CN108047404A - A kind of water base self-dispersion type thermosetting phenolic resin and preparation method thereof - Google Patents
A kind of water base self-dispersion type thermosetting phenolic resin and preparation method thereof Download PDFInfo
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- CN108047404A CN108047404A CN201711305712.4A CN201711305712A CN108047404A CN 108047404 A CN108047404 A CN 108047404A CN 201711305712 A CN201711305712 A CN 201711305712A CN 108047404 A CN108047404 A CN 108047404A
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- phenolic resin
- phenol
- water
- water base
- dispersion type
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 45
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 42
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 42
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000006185 dispersion Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 123
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007921 spray Substances 0.000 claims abstract description 20
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims abstract description 17
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 17
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000009833 condensation Methods 0.000 claims description 24
- 230000005494 condensation Effects 0.000 claims description 24
- 238000010792 warming Methods 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 238000006068 polycondensation reaction Methods 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 238000007792 addition Methods 0.000 claims description 13
- 230000018044 dehydration Effects 0.000 claims description 11
- 238000006297 dehydration reaction Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 229920001169 thermoplastic Polymers 0.000 claims description 11
- 239000004416 thermosoftening plastic Substances 0.000 claims description 11
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- JRNGUTKWMSBIBF-UHFFFAOYSA-N naphthalene-2,3-diol Chemical compound C1=CC=C2C=C(O)C(O)=CC2=C1 JRNGUTKWMSBIBF-UHFFFAOYSA-N 0.000 claims description 9
- 239000001103 potassium chloride Substances 0.000 claims description 9
- 235000011164 potassium chloride Nutrition 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 5
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 5
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000008098 formaldehyde solution Substances 0.000 claims description 2
- -1 is catalyzed Chemical compound 0.000 claims description 2
- DOBIZWYVJFIYOV-UHFFFAOYSA-N 7-hydroxynaphthalene-1,3-disulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C(S(O)(=O)=O)C2=CC(O)=CC=C21 DOBIZWYVJFIYOV-UHFFFAOYSA-N 0.000 claims 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims 2
- 150000003839 salts Chemical class 0.000 claims 2
- 208000005156 Dehydration Diseases 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 25
- 239000011347 resin Substances 0.000 abstract description 25
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 229910000831 Steel Inorganic materials 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000010959 steel Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000010790 dilution Methods 0.000 description 9
- 239000012895 dilution Substances 0.000 description 9
- PJKVFARRVXDXAD-UHFFFAOYSA-N 2-naphthaldehyde Chemical compound C1=CC=CC2=CC(C=O)=CC=C21 PJKVFARRVXDXAD-UHFFFAOYSA-N 0.000 description 7
- 235000013904 zinc acetate Nutrition 0.000 description 7
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical class [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 6
- 239000007788 liquid Substances 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- LZMCUTZPLPUFMB-UHFFFAOYSA-L dihydroxy(oxo)manganese Chemical class O[Mn](O)=O LZMCUTZPLPUFMB-UHFFFAOYSA-L 0.000 description 2
- 229920003987 resole Polymers 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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 invention belongs to high polymer material fields.Naphthol sulfonate is introduced on molecular resin main chain, it is water-soluble to assign resin system；Using phenol and the mixed system of naphthol sulfonate, synthesized under bivalent metal ion catalysts conditions.Water base self-dispersion type thermosetting phenolic resin of the present invention, is catalyzed, formaldehyde sprays and feeds intake in batches using bivalent metal ion, and naphthol sulfonate is contained in material system, and material composition includes：1 molar part of phenol, naphthol sulfonate are the 10~20% of phenol, and phenol/formaldehyde molar ratio is 1：1.5~2.0,14~24 mass parts of water, 0.5~5 mass parts of bivalent metal ion catalyst.Water base self-dispersion type thermosetting phenolic resin of the present invention, water dispersible is good, and storage stability is good, caking property and temperature tolerance higher, it is suitable as high shear strength, heat safe water base thermoset structure adhesive, the bonding particularly suitable for phenolic composite in brake block and steel.
Description
Technical field
The invention belongs to high polymer material field, it is related to the synthesis skill of polymer synthesis techniques, more particularly to phenolic resin
Art.
Background technology
Water dispersible phenolic resin is a kind of phenolic resin that can form stable homogeneous liquid dispersed phase in water, is stablized
Property is good, and during storage, appearance, viscosity, water-thinned remain unchanged, and volatile contaminant discharge capacity is small, by from polycondensation or
It adds waterborne curing agent to cure, high crosslink density and adhesion strength can be obtained, as adhesive in use, solvent can be substituted
Type phenolic resin bonds timber, metal, plastics etc..
US6130289 describes a kind of technology of preparing of self-emulsifying resol dispersion liquid.Using in water-soluble first
Introduced in rank phenolic resin containing phenolic resin can reactive functionality modifying agent, sulfonic group, sulphur are contained in the modifying agent side group
The sulfur-containing groups such as acidic group react into sticky opaque liquid at a certain temperature, after filtering grumeleuse, obtain translucent phenolic resin
Dispersion liquid.But this preparation method, it is to be modified on the basis of previously prepared water-soluble resol, in modification
During, there are polycondensation reaction between water-soluble A-stage resin, there is partial gel appearance, finished product rate reduces, Er Qiexu
Want two steps that could complete, preparation process is complicated, and cost is higher.
The content of the invention
The technical problems to be solved by the invention are to provide that a kind of molecular structure is controllable, molecular chain length, water dispersible are good, cut
Good environment protection water-based self-dispersion type thermosetting phenolic resin of shearing stress height, high temperature resistant, resistance to ag(e)ing and preparation method thereof.
The object of the present invention is achieved like this：In a manner of introducing naphthol sulfonate on molecular resin main chain, assign
Resin system is water-soluble；Using phenol and the mixed system of naphthol sulfonate, under bivalent metal ion catalyst action, by naphthalene
Sulfocarbolate is introduced into the molecular backbone of phenolic resin, and it is water-soluble to improve resin.
Water base self-dispersion type thermosetting phenolic resin of the present invention, be catalyzed using bivalent metal ion, formaldehyde in batches
Spraying feeds intake, and naphthol sulfonate is contained in material system, and material composition includes：
1 molar part of phenol, naphthol sulfonate are the 10~20% of phenol, and phenol/formaldehyde molar ratio is 1：1.5~2.0, water 14~
24 mass parts, 0.5~5 mass parts of bivalent metal ion catalyst.
Water base self-dispersion type thermosetting phenolic resin of the present invention, be catalyzed using bivalent metal ion, formaldehyde in batches
Spraying feeds intake, and naphthol sulfonate is contained in material system, and material composition includes：
1 molar part of phenol, naphthol sulfonate are the 13~17% of phenol, and phenol/formaldehyde molar ratio is 1：1.6~1.7, water 17~
21 mass parts, 2~4 mass parts of bivalent metal ion catalyst.
Water base self-dispersion type thermosetting phenolic resin of the present invention, the naphthol sulfonate are beta naphthal -6,8-
The double sylvite of disulfonic acid, one kind in 2,3- dihydroxy naphthlene -6- sodium sulfonates or its combination.
Water base self-dispersion type thermosetting phenolic resin of the present invention, the bivalent metal ion catalyst are hydrogen-oxygen
Change the combination of one or more of manganese, cobalt hydroxide, barium hydroxide, zinc acetate.
The preparation method of water base self-dispersion type thermosetting phenolic resin of the present invention, using formaldehyde is sprayed and fed intake in batches
Technique, including dispensing, one section of polycondensation, two sections of additions and dehydrating condensation process, it is characterised in that：
（1）Dispensing：Phenol, naphthol sulfonate, water, bivalent metal ion catalyst by proportion are added to reaction kettle, disperseed equal
It is even；
（2）One section of polycondensation：Stirring, is warming up to 85~90 DEG C, by formaldehyde and phenol molar ratio 1~1.05：1, it is even by atomizing
Speed adds in formalin to reaction kettle, reacts 1~2h, obtains high-ortho thermoplastic performed polymer；
（3）Two sections of additions：98~100 DEG C, in whipping process are warming up to, atomizing at the uniform velocity adds in residual formaldehyde solution, reaction 0.5
~1h obtains thermosetting property performed polymer；
（4）Dehydrating condensation：60~80 DEG C of vacuum dehydration condensations, polymerization speed reach 300~350 seconds（150±1℃）, obtain water
Base self-dispersing thermosetting phenolic resin.
The preparation method of water base self-dispersion type thermosetting phenolic resin of the present invention, formaldehyde charging is using metered charge
Atomizer, a diameter of 3~10 μm of atomizing particle.
The preparation method of water base self-dispersion type thermosetting phenolic resin of the present invention, uniformly distributed 3~4 metered charge mists
Change nozzle, 200~400L/h of load.
Water base self-dispersion type thermosetting phenolic resin of the present invention, molecular resin chain length, naphthol sulfonate are distributed in
In molecular backbone structure, water dispersible is good, and storage stability is good, and solidification crosslinking degree is high, and caking property and temperature tolerance higher are suitble to
As high shear strength, heat safe water base thermoset structure adhesive, particularly suitable for phenolic composite in brake block
With the bonding of steel.
Water base self-dispersion type thermosetting phenolic resin preparation method of the present invention, reacting balance is easily controllable, is not easy
Generation gel；Molecular structure and reaction process controllability are strong, and product quality uniformity is high.
Specific embodiment
With reference to embodiment, the invention will be further described, but not as the limitation to technical solution.
Embodiment 1
（1）Dispensing：By 94Kg (1000mol) phenol, the double sylvite of 38Kg (100mol) beta naphthals -6,8- disulfonic acid, 14Kg water,
0.5Kg manganous hydroxides are added to reaction kettle, are uniformly dispersed；
（2）One section of polycondensation：Stirring, is warming up to 85 DEG C, 80Kg formaldehyde is at the uniform velocity added in by 3 metered charge atomizer atomizings
Solution (formaldehyde 30Kg（1000mol）), spray load 200L/h, then a diameter of 3~6 μm of atomizing particle reacts 1h, obtains
High-ortho thermoplastic performed polymer；
（3）Two sections of additions：98 DEG C, in whipping process are warming up to, atomizing at the uniform velocity adds in 40Kg formalins（Formaldehyde 15Kg
（500mol））, spray load 200L/h, then a diameter of 3~6 μm of atomizing particle reacts 0.5h, obtains thermosetting property pre-polymerization
Body；
（4）Dehydrating condensation：78 DEG C of vacuum dehydration condensations, polymerization speed reach 300S（150℃）, reaction terminates, obtain it is water base from
Scattered thermosetting phenolic resin.
The resin is viscous light yellow transparent resin, and the viscosity of 50% aqueous solution is 210mPaS, and water dispersible is good, and water can
95 times of dilution ratio, room temperature shear strength 12.6MPa, 300 DEG C of shear strength 2.8MPa.
Embodiment 2
（1）Dispensing：By 94Kg (1000mol) phenol, the double sylvite of 57Kg (150mol) beta naphthals -6,8- disulfonic acid, 15Kg water,
2Kg cobalt hydroxides are added to reaction kettle, are uniformly dispersed；
（2）One section of polycondensation：Stirring, is warming up to 87 DEG C, 84Kg formaldehyde is at the uniform velocity added in by 3 metered charge atomizer atomizings
Solution (formaldehyde 31.5Kg（1050mol）), spray load 400L/h, then a diameter of 5~10 μm of atomizing particle reacts 2h,
Obtain high-ortho thermoplastic performed polymer；
（3）Two sections of additions：98 DEG C, in whipping process are warming up to, atomizing at the uniform velocity adds in 76Kg formalins（Formaldehyde 28.5Kg
（950mol））, spray load 350L/h, then a diameter of 5~10 μm of atomizing particle reacts 1h, obtains thermosetting property performed polymer；
（4）Dehydrating condensation：80 DEG C of vacuum dehydration condensations, polymerization speed reach 315S（149℃）, reaction terminates, obtain it is water base from
Scattered thermosetting phenolic resin.
The resin is viscous light yellow transparent resin, and the viscosity of 50% aqueous solution is 254mPaS, and water dispersible is good, and water can
100 times of dilution ratio, room temperature shear strength 13.5MPa.
Embodiment 3
（1）Dispensing：By 94Kg (1000mol) phenol, the double sylvite of 76Kg (200mol) beta naphthals -6,8- disulfonic acid, 24Kg water,
5Kg barium hydroxides are added to reaction kettle, are uniformly dispersed；
（2）One section of polycondensation：Stirring, is warming up to 90 DEG C, 81Kg formaldehyde is at the uniform velocity added in by 3 metered charge atomizer atomizings
Solution (formaldehyde 30.375Kg（1012.5mol）), spray load 220L/h, then a diameter of 7~10 μm of atomizing particle reacts
1h obtains high-ortho thermoplastic performed polymer；
（3）Two sections of additions：100 DEG C, in whipping process are warming up to, atomizing at the uniform velocity adds in 50Kg formalins（Formaldehyde 18.75Kg
（625mol））, spray load 300L/h, then a diameter of 7~10 μm of atomizing particle reacts 0.5h, obtains thermosetting property pre-polymerization
Body；
（4）Dehydrating condensation：75 DEG C of vacuum dehydration condensations, polymerization speed reach 320S（151℃）, reaction terminates, obtain it is water base from
Scattered thermosetting phenolic resin.
The resin is viscous light yellow transparent resin, and the viscosity of 50% aqueous solution is 267mPaS, and water dispersible is good, and water can
124 times of dilution ratio, 300 DEG C of shear strength 3.3MPa.
Embodiment 4
（1）Dispensing：By 94Kg (1000mol) phenol, 34.06Kg (130mol) 2,3- dihydroxy naphthlene -6- sodium sulfonates, 17Kg water,
2.5Kg zinc acetates are added to reaction kettle, are uniformly dispersed；
（2）One section of polycondensation：Stirring, is warming up to 86 DEG C, 81.6Kg first is at the uniform velocity added in by 4 metered charge atomizer atomizings
Aldehyde solution (formaldehyde 30.6Kg（1020mol）), spray load 320L/h, then a diameter of 3~6 μm of atomizing particle reacts
1.4h obtains high-ortho thermoplastic performed polymer；
（3）Two sections of additions：99 DEG C, in whipping process are warming up to, atomizing at the uniform velocity adds in 46.4Kg formalins（Formaldehyde 17.4Kg
（580mol））, spray load 360L/h, then a diameter of 3~6 μm of atomizing particle reacts 0.6h, obtains thermosetting property pre-polymerization
Body；
（4）Dehydrating condensation：70 DEG C of vacuum dehydration condensations, polymerization speed reach 335S（150℃）, reaction terminates, obtain it is water base from
Scattered thermosetting phenolic resin.
The resin is viscous light yellow transparent resin, and the viscosity of 50% aqueous solution is 290mPaS, and water dispersible is good, and water can
152 times of dilution ratio, room temperature shear strength 14.3MPa, 300 DEG C of shear strength 3.5MPa.
Embodiment 5
（1）Dispensing：By 94Kg (1000mol) phenol, 39.3Kg (150mol) 2,3- dihydroxy naphthlene -6- sodium sulfonates, 21Kg water,
1Kg zinc acetates are added to reaction kettle, are uniformly dispersed；
（2）One section of polycondensation：Stirring, is warming up to 85 DEG C, 82Kg formaldehyde is at the uniform velocity added in by 4 metered charge atomizer atomizings
Solution (formaldehyde 30.75Kg（1025mol）), spray load 350L/h, then a diameter of 7~10 μm of atomizing particle reacts
1.5h obtains high-ortho thermoplastic performed polymer；
（3）Two sections of additions：100 DEG C, in whipping process are warming up to, atomizing at the uniform velocity adds in 73Kg formalins（Formaldehyde
27.375Kg（912.5mol））, spray load 360L/h, then a diameter of 7~10 μm of atomizing particle reacts 1h, obtains heat
Solidity performed polymer；
（4）Dehydrating condensation：65 DEG C of vacuum dehydration condensations, polymerization speed reach 350S（150.5℃）, reaction terminates, obtains water base
Self-dispersing thermosetting phenolic resin.
The resin is viscous light yellow transparent resin, and the viscosity of 50% aqueous solution is 325mPaS, and water dispersible is good, and water can
179 times of dilution ratio, room temperature shear strength 14.8MPa.
Embodiment 6
（1）Dispensing：By 94Kg (1000mol) phenol, 44.54Kg (170mol) 2,3- dihydroxy naphthlene -6- sodium sulfonates, 20Kg water,
1.5Kg zinc acetates, 2Kg barium hydroxides are added to reaction kettle, are uniformly dispersed；
（2）One section of polycondensation：Stirring, is warming up to 87 DEG C, 82.4Kg first is at the uniform velocity added in by 3 metered charge atomizer atomizings
Aldehyde solution (formaldehyde 30.9Kg（1030mol）), spray load 370L/h, then a diameter of 3~6 μm of atomizing particle reacts
1.6h obtains high-ortho thermoplastic performed polymer；
（3）Two sections of additions：99 DEG C, in whipping process are warming up to, atomizing at the uniform velocity adds in 53.6Kg formalins（Formaldehyde 20.1Kg
（670mol））, spray load 370L/h, then a diameter of 3~6 μm of atomizing particle reacts 0.8h, obtains thermosetting property pre-polymerization
Body；
（4）Dehydrating condensation：78 DEG C of vacuum dehydration condensations, polymerization speed reach 321S（149℃）, reaction terminates, obtain it is water base from
Scattered thermosetting phenolic resin.
The resin is viscous light yellow transparent resin, and the viscosity of 50% aqueous solution is 270mPaS, and water dispersible is good, and water can
178 times of dilution ratio, room temperature shear strength 13.8MPa.
Embodiment 7
（1）Dispensing：By 94Kg (1000mol) phenol, 19Kg (50mol) beta naphthals -6,8- disulfonic acid double sylvite, 15.72Kg
(60mol) 2,3- dihydroxy naphthlene -6- sodium sulfonates, 18Kg water, 4Kg zinc acetates are added to reaction kettle, are uniformly dispersed；
（2）One section of polycondensation：Stirring, is warming up to 88 DEG C, 82Kg formaldehyde is at the uniform velocity added in by 3 metered charge atomizer atomizings
Solution (formaldehyde 30.75Kg（1025mol）), spray load 210L/h, then a diameter of 3~6 μm of atomizing particle reacts
1.5h obtains high-ortho thermoplastic performed polymer；
（3）Two sections of additions：100 DEG C, in whipping process are warming up to, atomizing at the uniform velocity adds in 45Kg formalins（Formaldehyde
16.875Kg（562.5mol））, spray load 200L/h, then a diameter of 3~6 μm of atomizing particle reacts 0.8h, obtains heat
Solidity performed polymer；
（4）Dehydrating condensation：76 DEG C of vacuum dehydration condensations, polymerization speed reach 334S（150℃）, reaction terminates, obtain it is water base from
Scattered thermosetting phenolic resin.
The resin is viscous light yellow transparent resin, and the viscosity of 50% aqueous solution is 285mPaS, and water dispersible is good, and water can
121 times of dilution ratio, 300 DEG C of shear strength 3.4MPa.
Embodiment 8
（1）Dispensing：By 94Kg (1000mol) phenol, 38Kg (100mol) beta naphthals -6,8- disulfonic acid double sylvite, 15.72Kg
(60mol) 2,3- dihydroxy naphthlene -6- sodium sulfonates, 17.5Kg water, 1Kg zinc acetates, 1.6Kg cobalt hydroxides are added to reaction kettle, point
It dissipates uniform；
（2）One section of polycondensation：Stirring, is warming up to 88 DEG C, 81.5Kg first is at the uniform velocity added in by 3 metered charge atomizer atomizings
Aldehyde solution (formaldehyde 30.5625Kg（1018.75mol）), spray load 280L/h, a diameter of 7~10 μm of atomizing particle, then
1h is reacted, obtains high-ortho thermoplastic performed polymer；
（3）Two sections of additions：99 DEG C, in whipping process are warming up to, atomizing at the uniform velocity adds in 55Kg formalins（Formaldehyde 20.625Kg
（687.5mol））, spray load 200L/h, then a diameter of 7~10 μm of atomizing particle reacts 0.75h, it is pre- to obtain thermosetting property
Aggressiveness；
（4）Dehydrating condensation：75 DEG C of vacuum dehydration condensations, polymerization speed reach 318S（151℃）, reaction terminates, obtain it is water base from
Scattered thermosetting phenolic resin.
The resin is viscous light yellow transparent resin, and the viscosity of 50% aqueous solution is 258mPaS, and water dispersible is good, and water can
108 times of dilution ratio, room temperature shear strength 13.6MPa.
Embodiment 9
（1）Dispensing：By 94Kg (1000mol) phenol, 28.5Kg (75mol) beta naphthals -6,8- disulfonic acid double sylvite, 26.2Kg
(100mol) 2,3- dihydroxy naphthlene -6- sodium sulfonates, 20Kg water, 1Kg zinc acetates, 2.2Kg manganous hydroxides are added to reaction kettle, disperse
Uniformly；
（2）One section of polycondensation：Stirring, is warming up to 88 DEG C, 80Kg formaldehyde is at the uniform velocity added in by 3 metered charge atomizer atomizings
Solution (formaldehyde 30Kg（1000mol）), spray load 330L/h, then a diameter of 3~6 μm of atomizing particle reacts 1.3h, obtains
To high-ortho thermoplastic performed polymer；
（3）Two sections of additions：99 DEG C, in whipping process are warming up to, atomizing at the uniform velocity adds in 66Kg formalins（Formaldehyde 24.75Kg
（825mol））, spray load 220L/h, then a diameter of 3~6 μm of atomizing particle reacts 1h, obtains thermosetting property performed polymer；
（4）Dehydrating condensation：60 DEG C of vacuum dehydration condensations, polymerization speed reach 309S（149℃）, reaction terminates, obtain it is water base from
Scattered thermosetting phenolic resin.
The resin is viscous light yellow transparent resin, and the viscosity of 50% aqueous solution is 228mPaS, and water dispersible is good, and water can
136 times of dilution ratio, 300 DEG C of shear strength 2.9MPa.
Claims (9)
1. a kind of water base self-dispersion type thermosetting phenolic resin, is catalyzed, formaldehyde sprays and feeds intake in batches, object using bivalent metal ion
Contain naphthol sulfonate in material system, material composition is：
1 molar part of phenol, naphthol sulfonate are the 10~20% of phenol, and phenol/formaldehyde molar ratio is 1：1.5~2.0, water 14~
24 mass parts, 0.5~5 mass parts of bivalent metal ion catalyst.
2. water base self-dispersion type thermosetting phenolic resin according to claim 1, it is characterised in that：Material forms：
1 molar part of phenol, naphthol sulfonate are the 13~17% of phenol, and phenol/formaldehyde molar ratio is 1：1.6~1.7, water 17~
21 mass parts, 2~4 mass parts of bivalent metal ion catalyst.
3. water base self-dispersion type thermosetting phenolic resin according to claim 1, it is characterised in that：The naphtholsulfonic acid
Salt is the double sylvite of 2-naphthol-6,8-disulfonic acid, one kind in 2,3- dihydroxy naphthlene -6- sodium sulfonates or its combination.
4. water base self-dispersion type thermosetting phenolic resin according to claim 2, it is characterised in that：The naphtholsulfonic acid
Salt is the double sylvite of 2-naphthol-6,8-disulfonic acid, one kind in 2,3- dihydroxy naphthlene -6- sodium sulfonates or its combination.
5. water base self-dispersion type thermosetting phenolic resin according to claim 1, it is characterised in that：The divalent metal
Ionic catalyst is the combination of one or more of manganous hydroxide, cobalt hydroxide, barium hydroxide, zinc acetate.
6. water base self-dispersion type thermosetting phenolic resin according to claim 2, it is characterised in that：The divalent metal
Ionic catalyst is the combination of one or more of manganous hydroxide, cobalt hydroxide, barium hydroxide, zinc acetate.
7. the preparation method of the water base self-dispersion type thermosetting phenolic resin according to claim 1~6 any one uses
Formaldehyde is sprayed charging technology in batches, including dispensing, one section of polycondensation, two sections of additions and dehydrating condensation process, it is characterised in that：
Dispensing：Phenol, naphthol sulfonate, water, bivalent metal ion catalyst by proportion are added to reaction kettle, are uniformly dispersed；
One section of polycondensation：Stirring, is warming up to 85~90 DEG C, by formaldehyde and phenol molar ratio 1~1.05：1, at the uniform velocity added by atomizing
Enter formalin to reaction kettle, react 1~2h, obtain high-ortho thermoplastic performed polymer；
Two sections of additions：It is warming up to 98~100 DEG C, in whipping process, atomizing at the uniform velocity adds in residual formaldehyde solution, reaction 0.5~
1h obtains thermosetting property performed polymer；
Dehydrating condensation：60~80 DEG C of vacuum dehydrations condensation, polymerization speed reach 300~350 seconds/150 ± 1 DEG C, obtain it is water base from
Scattered thermosetting phenolic resin.
8. the preparation method of water base self-dispersion type thermosetting phenolic resin according to claim 7, it is characterised in that：Formaldehyde
Charging is using metered charge atomizer, a diameter of 3~10 μm of atomizing particle.
9. the preparation method of water base self-dispersion type thermosetting phenolic resin according to claim 8, it is characterised in that：It is described
Atomizer is 3~4 uniformly distributed, 200~400L/h of load.
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