CN114805774B - Carboxylated nano chitin-based alkyd resin and preparation method thereof - Google Patents

Carboxylated nano chitin-based alkyd resin and preparation method thereof Download PDF

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CN114805774B
CN114805774B CN202210348894.8A CN202210348894A CN114805774B CN 114805774 B CN114805774 B CN 114805774B CN 202210348894 A CN202210348894 A CN 202210348894A CN 114805774 B CN114805774 B CN 114805774B
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chitin
acid
nano chitin
alkyd resin
parts
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CN114805774A (en
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石聪灿
唐桂明
王韬
朱伯承
江文俊
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Foshan Guohua New Mstar Technology Ltd
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    • 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
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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    • 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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Abstract

The invention discloses a carboxylated nano chitin-based alkyd resin and a preparation method thereof. The carboxylated nano chitin-based alkyd resin comprises the following components in parts by weight: 30-80 parts of carboxylated nano chitin, 10-25 parts of trimethylolpropane, 8-20 parts of polybasic acid, 10-30 parts of monobasic acid, 8-32 parts of polyalcohol, 4-8 parts of neutralizer, 50-80 parts of deionized water and 2-8 parts of catalyst. The invention has the advantages of low production cost, environmental protection, high value utilization of the shrimp shells and the crab shells and reduction of carbon emission of the shrimp shells and the crab shells in the traditional utilization mode.

Description

Carboxylated nano chitin-based alkyd resin and preparation method thereof
Technical Field
The invention belongs to the technical field of cross of high added value utilization of biomass resources and alkyd resin, and particularly relates to carboxylated nano chitin-based alkyd resin and a preparation method thereof.
Background
Alkyd resin was synthesized in germany in the middle of the 19 th century, and the alkyd resin was prepared by condensation of phthalic anhydride and glycerol in 1912, which is used by the american utility electrical company to replace the electrical insulation material-shellac. In 1927, r.h. kiren, usa developed a method for producing alkyd resins suitable for various applications, particularly, resins for coating materials using phthalic anhydride or maleic anhydride, by utilizing the characteristic that resin properties vary depending on polybasic acids, and was industrially produced by general electric company in the same year. The alkyd resin coating has a large yield, which accounts for about 20-25% of the total amount of the coating industry. However, as the scale of human production and living continues to grow, the global oil and gas resources are rapidly decreasing, and it is predicted that the oil resources on earth will be depleted within 100 years. Green and renewable bio-based materials become the most ideal petroleum substitute resource and are also important new materials for the technical development of the polymer chemical industry.
In the field of coating applications, biobased materials, particularly vegetable oils, have been widely used to prepare novel green and environmentally friendly coatings. The vegetable oil has the characteristics of no toxicity, low volatility, biodegradability, abundant and easily obtained raw materials and the like. Since the 19 th century, a series of studies have been conducted on vegetable oil-based polymers. For example, triglyceride in vegetable oil is subjected to glycerolysis to obtain monoglyceride for preparing alkyd resin; firstly, drying oil or fatty acid is subjected to maleic anhydride esterification, and then is subjected to ester exchange reaction with an epoxy prepolymer to prepare a fatty acid modified epoxy coating; the soybean oil is subjected to epoxidation treatment and then is combined with acrylate to prepare epoxidized soybean oil acrylate resin; monoglyceride is also a polyol, and can react with diisocyanate to prepare polyurethane, and vegetable oil for preparing water-based polyurethane includes sunflower oil, castor oil, rapeseed oil, soybean oil, etc.; the tung oil is thermally cross-linked and polymerized to directly form a biodegradable coating.
Chitin, also known as chitin, is a polysaccharide substance extracted from the shells of marine crustaceans, and is the second largest biobased green resource in the world, second only to cellulose. The chitin and the derivatives thereof can be used as the reinforcing filler of the coating, and can also be used as the synthetic raw material of coating resin or a film-forming substance.
Disclosure of Invention
The invention aims to provide a carboxylated nano chitin-based alkyd resin and a preparation method thereof, in particular to a biological alkyd resin produced by taking catering waste, namely shrimp shells or crab shells as raw materials.
The specific technical scheme is as follows:
a carboxylated nanochitin-based alkyd resin, comprising, in parts by weight: 30 to 80 portions of carboxylic nano chitin, 10 to 25 portions of trimethylolpropane, 8 to 20 portions of polybasic acid, 10 to 30 portions of monobasic acid, 8 to 32 portions of polyhydric alcohol, 4 to 8 portions of neutralizer, 50 to 80 portions of deionized water and 2 to 8 portions of catalyst.
In some of these embodiments, the carboxylated nano chitin-based alkyd comprises, in parts by weight: 40 to 70 portions of carboxylated nano chitin, 10 to 20 portions of trimethylolpropane, 8 to 15 portions of polybasic acid, 10 to 25 portions of monobasic acid, 10 to 25 portions of polyalcohol, 4 to 8 portions of neutralizer, 50 to 70 portions of deionized water and 2 to 5 portions of catalyst.
In some of these embodiments, the polyacid is at least one of phthalic anhydride, terephthalic acid, maleic anhydride, acetic anhydride, maleic anhydride.
In some of these embodiments, the monobasic acid is at least one of soy oleic acid, tall oil acid, lauric acid, myristic acid, palmitic acid.
In some of these embodiments, the polyol is at least one of glycerol, pentaerythritol, trimethylolethane, and 1,2, 5-pentanetriol.
In some of these embodiments, the neutralizing agent is at least one of triethylamine, dimethylethanolamine.
In some of these embodiments, the catalyst is at least one of indium trichloride, rhodium trichloride.
In some embodiments, the preparation of the carboxylated nano chitin comprises the following steps: (1) impurity removal: soaking shrimp shells or crab shells in seafood market in 5wt% sodium hydroxide solution for 12-24 hours, then washing the shrimp shells or the crab shells with water, and drying at 80-100 ℃ to obtain chitin; (2) crushing: crushing chitin by using a crusher, and screening by using a 60-mesh sieve; (3) oxidizing: oxidizing the crushed chitin by TEMPO oxidation to obtain sodium carboxylate nano chitin; (4) proton exchange: soaking the sodium carboxylate nano chitin in 3-5M hydrochloric acid solution for 12-24 hr, centrifuging, and washing with distilled water until the filtrate is neutral to obtain the carboxylated nano chitin.
In some of these embodiments, the TEMPO oxidation process comprises the specific steps of:
a. adding 3-5 g of TEMPO into 20-50 g of distilled water, heating to 80-100 ℃, and continuously stirring until the TEMPO is completely dissolved;
b. adding 100g of chitin into 500mL of distilled water, stirring at a stirring speed of 200-500 r/min, then sequentially adding a prepared TEMPO solution, 20-40 g of sodium bromide and 1000-2000 mL of a 12wt% sodium hypochlorite solution, adjusting the pH value of the mixed solution to be 10-10.5 by using a 5wt% sodium hydroxide solution, reacting at room temperature until the pH value of the mixed solution does not change within 3 minutes, and adding 20-50 mL of alcohol to terminate the reaction;
c. and c, filtering the mixed solution in the step b, washing the mixed solution with distilled water until the filtrate is neutral, and removing the filtrate to obtain the oxidized nano chitin.
In some embodiments, the specific steps of proton exchange are: soaking 100 oxidized nano chitin in 1000mL hydrochloric acid solution with the concentration of 2-5M, reacting at room temperature for 12-24 hours, and centrifuging to remove filtrate to obtain carboxylated nano chitin.
The invention also provides a preparation method of the carboxylated nano chitin-based alkyd resin, which comprises the following steps:
a. sequentially adding trimethylolpropane, monoacid, carboxylated nano chitin and a catalyst into a multifunctional reaction kettle according to the weight of a formula, stirring for 10-60 minutes at the rotating speed of 200-500 r/min while introducing nitrogen, and then continuously introducing nitrogen for 5 minutes;
b. stopping introducing nitrogen, heating to 110-120 ℃, keeping the temperature for 1 hour, continuously introducing nitrogen, taking out water vapor, removing free water, continuously heating to 205-220 ℃, keeping the temperature for 1-2 hours, then quickly heating to 260-270 ℃, starting an esterification reaction, performing a reflux reaction, and separating water generated by the reaction by using a water separator;
c. after the reaction is carried out for 1 hour, taking a sample every 30 minutes for acid value testing, and when the acid value is 5-10, sequentially adding the polybasic acid and the polyhydric alcohol according to the formula amount, keeping the temperature of the reaction kettle at 260-270 ℃, and preserving the temperature for 2-3 hours;
d. after the reaction is carried out for 2 hours, taking a sample every 30 minutes for acid value testing, and stopping the reaction when the acid value is 30-40; cooling to 50 ℃ and preserving heat, adding a neutralizer in the formula weight part, stirring at a high speed for dispersing for 30-60 minutes, adding deionized water in the formula amount, continuing stirring at a high speed for 30 minutes, then stirring at a low speed for 30 minutes, and filtering to obtain the carboxylated nano chitin-based alkyd resin.
The invention has the following advantages:
(1) The catering waste, namely the shrimp shells or the crab shells are used as raw materials, so that the production cost is low;
(2) The formula does not relate to the use of an organic solvent, and gas harmful to human health is not generated in the subsequent use of alkyd resin, so that the production concept of green and environmental protection is met;
(3) The shrimp shells and the crab shells are utilized in a high-value manner, so that the carbon emission of the shrimp shells and the crab shells in the traditional utilization mode is reduced;
(4) The carboxylated nano chitin can form network crosslinking with polyhydric alcohol in subsequent esterification reaction, so that the film forming strength of the alkyd resin is improved.
Drawings
FIG. 1 is an electron microscope image of carboxylated nano chitin prepared in example 2;
FIG. 2 electron micrograph of carboxylated nano chitin prepared in example 3;
FIG. 3 is the electron microscope image of the carboxylated nano chitin prepared in example 4.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings, technical process steps, specific implementation conditions and materials in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art based on the embodiments of the present invention without inventive step, are within the scope of the present invention.
Example 1
Soaking the collected shrimp shells and crab shells in 5wt% sodium hydroxide solution for 18 hours, filtering to remove filtrate, and cleaning the shrimp shells and the crab shells with distilled water until the cleaning solution is neutral. Putting the cleaned shrimp shells and crab shells into a drying oven at 90 ℃ and drying; and crushing the dried shrimp shells and crab shells by using a crusher, and screening by using a 60-mesh sieve to obtain primarily refined chitin for later use.
Example 2
Adding 3g of TEMPO into 30g of distilled water, heating to 80 ℃, and continuously stirring until TEMPO is completely dissolved; adding 100g of chitin prepared in example 1 into 500mL of distilled water, stirring at a stirring speed of 300r/min, then sequentially adding a prepared TEMPO solution, 30g of sodium bromide and 1500mL of a 12wt% sodium hypochlorite solution, adjusting the pH value of the mixed solution to be 10-10.5 by using a 5wt% sodium hydroxide solution, reacting at room temperature until the pH value of the mixed solution is not changed within 3 minutes, and adding 20mL of alcohol to stop the reaction; and filtering the mixed solution, washing the mixed solution by using distilled water until the filtrate is neutral, and removing the filtrate to obtain the oxidized nano chitin. Soaking the prepared nano chitin in 1000mL of 2M hydrochloric acid solution, reacting for 16 hours at room temperature, and centrifuging to remove filtrate to obtain the carboxylated nano chitin. The carboxyl content of the carboxylated nano chitin is 1.51mmol/g by a potentiometric titration method. The prepared carboxylated chitin has an average diameter of about 20nm and an average length of about 500nm, as shown in FIG. 1.
Example 3
Adding 4g TEMPO into 30g distilled water, heating to 90 ℃, and continuously stirring until TEMPO is completely dissolved; adding 100g of chitin prepared in example 1 into 500mL of distilled water, stirring at a stirring speed of 300r/min, then sequentially adding a prepared TEMPO solution, 40g of sodium bromide and 1800mL of a 12wt% sodium hypochlorite solution, adjusting the pH value of the mixed solution to be 10-10.5 by using a 5wt% sodium hydroxide solution, reacting at room temperature until the pH value of the mixed solution does not change within 3 minutes, and adding 40mL of alcohol to stop the reaction; and filtering the mixed solution, washing the mixed solution by using distilled water until the filtrate is neutral, and removing the filtrate to obtain the oxidized nano chitin. Soaking the prepared nano chitin in 1000mL of 2M hydrochloric acid solution, reacting for 16 hours at room temperature, and centrifuging to remove filtrate to obtain the carboxylated nano chitin. The carboxyl content of the carboxylated nano chitin is 1.85mmol/g by a potentiometric titration method. The prepared carboxylated nano chitin is soaked in the solution and is characterized by a scanning electron microscope, the average diameter of the prepared chitin is about 20nm, and the average length of the prepared chitin is about 300nm, as shown in figure 2.
Example 4
Adding 5g TEMPO into 50g distilled water, heating to 90 ℃, and continuously stirring until TEMPO is completely dissolved; adding 120g of chitin prepared in example 1 into 500mL of distilled water, stirring at a stirring speed of 300r/min, then sequentially adding a prepared TEMPO solution, 50g of sodium bromide and 1500mL of a 12wt% sodium hypochlorite solution, adjusting the pH value of the mixed solution to be 10-10.5 by using a 5wt% sodium hydroxide solution, reacting at room temperature until the pH value of the mixed solution does not change within 3 minutes, and adding 40mL of alcohol to stop the reaction; and filtering the mixed solution, washing the mixed solution by using distilled water until the filtrate is neutral, and removing the filtrate to obtain the oxidized nano chitin. The carboxyl content of the carboxylated nano chitin is 1.71mmol/g by a potentiometric titration method. The prepared chitin has an average diameter of about 20nm and an average length of about 400nm, as shown in FIG. 3, by characterization of a scanning electron microscope.
Example 5
The present embodiment provides a carboxylated nano chitin based alkyd resin, which has the following raw material composition as shown in table 1:
TABLE 1 EXAMPLE 5 compounding ratio of raw materials for alkyd resin synthesis
Carboxylated nano chitin 40 portions of
Trimethylolpropane 10 portions of
Terephthalic acid (TPA) 10 portions of
Glycerol 20 portions of
Soybean oil acid 15 portions of
Triethylamine 6 portions of
Indium trichloride 2 portions of
Deionized water 50 portions of
The carboxylated nano chitin in table 1 is the carboxylated nano chitin prepared by the method of example 2.
The preparation method of the carboxylated nano chitin-based alkyd resin comprises the following steps: sequentially adding trimethylolpropane, soybean oleic acid, carboxylated nano chitin and catalytic indium trichloride into a multifunctional reaction kettle according to the weight of a formula, stirring for 30 minutes at the rotating speed of 300r/min while introducing nitrogen, and then continuously introducing nitrogen for 5 minutes; stopping introducing nitrogen, heating to 110 ℃, keeping the temperature for 1 hour, continuously introducing nitrogen, taking out water vapor, removing free water, continuously heating to 210 ℃, keeping the temperature for 1 hour, then quickly heating to 260-270 ℃, starting an esterification reaction, carrying out a reflux reaction, and separating water generated by the reaction by using a water separator; after the reaction is carried out for 1 hour, taking a sample every 30 minutes for acid value testing, and when the acid value is 5-10, sequentially adding terephthalic acid and glycerol according to the formula amount, keeping the temperature of the reaction kettle at 260-270 ℃, and preserving the temperature for 2-3 hours; after the reaction is carried out for 2 hours, taking a sample every 30 minutes for acid value testing, and stopping the reaction when the acid value is 30-40; cooling to 50 ℃ and preserving heat, adding triethylamine according to the weight part of the formula, stirring at a high speed for dispersing for 30 minutes, adding deionized water according to the formula amount, continuing stirring at a high speed for 30 minutes, then stirring at a low speed for 30 minutes, and filtering to obtain the carboxylated nano chitin-based alkyd resin.
According to GB/T6739-1996 pencil test method for film hardness, the strength of the prepared alkyd resin after film formation is tested by a manual method, and the test result shows that the film strength is greater than B.
The VOC of the prepared alkyd resin is tested according to GB/T23985-2009 determination difference method of Volatile Organic Compound (VOC) content of colored paint and varnish, and the result is that the VOC is less than or equal to 280.
The water resistance of the prepared alkyd resin is tested according to GB/T1727-1992, and after the alkyd resin is soaked for 48 hours, the water absorption is 8.2%.
Example 6
The present embodiment provides a carboxylated nano chitin based alkyd resin, which has the following raw material composition as shown in table 2:
TABLE 2 EXAMPLE 6 compounding ratio of raw materials for alkyd resin synthesis
Carboxylated nano chitin 60 portions of
Trimethylolpropane 20 portions of
Terephthalic acid (TPA) 10 portions of
Pentaerythritol 20 portions of
Tall oil acid 20 portions of
Dimethylethanolamine 8 portions of
Rhodium trichloride 2 portions of
Deionized water 80 portions
The carboxylated nano chitin in table 2 is the carboxylated nano chitin prepared by the method of example 3.
The preparation method of the carboxylated nano chitin-based alkyd resin comprises the following steps: sequentially adding trimethylolpropane, tall oil acid, carboxylated nano chitin and rhodium trichloride into a multifunctional reaction kettle according to the weight of the formula, stirring for 30 minutes at the rotating speed of 200r/min while introducing nitrogen, and then continuously introducing nitrogen for 5 minutes; stopping introducing nitrogen, heating to 110 ℃, keeping the temperature for 1 hour, continuously introducing nitrogen, taking out water vapor, removing free water, continuously heating to 215 ℃, keeping the temperature for 1 hour, then quickly heating to 260-270 ℃, starting an esterification reaction, carrying out a reflux reaction, and separating water generated by the reaction by using a water separator; after the reaction is carried out for 1 hour, taking a sample every 30 minutes for acid value testing, and when the acid value is 5-10, sequentially adding terephthalic acid and pentaerythritol according to the formula amount, keeping the temperature of the reaction kettle at 260-270 ℃, and preserving the temperature for 2-3 hours; after the reaction is carried out for 2 hours, taking a sample every 30 minutes for acid value testing, and stopping the reaction when the acid value is 30-40; cooling to 50 ℃ and preserving heat, adding dimethylethanolamine according to the weight part of the formula, stirring at a high speed for dispersing for 60 minutes, adding deionized water according to the formula amount, continuing stirring at a high speed for 30 minutes, then stirring at a low speed for 30 minutes, and filtering to obtain the carboxylated nano chitin-based alkyd resin.
According to GB/T6739-1996 pencil test method for film hardness, the strength of the prepared alkyd resin after film formation is tested by a manual method, and the test result shows that the film strength is more than B.
The VOC of the prepared alkyd resin is tested according to GB/T23985-2009 determination difference method of content of Volatile Organic Compounds (VOC) of colored paint and varnish, and the result is that the VOC is less than or equal to 252.
The water resistance of the prepared alkyd resin was tested according to GB/T1727-1992, and the water absorption was 8.2% after soaking for 48 hours.
Example 7
The present embodiment provides a carboxylated nano chitin based alkyd resin, which has the following raw material composition as shown in table 3:
TABLE 3 example 7 raw material ratio for alkyd resin synthesis
Carboxylated nano chitin 70 portions of
Trimethylolpropane ester 25 portions of
Acetic anhydride 10 portions of
1,2, 5-pentanetriol 10 portions of
Tall oil acid 20 portions of
Dimethylethanolamine 8 portions of
Indium trichloride 5 portions of
Deionized water 80 portions of
The carboxylated nano chitin in table 3 is the carboxylated nano chitin prepared by the method of example 3.
The preparation method of the carboxylated nano chitin-based alkyd resin comprises the following steps: sequentially adding trimethylolpropane, tall oil acid, carboxylated nano chitin and indium trichloride into a multifunctional reaction kettle according to the weight of the formula, stirring for 30 minutes at the rotating speed of 500r/min while introducing nitrogen, and then continuously introducing nitrogen for 5 minutes; stopping introducing nitrogen, heating to 110 ℃, keeping the temperature for 1 hour, continuously introducing nitrogen, taking out water vapor, removing free water, continuously heating to 215 ℃, keeping the temperature for 1 hour, then quickly heating to 260-270 ℃, starting an esterification reaction, carrying out a reflux reaction, and separating water generated by the reaction by using a water separator; after the reaction is carried out for 1 hour, taking a sample every 30 minutes for acid value testing, when the acid value is 5-10, sequentially adding the polybasic acid and the polyalcohol according to the formula amount, keeping the temperature of the reaction kettle at 260-270 ℃, and preserving the temperature for 2-3 hours; after the reaction is carried out for 2 hours, taking a sample every 30 minutes for acid value testing, and stopping the reaction when the acid value is 30-40; cooling to 50 ℃ and preserving heat, adding dimethylethanolamine according to the weight part of the formula, stirring at a high speed for dispersing for 60 minutes, adding deionized water according to the formula amount, continuing stirring at a high speed for 30 minutes, then stirring at a low speed for 30 minutes, and filtering to obtain the carboxylated nano chitin-based alkyd resin.
According to GB/T6739-1996 pencil test method for film hardness, the strength of the prepared alkyd resin after film formation is tested by a manual method, and the test result shows that the film strength is greater than B.
The VOC of the prepared alkyd resin is tested according to GB/T23985-2009 determination difference method of content of Volatile Organic Compounds (VOC) of colored paint and varnish, and the result is that the VOC is less than or equal to 289.
The water resistance of the prepared alkyd resin was tested according to GB/T1727-1992, and the water absorption was 8.9% after soaking for 48 hours.
Example 8
The present embodiment provides a carboxylated nano chitin based alkyd resin, which has the following raw material composition as shown in table 4:
TABLE 4 EXAMPLE 8 compounding ratio of raw materials for alkyd resin synthesis
Carboxylated nano chitin 70 portions of
Trimethylolpropane ester 20 portions of
Maleic anhydride 12 portions of
Pentaerythritol 10 portions of
Palmitic acid 20 portions of
Triethylamine 8 portions of
Indium trichloride 5 portions of
Deionized water 80 portions
The carboxylated nano chitin in table 4 is the carboxylated nano chitin prepared by the method of example 3.
The preparation method of the carboxylated nano chitin-based alkyd resin comprises the following steps: sequentially adding trimethylolpropane, palmitic acid, carboxylated nano chitin and indium trichloride into a multifunctional reaction kettle according to the weight of a formula, stirring for 30 minutes at the rotating speed of 300r/min while introducing nitrogen, and then continuously introducing nitrogen for 5 minutes; stopping introducing nitrogen, heating to 110 ℃, keeping the temperature for 1 hour, continuously introducing nitrogen, taking out water vapor, removing free water, continuously heating to 210 ℃, keeping the temperature for 1 hour, then quickly heating to 260-270 ℃, starting an esterification reaction, carrying out a reflux reaction, and separating water generated by the reaction by using a water separator; after the reaction is carried out for 1 hour, taking a sample every 30 minutes for acid value testing, when the acid value is 5-10, sequentially adding maleic anhydride and pentaerythritol in a formula amount, keeping the temperature of the reaction kettle at 260-270 ℃, and preserving the temperature for 2-3 hours; after the reaction is carried out for 2 hours, taking a sample every 30 minutes for acid value testing, and stopping the reaction when the acid value is 30-40; cooling to 50 ℃ and preserving heat, adding triethylamine according to the weight part of the formula, stirring at a high speed for dispersing for 45 minutes, adding deionized water according to the formula amount, continuing stirring at a high speed for 30 minutes, then stirring at a low speed for 30 minutes, and filtering to obtain the carboxylated nano chitin-based alkyd resin.
According to GB/T6739-1996 pencil test method for film hardness, the strength of the prepared alkyd resin after film formation is tested by a manual method, and the test result shows that the film strength is greater than B.
The VOC of the prepared alkyd resin is tested according to GB/T23985-2009 determination difference method of content of Volatile Organic Compounds (VOC) of colored paint and varnish, and the result is that the VOC is less than or equal to 259.
The water resistance of the prepared alkyd resin is tested according to GB/T1727-1992, and the water absorption is 10.9% after soaking for 48 hours.
Example 9
The present embodiment provides a carboxylated nano chitin based alkyd resin, which has the following raw material composition as shown in table 5:
TABLE 5 EXAMPLE 9 compounding of raw materials for alkyd resin synthesis
Carboxylated nano chitin 50 portions of
Trimethylolpropane 15 portions of
Maleic anhydride 12 portions of
1,2, 5-pentanetriol 15 portions of
Myristic acid 30 portions of
Triethylamine 8 portions of
Indium trichloride 5 portions of
Deionized water 60 portions of
The carboxylated nano chitin in table 5 is the carboxylated nano chitin prepared by the method of example 4.
The preparation method of the carboxylated nano chitin-based alkyd resin comprises the following steps: sequentially adding trimethylolpropane, myristic acid, carboxylated nano chitin and indium trichloride into a multifunctional reaction kettle according to the weight of the formula, stirring for 30 minutes at the rotating speed of 400r/min while introducing nitrogen, and then continuously introducing nitrogen for 5 minutes; stopping introducing nitrogen, heating to 110 ℃, keeping the temperature for 1 hour, continuously introducing nitrogen, taking out water vapor, removing free water, continuously heating to 220 ℃, keeping the temperature for 1 hour, then quickly heating to 260-270 ℃, starting an esterification reaction, performing a reflux reaction, and separating water generated by the reaction by using a water separator; after the reaction is carried out for 1 hour, taking a sample every 30 minutes for acid value testing, and when the acid value is 5-10, sequentially adding maleic anhydride and 1,2, 5-pentanetriol according to the formula amount, keeping the temperature of the reaction kettle at 260-270 ℃, and preserving the temperature for 2-3 hours; after the reaction is carried out for 2 hours, taking a sample every 30 minutes for acid value testing, and stopping the reaction when the acid value is 30-40; cooling to 50 ℃ and preserving heat, adding triethylamine according to the weight part of the formula, stirring at a high speed for dispersing for 45 minutes, adding deionized water according to the formula amount, continuing stirring at a high speed for 30 minutes, then stirring at a low speed for 30 minutes, and filtering to obtain the carboxylated nano chitin-based alkyd resin.
According to GB/T6739-1996 pencil test method for film hardness, the strength of the prepared alkyd resin after film formation is tested by a manual method, and the test result shows that the film strength is greater than B.
The VOC of the prepared alkyd resin is tested according to GB/T23985-2009 determination difference method of Volatile Organic Compound (VOC) content of colored paint and varnish, and the result is that the VOC is less than or equal to 265.
The water resistance of the prepared alkyd resin was tested according to GB/T1727-1992, and the water absorption was 9.6% after soaking for 48 hours.
The skilled person should understand that: although the invention has been described in terms of the above specific embodiments, the inventive concept is not limited thereto and any modification applying the inventive concept is intended to be included within the scope of the patent claims.

Claims (6)

1. The carboxylated nano chitin based alkyd resin is characterized by comprising the following raw materials in parts by weight: 30 to 80 parts of carboxylated nano chitin, 10 to 25 parts of trimethylolpropane, 8 to 20 parts of polybasic acid, 10 to 30 parts of monobasic acid, 8 to 32 parts of polyalcohol, 4 to 8 parts of neutralizing agent, 50 to 80 parts of deionized water and 2 to 8 parts of catalyst;
the polyalcohol is at least one of glycerol, pentaerythritol, trimethylolethane and 1,2, 5-pentanetriol;
the preparation of the carboxylated nano chitin comprises the following steps: (1) impurity removal: soaking shrimp shells or crab shells in seafood market in 5wt% sodium hydroxide solution for 12-24 hours, then washing the shrimp shells or the crab shells with water, and drying at 80-100 ℃ to obtain chitin; (2) crushing: crushing chitin by using a crusher, and screening by using a 60-mesh sieve; (3) oxidizing: oxidizing the crushed chitin by using a TEMPO oxidation method to obtain sodium carboxylate nano chitin; (4) proton exchange: soaking sodium carboxylate nano chitin in a hydrochloric acid solution of 3-5M for 12-24 hours, centrifuging, and washing with distilled water until the filtrate is neutral to obtain carboxylated nano chitin;
the TEMPO oxidation method in the step (3) comprises the following specific steps:
a. adding 3-5 g of TEMPO into 20-50 g of distilled water, heating to 80-100 ℃, and continuously stirring until the TEMPO is completely dissolved;
b. adding 100g of chitin into 500mL of distilled water, stirring at a stirring speed of 200-500 r/min, then sequentially adding a prepared TEMPO solution, 20-40 g of sodium bromide and 1000-2000 mL of a 12wt% sodium hypochlorite solution, adjusting the pH value of the mixed solution to be kept between 10 and 10.5 by using a 5wt% sodium hydroxide solution, reacting at room temperature until the pH value of the mixed solution does not change within 3 minutes, and adding 20-50 mL of alcohol to terminate the reaction;
c. and c, filtering the mixed solution in the step b, washing the mixed solution with distilled water until the filtrate is neutral, and removing the filtrate to obtain the oxidized nano chitin.
2. The carboxylated nano chitin based alkyd resin of claim 1, wherein said polybasic acid is at least one of phthalic anhydride, terephthalic acid, acetic anhydride, maleic anhydride.
3. The carboxylated nano chitin based alkyd resin of claim 1, wherein said monoacid is at least one of soy oleic acid, tall oil acid, lauric acid, myristic acid, palmitic acid.
4. The carboxylated nano chitin based alkyd resin of claim 1, wherein said neutralizing agent is at least one of triethylamine and dimethylethanolamine.
5. The carboxylated nanocalcium alkyd resin of claim 1, wherein the catalyst is at least one of indium trichloride and rhodium trichloride.
6. The method for preparing carboxylated nano chitin-based alkyd resin according to any of claims 1 to 5, wherein the method comprises the following steps:
a. sequentially adding trimethylolpropane, monoacid, carboxylated nano chitin and a catalyst into a multifunctional reaction kettle according to the weight of a formula, introducing nitrogen, stirring at a rotating speed of 200-500 r/min for 10-60 minutes, and then continuously introducing nitrogen for 5 minutes;
b. stopping introducing nitrogen, heating to 110-120 ℃, keeping the temperature for 1 hour, continuously introducing nitrogen, taking out water vapor, removing free water, continuously heating to 205-220 ℃, keeping the temperature for 1-2 hours, then quickly heating to 260-270 ℃, starting an esterification reaction, carrying out a reflux reaction, and separating water generated by the reaction by using a water separator;
c. after the reaction is carried out for 1 hour, taking a sample every 30 minutes for acid value testing, and when the acid value is 5 to 10, sequentially adding polybasic acid and polyhydric alcohol according to the formula amount, keeping the temperature of the reaction kettle at 260 to 270 ℃, and keeping the temperature for 2 to 3 hours;
d. after the reaction is carried out for 2 hours, taking a sample every 30 minutes for acid value testing, and stopping the reaction when the acid value is 30 to 40; cooling to 50 ℃ and preserving heat, adding a neutralizer in the formula weight part, stirring at a high speed for dispersion for 30 to 60 minutes, adding deionized water in the formula amount, continuing stirring at a high speed for 30 minutes, then stirring at a low speed for 30 minutes, and filtering to obtain the carboxylated nano chitin-based alkyd resin.
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