CN108047404B - Water-based self-dispersion thermosetting phenolic resin and preparation method thereof - Google Patents
Water-based self-dispersion thermosetting phenolic resin and preparation method thereof Download PDFInfo
- Publication number
- CN108047404B CN108047404B CN201711305712.4A CN201711305712A CN108047404B CN 108047404 B CN108047404 B CN 108047404B CN 201711305712 A CN201711305712 A CN 201711305712A CN 108047404 B CN108047404 B CN 108047404B
- Authority
- CN
- China
- Prior art keywords
- water
- phenol
- formaldehyde
- based self
- naphthol
- 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
- 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
- C08G8/18—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenols substituted by carboxylic or sulfonic acid groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The present invention belongs to the field of high polymer material. Naphthol sulfonate is introduced into the main chain of the resin molecule to endow the resin system with water solubility; adopting a mixed system of phenol and naphthol sulfonate and synthesizing under the condition of a divalent metal ion catalyst. The invention relates to a water-based self-dispersion thermosetting phenolic resin, which is prepared by catalyzing by divalent metal ions and spraying formaldehyde in batches, wherein a material system contains naphthol sulfonate and comprises the following components: 1 part by mole of phenol, 10-20% of naphthol sulfonate, and the molar ratio of phenol to formaldehyde is 1: 1.5-2.0 parts of water, 14-24 parts of water and 0.5-5 parts of divalent metal ion catalyst. The water-based self-dispersion thermosetting phenolic resin has good water dispersibility, good storage stability and higher cohesiveness and temperature resistance, is suitable for being used as a water-based thermosetting structural adhesive with high shear strength and high temperature resistance, and is particularly suitable for adhering phenolic composite materials and steel in brake pads.
Description
Technical Field
The invention belongs to the field of high polymer materials, relates to a polymer synthesis technology, and particularly relates to a synthesis technology of phenolic resin.
Background
The water-dispersible phenolic resin can form a uniform and stable liquid dispersion phase in water, has good stability, maintains unchanged appearance, viscosity and water dilutability in the storage process, has small discharge amount of volatile pollutants, can obtain high crosslinking density and bonding strength by self-polycondensation or solidification by adding a water-based curing agent, and can replace solvent-based phenolic resin to bond wood, metal, plastic and the like when being used as an adhesive.
US6130289 describes a technique for the preparation of self-emulsifying resol dispersions. A modifier containing reactive functional groups of phenolic resin is introduced into water-soluble resol, the pendant group of the modifier contains sulfur-containing groups such as sulfonic group and sulfuric acid group, the modifier reacts at a certain temperature to form viscous opaque liquid, and after the viscous opaque liquid is filtered and coagulated, translucent phenolic resin dispersion liquid is obtained. However, the preparation method is to modify the water-soluble resol phenolic resin prepared in advance, and in the modification process, the water-soluble resol phenolic resin has polycondensation reaction, so that partial gel appears, the product yield is reduced, and the preparation method can be completed by two steps, so that the preparation process is complex and the cost is high.
Disclosure of Invention
The invention aims to solve the technical problem of providing the environment-friendly water-based self-dispersion thermosetting phenolic resin with controllable molecular structure, long molecular chain, good water dispersibility, high shear strength, high temperature resistance and good aging resistance and the preparation method thereof.
The purpose of the invention is realized as follows: the resin system is endowed with water solubility in a mode of introducing naphthol sulfonate on the main chain of resin molecules; the mixed system of phenol and naphthol sulfonate is adopted, and the naphthol sulfonate is introduced into the molecular main chain of the phenolic resin under the action of a divalent metal ion catalyst, so that the water solubility of the resin is improved.
The invention relates to a water-based self-dispersion thermosetting phenolic resin, which is prepared by catalyzing by divalent metal ions and spraying formaldehyde in batches, wherein a material system contains naphthol sulfonate and comprises the following components:
1 part by mole of phenol, 10-20% of naphthol sulfonate, and the molar ratio of phenol to formaldehyde is 1: 1.5-2.0 parts of water, 14-24 parts of water and 0.5-5 parts of divalent metal ion catalyst.
The invention relates to a water-based self-dispersion thermosetting phenolic resin, which is prepared by catalyzing by divalent metal ions and spraying formaldehyde in batches, wherein a material system contains naphthol sulfonate and comprises the following components:
1 part by mole of phenol, 13-17% of naphthol sulfonate, and the molar ratio of phenol to formaldehyde is 1: 1.6-1.7 parts of water, 17-21 parts of water and 2-4 parts of divalent metal ion catalyst.
The invention relates to a water-based self-dispersion thermosetting phenolic resin, wherein naphthol sulfonate is one or a combination of 2-naphthol-6, 8-disulfonic acid dipotassium salt and 2, 3-dihydroxy naphthalene-6-sodium sulfonate.
The invention relates to a water-based self-dispersion thermosetting phenolic resin, wherein a divalent metal ion catalyst is one or a combination of more of manganese hydroxide, cobalt hydroxide, barium hydroxide and zinc acetate.
The invention relates to a preparation method of water-based self-dispersion thermosetting phenolic resin, which adopts a formaldehyde batch spray feeding process and comprises the processes of material preparation, first-stage polycondensation, second-stage addition and dehydration condensation, and is characterized in that:
(1) preparing materials: adding phenol, naphthol sulfonate, water and a divalent metal ion catalyst into a reaction kettle in proportion, and uniformly dispersing;
(2) first-stage polycondensation: stirring, heating to 85-90 ℃, and mixing according to the molar ratio of formaldehyde to phenol of 1-1.05: 1, adding a formaldehyde solution into a reaction kettle at a constant speed in a spraying manner, and reacting for 1-2 hours to obtain a high-ortho thermoplastic prepolymer;
(3) and (3) second-stage addition: heating to 98-100 ℃, adding the rest formaldehyde solution at a uniform speed in a spraying manner during stirring, and reacting for 0.5-1 h to obtain a thermosetting prepolymer;
(4) dehydration and condensation: vacuum dehydrating and condensing at 60-80 ℃, wherein the polymerization speed reaches 300-350 seconds (150 +/-1 ℃) to obtain the water-based self-dispersing thermosetting phenolic resin.
The invention relates to a preparation method of a water-based self-dispersion thermosetting phenolic resin, wherein a metering charging atomizing nozzle is adopted for formaldehyde charging, and the diameter of atomized particles is 3-10 mu m.
The invention relates to a preparation method of water-based self-dispersion thermosetting phenolic resin, which is characterized in that 3-4 metering charging atomizing nozzles are uniformly distributed, and the discharge amount is 200-400L/h.
The water-based self-dispersion thermosetting phenolic resin has long resin molecular chain, the naphthol sulfonate is distributed in a molecular main chain structure, the water dispersibility is good, the storage stability is good, the curing crosslinking degree is high, the caking property and the temperature resistance are higher, and the water-based self-dispersion thermosetting phenolic resin is suitable for being used as a water-based thermosetting structural adhesive with high shear strength and high temperature resistance, and is particularly suitable for bonding a phenolic composite material and steel in a brake pad.
The preparation method of the water-based self-dispersion thermosetting phenolic resin has the advantages of stable reaction, easy control and difficult occurrence of gel; the molecular structure and the reaction process have strong controllability, and the product quality consistency is high.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1
(1) Preparing materials: adding 94Kg (1000mol) of phenol, 38Kg (100mol) of 2-naphthol-6, 8-disulfonic acid dipotassium salt, 14Kg of water and 0.5Kg of manganese hydroxide into a reaction kettle, and uniformly dispersing;
(2) first-stage polycondensation: stirring, heating to 85 ℃, adding 80Kg of formaldehyde solution (30 Kg (1000 mol)) through 3 metering feeding atomizing nozzles at uniform speed, spraying the mixture with the discharge amount of 200L/h and the diameter of atomized particles of 3-6 μm, and reacting for 1h to obtain the high-ortho thermoplastic prepolymer;
(3) and (3) second-stage addition: heating to 98 ℃, adding 40Kg of formaldehyde solution (15 Kg (500 mol)) at a uniform speed in a spraying manner during stirring, spraying the mixture to obtain 200L/h of atomized particles with the diameter of 3-6 μm, and reacting for 0.5h to obtain a thermosetting prepolymer;
(4) dehydration and condensation: vacuum dehydrating and condensing at 78 deg.c to reach polymerization speed of 300S (150 deg.c) to obtain the water-base self-dispersed thermosetting phenolic resin.
The resin is viscous light yellow transparent resin, the viscosity of 50% aqueous solution is 210 mPa.S, the water dispersibility is good, the water dilutability proportion is 95 times, the normal temperature shear strength is 12.6MPa, and the 300 ℃ shear strength is 2.8 MPa.
Example 2
(1) Preparing materials: adding 94Kg (1000mol) of phenol, 57Kg (150mol) of 2-naphthol-6, 8-disulfonic acid dipotassium salt, 15Kg of water and 2Kg of cobalt hydroxide into a reaction kettle, and uniformly dispersing;
(2) first-stage polycondensation: stirring, heating to 87 ℃, adding 84Kg of formaldehyde solution (31.5 Kg (1050 mol)) through 3 metering feeding atomizing nozzles at uniform speed, spraying the mixture with the discharge amount of 400L/h and the diameter of atomized particles of 5-10 mu m, and reacting for 2h to obtain the high-ortho thermoplastic prepolymer;
(3) and (3) second-stage addition: heating to 98 ℃, adding 76Kg of formaldehyde solution (28.5 Kg (950 mol)) at uniform speed in a spraying manner during stirring, spraying the mixture to obtain a material with the spraying discharge of 350L/h and the diameter of atomized particles of 5-10 μm, and reacting for 1h to obtain a thermosetting prepolymer;
(4) dehydration and condensation: vacuum dehydrating and condensing at 80 ℃, the polymerization speed reaches 315S (149 ℃), and the water-based self-dispersion thermosetting phenolic resin is obtained after the reaction is finished.
The resin is viscous light yellow transparent resin, the viscosity of 50% aqueous solution is 254 mPa.S, the water dispersibility is good, the water dilutability ratio is 100 times, and the normal temperature shear strength is 13.5 MPa.
Example 3
(1) Preparing materials: adding 94Kg (1000mol) of phenol, 76Kg (200mol) of 2-naphthol-6, 8-disulfonic acid dipotassium salt, 24Kg of water and 5Kg of barium hydroxide into a reaction kettle, and uniformly dispersing;
(2) first-stage polycondensation: stirring, heating to 90 ℃, adding 81Kg of formaldehyde solution (30.375 Kg (1012.5 mol)) through 3 metering feeding atomizing nozzles at a uniform speed, spraying the materials with a discharge amount of 220L/h and an atomized particle diameter of 7-10 μm, and reacting for 1h to obtain a high-ortho thermoplastic prepolymer;
(3) and (3) second-stage addition: heating to 100 ℃, adding 50Kg of formaldehyde solution (18.75 Kg (625 mol)) at a uniform spraying speed in the stirring process, spraying the mixture to obtain a material with the spraying discharge amount of 300L/h and the diameter of atomized particles of 7-10 mu m, and then reacting for 0.5h to obtain a thermosetting prepolymer;
(4) dehydration and condensation: vacuum dehydrating and condensing at 75 ℃, the polymerization speed reaches 320S (151 ℃), and the water-based self-dispersion thermosetting phenolic resin is obtained after the reaction is finished.
The resin is viscous light yellow transparent resin, the viscosity of 50% aqueous solution is 267 mPa.S, the water dispersibility is good, the water dilutability ratio is 124 times, and the shear strength at 300 ℃ is 3.3 MPa.
Example 4
(1) Preparing materials: adding 94Kg (1000mol) of phenol, 34.06Kg (130mol) of sodium 2, 3-dihydroxynaphthalene-6-sulfonate, 17Kg of water and 2.5Kg of zinc acetate into a reaction kettle, and uniformly dispersing;
(2) first-stage polycondensation: stirring, heating to 86 ℃, adding 81.6Kg of formaldehyde solution (30.6 Kg (1020 mol)) through 4 metering feeding atomizing nozzles at a uniform spraying speed, spraying the mixture with the discharge amount of 320L/h and the diameter of atomized particles of 3-6 μm, and reacting for 1.4h to obtain the high-ortho thermoplastic prepolymer;
(3) and (3) second-stage addition: heating to 99 ℃, adding 46.4Kg of formaldehyde solution (17.4 Kg (580 mol)) at a uniform spraying speed in the stirring process, spraying the mixture to discharge 360L/h, wherein the diameter of atomized particles is 3-6 μm, and then reacting for 0.6h to obtain a thermosetting prepolymer;
(4) dehydration and condensation: vacuum dehydrating and condensing at 70 ℃, the polymerization speed reaches 335S (150 ℃), and the water-based self-dispersion thermosetting phenolic resin is obtained after the reaction is finished.
The resin is viscous light yellow transparent resin, the viscosity of 50% aqueous solution is 290 mPa.S, the water dispersibility is good, the water dilutability ratio is 152 times, the normal temperature shear strength is 14.3MPa, and the 300 ℃ shear strength is 3.5 MPa.
Example 5
(1) Preparing materials: adding 94Kg (1000mol) of phenol, 39.3Kg (150mol) of 2, 3-dihydroxy naphthalene-6-sodium sulfonate, 21Kg of water and 1Kg of zinc acetate into a reaction kettle, and uniformly dispersing;
(2) first-stage polycondensation: stirring, heating to 85 ℃, adding 82Kg of formaldehyde solution (30.75 Kg (1025 mol)) through 4 metering feeding atomizing nozzles in a spraying manner at a constant speed, spraying the mixture with a discharge amount of 350L/h and an atomized particle diameter of 7-10 mu m, and reacting for 1.5h to obtain a high-ortho thermoplastic prepolymer;
(3) and (3) second-stage addition: heating to 100 ℃, adding 73Kg of formaldehyde solution (27.375 Kg of formaldehyde (912.5 mol)) at a uniform spraying speed in the stirring process, spraying the mixture to obtain 360L/h of atomized particles with the diameter of 7-10 mu m, and reacting for 1h to obtain a thermosetting prepolymer;
(4) dehydration and condensation: vacuum dehydrating and condensing at 65 ℃, the polymerization speed reaches 350S (150.5 ℃), and the water-based self-dispersion thermosetting phenolic resin is obtained after the reaction is finished.
The resin is viscous light yellow transparent resin, the viscosity of 50% aqueous solution is 325 mPa.S, the water dispersibility is good, the water dilutability is 179 times, and the normal temperature shear strength is 14.8 MPa.
Example 6
(1) Preparing materials: adding 94Kg (1000mol) of phenol, 44.54Kg (170mol) of 2, 3-dihydroxy naphthalene-6-sodium sulfonate, 20Kg of water, 1.5Kg of zinc acetate and 2Kg of barium hydroxide into a reaction kettle, and uniformly dispersing;
(2) first-stage polycondensation: stirring, heating to 87 ℃, adding 82.4Kg of formaldehyde solution (30.9 Kg (1030 mol)) through 3 metering feeding atomizing nozzles at uniform speed, spraying the materials with the discharge amount of 370L/h and the diameter of atomized particles of 3-6 μm, and reacting for 1.6h to obtain the high-ortho thermoplastic prepolymer;
(3) and (3) second-stage addition: heating to 99 ℃, adding 53.6Kg of formaldehyde solution (20.1 Kg (670 mol)) at a uniform spraying speed in the stirring process, spraying the mixture to obtain a material with the spraying discharge of 370L/h and the diameter of atomized particles of 3-6 μm, and then reacting for 0.8h to obtain a thermosetting prepolymer;
(4) dehydration and condensation: vacuum dehydrating and condensing at 78 deg.c to reach polymerization speed 321S (149 deg.c) to obtain the water-base self-dispersed thermosetting phenolic resin.
The resin is viscous light yellow transparent resin, the viscosity of 50% aqueous solution is 270 mPa.S, the water dispersibility is good, the water dilutability is 178 times, and the normal-temperature shear strength is 13.8 MPa.
Example 7
(1) Preparing materials: adding 94Kg (1000mol) of phenol, 19Kg (50mol) of 2-naphthol-6, 8-disulfonic acid dipotassium salt, 15.72Kg (60mol) of 2, 3-dihydroxy naphthalene-6-sodium sulfonate, 18Kg of water and 4Kg of zinc acetate into a reaction kettle, and uniformly dispersing;
(2) first-stage polycondensation: stirring, heating to 88 ℃, adding 82Kg of formaldehyde solution (30.75 Kg (1025 mol)) through 3 metering feeding atomizing nozzles at uniform speed, spraying the mixture with the discharge amount of 210L/h and the diameter of atomized particles of 3-6 μm, and reacting for 1.5h to obtain the high-ortho thermoplastic prepolymer;
(3) and (3) second-stage addition: heating to 100 ℃, adding 45Kg of formaldehyde solution (16.875 Kg of formaldehyde (562.5 mol)) at a uniform spraying speed during stirring, spraying the mixture at a discharge amount of 200L/h, wherein the diameter of atomized particles is 3-6 μm, and then reacting for 0.8h to obtain a thermosetting prepolymer;
(4) dehydration and condensation: vacuum dehydrating and condensing at 76 ℃, the polymerization speed reaches 334S (150 ℃), and the water-based self-dispersion thermosetting phenolic resin is obtained after the reaction is finished.
The resin is viscous light yellow transparent resin, the viscosity of 50% aqueous solution is 285 mPa.S, the water dispersibility is good, the water dilutability ratio is 121 times, and the shear strength at 300 ℃ is 3.4 MPa.
Example 8
(1) Preparing materials: adding 94Kg (1000mol) of phenol, 38Kg (100mol) of 2-naphthol-6, 8-disulfonic acid dipotassium salt, 15.72Kg (60mol) of 2, 3-dihydroxy naphthalene-6-sodium sulfonate, 17.5Kg of water, 1Kg of zinc acetate and 1.6Kg of cobalt hydroxide into a reaction kettle, and uniformly dispersing;
(2) first-stage polycondensation: stirring, heating to 88 ℃, adding 81.5Kg of formaldehyde solution (30.5625 Kg of formaldehyde (1018.75 mol)) at uniform speed by using 3 metering feeding atomizing nozzles, spraying the mixture with the discharge amount of 280L/h and the diameter of atomized particles of 7-10 mu m, and reacting for 1h to obtain a high-ortho thermoplastic prepolymer;
(3) and (3) second-stage addition: heating to 99 ℃, adding 55Kg of formaldehyde solution (20.625 Kg (687.5 mol)) at uniform speed in a spraying manner during stirring, spraying the mixture to obtain 200L/h of atomized particles with the diameter of 7-10 μm, and reacting for 0.75h to obtain a thermosetting prepolymer;
(4) dehydration and condensation: vacuum dehydrating and condensing at 75 ℃, the polymerization speed reaches 318S (151 ℃), and the water-based self-dispersion thermosetting phenolic resin is obtained after the reaction is finished.
The resin is viscous light yellow transparent resin, the viscosity of 50% aqueous solution is 258 mPa.S, the water dispersibility is good, the water dilutability ratio is 108 times, and the normal-temperature shear strength is 13.6 MPa.
Example 9
(1) Preparing materials: adding 94Kg (1000mol) of phenol, 28.5Kg (75mol) of 2-naphthol-6, 8-disulfonic acid dipotassium salt, 26.2Kg (100mol) of 2, 3-dihydroxy naphthalene-6-sodium sulfonate, 20Kg of water, 1Kg of zinc acetate and 2.2Kg of manganese hydroxide into a reaction kettle, and uniformly dispersing;
(2) first-stage polycondensation: stirring, heating to 88 ℃, adding 80Kg of formaldehyde solution (30 Kg (1000 mol)) through 3 metering feeding atomizing nozzles at uniform speed, spraying the mixture with the spraying discharge amount of 330L/h and the diameter of atomized particles of 3-6 μm, and reacting for 1.3h to obtain the high-ortho thermoplastic prepolymer;
(3) and (3) second-stage addition: heating to 99 ℃, adding 66Kg of formaldehyde solution (24.75 Kg (825 mol)) at uniform speed in a spraying manner during stirring, spraying the mixture to obtain a material with the spraying discharge of 220L/h and the diameter of atomized particles of 3-6 μm, and reacting for 1h to obtain a thermosetting prepolymer;
(4) dehydration and condensation: vacuum dehydrating and condensing at 60 ℃, wherein the polymerization speed reaches 309S (149 ℃), and the water-based self-dispersing thermosetting phenolic resin is obtained after the reaction is finished.
The resin is viscous light yellow transparent resin, the viscosity of 50% aqueous solution is 228 mPa.S, the water dispersibility is good, the water dilutability is 136 times, and the shear strength at 300 ℃ is 2.9 MPa.
Claims (7)
1. A water-based self-dispersing thermosetting phenolic resin is prepared by a one-stage polycondensation, two-stage addition and dehydration condensation process of divalent metal ion catalysis and formaldehyde batch spray feeding at the polymerization speed of 300-350 seconds/150 +/-1 ℃, the water dilution multiple of not less than 95, the normal-temperature shear strength of not less than 12.6MPa and the 300 ℃ shear strength of not less than 2.8MPa, wherein a material system contains naphthol sulfonate, and phenol, the naphthol sulfonate and formaldehyde are subjected to copolycondensation in the one-stage polycondensation process; the material composition is as follows: 1000 parts by mole of phenol, 10-20% parts by mole of naphthol sulfonate, and the molar ratio of phenol to formaldehyde is 1: 1.5-2.0, 14-24 kg of water and 0.5-5 kg of divalent metal ion catalyst, wherein the molar ratio of phenol/formaldehyde in the first-stage polycondensation process is 1: 1.0 to 1.05;
the divalent metal ion catalyst is one or a combination of more of manganese hydroxide, cobalt hydroxide, barium hydroxide and zinc acetate.
2. The water-based self-dispersing thermosetting phenol-formaldehyde resin according to claim 1, characterized in that: the material composition is as follows: 1000 parts by mole of phenol, 13-17% parts by mole of naphthol sulfonate, and the molar ratio of phenol to formaldehyde is 1: 1.6-1.7 kg of water, 17-21 kg of water and 2-4 kg of divalent metal ion catalyst.
3. The water-based self-dispersing thermosetting phenol-formaldehyde resin according to claim 1, characterized in that: the naphthol sulfonate is one or the combination of 2-naphthol-6, 8-disulfonic acid dipotassium salt and 2, 3-dihydroxy naphthalene-6-sodium sulfonate.
4. The water-based self-dispersing thermosetting phenol-formaldehyde resin according to claim 2, characterized in that: the naphthol sulfonate is one or the combination of 2-naphthol-6, 8-disulfonic acid dipotassium salt and 2, 3-dihydroxy naphthalene-6-sodium sulfonate.
5. The preparation method of the water-based self-dispersion thermosetting phenolic resin according to any one of claims 1 to 4, which adopts a formaldehyde batch spray feeding process, comprises the processes of material preparation, primary polycondensation, secondary addition and dehydration condensation, and is characterized in that:
preparing materials: adding phenol, naphthol sulfonate, water and a divalent metal ion catalyst into a reaction kettle in proportion, and uniformly dispersing;
first-stage polycondensation: stirring, heating to 85-90 ℃, and mixing according to the molar ratio of formaldehyde to phenol of 1-1.05: 1, adding a formaldehyde solution into a reaction kettle at a constant speed in a spraying manner, and reacting for 1-2 hours to obtain a high-ortho thermoplastic prepolymer;
and (3) second-stage addition: heating to 98-100 ℃, adding the rest formaldehyde solution at a uniform speed in a spraying manner during stirring, and reacting for 0.5-1 h to obtain a thermosetting prepolymer;
dehydration and condensation: and (3) carrying out vacuum dehydration condensation at the temperature of 60-80 ℃, wherein the polymerization speed reaches 300-350 seconds/150 +/-1 ℃, and thus obtaining the water-based self-dispersing thermosetting phenolic resin.
6. The method for preparing the water-based self-dispersing thermosetting phenol-formaldehyde resin according to claim 5, characterized in that: the formaldehyde feeding adopts a metering feeding atomization nozzle, and the diameter of atomized particles is 3-10 mu m.
7. The method for preparing the water-based self-dispersing thermosetting phenol-formaldehyde resin according to claim 6, characterized in that: 3 ~ 4 of atomizer equipartition, load 200 ~ 400L/h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711305712.4A CN108047404B (en) | 2017-12-11 | 2017-12-11 | Water-based self-dispersion thermosetting phenolic resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711305712.4A CN108047404B (en) | 2017-12-11 | 2017-12-11 | Water-based self-dispersion thermosetting phenolic resin and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108047404A CN108047404A (en) | 2018-05-18 |
| CN108047404B true CN108047404B (en) | 2020-12-22 |
Family
ID=62123741
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711305712.4A Active CN108047404B (en) | 2017-12-11 | 2017-12-11 | Water-based self-dispersion thermosetting phenolic resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108047404B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6476119B1 (en) * | 1998-01-27 | 2002-11-05 | Lord Corporation | Aqueous primer or coating |
| CN101177471A (en) * | 2007-12-12 | 2008-05-14 | 谢建军 | Method for producing phenol resin |
| CN103012704A (en) * | 2011-12-31 | 2013-04-03 | 柯美达（北京）科技有限公司 | Preparation method of toughening thermoset phenolic resin |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5239412B2 (en) * | 1973-02-06 | 1977-10-05 | ||
| JPH03137045A (en) * | 1989-10-20 | 1991-06-11 | Kao Corp | Cement dispersant |
| CN101880367B (en) * | 2010-08-03 | 2012-07-25 | 山东圣泉化工股份有限公司 | Method for preparing high-ortho thermoplastic phenolic resin |
| CN102174273B (en) * | 2011-03-08 | 2013-07-10 | 延边石岘白麓纸业股份有限公司 | Method for preparing lignin sulfonate dye dispersant |
| CN107236500A (en) * | 2016-03-29 | 2017-10-10 | 中国林业科学研究院林产化学工业研究所 | The preparation method of lignin sulfonate modified urea-phenolic resin |
| CN106085313A (en) * | 2016-06-13 | 2016-11-09 | 北京林业大学 | A kind of thermosetting high adjacent position phenolic resin adhesive and preparation method thereof |
-
2017
- 2017-12-11 CN CN201711305712.4A patent/CN108047404B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6476119B1 (en) * | 1998-01-27 | 2002-11-05 | Lord Corporation | Aqueous primer or coating |
| CN101177471A (en) * | 2007-12-12 | 2008-05-14 | 谢建军 | Method for producing phenol resin |
| CN103012704A (en) * | 2011-12-31 | 2013-04-03 | 柯美达（北京）科技有限公司 | Preparation method of toughening thermoset phenolic resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108047404A (en) | 2018-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2191802A (en) | Preparation of fusible ketonealdehyde synthetic resins | |
| CN103289604B (en) | A kind of containing attapulgite modified hot melt adhesive and preparation method thereof | |
| US5969071A (en) | Method for preparing phenolic rosin resins | |
| CN109943197A (en) | A kind of water-based antirusting paint operable with rust and preparation method thereof | |
| CN108047404B (en) | Water-based self-dispersion thermosetting phenolic resin and preparation method thereof | |
| US3896081A (en) | Rapid curing resin compositions employing aminoplast condensation polymer modified with a di-substituted bis-aryl amine | |
| CN103289606B (en) | A kind of Hot-melt adhesives for shoemaking and preparation method thereof | |
| CN101977983A (en) | Composition comprising a blend of resins | |
| CN109569441A (en) | A kind of method of reactor and serialization preparation small molecule polyetheramine | |
| CN101497680A (en) | Alcohol water-soluble copolymer resin, preparation and application thereof | |
| CN102504158B (en) | Cement grinding aid reinforcing agent and preparation method thereof | |
| CN102993978A (en) | Preparation method of polymerized rosin zinc salt | |
| AU2005310347A1 (en) | Hydroxy-aromatic compound, process for the preparation thereof, and use of the compound | |
| CN103154063B (en) | The preparation method of the reaction product of ring urea and multifunctional aldehyde | |
| CN107880710B (en) | High-temperature-resistant water-based adhesive | |
| CN102060964B (en) | Preparation method and application of amino acrylic resin | |
| CN113956443B (en) | Indole structure-containing cashew phenol aldehyde amine epoxy resin curing agent and preparation method thereof | |
| CN104804194B (en) | The preparation of poly- titanium Borosiloxane and the method for modifying to phenolic resin | |
| CN102134280A (en) | Biomass phenolic resin and preparation thereof | |
| CN102898884A (en) | Environment-friendly cashew amine epoxy curing agent for low volatile organic compound (VOC) anticorrosive coating and preparation method for curing agent | |
| US3931110A (en) | Rapid curing adhesive compositions comprising the reaction product of a ketone aldehyde condensation polymer and a primary aromatic amine | |
| CN107325486A (en) | A kind of nano-material modified multi-functional Lauxite composite and preparation method thereof | |
| CN114249881B (en) | Solvent-free cashew phenol aldehyde amine epoxy resin curing agent containing thiazole structure and preparation method thereof | |
| CN101104672A (en) | High-performance modified phenolic resin and its producing process | |
| CN101875754B (en) | Environmental-friendly type dextrin modified phenolic 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 |