WO2022007455A1 - 一种增强型瓷砖胶用改性羟乙基甲基纤维素及其制备方法和应用 - Google Patents

一种增强型瓷砖胶用改性羟乙基甲基纤维素及其制备方法和应用 Download PDF

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WO2022007455A1
WO2022007455A1 PCT/CN2021/086829 CN2021086829W WO2022007455A1 WO 2022007455 A1 WO2022007455 A1 WO 2022007455A1 CN 2021086829 W CN2021086829 W CN 2021086829W WO 2022007455 A1 WO2022007455 A1 WO 2022007455A1
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methyl cellulose
hydroxyethyl methyl
cellulose
tile adhesive
modified hydroxyethyl
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PCT/CN2021/086829
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English (en)
French (fr)
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滕鲲
赵明
滕波
李青华
姜爱梅
赵建玉
孟兆武
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山东一滕新材料股份有限公司
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Publication of WO2022007455A1 publication Critical patent/WO2022007455A1/zh
Priority to US17/867,650 priority Critical patent/US20220348800A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J101/00—Adhesives based on cellulose, modified cellulose, or cellulose derivatives
    • C09J101/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B11/00—Preparation of cellulose ethers
    • C08B11/02—Alkyl or cycloalkyl ethers
    • C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
    • C08B11/08—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals with hydroxylated hydrocarbon radicals; Esters, ethers, or acetals thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B11/00—Preparation of cellulose ethers
    • C08B11/193—Mixed ethers, i.e. ethers with two or more different etherifying groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B11/00—Preparation of cellulose ethers
    • C08B11/20—Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J101/00—Adhesives based on cellulose, modified cellulose, or cellulose derivatives
    • C09J101/08—Cellulose derivatives
    • C09J101/26—Cellulose ethers
    • C09J101/28—Alkyl ethers
    • C09J101/284—Alkyl ethers with hydroxylated hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
    • C09J103/04—Starch derivatives
    • C09J103/08—Ethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/346—Applications of adhesives in processes or use of adhesives in the form of films or foils for building applications e.g. wrap foil
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/10—Presence of inorganic materials
    • C09J2400/12—Ceramic
    • C09J2400/123—Ceramic in the substrate

Definitions

  • the invention relates to the technical field of building materials, in particular to a modified hydroxyethyl methyl cellulose for reinforced tile adhesive and a preparation method thereof.
  • ceramic tile As a decorative material, ceramic tile has a broad market, but with the continuous improvement of the specialization of the ceramic tile market, more and more consumers are pursuing the seamless effect of wall decoration, making large-scale ceramic tiles more and more popular.
  • the increasing popularity of residential buildings has also promoted the popularity of large-scale tiles. With the increasing size and quality of tiles, the requirements for safety are also getting higher and higher, and traditional tile adhesives have been unable to meet the requirements, so new types of tile adhesives have developed rapidly.
  • Hydroxyethyl methyl cellulose (Hydroxyethyl Methyl Cellulose, HEMC) is a cellulose mixed ether variety whose output, dosage and quality are rapidly improving in recent years.
  • the non-ionic cellulose mixed ether produced by the process has the HEMC molecular structure of [C 6 H 7 O 2 (OH) 3 ⁇ m ⁇ n (OCH 3 ) m (OCH 2 CH 2 OH) n ] x .
  • the production process of HEMC can be divided into two categories: liquid phase method and gas phase method. The internal pressure of the liquid-phase method equipment is small, the pressure-bearing capacity of the equipment is low, and the risk is small.
  • the reaction is usually not too large (typically 3 or less 15m), small production capacity to increase production, is bound to increase more than one reactor , and the reaction process requires a large amount of organic solvent as a carrier, and the reaction time is also long (generally more than 10 hours), which increases the solvent distillation recovery and time cost.
  • the gas phase method has compact equipment and high single-batch yield. The reaction is carried out in a horizontal autoclave, and the time (generally 5-8 hours) is shorter than that of the liquid phase method, and a complex solvent recovery system is not required.
  • the present invention provides a modified hydroxyethyl methyl cellulose for reinforced tile adhesive and a preparation method and application thereof, which change the existing method in the preparation of modified hydroxyethyl methyl cellulose.
  • the cumbersome operation of multi-step etherification through the control of special operating conditions, only needs one step of etherification, and because of the continued addition of physical modification steps, a product with better performance is obtained, which significantly improves the tensile bonding of tile adhesive.
  • the operating conditions of the one-step etherification treatment are significantly different from those of the prior art.
  • the alkali concentration of the system is increased by adding granular alkali, and the etherification efficiency of the etherifying agent is improved.
  • the etherification reaction pressure is carried out in stages, and it is carried out under higher pressure. While improving the uniformity of the product, the etherification efficiency of the etherifying agent is further improved, and the production cost is reduced without prolonging the reaction time.
  • a modified hydroxyethyl methyl cellulose for reinforced tile adhesive is prepared from the following raw materials by mass percentage: hydroxyethyl methyl cellulose 54%-94%, starch ether 5%-40%, dispersant 0.5% %-3% and rheology agent 0.5%-3%; wherein, the mass ratio of hydroxyethyl methyl cellulose is 1:(0.01-1.0):(0.02-2.1):(0.50-2.0):(0.01- 1.2) cellulose powder, granular caustic soda, liquid caustic soda, methyl chloride and ethylene oxide are prepared, preferably, hydroxyethyl methyl cellulose is 1:(0.1-0.7):(0.1-1.0) by mass ratio :(0.55-1.7):(0.05-0.9) of cellulose powder, granular caustic soda, liquid caustic soda, methyl chloride and ethylene oxide.
  • starch ethers are monobasic starch ethers (with a substituent, such as carboxymethyl starch, hydroxypropyl starch, hydroxyethyl starch, etc.), and dibasic starch ethers have two substituents, such as carboxymethyl hydroxypropyl base starch, hydroxypropyl hydroxyethyl starch, carboxymethyl hydroxyethyl starch, etc.), tribasic starch ether (with three substituents, such as carboxymethyl hydroxypropyl hydroxyethyl starch, hydroxypropyl hydroxyethyl starch, etc.) Any one or a mixture of ethyl starch, hydroxypropyl hydroxyethyl methyl starch, etc.).
  • the starch ether in the present invention has the functions of improving the anti-slip property of the tile adhesive and prolonging the opening time of the tile adhesive.
  • the starch ether selected in the present invention contains a variety of hydrophilic groups, which increases the content of branched-chain substituent groups, can synergize with the linear structure of hydroxypropyl methylcellulose, and improves the ability of tile adhesive to protect moisture. Extending its open time, at the same time, the various branched chain substituents of starch ether increase the steric hindrance of the tile adhesive and improve its anti-slip performance. ,
  • the above-mentioned dispersing agent is any one or a mixture of polyacrylamide, polyvinyl alcohol and polyethylene oxide, preferably anionic polyacrylamide, nonionic polyacrylamide, polyvinyl alcohol and polyethylene oxide. Any one or a mixture of several.
  • the further beneficial effect of adopting the above is that the dispersant in the present invention has the effect of increasing the bonding strength of the tile adhesive.
  • the selected dispersants of the present invention all have excellent water solubility and good compatibility with cellulose ethers, which can improve the water retention of cement slurry, greatly improve its transportability, and can inhibit the flying of dust and improve the production environment.
  • the above-mentioned rheological agent is any one or a mixture of guar gum, gum arabic, carrageenan and xanthan gum.
  • the rheology agent in the present invention has the functions of adjusting the viscosity of the product and synergistically improving the stability of the slurry with other components.
  • the selected rheological agents of the present invention all have excellent water solubility and good compatibility with cellulose ethers, which can improve the water retention of cement slurry and enhance its stability to heat, acid, alkali, enzyme and salt.
  • the above-mentioned cellulose powder is any one or a mixture of cotton cellulose, wood cellulose, bamboo cellulose and straw cellulose, preferably any one of cotton cellulose, wood cellulose and bamboo cellulose
  • the degree of polymerization of cellulose powder is 500-8000, preferably 1000-5000, more preferably 2400-3000
  • the particle size of the cellulose powder is 0.18-0.30mm, preferably 0.212-0.250mm
  • the bulk density of the cellulose powder is 150-200g/L.
  • the cellulose powder in the present invention as the main reaction raw material of the cellulose ether, has a macromolecular linear structure and has the effect of retaining water.
  • the selected cellulose powders in the present invention are all green and renewable resources, with huge reserves and easy preparation; the selected polymerization degree range in the present invention has good reactivity, and the post-reaction treatment is smooth; The system is easy to penetrate, the reaction efficiency is high, and the material discharge is smooth; the selected bulk density of the present invention is uniformly dispersed in the reaction system, which is easier for mass transfer and heat transfer, and the reaction efficiency is high.
  • the above-mentioned granular alkali is granular alkali metal hydroxide;
  • the alkali metal hydroxide is preferably sodium hydroxide and/or potassium hydroxide, more preferably sodium hydroxide;
  • the particle size of the granular alkali is 0.3-2.0mm, preferably 0.4-1.5mm, more preferably 0.5-1.0mm.
  • the granular alkali in the present invention has the functions of increasing the concentration of the lye and accelerating the reaction speed.
  • the selected granular alkali is easy to water, and has high solubility and dissolution speed, which can shorten the time of alkalization.
  • the selected particle size of the invention has good fluidity, is easy to operate, does not easily generate dust, and dissolves rapidly.
  • the above-mentioned liquid alkali is an aqueous solution of alkali metal hydroxide;
  • the alkali metal hydroxide is preferably sodium hydroxide and/or potassium hydroxide, more preferably sodium hydroxide;
  • the mass concentration of the alkali metal hydroxide in the liquid alkali is 40%-60%, preferably 45%-55%, more preferably 48%-52%, still more preferably 50%.
  • the water in the liquid caustic soda acts as a reaction dispersing agent, so that the material reaction is more uniform and the product quality is improved; It is alkali cellulose for subsequent etherification reaction.
  • the liquid caustic soda selected in the present invention has higher solubility; the liquid caustic soda with the selected mass concentration of the present invention has good fluidity at room temperature, which is convenient for pumping, and at the same time, the concentration of the lye liquid is high, the reaction efficiency of the system is high, and the efficiency of the etherifying agent can be improved. utilization.
  • a preparation method of modified hydroxyethyl methyl cellulose for enhanced tile adhesive specifically comprising the following steps:
  • each raw material is weighed according to the mass ratio of the above-mentioned reinforced type tile adhesive modified hydroxyethyl methyl cellulose;
  • the pressure of the first-stage etherification reaction is 1.8-2.0MPa, the temperature is 55-65°C, and the time is 0.5-1.5h; the pressure of the second-stage etherification reaction is 2.3-2.5MPa, and the temperature is 2.3-2.5MPa.
  • the time is 0.5-1.5h.
  • the above-mentioned further beneficial effect is that the pressure of the first-stage etherification reaction is 1.8-2.0MPa, which is more conducive to the reaction of ethylene oxide and improves the etherification efficiency of ethylene oxide; the pressure of the second-stage etherification reaction is 2.3-2.5MPa, which is more conducive to the reaction of methyl chloride and improves the etherification efficiency of methyl chloride.
  • the invention improves the uniformity of the reaction by adopting the reaction modes of two pressure stages, and at the same time, due to the high reaction pressure, the etherification efficiency is improved, the reaction time of the two pressure stages is shortened, and the total etherification reaction time is maintained within 3h , the production efficiency is improved, the production cost is reduced, and the entire reaction process is carried out in a reactor with a pressure resistance of 2.8-3.5 MPa, which ensures the safety of the reaction.
  • step (2) after the etherification reaction is finished, the following operation steps are also included: the unreacted etherifying agent is recovered by the three-stage condensation recovery process, the first-level direct pressure relief condensation recovery, and the reactor pressure is from 2.3-2.5 MPa pressure relief to 0.75-1.1MPa; secondary compression condensation recovery, reactor pressure relief from 0.75-1.1MPaMPa to 0.1-0.25MPa; tertiary vacuum + compression condensation recovery, reactor pressure relief from 0.1-0.25MPa to (-0.08)-(-0.1)MPa.
  • the recovery method of the etherifying agent in the present invention can reduce the consumption of the etherifying agent, make the pressure relief process of the autoclave smoother, safer and more environmentally friendly.
  • the utilization rate of the etherifying agent is reduced, and the production cost is reduced.
  • the neutralization process is as follows: adding acetic acid and/or hydrochloric acid, and adjusting the pH of the material to a value of 6-8.
  • the above-mentioned further beneficial effect is that the neutralization step of the present invention has the effect of adjusting the reaction system to be neutral, facilitating subsequent processing of materials, and stabilizing the pH value of the final product at neutral.
  • the acid selected in the present invention is a conventional acid, which is easy to pump, and the acidity is weak, which is beneficial to reduce the acid degradation of the material and stabilize the viscosity of the product.
  • the washing process is as follows: adding water for washing, and the temperature of adding water is 80-95 °C, preferably 85-95 °C, more preferably 90-95 °C; the amount of water added is 6-12 °C of the material quality. times, preferably 8-10 times.
  • the washing of the present invention is to remove the salts and other by-products generated by the reaction, improve the product purity, and at the same time wash the reaction kettle, which is convenient for the next feeding.
  • the water temperature selected in the present invention can ensure sufficient separation of materials and water, improve the dissolving speed of the salt, and increase the washing efficiency; the water addition amount selected in the present invention can thoroughly clean the reaction kettle without residue at the bottom of the kettle, and at the same time fully dissolve the salt and water in the reaction product.
  • the centrifugation process is as follows: the material is centrifuged, the centrifugation speed is 2800-3500r/min, and the time is 1.5-2.5h.
  • the above-mentioned further beneficial effect is that the function of the centrifugation step of the present invention is to separate the material and the salty wastewater, after centrifugation, the material with a moisture content of 45-55% enters the drying process, and the salty wastewater enters the sewage treatment process.
  • the centrifugation speed selected by the present invention can efficiently separate the material and the salty waste water, and ensure smooth discharge; the centrifugation time selected by the present invention can make the centrifugation process run smoothly, ensure the smooth connection of the front and rear processes, and improve the equipment utilization rate.
  • the drying process is as follows: drying the material, the drying temperature is 80-100° C., and the drying time is 1.5-2.5 h.
  • the function of the drying step of the present invention is to remove the moisture contained in the centrifuged material, and to control the moisture of the final product to be less than 5%.
  • the selected drying temperature of the present invention can ensure the rapid drying of centrifugal materials and reduce material degradation during the drying process; the selected time of the present invention can make the drying process proceed smoothly, ensure smooth connection between front and rear processes, and improve equipment utilization.
  • the pulverizing process is: pulverizing the material, and the particle size is 0.125-0.180 mm.
  • the function of the pulverizing step of the present invention is to reduce the roughness of the material and improve the fineness and bulk density of the material.
  • the selected particle size of the present invention improves the material fineness and bulk density, and at the same time, the product has better fluidity and texture, and is easy to package.
  • the rotating speed of the mixing and stirring is 10-70r/min, and the time is 40-60min.
  • the above-mentioned further beneficial effect is that the function of the mixing and stirring of the present invention is to uniformly mix the hydroxypropyl methylcellulose, the starch ether, the dispersant and the rheological agent, so as to achieve the purpose of physical modification.
  • the selected mixing speed and time of the present invention can ensure that the components are fully mixed to obtain a uniformly mixed product.
  • modified hydroxyethyl methyl cellulose for reinforced tile adhesive in the preparation of reinforced tile adhesive, wherein the modified hydroxyethyl methyl cellulose for reinforced tile adhesive accounts for the quality of the reinforced tile adhesive
  • the percentage is 0.2%-0.5%.
  • the preparation process from raw material (cellulose) to product (modified hydroxyethyl methyl cellulose) of the present invention does not require any excess solvent and solvent recovery system, using water and a small amount of liquid caustic soda in the raw material (cellulose)
  • the water is used as the solvent of the alkali, which avoids the use of a large amount of solvent and water in the preparation of modified hydroxyethyl methyl cellulose by the traditional liquid phase method.
  • the etherifying agent and the by-product dimethyl ether after the etherification reaction are recovered by condensation.
  • washing wastewater enters the sewage treatment system, and the product is prepared by high-pressure reaction, which greatly shortens the time for preparing modified hydroxyethyl methyl cellulose by traditional liquid phase method, and improves the use efficiency of etherifying agent, and the process and equipment are simple.
  • the obtained modified hydroxyethyl methyl cellulose product has stable quality, and has the function of improving the tensile bonding strength of tile adhesive.
  • the safety of the use of ceramic tiles meets the needs of customers.
  • the present invention obtains pure hydroxyethyl methyl cellulose by performing one-step etherification chemical modification of raw cellulose and various etherifying agents at the same time, and then continues through specific dosages of starch ether, dispersant and rheology agent.
  • the modified hydroxyethyl methyl cellulose is obtained by physical mixing and modification. Under the condition that the anti-slip performance of the tile adhesive is not affected, the product is dispersed in water to form a uniform network structure, which further improves the ability of the tile adhesive to retain moisture. Therefore, it has obvious bridging effect on the cement particles, endows the mortar with a larger mechanical anchoring force, and improves the tensile bond strength of the mortar.
  • the modified hydroxyethyl methyl cellulose prepared by the preparation method provided by the present invention is used for the reinforced tile adhesive, which can significantly improve the tensile bonding strength of the tile adhesive.
  • the operating conditions of the preparation method of the present invention are also significantly different, especially the chemical modification of the feeding method and the etherification reaction pressure.
  • the existing methods generally add the inhibitor dimethyl ether to inhibit the secondary The occurrence of the reaction, if dimethyl ether is not added, will produce the problems of reduced etherification efficiency, increased cost and increased side reactions.
  • the etherification reaction pressure in the existing method is generally below 2.35MPa, and the reaction is in a pressure stage. If it is carried out in different pressure stages, the reaction time will be prolonged, the production efficiency will be reduced and the cost will be raised within the pressure-resistant range of the existing reactor.
  • the alkali concentration of the system is increased by adding granular alkali, the progress of the positive reaction is accelerated, the occurrence of side reactions is suppressed, the etherification efficiency is improved, the cost is reduced, and the secondary reaction is simplified.
  • the recovery and reuse steps of methyl ether without adding the inhibitor dimethyl ether, the alkali concentration of the system is increased by adding granular alkali, the progress of the positive reaction is accelerated, the occurrence of side reactions is suppressed, the etherification efficiency is improved, the cost is reduced, and the secondary reaction is simplified.
  • the recovery and reuse steps of methyl ether is simplified.
  • the pressure of the etherification reaction is a higher 2.5MPa, and the reaction is carried out under two pressure stages, and the pressure of the first-stage etherification reaction is 1.8-2.0MPa, which is more conducive to the reaction of ethylene oxide, And improve the etherification efficiency of ethylene oxide, the pressure of the two-stage etherification reaction is 2.3-2.5MPa, which is more conducive to the reaction of methyl chloride, and improves the etherification efficiency of methyl chloride.
  • the uniformity of the reaction at the same time, due to the high reaction pressure, the etherification efficiency is improved, the reaction time of the two pressure stages is shortened, the total etherification reaction time is maintained within 3h, the production efficiency is improved, and the production cost is reduced.
  • the process is carried out in a reactor with a pressure resistance of 2.8-3.5MPa, which ensures the safety of the reaction; this modification process ensures the smooth and efficient progress of the preparation method, which not only simplifies the operation steps, but also saves resources and energy.
  • Fig. 1 is a process flow diagram of modified hydroxyethyl methyl cellulose for reinforced tile adhesive of the present invention.
  • the viscosity of hydroxyethyl methyl cellulose is the viscosity of a 2% aqueous solution (wet viscosity) measured at 20° C. with a B-type RVT viscometer, and the starch ether viscosity is measured with a B-type LVT viscometer at 5% aqueous solution viscosity (dry tack) measured at 20°C.
  • the modified hydroxyethyl methyl cellulose for reinforced tile adhesive is prepared from the following raw materials: 74 kg of hydroxyethyl methyl cellulose, hydroxypropyl starch (the content of hydroxypropoxy group is 19.5%, 5% type B LVT viscosity 1950cp, ash content 7.5%, produced by Shandong Yiteng New Material Co., Ltd.) 20kg, anionic polyacrylamide 3kg and guar gum 3kg;
  • hydroxyethyl methyl cellulose is composed of cotton cellulose powder (average degree of polymerization is 2638, particle size is 0.230mm, bulk density is 175g/L) 100kg, granular sodium hydroxide (particle size is 0.7mm) 27kg, hydrogen Sodium oxide aqueous solution (mass concentration is 50%) 63kg, methyl chloride 74kg and ethylene oxide 13kg are prepared.
  • the preparation method specifically includes the following steps:
  • each raw material is weighed according to the above-mentioned quality
  • step (3) adding the pure product of hydroxyethyl methylcellulose, hydroxypropyl starch, anionic polyacrylamide and guar gum obtained in step (2) into the mixer and mixing and stirring for 50min at a rotating speed of 50r/min, That is, the modified hydroxyethyl methyl cellulose for reinforced tile adhesive is obtained.
  • the modified hydroxyethyl methyl cellulose for reinforced tile adhesive is prepared from the following raw materials: 66 kg of hydroxyethyl methyl cellulose, hydroxypropyl starch (the content of hydroxypropoxy group is 19.5%, 5% type B LVT viscosity 1950cp, ash content 7.5%, produced by Shandong Yiteng New Material Co., Ltd.) 30kg, non-ionic polyacrylamide 2kg and gum arabic 2kg;
  • hydroxyethyl methyl cellulose is composed of wood cellulose powder (average degree of polymerization is 2873, particle size is 0.230mm, bulk density is 175g/L) 100kg, granular sodium hydroxide (particle size is 0.7mm) 35kg, hydrogen Sodium oxide aqueous solution (mass concentration is 50%) 52kg, methyl chloride 81kg and ethylene oxide 12kg are prepared.
  • the preparation method specifically includes the following steps:
  • each raw material is weighed according to the above-mentioned quality
  • step (3) adding the pure hydroxyethyl methylcellulose, hydroxypropyl starch, anionic polyacrylamide and guar gum obtained in step (2) into the mixer and mixing and stirring for 50min at a rotating speed of 10r/min, That is, the modified hydroxyethyl methyl cellulose for reinforced tile adhesive is obtained.
  • the modified hydroxyethyl methyl cellulose for reinforced tile adhesive is prepared from the following raw materials: 71 kg of hydroxyethyl methyl cellulose, hydroxypropyl starch (hydroxypropoxy content is 19.5%, 5% type B LVT viscosity 1950cp, ash content 7.5%, produced by Shandong Yiteng New Material Co., Ltd.) 25kg, polyvinyl alcohol 2kg and carrageenan 2kg;
  • hydroxyethyl methyl cellulose is composed of bamboo cellulose powder (average degree of polymerization is 1050, particle size is 0.18mm, bulk density is 150g/L) 20kg, wood cellulose powder (average degree of polymerization is 2520, particle size is 0.18mm, bulk density 150g/L) 60kg, cotton cellulose powder (average degree of polymerization 5010, particle size 0.18mm, bulk density 150g/L) 20kg, granular potassium hydroxide (particle size 0.3mm) 66kg , potassium hydroxide aqueous solution (mass concentration is 40%) 100kg, methyl chloride 168kg and ethylene oxide 53kg.
  • the preparation method specifically includes the following steps:
  • each raw material is weighed according to the above-mentioned quality
  • the first-stage direct pressure relief condensation recovery the reactor pressure is released from 2.4MPa to 0.75MPa; the second-stage compression condensation recovery, the reactor pressure is released from 0.75MPa to 0.1MPa; the third-stage vacuum + compression condensation recovery, the reactor pressure
  • the pressure is released from 0.1MPa to -0.08MPa), add hydrochloric acid to the reactor to adjust the pH value of the material to 6.5, then add 8 times the mass of the material to the reactor with 90°C hot water for washing, and centrifuge at 3500r/min. 1.5h, drying at 80°C for 1.5h, and pulverizing to a particle size of 0.180mm to obtain pure hydroxyethyl methylcellulose;
  • step (3) adding the pure product of hydroxyethyl methylcellulose, hydroxypropyl starch, polyvinyl alcohol and carrageenan prepared in step (2) into the mixer and mixing and stirring for 45min at a rotating speed of 70r/min to obtain an enhanced type Modified hydroxyethyl methyl cellulose for tile adhesives.
  • the modified hydroxyethyl methyl cellulose for reinforced tile adhesive is prepared from the following raw materials: 78 kg of hydroxyethyl methyl cellulose, hydroxypropyl starch (the content of hydroxypropoxy group is 19.5%, 5% type B LVT viscosity 1950cp, ash content 7.5%, produced by Shandong Yiteng New Material Co., Ltd.) 20kg, polyethylene oxide 1kg and xanthan gum 1kg;
  • hydroxyethyl methyl cellulose is composed of straw cellulose powder (average degree of polymerization is 500, particle size is 0.30mm, bulk density is 200g/L) 70kg, cotton cellulose powder (average degree of polymerization is 8000, particle size is 0.30mm, bulk density is 200g/L) 30kg, granular potassium hydroxide (particle size is 2.0mm) 51kg, potassium hydroxide aqueous solution (mass concentration is 60%) 80kg, methyl chloride 156kg and ethylene oxide 86kg are prepared.
  • the preparation method specifically includes the following steps:
  • each raw material is weighed according to the above-mentioned quality
  • Condensation recovery the reactor pressure is relieved from 2.4MPa to 0.75MPa; secondary compression condensation recovery, the reactor pressure is relieved from 0.75MPa to 0.1MPa; three-stage vacuum + compression condensation recovery, the reactor pressure is released from 0.1MPa to 0.1MPa -0.08MPa), add hydrochloric acid to the reactor to adjust the pH value of the material to 6.5, then add 8 times the mass of the material to the reactor with 90°C hot water for washing, centrifuge at 3500r/min for 2.5h, and at 100°C The temperature is dried for 2.5h, and pulverized to a particle size of 0.180mm to obtain pure hydroxyethyl methylcellulose;
  • step (3) adding the pure product of hydroxyethyl methylcellulose, hydroxypropyl starch, polyethylene oxide and xanthan gum obtained in step (2) into the mixer and mixing and stirring for 45min at a rotating speed of 70r/min to obtain Modified hydroxyethyl methyl cellulose for reinforced tile adhesives.
  • the modified hydroxyethyl methyl cellulose for reinforced tile adhesive is prepared from the following raw materials: 74 kg of hydroxyethyl methyl cellulose, hydroxypropyl starch (the content of hydroxypropoxy group is 19.5%, 5% type B LVT viscosity 1950cp, ash content 7.5%, produced by Shandong Yiteng New Material Co., Ltd.) 20kg, anionic polyacrylamide 3kg and guar gum 3kg;
  • hydroxyethyl methyl cellulose is composed of cotton cellulose powder (average degree of polymerization is 2526, particle size is 0.230mm, bulk density is 175g/L) 100kg, granular sodium hydroxide (particle size is 0.7mm) 18kg, hydrogen Sodium oxide aqueous solution (mass concentration is 50%) 42kg, methyl chloride 58kg and ethylene oxide 5kg are prepared.
  • the preparation method specifically includes the following steps:
  • each raw material is weighed according to the above-mentioned quality
  • step (3) adding the pure product of hydroxyethyl methylcellulose, hydroxypropyl starch, anionic polyacrylamide and guar gum obtained in step (2) into the mixer and mixing and stirring for 60min at a rotating speed of 50r/min, That is, the modified hydroxyethyl methyl cellulose for reinforced tile adhesive is obtained.
  • the modified hydroxyethyl methyl cellulose for reinforced tile adhesive is prepared from the following raw materials: 66 kg of hydroxyethyl methyl cellulose, hydroxypropyl starch (the content of hydroxypropoxy group is 19.5%, 5% type B LVT viscosity 1950cp, ash content 7.5%, produced by Shandong Yiteng New Material Co., Ltd.) 30kg, non-ionic polyacrylamide 2kg and gum arabic 2kg;
  • hydroxyethyl methyl cellulose is composed of cotton cellulose powder (average degree of polymerization is 2745, particle size is 0.230mm, bulk density is 175g/L) 100kg, granular sodium hydroxide (particle size is 0.7mm) 18kg, hydrogen Sodium oxide aqueous solution (mass concentration is 50%) 51kg, methyl chloride 61kg and ethylene oxide 6kg are prepared.
  • the preparation method specifically includes the following steps:
  • each raw material is weighed according to the above-mentioned quality
  • step (3) adding the pure product of hydroxyethyl methylcellulose, hydroxypropyl starch, nonionic polyacrylamide and gum arabic obtained in step (2) into the mixer and mixing and stirring for 50min at a rotating speed of 50r/min, That is, the modified hydroxyethyl methyl cellulose for reinforced tile adhesive is obtained.
  • the modified hydroxyethyl methyl cellulose for reinforced tile adhesive is prepared from the following raw materials: 71 kg of hydroxyethyl methyl cellulose, hydroxypropyl starch (hydroxypropoxy content is 19.5%, 5% type B LVT viscosity 1950cp, ash content 7.5%, produced by Shandong Yiteng New Material Co., Ltd.) 25kg, polyvinyl alcohol 2kg and carrageenan 2kg;
  • hydroxyethyl methyl cellulose is composed of cotton cellulose powder (average degree of polymerization is 2668, particle size is 0.230mm, bulk density is 175g/L) 100kg, granular sodium hydroxide (particle size is 0.7mm) 17kg, hydrogen Sodium oxide aqueous solution (mass concentration is 50%) 67kg, methyl chloride 63kg and ethylene oxide 12kg are prepared.
  • the preparation method specifically includes the following steps:
  • each raw material is weighed according to the above-mentioned quality
  • step (3) adding the pure product of hydroxyethyl methylcellulose, hydroxypropyl starch, polyvinyl alcohol and carrageenan prepared in step (2) into the mixer and mixing and stirring for 50min at a rotating speed of 50r/min to obtain an enhanced type Modified hydroxyethyl methyl cellulose for tile adhesives.
  • the modified hydroxyethyl methyl cellulose for reinforced tile adhesive is prepared from the following raw materials: 78 kg of hydroxyethyl methyl cellulose, hydroxypropyl starch (the content of hydroxypropoxy group is 19.5%, 5% type B LVT viscosity 1950cp, ash content 7.5%, produced by Shandong Yiteng New Material Co., Ltd.) 20kg, polyethylene oxide 1kg and xanthan gum 1kg;
  • hydroxyethyl methyl cellulose is composed of cotton cellulose powder (average degree of polymerization is 2436, particle size is 0.230mm, bulk density is 175g/L) 100kg, granular sodium hydroxide (particle size is 0.7mm) 44kg, hydrogen Sodium oxide aqueous solution (mass concentration is 50%) 67kg, methyl chloride 98kg and ethylene oxide 35kg are prepared.
  • the preparation method specifically includes the following steps:
  • each raw material is weighed according to the above-mentioned quality
  • step (3) adding the pure product of hydroxyethyl methylcellulose, hydroxypropyl starch, polyethylene oxide and xanthan gum obtained in step (2) into the mixer and mixing and stirring for 40min at a rotating speed of 50r/min to obtain Modified hydroxyethyl methyl cellulose for reinforced tile adhesives.
  • the hydroxyethyl methyl cellulose prepared in Examples 1-4 of the present invention has a higher total content of methoxy and hydroxyethoxy, and the total content is in the range of 36-46%, which is significantly higher than
  • the total content of methoxy and hydroxyethoxy prepared in Comparative Examples 1-3 is in the range of 25-35% of hydroxyethyl methylcellulose, but is far lower than that of methoxy and hydroxyethoxy prepared in Comparative Example 4
  • the total content is about 56% hydroxyethyl methyl cellulose.
  • Example 2 has higher methoxy content and lower hydroxyethoxy content
  • the hydroxyethyl methyl cellulose prepared in Example 4 has lower methoxy base content and higher hydroxyethoxy content.
  • both Examples 1-4 and Comparative Examples 1-4 have similar viscosity ranges and ash contents.
  • Example 1-4 Take a small amount of the modified hydroxyethyl methyl cellulose prepared in Example 1-4 and Comparative Example 1-4 to prepare the reinforced tile adhesive, respectively. Mix evenly in the mixer, add 25% water of the total weight of each component, stir according to the stirring equipment and stirring methods specified in the standard JC/T547-2005 "Ceramic Wall and Floor Tile Adhesive", and then carry out various performance tests according to the standard (slip, tensile bond strength, tensile bond strength after water immersion, tensile bond strength after heat aging, tensile bond strength after freeze-thaw cycles, and tensile bond strength after airing time 30min), test results as shown in Table 3.
  • the modified hydroxyethyl methyl cellulose prepared in Examples 1-4 of the present invention has the properties of improving the tensile bond strength of tile adhesive, wherein the tensile bond strength and the properties of the tensile bond strength after immersion, heat aging and The tensile bond strength after the freeze-thaw cycle meets the requirements of the index ⁇ 1.0Mpa, and meets the requirements of the anti-slip of the tile adhesive ⁇ 0.5mm and the tensile bond strength of the drying time 30min ⁇ 0.5Mpa, and both are excellent.
  • Each index corresponding to Comparative Examples 1-4. Among them, Embodiment 2 is the best embodiment.

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Abstract

一种增强型瓷砖胶用改性羟乙基甲基纤维素，由以下质量百分比的原料制得：羟乙基甲基纤维素54％-94％、淀粉醚5％-40％、分散剂0.5％-3％和流变剂0.5％-3％；其中，羟乙基甲基纤维素由纤维素粉、粒碱、液碱、氯甲烷和环氧乙烷制得。改性羟乙基甲基纤维素的制备方法为：（1）称取各原料；（2）将纤维素粉、粒碱、液碱、氯甲烷和环氧乙烷混合，进行醚化反应，然后再依次进行中和、洗涤、离心、干燥和粉碎，得到羟乙基甲基纤维素；（3）将羟乙基甲基纤维素、淀粉醚、分散剂和流变剂进行混合搅拌，即得。所得产品质量稳定，具有改善瓷砖胶拉伸粘结强度的功能，应用于现代尺寸大、质量大的瓷砖，能够显著提高瓷砖使用的安全性。

Description

一种增强型瓷砖胶用改性羟乙基甲基纤维素及其制备方法和应用 技术领域
本发明涉及建筑材料技术领域，更具体的说是涉及一种增强型瓷砖胶用改性羟乙基甲基纤维素及其制备方法。
背景技术
瓷砖作为一种装饰材料，市场广阔，但随着瓷砖市场的专业化程度不断提高，越来越多的消费者追求墙上装修的无缝效果，使得大规格瓷砖愈加受欢迎，同时，大面积住宅楼的日益流行，也推动了大规格瓷砖的走俏。随着瓷砖的尺寸与质量越来越大，对安全性的要求也越来越高，传统的瓷砖粘结剂已经难以满足要求，于是新型的瓷砖粘结剂迅速发展起来。
通常导致瓷砖脱落的原因主要有：(1)新混凝土基层干缩变形；(2)外界因素，如建筑沉降及蠕变；(3)温度的骤变产生变形；(4)多孔瓷砖中的水气膨胀而产生剪应力；(5)瓷砖表面比较光滑，胶粘剂与瓷砖之间机械锚固力非常小，导致因其它原因产生很小应力造成粘结力破坏。针对这些问题，普通型瓷砖胶粘剂只能满足一部分要求，而对于单块面积较大，如600mm×600mm以上的玻化砖，因其收缩率较大，普通型瓷砖胶粘剂用于粘贴这些高品质瓷砖经常会出现空鼓、掉砖等现象。因此，对于高品质瓷砖，需采用增强型瓷砖胶进行粘贴。
羟乙基甲基纤维素(HydroxyethylMethylCellulose，HEMC)是近年来产量、用量与质量都在迅速提升的纤维素混合醚品种，是由棉、木经碱化、环氧乙烷和氯甲烷醚化等过程制成的非离子型纤维素混合醚，HEMC分子结构为[C 6H 7O 2(OH) 3～m～n(OCH 3) m(OCH 2CH 2OH) n] x。目前HEMC的生产工艺可分为两 大类：液相法和气相法。液相法设备内部压力小，对设备承压能力要求低、危险性小，纤维素在碱液中浸渍后得到充分膨润和被碱化均匀的碱纤维素，碱液对纤维素渗透溶胀较好，可获得取代度和粘度都比较均匀的产品，品种也容易更换，但反应器通常不能太大(一般在15m 3以下)，生产能力较小，若要提高产量，势必增加多台反应器，而且反应过程需要大量有机溶剂作为载体，反应时间也较长(一般10小时以上)，增加了溶剂蒸馏回收和时间成本。气相法设备紧凑，单批产量高，反应在卧式高压釜中进行，时间(一般为5-8小时)较液相法短，而且不需要复杂的溶剂回收系统，反应完成后多余的氯甲烷和副产的二甲醚以气态的形式进入回收系统，分别回收重复利用，人工费用低，劳动强度小，生产成本比液相法低，但设备和自动控制投资大，技术含量高，投资建设费用大。
因此，如何提供一种增强型瓷砖胶用改性羟乙基甲基纤维素及其制备方法是本领域技术人员亟需解决的问题。
发明内容
为了弥补现有技术的不足，本发明提供了一种增强型瓷砖胶用改性羟乙基甲基纤维素及其制备方法和应用，改变了现有改性羟乙基甲基纤维素制备中多步醚化的繁琐操作，通过特殊操作条件的控制，只需一步醚化处理，且因为继续增加了物理改性步骤，获得了性能更好的产品，显著提高了瓷砖胶的拉伸粘结强度；同时，一步醚化处理的操作条件较现有技术具有显著区别，在不添加抑制剂二甲醚的情况下，通过添加粒碱提高体系的碱浓度，提高了醚化剂的醚化效率，同时醚化反应压力分段进行，并在更高压力下实施，在提高产品均匀性的同时，进一步提高了醚化剂的醚化效率，在不延长反应时间的情况下降低了生产成本，解决了现有技术中存在的问题。
为了实现上述目的，本发明采用如下技术方案：
一种增强型瓷砖胶用改性羟乙基甲基纤维素，由以下质量百分比的原料制得：羟乙基甲基纤维素54％-94％、淀粉醚5％-40％、分散剂0.5％-3％和流变剂0.5％-3％；其中，羟乙基甲基纤维素由质量比为1:(0.01-1.0):(0.02-2.1):(0.50-2.0):(0.01-1.2)的纤维素粉、粒碱、液碱、氯甲烷和环氧乙烷制得，优选的，羟乙基甲基纤维素由质量比为1:(0.1-0.7):(0.1-1.0):(0.55-1.7):(0.05-0.9)的纤维素粉、粒碱、液碱、氯甲烷和环氧乙烷制得。
进一步，上述淀粉醚为一元淀粉醚(具有一种取代基，例如羧甲基淀粉、羟丙基淀粉、羟乙基淀粉等)、二元淀粉醚具有两种取代基，例如羧甲基羟丙基淀粉、羟丙基羟乙基淀粉、羧甲基羟乙基淀粉等)、三元淀粉醚(具有三种取代基，例如羧甲基羟丙基羟乙基淀粉、羟丙基羟乙基乙基淀粉、羟丙基羟乙基甲基淀粉等)中的任一种或几种的混合。
采用上述进一步的有益效果在于，本发明中淀粉醚具有提升瓷砖胶抗滑移性和延长瓷砖胶开放时间的作用。本发明所选淀粉醚含有多种亲水性基团，增加了支链取代基团的含量，能够和羟丙基甲基纤维素的直链结构产生协同作用，提高瓷砖胶护持水分的能力，延长其开放时间，同时，淀粉醚的多种支链取代基增加了瓷砖胶的空间位阻，提升了其抗滑移性能。，
进一步，上述分散剂为聚丙烯酰胺、聚乙烯醇、聚氧化乙烯中的任一种或几种的混合，优选为阴离子型聚丙烯酰胺、非离子型聚丙烯酰胺、聚乙烯醇和聚氧化乙烯中的任一种或几种的混合。
采用上述进一步的有益效果在于，本发明中分散剂具有增加瓷砖胶粘结强度的作用。本发明所选分散剂均具有优越的水溶性，和纤维素醚的配伍性良好，能提高水泥浆料的保水性，同时大大提高其可输送性，并且可抑制粉尘的飞扬，改善生产环境。
进一步，上述流变剂为瓜尔胶、阿拉伯胶、卡拉胶、黄原胶中的任一种或几种的混合。
采用上述进一步的有益效果在于，本发明中流变剂具有调节产品粘度，和其他组分协同提高料浆稳定性的作用。本发明所选流变剂均具有优越的水溶性，和纤维素醚的配伍性良好，能提高水泥浆料的保水性，增强其对热、酸、碱、酶和盐的稳定性。
进一步，上述纤维素粉为棉纤维素、木纤维素、竹纤维素、秸秆纤维素中的任一种或几种的混合，优选为棉纤维素、木纤维素、竹纤维素中的任一种或几种的混合，更优选为棉纤维素和/或木纤维素，再优选为棉纤维素；纤维素粉的聚合度为500-8000，优选为1000-5000，更优选为2400-3000；纤维素粉的粒径为0.18-0.30mm，优选为0.212-0.250mm；纤维素粉的松密度为150-200g/L。
采用上述进一步的有益效果在于，本发明中纤维素粉作为纤维素醚的主反应原料，为大分子直链结构，有保持水分的作用。本发明所选纤维素粉均为绿色可再生资源，储量巨大，且容易制取；本发明所选聚合度范围具有很好的反应性，并且反应后处理顺畅；本发明所选粒径在反应体系中容易渗透，反应效率高，而且出料顺畅；本发明所选松密度在反应体系中分散均匀，更容易传质传热，反应效率高。
进一步，上述粒碱为粒状碱金属氢氧化物；碱金属氢氧化物优选为氢氧化钠和/或氢氧化钾，更优选为氢氧化钠；粒碱的粒径为0.3-2.0mm，优选为0.4-1.5mm，更优选为0.5-1.0mm。
采用上述进一步的有益效果在于，本发明中粒碱具有提高碱液浓度，加快反应速度的作用。所选粒碱易容易水，并具有较高的溶解度和溶解速度，可缩短化碱时间。本发明所选粒径具有很好的流动性，操作方便，不易产生粉尘，溶解迅速。
进一步，上述液碱为碱金属氢氧化物的水溶液；碱金属氢氧化物优选为氢氧化钠和/或氢氧化钾，更优选为氢氧化钠；液碱中碱金属氢氧化物的质量浓度为40％-60％，优选为45％-55％，更优选为48％-52％，再优选为50％。
采用上述进一步的有益效果在于，本发明中液碱中的水作为反应分散剂，使物料反应更均匀，提高产品品质；液碱中的碱具有激活纤维素分子中羟基的作用，使纤维素转化为碱纤维素，以进行后续的醚化反应。本发明所选液碱具有较高的溶解度；本发明所选质量浓度的液碱在室温下流动性良好，利于泵送，同时碱液浓度高，体系的反应效率高，可以提高醚化剂的利用率。
一种增强型瓷砖胶用改性羟乙基甲基纤维素的制备方法，具体包括以下步骤：
(1)按上述增强型瓷砖胶用改性羟乙基甲基纤维素的质量比称取各原料；
(2)将纤维素粉、粒碱、液碱、氯甲烷和环氧乙烷混合，依次进行一阶段醚化反应和二阶段醚化反应，然后再依次进行中和、洗涤、离心、干燥和粉碎，得到羟乙基甲基纤维素；
(3)将羟乙基甲基纤维素、淀粉醚、分散剂和流变剂进行混合搅拌，即得增强型瓷砖胶用改性羟乙基甲基纤维素。
进一步，上述步骤(2)中，一阶段醚化反应的压力为1.8-2.0MPa，温度为55-65℃，时间为0.5-1.5h；二阶段醚化反应的压力为2.3-2.5MPa，温度为75-85℃，时间为0.5-1.5h。
采用上述进一步的有益效果在于，一阶段醚化反应的压力为1.8-2.0MPa，更利于环氧乙烷的反应进行，并提高环氧乙烷的醚化效率；二阶段醚化反应的压力为2.3-2.5MPa，更利于氯甲烷的反应进行，并提高氯甲烷的醚化效率。本发明通过采用两种压力阶段的反应方式，提高了反应的均匀性，同时由于反应压力高，醚化效率提高，缩短了两种压力阶段的反应时间，使醚化反应 总时间维持在3h以内，提高了生产效率，降低了生产成本，同时整个反应过程在耐压2.8-3.5MPa的反应器中进行，保证了反应的安全性。
进一步，上述步骤(2)中，醚化反应结束后，还包括以下操作步骤：通过三级冷凝回收工艺回收未反应的醚化剂，一级直接卸压冷凝回收，反应器压力从2.3-2.5MPa卸压至0.75-1.1MPa；二级压缩冷凝回收，反应器压力从0.75-1.1MPaMPa卸压至0.1-0.25MPa；三级真空+压缩冷凝回收，反应器压力从0.1-0.25MPa卸压至(-0.08)-(-0.1)MPa。
采用上述进一步的有益效果在于，本发明中醚化剂的回收方式，可以降低醚化剂的消耗，使高压釜的卸压过程更加顺畅、安全和环保，同时醚化剂回收后重复使用，提高了醚化剂的使用率，降低了生产成本。
进一步，上述步骤(2)中，中和过程为：加入醋酸和/或盐酸，调节物料的pH为值6-8。
采用上述进一步的有益效果在于，本发明中和步骤的作用是将反应体系调整为中性，方便物料的后续处理，并使最终产品的pH值稳定在中性。本发明所选酸为常规酸，易于泵送，而且酸性偏弱，有利于降低物料的酸性降解，稳定产品粘度，同时中和过程生成的盐易溶于水，更利于后续洗涤除去。
进一步，上述步骤(2)中，洗涤过程为：加水进行洗涤，加水的温度为80-95℃，优选为85-95℃，更优选为90-95℃；加水量为物料质量的6-12倍，优选为8-10倍。
采用上述进一步的有益效果在于，本发明洗涤的作用是除去反应生成的盐和其他副产物，提高产品纯度，同时洗涤反应釜，方便下次投料。本发明所选加水温度可以保障物料和水充分分离，提高盐的溶解速度，增加洗涤效率；本发明所选加水量可以彻底清洗反应釜，釜底无残留，同时充分溶解反应产物中的盐和其他副产物，降低最终产品的灰分。
进一步，上述步骤(2)中，离心过程为：将物料进行离心，离心转速为2800-3500r/min，时间1.5-2.5h。
采用上述进一步的有益效果在于，本发明离心步骤的作用是将物料和含盐废水分离，离心后，含湿45-55％的物料进入干燥程序，含盐废水进入污水处理程序。本发明所选离心转速可以高效分离物料和含盐废水，保障出料顺畅；本发明所选离心时间可以使离心工序顺利进行，保障前后工序衔接顺畅，提高设备利用率。
进一步，上述步骤(2)中，干燥过程为：将物料进行干燥，干燥温度为80-100℃，时间为1.5-2.5h。
采用上述进一步的有益效果在于，本发明干燥步骤的作用是除去离心物料中含有的水分，将最终产品水分控制在5％以下。本发明所选干燥温度可以保障离心物料的快速烘干，并降低烘干过程中的物料降解；本发明所选时间可以使干燥工序顺利进行，保障前后工序衔接顺畅，提高设备利用率。
进一步，上述步骤(2)中，粉碎过程为：将物料进行粉碎，粒径为0.125-0.180mm。
采用上述进一步的有益效果在于，本发明粉碎步骤的作用是降低物料粗糙度，提高物料细度和堆积密度。本发明所选粒径在提高物料细度和堆积密度的同时，产品具有更好的流动度和质感，同时易于产品包装。
进一步，上述步骤(3)中，混合搅拌的转速为10-70r/min，时间为40-60min。
采用上述进一步的有益效果在于，本发明混合搅拌的作用是使羟丙基甲基纤维素、淀粉醚、分散剂和流变剂进行均匀混合，达到物理改性的目的。本发明所选混合搅拌转速和时间可以保障各组分之间充分混合，得到混合均匀的产品。
一种上述增强型瓷砖胶用改性羟乙基甲基纤维素在制备增强型瓷砖胶中的应用，其中，增强型瓷砖胶用改性羟乙基甲基纤维素占增强型瓷砖胶的质量百分比为0.2％-0.5％。
经由上述的技术方案可知，与现有技术相比，本发明的有益效果如下：
1、本发明从原料(纤维素)到产品(改性羟乙基甲基纤维素)的制备过程中不需要任何多余溶剂和溶剂回收系统，以原料(纤维素)中的水和少量液碱中的水作为碱的溶剂，避免了传统液相法制备改性羟乙基甲基纤维素时大量溶剂和水的使用，醚化反应后的醚化剂和副产物二甲醚经过冷凝回收再利用，洗涤废水进入污水处理系统，产品通过高压反应制备，大大缩短了传统液相法制备改性羟乙基甲基纤维素的时间，并且提高了醚化剂的使用效率，工艺及设备简单，易于操作，无三废排出，绿色环保，所得改性羟乙基甲基纤维素产品质量稳定，具有改善瓷砖胶拉伸粘结强度的功能，应用于现代尺寸大、质量大的瓷砖，能够显著提高瓷砖使用的安全性，满足客户的需求。
2、本发明通过对原料纤维素和多种醚化剂同时进行一步醚化化学改性得到羟乙基甲基纤维素纯品，再通过特定掺量的淀粉醚、分散剂和流变剂继续进行物理混合改性得到改性羟乙基甲基纤维素，在保证不影响瓷砖胶抗滑移性能的情况下，使产品分散在水中后形成均匀的网状结构，进一步提升瓷砖胶保持水分的能力，从而对水泥颗粒产生明显的桥接作用，赋予砂浆浆体较大的机械锚固力，提升砂浆的拉伸粘结强度。与现有技术相比，本发明提供的制备方法制得的改性羟乙基甲基纤维素用于增强型瓷砖胶，能够显著提升瓷砖胶的拉伸粘结强度。
3、本发明制备方法的操作条件相较现有改性方法也存在显著区别，尤其是化学改性的加料方式和醚化反应压力，现有方法一般都是添加抑制剂二甲醚以抑制副反应的发生，如果不加二甲醚会产生醚化效率降低、成本升高和副反应增多的问题，另外现有方法中醚化反应压力一般都是2.35MPa以下， 并且反应在一种压力阶段下进行，存在反应均匀性差的问题，如果分压力阶段进行，在现有反应器的耐压范围内会出现反应时间加长、生产效率降低和成本升高的问题。而本发明在不添加抑制剂二甲醚的情况下，通过添加粒碱提高体系的碱浓度，加快正反应进行，抑制副反应的发生，提高了醚化效率，降低了成本，同时简化了二甲醚的回收重新利用步骤。另外，本发明中醚化反应的压力为更高的2.5MPa，并且反应在两种压力阶段下进行，一阶段醚化反应的压力为1.8-2.0MPa，更利于环氧乙烷的反应进行，并提高环氧乙烷的醚化效率，二阶段醚化反应的压力为2.3-2.5MPa，更利于氯甲烷的反应进行，并提高氯甲烷的醚化效率，两种压力阶段的反应方式提高了反应的均匀性，同时由于反应压力高，醚化效率提高，缩短了两种压力阶段的反应时间，使醚化反应总时间维持在3h以内，提高了生产效率，降低了生产成本，同时整个反应过程在耐压2.8-3.5MPa的反应器中进行，保证了反应的安全性；这一改性处理过程保证了制备方法的顺利、高效进行，不但简化了操作步骤，也节省了资源和能源。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本实用新型的实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据提供的附图获得其他的附图。
图1为本发明增强型瓷砖胶用改性羟乙基甲基纤维素的工艺流程图。
具体实施方式
下面对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明 中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
以下实施例和对比例中，羟乙基甲基纤维素粘度为用B型RVT粘度计在20℃下测得的2％水溶液粘度(湿粘)，淀粉醚粘度为用B型LVT粘度计在20℃下测得的5％水溶液粘度(干粘)。
实施例1
增强型瓷砖胶用改性羟乙基甲基纤维素，由以下质量的原料制得：羟乙基甲基纤维素74kg、羟丙基淀粉(羟丙氧基含量为19.5％，5％B型LVT粘度1950cp，灰分7.5％，山东一滕新材料股份有限公司出品)20kg、阴离子型聚丙烯酰胺3kg和瓜尔胶3kg；
其中，羟乙基甲基纤维素由棉纤维素粉(平均聚合度为2638、粒径为0.230mm、松密度为175g/L)100kg、粒状氢氧化钠(粒径为0.7mm)27kg、氢氧化钠水溶液(质量浓度为50％)63kg、氯甲烷74kg和环氧乙烷13kg制得。
制备方法，具体包括以下步骤：
(1)按上述质量称取各原料；
(2)向有夹套的、搅拌中的、耐压为3.0MPa的反应器中依次加入棉纤维素粉、粒状氢氧化钠和氢氧化钠水溶液液碱，反应器排空并用氮气吹扫以除去氧气，再次排空，然后向反应器中依次加入醚化剂：环氧乙烷和氯甲烷，缓慢升温至60℃，压力为1.9MPa，反应0.5h，继续缓慢升温至80℃，压力为2.5MPa，反应1.5h，反应结束后降温卸压，回收未反应的醚化剂和副产物二甲醚(通过三级冷凝回收工艺回收未反应的醚化剂，一级直接卸压冷凝回收，反应器压力从2.5MPa卸压至1.1MPa；二级压缩冷凝回收，反应器压力从1.1MPa卸压至0.25MPa；三级真空+压缩冷凝回收，反应器压力从0.25MPa卸压至-0.1MPa)，向反应器中加入醋酸调节物料的pH值6.5，再向反应器中 加入8倍物料质量的90℃热水进行洗涤，以3000r/min的转速离心2h，以90℃的温度烘干2h，粉碎至粒径为0.15mm，得到羟乙基甲基纤维素纯品；
(3)将步骤(2)制得的羟乙基甲基纤维素纯品、羟丙基淀粉、阴离子型聚丙烯酰胺和瓜尔胶加入混料机中以50r/min的转速混合搅拌50min，即得增强型瓷砖胶用改性羟乙基甲基纤维素。
实施例2
增强型瓷砖胶用改性羟乙基甲基纤维素，由以下质量的原料制得：羟乙基甲基纤维素66kg、羟丙基淀粉(羟丙氧基含量为19.5％，5％B型LVT粘度1950cp，灰分7.5％，山东一滕新材料股份有限公司出品)30kg、非离子型聚丙烯酰胺2kg和阿拉伯胶2kg；
其中，羟乙基甲基纤维素由木纤维素粉(平均聚合度为2873、粒径为0.230mm、松密度为175g/L)100kg、粒状氢氧化钠(粒径为0.7mm)35kg、氢氧化钠水溶液(质量浓度为50％)52kg、氯甲烷81kg和环氧乙烷12kg制得。
制备方法，具体包括以下步骤：
(1)按上述质量称取各原料；
(2)向有夹套的、搅拌中的、耐压为3.0MPa的反应器中依次加入木纤维素粉、粒状氢氧化钠和氢氧化钠水溶液液碱，反应器排空并用氮气吹扫以除去氧气，再次排空，然后向反应器中依次加入醚化剂：环氧乙烷和氯甲烷，缓慢升温至60℃，压力为1.9MPa，反应0.5h，继续缓慢升温至80℃，压力为2.5MPa，反应1.5h，反应结束后降温卸压，回收未反应的醚化剂和副产物二甲醚(通过三级冷凝回收工艺回收未反应的醚化剂，一级直接卸压冷凝回收，反应器压力从2.5MPa卸压至1.1MPa；二级压缩冷凝回收，反应器压力从1.1MPa卸压至0.25MPa；三级真空+压缩冷凝回收，反应器压力从0.25MPa卸压至-0.1MPa)，向反应器中加入盐酸调节物料的pH值6.5，再向反应器中 加入8倍物料质量的90℃热水进行洗涤，以2800r/min的转速离心2.5h，以80℃的温度烘干2.5h，粉碎至粒径为0.125mm，得到羟乙基甲基纤维素纯品；
(3)将步骤(2)制得的羟乙基甲基纤维素纯品、羟丙基淀粉、阴离子型聚丙烯酰胺和瓜尔胶加入混料机中以10r/min的转速混合搅拌50min，即得增强型瓷砖胶用改性羟乙基甲基纤维素。
实施例3
增强型瓷砖胶用改性羟乙基甲基纤维素，由以下质量的原料制得：羟乙基甲基纤维素71kg、羟丙基淀粉(羟丙氧基含量为19.5％，5％B型LVT粘度1950cp，灰分7.5％，山东一滕新材料股份有限公司出品)25kg、聚乙烯醇2kg和卡拉胶2kg；
其中，羟乙基甲基纤维素由竹纤维素粉(平均聚合度为1050、粒径为0.18mm、松密度为150g/L)20kg、木纤维素粉(平均聚合度为2520、粒径为0.18mm、松密度为150g/L)60kg、棉纤维素粉(平均聚合度为5010、粒径为0.18mm、松密度为150g/L)20kg、粒状氢氧化钾(粒径为0.3mm)66kg、氢氧化钾水溶液(质量浓度为40％)100kg、氯甲烷168kg和环氧乙烷53kg制得。
制备方法，具体包括以下步骤：
(1)按上述质量称取各原料；
(2)向有夹套的、搅拌中的、耐压为3.0MPa的反应器中依次加入竹纤维素粉、木纤维素粉、棉纤维素粉、粒状氢氧化钾和氢氧化钾水溶液液碱，反应器排空并用氮气吹扫以除去氧气，再次排空，然后向反应器中依次加入醚化剂：环氧乙烷和氯甲烷，缓慢升温至60℃，压力为1.9MPa，反应1.5h，继续缓慢升温至80℃，压力为2.4MPa，反应0.5h，反应结束后降温卸压，回收未反应的醚化剂和副产物二甲醚(通过三级冷凝回收工艺回收未反应的醚化剂，一级直接卸压冷凝回收，反应器压力从2.4MPa卸压至0.75MPa；二级 压缩冷凝回收，反应器压力从0.75MPa卸压至0.1MPa；三级真空+压缩冷凝回收，反应器压力从0.1MPa卸压至-0.08MPa)，向反应器中加入盐酸调节物料的pH值6.5，再向反应器中加入8倍物料质量的90℃热水进行洗涤，以3500r/min的转速离心1.5h，以80℃的温度烘干1.5h，粉碎至粒径为0.180mm，得到羟乙基甲基纤维素纯品；
(3)将步骤(2)制得的羟乙基甲基纤维素纯品、羟丙基淀粉、聚乙烯醇和卡拉胶加入混料机中以70r/min的转速混合搅拌45min，即得增强型瓷砖胶用改性羟乙基甲基纤维素。
实施例4
增强型瓷砖胶用改性羟乙基甲基纤维素，由以下质量的原料制得：羟乙基甲基纤维素78kg、羟丙基淀粉(羟丙氧基含量为19.5％，5％B型LVT粘度1950cp，灰分7.5％，山东一滕新材料股份有限公司出品)20kg、聚氧化乙烯1kg和黄原胶1kg；
其中，羟乙基甲基纤维素由秸秆纤维素粉(平均聚合度为500、粒径为0.30mm、松密度为200g/L)70kg、棉纤维素粉(平均聚合度为8000、粒径为0.30mm、松密度为200g/L)30kg、粒状氢氧化钾(粒径为2.0mm)51kg、氢氧化钾水溶液(质量浓度为60％)80kg、氯甲烷156kg和环氧乙烷86kg制得。
制备方法，具体包括以下步骤：
(1)按上述质量称取各原料；
(2)向有夹套的、搅拌中的、耐压为3.0MPa的反应器中依次加入秸秆纤维素粉、棉纤维素粉、粒状氢氧化钾和氢氧化钾水溶液液碱，反应器排空并用氮气吹扫以除去氧气，再次排空，然后向反应器中依次加入醚化剂：环氧乙烷和氯甲烷，缓慢升温至60℃，压力为1.9MPa，反应1h，继续缓慢升温至80℃，压力为2.4MPa，反应1h，反应结束后降温卸压，回收未反应的醚化剂和副产物二甲醚(通过三级冷凝回收工艺回收未反应的醚化剂，一级直接 卸压冷凝回收，反应器压力从2.4MPa卸压至0.75MPa；二级压缩冷凝回收，反应器压力从0.75MPa卸压至0.1MPa；三级真空+压缩冷凝回收，反应器压力从0.1MPa卸压至-0.08MPa)，向反应器中加入盐酸调节物料的pH值6.5，再向反应器中加入8倍物料质量的90℃热水进行洗涤，以3500r/min的转速离心2.5h，以100℃的温度烘干2.5h，粉碎至粒径为0.180mm，得到羟乙基甲基纤维素纯品；
(3)将步骤(2)制得的羟乙基甲基纤维素纯品、羟丙基淀粉、聚氧化乙烯和黄原胶加入混料机中以70r/min的转速混合搅拌45min，即得增强型瓷砖胶用改性羟乙基甲基纤维素。
对比例1
增强型瓷砖胶用改性羟乙基甲基纤维素，由以下质量的原料制得：羟乙基甲基纤维素74kg、羟丙基淀粉(羟丙氧基含量为19.5％，5％B型LVT粘度1950cp，灰分7.5％，山东一滕新材料股份有限公司出品)20kg、阴离子型聚丙烯酰胺3kg和瓜尔胶3kg；
其中，羟乙基甲基纤维素由棉纤维素粉(平均聚合度为2526、粒径为0.230mm、松密度为175g/L)100kg、粒状氢氧化钠(粒径为0.7mm)18kg、氢氧化钠水溶液(质量浓度为50％)42kg、氯甲烷58kg和环氧乙烷5kg制得。
制备方法，具体包括以下步骤：
(1)按上述质量称取各原料；
(2)向有夹套的、搅拌中的、耐压为3.0MPa的反应器中依次加入棉纤维素粉、粒状氢氧化钠和氢氧化钠水溶液液碱，反应器排空并用氮气吹扫以除去氧气，再次排空，然后向反应器中依次加入醚化剂：环氧乙烷和氯甲烷，缓慢升温至60℃，压力为1.8MPa，反应1h，继续缓慢升温至80℃，压力为2.3MPa，反应1h，反应结束后降温卸压，回收未反应的醚化剂和副产物二甲醚(通过三级冷凝回收工艺回收未反应的醚化剂，一级直接卸压冷凝回收， 反应器压力从2.3MPa卸压至1.1MPa；二级压缩冷凝回收，反应器压力从1.1MPa卸压至0.25MPa；三级真空+压缩冷凝回收，反应器压力从0.25MPa卸压至-0.1MPa)，向反应器中加入醋酸调节物料的pH值6.5，再向反应器中加入8倍物料质量的90℃热水进行洗涤，以3000r/min的转速离心2h，以90℃的温度烘干2h，粉碎至粒径为0.15mm，得到羟乙基甲基纤维素纯品；
(3)将步骤(2)制得的羟乙基甲基纤维素纯品、羟丙基淀粉、阴离子型聚丙烯酰胺和瓜尔胶加入混料机中以50r/min的转速混合搅拌60min，即得增强型瓷砖胶用改性羟乙基甲基纤维素。
对比例2
增强型瓷砖胶用改性羟乙基甲基纤维素，由以下质量的原料制得：羟乙基甲基纤维素66kg、羟丙基淀粉(羟丙氧基含量为19.5％，5％B型LVT粘度1950cp，灰分7.5％，山东一滕新材料股份有限公司出品)30kg、非离子型聚丙烯酰胺2kg和阿拉伯胶2kg；
其中，羟乙基甲基纤维素由棉纤维素粉(平均聚合度为2745、粒径为0.230mm、松密度为175g/L)100kg、粒状氢氧化钠(粒径为0.7mm)18kg、氢氧化钠水溶液(质量浓度为50％)51kg、氯甲烷61kg和环氧乙烷6kg制得。
制备方法，具体包括以下步骤：
(1)按上述质量称取各原料；
(2)向有夹套的、搅拌中的、耐压为3.0MPa的反应器中依次加入棉纤维素粉、粒状氢氧化钠和氢氧化钠水溶液液碱，反应器排空并用氮气吹扫以除去氧气，再次排空，然后向反应器中依次加入醚化剂：环氧乙烷和氯甲烷，缓慢升温至60℃，压力为1.9MPa，反应1h，继续缓慢升温至80℃，压力为2.4MPa，反应1h，反应结束后降温卸压，回收未反应的醚化剂和副产物二甲醚(通过三级冷凝回收工艺回收未反应的醚化剂，一级直接卸压冷凝回收，反应器压力从2.4MPa卸压至0.75MPa；二级压缩冷凝回收，反应器压力从 0.75MPa卸压至0.1MPa；三级真空+压缩冷凝回收，反应器压力从0.1MPa卸压至-0.08MPa)，向反应器中加入醋酸调节物料的pH值6.5，再向反应器中加入8倍物料质量的90℃热水进行洗涤，以3000r/min的转速离心2h，以90℃的温度烘干2h，粉碎至粒径为0.15mm，得到羟乙基甲基纤维素纯品；
(3)将步骤(2)制得的羟乙基甲基纤维素纯品、羟丙基淀粉、非离子型聚丙烯酰胺和阿拉伯胶加入混料机中以50r/min的转速混合搅拌50min，即得增强型瓷砖胶用改性羟乙基甲基纤维素。
对比例3
增强型瓷砖胶用改性羟乙基甲基纤维素，由以下质量的原料制得：羟乙基甲基纤维素71kg、羟丙基淀粉(羟丙氧基含量为19.5％，5％B型LVT粘度1950cp，灰分7.5％，山东一滕新材料股份有限公司出品)25kg、聚乙烯醇2kg和卡拉胶2kg；
其中，羟乙基甲基纤维素由棉纤维素粉(平均聚合度为2668、粒径为0.230mm、松密度为175g/L)100kg、粒状氢氧化钠(粒径为0.7mm)17kg、氢氧化钠水溶液(质量浓度为50％)67kg、氯甲烷63kg和环氧乙烷12kg制得。
制备方法，具体包括以下步骤：
(1)按上述质量称取各原料；
(2)向有夹套的、搅拌中的、耐压为3.0MPa的反应器中依次加入棉纤维素粉、粒状氢氧化钠和氢氧化钠水溶液液碱，反应器排空并用氮气吹扫以除去氧气，再次排空，然后向反应器中依次加入醚化剂：环氧乙烷和氯甲烷，缓慢升温至60℃，压力为1.9MPa，反应1.5h，继续缓慢升温至80℃，压力为2.3MPa，反应0.5h，反应结束后降温卸压，回收未反应的醚化剂和副产物二甲醚(通过三级冷凝回收工艺回收未反应的醚化剂，一级直接卸压冷凝回收，反应器压力从2.3MPa卸压至1.1MPa；二级压缩冷凝回收，反应器压力从 1.1MPa卸压至0.25MPa；三级真空+压缩冷凝回收，反应器压力从0.25MPa卸压至-0.1MPa)，向反应器中加入醋酸调节物料的pH值6.5，再向反应器中加入8倍物料质量的90℃热水进行洗涤，以3000r/min的转速离心2h，以90℃的温度烘干2h，粉碎至粒径为0.15mm，得到羟乙基甲基纤维素纯品；
(3)将步骤(2)制得的羟乙基甲基纤维素纯品、羟丙基淀粉、聚乙烯醇和卡拉胶加入混料机中以50r/min的转速混合搅拌50min，即得增强型瓷砖胶用改性羟乙基甲基纤维素。
对比例4
增强型瓷砖胶用改性羟乙基甲基纤维素，由以下质量的原料制得：羟乙基甲基纤维素78kg、羟丙基淀粉(羟丙氧基含量为19.5％，5％B型LVT粘度1950cp，灰分7.5％，山东一滕新材料股份有限公司出品)20kg、聚氧化乙烯1kg和黄原胶1kg；
其中，羟乙基甲基纤维素由棉纤维素粉(平均聚合度为2436、粒径为0.230mm、松密度为175g/L)100kg、粒状氢氧化钠(粒径为0.7mm)44kg、氢氧化钠水溶液(质量浓度为50％)67kg、氯甲烷98kg和环氧乙烷35kg制得。
制备方法，具体包括以下步骤：
(1)按上述质量称取各原料；
(2)向有夹套的、搅拌中的、耐压为3.0MPa的反应器中依次加入棉纤维素粉、粒状氢氧化钠和氢氧化钠水溶液液碱，反应器排空并用氮气吹扫以除去氧气，再次排空，然后向反应器中依次加入醚化剂：环氧乙烷和氯甲烷，缓慢升温至60℃，压力为1.9MPa，反应1h，继续缓慢升温至80℃，压力为2.5MPa，反应1h，反应结束后降温卸压，回收未反应的醚化剂和副产物二甲醚(通过三级冷凝回收工艺回收未反应的醚化剂，一级直接卸压冷凝回收，反应器压力从2.5MPa卸压至1.1MPa；二级压缩冷凝回收，反应器压力从 1.1MPa卸压至0.25MPa；三级真空+压缩冷凝回收，反应器压力从0.25MPa卸压至-0.1MPa)，向反应器中加入醋酸调节物料的pH值6.5，再向反应器中加入8倍物料质量的90℃热水进行洗涤，以3000r/min的转速离心2h，以90℃的温度烘干2h，粉碎至粒径为0.15mm，得到羟乙基甲基纤维素纯品；
(3)将步骤(2)制得的羟乙基甲基纤维素纯品、羟丙基淀粉、聚氧化乙烯和黄原胶加入混料机中以50r/min的转速混合搅拌40min，即得增强型瓷砖胶用改性羟乙基甲基纤维素。
性能测试
1、分别对实施例1-4和对比例1-4步骤(2)中制得的羟乙基甲基纤维素纯品进行甲氧基含量、羟乙氧基含量、2％B型RVT粘度和灰分进行测定，结果如表1所示。
表1实施例1-4和对比例1-4羟乙基甲基纤维素纯品性能测试结果
Figure PCTCN2021086829-appb-000001
由表1可知，本发明实施例1-4制备的羟乙基甲基纤维素具有较高的甲氧基和羟乙氧基的总和含量，其总和含量范围为36-46％，明显高于对比例1-3制备的甲氧基和羟乙氧基总和含量范围为25-35％的羟乙基甲基纤维素，但又远低于对比例4制备的甲氧基和羟乙氧基总和含量约56％的羟乙基甲基纤维素。同时实施例2制备的羟乙基甲基纤维素具有较高的甲氧基含量和较低的羟乙氧基含量，而实施例4制备的羟乙基甲基纤维素具有较低的甲氧基含量 和较高的羟乙氧基含量。另外，实施例1-4和对比例1-4均具有接近的粘度范围和灰分含量。
2、各取少量实施例1-4和对比例1-4制得的改性羟乙基甲基纤维素分别进行增强型瓷砖胶的制备，方法为：分别按表2所示各组分投入混料机中混合均匀，加入各组分总重量的25％水，按照标准JC/T547-2005《陶瓷墙地砖胶粘剂》中规定的搅拌设备和搅拌方法进行搅拌，然后按照标准进行各项性能测试(滑移、拉伸粘结强度、浸水后拉伸粘结强度、热老化后拉伸粘结强度、冻融循环后拉伸粘结强度和晾置时间30min拉伸粘结强度)，测试结果如表3所示。
表2实施例1-4和对比例1-4瓷砖胶配方
Figure PCTCN2021086829-appb-000002
表3实施例1-4和对比例1-4瓷砖胶性能测试
Figure PCTCN2021086829-appb-000003
由表3可知，本发明实施例1-4制备的改性羟乙基甲基纤维素具有改善瓷砖胶的拉伸粘结强度性能，其中，拉伸粘结强度以及浸水后、热老化后和冻融循环后的拉伸粘结强度均达到了指标≥1.0Mpa的要求，而且满足瓷砖胶的抗滑移≤0.5mm和晾置时间30min拉伸粘结强度≥0.5Mpa的要求，且均优于对比例1-4对应的各项指标。其中，实施例2为最佳实施例。
以上试验说明，本发明工艺及设备简单，易于操作，无三废排出，绿色环保，所得改性羟乙基甲基纤维素产品质量稳定，具有改善瓷砖胶拉伸粘结强度的功能，应用于现代尺寸大、质量大的瓷砖，能够显著提高瓷砖使用的安全性，满足客户的需求。
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (10)

  1. 一种增强型瓷砖胶用改性羟乙基甲基纤维素，其特征在于，由以下质量百分比的原料制得：羟乙基甲基纤维素54％-94％、淀粉醚5％-40％、分散剂0.5％-3％和流变剂0.5％-3％；
    所述羟乙基甲基纤维素由质量比为1:(0.01-1.0):(0.02-2.1):(0.50-2.0):(0.01-1.2)的纤维素粉、粒碱、液碱、氯甲烷和环氧乙烷制得。
  2. 根据权利要求1所述的一种增强型瓷砖胶用改性羟乙基甲基纤维素，其特征在于，所述淀粉醚为一元淀粉醚、二元淀粉醚、三元淀粉醚中的任一种或几种的混合。
  3. 根据权利要求1所述的一种增强型瓷砖胶用改性羟乙基甲基纤维素，其特征在于，所述分散剂为聚丙烯酰胺、聚乙烯醇、聚氧化乙烯中的任一种或几种的混合。
  4. 根据权利要求1所述的一种增强型瓷砖胶用改性羟乙基甲基纤维素，其特征在于，所述流变剂为瓜尔胶、阿拉伯胶、卡拉胶、黄原胶中的任一种或几种的混合。
  5. 根据权利要求1所述的一种增强型瓷砖胶用改性羟乙基甲基纤维素，其特征在于，所述纤维素粉为棉纤维素、木纤维素、竹纤维素、秸秆纤维素中的任一种或几种的混合；
    所述纤维素粉的聚合度为500-8000；
    所述纤维素粉的粒径为0.18-0.30mm；
    所述纤维素粉的松密度为150-200g/L。
  6. 根据权利要求1所述的一种增强型瓷砖胶用改性羟乙基甲基纤维素，其特征在于，所述粒碱为粒状碱金属氢氧化物；
    所述碱金属氢氧化物为氢氧化钠和/或氢氧化钾；
    所述粒碱的粒径为0.3-2.0mm。
  7. 根据权利要求1所述的一种增强型瓷砖胶用改性羟乙基甲基纤维素，其特征在于，所述液碱为碱金属氢氧化物的水溶液；
    所述碱金属氢氧化物为氢氧化钠和/或氢氧化钾；
    所述液碱中碱金属氢氧化物的质量浓度为40％-60％。
  8. 一种增强型瓷砖胶用改性羟乙基甲基纤维素的制备方法，其特征在于，具体包括以下步骤：
    (1)按权利要求1-7任一项所述增强型瓷砖胶用改性羟乙基甲基纤维素的质量比称取各原料；
    (2)将纤维素粉、粒碱、液碱、氯甲烷和环氧乙烷混合，依次进行醚化反应、中和、洗涤、离心、干燥和粉碎，得到羟乙基甲基纤维素；
    (3)将羟乙基甲基纤维素、淀粉醚、分散剂和流变剂进行混合搅拌，即得所述增强型瓷砖胶用改性羟乙基甲基纤维素。
  9. 根据权利要求8所述的一种增强型瓷砖胶用改性羟乙基甲基纤维素的制备方法，其特征在于，步骤(2)中，所述醚化反应分为一阶段醚化反应和二阶段醚化反应；
    所述一阶段醚化反应的压力为1.8-2.0MPa，温度为55-65℃，时间为0.5-1.5h；
    步骤(2)中，所述二阶段醚化反应的压力为2.3-2.5MPa，温度为75-85℃，时间为0.5-1.5h；
    步骤(3)中，所述混合搅拌的转速为10-70r/min，时间为40-60min。
  10. 一种如权利要求1所述增强型瓷砖胶用改性羟乙基甲基纤维素在制备增强型瓷砖胶中的应用，其特征在于，所述增强型瓷砖胶用改性羟乙基甲基纤维素占所述增强型瓷砖胶的质量百分比为0.2％-0.5％。
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