CN114409350B - Solvent-free epoxy polymer modified cement mortar and preparation method thereof - Google Patents
Solvent-free epoxy polymer modified cement mortar and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/06—Aluminous cements
- C04B28/065—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/2015—Sulfate resistance
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
- C04B2201/52—High compression strength concretes, i.e. with a compression strength higher than about 55 N/mm2, e.g. reactive powder concrete [RPC]
Abstract
The invention provides solvent-free epoxy polymer modified cement mortar and a preparation method thereof, belonging to the technical field of building materials. The cement mortar provided by the invention comprises two components, namely a component A and a component B, wherein polythiol modified epoxy resin and vegetable oleic acid modified epoxy resin are introduced into the component A, so that the brittleness of bisphenol A epoxy resin is greatly improved, and the corrosion resistance of a system is improved; the modified graphene is introduced into the component B, so that the adhesive force of the system with a steel structure and concrete is greatly improved; the solvent-free epoxy polymer modified cement mortar obtained by mixing and curing the component A and the component B according to a certain proportion in the construction process has good flexibility, corrosion resistance and excellent adhesive force, and can play a good role in corrosion prevention and protection on steel structures and concrete.
Description
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to solvent-free epoxy polymer modified cement mortar and a preparation method thereof.
Background
With the great investment of the country on the foundation arrangement, the construction of buildings, rail transit, hydraulic engineering and the like is developed rapidly, the requirement on the material standard is improved, particularly, in coastal regions, the buildings are in saline-alkali environments, concrete structures, steel structures and the like are soaked in solutions containing chloride ions, sulfate ions and hydroxyl ions for a long time, the structures are corroded, and the safety of the main structure is affected finally, so that the durability protection of the main structure is an important task.
At present, the traditional anticorrosion and protection materials mainly comprise materials such as polyurethane and polyurea, the materials can be attached to the surface of a steel structure or concrete to form a waterproof layer, so that the waterproof effect is achieved, the adhesion of the materials is low, the materials are easily damaged due to external force impact or stress, the protection effect is lost, and the main structure is exposed to the environment again and corroded.
The polymer anticorrosive protective coating has very good prospect due to very good chemical corrosion resistance, physical property and strong price advantage. The polymer modified cement mortar has various varieties and can be divided into epoxy resin, ethylene polyester resin, unsaturated polyester resin, acrylic resin and the like according to different polymer varieties, the epoxy resin has been practically checked and widely accepted as a polymer with excellent physical and chemical properties, and the epoxy resin has the superior properties of high strength, good cohesiveness, chemical resistance, acid-base corrosion resistance and the like. The epoxy resin has good compatibility with most materials, can be compounded with most organic and inorganic materials, has high stability of modified functional groups, and is very stable in natural environment even under high temperature and strong acid and alkali conditions. The modified epoxy resin can give consideration to various properties such as physics, machinery, chemistry and the like, and is a material with very strong plasticity and very high stability. The structural reinforcement, the anticorrosion coating and the like of a plurality of important projects are epoxy resin materials, and the durability of the epoxy resin is examined by countless engineering examples, so that the epoxy resin with excellent comprehensive performance is selected as a basic raw material to be modified and chemically grafted to enhance the adhesive force and the toughness of the epoxy resin, meanwhile, long-chain aliphatic polymer groups are grafted into a curing agent molecular chain through chemical reaction to increase the water resistance and the corrosion resistance, the grading of the particle sizes of a plurality of nanoscale fillers is adopted, the workability and the construction convenience of performance mortar are improved by adopting a special functional auxiliary agent, the self performance of the material is ensured to meet the design requirements, the defects of cement mortar are overcome, and the novel epoxy polymer anticorrosion protective material with corrosion resistance, seepage resistance, good bonding property, high strength and strong toughness is prepared.
Chinese patent application 201410510917.6 discloses an epoxy polymer mortar and a production process thereof, and specifically discloses an epoxy polymer mortar prepared from bisphenol a epoxy resin, and the epoxy polymer mortar adopts dioctyl phthalate, trichloropropane and the like as plasticizers, which have the disadvantages of poor chemical corrosion resistance, low adhesive force and the like, and cannot achieve good anticorrosion protection effect on steel structures, concrete structures and the like.
The invention patent 202010522481.8 discloses a polymer mortar and a preparation method thereof, and particularly discloses a polymer mortar which is prepared by matching at least one of styrene-acrylic emulsion, styrene-butadiene emulsion, polyacrylate emulsion or neoprene latex emulsion with powder such as rapid hardening sulphoaluminate cement and the like, is used for ballastless track maintenance and the like, has certain strength, does not contain epoxy resin components, has the defects of poor chemical corrosion resistance, low adhesive force and the like, and can not achieve good anticorrosion protection effect on steel structures, concrete structures and the like.
Therefore, it is necessary to develop epoxy polymer modified cement mortar which has better strength, can be well bonded with a steel structure and a concrete structure, and has a good anticorrosion and protection effect on the steel structure, the concrete structure and the like.
Disclosure of Invention
Based on the problems in the prior art, the invention aims to provide the solvent-free epoxy polymer modified cement mortar and the preparation method thereof.
The specific technical scheme is as follows:
a solvent-free epoxy polymer modified cement mortar comprises a component A and a component B;
the component A comprises the following raw materials in parts by weight: 70-180 parts of epoxy polymer, 10-50 parts of epoxy resin modifier, 50-100 parts of calcium carbonate, 10-50 parts of silicon dioxide, 20-60 parts of calcium sulfate, 10-100 parts of superfine sulphoaluminate cement, 2-6 parts of organic silicon defoamer and 2-6 parts of flatting agent;
the component B comprises the following raw materials in parts by weight: 50-100 parts of sulfydryl modified curing agent, 20-50 parts of modified 1, 3-cyclohexyldimethylamine curing agent, 1-5 parts of accelerator and 1-5 parts of coupling agent.
Preferably, the solvent-free epoxy polymer modified cement mortar comprises a component A and a component B;
the component A comprises the following raw materials in parts by weight: 120-180 parts of epoxy polymer, 20-50 parts of epoxy resin modifier, 60-100 parts of calcium carbonate, 20-50 parts of silicon dioxide, 30-60 parts of calcium sulfate, 60-100 parts of superfine sulphoaluminate cement, 3-5 parts of organic silicon defoamer and 3-5 parts of flatting agent;
the component B comprises the following raw materials in parts by weight: 60-100 parts of sulfydryl modified curing agent, 30-50 parts of modified 1, 3-cyclohexyldimethylamine curing agent, 2-4 parts of accelerator and 2-4 parts of coupling agent.
Still preferably, the solvent-free epoxy polymer modified cement mortar comprises a component A and a component B;
the component A comprises the following raw materials in parts by weight: 180 parts of epoxy polymer 160-one, 40-50 parts of epoxy resin modifier, 80-100 parts of calcium carbonate, 30-50 parts of silicon dioxide, 40-60 parts of calcium sulfate, 80-100 parts of superfine sulphoaluminate cement, 3-4 parts of organic silicon defoamer and 3-4 parts of flatting agent;
the component B comprises the following raw materials in parts by weight: 80-100 parts of sulfydryl modified curing agent, 40-50 parts of modified 1, 3-cyclohexyl dimethylamine curing agent, 3-4 parts of accelerator and 3-4 parts of coupling agent.
As a preferred embodiment, the solvent-free epoxy polymer modified cement mortar comprises a component A and a component B;
the component A comprises the following raw materials in parts by weight: 180 parts of epoxy polymer, 50 parts of epoxy resin modifier, 100 parts of calcium carbonate, 50 parts of silicon dioxide, 60 parts of calcium sulfate, 100 parts of superfine sulphoaluminate cement, 3 parts of organic silicon defoamer and 3 parts of flatting agent;
the component B comprises the following raw materials in parts by weight: 100 parts of sulfydryl modified curing agent, 50 parts of modified 1, 3-cyclohexyl dimethylamine curing agent, 3 parts of accelerator and 3 parts of coupling agent.
As another preferred embodiment, the solvent-free epoxy polymer-modified cement mortar comprises a component A and a component B;
the component A comprises the following raw materials in parts by weight: 160 parts of epoxy polymer, 50 parts of epoxy resin modifier, 100 parts of calcium carbonate, 50 parts of silicon dioxide, 60 parts of calcium sulfate, 100 parts of superfine sulphoaluminate cement, 3 parts of organic silicon defoamer and 3 parts of flatting agent;
the component B comprises the following raw materials in parts by weight: 100 parts of sulfydryl modified curing agent, 50 parts of modified 1, 3-cyclohexyl dimethylamine curing agent, 3 parts of accelerator and 3 parts of coupling agent.
As a further preferred embodiment, the solvent-free epoxy polymer-modified cement mortar comprises a component A and a component B;
the component A comprises the following raw materials in parts by weight: 120 parts of epoxy polymer, 50 parts of epoxy resin modifier, 100 parts of calcium carbonate, 50 parts of silicon dioxide, 60 parts of calcium sulfate, 100 parts of superfine sulphoaluminate cement, 3 parts of organic silicon defoamer and 3 parts of flatting agent;
the component B comprises the following raw materials in parts by weight: 100 parts of sulfydryl modified curing agent, 50 parts of modified 1, 3-cyclohexyl dimethylamine curing agent, 3 parts of accelerator and 3 parts of coupling agent.
The epoxy polymer is a mixture of epoxy resin, vegetable oleic acid modified epoxy resin and polythiol modified epoxy resin, and the mass ratio of the epoxy resin to the vegetable oleic acid modified epoxy resin to the polythiol modified epoxy resin is 4-5:1-2: 1-2;
in some preferred embodiments, the mass ratio of the epoxy resin, the vegetable oleic acid modified epoxy resin and the polythiol modified epoxy resin is 4:2: 2;
in other preferred embodiments, the mass ratio of the epoxy resin, the vegetable oleic acid-modified epoxy resin and the polythiol-modified epoxy resin is 5:2: 2;
in other preferred embodiments, the mass ratio of the epoxy resin, the vegetable oleic acid modified epoxy resin and the polythiol modified epoxy resin is 4:1: 1.
The epoxy resin is bisphenol A type epoxy resin;
the vegetable oleic acid modified epoxy resin is vegetable oleic acid modified bisphenol A epoxy resin;
the polythiol modified epoxy resin is polythiol modified aliphatic epoxy resin, and the structural formula of the polythiol modified epoxy resin is shown as the following formula (1):
wherein R1 is- (CH) 2 ) 2 -O-CH 2 -O-(CH 2 ) 2 -，1＜n＜12。
The epoxy resin modifier is one or two of castor oil triglycidyl ether and glycerol triglycidyl ether.
The calcium carbonate is 1250-mesh calcium carbonate;
the silicon dioxide is 800-mesh silicon dioxide;
the calcium sulfate is 500 meshes of calcium sulfate;
the organic silicon defoaming agent is one or two of BYK-A530 and BYK-066N;
the leveling agent is one or more of BYK-306, BYK-361N and BYK-354;
the modified 1, 3-cyclohexyldimethylamine curing agent is a 1, 3-cyclohexyldimethylamine curing agent modified by dodecylphenol and bisphenol A epoxy resin;
the structural formula of the sulfydryl modified curing agent is shown as the following formula (2):
wherein R is- (CH) 2 ) 2 -O-CH 2 -O-(CH 2 ) 2 -，a+b+c＝n＜7。
The coupling agent is a silane coupling agent KH-550;
the accelerant is one or more of aminated graphene, piperazine modified aminated graphene and octadecylamine modified aminated graphene, and the structural formulas of the accelerant are respectively shown in the following formulas (3) to (5):
the invention also provides a preparation method of the solvent-free epoxy polymer modified cement mortar, which comprises the following steps:
(1) preparing a component A:
1.1 mixing and stirring uniformly the epoxy polymer, the epoxy resin modifier, the organic silicon defoamer and the flatting agent according to the formula dosage to obtain a mixture 1 for later use;
1.2 taking calcium carbonate, silicon dioxide, calcium sulfate and superfine sulphoaluminate cement according to the formula dosage, uniformly stirring, adding into the mixture 1, and continuously and uniformly mixing and stirring to obtain a component A;
(2) preparing a component B:
mixing the mercapto-modified curing agent, the modified 1, 3-cyclohexanediamine curing agent, the accelerator and the silane coupling agent according to the formula amount, and then uniformly stirring to obtain a component B;
(3) and mixing the component A and the component B according to the mass ratio of 2-5:1 to obtain the solvent-free epoxy polymer modified cement mortar.
Wherein, the modified 1, 3-cyclohexyldimethylamine curing agent is prepared by the following method: uniformly mixing 100 parts of 1, 3-cyclohexyldimethylamine, 20 parts of bisphenol A epoxy resin and 20 parts of dodecylphenol, adding 3 parts of triphenylphosphine, heating to 160 ℃, carrying out reflux reaction for 4 hours, cooling to 70 ℃, continuing to carry out reflux for 2 hours, then cooling to room temperature, and purifying to obtain the modified 1, 3-cyclohexyldimethylamine curing agent.
As a preferable scheme, the mass ratio of the component A to the component B is 3: 1.
Compared with the prior art, the invention has the beneficial effects that:
(1) the cement mortar provided by the invention comprises two components, namely a component A and a component B, wherein polythiol modified epoxy resin and vegetable oleic acid modified epoxy resin are introduced into the component A, so that the brittleness of bisphenol A epoxy resin is greatly improved, and the corrosion resistance of a system is improved; the modified graphene is introduced into the component B, so that the adhesive force of the system with a steel structure and concrete is greatly improved;
(2) the solvent-free epoxy polymer modified cement mortar obtained by mixing and curing the component A and the component B according to a certain proportion in the construction process has good flexibility, corrosion resistance and excellent adhesive force, and can play a good role in corrosion prevention and protection on steel structures and concrete.
(3) The polythiol modified epoxy resin and the vegetable oil acid modified epoxy resin are introduced into the components, and are modified by the reactive diluent without any solvent, so that the defects of poor chemical resistance, poor corrosion resistance, low adhesive force and low strength of the material are overcome, and the corrosion-resistant and protective effects on steel structures and concrete can be well achieved;
(4) the technical scheme of the application for protection uses polymer modified epoxy resin as a main body, especially uses the mixture of epoxy resin, vegetable oleic acid modified epoxy resin and polythiol modified epoxy resin as epoxy polymer, so that the solvent-free epoxy polymer modified cement mortar has good corrosion resistance, high strength and good adhesive force, forms a compact solidified body after solidification, prevents water and harmful ions such as chloride ions and sulfate ions in the water from permeating, and achieves good corrosion prevention and protection effects.
Detailed Description
The features mentioned above in the description, or the features mentioned in the embodiments, may be combined arbitrarily. All the features disclosed in this specification may be combined in any suitable manner and each feature disclosed in this specification may be replaced by an alternative feature serving the same, equivalent or similar purpose. Thus, unless expressly stated otherwise, the features disclosed are merely generic examples of equivalent or similar features.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are exemplary only.
The types and purchase manufacturers of the raw materials described in the following examples are:
basic example preparation of modified 1, 3-Cyclohexanediamine curing agent
Uniformly mixing 100 parts of 1, 3-cyclohexyldimethylamine, 20 parts of bisphenol A epoxy resin and 20 parts of dodecylphenol, adding 3 parts of triphenylphosphine, heating to 160 ℃, carrying out reflux reaction for 4 hours, cooling to 70 ℃, continuing to carry out reflux for 2 hours, then cooling to room temperature, and purifying to obtain the modified 1, 3-cyclohexyldimethylamine curing agent.
Example 1A solvent-free epoxy polymer-modified Cement mortar and method for preparing the same
The solvent-free epoxy polymer modified cement mortar comprises a component A and a component B;
the component A comprises the following raw materials in parts by weight: 100 parts of bisphenol A epoxy resin, 40 parts of vegetable oleic acid modified bisphenol A epoxy resin, 40 parts of polythiol modified epoxy resin, XY 63350 parts, 100 parts of 1250-mesh calcium carbonate, 50 parts of 800-mesh silica, 60 parts of 500-mesh calcium sulfate, 100 parts of superfine sulphoaluminate cement, BYK-A5303 parts and BYK-3543 parts;
the component B comprises the following raw materials in parts by weight: 100 parts of sulfydryl modified curing agent, 50 parts of modified 1, 3-cyclohexyldimethylamine curing agent prepared in basic example, 3 parts of aminated graphene and KH-5503 parts.
The preparation method comprises the following steps:
(1) preparing a component A:
1.1, uniformly mixing and stirring bisphenol A epoxy resin, vegetable oleic acid modified bisphenol A epoxy resin, polythiol modified epoxy resin, XY633, BYK-A530 and BYK-354 according to the formula dosage to obtain a mixture 1 for later use;
1.2, taking 1250-mesh calcium carbonate, 800-mesh silicon dioxide, 500-mesh calcium sulfate and superfine sulphoaluminate cement according to the formula dosage, uniformly stirring, adding into the mixture 1, and continuously and uniformly mixing and stirring to obtain a component A;
(2) preparing a component B:
taking the mercapto-modified curing agent, the modified 1, 3-cyclohexanediamine curing agent, the aminated graphene and KH-550 in the formula amount, mixing and uniformly stirring to obtain a component B;
(3) and mixing the component A with the component B according to the mass ratio of 3:1 to obtain the solvent-free epoxy polymer modified cement mortar.
Example 2 solvent-free epoxy polymer modified cement mortar and preparation method thereof
The solvent-free epoxy polymer modified cement mortar comprises a component A and a component B;
the component A comprises the following raw materials in parts by weight: 100 parts of bisphenol A epoxy resin, 40 parts of vegetable oleic acid modified bisphenol A epoxy resin, 20 parts of polythiol modified epoxy resin, XY 63350 parts, 100 parts of 1250-mesh calcium carbonate, 50 parts of 800-mesh silica, 60 parts of 500-mesh calcium sulfate, 100 parts of superfine sulphoaluminate cement, BYK-A5303 parts and BYK-3543 parts;
the component B comprises the following raw materials in parts by weight: 100 parts of sulfydryl modified curing agent, 50 parts of modified 1, 3-cyclohexyldimethylamine curing agent prepared in basic example, 3 parts of aminated graphene and KH-5503 parts.
The preparation method comprises the following steps:
(1) preparing a component A:
1.1, uniformly mixing and stirring bisphenol A epoxy resin, vegetable oleic acid modified bisphenol A epoxy resin, polythiol modified epoxy resin, XY633, BYK-A530 and BYK-354 according to the formula dosage to obtain a mixture 1 for later use;
1.2, taking 1250-mesh calcium carbonate, 800-mesh silicon dioxide, 500-mesh calcium sulfate and superfine sulphoaluminate cement according to the formula dosage, uniformly stirring, adding into the mixture 1, and continuously and uniformly mixing and stirring to obtain a component A;
(2) preparing a component B:
taking the mercapto-modified curing agent, the modified 1, 3-cyclohexanediamine curing agent, the aminated graphene and KH-550 in the formula amount, mixing and uniformly stirring to obtain a component B;
(3) and mixing the component A with the component B according to the mass ratio of 3:1 to obtain the solvent-free epoxy polymer modified cement mortar.
Example 3A solvent-free epoxy polymer-modified Cement mortar and method for preparing the same
The solvent-free epoxy polymer modified cement mortar comprises a component A and a component B;
the component A comprises the following raw materials in parts by weight: 100 parts of bisphenol A epoxy resin, 20 parts of vegetable oleic acid modified bisphenol A epoxy resin, 40 parts of polythiol modified epoxy resin, 96650 parts of XY, 100 parts of 1250-mesh calcium carbonate, 50 parts of 800-mesh silica, 60 parts of 500-mesh calcium sulfate, 100 parts of superfine sulphoaluminate cement, 5303 parts of BYK-A, and 3443 parts of BYK-3443;
the component B comprises the following raw materials in parts by weight: 100 parts of sulfydryl modified curing agent, 50 parts of modified 1, 3-cyclohexyldimethylamine curing agent prepared in basic example, 3 parts of aminated graphene and KH-5503 parts.
The preparation method comprises the following steps:
(1) preparing a component A:
1.1, uniformly mixing and stirring bisphenol A epoxy resin, vegetable oleic acid modified bisphenol A epoxy resin, polythiol modified epoxy resin, XY966, BYK-A530 and BYK-344 according to the formula dosage to obtain a mixture 1 for later use;
1.2, taking 1250-mesh calcium carbonate, 800-mesh silicon dioxide, 500-mesh calcium sulfate and superfine sulphoaluminate cement according to the formula dosage, uniformly stirring, adding into the mixture 1, and continuously and uniformly mixing and stirring to obtain a component A;
(2) preparing a component B:
taking the mercapto-modified curing agent, the modified 1, 3-cyclohexanediamine curing agent, the aminated graphene and KH-550 in the formula amount, mixing and uniformly stirring to obtain a component B;
(3) and mixing the component A with the component B according to the mass ratio of 3:1 to obtain the solvent-free epoxy polymer modified cement mortar.
Example 4A solvent-free epoxy polymer-modified Cement mortar and method for preparing the same
The solvent-free epoxy polymer modified cement mortar comprises a component A and a component B;
the component A comprises the following raw materials in parts by weight: 80 parts of bisphenol A type epoxy resin, 40 parts of vegetable oleic acid modified bisphenol A type epoxy resin, 40 parts of polythiol modified epoxy resin, XY 63350 parts, 100 parts of 1250-mesh calcium carbonate, 50 parts of 800-mesh silicon dioxide, 60 parts of 500-mesh calcium sulfate, 100 parts of superfine sulphoaluminate cement, BYK-A5303 parts and BYK-3013 parts;
the component B comprises the following raw materials in parts by weight: 100 parts of sulfydryl modified curing agent, 50 parts of modified 1, 3-cyclohexyldimethylamine curing agent prepared in basic example, 3 parts of aminated graphene and KH-5503 parts.
The preparation method comprises the following steps:
(1) preparing a component A:
1.1, uniformly mixing and stirring bisphenol A epoxy resin, vegetable oleic acid modified bisphenol A epoxy resin, polythiol modified epoxy resin, XY633, BYK-A530 and BYK-301 according to the formula dosage to obtain a mixture 1 for later use;
1.2, taking 1250-mesh calcium carbonate, 800-mesh silicon dioxide, 500-mesh calcium sulfate and superfine sulphoaluminate cement according to the formula dosage, uniformly stirring, adding into the mixture 1, and continuously and uniformly mixing and stirring to obtain a component A;
(2) preparing a component B:
taking the mercapto-modified curing agent, the modified 1, 3-cyclohexanediamine curing agent, the aminated graphene and KH-550 in the formula amount, mixing and uniformly stirring to obtain a component B;
(3) and mixing the component A with the component B according to the mass ratio of 3:1 to obtain the solvent-free epoxy polymer modified cement mortar.
Example 5A solvent-free epoxy polymer-modified Cement mortar and method for preparing the same
The solvent-free epoxy polymer modified cement mortar comprises a component A and a component B;
the component A comprises the following raw materials in parts by weight: 100 parts of bisphenol A epoxy resin, 40 parts of vegetable oleic acid modified bisphenol A epoxy resin, 40 parts of polythiol modified epoxy resin, 96650 parts of XY, 100 parts of 1250-mesh calcium carbonate, 50 parts of 800-mesh silicon dioxide, 60 parts of 500-mesh calcium sulfate, 100 parts of superfine sulphoaluminate cement, 5303 parts of BYK-A, and 3013 parts of BYK-3013;
the component B comprises the following raw materials in parts by weight: 80 parts of sulfydryl modified curing agent, 50 parts of modified 1, 3-cyclohexyldimethylamine curing agent prepared in basic example, 3 parts of aminated graphene and KH-5503 parts.
The preparation method comprises the following steps:
(1) preparing a component A:
1.1, uniformly mixing and stirring bisphenol A epoxy resin, vegetable oleic acid modified bisphenol A epoxy resin, polythiol modified epoxy resin, BYK-301, BYK-A530 and BYK-301 according to the formula dosage to obtain a mixture 1 for later use;
1.2, taking 1250-mesh calcium carbonate, 800-mesh silicon dioxide, 500-mesh calcium sulfate and superfine sulphoaluminate cement according to the formula dosage, uniformly stirring, adding into the mixture 1, and continuously and uniformly mixing and stirring to obtain a component A;
(2) preparing a component B:
taking the mercapto-modified curing agent, the modified 1, 3-cyclohexanediamine curing agent, the aminated graphene and KH-550 in the formula amount, mixing and uniformly stirring to obtain a component B;
(3) and mixing the component A with the component B according to the mass ratio of 3:1 to obtain the solvent-free epoxy polymer modified cement mortar.
Example 6A solvent-free epoxy polymer-modified Cement mortar and method for preparing the same
The solvent-free epoxy polymer modified cement mortar comprises a component A and a component B;
the component A comprises the following raw materials in parts by weight: 100 parts of bisphenol A epoxy resin, 40 parts of vegetable oleic acid modified bisphenol A epoxy resin, 40 parts of polythiol modified epoxy resin, XY 63350 parts, 100 parts of 1250-mesh calcium carbonate, 50 parts of 800-mesh silica, 60 parts of 500-mesh calcium sulfate, 100 parts of superfine sulphoaluminate cement, BYK-A5303 parts and BYK-3543 parts;
the component B comprises the following raw materials in parts by weight: 100 parts of sulfydryl modified curing agent, 30 parts of modified 1, 3-cyclohexyldimethylamine curing agent prepared in basic example, 3 parts of aminated graphene and KH-5503 parts.
The preparation method comprises the following steps:
(1) preparing a component A:
1.1, uniformly mixing and stirring bisphenol A epoxy resin, vegetable oleic acid modified bisphenol A epoxy resin, polythiol modified epoxy resin, XY633, BYK-A530 and BYK-354 according to the formula dosage to obtain a mixture 1 for later use;
1.2, taking 1250-mesh calcium carbonate, 800-mesh silicon dioxide, 500-mesh calcium sulfate and superfine sulphoaluminate cement according to the formula dosage, uniformly stirring, adding into the mixture 1, and continuously and uniformly mixing and stirring to obtain a component A;
(2) preparing a component B:
taking the sulfhydryl modified curing agent, the modified 1, 3-cyclohexyldimethylamine curing agent, the aminated graphene and KH-550 in formula amount, mixing and uniformly stirring to obtain a component B;
(3) and mixing the component A with the component B according to the mass ratio of 3:1 to obtain the solvent-free epoxy polymer modified cement mortar.
Comparative example 1
The difference from example 1 is that: the weight portion of the vegetable oleic acid modified bisphenol A epoxy resin in the component A is 5 portions, and other operations and steps are the same as those in the example 1.
Comparative example 2
The difference from example 1 is that: the weight portion of the mercapto group modified curing agent in the component B is 20 portions, and other operations and steps are the same as those in the example 1.
Comparative example 3
The difference from example 1 is that: the modified 1, 3-cyclohexyldimethylamine curing agent in the component B is 5 parts by weight, and other operations and steps are the same as those in the example 1.
Comparative example 4
The difference from example 1 is that: the vegetable oleic acid-modified bisphenol a epoxy resin in the component a was replaced with a urethane-modified bisphenol a epoxy resin, and the other operations and steps were the same as in example 1.
Comparative example 5
The difference from example 1 is that: the mercapto group modified curing agent in the component B was replaced with phenolic amine curing agent T31, and the other operations and steps were the same as in example 1.
Comparative example 6
The difference from example 1 is that: the modified 1, 3-cyclohexanediamine curing agent in the component B is replaced by the isophorone diamine curing agent, and other operations and steps are the same as those in the example 1.
Effect test
1. Mechanical Property and Permeability measurements
The compressive strength is detected according to the method disclosed in JC/T1041-. The specific test results are shown in Table 1 below.
TABLE 1 mechanical Properties and Permeability tests of Cement mortars prepared in examples 1-6 and comparative examples 1-6
According to the detection data in the table 1, the solvent-free epoxy polymer modified cement mortar prepared in the embodiments 1-6 has the advantages of good corrosion resistance, high strength and good adhesion, and can form a compact solidified body after solidification, so that water and harmful ions such as chloride ions and sulfate ions in water can be prevented from permeating, and a good corrosion prevention effect can be achieved.
In examples 1 to 6, based on example 1 as a basic experiment, in example 2, 10 parts of polythiol-modified epoxy resin was used, and polythiol-modified epoxy resin was used as a long molecular chain component, which is superior in flexibility, and the strength was increased to some extent after the addition of a small amount of polythiol-modified epoxy resin, and the flexibility was decreased, so that the adhesion was decreased.
In example 3, compared to example 1, the amount of the vegetable oleic acid modified epoxy resin is 10 parts less, the vegetable oleic acid modified epoxy resin is also a long molecular chain component, and the flexibility is good, and after the amount of the vegetable oleic acid modified epoxy resin is less, the strength is correspondingly increased to a certain extent, the flexibility is reduced, and the adhesion is reduced.
In example 4, compared to example 1, the amount of the bisphenol a epoxy resin added is 10 parts less, the bisphenol a epoxy resin is a relatively short molecular chain component, the brittleness is relatively high, the strength is correspondingly reduced to a certain extent after the amount of the bisphenol a epoxy resin added is less, the flexibility is improved, and the adhesion is improved.
In example 5, compared with example 1, the addition amount of the mercapto-modified curing agent is 20 parts less, the mercapto-modified curing agent is also a long molecular chain component, the flexibility is good, and after the addition amount is less, the strength is correspondingly increased to a certain extent, the flexibility is reduced, and therefore, the adhesive force is reduced.
In example 6, compared to example 1, the addition amount of the modified m-xylylenediamine curing agent is 20 parts less, the modified 1, 3-cyclohexyldimethylamine curing agent is a relatively short molecular chain component, the brittleness is relatively high, the strength is correspondingly reduced to a certain extent after the addition amount is less, the flexibility is improved, and the adhesion is improved.
Comparative example 1 the content of the vegetable oleic acid modified bisphenol A epoxy resin in the component A is reduced to 5 parts, and the obtained cement mortar has higher compressive strength and tensile strength, but the adhesive force and the anti-corrosion protection effect are obviously deteriorated, the relative permeability coefficient and the chloride ion migration coefficient are increased, and the permeability resistance is reduced;
comparative example 2 the content of the mercapto group modified curing agent in the component B is reduced to 20 parts, and the obtained cement mortar is similar to the cement mortar obtained in comparative example 1, although the cement mortar has higher compressive strength and tensile strength, the adhesion and the anti-corrosion protection effect are obviously deteriorated, the relative permeability coefficient and the chloride ion migration coefficient are increased, and the permeability resistance is reduced;
the comparative example 3 reduces the content of the modified 1, 3-cyclohexanediamine curing agent in the component B to 5 parts, and the obtained cement mortar has obviously poor compressive strength, tensile strength, adhesive force and anticorrosion protection effect.
Comparative example 4 vegetable oleic acid modified bisphenol A type epoxy resin in the component A is replaced by polyurethane modified bisphenol A type epoxy resin, and the obtained cement mortar has higher compressive strength and tensile strength, but the adhesive force is obviously reduced, the anti-corrosion protection effect is obviously deteriorated, the relative permeability coefficient and the chloride ion migration coefficient are increased, and the permeability resistance is reduced;
the comparative example 5 replaces the mercapto-modified curing agent in the component B with a phenolic aldehyde amine curing agent, and the comparative example 6 replaces the modified 1.3-cyclohexanediamine curing agent in the component B with an isophorone diamine curing agent, so that the compressive strength, tensile strength, adhesive force and anticorrosion protection effect of the obtained cement mortar are obviously poor.
Meanwhile, compared with a comparative example, the technical scheme provided by the invention has the advantages that only the components such as the vegetable oleic acid modified epoxy resin, the polythiol modified epoxy resin, the sulfydryl modified curing agent, the modified 1.3-cyclohexanediamine curing agent, the promoter aminated graphene and the like are added, and in the protection range of the scheme, the adhesive force, the impermeability and the chloride ion migration coefficient performance are all very good, and the compressive strength of a product corresponding to the scheme are also higher, so that the performance requirements of the same type of products are completely met. And one or more of the compressive strength, the tensile strength, the adhesive force, the anticorrosion protection effect, the relative permeability coefficient and the chloride ion migration coefficient of the material which is outside the protection range of the scheme or does not contain any one of the components in the scheme are obviously reduced, and the requirements of the product performance can not be met.
2. Chemical resistance test
The acid resistance, alkali resistance and salt resistance are all detected according to the method specified in JC/T2217-2014, and the specific detection results are shown in the following table 2.
TABLE 2 examination of chemical resistance of Cement mortars prepared in examples 1 to 6 and comparative examples 1 to 6
According to the detection data in the table 2, the solvent-free epoxy polymer modified cement mortars prepared in the examples 1 to 6 form a compact solidified body after being solidified, and prevent the permeation of water and harmful ions such as chloride ions and sulfate ions in the water, so that the cement mortars have good chemical corrosion resistance, and the coating can not crack, peel or fall off after being treated by acid, alkali or salt.
In comparative examples 1 to 6, the content of the vegetable oleic acid modified bisphenol a epoxy resin was reduced, or the content of the mercapto-modified curing agent was increased, or the content of the modified 1.3-cyclohexyldimethylamine curing agent was reduced, or the vegetable oleic acid modified bisphenol a epoxy resin was replaced with the polyurethane modified bisphenol a epoxy resin, or the mercapto-modified curing agent was replaced with the phenalkamine curing agent, or the modified 1.3-cyclohexyldimethylamine curing agent was replaced with the isophorone diamine curing agent, and the adhesion and the anti-seepage effect of the cement mortar prepared therefrom were significantly reduced, so that the chemical corrosion resistance of the cement mortar was significantly reduced, and the cracking, peeling and peeling of the coating occurred after the treatment with the acid-base salt, thereby affecting the use of the cement mortar.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner; the present invention may be readily implemented by those of ordinary skill in the art having reference to the foregoing specification and claims; however, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention; meanwhile, any changes, modifications, and evolutions of the equivalent changes of the above embodiments according to the actual techniques of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (9)
1. A solvent-free epoxy polymer modified cement mortar is characterized in that: comprises a component A and a component B;
the component A comprises the following raw materials in parts by weight: 70-180 parts of epoxy polymer, 10-50 parts of epoxy resin modifier, 50-100 parts of calcium carbonate, 10-50 parts of silicon dioxide, 20-60 parts of calcium sulfate, 10-100 parts of superfine sulphoaluminate cement, 2-6 parts of organic silicon defoamer and 2-6 parts of flatting agent;
the component B comprises the following raw materials in parts by weight: 50-100 parts of sulfydryl modified curing agent, 20-50 parts of modified 1, 3-cyclohexyldimethylamine curing agent, 1-5 parts of accelerator and 1-5 parts of coupling agent;
the epoxy polymer is a mixture of epoxy resin, vegetable oleic acid modified epoxy resin and polythiol modified epoxy resin; the mass ratio of the epoxy resin, the vegetable oleic acid modified epoxy resin and the polythiol modified epoxy resin is 4-5:1-2: 1-2;
the polythiol modified epoxy resin is polythiol modified aliphatic epoxy resin, and the structural formula of the polythiol modified epoxy resin is shown as the following formula (1):
formula (1)
Wherein R is 1 Is- (CH) 2 ) 2 -O-CH 2 -O-(CH 2 ) 2 -，1＜n＜12；
The modified 1, 3-cyclohexyldimethylamine curing agent is a 1, 3-cyclohexyldimethylamine curing agent modified by dodecylphenol and bisphenol A epoxy resin;
the modified 1, 3-cyclohexyldimethylamine curing agent is prepared by the following method: uniformly mixing 100 parts of 1, 3-cyclohexyldimethylamine, 20 parts of bisphenol A epoxy resin and 20 parts of dodecylphenol, adding 3 parts of triphenylphosphine, heating to 160 ℃, carrying out reflux reaction for 4 hours, cooling to 70 ℃, continuing to carry out reflux for 2 hours, then cooling to room temperature, and purifying to obtain a modified 1, 3-cyclohexyldimethylamine curing agent;
the structural formula of the sulfydryl modified curing agent is shown as the following formula (2):
（2）
wherein R is- (CH) 2 ) 2 -O-CH 2 -O-(CH 2 ) 2 -，a+b+c=n＜7；
The accelerant is one or more of aminated graphene, piperazine modified aminated graphene and octadecylamine modified aminated graphene.
2. The solventless epoxy polymer modified cement mortar of claim 1, wherein: comprises a component A and a component B;
the component A comprises the following raw materials in parts by weight: 120-180 parts of epoxy polymer, 20-50 parts of epoxy resin modifier, 60-100 parts of calcium carbonate, 20-50 parts of silicon dioxide, 30-60 parts of calcium sulfate, 60-100 parts of superfine sulphoaluminate cement, 3-5 parts of organic silicon defoamer and 3-5 parts of flatting agent;
the component B comprises the following raw materials in parts by weight: 60-100 parts of sulfydryl modified curing agent, 30-50 parts of modified 1, 3-cyclohexyldimethylamine curing agent, 2-4 parts of accelerator and 2-4 parts of coupling agent.
3. The solventless epoxy polymer modified cement mortar of claim 2, wherein: comprises a component A and a component B;
the component A comprises the following raw materials in parts by weight: 180 parts of epoxy polymer 160-one, 40-50 parts of epoxy resin modifier, 80-100 parts of calcium carbonate, 30-50 parts of silicon dioxide, 40-60 parts of calcium sulfate, 80-100 parts of superfine sulphoaluminate cement, 3-4 parts of organic silicon defoamer and 3-4 parts of flatting agent;
the component B comprises the following raw materials in parts by weight: 80-100 parts of sulfydryl modified curing agent, 40-50 parts of modified 1, 3-cyclohexyl dimethylamine curing agent, 3-4 parts of accelerator and 3-4 parts of coupling agent.
4. The solventless epoxy polymer modified cement mortar of claim 1, wherein: the mass ratio of the epoxy resin, the vegetable oleic acid modified epoxy resin and the polythiol modified epoxy resin is 4:2: 2.
5. The solventless epoxy polymer modified cement mortar of claim 1, wherein: the mass ratio of the epoxy resin, the vegetable oleic acid modified epoxy resin and the polythiol modified epoxy resin is 5:2: 2.
6. The solventless epoxy polymer modified cement mortar of claim 1, wherein: the mass ratio of the epoxy resin, the vegetable oleic acid modified epoxy resin and the polythiol modified epoxy resin is 4:1: 1.
7. The solventless epoxy polymer modified cement mortar of claim 1, wherein: the epoxy resin is bisphenol A type epoxy resin.
8. The solventless epoxy polymer modified cement mortar of claim 1, wherein: the vegetable oleic acid modified epoxy resin is vegetable oleic acid modified bisphenol A epoxy resin.
9. The method for preparing solvent-free epoxy polymer modified cement mortar according to any one of claims 1 to 8, wherein: the method comprises the following steps:
preparing a component A:
1, uniformly mixing and stirring the epoxy polymer, the epoxy resin modifier, the organic silicon defoamer and the flatting agent according to the formula dosage to obtain a mixture 1 for later use;
2, uniformly stirring the calcium carbonate, the silicon dioxide, the calcium sulfate and the superfine sulphoaluminate cement according to the formula, adding the mixture into the mixture 1, and continuously and uniformly mixing and stirring to obtain a component A;
preparing a component B:
mixing the mercapto-modified curing agent, the modified 1, 3-cyclohexanediamine curing agent, the accelerator and the silane coupling agent according to the formula amount, and then uniformly stirring to obtain a component B;
(3) and mixing the component A and the component B according to the mass ratio of 2-5:1 to obtain the solvent-free epoxy polymer modified cement mortar.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103359977A (en) * | 2013-06-25 | 2013-10-23 | 中科院广州化学有限公司 | Abrasion-resistant epoxy mortar and preparation method thereof |
| CN105419241A (en) * | 2015-12-29 | 2016-03-23 | 广州盈天建材科技有限公司 | Transparent and environment-friendly underwater consolidated solvent-free epoxy grouting material and preparation method and application thereof |
| WO2017181323A1 (en) * | 2016-04-18 | 2017-10-26 | Evonik Degussa Gmbh | Epoxy modified cement composition |
| EP3290457A1 (en) * | 2016-08-30 | 2018-03-07 | HILTI Aktiengesellschaft | Dual component mortar composition and its use |
| CN113480268A (en) * | 2021-08-06 | 2021-10-08 | 广东水电二局股份有限公司 | Epoxy polymer modified cement mortar and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103359977A (en) * | 2013-06-25 | 2013-10-23 | 中科院广州化学有限公司 | Abrasion-resistant epoxy mortar and preparation method thereof |
| CN105419241A (en) * | 2015-12-29 | 2016-03-23 | 广州盈天建材科技有限公司 | Transparent and environment-friendly underwater consolidated solvent-free epoxy grouting material and preparation method and application thereof |
| WO2017181323A1 (en) * | 2016-04-18 | 2017-10-26 | Evonik Degussa Gmbh | Epoxy modified cement composition |
| EP3290457A1 (en) * | 2016-08-30 | 2018-03-07 | HILTI Aktiengesellschaft | Dual component mortar composition and its use |
| CN113480268A (en) * | 2021-08-06 | 2021-10-08 | 广东水电二局股份有限公司 | Epoxy polymer modified cement mortar and preparation method thereof |
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