CN107385911B - Adhesion promoter and preparation method and application thereof - Google Patents
Adhesion promoter and preparation method and application thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
The invention provides an adhesion promoter, a preparation method and application thereof. The adhesion promoter comprises, by weight, 90-98 parts of an oil/water amphiphilic starch derivative, 1-6 parts of a hydroxyl plasticizer and 1-8 parts of an amino plasticizer. The surface activity of the oil/water amphiphilic starch derivative is utilized to reduce the surface tension of the starch slurry so as to adapt to the low-energy characteristic of the surface of the polyester fiber, improve the wettability and the spreadability of the starch slurry on the fiber and increase the permeation degree of the slurry on polyester-containing warp yarns; the brittleness of a starch adhesive layer between fibers is reduced by using a plasticizer, the impact resistance of the starch adhesive layer is improved, and the adhesive strength of starch slurry to polyester staple fibers is improved; when 10-30% of the adhesion promoter is added into the starch slurry, the adhesive strength of the starch slurry to the polyester staple fibers can be improved by 15-40%.
Description
Technical Field
The invention relates to the technical field of adhesion promoters, in particular to an adhesion promoter, a preparation method and application thereof, and especially relates to an adhesion promoter containing an oil/water amphiphilic starch derivative, a preparation method and application thereof, and in particular relates to an adhesion promoter containing an oil/water amphiphilic starch derivative and used for improving the adhesion strength of starch slurry to polyester staple fibers, a preparation method and application thereof.
Background
The sizing difficulty of the polyester staple fiber warp yarns is obviously higher than that of pure cotton warp yarns, which is not only because the polyester is hydrophobic fibers and has poor pulp absorption and is difficult to realize or reach the required sizing rate, but also because the surface tension of the polyester fibers is low and is difficult to satisfy a wetting equation when contacting with polar starch slurry, the wetting and spreading performance of the starch slurry on the fibers is poor, the warp yarns have high soaking difficulty, so the bonding strength is poor, and the sizing quality of the polyester staple fiber warp yarns is difficult to satisfy the requirements of weaving production. In order to ensure the weavability of the warp containing polyester staple fibers, synthetic sizing agents such as polyvinyl alcohol (PVA), polyacrylic acids, polyester and the like with poor biodegradability have to be used in large quantities in sizing production. Although the production mode is beneficial to improving the sizing quality of the warp containing the polyester staple fibers and meeting the weaving requirement, the difficulty of printing and dyeing wastewater treatment is increased and serious negative effects are caused to the ecological environment. At present, the COD discharged by the textile industry accounts for 18.53 percent of the national amount, wherein 55 percent of the COD is caused by printing and dyeing desizing sewage, and the main cause is the dirty size PVA used in the production of slashing. Therefore, research on methods for improving the use effect of starch slurry and replacing PVA (polyvinyl alcohol) of unclean slurry with starch has become an effective means for reducing the pollution of desizing wastewater.
The starch has abundant sources, low price, environmental friendliness, easy microbial degradation and biological enzyme desizing, and is easy to perform ecological treatment after desizing, so that the starch is widely used in sizing production of natural fiber warps, however, the starch molecular chain has numerous hydroxyl groups and has strong polarity, the hydrophobic synthetic fibers are nonpolar, and the surface energy factor determines that the interface between the polyester fibers and the starch adhesive layer cannot have strong interaction.
It must be clear that, due to the desizing requirement of the grey cloth, the salt bond, covalent bond and other ways cannot be adopted to improve the bonding strength of the starch to the polyester staple fiber, otherwise, the size contained in the grey cloth is difficult to remove in the desizing process, and the dyeing, printing and finishing processes of the fabric are endangered. Heretofore, chemical modification of starch has been mainly used to improve the adhesion strength of the starch to polyester staple fibers.
The research results show that the organic esterification modification of the starch can improve the adhesive strength of the starch slurry to the polyester fiber. The principle of the modification is that corresponding acid anhydride is adopted to esterify with hydroxyl of starch, organic acid ester substituent groups are introduced on starch molecular chains, and the association of the hydroxyl among starch molecules is disturbed to form internal plasticization to improve the toughness of a starch adhesive layer and improve the adhesive strength of the starch to polyester fibers. And secondly, the organic acid ester group has an organic ester atomic group similar to that of terylene, which is beneficial to increasing Van der Waals force on the interface between the starch adhesive layer and the fiber and reducing the possibility of interface damage, so that the organic esterification modification of the starch can improve the adhesive strength of the starch to the terylene fiber and improve the sizing performance of the starch to the warp containing the terylene short fiber. Scientific research and production practice show that acetate starch has good sizing performance on polyester warps, but the volume of acetate groups is small, the steric hindrance effect is weak, and the formed internal plasticization effect is limited; therefore, organic acid ester substituent groups with larger volume, such as propionate, maleate and octenyl succinate, are introduced into starch molecules to improve the internal plasticizing effect of the substituent groups on the starch and improve the adhesive strength of the starch on terylene, but the organic acid ester groups have strong hydrophobicity, so that the water dispersibility of the starch is obviously reduced, and the sizing performance of the starch is influenced. Therefore, the problem of insufficient bonding strength of starch to polyester fiber cannot be solved completely, and a modification mode of increasing the volume of the organic acid ester substituent group cannot be adopted.
Needless to say, the polarity of the starch adhesive layer is opposite to that of the polyester fiber, the interaction on the adhesive interface is weak, the interface is easy to break, and strong adhesive strength cannot be formed, so that the starch and the modified starch are difficult to strongly adhere to the polyester staple fiber in the sizing process, the reinforcement rate, the wear resistance and the hairiness reduction rate of the warp containing the polyester staple fiber are seriously influenced, and the sizing quality of the warp containing the polyester staple fiber by the starch is not high and is far inferior to that of synthetic sizing agents such as PVA, polyacrylic acid and polyester. Therefore, the development of an adhesion promoter suitable for starch slurry is urgently needed to improve the wetting and spreading performance of the starch slurry on polyester fibers, reduce the brittleness of a starch adhesive layer, improve the adhesive strength of the starch slurry on polyester staple fibers and improve the sizing quality of warp yarns containing the polyester staple fibers.
The adhesion promoter is used for improving the adhesive strength of the starch slurry to the polyester fiber, and is an effective way for improving the sizing performance of the starch slurry. The invention relates to a symplectic peak et al (ZL201210321322.7) discloses an aliphatic waterborne polyester graft copolymer as an adhesion promoter for improving the adhesion strength of starch slurry to polyester fibers. The main chain of the graft copolymer is a random copolymer of hydrophobic polyester chain segment aliphatic dicarboxylic acid dihydric alcohol ester and hydrophilic polyester chain segment aliphatic dicarboxylic acid ester; the graft branch is a random copolymer of acrylamide and vinyl carboxylate. The adhesion promoter can effectively improve the adhesive strength of the starch slurry to the polyester fiber and improve the sizing quality of the starch slurry to the polyester warp. However, the main component of the invented adhesion promoter is still synthetic high polymer, the biodegradability is not as good as starch, and a certain process measure is still needed to be adopted for treatment in the process of desizing and desizing wastewater treatment, which is not beneficial to simplifying the production process. Therefore, the development of a starch-based adhesion promoter for sizing hydrophobic polyester-containing short fiber warp yarns is urgently needed, so that the adhesion strength of starch slurry to polyester fibers is improved, the slashing quality is improved, the desizing process is simplified, and the treatment difficulty of desizing wastewater is reduced.
Disclosure of Invention
In view of the defects of the prior art, an object of the present invention is to provide an adhesion promoter to improve the adhesion strength of starch slurry to polyester staple fibers.
In order to achieve the purpose, the invention adopts the following technical scheme:
the adhesion promoter comprises, by weight, 90-98 parts of an oil/water amphiphilic starch derivative, 1-6 parts of a hydroxyl plasticizer and 1-8 parts of an amino plasticizer.
The adhesion promoter comprises, by weight, 90-98 parts of an oil/water amphiphilic starch derivative, 1-6 parts of a hydroxyl plasticizer and 1-8 parts of an amino plasticizer; for example, the oil/water amphiphilic starch derivative is 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts and 98 parts by weight, the hydroxyl plasticizer is 1 part, 2 parts, 3 parts, 4 parts, 5 parts and 6 parts by weight, and the amino plasticizer is 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts and 8 parts by weight.
The oil/water amphiphilic starch derivative is modified starch containing propionate substituent and carboxymethyl substituent on a molecular chain.
The total degree of substitution of the propionate substituent and the carboxymethyl substituent is 0.025 to 0.062, for example, 0.025, 0.03, 0.031, 0.032, 0.033, 0.034, 0.035, 0.036, 0.037, 0.038, 0.039, 0.04, 0.041, 0.042, 0.043, 0.044, 0.045, 0.046, 0.047, 0.048, 0.049, 0.05, 0.051, 0.052, 0.053, 0.054, 0.055, 0.056, 0.057, 0.058, 0.059, 0.06, 0.061, 0.062, preferably 0.039 to 0.062.
Preferably, the substitution degree of the propionate substituent is 0.016 to 0.041, such as 0.016, 0.017, 0.018, 0.019, 0.02, 0.021, 0.022, 0.023, 0.024, 0.025, 0.026, 0.027, 0.028, 0.029, 0.3, 0.031, 0.032, 0.033, 0.034, 0.035, 0.036, 0.037, 0.038, 0.039, 0.04, 0.041, preferably 0.024 to 0.038.
Preferably, the degree of substitution of the carboxymethyl substituent is 0.009 to 0.034, such as 0.009, 0.01, 0.011, 0.012, 0.013, 0.014, 0.015, 0.016, 0.017, 0.018, 0.019, 0.02, 0.021, 0.022, 0.023, 0.024, 0.025, 0.026, 0.027, 0.028, 0.029, 0.03, 0.031, 0.032, 0.033, 0.034, preferably 0.015 to 0.024.
The molar ratio of the propionate substituent to the carboxymethyl substituent is 32/68-82/18, such as 32/68, 35/65, 40/60, 45/55, 50/50, 55/45, 60/40, 65/35, 70/30, 75/25, 80/20, 81/19, and 82/18, preferably 49/51-82/18.
The hydroxy plasticizer is selected from one or a mixture of at least two of glycerol, ethylene glycol, 1, 2-propylene glycol, 1,1, 1-trimethylolpropane, pentaerythritol, xylitol and sorbitol, typical but non-limiting examples of the mixture being a mixture of glycerol and ethylene glycol, a mixture of glycerol and 1, 2-propylene glycol, a mixture of glycerol and 1,1, 1-trimethylolpropane, a mixture of glycerol and pentaerythritol, a mixture of glycerol and xylitol, a mixture of glycerol and sorbitol; the mixture can also be selected from mixtures of three hydroxy plasticizers, such as mixtures of glycerol, ethylene glycol, 1, 2-propanediol, mixtures of glycerol, ethylene glycol, 1, 1-trimethylolpropane, mixtures of glycerol, ethylene glycol, pentaerythritol, mixtures of glycerol, ethylene glycol, xylitol, mixtures of glycerol, ethylene glycol, sorbitol, mixtures of glycerol, 1, 2-propanediol, 1,1, 1-trimethylolpropane, mixtures of glycerol, 1, 2-propanediol, pentaerythritol, mixtures of glycerol, 1, 2-propanediol, xylitol, mixtures of glycerol, 1, 2-propanediol, sorbitol, mixtures of ethylene glycol, 1, 2-propanediol, 1,1, 1-trimethylolpropane, mixtures of ethylene glycol, 1, 2-propanediol, 1, 1-trimethylolpropane, A mixture of pentaerythritol, a mixture of ethylene glycol, 1, 2-propylene glycol, xylitol, a mixture of ethylene glycol, 1, 2-propylene glycol, sorbitol, a mixture of ethylene glycol, 1,1, 1-trimethylolpropane, pentaerythritol, a mixture of ethylene glycol, 1,1, 1-trimethylolpropane, xylitol, a mixture of ethylene glycol, 1,1, 1-trimethylolpropane, sorbitol, a mixture of ethylene glycol, pentaerythritol, xylitol, a mixture of ethylene glycol, pentaerythritol, sorbitol, a mixture of ethylene glycol, xylitol and sorbitol; the mixture can also be selected from mixtures of four hydroxy plasticizers, such as mixtures of glycerol, ethylene glycol, 1, 2-propanediol, 1,1, 1-trimethylolpropane, mixtures of glycerol, ethylene glycol, 1, 2-propanediol, pentaerythritol, mixtures of glycerol, ethylene glycol, 1, 2-propanediol, xylitol, mixtures of glycerol, ethylene glycol, 1, 2-propanediol, sorbitol, mixtures of glycerol, ethylene glycol, 1,1, 1-trimethylolpropane, pentaerythritol, mixtures of glycerol, ethylene glycol, 1,1, 1-trimethylolpropane, xylitol, mixtures of glycerol, ethylene glycol, 1,1, 1-trimethylolpropane, sorbitol, mixtures of glycerol, ethylene glycol, pentaerythritol, xylitol, mixtures of glycerol, ethylene glycol, pentaerythritol, mixtures of glycerol, pentaerythritol, mixtures of xylitol, mixtures of glycerol, ethylene glycol, pentaerythritol, mixtures of glycerol, and mixtures of glycerol, ethylene glycol, pentaerythritol, and mixtures of pentaerythritol, a mixture of sorbitol, a mixture of glycerol, ethylene glycol, xylitol and sorbitol, a mixture of ethylene glycol, 1, 2-propylene glycol, 1,1, 1-trimethylolpropane and pentaerythritol, a mixture of ethylene glycol, 1, 2-propylene glycol, 1,1, 1-trimethylolpropane and xylitol, a mixture of ethylene glycol, 1, 2-propylene glycol, 1,1, 1-trimethylolpropane and sorbitol, a mixture of 1, 2-propylene glycol, 1,1, 1-trimethylolpropane, pentaerythritol and xylitol, a mixture of 1, 2-propylene glycol, 1,1, 1-trimethylolpropane, pentaerythritol and sorbitol, a mixture of 1,1, 1-trimethylolpropane, pentaerythritol, xylitol and sorbitol; the mixture can also be selected from mixtures of five hydroxy plasticizers, for example mixtures of glycerol, ethylene glycol, 1, 2-propanediol, 1,1, 1-trimethylolpropane, pentaerythritol, mixtures of glycerol, ethylene glycol, 1, 2-propanediol, 1,1, 1-trimethylolpropane, xylitol, mixtures of glycerol, ethylene glycol, 1, 2-propanediol, 1,1, 1-trimethylolpropane, sorbitol, mixtures of ethylene glycol, 1, 2-propanediol, 1,1, 1-trimethylolpropane, pentaerythritol, xylitol, mixtures of ethylene glycol, 1, 2-propanediol, 1,1, 1-trimethylolpropane, pentaerythritol, sorbitol, mixtures of 1, 2-propanediol, 1,1, 1-trimethylolpropane, pentaerythritol, sorbitol, 1, 2-propanediol, 1,1, 1-trimethylolpropane, pentaerythritol, xylitol, mixtures of five hydroxy plasticizers, for example mixtures of glycerol, ethylene glycol, 1, 2-propanediol, 1,1, 1-trimethylolpropane, pentaerythritol, A mixture of xylitol and sorbitol; the mixture can also be selected from a mixture of six kinds of hydroxy plasticizers, such as glycerol, ethylene glycol, 1, 2-propylene glycol, 1,1, 1-trimethylolpropane, pentaerythritol, a mixture of xylitol, a mixture of glycerol, ethylene glycol, 1, 2-propylene glycol, 1,1, 1-trimethylolpropane, pentaerythritol, a mixture of sorbitol, a mixture of ethylene glycol, 1, 2-propylene glycol, 1,1, 1-trimethylolpropane, pentaerythritol, xylitol, a mixture of sorbitol, etc.; the mixture may also be selected from a mixture of seven hydroxy plasticizers, such as a mixture of glycerol, ethylene glycol, 1, 2-propanediol, 1,1, 1-trimethylolpropane, pentaerythritol, xylitol and sorbitol.
The amino plasticizer is selected from one or a mixture of at least two of urea, aniline and monoethanolamine, typical but non-limiting examples of the mixture are a mixture of urea and aniline, a mixture of urea and monoethanolamine, and a mixture of aniline and monoethanolamine; the mixture can also be selected from a mixture of three amino plasticizers, for example a mixture of urea, aniline and monoethanolamine.
The invention also aims to provide a preparation method of the adhesion promoter, which comprises the following steps: according to the weight portion, 90-98 portions of oil/water amphiphilic starch derivative, 1-6 portions of hydroxyl plasticizer and 1-8 portions of amino plasticizer are uniformly mixed to prepare the adhesion promoter.
In order to alleviate the defect that the starch adhesive layer is brittle and hard, the hydroxyl plasticizer and the amino plasticizer are adopted to plasticize the starch adhesive layer, so that the brittleness of the starch adhesive layer among fibers is reduced, the impact resistance of the starch adhesive layer is improved, and the bonding strength of starch slurry to polyester staple fibers is improved.
Wherein the oil/water amphiphilic starch derivative is prepared by a two-step reaction method of a carboxymethyl etherification reaction and a propionic acid esterification reaction, and the carboxymethyl etherification reaction is carried out before the propionic acid esterification reaction.
The method is characterized in that hydrophilic carboxymethyl and hydrophobic propionate functional groups are introduced to a starch molecular chain at the same time, so that the starch obtains certain surface activity, the surface tension of starch slurry is reduced, the wetting and spreading capacity of the slurry on hydrophobic polyester fibers is improved, the wettability and the spreading performance of the starch slurry on the fibers are improved, the permeation degree of the slurry on polyester-containing warp yarns is increased, and the bonding strength of the starch on the polyester fibers is improved; secondly, the steric hindrance effect generated by the two substituent groups introduced into the molecular chain of the starch can interfere the association of hydroxyl groups among starch molecules, improve the anti-gelling property of starch slurry, improve the toughness of a starch adhesive layer through the internal plasticization effect, reduce the internal stress and stress concentration of the starch adhesive layer, and is beneficial to improving the adhesive strength of the starch to polyester fibers; thirdly, hydroxyl and amino plasticizer in the adhesion promoter component can further reduce the brittleness of the starch adhesive layer through external plasticizing action, and reduce the possibility of adhesive damage so as to improve the adhesive strength of the starch to the polyester fiber.
Carboxymethyl and propionate functional groups are introduced on a starch molecular chain, wherein the carboxymethyl and propionate functional groups are etherified substituent groups and have good alkali resistance; the latter are organic ester substituents and are susceptible to base-catalyzed hydrolysis. In order to prevent hydrolysis of the propionate functions during the carboxymethylation reaction, the oil/water amphiphilic starch derivative component of the adhesion promoter of the present invention must be prepared by a process route that employs a sequence of carboxymethylation followed by esterification of propionic acid.
The carboxymethyl etherification reaction is a reaction between monochloroacetic acid as an etherifying agent and starch; the specific steps of the carboxymethyl etherification reaction are as follows: sequentially adding 200-600 parts by weight of 95% ethanol by volume fraction into a reactor, adding 120 parts by weight of starch and 1.5-6 parts by weight of 40% NaOH aqueous solution under stirring, heating to 35 ℃, and alkalizing for 0.5-1 h under stirring; then heating to 40-60 ℃; dissolving 1-4 parts by weight of monochloroacetic acid with 20-60 parts by weight of ethanol with volume fraction of 95%, neutralizing with 1.05-4.2 parts by weight of NaOH aqueous solution with mass fraction of 40%, slowly adding into a reactor, controlling feeding speed, dropwise adding sodium monochloroacetate ethanol solution into the reactor within 0.5-1 h, stirring and reacting for 2-3 h at 40-60 ℃, neutralizing the product with glacial acetic acid until the pH value is 6-7 after the reaction is finished, filtering, washing with 80% ethanol, drying at 60 ℃, and crushing to finish the carboxymethyl etherification reaction to obtain the carboxymethylated starch.
The propionic acid esterification reaction is an esterification reaction of propionic anhydride serving as an esterifying agent and the carboxymethylated starch in a sodium sulfate aqueous solution; the propionic acid esterification reaction comprises the following specific steps: 150-400 parts by weight of water and 5-20 parts by weight of Na are sequentially added into a reactor2SO4And 100 parts by weightUniformly stirring the carboxymethylated starch, heating to 30-40 ℃, adjusting the pH value of materials in a reactor to 8-9 by using NaOH aqueous solution with the mass fraction of 3%, slowly dropwise adding 4-16 parts by weight of propionic anhydride, controlling the pH value of reaction materials in the reactor to 8-9 by using NaOH aqueous solution with the mass fraction of 3% in the reaction process, continuously reacting for 1-3 hours at 30-40 ℃ and at the pH of 8-9 after the dropwise adding of the propionic anhydride is finished, neutralizing to the pH of 6.5-7 by using dilute hydrochloric acid after the reaction is finished, and performing suction filtration, washing, drying and crushing to obtain the oil/water amphiphilic starch derivative.
Preferably, the starch is selected from one or a mixture of at least two of corn starch, tapioca starch, potato starch and wheat starch, typical but non-limiting examples of which are corn starch, tapioca starch, corn starch, potato starch, corn starch, wheat starch, tapioca starch, potato starch, tapioca starch, wheat starch, potato starch, wheat starch; the mixture can also be a mixture of three starches, such as a mixture of corn starch, tapioca starch, potato starch, a mixture of corn starch, tapioca starch, wheat starch, a mixture of corn starch, potato starch, wheat starch, tapioca starch, potato starch, wheat starch; the mixture can also be a mixture of four starches, such as corn starch, tapioca starch, potato starch and wheat starch.
The invention also aims to provide the application of the adhesion promoter, and the adhesion promoter is used for improving the adhesive strength of the starch size to the polyester staple fiber.
The starch-based adhesion promoter is characterized in that the starch slurry applicable to the starch-based adhesion promoter comprises native starch and modified starch, wherein the native starch can be corn starch, cassava starch, potato starch or wheat starch and other natural starch, the modified starch is modified native starch, and the modified starch can be acidolysis starch, oxidized starch, carbamate starch, phosphate starch and acetate starch, or any combination of acidolysis starch, oxidized starch, carbamate starch, phosphate starch and acetate starch; the starch-based adhesion promoter is suitable for warp sizing of a cotton sizing machine. The sized slashing can be woven by a common shuttle loom and can meet the weaving requirement of a high-speed loom.
Compared with the prior art, the invention has the beneficial effects that:
(1) when 10-30% of the adhesion promoter is added into the starch slurry, the adhesive strength of the starch slurry to the polyester staple fibers can be improved by 15-40%.
(2) The invention utilizes the surface activity of the oil/water amphiphilic starch derivative to reduce the surface tension of the starch slurry so as to adapt to the low-energy characteristic of the surface of the polyester fiber, improve the wettability and the spreadability of the starch slurry on the fiber, increase the permeation degree of the slurry on polyester-containing warp yarns and improve the bonding strength of the starch on polyester staple fibers.
(3) The adhesion promoter reduces the brittleness of a starch adhesive layer between fibers by using the hydroxyl plasticizer and the amino plasticizer, improves the impact resistance of the starch adhesive layer, and improves the adhesive strength of starch slurry to polyester staple fibers.
(4) The adhesion promoter belongs to a starch-based mixture, has the same requirements on a desizing process as starch, and can be treated together with desizing wastewater of starch slurry.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Unless otherwise specified, various starting materials of the present invention are commercially available or prepared according to conventional methods in the art.
Example 1
(1) Carboxymethyl etherification of starch: sequentially adding 300 parts by weight of 95% ethanol by volume fraction into a reactor, adding 120 parts by weight of corn starch and 3 parts by weight of 40% NaOH aqueous solution under stirring, heating to 35 ℃, and alkalizing for 0.5h under stirring; then heating to 50 ℃; dissolving 2 parts by weight of monochloroacetic acid in 40 parts by weight of ethanol with volume fraction of 95%, neutralizing with 2.1 parts by weight of NaOH aqueous solution with mass fraction of 40%, slowly adding into a reactor, controlling the feeding speed, dropwise adding the sodium monochloroacetate ethanol solution into the reactor within 1h, and then stirring and reacting for 2h at 50 ℃. After the reaction is finished, neutralizing the product to pH 7 by using glacial acetic acid, filtering, washing by using 80% ethanol, drying at 60 ℃, and crushing to finish the carboxymethyl etherification reaction.
(2) Propionic acid esterification of starch: 200 parts by weight of water and 10 parts by weight of Na were sequentially charged into the reactor2SO4And 100 parts by weight of the carboxymethylated starch, stirring uniformly, and then heating to 40 ℃. And (2) adjusting the pH value of the materials in the reactor to 8-9 by using a NaOH aqueous solution with the mass fraction of 3%, then slowly dropwise adding 12 parts by weight of propionic anhydride, and controlling the pH value of the reaction materials in the reactor to 8-9 by using the NaOH aqueous solution with the mass fraction of 3% in the reaction process. After the dropwise addition of the propionic anhydride, continuously reacting for 2 hours at 40 ℃ and at the pH of 8-9. And after the reaction is finished, neutralizing the reaction product by using dilute hydrochloric acid until the pH value is 6.5-7, performing suction filtration, washing, drying and crushing to obtain the oil/water amphiphilic starch derivative.
The oil/water amphiphilic starch derivative prepared in this example had a degree of substitution of 0.032 for propionate substituents, a degree of substitution of 0.019 for carboxymethyl substituents, a total degree of substitution of 0.051 for propionate and carboxymethyl substituents, and a molar ratio of propionate to carboxymethyl being 62.7/37.3. The surface tension of the oil/water amphiphilic starch derivative prepared in this example was 52.2 mN/M.
(3) And uniformly mixing 92 parts by weight of oil/water amphiphilic starch derivative, 3 parts by weight of glycerol and 5 parts by weight of urea to obtain the adhesion promoter.
The effect of the adhesion promoter was evaluated according to the method specified in the textile industry Standard of the people's republic of China FZ/T15001-2008: when the addition amount (dry weight ratio) of the prepared adhesion promoter to the corn starch is 10%, 20% and 30%, respectively, the adhesion strength of the corn starch doped with the prepared adhesion promoter to the polyester staple fiber is 30.6cN/tex, 32.5cN/tex and 32.9cN/tex, respectively, while the adhesion strength of the corn starch without the adhesion promoter to the polyester staple fiber is only 24.5 cN/tex.
Example 2
(1) Carboxymethyl etherification of starch: sequentially adding 200 parts by weight of 95% ethanol by volume into a reactor, adding 120 parts by weight of potato starch and 1.5 parts by weight of 40% NaOH aqueous solution under stirring, heating to 35 ℃, and alkalizing for 1h under stirring; then heating to 60 ℃; dissolving 1 part by weight of monochloroacetic acid in 20 parts by weight of ethanol with volume fraction of 95%, neutralizing with 1.05 parts by weight of NaOH aqueous solution with mass fraction of 40%, slowly adding into a reactor, controlling the feeding speed, dropwise adding the sodium monochloroacetate ethanol solution into the reactor within 0.5-1 h, and then stirring and reacting for 2.5h at 60 ℃. After the reaction is finished, neutralizing the product to pH6 by using glacial acetic acid, filtering, washing by using 80% ethanol, drying at 60 ℃, and crushing to finish the carboxymethyl etherification reaction.
(2) Propionic acid esterification of starch: 400 parts by weight of water and 20 parts by weight of Na were sequentially charged into the reactor2SO4And 100 parts by weight of the carboxymethylated starch, stirring uniformly, and then heating to 35 ℃. And (2) adjusting the pH value of the materials in the reactor to 8-9 by using a NaOH aqueous solution with the mass fraction of 3%, then slowly dropwise adding 16 parts by weight of propionic anhydride, and controlling the pH value of the reaction materials in the reactor to 8-9 by using the NaOH aqueous solution with the mass fraction of 3% in the reaction process. After the dropwise addition of the propionic anhydride, continuously reacting for 3 hours at 35 ℃ and pH 8-9. And after the reaction is finished, neutralizing the reaction product by using dilute hydrochloric acid until the pH value is 6.5-7, performing suction filtration, washing, drying and crushing to obtain the oil/water amphiphilic starch derivative.
The oil/water amphiphilic starch derivative prepared in this example had a degree of substitution of 0.041 for propionate substituents, a degree of substitution of 0.009 for carboxymethyl substituents, a total degree of substitution of 0.05 for propionate and carboxymethyl substituents, and a molar ratio of propionate to carboxymethyl of 82.0/18.0 in the molecular chain. The surface tension of the oil/water amphiphilic starch derivative prepared in this example was 53 mN/M.
(3) And uniformly mixing 91 parts by weight of oil/water amphiphilic starch derivative, 1 part by weight of glycerol and 8 parts by weight of urea to obtain the adhesion promoter.
The effect of the adhesion promoter was evaluated according to the method specified in the textile industry Standard of the people's republic of China FZ/T15001-2008: when the amount of the adhesion promoter prepared in this example added to wheat starch (dry weight ratio) was 20%, the adhesion strength of wheat starch doped with the adhesion promoter prepared in this example to polyester staple fibers was 30.2cN/tex, while the adhesion strength of wheat starch without the adhesion promoter to polyester staple fibers was only 23.5 cN/tex.
Example 3
(1) Carboxymethyl etherification of starch: sequentially adding 600 parts by weight of 95% ethanol by volume into a reactor, adding 120 parts by weight of wheat starch and 6 parts by weight of 40% NaOH aqueous solution under stirring, heating to 35 ℃, and alkalizing for 0.5h under stirring; then heating to 40 ℃; dissolving 4 parts by weight of monochloroacetic acid in 60 parts by weight of ethanol with volume fraction of 95%, neutralizing with 4.2 parts by weight of NaOH aqueous solution with mass fraction of 40%, slowly adding into a reactor, controlling the feeding speed, dropwise adding the sodium monochloroacetate ethanol solution into the reactor within 0.5-1 h, and then stirring and reacting for 3h at 40 ℃. And after the reaction is finished, neutralizing the product with glacial acetic acid until the pH value is 6-7, filtering, washing with 80% ethanol, drying at 60 ℃, and crushing to finish the carboxymethyl etherification reaction.
(2) Propionic acid esterification of starch: 150 parts by weight of water and 5 parts by weight of Na were sequentially charged into the reactor2SO4And 100 parts by weight of the carboxymethylated starch, stirring uniformly, and then heating to 30 ℃. And (2) adjusting the pH value of the materials in the reactor to 8-9 by using a NaOH aqueous solution with the mass fraction of 3%, then slowly dropwise adding 4 parts by weight of propionic anhydride, and controlling the pH value of the reaction materials in the reactor to 8-9 by using the NaOH aqueous solution with the mass fraction of 3% in the reaction process. After the dropwise addition of the propionic anhydride, continuously reacting for 1h at 30 ℃ and at the pH of 8-9. And after the reaction is finished, neutralizing the reaction product by using dilute hydrochloric acid until the pH value is 6.5-7, performing suction filtration, washing, drying and crushing to obtain the oil/water amphiphilic starch derivative.
The oil/water amphiphilic starch derivative prepared in this example had a degree of substitution of 0.016 for propionate substituents, 0.034 for carboxymethyl substituents, a total degree of substitution of 0.05 for propionate and carboxymethyl substituents, and a molar ratio of 32.0/68.0 for propionate to carboxymethyl. The surface tension of the oil/water amphiphilic starch derivative prepared in this example was 58.8 mN/M.
(3) And (2) uniformly mixing 98 parts by weight of oil/water amphiphilic starch derivative, 1 part by weight of glycerol and 1 part by weight of urea to obtain the adhesion promoter.
The effect of the adhesion promoter was evaluated according to the method specified in the textile industry Standard of the people's republic of China FZ/T15001-2008: when the amount of the adhesion promoter prepared in this example added to starch (dry weight ratio) was 30%, the adhesion strength of the potato starch doped with the adhesion promoter prepared in this example to the polyester staple fiber was 31.2cN/tex, while the adhesion strength of the potato starch without the adhesion promoter to the polyester staple fiber was only 25.3 cN/tex.
Example 4
(1) Carboxymethyl etherification of starch: sequentially adding 300 parts by weight of 95% ethanol by volume into a reactor, adding 120 parts by weight of cassava starch and 3.75 parts by weight of 40% NaOH aqueous solution by mass under stirring, heating to 35 ℃, and alkalizing for 0.5h under stirring; then heating to 50 ℃; 2.5 parts by weight of monochloroacetic acid are dissolved in 40 parts by weight of 95% by volume ethanol, neutralized with 2.625 parts by weight of 40% by weight aqueous NaOH solution and the carboxymethyl etherification reaction is carried out according to the method and procedure of example 1 of the patent specification.
(2) Propionic acid esterification of starch: 200 parts by weight of water and 10 parts by weight of Na were sequentially charged into the reactor2SO4And 100 parts by weight of the carboxymethylated starch, stirring uniformly, and then heating to 40 ℃. Adjusting the pH value of materials in the reactor to 8-9 by using NaOH aqueous solution with the mass fraction of 3%, slowly dropwise adding 16 parts by weight of propionic anhydride, and finishing propionic esterification according to the method and the steps of the patent specification example 1 to obtain the oil/water amphiphilic starch derivative.
The oil/water amphiphilic starch derivative prepared in this example had a degree of substitution of 0.038 for the propionate substituent, a degree of substitution of 0.024 for the carboxymethyl substituent, a total degree of substitution of 0.062 for the propionate and carboxymethyl substituents, and a molar ratio of propionate to carboxymethyl of 61.3/38.7. The surface tension of the oil/water amphiphilic starch derivative prepared in this example was 51.5 mN/M.
(3) And (2) uniformly mixing 93 parts by weight of oil/water amphiphilic starch derivative, 6 parts by weight of glycerol and 1 part by weight of urea to obtain the adhesion promoter.
The effect of the adhesion promoter was evaluated according to the method specified in the textile industry Standard of the people's republic of China FZ/T15001-2008: when the amount of the adhesion promoter prepared in this example added to starch (dry weight ratio) was 20%, the adhesive strength of tapioca starch doped with the adhesion promoter prepared in this example to polyester staple fibers was 32.8cN/tex, while the adhesive strength of tapioca starch without the adhesion promoter to polyester staple fibers was only 24.0 cN/tex.
Example 5
(1) Carboxymethyl etherification of starch: sequentially adding 300 parts by weight of 95% ethanol, 60 parts by weight of corn starch and 60 parts by weight of cassava starch, and 1.5 parts by weight of 40% NaOH aqueous solution into a reactor, stirring, heating to 35 ℃, and alkalizing for 0.5 h; then heating to 50 ℃; 1.0 part by weight of monochloroacetic acid was dissolved in 20 parts by weight of 95% by volume ethanol, neutralized with 1.05 parts by weight of 40% by weight aqueous NaOH solution, and then the carboxymethyl etherification reaction was carried out according to the method and procedure of example 1 of the present patent specification.
(2) Propionic acid esterification of starch: 200 parts by weight of water and 10 parts by weight of Na were sequentially charged into the reactor2SO4And 100 parts by weight of the carboxymethylated starch, stirring uniformly, and then heating to 40 ℃. Adjusting the pH value of materials in the reactor to 8-9 by using NaOH aqueous solution with the mass fraction of 3%, slowly dropwise adding 4 parts by weight of propionic anhydride, and finishing propionic esterification according to the method and the steps of the patent specification example 1 to obtain the oil/water amphiphilic starch derivative.
The oil/water amphiphilic starch derivative prepared in this example had a degree of substitution of propionate substituents of 0.016, a degree of substitution of carboxymethyl substituents of 0.009, a total degree of substitution of propionate and carboxymethyl substituents of 0.025, and a molar ratio of propionate to carboxymethyl of 64.0/36.0 in the molecular chain. The surface tension of the oil/water amphiphilic starch derivative prepared in this example was 58.6 mN/M.
(3) And uniformly mixing 90 parts by weight of oil/water amphiphilic starch derivative, 4 parts by weight of glycerol and 6 parts by weight of urea to obtain the adhesion promoter.
The effect of the adhesion promoter was evaluated according to the method specified in the textile industry Standard of the people's republic of China FZ/T15001-2008: when the amount of the adhesion promoter prepared in this example added to starch (dry weight ratio) was 20%, the adhesion strength of the acid-hydrolyzed starch doped with the adhesion promoter prepared in this example to the polyester staple fiber was 29.0cN/tex, while the adhesion strength of the acid-hydrolyzed starch without the adhesion promoter to the polyester staple fiber was only 23.7 cN/tex.
Example 6
(1) Carboxymethyl etherification of starch: sequentially adding 300 parts by weight of 95% ethanol by volume into a reactor, adding 120 parts by weight of potato starch and 2.25 parts by weight of 40% NaOH aqueous solution by mass under stirring, heating to 35 ℃, and alkalizing for 0.5h under stirring; then heating to 50 ℃; 1.6 parts by weight of monochloroacetic acid were dissolved in 40 parts by weight of 95% by volume ethanol, neutralized with 1.68 parts by weight of 40% by weight aqueous NaOH solution, and then the carboxymethyl etherification reaction was carried out according to the method and procedure of example 1 of the present patent specification.
(2) Propionic acid esterification of starch: 200 parts by weight of water and 10 parts by weight of Na were sequentially charged into the reactor2SO4And 100 parts by weight of the carboxymethylated starch, stirring uniformly, and then heating to 40 ℃. And (2) adjusting the pH value of the material in the reactor to 8-9 by using NaOH aqueous solution with the mass fraction of 3%, slowly dropwise adding 8 parts by weight of propionic anhydride, and finishing propionic esterification according to the method and the steps of the patent specification example 1 to obtain the oil/water amphiphilic starch derivative.
The oil/water amphiphilic starch derivative prepared in this example had a degree of substitution of 0.024 for the propionate substituent, a degree of substitution of 0.015 for the carboxymethyl substituent, a total degree of substitution of 0.039 for the propionate and carboxymethyl substituents, and a molar ratio of propionate to carboxymethyl of 61.5/38.5. The surface tension of the oil/water amphiphilic starch derivative prepared in this example was 54.8 mN/M.
(3) And uniformly mixing 92 parts by weight of oil/water amphiphilic starch derivative, 4 parts by weight of glycerol and 4 parts by weight of urea to obtain the adhesion promoter.
The effect of the adhesion promoter was evaluated according to the method specified in the textile industry Standard of the people's republic of China FZ/T15001-2008: when the amount of the adhesion promoter prepared in this example added to the urethane starch was 20% (dry weight ratio), the adhesion strength of the urethane starch doped with the adhesion promoter prepared in this example to the polyester staple fibers was 32.3cN/tex, whereas the adhesion strength of the urethane starch without the adhesion promoter to the polyester staple fibers was only 23.1 cN/tex.
Example 7
An oil/water amphiphilic starch derivative was synthesized to prepare an adhesion promoter according to the method and procedure of example 1 of the present patent specification.
The effect of the adhesion promoter was evaluated according to the method specified in the textile industry Standard of the people's republic of China FZ/T15001-2008: when the amount of the adhesion promoter prepared in this example added to starch (dry weight ratio) was 20%, the adhesion strengths of oxidized starch, phosphate starch, carbamate starch, and acetate starch, which were blended with the adhesion promoter prepared in this example, to the polyester staple fiber were 30.0, 32.4, 33.2, and 34.4cN/tex, respectively, while the adhesion strengths of oxidized starch, phosphate starch, carbamate starch, and acetate starch, which were not blended with the adhesion promoter, to the polyester staple fiber were only 23.3, 25.9, 24.5, and 27.8 cN/tex.
Example 8
An oil/water amphiphilic starch derivative was synthesized according to the method and procedure of example 1 of the present patent specification, except that 120 parts by weight of starch raw material to be charged into a reactor for carboxymethyl etherification of the oil/water amphiphilic starch derivative in this example was: 40 parts by weight of corn starch, 20 parts by weight of tapioca starch, 30 parts by weight of corn starch and 20 parts by weight of tapioca starch.
In the oil/water amphiphilic starch derivative prepared in this example, the substitution degree of propionate substituent on the molecular chain is 0.031, the substitution degree of carboxymethyl substituent is 0.02, the total substitution degree of propionate and carboxymethyl substituents is 0.051, and the molar ratio between propionate and carboxymethyl is 60.8/39.2. The surface tension of the oil/water amphiphilic starch derivative prepared in this example was 52.7 mN/M.
And uniformly mixing 95 parts by weight of oil/water amphiphilic starch derivative, 3 parts by weight of hydroxyl plasticizer and 2 parts by weight of amino plasticizer to obtain the adhesion promoter.
The effect of the adhesion promoter was evaluated according to the method specified in the textile industry Standard of the people's republic of China FZ/T15001-2008: when the amount of the adhesion promoter prepared in this example added to starch (dry weight ratio) was 10%, the adhesion strength of the acetate starch to the polyester staple fiber incorporated with the adhesion promoter prepared in this example was 33.4cN/tex, while the adhesion strength of the acetate starch without the adhesion promoter to the polyester staple fiber was only 27.8 cN/tex.
Example 9
An oil/water amphiphilic starch derivative was synthesized to prepare an adhesion promoter according to the method and procedure of example 1 of the present patent specification. Except that ethylene glycol was used as the plasticizer instead of glycerin and aniline instead of urea in this example.
The effect of the adhesion promoter was evaluated according to the method specified in the textile industry Standard of the people's republic of China FZ/T15001-2008: when the amount of the adhesion promoter prepared in this example added to starch (dry weight ratio) was 20%, the adhesion strength of the oxidized starch to the polyester staple fiber, which was doped with the adhesion promoter prepared in this example, was 32.0cN/tex, whereas the adhesion strength of the oxidized starch without the adhesion promoter to the polyester staple fiber was only 23.3 cN/tex.
Example 10
An oil/water amphiphilic starch derivative was synthesized to prepare an adhesion promoter according to the method and procedure of example 1 of the present patent specification. Except that ethylene glycol was used as the plasticizer instead of glycerin and monoethanolamine instead of urea in this example.
The effect of the adhesion promoter was evaluated according to the method specified in the textile industry Standard of the people's republic of China FZ/T15001-2008: when the amount of the adhesion promoter prepared in this example added to starch (dry weight ratio) was 20%, the adhesion strength of the phosphate ester starch doped with the adhesion promoter prepared in this example to the polyester staple fiber was 31.6cN/tex, while the adhesion strength of the phosphate ester starch without the adhesion promoter to the polyester staple fiber was only 25.9 cN/tex.
Example 11
An oil/water amphiphilic starch derivative was synthesized to prepare an adhesion promoter according to the method and procedure of example 1 of the present patent specification. Except that 1, 2-propanediol was used as the plasticizer instead of glycerol in this example.
The effect of the adhesion promoter was evaluated according to the method specified in the textile industry Standard of the people's republic of China FZ/T15001-2008: when the amount of the adhesion promoter prepared in this example added to starch (dry weight ratio) was 20%, the adhesion strength of the urethane starch doped with the adhesion promoter prepared in this example to the polyester staple fibers was 31.8cN/tex, while the adhesion strength of the urethane starch without the adhesion promoter to the polyester staple fibers was only 24.5 cN/tex.
Example 12
An oil/water amphiphilic starch derivative was synthesized to prepare an adhesion promoter according to the method and procedure of example 1 of the present patent specification. Except that 1,1, 1-trimethylolpropane is substituted for glycerol as the plasticizer in this example.
The effect of the adhesion promoter was evaluated according to the method specified in the textile industry Standard of the people's republic of China FZ/T15001-2008: when the amount of the adhesion promoter prepared in this example added to starch (dry weight ratio) was 20%, the adhesion strength of the acetate starch to the polyester staple fiber incorporated with the adhesion promoter prepared in this example was 33.5cN/tex, while the adhesion strength of the acetate starch without the adhesion promoter to the polyester staple fiber was only 27.8/tex.
Example 13
An oil/water amphiphilic starch derivative was synthesized to prepare an adhesion promoter according to the method and procedure of example 1 of the present patent specification. Except that in this example pentaerythritol was used as the plasticizer instead of glycerol.
The effect of the adhesion promoter was evaluated according to the method specified in the textile industry Standard of the people's republic of China FZ/T15001-2008: when the amount of the adhesion promoter prepared in this example added to starch (dry weight ratio) was 20%, the adhesive strength of the acetate starch to the polyester staple fiber incorporated with the adhesion promoter prepared in this example was 32.9cN/tex, while the adhesive strength of the acetate starch without the adhesion promoter to the polyester staple fiber was only 27.8/tex.
Example 14
An oil/water amphiphilic starch derivative was synthesized to prepare an adhesion promoter according to the method and procedure of example 1 of the present patent specification. Except that xylitol was used as a plasticizer instead of glycerin in this example.
The effect of the adhesion promoter was evaluated according to the method specified in the textile industry Standard of the people's republic of China FZ/T15001-2008: when the amount of the adhesion promoter prepared in this example added to starch (dry weight ratio) was 20%, the adhesion strength of the acetate starch to the polyester staple fiber incorporated with the adhesion promoter prepared in this example was 33.0cN/tex, while the adhesion strength of the acetate starch without the adhesion promoter to the polyester staple fiber was only 27.8/tex.
Example 15
An oil/water amphiphilic starch derivative was synthesized to prepare an adhesion promoter according to the method and procedure of example 1 of the present patent specification. Except that sorbitol was used as the plasticizer instead of glycerin in this example.
The effect of the adhesion promoter was evaluated according to the method specified in the textile industry Standard of the people's republic of China FZ/T15001-2008: when the amount of the adhesion promoter prepared in this example added to starch (dry weight ratio) was 20%, the adhesion strength of the acetate starch to the polyester staple fiber incorporated with the adhesion promoter prepared in this example was 33.8cN/tex, while the adhesion strength of the acetate starch without the adhesion promoter to the polyester staple fiber was only 27.8/tex.
Example 16
An oil/water amphiphilic starch derivative was synthesized to prepare an adhesion promoter according to the method and procedure of example 1 of the present patent specification. The difference from example 1 is that in this example, a mixture of 1 part by weight of ethylene glycol, 1 part by weight of 1, 2-propanediol and 1 part by weight of pentaerythritol was used instead of 3 parts by weight of glycerol as the hydroxy plasticizer and a mixture of 2 parts by weight of aniline and 3 parts by weight of monoethanolamine was used instead of 5 parts by weight of urea as the amino plasticizer.
The effect of the adhesion promoter was evaluated according to the method specified in the textile industry Standard of the people's republic of China FZ/T15001-2008: when the amount of the adhesion promoter prepared in this example added to the corn starch was 30% (dry weight ratio), the adhesion strength of the corn starch doped with the adhesion promoter prepared in this example to the polyester staple fiber was 31.8cN/tex, while the adhesion strength of the corn starch without the adhesion promoter to the polyester staple fiber was only 24.5 cN/tex.
Example 17
An oil/water amphiphilic starch derivative was synthesized to prepare an adhesion promoter according to the method and procedure of example 1 of the present patent specification. The difference from example 1 is that in this example, a mixture of 1 part by weight of glycerin, 1 part by weight of ethylene glycol, 1 part by weight of 1, 2-propanediol, 0.5 part by weight of 1,1, 1-trimethylolpropane, 0.5 part by weight of pentaerythritol, 0.5 part by weight of xylitol and 0.5 part by weight of sorbitol is used instead of glycerin as a hydroxy plasticizer, and a mixture of 1 part by weight of urea, 1 part by weight of aniline and 1 part by weight of monoethanolamine is used as an amino plasticizer.
The effect of the adhesion promoter was evaluated according to the method specified in the textile industry Standard of the people's republic of China FZ/T15001-2008: when the amount of the adhesion promoter prepared in this example added to corn starch was 30% (dry weight ratio), the adhesion strength of corn starch to polyester staple fiber incorporating the adhesion promoter prepared in this example was 32.8cN/tex, while the adhesion strength of corn starch without adhesion promoter to polyester staple fiber was only 24.5 cN/tex.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process and process flow, i.e. it is not meant to imply that the present invention must rely on the above detailed process and process flow to be practiced. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (16)
1. The adhesion promoter is characterized by comprising 90-98 parts by weight of oil/water amphiphilic starch derivative, 1-6 parts by weight of hydroxyl plasticizer and 1-8 parts by weight of amino plasticizer; the oil/water amphiphilic starch derivative is modified starch containing propionate substituent and carboxymethyl substituent on a molecular chain; the oil/water amphiphilic starch derivative is prepared by adopting a two-step reaction method of a carboxymethyl etherification reaction and a propionic acid esterification reaction, wherein the carboxymethyl etherification reaction is carried out before the propionic acid esterification reaction;
the total substitution degree of the propionate substituent and the carboxymethyl substituent is 0.025-0.062, the substitution degree of the propionate substituent is 0.016-0.041, and the substitution degree of the carboxymethyl substituent is 0.009-0.034.
2. The adhesion promoter as claimed in claim 1, wherein the total degree of substitution of the propionate substituent and the carboxymethyl substituent is 0.039 to 0.062.
3. The adhesion promoter as claimed in claim 1, wherein the degree of substitution of the propionate substituent is 0.024 to 0.038.
4. The adhesion promoter as claimed in claim 1, wherein the degree of substitution of the carboxymethyl substituent is 0.015 to 0.024.
5. The adhesion promoter as claimed in claim 1, wherein the molar ratio of the propionate substituent to the carboxymethyl substituent is 32/68-82/18.
6. The adhesion promoter as claimed in claim 5, wherein the molar ratio of the propionate substituent to the carboxymethyl substituent is 49/51-82/18.
7. The adhesion promoter of claim 1, wherein the hydroxy plasticizer is selected from one or a mixture of at least two of glycerol, ethylene glycol, 1, 2-propanediol, 1,1, 1-trimethylolpropane, pentaerythritol, xylitol, and sorbitol.
8. The adhesion promoter as claimed in claim 1, wherein the amino plasticizer is selected from one or a mixture of at least two of urea, aniline and monoethanolamine.
9. A method for preparing an adhesion promoter as claimed in any one of claims 1 to 8, comprising the steps of: according to the weight portion, 90-98 portions of oil/water amphiphilic starch derivative, 1-6 portions of hydroxyl plasticizer and 1-8 portions of amino plasticizer are uniformly mixed to prepare the adhesion promoter.
10. The method of claim 9, wherein the oil/water amphiphilic starch derivative is prepared by a two-step reaction method of carboxymethyletherification and propionic esterification, and the carboxymethyletherification is performed before the propionic esterification.
11. The method according to claim 10, wherein the carboxymethyl etherification reaction is a reaction with starch using monochloroacetic acid as an etherification agent.
12. The method according to claim 10, wherein the carboxymethyl etherification reaction comprises the following specific steps: sequentially adding 200-600 parts by weight of 95% ethanol by volume fraction into a reactor, adding 120 parts by weight of starch and 1.5-6 parts by weight of 40% NaOH aqueous solution under stirring, heating to 35 ℃, and alkalizing for 0.5-1 h under stirring; then heating to 40-60 ℃; dissolving 1-4 parts by weight of monochloroacetic acid with 20-60 parts by weight of ethanol with volume fraction of 95%, neutralizing with 1.05-4.2 parts by weight of NaOH aqueous solution with mass fraction of 40%, slowly adding into a reactor, controlling feeding speed, dropwise adding sodium monochloroacetate ethanol solution into the reactor within 0.5-1 h, stirring and reacting for 2-3 h at 40-60 ℃, neutralizing the product with glacial acetic acid until the pH value is 6-7 after the reaction is finished, filtering, washing with 80% ethanol, drying at 60 ℃, and crushing to finish the carboxymethyl etherification reaction to obtain the carboxymethylated starch.
13. The method according to claim 10, wherein the propionic esterification reaction is an esterification reaction of propionic anhydride as an esterifying agent with the carboxymethylated starch in an aqueous solution of sodium sulfate.
14. The preparation method according to claim 10, wherein the propionic acid esterification reaction comprises the following specific steps: 150-400 parts by weight of water and 5-20 parts by weight of Na are sequentially added into a reactor2SO4And 100 parts by weight of the carboxymethylated starch, uniformly stirring, heating to 30-40 ℃, adjusting the pH value of materials in the reactor to 8-9 by using a NaOH aqueous solution with the mass fraction of 3%, slowly dropwise adding 4-16 parts by weight of propionic anhydride, controlling the pH value of reaction materials in the reactor to 8-9 by using a NaOH aqueous solution with the mass fraction of 3% in the reaction process, continuously reacting for 1-3 hours at 30-40 ℃ and under the pH value of 8-9 after the dropwise adding of the propionic anhydride is finished, neutralizing to the pH value of 6.5-7 by using dilute hydrochloric acid after the reaction is finished, and performing suction filtration, washing, drying and crushing to obtain the oil/water amphiphilic starch derivative.
15. The method of claim 12 or 14, wherein the starch is selected from one or a mixture of at least two of corn starch, tapioca starch, potato starch and wheat starch.
16. Use of an adhesion promoter according to any of claims 1 to 8 for improving the adhesion strength of starch slurry to polyester staple fibers.
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