CN118047922A - Liquid phenolic resin and preparation method and application thereof - Google Patents

Liquid phenolic resin and preparation method and application thereof Download PDF

Info

Publication number
CN118047922A
CN118047922A CN202211472861.0A CN202211472861A CN118047922A CN 118047922 A CN118047922 A CN 118047922A CN 202211472861 A CN202211472861 A CN 202211472861A CN 118047922 A CN118047922 A CN 118047922A
Authority
CN
China
Prior art keywords
acid
phenolic resin
groups
resin
liquid phenolic
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.)
Pending
Application number
CN202211472861.0A
Other languages
Chinese (zh)
Inventor
狄晨杰
张坤
鲁代仁
董栋
张宁
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Tongcheng Electronic Materials Co ltd
Sino Legend China Chemical Co ltd
Tongcheng Chemical China Co ltd
Red Avenue New Materials Group Co Ltd
Original Assignee
Shanghai Tongcheng Electronic Materials Co ltd
Sino Legend China Chemical Co ltd
Tongcheng Chemical China Co ltd
Red Avenue New Materials Group Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shanghai Tongcheng Electronic Materials Co ltd, Sino Legend China Chemical Co ltd, Tongcheng Chemical China Co ltd, Red Avenue New Materials Group Co Ltd filed Critical Shanghai Tongcheng Electronic Materials Co ltd
Priority to CN202211472861.0A priority Critical patent/CN118047922A/en
Publication of CN118047922A publication Critical patent/CN118047922A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
    • C08G14/10—Melamines
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints

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 discloses a liquid phenolic resin and a preparation method thereof, wherein the structure of the resin comprises one or more combinations of structures shown in formulas (I) - (IV). The invention introduces a benzoxazine structure into the phenolic resin structure, and simultaneously retains part of hydroxymethyl. The method of the invention comprises the following steps: firstly mixing phenols, formaldehyde and alcohols, carrying out methylolation and etherification under the condition of an alkaline catalyst, then adding formaldehyde, amines and toluene for Mannich reaction to form benzoxazine resin, and then adding alcohols for reduced pressure distillation, wherein the solid content is 30-70%. The invention also discloses a coiled material coating composition containing the liquid phenolic resin and application thereof. The invention further improves the corrosion resistance and the processing property of the coating by introducing the benzoxazine system into the phenolic aldehyde component, and the hydroxymethyl of the side chain keeps the reactivity of the phenolic aldehyde curing agent, so that the phenolic aldehyde-free coating curing agent can replace the phenolic aldehyde and amino curing BPA-free coating system curing agent.

Description

Liquid phenolic resin and preparation method and application thereof
Technical Field
The invention belongs to the technical field of paint formula resin, and relates to liquid phenolic resin, a preparation method and application thereof.
Background
At present, the requirements of the inner coating for can hearing are that the inner coating can resist the corrosion requirements of various foods and protect metal base materials from corrosion, and meanwhile, the problems of impact, necking and boiling resistance and the like of a can body in the processing and sterilization processes are required to be met; in addition, various groups have identified the hazard of BPA and its derivative bisphenol a-diglycidyl ether (BADGE) to humans, and therefore it is desirable to minimize the content of free BPA from the formulation components.
The existing epoxy-phenolic resin coating generally uses a compound formula of epoxy, phenolic and amino resin to meet the packaging requirements of acidic foods, such as tomato catsup and sardine food cans, and has thicker coating film thickness; the compact coating is formed in this way, the crosslinking density is obviously increased, although the epoxy resin can be ensured to be fully solidified, the processing performance of the coating is correspondingly reduced, and the coating is more likely to have the application problems of blushing, cracking, feathering and the like in the processing process; the invention patent CN101935491B discloses an epoxy-phenolic-amino paint formula for improving the corrosion resistance of a coating, but the addition of amino resin can lead to the increase of crosslinking density, the processing performance of the coating is reduced, and the coating is easy to crack and fall off in the processes of shallow punching and necking of a plate;
Compared with the traditional phenolic resin, the benzoxazine resin has more excellent heat resistance, hydrophobicity and corrosion resistance, and is widely used in the fields of composite materials, electronic circuit boards, heavy duty corrosion resistance and the like. The invention patent CN110938347A discloses a benzoxazine anticorrosive paint formula, which is prepared from benzoxazine monomers, epoxy resin and nano particles, and the benzoxazine resin has high curing condition requirement, and is cured for 1-3 hours at 180-230 ℃ under common processing conditions, and the baking process cannot be matched for coil coating and sheet coating used on tin or aluminum, so that the benzoxazine resin has little application in the industry of metal beverage cans.
Disclosure of Invention
In order to solve the defects existing in the prior art, the invention aims to provide liquid phenolic resin and a preparation method and application thereof. The coating composition formed by the liquid phenolic resin and the epoxy resin can further improve the curing effect of the epoxy-phenolic system coating, effectively reduce Free BPA of the product and achieve BPA-Free; and has coating properties superior to conventional phenolic curatives, particularly better processability and retort resistance.
The invention provides a liquid phenolic resin (namely, a benzoxazine liquid resin containing hydroxyl), which comprises one or more combinations of structures shown in the following formulas (I), (II), (III) and (IV):
wherein,
R 1 is H, a linear, branched alkane of C 1～C18, or a cyclic alkane of C 3～C18;
R 2 is one of the following structures (V) and (VI);
r 3 is one of the following structures (VII), (VIII);
R 4 is C 2～C4 alkane.
The invention also provides a preparation method of the liquid phenolic resin, which comprises the following steps:
Firstly, mixing phenols, an alkaline catalyst and alcohols A, and adding formaldehyde to carry out methylolation and etherification reaction to obtain a phenol intermediate;
Step (2), adding amine, formaldehyde and toluene into the phenolic intermediate obtained in the step (1), forming benzoxazine through a Mannich reaction, then adding an acid terminator for neutralization, and washing to obtain benzoxazine resin;
And (3) adding alcohols B into the benzoxazine resin obtained in the step (2), and then distilling under reduced pressure to remove water to obtain the liquid phenolic resin with the solid content of 30-70%.
The reaction equation of the step (1) is shown as a formula (IX) or (X):
the reaction equation of the step (2) is shown as a formula (XI) or (XII):
wherein,
R 1 is H, a linear, branched alkane of C 1～C18, or a cyclic alkane of C 3～C18;
R 2 is one of the following structures (V) and (VI);
r 3 is one of the following structures (VII), (VIII);
R 4 is C 2～C4 alkane.
In the step (1), the phenol may be phenol, or may be one or more of alkylphenols containing a linear or branched alkyl group of C 1～C18 or a cyclic alkyl group of C 3～C18; preferably, the compound is one or more of o-cresol, m-cresol, p-tert-butylphenol, p-tert-octylphenol and cardanol; further preferred are phenol, m-cresol, p-tert-butylphenol, cardanol.
In the step (1), the alkaline catalyst is one or more of inorganic alkali such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, ammonia water and the like; or one or more of organic bases such as ethanolamine, diethanolamine, trimethylamine, triethylamine and the like; preferably sodium hydroxide.
In the step (1), the alcohol A is one or more of organic alcohols containing C 2～C12; preferably, an organic alcohol of C 2～C4; further preferably, n-butanol.
In the step (1), the molar ratio of phenols, formaldehyde, alcohols A and alkaline catalyst is 1: (0.5-1.5): (1-2): (0.02-0.2); preferably, it is 1: (0.8-1.2): (1.2-1.6): (0.05-0.1).
In the step (1), the temperature of the methylolation reaction is 40-90 ℃; preferably 50-70 ℃.
In the step (1), the methylolation reaction time is 1-7 hours; preferably 2-4 hours.
In the step (2), the acid terminator is an inorganic acid or an organic acid, and is selected from one or more of oxalic acid, citric acid, phosphoric acid, sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-hydroxybenzenesulfonic acid and the like; preferably oxalic acid or citric acid.
In step (2), the amine is selected from one or more of melamine, benzomelamine and the like.
In the step (2), the molar ratio of formaldehyde, amine and toluene is (1-3): (0.2-4): (1-2) 1mol of phenols; preferably, (1.5-2.5): (0.5-3): (1-2).
In the step (2), the temperature of the reaction is 60-100 ℃; preferably 70-90 ℃.
In the step (2), the reaction time is 3-15 hours; preferably 5-10 hours.
In the step (3), the alcohol B is one or more of organic alcohols containing C 2～C12; preferably, an organic alcohol of C 4～C5; further preferably, n-butanol.
In the step (3), the molar ratio of the alcohols B to the phenols is (1-5): 1, a step of; preferably, (2-4): 1.
In step (3), the temperature of the reduced pressure distillation is 30 to 100 ℃, preferably 40 to 70 ℃.
In step (3), the solids content of the liquid phenolic resin is preferably 50-65%.
The invention also provides the liquid phenolic resin obtained by the preparation method.
In a specific implementation method, the preparation method of the liquid phenolic resin comprises the following steps:
firstly, mixing phenols, an alkaline catalyst and alcohols A, heating to 60-80 ℃, adding formaldehyde A, and carrying out methylolation at 50-70 ℃ for 2-4 hours to obtain hydroxymethyl phenols;
Step (2), adding amine, formaldehyde B and toluene into the methylol phenols obtained in the step (1), performing Mannich reaction for 5-10 hours at the temperature of 60-100 ℃, then adding an acid terminator for neutralization, and washing to obtain methylol benzoxazine resin;
And (3) adding alcohols B into the resin obtained in the step (2), and distilling under reduced pressure at the temperature of 40-70 ℃ to remove water until the liquid phenolic resin with the solid content of 50-65% is obtained.
The invention also provides a coiled material coating composition containing the liquid phenolic resin, wherein the content ratio (mass percent%) of each component in the composition is as follows: 5-30% of liquid phenolic resin, 20-65% of epoxy resin, 0.5-5% of auxiliary agent and diluent until the total amount of the composition is 100%; preferably, the content ratio (mass percent%) of each component is: 5-20% of liquid phenolic resin, 30-50% of epoxy resin, 1-3% of auxiliary agent and adding a diluent until the total amount of the composition is 100%.
In the composition, the auxiliary agent is one or more of a leveling agent, a curing accelerator, an adhesion promoter, a defoaming agent, a lubricant and the like.
In the above composition, the diluent is one or more of the combination of low molecular organic solvents, specifically, aromatic hydrocarbon solvents: one or more of toluene, xylene, aromatic hydrocarbon 100, aromatic hydrocarbon 120, aromatic hydrocarbon 150 and the like; ester solvents: one or more of methyl acetate, ethyl acetate, butyl acetate, ethyl formate and the like; ketone solvents: one or more of acetone, 2-butanone, methyl isobutyl ketone, cyclohexanone, etc.; alcohol solvents: one or more of ethanol, propanol, isopropanol, n-butanol, etc.; ether solvents: one or more of ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, monobutyl ether and the like; preferably, the diluent is selected from one or more of xylene, aromatic hydrocarbon 100, aromatic hydrocarbon 150, ethylene glycol monobutyl ether and n-butanol.
The invention also provides application of the liquid phenolic resin or the composition in preparation of coil coating.
The beneficial effects of the invention are as follows:
(1) The liquid phenolic resin prepared by the invention contains benzoxazine in the structure, and the benzoxazine is matched with epoxy resin for use, and can carry out ring-opening curing on the benzoxazine by itself in addition to the curing reaction with the traditional phenolic resin, so that the liquid phenolic resin has flexibility superior to that of the traditional phenolic resin and epoxy.
(2) The coating system obtained by the invention solves the problem of poor processing performance caused by adding amino resin and improving corrosion resistance in use of an epoxy-phenolic-amino formula coating formula, and can be exemplified by: coating cracks and falling off easily occur in the process of shallow punching and necking. Meanwhile, in the formula, the dosage of the curing agent is properly increased, so that the epoxy system can be effectively ensured to be fully cured, and the content of free BPA in the coating system is further reduced.
Detailed Description
The present invention will be further described in detail with reference to the following specific examples. The procedures, conditions, experimental methods, etc. for carrying out the present invention are common knowledge and common knowledge in the art, except for the following specific references, and the present invention is not particularly limited.
Example 1
112.8G of phenol, 11.3g of 35% sodium hydroxide and 180g of n-butanol are put into a 1L four-neck flask, the temperature is raised to 55 ℃, 72g of 50% liquid aldehyde is added, and the temperature is kept at 55 ℃ for reaction for 2 hours. After the reaction is finished, 75.6g of melamine, 78g of 92% paraformaldehyde and 220g of toluene are added, the temperature is raised to 80 ℃ for heat preservation reaction for 5 hours, then 6.4g of citric acid is added for neutralization and water washing are carried out twice, and the methylolated benzoxazine resin is obtained; and finally adding 200g of n-butanol, heating to 80 ℃ and distilling under reduced pressure to remove part of the solvent, thereby finally obtaining the liquid phenolic resin with the solid content of 60%.
Example 2
270G of p-tert-butylphenol, 2.7g of 35% sodium hydroxide and 270g of n-butanol are put into a 2L four-necked flask, the temperature is raised to 65 ℃, 162g of 50% liquid aldehyde is added, and the reaction is carried out for 4 hours at 65 ℃. After the reaction is finished, 113.4g of melamine, 117g of 92% paraformaldehyde and 330g of toluene are added, the temperature is raised to 80 ℃ for heat preservation reaction for 5 hours, then 14.4g of oxalic acid is added for neutralization and water washing are carried out twice, and the methylolated benzoxazine resin is obtained; and finally 400g of n-butanol is added, the temperature is raised to 80 ℃ and reduced pressure distillation is carried out to remove part of the solvent, and finally the liquid phenolic resin with the solid content of 60% is obtained.
Example 3
120G of p-tert-butylphenol, 43.2g of m-cresol, 16g of 35% sodium hydroxide and 180g of n-butanol are put into a 1L four-necked flask, the temperature is raised to 55 ℃, 39g of 92% paraformaldehyde is added, and the reaction is carried out at 60 ℃ for 2 hours. After the reaction is finished, 75.6g of melamine, 78g of 92% paraformaldehyde and 220g of toluene are added, the temperature is raised to 90 ℃ for heat preservation reaction for 4 hours, then 9.1g of citric acid is added for neutralization and water washing are carried out twice, and the methylolated benzoxazine resin is obtained; and finally adding 200g of n-butanol, heating to 80 ℃ and distilling under reduced pressure to remove part of the solvent, thereby finally obtaining the liquid phenolic resin with the solid content of 60%.
Example 4
94G of phenol, 30g of cardanol, 13.4g of 35% sodium hydroxide and 180g of n-butanol are put into a 1L four-necked flask, the temperature is raised to 55 ℃, 39g of 92% paraformaldehyde is added, and the reaction is carried out at 60 ℃ for 3 hours. After the reaction is finished, adding 75.6g of melamine, 78g of 92% paraformaldehyde and 220g of toluene, heating to 75 ℃, preserving heat and reacting for 5 hours, then adding 7.6g of citric acid for neutralization and washing twice to obtain methylolated benzoxazine resin; and finally adding 200g of n-butanol, heating to 80 ℃ and distilling under reduced pressure to remove part of the solvent, thereby finally obtaining the liquid phenolic resin with the solid content of 60%.
Examples 5-10 are preparations of can-primer coating compositions and were each tested as follows.
Mixing and dissolving epoxy resin, phenolic resin and organic solvent, adding various auxiliary agents to obtain the metal internal coating, and carrying out the following test:
(1) Flexibility and hardness test
Flexibility was tested according to GB/T1731-1993 and expressed as the smallest bar axis diameter that does not cause paint film failure, where 1mm indicates the best flexibility and 15mm indicates the worst;
Hardness was tested according to GB/T6793-2006 and expressed as the hardest pencil hardness, with 6H being the hardest and 6B being the softest.
(2) Coefficient of friction test
The weight was 1Kg, and the speed was 20inchs/min, using a slip meter (U.S. ALREK-9505B).
(3) Solvent resistant wiping
Six layers of round gauze with a diameter of about 40mm were moistened with a 2-butanone solvent, a wiping head was fitted, and the coated surface was wiped back and forth using a solvent wiper to record back and forth as one time until the coated surface was damaged and the substrate was exposed, and the number of wipes was recorded.
(4) Adhesion test
According to QB/T2763-2006, a cross-cut experiment is carried out, an adhesive tape is used for testing, the evaluation is carried out according to the torn area of a coating film, the comparison is carried out according to 0-10 parts, the 10 parts are optimal, and the tearing area is more than or equal to 50% below 6 and cannot be used;
(5) Digestion resistance test
According to QB/T2763-2006, respectively carrying out distilled water boiling, 3% acetic acid water boiling, 3% citric acid water boiling and sulfur resistance test liquid (L-cysteine hydrochloride, potassium dihydrogen sulfate and sodium dihydrogen phosphate mixed liquid) at 121 ℃ for 30 minutes (a vertical high-temperature sterilizer: shanghai Shen An LDZX-50L), cooling after finishing, taking out a sample, cleaning, drying, observing the boiling condition of the surface and the bending part of the coating, and grading by 0-10, wherein 10 is optimal, and the boiling result of the coating below 6 minutes is unacceptable;
(6) Impact resistance
According to QB/T2763-2006, using an impact instrument to impact a sample, immersing the impact sample into 50gL of copper sulfate solution 30minn, observing the corrosion condition of the surface, grading by 0-10, and optimally dividing by 10, wherein less than 6 indicates that the impact resistance of the coating is unacceptable;
Examples 5 to 10 of the present invention are the liquid phenolic resins of examples 1 to 4 of the present invention, respectively, and the phenolic resins selected (Zhanxin PR 565, 60% solids) and an amino resin (cyanogen CYMEL 303, 98% solids) were used as curing agents for comparison.
Firstly, bisphenol A epoxy resin (Van EPON 1007F, epoxy equivalent=1700-2300 g/eq), organic solvent glycol monobutyl ether, arene 150# and n-butanol are mixed, stirred for 1h at the temperature of 100 ℃ to be dissolved, then corresponding curing agent such as phenolic resin or amino resin, catalyst phosphoric acid (85%), defoamer (BKY) are added, high-speed stirring is carried out for 30 minutes, and finally, the temperature is reduced to below 40 ℃ to obtain the prepared coating.
TABLE 1 examples 5-10 coating compositions
The coatings prepared in examples 5-10 above were coated on tinplate using a # 20 wire bar and baked at 200 ℃ for 12min, after which the test pieces were cooled and tested as follows. The results of the comprehensive tests of examples 5 to 10 of the present invention are summarized in Table 2, and the results show that:
The phenolic resin coating disclosed in the examples 1-4 has good steaming resistance and corrosion resistance, and meanwhile, has stronger impact resistance and flexibility compared with the traditional phenolic aldehyde and amino curing system, because of the advantages brought by structural modification of the phenolic resin.
Table 2: examples 5 to 10 comprehensive Performance test comparison
The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions, combinations, and simplifications can be made in the practice of the invention without departing from the spirit or scope thereof.

Claims (10)

1. The liquid phenolic resin is characterized by comprising one or more of the following structures shown in the formula (I), the formula (II), the formula (III) and the formula (IV):
wherein,
R 1 is H, a linear, branched alkane of C 1～C18, or a cyclic alkane of C 3～C18;
R 2 is one of the following structures (V) and (VI);
r 3 is one of the following structures (VII), (VIII);
R 4 is C 2～C4 alkane.
2. A preparation method of liquid phenolic resin is characterized in that the preparation method is that
Firstly, mixing phenols, an alkaline catalyst and alcohols A, and adding formaldehyde to carry out methylolation and etherification reaction to obtain a phenol intermediate;
Step (2), adding amine, formaldehyde and toluene into the phenolic intermediate obtained in the step (1), forming benzoxazine through a Mannich reaction, then adding an acid terminator for neutralization, and washing to obtain benzoxazine resin;
Step (3), adding alcohols B into the benzoxazine resin obtained in the step (2), and then distilling under reduced pressure to remove water to obtain liquid phenolic resin with 30% -70% of solid content;
The reaction equation of the step (1) is shown as a formula (IX) or (X):
the reaction equation of the step (2) is shown as a formula (XI) or (XII):
wherein,
R 1 is H, a linear, branched alkane of C 1～C18, or a cyclic alkane of C 3～C18;
R 2 is one of the following structures (V) and (VI);
r 3 is one of the following structures (VII), (VIII);
R 4 is C 2～C4 alkane.
3. The method of claim 2, wherein the phenol is one or more of phenol, alkylphenols having a C 1～C18 linear, branched alkyl group, or alkylphenols having a C 3～C18 cyclic alkyl group; and/or, the alcohol A is one or more of organic alcohols containing C 2～C12.
4. The method according to claim 2, wherein in the step (1), the basic catalyst is an inorganic base or an organic base, and the inorganic base is one or more selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide and ammonia water; the organic base is selected from one or more of ethanolamine, diethanolamine, trimethylamine and triethylamine; and/or the number of the groups of groups,
In the step (2), the acid terminator is an inorganic acid or an organic acid, wherein the inorganic acid is one or more selected from sulfuric acid, phosphoric acid and hydrochloric acid; the organic acid is selected from one or more of p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-hydroxybenzenesulfonic acid, oxalic acid and citric acid; and/or the number of the groups of groups,
The alcohols B are one or more of organic alcohols containing C 2～C12.
5. The method of claim 2, wherein,
In the step (1), the molar ratio of phenols, formaldehyde, alcohols A and alkaline catalyst is 1: (0.5-1.5): (1-2): (0.02-0.2); and/or the number of the groups of groups,
In the step (2), the molar ratio of formaldehyde, amine and toluene is (1-3): (0.2-4): (1-2); and/or the number of the groups of groups,
In the step (3), the molar ratio of the alcohols B to the phenols is (1-5): 1.
6. The method of claim 2, wherein,
In the step (1), the temperature of the reaction is 40-90 ℃, and the reaction time is 1-7 hours; and/or the number of the groups of groups,
In the step (2), the temperature of the reaction is 60-100 ℃, and the reaction time is 3-15 hours; and/or the number of the groups of groups,
In the step (3), the temperature of the reduced pressure distillation is 30-100 ℃.
7. A liquid phenolic resin prepared by the process of any one of claims 2-6.
8. A coil coating composition comprising the liquid phenolic resin of claim 1 or 7, wherein the composition comprises the following components in percentage by mass: the liquid phenolic resin of claim 1 or 7, wherein the liquid phenolic resin comprises 5-30% of epoxy resin, 20-65% of auxiliary agent, 0.5-5% of diluent and the total of the rest components is 100%.
9. The composition of claim 8, wherein the auxiliary agent is one or more of a leveling agent, a curing accelerator, an adhesion promoter, an antifoaming agent, and a lubricant; and/or the diluent is one or more of aromatic hydrocarbon solvent, ester solvent, ketone solvent, alcohol solvent and ether solvent; wherein the aromatic hydrocarbon solvent is one or more of toluene, dimethylbenzene, aromatic hydrocarbon 100, aromatic hydrocarbon 120 and aromatic hydrocarbon 150; the ester solvent is one or more of methyl acetate, ethyl acetate, butyl acetate and ethyl formate; the ketone solvent is one or more of acetone, 2-butanone, methyl isobutyl ketone and cyclohexanone; the alcohol solvent is one or more of ethanol, propanol, isopropanol and n-butanol, and the ether solvent is one or more of ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether and n-butyl ether.
10. Use of a liquid phenolic resin as claimed in claim 1 or 7 or a coil coating composition as claimed in claim 8 or 9 in the preparation of a coil coating.
CN202211472861.0A 2022-11-17 2022-11-17 Liquid phenolic resin and preparation method and application thereof Pending CN118047922A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211472861.0A CN118047922A (en) 2022-11-17 2022-11-17 Liquid phenolic resin and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211472861.0A CN118047922A (en) 2022-11-17 2022-11-17 Liquid phenolic resin and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN118047922A true CN118047922A (en) 2024-05-17

Family

ID=91045531

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211472861.0A Pending CN118047922A (en) 2022-11-17 2022-11-17 Liquid phenolic resin and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN118047922A (en)

Similar Documents

Publication Publication Date Title
US20030109613A1 (en) Adhesion promoting surface treatment or surface cleaner for metal substrates
CA1052030A (en) Metal coating compositions prepared from aqueous dispersions of carboxyl containing polyester resins
US4086292A (en) Surface-coating binders
US20030170396A1 (en) Epoxy resin, coating composition, and method of can inside coating
US20030232145A1 (en) Coating composition and method of can inside coating
KR20110008212A (en) Epoxy resin compositions having improved low temperature cure properties and processes and intermediates for making the same
CA1173994A (en) Polyadduct/polycondensate containing basic nitrogen groups, and its use
PL75254B1 (en) Water-soluble coating compositions[us3658795a]
KR20040054727A (en) Process for coating metallic bodies and primer compositions to be used in the process
CN118047922A (en) Liquid phenolic resin and preparation method and application thereof
US2856094A (en) Blends of alkenylphenol-aldehyde resins with polyepoxide resins and metallic surfaces coated therewith
CN117623877A (en) Cardanol bisphenol and preparation method and application thereof
US4731430A (en) Modified phenol resole ether resins and their preparation
JP2002080556A (en) Epoxy resin composition
CN115926085A (en) Water-based phenylamine resin and preparation method and application thereof
CN114516944B (en) Liquid phenolic resin and preparation method and application thereof
CN116253847A (en) Liquid phenolic resin and preparation method and application thereof
CN118027322A (en) Etherified liquid phenolic resin and preparation method and application thereof
US4427514A (en) Polyadduct/polycondensate which contains basic nitrogen groups, and its use
EP4116345A1 (en) Alkoxylated resol-type phenol resin and method for producing same
JPH0125488B2 (en)
KR101082364B1 (en) Epoxy resin hardener
KR100559058B1 (en) Water-dispersed polymer compositon and method of manufacturing the same
JPH0120193B2 (en)
JP3508033B2 (en) Epoxy resin composition

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