CN111269252A - Novel boric acid ester and preparation method thereof - Google Patents
Novel boric acid ester and preparation method thereof Download PDFInfo
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- CN111269252A CN111269252A CN202010223879.1A CN202010223879A CN111269252A CN 111269252 A CN111269252 A CN 111269252A CN 202010223879 A CN202010223879 A CN 202010223879A CN 111269252 A CN111269252 A CN 111269252A
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- borate
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- ethanolamine
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- -1 boric acid ester Chemical class 0.000 title claims abstract description 34
- 239000004327 boric acid Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 10
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000003960 organic solvent Substances 0.000 claims abstract description 21
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- NDVWOBYBJYUSMF-UHFFFAOYSA-N 2-methylcyclohexan-1-ol Chemical compound CC1CCCCC1O NDVWOBYBJYUSMF-UHFFFAOYSA-N 0.000 claims abstract description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- 239000006227 byproduct Substances 0.000 claims abstract description 4
- 238000005886 esterification reaction Methods 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000005917 acylation reaction Methods 0.000 claims abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 5
- GBIUMNKDHLXIIA-UHFFFAOYSA-N (2-methylcyclohexyl)oxyboronic acid Chemical compound CC1CCCCC1OB(O)O GBIUMNKDHLXIIA-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 150000001642 boronic acid derivatives Chemical class 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- 239000007822 coupling agent Substances 0.000 description 17
- 239000002131 composite material Substances 0.000 description 7
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 229940043237 diethanolamine Drugs 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 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 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- LBZRRXXISSKCHV-UHFFFAOYSA-N [B].[O] Chemical group [B].[O] LBZRRXXISSKCHV-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000006277 exogenous ligand Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005303 weighing Methods 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
- C07F5/04—Esters of boric acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The invention relates to the field of organic borate compounds, in particular to a novel borate and a preparation method thereof, which comprises the following steps: firstly, carrying out esterification reaction on boric acid and 2-methylcyclohexanol in an organic solvent I by using a solvent method according to the following reaction formula 1), and purifying to obtain an intermediate o-methyl cyclohexyl borate after anhydrous generation; and secondly, dissolving the intermediate o-methyl cyclohexyl borate in an organic solvent II, performing acylation reaction with ethanolamine according to the following reaction formula 2), evaporating the organic solvent II under normal pressure until no water is generated, and evaporating excessive ethanolamine and byproducts under reduced pressure to obtain the borate shown in the structural formula (I). Compared with the prior art, the invention has the following beneficial effects: 1) can increase the steric hindrance of molecules, slow down the hydrolysis speed of the modified material and improve the compatibility with the polymer. 2) The product has low toxicity, high efficiency and environmental protection. 3) The preparation method has simple operation, mild condition and easy control.
Description
Technical Field
The invention relates to the field of organic borate compounds, in particular to novel borate and a preparation method thereof.
Background
The borate coupling agent is a novel coupling agent developed in the 80 th century, is an effective coupling agent for plastic fillers, has excellent characteristics which are not possessed by the traditional coupling agents such as silane coupling agents, titanate coupling agents and the like, has a molecular structure with a boron-oxygen skeleton, and can generate good physical adsorption with inorganic fillers. The production raw materials of the borate coupling agent mainly comprise boric acid and long-chain fatty alcohol, the production process is simple, the production cost is low, and the borate coupling agent is a coupling agent with high cost performance and is a boron fine chemical product with a good application prospect.
Because boron atoms in the center of the borate coupling agent have unique valence electron configuration and strong molecular designability, the borate coupling agent has excellent characteristics which are not possessed by other traditional coupling agents, such as antistatic property, wear resistance, lubricity, antibacterial property, corrosion resistance, flame retardant property and the like, the talc powder is modified by the borate coupling agent, the process is simple, the cost is low, and the modification effect is good, so the synthesis and performance research of the borate coupling agent is concerned all the time.
Because the boron atom in the center of the borate is sp2 hybridized, there is an empty p orbital which is susceptible to attack by nucleophiles such as water with unshared electron pairs to hydrolyze the borate to the boronic acid and the corresponding alcohol. However, the molecular structure of the borate ester can be designed, so that the hydrolytic stability is improved, and the attack of water molecules is inhibited. The hydrolysis resistance of the borate is related to the structure in the molecule, the longer the alkyl chain is, the less susceptible to attack by nucleophilic reagents, and in addition, the steric hindrance of the ester group can inhibit the hydrolysis of the borate coupling agent to a certain extent.
Disclosure of Invention
The invention aims to provide a novel boric acid ester and a preparation method thereof, overcomes the defects of the prior art, and develops a boric acid ester coupling agent with a novel structure, and a cycloalkyl functional group is connected to a B-O bond of the boric acid ester coupling agent to play a role in increasing molecular steric hindrance and slowing down hydrolysis speed.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the technical scheme is as follows: a novel boric acid ester is characterized in that the structure is shown as formula (I):
the second technical proposal is that: a preparation method of novel borate is characterized by comprising the following specific steps:
firstly, carrying out esterification reaction on boric acid and 2-methylcyclohexanol in an organic solvent I according to the following reaction formula 1) by using a solvent method, dripping the 2-methylcyclohexanol into a mixture of the boric acid and the organic solvent I at the temperature of 20-40 ℃, heating the mixed solution to 110-130 ℃, reacting for 4-7 h until no water is generated, and purifying to obtain an intermediate o-methylcyclohexyl borate shown in a structural formula (II);
And secondly, dissolving the intermediate o-methyl cyclohexyl borate synthesized in the first step in an organic solvent II to perform esterification reaction with ethanolamine according to the following reaction formula 2), dropwise adding ethanolamine into a mixture of the intermediate o-methyl cyclohexyl borate and the organic solvent II at normal temperature, heating the mixed solution to 110-130 ℃, reacting for 18-30 h, evaporating the organic solvent II under normal pressure until no water is generated, and then evaporating excessive ethanolamine and byproducts under reduced pressure to obtain the borate shown in the structural formula (I).
The molar ratio of the boric acid to the 2-methylcyclohexanol in the first-step reaction is 1: 1.
The organic solvent I and the organic solvent II are chloroform or toluene.
In the first step of reaction, when the 2-methyl cyclohexanol is added, the temperature of the mixture of the boric acid and the organic solvent I is preferably 30 ℃, and then the temperature of the mixture is raised to 120 ℃, and the heating mode is oil bath.
In the first-step reaction, the stirring speed is 45-150 r/min, and the 2-methylcyclohexanol is dripped off within 60 seconds.
In the first-step reaction, a reflux device is connected to the reaction device.
The molar ratio of the intermediate o-methyl cyclohexyl borate to the ethanolamine in the second step of reaction is 1: 2.
In the second-step reaction, ethanolamine is dropwise added into a mixture of the intermediate o-methylcyclohexyl borate and the organic solvent II at normal temperature, and then the mixture is heated to 120 ℃.
In the second step of reaction, the stirring speed is 45-150 r/min, and the ethanolamine is dripped within 120 seconds.
Compared with the prior art, the invention has the following beneficial effects: 1) the novel boric acid ester provided by the invention can be connected with a naphthenic base functional group on a B-O bond, so that the molecular steric hindrance can be increased, the water erosion can be effectively inhibited, the hydrolysis speed of the modified material can be slowed down, and meanwhile, the amino groups on the branched chains on the other two sides can provide an exogenous ligand and can improve the compatibility with a polymer. 2) The novel borate provided by the invention has the advantages of low toxicity, high efficiency and environmental protection, and is beneficial to sustainable development. 3) The preparation method provided by the invention has the advantages of simple operation, mild conditions and easy control, and does not need complex post-treatment.
Detailed Description
The following examples are presented to further illustrate embodiments of the present invention:
examples are given.
1. Preparation of boric acid o-methylcyclohexanol diethanolamine ester
Firstly, adding 12.4g (0.2 moL) of boric acid and 2moL of toluene solvent into a 250ml three-neck flask with a magnetic stirrer and a water separator, starting stirring, slowly dropwise adding 22ml (0.2 moL) of 2-methylcyclohexanol at 30 ℃, heating to 120 ℃ after dropwise adding (about 60 min), carrying out reflux reaction until no water is generated in the water separator (about 6 h), and purifying by using a rotary evaporator to obtain 27.49g (0.174 moL) of intermediate o-methylcyclohexyl borate (hereinafter abbreviated as MCLB).
And secondly, adding MCLB15.8g (0.1 mol) into a 500ml three-necked bottle, adding 186ml of toluene solution, slowly dropwise adding 13.4ml (0.22mol) of ethanolamine at normal temperature, heating to 120 ℃ after dropwise adding (about 80 min), carrying out reflux reaction under magnetic stirring until no water is generated in a water separator (about 22 h), and cooling to room temperature after reaction is stopped. And (3) installing a distillation device, distilling off toluene at normal pressure, and then distilling off excessive ethanolamine and byproducts at reduced pressure to obtain 17.46g (0.0745 mol) of boric acid o-methylcyclohexanol diethanol amine ester (MCDAB).
2. Preparation of boric acid o-methylcyclohexanol diethanol amine ester modified talcum powder/polypropylene composite material
Firstly, 10g of boric acid o-methylcyclohexanol diethanol amine ester is dissolved in an ethanol solution, sprayed on 2000g of talcum powder, mixed for 10min by a high-speed mixer, and then dried in vacuum for standby. And secondly, weighing 1000g of polypropylene and 100g of modified talcum powder respectively, and preparing the polypropylene composite material through extrusion, granulation and molding.
The unmodified talcum powder/PP composite material and the KH550 modified talcum powder/PP composite material are respectively prepared by the same method and using amount, the mechanical properties of the composite materials are respectively tested (as shown in table 1), and the table 1 shows that the mechanical properties of the talcum powder composite material modified by the boric acid o-methylcyclohexanol diethanol amine ester are greatly improved, so that the boric acid o-methylcyclohexanol diethanol amine ester as a coupling agent has a good coupling effect on an interface.
TABLE 1 mechanical Properties of the composites
Claims (10)
1. A novel boric acid ester is characterized in that the structure is shown as formula (I):
2. the method for preparing the novel borate ester according to claim 1, comprising the following steps:
firstly, boric acid and 2-methylcyclohexanol are subjected to esterification reaction in an organic solvent I according to the following reaction formula 1) by using a solvent method, 2-methylcyclohexanol is dripped into a mixture of the boric acid and the organic solvent I at the temperature of 20-40 ℃, the temperature of a mixed solution is increased to 110-130 ℃, the reaction is carried out for 4-7 h until no water is generated, and the intermediate o-methylcyclohexyl borate shown in the structural formula (II) is obtained after purification
Secondly, dissolving the intermediate o-methyl cyclohexyl borate synthesized in the first step into an organic solvent II, and carrying out acylation reaction with ethanolamine according to the following reaction formula 2), dropwise adding ethanolamine into a mixture of the intermediate o-methyl cyclohexyl borate and the organic solvent II at normal temperature, heating the mixed solution to 110-130 ℃, reacting for 18-30 h, evaporating the organic solvent II under normal pressure until no water is generated, and then evaporating excess ethanolamine and byproducts under reduced pressure to obtain the borate shown in the structural formula (I);
formula 2)
3. The method for producing a novel borate according to claim 2, wherein the molar ratio of boric acid to 2-methylcyclohexanol in the first-step reaction is 1 moL: 1 moL.
4. The method for preparing the novel borate ester according to claim 2, wherein the organic solvent I and the organic solvent II are chloroform, toluene, xylene or a mixture thereof in any proportion.
5. The method for preparing a novel borate according to claim 2, wherein in the first reaction step, when the 2-methylcyclohexanol is added, the temperature of the mixture of the boric acid and the first organic solvent is preferably 20 to 40 ℃, and thereafter the temperature of the mixture is raised to 110 to 130 ℃, and the heating means is an oil bath.
6. The method for producing a novel borate ester according to claim 2, wherein in the first-step reaction, the stirring speed is 45 to 150 rpm, and the 2-methylcyclohexanol is dropped within 60 seconds.
7. The method for producing a novel boronic acid ester according to claim 2, wherein a reflux apparatus is connected to the reaction apparatus in the first-step reaction.
8. The method for producing a novel boronic acid ester according to claim 2, wherein the molar ratio of the intermediate o-methylcyclohexyl boronic acid ester to the ethanolamine in the second-step reaction is 1: 2.
9. The method for producing a novel boronic acid ester according to claim 2, wherein in the second-step reaction, ethanolamine is added dropwise to a mixture of the intermediate o-methylcyclohexyl boronic acid ester and the organic solvent ii at room temperature, and thereafter the mixture is heated to 110 to 130 ℃.
10. The method for producing a novel boronic acid ester according to claim 2, wherein in the second-step reaction, the stirring speed is 45 to 150 rpm, and the ethanolamine is dropped within 120 seconds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010223879.1A CN111269252A (en) | 2020-03-26 | 2020-03-26 | Novel boric acid ester and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010223879.1A CN111269252A (en) | 2020-03-26 | 2020-03-26 | Novel boric acid ester and preparation method thereof |
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| Publication Number | Publication Date |
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| CN111269252A true CN111269252A (en) | 2020-06-12 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202010223879.1A Withdrawn CN111269252A (en) | 2020-03-26 | 2020-03-26 | Novel boric acid ester and preparation method thereof |
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| Country | Link |
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| CN (1) | CN111269252A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113004779A (en) * | 2021-03-01 | 2021-06-22 | 青岛爱尔家佳新材料股份有限公司 | Polyurea coating for seepage prevention of storage power station warehouse basin and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4073766A (en) * | 1976-12-15 | 1978-02-14 | Dart Industries, Inc. | Organic borate coupling agents |
| CN102000527A (en) * | 2010-09-30 | 2011-04-06 | 青岛四维化工有限公司 | Modified boric acid ester interface activating agent and preparation method thereof |
-
2020
- 2020-03-26 CN CN202010223879.1A patent/CN111269252A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4073766A (en) * | 1976-12-15 | 1978-02-14 | Dart Industries, Inc. | Organic borate coupling agents |
| CN102000527A (en) * | 2010-09-30 | 2011-04-06 | 青岛四维化工有限公司 | Modified boric acid ester interface activating agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王中华 等: ""新型硼酸酯偶联剂的合成及其应用"", 《塑料》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113004779A (en) * | 2021-03-01 | 2021-06-22 | 青岛爱尔家佳新材料股份有限公司 | Polyurea coating for seepage prevention of storage power station warehouse basin and preparation method thereof |
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