyl polyricinoleate reaction conditions
The condition of the reaction No. 2 is selected as the best condition through condition screening, namely: the consumption of boron trifluoride-methanol solution is 0.1mL/g, the consumption of solvent methanol is 2mL/g, the reaction temperature and the reaction time are respectively 90 ℃ and 8 hours, and under the condition, the yield of the product methyl ricinoleate is 86%.
Example 2 screening of conditions for epoxidation of methyl polyricinoleate
Epoxidation was carried out using methyl polyricinoleate as a starting material in example 1, and the optimum conditions for epoxidation were examined. The method comprises the following specific steps:
8.6g of methyl polyricinoleate is evenly dispersed into 40-60 mL of diethyl ether, 5-8 g of m-chloroperoxybenzoic acid is slowly added, and the mixture is stirred and reacted for 12-36 hours at room temperature. The mixture was washed 3 times with 30mL of a saturated sodium thiosulfate solution, 30mL of a saturated sodium bicarbonate solution and 30mL of a saturated sodium chloride solution in this order. Finally, diethyl ether in the organic phase is removed to obtain the epoxidized methyl polyricinoleate in colorless oily liquid.
TABLE 2 screening of conditions for epoxidation of methyl polyricinoleate
Through condition screening, selecting the reaction condition No. 3 as the optimal condition for the epoxidation of the methyl polyricinoleate, namely: the amount of ethyl ether used as solvent was 4.7mL/g polyricinoleic acid, the molar ratio of m-chloroperoxybenzoic acid to double bond was 1.2:1, the reaction time was 24 hours, and under this condition the yield of methyl ricinoleate was 82%.
EXAMPLE 3 Polyepoxyricinoleic acid methyl ester with CO 2 Cycloaddition reaction condition screening
7.05g of epoxidized methyl polyricinoleate obtained in example 2 was dissolved in 30-40 mL of DMF and transferred to a high-pressure reaction vessel, followed by the addition of 0.14-0.35 g (0.66 mmol) of tetrabutylammonium bromide, charging carbon dioxide to 2-5 MPa and reacting at 120-140℃for 18-36 h. After the reaction is finished, the catalyst is removed by washing, and the solvent in the organic phase is removed to obtain yellow brown oily liquid, namely the poly cyclic carbonate methyl ricinoleate.
TABLE 3 polyepoxy methyl ricinoleate and CO 2 Cycloaddition reaction condition screening
The condition of the reaction No. 2 is selected as the best condition through condition screening, namely: the dosage of tetrabutylammonium bromide serving as a catalyst is 3% of the mass of the substrate poly (epoxy ricinoleic acid) methyl ester, and the dosage of DMF serving as a solvent is 4.2mL/g poly (epoxy ricinoleic acid) methyl ester, CO 2 The pressure of the obtained poly (cyclic carbonate) methyl ricinoleate is 3MPa, the reaction temperature is 140 ℃, the reaction time is 24 hours, and the yield of the obtained poly (cyclic carbonate) methyl ricinoleate is 90%.
Example 4
Polyricinoleic acid with an acid value of 30mg KOH/g is taken as a raw material and subjected to methyl esterification, epoxidation and CO 2 And (3) after cycloaddition, obtaining a polyurethane precursor, and then curing the polyurethane precursor with hexamethylenediamine to obtain the polyurethane. The method comprises the following specific steps:
(1) 10g of polyricinoleic acid having an acid value of 30mg KOH/g, 20mL of methanol and 1mL of boron trifluoride-methanol solution were charged into a 50mL flask. After reflux reaction at 90℃for 12 hours, methanol was removed by rotary evaporator. After further dilution with 30mL of diethyl ether, the mixture was transferred to a separatory funnel and washed 3 times with water. The solvent was removed from the organic phase to finally obtain 8.6g of methyl polyricinoleate as a yellow oily liquid in 86% yield.
(2) 8.6g of methyl polyricinoleate obtained in the step (1) is uniformly dispersed in 40mL of diethyl ether, 6g (34.4 mmol) of m-chloroperoxybenzoic acid is slowly added, and the reaction is stirred at room temperature for 24 hours. The mixture was washed 3 times with 30mL of a saturated sodium thiosulfate solution, 30mL of a saturated sodium bicarbonate solution and 30mL of a saturated sodium chloride solution in this order. Finally, diethyl ether was removed from the organic phase to give 7.05g of methyl polyricinoleate as a colourless oily liquid in 82% yield.
(3) 7.05g of the poly (epoxidized methyl ricinoleate obtained in the step (2) was dissolved in 30mL of DMF and transferred to a high-pressure reaction vessel, followed by adding 0.21g (0.66 mmol) of tetrabutylammonium bromide, charging carbon dioxide to 3MPa, and reacting at 140℃for 24 hours. After the reaction, the catalyst was removed by washing with water, and the solvent in the organic phase was removed to obtain 6.34g of yellow brown oily liquid, which was poly cyclic carbonate methyl ricinoleate, with a yield of 90%.
(4) 6.34g of polyurethane precursor obtained in the step (3) and 2.16g of hexamethylenediamine are mixed and stirred for 30 minutes, then poured into a mold, reacted for 7 hours at 70 ℃, and then heated to 100 ℃ for 5 hours, thus obtaining 8.23g of polyurethane PU-30-hexamethylenediamine, which is yellow soft solid.
Example 5
Polyricinoleic acid with acid value of 45mg KOH/g is taken as raw material and subjected to methyl esterification, epoxidation and CO 2 And (3) after cycloaddition, obtaining a polyurethane precursor, and then curing the polyurethane precursor with hexamethylenediamine to obtain the polyurethane. The method comprises the following specific steps:
(1) 10g of polyricinoleic acid having an acid value of 45mg KOH/g, 20mL of methanol and 1mL of boron trifluoride-methanol solution were charged into a 50mL flask. After reflux reaction at 90℃for 12 hours, methanol was removed by rotary evaporator. After further dilution with 30mL of diethyl ether, the mixture was transferred to a separatory funnel and washed 3 times with water. The solvent was removed from the organic phase to finally obtain 8.6g of methyl polyricinoleate as a yellow oily liquid in 86% yield.
(2) 8.6g of methyl polyricinoleate obtained in the step (1) is uniformly dispersed in 40mL of diethyl ether, 6g (34.4 mmol) of m-chloroperoxybenzoic acid is slowly added, and the reaction is stirred at room temperature for 24 hours. The mixture was washed 3 times with 30mL of a saturated sodium thiosulfate solution, 30mL of a saturated sodium bicarbonate solution and 30mL of a saturated sodium chloride solution in this order. Finally, the diethyl ether in the organic phase was removed to give 7.05g of a colourless oily liquid polyepoxide methylricinoleate in 82% yield.
(3) 7.05g of the poly (epoxidized methyl ricinoleate obtained in the step (2) was dissolved in 30mL of DMF and transferred to a high-pressure reaction vessel, followed by adding 0.21g (0.66 mmol) of tetrabutylammonium bromide, charging carbon dioxide to 3MPa, and reacting at 140℃for 24 hours. After the reaction, washing to remove the catalyst, and removing the solvent in the organic phase to obtain 6.34g of yellow brown oily liquid, namely polyurethane precursor poly cyclic carbonate methyl ricinoleate with the yield of 90%.
(4) 6.34g of polyurethane precursor obtained in the step (3) and 2.16g of hexamethylenediamine are mixed and stirred for 30 minutes, then poured into a mold, reacted for 7 hours at 70 ℃, and then heated to 100 ℃ for 5 hours, thus obtaining 8.23g of polyurethane PU-45-hexamethylenediamine, which is yellow soft solid.
Example 6
Polyricinoleic acid with acid value of 60mg KOH/g is taken as raw material and subjected to methyl esterification, epoxidation and CO 2 And (3) after cycloaddition, obtaining a polyurethane precursor, and then curing the polyurethane precursor with hexamethylenediamine to obtain the polyurethane. The method comprises the following specific steps:
(1) 10g of polyricinoleic acid having an acid value of 60mg KOH/g, 20mL of methanol and 1mL of boron trifluoride-methanol solution were charged into a 50mL flask. After reflux reaction at 90℃for 12 hours, methanol was removed by rotary evaporator. After further dilution with 30mL of diethyl ether, the mixture was transferred to a separatory funnel and washed 3 times with water. The solvent was removed from the organic phase to finally obtain 8.6g of methyl polyricinoleate as a yellow oily liquid in 86% yield.
(2) 8.6g of methyl polyricinoleate obtained in the step (1) is uniformly dispersed in 40mL of diethyl ether, 6g (34.4 mmol) of m-chloroperoxybenzoic acid is slowly added, and the reaction is stirred at room temperature for 24 hours. The mixture was washed 3 times with 30mL of a saturated sodium thiosulfate solution, 30mL of a saturated sodium bicarbonate solution and 30mL of a saturated sodium chloride solution in this order. Finally, the diethyl ether in the organic phase was removed to give 7.05g of a colourless oily liquid polyepoxide methylricinoleate in 82% yield.
(3) 7.05g of the poly (epoxidized methyl ricinoleate obtained in the step (2) was dissolved in 30mL of DMF and transferred to a high-pressure reaction vessel, followed by adding 0.21g (0.66 mmol) of tetrabutylammonium bromide, charging carbon dioxide to 3MPa, and reacting at 140℃for 24 hours. After the reaction, washing to remove the catalyst, and removing the solvent in the organic phase to obtain 6.34g of yellow brown oily liquid, namely polyurethane precursor poly cyclic carbonate methyl ricinoleate with the yield of 90%.
(4) 6.34g of polyurethane precursor obtained in the step (3) and 2.16g of hexamethylenediamine are mixed and stirred for 30 minutes, then poured into a mold, reacted for 7 hours at 70 ℃, and then heated to 100 ℃ for 5 hours, thus obtaining 8.23g of polyurethane PU-60-hexamethylenediamine as yellow soft solid.
Example 7
Polyricinoleic acid with an acid value of 30mg KOH/g is taken as a raw material and subjected to methyl esterification, epoxidation and CO 2 And (3) after cycloaddition, obtaining a polyurethane precursor, and then curing the polyurethane precursor with hexamethylenediamine to obtain the polyurethane. The method comprises the following specific steps:
(1) 10g of polyricinoleic acid having an acid value of 30mg KOH/g, 20mL of methanol and 1mL of boron trifluoride-methanol solution were charged into a 50mL flask. After reflux reaction at 90℃for 12 hours, methanol was removed by rotary evaporator. After further dilution with 30mL of diethyl ether, the mixture was transferred to a separatory funnel and washed 3 times with water. The solvent was removed from the organic phase to finally obtain 8.6g of methyl polyricinoleate as a yellow oily liquid in 86% yield.
(2) 8.6g of methyl polyricinoleate obtained in the step (1) is uniformly dispersed in 40mL of diethyl ether, 6g (34.4 mmol) of m-chloroperoxybenzoic acid is slowly added, and the reaction is stirred at room temperature for 24 hours. The mixture was washed 3 times with 30mL of a saturated sodium thiosulfate solution, 30mL of a saturated sodium bicarbonate solution and 30mL of a saturated sodium chloride solution in this order. Finally, the diethyl ether in the organic phase was removed to give 7.05g of a colourless oily liquid polyepoxide methylricinoleate in 82% yield.
(3) 7.05g of the epoxidized methyl polyricinoleate obtained in the step (2) was dissolved in 30mL of DMF and transferred to a high-pressure reaction vessel, followed by adding 0.21g (0.66 mmol) of tetrabutylammonium bromide, charging carbon dioxide to 3MPa, and reacting at 140℃for 24 hours. After the reaction, washing to remove the catalyst, and removing the solvent in the organic phase to obtain 6.34g of yellow brown oily liquid, namely polyurethane precursor poly cyclic carbonate methyl ricinoleate with the yield of 90%.
(4) Mixing and stirring 6.34g of polyurethane precursor obtained in the step (3) and 3.17g of isophorone diamine for 30 minutes, pouring into a mold, reacting for 7 hours at 70 ℃, and heating to 100 ℃ for reacting for 5 hours to obtain 9.16g of polyurethane PU-30-isophorone diamine as yellow soft solid.
Example 8
Polyricinoleic acid with acid value of 45mg KOH/g is taken as raw material and subjected to methyl esterification, epoxidation and CO 2 And (3) after cycloaddition, obtaining a polyurethane precursor, and then curing the polyurethane precursor with hexamethylenediamine to obtain the polyurethane. The method comprises the following specific steps:
(1) 10g of polyricinoleic acid having an acid value of 45mg KOH/g, 20mL of methanol and 1mL of boron trifluoride-methanol solution were charged into a 50mL flask. After reflux reaction at 90℃for 12 hours, methanol was removed by rotary evaporator. After further dilution with 30mL of diethyl ether, the mixture was transferred to a separatory funnel and washed 3 times with water. The solvent was removed from the organic phase to finally obtain 8.6g of methyl polyricinoleate as a yellow oily liquid in 86% yield.
(2) 8.6g of methyl polyricinoleate obtained in the step (1) is uniformly dispersed in 40mL of diethyl ether, 6g (34.4 mmol) of m-chloroperoxybenzoic acid is slowly added, and the reaction is stirred at room temperature for 24 hours. The mixture was washed 3 times with 30mL of a saturated sodium thiosulfate solution, 30mL of a saturated sodium bicarbonate solution and 30mL of a saturated sodium chloride solution in this order. Finally, the diethyl ether in the organic phase was removed to give 7.05g of a colourless oily liquid polyepoxide methylricinoleate in 82% yield.
(3) 7.05g of the poly (epoxidized methyl ricinoleate obtained in the step (2) was dissolved in 30mL of DMF and transferred to a high-pressure reaction vessel, followed by adding 0.21g (0.66 mmol) of tetrabutylammonium bromide, charging carbon dioxide to 3MPa, and reacting at 140℃for 24 hours. After the reaction, washing to remove the catalyst, and removing the solvent in the organic phase to obtain 6.34g of yellow brown oily liquid, namely polyurethane precursor poly cyclic carbonate methyl ricinoleate with the yield of 90%.
(4) 6.34g of polyurethane precursor obtained in the step (3) and 3.17g of isophorone diamine are mixed and stirred for 30 minutes, then poured into a mold, reacted for 7 hours at 70 ℃, and then heated to 100 ℃ for 5 hours, thus obtaining 9.16g of polyurethane PU-45-isophorone diamine as yellow soft solid.
Example 9
Polyricinoleic acid with acid value of 60mg KOH/g is taken as raw material and subjected to methyl esterification, epoxidation and CO 2 And (3) after cycloaddition, obtaining a polyurethane precursor, and then curing the polyurethane precursor with hexamethylenediamine to obtain the polyurethane. The method comprises the following specific steps:
(1) 10g of polyricinoleic acid having an acid value of 60mg KOH/g, 20mL of methanol and 1mL of boron trifluoride-methanol solution were charged into a 50mL flask. After reflux reaction at 90℃for 12 hours, methanol was removed by rotary evaporator. After further dilution with 30mL of diethyl ether, the mixture was transferred to a separatory funnel and washed 3 times with water. The solvent was removed from the organic phase to finally obtain 8.6g of methyl polyricinoleate as a yellow oily liquid in 86% yield.
(2) 8.6g of methyl polyricinoleate obtained in the step (1) is uniformly dispersed in 40mL of diethyl ether, 6g (34.4 mmol) of m-chloroperoxybenzoic acid is slowly added, and the reaction is stirred at room temperature for 24 hours. The mixture was washed 3 times with 30mL of a saturated sodium thiosulfate solution, 30mL of a saturated sodium bicarbonate solution and 30mL of a saturated sodium chloride solution in this order. Finally, the diethyl ether in the organic phase was removed to give 7.05g of a colourless oily liquid polyepoxide methylricinoleate in 82% yield.
(3) 7.05g of the poly (epoxidized methyl ricinoleate obtained in the step (2) was dissolved in 30mL of DMF and transferred to a high-pressure reaction vessel, followed by adding 0.21g (0.66 mmol) of tetrabutylammonium bromide, charging carbon dioxide to 3MPa, and reacting at 140℃for 24 hours. After the reaction, washing to remove the catalyst, and removing the solvent in the organic phase to obtain 6.34g of yellow brown oily liquid, namely polyurethane precursor poly cyclic carbonate methyl ricinoleate with the yield of 90%.
(4) Mixing and stirring 6.34g of polyurethane precursor obtained in the step (3) and 3.17g of isophorone diamine for 30 minutes, pouring into a mold, reacting for 7 hours at 70 ℃, and heating to 100 ℃ for reacting for 5 hours to obtain 9.16g of polyurethane PU-60-isophorone diamine as yellow soft solid.
EXAMPLE 10 investigation of reaction temperature and time
6.34g of a polyurethane precursor prepared from polyricinoleic acid with an acid value of 60mg KOH/g and 3.17g of isophorone diamine or 2.16g of hexamethylene diamine are mixed and stirred for 30 minutes, and then poured into a mold, and the properties of the obtained polyurethane are analyzed at different temperatures and reaction times, and the results are shown in Table 4. The optimal condition for preparing the castor-based polyurethane is that the castor-based polyurethane is reacted for 7 hours at 60 ℃, and then the temperature is raised to 100 ℃ for reaction for 5 hours. Under these conditions, the polyurethane obtained is a solid.
TABLE 4 morphology of polyurethane prepared at different reaction temperatures and times
Example 11 Effect of average degree of polymerization of Polyricinoleic acid on product Properties
6.34g of polyurethane precursor prepared from polyricinoleic acid with different polymerization degrees and 3.17g of isophorone diamine or 2.16g of hexamethylene diamine are mixed and stirred for 30 minutes, then poured into a mold to react for 7 hours at 60 ℃, and then heated to 100 ℃ to react for 5 hours to obtain polyurethane for analysis, and the properties are shown in table 5. Polyurethane prepared from hexamethylenediamine is soft and elastic, and polyurethane prepared from isophorone diamine is hard and brittle, which is related to the fact that it contains rigid rings. The color of the polyurethane darkens with decreasing acid number.
TABLE 5 preparation of polyurethanes Using ricinoleic acid with different degrees of polymerization as raw materials
Example 12 performance test of polyurethane coating materials:
(1) mechanical property test
The samples prepared in examples 1 to 6 were according to GB/T1732-93 standardMechanical property tests were performed at room temperature in a stretching mode on a UTM6103 mechanical tester (Shenzhen solar technologies Co., ltd., china) at a stretching speed of 10mm min -1 For loading and unloading test analysis, see table 6.
TABLE 6 mechanical Property testing of polyurethanes
a. After three days of illumination by ultraviolet lamp
Polyurethanes made with isophorone diamine have higher strength than polyurethanes made with hexamethylene diamine because isophorone diamine has a cycloaliphatic structure, thus making the cured backbone rigid. Experiments show that the tensile strength of polyurethane with higher polymerization degree is lower. Because it contains more long chains of different lengths, the segments are irregular, resulting in lower tensile strength. All polyurethanes were exposed to uv light for 3 days to examine uv stability of the coating, and the results showed that all polyurethane coatings did not show significant decrease in mechanical properties even after exposure to uv light for 3 days.
(2) Test of Water and solvent resistance
The samples prepared in examples 1 to 6 were subjected to a water resistance test, immersed in water and toluene for 7 days, taken out, immediately wiped off the surface water or toluene with filter paper, and the samples obtained after adsorbing the solvent were weighed to calculate the adsorption rate. See table 7.
Table 7 test of the water resistance of polyurethanes
The results in the table show that polyurethanes made from hexamethylenediamine absorb water more, probably due to the highly amorphous nature of the hexamethylenediamine cured polyurethane backbone. When hydrophobic isophorone diamine is cured into polyurethane, its water absorption is reduced compared to long chains due to its cycloaliphatic nature, as its cycloaliphatic nature can provide greater compactness and helps to protect hydroxyl groups. The toluene absorption of polyurethane is relatively high due to the crosslinked structure.
(3) Acid and alkali resistance and water immersion test
The samples prepared in examples 1 to 6 were subjected to an acid-alkali resistance test according to ASTM standards, immersed in 10% hydrochloric acid solution, 10% sodium hydroxide solution and distilled water for 24 hours, respectively, and then analyzed for morphology change, as shown in Table 8.
Table 8 acid and alkali resistance test of polyurethanes
A-No effect；B-loss of gloss；C-blistering；D-film removes.
It can be seen that the castor-based polyurethane has water resistance and acid and alkali resistance. The polyurethane with smaller polymerization degree has better acid resistance and alkali resistance. The isophorone diamine based coating has a higher resistance due to its cycloaliphatic structure, providing higher compactness and helping to protect the hydroxyl groups, compared to the hexamethylenediamine based polyurethane.
(4) Thermal performance testing
Thermogravimetric analysis (TGA) using a NETZSCH TG 209 meter, a sample of approximately 5-7mg was placed in an aluminum crucible, N 2 Purge flow rate 50mL/min, heating rate 10 ℃/min, thermal weight loss analysis at 25℃to 900℃and determination of sample weight loss 25% and 50% temperature (T 25 And T 50 ). DSC measurement analysis of the samples using a Mettler-Toledo DSC1 differential scanning calorimeter, packaging about 10mg of the samples in a 40. Mu.L aluminum kettle with a N2 flow rate of 50mL/min and a cooling/heating rate of 20 ℃/min, repeatedly heating and cooling the samples between-50℃and 200℃with the 5 th heating scan in heat flow variationPoint as T g Values.
As can be seen from Table 9, the polyurethane has excellent thermal stability and remains stable at 200 ℃. And the polyurethane prepared from isophorone diamine has better thermal stability than the polyurethane prepared from hexamethylene diamine, which benefits from the cycloaliphatic structure in isophorone diamine coating.
Table 9 thermal performance testing of polyurethanes
The foregoing description of several embodiments of the invention is not to be construed as limiting the scope of the invention. All equivalent changes and modifications within the scope of the present invention are intended to be covered by the present invention.
Claims (2)
1. The preparation method of the novel castor-based polyurethane coating material is characterized by comprising the following steps:
1) Methyl polyricinoleate reaction: polyricinoleic acid with a certain acid value is taken as a raw material, the polyricinoleic acid, a catalyst boron trifluoride methanol complex and excessive methanol are subjected to reflux reaction for a period of time at a certain temperature, then the excessive methanol is distilled out under reduced pressure, and the residual methanol and the catalyst are removed by water washing for three times, so that an obtained organic phase is the polyricinoleic acid methyl ester;
2) Epoxidation of methyl polyricinoleate: adding the methyl polyricinoleate obtained in the step 1 into a reaction bottle, then adding a certain amount of oxidizing agent m-chloroperoxybenzoic acid and solvent diethyl ether into the reaction bottle, reacting for a period of time at room temperature, and then washing with a certain amount of sodium thiosulfate, sodium bicarbonate and water for three times respectively to obtain the methyl polyricinoleate;
3) Preparation of the polycyclic carbonic ester methyl ricinoleate: adding the polyepoxy ricinoleic acid methyl ester obtained in the step 2, a catalyst tetrabutylammonium bromide and a solvent N, N-dimethylformamide into a high-pressure reaction kettle, then introducing carbon dioxide with certain pressure into the high-pressure reaction kettle, heating to react, and washing with water for three times after the reaction is finished to remove the solvent and the catalyst, thereby obtaining a polyurethane precursor, namely the polycyclic carbonate ricinoleic acid methyl ester;
4) Feeding the polyurethane precursor obtained in the step 3) and diamine according to a certain proportion, and reacting for a certain time at a certain temperature to obtain the final product, namely the castor-based polyurethane;
the acid value of the raw material polyricinoleic acid used in the step 1) is 30-60 mg KOH/g, the consumption of boron trifluoride methanol complex as a catalyst is 0.05-0.3 mL/g polyricinoleic acid, the consumption of methanol as a solvent is 2-5 mL/g polyricinoleic acid, the reaction temperature is 70-100 ℃, and the reaction time is 6-16 h;
in the step 2), the molar ratio of the oxidizing agent m-chloroperoxybenzoic acid to the double bond in the polyricinoleic acid methyl ester structure is 1-1.5, the consumption of the solvent diethyl ether is 4-6 mL/g polyricinoleic acid methyl ester, and the reaction time is 12-36 h;
the dosage of the catalyst tetrabutylammonium bromide in the step 3) is 2-5% of the mass of the poly (epoxy ricinoleic acid) methyl ester, the dosage of the solvent N, N-dimethylformamide is 2-4 mL/g of the poly (epoxy ricinoleic acid) methyl ester, and CO is generated in the reaction 2 The pressure range is 2-5 MPa, the reaction temperature is 120-160 ℃, and the reaction time is 18-36 h;
in the step 4), the molar ratio of the cyclic carbonate group to the diamine amine group in the polyurethane precursor is 1:1, and the selected diamine comprises hexamethylenediamine and isophorone diamine, and the reaction temperature is 60-120 ℃.
2. The method for preparing the novel castor-based polyurethane coating material according to claim 1, which is characterized in that: the tensile strength of the prepared polyurethane coating is 0.6-2.4 MPa, and the elongation at break is 75% -255%.
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| 新一代环保型聚氨酯――非异氰酸酯聚氨酯的研究进展;陈彩凤;刘贵锋;孔振武;吴国民;;生物质化学工程(第06期);第47-54页 * |
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