CN110372844B - Polyurethane grouting material, preparation method and application - Google Patents
Polyurethane grouting material, preparation method and application Download PDFInfo
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- CN110372844B CN110372844B CN201910525634.1A CN201910525634A CN110372844B CN 110372844 B CN110372844 B CN 110372844B CN 201910525634 A CN201910525634 A CN 201910525634A CN 110372844 B CN110372844 B CN 110372844B
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Abstract
The invention relates to a polyurethane grouting material, a preparation method and application thereof, and discloses a polyurethane compound for grouting, a preparation method and application thereof, wherein the polyurethane compound consists of A, B components, and the component A comprises the following components: polyether polyol, amine-based polyol, epoxy resin, a foaming agent, a toughening agent, a phase change material, a reactive diluent, a compatilizer and a retarder; the component B is polyisocyanate. The polyurethane grouting material has the characteristics of good toughness, excellent bonding effect, cooling property, self-catalysis and oleophylic and hydrophilic grouting, can be suitable for repairing defects such as voids, cracks and slurry pumping of road surface base layers of highway tunnels and bridge engineering butt straps, voids and subsidence of bridge engineering butt straps, and can also be used for waterproof treatment, maintenance and reinforcement of water conservancy and electric power facilities, mineral resource exploitation, underground and underwater building engineering and fault emergency repair treatment of water leakage and water permeability.
Description
Technical Field
The invention relates to the field of high polymer materials and the technical field of grouting engineering, in particular to a polyurethane grouting material and a preparation method thereof.
Background
The mileage of the vehicle reaches 13.6 kilometers by 2017, and as the construction mileage increases, the road maintenance becomes one of important tasks in the road construction industry. The deep cracks and the void of the highway are one of the most common diseases, the cracks and the void not only influence the driving comfort of the road and reduce the bearing capacity of a surface layer, but also easily expand into the structural damage of the road surface and shorten the service life of the road if the cracks and the void cannot be repaired under complex climate change and heavy traffic load. The traditional work of excavation, backfilling, milling, surface covering and the like has long maintenance time, great influence on traffic and high maintenance cost, and the polyurethane grouting material is used as a new process for repairing cracks, can realize the rapid repair of cracks and voids of roads, prevents the further development of the cracks and voids, reduces the cost of repairing the cracks and voids of the roads, has important social significance and economic value on the rapid maintenance of the cracks and voids of the roads, and has wide application prospect.
Traditional polyurethane grouting materials can be classified into oil-soluble polyurethane and water-soluble polyurethane according to whether the materials are hydrophilic or not. The oil-soluble polyurethane has high reaction activity, high strength of a consolidation body and good impermeability, and is used for projects of reinforcing low grades and preventing water and leaking stoppage. The water-soluble polyurethane grouting material has good hydrophilicity and large water-wrapping amount, concretes have good elasticity, permeability and low temperature resistance, have good bonding performance on rocks, concrete, soil particles and the like, and are suitable for plugging moist cracks, plugging water in flowing water stratums, protecting moist soil surface layers and the like. However, the polyurethane grouting material belongs to exothermic reaction, and the reaction is violent, the speed is high, a large amount of heat is generated, so that local cells are ablated and collapsed, the strength is influenced, and even safety accidents occur.
Disclosure of Invention
The polyurethane grouting material has the characteristics of good toughness, excellent bonding effect, cooling property, autocatalysis, oleophylic and hydrophilic grouting, is widely applicable to occasions, can be suitable for repairing defects such as cavities, cracks and grout in road base layers of highway tunnels, cavities and subsides of bridge engineering butt straps and the like, and can also be used for waterproof treatment, maintenance, reinforcement and water leakage and water permeation of water conservancy and power facilities, mineral resource exploitation, underground and underwater building engineering.
In order to achieve the purpose of the invention, the invention provides a polyurethane grouting material which is composed of A, B components, wherein: the component A comprises: polyether polyol, amine-based polyol compound, epoxy resin, foaming agent, toughening agent, phase-change material, reactive diluent, compatilizer and retarder; the component B is polyisocyanate.
Wherein the weight part ratio of the component A to the component B is 1: (0.5-2), preferably 1: (0.5-1).
Particularly, the component A comprises the following raw materials in parts by weight: 100 parts of polyether polyol, 20-50 parts of amine-based polyol, 10-50 parts of epoxy resin, 5-60 parts of foaming agent, 0-20 parts of toughening agent, 5-20 parts of phase change material, 10-30 parts of reactive diluent, 0.2-5 parts of compatilizer and 0.1-1.0 part of retarder.
In particular, the polyether polyol has an average functionality of 2-8, an average molecular weight of 200-4000 and a hydroxyl value of 20-1000 mgKOH/g; the average functionality of the amine-based polyol is 2-4, the average molecular weight is 200-4000, and the hydroxyl value is 20-1000 mgKOH/g; the epoxy value of the epoxy resin is 0.4-0.6; the molecular weight of the toughening agent is 2000-4500; the isocyanate has a-NCO content of 20-50% and an average functionality of 2-3.
In particular, the polyether polyol is one or more of polyoxypropylene diol, polyoxypropylene triol, oxypropylene-oxyethylene copolyether triol, polyoxypropylene castor oil polyol, pentaerythritol polyether tetraol, polyether pentaol, hexahydroxy polyether, sucrose polyether, polytetrahydrofuran diol, polyurea polyol and rosin ester polyol;
the amine-based polyol is one or more of ethylenediamine polyether tetrol, toluene diamine polyether tetrol, diaminodiphenyl methane polyether tetrol or m-xylene diamine polyether tetrol;
the epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, bisphenol S epoxy resin, resorcinol epoxy resin or cardanol epoxy resin;
the foaming agent is water or/and pentane;
the toughening agent is hydroxyl-terminated liquid nitrile rubber or/and hydroxyl-terminated butadiene styrene rubber;
the phase-change material is one or more of sodium sulfate decahydrate, sodium acetate trihydrate, calcium chloride hexahydrate, calcium bromide hexahydrate, sodium hydrogen phosphate decahydrate, paraffin, stearic acid, n-tridecanol, n-hexadecanol or n-octadecanol;
the active diluent is one or more of oxazolidine, oxazolidine-aldimine, bicyclic oxazolidine, propylene carbonate and gamma-butyrolactone;
the compatilizer is one or more of gamma-aminopropyltriethoxysilane, N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, polysorbate 80 and water-soluble silicone oil;
the retarder is benzoyl chloride or/and p-toluenesulfonyl chloride.
In particular, the polyether polyol is a mixture of one or more of polyoxypropylene diol, polyoxypropylene triol, oxypropylene-oxyethylene copolyether triol, polyoxypropylene-castor oil polyol, pentaerythritol-based polyether tetraol, polyether pentaol, hexahydroxy polyether, sucrose polyether, polytetrahydrofuran diol, polyurea polyol and rosin ester polyol which are mixed in any proportion.
In particular, the amine-based polyol is one or a mixture of more of ethylenediamine polyether tetrol, toluene diamine polyether tetrol, diaminodiphenyl methane polyether tetrol or m-xylene diamine polyether tetrol mixed in any proportion.
In particular, the polyisocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, p-xylylene diisocyanate, polymethylene polyphenyl isocyanate, liquefied diphenylmethane diisocyanate and isophorone diisocyanate.
In particular, the polyisocyanate is a mixture of one or more of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, p-xylylene diisocyanate, polymethylene polyphenyl isocyanate, liquefied diphenylmethane diisocyanate and isophorone diisocyanate in any proportion.
The invention also provides a preparation method of the polyurethane grouting material, which comprises the following steps:
1) preparing the raw materials of the component A according to the following weight parts:
2) uniformly mixing polyether polyol, amine-based polyol, epoxy resin, a foaming agent, a toughening agent, a reactive diluent, a compatilizer and a retarder, heating to 40-100 ℃, carrying out heat preservation reaction for 1-10 hours, cooling to room temperature, and then adding a phase change material to prepare a component A of the grouting material for later use;
3) uniformly mixing the component A and the component B to obtain the polyurethane grouting material, wherein the component B comprises the following components: 100-200 parts by weight of polyisocyanate.
The invention also provides a preparation method of the polyurethane grouting material, which comprises the following steps:
A) preparing the raw materials of the component A according to the following weight parts:
B) preparing the raw materials of the component B according to the following weight parts:
polyisocyanate 100-
C) Mixing part of polyether polyol of the component A, part of amino polyol and polyisocyanate of the component B, and reacting for 0.5-2h at 70-100 ℃ to prepare a grouting material prepolymer;
D) and adding the rest polyether polyol, the rest amino polyol, epoxy resin, foaming agent, toughening agent, phase-change material, reactive diluent, compatilizer and retarder into the prepolymer, and uniformly stirring to obtain the polyurethane grouting material.
Wherein, the polyether polyol of the component A in the step 1) and the step A) is one or more of polyoxypropylene diol, polyoxypropylene triol, oxypropylene-oxyethylene copolyether triol, polyoxypropylene-castor oil polyol, pentaerythritol polyether tetrol, polyether pentol, hexahydroxy polyether, sucrose polyether, polytetrahydrofuran diol, polyurea polyol and rosin ester polyol; the amine-based polyol is one or more of ethylenediamine polyether tetrol, toluene diamine polyether tetrol, diaminodiphenyl methane polyether tetrol or m-xylene diamine polyether tetrol; the epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, bisphenol S epoxy resin, resorcinol epoxy resin or cardanol epoxy resin; the foaming agent is water or/and pentane; the toughening agent is hydroxyl-terminated liquid nitrile rubber or/and hydroxyl-terminated butadiene styrene rubber; the phase-change material is one or more of sodium sulfate decahydrate, sodium acetate trihydrate, calcium chloride hexahydrate, calcium bromide hexahydrate, sodium hydrogen phosphate decahydrate, paraffin, stearic acid, n-tridecanol, n-hexadecanol or n-octadecanol; the active diluent is one or more of oxazolidine, oxazolidine-aldimine, bicyclic oxazolidine, propylene carbonate and gamma-butyrolactone; the compatilizer is one or more of gamma-aminopropyltriethoxysilane, N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, polysorbate 80 and water-soluble silicone oil; the retarder is benzoyl chloride or/and p-toluenesulfonyl chloride.
In particular, the polyether polyol is a mixture of one or more of polyoxypropylene diol, polyoxypropylene triol, oxypropylene-oxyethylene copolyether triol, polyoxypropylene castor oil polyol, pentaerythritol polyether tetraol, polyether pentaol, hexahydroxy polyether, sucrose polyether, polytetrahydrofuran diol, polyurea polyol and rosin ester polyol which are mixed in any proportion; the amine-based polyol is a mixture of one or more of ethylenediamine polyether tetrol, toluene diamine polyether tetrol, diaminodiphenyl methane polyether tetrol or m-xylene diamine polyether tetrol mixed in any proportion.
Wherein, the polyisocyanate of the component B in the step 3) and the step B) is one or more of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, p-xylylene diisocyanate, polymethylene polyphenyl isocyanate, liquefied diphenylmethane diisocyanate and isophorone diisocyanate.
In particular, the polyisocyanate is a mixture of one or more of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, p-xylylene diisocyanate, polymethylene polyphenyl isocyanate, liquefied diphenylmethane diisocyanate and isophorone diisocyanate in any proportion.
Wherein, the prepolymer in the step C) is a prepolymer with NCO groups.
In particular, the amount of the part of polyether polyol used in the preparation of the prepolymer in the step C) accounts for 50-70%, preferably 50-60% of the total amount of the polyether polyol compound in the raw materials of the component A; the amount of partial amine-based polyol used in the step 3) for preparing the prepolymer accounts for 20-50% of the total amount of the amine-based polyol in the raw materials of the component A.
The invention also provides an application of the polyurethane grouting material in repairing road surface diseases of highways and tunnels; the method is applied to the fault first-aid repair treatment of water conservancy and electric power facilities, mineral resource exploitation, underground and underwater building engineering waterproof treatment, maintenance, reinforcement or/and water leakage and water permeation.
The road surface diseases of the highway and the tunnel are voids, cracks and grout spurs of a road surface base layer, voids, subsidence and the like of a bridge engineering butt strap.
In particular to application of the polyurethane grouting material in preparing a repairing agent for repairing highway pavement diseases.
The invention also provides an application of the polyurethane grouting material, wherein the application is in repairing highway tunnel pavement diseases; the method is applied to repairing the defects of the road surface base course of the highway tunnel, such as the void, crack and grout pumping, the void of the bridge engineering butt strap, subsidence and the like; the method is applied to the water conservancy and electric power facilities, mineral resource exploitation, underground and underwater building engineering waterproof treatment, maintenance and reinforcement, and the fault emergency repair treatment of water leakage and water permeation.
Compared with the prior art, the invention has the following beneficial effects:
1) the epoxy resin adopted by the invention has hydroxyl and epoxy groups, can react with isocyanate groups, can form a cross-linked network structure on a molecular chain, has continuously-changed cross-linking points, increases the proportion of hard segments in the molecular chain, can form an interpenetrating network structure, has increased compatibility, and further adopts the hydroxyl-terminated rubber for toughening, thereby increasing the compression strength and toughness of the material and improving the mechanical property of the material.
2) The phase-change material adopted by the invention undergoes chemical and physical changes to change phase, so as to achieve the effect of cooling, thereby preventing the material from being ablated due to too fast temperature rise inside the material to reduce the strength of the material, and avoiding potential safety hazards.
3) The amine-based polyol adopted by the invention has tertiary amine groups in a molecular structure, has an autocatalysis effect, has high reaction activity with polyisocyanate, can reduce the dosage of an amine catalyst, and is suitable for occasions of rapid curing, foaming and molding. In addition, the reactive diluent is adopted to reduce the viscosity of the system and participate in the reaction, so that the performance of the material is not influenced.
4) The grouting material disclosed by the invention has the characteristics of water solubility and oil solubility, not only has the characteristics of high oil solubility reaction activity and high consolidation strength, but also has the characteristic that water-soluble polyurethane can be mixed with water in any proportion, is wide in application occasions, is suitable for repairing diseases such as cavities, cracks and sludges of road surface base layers of highway tunnels, cavities and subsides of bridge engineering butt straps, and can also be used for waterproof treatment, maintenance and reinforcement of water conservancy and power facilities, mineral resource exploitation, underground and underwater building engineering, and fault emergency repair treatment of water leakage and water permeation.
Detailed Description
The invention will be further described with reference to specific embodiments, and the advantages and features of the invention will become apparent as the description proceeds. These examples are illustrative only and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.
Example 1:
1. preparation of A component of polyurethane grouting material
1A) Preparing a component A raw material (g) according to the following weight ratio:
wherein: the polyether polyol comprises propylene oxide-ethylene oxide copolyether triol and polypropylene oxide triol, wherein the functionality of the propylene oxide-ethylene oxide copolyether triol is 3, the average molecular weight is 600, and the hydroxyl value is 330 mgKOH/g; the polyoxypropylene triol has a functionality of 3, an average molecular weight of 3000 and a hydroxyl value of 36 KOH/g; the weight ratio of the propylene oxide-ethylene oxide copolyether triol to the polyoxypropylene triol is 1:1, namely 50g of the propylene oxide-ethylene oxide copolyether triol and 50g of the polyoxypropylene triol; the functionality of the ethylenediamine polyether tetraol is 4, the average molecular weight is 300, and the hydroxyl value is 770 mgKOH/g; the bisphenol A epoxy resin is E44; the average molecular weight of the hydroxyl-terminated liquid nitrile rubber is 3500;
in the polyether polyol composite of this example, the ratio of the propylene oxide-ethylene oxide copolyether triol to the polyoxypropylene triol in the weight ratio is 1: the mixing ratio of 1 is described as an example, and any other mixing ratio is applicable to the present invention.
The polyether polyols having an average functionality of 2-8, an average molecular weight of 200-4000 and a hydroxyl number of 20-1000mgKOH/g in any proportions are suitable for use in the present invention.
In this embodiment, the amine-based polyol is exemplified by ethylenediamine polyether tetrol, and the amine-based polyol in the present invention may be one or more, and when a plurality of amine-based polyols are included, the plurality of amine-based polyols may be mixed in any ratio.
Aminopolyols having an average functionality of from 2 to 4, an average molecular weight of 200-4000 and a hydroxyl number of from 20 to 1000mgKOH/g are suitable for use in the present invention.
In this example, the polyether polyol is exemplified by a propylene oxide-ethylene oxide copolyether triol and a polyoxypropylene triol; the polyether polyol in the present invention may be one or more polyols, and when a plurality of polyols are included, the plurality of polyols may be mixed in any proportion.
In this example, bisphenol A epoxy resin E44 is used as an example, and other epoxy resins having an epoxy value of 0.4 to 0.6 are suitable for the present invention.
In this embodiment, the toughening agent is hydroxyl-terminated liquid nitrile rubber with an average molecular weight of 3500 as an example, and other toughening agents with an average molecular weight of 2000-4500 are suitable for the invention.
1B) Uniformly mixing propylene oxide-ethylene oxide copolyether triol, polypropylene oxide triol, ethylenediamine polyether tetrol, bisphenol A epoxy resin (E44), water, hydroxyl-terminated liquid nitrile rubber, oxazolidine, gamma-aminopropyltriethoxysilane and benzoyl chloride, heating to 40 ℃ (usually 40-100 ℃), reacting for 10h (usually 1-10 h) at a constant temperature, cooling to room temperature, then adding sodium sulfate decahydrate, and uniformly stirring and mixing to obtain a component A;
2. preparing raw materials (g) of the component B according to the following weight ratio
Polyisocyanate Complex 180g
Wherein the polyisocyanate compound comprises polymethylene polyphenyl isocyanate and toluene diisocyanate, wherein the polymethylene polyphenyl isocyanate is 100g, and the toluene diisocyanate is 80 g; the-NCO content of the polymethylene polyphenyl isocyanate and the toluene diisocyanate is respectively 30 percent and 48 percent, and the average functionality is respectively 2.5 and 2;
polyisocyanates having an NCO content of 20% to 50% and an average functionality of 2 to 3 are suitable for use in the present invention.
In the polyisocyanate composite of the embodiment of the invention, the weight ratio of the polymethylene polyphenyl isocyanate to the toluene diisocyanate is 100: 80, and any other mixing ratio is suitable for use in the present invention.
3. Preparation of polyurethane grouting material
And stirring and mixing the prepared component A and the polyisocyanate compound component B at room temperature for 5-300s to obtain the polyurethane grouting material.
The polyurethane grouting material prepared by the invention can be used for repairing road surface diseases of highways and tunnels in an injection or spraying mode; or the water conservancy and electric power facilities, mineral resource exploitation, underground and underwater building engineering waterproof treatment, maintenance and reinforcement or/and the fault emergency repair treatment of water leakage and water permeation are carried out.
Example 2
1. Preparation of A component of polyurethane grouting material
1A) Preparing a component A raw material (g) according to the following weight:
wherein: polyether polyols include polyoxypropylene diols having a functionality of 2, an average molecular weight of 2000 and a hydroxyl number of 56, and rosin ester polyols; the rosin ester polyol has a functionality of 3, an average molecular weight of 280 and a hydroxyl value of 400 mgKOH/g; the weight ratio of the polyoxypropylene glycol to the rosin ester polyol was 1:1, that is, 50g of the polyoxypropylene glycol and 50g of the rosin ester polyol; the functionality of the toluene diamine polyether tetrol is 4, the average molecular weight is 600, and the hydroxyl value is 410 mgKOH/g; bisphenol F epoxy resin NPEF-170;
in the polyether polyol composite of this example, the ratio of the polyoxypropylene glycol to the rosin ester polyol in the weight ratio of 1: the mixing ratio of 1 is described as an example, and any other mixing ratio is applicable to the present invention.
The polyether polyol with the average functionality of 2-8, the average molecular weight of 200-4000 and the hydroxyl value of 20-1000mgKOH/g is mixed in any proportion to form the compound which is suitable for the invention; aminopolyols having an average functionality of from 2 to 4, an average molecular weight of 200-4000 and a hydroxyl number of from 20 to 1000mgKOH/g are suitable for use in the present invention.
The polyether polyols in this example are illustrated by way of example for polyoxypropylene glycol and rosin ester polyol; the polyether polyol in the present invention may be one or more polyols, and when a plurality of polyols are included, the plurality of polyols may be mixed in any proportion.
In this embodiment, the amine-based polyol is exemplified by tolylenediamine polyether tetrol, and when the amine-based polyol in the present invention may be one or a plurality of amine-based polyols, and includes a plurality of amine-based polyols, the plurality of amine-based polyols may be mixed in any ratio.
1B) Heating polyoxypropylene glycol, rosin ester polyol, toluene diamine polyether tetrol, bisphenol F epoxy resin, water, oxazolidine-aldimine, water-soluble silicone oil and benzoyl chloride to 60 ℃ (usually 40-100 ℃), reacting for 2h (usually 1-10 h), cooling to room temperature, adding sodium acetate trihydrate, and stirring uniformly to obtain a component A;
2. the raw materials (g) of component B were prepared in the following weight proportions
Polyisocyanate Complex 100g
Wherein the polyisocyanate compound comprises polymethylene polyphenyl isocyanate and liquefied diphenylmethane diisocyanate, wherein 80g of polymethylene polyphenyl isocyanate and 20g of liquefied diphenylmethane diisocyanate are contained; the-NCO content of the polymethylene polyphenyl isocyanate and the toluene diisocyanate is 30 percent and 48 percent respectively; the functionalities are all 2.
Polyisocyanates having an NCO content of 20% to 50% and an average functionality of 2 to 3 are suitable for use in the present invention.
In the polyisocyanate compound of the embodiment of the invention, the weight ratio of the polymethylene polyphenyl isocyanate to the liquefied diphenylmethane diisocyanate is 80: 20 for illustration, any other mixing ratio is suitable for use in the present invention.
3. Preparation of polyurethane grouting material
And stirring and mixing the prepared component A and the polyisocyanate compound component B at room temperature for 5-300s to obtain the polyurethane grouting material.
The polyurethane grouting material prepared by the invention can be used for repairing road surface diseases of highways and tunnels in an injection or spraying mode; or the water conservancy and electric power facilities, mineral resource exploitation, underground and underwater building engineering waterproof treatment, maintenance and reinforcement or/and the fault emergency repair treatment of water leakage and water permeation are carried out.
Example 2A
1. Preparation of A component of polyurethane grouting material
1A) Preparing a component A raw material (g) according to the following weight:
wherein: the polyether polyol is polyoxypropylene triol, wherein the functionality of the polyoxypropylene triol is 3, the average molecular weight is 350, and the hydroxyl value is 500 mgKOH/g; the m-xylene diamine polyether tetrol has the functionality of 4, the average molecular weight of 300 and the hydroxyl value of 760 mgKOH/g; bisphenol S type epoxy resin 185S; the average molecular weight of the hydroxyl-terminated liquid nitrile rubber is 3000;
in this embodiment, the polyoxypropylene triol in the polyether polyol composite is exemplified, and in the present invention, the polyether polyol may be one or more polyols, and when the polyether polyol includes a plurality of polyols, the plurality of polyols may be mixed in any ratio.
The polyether polyols having an average functionality of 2-8, an average molecular weight of 200-4000 and a hydroxyl number of 20-1000mgKOH/g in any proportions are suitable for use in the present invention.
In this embodiment, the amine-based polyol is illustrated by meta-xylene diamine-based polyether tetrol, and when the amine-based polyol in the present invention is one or more, and includes a plurality of amine-based polyols, the plurality of amine-based polyols may be mixed in any ratio.
Aminopolyols having an average functionality of from 2 to 4, an average molecular weight of 200-4000 and a hydroxyl number of from 20 to 1000mgKOH/g are suitable for use in the present invention.
1B) Heating polyoxypropylene triol, m-xylene diamine polyether tetrol, bisphenol S type epoxy resin, water, hydroxyl-terminated liquid nitrile rubber, propylene carbonate, gamma-glycidoxypropyltrimethoxysilane and p-toluenesulfonyl chloride to 80 ℃ (usually 40-100 ℃), reacting for 5h (usually 1-10 h) while keeping the temperature, cooling to room temperature, then adding paraffin and stirring uniformly to obtain a component A;
2. the raw materials (g) of component B were prepared in the following weight proportions
Polyisocyanate Complex 200g
Wherein the polyisocyanate compound is hexamethylene diisocyanate; the hexamethylene diisocyanate had a-NCO content of 49%; the functionality is 2.
Polyisocyanates having an NCO content of 20% to 50% and an average functionality of 2 to 3 are suitable for use in the present invention.
In this example, hexamethylene diisocyanate is used as an example of the polyisocyanate; the polyisocyanate in the present invention may be one or more kinds of polyisocyanates, and when plural kinds of polyisocyanates are included, plural kinds of polyisocyanates may be mixed in any ratio.
3. Preparation of polyurethane grouting material
And stirring and mixing the prepared component A and the polyisocyanate compound component B at room temperature for 5-300s to obtain the polyurethane grouting material.
The polyurethane grouting material prepared by the invention can be used for repairing road surface diseases of highways and tunnels in an injection or spraying mode; or the water conservancy and electric power facilities, mineral resource exploitation, underground and underwater building engineering waterproof treatment, maintenance and reinforcement or/and the fault emergency repair treatment of water leakage and water permeation are carried out.
Example 3:
1. preparing a component A raw material (g) according to the following weight ratio:
wherein the polyoxypropylene diol has a functionality of 2, an average molecular weight of 400, and a hydroxyl value of 280 mgKOH/g; diaminodiphenylmethyl polyether tetrol functionality is 4, average molecular weight is 600, and hydroxyl value is 374 mgKOH/g; cardanol epoxy resin C40; the average molecular weight of the hydroxyl-terminated styrene-butadiene rubber is 2800;
the polyether polyol of this example is illustrated by a polyoxypropylene diol, a polyol; the polyether polyol in the present invention may be one or more polyether polyols, and when a plurality of polyether polyols are included, the plurality of polyether polyols may be mixed in any proportion.
In this embodiment, the amine-based polyol is described by taking diaminodiphenyl methyl polyether tetrol as an example, and when the amine-based polyol in the present invention is one or more, and includes a plurality of amine-based polyols, the plurality of amine-based polyols may be mixed in any ratio.
Aminopolyols having an average functionality of from 2 to 4, an average molecular weight of 200-4000 and a hydroxyl number of from 20 to 1000mgKOH/g are suitable for use in the present invention.
In this example, cardanol epoxy resin C40 is used as an example, and other epoxy resins having an epoxy value of 0.4 to 0.6 are suitable for the present invention.
In this embodiment, the toughening agent is hydroxyl-terminated liquid nitrile rubber with an average molecular weight of 3500 as an example, and other toughening agents with an average molecular weight of 2000-4500 are suitable for the invention.
2. Preparing a component B raw material (g) according to the following weight ratio:
diphenylmethane diisocyanate 200
Wherein the diphenylmethane diisocyanate has a-NCO content of 33%; a functionality of 2;
polyisocyanates having an NCO content of 20% to 50% and an average functionality of 2 to 3 are suitable for use in the present invention.
In this example, diphenylmethane diisocyanate is used as an example of the polyisocyanate; the polyisocyanate in the present invention may be one or more kinds of polyisocyanates, and when plural kinds of polyisocyanates are included, plural kinds of polyisocyanates may be mixed in any ratio.
3. Preparation of a prepolymer
200g of diphenylmethane diisocyanate, 50g of partial polyoxypropylene glycol and 25g of partial diaminodiphenyl methyl polyether tetrol are subjected to heat preservation reaction for 2 hours (usually 0.5 to 2 hours) at 70 ℃ (usually 70 to 100 ℃) to prepare a prepolymer with an NCO group; wherein, part of the polyoxypropylene glycol used for preparing the prepolymer accounts for 50 percent of the total polyoxypropylene glycol; part of diaminodiphenyl methyl polyether tetrol used for preparing the prepolymer accounts for 50 percent of the total amount of all the amine-based polyols;
in the process of preparing the prepolymer in this example, the polyoxypropylene glycol accounts for 50% of the total amount of the polyether polyol in the raw materials of the component A; the polyether polyol compound accounts for 50-70% of the total amount of the polyether polyol compound in the raw materials of the component A, and is suitable for the invention.
In this example, in the process of preparing the prepolymer, the diaminodiphenyl methyl polyether tetrol accounts for 50% of the total amount of the amine-based polyol in the raw materials of the component a, and the amine-based polyol accounts for 20-50% of the total amount of the amine-based polyol in the raw materials of the component a, which is suitable for the present invention.
4. And preparing the polyurethane grouting material.
Adding the rest of polyoxypropylene glycol, cardanol epoxy resin, water, hydroxyl-terminated styrene-butadiene rubber, n-octadecanol, gamma-butyrolactone, polysorbate 80 and p-toluenesulfonyl chloride into the prepolymer, and stirring and mixing uniformly for 5-300s to obtain the polyurethane grouting material
The polyurethane grouting material prepared by the invention can be used for repairing road surface diseases of highways and tunnels in an injection or spraying mode; or the water conservancy and electric power facilities, mineral resource exploitation, underground and underwater building engineering waterproof treatment, maintenance and reinforcement or/and the fault emergency repair treatment of water leakage and water permeation are carried out.
Example 3A:
1. preparing a component A raw material (g) according to the following weight ratio:
wherein the polyether polyol comprises: pentaerythritol based polyether tetrols and propylene oxide-ethylene oxide copolyether triols, wherein the pentaerythritol based polyether tetrols have a functionality of 4, an average molecular weight of 500 and a hydroxyl value of 448 mgKOH/g; the oxypropylene-oxyethylene copolyether triol has a functionality of 3, an average molecular weight of 1010 and a hydroxyl number of 165 mgKOH/g; the weight ratio of pentaerythritol polyether tetraol to propylene oxide-ethylene oxide copolyether triol is 20: 80, namely 20g of pentaerythritol-based polyether tetrol and 80g of propylene oxide-ethylene oxide copolyether triol; the functionality of the toluene diamine polyether tetrol is 4, the average molecular weight is 600, and the hydroxyl value is 410 mgKOH/g; resorcinol epoxy resin 680; the average molecular weight of the hydroxyl-terminated styrene-butadiene rubber is 3600;
in the polyether polyol compound of this embodiment, the weight ratio of pentaerythritol-based polyether tetraol to propylene oxide-ethylene oxide copolyether triol is 20: the mixing ratio of 80 is exemplified, and any other mixing ratio is applicable to the present invention.
The polyether polyols having an average functionality of 2-4, an average molecular weight of 200-4000 and a hydroxyl number of 20-1000mgKOH/g in any proportions are suitable for use in the present invention.
In this embodiment, the amine-based polyol is exemplified by tolylenediamine polyether tetrol, and the amine-based polyol in the present invention may be one or more, and when a plurality of amine-based polyols are included, the plurality of amine-based polyols may be mixed in any ratio.
Aminopolyols having an average functionality of from 2 to 4, an average molecular weight of 200-4000 and a hydroxyl number of from 20 to 1000mgKOH/g are suitable for use in the present invention.
In this example, resorcinol epoxy resin 680 is used as an example, and other epoxy resins having an epoxy value of 0.4 to 0.6 are suitable for the present invention.
In this embodiment, the toughening agent is exemplified by hydroxy-terminated styrene-butadiene rubber with an average molecular weight of 3600, and other toughening agents, hydroxy-terminated liquid nitrile-butadiene rubber or/and hydroxy-terminated styrene-butadiene rubber with an average molecular weight of 2000-4500, are suitable for the present invention.
2. Preparing a component B raw material (g) according to the following weight ratio:
polyisocyanate composite 200
Wherein the polyisocyanate compound comprises polymethylene polyphenyl isocyanate and toluene diisocyanate, wherein the polymethylene polyphenyl isocyanate is 150g, and the toluene diisocyanate is 50; the-NCO content of the polymethylene polyphenyl isocyanate and the toluene diisocyanate is 30 percent and 48 percent respectively; the functionality was 3, 2.
In the polyisocyanate composite in the embodiment of the invention, the weight ratio of the polymethylene polyphenyl isocyanate to the toluene diisocyanate is 150: 50 for illustration, any other mixing ratio is suitable for use in the present invention.
In this example, the polyisocyanate is exemplified by polymethylene polyphenyl isocyanate and toluene diisocyanate; the polyisocyanate in the present invention may be one or more kinds of polyisocyanates, and when plural kinds of polyisocyanates are included, plural kinds of polyisocyanates may be mixed in any ratio.
3. Preparation of a prepolymer
Preparing a prepolymer with NCO groups by reacting 150g of polymethylene polyphenyl isocyanate, 50g of toluene diisocyanate, part of polyether polyol (12 g of pentaerythritol polyether tetrol, 40g of propylene oxide-ethylene oxide copolyether triol) and 6g of toluene diamine polyether tetrol at 100 ℃ (usually 70-100 ℃) for 0.5h (usually 0.5-2 h); wherein, part of polyether polyol used in the preparation of the prepolymer accounts for 50-60% of the total polyether polyol; wherein the pentaerythritol polyether tetrol and the propylene oxide-ethylene oxide copolyether triol respectively account for 60 percent and 50 percent of the total amount of the pentaerythritol polyether tetrol and the propylene oxide-ethylene oxide copolyether triol in the raw materials of the component A; part of toluene diamine polyether tetrol used for preparing the prepolymer accounts for 20 percent of the total amount of all amine-based polyols;
in this example, in the process of preparing the prepolymer, the polyether polyols (pentaerythritol-based polyether tetraol and propylene oxide-ethylene oxide copolyether triol) account for 50-60% of the total amount of the polyether polyols in the raw materials of the component a, i.e., the pentaerythritol-based polyether tetraol and the propylene oxide-ethylene oxide copolyether triol account for 60% and 50% of the total amount of the pentaerythritol-based polyether tetraol and the propylene oxide-ethylene oxide copolyether triol in the raw materials of the component a, respectively; the polyether polyol compound accounts for 50-70% of the total amount of the polyether polyol compound in the raw materials of the component A, and is suitable for the invention.
In this example, in the process of preparing the prepolymer, the toluene diamine polyether tetrol accounts for 20% of the total amount of the amine-based polyol in the raw material of the component a, and the amine-based polyol accounts for 20-50% of the total amount of the amine-based polyol in the raw material of the component a, which is suitable for the present invention.
4. And preparing the polyurethane grouting material.
Adding the rest polyether polyol (pentaerythritol polyether tetrol and propylene oxide-ethylene oxide copolyether triol), the rest toluene diamine polyether tetrol, resorcinol epoxy resin, water, hydroxyl-terminated styrene-butadiene rubber, sodium hydrogen phosphate decahydrate, oxazolidine-aldimine, gamma-glycidoxypropyltrimethoxysilane and benzoyl chloride into the prepolymer, stirring and mixing uniformly for 5-300s usually to obtain the polyurethane grouting material
The polyurethane grouting material prepared by the invention can be used for repairing road surface diseases of highways and tunnels in an injection or spraying mode; or the water conservancy and electric power facilities, mineral resource exploitation, underground and underwater building engineering waterproof treatment, maintenance and reinforcement or/and the fault emergency repair treatment of water leakage and water permeation are carried out.
The polyurethane grouting materials prepared in example 1, example 2A, example 3 and example 3A are tested according to JC/T2041-2010 standard, and the test results are shown in Table 1:
TABLE 1 polyurethane grouting material Performance test results
| Test items | Example 1 | Example 2 | Example 2A | Example 3 | Example 3A |
| Viscosity (mPa.s) | 28 | 135 | 57 | 85 | 307 |
| Curing time(s) | 131 | 103 | 207 | 84 | 59 |
| Foaming ratio (%) | 19 | 17 | 48 | 26 | 14 |
| Compressive strength (MPa) | 12.4 | 18.2 | 13.5 | 25.7 | 30.1 |
| Maximum reaction temperature (. degree.C.) of the system | 80 | 87 | 76 | 70 | 93 |
The embodiment of the invention can adjust each component, time, strength and viscosity, has the characteristics of high reaction activity and high strength, is convenient to construct and wide in application occasions, is not only suitable for repairing diseases such as voids, cracks and mudjacking of a road surface base layer of a highway tunnel, voids and subsidence of a bridge engineering butt plate, but also can be used for water conservancy and power facilities, mining of mineral resources, waterproof treatment, maintenance and reinforcement of underground and underwater building engineering and fault emergency repair treatment of water leakage and water permeation.
Claims (8)
1. The polyurethane grouting material is composed of A, B components, and is characterized in that the component A comprises the following raw materials in parts by weight: 100 parts of polyether polyol, 20-50 parts of amine-based polyol, 10-50 parts of epoxy resin, 5-60 parts of foaming agent, 0-20 parts of toughening agent, 5-20 parts of phase change material, 10-30 parts of reactive diluent, 0.2-5 parts of compatilizer and 0.1-1.0 part of retarder; the component B is polyisocyanate; wherein:
the polyether polyol is one or more of polyoxypropylene diol, polyoxypropylene triol, oxypropylene-oxyethylene copolyether triol, polyoxypropylene-castor oil polyol, pentaerythritol polyether tetrol, polyether pentol, hexahydroxy polyether, sucrose polyether, polytetrahydrofuran diol, polyurea polyol and rosin ester polyol;
the amine-based polyol is one or more of ethylenediamine polyether tetrol, toluene diamine polyether tetrol, diaminodiphenyl methane polyether tetrol or m-xylene diamine polyether tetrol;
the epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, bisphenol S epoxy resin, resorcinol epoxy resin or cardanol epoxy resin;
the foaming agent is water or/and pentane;
the toughening agent is hydroxyl-terminated liquid nitrile rubber or/and hydroxyl-terminated butadiene styrene rubber;
the phase-change material is one or more of sodium sulfate decahydrate, sodium acetate trihydrate, calcium chloride hexahydrate, calcium bromide hexahydrate, sodium hydrogen phosphate decahydrate, paraffin, stearic acid, n-tridecanol, n-hexadecanol or n-octadecanol;
the active diluent is one or more of oxazolidine, oxazolidine-aldimine, propylene carbonate and gamma-butyrolactone;
the compatilizer is one or more of gamma-aminopropyltriethoxysilane, N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, polysorbate 80 and water-soluble silicone oil;
the retarder is benzoyl chloride or/and p-toluenesulfonyl chloride.
2. The grouting material of claim 1, wherein the reactive diluent is a bicyclic oxazolidine.
3. Grouting material according to claim 1 or 2, characterised in that,
the polyether polyol has the average functionality of 2-8, the average molecular weight of 200-4000 and the hydroxyl value of 20-1000 mgKOH/g;
the average functionality of the amine-based polyol is 2-4, the average molecular weight is 200-4000, and the hydroxyl value is 20-1000 mgKOH/g;
the epoxy value of the epoxy resin is 0.4-0.6;
the molecular weight of the toughening agent is 2000-4500;
the polyisocyanate has a-NCO content of 20-50% and an average functionality of 2-3.
4. The grouting material according to claim 1 or 2, characterized in that the polyisocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, p-xylylene diisocyanate, polymethylene polyphenyl isocyanate, liquefied diphenylmethane diisocyanate, isophorone diisocyanate.
5. A method for preparing the polyurethane grouting material according to claim 1, characterized by comprising the steps of:
1) preparing the raw materials of the component A according to the following weight parts:
2) uniformly mixing polyether polyol, amine-based polyol, epoxy resin, a foaming agent, a toughening agent, a reactive diluent, a compatilizer and a retarder, heating to 40-100 ℃, carrying out heat preservation reaction for 1-10 hours, cooling to room temperature, and then adding a phase change material to prepare a component A of the grouting material for later use;
3) uniformly mixing the component A and the component B to obtain the polyurethane grouting material, wherein the component B comprises the following components: 100-200 parts by weight of polyisocyanate.
6. A method for preparing the polyurethane grouting material according to claim 1, characterized by comprising the steps of:
A) preparing the raw materials of the component A according to the following weight parts:
B) preparing the raw materials of the component B according to the following weight parts:
polyisocyanate 100-
C) Mixing part of polyether polyol of the component A, part of amino polyol and polyisocyanate of the component B, and reacting for 0.5-2h at 70-100 ℃ to prepare a grouting material prepolymer;
D) and adding the rest polyether polyol, amino polyol and epoxy resin, foaming agent, toughening agent, phase-change material, reactive diluent, compatilizer and retarder into the prepolymer, and uniformly stirring to obtain the polyurethane grouting material.
7. The method of claim 6 wherein the amount of the portion of polyether polyol used in step C) to prepare the prepolymer is 50-70% of the total amount of polyether polyol complex in the raw materials of component A; the amount of partial amine-based polyol used in the step C) for preparing the prepolymer accounts for 20-50% of the total amount of the amine-based polyol in the raw materials of the component A.
8. The application of the polyurethane grouting material of claim 1 in repairing road surface diseases of highways and tunnels; the method is applied to the fault first-aid repair treatment of water conservancy and electric power facilities, mineral resource exploitation, underground and underwater building engineering waterproof treatment, maintenance, reinforcement or/and water leakage and water permeation.
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