CN115926129A - Castor oil-based alkyd resin and preparation method thereof - Google Patents
Castor oil-based alkyd resin and preparation method thereof Download PDFInfo
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- 239000004359 castor oil Substances 0.000 title claims abstract description 142
- 235000019438 castor oil Nutrition 0.000 title claims abstract description 142
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- 229920000180 alkyd Polymers 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims abstract description 55
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- 238000003756 stirring Methods 0.000 claims abstract description 46
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- 239000012295 chemical reaction liquid Substances 0.000 claims description 30
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
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- 239000002994 raw material Substances 0.000 claims description 24
- 229940075507 glyceryl monostearate Drugs 0.000 claims description 22
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- 238000000034 method Methods 0.000 claims description 16
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 12
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 7
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- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 6
- 235000011037 adipic acid Nutrition 0.000 claims description 6
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- 229910000464 lead oxide Inorganic materials 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 150000002148 esters Chemical group 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
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- 238000006555 catalytic reaction Methods 0.000 claims 1
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- 239000000126 substance Substances 0.000 description 3
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 2
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 2
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses castor oil based alkyd resin and a preparation method thereof, wherein the castor oil based alkyd resin comprises the following components in parts by weight: 20-30 parts of castor oil glycerin monostearate, 10-20 parts of castor oil-based modified polyol, 20-40 parts of polybasic acid, 1-3 parts of catalyst and 5-20 parts of diluent; in a multifunctional reaction kettle, the weight portion is 100:10:0.1 to 100:20:0.1 adding castor oil glycerin monostearate, hexahydrophthalic anhydride and tetra-n-butyl titanate; heating to 190-210 ℃ at the heating rate of 5 ℃/min, continuously introducing nitrogen, and continuously stirring for 1-2 hours at the speed of 2000-3000 r/min; and when the acid value of the liquid in the reaction kettle is lower than 5mgKOH/g, stopping introducing nitrogen, stopping heating and stirring, and cooling to 20-30 ℃ to obtain the castor oil based modified polyol. The castor oil based alkyd resin produced by the invention has the advantages of environmental friendliness, lower viscosity, scratch resistance and excellent adhesive force.
Description
Technical Field
The invention belongs to the technical field of biomass resource high added value utilization and alkyd resin intersection, and particularly relates to castor oil-based alkyd resin produced by using castor oil as a raw material and a preparation method thereof.
Background
With the development of industry and the progress of human society, the amount of polymer materials used is gradually increasing, and the traditional approach of synthesizing polymers from petroleum is not viewed by most countries along with the increasingly severe energy crisis of petroleum. The development of green renewables has been a target sought after by humans over the twenty-first century. In the chemical industry, bio-based materials are favored because of the renewable nature of the raw materials from which they are produced. There are many studies currently underway to extract effective substances from renewable bio-based materials to replace a portion of the raw materials to produce environmentally friendly polymer products. The bio-based polymers have the characteristics of good renewability and environmental friendliness. Alkyd resins are prepared from polyols, polybasic acids and monobasic fatty acids or oils by condensation and are conveniently and widely used in paints, surface coatings, adhesives and the like. Many reports have also demonstrated the use of agricultural feedstocks such as: vegetable oils, carbohydrates, proteins, lignin, etc., as new substitutes to replace petroleum raw materials. Therefore, the adoption of bio-based materials to replace the substances extracted from traditional petroleum for producing alkyd resins has great practical significance.
The castor-oil plant tree grows fast, widely grows in tropical forest of Africa, and has wide planting foundation as economic crop in China, southern provinces and cities. The mixture of triglyceride and unsaturated chain in castor oil is up to 80%, including conjugated diene, linoleic acid, oleic acid, stearic acid, etc., which are abundant raw material sources for organic synthesis. As a natural plant polyol, castor oil is used, and compared with petroleum-based polymers, the synthesized polymer has the advantages of better mechanical property, low cost and reproducibility.
The carbon-carbon double bond contained in the castor oil can be oxidized and self-crosslinked to prepare the polymer, but the polymer prepared by the method is easy to block and has poor fluidity in the actual operation process, and the existence of secondary hydroxyl in the castor oil molecular chain causes lower reaction activity. The invention therefore proposes: castor oil is used as a raw material to synthesize castor oil modified polyol with low viscosity, in addition, castor oil glyceryl monostearate is obtained through alcoholysis to improve the activity of hydroxyl in a castor oil molecular chain, and the castor oil modified polyol is used as a reactant to efficiently synthesize castor oil-based alkyd resin with low viscosity, scratch resistance and good adhesion.
Disclosure of Invention
The invention aims to provide castor oil-based alkyd resin and a preparation method thereof, and particularly relates to biological alkyd resin produced by taking castor oil extracted from castor oil fruits which is rich in grease and can not be used for cooking as a raw material.
In order to achieve the purpose, the invention adopts the following technical scheme: the castor oil based alkyd resin comprises the following components in parts by weight: 20-30 parts of castor oil glyceryl monostearate, 10-20 parts of castor oil-based modified polyol, 20-40 parts of polybasic acid, 1-3 parts of catalyst and 5-20 parts of diluent; the castor oil glycerin monostearate comprises the following steps: (1) removing impurities: drying castor oil with anhydrous sodium sulfate at a certain temperature and filtering to remove impurities; (2) transesterification: the castor oil, glycerol and adipic acid are catalyzed by lithium hydroxide to obtain an ester exchange product, namely castor oil glyceryl monostearate; the castor oil modified polyol is obtained by catalytically polymerizing castor oil glyceryl monostearate and hexahydrophthalic anhydride at 180-230 ℃ by tetrabutyl titanate.
In a further technical scheme, the polybasic acid is selected from one or more of phthalic anhydride, maleic anhydride, itaconic acid, sebacic acid and terephthalic acid.
In a further technical scheme, the catalyst is selected from one or more of lead oxide, calcium oxide and lithium hydroxide.
In a further technical scheme, the diluent is selected from one or more of anhydrous xylene, cyclohexanone, no. 200 solvent oil and butyl acetate.
In a further technical scheme, the method comprises the following steps of (1): in a multifunctional reaction kettle, according to the weight part of 1:0.06 to 1:0.1 adding castor oil and anhydrous sodium sulfate, introducing nitrogen, heating to 50-80 ℃, simultaneously stirring at the speed of 2000-3000 r/min for 1-2 hours, stopping heating and stirring, cooling to 20-30 ℃, and filtering to remove impurities; step (2): a. in a multifunctional reaction kettle, the weight portion is 100:20:25:0.05 to 100:50:25:0.05 adding castor oil, glycerol, adipic acid and lithium hydroxide, introducing nitrogen, stirring at the speed of 2000-3000 r/min, and preserving heat for 2-4 hours at the temperature of 180-210 ℃; b. taking the reaction liquid and methanol according to the weight part 4:1, mixing, and pouring out the liquid in the reaction kettle to obtain the castor oil glycerin monostearate if the reaction liquid is completely dissolved in the methanol.
In a further technical scheme, the castor oil based modified polyol comprises the following specific steps:
a. in a multifunctional reaction kettle, the weight portion is 100:10:0.1 to 100:20:0.1 adding castor oil glycerin monostearate, hexahydrophthalic anhydride and tetra-n-butyl titanate;
b. heating to 190-210 ℃ at the heating rate of 5 ℃/min, continuously introducing nitrogen, and continuously stirring for 1-2 hours at the speed of 2000-3000 r/min;
c. and when the acid value of the liquid in the reaction kettle is lower than 5mgKOH/g, stopping introducing nitrogen, stopping heating and stirring, and cooling to 20-30 ℃ to obtain the castor oil based modified polyol.
The castor oil-based modified polyol obtained after modification has lower viscosity, and the castor oil-based alkyd resin prepared by using the modified castor oil-based modified polyol also has lower viscosity, so that the problems of easy blockage and poor fluidity in the actual operation process are solved.
In a further technical scheme, the preparation method of the castor oil based alkyd resin comprises the following specific steps: a. sequentially adding castor oil-based modified polyol, castor oil glyceryl monostearate, polybasic acid, a catalyst and a diluent in parts by weight into a multifunctional reaction kettle, and heating to 120-130 ℃. Stirring for 30-60 minutes at the rotating speed of 500-800 r/min while adding; b. after stirring, raising the temperature to 160-190 ℃ for dehydration reaction, taking reaction liquid every 30 minutes to measure the acid value, and stopping the reaction when the acid value is lower than 15 mgKOH/g; c. after the reaction is stopped, continuously stirring to ensure that the reaction liquid is uniformly dispersed and the temperature of the reaction kettle is reduced to 40-50 ℃; d. and (3) removing the diluent by reduced pressure distillation at 10-30 kPa, and pouring out the residual kettle liquid to obtain the castor oil based alkyd resin.
The alcoholysis reaction of the castor oil can overcome the defect of high content of secondary hydroxyl in the molecular chain of the castor oil, so that the process of synthesizing the alkyd resin is more efficient, and the utilization rate of the castor oil in the process of synthesizing the alkyd resin is highest.
According to the technical scheme, compared with the prior art, the invention has the following beneficial technical effects: (1) According to the invention, the castor oil is used for replacing petroleum resources to produce the alkyd resin, and compared with petroleum-based polymers, the alkyd resin has the advantages of better mechanical property and low cost, can greatly reduce the dependence on petroleum raw materials, saves energy, and is beneficial to sustainable development;
(2) The castor oil alkyd resin produced by the invention has lower viscosity, excellent adhesive force and scratch resistance.
Detailed Description
The present invention will be further described with reference to the following examples, which are not intended to limit the scope of the present invention.
Example 1
In a multifunctional reaction kettle, according to the weight part of 1: 0.06-1: 0.1 adding castor oil and anhydrous sodium sulfate, introducing nitrogen, heating to 50-80 ℃, simultaneously stirring at the speed of 2000-3000 r/min for 1-2 hours, stopping heating and stirring, cooling to 20-30 ℃, and filtering to remove impurities.
Example 2
In a multifunctional reaction kettle, the weight portion is 100:20:25:0.05 addition of castor oil, glycerol, adipic acid and lithium hydroxide from example 1, stirring at 2000r/min with nitrogen and incubation at 180 ℃ for 4 hours. Taking the reaction liquid and methanol according to the weight portion of 4:1, mixing, pouring out the liquid in the reaction kettle when the reaction liquid is completely dissolved in the methanol to obtain the castor oil glyceryl monostearate.
Example 3
In a multifunctional reaction kettle, the weight portion is 100:40:25:0.05 of the castor oil of example 1, glycerol, adipic acid and lithium hydroxide are added, nitrogen is passed and stirring is carried out at 3000r/min, and the mixture is incubated at 210 ℃ for 3 hours. Taking the reaction liquid and methanol according to the weight part 4:1, mixing, pouring out the liquid in the reaction kettle when the reaction liquid is completely dissolved in the methanol to obtain the castor oil glyceryl monostearate.
Example 4
In a multifunctional reaction kettle, the weight portion is 100:10:0.1 portion of the castor oil glyceryl monostearate, hexahydrophthalic anhydride and tetra-n-butyl titanate obtained in example 2 was added. Heating to 200 ℃ at the heating rate of 5 ℃/min and continuously introducing nitrogen. While stirring was continued at 3000r/min for 2 hours. Stopping introducing nitrogen when the acid value of the liquid in the reaction kettle is lower than 5mgKOH/g, stopping heating and stirring, and cooling to 20 ℃ to obtain the castor oil based modified polyol.
Example 5
In a multifunctional reaction kettle, the weight portion is 100:15:0.1 Glycerol monostearate, hexahydrophthalic anhydride and tetra-n-butyl titanate from example 3 were added. The temperature is raised to 190 ℃ at the temperature raising rate of 5 ℃/min and the nitrogen is continuously introduced. While stirring was continued at 2000r/min for 2 hours. And stopping introducing nitrogen when the acid value of the liquid in the reaction kettle is lower than 5mgKOH/g, stopping heating and stirring, and cooling to 20 ℃ to obtain the castor oil based modified polyol.
Example 6
In a multifunctional reaction kettle, the weight portion is 100:20:0.1 Glycerol monostearate, hexahydrophthalic anhydride and tetra-n-butyl titanate from example 3 were added. The temperature is raised to 210 ℃ at the heating rate of 5 ℃/min and nitrogen is continuously introduced. While stirring was continued at 3000r/min for 2 hours. And stopping introducing nitrogen when the acid value of the liquid in the reaction kettle is lower than 5mgKOH/g, stopping heating and stirring, and cooling to 20 ℃ to obtain the castor oil based modified polyol.
In conclusion, the castor oil based modified polyol prepared in the embodiments 4-6 has lower viscosity, which is beneficial to the subsequent preparation of the castor oil based alkyd resin with low viscosity.
Example 7
Sequentially adding castor oil glyceryl monostearate, castor oil-based modified polyol, polybasic acid, a catalyst and a diluent in parts by weight into a multifunctional reaction kettle, heating to 120 ℃, adding and stirring at the rotation speed of 800r/min for 60 minutes, raising the temperature to 180 ℃ after stirring to perform dehydration reaction, taking reaction liquid every 30 minutes to measure the acid value of the reaction liquid, and stopping the reaction when the acid value is lower than 15 mgKOH/g; after the reaction is stopped, continuously stirring to ensure that the reaction liquid is uniformly dispersed, reducing the temperature of the reaction kettle to 40 ℃, removing the diluent through reduced pressure distillation under 10kPa, and then pouring out the residual kettle liquid to obtain the castor oil based alkyd resin; the formula of each raw material is shown in table 1:
TABLE 1 EXAMPLE 7 compounding of raw materials for alkyd resin synthesis
| Castor oil based modified polyol | 20 portions of |
| Castor oil glyceryl monostearate | 25 portions of |
| Phthalic anhydride | 30 portions of |
| Calcium oxide | 2 |
| Anhydrous xylene | 12 |
The castor oil based modified polyol in table 1 is the castor oil based modified polyol prepared by the method of example 4; castor oil monostearate was the castor oil based modified polyol prepared in example 2.
The adhesion was determined on the alkyd resin prepared according to GB/T9286-1998 test division of paint and varnish films, the result being a rating of 0.
The prepared alkyd resins were tested for scratch resistance according to GB/T31591-2015 determination of scratch resistance for paints and varnishes, the test result being 1400g.
The prepared alkyd resin was subjected to viscosity measurement according to GB/T9751-1988, determination of viscosity of coating at high shear rate, and the measurement result was 1200mPa.s.
Example 8
Sequentially adding castor oil glyceryl monostearate, castor oil-based modified polyol, polybasic acid, a catalyst and a diluent in parts by weight into a multifunctional reaction kettle, heating to 120 ℃, adding while stirring for 60 minutes at a rotating speed of 500r/min, raising the temperature to 170 ℃ after stirring to perform dehydration reaction, taking reaction liquid every 30 minutes to measure the acid value of the reaction liquid, and stopping the reaction when the acid value is lower than 15 mgKOH/g; after the reaction is stopped, continuously stirring to ensure that the reaction liquid is uniformly dispersed, reducing the temperature of the reaction kettle to 40 ℃, removing the diluent through reduced pressure distillation under 30kPa, and then pouring out the residual kettle liquid to obtain the castor oil based alkyd resin; the formula of each raw material is shown in table 2:
TABLE 2 EXAMPLE 8 compounding of raw materials for alkyd resin synthesis
| Castor oil based modified polyol | 15 portions of |
| Castor oil monoglyceride stearate | 30 portions of |
| Maleic anhydride | 25 portions of |
| Calcium oxide | 1 |
| Anhydrous xylene | 8 |
The castor oil based modified polyol in table 2 is the castor oil based modified polyol prepared by the method of example 5; castor oil monostearate is the castor oil based modified polyol prepared by the method of example 3.
The adhesion was determined on the alkyd resin prepared according to GB/T9286-1998 test cut-out for paint and varnish films, with a result of grade 2.
The prepared alkyd resins were tested for scratch resistance according to GB/T31591-2015 "determination of scratch resistance in paints and varnishes", the test result being 1500g.
The prepared alkyd resin was tested for viscosity according to GB/T9751-1988 viscosity at high shear rate test, which gave a viscosity of 1260mPa.s.
Example 9
Sequentially adding castor oil glyceryl monostearate, castor oil-based modified polyol, polybasic acid, a catalyst and a diluent in parts by weight into a multifunctional reaction kettle, heating to 120 ℃, adding and stirring at the rotating speed of 500r/min for 30 minutes, raising the temperature to 175 ℃ after stirring to perform dehydration reaction, taking reaction liquid every 30 minutes to measure the acid value of the reaction liquid, and stopping the reaction when the acid value is lower than 15 mgKOH/g; after the reaction is stopped, continuously stirring to ensure that the reaction liquid is uniformly dispersed, reducing the temperature of the reaction kettle to 50 ℃, removing the diluent through reduced pressure distillation under 10kPa, and then pouring out the residual kettle liquid to obtain the castor oil based alkyd resin; the formula of each raw material is shown in table 3:
TABLE 3 example 9 compounding ratio of raw materials for synthesizing alkyd resin
The castor oil based modified polyol in table 3 is the castor oil based modified polyol prepared by the method of example 6; castor oil monostearate was the castor oil based modified polyol prepared in example 3.
The adhesion was determined on the alkyd resin prepared according to GB/T9286-1998 test cut-out for paint and varnish films, with a rating of 1.
The prepared alkyd resins were tested for scratch resistance according to GB/T31591-2015 "determination of scratch resistance in paints and varnishes", test result 1400g.
The prepared alkyd resin was subjected to a viscosity test according to GB/T9751-1988 viscosity measurement of paint at high shear rate, which gave a measurement result of 1220mPa.s.
Example 10
Sequentially adding castor oil glyceryl monostearate, castor oil-based modified polyol, polybasic acid, a catalyst and a diluent in parts by weight into a multifunctional reaction kettle, heating to 120 ℃, adding and stirring at the rotating speed of 500r/min for 30 minutes, raising the temperature to 180 ℃ after stirring to perform dehydration reaction, taking reaction liquid every 30 minutes to measure the acid value of the reaction liquid, and stopping the reaction when the acid value is lower than 15 mgKOH/g; after the reaction is stopped, continuously stirring to ensure that the reaction liquid is uniformly dispersed, reducing the temperature of the reaction kettle to 40 ℃, removing the diluent through reduced pressure distillation under 10kPa, and then pouring out the residual kettle liquid to obtain the castor oil based alkyd resin; the formulation of each raw material is shown in table 4:
TABLE 4 EXAMPLE 10 compounding of raw materials for alkyd resin synthesis
| Castor oil-based modified polyol | 20 portions of |
| Castor oil glyceryl monostearate | 20 portions of |
| Phthalic anhydride | 40 portions of |
| Calcium oxide | 3 |
| Anhydrous xylene | 15 |
The castor oil based modified polyol in table 4 is the castor oil based modified polyol prepared by the method of example 5; castor oil monostearate is the castor oil based modified polyol prepared by the method of example 3.
The adhesion was determined on the alkyd resin prepared according to GB/T9286-1998 "test for marking of paint and varnish films" and the result is grade 1.
The prepared alkyd resins were tested for scratch resistance according to GB/T31591-2015 "determination of scratch resistance in paints and varnishes", the test result being 1500g.
The prepared alkyd resin was subjected to viscosity measurement according to GB/T9751-1988, determination of viscosity of coating at high shear rate, and the measurement result was 1300mPa.s.
Example 11
Sequentially adding castor oil glyceryl monostearate, castor oil-based modified polyol, polybasic acid, a catalyst and a diluent in parts by weight into a multifunctional reaction kettle, heating to 125 ℃, adding while stirring at the speed of 500r/min for 45 minutes, raising the temperature to 185 ℃ after stirring to perform dehydration reaction, taking reaction liquid every 30 minutes to measure the acid value of the reaction liquid, and stopping the reaction when the acid value is lower than 15 mgKOH/g; after the reaction is stopped, continuously stirring to ensure that the reaction liquid is uniformly dispersed, reducing the temperature of the reaction kettle to 50 ℃, removing the diluent by reduced pressure distillation under 10kPa, and then pouring out the residual kettle liquid to obtain the castor oil based alkyd resin; the formulation of each raw material is shown in table 5:
TABLE 5 EXAMPLE 11 compounding of raw materials for alkyd resin synthesis
| Castor oil based modified polyol | 15 portions of |
| Castor oil glyceryl monostearate | 20 portions of |
| Phthalic anhydride | 25 portions of |
| Lithium hydroxide | 1 |
| Cyclohexanone | 10 |
The castor oil based modified polyol in table 5 is the castor oil based modified polyol prepared by the method of example 6; castor oil monostearate is the castor oil based modified polyol prepared by the method of example 3.
The adhesion was determined on the alkyd resin prepared according to GB/T9286-1998 test division of paint and varnish films, the result being a rating of 0.
The prepared alkyd resins were tested for scratch resistance according to GB/T31591-2015 "determination of scratch resistance in paints and varnishes", the test result being 1300g.
The prepared alkyd resin was subjected to a viscosity test according to GB/T9751-1988 viscosity measurement of coating at high shear rate, which gave a measurement result of 1300mPa.s.
Example 12
Sequentially adding castor oil glyceryl monostearate, castor oil-based modified polyol, polybasic acid, a catalyst and a diluent in parts by weight into a multifunctional reaction kettle, heating to 125 ℃, adding and stirring at the rotating speed of 800r/min for 60 minutes, raising the temperature to 175 ℃ after stirring to perform dehydration reaction, taking reaction liquid every 30 minutes to measure the acid value of the reaction liquid, and stopping the reaction when the acid value is lower than 15 mgKOH/g; after the reaction is stopped, continuously stirring to ensure that the reaction liquid is uniformly dispersed, reducing the temperature of the reaction kettle to 45 ℃, removing the diluent through reduced pressure distillation under 10kPa, and then pouring out the residual kettle liquid to obtain the castor oil based alkyd resin; the formulation of each raw material is shown in table 6:
TABLE 6 EXAMPLE 12 compounding of raw materials for alkyd resin synthesis
| Castor oil-based modified polyol | 20 portions of |
| Castor oil monoglyceride stearate | 20 portions of |
| Phthalic anhydride | 40 portions of |
| Lead oxide | 3 |
| Anhydrous xylene | 15 |
The castor oil based modified polyol in table 6 is the castor oil based modified polyol prepared by the method of example 6; castor oil monostearate was the castor oil based modified polyol prepared in example 3.
The adhesion was determined on the alkyd resin prepared according to GB/T9286-1998 test division of paint and varnish films, the result being a rating of 0.
The prepared alkyd resins were tested for scratch resistance according to GB/T31591-2015 determination of scratch resistance for paints and varnishes, the test result being 1600g.
The viscosity of the alkyd resin prepared was measured according to GB/T9751-1988 viscosity measurement at high shear rate, and the measurement result was 1350mPa.s.
The properties of the castor oil based alkyd resins obtained from examples 7-12 are shown in Table 7:
TABLE 7 castor oil based alkyd resin performance tables prepared in examples 7-12
| Examples | Grade of adhesion | Scratch resistance (g) | Viscosity (mPa.s) |
| Example 7 | 0 | 1400 | 1200 |
| Example 8 | 0 | 1500 | 1260 |
| Example 9 | 0 | 1400 | 1220 |
| Example 10 | 0 | 1500 | 1300 |
| Example 11 | 0 | 1300 | 1300 |
| Example 12 | 0 | 1600 | 1350 |
In conclusion, the alkyd resin prepared by using the castor oil as the raw material has lower viscosity, solves the problem of high viscosity and easy blockage, and has excellent adhesive force and scratch resistance; the raw materials are renewable, the cost is low, the dependence on raw materials from petroleum can be greatly reduced, the energy is saved, and the sustainable development is facilitated.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. A castor oil based alkyd resin is characterized in that: the castor oil based alkyd resin comprises the following components in parts by weight: 20-30 parts of castor oil glyceryl monostearate, 10-20 parts of castor oil-based modified polyol, 20-40 parts of polybasic acid, 1-3 parts of catalyst and 5-20 parts of diluent; the castor oil glycerin monostearate comprises the following steps: (1) removing impurities: drying castor oil with anhydrous sodium sulfate at a certain temperature and filtering to remove impurities; (2) transesterification: obtaining an ester exchange product, namely castor oil glyceryl monostearate by the castor oil, the glycerol and the adipic acid under the catalysis of lithium hydroxide; the castor oil modified polyol is obtained by catalytically polymerizing castor oil glyceryl monostearate and hexahydrophthalic anhydride at 180-230 ℃ by tetrabutyl titanate.
2. The castor oil-based alkyd resin of claim 1, wherein: the polybasic acid is selected from one or more of phthalic anhydride, maleic anhydride, itaconic acid, sebacic acid and terephthalic acid.
3. The castor oil-based alkyd resin of claim 1, wherein: the catalyst is selected from one or more of lead oxide, calcium oxide and lithium hydroxide.
4. The castor oil-based alkyd resin of claim 1, wherein: the diluent is selected from one or more of anhydrous xylene, cyclohexanone, no. 200 solvent oil and butyl acetate.
5. The castor oil-based alkyd resin of claim 1, wherein: comprises the following steps of (1): in a multifunctional reaction kettle, according to the weight part of 1: 0.06-1: 0.1 adding castor oil and anhydrous sodium sulfate, introducing nitrogen, heating to 50-80 ℃, simultaneously stirring at the speed of 2000-3000 r/min for 1-2 hours, stopping heating and stirring, cooling to 20-30 ℃, and filtering to remove impurities;
step (2): a. and (3) adding 100 parts by weight of the raw materials into a multifunctional reaction kettle: 20:25:0.05 to 100:50:25:0.05 adding castor oil, glycerol, adipic acid and lithium hydroxide, introducing nitrogen, stirring at the speed of 2000-3000 r/min, and preserving heat for 2-4 hours at the temperature of 180-210 ℃ to obtain reaction liquid;
b. taking the reaction liquid and methanol according to the weight portion of 4:1, mixing, completely dissolving the reaction solution in methanol, and pouring out the liquid in the reaction kettle to obtain the castor oil glyceryl monostearate.
6. The castor oil based alkyd according to claim 1, wherein: the castor oil based modified polyol comprises the following specific steps:
a. in a multifunctional reaction kettle, the weight portion is 100:10:0.1 to 100:20:0.1 adding castor oil glycerin monostearate, hexahydrophthalic anhydride and tetra-n-butyl titanate;
b. heating to 190-210 ℃ at the heating rate of 5 ℃/min and continuously introducing nitrogen. Meanwhile, continuously stirring for 1-2 hours at the speed of 2000-3000 r/min;
c. and stopping introducing nitrogen when the acid value of the liquid in the reaction kettle is lower than 5mg KOH/g, stopping heating and stirring, and cooling to 20-30 ℃ to obtain the castor oil based modified polyol.
7. A method of making the castor oil-based alkyd according to any of claims 1 to 6, wherein: the method comprises the following specific steps:
a. sequentially adding castor oil-based modified polyol, castor oil glyceryl monostearate, polybasic acid, a catalyst and a diluent in parts by weight into a multifunctional reaction kettle, heating to 120-130 ℃, and stirring for 30-60 minutes at a rotating speed of 500-800 r/min while adding;
b. after stirring, raising the temperature to 160-190 ℃ for dehydration reaction, taking reaction liquid every 30 minutes to measure the acid value, and stopping the reaction when the acid value is lower than 15 mgKOH/g;
c. after the reaction is stopped, continuously stirring to uniformly disperse the reaction liquid and reduce the temperature of the reaction kettle to 40-50 ℃;
d. and (3) removing the diluent by reduced pressure distillation at 10-30 kPa, and pouring out the residual kettle liquid to obtain the castor oil based alkyd resin.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2230351A (en) * | 1937-07-13 | 1941-02-04 | Ici Ltd | Halogenated castor oil-polycarboxylic acid products |
| GB750506A (en) * | 1953-05-15 | 1956-06-20 | Ici Ltd | Improvements in or relating to modified alkyd resins |
| CN114075424A (en) * | 2020-08-17 | 2022-02-22 | 上海天洋热熔粘接材料股份有限公司 | Low-surface-energy single-component moisture-curing polyurethane hot melt adhesive and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2230351A (en) * | 1937-07-13 | 1941-02-04 | Ici Ltd | Halogenated castor oil-polycarboxylic acid products |
| GB750506A (en) * | 1953-05-15 | 1956-06-20 | Ici Ltd | Improvements in or relating to modified alkyd resins |
| CN114075424A (en) * | 2020-08-17 | 2022-02-22 | 上海天洋热熔粘接材料股份有限公司 | Low-surface-energy single-component moisture-curing polyurethane hot melt adhesive and preparation method thereof |
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