CN108102546B - Rosin modified phenolic resin for high-grade vacuum paint spraying paint and preparation method thereof - Google Patents
Rosin modified phenolic resin for high-grade vacuum paint spraying paint and preparation method thereof Download PDFInfo
- Publication number
- CN108102546B CN108102546B CN201810009158.3A CN201810009158A CN108102546B CN 108102546 B CN108102546 B CN 108102546B CN 201810009158 A CN201810009158 A CN 201810009158A CN 108102546 B CN108102546 B CN 108102546B
- Authority
- CN
- China
- Prior art keywords
- rosin
- phenolic resin
- modified phenolic
- resin
- paint
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D193/00—Coating compositions based on natural resins; Coating compositions based on derivatives thereof
- C09D193/04—Rosin
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention belongs to the technical field of forest chemical manufacturing, and particularly relates to rosin modified phenolic resin for a high-grade vacuum spray paint and a preparation method thereof. The preparation method of the rosin modified phenolic resin for the high-grade vacuum paint spraying paint provided by the invention comprises the following steps: the method comprises the steps of firstly reacting p-tert-octylphenol and formaldehyde in different proportions under sodium hydroxide to prepare phenolic resins with different solubilities, esterifying rosin with pentaerythritol to obtain rosin resin, carrying out synthetic reaction on the phenolic resins and the rosin resin in different proportions, then adding an antioxidant and an anti-ultraviolet auxiliary agent, and refining to obtain the product. The method prepares the rosin modified phenolic resin for the high-grade vacuum spray paint by a numerical control method, the conditions are easy to control, the rosin modified phenolic resin with different softening points and different dissolvability can be produced, and the prepared rosin modified phenolic resin has excellent performance, high softening point, light color, small acid value, high viscosity, abnormally high dissolvability and molecular weight, and the product quality is easy to control.
Description
Technical Field
The invention belongs to the technical field of forest chemical manufacturing, and particularly relates to rosin modified phenolic resin for a high-grade vacuum spray paint and a preparation method thereof.
Background
With the continuous improvement of the living standard of people and the development of the automobile industry, the society has more and more demands on automobile paint spraying coatings. The paint has various types and different performances, and for the paint for spraying the automobile, the paint needs to have the characteristics of good fluidity and adhesion under the vacuum condition and quick drying, and the key points are the paint resins with high quality. The method has the advantages of developing the extensive industry of rosin, manufacturing the high-quality rosin modified phenolic resin, improving the quality of fine chemical products, reducing the dependence on petroleum resources, and having very important practical significance for the sustainable development of China and Guangdong province and the conversion to the low-carbon economic development mode.
The rosin modified phenolic resin is a high-grade paint component. The performance indexes of the resin include softening point, acid value, viscosity, solvent solubility, molecular weight and distribution, and the solubility is one of the most important performance indexes. The solubility of the resin determines the intermiscibility of the resin, the action of the resin is different in the use of each coating, and the resin with high solubility can improve the intermiscibility of the pigment in the coating and the flowing property of the coating, thereby being beneficial to the implementation of the automobile paint spraying process. Resins with good properties, in addition to having a high solubility, also have a suitable softening point, viscosity, relatively high molecular weight and a suitable distribution thereof, since this determines their overall properties. However, it is not easy to achieve this excellent combination of properties with rosin-modified phenolic resins. Therefore, the preparation of the high-performance rosin modified phenolic resin becomes a key technology for producing high-quality vacuum spray paint. The manufacturing technology for producing the high-quality rosin modified phenolic resin suitable for vacuum spray painting high-grade paint by a plurality of large resin production enterprises abroad is secret and undeniable.
Rosin-modified phenolic resins are the main representatives of the resins used in paints, and are the resins used in the largest amount in paints, and the properties of the resins determine the quality grade of the paints. In the 30's of the 20 th century, Ruzicka et al discovered that rosin as a diene could undergo Diels-Alde addition reactions with a number of dienophilic species. Abietic acid type resin acid in rosin is easy to generate isomerization reaction under the heat or the influence of acid, so as to form a conjugated double-bond type levopimaric acid structure and achieve dynamic balance. After the conjugated double bonds are subjected to addition reaction under certain conditions, various rosin addition products can be generated. In addition, the carboxyl group in the resin acid may be esterified with various polyhydric alcohols. This forms the chemical basis for rosin modification.
How to improve the viscosity and the solvent solubility of the rosin modified phenolic resin is a key for improving the quality of the coating and is a difficult problem to be solved in the production of the resin. The early rosin modified phenolic resin is prepared by melting phenol and rosin, adding a urotropine catalyst, adding formaldehyde at about 100 ℃ to synthesize the phenolic resin, then dehydrating and slowly raising the temperature to 170-220 ℃, and carrying out Diels-Alder addition reaction on the rosin and the dehydrated phenolic resin. And finally, adding glycerol for esterification until the acid value is less than 20mgKOH/g, and vacuumizing to remove low fraction to obtain the product. The rosin modified phenolic resin synthesized by the method has low solvent resolvability, low brightness of the coating, low softening point of the resin, only higher than 130 ℃ and poor ageing resistance. The development of rosin modified phenolic resin with excellent comprehensive performance by improving the performance of the rosin modified phenolic resin is always the direction of research. At present, rosin modified phenolic resin is synthesized by condensing alkylphenol and formaldehyde into a product in the first stage under the alkaline condition, and then reacting the product with rosin to obtain oil-soluble solid resin through esterification of polyhydric alcohol. This production process can be generally achieved by two methods: namely one-step and two-step processes.
(1) A one-step method: the technology for synthesizing the rosin modified phenolic resin by the one-step method is mature day by day. In the presence of rosin, alkyl phenol and formaldehyde are condensed by using hexamethylenetetramine as a catalyst. Rosin is very weak in acidity and the reaction is carried out in an aqueous medium. The reaction of phenol and aldehyde still belongs to alkaline polycondensation, and the generated hydroxymethyl phenol is quickly dissolved in the rosin to prevent the further polycondensation of the hydroxymethyl phenol. When the temperature rises, the hydroxymethyl phenol is dehydrated to generate the methine ketone to be added with the rosin, and then the polyalcohol is added for esterification reaction. The resin thus produced has relatively uniform molecular weight, and no excessive condensation between phenol and aldehyde.
(2) A two-step method: the two-step method is that firstly phenol and formaldehyde react under alkaline condition to prepare soluble phenolic resin, then the soluble phenolic resin is slowly added into molten rosin at about 180 ℃ to carry out addition reaction, and then polyhydric alcohols are used for esterification. The disadvantage is that the end point of the phenolic resin is not easy to be controlled, and the solubility of the phenolic resin in rosin is reduced and the addition reaction is influenced if the phenolic resin is excessively condensed or is left for a long time.
Chinese patent CN104744654B discloses a rosin modified phenolic resin and a preparation method thereof, wherein the method comprises the following steps: (1) weighing alkylphenol and placing the alkylphenol in a reaction container, and heating the alkylphenol to be melted when the alkylphenol is solid; adding catalyst and formaldehyde, stirring, and reacting at 70-140 deg.C to obtain resol; wherein the catalyst is an organic amine having a boiling point above 200 ℃; (2) weighing rosin, heating to be melted, adding the resol prepared in the step (1), and reacting at 180-240 ℃; (3) adding polyhydric alcohol into the mixture obtained by the reaction in the step (2), and carrying out esterification reaction at the temperature of 240 ℃ and 280 ℃ to obtain the rosin modified phenolic resin. The invention can synthesize the resol with stable quality by taking the organic amine which is difficult to volatilize or nonvolatile as the catalyst, but the solubility of the prepared rosin modified phenolic resin is relatively low.
In general, the development trend of rosin modified phenolic resin is toward the development of high performance (high molecular weight, high softening point, small acid value, good solubility, high solution viscosity and small viscosity) and excellent comprehensive performance, so as to meet the requirement of high-quality paint in the automobile paint spraying industry. At present, the performance levels of the commercial rosin modified phenolic resin are as follows: the solubility of the resin is generally not higher than 30mL/2g, and the average molecular weight is generally not more than 4 ten thousand at 25 ℃. At present, the performance of the rosin modified phenolic resin sold on the market can not meet the requirement of producing high-quality vacuum paint spraying high-grade paint basically, so that domestic enterprises produce the high-grade vacuum paint spraying paint at the low end of a quality chain all the time. Therefore, the rosin modified phenolic resin for the high-grade vacuum paint spraying paint with high performance of a new generation is developed, which not only meets the requirement of domestic enterprises on producing the high-grade vacuum paint spraying paint with high quality, but also gets rid of the technical monopoly of foreign companies and the requirement on developing independent intellectual property rights.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of rosin modified phenolic resin for high-grade paint for vacuum spray painting. The method prepares the rosin modified phenolic resin for the high-grade vacuum spray paint by a numerical control method, the conditions are easy to control, the rosin modified phenolic resin with different softening points and different dissolvability can be produced, and the prepared rosin modified phenolic resin has excellent performance, high softening point, light color, small acid value, high viscosity, abnormally high dissolvability and molecular weight, and the product quality is easy to control.
The technical scheme of the invention is as follows:
a preparation method of rosin modified phenolic resin for high-grade vacuum paint spraying paint comprises the following steps:
s1, placing p-tert-octylphenol in a reaction vessel, heating until the p-tert-octylphenol is completely melted, adding formaldehyde and sodium hydroxide, stirring, heating to 96-100 ℃, and reacting for 4 hours under heat preservation to obtain phenolic resin;
s2, putting rosin in a reaction vessel, heating to completely melt the rosin, stirring, adding pentaerythritol and a catalyst, heating to 268-272 ℃, and carrying out heat preservation reaction for 10 hours to obtain rosin resin;
s3, placing the phenolic resin obtained in the step S1 and the rosin resin obtained in the step S2 into a reaction container, adding magnesium oxide, heating to 248-.
Further, the adding amount of the sodium hydroxide in the step S1 is 2-3% of the mass of the p-tert-octylphenol; the mass ratio of the tert-octyl phenol to the formaldehyde is 1: 0.15-0.35.
Further, the adding amount of the sodium hydroxide in the step S1 is 2.4% of the mass of the p-tert-octylphenol; the mass ratio of tert-octyl phenol to formaldehyde is 1: 0.2.
Further, the adding amount of the pentaerythritol in the step S2 is 15-30% of the mass of the rosin.
Further, the pentaerythritol in the step S2 is added in an amount of 20% by mass of the rosin.
Further, the adding amount of the catalyst in the step S2 is 0.4-0.8% of the mass of the rosin.
Further, the catalyst of step S2 is added in an amount of 0.6% by mass of the rosin.
Further, the step S2 catalyst is composed of titanium oxide and magnesium oxide according to the mass ratio of 5-9: 1-3.
Further, the step S2 catalyst is composed of titanium oxide and magnesium oxide at a mass ratio of 7: 2.
Further, the mass ratio of the phenolic resin to the rosin resin in the step S3 is 0.3-0.7: 1.
Further, the mass ratio of the phenolic resin to the rosin resin in the step S3 is 0.4: 1.
Further, the adding amount of the magnesium oxide in the step S3 is 0.3-0.6% of the total mass of the phenolic resin and the rosin resin; the addition amount of the antioxidant is 0.06-0.12 percent of the total mass of the phenolic resin and the rosin resin; the addition amount of the anti-ultraviolet auxiliary agent is 0.2-0.6 percent of the total mass of the phenolic resin and the rosin resin.
Furthermore, the adding amount of the magnesium oxide in the step S3 is 0.4 percent of the total mass of the phenolic resin and the rosin resin; the addition of the antioxidant is 0.08 percent of the total mass of the phenolic resin and the rosin resin; the addition amount of the ultraviolet resistant auxiliary agent is 0.4 percent of the total mass of the phenolic resin and the rosin resin.
Further, the antioxidant of the step S3 is composed of dithio bis-diamyl phenol and phosphite ester according to the mass ratio of 2-5: 8-10; the anti-ultraviolet auxiliary agent consists of nano titanium dioxide, 2- (2' -hydroxy-3 ',5' -di-tert-butylphenyl) -5-chlorobenzotriazole and salicylic acid-4-tert-butyl phenyl ester according to the mass ratio of 12-15:7-9: 2-4.
Further, the antioxidant of step S3 is composed of dithio bis-diamyl phenol and phosphite ester according to the mass ratio of 4: 9; the anti-ultraviolet auxiliary agent consists of nano titanium dioxide, 2- (2' -hydroxy-3 ',5' -di-tert-butylphenyl) -5-chlorobenzotriazole and salicylic acid-4-tert-butyl phenyl ester according to the mass ratio of 14:8: 3.
The invention innovatively adopts a numerical control method to prepare rosin modified phenolic resin for high-grade vacuum paint spraying paint, namely, p-tert-octylphenol and formaldehyde are reacted under alkaline conditions in different proportions to prepare phenolic resin with different solubilities, rosin is esterified by pentaerythritol to obtain rosin resin, the phenolic resin and the rosin resin are subjected to synthetic reaction in different proportions according to the requirements of the softening point and the solubility of the paint resin, then an antioxidant and an anti-ultraviolet auxiliary agent are added, and the rosin modified phenolic resin for the high-grade vacuum paint spraying paint is obtained by refining.
The antioxidant and the anti-ultraviolet auxiliary agent are introduced in the preparation of the rosin modified phenolic resin for the high-grade vacuum paint spraying paint, so that the quality of the paint can be improved, the ageing resistance of the product can be improved, the anti-ultraviolet auxiliary agent is introduced, the product is prevented from being oxidized by illumination, the rosin modified phenolic resin is more suitable for outdoor paint, and the rosin modified phenolic resin has obvious advantages.
The invention also aims to provide the rosin modified phenolic resin for the high-grade vacuum paint spraying paint, which is prepared by the preparation method of the rosin modified phenolic resin for the high-grade vacuum paint spraying paint, and has the softening point of 160-200 ℃, the viscosity of 4500-6500mpa.s, the weight average molecular weight of 20-25 ten thousand, the acid value of 12-22mg KOH/g and the solvent solubility of 100-150mL/2 g.
Compared with the prior art, the invention has the following advantages:
(1) the rosin modified phenolic resin for the high-grade vacuum paint spraying paint prepared by the invention has the weight average molecular weight higher than 20 ten thousand, has abnormally high solubility (higher than 100mL/2g and 25 ℃), has excellent performances of high softening point, light color, small acid value, high viscosity and the like, and is suitable for manufacturing the high-grade vacuum paint spraying paint.
(2) The antioxidant and the anti-ultraviolet auxiliary agent are introduced, so that the quality of the coating can be improved, the ageing resistance of the product can be improved, the product is prevented from being oxidized by illumination, and the coating is more suitable for being used as an outdoor coating.
(3) The invention adopts numerical control method process to prepare rosin modified phenolic resin for vacuum spray paint high-grade paint, conditions are easy to control, rosin modified phenolic resin with different softening points and different dissolubility can be produced according to different proportions of p-tert-octylphenol and formaldehyde and different proportions of rosin resin and phenolic resin, and product quality is easy to control.
Detailed Description
The present invention is further described in the following description of the specific embodiments, which is not intended to limit the invention, but various modifications and improvements can be made by those skilled in the art according to the basic idea of the invention, within the scope of the invention, as long as they do not depart from the basic idea of the invention.
Example 1 preparation method of rosin modified phenolic resin for high-grade vacuum paint spraying coating
The preparation method of the rosin modified phenolic resin for the high-grade vacuum paint spraying paint comprises the following steps:
s1, placing 100kg of p-tert-octylphenol in a reaction vessel, heating until the p-tert-octylphenol is completely melted, adding 15kg of formaldehyde and 2kg of sodium hydroxide, stirring, heating to 96 ℃, and carrying out heat preservation reaction for 4 hours to obtain phenolic resin;
s2, placing 100kg of rosin in a reaction container, heating to completely melt the rosin, stirring, adding 15kg of pentaerythritol and 0.4kg of catalyst consisting of titanium oxide and magnesium oxide according to the mass ratio of 5:3, heating to 268 ℃, and carrying out heat preservation reaction for 10 hours to obtain rosin resin;
s3, placing 30kg of the phenolic resin obtained in the step S1 and 100kg of the rosin resin obtained in the step S2 into a reaction container, adding 0.39kg of magnesium oxide, heating to 248 ℃, keeping the temperature for reaction for 15 hours, adding 0.078kg of antioxidant consisting of dithio-bis-diamyl phenol and phosphite ester according to the mass ratio of 2:10 and 0.26kg of ultraviolet-resistant auxiliary agent consisting of nano titanium dioxide, 2- (2' -hydroxy-3 ',5' -di-tert-butylphenyl) -5-chlorobenzotriazole and salicylic acid-4-tert-butyl phenyl ester according to the mass ratio of 12:9:4, and refining to obtain the ultraviolet-resistant phenolic resin.
Embodiment 2 preparation method of rosin modified phenolic resin for vacuum spray paint high-grade paint
The preparation method of the rosin modified phenolic resin for the high-grade vacuum paint spraying paint comprises the following steps:
s1, placing 100kg of p-tert-octylphenol in a reaction vessel, heating until the p-tert-octylphenol is completely melted, adding 35kg of formaldehyde and 3kg of sodium hydroxide, stirring, heating to 100 ℃, and carrying out heat preservation reaction for 4 hours to obtain phenolic resin;
s2, placing 100kg of rosin in a reaction container, heating to completely melt the rosin, stirring, adding 30kg of pentaerythritol and 0.8kg of catalyst consisting of titanium oxide and magnesium oxide according to the mass ratio of 9:1, heating to 272 ℃, and carrying out heat preservation reaction for 10 hours to obtain rosin resin;
s3 putting 70kg of the phenolic resin obtained in the step S1 and 100kg of the rosin resin obtained in the step S2 into a reaction container, adding 1.02kg of magnesium oxide, heating to 252 ℃, keeping the temperature for reaction for 15h, adding 0.204kg of antioxidant consisting of dithio-bis-diamyl phenol and phosphite ester according to the mass ratio of 5:8 and 1.02kg of ultraviolet-resistant auxiliary agent consisting of nano titanium dioxide, 2- (2' -hydroxy-3 ',5' -di-tert-butylphenyl) -5-chlorobenzotriazole and salicylic acid-4-tert-butyl phenyl ester according to the mass ratio of 15:7:2, and refining to obtain the product.
Example 3 preparation method of rosin modified phenolic resin for vacuum spray paint high-grade paint
The preparation method of the rosin modified phenolic resin for the high-grade vacuum paint spraying paint comprises the following steps:
s1, placing 100kg of p-tert-octylphenol in a reaction vessel, heating until the p-tert-octylphenol is completely melted, adding 20kg of formaldehyde and 2.4kg of sodium hydroxide, stirring, heating to 98 ℃, and carrying out heat preservation reaction for 4 hours to obtain phenolic resin;
s2, placing 100kg of rosin in a reaction container, heating to completely melt the rosin, stirring, adding 20kg of pentaerythritol and 0.6kg of catalyst consisting of titanium oxide and magnesium oxide according to the mass ratio of 7:2, heating to 270 ℃, and carrying out heat preservation reaction for 10 hours to obtain rosin resin;
s3, putting 40kg of the phenolic resin obtained in the step S1 and 100kg of the rosin resin obtained in the step S2 into a reaction container, adding 0.56kg of magnesium oxide, heating to 250 ℃, keeping the temperature for reaction for 15 hours, adding 0.112kg of antioxidant consisting of dithio-bis-diamyl phenol and phosphite ester according to the mass ratio of 4:9 and 0.56kg of ultraviolet-resistant auxiliary agent consisting of nano titanium dioxide, 2- (2' -hydroxy-3 ',5' -di-tert-butylphenyl) -5-chlorobenzotriazole and salicylic acid-4-tert-butyl phenyl ester according to the mass ratio of 14:8:3, and refining to obtain the UV-resistant phenolic resin.
Comparative example 1 preparation method of rosin modified phenolic resin for vacuum spray paint high-grade paint
The preparation method of the rosin modified phenolic resin for the high-grade vacuum paint spraying paint is similar to that of the embodiment 3.
The difference from the example 3 is that in the step S1, 100kg of p-tert-octylphenol is placed in a reaction vessel, and after the p-tert-octylphenol is heated to be completely melted, 20kg of formaldehyde and 2.4kg of sodium hydroxide are added, and the mixture is stirred, heated to 65 ℃, and kept for reaction for 4 hours, so as to obtain the phenolic resin.
Comparative example 2 preparation method of rosin modified phenolic resin for vacuum spray paint high-grade paint
The preparation method of the rosin modified phenolic resin for the high-grade vacuum paint spraying paint is similar to that of the embodiment 3.
The difference from example 3 is that the catalyst in the step S2 consists of titanium oxide and magnesium oxide in a mass ratio of 1: 1.
Comparative example 3 preparation method of rosin modified phenolic resin for vacuum spray paint high-grade paint
The preparation method of the rosin modified phenolic resin for the high-grade vacuum paint spraying paint is similar to that of the embodiment 3.
The difference from example 3 is that the catalyst in step S2 is titanium oxide.
Comparative example 4 preparation method of rosin modified phenolic resin for vacuum spray paint high-grade paint
The preparation method of the rosin modified phenolic resin for the high-grade vacuum paint spraying paint is similar to that of the embodiment 3.
The difference from the embodiment 3 is that in the step S3, 100kg of the phenolic resin obtained in the step S1 and 40kg of the rosin resin obtained in the step S2 are placed in a reaction container, 0.56kg of magnesium oxide is added, the temperature is raised to 250 ℃, the heat preservation reaction is carried out for 15 hours, 0.112kg of antioxidant consisting of dithio-bis-diamyl phenol and phosphite ester according to the mass ratio of 4:9 and 0.56kg of anti-ultraviolet auxiliary agent consisting of nano titanium dioxide, 2- (2' -hydroxy-3 ',5' -di-tert-butylphenyl) -5-chlorobenzotriazole and salicylic acid-4-tert-butyl phenyl ester according to the mass ratio of 14:8:3 are added, and the mixture is refined, so as to obtain the product.
Test example I, Performance index test
1. Test materials: rosin modified phenolic resin for vacuum spray paint high-grade paint prepared in example 1, example 2, example 3, comparative example 1, comparative example 2, comparative example 3 and comparative example 4.
2. The test method comprises the following steps: various performance indexes of the rosin modified phenolic resin for the vacuum spray paint high-grade paint are measured according to related measuring methods.
3. And (3) test results: the test results are shown in table 1.
Table 1: performance index comparison table of rosin modified phenolic resin for vacuum spray paint high-grade paint
As can be seen from Table 1, the rosin modified phenolic resin for the high-grade vacuum spray paint prepared by the invention has excellent performance, high weight average molecular weight, high softening point, light color, small acid value, high viscosity and high solvent solubility, and is suitable for manufacturing the high-grade vacuum spray paint, wherein each performance index of the example 3 is the best example of the invention; compared with comparative examples 1, 2, 3 and 4, the rosin modified phenolic resin for the vacuum spray paint high-grade paint prepared in example 3 has better performance indexes.
Claims (6)
1. The preparation method of the rosin modified phenolic resin for the high-grade vacuum paint spraying paint is characterized by comprising the following steps:
s1, placing p-tert-octylphenol in a reaction vessel, heating until the p-tert-octylphenol is completely melted, adding formaldehyde and sodium hydroxide, stirring, heating to 96-100 ℃, and reacting for 4 hours under heat preservation to obtain phenolic resin;
s2, putting rosin in a reaction vessel, heating to completely melt the rosin, stirring, adding pentaerythritol and a catalyst, heating to 268-272 ℃, and carrying out heat preservation reaction for 10 hours to obtain rosin resin;
s3, placing the phenolic resin obtained in the step S1 and the rosin resin obtained in the step S2 into a reaction container, adding magnesium oxide, heating to 248-;
the adding amount of the sodium hydroxide in the step S1 is 2-3% of the mass of the p-tert-octylphenol; the mass ratio of the p-tert-octyl phenol to the formaldehyde is 1: 0.15-0.35;
the step S2 catalyst consists of titanium oxide and magnesium oxide according to the mass ratio of 5-9: 1-3;
the mass ratio of the phenolic resin to the rosin resin in the step S3 is 0.3-0.7: 1.
2. The method for preparing rosin modified phenolic resin for high-grade paint of vacuum spray painting according to claim 1, wherein the amount of pentaerythritol added in step S2 is 15-30% of the mass of rosin.
3. The method for preparing rosin modified phenolic resin for high-grade paint of vacuum spray painting according to claim 1, wherein the amount of the catalyst added in step S2 is 0.4-0.8% of the mass of rosin.
4. The method for preparing the rosin modified phenolic resin for the high-grade paint for vacuum painting according to claim 1, wherein the addition amount of the magnesium oxide in the step S3 is 0.3-0.6% of the total mass of the phenolic resin and the rosin resin; the addition amount of the antioxidant is 0.06-0.12 percent of the total mass of the phenolic resin and the rosin resin; the addition amount of the anti-ultraviolet auxiliary agent is 0.2-0.6 percent of the total mass of the phenolic resin and the rosin resin.
5. The method for preparing the rosin modified phenolic resin for the high-grade paint of vacuum spray painting according to claim 1, wherein the antioxidant of the step S3 consists of dithio bis-diamyl phenol and phosphite ester according to the mass ratio of 2-5: 8-10; the anti-ultraviolet auxiliary agent consists of nano titanium dioxide, 2- (2' -hydroxy-3 ',5' -di-tert-butylphenyl) -5-chlorobenzotriazole and salicylic acid-4-tert-butyl phenyl ester according to the mass ratio of 12-15:7-9: 2-4.
6. The method for preparing the rosin modified phenolic resin for the high-grade paint of vacuum paint spraying as claimed in claim 5, wherein the antioxidant of step S3 is composed of dithio bis-diamyl phenol and phosphite ester according to the mass ratio of 4: 9; the anti-ultraviolet auxiliary agent consists of nano titanium dioxide, 2- (2' -hydroxy-3 ',5' -di-tert-butylphenyl) -5-chlorobenzotriazole and salicylic acid-4-tert-butyl phenyl ester according to the mass ratio of 14:8: 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810009158.3A CN108102546B (en) | 2018-01-04 | 2018-01-04 | Rosin modified phenolic resin for high-grade vacuum paint spraying paint and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810009158.3A CN108102546B (en) | 2018-01-04 | 2018-01-04 | Rosin modified phenolic resin for high-grade vacuum paint spraying paint and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108102546A CN108102546A (en) | 2018-06-01 |
| CN108102546B true CN108102546B (en) | 2020-02-14 |
Family
ID=62219436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810009158.3A Active CN108102546B (en) | 2018-01-04 | 2018-01-04 | Rosin modified phenolic resin for high-grade vacuum paint spraying paint and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108102546B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112980230A (en) * | 2021-03-30 | 2021-06-18 | 德庆华彩合成树脂有限公司 | Anticorrosive paint added with modified phenolic resin |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1077461A (en) * | 1993-05-12 | 1993-10-20 | 福建省龙岩地区林产工业公司 | The manufacture method of light colour modified rosin phenolic aldehyde resin |
| JP2004137441A (en) * | 2002-10-18 | 2004-05-13 | Hitachi Kasei Polymer Co Ltd | Rosin-modified phenolic resin |
| CN103772633A (en) * | 2012-10-22 | 2014-05-07 | 鹤壁百运佳印务有限公司 | Preparation method of high-glossiness resin for offset ink |
| CN104558462A (en) * | 2013-12-07 | 2015-04-29 | 广西梧州日成林产化工股份有限公司 | Method for preparing rosin-modified phenolic resin |
| CN105175666A (en) * | 2015-08-31 | 2015-12-23 | 桂林兴松林化有限责任公司 | Preparation method for rosin modified phenolic resin |
-
2018
- 2018-01-04 CN CN201810009158.3A patent/CN108102546B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1077461A (en) * | 1993-05-12 | 1993-10-20 | 福建省龙岩地区林产工业公司 | The manufacture method of light colour modified rosin phenolic aldehyde resin |
| JP2004137441A (en) * | 2002-10-18 | 2004-05-13 | Hitachi Kasei Polymer Co Ltd | Rosin-modified phenolic resin |
| CN103772633A (en) * | 2012-10-22 | 2014-05-07 | 鹤壁百运佳印务有限公司 | Preparation method of high-glossiness resin for offset ink |
| CN104558462A (en) * | 2013-12-07 | 2015-04-29 | 广西梧州日成林产化工股份有限公司 | Method for preparing rosin-modified phenolic resin |
| CN105175666A (en) * | 2015-08-31 | 2015-12-23 | 桂林兴松林化有限责任公司 | Preparation method for rosin modified phenolic resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108102546A (en) | 2018-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103013296B (en) | A kind of containing attapulgite modified powder coating and preparation method thereof | |
| CN101712739B (en) | Preparation method of rosin modified phenolic resin | |
| CN104014723A (en) | Expansible graphite alcohol-group casting coating and preparation method thereof | |
| CN103045044A (en) | Energy-saving and environment-friendly powder coating and preparation method thereof | |
| CN103059696A (en) | Powder coating containing modified sepiolite powder and preparing method thereof | |
| CN108102546B (en) | Rosin modified phenolic resin for high-grade vacuum paint spraying paint and preparation method thereof | |
| CN102977301B (en) | A kind of preparation method of rosin modified phenolic ink resin | |
| CN106750062A (en) | A kind of phenolic resin of modified by cardanol and the preparation method of phenolaldehyde moulding compound | |
| CN104693679A (en) | Preparation method of nano-silica rosin modified phenolic resin | |
| CN105367728A (en) | Rosin modified phenol-formaldehyde resin and preparation method therefor | |
| CN102532446B (en) | Preparation method of mixed phenolic rosin modified phenolic resin | |
| CN104152048B (en) | A kind of new rosin resin for painting | |
| CN104190858A (en) | Sillimanite/titanium dioxide composite alcohol-based casting paint and preparation method thereof | |
| CN111748083B (en) | High-toughness polyester resin and synthesis method thereof | |
| CN111205799B (en) | Production process of cardanol modified phenolic resin adhesive | |
| CN103059240A (en) | Preparation method of maleated rosin pentaerythritol modified phenolic resin | |
| CN101381505B (en) | Synthetic resin produced by renewable resource and preparation method thereof | |
| CN105508478A (en) | High-temperature-resistant brake block and manufacturing method thereof | |
| CN106496480A (en) | One-step method environmental protection type resin and its preparation technology | |
| CN103804988A (en) | Heat-resistant and oxidation-resistant printing ink and preparation method thereof | |
| CN102977300B (en) | Preparation method of maleated rosin glycerin ester phenol formaldehyde resin | |
| CN108589298B (en) | Full-bio-based composite material based on bio-based benzoxazine and plant fiber and preparation method thereof | |
| CN105330800B (en) | A kind of structural resin for high speed offset ink and preparation method thereof | |
| CN102558476B (en) | Method for preparing bisphenol A rosin modified phenolic resin | |
| CN110903745B (en) | Anti-corrosion wear-resistant polyester resin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Rosin modified phenolic resin for vacuum spray painting high-end coatings and its preparation method Effective date of registration: 20230323 Granted publication date: 20200214 Pledgee: Bank of China Limited Zhaoqing branch Pledgor: FENGKAI HAILAN CHEMICAL Co.,Ltd. Registration number: Y2023980035962 |