CN114957746B - Polyaldehydic sucrose cross-linked polyhydroxyethyl acrylate-starch film and preparation method thereof - Google Patents

Polyaldehydic sucrose cross-linked polyhydroxyethyl acrylate-starch film and preparation method thereof Download PDF

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CN114957746B
CN114957746B CN202210520595.8A CN202210520595A CN114957746B CN 114957746 B CN114957746 B CN 114957746B CN 202210520595 A CN202210520595 A CN 202210520595A CN 114957746 B CN114957746 B CN 114957746B
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sucrose
spa
polyaldehyde
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张淑芬
庄雪辰
具本植
牛文斌
唐炳涛
马威
武素丽
吕荣文
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Dalian University of Technology
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Abstract

The invention discloses a multi-aldehyde sucrose cross-linked polyhydroxyethyl acrylate-starch film and a preparation method thereof. Crosslinking polyhydroxyethyl acrylate (PHEA) and starch (St) by using a crosslinking agent polyaldehyde Sucrose (SPA) to prepare a novel composite PHEA-SPA-St membrane. When the mass ratio of PHEA to St is 3.5, and SPA is 28wt% of starch, when the PHEA-SPA-St film is stretched, the tensile strength reaches 11.5MPa, the elongation at break is 147.7%, and both higher strength and better flexibility are considered; the glass transition temperature of the composite material is 25 ℃, the composite material is in a rubber state, and the composite material has certain biodegradability.

Description

Polyaldehydic sucrose cross-linked polyhydroxyethyl acrylate-starch film and preparation method thereof
Technical Field
The invention relates to the field of composite high polymer materials, in particular to a multi-aldehyde sucrose cross-linked polyhydroxyethyl acrylate-starch film and a preparation method thereof, belonging to the field of composite materials.
Background
Polyhydroxyethyl acrylate (PHEA) is a widely used polymer, and the hydrogel can absorb a large amount of water, has good biocompatibility and low glass transition temperature, is in a rubber state at room temperature, has good flexibility, and can be applied to biological materials, coatings and medical materials; however, the PHEA structure is a flexible chain, which causes the mechanical strength of the film made of PHEA to be low, so that the PHEA film needs to be compounded with other materials to improve the comprehensive properties such as the strength and the like so as to meet the application requirements. The addition of cross-linking agents is often required during the preparation of cross-linked polymers, however, traditional cross-linking agents such as glutaraldehyde and the like are toxic and thus the use of highly reactive and less toxic cross-linking agents is desirable for green chemistry.
Disclosure of Invention
The invention aims to provide a multi-aldehyde sucrose cross-linked polyhydroxyethyl acrylate-starch film and a preparation method thereof, and the multi-aldehyde sucrose cross-linked polyhydroxyethyl acrylate-starch film has better flexibility, mechanical strength and biocompatibility.
The invention provides a novel composite material polyhydroxyethyl acrylate-polyaldehyde sucrose-starch (PHEA-SPA-St) membrane, wherein polyaldehyde Sucrose (SPA) is used as a cross-linking agent, hydroxyl in polyhydroxyethyl acrylate (PHEA) and hydroxyl in starch (St) are formed into the composite material PHEA-SPA-St membrane which is cross-linked by mixing acetal and hemiacetal through aldehyde groups, and the structural schematic formula is as follows:
-St-St-SPA-PHEA-SPA-St-SPA-PHEA-SPA-St-SPA-PHEA-PHEA-SPA-
the novel composite material PHEA-SPA-St membrane provided by the invention is characterized in that the used polyaldehyde sucrose cross-linking agent is polyaldehyde Sucrose (SPA) which is generated by oxidizing sucrose by periodate and has the average content of aldehyde group of each sucrose molecule more than 3, wherein the molar ratio of sucrose to periodate (such as sodium periodate) is 1-1. The oxidation reaction and the structure of the aldehydic sucrose mixture are shown as follows:
Figure BDA0003641393170000011
the novel composite material PHEA-SPA-St membrane provided by the invention is a polymer with polymerization degree of 10-10000, which is obtained by polymerization initiated by 500-1000W and 200-400 nm ultraviolet light for 1-10 min in the presence of a photoinitiator, wherein the hydroxyethyl acrylate (PHEA) is used;
Figure BDA0003641393170000021
n is an integer of 10 to 10000
The starch used in the novel composite PHEA-SPA-St film provided by the invention comprises one or mixture of two or more of corn starch, potato starch, tapioca starch and wheat starch.
The photoinitiator provided by the invention comprises one or two or more photoinitiators selected from Benzoyl Peroxide (BPO), a photoinitiator 184, a photoinitiator 907, a photoinitiator 369 and a photoinitiator 1173.
The invention also provides a preparation method of the novel composite PHEA-SPA-St membrane, which comprises the following steps:
(1) Adding starch and formic acid into water, and gelatinizing at 85-95 ℃ for 20-60 min to obtain a clear transparent solution; wherein, the concentration of the starch in the water is 5 to 10 weight percent, preferably 5 weight percent;
(2) Adding hydroxyethyl acrylate (HEA) and a photoinitiator into the clear transparent solution, stirring for 10-30 min to obtain a clear transparent solution, carrying out ultrasonic treatment for 5-30 min to eliminate bubbles in the solution, carrying out polymerization on the obtained solution for 1-10 min by adopting ultraviolet light of 1000W and 365nm, polymerizing HEA monomers in the clear transparent solution into PHEA, and forming gel from the clear transparent solution; wherein, the weight ratio of the hydroxyethyl acrylate (HEA) to the starch is 2.7-10;
(3) Preparing polyaldehyde Sucrose (SPA) into a water solution with the concentration of 3.5-8.75 wt%, adding the water solution into the gel system, and volatilizing the solvent to form a film by water at room temperature to 45 ℃ without air flow disturbance; then the removed film is placed in a drying furnace at the temperature of 110-120 ℃ to be cured for 1-3 h for complete crosslinking to form a three-dimensional network novel composite material PHEA-SPA-St film; wherein, the amount of the polyaldehyde group Sucrose (SPA) accounts for 7 to 38.5 weight percent of the starch, and preferably 20 to 30 weight percent.
According to the above technical scheme, in the step (1), the amount of formic acid is 10-20 wt%, preferably 10-15 wt% of the starch.
According to the above technical scheme, in the step (2), the amount of the photoinitiator is 1wt% to 5wt%, preferably 2wt% to 3wt% of the hydroxyethyl acrylate.
According to the above technical solution, the preferred conditions are as follows: firstly, adding starch (the concentration of the starch in the water is 5 wt%) and formic acid (the addition amount of the formic acid is 10-15 wt% of the weight of the starch) into water, and gelatinizing for 30min at 90 ℃ to obtain a clear and transparent solution. Adding HEA and photoinitiator into the obtained clear transparent solution according to the weight ratio of 3.5-5% of HEA to 1, wherein the addition amount of the photoinitiator is 2-3 wt% of HEA, stirring for 10min to form a uniform mixture, and performing ultrasonic treatment for 5min to remove bubbles; pouring the solution into a bottom area of 300cm 2 3cm deep in a polytetrafluoroethylene mold; initiating polymerization for 3-5 min by adopting 1000W and 365nm ultraviolet light to polymerize the HEA monomer in the mixture into PHEA, wherein the mixture forms gel in the polymerization process of the HEA monomer; and then adding a polyaldehyde sucrose solution (the concentration of the polyaldehyde sucrose solution is 3.5-8.75 wt%, and the dosage of the polyaldehyde sucrose accounts for 20-30 wt% of the starch) into the gel system, volatilizing a solvent to form a film under the condition of no air flow disturbance at 40 ℃, and curing for 3 hours at 110 ℃ when the film can be removed to carry out complete crosslinking to form the novel three-dimensional network composite material PHEA-SPA-St.
The invention also aims to provide a novel composite PHEA-SPA-ST membrane with better flexibility, mechanical strength and biocompatibility.
The invention uses cross-linking agent polyaldehyde group Sucrose (SPA) to cross-link polyhydroxyethyl acrylate (PHEA) and starch (St) to prepare a novel composite PHEA-SPA-St film.
Starch (St) is a natural polymer with wide sources, has the characteristics of low price, biodegradability, renewability and the like, is widely researched and reported as a packaging material used in the fields of agriculture, biomedicine and the like, and the molecular chain of the starch is a rigid chain, and the strength and the biodegradability of the composite material can be improved by mixing the starch into the composite material. Both the PHEA and the starch have a large number of hydroxyl groups in molecular structures, and have good compatibility. The covalent crosslinking method is adopted to crosslink the PHEA and hydroxyl groups in the starch to form a network structure, when the PHEA and the starch are stretched, the rigid starch network is broken to dissipate energy, and the flexible PHEA network maintains the structural integrity, so that the integral mechanical strength of the material can be improved. A chemical bond cross-linking structure exists between the PHEA and the starch, hydroxyl groups among molecules of the PHEA and the starch can also form hydrogen bonds, the hydrogen bonds play a role in energy dissipation, the strength of the composite material is further ensured, the starch can be effectively prevented from forming the hydrogen bonds to form a crystallization area, and the brittleness of the material is prevented.
The polyaldehyde group Sucrose (SPA) is a biomass cross-linking agent, is a polyaldehyde group compound produced by oxidizing sucrose with sodium periodate, has a skeleton structure similar to that of glutaraldehyde, has high reaction efficiency and low toxicity, and is a green cross-linking agent. The low-toxicity polyaldehyde group Sucrose (SPA) is adopted to crosslink the PHEA chain and the starch chain, so that the biocompatibility of the composite membrane material can be improved.
The beneficial effects of the invention are as follows:
the invention utilizes PHEA and starch molecular structures to take hydroxyl as a reaction group, mixes two biocompatible materials of a PHEA flexible chain and a starch rigid chain, and adopts biocompatible polyaldehyde group cane sugar as a cross-linking agent to prepare the novel composite material PHEA-SPA-St membrane.
When the film material is stretched, the starch (St) rigid chain is broken to dissipate energy, the PHEA flexible chain is used for maintaining structural integrity, so that the material has better mechanical property, and hydroxyl groups between the starch (St) rigid chain and the PHEA flexible chain form hydrogen bonds to play a role in dissipating energy, so that the integral mechanical strength and flexibility of the material are further ensured; when the mass ratio of HEA to St is 3.5 and SPA is 28wt% of the mass of starch, the tensile strength of the material reaches 11.5MPa, the elongation at break is 147.7%, and both higher strength and better flexibility are taken into consideration; the glass transition temperature of the composite material is 25 ℃, namely the composite material is in a rubbery soft state at the temperature of over 25 ℃ and has better biocompatibility and biodegradability.
Drawings
FIG. 1 (a) IR spectra of sucrose and SPA prepared; and (b) nuclear magnetic spectrum of sucrose and prepared SPA.
FIG. 2 Tan. Delta. Of the composite PHEA-SPA-St (the mass ratio of HEA to St is 3.5, SPA is 28wt% of the mass of starch).
FIG. 3 digital photographs of PHEA-SPA-St soaked in aquarium water for (a) 0 days, (b) 7 days, (c) 21 days, and (d) 35 days; PHEA-SPA-St was soaked in sterile water for (a) 0 days, (b) 7 days, (c) 21 days, and (d) 35 days of digital photographs.
Detailed Description
The following non-limiting examples will allow a person skilled in the art to more fully understand the invention, but do not limit it in any way.
The experimental preparation methods described in the following examples are all conventional operation methods unless otherwise specified; the materials and reagents are commercially available, unless otherwise specified.
EXAMPLE 1 preparation of polyaldehyde sucrose
192.5g of sodium periodate was added to 900mL of deionized water at 35 ℃ and dissolved by stirring to obtain a uniform solution, and 102.7g of sucrose was added to the solution. The temperature was kept at 35 ℃ and the reaction was carried out for 1h in the dark. Filtering to remove solid sodium iodate after reaction, heating and concentrating the filtrate to obtain solid, and placing the solid in a vacuum drying oven at 60 ℃ to dry until the weight is constant to obtain a solid product polyaldehyde base Sucrose (SPA).
The aldehyde group content was measured by reacting polyaldehyde Sucrose (SPA) with hydroxylamine hydrochloride to release hydrochloric acid and titrating with sodium hydroxide. The test shows that the aldehyde group content of the obtained polyaldehyde group Sucrose (SPA) is 3.4 per sucrose molecule on average.
Performing FTIR test on SPA and sucrose by using a high-grade Fourier transform infrared spectrometer (6700); SPA and sucrose were subjected to magnetic resonance spectroscopy (Varian INOVA 500) 1 H NMR measurement, samples dissolved in DMSO-d6. The test results are shown in FIG. 1. In FTIR contrast, SPA at 1723cm -1 The peak is a stretching vibration peak of C = O, indicating the formation of aldehyde groups after oxidation. At the same time, in 1 In the H NMR chart, the formation of aldehyde groups is further illustrated by the existence of peaks at the SPA chemical shift of 8-10 ppm. In addition, a cluster of peaks exist at the chemical shift of 4.5-5.5, which indicates that the aldehyde group of SPA and the hydroxyl group form hemiacetal, so that the aldehyde group can exist stably.
Example 2
(1) Adding 2.5g of starch and 0.25g of formic acid into 50mL of water, and gelatinizing for 60min at 85 ℃ to obtain starch gelatinizing liquid.
(2) Adding 6.75g of HEA (the mass ratio of HEA to starch is 2.7 2 Polymerizing 1min in a 3cm deep polytetrafluoroethylene mold by ultraviolet light of 1000W and 365nm, and polymerizing the HEA monomer in the clear transparent solution into PHEA which is in a gel shape.
(3) The SPA prepared in example 1 was prepared into 5wt% aqueous solution, 20mL SPA aqueous solution (SPA is 10wt% of starch) was added to the gel-like material, and the solvent was evaporated to form a film at 40 ℃ without air flow disturbance. And (3) placing the film in an oven to be cured for 2h at the temperature of 115 ℃ to form the novel three-dimensional network composite material PHEA-SPA-St.
The tensile strength of the film was 9.5MPa and the elongation at break was 71.3% as measured with a Universal tensile machine PT-307 manufactured by Procter detection Equipment Ltd.
Example 3
(1) Adding 2.5g of starch and 0.3g of formic acid into 50mL of water, and gelatinizing for 30min at 90 ℃ to obtain starch gelatinizing liquid.
(2) Adding 8.75g of HEA (the mass ratio of HEA to starch is 3.5 2 Polymerizing HEA monomer in clear transparent solution into PHEA in gel form in a polytetrafluoroethylene mold with depth of 3cm for 3min under the initiation of ultraviolet light of 1000W and 365 nm.
(3) The SPA prepared in example 1 was prepared into 3.5wt% aqueous solution, 20mL of 3.5wt% aqueous SPA solution (SPA 28wt% of starch) was added to the gel-like mass, and the solvent was evaporated to form a film at 40 ℃ without flow disturbance. And (3) placing the membrane in an oven to be cured for 3 hours at 110 ℃ to form the three-dimensional network novel composite material PHEA-SPA-St.
Protechs of Protechs, ltdThe tensile strength of the film is 11.5MPa and the elongation at break is 147.7 percent by measurement of a produced universal tensile machine PT-307. Tan delta represents the loss factor, the peak of which represents the glass transition temperature (T) of the material g ). From FIG. 2, the T of the composite material can be seen g It was 25 ℃.
Example 4
(1) Adding 2.5g of starch and 0.35g of formic acid into 50mL of water, and gelatinizing for 40min at 90 ℃ to obtain starch gelatinizing liquid.
(2) Adding 12.5g of HEA (the mass ratio of HEA to starch is 5 2 Polymerizing for 5min in a polytetrafluoroethylene mold with the depth of 3cm by using ultraviolet light of 1000W and 365nm, and polymerizing the HEA monomer in the clear transparent solution into PHEA which is in a gel shape.
(3) The SPA prepared in example 1 was prepared into 5wt% aqueous solution, and 7.5mL SPA aqueous solution (SPA is 15wt% of starch) with concentration of 5% was added to the gel-like material, and the solvent was evaporated to form a film at 40 ℃ without air flow disturbance. And (3) placing the membrane in an oven to be cured for 1h at 120 ℃ to form the novel three-dimensional network composite material PHEA-SPA-St.
The tensile strength of the film was 6.8MPa and the elongation at break was 313.3% as measured with a Universal tensile machine PT-307 manufactured by Procter inspection Equipment Ltd.
Example 5
(1) Adding 2.5g of starch and 0.25g of formic acid into 50mL of water, and gelatinizing for 20min at 95 ℃ to obtain starch gelatinized liquid.
(2) Adding 18.75g of HEA (the mass ratio of HEA to starch is 7.5 2 Polymerizing HEA monomer in clear transparent solution into PHEA in gel state in a 3cm deep polytetrafluoroethylene mold for 7.5min under the initiation of 1000W and 365nm ultraviolet light.
(3) The SPA prepared in example 1 was prepared into 5wt% aqueous solution, 10mL SPA aqueous solution (SPA is 20wt% of starch) was added to the gel-like material, and the solvent was evaporated to form a film at 40 ℃ without air flow disturbance. And (3) placing the membrane in an oven to be cured for 3 hours at 110 ℃ to form the three-dimensional network novel composite material PHEA-SPA-St.
The tensile strength of the film was 5.0MPa and the elongation at break was 600.7% as measured by a Universal tensile machine PT-307 manufactured by Procter detection Equipment Ltd.
Example 6
(1) Adding 2.5g of starch and 0.50g of formic acid into 50mL of water, and gelatinizing at 85 ℃ for 30min to obtain starch gelatinizing liquid.
(2) Adding 25g of HEA (the mass ratio of HEA to starch is 10 2 Polymerizing for 6min in a polytetrafluoroethylene mold with the depth of 3cm by using ultraviolet light of 1000W and 365nm, and polymerizing the HEA monomer in the clear transparent solution into PHEA which is in a gel shape.
(3) The SPA prepared in example 1 was prepared into an aqueous solution with a concentration of 4.8125wt%, 20mL of the aqueous SPA solution with a concentration of 4.8125wt% (SPA was 38.5wt% of starch) was added to the gel-like mass, and the solvent was evaporated to form a film at 40 ℃ without air flow disturbance. And (3) placing the membrane in an oven to be cured for 1h at 120 ℃ to form the three-dimensional network novel composite material PHEA-SPA-St.
The tensile strength of the film was 3.5MPa and the elongation at break was 674.2%, as measured with a Universal tensile machine PT-307 manufactured by Procet test Equipment Ltd.
Example 7
(1) Adding 2.5g of starch and 0.25g of formic acid into 50mL of water, and gelatinizing for 20min at 90 ℃ to obtain starch gelatinizing liquid.
(2) Adding 8.75g of HEA (the mass ratio of HEA to starch is 3.5 2 Polymerizing HEA monomer in clear transparent solution into PHEA by initiating polymerization for 3min with ultraviolet light of 1000W and 365nm in a polytetrafluoroethylene mold with depth of 3cmIn the form of gel.
(3) Directly volatilizing the solvent to form a film on the gel material at 40 ℃ under the condition of no air flow disturbance. And (3) placing the film in an oven for curing for 3h at 110 ℃ to form the novel three-dimensional network composite material PHEA-SPA-St.
The tensile strength of the film was 2.9MPa and the elongation at break was 197.4% as measured with a Universal tensile machine PT-307 manufactured by Procter inspection Equipment Ltd.
Example 8
(1) Adding 2.5g of starch and 0.25g of formic acid into 50mL of water, and gelatinizing for 20min at 90 ℃ to obtain starch gelatinizing liquid.
(2) Adding 25g of HEA (the mass ratio of HEA to starch is 10 2 Polymerizing HEA monomer in clear transparent solution into PHEA in gel form in a polytetrafluoroethylene mold with depth of 3cm for 10min under the initiation of ultraviolet light of 1000W and 365 nm.
(3) The SPA prepared in example 1 was prepared into a 3.5wt% aqueous solution, 5mL of the 3.5wt% aqueous solution of SPA (SPA was 7wt% based on starch) was added to the gel-like mass, and the solvent was evaporated to form a film at 40 ℃ without flow disturbance. And (3) placing the membrane in an oven to be cured for 3 hours at 110 ℃ to form the three-dimensional network novel composite material PHEA-SPA-St.
The tensile strength of the film was 4.4MPa and the elongation at break was 187.3% as measured by a Universal tensile machine PT-307 manufactured by Prositter test Equipment Ltd.
Example 9
(1) Adding 2.5g of starch and 0.45g of formic acid into 50mL of water, and gelatinizing for 60min at 85 ℃ to obtain starch gelatinizing liquid.
(2) Adding 12.5g of HEA (the mass ratio of HEA to starch is 5 2 Initiating polymerization with 1000W and 365nm ultraviolet light in 3cm deep polytetrafluoroethylene mold for 9min, and polymerizing HEA monomer in clear transparent solutionPHEA in gel form.
(3) The SPA prepared in example 1 was prepared into an aqueous solution with a concentration of 8.75wt%, 5mL of the aqueous SPA solution with a concentration of 8.75wt% (SPA was 17.5wt% of starch) was added to the gel-like mass, and the solvent was evaporated to form a film at 40 ℃ without flow disturbance. And (3) placing the film in an oven to be cured for 2h at the temperature of 115 ℃ to form the novel three-dimensional network composite material PHEA-SPA-St.
The tensile strength of the film was 7.2MPa and the elongation at break was 167.1% as measured with a Universal tensile machine PT-307 manufactured by Procter detection Equipment Ltd.
Example 10
(1) Adding 2.5g of starch and 0.5g of formic acid into 50mL of water, and gelatinizing at 85 ℃ for 20min to obtain starch gelatinizing liquid.
(2) Adding 8.75g of HEA and 0.175g of photoinitiator 1173 into the starch gelatinization liquid, stirring for 10min, performing ultrasonic treatment for 5min, pouring the obtained solution into the container with bottom area of 300cm 2 Polymerizing HEA monomer in clear transparent solution into PHEA in gel form in a polytetrafluoroethylene mold with depth of 3cm for 10min under the initiation of ultraviolet light of 1000W and 365 nm.
(3) The SPA prepared in example 1 was prepared into a 5wt% aqueous solution, 19.25mL of the 5wt% aqueous solution of SPA (SPA was 38.5wt% based on starch) was added to the gel-like mass, and the solvent was evaporated to form a film at 40 ℃ without flow disturbance. And (3) placing the film in an oven for curing for 3h at 110 ℃ to form the novel three-dimensional network composite material PHEA-SPA-St.
The tensile strength of the film was 15.9MPa and the elongation at break was 55.0% as measured by a Universal tensile machine PT-307 manufactured by Procter detection Equipment Ltd.
Example 11
In order to measure the biodegradability of the novel composite PHEA-SPA-St membrane created by the present invention, the membrane material prepared in example 3 was soaked in aquarium water for 35 days. The fish tank water is a small ecological system after fish culture, and contains nitrobacteria, photosynthetic bacteria, bacillus and the like. As can be seen from FIG. 3, the swollen surface of the membrane was almost flat at 7 days, the swelling of the membrane was evident at 21 days, and the surface had colonies although the membrane remained intact, while at 35 days, the membrane could not be found in the aquarium water, indicating that the material was substantially completely degraded. The starch in the film material is a biodegradable material, and the oligomeric PHEA and the starch are both good hydrophilic materials, so that the film material disappears in the fish tank water finally, and the material has certain biodegradability. In contrast, the PHEA-SPA-St membrane was also soaked in sterile water for more than 35 days, and the digital photographs are shown in FIGS. e-h. The mass concentration of the sample in the sterile water is the same as that in the fish tank water, and is 0.013 percent of the weight of water. The composite membrane swelled but did not disappear after 35 days, indicating that the PHEA-SPA-St membrane could be biodegraded by bacteria.

Claims (8)

1. The polyhydroxyethyl acrylate-polyaldehyde sucrose-starch film composite material is characterized in that polyaldehyde sucrose is used as a cross-linking agent, hydroxyl in polyhydroxyethyl acrylate and hydroxyl in starch are formed into a composite material PHEA-SPA-St film which is cross-linked by mixing acetal and hemiacetal through aldehyde groups, and the structural schematic formula of the PHEA-SPA-St film is as follows:
-St-St-SPA-PHEA-SPA-St-SPA-PHEA-SPA-St-SPA-PHEA-PHEA-SPA-；
wherein the weight ratio of the hydroxyethyl acrylate to the starch is 3-7.5.
2. The polyhydroxyethyl acrylate-polyaldehyde sucrose-starch film composite according to claim 1, wherein the polyaldehyde sucrose cross-linking agent is polyaldehyde sucrose which is prepared by periodate oxidation of sucrose and has an average content of aldehyde groups per sucrose molecule of more than 3.
3. The polyhydroxyethyl acrylate-polyaldehyde sucrose-starch film composite material of claim 2, wherein the molar ratio of the sucrose to the periodate is 1-1.
4. The polyhydroxyethylacrylate-polyaldehyde sucrose-starch film composite material of claim 1, wherein the polyhydroxyethylacrylate is a polymer obtained by polymerizing hydroxyethyl acrylate in the presence of a photoinitiator under the initiation of ultraviolet light of 500-1000W and 200-400 nm for 1-10 min.
5. The polyhydroxyethyl acrylate-polyaldehyde sucrose-starch film composite of claim 1 wherein the starch comprises one or a mixture of two or more of corn starch, potato starch, tapioca starch, wheat starch.
6. The polyhydroxyethyl acrylate-polyaldehyde sucrose-starch film composite material of claim 4, wherein the photoinitiator comprises one or two or more of benzoyl peroxide, photoinitiator 184, photoinitiator 907, photoinitiator 369 and photoinitiator 1173.
7. The method for preparing polyhydroxyethyl acrylate-polyaldehyde sucrose-starch film composite material according to any one of claims 1 to 6, which comprises the following steps:
(1) Adding starch and formic acid into water, and gelatinizing at 85-95 ℃ for 20-60 min to obtain a clear transparent solution; wherein the concentration of the starch in the water is 5-10 wt%;
(2) Adding hydroxyethyl acrylate and a photoinitiator into the clear transparent solution, stirring for 10-30 min to obtain a clear transparent solution, carrying out ultrasonic treatment for 5-30 min, and carrying out polymerization on the obtained solution for 1-10 min by adopting ultraviolet light with the wavelength of 500-1000W and 200-400 nm to form gel; wherein, the weight ratio of the hydroxyethyl acrylate to the starch is 3-7.5;
(3) Preparing polyaldehyde sucrose into a water solution with the concentration of 3.5-8.75 wt%, adding the water solution into the gel system, and volatilizing a solvent to form a film at room temperature to 45 ℃ without air flow disturbance; curing the film at 110-120 ℃ for 1-3 h for complete crosslinking to form the polyhydroxyethyl acrylate-polyaldehyde sucrose-starch film composite material; wherein, the dosage of the polyaldehyde group cane sugar accounts for 7 to 38.5 weight percent of the starch.
8. The method for preparing polyhydroxyethyl acrylate-polyaldehyde sucrose-starch film composite material of claim 7, wherein in step (1), the amount of formic acid is 10-20 wt% of starch; in the step (2), the dosage of the photoinitiator is 1 to 5 weight percent of the hydroxyethyl acrylate.
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