CN109370149B - Modified urea-formaldehyde resin filling material for coal mine and preparation method thereof - Google Patents
Modified urea-formaldehyde resin filling material for coal mine and preparation method thereof Download PDFInfo
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- CN109370149B CN109370149B CN201811130470.4A CN201811130470A CN109370149B CN 109370149 B CN109370149 B CN 109370149B CN 201811130470 A CN201811130470 A CN 201811130470A CN 109370149 B CN109370149 B CN 109370149B
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- 239000000463 material Substances 0.000 title claims abstract description 37
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical class OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 title claims abstract description 27
- 239000003245 coal Substances 0.000 title claims abstract description 26
- 238000011049 filling Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000006260 foam Substances 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003381 stabilizer Substances 0.000 claims abstract description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000005187 foaming Methods 0.000 claims abstract description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004088 foaming agent Substances 0.000 claims abstract description 7
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 7
- 150000007524 organic acids Chemical class 0.000 claims abstract description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 7
- 239000004202 carbamide Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- -1 aldehyde compounds Chemical class 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 229940015043 glyoxal Drugs 0.000 claims description 3
- 229920002866 paraformaldehyde Polymers 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008098 formaldehyde solution Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003607 modifier Substances 0.000 abstract description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 7
- 238000005303 weighing Methods 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 230000007547 defect Effects 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
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
-
- 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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/10—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with acyclic compounds having the moiety X=C(—N<)2 in which X is O, S or —N
- C08G12/12—Ureas; Thioureas
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2361/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08J2361/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention belongs to the technical field of novel materials, and particularly relates to a modified urea-formaldehyde resin filling material for a coal mine and a preparation method thereof. The material consists of a component A and a component B, wherein the component A consists of the following raw materials in parts by mass: 90-120 parts of aldehyde compounds; 30-50 parts of urea; 15-30 parts of polyvinyl alcohol; 1-2 parts of an alkaline catalyst; 1-3 parts of a foam stabilizer; 3-8 parts of a foaming agent; the component B comprises the following raw materials in parts by mass: 25-35 parts of inorganic acid; 45-60 parts of organic acid; 5-30 parts of water. According to the invention, the polyvinyl alcohol toughening modifier is added, so that the toughness of the phenolic filling material is improved, and the sodium bicarbonate is used as a foaming agent, so that the modified urea-formaldehyde resin filling material for coal mines has the characteristics of large foaming multiplying power, low viscosity, good foam toughness, low reaction temperature, high strength, good fluidity and low price; the preparation method is energy-saving, safe and environment-friendly.
Description
Technical Field
The invention belongs to the technical field of novel materials, and particularly relates to a modified urea-formaldehyde resin filling material for a coal mine and a preparation method thereof.
Background
In the underground coal mine excavation construction process, coal and rock cavities, various cracks and goafs in a high caving region are easy to become an underground gas emission channel and a gathering region, so that certain potential safety hazards are brought. The filling materials used in the prior coal mine are mainly phenolic and polyurethane materials, have good gas barrier property and foamability, and are widely applied to permanent (temporary) sealing of coal mines and tunnels to prevent air leakage and gas emission and aggregation in goafs. The polyurethane filling material has excellent mechanical property and good toughness, but has poor flame retardance, high reaction temperature, easy heat accumulation during reaction (the internal reaction temperature can reach over 160 ℃), and even fuming and spontaneous combustion under certain conditions. The phenolic filling material has the advantages of large foaming multiplying power and excellent flame-retardant antistatic performance, but the phenolic filling material has the defects of large slurry viscosity, poor pourability, low foam strength, easy pulverization and shedding and the like, and in addition, the polyurethane and phenolic filling materials have the disadvantage of higher price, thereby influencing the application thereof from the economic perspective.
The urea-formaldehyde resin is mostly in a rigid structure and lacks flexible groups, so that the toughness of the urea-formaldehyde resin filling material foam is poor.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a modified urea-formaldehyde resin filling material for coal mines, which has the advantages of large foaming ratio, low viscosity, good foam toughness, low reaction temperature, high strength, good fluidity and low price; the invention also provides a preparation method of the composite material, which is energy-saving, safe and environment-friendly.
The modified urea-formaldehyde resin filling material for coal mines consists of a component A and a component B, wherein,
the component A comprises the following raw materials in parts by mass:
the component B comprises the following raw materials in parts by mass:
25-35 parts of inorganic acid;
45-60 parts of organic acid;
5-30 parts of water.
Wherein:
the aldehyde compound is one or more of 37% formaldehyde solution, glyoxal, glutaraldehyde or paraformaldehyde.
The alkaline catalyst is one or more of sodium hydroxide, potassium hydroxide or sodium carbonate.
The foam stabilizer is an organic silicon foam stabilizer. Preferably AK8805, manufactured by Jiangsu Mesde Chemicals GmbH.
The foaming agent is sodium bicarbonate.
The inorganic acid is one or more of hydrochloric acid, dilute sulfuric acid or phosphoric acid.
The organic acid is one or more of acetic acid, oxalic acid, p-toluenesulfonic acid, citric acid, benzoic acid or terephthalic acid.
The preparation method of the modified urea-formaldehyde resin filling material for the coal mine comprises the following steps:
1) preparation of component A: stirring and reacting an aldehyde compound, urea and an alkaline catalyst at 70-80 ℃ for 1-1.5 h; adding polyvinyl alcohol, and continuously stirring and keeping the temperature for 1-1.5h at 60-80 ℃; cooling to 20-35 deg.C, adding foam stabilizer and foaming agent, and stirring to obtain component A;
2) preparation of the component B: mixing inorganic acid, organic acid and water uniformly to obtain a component B;
3) when in use, the component A and the component B are mixed according to the ratio of A: b is 4: 1-1: 1, and carrying out foaming reaction to obtain the modified urea-formaldehyde resin filling material for coal mine.
The urea resin has the following structure:
the polyvinyl alcohol is introduced into the urea-formaldehyde resin structure to modify the urea-formaldehyde resin, so that the urea-formaldehyde resin is structurally toughened and modified, and the toughness of the phenolic resin is improved. The structure of the modified urea resin is as follows:
compared with the prior art, the invention has the following beneficial effects:
1. the toughness of the traditional urea resin filling material is greatly improved by adding the polyvinyl alcohol toughening modifier.
2. The sodium bicarbonate is used as the foaming agent, so that the cost can be effectively reduced and the pollution can be reduced.
3. The acidity degree of the component B is increased and decreased by changing the using amount of each component in the component B, when the acidity is enhanced, the curing speed of the material is increased, otherwise, the curing speed of the material is reduced, so that various working condition requirements are met.
4. The modified urea-formaldehyde resin filling material for coal mines prepared by the invention has the advantages of low material cost, high foaming ratio, low viscosity, low reaction temperature (the internal reaction temperature is less than 50 ℃), high strength and good fluidity.
5. The preparation method disclosed by the invention is energy-saving, safe and environment-friendly.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1
Weighing 87g of 37% formaldehyde water solution, 23g of paraformaldehyde, 40g of urea, 1.5g of sodium hydroxide and 0.8g of sodium carbonate, stirring and reacting at 80 ℃ for 1.5h, then adding 20g of polyvinyl alcohol, continuing stirring and reacting at 70 ℃ for 1.5h, cooling to 20 ℃, adding 2g of foam stabilizer AK8805 and 3g of sodium bicarbonate into the reaction product, and uniformly stirring to obtain a component A; weighing 120g of p-toluenesulfonic acid, 40g of phosphoric acid (85%), 25g of hydrochloric acid and 20g of water, and uniformly mixing to obtain the component B.
A, B components are mixed according to the proportion of A: b is 1: 1, and foaming to obtain the modified urea-formaldehyde resin filling material for the coal mine, wherein the detection performance is as follows:
example 2
Weighing 70g of glyoxal, 52g of 37% formaldehyde water solution, 40g of urea, 1.5g of sodium hydroxide and 0.8g of sodium carbonate, stirring and reacting at 80 ℃ for 1.5h, then adding 20g of polyvinyl alcohol, continuing stirring and reacting at 60 ℃ for 1.5h, cooling to 30 ℃, adding 2g of foam stabilizer AK8805 and 7g of sodium bicarbonate into the reaction product, and uniformly stirring to obtain a component A; weighing 120g of p-toluenesulfonic acid, 40g of phosphoric acid (85%), 25g of hydrochloric acid and 20g of water, and uniformly mixing to obtain the component B.
A, B components are mixed according to the proportion of A: b is 4: 1, and foaming to obtain the modified urea-formaldehyde resin filling material for the coal mine, wherein the detection performance is as follows:
example 3
Weighing 110g of 37% formaldehyde water solution, 40g of urea and 1.5g of sodium hydroxide, stirring and reacting at 80 ℃ for 1.5h, then adding 30g of polyvinyl alcohol, continuing to stir and react at 80 ℃ for 1.5h, cooling to 35 ℃, adding 2g of foam stabilizer AK8805 and 5g of sodium bicarbonate into the reaction product, and uniformly stirring to obtain a component A; weighing 70g of benzoic acid, 30g of terephthalic acid, 50g of phosphoric acid (85%), 15g of hydrochloric acid and 20g of water, and uniformly mixing to obtain the component B.
A, B components are mixed according to the proportion of A: b is 1: 1, and foaming to obtain the modified urea-formaldehyde resin filling material for the coal mine, wherein the detection performance is as follows:
Claims (8)
1. the modified urea-formaldehyde resin filling material for the coal mine is characterized in that: consists of a component A and a component B, wherein,
the component A comprises the following raw materials in parts by mass:
the component B comprises the following raw materials in parts by mass:
25-35 parts of inorganic acid;
45-60 parts of organic acid;
5-30 parts of water.
2. The modified urea-formaldehyde resin filler material for coal mines as set forth in claim 1, wherein: the aldehyde compound is one or more of 37% formaldehyde solution, glyoxal, glutaraldehyde or paraformaldehyde.
3. The modified urea-formaldehyde resin filler material for coal mines as set forth in claim 1, wherein: the alkaline catalyst is one or more of sodium hydroxide, potassium hydroxide or sodium carbonate.
4. The modified urea-formaldehyde resin filler material for coal mines as set forth in claim 1, wherein: the foam stabilizer is an organic silicon foam stabilizer.
5. The modified urea-formaldehyde resin filler material for coal mines as set forth in claim 1, wherein: the foaming agent is sodium bicarbonate.
6. The modified urea-formaldehyde resin filler material for coal mines as set forth in claim 1, wherein: the inorganic acid is one or more of hydrochloric acid, dilute sulfuric acid or phosphoric acid.
7. The modified urea-formaldehyde resin filler material for coal mines as set forth in claim 1, wherein: the organic acid is one or more of acetic acid, oxalic acid, p-toluenesulfonic acid, citric acid, benzoic acid or terephthalic acid.
8. The preparation method of the modified urea-formaldehyde resin filling material for the coal mine as claimed in any one of claims 1 to 7, which is characterized by comprising the following steps: the method comprises the following steps:
1) preparation of component A: stirring and reacting an aldehyde compound, urea and an alkaline catalyst at 70-80 ℃ for 1-1.5 h; adding polyvinyl alcohol, and continuously stirring and keeping the temperature for 1-1.5h at 60-80 ℃; cooling to 20-35 deg.C, adding foam stabilizer and foaming agent, and stirring to obtain component A;
2) preparation of the component B: mixing inorganic acid, organic acid and water uniformly to obtain a component B;
3) when in use, the component A and the component B are mixed according to the ratio of A: b is 4: 1-1: 1, and carrying out foaming reaction to obtain the modified urea-formaldehyde resin filling material for coal mine.
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| CN103214789B (en) * | 2013-04-17 | 2015-04-29 | 北京东方雨虹防水技术股份有限公司 | Urea formaldehyde filling material and preparation method thereof |
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|---|---|
| CN109370149A (en) | 2019-02-22 |
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Address after: No. 1001, Sujia village, Beijiao Town, Zhoucun District, Zibo City, Shandong 255300 Patentee after: SHANDONG RUNKING ENVIRONMENTAL PROTECTION NEW MATERIAL TECHNOLOGY CO.,LTD. Address before: 255300 Sujia village, Beijiao Town, Zhoucun District, Zibo City, Shandong Province (south of Shitai Road, east of Suyuan Road) Patentee before: SHANDONG RUNKING ENVIRONMENTAL PROTECTION NEW MATERIAL TECHNOLOGY CO.,LTD. |
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Denomination of invention: Modified urea formaldehyde resin filling material and its preparation method for coal mines Effective date of registration: 20230629 Granted publication date: 20210709 Pledgee: Agricultural Bank of China Limited Zibo Zhoucun sub branch Pledgor: SHANDONG RUNKING ENVIRONMENTAL PROTECTION NEW MATERIAL TECHNOLOGY CO.,LTD. Registration number: Y2023980046166 |
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Granted publication date: 20210709 Pledgee: Agricultural Bank of China Limited Zibo Zhoucun sub branch Pledgor: SHANDONG RUNKING ENVIRONMENTAL PROTECTION NEW MATERIAL TECHNOLOGY CO.,LTD. Registration number: Y2023980046166 |
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Denomination of invention: Modified urea formaldehyde resin filling material and its preparation method for coal mines Granted publication date: 20210709 Pledgee: Agricultural Bank of China Limited Zibo Zhoucun sub branch Pledgor: SHANDONG RUNKING ENVIRONMENTAL PROTECTION NEW MATERIAL TECHNOLOGY CO.,LTD. Registration number: Y2024980006276 |
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