CN105921686B - A kind of 3D molding sand printing chill phenolic resin and preparation method thereof - Google Patents
A kind of 3D molding sand printing chill phenolic resin and preparation method thereof Download PDFInfo
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- CN105921686B CN105921686B CN201610431421.9A CN201610431421A CN105921686B CN 105921686 B CN105921686 B CN 105921686B CN 201610431421 A CN201610431421 A CN 201610431421A CN 105921686 B CN105921686 B CN 105921686B
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- phenol
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- 239000003110 molding sand Substances 0.000 title claims abstract description 52
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 52
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 49
- 238000007639 printing Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 42
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims abstract description 42
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 22
- 239000004677 Nylon Substances 0.000 claims abstract description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910000410 antimony oxide Inorganic materials 0.000 claims abstract description 21
- 150000004702 methyl esters Chemical class 0.000 claims abstract description 21
- 229920001778 nylon Polymers 0.000 claims abstract description 21
- 239000003208 petroleum Substances 0.000 claims abstract description 21
- 235000011056 potassium acetate Nutrition 0.000 claims abstract description 21
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims abstract description 20
- 229940106691 bisphenol a Drugs 0.000 claims abstract description 20
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 20
- 229930195729 fatty acid Natural products 0.000 claims abstract description 20
- 239000000194 fatty acid Substances 0.000 claims abstract description 20
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 20
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003849 aromatic solvent Substances 0.000 claims abstract description 19
- 229940046892 lead acetate Drugs 0.000 claims abstract description 19
- ZJTLZYDQJHKRMQ-UHFFFAOYSA-N menadiol Chemical compound C1=CC=CC2=C(O)C(C)=CC(O)=C21 ZJTLZYDQJHKRMQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 15
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 11
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims abstract description 6
- 150000001896 cresols Chemical class 0.000 claims abstract 4
- 238000003756 stirring Methods 0.000 claims description 31
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 30
- 238000010792 warming Methods 0.000 claims description 24
- 230000018044 dehydration Effects 0.000 claims description 19
- 238000006297 dehydration reaction Methods 0.000 claims description 19
- 238000009413 insulation Methods 0.000 claims description 19
- 238000007664 blowing Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 210000003298 dental enamel Anatomy 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 8
- -1 neopelex Chemical compound 0.000 claims description 8
- 238000004806 packaging method and process Methods 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 4
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 claims 1
- 238000005266 casting Methods 0.000 abstract description 14
- 239000000853 adhesive Substances 0.000 abstract description 11
- 230000001070 adhesive effect Effects 0.000 abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001208 Crucible steel Inorganic materials 0.000 abstract description 5
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 3
- 230000007812 deficiency Effects 0.000 abstract description 2
- 125000000853 cresyl group Chemical class C1(=CC=C(C=C1)C)* 0.000 description 17
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 239000004576 sand Substances 0.000 description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920006324 polyoxymethylene Polymers 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000010146 3D printing Methods 0.000 description 3
- 206010039509 Scab Diseases 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 210000003462 vein Anatomy 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910021652 non-ferrous alloy Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
Abstract
The present invention relates to casting auxiliary material field, and in particular to a kind of 3D molding sand printing chill phenolic resin and preparation method thereof.The 3D molding sand is printed with the chemical composition of chill phenolic resin：Phenol, cresols, bisphenol-A, paraformaldehyde, acetaldehyde, antimony oxide, tricresyl phosphate, aromatic solvent naphtha, nylon acid methyl esters, petroleum ether, fatty acid sorbitan, neopelex, lead acetate, potassium acetate, dimethylaminopropylamine, methylnaphthohydroquinone.The purpose of the present invention is overcome the deficiencies in the prior art, is developed a kind of suitable for the low viscosity in large complicated accurate casting iron field and cast steel field, high activity, high intensity, high carbon residue, the chill phenolic resin adhesive of resistant to elevated temperatures new 3D molding sand printing.
Description
Technical field
The present invention relates to casting auxiliary material field, and in particular to a kind of printing of 3D molding sand chill phenolic resin and its system
Preparation Method.
Background technology
3 D-printing（Three Dimensional Printing, 3DP) proposed by E. Sachs et al. in 1992, be
According to ink-jet printer principle, material droplet is ejected from nozzle, by certain path successively curing molding.
At present, the 3D molding sand printing that casting industry generally uses with binding agent be furane resins, inorganic salts binding agent and
Three kinds of thermmohardening phenolic resin.Although furane resins binding agent can realize normal temperature rapid curing, meet industrial 3D molding sand printing
Main technique requirements, but because its normal temperature strength is relatively low, resistance to elevated temperatures is poor, cause later stage casting scab and arteries and veins when pouring into a mould
Line defect is serious, and what this defect showed when pouring into a mould thin wall steel-casting is especially apparent, and limits furane resins binding agent and exists
The further development in industrial 3D molding sand printing field.
On the other hand, although inorganic salts binding agent has the advantages of its is unique in nonferrous alloy casting field, due to nothing
Machine salt adhesive strength is relatively low, resistance to elevated temperatures is poor, limits it in large complicated accurate casting iron field and cast steel field
Development.
Thermmohardening phenolic resin has excellent resistance to elevated temperatures and higher adhesion strength, can solve furane resins by
In resistance to elevated temperatures difference and the casting scab brought and vein defect.But due to its special hardening process, needed in print procedure
Printer casing is wanted to maintain 80-100 DEG C of high temperature, prolonged high temperature can cause the printer module lost of life, change component
The rising of production cost and the decline of production efficiency can be caused.Meanwhile hot environment can also limit the operability of field worker,
Increase operational risk.Another aspect thermmohardening phenolic resin needs the special 3D molding sand printer with heating system, can not be with furan
3D molding sand printers used in furane resins and inorganic salts binding agent are general, and generalization is poor.At present, the country there is no production 3D molding sand
The enterprise of the chill phenolic resin adhesive of printing.
Therefore, develop it is a kind of suitable for the low viscosity in large complicated accurate casting iron field and cast steel field, it is high activity, high-strength
Degree, high carbon residue, resistant to elevated temperatures new 3D molding sand printing are that whole industrial 3D molding sand prints industry with chill phenolic resin adhesive
The problem paid close attention to jointly.
The content of the invention
In view of the shortcomings of the prior art, it is applied to large complicated accurate casting iron field the invention provides one kind and cast steel is led
The low viscosity in domain, high activity, high intensity, high carbon residue, the chill phenolic resin adhesive of resistant to elevated temperatures new 3D molding sand printing.
In order to solve the above-mentioned technical problem, the technical solution that uses of the present invention is：
A kind of chill phenolic resin of 3D molding sand printing, it is characterised in that including：Phenol, cresols, bisphenol-A, poly first
Aldehyde, acetaldehyde, antimony oxide, tricresyl phosphate, aromatic solvent naphtha, nylon acid methyl esters, petroleum ether, fatty acid sorbitan, ten
Dialkyl benzene sulfonic acids sodium, lead acetate, potassium acetate, dimethylaminopropylamine and methylnaphthohydroquinone.
Further, the mass percent of above chemical constituent is respectively：Phenol 12-28%, cresols 1.5-4.5%, bisphenol-A
5-11%, paraformaldehyde 1-5%, acetaldehyde 0.5-2.5%, antimony oxide 0.4-0.8%, tricresyl phosphate 0.4-0.8%, aromatic hydrocarbons
Solvent naphtha 15-65%, nylon acid methyl esters 6-18%, petroleum ether 4-14%, fatty acid sorbitan 0.2-0.6%, DBSA
Sodium 0.2-0.6%, lead acetate 0.1-0.3%, potassium acetate 0.1-0.3%, dimethylaminopropylamine 0.3-0.9%, methylnaphthohydroquinone 0.2-
0.8%。
Further, in the chemical constituent, phenol, cresols, bisphenol-A, paraformaldehyde and acetaldehyde are anti-as phenolic resin
The raw matrix materials answered, antimony oxide and tricresyl phosphate are as fire retardant, fatty acid sorbitan and detergent alkylate sulphur
Sour sodium is as surfactant, and aromatic solvent naphtha, nylon acid methyl esters and petroleum ether are as solvent, and lead acetate and potassium acetate are as cold
The catalyst of hard phenolic resin addition reaction and polycondensation reaction, dimethylaminopropylamine is as hardening catalyst, methylnaphthohydroquinone conduct
High-efficiency polymerization inhibitor.
Meanwhile the invention provides a kind of preparation method of the chill phenolic resin of 3D molding sand printing, it is characterised in that bag
Include following steps：
1. dissolving phenol is added in enamel reaction still, stirring is started, adds cresols, bisphenol-A, paraformaldehyde, acetaldehyde, second
Lead plumbate and potassium acetate；
2. opening steam valve, 105-115 DEG C is warming up in 30-40 minutes, timing insulation 40-70 minutes；
3. after insulation terminates, 120-135 DEG C is warming up in 10-20 minutes, 50-80 minutes are incubated；
4. after insulation terminates, 140-160 DEG C is warming up in 10-20 minutes, 60-100 minutes are incubated, normal pressure dehydration；
5. continue vacuum dehydration, until reaching standard dehydration amount；
6. being cooled to 90 DEG C, aromatic solvent naphtha, nylon acid methyl esters and petroleum ether are added, stirs 30-60 minutes；
7. being cooled to 60 DEG C, antimony oxide, tricresyl phosphate are added, stirs 15-40 minutes；
8. being cooled to 35 DEG C, fatty acid sorbitan, neopelex, dimethylaminopropylamine and methyl hydrogen are added
Quinone, stir 20-60 minutes, blowing, detection, packaging.
Beneficial effects of the present invention are as follows：
（1）3D molding sand printing viscosity ＜ 5mpa.s during 25 DEG C of chill phenolic resin adhesive, viscosity is extremely low, meets sand
Requirement of the type inkjet technology for resin viscosity.Meanwhile extremely low viscosity accelerates the jet velocity of resin, improves 3D
The operating efficiency of molding sand printer.
（2）The 3D molding sand is printed with the normal sand test block of chill phenolic resin adhesive in 1000 DEG C of hot environment,
Its tensile strength reaches more than 1.4MPa, and resistance to elevated temperatures is excellent.Under the same conditions, 3D printing is high with furan resin-sand test block
Warm tensile strength is only 0.15MPa or so, and the printing of 3D molding sand is only with hot hard phenol resin sand test block Testing Tensile Strength at Elevated Temperature
0.8MPa or so.
（3）3D molding sand printing is high with chill phenolic resin adhesive normal temperature strength, resin when reaching regulation sand mold intensity
Addition is few, reduces the cost of 3D molding sand printing production, improves the efficiency of 3D molding sand printing production.
（4）The 3D molding sand prints up time t≤1.5min with chill phenolic resin adhesive sand, up time
It is short, resin activity is high, can realize quick-hardening, improved while meeting sand mold inkjet printing requirement 3D sand molds printing
The operating efficiency of machine.
（5）3D molding sand printing compared with 3D printing furane resins, thoroughly solves 3D furans with chill phenolic resin
Resin the casting scab brought and vein defect due to resistance to elevated temperatures difference, improve casting quality.
（6）3D molding sand printing can realize normal temperature rapid curing with chill phenolic resin, solve 3D molding sand printing heat
Damage of the heat setting shaping environment of hard phenolic resin for 3D molding sand printer modules, extends 3D molding sand printer modules
Service life, reduce 3D molding sand printing production cost.
（7）3D molding sand printing is stable with chill phenolic resin system, the precipitation of long-time storage nodeless mesh, also will not be because of
Autohemagglutination and cause resin viscosity increase.
Embodiment
It is applied to large complicated accurate casting iron field and cast steel neck in view of the deficiencies of the prior art, the present invention provides a kind of
The low viscosity in domain, high activity, high intensity, high carbon residue, resistant to elevated temperatures new 3D molding sand printing with chill phenolic resin adhesive and
Its preparation method.
In order to realize goal of the invention, the present invention realizes in the following way：
The invention provides a kind of low viscosity, high activity, high intensity, high carbon residue, resistant to elevated temperatures new 3D molding sand printing to use
Chill phenolic resin adhesive, the mass percent of each chemical composition are：Phenol 12-28%, cresols 1.5-4.5%, bisphenol-A
5-11%, paraformaldehyde 1-5%, acetaldehyde 0.5-2.5%, antimony oxide 0.4-0.8%, tricresyl phosphate 0.4-0.8%, aromatic hydrocarbons
Solvent naphtha 15-65%, nylon acid methyl esters 6-18%, petroleum ether 4-14%, fatty acid sorbitan 0.2-0.6%, DBSA
Sodium 0.2-0.6%, lead acetate 0.1-0.3%, potassium acetate 0.1-0.3%, dimethylaminopropylamine 0.3-0.9%, methylnaphthohydroquinone 0.2-
0.8%.Wherein, phenol, cresols, bisphenol-A, paraformaldehyde and acetaldehyde are the raw matrix materials of reactive modified phenolic resin, anti-by addition
Phenolic resin should be generated with polycondensation reaction；Antimony oxide and tricresyl phosphate are fire retardant, suppress resin in the condition of high temperature
Under burning, improve the resistance to elevated temperatures of phenol resin sand；Fatty acid sorbitan and neopelex are surface-active
Agent, improve resin surface activity；Aromatic solvent naphtha, nylon acid methyl esters and petroleum ether are solvent, while reducing resin viscosity, are carried
High chill phenolic resin resistance to elevated temperatures；Lead acetate and the catalysis that potassium acetate is chill phenolic resin addition reaction and polycondensation reaction
Agent；Dimethylaminopropylamine is hardening catalyst, and its role is to accelerate the hardened forming speed of chill phenol resin sand；Methyl hydrogen
Quinone is high-efficiency polymerization inhibitor, prevents phenolic resin from further polymerizeing, and viscosity will not excessively increase during ensureing phenolic resin storage.
Meanwhile the invention provides a kind of 3D molding sand printing preparation method of chill phenolic resin, comprise the following steps：
1. dissolving phenol is added in enamel reaction still, stirring is started, adds cresols, bisphenol-A, paraformaldehyde, acetaldehyde, second
Lead plumbate and potassium acetate；
2. opening steam valve, 105-115 DEG C is warming up in 30-40 minutes, timing insulation 40-70 minutes；
3. after insulation terminates, 120-135 DEG C is warming up in 10-20 minutes, 50-80 minutes are incubated；
4. after insulation terminates, 140-160 DEG C is warming up in 10-20 minutes, 60-100 minutes are incubated, normal pressure dehydration；
5. continue vacuum dehydration, until reaching standard dehydration amount；
6. being cooled to 90 DEG C, aromatic solvent naphtha, nylon acid methyl esters and petroleum ether are added, stirs 30-60 minutes；
7. being cooled to 60 DEG C, antimony oxide, tricresyl phosphate are added, stirs 15-40 minutes；
8. being cooled to 35 DEG C, fatty acid sorbitan, neopelex, dimethylaminopropylamine and methyl hydrogen are added
Quinone, stir 20-60 minutes, blowing, detection, packaging.
Embodiment one
A kind of 3D molding sand is printed with the chemical composition of chill phenolic resin：Phenol 20%, cresols 3%, bisphenol-A 8%, poly
Formaldehyde 3%, acetaldehyde 1.5%, antimony oxide 0.6%, tricresyl phosphate 0.6%, aromatic solvent naphtha 40%, nylon acid methyl esters 12%,
Petroleum ether 9%, fatty acid sorbitan 0.4%, neopelex 0.4%, lead acetate 0.2%, potassium acetate 0.2%, dimethylamino
Propylamine 0.6%, methylnaphthohydroquinone 0.5%.
A kind of 3D molding sand printing preparation method of chill phenolic resin, comprises the following steps：
I, dissolvings phenol 200Kg is added in enamel reaction still, starts stirring, addition cresols 30Kg, bisphenol-A 80kg,
Paraformaldehyde 30Kg, acetaldehyde 15Kg, lead acetate 2Kg and potassium acetate 2Kg；
II, opens steam valve, 110 ± 1 DEG C is warming up in 30-40 minutes, timing is incubated 50 minutes；
After III, insulations terminate, 130 ± 1 DEG C are warming up in 10-20 minutes, is incubated 50 minutes；
After IV, insulations terminate, 145 ± 1 DEG C are warming up in 10-20 minutes, is incubated 80 minutes, normal pressure dehydration；
V, continues vacuum dehydration, until dehydrating amount reaches 72Kg；
VI, is cooled to 90 DEG C, adds aromatic solvent naphtha 400Kg, nylon acid methyl esters 120Kg and petroleum ether 90Kg, stirring 40
Minute；
VII, is cooled to 60 DEG C, adds antimony oxide 6Kg, tricresyl phosphate 6Kg, stirs 25 minutes；
VIII, is cooled to 35 DEG C, adds fatty acid sorbitan 4Kg, neopelex 4Kg, dimethylaminopropylamine
6Kg and methylnaphthohydroquinone 5Kg, stir 20 minutes, blowing, detection, packaging.
With chill phenolic resin, the viscosity at 25 DEG C is 4.6mpa.s for 3D molding sand printing；Up time t≤1.5min；
Addition is 1.5%（Account for the proportion of normal sand）When, its 24h room temperature tensile strength is 2.22Mpa；High temperature of the test block at 1000 DEG C
In environment, tensile strength 1.56Mpa.
Embodiment two
A kind of 3D molding sand is printed with the chemical composition of chill phenolic resin：Phenol 22%, cresols 2%, bisphenol-A 9%, poly
Formaldehyde 4%, acetaldehyde 2%, antimony oxide 0.7%, tricresyl phosphate 0.5%, aromatic solvent naphtha 33.8%, nylon acid methyl esters 11%,
Petroleum ether 12%, fatty acid sorbitan 0.5%, neopelex 0.4%, lead acetate 0.3%, potassium acetate 0.3%, diformazan ammonia
Base propylamine 0.8%, methylnaphthohydroquinone 0.7%.
A kind of 3D molding sand printing preparation method of chill phenolic resin, comprises the following steps：
I, dissolvings phenol 220Kg is added in enamel reaction still, starts stirring, addition cresols 20Kg, bisphenol-A 90kg,
Paraformaldehyde 40Kg, acetaldehyde 20Kg, lead acetate 3Kg and potassium acetate 3Kg；
II, opens steam valve, 106 ± 1 DEG C is warming up in 30-40 minutes, timing is incubated 70 minutes；
After III, insulations terminate, 135 ± 1 DEG C are warming up in 10-20 minutes, is incubated 50 minutes；
After IV, insulations terminate, 150 ± 1 DEG C are warming up in 10-20 minutes, is incubated 70 minutes, normal pressure dehydration；
V, continues vacuum dehydration, until dehydrating amount reaches 75Kg；
VI, is cooled to 90 DEG C, adds aromatic solvent naphtha 338Kg, nylon acid methyl esters 110Kg and petroleum ether 120Kg, stirring
35 minutes；
VII, is cooled to 60 DEG C, adds antimony oxide 7Kg, tricresyl phosphate 5Kg, stirs 28 minutes；
VIII, is cooled to 35 DEG C, adds fatty acid sorbitan 5Kg, neopelex 4Kg, dimethylaminopropylamine
8Kg and methylnaphthohydroquinone 7Kg, stir 45 minutes, blowing, detection, packaging.
With chill phenolic resin, the viscosity at 25 DEG C is 4.8mpa.s for 3D molding sand printing；Up time t≤1.5min；
Addition is 1.5%（Account for the proportion of normal sand）When, its 24h room temperature tensile strength is 2.36Mpa；High temperature of the test block at 1000 DEG C
In environment, tensile strength 1.61Mpa.
Embodiment three
A kind of 3D molding sand is printed with the chemical composition of chill phenolic resin：It is phenol 24%, cresols 3.5%, bisphenol-A 7%, more
Polyformaldehyde 3%, acetaldehyde 1%, antimony oxide 0.5%, tricresyl phosphate 0.5%, aromatic solvent naphtha 40.9%, nylon acid methyl esters
10%th, petroleum ether 7%, fatty acid sorbitan 0.4%, neopelex 0.5%, lead acetate 0.2%, potassium acetate 0.2%, diformazan
Amino propylamine 0.7%, methylnaphthohydroquinone 0.6%.
A kind of 3D molding sand printing preparation method of chill phenolic resin, comprises the following steps：
I, dissolvings phenol 240Kg is added in enamel reaction still, starts stirring, addition cresols 35Kg, bisphenol-A 70kg,
Paraformaldehyde 30Kg, acetaldehyde 10Kg, lead acetate 2Kg and potassium acetate 2Kg；
II, opens steam valve, 112 ± 1 DEG C is warming up in 30-40 minutes, timing is incubated 65 minutes；
After III, insulations terminate, 128 ± 1 DEG C are warming up in 10-20 minutes, is incubated 65 minutes；
After IV, insulations terminate, 155 ± 1 DEG C are warming up in 10-20 minutes, is incubated 65 minutes, normal pressure dehydration；
V, continues vacuum dehydration, until dehydrating amount reaches 70Kg；
VI, is cooled to 90 DEG C, adds aromatic solvent naphtha 409Kg, nylon acid methyl esters 100Kg and petroleum ether 70Kg, stirring 45
Minute；
VII, is cooled to 60 DEG C, adds antimony oxide 5Kg, tricresyl phosphate 5Kg, stirs 15 minutes；
VIII, is cooled to 35 DEG C, adds fatty acid sorbitan 4Kg, neopelex 5Kg, dimethylaminopropylamine
7Kg and methylnaphthohydroquinone 6Kg, stir 55 minutes, blowing, detection, packaging.
With chill phenolic resin, the viscosity at 25 DEG C is 4.3mpa.s for 3D molding sand printing；Up time t≤1.5min；
Addition is 1.5%（Account for the proportion of normal sand）When, its 24h room temperature tensile strength is 2.18Mpa；High temperature of the test block at 1000 DEG C
In environment, tensile strength 1.41Mpa.
Example IV
A kind of 3D molding sand is printed with the chemical composition of chill phenolic resin：It is phenol 18%, cresols 4%, bisphenol-A 10%, more
Polyformaldehyde 4%, acetaldehyde 2.5%, antimony oxide 0.6%, tricresyl phosphate 0.7%, aromatic solvent naphtha 38.5%, nylon acid methyl esters
9%th, petroleum ether 10%, fatty acid sorbitan 0.5%, neopelex 0.4%, lead acetate 0.3%, potassium acetate 0.1%, diformazan
Amino propylamine 0.8%, methylnaphthohydroquinone 0.6%.
A kind of 3D molding sand printing preparation method of chill phenolic resin, comprises the following steps：
I, dissolvings phenol 180Kg is added in enamel reaction still, starts stirring, addition cresols 40Kg, bisphenol-A 100kg,
Paraformaldehyde 40Kg, acetaldehyde 25Kg, lead acetate 3Kg and potassium acetate 1Kg；
II, opens steam valve, 109 ± 1 DEG C is warming up in 30-40 minutes, timing is incubated 65 minutes；
After III, insulations terminate, 125 ± 1 DEG C are warming up in 10-20 minutes, is incubated 70 minutes；
After IV, insulations terminate, 150 ± 1 DEG C are warming up in 10-20 minutes, is incubated 90 minutes, normal pressure dehydration；
V, continues vacuum dehydration, until dehydrating amount reaches 74Kg；
VI, is cooled to 90 DEG C, adds aromatic solvent naphtha 385Kg, nylon acid methyl esters 90Kg and petroleum ether 100Kg, stirring 60
Minute；
VII, is cooled to 60 DEG C, adds antimony oxide 6Kg, tricresyl phosphate 7Kg, stirs 35 minutes；
VIII, is cooled to 35 DEG C, adds fatty acid sorbitan 5Kg, neopelex 4Kg, dimethylaminopropylamine
8Kg and methylnaphthohydroquinone 6Kg, stir 45 minutes, blowing, detection, packaging.
With chill phenolic resin, the viscosity at 25 DEG C is 4.5mpa.s for 3D molding sand printing；Up time t≤1.5min；
Addition is 1.5%（Account for the proportion of normal sand）When, its 24h room temperature tensile strength is 2.32Mpa；High temperature of the test block at 1000 DEG C
In environment, tensile strength 1.52Mpa.
Embodiment five
A kind of 3D molding sand is printed with the chemical composition of chill phenolic resin：Phenol 23%, cresols 3%, bisphenol-A 8%, poly
Formaldehyde 3%, acetaldehyde 2%, antimony oxide 0.7%, tricresyl phosphate 0.7%, aromatic solvent naphtha 35.4%, nylon acid methyl esters 11%,
Petroleum ether 11%, fatty acid sorbitan 0.4%, neopelex 0.3%, lead acetate 0.2%, potassium acetate 0.2%, diformazan ammonia
Base propylamine 0.7%, methylnaphthohydroquinone 0.4%.
A kind of 3D molding sand printing preparation method of chill phenolic resin, comprises the following steps：
I, dissolvings phenol 230Kg is added in enamel reaction still, starts stirring, addition cresols 30Kg, bisphenol-A 80kg,
Paraformaldehyde 30Kg, acetaldehyde 20Kg, lead acetate 2Kg and potassium acetate 2Kg；
II, opens steam valve, 113 ± 1 DEG C is warming up in 30-40 minutes, timing is incubated 60 minutes；
After III, insulations terminate, 122 ± 1 DEG C are warming up in 10-20 minutes, is incubated 75 minutes；
After IV, insulations terminate, 155 ± 1 DEG C are warming up in 10-20 minutes, is incubated 85 minutes, normal pressure dehydration；
V, continues vacuum dehydration, until dehydrating amount reaches 75Kg；
VI, is cooled to 90 DEG C, adds aromatic solvent naphtha 354Kg, nylon acid methyl esters 110Kg and petroleum ether 110Kg, stirring
40 minutes；
VII, is cooled to 60 DEG C, adds antimony oxide 7Kg, tricresyl phosphate 7Kg, stirs 40 minutes；
VIII, is cooled to 35 DEG C, adds fatty acid sorbitan 4Kg, neopelex 3Kg, dimethylaminopropylamine
7Kg and methylnaphthohydroquinone 4Kg, stir 50 minutes, blowing, detection, packaging.
With chill phenolic resin, the viscosity at 25 DEG C is 4.4mpa.s for 3D molding sand printing；Up time t≤1.5min；
Addition is 1.5%（Account for the proportion of normal sand）When, its 24h room temperature tensile strength is 2.27Mpa；High temperature of the test block at 1000 DEG C
In environment, tensile strength 1.45Mpa.
Finally it should be noted that：The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention,
Although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it still may be used
To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic.
Within the spirit and principles of the invention, any modification, equivalent substitution and improvements made etc., it should be included in the present invention's
Within protection domain.
Claims (2)
1. the chill phenolic resin of a kind of 3D molding sand printing, it is characterised in that be made up of following chemical constituent：It is phenol, cresols, double
Phenol A, paraformaldehyde, acetaldehyde, antimony oxide, tricresyl phosphate, aromatic solvent naphtha, nylon acid methyl esters, petroleum ether, aliphatic acid
Sorb is smooth, neopelex, lead acetate, potassium acetate, dimethylaminopropylamine and methylnaphthohydroquinone；Above-mentioned each chemical constituent
Mass percent be respectively：Phenol 12-28%, cresols 1.5-4.5%, bisphenol-A 5-11%, paraformaldehyde 1-5%, acetaldehyde 0.5-
2.5%th, antimony oxide 0.4-0.8%, tricresyl phosphate 0.4-0.8%, aromatic solvent naphtha 15-65%, nylon acid methyl esters 6-
18%th, petroleum ether 4-14%, fatty acid sorbitan 0.2-0.6%, neopelex 0.2-0.6%, lead acetate 0.1-0.3%,
Potassium acetate 0.1-0.3%, dimethylaminopropylamine 0.3-0.9%, methylnaphthohydroquinone 0.2-0.8%.
A kind of 2. preparation method of the chill phenolic resin of 3D molding sand printing as claimed in claim 1, it is characterised in that including
Following steps：
1. dissolving phenol is added in enamel reaction still, stirring is started, adds cresols, bisphenol-A, paraformaldehyde, acetaldehyde, lead acetate
And potassium acetate；
2. opening steam valve, 105-115 DEG C is warming up in 30-40 minutes, timing insulation 40-70 minutes；
3. after insulation terminates, 120-135 DEG C is warming up in 10-20 minutes, 50-80 minutes are incubated；
4. after insulation terminates, 140-160 DEG C is warming up in 10-20 minutes, 60-100 minutes are incubated, normal pressure dehydration；
5. vacuum dehydration, until reaching standard dehydration amount；
6. being cooled to 90 DEG C, aromatic solvent naphtha, nylon acid methyl esters and petroleum ether are added, stirs 30-60 minutes；
7. being cooled to 60 DEG C, antimony oxide, tricresyl phosphate are added, stirs 15-40 minutes；
8. being cooled to 35 DEG C, fatty acid sorbitan, neopelex, dimethylaminopropylamine and methylnaphthohydroquinone are added, is stirred
Mix 20-60 minutes, blowing, detection, packaging.
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| CN201610431421.9A CN105921686B (en) | 2016-06-17 | 2016-06-17 | A kind of 3D molding sand printing chill phenolic resin and preparation method thereof |
| PCT/CN2016/096497 WO2017215117A1 (en) | 2016-06-17 | 2016-08-24 | Cold-curing phenolic resin for 3d moulding sand printing and preparation method therefor |
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| JP4398299B2 (en) * | 2004-05-19 | 2010-01-13 | 旭有機材工業株式会社 | Organic binder for mold, foundry sand composition obtained using the same, and mold |
| CN103059505B (en) * | 2012-11-23 | 2015-06-10 | 沈阳铸造研究所 | CO2 cured alkaline phenolic resin and preparation method thereof |
| EP3040136B1 (en) * | 2013-08-30 | 2021-04-07 | Asahi Yukizai Corporation | Molding method for laminated mold |
| CN105057601B (en) * | 2015-09-02 | 2017-08-01 | 华中科技大学 | A kind of method of three-dimensional spray printing shape casting core |
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- 2016-08-24 WO PCT/CN2016/096497 patent/WO2017215117A1/en active Application Filing
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|---|---|---|---|---|
| CN1086829A (en) * | 1992-09-04 | 1994-05-18 | 三井东压化学株式会社 | Phenol resin composition |
| EP1445268B1 (en) * | 2001-11-16 | 2008-05-21 | Asahi Organic Chemicals Industry Co., Ltd. | Process for the production of phenolic novolaks |
| CN101092473A (en) * | 2007-08-13 | 2007-12-26 | 山东圣泉化工股份有限公司 | Anti hot cracking phenol-formaldehyde resin in use for foundry |
| CN103951932A (en) * | 2014-05-12 | 2014-07-30 | 山东圣泉化工股份有限公司 | Phenol-formaldehyde resin composition for coated sand and preparation method thereof |
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| WO2017215117A1 (en) | 2017-12-21 |
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