CN115838467B - A preparation method and product of a natural biomass chitin-modified single-component water-soluble polyurethane chemical grouting material - Google Patents
A preparation method and product of a natural biomass chitin-modified single-component water-soluble polyurethane chemical grouting material Download PDFInfo
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Abstract
The invention discloses a method for preparing a natural biomass chitin modified single-component water-soluble polyurethane chemical grouting material and a product thereof. The method uses the N-ether-based chitosan polyol oligomer to replace chemical polyether polyol, widens the application field of natural chitin high polymer materials, improves the use amount of biomass chitin, reduces the use cost of raw materials, improves the compatibility and uniformity of the modified single-component water-soluble polyurethane chemical grouting material, reduces the use of organic solvents, realizes the environmental protection in the production process of the chemical grouting material, and improves the long-term storage stability of the single-component water-soluble polyurethane chemical grouting material by using the stabilizer. The natural biomass chitin modified single-component water-soluble polyurethane chemical grouting material has better storage stability, larger water-in-package quantity, volume expansion rate, curing time, better elastomer compressive strength and other application performances.
Description
Technical Field
The invention relates to a preparation method of a natural biomass chitin modified single-component water-soluble polyurethane chemical grouting material and a product thereof, belonging to the field of biomass material recycling and repair material preparation.
Background
The concrete material has the characteristics of wide sources of raw materials, high strength, high toughness, easy compaction, difficult segregation, long-term maintenance of service performance in complex environments and the like, is the most common civil engineering material in the world, and is widely used in civil engineering construction of high-rise buildings, highways, high-speed railways, urban rail transit, dams, ports, bridges and the like. The concrete material is a non-homogeneous composite material composed of cement, mineral admixture, coarse and fine aggregate, additive and mixed water. The concrete can be damaged and destroyed by crack in the preparation and use processes, the reason and the formation mechanism of the formed crack are complex, and the concrete has the reasons of the materials, the influence of the construction process and the environmental factors. Related researches show that when the fresh concrete is hardened, cement slurry and coarse aggregate in the concrete material, The fine aggregate is deformed inconformity and can generate initial stress which is restrained mutually, fine cracks are generated between cement paste and aggregate bonding surfaces or between cement paste bodies, in the hardening process of the concrete, the concrete is dehydrated and dried, tensile stress is generated in the concrete, when the tensile stress exceeds the limit value of the tensile strength of the concrete, dry shrinkage cracks are generated in the concrete, the concrete also has the property of thermal expansion and cold shrinkage, the heat generated by hydration of the hardened cement of the concrete causes volume expansion in the concrete, the external concrete contracts along with temperature reduction, the expansion and the external contraction of the internal concrete are restrained mutually to generate tensile stress, when the tensile stress in the concrete exceeds the limit value of the tensile strength of the concrete, the concrete generates temperature cracks, the bridge deck of the cement concrete, In the use process of the pavement, the tensile strength and the bending strength of the concrete are reduced due to dynamic load, static load and uneven subsidence, cracks are easily formed in a tensile area of the concrete, water, oxygen, carbon dioxide, sulfate and chloride ion mediums in the external environment invade into a concrete structure in the service period, react with cement hydration products and reinforcing steel bars of the concrete to expand the concrete body, the generated expansion extrudes the concrete to generate tensile stress, and when the tensile stress exceeds the bearing capacity of the concrete, longitudinal cracks are generated on the surface of the concrete. the appearance of the civil engineering structure is affected by the generation of cracks, and small cracks can be accelerated to extend into penetrating cracks to reduce the overall rigidity and integrity of the structure, so that the bearing capacity of the structure is reduced. The crack can accelerate water seepage, corrosion and steel bar corrosion of engineering structures as a channel for harmful ion corrosion, and the durability and the service life of civil engineering structures are reduced. According to statistics, the proportion of cracks on the roofs and basements of the existing urban high-rise buildings in China is up to 95.33% and 57.51%, the mileage of cement concrete pavement in China is up to 6000 km in 2010, wherein 25-32% of cement concrete pavement needs to be maintained due to the occurrence of cracks, cracks are formed in more than 60 seats in a concrete dam with the length of more than 70 m and in a concrete lining tunnel with the length of 600km at different degrees, the newly built concrete bridge is cracked after 3-5 years of use, and the situation that the cracks which are formed after the new concrete bridge is not put into use are individually built and exceed the allowable crack width is brought with great challenges to the structural safety of civil engineering. Concrete cracking is the most interesting subject for those skilled in the art of civil engineering. In order to ensure the quality and normal use of the civil engineering structure, the concrete cracks must be properly repaired, and the cracks are isolated from the corrosive environment, which has important significance for improving the durability of the structural concrete.
The current repairing method of concrete cracks mainly comprises a surface repairing treatment method, a filling method, a structure reinforcing method, a self-repairing method, a chemical grouting method and the like. The chemical grouting method is to prepare organic and inorganic materials into true solution, and squeeze the grouting materials to the gaps of the concrete under the action of a chemical grouting pump, so that the grouting materials are diffused, gelled and solidified to increase the strength of the concrete structure, reduce the permeability of the concrete and prevent the concrete from deforming, thereby achieving the purpose of improving the integral service performance of the concrete structure. The chemical grouting method has the characteristics of good grouting property, effective filling of fine cracks and rapid solidification within a controllable time range, and the solidified body has the functions of seepage prevention and leakage stoppage and certain bearing capacity, and is the most common and main means for treating the cracks of the concrete structure. Common chemical grouting materials include water glass, epoxy resin, acrylamide, methyl methacrylate and polyurethane. The water glass slurry consists of water glass solution, salt and acid gelatinizer, and is filled into crack to form silicate gel to fill concrete hole and crack and to take the functions of solidification, seepage prevention and leakage blocking. The water glass chemical grouting material has the characteristics of rich sources and low price, but the water glass slurry takes calcium chloride as a gelling agent, the calcium chloride reacts rapidly when meeting water glass, the gel time is short, the slurry viscosity is larger, the diffusion distance in concrete is short, the gel durability of the water glass chemical slurry material is poor, and the defects limit the popularization and the application of the water glass chemical grouting material. the epoxy resin grouting material is formed by taking epoxy resin as a main agent, adding auxiliary agents such as an amine curing agent, a diluent, a toughening agent and the like, and crosslinking the linear epoxy resin and the curing agent to form a space network structure so as to play a role in consolidation reinforcement. The epoxy resin chemical grouting material has the characteristics of low cost, strong compressive and tensile strength of the consolidated body, good chemical stability and capability of resisting acid and alkali medium corrosion. However, the epoxy resin grouting material has high viscosity, and is difficult to fill in micro cracks, and the addition of the diluent can reduce the viscosity of the grouting material, but the addition of the diluent can reduce the curing effect of the product. The amine curing agent has high normal-temperature reactivity and lower low-temperature reactivity, the curing speed and the strength performance of the epoxy resin grouting material are reduced at low temperature, the amine curing agent also has certain toxicity, and the bonding property of the epoxy resin grouting material concretes with structural concrete in a humid environment is poor. These disadvantages limit the use of epoxy grouting materials in the repair of cracks in civil engineering structures. The acrylamide grouting material is formed by taking acrylamide slurry as a main agent, N, N-methylene bisacrylamide as a cross-linking agent, and adding an accelerator and an initiator. When the acrylamide grouting material slurry is poured into concrete cracks, the acrylamide molecules undergo free radical polymerization reaction under the action of an initiator, so that the aqueous gel which is insoluble in water, has a linear long-chain structure and has certain elasticity is obtained. The acrylamide slurry has the characteristics of low viscosity, good pourability and strong permeability, and is suitable for filling micro cracks of structural concrete. The gel time of the acrylamide slurry can be adjusted by changing the amount of the polymerization inhibitor so that the acrylamide slurry forms a gel in a few minutes to several hours. However, the acrylamide grouting material has low consolidation strength, and the polymerized monomer acrylamide has certain toxicity, such as improper slurry preparation or insufficient mixing in construction, can pollute the surrounding water environment, and is prohibited in many countries in the world. Methyl methacrylate methyl chemical grouting material is subjected to free radical polymerization reaction under the action of an initiator to form a concretion body to seal concrete cracks. The methyl methacrylate grouting material has the advantages of low viscosity, good fluidity, capability of filling microcracks, good physical property of consolidation, high cohesiveness with a concrete structure, capability of better recovering the integral service performance of cracked concrete, and the like. However, the consolidated body formed by the methyl methacrylate grouting material lacks elasticity, the volume shrinkage of the consolidated body can cause partial void between the consolidated body and the gap, the effect of repairing the gap is poor, and the use amount of the methyl methacrylate grouting material is limited. the polyurethane grouting material is a novel chemical grouting material which appears after water glass, epoxy resin, acrylamide and methyl methacrylate, and consists of isocyanate group end-capped prepolymer, catalyst, retarder, surfactant and plasticizer which are obtained by reacting polyisocyanate with polyether polyol. The polyurethane grouting material is pressed into the concrete cracks, the isocyanate group end-capped prepolymer and water in the cracks undergo chain extension and crosslinking reaction, and the polyurethane grouting material is expanded and solidified in the concrete cracks to form gel-like concretes with certain strength, and the polyurethane concretes have strong binding power with the concrete, so that the effects of repairing the cracks and improving the strength of the concrete are achieved. Compared with the traditional water glass, epoxy resin, acrylamide and methyl methacrylate chemical grouting materials, the polyurethane grouting material has the advantages of convenient storage, small slurry viscosity, strong fluidity, capability of controlling the gelation time according to the needs, compact structure of a concretion body, excellent mechanical property, good impermeability, simple construction process and the like. The polyurethane material is one of chemical grouting materials with the best use performance, the widest use range and wide application prospect at present.
Polyurethane chemical grouting materials can be classified into oil-soluble polyurethane grouting materials and water-soluble polyurethane grouting materials according to the hydrophilicity of raw materials. The oil-soluble polyurethane grouting material mainly comprises prepolymer obtained by reacting polyisocyanate with non-water-soluble polyether polyol, acetone, a plasticizer, a surfactant and a catalyst auxiliary agent. The oil-soluble polyurethane grouting material can effectively strengthen a concrete structure while plugging concrete cracks. The water-soluble polyurethane grouting material is mainly composed of a prepolymer generated by the reaction of toluene diisocyanate and hydrophilic polyether polyol, acetone and a plasticizer, and the water-soluble chemical grouting material is subjected to polymerization reaction after meeting water to generate CO 2 gas, and the generated pressure enables slurry to enter fine cracks and form a consolidated body with surrounding cement slurry and coarse and fine aggregates, so that the water-soluble polyurethane grouting material is suitable for grouting and plugging of concrete cracks with large plugging areas at low temperature and humidity. In addition, the polyurethane grouting materials can be classified into one-component polyurethane grouting materials and two-component polyurethane grouting materials according to the composition mode of polyurethane slurry. The single-component polyurethane grouting material is prepared by reacting a polyol compound with isocyanate to obtain a polyurethane prepolymer, adding a diluent, a catalyst, a retarder and a plasticizer into the polyurethane prepolymer, sealing and preserving the polyurethane prepolymer, and directly using the polyurethane prepolymer when grouting is needed. The bi-component polyurethane grouting material is prepared by reacting a polyol ether compound with an isocyanate compound to obtain a prepolymer (component A), wherein a diluent, a catalyst, a retarder and a plasticizer mixture are used as component B, and the component A and the component B are mixed in proportion for chemical grouting when in use. Compared with the two-component polyurethane chemical grouting material, the single-component water-soluble polyurethane chemical grouting material has the advantages of small viscosity, strong permeability, no use of solvent, long storage time, simple preparation, convenient use and the like, and becomes the chemical grouting material with the largest use amount in the field of crack repair.
At present, polyether polyol used for preparing single-component water-soluble polyurethane chemical grouting materials is mostly petroleum chemicals. Along with the aggravation of global energy crisis and petroleum resource consumption, the yield of the artificial chemical polyether polyol is reduced, the material price is rapidly increased, the release amount of the toxic solvent in the polyether polyol preparation process is large, serious injury and pollution are caused to the body of production workers and the surrounding environment, the traditional single-component water-soluble polyurethane chemical grouting material is a non-degradable high polymer material, the mass use of the traditional single-component water-soluble polyurethane chemical grouting material can negatively affect soil and underground water, and the triethylamine catalyst can reduce the mechanical strength of the water-soluble polyurethane elastomer and the long-term storability of the slurry material is poor in the traditional single-component water-soluble polyurethane chemical grouting material preparation process. The natural biomass material is modified to replace polyether polyol chemicals, and a single-component water-soluble polyurethane chemical grouting material which has the advantages of wide raw material sources, low cost, good storage stability, good consolidation body elasticity, high elastomer compressive strength, easiness in biodegradation and environmental friendliness is researched and developed, so that the single-component water-soluble polyurethane chemical grouting material is an important way for realizing sustainable development of polyurethane industry.
Chitin is a natural biomass polymer compound widely existing in cell walls of fungi, mushroom fungus and algae, arthropod bones, snails, hornshells and cuttlefish mollusks, amoeba and paramotors, tubularia, jellyfish and nepheline coelenterates, and earthworm and hornworm annelid animals. Chitin high polymer is a natural biomass material with the most abundant reserve on the earth after cellulose, and the synthesis amount of chitin in the natural world is up to trillion tons each year. The chitin molecule is composed of C, H, O, N elements, the chemical formula is (C 8H13NO5)n, the chitin molecule is connected by N-acetyl-2-amino-2-deoxy-D-glucose through beta- (l, 4) glycosidic bond to form a linear natural high molecular aminopolysaccharide structure, acetyl is arranged on carbon at 2 position, hydroxyl is arranged on carbon at 3 position, hydroxymethyl is arranged on carbon at 5 position, a large number of hydroxyl groups exist to cause strong polar hydrogen bonds among chitin molecules to form an ordered and highly crystallized molecular structure, the chitin is insoluble in water and insoluble in dilute acid, concentrated alkali and organic solvent, but the linear chitin polymer is subjected to fracture degradation of a molecular main chain under the action of strong acid such as hydrochloric acid, phosphoric acid and formic acid, the molecular weight is reduced, and the water solubility is improved.
At present, a report of using natural chitin to modify aqueous polyurethane materials is that Zeng Ming (chitin derivative/polyurethane composite structure and performance, doctor's academic paper, wuhan university: wuhan, 2004) and Li Aiping (chitin whisker/aqueous polyurethane composite structure and performance research, the doctor's academic paper, china geological university: wuhan, 2007) blend carboxymethyl chitin and aqueous polyurethane to modify aqueous polyurethane, and the carboxymethyl chitin and aqueous polyurethane are not completely compatible, but compared with pure aqueous polyurethane, the addition of carboxymethyl chitin can obviously improve the mechanical property, the mechanical property and the property of the aqueous polyurethane blend, Thermal stability and organic solvent resistance. The addition of the triethylamine catalyst can improve the compatibility of the carboxymethyl chitin and the aqueous polyurethane blend, but reduces the mechanical strength of the blend. The preparation method of chitin whisker modified waterborne polyurethane is disclosed in the rest of the society et al (Chinese patent invention, CN 201110005529.9), wherein the preparation method of chitin whisker emulsified modified waterborne polyurethane resin is disclosed, polyisocyanate and polyester polyol/polyether polyol are used as raw materials to prepare polyurethane prepolymer, a small molecular chain extender is added for viscosity reduction, and then acid hydrolysis is carried out to obtain chitin whisker, and then the chitin whisker is added into waterborne polyurethane emulsion to prepare the chitin whisker modified waterborne polyurethane material. The chitin modified waterborne polyurethane prepared by the method not only ensures that the product has higher elongation at break, but also improves the tensile strength and Young modulus of the elastomer. Gu Xudong et al (preparation method of chitosan-polyurethane ionic compound elastomer material, chinese patent invention, CN 20091002835) propose that after deacylation of natural chitin, dilute acid is used for dissolving to obtain cationic chitosan aqueous solution, anionic polyurethane emulsion and cationic chitosan aqueous solution are reacted to form chitosan-polyurethane ionic compound emulsion, and the chitosan-polyurethane ionic compound elastomer material is obtained by drying and solidifying. gu Xudong et al (Novel blood compatible water borne polyurethane using chitosan as an extender.Journal of Applied Polymer Science,2008,109(1),240-246) also prepared an-NCO-terminated prepolymer from polytetramethylene adipamide diol oxide, isophorone diisocyanate (IPDI), and dimethylolpropionic acid as reaction monomers, and prepared an aqueous polyurethane/chitosan block copolymer from a self-emulsifying process using triethylamine-neutralized low molecular weight water-soluble chitosan as a chain extender, which showed that the aqueous polyurethane/chitosan block copolymer contained hydrophilic groups, but the cross-linking effect reduced the solubility of the block copolymer. At present, researches on the use of natural chitin modified waterborne polyurethane materials exist, but the related technology is mainly focused on the aspects of physical blending and emulsification modification of the natural chitin and the waterborne polyurethane, the proportion of the natural chitin is smaller when the natural chitin and the waterborne polyurethane are blended and modified, the blend is incompletely compatible and has poor uniformity, and an ultrasonic treatment method is needed to improve the compatibility of the natural chitin and the waterborne polyurethane, so that the production steps and time of the natural chitin modified waterborne polyurethane are increased. The modified aqueous polyurethane is prepared by adopting a natural chitin emulsion copolymerization method, and the addition of the emulsion aggravates the reaction difficulty and controllability in the polymerization reaction process and increases the production cost. Meanwhile, the prior art of natural chitin modified waterborne polyurethane can not effectively reduce the usage amount of polyether polyol serving as an artificial chemical, which leads to the high use cost and poor market acceptance of the natural chitin modified waterborne polyurethane material, and is difficult to popularize and apply in engineering on a large scale. Therefore, other preparation methods of the natural chitin modified single-component water-soluble polyurethane chemical grouting material have the advantages of low cost, simple process, good product compatibility, high substitution ratio of polyether polyol chemicals, high hydroxyl reaction activity, good mechanical property and environmental friendliness.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a single-component water-soluble polyurethane chemical grouting material modified by natural biomass chitin.
The invention also solves the technical problem of providing the natural biomass chitin modified single-component water-soluble polyurethane chemical grouting material prepared by the method.
The invention provides a method for preparing a natural biomass chitin modified single-component water-soluble polyurethane chemical grouting material, which aims to solve the technical problems and comprises the following steps:
(1) Placing chitin high polymer and water into a reaction vessel provided with a stirrer, a thermometer, a dropping funnel and a reflux condenser, heating to 85-90 ℃, rapidly stirring, and dispersing the chitin high polymer into the water to obtain chitin high polymer suspension solution;
(2) Heating the chitin high polymer suspension solution to 85-90 ℃, adding sodium hydroxide solution, and stirring for 16-24 hours to obtain an amino-containing chitosan high polymer suspension solution;
(3) Adding ferrous sulfate as catalyst into the amino-containing chitosan polymer suspension, placing into a polytetrafluoroethylene tank, placing into a stainless steel high-pressure reaction vessel, sealing and reacting at 155-160 ℃ for 18-20 hours, taking out the degraded amino-containing chitosan polymer solution after the reaction is finished, keeping the temperature of the degraded amino-containing chitosan polymer solution at 80-85 ℃, slowly dropwise adding hydrogen peroxide and ammonium persulfate composite oxidant in 25-30 minutes, heating to 90-95 ℃, and reacting at the temperature for 6-8 hours to obtain amino-containing chitosan oligomer solution;
(4) Regulating the pH value of a mixed solution of polyethylene glycol and epichlorohydrin, keeping the temperature at 45-50 ℃, dropwise adding catalyst tetra-n-butyl ammonium bromide within 20-40 minutes, heating to 50-60 ℃, and continuously stirring and reacting for 2-3 hours at the temperature to obtain epoxy group-capped polyethylene glycol glycidyl ether liquid, regulating the pH value of a system to 1-2 by using dilute sulfuric acid, and hydrolyzing for 2-3 hours at room temperature to obtain epoxy group-capped polyethylene glycol glycidyl ether hydrolysis solution;
(5) Adding the chitosan oligomer solution containing amino groups, which is prepared in the step (3), into the epoxy group-terminated polyethylene glycol glycidyl ether hydrolysis solution, slowly dropwise adding a catalyst tetrafluoroboric acid within 20-30 minutes at the temperature of 45-50 ℃, and heating to 80-85 ℃ for reacting for 4-5 hours at the temperature to obtain an N-ether-based chitosan polyol oligomer solution;
(6) Placing polytetrahydrofuran ether glycol and N-ether chitosan polyol oligomer into a reaction container provided with a stirrer, a thermometer, a dropping funnel and a reflux condenser, heating to 95-100 ℃, dehydrating for 8-10 hours under the vacuum degree of 0.01-0.02MPa, stopping vacuumizing when the water content of the mixed polyether polyol is less than 0.03%, cooling to 50-55 ℃, performing nitrogen protection, slowly dropwise adding toluene diisocyanate solution, heating to 75-85 ℃, reacting for 2-3 hours, and adding benzoyl chloride serving as a stabilizer to obtain a prepolymer capped by an-NCO group;
(7) Mixing the prepolymer capped by the-NCO group, stannous oleate and dioctyl sebacate, vacuum dehydrating for 2-3 hours at the temperature of 95-100 ℃ and the vacuum degree of 0.01-0.02MPa, and cooling to 20-30 ℃ after releasing the vacuum to obtain the single-component water-soluble polyurethane chemical grouting material.
Wherein the mass ratio of the chitin polymer to the water in the step (1) is 1:2-2.1.
Wherein the mass ratio of the chitin high polymer suspension solution to the sodium hydroxide solution in the step (2) is 1.875-2:1.
Wherein the dosage of the catalyst ferrous sulfate in the step (3) is 0.10-0.15% of the weight of the chitosan polymer suspension solution containing amino.
Wherein the dosage of the mixed solution of the hydrogen peroxide and the ammonium persulfate composite oxidant in the step (3) is 1.0-1.5 percent of the weight of the chitosan high polymer suspension solution containing amino.
Wherein the mass ratio of polyethylene glycol to epichlorohydrin in the step (4) is 3-3.4:1, the pH value of the mixed solution of polyethylene glycol and epichlorohydrin is 12-13, and the mass ratio of the mixed solution of polyethylene glycol and epichlorohydrin to tetra-n-butyl ammonium bromide catalyst is 106-115:1.
Wherein the mass ratio of the epoxy group end capped polyethylene glycol glycidyl ether liquid to the chitosan oligomer solution containing amino groups in the step (5) is 1:25.7-27.5, and the mass ratio of the epoxy group end capped polyethylene glycol glycidyl ether liquid to the tetrafluoroboric acid catalyst is 24-26:1.
Wherein the mass ratio of the polytetrahydrofuran ether glycol to the N-ether-based chitosan polyol oligomer solution in the step (6) is 1:6.0-6.4, the mass ratio of the polytetrahydrofuran ether glycol to the N-ether-based chitosan polyol oligomer to the toluene diisocyanate solution is 9.5-10.0:1, and the dosage of the benzoyl chloride stabilizer is 0.045-0.05% of the total weight of the polytetrahydrofuran ether glycol and the N-ether-based chitosan polyol oligomer.
Wherein the mass ratio of the prepolymer blocked by the-NCO group to the dioctyl sebacate in the step (7) is 4.0-4.2:1, and the stannous oleate accounts for 0.25-0.30% of the total weight of the prepolymer blocked by the-NCO group and the dioctyl sebacate.
The invention also provides the single-component water-soluble polyurethane chemical grouting material prepared by the method.
The reaction mechanism is based on the characteristics that the natural chitin has a plurality of hydroxyl groups, the molecular structure of the natural chitin is similar to that of organic synthetic chemical polyalcohol, the molecular structure of the chitin is more regular, and the hydroxyl reaction activity can be improved through high-temperature oxidative degradation. Firstly, deacylation treatment is carried out on the chitin high polymer under the conditions of high temperature and strong alkali, and the chitin high polymer is degraded into chitosan oligomer with-CH 2OH、-OH、-NH2 groups by high temperature catalysis and strong oxidation. Then, the polyethylene glycol and epichlorohydrin are polymerized into an epoxy-terminated polyethylene glycol glycidyl ether hydrolysis solution. And then, carrying out ring-opening etherification reaction on the chitosan oligomer containing amino and epoxy group end-capped polyethylene glycol glycidyl ether to obtain the N-ether-based chitosan polyol oligomer. Finally, the N-ether chitosan polyol oligomer is used for partially replacing the polyether polyol of the synthetic chemical, the mixed ether alcohol is dehydrated in vacuum at high temperature, and under the condition of excessive isocyanate, the mixed ether alcohol and the polyisocyanate are subjected to polymerization reaction to obtain the-NCO group end-capped prepolymer. The prepolymer, the curing agent and the plasticizer are mixed and dehydrated in vacuum to prepare the natural biomass chitin modified single-component water-soluble polyurethane chemical grouting material.
Compared with the prior art, the invention has the following remarkable advantages:
1. In the preparation process of the water-soluble polyurethane chemical grouting material, the N-ether-based chitosan polyol oligomer replaces chemical polyether polyol to prepare a single-component water-soluble polyurethane chemical grouting material, so that the application field of a natural chitin polymer material is widened, the use amount of biomass chitin is increased, a large amount of natural chitin material is consumed, the material use cost in the preparation process of the single-component water-soluble polyurethane chemical grouting material is reduced, and the cost of the synthetic chemical polyether polyol material can be saved by 7.58 yuan per ton of the single-component water-soluble polyurethane chemical grouting material modified by the natural biomass chitin;
2. compared with the preparation method of the biomass chitin physical blending modified aqueous polyurethane material, the natural biomass chitin etherified modified single-component water-soluble polyurethane chemical grouting material improves the compatibility and uniformity of the modified single-component water-soluble polyurethane chemical grouting material;
3. The single-component water-soluble polyurethane chemical grouting material prepared by the method reduces the use of organic solvents, avoids the negative influence of the organic solvents on the environment and the health of operators, realizes the green and environment-friendly production process of the chemical grouting material, and can generate economic benefits of 3.43 yuan per ton of products;
4. The use of the stabilizer improves the long-term storage stability of the single-component water-soluble polyurethane chemical grouting material, and each ton of the single-component water-soluble polyurethane chemical grouting material can generate economic benefit of 2.13 yuan;
5. The natural biomass chitin modified single-component water-soluble polyurethane chemical grouting material has better storage stability than the traditional single-component water-soluble polyurethane chemical grouting material. Under the condition of foaming with the same water consumption, the natural biomass chitin modified single-component water-soluble polyurethane chemical grouting material has larger water-packing quantity, volume expansion rate, curing time and better elastomer compressive strength;
6. The natural biomass chitin modified single-component water-soluble polyurethane can be biodegraded, so that the problem of environmental pollution caused by the undegradability of the traditional polyurethane material is avoided;
7. The preparation of the single-component water-soluble polyurethane chemical grouting material by modifying the natural biomass chitin can produce good technical, economic, social and environmental benefits;
In summary, according to the embodiment 1 of the present invention, the cost of raw materials of chemical polyether polyol and organic solvent can be saved by 4.40 ten thousand yuan per 4000 tons of the biomass chitin modified single-component water-soluble polyurethane chemical grouting material produced each year. The economic benefit of 2.43 ten thousand yuan can be brought by reducing the investment of production equipment, simplifying the process and the production time and improving the storage time. Compared with the traditional single-component water-soluble polyurethane chemical grouting material, the 4000 tons of single-component biomass chitin modified water-soluble polyurethane chemical grouting material can treat 5.56 multiplied by 10 6 square concrete cracks each year, and the cost of the chemical grouting material can be saved by 6.89 ten thousand under the same crack repairing effect. The production of 4000 tons of biomass chitin modified single-component water-soluble polyurethane chemical grouting material can produce 13.72 ten thousand yuan economic benefit.
Drawings
FIG. 1 is a flow chart of the preparation of a biomass chitin modified single-component water-soluble polyurethane chemical grouting material;
FIG. 2 is a graph showing the change of-NCO content in two single-component water-soluble polyurethane chemical grouting materials with respect to storage time;
FIG. 3 shows the water-coated amounts of two single-component water-soluble polyurethane chemical grouting materials under different water amounts;
FIG. 4 shows the volume expansion rate of two single-component water-soluble polyurethane chemical grouting materials under different water amounts;
FIG. 5 shows the curing times of two single-component water-soluble polyurethane chemical grouting materials under different water amounts;
FIG. 6 is a graph showing the compressive strength of two single component water soluble polyurethane elastomers at different water levels;
FIG. 7A shows the tensile strength of two single-component water-soluble polyurethane elastomers with different amounts of water, and FIG. 7B shows the tensile elongation of two single-component water-soluble polyurethane elastomers with different amounts of water.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
Raw materials are chitin high polymer (weight average molecular weight 33.54 ten thousand) produced by Nantong Langshan Xingzhi biochemical product factory; sodium hydroxide (97% purity) is produced by Hebei Xincheng chemical products limited, ferrous sulfate (90.0% purity or more) is produced by Karl chemical products limited of Kanji, hydrogen peroxide (30% concentration) is produced by Hangzhou Jingxin chemical limited, ammonium persulfate (90.0% purity or more) is produced by Fujian developing chemical limited, polyethylene glycol (PEG-600, weight average molecular weight 600, analytical purity 99%) is produced by Tian Lian Chemical chemical reagent factory in Tianjin, epichlorohydrin (93% purity) is produced by Jiangsu-in chemical limited, tetra-n-butyl ammonium bromide (99% purity or more) is produced by Shandon Bao-name poly chemical limited, dilute sulfuric acid (30-32% concentration) is produced by Suzhou coursedge chemical limited, tetrafluoroboric acid (92% purity) is produced by Jinan Feng chemical limited, polytetrahydrofuran ether glycol (G3000, weight average molecular weight 3000, PTG) is produced by Korea, and toluene dion-95% is produced by Jiangsu-chemical limited, and has a chemical grade of Jiangsu-type chemical industry grade, as well as toluene (99% of Jiangsu-type chemical industry grade, 99%) is produced by Jiangsu-Naku chemical limited, purity 99%) is produced by Shandong Weifang Hansheng chemical Co., ltd.
Example 1 preparation of Natural Biomass chitin modified one-component Water-soluble polyurethane chemical grouting Material
FIG. 1 is a step of preparing a natural biomass chitin modified single-component water-soluble polyurethane chemical grouting material.
1. Preparation of amino group-containing Chitosan oligomers
Firstly, preparing a chitin high polymer suspension solution, namely placing 500kg of natural chitin high polymer and 1000kg of water into a reaction kettle provided with a stirrer, a thermometer, a dropping funnel and a reflux condenser, raising the temperature to 85 ℃ and rapidly stirring the mixture to fully and uniformly mix the chitin high polymer and the water to obtain the chitin high polymer suspension solution.
Secondly, preparing the chitosan polymer containing amino groups, namely adding 750kg of sodium hydroxide solution (the concentration is 40%) into 1500kg of chitosan polymer suspension solution, stirring for 24 hours at the temperature of 85 ℃, and removing acetyl groups on molecules of the chitosan polymer to obtain the chitosan polymer containing amino groups. The degree of deacylation of the chitosan polymer was 92.58%.
Finally, preparing the amino-containing chitosan oligomer, namely adding 2.5kg of catalyst ferrous sulfate into 2250kg of amino-containing chitosan polymer suspension solution, placing the mixture into a polytetrafluoroethylene tank, and placing the polytetrafluoroethylene tank into a stainless steel high-pressure reaction kettle for hydrothermal reaction for 20 hours under high-temperature sealing at 155 ℃. After the reaction, taking out the degraded chitosan polymer solution containing amino groups, keeping the temperature of the degraded chitosan polymer solution containing amino groups at 85 ℃, slowly dropwise adding 24.0kg of a mixed solution of hydrogen peroxide and ammonium persulfate composite oxidant (hydrogen peroxide: ammonium persulfate=1:1) in 25 minutes, raising the temperature to 95 ℃, and reacting at the temperature for 7 hours to obtain 2249.9kg of chitosan oligomer solution containing amino groups. The weight average molecular weight of the chitosan oligomer containing amino groups is 4878 as determined by gel permeation chromatography.
2. Preparation of epoxy-terminated polyethylene glycol glycidyl ether
61.0Kg of polyethylene glycol and 18.7kg of epichlorohydrin are put into a reaction kettle provided with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 14.8kg of sodium hydroxide solution (the concentration is 40%) is added to adjust the pH value of the system to 12.17, the solution temperature is kept at 50 ℃, 0.72kg of tetra-n-butyl ammonium bromide serving as a catalyst is slowly added dropwise within 25 minutes, the temperature is raised to 55 ℃, the reaction is continued for 3 hours at the temperature, 91.59kg of light yellow epoxy-terminated polyethylene glycol glycidyl ether liquid is obtained, the pH value of the system is adjusted to 1.59 by using dilute sulfuric acid, and the hydrolysis solution of epoxy-terminated polyethylene glycol glycidyl ether is obtained after 3 hours of hydrolysis at room temperature.
3. Preparation of N-ether chitosan polyalcohol oligomer
73.48Kg of epoxy-terminated polyethylene glycol glycidyl ether hydrolysis solution was added with 1938kg of amino-containing chitosan oligomer solution, the temperature of the mixed solution was maintained at 50 ℃, 2.89kg of tetrafluoroboric acid catalyst was slowly added dropwise over 25 minutes, the temperature was raised to 85 ℃, and the reaction was carried out at this temperature for 5 hours. The amino group on the chitosan oligomer and the polyethylene glycol glycidyl ether end-capped epoxy group are subjected to ring opening etherification reaction, so that 2006.14kg of N-ether-based chitosan polyol oligomer solution is obtained.
4. Preparation of the prepolymer
300Kg of polytetrahydrofuran ether glycol and 1850kg of N-ether-based chitosan polyol oligomer solution are placed into a reaction kettle provided with a stirrer, a thermometer, a dropping funnel and a reflux condenser, the temperature is raised to 95 ℃, dehydration is carried out for 10 hours under the vacuum degree of 0.015MPa, and vacuumizing is stopped when the water content of the mixed polyether polyol is less than 0.03%. The temperature is reduced to 55 ℃, nitrogen protection is carried out, and 220kg of toluene diisocyanate solution is slowly added dropwise. After the toluene diisocyanate solution is added, the temperature is raised to 80 ℃, the mixed polyether polyol and the toluene diisocyanate are polymerized for 3 hours under the condition of excessive isocyanate, 1.03kg of stabilizer benzoyl chloride is added to obtain 928.23kg of prepolymer with-NCO groups blocked, and the-NCO value of the prepolymer is 7.03%.
5. Preparation of natural biomass chitin modified single-component water-soluble polyurethane chemical grouting material
805Kg of the-NCO-terminated prepolymer, 2.62kg of stannous oleate and 195kg of dioctyl sebacate were placed in a reaction kettle with a stirrer, a thermometer, a dropping funnel and a reflux condenser, and vacuum dehydrated for 3 hours at a temperature of 95℃and a vacuum of 0.017 MPa. Cooling to 30 ℃ after releasing vacuum to obtain 997.19kg of light yellow and viscous single-component water-soluble polyurethane chemical grouting material. Placing into a sealed container, and standing at 23deg.C for use.
Example 2
1. Preparation of amino group-containing Chitosan oligomers
Firstly, preparing a chitin high polymer suspension solution, namely placing 510kg of natural chitin high polymer and 1025kg of water into a reaction kettle provided with a stirrer, a thermometer, a dropping funnel and a reflux condenser, raising the temperature to 90 ℃ and rapidly stirring the mixture to fully and uniformly mix the chitin high polymer and the water to obtain the chitin high polymer suspension solution.
Then, 1525kg of chitin high polymer suspension solution is added with 770kg of sodium hydroxide solution (the concentration is 40%), the temperature of the chitin high polymer suspension solution is 90 ℃, and the mixture is stirred for 20 hours, acetyl on the chitin high polymer molecules is removed, and the amino-containing chitosan high polymer suspension solution is obtained. The degree of deacylation of the chitosan polymer was 92.09%.
Finally, preparing the amino-containing chitosan oligomer, namely adding 2.7kg of ferrous sulfate serving as a catalyst into 2295kg of the amino-containing chitosan polymer suspension, putting the mixture into a polytetrafluoroethylene tank, and placing the polytetrafluoroethylene tank into a stainless steel high-pressure reaction kettle for hydrothermal reaction for 20 hours under the condition of high-temperature sealing at 160 ℃. After the reaction, taking out the degraded chitosan polymer solution containing amino groups, keeping the temperature of the degraded chitosan polymer solution containing amino groups at 85 ℃, slowly dropwise adding 25.5kg of a mixed solution of hydrogen peroxide and ammonium persulfate composite oxidant (hydrogen peroxide: ammonium persulfate=1:1) in 25 minutes, raising the temperature to 95 ℃, and reacting at the temperature for 8 hours to obtain 2297.35kg of chitosan oligomer solution containing amino groups. The weight average molecular weight of the chitosan oligomer containing amino groups is 4855 measured by gel permeation chromatography.
2. Preparation of epoxy-terminated polyethylene glycol glycidyl ether
61.25Kg of polyethylene glycol and 18.75kg of epichlorohydrin are put into a reaction kettle provided with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 14.92kg of sodium hydroxide solution (with the concentration of 40%) is added to adjust the pH value of the system to 12.89, the temperature of the solution is kept at 50 ℃, 0.735kg of tetra-n-butyl ammonium bromide serving as a catalyst is slowly added dropwise within the period of 40 minutes, the temperature is raised to 60 ℃, the reaction is continued for 3 hours at the temperature, 94.22kg of light yellow epoxy-terminated polyethylene glycol glycidyl ether liquid is obtained, the pH value of the system is adjusted to 1.76 by using dilute sulfuric acid, and the hydrolysis solution of epoxy-terminated polyethylene glycol glycidyl ether is obtained after 3 hours at room temperature.
3. Preparation of N-ether chitosan polyalcohol oligomer
To 73.5kg of epoxy-terminated polyethylene glycol glycidyl ether hydrolysis solution was added 1938.5kg of an amino group-containing chitosan oligomer solution, and 2.90kg of catalyst tetrafluoroboric acid was slowly added dropwise over a period of 30 minutes while maintaining the temperature of the mixed solution at 50℃and the temperature was raised to 85℃and reacted at this temperature for 5 hours. The amino group on the chitosan oligomer and the polyethylene glycol glycidyl ether end-capped epoxy group are subjected to ring opening etherification reaction, so that 2007.22kg of N-ether-based chitosan polyol oligomer solution is obtained.
4. Preparation of the prepolymer
302.5Kg of polytetrahydrofuran ether glycol and 1875.5kg of N-ether chitosan polyol oligomer solution are placed into a reaction kettle provided with a stirrer, a thermometer, a dropping funnel and a reflux condenser, the temperature is raised to 95 ℃, dehydration is carried out for 9 hours under the vacuum degree of 0.019MPa, and vacuumizing is stopped when the water content of the mixed polyether polyol is less than 0.03%. The temperature was lowered to 50℃and nitrogen protection was carried out, and 222.5kg of toluene diisocyanate solution was slowly added dropwise. After the toluene diisocyanate solution is added, the temperature is raised to 80 ℃, the mixed polyether polyol and the toluene diisocyanate react for 3 hours under the condition of excessive isocyanate, 1.07kg of stabilizer benzoyl chloride is added to obtain 927.4kg of-NCO group blocked prepolymer, and the-NCO value of the prepolymer is 6.89%.
5. Preparation of natural biomass chitin modified single-component water-soluble polyurethane chemical grouting material
805Kg of the-NCO-terminated prepolymer, 2.78kg of stannous oleate and 195.5kg of dioctyl sebacate were placed in a reaction kettle with a stirrer, a thermometer, a dropping funnel and a reflux condenser, and dehydrated in vacuo at 95℃and a vacuum of 0.015MPa for 3 hours. Cooling to 30 ℃ after releasing vacuum to obtain 995.09kg of light yellow and viscous single-component water-soluble polyurethane chemical grouting material. Filled into a sealed container and placed at 22 ℃ for standby.
Example 3
1. Preparation of amino group-containing Chitosan oligomers
Firstly, preparing a chitin high polymer suspension solution, namely placing 520kg of natural chitin high polymer and 1050kg of water into a reaction kettle provided with a stirrer, a thermometer, a dropping funnel and a reflux condenser, raising the temperature to 90 ℃ and rapidly stirring the mixture to fully and uniformly mix the chitin high polymer and the water to obtain the chitin high polymer suspension solution.
Then, 1550kg sodium hydroxide solution (the concentration is 40%) is added into 1550kg chitin polymer suspension, the temperature of the suspension is 90 ℃, and the mixture is stirred for 22 hours, acetyl on the chitin polymer molecules is removed, and the chitosan polymer suspension containing amino groups is obtained. The degree of deacylation of the chitosan polymer was 93.54%.
Finally, preparing the amino-containing chitosan oligomer, namely adding 2.83kg of ferrous sulfate serving as a catalyst into 2330kg of the amino-containing chitosan polymer suspension, putting the mixture into a polytetrafluoroethylene tank, and performing hydrothermal reaction for 20 hours under the condition of high-temperature sealing at 155-160 ℃. After the reaction, the degraded amino group-containing chitosan polymer solution was taken out, the temperature of the degraded amino group-containing chitosan polymer solution was kept at 85 ℃, 26.8kg of a mixed solution of hydrogen peroxide and ammonium persulfate composite oxidant (hydrogen peroxide: ammonium persulfate=1:1) was slowly added dropwise over 30 minutes, the temperature was raised to 95 ℃, and the reaction was carried out at this temperature for 7 hours to obtain 2322.5kg of an amino group-containing chitosan oligomer solution. The weight average molecular weight of the chitosan oligomer containing amino groups was determined to be 4679 by gel permeation chromatography.
2. Preparation of epoxy-terminated polyethylene glycol glycidyl ether
61.3Kg of polyethylene glycol and 18.92kg of epichlorohydrin are put into a reaction kettle provided with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 14.78kg of sodium hydroxide solution (the concentration is 40%) is added to adjust the pH value of the system to 12.47, the temperature of the solution is kept at 50 ℃, 0.729kg of tetra-n-butyl ammonium bromide serving as a catalyst is slowly added dropwise within 40 minutes, the temperature is raised to 60 ℃, the reaction is continued for 2-3 hours at the temperature, 93.16kg of light yellow epoxy-terminated polyethylene glycol glycidyl ether liquid is obtained, the pH value of the system is adjusted to 1.33 by using dilute sulfuric acid, and the hydrolysis solution of epoxy-terminated polyethylene glycol glycidyl ether is obtained after 3 hours at room temperature.
3. Preparation of N-ether chitosan polyalcohol oligomer
To 73.2kg of epoxy-terminated polyethylene glycol glycidyl ether hydrolysis solution was added 1939.5kg of an amino group-containing chitosan oligomer solution, and 2.90kg of a catalyst tetrafluoroboric acid was slowly added dropwise over a period of 30 minutes while maintaining the temperature of the mixed solution at 50℃and the temperature was raised to 85℃and reacted at this temperature for 4.5 hours. The amino group on the chitosan oligomer and the polyethylene glycol glycidyl ether end-capped epoxy group are subjected to ring opening etherification reaction, so that 2011.33kg of N-ether-based chitosan polyol oligomer solution is obtained.
4. Preparation of the prepolymer
303.8Kg of polytetrahydrofuran ether glycol and 1890kg of N-ether-based chitosan polyol oligomer solution are placed into a reaction kettle provided with a stirrer, a thermometer, a dropping funnel and a reflux condenser, the temperature is raised to 95 ℃, dehydration is carried out for 9 hours under the vacuum degree of 0.013MPa, and vacuumizing is stopped when the water content of the mixed polyether polyol is less than 0.03%. Cooling to 55 ℃, performing nitrogen protection, and slowly dropwise adding 221.9kg of toluene diisocyanate solution. After the toluene diisocyanate solution is added, the temperature is raised to 85 ℃, the mixed polyether polyol and the toluene diisocyanate are polymerized for 3 hours under the condition of excessive isocyanate, and then 1.06kg of benzoyl chloride stabilizer is added to obtain 929.1kg of-NCO group blocked prepolymer, and the prepolymer-NCO value is 7.06%.
5. Preparation of natural biomass chitin modified single-component water-soluble polyurethane chemical grouting material
807.2Kg of a-NCO-terminated prepolymer, 2.83kg of stannous oleate and 193.6kg of dioctyl sebacate were placed in a reaction kettle with a stirrer, a thermometer, a dropping funnel and a reflux condenser, and vacuum dehydrated for 3 hours at 95℃and a vacuum of 0.015 MPa. Cooling to 30 ℃ after releasing vacuum to obtain 995.42kg of light yellow and viscous single-component water-soluble polyurethane chemical grouting material. Placing into a sealed container, and standing at 21deg.C for use.
EXAMPLE 4 storage stability of Natural Biomass chitin modified one-component Water-soluble polyurethane chemical grouting Material
The storage stability of the natural biomass chitin modified single-component water-soluble polyurethane chemical grouting material is an important performance index. The method comprises the steps of placing a traditional single-component water-soluble polyurethane chemical grouting material (N-WPU) and a natural biomass Chitin modified single-component water-soluble polyurethane chemical grouting material (statin-WPU) at room temperature for 0,30,60,180 days, determining the isocyanate content (bromocresol green is an indicator and 0.1moI/L HCl is a standard solution) in the two chemical grouting materials by using a di-N-butylamine-acetone titration method, and evaluating the storage stability of the two single-component water-soluble polyurethane chemical grouting materials according to the change of isocyanate (-NCO content) in the grouting materials.
As shown in FIG. 2, the-NCO content of both one-component water-soluble polyurethane chemical grouting materials was reduced with the increase of the storage time. In the same storage time, the NCO content reduction rate of the natural biomass chitin modified single-component water-soluble polyurethane chemical grouting material is slower than that of the traditional single-component water-soluble polyurethane chemical grouting material, and the natural biomass chitin modified single-component water-soluble polyurethane chemical grouting material has better storage stability than that of the traditional single-component water-soluble polyurethane chemical grouting material.
Example 5 grouting Performance detection of Natural Biomass chitin modified one-component Water-soluble polyurethane grouting Material
1. Water-in-package quantity detection
Under standard test conditions, the chemical grouting material and quantitative water are mixed and completely react with the water, the slurry is solidified into gel within 200 seconds, the solidification body has no bleeding, and the multiple of the amount of the water coated in the solidification body of the chemical grouting material and the amount of the chemical grouting material is called the slurry coated water amount. Weighing 5g of a traditional single-component water-soluble polyurethane chemical grouting material (N-WPU) and a natural biomass Chitin modified single-component water-soluble polyurethane chemical grouting material (statin-WPU), mixing with 50g,55g and 60g of water under stirring, performing gel curing on the chemical grouting materials within a specified time, and detecting the water-covering quantity of the two single-component water-soluble polyurethane chemical grouting materials.
As shown in FIG. 3, as the water consumption increases, the water-covering amount of both the one-component water-soluble polyurethane chemical grouting materials increases. Under the same grouting material/water consumption ratio, the natural biomass chitin modified single-component water-soluble polyurethane chemical grouting material has higher water coating amount than the traditional single-component water-soluble polyurethane chemical grouting material.
2. Volume expansion rate detection
Referring to the detection method of JC/T2041-2010 polyurethane grouting material, under standard test conditions, 50g of traditional single-component water-soluble polyurethane chemical grouting material (N-WPU) and natural biomass Chitin modified single-component water-soluble polyurethane chemical grouting material (Chitin-WPU) are respectively put into a 500ml measuring cup with 70g,75g and 80g of water to be uniformly stirred, and when foaming of the water-soluble polyurethane slurry is finished, the volume of the slurry before and after solidification is recorded. The rate of increase of the volume of the foamed solid formed by the two water-soluble polyurethane chemical grouting materials relative to the volume of the original slurry solution after water foaming is defined as the volume expansion rate of the chemical grouting materials, and is expressed as a percentage.
As shown in FIG. 4, as the water consumption increases, the volume expansion rate of both the one-component water-soluble polyurethane chemical grouting materials increases. Under the same grouting material/water consumption ratio, the natural biomass chitin modified single-component water-soluble polyurethane chemical grouting material has higher volume expansion rate than the traditional single-component water-soluble polyurethane chemical grouting material.
3. Curing time
Referring to the detection method of JC/T2041-2010 polyurethane grouting material, under standard test conditions, 20g of traditional single-component water-soluble polyurethane chemical grouting material (N-WPU) and natural biomass Chitin modified single-component water-soluble polyurethane chemical grouting material (Chitin-WPU) are weighed into a 500ml measuring cup, 1g,1.5g and 2g of water are added into the 500ml measuring cup, the chemical grouting material is uniformly stirred by a glass rod, the chemical grouting material foams when meeting water, the foaming body is considered to be completely solidified after stopping foaming, and the time from stirring to curing of the grouting material is defined as the curing time.
As shown in fig. 5, as the water consumption increases, the curing time of both the one-component water-soluble polyurethane chemical grouting materials increases. Under the same grouting material/water consumption ratio, the natural biomass chitin modified single-component water-soluble polyurethane chemical grouting material has longer curing time than the traditional single-component water-soluble polyurethane chemical grouting material.
4. Compressive Strength of polyurethane elastomer
Referring to a detection method of JC/T2041-2010 polyurethane grouting material, under standard test conditions, a traditional single-component water-soluble polyurethane chemical grouting material (N-WPU), a natural biomass Chitin modified single-component water-soluble polyurethane chemical grouting material (Chitin-WPU) and water are prepared into slurry according to the proportion of 20:1.0,20:1.5 and 20:2.0, the prepared slurry is poured into a polytetrafluoroethylene test mold with the thickness of 70mm multiplied by 70mm for molding, the temperature is constant for curing for 10 hours after demolding, a polyurethane elastomer sample is placed on a universal tester for 7 days at room temperature, the sample is continuously loaded at a loading speed of 0.3MPa/s-0.5MPa/s, and when the sample is close to being destroyed and begins to deform rapidly, the throttle is stopped to be adjusted until the sample is destroyed, and the destroyed load is recorded. The breaking load per unit area of the polyurethane elastomer is defined as the compressive strength of the polyurethane elastomer.
As shown in fig. 6, the compressive strength of both the one-component water-soluble polyurethane chemical grout material elastomers was reduced with the increase of water consumption. Under the same grouting material/water consumption ratio, the natural biomass chitin modified single-component water-soluble polyurethane chemical grouting material elastomer has higher compressive strength than the traditional single-component water-soluble polyurethane chemical grouting material elastomer.
5. Tensile Strength and tensile elongation of polyurethane elastomer
Referring to the detection method of JC/T2041-2010 polyurethane grouting material, under standard test conditions, adding 1g,1.5g and 2g of water into 20g of traditional single-component water-soluble polyurethane chemical grouting material (N-WPU) and natural biomass Chitin modified single-component water-soluble polyurethane chemical grouting material (Chitin-WPU), uniformly stirring, pouring into a polytetrafluoroethylene mould, paving, putting the mould into a vacuum drying oven, curing at a constant temperature for 10 hours to obtain a polyurethane elastomer sample, and standing the sample at room temperature for 7 days. The polyurethane elastomer film was produced into dumbbell-shaped test pieces, and the thickness and width of the test pieces were measured, respectively, and the average value thereof was taken. In the specified test time, a dumbbell-shaped sample is loaded at a stretching speed of 100mm/min by using a universal electronic stretching experiment machine, the maximum stretching stress in the process that the sample is stretched to break is taken as the stretching strength, and the ratio of the maximum stretching length of the sample to the original length of the sample is defined as the stretching elongation.
As shown in FIG. 7, as the amount of water used increases, the tensile strength and tensile elongation of the two one-component water-soluble polyurethane chemical grout material elastomers increases. Under the same grouting material/water consumption ratio, the natural biomass chitin modified single-component water-soluble polyurethane chemical grouting material elastomer has slightly lower tensile strength and tensile elongation than the traditional single-component water-soluble polyurethane chemical grouting material elastomer.
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