CN106349262B - Inorganic hybridization methylolurea and preparation method thereof - Google Patents
Inorganic hybridization methylolurea and preparation method thereof Download PDFInfo
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- CN106349262B CN106349262B CN201610620403.5A CN201610620403A CN106349262B CN 106349262 B CN106349262 B CN 106349262B CN 201610620403 A CN201610620403 A CN 201610620403A CN 106349262 B CN106349262 B CN 106349262B
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- VGGLHLAESQEWCR-UHFFFAOYSA-N N-(hydroxymethyl)urea Chemical compound NC(=O)NCO VGGLHLAESQEWCR-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000009396 hybridization Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 229910052796 boron Inorganic materials 0.000 claims abstract description 8
- 238000007031 hydroxymethylation reaction Methods 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 230000008025 crystallization Effects 0.000 claims abstract description 7
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003063 flame retardant Substances 0.000 abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 7
- 239000011733 molybdenum Substances 0.000 abstract description 7
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 5
- 239000002023 wood Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- YZYDPPZYDIRSJT-UHFFFAOYSA-K boron phosphate Chemical compound [B+3].[O-]P([O-])([O-])=O YZYDPPZYDIRSJT-UHFFFAOYSA-K 0.000 description 1
- 229910000149 boron phosphate Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011094 fiberboard Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/90—Antimony compounds
- C07F9/902—Compounds without antimony-carbon linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention belongs to inorganic hybridization technical field of polymer materials, in particular to a kind of inorganic hybridization methylolurea and preparation method thereof.It mainly includes the following steps that：(1) urea, formaldehyde and water are added into reaction kettle for hydroxymethylation, and methylol reaction is carried out under the conditions of weak alkaline medium, obtains methylolurea；(2) hydridization is reacted, and is reacted with inorganic hybridization compound；(3) cold filtration is cooled to 40~80 DEG C of crystallization filterings, obtains inorganic hybridization methylolurea.Inorganic hybridization methylolurea made from the method through the invention, by being reacted with the hybrid cross-linked of inorganic hybridization compound, so that the methylolurea ultimately generated introduces the heat-resistant fireproofs element such as boron, molybdenum, antimony, to improve the high temperature resistance and flame retardant property of methylolurea.
Description
Technical field
The invention belongs to inorganic hybridization technical field of polymer materials, in particular to a kind of inorganic hybridization methylolurea and
Preparation method.
Background technique
In the past 30 years, the timber industry in China has obtained unconventional fast development to reform and opening-up.China's wood-based plate in 2004
5446.5 ten thousand stere of (fiberboard, particieboard and glued board) total output, has reached 6393 ten thousand steres in 2005, amplification reaches
17.4%, it is 3.19 times in 2000, has gone up as the first in the world Wood-based Panel Production big country, wherein wood-based plate gluing in 2005
Agent dosage (100% solid content meter) is more than 3,500,000 tons, and urea-formaldehyde resin adhesive accounts for 90% or more of wood-based plate glue consumption,
It is the maximum kind of dosage in adhesive.Why urea-formaldehyde resin adhesive can largely use in timber industry, be due to it
With incomparable busy of other resins, it is cheapest in synthetic resin that mainly its raw material is sufficient, cheap.
In addition, Lauxite also has lot of advantages, if glue-joint strength is higher, rapidly, the glue-line after solidification is of light color for solidification, will not be dirty
Dye is glued the plate face of object, good water solubility, appropriate viscosity required for being easily modulated to and concentration.
It is well known that Lauxite also have the shortcomings that it is some obvious, as resistance to ag(e)ing is poor, heat-resisting quantity is poor, resistance
Combustion property difference etc., with the increasingly raising that people's quality of life is realized, how to improve its high temperature resistance and flame retardant property becomes
The technical problem of this field.
Summary of the invention
In order to solve the above problems existing in the present technology, the present invention provides a kind of inorganic hybridization methylolurea and its systems
Preparation Method, using urea as raw material, under the conditions of weak alkaline medium, with formaldehyde and water heating carry out hydroxymethylation, then with nothing
Machine hybrid compounds are reacted, and inorganic hybridization methylolurea, flame retardant property and high temperature resistance with higher are generated.
The technical solution adopted in the present invention is as follows：
Inorganic hybridization methylolurea, it is characterised in that：Molecular structure is as follows：
X in the molecular structure is inorganic hybridization element, including one of B or Sb.
The preparation method of the inorganic hybridization methylolurea, it is characterised in that：It mainly includes the following steps that：
By urea, formaldehyde and water, under the conditions of weak alkaline medium, heating carries out hydroxymethylation and generates methylolurea；
The methylolurea of generation is reacted 0.5~2 hour under conditions of 100~110 DEG C with inorganic hybridization compound, it is miscellaneous
Change reaction to complete, is cooled to 40~80 DEG C of crystallization filterings, obtains inorganic hybridization methylolurea.
The preparation method of the inorganic hybridization methylolurea, it is characterised in that：Including step in detail below：
(1) hydroxymethylation
Urea, formaldehyde and water are added into reaction kettle, adding alkali to adjust pH is 8.0~9.0, under conditions of 35~65 DEG C,
60~80 revs/min of revolving speed, 30~120min of heat preservation carries out methylol reaction, obtains methylolurea；
(2) hydridization is reacted
Inorganic hybridization compound and water are added into reaction kettle, is warming up to 100~110 DEG C and reacts 0.5~2 hour, hydridization
Reaction is completed；
(3) cold filtration
40~80 DEG C of crystallization filterings are cooled to, inorganic hybridization methylolurea is obtained.
The preparation method of the inorganic hybridization methylolurea, it is characterised in that：Inorganic hybridization in the step (2)
Closing object is：Boratex, potassium borate, boric acid, zinc borate, boron phosphate, four water, eight Boratex, antimony oxide, antimony pentoxide, molybdenum
One of sour sodium, potassium molybdate, zinc molybdate, ammonium molybdate, ammonium tetramolybdate or ammonium heptamolybdate.
The preparation method of the inorganic hybridization methylolurea, it is characterised in that：Alkali used in pH is adjusted in the step (1)
For sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide or potassium carbonate, mass concentration 25-35%.
The inorganic hybridization reaction principle of the invention patent：
The principle reacted can be crosslinked with boron, molybdenum, antimony element using the methylol contained on compound, realize this hair
The hydridization reaction process of bright patent eliminates reactive group because enclosing methylol, and the temperature in reaction process can be substantially
Degree is improved to 110 DEG C, and boron, molybdenum, antimony ignition-proof element are introduced on molecular structure, so that the stability of product, flame retardant property
It is substantially improved with high temperature resistance.
Above-mentioned technical proposal of the invention compared with prior art, has the following advantages that：
1, it is reacted by methylolated urea with the hybrid cross-linked of inorganic hybridization compound, so that is ultimately generated is inorganic
Hydridization methylolurea introduces the heat-resistant fireproofs element such as boron, antimony, molybdenum, to improve the high temperature resistance and resistance of methylolurea
Performance is fired, compared with the methylolurea before non-hydridization, high temperature resistance improves 50 DEG C or more, and flame retardant property improves at least
20%.
2, the preparation of the inorganic hybridization methylolurea overcomes the technology hardly possible that methylolurea molecular structure introduces ignition-proof element
Topic solves the technical problems such as outer influence and flame retardant effect of the addition fire retardant to product physical mechanical property be undesirable.
Specific embodiment
The present invention will be described in detail combined with specific embodiments below, but the invention is not limited to specific embodiments.
Embodiment 1
The preparation of boron hydridization methylolurea
Molecular structural formula：
Raw material proportioning：
(1) hydroxymethylation
Urea, formaldehyde and water is added into reaction kettle according to the above ratio, it is 8.0 that adding sodium hydroxide, which adjusts pH, at 35 DEG C
Under the conditions of, 60 revs/min of revolving speed, heat preservation 120min carries out methylol reaction, obtains methylolurea；
(2) hydridization is reacted
Four water, eight Boratex and water are added into reaction kettle, is warming up to 100 DEG C and reacts 2 hours, hydridization reaction is completed；
(3) cold filtration
40 DEG C of crystallization filterings are cooled to, boron hydridization methylolurea is obtained.
Embodiment 2
The preparation of stilba methylolurea
Molecular structural formula：
Raw material proportioning：
(1) hydroxymethylation
Urea, formaldehyde and water is added into reaction kettle according to the above ratio, adding potassium hydroxide to adjust pH is 9.0, at 65 DEG C
Under the conditions of, 80 revs/min of revolving speed, heat preservation 30min carries out methylol reaction, obtains methylolurea；
(2) hydridization is reacted
Antimony oxide and water are added into reaction kettle, is warming up to 110 DEG C and reacts 0.5 hour, hydridization reaction is completed；
(3) cold filtration
80 DEG C of crystallization filterings are cooled to, stilba methylolurea is obtained.
Embodiment 3
The preparation of molybdenum hydridization methylolurea
Molecular structural formula：
Raw material proportioning：
(1) hydroxymethylation
Urea, formaldehyde and water is added into reaction kettle according to the above ratio, adding sodium bicarbonate to adjust pH is 8.5, at 50 DEG C
Under the conditions of, 75 revs/min of revolving speed, heat preservation 90min carries out methylol reaction, obtains methylolurea；
(2) hydridization is reacted
Sodium molybdate and water are added into reaction kettle, is warming up to 105 DEG C and reacts 1.5 hours, hydridization reaction is completed；
(3) cold filtration
60 DEG C of crystallization filterings are cooled to, molybdenum hydridization methylolurea is obtained.
Claims (3)
1. inorganic hybridization methylolurea, it is characterised in that：Molecular structure is as follows：
X in the molecular structure is inorganic hybridization element, is selected from one of B or Sb.
2. the preparation method of inorganic hybridization methylolurea as described in claim 1, it is characterised in that：It mainly include following step
Suddenly：
(1) hydroxymethylation
Urea, formaldehyde and water are added into reaction kettle, adding alkali to adjust pH is 8.0~9.0, under conditions of 35~65 DEG C, revolving speed
60~80 revs/min, 30~120min of heat preservation carries out methylol reaction, obtains methylolurea；
(2) hydridization is reacted
Inorganic hybridization compound and water are added into reaction kettle, is warming up to 100~110 DEG C and reacts 0.5~2 hour, hydridization reaction
It completes；
Inorganic hybridization compound in the step (2) is：One of four water, eight Boratex, antimony oxide, sodium molybdate；
(3) cold filtration
40~80 DEG C of crystallization filterings are cooled to, inorganic hybridization methylolurea is obtained.
3. the preparation method of inorganic hybridization methylolurea according to claim 2, it is characterised in that：In the step (1)
Adjusting alkali used in pH is sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide or potassium carbonate, mass concentration 25-35%.
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| CN201610620403.5A CN106349262B (en) | 2016-08-01 | 2016-08-01 | Inorganic hybridization methylolurea and preparation method thereof |
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| CN201610620403.5A CN106349262B (en) | 2016-08-01 | 2016-08-01 | Inorganic hybridization methylolurea and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1194633A (en) * | 1995-07-28 | 1998-09-30 | 凯米拉农业公司 | Method for production of oligomethyleneurea |
| CN103848950A (en) * | 2014-03-06 | 2014-06-11 | 山东海冠化工科技有限公司 | Method for modifying phenolic resin by adopting methylolurea and method for preparing foam by utilizing modified phenolic resin |
| CN105541419A (en) * | 2015-12-28 | 2016-05-04 | 中海石油化学股份有限公司 | Preparation method of urea formaldehyde liquid fertilizer |
-
2016
- 2016-08-01 CN CN201610620403.5A patent/CN106349262B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1194633A (en) * | 1995-07-28 | 1998-09-30 | 凯米拉农业公司 | Method for production of oligomethyleneurea |
| CN103848950A (en) * | 2014-03-06 | 2014-06-11 | 山东海冠化工科技有限公司 | Method for modifying phenolic resin by adopting methylolurea and method for preparing foam by utilizing modified phenolic resin |
| CN105541419A (en) * | 2015-12-28 | 2016-05-04 | 中海石油化学股份有限公司 | Preparation method of urea formaldehyde liquid fertilizer |
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| CN106349262A (en) | 2017-01-25 |
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