CN110283426B - Bio-based degradable starch filled epoxy resin composite material and preparation method thereof - Google Patents
Bio-based degradable starch filled epoxy resin composite material and preparation method thereof Download PDFInfo
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- CN110283426B CN110283426B CN201910624519.XA CN201910624519A CN110283426B CN 110283426 B CN110283426 B CN 110283426B CN 201910624519 A CN201910624519 A CN 201910624519A CN 110283426 B CN110283426 B CN 110283426B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/08—Ethers
- C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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Abstract
The invention discloses a bio-based degradable starch filled epoxy resin composite material and a preparation method thereof. The weight of the biodegradable starch is 1-120 parts, and the weight of the curing agent is 20-300 parts, based on 100 parts of the epoxy resin. The composite material obtained by the invention is partially biodegradable, has excellent mechanical property, low price and controllable structure and performance, is a green and environment-friendly material, is environment-friendly, and is easy to realize industrial production.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a bio-based degradable starch filled epoxy resin composite material and a preparation method thereof.
Background
The epoxy resin has the advantages of low curing shrinkage, strong bonding force, high mechanical property of cured products, good chemical resistance, good electrical insulation property and the like, has an irreplaceable status in the fiber reinforced resin matrix composite material, and is widely applied to the fields of spaceflight, aviation, automobiles, buildings and the like. However, the traditional epoxy resin has large dependence on petroleum resources, causes environmental pollution in the production process and is difficult to degrade. The use and disposal of a large amount of white pollution become one of the sources of white pollution, and become a problem of social concern, and how to solve the white pollution problem is a significant issue worthy of research. The vigorous development of biodegradable plastics to gradually replace traditional plastics is one of the effective ways to solve the white pollution.
The starch filled thermosetting resin has low cost, relatively simple process and easily available starch source, reduces the dependence of the plastic industry on petroleum resources from the development trend of low-carbon economy, reduces the pollution of petroleum-based chemical raw materials to the environment in the production process, has double effects of saving the petroleum resources and protecting the environment, and has wide application prospect.
At present, although researches on modification of a simple epoxy resin system by using starch are still in the beginning stage, the problems of difficult dispersion of starch and unobvious modification effect exist, and the filling ratio is also maintained at a low level, for example, patent CN102516714A discloses that the epoxy resin is toughened and modified by using starch nanocrystals, but the filling ratio with the best effect is only increased by 33% compared with the elongation at break of the original resin, and the performance begins to be reduced when the filling ratio is more than 5%. The paper RSC adv, 2015,5,64456 and 64465 use the grafting reaction of epoxy resin and starch to prepare starch-based epoxy resin, which has better resin performance, but the chemical grafting method is more complicated, and the starch filling ratio is not high, only 20%, due to the problem of grafting efficiency. The preparation method provided by the patent is simple to operate, has an obvious toughening effect, can achieve a high filling proportion, achieves the effects of reducing cost and biodegradation, and has a good industrial application prospect.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a bio-based degradable starch filled epoxy resin composite material and a preparation method thereof. The composite material obtained by the invention is biodegradable, has excellent mechanical property, low price and controllable structure and performance, is a green and environment-friendly material, is environment-friendly and is easy to realize industrial production.
The technical scheme of the invention is as follows:
the composite material is characterized by comprising 1-120 parts by weight, preferably 3-90 parts by weight of biodegradable modified starch and 100 parts by weight of epoxy resin, and 20-300 parts by weight, preferably 50-150 parts by weight of curing agent.
The epoxy resin comprises at least one of bisphenol A type, bisphenol F type, bisphenol S type and other epoxy resins.
The curing agent comprises at least one of anhydride curing agents such as methyl tetrahydrophthalic anhydride and methyl hexahydrophthalic anhydride, aliphatic polyamine curing agents and polyether amine.
The epoxy modified starch is prepared by reacting the following components: 100 parts of active starch; 50-1000 parts of solvent, preferably 100-400 parts; 5-100 parts of modifier, preferably 10-30 parts; 1 to 30 parts by weight of catalyst, preferably 5 to 20 parts by weight.
Wherein the natural starch source is potato, corn starch, wheat, cassava, etc.
The solvent is at least one selected from small molecular esters, alcohols, water, dimethyl sulfoxide and chloroform;
the modifier is aliphatic hydrocarbon containing halogen end group and epoxy group such as epichlorohydrin and epoxy bromopropane.
The catalyst is selected from at least one of inorganic base or organic base, such as pyridine, pyrrole, and sodium hydroxide solution.
The preparation method of the epoxy modified starch comprises the following steps:
(a) dispersing natural starch in a solvent, activating the natural starch by adopting an enzymolysis or hydrolysis mode, and neutralizing a reaction system to pH 7 to obtain the active starch.
(b) Dispersing active starch into solvent, adding catalyst and modifier, and reacting at 45-70 deg.C for 1-48 h. Washing the obtained product with water, washing with alcohol, and drying at low temperature.
Wherein, when hydrochloric acid is added in a hydrolysis mode, the mass ratio of the natural starch to the hydrochloric acid is 100: 1-100; when the amylase is added in an enzymolysis mode, the mass ratio of the natural starch to the amylase is 100: 1-100.
The preparation method of the bio-based degradable starch filled epoxy resin composite material comprises the following steps: and mixing the epoxy modified starch, the curing agent and the epoxy resin in proportion, removing bubbles in vacuum, pouring into a mold, and performing thermosetting molding to obtain the composite material.
The thermosetting is divided into three stages: curing at 60-100 ℃ for 1-4h, 100-140 ℃ for 1-4h and 20-100 ℃ for 10-100 h.
The molecular weight of the active starch is 104～107g/mol。
The composite material comprises two parts of biodegradable starch and an epoxy resin matrix, the compatibility of the starch and the epoxy resin is improved through the epoxy modified starch, the combination of starch particles and the epoxy resin matrix is enhanced, and the problem of poor mechanical property caused by poor blending compatibility of common starch and the epoxy resin is solved.
The invention has the beneficial effects that: the bio-based degradable starch filled epoxy resin composite material obtained by the preparation method provided by the invention has the advantages of large starch filling proportion, low cost, excellent mechanical property, controllable structure and performance, capability of being prepared on traditional simple pouring forming equipment, environmental friendliness and easiness in realizing industrial production.
Detailed Description
The present invention will be further described with reference to the following examples.
Preparation of epoxy modified starch
Example 1:
weighing 100g of corn starch, dispersing in 200g of ethanol/water solution (the volume ratio of ethanol to water is 7:3), dropwise adding 10ml of concentrated hydrochloric acid while stirring, heating to 55 ℃, stopping reaction after 24 hours of reaction, adjusting the pH value to 7 by using a sodium hydroxide water solution, filtering, washing and drying to obtain the active starch.
Weighing 100g of active starch, adding the active starch into 200g of water/ethanol solution (the volume ratio of ethanol to water is 7:3), uniformly stirring and dispersing, adding sodium hydroxide to adjust the pH to 9 (the pH is adjusted by introducing the sodium hydroxide into a system for preparing modified starch as a catalyst), heating to 60 ℃, adding 10g of pyridine and 15g of epoxy chloropropane, and continuing to react for 2 hours to stop the reaction. Washing the obtained product with water and alcohol to remove impurities and byproducts, and drying at low temperature to obtain the epoxy modified starch.
The epoxy value of the prepared epoxy modified starch is detected by a hydrochloric acid-acetone method, and the detected epoxy value is 0.054mol/100 g.
Example 2:
weighing 100g of corn starch, dispersing the corn starch in 200g of ethanol solution with volume fraction of 70%, dropwise adding 10ml of concentrated hydrochloric acid in the stirring process, heating to 55 ℃, stopping the reaction after reacting for 24 hours, adjusting the pH value to 7 by using sodium hydroxide aqueous solution, filtering, washing and drying to obtain the active starch.
Weighing 100g of active starch, adding the active starch into 200g of ethyl acetate solution, uniformly stirring and dispersing, heating to 60 ℃, adding 10g of pyridine and 15g of epoxy chloropropane, reacting for 30 minutes, supplementing 10g of pyridine, and continuing to react for 2 hours to stop the reaction. Washing the obtained product with water and alcohol to remove impurities and byproducts, and drying at low temperature to obtain the epoxy modified starch.
The epoxy value of the prepared epoxy modified starch is detected by a hydrochloric acid-acetone method, and the detected epoxy value is 0.091mol/100 g.
Example 3:
weighing 100g of corn starch, dispersing the corn starch in 200g of ethanol solution with volume fraction of 70%, dropwise adding 10ml of concentrated hydrochloric acid in the stirring process, heating to 55 ℃, stopping the reaction after reacting for 24 hours, adjusting the pH value to 7 by using sodium hydroxide aqueous solution, filtering, washing and drying to obtain the active starch.
Weighing 100g of active starch, adding the active starch into 100g of ethyl acetate solution, uniformly stirring and dispersing, heating to 60 ℃, adding 10g of pyridine and 15g of epoxy chloropropane, and continuing to react for 2 hours to stop the reaction. Washing the obtained product with water and alcohol to remove impurities and byproducts, and drying at low temperature to obtain the epoxy modified starch.
The epoxy value of the prepared epoxy modified starch is detected by a hydrochloric acid-acetone method, and the detected epoxy value is 0.060mol/100 g.
Example 4:
weighing 100g of potato starch, dispersing in 200g of 70% ethanol solution by volume fraction, dropwise adding 10ml of concentrated hydrochloric acid while stirring, heating to 55 ℃, stopping reaction after 24 hours of reaction, adjusting the pH value to 7 by using sodium hydroxide aqueous solution, filtering, washing and drying to obtain the active starch.
Weighing 100g of acidolysis starch, adding into 200g of ethyl acetate solution, stirring and dispersing uniformly, heating to 60 ℃, adding 5g of pyridine and 15g of epichlorohydrin, and continuing to react for 2h to stop the reaction. Washing the obtained product with water and alcohol to remove impurities and byproducts, and drying at low temperature to obtain the epoxy modified starch.
The epoxy value of the prepared epoxy modified starch is detected by a hydrochloric acid-acetone method, and the detected epoxy value is 0.060mol/100 g.
Example 5:
weighing 100g of potato starch, dispersing in 200g of 70% ethanol solution by volume fraction, dropwise adding 10ml of concentrated hydrochloric acid while stirring, heating to 55 ℃, stopping reaction after 24 hours of reaction, adjusting the pH value to 7 by using sodium hydroxide aqueous solution, filtering, washing and drying to obtain the active starch.
Weighing 100g of acidolysis starch, adding into 200g of ethyl acetate solution, stirring and dispersing uniformly, heating to 60 ℃, adding 20g of pyridine and 20g of epichlorohydrin, reacting for 10h, and stopping the reaction. Washing the obtained product with water and alcohol to remove impurities and byproducts, and drying at low temperature to obtain the epoxy modified starch.
The epoxy value of the prepared epoxy modified starch is detected by a hydrochloric acid-acetone method, and the detected epoxy value is 0.056mol/100 g.
Preparation of composite material
Example 6
100 parts of epoxy E-44 resin, 80 parts of curing agent methyl tetrahydrophthalic anhydride and 3 parts of epoxy modified starch in example 2 are mixed, fully stirred and uniformly mixed by a homogenizer, bubbles are removed in vacuum, the mixture is poured into a preheated mold, and the mold is placed at 80 ℃ for 2h, is reacted and cured at 120 ℃ for 2h and is then placed at 80 ℃ for overnight to be fully cured. The mold comprises dumbbell-shaped sample strips and cuboid sample strips which are respectively used for a tensile test and an impact test, and various test results are shown in table 1.
Example 7
100 parts of epoxy E-44 resin, 80 parts of curing agent methyl tetrahydrophthalic anhydride and 20 parts of epoxy modified starch in example 2 are mixed, fully stirred and uniformly mixed by a homogenizer, bubbles are removed in vacuum, the mixture is poured into a preheated mold, and the mold is placed at 80 ℃ for 2h, is reacted and cured at 120 ℃ for 2h and is then placed at 80 ℃ for overnight to be fully cured. The mold comprises dumbbell-shaped sample strips and cuboid sample strips which are respectively used for a tensile test and an impact test, and various test results are shown in table 1.
Example 8
100 parts of epoxy E-44 resin, 80 parts of curing agent methyl tetrahydrophthalic anhydride and 40 parts of epoxy modified starch in example 2 are mixed, fully stirred and uniformly mixed by a homogenizer, bubbles are removed in vacuum, the mixture is poured into a preheated mold, and the mold is placed at 80 ℃ for 2h, is reacted and cured at 120 ℃ for 2h and is then placed at 80 ℃ for overnight to be fully cured. The mold comprises dumbbell-shaped sample strips and cuboid sample strips which are respectively used for a tensile test and an impact test, and various test results are shown in table 1.
Example 9
100 parts of epoxy E-44 resin, 80 parts of curing agent methyl tetrahydrophthalic anhydride and 90 parts of epoxy modified starch in example 2 are mixed, fully stirred and uniformly mixed by a homogenizer, bubbles are removed in vacuum, the mixture is poured into a preheated mold, and the mold is placed at 80 ℃ for 2h, is reacted and cured at 120 ℃ for 2h and is then placed at 80 ℃ for overnight to be fully cured. The mold comprises dumbbell-shaped sample strips and cuboid sample strips which are respectively used for a tensile test and an impact test, and various test results are shown in table 1.
Comparative example 1
100 parts of epoxy E-44 resin, 80 parts of curing agent methyl tetrahydrophthalic anhydride and 20 parts of natural starch are mixed, fully stirred and uniformly mixed by a homogenizer, bubbles are removed in vacuum, the mixture is poured into a preheated mould, and the mould is placed at 80 ℃ for 2h, is reacted and cured at 120 ℃ for 2h and is then placed at 80 ℃ for overnight to be fully cured. The mold comprises dumbbell-shaped sample strips and cuboid sample strips which are respectively used for a tensile test and an impact test, and various test results are shown in table 1.
Comparative example 2
100 parts of epoxy E-44 resin and 80 parts of curing agent methyl tetrahydrophthalic anhydride are mixed, fully stirred and uniformly mixed by a homogenizer, bubbles are removed in vacuum, the mixture is poured into a preheated mould, and the mould is placed at 80 ℃ for 2 hours and 120 ℃ for 2 hours for reaction and curing and then is fully cured at 80 ℃ overnight. The mold comprises dumbbell-shaped sample strips and cuboid sample strips which are respectively used for a tensile test and an impact test, and various test results are shown in table 1.
TABLE 1
As can be seen from the results in Table 1, the comparative examples 1 and 2 have poor performance and extremely low elongation at break, and particularly after the natural starch is added into the comparative example 1, the elongation at break and the tensile strength are obviously reduced due to poor compatibility with a matrix; compared with the pure epoxy resin in the comparative example 2, the epoxy modified starch filled epoxy resin composite material has excellent performance, and the production cost can be greatly reduced by filling the epoxy modified starch. Examples 6-9 show that: after the epoxy modified starch is added, the compatibility of the epoxy modified starch and the matrix is good, and meanwhile, the starch particles absorb energy in the breaking process, so that crack extension is prevented, and the toughening effect on the epoxy resin matrix is achieved. Therefore, the invention provides the bio-based degradable starch filled epoxy resin composite material and the preparation method thereof, the method is simple and convenient to operate, environment-friendly, and easy to realize industrial production, and a feasible thought is provided for epoxy resin toughening, environment-friendly filling, cost regulation and control and the like.
The foregoing examples are merely illustrative and are provided to illustrate some of the features of the present invention. The appended claims are intended to claim the broadest possible scope, and the examples presented herein are merely illustrative of selected embodiments in all possible combinations of examples and are not intended to limit the invention in any way, so that any simple modification, equivalent change or modification of the above examples in accordance with the technical spirit of the invention, without departing from the scope of the invention.
Claims (9)
1. The bio-based degradable starch filled epoxy resin composite material is characterized by being prepared by blending and curing epoxy modified starch, a curing agent and epoxy resin, wherein the addition amount of each substance is calculated according to 100 parts by weight of the epoxy resin, the epoxy modified starch is 1-120 parts by weight, and the curing agent is 20-300 parts by weight; the epoxy modified starch is obtained by heating the following raw materials: 100 parts of active starch, 50-1000 parts of solvent, 5-100 parts of modifier and 1-30 parts of catalyst; the active starch is enzymolysis or/and hydrolysis starch; the modifier is aliphatic hydrocarbon containing halogen end group and epoxy group; the catalyst is one or two of pyridine and pyrrole; the preparation method of the epoxy modified starch comprises the following steps:
(a) dispersing natural starch in a solvent, activating the natural starch in an enzymolysis or hydrolysis mode, and neutralizing a reaction system to pH 7 to obtain active starch;
(b) dispersing active starch into a solvent, adding a catalyst and a modifier, and reacting for 5-48h at 45-70 ℃; washing the obtained product with water, washing with alcohol, and drying at low temperature;
the natural starch source is potato starch, corn starch, wheat starch or cassava starch.
2. The bio-based degradable starch filled epoxy resin composite material as claimed in claim 1, wherein the raw material components for preparing the composite material are: 100 parts by weight of epoxy resin, 3-90 parts by weight of epoxy modified starch and 50-150 parts by weight of curing agent; the raw material components for preparing the epoxy modified starch are as follows: 100 parts of active starch, 100 parts of solvent, 400 parts of modifier, 10-30 parts of catalyst and 5-20 parts of catalyst.
3. The bio-based degradable starch filled epoxy resin composite material as claimed in claim 1 or 2, wherein the epoxy resin is one or more of bisphenol A type, bisphenol F type or bisphenol S type epoxy resin; the curing agent is one or more of anhydride curing agent, aliphatic polyamine curing agent and polyether amine.
4. The biodegradable starch-filled epoxy resin composite material as claimed in claim 1 or 2, wherein the curing agent is one or a mixture of methyl tetrahydrophthalic anhydride and methyl hexahydrophthalic anhydride; the solvent is one or more than two of esters of C1-C10, alcohols, water, dimethyl sulfoxide and trichloromethane; the modifier is one or a mixture of epoxy chloropropane and epoxy bromopropane.
5. The bio-based degradable starch filled epoxy resin composite material as claimed in claim 3, wherein said curing agent is one or a mixture of methyl tetrahydrophthalic anhydride and methyl hexahydrophthalic anhydride; the solvent is one or more than two of esters of C1-C10, alcohols, water, dimethyl sulfoxide and trichloromethane; the modifier is one or a mixture of epoxy chloropropane and epoxy bromopropane.
6. The bio-based degradable starch filled epoxy resin composite material as claimed in claim 4, wherein said solvent is ethyl acetate or ethanol/water mixed solvent.
7. The bio-based degradable starch filled epoxy resin composite material as claimed in claim 5, wherein said solvent is ethyl acetate or ethanol/water mixed solvent.
8. The preparation method of the bio-based degradable starch filled epoxy resin composite material of any one of claims 1 to 7, characterized by comprising the following steps: and mixing the epoxy modified starch, the curing agent and the epoxy resin in proportion, removing bubbles in vacuum, pouring into a mold, and performing thermosetting molding to obtain the composite material.
9. The production method according to claim 8, wherein the thermosetting is divided into three stages: curing at 60-100 ℃ for 1-4h, 100-140 ℃ for 1-4h and 20-100 ℃ for 10-100 h.
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| CN115926583A (en) * | 2022-11-30 | 2023-04-07 | 广东美涂士建材股份有限公司 | Environment-friendly modified epoxy resin coating and preparation method thereof |
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