CN110078875A - It reduces the method for free phenol content and phenolic resin in phenolic resin and cleans preparation method - Google Patents
It reduces the method for free phenol content and phenolic resin in phenolic resin and cleans preparation method Download PDFInfo
- Publication number
- CN110078875A CN110078875A CN201910406876.9A CN201910406876A CN110078875A CN 110078875 A CN110078875 A CN 110078875A CN 201910406876 A CN201910406876 A CN 201910406876A CN 110078875 A CN110078875 A CN 110078875A
- Authority
- CN
- China
- Prior art keywords
- phenolic resin
- phenol
- organic solvent
- resin
- alkali cleaning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 157
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 69
- 239000005011 phenolic resin Substances 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 45
- 239000003513 alkali Substances 0.000 claims abstract description 32
- 238000004140 cleaning Methods 0.000 claims abstract description 32
- 239000003960 organic solvent Substances 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 238000004064 recycling Methods 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 19
- 238000001704 evaporation Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 150000001299 aldehydes Chemical class 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 9
- -1 alkyl halide hydrocarbon Chemical class 0.000 claims description 9
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 7
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- XSXWOBXNYNULJG-UHFFFAOYSA-N 2-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=CC=C1O XSXWOBXNYNULJG-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 2
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical compound [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-N 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 20
- 239000011347 resin Substances 0.000 abstract description 20
- 229920001971 elastomer Polymers 0.000 abstract description 9
- 239000005060 rubber Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000006378 damage Effects 0.000 abstract description 3
- 238000003672 processing method Methods 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 16
- 238000001816 cooling Methods 0.000 description 12
- 239000012071 phase Substances 0.000 description 12
- 238000001514 detection method Methods 0.000 description 10
- 238000006482 condensation reaction Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 description 8
- 235000011152 sodium sulphate Nutrition 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000007524 organic acids Chemical group 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- LBBOQIHGWMYDPM-UHFFFAOYSA-N 2-tert-butylphenol;formaldehyde Chemical compound O=C.CC(C)(C)C1=CC=CC=C1O LBBOQIHGWMYDPM-UHFFFAOYSA-N 0.000 description 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 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 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 1
- 239000007836 KH2PO4 Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- RIIPKNZLLQVCRR-UHFFFAOYSA-N formaldehyde;2-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound O=C.CC(C)(C)CC(C)(C)C1=CC=CC=C1O RIIPKNZLLQVCRR-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- GUGLPELUECBSDK-UHFFFAOYSA-N phenol;urea Chemical compound NC(N)=O.OC1=CC=CC=C1 GUGLPELUECBSDK-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene 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
-
- 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
- C08G8/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a kind of methods of free phenol content in reduction phenolic resin and phenolic resin to clean preparation method, the present invention effectively reduces the free phenol content in phenolic resin by alkali cleaning, avoid influence of the free phenol to resin property and the harm to environment and human body, the operation is succinct, efficient, at low cost compared with existing processing method, it will not influence resin property, it is convenient to carry out.In resin preparation process, organic solvent, water, inorganic salts, phenol sufficient recycling has all been subjected to, it realizes and recycles, technique clean and environmental protection, with great economy and society meaning, gained phenolic resin has excellent viscosity and permanent tack, is a kind of good tackifying resin, is particularly suitable in the manufacture and production of tire using as rubber long-acting tackifying resin.
Description
Technical field
The present invention relates to a kind of methods of free phenol content in reduction phenolic resin, further relate to a kind of low-free phenol content
Phenolic resin cleans preparation method, belongs to technical field of fine.
Background technique
In rubber tyre or product process, especially in radial and bias tire process, frequently with
The molding of fitting method, this requires unvulcanized sizing material molding viscosity with higher.Natural rubber has good tack, thus
Processing performance is good, although and synthetic rubber have the advantages that it is wear-resisting, ageing-resistant and some other, its tack is poor, at
Type process bands are next difficult, to limit the use of synthetic rubber.
If lacking viscosity between sizing material, especially for synthetic rubber rubber compound, semi-finished product glue part not only can be because of creep
Make size distortion, and can be because of molding when expansion cause glue part to paste position to disengage, it is therefore desirable to rubber unvulcanizate have compared with
High molding viscosity.In order to solve this problem, the method that advance works generally use brushing gasoline or rubber cement.This method at
This is higher, and solvent volatilization causes environmental pollution and production safety hidden danger, and tire plant has generally eliminated this method at present, adopts
The bonding of each glue part is improved with the method for phenolic resin is added directly in rubber.
Generally use phenolic resin as tackifier currently on the market, phenolic resin is one formed using phenol and aldehyde reaction
Kind tackifying resin, general phenol inventory is bigger than aldehyde during the preparation process, inevitably residual in gained phenolic resin finished product
There are free phenols.The free phenol technical indicator of phenolic resin in the market is typically all≤5wt%, and the residual of phenol will affect phenol
The application performance of urea formaldehyde, therefore, reducing the phenol residual quantity in phenolic resin is to improve one of the key factor of its application performance；
And free phenol can sublimate into air environment in resin use process, pollute environment, and it is very big to personal injury, so,
Pulvis resorcinol, resorcinol predispersion are substantially replaced high-quality resin.
Currently, the method for reducing the free phenol content in phenolic resin has distillation the removal method, (catalysis of height ratio catalyst method
Agent dosage is high), urea and phenol reaction method and fatty acid esterification process etc. is added.The shortcomings that distilling removal method is that phenol is set in pipeline etc.
It is easy crystallisation by cooling in standby and blocks pipeline, and higher boiling alkyl phenol needs high vacuum, industrialization is difficult to realize；Height ratio catalyst
It is invalid that method is reduced to 0.1% or less for phenol；Urea is added and reacts the stability that can destroy resin with phenol；Though fatty acid esterification process
It so can reduce phenol content, but impurity can be introduced and influence resin property.
Summary of the invention
For deficiency existing for existing phenolic resin free phenol minimizing technology, the present invention provides a kind of reduction phenolic resin
The method of middle free phenol content, this method is simple, it is efficient, at low cost, be easy to realization of industrialization, resin property, energy will not be destroyed
Enough effectively reduce the content of free phenol in final phenolic resin finished product.
The present invention also provides a kind of preparation methods that cleans of phenolic resin, and this method is easy to operate, easy to implement, phenol
Aldehyde molar ratio is small, and raw material availability is high, free phenol content≤0.5wt %, preferably≤0.1wt %, and used in production process
Water, phenol and inorganic salts product can recycle, and realization recycles, and entirely prepare clean and environmental protection, have great economy and society
It can meaning.
Specific technical solution of the present invention is as follows:
A kind of method of free phenol content in reduction phenolic resin, this method include that phenolic resin is carried out alkali cleaning to reduce phenolic aldehyde tree
In rouge the step of free phenol content.The phenolic resin refers to the phenolic resin directly obtained after phenol and aldehyde reaction, either
Have passed through certain processing, for example, except phenol, except the phenolic resin of aldehyde processing.
Further, in the above method, alkali cleaning is carried out using alkaline aqueous solution.The purpose of alkali cleaning is will be in phenolic resin
Phenol becomes water-soluble salt, and to remove from phenolic resin, all alkaline aqueous solutions for meeting this requirement may be incorporated for this
Invention.For example, alkaline aqueous solution can be ammonium hydroxide, sodium hydroxide solution, sodium carbonate liquor or sodium bicarbonate solution etc., preferably
Sodium hydroxide solution, in order to recycle.The concentration of alkaline aqueous solution is preferably 1%~32wt %, more preferably 1-10wt%.
Further, alkali cleaning carries out at 70~90 DEG C, can accelerate reaction speed and free phenol removal effect.Alkaline water
The slightly excessive mole in free phenol of the dosage of the alkaline matter to react in solution with phenol, it is preferred that alkaline matter and trip
Molar ratio from phenol is 1.01~1.05:1, and after the completion of alkali cleaning, phenolic resin is in neutrality or slightly meta-alkalescence.
Preferably, when alkali cleaning, alkali cleaning aqueous solution is divided into more parts, phenolic resin is washed in batches, preferably by alkaline water
Solution, which divides 2-5 times, washs phenolic resin.
Further, first phenolic resin is dissolved in organic solvent, then carries out alkali cleaning again；The organic solvent is can
Dissolve phenolic resin and organic solvent unmixing with water, such as aromatic hydrocarbons organic solvent, paraffinic organic solvent, cycloalkane
Class organic solvent, alkyl halide hydrocarbon organic solvent, solvent naphtha etc. specifically can choose toluene, dimethylbenzene, benzene, solvent naphtha, positive heptan
Alkane, n-hexane etc..
Further, after the method for the present invention is handled, free phenol content≤0.5wt % in gained phenolic resin, more
It is preferred that≤0.1wt %.
Preparation method is cleaned the present invention also provides a kind of phenolic resin, method includes the following steps:
(1) phenol and aldehyde reaction are obtained into phenolic resin；
(2) phenolic resin is dissolved in organic solvent, alkaline aqueous solution is then added according to methods described above and carries out alkali cleaning,
Liquid separation after alkali cleaning, gained oil are mutually washed to neutrality, then vacuum removal organic solvent and recycle, it is low to obtain free phenol content
Phenolic resin；
(3) step (2) resulting water phase adds acid for adjusting pH to neutrality, is then concentrated by evaporation and removes part water, the water phase after concentration
Acid out recycles phenol, and remaining water phase is evaporated water after recycling phenol, obtains inorganic salts.
Further, it the method for above-mentioned reduction free phenol content and cleans in preparation method, the phenol is phenol, isophthalic
Diphenol, ortho-methyl phenol, m-methyl phenol, p-methyl phenol, p-tert-butylphenol and at least one of tert-octyl phenol；
The aldehyde is at least one of formaldehyde, acetaldehyde and furfural.Preferably, the molar ratio of phenol and aldehyde is 1:0.9~0.99, more preferably
For 1:0.95.
Further, the step of phenol and aldehyde reaction prepare phenolic resin can be carried out using the method reported in the prior art
Operation, reaction carry out in the presence of a catalyst, and catalyst is organic acid or inorganic acid, and inorganic acid has sulfuric acid, hydrochloric acid, phosphoric acid, nitre
Acid etc., organic acid have formic acid, acetic acid, p-methyl benzenesulfonic acid, benzene sulfonic acid etc., sour strong and weak carry out degree, yield and product to reaction
Matter is extremely crucial, and preferably the concentrated sulfuric acid is catalyst.
Further, in above-mentioned steps (2), the organic solvent of recycling can be with recycled, in step (3), evaporation gained
Water can recycle.
Further, the above-mentioned preparation method that cleans can use following steps: phenol and catalyst are added in reaction kettle
And heating melting, aldehyde is added dropwise while stirring, aldehyde is added dropwise to complete rear back flow reaction for a period of time, and organic solvent is then added and contracts
Poly- reaction and dehydration, obtain phenolic resin, phenolic resin are dissolved in organic solvent, and the alkaline aqueous solution that heat is then added stirs
It mixes, wash, be dissolved in phenol in alkaline aqueous solution, then liquid separation, oily phase and aqueous phase separation are mutually washed into hot water by oily
Property, the organic solvent being concentrated by evaporation recycles, and is the low phenolic resin of free phenol content after residue is cooling；Liquid separation
Gained water phase is adjusted with acid to neutrality, is evaporated concentration, and the water evaporated recycles, and residue carries out acid out with acid, acid
Obtained phenol separating and recovering is analysed, the raffinate re-evaporation after separating phenol is concentrated and separated, the water reuse evaporated, and obtained inorganic salts are solid
Body carries out for sale.Preparation method of the present invention realizes the reuse of organic solvent, phenol and water, technique clean and environmental protection, gained nothing
Machine salt by-product can be for sale, improves added value of product.
The present invention effectively reduces the free phenol content in phenolic resin by alkali cleaning, avoids free phenol to resinousness
Can influence and harm to environment and human body, the operation is succinct, efficient, at low cost compared with existing processing method, Bu Huiying
Resin property is rung, it is convenient to carry out.In resin preparation process, organic solvent, water, inorganic salts, phenol are all carried out adequately to return
It receives and utilizes, realize and recycle, technique clean and environmental protection has great economy and society meaning, and gained phenolic resin has
Excellent viscosity and permanent tack, are a kind of good tackifying resins, are particularly suitable for conduct in the manufacture and production of tire
Rubber is used with long-acting tackifying resin.The initial viscosity and permanent tack power for adding the sizing material of resin of the present invention are greatly mentioned
It is high, it is possible to reduce the defect ware rate of tire or rubber product, the quality of tire or rubber product can be improved, reduce production cost and
Production efficiency is improved, there is fine economic and social benefit, wide market.
Specific embodiment
Several specific embodiments of the invention are set forth below, so that those skilled in the art have further the present invention
Understand, but implementation of the invention is without being limited thereto.In following embodiments, unless otherwise instructed, the concentration is mass concentration.
In following embodiments, free phenol is tested using high performance liquid chromatography, and instrument is Shimadzu liquid chromatograph LC-
20AT, column model C18 packed column, Detection wavelength 275nm, mobile phase: methanol: KH2PO4=36:64(volume ratio), flow velocity
1ml/min, 35 DEG C of column temperature.
Embodiment 1
The concentrated sulfuric acid of the p-tert-butylphenol of 97 wt% of 154.88g and 3.0g 98wt% is added in three-necked flask, is warming up to
90 DEG C, be added dropwise 37wt% formaldehyde 77.0g, then flow back condensation reaction 2.0 hours at 100~105 DEG C, condensation reaction completion
Afterwards be added liquid alkaline be neutralized to neutrality, then be added toluene the water that condensation reaction generates is taken out of, when being flowed out there is no liquid into
Row polycondensation reaction stops reaction when temperature rises to 170~180 DEG C, obtains phenolic resin and precise its quality is
166.27g, sample detection free phenol content are 2wt%.Obtained phenolic resin is added in the hot toluene of 249g and is dissolved, then
It is washed with the sodium hydroxide solution 44.7g of 90 DEG C of 2wt% concentration points 4 times, during the water phase after alkali cleaning is adjusted to sulfuric acid
Property be evaporated concentration, the underwater secondary reuse evaporated, residue sulfuric acid acid out, reuse after phenol that acid out obtains is dry, filter
Liquid re-evaporation concentration and separation sodium sulphate and water, water reuse, sodium sulphate are externally sold；Oil after alkali cleaning is mutually washed with hot water into
Property, then vacuum removal toluene reuse next time, surplus material cooling obtains p tert butylphenol formaldehyde resin, through high-efficient liquid phase color
The free phenol content that spectrometer detects phenolic resin is 0.01wt%.
Embodiment 2
Phenolic resin is prepared according to the method for embodiment 1, obtains the phenolic resin that 166.27g free phenol content is 2wt%.Will
To phenolic resin 249g is added hot toluene in dissolve, then divide 2 with the sodium hydroxide solution 17.9g of 90 DEG C of 5wt% concentration
Secondary to be washed, the complete water phase of alkali cleaning is adjusted to neutrality with sulfuric acid is evaporated concentration, the underwater secondary reuse evaporated, residue
With sulfuric acid acid out, reuse after the phenol of precipitation is dry, filtrate re-evaporation is concentrated and separated sodium sulphate and water, water reuse, sodium sulphate are external
It sells；Oil after alkali cleaning is mutually washed with hot water to neutrality, then vacuum removal toluene reuse next time, and surplus material is cooling to be obtained pair
T-Butylphenol formaldehyde resin, the free phenol content through high performance liquid chromatograph detection phenolic resin is 0.10wt%.
Embodiment 3
Phenolic resin is prepared according to the method for embodiment 1, obtains the phenolic resin that 166.27g free phenol content is 2wt%.Will
To phenolic resin 249g is added hot toluene in dissolve, then divide 2 with the sodium hydroxide solution 47.7g of 90 DEG C of 2wt% concentration
Secondary to be washed, the water phase after alkali cleaning is adjusted to neutrality with sulfuric acid is evaporated concentration, the underwater secondary reuse evaporated, residue
With sulfuric acid acid out, reuse after the phenol that acid out obtains is dry, filtrate re-evaporation is concentrated and separated sodium sulphate and water, water reuse, sodium sulphate
Externally sell；Oil after alkali cleaning mutually washs with hot water to neutrality, then vacuum removal toluene reuse next time, and surplus material is cooling
To p tert butylphenol formaldehyde resin, the free phenol content through high performance liquid chromatograph detection phenolic resin is 0.07wt%.
Embodiment 4
Phenolic resin is prepared according to the method for embodiment 1, obtains the phenolic resin that 166.27g free phenol content is 2wt%.Will
To phenolic resin 249g is added hot toluene in dissolve, then divide 4 with the sodium hydroxide solution 47.7g of 70 DEG C of 2wt% concentration
Secondary to be washed, the water phase after alkali cleaning is adjusted to neutrality with sulfuric acid is evaporated concentration, the underwater secondary reuse evaporated, residue
With sulfuric acid acid out, reuse after the phenol that acid out obtains is dry, filtrate re-evaporation is concentrated and separated sodium sulphate and water, water reuse, sodium sulphate
Externally sell；Oil after alkali cleaning mutually washs with hot water to neutrality, then vacuum removal toluene reuse next time, and surplus material is cooling
To p tert butylphenol formaldehyde resin, the free phenol content through high performance liquid chromatograph detection phenolic resin is 0.06wt%.
Embodiment 5
The hydrochloric acid of the p-tert-butylphenol of 97 wt% of 154.88g and 3.5g 31wt% is added in three-necked flask and is warming up to 94
DEG C, be added dropwise 37wt% formaldehyde 73.05g, then flow back condensation reaction 2.5 hours at 99~103 DEG C, sodium carbonate be then added
It is neutralized to neutrality, dimethylbenzene is added and takes the water that condensation reaction generates out of, polycondensation reaction is carried out when flowing out there is no liquid, instead
It is 164.5g that cooling its quality that weighs should be poured out after the completion, and sample detection free phenol content is 5 wt %.The phenolic aldehyde tree that will be obtained
Rouge is added to stirring and dissolving in hot xylene solvent, and with 72 DEG C of 6 wt % sodium carbonate liquor 49.8g points of 4 washings, alkali cleaning is complete
Water phase be adjusted to neutrality with hydrochloric acid after be concentrated by evaporation, the underwater secondary reuse evaporated, residue hydrochloric acid acid out, be precipitated
P-tert-butylphenol it is dry after reuse, filtrate re-evaporation concentration and separation sodium chloride and water, water reuse, sodium chloride are externally sold.
Oil after alkali cleaning is mutually washed with hot water to neutrality, then vacuum removal dimethylbenzene reuse, and residue cooling is obtained to tert-butyl benzene
Fluosite, by high performance liquid chromatography detection, free phenol content 0.07wt%.
Embodiment 6
The nitric acid of tert-octyl phenol and 4.0g 35wt% be added in three-necked flask and be warming up to 104.2g 99wt% 92
DEG C, be added dropwise 37wt% formaldehyde 37.8g, then flow back condensation reaction 3.0 hours at 100~104 DEG C, bicarbonate be then added
Sodium is neutralized to neutrality, and benzene is added and takes the water that condensation reaction generates out of, polycondensation reaction is carried out when flowing out there is no liquid, reacts
Pouring out cooling its quality that weighs after the completion is 109.7g, and sample detection free phenol content is 4 wt %.The phenolic resin that will be obtained
It is added to stirring and dissolving in the hot benzene of 220g, divides 3 washings with 82 DEG C of 6 wt % sodium bicarbonate solution 30.1g, the water after alkali cleaning
Mutually be adjusted to neutrality with nitric acid after be concentrated by evaporation, the water reuse evaporated, residue nitric acid acid out, precipitation to tertiary pungent
Reuse after base phenol is dry, filtrate re-evaporation concentration and separation sodium nitrate and water, water reuse, sodium nitrate are externally sold；After alkali cleaning
Oily mutually to be washed with hot water to neutrality, then vacuum removal benzene reuse, residue is cooling to be obtained to t-Octylphenol formaldehyde resin, warp
Cross high performance liquid chromatography detection, free phenol content 0.10wt%.
Embodiment 7
The phosphoric acid of the phenol of 95.1g 99wt% and 3.0g 99wt% is added in three-necked flask and is warming up to 95 DEG C, is added dropwise
Then the formaldehyde 77.1g of 37wt% flows back condensation reaction 2.5 hours at 101~105 DEG C, sodium bicarbonate is then added and is neutralized to
Neutrality is added normal heptane and takes the water that condensation reaction generates out of, and polycondensation reaction is carried out when flowing out there is no liquid, and reaction is completed
After to pour out cooling its quality that weighs be 106.5g, sample detection free phenol content is 3wt %.Obtained phenolic resin is added to
Stirring and dissolving in the hot normal heptane of 160g divides 3 washings with 90 DEG C of 10 wt % sodium bicarbonate solution 29.1g, the water phase after alkali cleaning
It is concentrated by evaporation after being adjusted to neutrality with phosphoric acid, evaporates effluent reuse, residue phosphoric acid acid out, after the phenol of precipitation is dry
Reuse, filtrate re-evaporation concentration and separation sodium phosphate and water, water reuse, sodium phosphate are externally sold；Oil after alkali cleaning mutually uses hot water wash
It washs to neutrality, then vacuum removal normal heptane reuse, residue cooling obtains phenol formaldehyde resin, examines by high performance liquid chromatography
It surveys, free phenol content 0.06wt%.
Claims (10)
1. a kind of method for reducing free phenol content in phenolic resin, it is characterized in that: including that phenolic resin is carried out alkali cleaning reduction
In phenolic resin the step of free phenol content.
2. according to the method described in claim 1, it is characterized in that: alkali cleaning is carried out using alkaline aqueous solution.
3. according to the method described in claim 2, it is characterized in that: the alkaline aqueous solution is ammonium hydroxide, sodium hydroxide solution, carbonic acid
Sodium solution or sodium bicarbonate solution, preferably sodium hydroxide solution.
4. method according to any one of claim 1-3, it is characterized in that: alkali cleaning carries out at 70~90 DEG C.
5. method according to any one of claim 1-3, it is characterized in that: alkaline matter in alkaline aqueous solution and free
The molar ratio of phenol is 1.01~1.05:1.
6. method according to any one of claim 1-3, it is characterized in that: phenolic resin is dissolved in organic solvent, so
After carry out alkali cleaning；The organic solvent is water-immiscible organic solvent, and preferably aromatic hydrocarbons organic solvent, paraffinic has
It is solvent, cycloalkane organic solvent, alkyl halide hydrocarbon organic solvent or solvent naphtha, more preferably toluene, dimethylbenzene, benzene, molten
Agent oil, normal heptane or n-hexane.
7. a kind of phenolic resin cleans preparation method, it is characterized in that the following steps are included:
(1) phenol and aldehyde reaction are obtained into phenolic resin；
(2) phenolic resin is dissolved in organic solvent, alkaline aqueous solution is then added according to described in any one of claim 1-5
Reduce phenolic resin in free phenol content method carry out alkali cleaning, liquid separation after alkali cleaning, gained oil is mutually washed to neutrality, then very
Sky removing organic solvent simultaneously recycles, and obtains the low phenolic resin of free phenol content；
(3) step (2) resulting water phase adds acid for adjusting pH to neutrality, is then concentrated by evaporation and removes part water, the water phase after concentration
Acid out recycles phenol, and remaining water phase is evaporated water after recycling phenol, obtains inorganic salts.
8. preparation method according to claim 7, it is characterized in that: the phenol be phenol, resorcinol, ortho-methyl phenol,
M-methyl phenol, p-methyl phenol, p-tert-butylphenol and at least one of tert-octyl phenol；The aldehyde is formaldehyde, second
At least one of aldehyde and furfural.
9. preparation method according to claim 7, it is characterized in that: evaporating resulting water reuse in step (3).
10. preparation method according to claim 7, it is characterized in that: the molar ratio of phenol and aldehyde is 1:0.9~0.99, preferably
For 1:0.95.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910406876.9A CN110078875A (en) | 2019-05-16 | 2019-05-16 | It reduces the method for free phenol content and phenolic resin in phenolic resin and cleans preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910406876.9A CN110078875A (en) | 2019-05-16 | 2019-05-16 | It reduces the method for free phenol content and phenolic resin in phenolic resin and cleans preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110078875A true CN110078875A (en) | 2019-08-02 |
Family
ID=67420414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910406876.9A Pending CN110078875A (en) | 2019-05-16 | 2019-05-16 | It reduces the method for free phenol content and phenolic resin in phenolic resin and cleans preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110078875A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112275329A (en) * | 2020-09-30 | 2021-01-29 | 石家庄惠洁科技有限公司 | Clean production process of 122 type cation exchange resin |
| CN116376487A (en) * | 2023-05-25 | 2023-07-04 | 兰溪市克莱森助剂有限公司 | A kind of wastewater-free preparation method of rubber adhesive RE |
| EP4212563A4 (en) * | 2020-09-07 | 2024-10-09 | Sumitomo Bakelite Co., Ltd. | WATER-SOLUBLE RESOLPHENOL RESIN |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1095895A (en) * | 1996-09-24 | 1998-04-14 | Sumitomo Bakelite Co Ltd | Phenolic resin molding material |
| CN101338013A (en) * | 2008-08-11 | 2009-01-07 | 华奇（张家港）化工有限公司 | Improved Process for Production of Alkylphenol Thermoplastic Resin |
| CN101613256A (en) * | 2009-07-01 | 2009-12-30 | 新奥科技发展有限公司 | A method for producing phenolic products from coal |
| CN107585821A (en) * | 2017-09-28 | 2018-01-16 | 安徽时联特种溶剂股份有限公司 | A kind of method of phenolic compound in extraction wastewater |
-
2019
- 2019-05-16 CN CN201910406876.9A patent/CN110078875A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1095895A (en) * | 1996-09-24 | 1998-04-14 | Sumitomo Bakelite Co Ltd | Phenolic resin molding material |
| CN101338013A (en) * | 2008-08-11 | 2009-01-07 | 华奇（张家港）化工有限公司 | Improved Process for Production of Alkylphenol Thermoplastic Resin |
| CN101613256A (en) * | 2009-07-01 | 2009-12-30 | 新奥科技发展有限公司 | A method for producing phenolic products from coal |
| CN107585821A (en) * | 2017-09-28 | 2018-01-16 | 安徽时联特种溶剂股份有限公司 | A kind of method of phenolic compound in extraction wastewater |
Non-Patent Citations (2)
| Title |
|---|
| 尚建选等: "《低阶煤分质转化多联产技术》", 31 May 2013, 煤炭工业出版社 * |
| 谢昕: "《有机化学》", 31 August 2008, 黄河水利出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4212563A4 (en) * | 2020-09-07 | 2024-10-09 | Sumitomo Bakelite Co., Ltd. | WATER-SOLUBLE RESOLPHENOL RESIN |
| CN112275329A (en) * | 2020-09-30 | 2021-01-29 | 石家庄惠洁科技有限公司 | Clean production process of 122 type cation exchange resin |
| CN112275329B (en) * | 2020-09-30 | 2022-08-05 | 石家庄惠洁科技有限公司 | Clean production process of 122 type cation exchange resin |
| CN116376487A (en) * | 2023-05-25 | 2023-07-04 | 兰溪市克莱森助剂有限公司 | A kind of wastewater-free preparation method of rubber adhesive RE |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110078875A (en) | It reduces the method for free phenol content and phenolic resin in phenolic resin and cleans preparation method | |
| CZ289195A3 (en) | Regeneration process of ethylene glycol being a waste when preparing polyethylene terephthalate including ethylene glycol contained in distillation residues after its purification by distillation | |
| CN110818543A (en) | Novel method for efficiently synthesizing dibenzoyl methane | |
| JP7613067B2 (en) | Method for producing bisphenol and method for producing recycled polycarbonate resin | |
| KR101166005B1 (en) | Method for producing aqueous solution of alkali metal salt of aromatic dihydroxy compound from waste aromatic polycarbonate | |
| US4161576A (en) | Control of procedures for formation of water-immiscible thermosetting phenol-formaldehyde resins | |
| Heath | Aldehyde polymers: phenolics and aminoplastics | |
| CN104628991A (en) | Method for synthesizing o-cresol formaldehyde epoxy resin by using cosolvent and recovering cosolvent | |
| JP4118914B2 (en) | Method for producing resorcin formalin resin | |
| JPH10259151A (en) | Production of carbonic acid dialkyl ester and bisphenol from polycarbonate | |
| JP2005126358A (en) | Method for obtaining aromatic dihydroxy compound metal salt aqueous solution from waste aromatic polycarbonate | |
| US3677986A (en) | Production of para-substituted phenol/formaldehyde resins | |
| CN108329444A (en) | A kind of catalysis synthetic method for solid acid of thickening alkyl phenolic resin | |
| US3974084A (en) | Process for the manufacture of anhydrous alkali metal arylate solutions and separation of the arylates from alkali metal sulfite | |
| US2732368A (en) | Type hi phenolic resins and their | |
| CA1164141A (en) | Liquid novolak resin and products made therefrom | |
| CN115466165B (en) | Synthesis method of 4,4' -biphenol | |
| CN105085867A (en) | Method for synthesizing phenolic ketone epoxy resin through solvent | |
| JP7524721B2 (en) | Method for producing bisphenol and method for producing recycled polycarbonate resin | |
| WO2007143356A2 (en) | Alkoxylations in ketone solvents | |
| EP3083558B1 (en) | Process for the production of phthalimides | |
| US3763104A (en) | Production of para substituted phenol formaldehyde resins using heterogeneous multi phase reaction medium | |
| JP2012116779A (en) | Method for producing polyester monomer from polyester | |
| JP2899100B2 (en) | Method for producing phenolic polymer | |
| CN111205417A (en) | Method for preparing alkylphenol phenolic resin by one-pot method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190802 |
|
| RJ01 | Rejection of invention patent application after publication |