CN108822284B - Method for preparing near-zero VOC alkyd resin by using illegal cooking oil and alkyd resin - Google Patents
Method for preparing near-zero VOC alkyd resin by using illegal cooking oil and alkyd resin Download PDFInfo
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- CN108822284B CN108822284B CN201810587014.6A CN201810587014A CN108822284B CN 108822284 B CN108822284 B CN 108822284B CN 201810587014 A CN201810587014 A CN 201810587014A CN 108822284 B CN108822284 B CN 108822284B
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- cooking oil
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/46—Polyesters chemically modified by esterification
- C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
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- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
Abstract
The invention discloses a method for preparing near-zero VOC alkyd resin by using illegal cooking oil and the alkyd resin. The method comprises the following steps: s1, uniformly mixing 8-10 parts by mass of dihydric alcohol, 10-15 parts by mass of sodium m-phthalate-5-sulfonate and a proper amount of catalyst; s2, heating the mixture obtained in the step S1, then adding 33-40 parts by mass of the illegal cooking oil alcoholization liquid, 5-10 parts by mass of trimethylolpropane and 15-30 parts by mass of anhydride, heating for reaction for a period of time, and cooling for later use when the viscosity of the product reaches a preset value. The method can obtain 100% solid alkyd resin, avoids the use of volatile organic solvent, obtains the near-zero VOC alkyd resin, and has excellent environmental protection property. The invention utilizes the illegal cooking oil to prepare the alkyd resin, reduces the production cost of the alkyd resin and realizes the reutilization of the illegal cooking oil.
Description
Technical Field
The invention relates to the field of coatings, in particular to a method for preparing near-zero VOC alkyd resin by using illegal cooking oil and the alkyd resin.
Background
Along with the enhancement of environmental awareness, people pay more and more attention to products with less pollution and high added value. The solvent-based coating is a solid coating from a flowing state, and the solvent is volatilized, so that the atmosphere is greatly polluted, the use of harmful solvents is reduced or even prohibited, and the realization of the water-based technology of the coating is particularly critical.
In the coating industry, polyesters prepared by reacting fatty acids or oleic acid with polyols, polyacids, are called alkyds. The synthetic method of the water-based alkyd resin mainly comprises a salt forming method, a method of introducing hydrophilic nonionic groups into polymers and a method of converting the polymers into zwitterionic intermediates. Although the Volatile Organic Compounds (VOC) of the water-based alkyd resin are much lower than those of the solvent-based alkyd resin, the water-based alkyd resin in the prior art still has certain volatile organic compounds, and zero VOC cannot be achieved.
The illegal cooking oil, a bio-based material, is currently widely studied in the preparation of biodiesel, and the process of using illegal cooking oil in the preparation of alkyd resins is also documented in the literature. The alkyd resin prepared from the treated illegal cooking oil solves the problem of recycling the illegal cooking oil, is favorable for reducing the cost of the alkyd resin and has good application prospect. However, the alkyd resin prepared by using the illegal cooking oil at present also has an organic volatile solvent, and zero VOC can not be achieved.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for preparing a near-zero VOC alkyd resin by using illegal cooking oil, and the obtained alkyd resin can basically reach zero VOC emission.
Another object of the present invention is to provide an alkyd resin prepared by the above method.
One of the purposes of the invention is realized by adopting the following technical scheme:
the method for preparing the near-zero VOC alkyd resin by using the illegal cooking oil comprises the following steps:
s1, uniformly mixing 8-10 parts by mass of dihydric alcohol, 10-15 parts by mass of sodium m-phthalate-5-sulfonate and a proper amount of catalyst;
s2, heating the mixture obtained in the step S1, then adding 33-40 parts by mass of the illegal cooking oil alcoholization liquid, 5-10 parts by mass of trimethylolpropane and 15-30 parts by mass of anhydride, heating for reaction for a period of time, and cooling for later use when the viscosity of the product reaches a preset value.
Further, step S2 includes the steps of:
s21, heating the mixture obtained in the step S1, slowly raising the temperature to 190-210 ℃ within 4-5 hours, and keeping the temperature for 50-60 min;
s22, adding 33-40 parts by mass of illegal cooking oil alcoholization liquid, 5-10 parts by mass of trimethylolpropane and 15-30 parts by mass of anhydride into the mixture obtained in the step S21, heating to 220-230 ℃, and then preserving heat for 50-60 min;
and S23, when the viscosity of the product in the step S22 reaches a preset value, cooling for later use.
Further, in step S2, the preset values of product viscosity are: when the product and ethylene glycol monobutyl ether are mixed in a mass ratio of 1:1, the grignard viscosity is more than 1 second.
Further, the diol is neopentyl glycol.
Further, the acid anhydride comprises 15-25 parts of phthalic anhydride and 2-5 parts of maleic anhydride.
Further, in step S1, the catalyst is stannous octoate.
Further, in step S2, the illegal cooking oil alcoholysis solution is prepared by the following method: putting 70-90 parts by weight of refined illegal cooking oil and 10-20 parts by weight of pentaerythritol into a reaction kettle, heating to 170-190 ℃, adding a catalyst, continuously heating to 260-280 ℃, reacting for 1-3 hours, and cooling for later use.
Further, when the illegal cooking oil alcoholic solution is prepared, after a catalyst is added for heating reaction, when the mass ratio of the illegal cooking oil alcoholic solution to ethanol is 1:1 when the mixture obtained by mixing is clear and transparent, the reaction can be finished, and the temperature is reduced for standby.
Compared with the prior art, the invention has the beneficial effects that:
(1) the alkyd resin with 100% of solid content can be obtained, the use of volatile organic solvent is avoided, the near-zero VOC alkyd resin is obtained, and the environment-friendly property is excellent;
(2) the method utilizes the sodium m-phthalate-5-sulfonate to realize self-emulsification dispersion of the resin, and simultaneously endows the alkyd resin with water solubility, and when the alkyd resin is used, the alkyd resin prepared by the method is dissolved in a mixed solution of water and ethanol;
(3) the invention utilizes the illegal cooking oil to prepare the alkyd resin, reduces the production cost of the alkyd resin and realizes the reutilization of the illegal cooking oil.
Detailed Description
The present invention is further described below with reference to specific embodiments, and it should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment.
The invention provides a near-zero VOC alkyd resin prepared from illegal cooking oil, which comprises the following raw materials in parts by weight:
in the invention, the self-emulsifying dispersion of the resin is realized by using the sodium m-phthalate-5-sulfonate, and no additional solvent is required to be added, so that the 100% solid alkyd resin is obtained. Zero VOC is essentially achieved due to the absence of co-solvent. In addition, the invention utilizes the illegal cooking oil as a production raw material, thereby being beneficial to reducing the production cost.
Preferably, the diol is neopentyl glycol.
Preferably, the catalyst is stannous octoate.
Preferably, the acid anhydride comprises 15-25 parts of phthalic anhydride and 2-5 parts of maleic anhydride.
The illegal cooking oil alcoholization liquid comprises the following raw materials: 70-90 parts by weight of illegal cooking oil; 10-20 parts by weight of pentaerythritol; an appropriate amount of catalyst. Preferably, the catalyst in the illegal cooking oil alcoholysis solution is lithium hydroxide.
Preferably, the illegal cooking oil alcoholysis solution is prepared by the following method: adding the illegal cooking oil and pentaerythritol into a reaction kettle, heating to 170-190 ℃, adding a catalyst, continuously heating to 260-280 ℃, reacting for 1-3 hours, and cooling for later use. The obtained illegal cooking oil alcoholization liquid and ethanol are mixed according to the mass ratio of 1:1, clear and transparent when mixed. In other words, when the mass ratio of the illegal cooking oil alcoholized liquid to the ethanol is 1:1 when the mixture obtained by mixing is clear and transparent, the reaction can be finished, and the temperature is reduced for standby.
It is worth mentioning that the illegal cooking oil is preprocessed illegal cooking oil, and the preprocessing steps comprise impurity removal, centrifugal separation, alkali washing, refining and the like. The pretreatment of the illegal cooking oil can refer to the prior art, and the invention is not described in detail.
Preferably, the alkyd resin is prepared by the steps of:
s1, uniformly mixing 8-10 parts by mass of dihydric alcohol, 10-15 parts by mass of sodium m-phthalate-5-sulfonate and a proper amount of catalyst;
s2, heating the mixture obtained in the step S1, then adding 33-40 parts by mass of the illegal cooking oil alcoholization liquid, 5-10 parts by mass of trimethylolpropane and 15-30 parts by mass of anhydride, heating for reaction for a period of time, and cooling for later use when the viscosity of the product reaches a preset value.
Preferably, step S2 includes the steps of:
s21, heating the mixture obtained in the step S1, slowly raising the temperature to 190-210 ℃ within 4-5 hours, and keeping the temperature for 50-60 min;
s22, adding 33-40 parts by mass of illegal cooking oil alcoholization liquid, 5-10 parts by mass of trimethylolpropane and 15-30 parts by mass of anhydride into the mixture obtained in the step S21, heating to 220-230 ℃, and then preserving heat for 50-60 min;
and S23, when the viscosity of the product in the step S22 reaches a preset value, cooling for later use.
Preferably, in step S2, the preset values of product viscosity are: when the product and ethylene glycol monobutyl ether are mixed in a mass ratio of 1:1, the grignard viscosity is more than 1 second.
[ example 1 ]
Preparation of illegal cooking oil alcoholization liquid: putting 85 parts by mass of refined gutter oil and 15 parts by mass of pentaerythritol into a reaction kettle, heating to 180 ℃, adding 0.03 part by mass of lithium hydroxide, continuously heating to 270 ℃, and reacting for about 2 hours, wherein when the mass ratio of a reaction product to ethanol is 1:1 when the mixture obtained by mixing is clear and transparent, the reaction can be finished, and the temperature is reduced for standby.
Wherein, the refined illegal cooking oil is purchased from Zhejiang Qingcao province GmbH.
[ example 2 ]
An environment-friendly alkyd resin prepared from illegal cooking oil is prepared by the following steps:
uniformly mixing 8 parts by mass of neopentyl glycol, 10 parts by mass of 5-sodium sulfoisophthalate and 0.02 part by mass of stannous octoate; slowly raising the temperature to 200 ℃ within 5 hours; and (3) preserving heat for 1 hour, adding 33 parts by mass of hogwash oil alcoholized liquid, 5 parts by mass of trimethylolpropane, 15 parts by mass of phthalic anhydride and 2 parts by mass of maleic anhydride, heating to 220 ℃, preserving heat for about 1 hour, and cooling, filtering and packaging when the viscosity of the product reaches a preset value.
It is worth mentioning that the predetermined values of viscosity are: when the product and ethylene glycol monobutyl ether are mixed in a mass ratio of 1:1, the grignard viscosity is more than 1 second.
[ example 3 ]
An environment-friendly alkyd resin prepared from illegal cooking oil is prepared by the following steps:
uniformly mixing 10 parts by mass of neopentyl glycol, 15 parts by mass of sodium 5-sulfoisophthalate and 0.02 part by mass of stannous octoate; slowly raising the temperature to 200 ℃ within 5 hours; and (3) after preserving heat for 1 hour, adding 40 parts by mass of hogwash oil alcoholization liquid, 10 parts by mass of trimethylolpropane, 25 parts by mass of phthalic anhydride and 5 parts by mass of maleic anhydride, heating to 220 ℃, preserving heat for about 1 hour, and when the viscosity of the product reaches a preset value, cooling, filtering and packaging.
It is worth mentioning that the predetermined values of viscosity are: when the product and ethylene glycol monobutyl ether are mixed in a mass ratio of 1:1, the grignard viscosity is more than 1 second.
The alkyd resin prepared in the embodiments 2 and 3 is uniformly mixed with water, and is coated on the surface of a standard tin plate by a spraying mode, after the alkyd resin is placed at room temperature for 7 days, a coating film with the thickness of 25-30 mu m is formed on the surface of the iron plate, and then various performances are tested. The drying performance is tested according to GB/T1728, the adhesion grade is tested according to GB/T1720-1988, the water resistance is tested according to GB/T1733-93, and the test data are shown in Table 1.
| Test items | Drying Property | Adhesion force | Water resistance (240h) |
| Example 2 | The surface dryness is less than or equal to 1 h; the actual dryness is less than or equal to 12h | Level 0 | Does not foam or fall off |
| Example 3 | The surface dryness is less than or equal to 1 h; the actual dryness is less than or equal to 12h | Level 0 | Does not foam or fall off |
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (7)
1. The method for preparing the near-zero VOC alkyd resin by using the illegal cooking oil is characterized by comprising the following steps of:
s1, uniformly mixing 8-10 parts by mass of dihydric alcohol, 10-15 parts by mass of sodium m-phthalate-5-sulfonate and a proper amount of catalyst;
s2, heating the mixture obtained in the step S1, then adding 33-40 parts by mass of hogwash oil alcoholization liquid, 5-10 parts by mass of trimethylolpropane and 15-30 parts by mass of anhydride, heating for reaction for a period of time, and cooling for later use when the viscosity of the product reaches a preset value;
the acid anhydride comprises 15-25 parts of phthalic anhydride and 2-5 parts of maleic anhydride;
the catalyst is stannous octoate.
2. The method according to claim 1, wherein step S2 comprises the steps of:
s21, heating the mixture obtained in the step S1, slowly raising the temperature to 190-210 ℃ within 4-5 hours, and keeping the temperature for 50-60 min;
s22, adding 33-40 parts by mass of illegal cooking oil alcoholization liquid, 5-10 parts by mass of trimethylolpropane and 15-30 parts by mass of anhydride into the mixture obtained in the step S21, heating to 220-230 ℃, and then preserving heat for 50-60 min;
and S23, when the viscosity of the product in the step S22 reaches a preset value, cooling for later use.
3. The method according to claim 1, wherein in step S2, the preset values of product viscosity are: when the product and ethylene glycol monobutyl ether are mixed in a mass ratio of 1:1, the grignard viscosity is more than 1 second.
4. The method according to any one of claims 1 to 3, wherein in step S1, the diol is neopentyl glycol.
5. The method as claimed in any one of claims 1 to 3, wherein the illegal cooking oil alcoholized solution is passed through in step S2
The preparation method comprises the following steps: 70-90 parts by weight of illegal cooking oil and 10-20 parts by weight of pentaerythritol are added into a reaction kettle, the temperature is raised to 170-190 ℃, then a catalyst is added, the temperature is continuously raised to 260-280 ℃, and the temperature is reduced for standby after the reaction is carried out for 1-3 hours.
6. The method as claimed in claim 5, wherein when the illegal cooking oil alcoholysis solution is prepared, after a catalyst is added for temperature rise reaction, when the mass ratio of the illegal cooking oil alcoholysis solution to ethanol is 1:1 when the mixture obtained by mixing is clear and transparent, the reaction can be finished, and the temperature is reduced for standby.
7. An alkyd resin prepared by the process of any one of claims 1-6.
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| CN201810587014.6A CN108822284B (en) | 2018-06-06 | 2018-06-06 | Method for preparing near-zero VOC alkyd resin by using illegal cooking oil and alkyd resin |
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| CN114805774B (en) * | 2022-04-01 | 2023-04-04 | 佛山市国化新材料科技有限公司 | Carboxylated nano chitin-based alkyd resin and preparation method thereof |
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| KR101736399B1 (en) * | 2016-09-28 | 2017-05-16 | (주)부영산업 | Eco-friendly varnish compositions and methods for their production |
| CN107857873B (en) * | 2017-09-30 | 2019-11-29 | 合众（佛山）化工有限公司 | A kind of alkyd resin and preparation method thereof of 90% large arch dam |
| CN107513340A (en) * | 2017-10-10 | 2017-12-26 | 临汾铁环漆业有限公司 | A kind of self-drying aqueous alkyd paint of high rigidity and preparation method thereof |
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Effective date of registration: 20230216 Address after: 312030 Building 2-3, Xiner Village, Binhai Industrial Zone, Keqiao District, Shaoxing City, Zhejiang Province Patentee after: SHAOXING CHANGMU NEW MATERIAL TECHNOLOGY Co.,Ltd. Address before: 315000 south of the first floor of Building 29, No. 1299, Juxian Road, high tech Zone, Ningbo City, Zhejiang Province Patentee before: LONGWOOD (NINGBO) NEW MATERIAL TECHNOLOGY CO.,LTD. |