CN106905657A - A kind of coal and rock reinforcement material and its preparation facilities - Google Patents
A kind of coal and rock reinforcement material and its preparation facilities Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08L61/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08L61/24—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
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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- 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
- C08G2101/00—Manufacture of cellular products
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention provides a kind of coal and rock reinforcement material, the reinforcement material is by component A and B component in mass ratio 12：1 composition, the component A is polyurethane high molecule material, and the B component is urea-formaldehyde materials；The compounding of rational proportion is carried out while of the invention creative using polyurethane high molecule reinforcement material and Lauxite reinforcement material, at the same time while two kinds of reinforcement material excellent properties of summary, also compensate for respective defect, preparation-obtained composite consolidation material has very excellent cohesiveness, resistance to compression tensile property and impact resistance acid-proof alkaline, and a kind of suitable reinforcement material is provided for the coal petrography colliery of high request reinforces.
Description
Technical field
The invention belongs to Grouting field of material technology, and in particular to a kind of coal and rock reinforcement material and its preparation facilities.
Background technology
Rich coal resources in China, extensively, coal bed texture is complicated for distributional region.In the mining process in colliery, can not keep away
Exempt to run into the coal body of loose crushing, low intensity, stability is poor, and side fall roof easily occurs in tunneling process, therefore in order to protect
Card mine safety production must carry out advance reinforcement to breaking roof, efficiently control country rock and be caving.
In last century, underground mine use reinforcement material mainly injects the advance reinforcement branch for being used as coal and rock with cement mortar
Shield, but cement mortar reinforcing hardening time is oversize, and or so one week of needs is fully cured, and greatly reduces production efficiency, and oneself takes
Disappear and use.
Into the beginning of this century, China introduces polyurethane material and carries out advance reinforcement supporting from foreign countries.The reference of polyurethane, contracting
Short hardening time, being fully cured only needs or so hour, improves the production efficiency of coal.Polyurethane injecting paste material be with
Polyisocyanates and rob more based compound it is aggregated reaction prepare chemical slip casting material, be widely used in water conservancy and hydropower, building,
In traffic engineering and field of mining, waterproofing and leakage-stopping effect is played to movement joint, construction joint, structural joint, it is complicated to structure foundation
Play the effect such as reinforcement and strengthening in stratum.However, existing hydrophilic polyurethane water reinforcement material is generally prepolymer method preparing, obtain
To performed polymer viscosity it is larger, it is necessary to adding solvent is diluted to suitable viscosity.The diluent for using mostly acetone, dimethylbenzene etc.
Organic solvent.Low boiling point, it is inflammable.Either there is larger harm to direct labor or workmen.In mining environment,
Due to the volatilization of organic solvent, the danger of blast is had.And for many years, have both at home and abroad a large amount of because cutting grouting soil draws
The report of the fire for rising.And due to its volatilization, inflammability, high is compared with the equipment requirement of transport to storage, improves into wood,
Also there is potential safety hazard during the use of colliery.And urea-formaldehyde materials internal reaction temperature is relatively low below 60 DEG C, use
Urea-formaldehyde materials are reinforced, and cost has been saved while mining safety is improved, but prior art Lauxite class slip casting
Material, when in use easily foaming causes that compression strength is low, poor toughness, it is difficult to popularization and application.Prior art is not related to also together
When carry out rational proportion using polyurethane and Lauxite and prepare the report of reinforcement material, exploitation is provided simultaneously with polyurethane and urea
The reinforcement material of urea formaldehyde advantage is a new direction of reinforcement of coal and rock investigation of materials.
The content of the invention
It is short it is an object of the invention to provide a kind of hardening time for above-mentioned deficiency of the prior art, resistance to compression, tensile strength with
And bond strength is high, impact resistance, the compound coal petrography reinforcement material of acid-fast alkali-proof excellent performance.
To solve the above problems, the technical solution adopted by the present invention is：
A kind of coal and rock reinforcement material, the reinforcement material is by component A and B component 1-2 in mass ratio：1 composition；
Wherein, the component A is made up of A1 components and A2 components, and A1 components are by PPG 30-50 parts, PEPA
20-40 parts, composite catalyst 0.5-2 parts, fire retardant 5-10 parts, foam stabiliser 0.5-1 parts of composition；A2 components are more sub-
Methyl polyphenyl polyisocyanate；
The B component is made up of resin components with curing agent component, and the resin components include Lauxite 40-60 parts, poly- second
Glycol 10-20 parts, 10-20 parts, antistatic additive 5-10 parts of dispersant of dilution；The curing agent by benzene sulfonic acid 20-40 parts, it is inorganic
Sour 20-30 parts, inorganic ammonium salt 2-4 parts and water 5-30 parts of composition.
In addition, the volume ratio of the A1 and A2 components is 1：1；The volume ratio of resin components and curing agent component in B component
It is 4：1.
The composite catalyst is tertiary amine catalyst and organic tin catalyst according to 10：1 mass ratio is composited；
The tertiary amine catalyst is triethylene diamine or five methyl diethylentriamine, and the organic tin catalyst is tin dilaurate
Dioctyltin or dibutyltin diacetate.
The degree of functionality of described PPG is 2-4, and molecular weight is 500-800, and hydroxyl value is 100-500mgKOH/g；Institute
The degree of functionality of the PEPA stated is 2-6, and molecular weight is 300-900, and hydroxyl value is 200-400mgKOH/g.
The fire retardant is TCPP；The foam stabiliser is silicone oil foam stabiliser, specially AK-
8803 or H-3612 foam stabilisers.
The viscosity of the poly methylene poly phenyl poly isocyanate is 180-240mPa.s, and-NCO (wt%) is 30-34%.
The antistatic additive is one or more in sodium alkyl sulfonate, tween.
The inorganic acid is sulfuric acid or hydrochloric acid, and the inorganic ammonium salt is ammonium sulfate or ammonium chloride, and the dilution dispersant is
Propylene carbonate.
The preparation method of the A1 components is：To be mixed and stirred in PPG, PEPA input reactor
Uniformly, stirred in catalyst, fire retardant and foam stabiliser then being added into reactor；Resin in the B component
The preparation method of component is：During Lauxite, polyethylene glycol, dilution dispersant and antistatic additive first put into reactor successively,
Stir, then add alkali regulation pH between 8-9, to be warming up to 60-80 DEG C of reaction 2-3h, stop heating, then acid adding regulation
It is 20-30s that pH is 6-7 and adjusts viscosity, is cooled to 30 DEG C of dischargings.
In addition, the present invention is also claimed the preparation facilities of the reinforcement material, the preparation facilities is stirred for Electromagnetic Heating
Mix tank.
Technique effect of the invention is：Polyurethane high molecule reinforcement material and ureaformaldehyde are used while of the invention creative
Resin reinforcement material carries out the compounding of rational proportion, at the same time while two kinds of reinforcement material excellent properties of summary, also more
Mended respective defect, preparation-obtained composite consolidation material have very excellent cohesiveness, resistance to compression tensile property and
Impact resistance acid-proof alkaline, a kind of suitable reinforcement material is provided for the coal petrography colliery of high request reinforces.
Specific embodiment
Technical scheme is further elaborated with reference to embodiment：
Embodiment 1
The preparation of A1 components：It is 3 to take degree of functionality, and molecular weight is 600, and hydroxyl value is 40 parts of PPG, the official of 300mgKOH/g
Energy degree is 5, and molecular weight is 700, and hydroxyl value is uniform to be mixed and stirred in 30 parts of input reactors of 300mgKOH/g PEPAs,
Then by 1 part of composite catalyst, 0.8 part of addition reactor of 8 parts of fire retardant TCPP and AK-8803 foam stabilisers
In stir；The composite catalyst is triethylene diamine and Bis(lauroyloxy)dioctyltin according to 10：1 mass ratio
It is composited；
The preparation of resin components in B component：First by 50 parts of Lauxite, 15 parts of polyethylene glycol, dilution dispersant propane diols carbonic acid
8 parts of 15 parts of ester and antistatic additive sodium alkyl sulfonate put into reactor successively, stir, and then ammonification water regulation pH is 8.5,
70 DEG C of reaction 2.5h are warming up to, stop heating, then add watery hydrochloric acid regulation pH to be 6.5 and adjust viscosity for 25s, be cooled to 30 DEG C
Discharging；
The preparation of curing agent component in B component：By 30 parts of benzene sulfonic acid, 25 parts of sulfuric acid, 20 parts of addition reactors of 3 parts of ammonium chloride and water
In, stirring mixing at room temperature discharges for 1 hour；
The preparation of curing agent：It is 200mPa.s by A1 components and viscosity ,-NCO (wt%) is 32% polymethylene polyphenyl polyisocyanate
The A2 components of cyanate by volume 1：1, resin components and curing agent component by volume 4 in B component：Stirred after 1 reaction
Mixing is mixed, and component A is controlled to 1 with the mass ratio of B component：2.
Embodiment 2
The preparation of A1 components：It is 2 to take degree of functionality, and molecular weight is 500, and hydroxyl value is 30 parts of PPG, the official of 200mgKOH/g
Energy degree is 4, and molecular weight is 600, and hydroxyl value is uniform to be mixed and stirred in 20 parts of input reactors of 400mgKOH/g PEPAs,
Then 0.8 part of 1.5 parts of composite catalyst, 8 parts of fire retardant TCPP and H-3612 foam stabilisers are added into reaction
Stirred in kettle；The composite catalyst be five methyl diethylentriamine and Bis(lauroyloxy)dioctyltin according to
10：1 mass ratio is composited；
The preparation of resin components in B component：First by 40 parts of Lauxite, 10 parts of polyethylene glycol, dilution dispersant propane diols carbonic acid
7 parts of 15 parts of ester and antistatic additive tween put into reactor successively, stir, and then ammonification water regulation pH is 8, is warming up to 65
Then plus watery hydrochloric acid regulation pH is 7 and adjusts viscosity for 28s DEG C reaction 2.5h, stops heating, is cooled to 30 DEG C of dischargings；
The preparation of curing agent component in B component：By 20 parts of benzene sulfonic acid, 25 parts of hydrochloric acid, 20 parts of addition reactors of 3 parts of ammonium sulfate and water
In, stirring mixing at room temperature discharges for 1 hour；
The preparation of curing agent：It is 200mPa.s by A1 components and viscosity ,-NCO (wt%) is 31% polymethylene polyphenyl polyisocyanate
The A2 components of cyanate by volume 1：1, resin components and curing agent component by volume 4 in B component：Stirred after 1 reaction
Mixing is mixed, and component A is controlled to 1 with the mass ratio of B component：1.5.
Embodiment 3
The preparation of A1 components：It is 4 to take degree of functionality, and molecular weight is 800, and hydroxyl value is 50 parts of PPG, the official of 400mgKOH/g
Energy degree is 6, and molecular weight is 900, and hydroxyl value is uniform to be mixed and stirred in 40 parts of input reactors of 400mgKOH/g PEPAs,
Then by 2 parts of composite catalyst, 0.8 part of addition reactor of 8 parts of fire retardant TCPP and AK-8803 foam stabilisers
In stir；The composite catalyst is triethylene diamine and dibutyltin diacetate according to 10：1 mass ratio is combined
Form；
The preparation of resin components in B component：First by 60 parts of Lauxite, 20 parts of polyethylene glycol, dilution dispersant propane diols carbonic acid
8 parts of 15 parts of ester and antistatic additive sodium alkyl sulfonate put intos in reactor successively, stir, then ammonification water regulation pH for 9 it
Between, 70 DEG C of reaction 3h are warming up to, stop heating, then add watery hydrochloric acid regulation pH to be 7 and adjust viscosity for 25s, it is cooled to 30 DEG C
Discharging；
The preparation of curing agent component in B component：By 40 parts of benzene sulfonic acid, 30 parts of sulfuric acid, 30 parts of addition reactors of 4 parts of ammonium chloride and water
In, stirring mixing at room temperature discharges for 1 hour；
The preparation of curing agent：It is 240mPa.s by A1 components and viscosity ,-NCO (wt%) is 30% polymethylene polyphenyl polyisocyanate
The A2 components of cyanate by volume 1：1, resin components and curing agent component by volume 4 in B component：Stirred after 1 reaction
Mixing is mixed, and component A is controlled to 1 with the mass ratio of B component：2.
Comparative example 1
The preparation of A1 components：It is 3 to take degree of functionality, and molecular weight is 600, and hydroxyl value is 40 parts of PPG, the official of 300mgKOH/g
Energy degree is 5, and molecular weight is 700, and hydroxyl value is uniform to be mixed and stirred in 30 parts of input reactors of 300mgKOH/g PEPAs,
Then by 1 part of composite catalyst, 0.8 part of addition reactor of 8 parts of fire retardant TCPP and AK-8803 foam stabilisers
In stir；The composite catalyst is triethylene diamine and Bis(lauroyloxy)dioctyltin according to 10：1 mass ratio
It is composited；
The preparation of curing agent：It is 200mPa.s by A1 components and viscosity ,-NCO (wt%) is 32% polymethylene polyphenyl polyisocyanate
The A2 components of cyanate by volume 1：1 carries out reaction stirring mixing.
Comparative example 2
The preparation of resin components in B component：First by 50 parts of Lauxite, 15 parts of polyethylene glycol, dilution dispersant propane diols carbonic acid
8 parts of 15 parts of ester and antistatic additive sodium alkyl sulfonate put into reactor successively, stir, and then ammonification water regulation pH is 8.5,
70 DEG C of reaction 2.5h are warming up to, stop heating, then add watery hydrochloric acid regulation pH to be 6.5 and adjust viscosity for 25s, be cooled to 30 DEG C
Discharging；
The preparation of curing agent component in B component：By 30 parts of benzene sulfonic acid, 25 parts of sulfuric acid, 20 parts of addition reactors of 3 parts of ammonium chloride and water
In, stirring mixing at room temperature discharges for 1 hour；
The preparation of curing agent：By resin components in B component and curing agent component by volume 4：Mixing is stirred after 1 reaction i.e.
Can.
Performance to embodiment 1-3 and the product of comparative example 1-2 is evaluated, and is shown in Table 1：
Can be drawn from the experimental data of table 1：Reinforcement material of the invention is in hardening time, compression strength, bending strength, shearing resistance
Shearing stress and adhesion strength all embody excellent performance, are the preferred materials of coal petrography coal mine reinforcing material.
Finally it should be noted that：The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention,
Although being described in detail to the present invention with reference to the foregoing embodiments, for a person skilled in the art, it still may be used
Modified with to the technical scheme described in foregoing embodiments, or equivalent is carried out to which part technical characteristic.
All any modification, equivalent substitution and improvements within the spirit and principles in the present invention, made etc., should be included in of the invention
Within protection domain.
Claims (10)
1. a kind of coal and rock reinforcement material, it is characterised in that the reinforcement material is by component A and B component 1-2 in mass ratio：1 group
Into；
Wherein, the component A is made up of A1 components and A2 components, and A1 components are by PPG 30-50 parts, PEPA
20-40 parts, composite catalyst 0.5-2 parts, fire retardant 5-10 parts, foam stabiliser 0.5-1 parts of composition；A2 components are more sub-
Methyl polyphenyl polyisocyanate；
The B component is made up of resin components with curing agent component, and the resin components include Lauxite 40-60 parts, poly- second
Glycol 10-20 parts, 10-20 parts, antistatic additive 5-10 parts of dispersant of dilution；The curing agent by benzene sulfonic acid 20-40 parts, it is inorganic
Sour 20-30 parts, inorganic ammonium salt 2-4 parts and water 5-30 parts of composition.
2. coal and rock reinforcement material according to claim 1, it is characterised in that the volume ratio of the A1 and A2 components is 1：
1；Resin components and the volume ratio of curing agent component are 4 in B component：1.
3. coal and rock reinforcement material according to claim 1, it is characterised in that the composite catalyst is tertiary amines catalysis
Agent is with organic tin catalyst according to 10：1 mass ratio is composited；The tertiary amine catalyst is triethylene diamine or five first
Base diethylenetriamines, the organic tin catalyst is Bis(lauroyloxy)dioctyltin or dibutyltin diacetate.
4. coal and rock reinforcement material according to claim 2, it is characterised in that the degree of functionality of described PPG is
2-4, molecular weight is 500-800, and hydroxyl value is 100-500mgKOH/g；The degree of functionality of described PEPA is 2-6, molecular weight
It is 300-900, hydroxyl value is 200-400mgKOH/g.
5. coal and rock reinforcement material according to claim 3, it is characterised in that the fire retardant is TCPP；
The foam stabiliser is silicone oil foam stabiliser.
6. coal and rock reinforcement material according to claim 4, it is characterised in that the polymethylene polyphenyl polyisocyanic acid
The viscosity of ester is 180-240mPa.s, and-NCO (wt%) is 30-34%.
7. coal and rock reinforcement material according to claim 4, it is characterised in that the antistatic additive be sodium alkyl sulfonate,
One or more in tween.
8. coal and rock reinforcement material according to claim 4, it is characterised in that the inorganic acid is sulfuric acid or hydrochloric acid, institute
Inorganic ammonium salt is stated for ammonium sulfate or ammonium chloride, the dilution dispersant is propylene carbonate.
9. coal and rock reinforcement material according to claim 4, it is characterised in that the preparation method of the A1 components is：Will
It is mixed and stirred for uniformly, then by catalyst, fire retardant and foam stabilization in PPG, PEPA input reactor
Agent stirs in adding reactor；The preparation method of resin components is in the B component：First by Lauxite, poly- second
Glycol, dilution dispersant and antistatic additive put into reactor successively, stir, and then add alkali regulation pH between 8-9, to rise
Temperature stops heating to 60-80 DEG C of reaction 2-3h, then adds acid for adjusting pH to be 6-7 and adjust viscosity for 20-30s, is cooled to 30 DEG C
Discharging.
10. the preparation facilities of reinforcement material described in a kind of claim 9, it is characterised in that the preparation facilities is Electromagnetic Heating
Agitator tank.
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| CN201710227390.XA CN106905657B (en) | 2017-04-10 | 2017-04-10 | A kind of coal and rock reinforcement material |
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|---|---|---|---|
| CN201710227390.XA CN106905657B (en) | 2017-04-10 | 2017-04-10 | A kind of coal and rock reinforcement material |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0084700A1 (en) * | 1981-11-06 | 1983-08-03 | Abelard Management Services Limited | Process for the manufacture of polyureas containing urethane groups and the products so obtained |
| CN102532455A (en) * | 2011-12-23 | 2012-07-04 | 山东东大一诺威新材料有限公司 | Polyurethane polymer material for coal rock mass reinforcement and preparation method thereof |
| CN102558498A (en) * | 2012-01-04 | 2012-07-11 | 山西兆信生物科技有限公司 | Polyurethane reinforcing and filling materials for coal mine |
| CN103160075A (en) * | 2013-04-03 | 2013-06-19 | 巴斯夫浩珂矿业化学（中国）有限公司 | Urea resin injecting paste material for reinforcing coal body |
| CN103739802A (en) * | 2013-12-13 | 2014-04-23 | 山东一诺威新材料有限公司 | Modified urea-formaldehyde resin reinforced material used for coal mine and preparation method thereof |
-
2017
- 2017-04-10 CN CN201710227390.XA patent/CN106905657B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0084700A1 (en) * | 1981-11-06 | 1983-08-03 | Abelard Management Services Limited | Process for the manufacture of polyureas containing urethane groups and the products so obtained |
| CN102532455A (en) * | 2011-12-23 | 2012-07-04 | 山东东大一诺威新材料有限公司 | Polyurethane polymer material for coal rock mass reinforcement and preparation method thereof |
| CN102558498A (en) * | 2012-01-04 | 2012-07-11 | 山西兆信生物科技有限公司 | Polyurethane reinforcing and filling materials for coal mine |
| CN103160075A (en) * | 2013-04-03 | 2013-06-19 | 巴斯夫浩珂矿业化学（中国）有限公司 | Urea resin injecting paste material for reinforcing coal body |
| CN103739802A (en) * | 2013-12-13 | 2014-04-23 | 山东一诺威新材料有限公司 | Modified urea-formaldehyde resin reinforced material used for coal mine and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 吴蓁等: "新型脲醛树脂胶黏剂的改性", 《化工进展》 * |
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