CN100427526C - A kind of aqueous nanocomposite polyester resin, its preparation method and application - Google Patents

Abstract

The invention relates to the field of chemical industry, and relates to a high-hardness water-based nano-composite polyester resin, a preparation method and application thereof. The present invention adopts sonochemical synthesis method, reacts nanoparticles with hydroxyl or alkoxy groups on the surface with polyols, grafts polyols on the surface of nanoparticles, reacts with polyols, dihydroxy carboxylic acids, carboxylic acids, and synthesizes in situ Nano-composite polyester resin, and then use alkali to neutralize the hydrophilic carboxylic acid group in the polyester resin, add water to prepare high-hardness water-based nano-composite polyester resin with stable performance. By adopting the preparation method provided by the invention, the polyester chain segments are easily grafted on the nanoparticles, and the nanoparticles are uniformly distributed in the polyester resin. The water-based nanocomposite polyester resin prepared by the invention has good storage stability, high hardness and good transparency, and can be used to prepare coating materials with excellent properties.

Description

A kind of aqueous nanocomposite polyester resin, its preparation method and application

technical field

The invention relates to the field of chemical industry, and relates to a high-hardness water-based nano-composite polyester resin, a preparation method and application thereof.

Background technique

With the improvement of people's living standards, the requirements for coatings and resins should not only have protective effects and high decorative properties, but also have environmentally friendly functions. Water-based resins and water-based coatings have many distinctive features and advantages. They do not contain or only contain A small amount of solvent, non-toxic and safe. Patent CN1357582 such as Xia Fanwu etc. has introduced the preparation method of a kind of water-dispersible resin and coating thereof that coating is used in automobile; The patent CN1497032 of Gas Products Polymer Company has introduced a kind of water-based adhesive combination that uses water-based polyester The preparation method of the compound; US20040249077 has introduced a kind of preparation method of the aqueous film-forming composition containing the alternating copolymer of isobutylene monomer. However, compared with solvent-based resins and coatings, due to the different film-forming mechanisms, the coating films formed by water-based resins and water-based coatings are not as dense as solvent-based resins and coatings, resulting in defects in the coating film. In addition, the volatilization of water and the balance in the atmosphere are also It affects the performance of the coating film. Compared with solvent resins and coatings with the same or similar molecular structure, it is difficult to achieve the performance of solvent-based resins and coatings.

Existing studies have shown that nano-polymer composite coatings are of positive significance in improving the traditional properties of coatings (such as aging resistance, scratch resistance, abrasion resistance, and UV resistance), but the direct co-production of nanoparticles Mixing or in-situ polymerization added to the resin, the nanoparticles are prone to agglomeration and precipitation, the viscosity of the resin increases, and it is impossible to prepare a stable nanoparticle-modified resin, let alone a water-based nanoparticle-modified resin. If surface-modified nanoparticles are added to the resin, the performance of the resin will be reduced due to the presence of external additives. The preparation of water-based nanocomposite polyester resins by in-situ polymerization of nanoparticles has not been reported yet.

Contents of the invention

The purpose of the present invention is to provide a water-based nanocomposite polyester resin with high hardness, low VOC, high performance, environmental protection and safety.

Composite polyester resin.

Another object of the present invention is to provide a preparation method of the above-mentioned water-based nanocomposite polyester resin.

Another object of the present invention is to provide the application of the above-mentioned water-based nanocomposite polyester resin.

The invention provides a water-based nano composite polyester resin. The resin is a water-based nano-composite polyester resin. The nano-composite polyester resin is formed by grafting polyols on the surface of nanoparticles with hydroxyl or alkoxy groups on the surface and then melting and polymerizing with carboxylic acid. The molecular weight is 1000-50000. The value is 20-70mgKOH/g, the hydroxyl value is 60-250mgKOH/g, the nano particle content accounts for 1-15wt% of the total weight of the nanocomposite polyester resin, and the solid content of the water-based nanocomposite polyester resin is 20-55wt%.

Specifically, the water-based nanocomposite polyester resin of the present invention is composed of nanocomposite polyester resin, alkali and water, and meets two conditions: it contains a nanocomposite polyester resin; it contains a kind of alkali.

The nanocomposite polyester resin is composed of nanoparticles, polyols, dihydroxy carboxylic acids, and carboxylic acids, and meets the following conditions, A. Contains at least one nanoparticle with a nanometer size; B. Contains at least one nanoparticle with a molecular weight of 60-1000 Dihydric alcohols and trihydric alcohols are used as polyol components, C. contain a dihydroxy carboxylic acid; D. contain at least one carboxylic acid.

The present invention also provides the preparation method of the above-mentioned water-based nanocomposite polyester resin, which is to graft polyol on the surface of nanoparticles, and then blend with polyol and carboxylic acid to synthesize nanocomposite polyester resin by melting and in-situ polymerization, which is characterized in that The method includes the following steps:

(1) Blend nanoparticles with hydroxyl or alkoxy groups on the surface with polyols, and graft polyols on the surface of nanoparticles by sonochemical synthesis; control the ultrasonic frequency at 100-2000kHz, the reaction temperature at 0-100°C, and the ultrasonic time 10-60 minutes; the amount of polyol used is 20-100% of the total molar amount of polyol; the amount of nanoparticles used is 2-60wt% of the total amount of polyol;

(2) Blending and melt-polymerizing the product obtained in (1) with the remaining polyol, dihydroxy carboxylic acid, and carboxylic acid to synthesize a nanocomposite polyester resin; the reaction conditions for melt polymerization are 100-240° C., 2-12 hours; The amount of substance of hydroxycarboxylic acid is 1-40% of the sum of the amount of polyol molar total amount and dihydroxycarboxylic acid substance; the molar ratio of the sum of the amount of acid and alcohol and dihydroxycarboxylic acid substance is 1: 2～1 : 1.1;

(3) the nanocomposite polyester resin containing carboxyl is neutralized with alkali, and the consumption of alkali is to make the degree of neutralization (the degree of neutralization is the percentage of the amount of acid in the alkali and resin) of the acid in the nanocomposite polyester resin reach 70 -120%. , and add water to obtain a water-based nanocomposite polyester resin with a solid content of 2055 wt%.

Specifically, the nanocomposite polyester resin is composed of nanoparticles, polyols, dihydroxycarboxylic acids, and carboxylic acids other than the dihydroxycarboxylic acids, and meets the following conditions at the same time, A. Containing at least one nanometer particle size Particles; B. contain at least one diol and triol with a molecular weight of 60-1000 as a polyol component, C. contain a dihydroxy carboxylic acid; D. contain at least one carboxylic acid.

In the above preparation method, 1-3 kinds of inorganic nano-oxides with a particle size of 10-200 nm, hydroxyl groups or/and alkoxy groups on the surface, and a particle size of 10-200 nm are used. Such as nano-silica, nano-titanium oxide, nano-alumina, nano-iron oxide, nano-zirconia, nano-zinc oxide. The content of the nanoparticles accounts for 1-15 wt% of the total weight of the nanocomposite polyester resin.

In the above preparation method, the molar ratio of acid to alcohol (including dihydroxy carboxylic acid) is COOH:OH=1:2˜1:1.1.

In the above preparation method, the polyol is a diol or a triol with a molecular weight of 60-1000, and 1-5 of them are used. Diols used such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 2,2-diol Methyl-1,3-propanediol, diethylene glycol, 2-ethyl-2-propyl-1,3-propanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, polyethylene glycol Alcohols, polyether diols, and trihydric alcohols such as glycerin, trimethylolpropane, polyether triols, etc.

In the above preparation method, the dihydroxy carboxylic acid is one of dihydroxy alkanoic acid and dihydroxy aromatic acid, and the dosage is 1-40% of the total molar amount of the mixture of polyhydric alcohol and dihydroxy carboxylic acid. Dihydroxycarboxylic acids used include dimethylolpropionic acid, dimethylolbutyric acid, 9,10-dihydroxyoctadecanoic acid, 2,4-dihydroxybenzoic acid and the like.

In the above-mentioned preparation method, (1) the polyhydric alcohol that adopts is the dibasic alcohol or/and the tribasic alcohol of molecular weight 60-1000, and consumption is 20-100% of polyol total molar amount; 2-60wt%.

In the above preparation method, the carboxylic acid is 1-5 kinds of aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, aromatic dicarboxylic acid, acid anhydride and caprolactone. Such as succinic acid, adipic acid, azelaic acid, pimelic acid, suberic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, Five carbon dibasic acid, sixteen carbon dibasic acid, octadecane dibasic acid, isophthalic acid, terephthalic acid, phthalic acid, isophthalic anhydride, terephthalic anhydride, phthalic anhydride Formic anhydride, hexahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid, ε-caprolactone, etc.

In the above-mentioned preparation method, the catalyst is preferably used in the melt polymerization reaction, and the catalyst is any one of antimony series, germanium series, titanium series and tin series, such as antimony acetate, antimony ethylene glycol, germanium acetate, stannous octoate, dilauric acid Dibutyltin dibutyltin, tetraisopropyl titanate, titanium glycolate, etc., used in an amount of 0.01%-0.5wt% of the total amount of alcohol and acid.

In the above preparation method, the melt polymerization reaction temperature is 100-240° C., and the reaction time is 2-12 hours.

In the above preparation method, the base is one of metal hydroxide, ammonia, primary amine, secondary amine, and tertiary amine. Such as sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, primary amines such as isopropylamine, butylamine, ethanolamine, 3-amino-1-propanol, secondary amines such as morpholine, diethylamine, N-methylamine Ethanolamine, diethanolamine, tertiary amines such as trimethylamine, N,N-dimethylethanolamine, triethylamine, triethylpropylamine, N,N-diethylethanolamine, N-ethylmorpholine.

In the above preparation method, the amount of the alkali is such that the neutralization degree of the acid in the nanocomposite polyester resin reaches 70-120%.

The present invention also provides the application of the above water-based nanocomposite polyester resin.

The water-based nano-composite polyester resin and the water-based blocked polyisocyanate crosslinking reaction of the present invention can obtain the water-based nano-composite polyester resin coating material with excellent performance.

The water-based nano-composite polyester resin and the water-based amino resin can be cross-linked to obtain a water-based nano-composite polyester resin coating material with excellent performance.

A kind of high-hardness water-based nano-composite polyester resin and its preparation method proposed by the present invention have the following advantages: the present invention adopts inorganic nano-oxide particles with a particle diameter of 10-200nm and a hydroxyl group or/and alkoxy group on the surface, and uses acoustic The chemical synthesis method grafts polyols on its surface to prepare a clear and transparent nanoparticle alcohol solution. Without any additional reagents, the nanoparticles can be evenly dispersed in the resin system during the melt polymerization process, and polyester molecules can be directly formed on the surface. The coating layer avoids the agglomeration of nanoparticles in the resin, and at the same time greatly reduces the hydrogen bond between the hydroxyl groups on the surface of the nanoparticles and the resin molecules, which will not increase the viscosity of the resin and ensure that the nanocomposite polyester resin is water-based without appearing Sedimentation of nanoparticles. The prepared water-based nano-composite polyester resin has a concentration of more than 50%, good storage stability, no subsidence for one year at normal temperature, high coating hardness, good wear resistance, and excellent construction performance. By adopting the preparation method provided by the invention, the water-based nano-composite polyester resin with stability, good transparency and high hardness can be obtained.

Description of drawings

Figure 1 is a transmission electron microscope (TEM) image of sonochemically synthesized nano-silica alcohol solution.

Figure 2 is a schematic diagram of the preparation of nanocomposite polyester resin.

Detailed ways

Example 1:

In a four-necked flask equipped with a thermometer, a condenser, and a stirrer, add 30 grams of nano-silica, 1.0 mol 1,4-butanediol (90 grams), stir and mix at 1000 rpm for 10 minutes, and use sonochemical Synthesize for 40 minutes, during the reaction, control ultrasonic frequency 1200kHz, reaction temperature 50 ℃, add 1.0mol adipic acid (114 grams), 0.8mol cyclohexanedimethanol (115.2 grams), 0.2mol dimethylolpropionic acid (20.4 g), add 0.15 grams of dibutyltin dilaurate, heat up to 110-120°C for 2 hours, continue to heat up to 160-180°C, react for 4 hours, then heat up to 200-220°C, react for 2 hours to obtain a nanocomposite polyester resin.

Slowly cool the nanocomposite polyester resin to 80°C, pour it into a dispersion tank, add N,N-dimethylethanolamine to neutralize the acid in the resin, and make the neutralization degree 85%, add measured deionized water, The solid content of the resin is 50 wt%, and the high-hardness water-based nano-composite polyester resin can be prepared by stirring at a high speed of 2500 rpm for 30 minutes.

Example 2:

In a four-necked flask equipped with a thermometer, a condenser, and a stirrer, add 100 grams of nano-alumina and 0.5 mol of polyethylene glycol (200 grams) with an average molecular weight of 400, and stir and mix for 20 minutes at a speed of 1000 rpm. Synthesize for 60 minutes, during the reaction, control the ultrasonic frequency to 500kHz, and the reaction temperature to 80°C, add 0.6mol undecanedibasic acid (112.8 grams), 0.4mol 1,4-cyclohexanedicarboxylic acid (68.8 grams), 0.5mol a Diethylene glycol acetal (53 grams), 0.2mol 2-ethyl-2-propyl-1,3-propanediol (29.2 grams), 0.1mol trimethylolpropane (13.4 grams), 0.3mol dimethylol Butyric acid (44.4 g), add 0.10 g of titanium glycolate, heat up to 110-120 ° C for 3 hours, heat up to 130-150 ° C for 3 hours, continue to heat up to 170-190 ° C for 3 hours, to obtain a nanocomposite polyester resin.

Slowly cool the nanocomposite polyester resin to 80°C, pour it into a dispersion kettle, add 3-amino-1-propanol to neutralize the acid in the resin, and make the neutralization degree 100%, add measured deionized water, The solid content of the resin is 38 wt%, and the high-hardness water-based nano-composite polyester resin can be prepared by stirring at a high speed of 3500 rpm for 50 minutes.

Example 3:

In a four-necked flask equipped with a thermometer, a condenser, and a stirrer, add 60 grams of nano-titanium oxide, 1.0 mol of propylene glycol (76 grams), 0.2 mol of 1,6-hexanediol (23 grams), and 0.1 mol of an average molecular weight of 500 The polyether trihydric alcohol (50 grams) is stirred and mixed at 1000 rpm for 10 minutes, and is synthesized by sonochemistry for 30 minutes. During the reaction, the ultrasonic frequency is controlled at 1000 kHz, the reaction temperature is 120 ° C, and 0.5 mol of adipic acid (57.0 grams) is added. , 0.3mol terephthalic acid (37.8 grams), 0.2mol isophthalic anhydride (29.6 grams), 0.1mol2,4-dihydroxybenzoic acid (13.8 grams), add 3 grams of germanium acetate, and heat up to 110-120 ℃ for 1 hour, the temperature is raised to 130-150 ℃ for 3 hours, the temperature is further raised to 160-180 ℃ for 3 hours, and the temperature is raised to 220-240 ℃ for 2 hours to obtain a nanocomposite polyester resin.

Slowly cool the nanocomposite polyester resin to 90°C, pour it into a dispersing kettle, add isopropylamine to neutralize the acid in the resin to make the neutralization degree 75%, add measured deionized water to make the resin solid content The high-hardness water-based nano-composite polyester resin can be prepared by stirring at a high speed of 3000 rpm for 20 minutes.

Example 4:

In a four-necked flask equipped with a thermometer, a condenser, and a stirrer, add 10 grams of nano-zirconia, 0.2 mol of polyether triol (100 grams) with a molecular weight of 1000, and stir and mix at 1000 rpm for 20 minutes. Synthesize for 20 minutes, during the reaction, control the ultrasonic frequency at 1500kHz, and the reaction temperature at 80°C, add 0.3mol succinic acid (35.4 grams), 0.4mol hexahydrophthalic anhydride (67.2 grams), 0.3mol azelaic acid (56.4 grams ), 0.8mol cyclohexanedimethanol (115.2 grams), 0.4mol9,10-dihydroxy octadecanoic acid (29.2 grams), add 0.3 grams of dibutyltin dilaurate, heat up to 150-170 ° C for 6 hours, continue Raise the temperature to 190-210°C and react for 3 hours to obtain a nanocomposite polyester resin.

Slowly cool the nanocomposite polyester resin to 70°C, pour it into a dispersing kettle, add ammonia water to neutralize the acid in the resin to make the neutralization degree 120%, add measured deionized water to make the resin solid content 45wt% , high-speed stirring at 2500rpm for 30 minutes to prepare high-hardness water-based nanocomposite polyester resin.

Example 5:

In the four-necked flask that thermometer, condenser, stirrer are housed, add the polyether diol (40 gram) of 20 gram nano zinc oxides, 0.5mol ethylene glycol (31 gram), 0.2mol molecular weight 200, at 1500rpm Stir and mix at a rotating speed for 30 minutes, and use sonochemical synthesis for 50 minutes. During the reaction, control the ultrasonic frequency at 1000kHz, and the reaction temperature at 20°C. Add 1.0mol phthalic acid (150g), 0.5mol 2-ethyl-2-propyl -1,3-propanediol (73 grams), 0.3mol dimethylol propionic acid (30.6 grams), add 0.2 grams of stannous octoate, heat up to 100-120 ° C for 3 hours, heat up to 140-160 ° C for reaction 3 After 1 hour, continue to raise the temperature to 180-200° C. for 2 hours, then raise the temperature to 220-240° C. for 1 hour to obtain a nanocomposite polyester resin.

Slowly cool the nanocomposite polyester resin to 90°C, pour it into a dispersion kettle, add N-methylethanolamine to neutralize the acid in the resin, and make the neutralization degree 90%, add measured deionized water, and make the resin solidify The content is 45wt%, and the high-hardness water-based nano-composite polyester resin can be prepared by stirring at a high speed of 3000rpm for 40 minutes.

Embodiment 6:

In a four-necked flask equipped with a thermometer, a condenser, and a stirrer, add 75 grams of nano-silica, 0.2 mol of polyethylene glycol (160 grams) with a molecular weight of 800, and stir and mix at 1000 rpm for 20 minutes. Synthesize for 40 minutes, during the reaction, control the ultrasonic frequency to 2000kHz, and the reaction temperature to 100°C, add 0.8mol of isophthalic anhydride (118.4 grams), 0.2mol of pentadecanedioic acid (48 grams), 0.8mol of 1,5-hexanedicarboxylic acid Alcohol (94.4 grams), 0.4mol dimethylol butyric acid (59.2 grams), add 0.4 grams of dibutyltin dilaurate, heat up to 140-160 ° C for 5 hours, continue to heat up to 190-210 ° C for 4 hours, A nanocomposite polyester resin is obtained.

Slowly cool the nanocomposite polyester resin to 80°C, pour it into a dispersion kettle, add N-ethylmorpholine to neutralize the acid in the resin, and make the neutralization degree 80%, add measured deionized water, and make the resin The solid content is 40wt%, and the high-hardness water-based nano-composite polyester resin can be prepared by stirring at a high speed of 3000 rpm for 30 minutes.

Claims (9)

1. A preparation method of water-based nanocomposite polyester resin, characterized in that the method is to graft polyhydric alcohol on the surface of nanoparticles, then blend with remaining polyhydric alcohol, dihydroxy carboxylic acid, carboxylic acid and synthesize in situ polymerization method Nano composite polyester resin; the method specifically includes the following steps: (1) Blend nanoparticles with hydroxyl or alkoxy groups on the surface with polyols, and graft polyols on the surface of nanoparticles by sonochemical synthesis; control the ultrasonic frequency at 100-2000kHz, the reaction temperature at 0-100°C, and the ultrasonic time 10-60 minutes; the amount of polyol used is 20-100% of the total molar amount of polyol; the amount of nanoparticles used is 2-60wt% of the total amount of polyol; (2) Blending and melt-polymerizing the product obtained in (1) with the remaining polyol, dihydroxy carboxylic acid, and carboxylic acid to synthesize a nanocomposite polyester resin; the reaction conditions for melt polymerization are 100-240° C., 2-12 hours; The molar weight of hydroxycarboxylic acid accounts for 1-40% of the sum of the molar weight of dihydroxy carboxylic acid and polyol; the ratio of the molar weight of acid to the sum of the molar weight of alcohol and dihydroxy carboxylic acid is 1: 1.1～2; (3) neutralizing the carboxyl-containing nanocomposite polyester resin with an alkali, the amount of the alkali is to make the neutralization degree of the acid in the nanocomposite polyester resin reach 70-120%, and add water to obtain the water-based nanocomposite polyester resin, The solid content is 20-55wt%. 2. The preparation method according to claim 1, characterized in that the nanoparticles used are 1-3 of the inorganic nano-oxides with hydroxyl or/and alkoxy groups on the surface and a particle size of 10-200 nm. 3. The preparation method according to claim 2, wherein the nanoparticles used are 1-3 of nano-silica, nano-titanium oxide, nano-alumina, nano-iron oxide, nano-zirconia, and nano-zinc oxide . 4. The preparation method according to claim 1, characterized in that the polyhydric alcohols used are 1-5 of dibasic alcohols and tribasic alcohols with a molecular weight of 60-1000. 5. The preparation method according to claim 1, characterized in that the dihydroxy carboxylic acid used is one of dihydroxy alkanoic acid and dihydroxy aromatic acid. 6. preparation method according to claim 1 is characterized in that carboxylic acid is 1-5 in aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, aromatic dicarboxylic acid, acid anhydride, caprolactone kind. 7. The preparation method according to claim 1, characterized in that a catalyst is used in the melt polymerization reaction, and the catalyst is one of antimony series, germanium series, titanium series and tin series catalysts, and the consumption is 0.01-0.5% of the total amount of alcohol and acid wt%. 8. The preparation method according to claim 1, characterized in that the alkali is one of metal hydroxides, ammonia, primary amines, secondary amines, and tertiary amines. 9. The application of the water-based nano-composite polyester resin obtained by the preparation method according to claim 1, characterized in that the resin forms a coating material with water-based blocked polyisocyanate or water-based amino resin.

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