Preparation method of modified starch ether for improving anti-sliding property of ceramic tile adhesive

Abstract

The present disclosure relates to the technical field of building additives, and in particular to a preparation method of modified starch ether for improving the anti-sliding property of a ceramic tile adhesive. The preparation method includes chemical modification of subjecting starch to one-step etherification to obtain starch ether, followed by physical modification. In the preparation method, the cumbersome multi-step etherification in existing methods for preparing modified starch ether is avoided, and only one-step etherification is used to obtain modified starch ether of better properties. Because physical modification is added, the obtained product can significantly improve the anti-sliding property of a ceramic tile adhesive. Moreover, the conditions for one-step etherification are significantly different from the prior art.

Claims

1. A preparation method of modified starch ether for improving the anti-sliding property of a ceramic tile adhesive, comprising chemical modification of subjecting starch to one-step etherification to obtain starch ether, followed by physical modification; wherein, the chemical modification of one-step etherification comprises: mixing tapioca starch, an alkalizer, an alcohol and an inhibitor to form a mixture, into which an etherifying agent is added; and subjecting the mixture to etherification, which is initially conducted at a lowered temperature of 10 to 20° C. for 1.5 to 2.5 hours, and then conducted in stages at different raised temperatures, comprising a stage at 40° C. for a period of 2.5 to 3 hours and a further stage at 60° for a period of 4 to 5 hours; wherein, the tapioca starch, the alkalizer and the etherifying agent are used in the onestep etherification at a mass ratio of 1:(0.01-1):(0.02-1.2); wherein, the etherifying agent is a mixture of propylene oxide and ethylene oxide, or a mixture of chloroacetic acid, propylene oxide, and ethylene oxide; and wherein, the tapioca starch and the alcohol are used in the one-step etherification at a mass ratio of 1:(0.1-0.3); and wherein, the physical modification is conducted by mixing the starch ether with an thickener and a rheological agent for 40 min to 60 min; wherein, the thickener is hydroxypropyl methyl cellulose and/or hydroxyethyl methyl cellulose, the rheological agent is one or more of guar gum, carrageenan and xanthan gum, and the starch ether, the thickener and the rheological agent, in percentage by weight, are 20% to 30%, 64% to 76%, and 4% to 6%, respectively.

2. The preparation method of modified starch ether for improving the anti-sliding property of a ceramic tile adhesive according to claim 1, wherein the alkalizer is alkali metal hydroxide powder; the alcohol is one or more of methanol, ethanol, isopropanol, n-butanol, tertbutanol, and diethylene glycol; and the inhibitor is an alkali metal salt.

3. The preparation method of modified starch ether for improving the anti-sliding property of a ceramic tile adhesive according to claim 1, wherein the alkalizer is NaOH and/or KOH; the alcohol is ethanol and/or isopropanol; and the inhibitor is Na.sub.2SO.sub.4 and/or NaCl.

4. The preparation method of modified starch ether for improving the anti-sliding property of a ceramic tile adhesive according to claim 1, wherein the alkalizer is NaOH; the alcohol is ethanol; and the inhibitor is Na.sub.2SO.sub.4.

5. The preparation method of modified starch ether for improving the anti-sliding property of a ceramic tile adhesive according to claim 1, wherein the tapioca starch and the inhibitor are used in the one-step etherification at a mass ratio of 1:(0.05-0.1).

6. A modified starch ether for improving the anti-sliding property of a ceramic tile adhesive formed by: chemical modification of subjecting starch to one-step etherification to obtain starch ether, followed by physical modification, wherein, the chemical modification of one-step etherification comprises: mixing tapioca starch, an alkalizer, an alcohol and an inhibitor to form a mixture, into which an etherifying agent is added; and subjecting the mixture to etherification, which is initially conducted at a lowered temperature of 10 to 20° C. for 1.5 to 2.5 hours, and then conducted in stages at different raised temperatures, comprising a stage at 40° C. for a period of 2.5 to 3 hours and a further stage at 60° for a period of 4 to 5 hours; wherein, the tapioca starch, the alkalizer and the etherifying agent are used in the one step etherification at a mass ratio of 1:(0.01-1):(0.02-1.2); wherein, the etherifying agent is a mixture of propylene oxide and ethylene oxide, or a mixture of chloroacetic acid, propylene oxide, and ethylene oxide; and wherein, the tapioca starch and the alcohol are used in the one-step etherification at a mass ratio of 1:(0.1-0.3); and wherein, the physical modification is conducted by mixing the starch ether with an thickener and a rheological agent for 40 min to 60 min; wherein, the thickener is hydroxypropyl methyl cellulose and/or hydroxyethyl methyl cellulose, the rheological agent is one or more of guar gum, carrageenan and xanthan gum, and the starch ether, the thickener and the rheological agent, in percentage by weight, are 20% to 30%, 64% to 76%, and 4% to 6%, respectively.

7. The modified starch ether of claim 6, wherein the alkalizer is alkali metal hydroxide powder; the alcohol is one or more of methanol, ethanol, isopropanol, n-butanol, tertbutanol, and diethylene glycol; and the inhibitor is an alkali metal salt.

8. The modified starch ether of claim 6, wherein the alkalizer is NaOH and/or KOH; the alcohol is ethanol and/or isopropanol; and the inhibitor is Na.sub.2SO.sub.4 and/or NaCl.

9. The modified starch ether of claim 6, wherein the alkalizer is NaOH; the alcohol is ethanol; and the inhibitor is Na.sub.2SO.sub.4.

10. The modified starch ether of claim 6, wherein the tapioca starch and the inhibitor are used in the one-step etherification at a mass ratio of 1:(0.05-0.1).

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a flowchart of a process according to the present disclosure;

(2) FIG. 2 is an isosbestic plot for the measuring wavelengths and reference wavelengths of amylose and amylopectin;

(3) FIG. 3 is a structural diagram of carboxymethyl hydroxypropyl hydroxyethyl starch obtained by chemical modification of the present disclosure;

(4) FIG. 4 is a structural diagram of carboxymethyl hydroxypropyl starch obtained by chemical modification of the present disclosure; and

(5) FIG. 5 is a structural diagram of hydroxypropyl hydroxyethyl starch obtained by chemical modification of the present disclosure.

DETAILED DESCRIPTION

(6) In order to clearly explain the technical features of the solution, the present disclosure will be described in detail below through specific implementations with reference to accompanying drawings.

(7) The content of amylose, amylopectin and total starch in the raw starch used in each example is determined by the dual-wavelength colorimetry.

(8) 1) Preparation of Reagents

(9) Iodine reagent: 2.000 (±0.005) g of potassium iodide is weighed and dissolved in an appropriate amount of distilled water to obtain a saturated solution, and then 0.200 (±0.001) g of iodine is added. After iodine is completely dissolved, the solution is transferred to a 100 mL volumetric flask and precisely diluted to 100 mL with distilled water. This reagent is prepared just before use and stored in the dark.

(10) Amylose standard solution: 0.1000 g of amylose standards is weighed and added to a 50 mL beaker, and a few drops of anhydrous ethanol are added to wet amylose. Then 10 mL of 0.5 mol/L KOH solution is added. After amylose is completely dissolved at 80 (±1)° C. under a water bath, the resulting solution is precisely diluted to 100 mL with distilled water. A 1 mg/mL amylose standard solution is obtained. 1 mL of 1 mg/mL amylose standard solution is added to a 50 mL volumetric flask, and 30 mL of distilled water is added. The pH of the solution is adjusted to 3.0 with a 0.1 mol/L HCL solution, and then 0.5 mL of iodine reagent is added. The resulting solution is precisely diluted to 50 mL with distilled water, and then stands for 20 min With distilled water including 0.1 mol/L HCL and iodine reagent as blank, ultraviolet-visible spectroscopy is performed on the amylose standard solution at a wavelength range of 400 nm to 900 nm to obtain an absorption curve for amylose. 0 mL, 0.3 mL, 0.6 mL, 0.9 mL, 1.2 mL, 1.5 mL and 1.8 mL of 1 mg/mL amylose standard solution are respectively added to 50 mL volumetric flasks, and 20 mL to 30 mL of distilled water is added to each flask. The pH of each solution is adjusted to 3.0 with 0.1 mol/L HCL, and then 0.5 mL of iodine reagent is added. The resulting solutions are precisely diluted to 50 mL and thoroughly mixed to obtain a series of standard solutions at concentrations of 0 μg/mL, 6 μg/mL, 12 μg/mL, 18 μg/mL, 24 μg/mL, 30 μg/mL and 36 μg/mL.

(11) Amylopectin standard solution: 0.1000 g of amylopectin standards is weighed, and then a 1 mg/mL amylopectin standard solution is prepared according to the preparation method of amylose standard solution. 3 mL of 1 mg/mL amylopectin standard solution is added to a 50 mL volumetric flask, and the subsequent operations are the same as that for amylose. An absorption curve within the visible spectrum is obtained in the same coordinate system for amylopectin. 0 mL, 2.0 mL, 2.5 mL, 3.0 mL, 3.5 mL, 4.0 mL, 4.5 mL and 5.0 mL of 1 mg/mL amylopectin standard solution are used to prepare a series of amylopectin standard solutions at concentrations of 0 μg/mL, 40 μg/mL, 50 μg/mL, 60 μg/mL, 70 μg/mL, 80 μg/mL, 90 μg/mL and 100 μg/mL.

(12) The measuring wavelength λ1 and reference wavelength λ2 of amylose and the measuring wavelength λ3 and reference wavelength λ4 of amylopectin are determined according to an isosbestic plot (see FIG. 2). With distilled water as blank, Aλ1 and Aλ2 are measured at λ1 and λ2 respectively, and Δ.sub.Aamylose is calculated as: Δ.sub.Aamylose=Aλ1−Aλ2; and with Δ.sub.Aamylose as y-coordinate and amylose concentration (μg/mL) as x-coordinate, a dual wavelength amylose standard curve is plotted, and a regression equation is obtained for amylose. With distilled water as blank, Aλ3 and Aλ4 are measured at λ3 and λ4 respectively, and Δ.sub.Aamylopectin is calculated as: Δ.sub.Aamylopectin=Aλ3−Aλ4; and with Δ.sub.Aamylopectin as y-coordinate and amylose concentration (μg/mL) as x-coordinate, a dual wavelength amylopectin standard curve is plotted, and a regression equation is obtained for amylopectin.

(13) 2) Treatment of Samples and Preparation of Sample Solutions

(14) An air-dried starch sample is ground and screened by a 0.180 mm sieve. The treated sample is dried in a blast drying oven at 105 (±1)° C., and then moisture content of the test raw sample is determined as W1(%). The dried sample is put into the Soxhlet extractor. Diethyl ether is first added, and the resulting mixture is heated to reflux for 3 h of defatting. Then 85% ethanol is added, and the resulting mixture is heated to reflux for 3 h of desugarization. The product is dried in a blast drying oven at 105 (±1)° C., cooled, and weighed to obtain a constant weight. The fat and sugar content W2(%) is determined.

(15) 0.1000 g±0.0050 g of defatted and desugared sample is weighed and added to a 50 mL beaker, and a few drops of anhydrous ethanol are added to wet the sample. 10 mL of 0.5 mol/L KOH solution is added, and the sample is dispersed and dissolved for 10 min at 80 (±1)° C. under a water bath. The resulting solution is precisely diluted to 50.00 mL with distilled water and thoroughly mixed. Two sample solutions each of 2.50 mL (i.e., sample solution and sample blank solution) are added to respective volumetric flasks. 20 mL to 30 mL of distilled water is added to each flask, and the pH is adjusted to 3.0 with 0.1 mol/L HCL. 0.5 ml of iodine reagent is added to the sample solution, but no iodine reagent is added to the sample blank solution. The two solutions are precisely diluted to 50.00 mL, thoroughly mixed, stand for 20 min. The sample blank solution is adopted as a colorimetric reference.

(16) 3) Determination of Samples and Calculation of Results

(17) With distilled water as blank, the absorbance values are determined with 1 cm cuvettes, and then the amylose concentration C.sub.amylose (μg/mL) and amylopectin concentration C.sub.amylopectin (μg/mL) in the sample solution are calculated according to the regression equation. The amylose content, amylopectin content and total starch content are calculated according to formula (1), formula (2) and formula (3) respectively:

(18) $\begin{matrix} Amylose (%) = \frac{C_{amylose} \times 50 \times 50 \times (1 - W_{1} - W_{2})}{2.5 \times m \times 1000000} \times 100 & (1) \\ Amylopectin (%) = \frac{\begin{matrix} C_{amylopectin} \times 50 \times 50 \times \\ (1 - W_{1} - W_{2}) \end{matrix}}{2.5 \times m \times 1000000} \times 100 & (2) \\ Starch (%) = Amylose (%) + Amylopectin (%) & (3) \end{matrix}$

(19) In the formula, 50 and 50 represent the final volumes of sample solution and test solution (mL) respectively, 2.5 is the volume of sample solution (mL) pipetted for the preparation of a test solution, m is the mass of the defatted and desugared sample (g) weighed for the preparation of a sample solution, W1 is the moisture content of the raw sample (%), and W2 is the fat and sugar content (%).

(20) Degree of substitution (DS) by carboxymethyl in the starch ether prepared in each of examples and comparative examples is determined by the following method.

(21) The fully-washed starch ether sample without Cl.sup.− is dried, slowly heated to 700° C. in a muffle furnace, and burned for 1 h to completely ash the sample and quantitatively convert it to Na.sub.2O. The ash is dissolved in a sulfuric acid standard solution for quantification, and then excess sulfuric acid is titrated with a NaOH standard solution. Degree of substitution by carboxymethyl of starch ether is calculated according to formula (4):
DS=0.162B/(1−0.08B) (4)

(22) In formula (4), B is the millimolar quantity of ½H.sub.2SO.sub.4 consumed per gram of sample, and it is calculated according to formula (5):
B=(C(½H.sub.2SO.sub.4)×V(½H.sub.2SO.sub.4)−C NaOH×V NaOH)/W (5)

(23) In formula (5),

(24) C(½H.sub.2SO.sub.4): molar concentration of the sulfuric acid used, mol/L;

(25) V(½H.sub.2SO.sub.4): volume of the sulfuric acid used, mL;

(26) C NaOH: molar concentration of the sodium hydroxide solution used, mol/L;

(27) V NaOH: volume of the sodium hydroxide solution used, mL; and

(28) W: mass of the starch ether sample dried to constant weight, g.

(29) The content of methoxy and hydroxyalkoxy in starch ether and cellulose ether prepared in examples and comparative examples is determined according to methods for determining the content of groups in cellulose ether in Appendix D of JC/T2190-2013 “Cellulose Ether for the Dry-Mixed Mortar”. Alkoxy and hydroxyalkoxy are quantitatively cleaved by hydroiodic acid under the catalyzation of adipic acid, and then the content of alkoxy and hydroxyalkoxy in starch ether and cellulose ether is determined by gas chromatography.

(30) The viscosity of starch ether prepared in each example is measured in a 5% aqueous solution at 20° C. with an NDJ-1 viscometer, and the viscosity of cellulose ether is measured in a 2% aqueous solution at 20° C. with a B-type RVT viscometer.

Example 1

(31) A preparation method of modified starch ether for improving the anti-sliding property of a ceramic tile adhesive includes the following steps: Chemical modification: starch was etherified, dried and ground.

(32) Tapioca starch, NaOH, ethanol and Na.sub.2SO.sub.4 were added to a jacketed reactor with a stirrer in sequence. The reactor was evacuated and purged with nitrogen to remove oxygen, and then evacuated once again. Chloroacetic acid, propylene oxide and ethylene oxide were added, and then etherification was conducted at 20° C. for 1.5 h, then at 40° C. for 2.5 h, and then at 60° C. for 4 h. At the end of reaction, ethanol was recovered, and the product was dried and ground.

(33) The tapioca starch, sodium hydroxide, chloroacetic acid, propylene oxide and ethylene oxide were used at a mass ratio of 1:0.09:0.10:0.12:0.02.

(34) The tapioca starch and Na.sub.2SO.sub.4 were used at a mass ratio of 1:0.05.

(35) The tapioca starch and ethanol were used at a mass ratio of 1:0.3.

(36) The tapioca starch includes 17.32% of amylose, 68.73% of amylopectin, and 86.05% of total starch. The prepared carboxymethyl hydroxypropyl hydroxyethyl starch has a structure shown in FIG. 3, a degree of substitution by carboxymethyl of 0.17, and a viscosity of 8,000 cp in a 5% aqueous solution, and includes 12.5% of hydroxypropoxy, 2.5% of hydroxyethoxy, and 16% of ash.

(37) (2) Physical modification: the starch ether obtained in step (1), hydroxypropyl methyl cellulose (methoxy content: 28.0% to 30.0%, hydroxypropoxy content: 7.5% to 12.0%, viscosity measured in a 2% aqueous solution with a B-type RVT viscometer: 60,000 cp, purchased from Shandong Yiteng New Materials Co., Ltd.) and guar gum were mixed.

(38) The carboxymethyl hydroxypropyl hydroxyethyl starch obtained in step (1), thickener and rheological agent were added to a blender for 40 min to 60 min of mixing to obtain modified carboxymethyl hydroxypropyl hydroxyethyl starch.

(39) The carboxymethyl hydroxypropyl hydroxyethyl starch, thickener and rheological agent were used at a mass percentage content of 30%, 65% and 5% respectively.

(40) The modified carboxymethyl hydroxypropyl hydroxyethyl starch prepared by the preparation method of Example 1 was used for the preparation of a ceramic tile adhesive. Components shown in Table 1 were added to a blender and thoroughly mixed, and then 26% of water, based on the total weight of all components, was added. The resulting mixture was mixed with the mixing equipment and mixing method required in JC/T547-2005 “Ceramic Tile Adhesive”, and various performance tests were conducted according to the standard. The results are shown in Table 2.

Comparative Example 1

(41) A preparation method of modified starch ether for improving the anti-sliding property of a ceramic tile adhesive includes the following steps: YT-A03 hydroxypropyl starch (purchased from Shandong Yiteng New Materials Co., Ltd., hydroxypropoxy content: 18.0% to 21.0%, viscosity measured in a 5% aqueous solution: 3,000 cp to 4,000 cp, ash content: custom character 10%) was used without chemical modification. The ordinary starch ether in step (1), thickener and rheological agent were mixed.

(42) YT-A03 hydroxypropyl starch in step (1), thickener and rheological agent were added to a blender for 40 min to 60 min of mixing to obtain 1# modified hydroxypropyl starch.

(43) YT-A03 hydroxypropyl starch, thickener and rheological agent were used at the same mass percentage content as that in Example 1. The thickener and rheological agent were the same as in Example 1.

(44) The modified starch ether prepared in Comparative Example 1 was used for the preparation of a ceramic tile adhesive. Components shown in Table 1 were added to a blender and thoroughly mixed, and then 26% of water, based on the total weight of all components, was added. The resulting mixture was mixed with the mixing equipment and mixing method required in JC/T547-2005 “Ceramic Tile Adhesive”, and various performance tests were conducted according to the standard. The results are shown in Table 2.

(45) TABLE-US-00001 TABLE 1 The formulas for ceramic tile adhesives using the products of Example 1 and Comparative Example 1 Component Comparative Example 1 Example 1 Cement 42.5 400 g 400 g Fine sand 450 g 450 g Heavy calcium carbonate 121.5 g 121.5 g Redispersible latex powder 20 g 20 g Calcium formate 3.5 g 3.5 g Lignocellulose 1 g 1 g 1# modified hydroxypropyl 4 g starch Modified carboxymethyl 4 g hydroxypropyl hydroxyethyl starch

(46) TABLE-US-00002 TABLE 2 Properties for ceramic tile adhesives using the products of Example 1 and Comparative Example 1 Original Tensile adhesive Tensile adhesive Tensile adhesive tensile strength after strength after strength after a adhesive soaking in thermal cycle of freezing Example Sliding strength/MPa water/MPa aging/MPa and thawing/MPa Comparative no sliding for 200 1.018 0.655 0.822 0.764 Example 1 g ceramic tile, 3 mm of sliding for 500 g ceramic tile Example 1 no sliding for 200 1.056 0.680 0.866 0.818 g ceramic tile, 0.1 mm of sliding for 500 g ceramic tile

(47) It can be seen from Table 2 that the modified carboxymethyl hydroxypropyl hydroxyethyl starch prepared in the present disclosure can improve the anti-sagging property of a ceramic tile adhesive, making the anti-sliding property meet the requirement of sliding custom character 0.5 mm. Moreover, other requirements for the binding property of a ceramic tile adhesive are met. The ceramic tile adhesive of the present disclosure is even superior to the ceramic tile adhesive including 1# modified hydroxypropyl starch in terms of properties, such as the original tensile adhesive strength, the tensile adhesive strength after soaking in water, the tensile adhesive strength after thermal aging and the tensile adhesive strength after a cycle of freezing and thawing in Table 2.

Example 2

(48) A preparation method of modified starch ether for improving the anti-sliding property of a ceramic tile adhesive includes the following steps: Another starch ether of the present disclosure was prepared according to the description in step (1) of Example 1 except that the etherifying agents were chloroacetic acid and propylene oxide, starch, sodium hydroxide, chloroacetic acid and propylene oxide were used at a mass ratio of 1:0.09:0.10:0.12, and etherification was conducted at 40° C. for 3 h, and then at 60° C. for 5 h.

(49) The raw starch includes 17.23% of amylose, 68.78% of amylopectin, and 86.01% of total starch. The prepared carboxymethyl hydroxypropyl starch has a structure shown in FIG. 4, a degree of substitution by carboxymethyl of 0.16, and a viscosity of 7,000 cp in a 5% aqueous solution, and includes 12.6% of hydroxypropoxy and 16% of ash.

(50) (2) Physical modification: the starch ether obtained in step (1), thickener and rheological agent were mixed.

(51) The carboxymethyl hydroxypropyl starch obtained in step (1), thickener and rheological agent were added to a blender for 40 min to 60 min of mixing to obtain modified carboxymethyl hydroxypropyl starch.

(52) The carboxymethyl hydroxypropyl starch obtained in step (1) of Example 2, thickener and rheological agent were used at a mass percentage content of 25%, 70% and 5% respectively.

(53) The thickener was hydroxypropyl methyl cellulose (methoxy content: 19.0% to 24.0%, hydroxypropoxy content: 4.0% to 12.0%, viscosity measured in a 2% aqueous solution with a B-type RVT viscometer: 50,000 cp, purchased from Shandong Yiteng New Materials Co., Ltd.); and the rheological agent was xanthan gum.

(54) The modified carboxymethyl hydroxypropyl starch prepared in Example 2 was used for the preparation of a ceramic tile adhesive. Components shown in Table 3 were added to a blender and thoroughly mixed, and then 26% of water, based on the total weight of all components, was added. The resulting mixture was mixed with the mixing equipment and mixing method required in JC/T547-2005 “Ceramic Tile Adhesive”, and various performance tests were conducted according to the standard. The results are shown in Table 4.

Comparative Example 2

(55) A preparation method of modified starch ether for improving the anti-sliding property of a ceramic tile adhesive includes the following steps: YT-B03 hydroxypropyl starch (purchased from Shandong Yiteng New Materials Co., Ltd., hydroxypropoxy content: 11.0% to 14.0%, viscosity measured in a 5% aqueous solution: 3,000 cp to 4,000 cp, ash content: custom character 10%) was used without chemical modification. The starch ether in step (1), thickener and rheological agent were mixed.

(56) YT-B03 hydroxypropyl starch, thickener and rheological agent were added to a blender for 40 min to 60 min of mixing to obtain 2# modified hydroxypropyl starch.

(57) YT-B03 hydroxypropyl starch, thickener and rheological agent were used at the same mass percentage content as that in Example 2.

(58) The thickener and rheological agent were the same as in Example 2.

(59) The 2# modified hydroxypropyl starch prepared in Comparative Example 2 was used for the preparation of a ceramic tile adhesive. Components shown in Table 3 were added to a blender and thoroughly mixed, and then 26% of water, based on the total weight of all components, was added. The resulting mixture was mixed with the mixing equipment and mixing method required in JC/T547-2005 “Ceramic Tile Adhesive”, and various performance tests were conducted according to the standard. The results are shown in Table 4.

(60) TABLE-US-00003 TABLE 3 The formulas for ceramic tile adhesives using the products of Example 2 and Comparative Example 2 Component Comparative Example 2 Example 2 Cement 42.5 400 g 400 g Fine sand 450 g 450 g Heavy calcium carbonate 121.5 g 121.5 g Redispersible latex powder 20 g 20 g Calcium formate 3.5 g 3.5 g Lignocellulose 1 g 1 g 2# modified hydroxypropyl 4 g starch Modified carboxymethyl 4 g hydroxypropyl starch

(61) TABLE-US-00004 TABLE 4 Properties for ceramic tile adhesives using the products of Example 2 and Comparative Example 2 Original Tensile adhesive Tensile adhesive Tensile adhesive tensile strength after strength after strength after a adhesive soaking in thermal cycle of freezing Example Sliding strength/MPa water/MPa aging/MPa and thawing/MPa Comparative 0.3 mm of sliding 0.948 0.595 0.784 0.729 Example 2 for 200 g ceramic tile Example 2 no sliding for 200 1.006 0.642 0.825 0.786 g ceramic tile, 0.3 mm of sliding for 500 g ceramic tile

(62) It can be seen from Table 4 that the modified carboxymethyl hydroxypropyl starch prepared in the present disclosure can improve the anti-sagging property of a ceramic tile adhesive, making the anti-sliding property meet the requirement of sliding custom character 0.5 mm. Moreover, other requirements for the binding property of a ceramic tile adhesive are met. The ceramic tile adhesive of the present disclosure is even superior to the ceramic tile adhesive including 2# modified hydroxypropyl starch in terms of properties, such as the original tensile adhesive strength, the tensile adhesive strength after soaking in water, the tensile adhesive strength after thermal aging and the tensile adhesive strength after a cycle of freezing and thawing in Table 4.

Example 3

(63) A preparation method of modified starch ether for improving the anti-sliding property of a ceramic tile adhesive includes the following steps: Another starch ether of the present disclosure was prepared according to the description in step (1) of Example 1 except that the etherifying agents were propylene oxide and ethylene oxide, starch, sodium hydroxide, propylene oxide and ethylene oxide were used at a mass ratio of 1:0.02:0.12:0.05, and etherification was conducted at 20° C. for 2.5 h, at 40° C. for 2.5 h, and at 60° C. for 4 h.

(64) The raw starch includes 17.16% of amylose, 68.73% of amylopectin, and 85.89% of total starch. The prepared hydroxypropyl hydroxyethyl starch is named as 1# hydroxypropyl hydroxyethyl starch. 1# hydroxypropyl hydroxyethyl starch has a structure shown in FIG. 5 and a viscosity of 7,000 cp in a 5% aqueous solution, and includes 12.5% of hydroxypropoxy, 6.5% of hydroxyethoxy, and 8% of ash.

(65) (2) Physical modification: the 1# hydroxypropyl hydroxyethyl starch in step (1), thickener and rheological agent were mixed.

(66) The 1# hydroxypropyl hydroxyethyl starch, thickener and rheological agent were added to a blender for 40 min to 60 min of mixing to obtain 1# modified hydroxypropyl hydroxyethyl starch.

(67) The starch ether, thickener and rheological agent were used at a mass percentage content of 30%, 65% and 5% respectively.

(68) The thickener was hydroxyethyl methyl cellulose (methoxy content: 19.0% to 24.0%, hydroxypropoxy content: 4.0% to 12.0%, viscosity measured in a 2% aqueous solution with a B-type RVT viscometer: 60,000 cp, purchased from Shandong Yiteng New Materials Co., Ltd.); and the rheological agent was carrageenan.

(69) The 1# modified hydroxypropyl hydroxyethyl starch prepared in Example 3 was used for the preparation of a ceramic tile adhesive. Components shown in Table 5 were added to a blender and thoroughly mixed, and then 26% of water, based on the total weight of all components, was added. The resulting mixture was mixed with the mixing equipment and mixing method required in JC/T547-2005 “Ceramic Tile Adhesive”, and various performance tests were conducted according to the standard. The results are shown in Table 6.

Comparative Example 3

(70) A preparation method of modified starch ether for improving the anti-sliding property of a ceramic tile adhesive includes the following steps: YT-A03 hydroxypropyl starch (purchased from Shandong Yiteng New Materials Co., Ltd., hydroxypropoxy content: 18.0% to 21.0%, viscosity measured in a 5% aqueous solution: 3,000 cp to 4,000 cp, ash content: custom character 10%) was used without chemical modification. The starch ether in step (1), thickener and rheological agent were mixed.

(71) YT-A03 hydroxypropyl starch, thickener and rheological agent were added to a blender for 40 min to 60 min of mixing to obtain 3# modified hydroxypropyl starch.

(72) YT-A03 hydroxypropyl starch, thickener and rheological agent were used at the same mass percentage content as that in Example 3.

(73) The thickener and rheological agent were the same as in Example 3.

(74) The 3# modified hydroxypropyl starch prepared in Comparative Example 3 was used for the preparation of a ceramic tile adhesive. Components shown in Table 5 were added to a blender and thoroughly mixed, and then 26% of water, based on the total weight of all components, was added. The resulting mixture was mixed with the mixing equipment and mixing method required in JC/T547-2005 “Ceramic Tile Adhesive”, and various performance tests were conducted according to the standard. The results are shown in Table 6.

(75) TABLE-US-00005 TABLE 5 The formulas for ceramic tile adhesives using the products of Example 3 and Comparative Example 3 Component Comparative Example 3 Example 3 Cement 42.5 400 g 400 g Fine sand 450 g 450 g Heavy calcium carbonate 121.5 g 121.5 g Redispersible latex powder 20 g 20 g Calcium formate 3.5 g 3.5 g Lignocellulose 1 g 1 g 3# modified hydroxypropyl 4 g starch 1# modified hydroxypropyl 4 g hydroxyethyl starch

(76) TABLE-US-00006 TABLE 6 Properties for ceramic tile adhesives using the products of Example 3 and Comparative Example 3 Original Tensile adhesive Tensile adhesive Tensile adhesive tensile strength after strength after strength after a adhesive soaking in thermal cycle of freezing Example Sliding strength/MPa water/MPa aging/MPa and thawing/MPa Comparative 0.4 mm of 1.008 0.624 0.802 0.736 Example 3 sliding for 200 g ceramic tile Example 3 no sliding for 1.066 0.675 0.846 0.772 200 g ceramic tile, 0.4 mm of sliding for 500 g ceramic tile

(77) It can be seen from Table 6 that the 1# modified hydroxypropyl hydroxyethyl starch prepared in the present disclosure can improve the anti-sagging property of a ceramic tile adhesive, making the anti-sliding property meet the requirement of sliding custom character 0.5 mm. Moreover, other requirements for the binding property of a ceramic tile adhesive are met. The ceramic tile adhesive of the present disclosure is even superior to the ceramic tile adhesive including 3# modified hydroxypropyl starch in terms of properties, such as the original tensile adhesive strength, the tensile adhesive strength after soaking in water, the tensile adhesive strength after thermal aging and the tensile adhesive strength after a cycle of freezing and thawing in Table 6.

Example 4

(78) A preparation method of modified starch ether for improving the anti-sliding property of a ceramic tile adhesive includes the following steps: 1. Another starch ether of the present disclosure was prepared according to the description in step (1) of Example 1 except that the etherifying agents were propylene oxide and ethylene oxide, starch, sodium hydroxide, propylene oxide and ethylene oxide were used at a mass ratio of 1:0.02:0.18:0.02, and etherification was conducted at 20° C. for 2 h, at 40° C. for 3 h, and at 60° C. for 5 h.

(79) The raw starch includes 17.19% of amylose, 68.78% of amylopectin, and 85.97% of total starch. The prepared hydroxypropyl hydroxyethyl starch is named as 2# hydroxypropyl hydroxyethyl starch. 2# hydroxypropyl hydroxyethyl starch has a structure shown in FIG. 5 and a viscosity of 3,500 cp in a 5% aqueous solution, and includes 16.5% of hydroxypropoxy, 2.5% of hydroxyethoxy, and 8% of ash.

(80) (2) Physical modification: the starch ether obtained in step (1), thickener and rheological agent were mixed.

(81) The 2# hydroxypropyl hydroxyethyl starch, thickener and rheological agent were added to a blender for 40 min to 60 min of mixing to obtain 2# modified hydroxypropyl hydroxyethyl starch.

(82) The 2# hydroxypropyl hydroxyethyl starch, thickener and rheological agent were used at a mass percentage content of 20%, 75% and 5% respectively.

(83) The thickener was hydroxyethyl methyl cellulose (methoxy content: 19.0% to 24.0%, hydroxypropoxy content: 4.0% to 12.0%, viscosity measured in a 2% aqueous solution with a B-type RVT viscometer: 40,000 cp, purchased from Shandong Yiteng New Materials Co., Ltd.); and the rheological agent was guar gum.

(84) The 2# modified hydroxypropyl hydroxyethyl starch prepared in Example 4 was used for the preparation of a ceramic tile adhesive. Components shown in Table 7 were added to a blender and thoroughly mixed, and then 26% of water, based on the total weight of all components, was added. The resulting mixture was mixed with the mixing equipment and mixing method required in JC/T547-2005 “Ceramic Tile Adhesive”, and various performance tests were conducted according to the standard. The results are shown in Table 8.

b. Comparative Example 4

(85) A preparation method of modified starch ether for improving the anti-sliding property of a ceramic tile adhesive includes the following steps: YT-B03 hydroxypropyl starch (purchased from Shandong Yiteng New Materials Co., Ltd., hydroxypropoxy content: 11.0% to 14.0%, viscosity measured in a 5% aqueous solution: 3,000 cp to 4,000 cp, ash content: custom character 10%) was used without chemical modification. The starch ether in step (1), thickener and rheological agent were mixed.

(86) YT-B03 hydroxypropyl starch, thickener and rheological agent were added to a blender for 40 min to 60 min of mixing to obtain 4# modified hydroxypropyl starch.

(87) YT-B03 hydroxypropyl starch, thickener and rheological agent were used at the same mass percentage content as that in Example 4.

(88) The starch ether was the hydroxypropyl starch described in step (1) of Comparative Example 4. The thickener and rheological agent were the same as in Example 4.

(89) The 4# modified hydroxypropyl starch prepared in Comparative Example 4 was used for the preparation of a ceramic tile adhesive. Components shown in Table 7 were added to a blender and thoroughly mixed, and then 26% of water, based on the total weight of all components, was added. The resulting mixture was mixed with the mixing equipment and mixing method required in JC/T547-2005 “Ceramic Tile Adhesive”, and various performance tests were conducted according to the standard. The results are shown in Table 8.

(90) TABLE-US-00007 TABLE 7 The formulas for ceramic tile adhesives using the products of Example 4 and Comparative Example 4 Component Comparative Example 4 Example 4 Cement 42.5 400 g 400 g Fine sand 450 g 450 g Heavy calcium carbonate 121.5 g 121.5 g Redispersible latex powder 20 g 20 g Calcium formate 3.5 g 3.5 g Lignocellulose 1 g 1 g 4# modified hydroxypropyl 4 g starch 2# modified hydroxypropyl 4 g hydroxyethyl starch

(91) TABLE-US-00008 TABLE 8 Properties for ceramic tile adhesives using the products of Example 4 and Comparative Example 4 Original Tensile adhesive Tensile adhesive Tensile adhesive tensile strength after strength after strength after a adhesive soaking in thermal cycle of freezing Example Sliding strength/MPa water/MPa aging/MPa and thawing/MPa Comparative 0.35 mm of 0.977 0.615 0.803 0.746 Example 4 sliding for 200 g ceramic tile Example 4 no sliding for 1.048 0.649 0.834 0.761 200 g ceramic tile, 0.35 mm of sliding for 500 g ceramic tile

(92) It can be seen from Table 8 that the 2# modified hydroxypropyl hydroxyethyl starch prepared in the present disclosure can improve the anti-sagging property of a ceramic tile adhesive, making the anti-sliding property meet the requirement of sliding custom character 0.5 mm. Moreover, other requirements for the binding property of a ceramic tile adhesive are met. The ceramic tile adhesive of the present disclosure is even superior to the ceramic tile adhesive including 4# modified hydroxypropyl starch in terms of properties, such as the original tensile adhesive strength, the tensile adhesive strength after soaking in water, the tensile adhesive strength after thermal aging and the tensile adhesive strength after a cycle of freezing and thawing in Table 8.

(93) The above exemplary implementations should not be considered as limiting the protection or scope of the present disclosure. It should be appreciated by those skilled in the art that many alternative improvements or changes can be made to the implementations of the present disclosure while still falling within the protection and scope of the present disclosure.

(94) Anything that is not detailed in the present disclosure is a well-known technique of those skilled in the art.

Preparation method of modified starch ether for improving anti-sliding property of ceramic tile adhesive

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