CN108440730A - A kind of polishing purification method of casting high quality phenolic resin - Google Patents
A kind of polishing purification method of casting high quality phenolic resin Download PDFInfo
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- CN108440730A CN108440730A CN201810328091.XA CN201810328091A CN108440730A CN 108440730 A CN108440730 A CN 108440730A CN 201810328091 A CN201810328091 A CN 201810328091A CN 108440730 A CN108440730 A CN 108440730A
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- phenolic resin
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- polishing purification
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- 238000000034 method Methods 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
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 41
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 41
- 238000005498 polishing Methods 0.000 title claims abstract description 16
- 238000000746 purification Methods 0.000 title claims abstract description 16
- 238000005266 casting Methods 0.000 title claims abstract description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000000199 molecular distillation Methods 0.000 claims abstract description 18
- 230000018044 dehydration Effects 0.000 claims abstract description 17
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 6
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 6
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 150000002989 phenols Chemical class 0.000 claims abstract description 5
- 238000012545 processing Methods 0.000 claims abstract description 3
- -1 aldehyde compound Chemical class 0.000 claims abstract 3
- 239000000463 material Substances 0.000 claims description 20
- 150000001299 aldehydes Chemical class 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000007171 acid catalysis Methods 0.000 claims description 4
- 238000005815 base catalysis Methods 0.000 claims description 4
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 229920002866 paraformaldehyde Polymers 0.000 claims description 4
- 239000003377 acid catalyst Substances 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- 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 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims 2
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 claims 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims 1
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 239000000908 ammonium hydroxide Substances 0.000 claims 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims 1
- 229910001863 barium hydroxide Inorganic materials 0.000 claims 1
- 229940106691 bisphenol a Drugs 0.000 claims 1
- 150000001896 cresols Chemical class 0.000 claims 1
- 235000019253 formic acid Nutrition 0.000 claims 1
- 235000011167 hydrochloric acid Nutrition 0.000 claims 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 claims 1
- 150000003751 zinc Chemical class 0.000 claims 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims 1
- 229960001763 zinc sulfate Drugs 0.000 claims 1
- 229910000368 zinc sulfate Inorganic materials 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001807 Urea-formaldehyde Polymers 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 235000013904 zinc acetate Nutrition 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical class [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 235000015114 espresso Nutrition 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000004246 zinc acetate 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
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
-
- 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
- B22C1/2233—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 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- B22C1/2246—Condensation polymers of aldehydes and ketones
- B22C1/2253—Condensation polymers of aldehydes and ketones with phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a kind of polishing purification method of casting phenolic resin, especially free phenol content reach 0.01% very high purity below, using process free from extraneous odour phenolic resin polishing purification method.The phenolic compound, aldehyde compound, catalyst of metering are added in reaction kettle this method, such as acid catalyzed reaction, base catalyzed reactions, metal salt catalyst reaction under certain process conditions, thermoplastic phenolic resin, thermosetting phenolic resin and high adjacent position phenolic resin are respectively obtained.After polymerisation, polishing purification processing is carried out by normal pressure or vacuum dehydration, finally by molecular distillation technique, prepares free phenol and the extremely low phenolic resin of content of free aldehyde.This method is simple for process, favorable repeatability, and required equipment volume is small, energy efficiency is high, can effectively improve mass transfer, heat transfer efficiency, and can significantly promote product quality, is particularly suitable for large-scale industrial production.
Description
Technical field
The present invention relates to a kind of polishing purification method of casting phenolic resin, especially free phenol content reaches 0.01%
Very high purity below, using process free from extraneous odour phenolic resin polishing purification method.
Background technology
Phenolic resin be by phenols and aldehydes under acid or basic catalyst effect, be made through polycondensation reaction.Current
In casting phenolic resin synthetic technology, still the free phenol containing high level, free aldehyde monomer, these " impurity " are tight in product
The quality of product is affected again and smell is larger in use, while also endangering the health of execute-in-place worker.
If being difficult to remove free phenol, free aldehyde monomer totally from phenolic resin using conventional distil-lation method；In addition, conventional distillation
Method operation temperature is higher, and phenolic resin can be caused further to be condensed and its performance is made to change.
Molecular distillation technique is separating monomer or impurity under extremely high vacuum degree and lower temperature, it can admirably protect height
The quality of copolymer product, therefore molecular distillation technique is used as the ideal method of polymer monomer and impurity removal.
Molecular distillation is a kind of special liquid -- liquid isolation technics, and it is former by boiling-point difference separation that it is different from Conventional espresso
Reason, but realize separation by the difference of different material molecular tools.When liquid mixture flows simultaneously along heating plate
It being heated, light, weight molecule can escape liquid level and enter gas phase, since light, weight molecule free path is different, different material
Molecule it is different from displacement distance after liquid level effusion, if one piece of cold plate can be appropriately set, light molecule reaches cold plate quilt
Condensation discharge, and weight molecule is not achieved cold plate and is discharged along mixed liquor.In this way, achieving the purpose that substance detaches.
The advantages of molecular distillation technique, is as follows：
(1) vapo(u)rizing temperature is low, and molecular distillation is operated at a temperature of far below boiling point, simply by the presence of temperature difference
Separation purpose can be reached, this is molecular distillation and the essential distinction of conventional distil-lation.
(2) distillation vacuum degree is high, and molecular distillation apparatus can obtain very high vacuum degree inside it, therefore material is not easy oxygen
Change impaired.
(3) material heated time is short, the liquid level heated with plus the distance between cryosurface be less than light molecule it is average from
By journey, so almost just reaching cryosurface without collision by the light molecule of liquid level effusion.Therefore, distilling material heated time is short,
The residence time generally between several seconds to tens seconds, reduces the chance of material thermal decomposition at the distillation temperature.
(4) without boiling bubbling phenomenon, molecular distillation is freely evaporating on liquid layer surface, is carried out at low pressures, liquid
Air without dissolving in body, therefore entire liquid boiling cannot be made in distillation process, without bubbling phenomenon.
(5) pure safe product can be obtained in nontoxic, harmless, pollution-free, noresidue, and operating procedure is simple, equipment
It is few.
Invention content
The technical problem to be solved by the present invention is in the product prepared by normal casting phenolic resin synthetic technology for containing
There are more free phenol, free aldehyde impurity, it is proposed that the phenol for acid, alkali or metal salt catalyst being synthesized using molecularly distilled
Urea formaldehyde further carries out polishing purification, and the free monomer such as free phenol in resin is removed to 0.01% hereinafter, ensureing to set simultaneously
Lipid can be constant.It is as follows：
(1) synthesis of phenolic resin：Thermosetting property phenol is synthesized using acid catalysis synthetic thermoplastic phenolic aldehyde resin art, base catalysis
Any one technique in urea formaldehyde technique and metal salt catalyst synthesis high adjacent position phenolic resin technique, i.e.,：It is counted according to chemistry
Ratio is measured, one in phenolic compound and corresponding acid catalyst, base catalyst and metal salt catalyst is added in a kettle
Kind, after being sufficiently stirred mixing, when being heated to 70-100 DEG C, aldehyde material is uniformly added into 2-3 hours, and ceaselessly stir；
After addition, continue insulation reaction 1-4 hours.
(2) dehydration：Step 1 after reaction, starts normal pressure and vacuum dehydration, until the pressure drop in reaction kettle
For -0.1Mpa, when temperature reaches 70-180 DEG C, dehydration terminates.
(3) molecular distillation is handled：The product that step 2 obtains is transferred in molecular still, molecular distillation processing is carried out,
The interior pressure of molecular still is -0.1Mpa, and temperature is 100-220 DEG C.After distillation, the phenol of high-purity is collected with receiving flask
Urea formaldehyde product.
The advantageous effect that technical solution provided by the invention is brought is：The present invention provides a kind of casting phenolic resin
Polishing purification method is removed the impurity such as free phenol in phenolic resin, free aldehyde, is made in phenolic resin by molecular distillation technique
Free phenol content reaches 0.01% or less.This method is simple for process, favorable repeatability, required equipment volume is small, energy efficiency is high,
Mass transfer, heat transfer efficiency can be effectively improved, and can significantly promote product quality, is particularly suitable for large-scale industrial production.
Embodiment
Embodiment 1：Acid catalysis synthetic thermoplastic phenolic aldehyde resin art
According to disposable input aldehydes matter such as phenol and the acid catalyst such as oxalic acid of metering, stirring starts to rise after 2-5 minutes
Temperature, when temperature reaches 80-95 DEG C when 2-3 is small the interior continuous liquid for dripping the aldehyde material all measured for example a concentration of 37%
Body formaldehyde, adds latter insulation reaction 1-4 hours, after reaction, starts normal pressure and vacuum dehydration, when vacuum degree reaches-
Reaction product is continuously added in molecular still by 0.1Mpa, temperature after reaching 100-180 DEG C, in molecular still pressure be-
0.1Mpa, temperature are 120-220 DEG C.After material adds, the phenolic resin product of high-purity is collected with receiving flask.
Embodiment 2：Base catalysis synthesizes thermosetting phenolic resin technique
According to disposable input aldehydes matter such as phenol and the base catalyst such as triethylamine of metering, stirring starts after 2-5 minutes
Heating, it is interior when 2-3 is small when temperature reaches 70-95 DEG C continuously to drip the aldehyde material all measured for example a concentration of 37%
Liquid formaldehyde, adds latter insulation reaction 1-4 hours, acid such as sulfuric acid tune pH value is then added into reactant to neutrality,
Reaction terminates to start vacuum dehydration, and when vacuum degree reaches -0.1Mpa, reaction product is continuously added to by temperature after reaching 70-100 DEG C
In molecular still, pressure is -0.1Mpa in molecular still, and temperature is 100-160 DEG C.After material adds, received with receiving flask
Collect the phenolic resin product of high-purity.
Embodiment 3：Metal salt catalyst synthesizes high adjacent position phenolic resin technique
According to disposable input aldehydes matter such as phenol, the aldehyde material such as paraformaldehyde of 92% purity, alcohols object of metering
Matter such as butanol and metal salt catalyst such as zinc acetate, stirring are started to warm up after 2-5 minutes, are protected when temperature reaches 70-100 DEG C
Temperature reaction 1-5 hours, reaction terminates, and starts normal pressure and vacuum dehydration, when vacuum degree reaches -0.1Mpa, temperature reaches 110-140
Reaction product is continuously added in molecular still after DEG C, pressure is -0.1Mpa in molecular still, and temperature is 130-180 DEG C.
After material adds, the phenolic resin product of high-purity is collected with receiving flask.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments be only used for the present invention without
For limiting the scope of the invention.Externally it should be understood that after having read present disclosure, those skilled in the art are to this hair
Bright to make various changes or modifications, these equivalent forms also fall within the scope of the appended claims of the present application.
Embodiment 1：
550g phenol and 9g oxalic acid are added in the reactor of 1000ml, stirring starts to warm up after five minutes, when temperature reaches
305g formaldehyde (37%) is continuously dripped at 90 DEG C in 2 hours, adds rear insulation reaction 4 hours, after reaction, is started normal
Pressure and vacuum dehydration, when vacuum degree reaches -0.1Mpa, reaction product is continuously added to molecular still by temperature after reaching 120 DEG C
In, pressure is -0.1Mpa in molecular still, and temperature is 160 DEG C.After material adds, material in receiving flask is poured out, is thus obtained
Obtain 522g resins.
Embodiment 2：
340g phenol and 36g triethylamines are added in the reactor of 1000ml, stirring starts to warm up after five minutes, works as temperature
514g formaldehyde (37%) is continuously dripped when reaching 90 DEG C in 2 hours, adds rear insulation reaction 2 hours, reaction terminates, and starts
Vacuum dehydration, when vacuum degree reaches -0.1Mpa, reaction product is continuously added in molecular still by temperature after reaching 90 DEG C, point
Pressure is -0.1Mpa in sub- distiller, and temperature is 120 DEG C.After material adds, the material in receiving flask is poured out, thus to obtain
412g resins.
Embodiment 3：
510g phenol, 264g paraformaldehydes (92%), 25g butanol, 1.0g zinc acetates are added in the reactor of 1000ml,
Stirring starts to warm up after five minutes, and when temperature reaches 90 DEG C, insulation reaction 2 is small, reaction terminates, and starts normal pressure and vacuum is de-
Water, when vacuum degree reaches -0.1Mpa, reaction product is continuously added in molecular still by temperature after reaching 120 DEG C, molecular distillation
Pressure is -0.1Mpa in device, and temperature is 160 DEG C.After material adds, the material in receiving flask is poured out, thus to obtain 541g trees
Fat.
Comparative example 1：
550g phenol and 9g oxalic acid are added in the reactor of 1000ml, stirring starts to warm up after five minutes, when temperature reaches
305g formaldehyde (37%) is continuously dripped at 90 DEG C in 2 hours, adds rear insulation reaction 4 hours, after reaction, is started normal
Pressure and vacuum dehydration, when vacuum degree reaches -0.1Mpa, temperature is reacted after reaching 160 DEG C to be terminated.By reaction product from reactor
It pours out, thus to obtain 527g resins.
Comparative example 2：
340g phenol and 36g triethylamines are added in the reactor of 1000ml, stirring starts to warm up after five minutes, works as temperature
514g formaldehyde (37%) is continuously dripped when reaching 90 DEG C in 2 hours, adds rear insulation reaction 2 hours, reaction terminates, and starts
Vacuum dehydration, when vacuum degree reaches -0.1Mpa, temperature is reacted after reaching 90 DEG C to be terminated.Reaction product is poured out from reactor,
Thus to obtain 424g resins.
Comparative example 3：
510g phenol, 264g paraformaldehydes (92%), 25g butanol, 1.0g zinc acetates are added in the reactor of 1000ml,
Stirring starts to warm up after five minutes, and when temperature reaches 90 DEG C, insulation reaction 2 is small, reaction terminates, and starts normal pressure and vacuum is de-
Water, when vacuum degree reaches -0.1Mpa, temperature is reacted after reaching 120 DEG C to be terminated.Reaction product is poured out from reactor, thus
Obtain 561g resins.
The free phenol content of phenolic resin obtained by 1 embodiment of table and comparative example
Claims (7)
1. a kind of polishing purification method of casting high quality phenolic resin, it is characterised in that：This method comprises the following steps：
(1) synthesis of phenolic resin：Thermosetting phenolic tree is synthesized using acid catalysis synthetic thermoplastic phenolic aldehyde resin art, base catalysis
Any one technique in fat technique and metal salt catalyst synthesis high adjacent position phenolic resin technique, i.e.,：According to stoichiometric ratio,
One kind in phenolic compound and corresponding acid catalyst, base catalyst and metal salt catalyst is added in a kettle, fills
Divide after stirring and evenly mixing, when being heated to 70-100 DEG C, aldehyde material is uniformly added into 2-3 hours, and ceaselessly stir；It has been added
Bi Hou, continues insulation reaction 1-4 hours.
(2) dehydration：Step 1 after reaction, starts normal pressure and vacuum dehydration, until the pressure in reaction kettle be reduced to-
0.1Mpa, when temperature reaches 70-180 DEG C, dehydration terminates.
(3) molecular distillation is handled：The product that step 2 obtains is transferred in molecular still, molecular distillation processing, molecule are carried out
The interior pressure of distiller is -0.1Mpa, and temperature is 100-220 DEG C.After distillation, the phenolic aldehyde tree of high-purity is collected with receiving flask
Fat product.
2. a kind of polishing purification method of casting high quality phenolic resin according to claim 1, it is characterised in that：Step
Phenolic compound described in 1 is any one in phenol, cresols, xylenol, resorcinol, tert-butyl phenol, nonyl phenol, bisphenol-A
Kind is a variety of.
3. according to a kind of polishing purification method of casting high quality phenolic resin described in claim 1-2, it is characterised in that：Step
Aldehyde compound described in rapid 1 is any one or more in formaldehyde, acetaldehyde, paraformaldehyde, furfural.
4. according to a kind of polishing purification method of casting high quality phenolic resin described in claim 1-3, it is characterised in that：Institute
It states in acid catalysis synthetic thermoplastic phenolic aldehyde resin art, the acid is one or more in sulfuric acid, hydrochloric acid, oxalic acid, formic acid；Institute
It is 70-100 DEG C, preferably 80-95 DEG C to state thermoplastic phenolic resin synthesis temperature；The dehydration temperaturre is 70-180 DEG C, preferably
100-180℃；The temperature of the molecular distillation is 100-220 DEG C, preferably 120-220 DEG C.
5. according to a kind of polishing purification method of casting high quality phenolic resin described in claim 1-4, it is characterised in that：Institute
It states in base catalysis synthesis thermosetting phenolic resin technique, the alkali is sodium hydroxide, potassium hydroxide, barium hydroxide, ammonium hydroxide, three second
It is one or more in amine；The thermosetting phenolic resin synthesis temperature is 70-100 DEG C；The dehydration temperaturre is 70-180 DEG C,
It is preferred that 70-100 DEG C；The temperature of the molecular distillation is 100-220 DEG C, preferably 100-160 DEG C.
6. according to a kind of polishing purification method of casting high quality phenolic resin described in claim 1-5, it is characterised in that：Institute
It states in metal salt catalyst synthesis high adjacent position phenolic resin technique, the metal salt is divalent metal salt, preferably zinc salt, such as acetic acid
Zinc, zinc sulfate etc.；The high adjacent position phenolic resin synthesis temperature is 70-100 DEG C；The dehydration temperaturre is 70-180 DEG C, preferably
110-140℃；The temperature of the molecular distillation is 100-220 DEG C, preferably 100-160 DEG C.
7. according to a kind of polishing purification method of casting high quality phenolic resin described in claim 1-6, it is characterised in that：Institute
State method preparation high quality phenolic resin free monomers content it is extremely low, as free phenol content 0.01% hereinafter, simultaneously
Keep original performance of resin constant.
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| CN110918868A (en) * | 2020-01-02 | 2020-03-27 | 四川东树新材料有限公司 | Ester-cured phenolic resin for large-scale casting and molding and preparation method thereof |
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| CN115073683B (en) * | 2022-07-27 | 2024-02-06 | 东营市赫邦化工有限公司 | Preparation method of low-free phenol-formaldehyde resin and product obtained by preparation method |
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