CN115246716A - Method for preparing high-performance naphthalene water reducer by utilizing thermosetting resin composite material waste - Google Patents
Method for preparing high-performance naphthalene water reducer by utilizing thermosetting resin composite material waste 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/20—Sulfonated aromatic compounds
- C04B24/22—Condensation or polymerisation products thereof
- C04B24/226—Sulfonated naphtalene-formaldehyde condensation products
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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Abstract
The invention belongs to the technical field of recycling of thermosetting resin composite material waste and preparation of a naphthalene water reducer, and particularly relates to a method for preparing a high-performance naphthalene water reducer by using thermosetting resin composite material waste. The thermosetting resin composite material waste and concentrated sulfuric acid are used for generating and dissolving an oxonium salt ionized polymer, and then degraded resin waste liquid is used as a sulfonating agent to carry out sulfonation reaction with a modifier and naphthalene together to obtain a sulfonated material; and (3) sequentially carrying out hydrolysis reaction, condensation reaction and neutralization reaction on the sulfonated material to obtain the sulfonated thermosetting resin graft modified naphthalene sulfonate formaldehyde polymer water reducing agent, and forming the dendritic macromolecular water reducing agent with a cross-linked structure. The water reducing agent obtained by the invention has good water reducing and slump retaining effects, meets the requirements of corresponding national standards, and has low production cost; meanwhile, the degradation conditions of high temperature, high pressure and high energy consumption required by the regeneration of the modified filler in the thermosetting resin composite material waste are avoided, and the problem that the thermosetting resin degradation liquid is difficult to recycle is solved.
Description
Technical Field
The invention belongs to the technical field of recycling of thermosetting composite material waste and preparation of water reducing agents, and particularly relates to a method for preparing a high-performance naphthalene water reducing agent by using thermosetting resin composite material waste.
Background
The water reducing agent is a concrete admixture capable of reducing the water consumption for mixing under the condition of maintaining the slump constant of concrete basically. Most of them are anionic surfactants, such as lignosulfonate and naphthalene sulfonate formaldehyde polymer. After the concrete mixture is added, the dispersion effect on cement particles is achieved, the workability of the concrete mixture can be improved, the unit water consumption is reduced, and the fluidity of the concrete mixture is improved; or the unit cement consumption is reduced, and the cement is saved. The water reducing rate of the first generation of high efficiency water reducing agent, namely naphthyl high efficiency water reducing agent and melamine resin based high efficiency water reducing agent, can reach more than 20 percent. The high-efficiency water reducing agent has strong dispersion effect on cement, can greatly improve the fluidity of a cement mixture and the slump of concrete, simultaneously greatly reduces the water consumption, and obviously improves the workability of the concrete. However, some high-efficiency water reducing agents can accelerate the slump loss of concrete, and bleeding is caused when the mixing amount is too large. The high-efficiency water reducing agent basically does not change the setting time of concrete, has a slight retarding effect when the mixing amount is large, but does not delay the increase of the early strength of the hardened concrete, and can greatly reduce the water consumption so as to obviously improve the strength of the concrete at each age; the concrete anti-permeability, freeze-thaw resistance and corrosion resistance can be enhanced, and the durability of the concrete is improved.
The polycarboxylate superplasticizer has the outstanding advantages of low mixing amount, good slump retaining performance, low concrete shrinkage, strong adjustability in molecular structure, large potential of high performance and the like. The early and later strength of the concrete is greatly improved. Low chloride ion content and alkali content, and is beneficial to the durability of concrete. The water reducing rate of the polycarboxylic acid water reducing agent is obviously higher than that of the naphthalene water reducing agent, and under the condition of reaching the same water reducing rate, the mixing amount of the polycarboxylic acid water reducing agent is far lower than that of the naphthalene water reducing agent, and the water reducing rate can reach 45%. The polycarboxylic acid series high-efficiency water reducing agent products are divided into two categories: the polyether with different side chain lengths is grafted by taking acrylic acid or methacrylic acid as a main chain. The other type is polyether with different side chain lengths grafted by maleic anhydride as a main chain. The ideal structure of the polycarboxylic acid water reducing agent is a linear multi-branched comb copolymer, a hydrophobic molecular main chain is forged with hydrophilic groups such as carboxylic acid groups, sulfonic acid groups and amino groups, and side chains are forged with hydrophilic different polyoxyethylene. The current commercial polycarboxylate water reducer (PCE) product comprises polycarboxylate macromonomer TPEG, HPEG, APEG, MPEG, VPEG and the like which are grafted to main chains of other monomer polymers through Polyethoxy (PEO) side chains, and the PEO side chains generate steric hindrance effect among cement particles suspended in a water phase.
Thermosetting composite materials are plastics which are formed into products by using thermosetting resins as main components and adding various necessary additives through a cross-linking and curing process. The liquid state is at the early stage of the manufacturing or forming process, and after solidification, the liquid state is insoluble and infusible, and can not be melted or softened again. Phenolic plastics, epoxy plastics, aminoplasts, unsaturated polyesters, alkyd plastics and the like are common. Thermosetting refers to the property of not softening and repeatedly molding upon heating, nor dissolving in a solvent. For example, a fiber reinforced composite (FRP) is a composite structural material in which a synthetic resin such as epoxy resin (EPR), unsaturated Polyester (UPR), phenol resin (PFR), polyamide (Polyamide), bismaleimide (BMI), or thermoplastic Polyethylene (PE), polystyrene (PS), polyphenylene sulfide (PPS), or polyether ether ketone (PEEK) is used as a matrix, and is formed by hand lay-up, lamination, spraying, or winding, and glass fiber, carbon fiber, or a product thereof is used as a reinforcing material. With the widespread use of thermosetting composite materials, the waste thereof is rapidly increasing. Due to the characteristics of high strength, good corrosion resistance and the like of the thermosetting composite material, the disposal and utilization of the thermosetting composite material waste are very difficult.
Unsaturated polyester resin and epoxy resin are common materials for thermosetting resin matrix, which means a solution of unsaturated polyester in vinyl crosslinking monomer (such as styrene), and the unsaturated polyester is usually prepared by polycondensation of unsaturated dicarboxylic acid (or anhydride), saturated dicarboxylic acid (or anhydride) and polyhydric alcohol, and a certain amount of vinyl crosslinking monomer is added into the mixture while the polycondensation reaction is hot to form viscous liquid resin. The unsaturated polyester resin can be prepared by radical copolymerization of double bonds in the unsaturated polyester and polymerizable vinyl monomers (usually styrene) initiated by an initiator, light, high-energy radiation, etc., so that the linear polyester molecular chains are crosslinked into infusible and insoluble three-dimensional molecules with a three-dimensional network structure. The epoxy resin is a high molecular polymer and is a generic name of a polymer containing more than two epoxy groups in a molecule. It is a polycondensation product of epichlorohydrin and bisphenol a or a polyol. Because of the chemical activity of the epoxy group, the epoxy group can be opened by a plurality of compounds containing active hydrogen, and the epoxy group is cured and crosslinked to form a network structure, so that the epoxy group is a thermosetting resin. The material composition shows that the chain forging of the polymeric polyol and the carboxyl contained in the epoxy resin or the unsaturated polyester matrix are one of the main components of the polycarboxylic acid water reducing agent, wherein the chain forging of the polystyrene or bisphenol A benzene ring also has a surface activity function after sulfonation reaction, the phenolic resin also has a structure similar to that of the naphthalene water reducing agent after sulfonation, the thermosetting resin matrix has a certain crosslinking degree, the molecules of the water reducing agent can be prevented from being inserted into a silicate lamellar structure of clay, so that the molecules of the water reducing agent are adsorbed on the surface of cement particles, and the structural characteristics show that the comprehensive performance of the naphthalene water reducing agent can be improved after the thermosetting matrix resin is subjected to sulfonation reaction.
Chinese patent CN1887776A discloses a preparation method of a naphthalene water reducer, which sequentially comprises the steps of sulfonation, hydrolysis, condensation, neutralization, drying until a finished product is obtained, and the condensation step comprises the following steps: a) Cooling the hydrolyzed sulfonated substance to below 100 ℃; b) Putting the formaldehyde required in the condensation reaction process at one time; c) After the formaldehyde is added, the procedure is strictly controlled, the reaction temperature is controlled at 115-120 ℃, and the condensation reaction process is controlled to be completed within 4-5 hours. Concentrated sulfuric acid added in the sulfonation process in the patent does not contain thermosetting resin components and does not relate to recycling of thermosetting resin composite material wastes.
At present, no relevant patent or literature report of the thermosetting resin composite material for preparing the water reducing agent is found.
Disclosure of Invention
The invention aims to provide a method for preparing a high-performance naphthalene water reducer by utilizing thermosetting resin composite waste, wherein degraded resin waste liquid obtained by degrading the thermosetting resin composite waste is used as a sulfonating agent and a grafting modifier in the preparation process of the naphthalene water reducer, so that the obtained water reducer has good water reducing and slump retaining effects; meanwhile, the problems of resin recovery and modified filler recycling in thermosetting resin composite waste are solved, and the problems that the thermosetting resin composite waste cannot be completely modified and the degraded resin waste liquid is recycled due to high temperature, high pressure and high energy consumption in the conventional process are solved.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention discloses a method for preparing a high-performance naphthalene water reducer by utilizing thermosetting resin composite material waste, which comprises the following steps of: performing sulfonation reaction on degraded resin waste liquid obtained by degrading thermosetting resin composite material waste and naphthalene to obtain a sulfonated material; and (3) sequentially carrying out hydrolysis reaction, condensation reaction and neutralization reaction on the sulfonated material to obtain the high-performance naphthalene water reducer.
The thermosetting resin composite material is epoxy resin, phenolic resin or unsaturated polyester resin and thermosetting resin or composite material thereof modified by the epoxy resin, phenolic resin or unsaturated polyester resin and containing ether bonds and ester groups in molecular chain forging.
The method for preparing the high-performance naphthalene water reducer by utilizing the thermosetting resin composite material waste comprises the following steps of:
(1) Immersing thermosetting resin composite material waste into concentrated sulfuric acid to obtain degraded resin waste liquid, and carrying out sulfonation reaction on the degraded resin waste liquid and naphthalene to obtain a sulfonated material;
(2) Adding water into the sulfonated material to perform hydrolysis reaction to obtain a hydrolyzed material;
(3) Adding a formaldehyde solution into the hydrolyzed material, and performing condensation reaction to obtain a formaldehyde condensate;
(4) And adding sodium hydroxide solution into the formaldehyde condensation material to perform neutralization reaction to obtain the high-performance naphthalene water reducer.
Wherein:
the molar ratio of concentrated sulfuric acid, water, formaldehyde and sodium hydroxide in the naphthalene and degraded resin waste liquid is as follows: 1.0-1.5; the mass concentration of the formaldehyde solution is 30-37%; the mass concentration of the sodium hydroxide solution is 20-35%.
The preparation of the resin degradation waste liquid in the step (1) is as follows: (1) collecting the thermosetting resin composite material waste, removing impurities, washing and drying; (2) under the conditions of normal pressure and normal temperature (0-40 ℃), the thermosetting resin composite material waste is directly or after mechanical cutting or crushing, immersed into concentrated sulfuric acid and soaked until the filler and the matrix resin are completely degraded and separated; (3) and (3) carrying out filter pressing or centrifugal separation on the completely degraded thermosetting resin composite material mixture to obtain the modified filler and the degraded resin waste liquid.
The mass ratio of the thermosetting resin composite waste to concentrated sulfuric acid is 1.5-10, wherein the concentrated sulfuric acid is 80-100% sulfuric acid or fuming sulfuric acid.
The modified filler is one or more of carbon fiber, glass fiber, silicon carbide, graphite, carbon black, white carbon black, glass microspheres, glass powder, ceramic powder, titanium dioxide, talcum powder, quartz powder, carborundum or asbestos.
In the step (1), after naphthalene is melted, heating to 120-150 ℃, dropwise adding the degraded resin waste liquid, and then carrying out sulfonation reaction at 160-175 ℃ for 2-10h, wherein the acidity of the feed liquid is controlled to be 28-35% at the end of the reaction, so as to obtain the sulfonated material.
In the step (1), unsaturated polyester, phenolic resin or epoxy resin waste without filler is added in the sulfonation reaction process to participate in the sulfonation reaction together with naphthalene so as to further reduce the cost of the naphthalene raw material, wherein the addition amount of the unsaturated polyester, phenolic resin or epoxy resin waste without filler is 1-30% of the mass of the naphthalene.
In the step (2), the sulfonated material is cooled to 115-125 ℃, then water with the mole number of 1.5-3.0 times of naphthalene is slowly dripped, and hydrolysis reaction is carried out for 0.5-3h at 100-130 ℃, so as to obtain the hydrolyzed material.
In the step (3), adding a formaldehyde solution when the temperature of the hydrolysis material is 90-105 ℃, controlling the adding temperature of the formaldehyde solution to be 105-120 ℃, then continuing to perform heat preservation condensation reaction at 100-115 ℃ for 3-5h, and slowly dropwise adding water with the mol number of 6-12 times of naphthalene during the period to obtain the formaldehyde condensation material.
In the step (4), a water bath or liquid nitrogen cooling method is adopted, the temperature of the neutralization reaction is controlled to be 30-60 ℃, sodium hydroxide solution is added into the formaldehyde condensation material at 30-60 ℃ for neutralization reaction until the pH value of the material liquid is 6-9, and the high-performance naphthalene water reducer is obtained.
The high-performance naphthalene water reducer obtained by the invention has wide application fields, and relates to common concrete, large-volume concrete, dam concrete, hydraulic concrete, pump concrete, concrete for slip form construction and waterproof concrete.
The invention immerses thermosetting resin composite material waste into concentrated sulfuric acid to obtain degraded resin waste liquid, the thermosetting resin matrix in the degraded resin waste liquid reacts with the concentrated sulfuric acid to obtain oxonium salt ionic liquid resin polymer, and the oxonium salt ionic liquid resin polymer and naphthalene are subjected to sulfonation reaction, hydrolysis reaction, condensation reaction and neutralization reaction together to obtain the high-performance naphthalene water reducer containing thermosetting resin grafted naphthalene sulfonate formaldehyde polymer:
(1) The reaction process for preparing the high-performance naphthalene water reducer by the oxidative onium salt ionization degradation of the unsaturated polyester resin composite material waste and the sulfonated unsaturated polyester grafted naphthalene sulfonate formaldehyde polymer is as follows: the method comprises the steps of sulfonating and hydrolyzing an oxonium salt ion liquid unsaturated resin polymer generated by unsaturated polyester and concentrated sulfuric acid together with naphthalene under the heating condition, grafting a naphthalenesulfonate formaldehyde polymer on a sulfonated unsaturated polyester resin side chain through a condensation reaction of formaldehyde, forming water reducer macromolecules with a dendritic cross-linking structure through a neutralization reaction, and forming a composite naphthalene water reducer system with a naphthalenesulfonate formaldehyde polymer water reducer and a sulfonated unsaturated polyester resin water reducer which are not grafted, so that the compression strength and the water reducing performance of concrete can be improved, the bleeding rate is reduced, the initial setting time is delayed, and the comprehensive performance of the naphthalene water reducer is improved through the grafting reaction.
(2) The process of preparing the oxonium salt ionic liquid epoxy resin polymer by firstly curing and crosslinking the waste of the epoxy resin composite material and then degrading the waste to generate the oxonium salt ionic liquid epoxy resin polymer and the reaction process of preparing the high-performance naphthalene series water reducing agent by sulfonating and grafting the oxonium salt ionic liquid epoxy resin polymer with the naphthalene sulfonate formaldehyde polymer are as follows: after being cured and crosslinked, the epoxy polyester is sulfonated and hydrolyzed together with naphthalene under the heating condition with oxonium salt ion liquid epoxy resin polymer generated by concentrated sulfuric acid, then naphthalene sulfonate formaldehyde polymer is grafted on a sulfonated epoxy resin side chain through a condensation reaction of formaldehyde, and then a water reducing agent macromolecule with a dendritic crosslinking structure is formed through a neutralization reaction, and forms a composite naphthalene water reducing agent system with a naphthalene sulfonate formaldehyde polymer water reducing agent and a sulfonated epoxy resin water reducing agent which are not grafted, so that the compression strength and the water reducing performance of concrete can be improved, the bleeding rate is reduced, the initial setting time is delayed, and the comprehensive performance of the naphthalene water reducing agent is improved through the grafting reaction.
(3) The reaction process for preparing the high-performance naphthalene water reducer by the oxidative onium salt ionization degradation of phenolic resin composite material waste and the sulfonated unsaturated polyester grafted naphthalene sulfonate formaldehyde polymer is as follows: the method comprises the steps of sulfonating and hydrolyzing an oxonium salt ion liquid unsaturated resin polymer generated by phenolic resin and concentrated sulfuric acid together with naphthalene under the heating condition, grafting a naphthalenesulfonate formaldehyde polymer on a sulfonated phenolic resin side chain through a condensation reaction of formaldehyde, forming water reducer macromolecules with a dendritic cross-linking structure through a neutralization reaction, and forming a composite naphthalene water reducer system with a naphthalenesulfonate formaldehyde polymer water reducer and a sulfonated phenolic resin water reducer which are not grafted, so that the compression strength and the water reducing performance of concrete can be improved, the bleeding rate is reduced, the initial setting time is delayed, and the comprehensive performance of the naphthalene water reducer is improved through the grafting reaction.
The invention has the following beneficial effects:
(1) The thermosetting resin composite material waste is soaked in concentrated sulfuric acid, soluble oxonium salt ionic liquid resin polymer is generated through the concentrated sulfuric acid and oxygen-containing groups of the thermosetting resin matrix, so that the thermosetting resin matrix is swelled and degraded and is continuously dissolved in the concentrated sulfuric acid, and modified filler is separated out through filtration or centrifugation to obtain degraded resin waste liquid, so that the thermosetting resin matrix and the modified filler are separated; and then the degraded resin waste liquid is used as a sulfonating agent and a grafting modifier of the naphthalene water reducer to prepare the high-performance naphthalene water reducer. On one hand, the waste concentrated sulfuric acid in the degraded resin waste liquid is used as a sulfonating agent, the oxonium salt ionic liquid resin polymer and naphthalene are subjected to sulfonation reaction together, and then hydrolysis reaction, condensation reaction and neutralization reaction are carried out to obtain the thermosetting resin graft modified high-performance naphthalene water reducing agent, so that water reducing agent macromolecules with a dendritic cross-linking structure are formed, and a composite naphthalene water reducing agent system is formed by the thermosetting resin graft modified high-performance naphthalene water reducing agent macromolecules and the non-grafted naphthalene sulfonate formaldehyde polymer water reducing agent and the sulfonated phenolic resin water reducing agent, so that the compression strength and the water reducing performance of concrete can be improved, the bleeding rate is reduced, the initial setting time is delayed, and the comprehensive performance of the naphthalene water reducing agent is improved through the dendritic macromolecule structure. On the other hand, the characteristic structure of the water reducing agent is formed by the polyol polymer chain forging, the sulfonated polystyrene chain forging or the sulfonated phenolic resin chain forging in the oxonium salt ionic liquid resin polymer in the degraded resin waste liquid, so that the water reducing agent can play a role in synergy with the naphthalene water reducing agent, and the problems that the water reducing agent cannot be used in a complex way with the naphthalene water reducing agent and the cement is excessively retarded due to a large amount of carboxyl in the polycarboxylic acid water reducing agent can be avoided.
(2) In the process of adding the formaldehyde condensate into sodium hydroxide for neutralization reaction, a water bath or liquid nitrogen cooling method is adopted, so that the neutralization reaction temperature is controlled between 30 and 60 ℃, excessive hydrolysis of sulfonic acid groups on macromolecules of the water reducing agent can be avoided as much as possible, the water solubility of water reducing agent molecules is kept, the generation of precipitation polymers is prevented, the solid content of the water reducing agent is increased, and the generation of solid wastes is reduced. The thermosetting resin degradation product with a polyether glycol structure and benzene sulfonic acid groups in the water reducing agent is adsorbed on the surface of cement, so that a large number of sulfonate ions are adsorbed on the surface of cement particles, the cement particles are negatively charged, and the cement is dispersed due to mutual repulsion between negative charges, so that the water consumption in mixing can be effectively reduced. The waste sulfuric acid in the degradation liquid can reduce sulfonation cost, and the sulfonated thermosetting resin plays a role of a high-performance water reducing agent for cement, so that the problems of separation of fillers with high energy consumption and high added value in the thermosetting composite material and recycling of thermosetting matrix resin are solved. The invention has obvious economic benefit, degrades and recovers the thermosetting composite material waste at normal temperature and normal pressure, successfully realizes the regeneration of fillers such as glass fiber and the like and the reutilization of thermosetting resin matrix, has simple degradation process flow of the composite material, does not need mechanical crushing and preprocessing, and can completely reserve the original length and shape of the reinforced fiber even if the degradation and the separation of large-size FRP composite materials such as glass steel pipelines or wind power blades and the like.
(3) The normal-temperature and normal-pressure degradation condition of the invention is close to zero energy consumption, the equipment is simple, the regenerated fiber is not corroded, the fiber damage is small, the surface treatment is clean and complete, the required equipment cost is low, and the high-energy-consumption and high-added-value modified filler can be regenerated; meanwhile, the thermosetting resin grafted modified naphthalene high-performance water reducing agent is prepared, has a good slump retaining effect, meets the requirements of corresponding national standards, promotes energy conservation and emission reduction, is beneficial to realizing the carbon peak reaching and carbon neutralization targets, and converts thermosetting composite material wastes into resource materials.
Drawings
FIG. 1 is a process flow of preparing a high-performance naphthalene water reducer by using thermosetting resin composite waste according to the present invention;
FIG. 2 is a photograph showing a process of osmotically degrading a carbon fiber-reinforced epoxy resin composite material with concentrated sulfuric acid in example 1;
FIG. 3 is a photograph of a process of concentrated sulfuric acid infiltration degradation of a glass fiber reinforced epoxy resin composite in example 2.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
And degrading, sulfonating and grafting a naphthalene sulfonate formaldehyde polymer to the carbon fiber reinforced epoxy resin composite material to prepare the high-performance naphthalene water reducer.
Under the conditions of normal pressure and normal temperature, 132g of a carbon fiber strong epoxy resin composite matte pipe is subjected to impurity removal, washing and drying, then is immersed in a wide-mouth bottle filled with 30098wt.% of concentrated sulfuric acid, is taken out after being immersed for 10 hours, 60g of regenerated carbon fibers are obtained (the degradation and separation process is shown in figure 2), the regenerated carbon fibers are stored for later use, 360g of degraded resin waste liquid is obtained after the carbon fibers are filtered and separated, and the degraded resin waste liquid is used for preparing the high-performance naphthalene water reducer:
(1) Weighing 213g of industrial naphthalene, pouring the industrial naphthalene into a four-neck flask, heating the industrial naphthalene to be molten, heating the industrial naphthalene to 150 ℃ under stirring, dripping 275g of degraded resin waste liquid, controlling the temperature to be 160-165 ℃ until the dripping is finished, and carrying out heat preservation sulfonation reaction for 2 hours at 160-165 ℃. Measuring the sulfonation acidity at 32.5 percent to obtain a sulfonated material.
(2) Cooling the sulfonated material to 120 ℃, slowly dripping 53g of water, and carrying out thermal insulation hydrolysis reaction at 115-125 ℃ for 30min; measuring the acidity after hydrolysis to 19.6 percent to obtain a hydrolyzed material.
(3) When the temperature of the hydrolyzed material is reduced to 105 ℃ by cooling water, 150g of formaldehyde solution (the mass concentration of the formaldehyde solution is 30%) is dripped, the temperature is controlled to be 105-110 ℃, the temperature is kept at 105-110 ℃ for condensation reaction for 4h, and warm water accounting for about 300g is dripped slowly in each time to obtain the formaldehyde condensate.
(4) Cooling the formaldehyde condensate to 30-40 ℃ by using cooling water, slowly adding 380g of sodium hydroxide solution (the mass concentration is 32%), keeping the temperature not to exceed 60 ℃, detecting by using pH test paper, and obtaining the high-performance naphthalene water reducer of the sulfonated epoxy resin grafted naphthalene sulfonate formaldehyde polymer, wherein the neutralization end point pH = 9.
Example 2
Degrading and sulfonating the glass fiber reinforced epoxy resin composite material, and grafting a naphthalene sulfonate formaldehyde polymer to prepare the high-performance naphthalene water reducer.
Under the conditions of normal pressure and normal temperature, 3.1 kg of thermosetting epoxy resin glass reinforced plastic pipe is washed and dried and then is put into a 5L wide-mouth bottle with a corresponding size, 3.1 kg of 98wt.% concentrated sulfuric acid is added to immerse the glass reinforced plastic pipe, after the glass reinforced plastic pipe is soaked for 48 hours, 1.8 kg of glass fiber is filtered and taken out (the degradation and separation process is shown in figure 3), the glass fiber is collected and stored for standby, 4.3 kg of degradation resin waste liquid is obtained, and the degradation resin waste liquid is used for preparing the high-performance naphthalene water reducer:
(1) Weighing 213g of industrial naphthalene, pouring the industrial naphthalene into a four-neck flask, slowly heating the industrial naphthalene to be molten by using an electrothermal sleeve, heating the industrial naphthalene to 150 ℃ under stirring, slowly dripping 275g of degraded resin waste liquid, controlling the temperature to be 160-165 ℃ until the degradable resin waste liquid is completely dripped, and preserving the temperature at 160-165 ℃ for sulfonation reaction for 2 hours. Measuring the sulfonation acidity to be 32.0 percent to obtain a sulfonated material.
(2) Cooling the sulfonated material to 120 ℃, adding 53g of water by using a peristaltic pump, and carrying out heat preservation hydrolysis reaction for 30min at the temperature of 115-125 ℃; measuring the acidity after hydrolysis to be 30 percent to obtain hydrolyzed material.
(3) And (2) when the temperature of the hydrolyzed material is reduced to 105 ℃ by cooling water, slowly dripping 150g of formaldehyde solution (the mass concentration of the formaldehyde solution is 30%), controlling the temperature to be completely dripped at 105-110 ℃, carrying out heat preservation condensation reaction for 4 hours at 105-110 ℃, and dripping 304g of warm water in total in each time to obtain the formaldehyde condensate.
(4) Cooling the formaldehyde condensation material to 30-40 ℃ by using cooling water, slowly dropwise adding 376g of sodium hydroxide solution (the mass concentration is 32%), keeping the temperature not to exceed 60 ℃, detecting by using pH test paper, and obtaining the high-performance naphthalene water reducer of the sulfonated epoxy resin grafted naphthalene sulfonate formaldehyde polymer, wherein the neutralization end point pH = 9.
Example 3
And degrading, sulfonating and grafting a naphthalene sulfonate formaldehyde polymer to the glass fiber reinforced unsaturated polyester resin composite material to prepare the high-performance naphthalene water reducer.
Under the conditions of normal pressure and normal temperature, 2 kg of glass fiber reinforced unsaturated polyester resin composite material pipe is washed and dried, then is put into a 5L wide-mouth glass bottle with a corresponding size, 3 kg of 98wt.% concentrated sulfuric acid is added to immerse the glass pipe, and after the glass pipe is soaked for 28 hours under the condition of standing or stirring, 1.2 kg of glass fiber is filtered and taken out for storage and standby application, 3.7 kg of degraded resin waste liquid is obtained, and the degraded resin waste liquid is used for preparing a high-performance naphthalene water reducer:
(1) Weighing 213g of industrial naphthalene, pouring the industrial naphthalene into a four-neck flask, slowly heating the industrial naphthalene to be molten by using an electrothermal sleeve, heating the industrial naphthalene to 150 ℃ under stirring, slowly dripping 275g of degraded resin waste liquid, controlling the temperature to be 160-165 ℃ until the degradable resin waste liquid is completely dripped, and preserving the temperature at 160-165 ℃ for sulfonation reaction for 2 hours. Measuring the sulfonation acidity to be 31.8 percent to obtain a sulfonated material.
(2) Cooling the sulfonated material to 120 ℃, slowly dripping 53g of water, and carrying out thermal insulation hydrolysis reaction at 115-125 ℃ for 30min; and measuring the acidity after hydrolysis to be 29.5 percent to obtain the hydrolyzed material.
(3) And (2) when the hydrolyzed material is cooled to 105 ℃ by cooling water, slowly dropwise adding 150g of formaldehyde solution (the mass concentration of the formaldehyde solution is 30%), controlling the temperature to be completely dropped at 105-110 ℃, carrying out heat preservation condensation reaction for 4 hours at 105-110 ℃, and dropwise adding warm water accounting for 307g in total in the period to obtain the formaldehyde condensate.
(4) Cooling the formaldehyde condensation material to 30-40 ℃ by using cooling water, slowly dropwise adding 370g of sodium hydroxide solution (the mass concentration is 32%), keeping the temperature not to exceed 60 ℃, detecting by using pH test paper, and neutralizing the end point pH =9 to obtain the high-performance naphthalene water reducer of the sulfonated unsaturated polyester grafted naphthalene sulfonate formaldehyde polymer.
Example 4
And degrading, sulfonating and grafting a naphthalene sulfonate formaldehyde polymer to the glass fiber reinforced unsaturated polyester resin composite material to prepare the high-performance naphthalene water reducer.
Under the conditions of normal pressure and normal temperature, 2 kg of glass fiber reinforced unsaturated polyester resin composite material pipe is washed and dried, then is put into a 5L wide-mouth glass bottle with a corresponding size, 3 kg of 98wt.% concentrated sulfuric acid is added to immerse the glass pipe, and after the glass pipe is soaked for 28 hours under the condition of standing or stirring, 1.2 kg of glass fiber is filtered and taken out for storage and standby application, 3.7 kg of degraded resin waste liquid is obtained, and the degraded resin waste liquid is used for preparing a high-performance naphthalene water reducer:
(1) Weighing 23g of unsaturated polyester resin waste without filler and 190g of solid naphthalene, pouring the unsaturated polyester resin waste and the solid naphthalene into a four-neck flask, slowly heating the mixture to be molten by using an electrothermal sleeve, heating the mixture to 150 ℃ under stirring, slowly dripping 275g of degraded resin waste liquid, controlling the temperature to be 160-165 ℃ until the dripping is finished, and preserving the heat at 160-165 ℃ for sulfonation reaction for 2 hours. Measuring the sulfonation acidity to be 32.5 percent to obtain a sulfonated material.
(2) Cooling the sulfonated material to 120 ℃, adding 54g of water by using a peristaltic pump, and carrying out heat preservation hydrolysis reaction for 30min at the temperature of 115-125 ℃; measuring the acidity after hydrolysis to be 30 percent to obtain hydrolyzed material.
(3) And (2) when the hydrolyzed material is cooled to 105 ℃ by cooling water, slowly dripping 150g of formaldehyde solution (the mass concentration of the formaldehyde solution is 30%), controlling the temperature to be completely dripped at 105-110 ℃, carrying out heat preservation condensation reaction for 4 hours at 105-110 ℃, and dripping warm water accounting for 302g in total in each time to obtain the formaldehyde condensate.
(4) Cooling the formaldehyde condensate material to 30-40 ℃ by using cooling water, slowly adding 375g of sodium hydroxide solution (the mass concentration is 32%), keeping the temperature not to exceed 60 ℃, detecting by using pH test paper, and obtaining the high-performance naphthalene water reducer of the sulfonated unsaturated polyester grafted naphthalene sulfonate formaldehyde polymer, wherein the neutralization end point pH = 9.
Example 5
Degrading and sulfonating the glass fiber reinforced phenolic resin composite material, and grafting a naphthalene sulfonate formaldehyde polymer to prepare the high-performance naphthalene water reducer.
Under the conditions of normal pressure and normal temperature, 1 kg of glass fiber reinforced phenolic resin composite material plate is washed and dried and then is put into a 5L wide-mouth glass bottle with a corresponding size, 2 kg of 98wt.% concentrated sulfuric acid is added to immerse the glass plate, and after the glass plate is soaked for 28 hours under the condition of standing or stirring, 0.7 kg of glass fiber is filtered and taken out for storage and standby application, 2.2 kg of degraded resin waste liquid is obtained and is used for preparing a high-performance naphthalene water reducer:
(1) Weighing 213g of industrial naphthalene, pouring the industrial naphthalene into a four-neck flask, slowly heating the industrial naphthalene to be molten by using an electrothermal sleeve, heating the industrial naphthalene to 150 ℃ under stirring, slowly dropwise adding 275g of degraded resin waste liquid, controlling the temperature to be 160-165 ℃ until the addition is finished, and preserving the temperature at 160-165 ℃ for sulfonation reaction for 2 hours. Measuring the sulfonation acidity to be 31.8 percent to obtain a sulfonated material.
(2) Cooling the sulfonated material to 120 ℃, slowly dripping 60g of water, and carrying out heat preservation hydrolysis reaction for 30min at the temperature of 115-125 ℃; and measuring the acidity after hydrolysis to be 29.5 percent to obtain the hydrolyzed material.
(3) And (2) when the hydrolyzed material is cooled to 105 ℃ by cooling water, slowly dripping 150g of formaldehyde solution (the mass concentration of the formaldehyde solution is 30%), controlling the temperature to be completely dripped at 105-110 ℃, carrying out heat preservation condensation reaction for 4 hours at 105-110 ℃, and dripping warm water accounting for about 300g in total in each time to obtain the formaldehyde condensate.
(4) Cooling the formaldehyde condensation material to 30-40 ℃ by using cooling water, slowly dropwise adding 365g of sodium hydroxide solution (the mass concentration is 32%), keeping the temperature not to exceed 60 ℃, detecting by using pH test paper, and neutralizing the end point pH =9 to obtain the high-performance naphthalene water reducer of the sulfonated phenolic resin grafted naphthalene sulfonate formaldehyde polymer.
Comparative example 1
Preparing a naphthalene sulfonate formaldehyde polymer water reducing agent. The difference from example 1 is: the same procedure as in example 1 was repeated except that 98wt.% concentrated sulfuric acid was added in the sulfonation stage instead of the waste resin degradation solution.
(1) Weighing 213g of industrial naphthalene, pouring the industrial naphthalene into a four-neck flask, heating the industrial naphthalene to be molten, heating the industrial naphthalene to 150 ℃ under stirring, dripping 260g of concentrated sulfuric acid with the mass percent concentration of 98wt.%, controlling the temperature to be 160-165 ℃ and finishing dripping, and preserving the temperature and sulfonating the mixture for 2 hours at 160-165 ℃. Measuring the sulfonation acidity to be 33.0 percent to obtain a sulfonated material.
(2) Cooling the sulfonated material to 120 ℃, slowly dripping 60g of water, and carrying out thermal insulation hydrolysis reaction at 115-125 ℃ for 30min; and measuring the acidity after hydrolysis to be 29.8 percent to obtain a hydrolyzed material.
(3) And (2) when the hydrolyzed material is cooled to 105 ℃ by cooling water, slowly dripping 150g of formaldehyde solution (the mass concentration of the formaldehyde solution is 30%), controlling the temperature to be completely dripped at 105-110 ℃, preserving the temperature at 105-110 ℃ for condensation reaction for 4 hours, and dripping total about 300g of warm water in each time to obtain the condensed material.
(4) And (3) cooling the condensation material to 30-40 ℃ by using cooling water, slowly dropwise adding 380g of sodium hydroxide solution, keeping the temperature not to exceed 60 ℃, detecting by using pH test paper, and obtaining the naphthalenesulfonate formaldehyde polymer water reducer with the neutralization end point pH = 9.
In order to further prove that the performances of the naphthalene water reducing agent obtained by the invention are detected according to national standards GB8076-2008 'concrete admixture', GB/T50080-2016 'standard for testing the performance of common concrete mixture', GB/T50081-2019 'standard for testing the physical and mechanical properties of concrete', GB/T50082-2009 'test method for testing the long-term performance and durability of common concrete', and the detection results are shown in Table 1.
TABLE 1 data for the performance measurements of the water reducers in examples 1 to 5 and comparative example 1
As shown in table l, compared with the high-concentration naphthalene water reducer prepared by the prior art, the thermosetting resin modified naphthalene water reducer prepared by the invention has the following advantages: the invention uses the degraded resin waste liquid, reduces the cost of the naphthalene sulfonation reagent, simultaneously, the obtained thermosetting resin sulfonated graft modified naphthalene sulfonate formaldehyde polymer water reducing agent has higher water reducing rate, reduced bleeding rate and increased compressive strength, can synergize the product quality of the naphthalene water reducing agent, and the obtained product can meet the national standard requirements.
Claims (10)
1. A method for preparing a high-performance naphthalene water reducer by utilizing thermosetting resin composite material waste is characterized by comprising the following steps: performing sulfonation reaction on a degradable resin waste liquid obtained by degrading thermosetting resin composite material waste and naphthalene to obtain a sulfonated material; and (3) sequentially carrying out hydrolysis reaction, condensation reaction and neutralization reaction on the sulfonated material to obtain the high-performance naphthalene water reducer.
2. The method for preparing a high-performance naphthalene water reducer by using thermosetting resin composite waste according to claim 1, wherein the method comprises the following steps: the thermosetting resin composite material is epoxy resin, phenolic resin or unsaturated polyester resin and thermosetting resin or composite material thereof modified by the epoxy resin, the phenolic resin or the unsaturated polyester resin and containing ether bonds and ester groups in molecular chain forging.
3. The method for preparing the high-performance naphthalene water reducer by using the thermosetting resin composite waste material according to claim 1, comprising the following steps of:
(1) Immersing thermosetting resin composite material waste into concentrated sulfuric acid to obtain degraded resin waste liquid, and carrying out sulfonation reaction on the degraded resin waste liquid and naphthalene to obtain a sulfonated material;
(2) Adding water into the sulfonated material to perform hydrolysis reaction to obtain a hydrolyzed material;
(3) Adding a formaldehyde solution into the hydrolyzed material, and performing condensation reaction to obtain a formaldehyde condensate;
(4) And adding sodium hydroxide solution into the formaldehyde condensation material to perform neutralization reaction to obtain the high-performance naphthalene water reducer.
4. The method for preparing a high-performance naphthalene water reducer by using thermosetting resin composite waste according to claim 3, wherein the method comprises the following steps: the molar ratio of concentrated sulfuric acid, water, formaldehyde and sodium hydroxide in the naphthalene and degraded resin waste liquid is as follows: 1.0-1.5; the mass concentration of the formaldehyde solution is 30-37%; the mass concentration of the sodium hydroxide solution is 20-35%.
5. The method for preparing a high-performance naphthalene water reducer by using thermosetting resin composite waste according to claim 3, wherein the method comprises the following steps: the preparation of the resin degradation waste liquid in the step (1) is as follows: (1) collecting the thermosetting resin composite material waste, removing impurities, washing and drying; (2) then the thermosetting resin composite material waste is directly or after mechanical cutting or crushing, immersed into concentrated sulfuric acid and soaked until the filler and the matrix resin are completely degraded and separated; (3) and (3) carrying out filter pressing or centrifugal separation on the completely degraded thermosetting resin composite material mixture to obtain the modified filler and the degraded resin waste liquid.
6. The method for preparing a high-performance naphthalene water reducer by using the thermosetting resin composite waste material according to claim 5, wherein the method comprises the following steps: the mass ratio of the thermosetting resin composite material waste to concentrated sulfuric acid is 1.5-10, wherein the concentrated sulfuric acid is 80-100% sulfuric acid or fuming sulfuric acid in percentage by mass.
7. The method for preparing a high-performance naphthalene water reducer by using the thermosetting resin composite waste material according to claim 3, wherein the method comprises the following steps: in the step (1), after naphthalene is melted, heating to 120-150 ℃, dropwise adding the degraded resin waste liquid, and then carrying out sulfonation reaction at 160-175 ℃ for 2-10h, wherein the acidity of the feed liquid is controlled to be 28-35% at the end of the reaction, so as to obtain the sulfonated material.
8. The method for preparing a high-performance naphthalene water reducer by using thermosetting resin composite waste according to claim 3, wherein the method comprises the following steps: in the step (1), unsaturated polyester, phenolic resin or epoxy resin waste without filler is added in the sulfonation reaction process to participate in the sulfonation reaction together with naphthalene, wherein the addition amount of the unsaturated polyester, phenolic resin or epoxy resin waste without filler is 1-30% of the mass of the naphthalene.
9. The method for preparing a high-performance naphthalene water reducer by using thermosetting resin composite waste according to claim 3, wherein the method comprises the following steps: in the step (2), cooling the sulfonated material to 115-125 ℃, dripping water, and carrying out hydrolysis reaction for 0.5-3h at 100-130 ℃ to obtain a hydrolyzed material; in the step (3), adding a formaldehyde solution when the temperature of the hydrolyzed material is 90-105 ℃, controlling the adding temperature of the formaldehyde solution to be 105-120 ℃, then continuing to perform heat preservation condensation reaction for 3-5h at 100-115 ℃, and dropwise adding water with the mole number 6-12 times that of naphthalene to obtain a formaldehyde condensate.
10. The method for preparing a high-performance naphthalene water reducer by using thermosetting resin composite waste according to claim 3, wherein the method comprises the following steps: in the step (4), sodium hydroxide solution is added into the formaldehyde condensation material at 30-60 ℃ for neutralization reaction until the pH value of the material liquid is 6-9, and the high-performance naphthalene water reducer is obtained.
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