CN113462004A - Thermosetting starch/furfuryl alcohol foam material and preparation method thereof - Google Patents
Thermosetting starch/furfuryl alcohol foam material and preparation method thereof Download PDFInfo
- Publication number
- CN113462004A CN113462004A CN202110737468.9A CN202110737468A CN113462004A CN 113462004 A CN113462004 A CN 113462004A CN 202110737468 A CN202110737468 A CN 202110737468A CN 113462004 A CN113462004 A CN 113462004A
- Authority
- CN
- China
- Prior art keywords
- starch
- furfuryl alcohol
- foam
- formaldehyde
- foam material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/142—Compounds containing oxygen but no halogen atom
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
- C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
- C08G16/04—Chemically modified polycondensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a thermosetting starch/furfuryl alcohol foam material, which is obtained by copolycondensation reaction of unmodified starch, furfuryl alcohol and formaldehyde. Wherein, the unmodified starch has low price and wide source; the furfuryl alcohol has better reactivity and thermal stability, so that the free hydroxyl content of the starch can be reduced, and the thermal stability and mechanical strength of the starch can be improved; meanwhile, a small amount of formaldehyde is added in the reaction process to react with the hydroxyl of the starch, so that the degree of polycondensation of the starch and the furfuryl alcohol can be increased, the free hydroxyl content of the starch is reduced, the viscosity of the starch is finally reduced, and the processing and forming of the starch-based material are facilitated. The raw materials are all derived from biomass materials and are natural and renewable. Compared with pure starch-based foam materials, the foam material obtained by the invention has better thermal stability and compressive strength. The invention also provides a preparation method of the foam material.
Description
Technical Field
The invention relates to the technical field of starch-based foam materials, in particular to a thermosetting starch/furfuryl alcohol foam material and a preparation method of the foam material.
Background
Petrochemical polymers dominate the packaging field due to their excellent properties, and commonly used petrochemical polymer packaging materials mainly include Polyethylene (PE), polypropylene (PP), Polystyrene (PS), polyvinyl chloride (PVC) and polyethylene terephthalate (PET). The foam packaging material is mostly prepared from Polystyrene (PS), and is widely applied to packaging of industrial products such as electronics and precision equipment and living goods. However, the raw materials for preparing these foam packaging materials are derived from petroleum, which is a non-renewable energy source, and the search for new renewable materials to replace petrochemical polymer foam materials is a development trend in the future.
Starch is widely available and is second only to cellulose in nature. The starch-based material has the advantages of low cost, degradability and the like, but the starch-based material has more hydroxyl content, strong water absorption, large viscosity, low mechanical strength and poor thermal stability. In order to improve the mechanical properties and processing flow properties of starch-based materials, plasticizers may be added to the starch or inorganic materials, such as fillers like calcium carbonate, talc, sodium chloride and calcium chloride, may be added to the starch-based materials to enhance the mechanical properties of the starch-based materials. Meanwhile, in order to solve the problem of poor stability of the starch-based material, degradable polyester substances, such as polylactic acid (PLA), poly (epsilon-caprolactone) (PCL), poly (hydroxy ester ether) (PHEE), polyhydroxybutyrate/valerate (PHBV), and the like, may be added to the starch-based material. However, in China with immature and low popularization rate in the prior art, the modified starch-based foam material is still more expensive than a non-degradable foam product, the process is complicated, and a plasticizer, a filler and a polymer with good water resistance need to be added simultaneously to improve the comprehensive performance. Relevant investigation shows that the price of degradable foam prepared by modified starch is more than half higher than that of the traditional non-degradable foam product. Therefore, a new substance is needed to modify the starch-based foam material, so that the cost is reduced, and the starch-based foam material has better mechanical property and thermal stability.
In view of this, the invention is particularly proposed.
Disclosure of Invention
It is a first object of the present invention to provide a thermosetting starch/furfuryl alcohol foam.
The second purpose of the invention is to provide a preparation method of the foam material.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention relates to a thermosetting starch/furfuryl alcohol foam material, which is obtained by a copolycondensation reaction of raw materials comprising starch and furfuryl alcohol.
The invention also relates to a preparation method of the foam material, which comprises the following steps:
(1) preparation of thermosetting starch/furfuryl alcohol resin:
(i) mixing starch with water, adding NaOH to adjust the pH value to 9-10, then adding water and stirring to obtain paste;
preferably, the starch is selected from at least one of corn starch, tapioca starch, wheat starch, potato starch, sweet potato starch, bean starch and rice starch.
Preferably, the mass ratio of the starch to the water is 1 (1-2).
Preferably, the NaOH is added in the form of an aqueous solution, and the mass concentration of the sodium hydroxide solution is 20-40%.
(ii) Mixing the paste with furfuryl alcohol and formaldehyde, adding p-toluenesulfonic acid to adjust the pH value to 2-3, and stirring at 50-70 ℃ for 2-3 hours to obtain SF resin;
preferably, the mass ratio of the starch to the furfuryl alcohol is 1 (0.5-1).
Preferably, the stirring reaction is carried out under water bath conditions.
Preferably, the formaldehyde and the p-toluenesulfonic acid are added in the form of aqueous solutions, the mass concentration of the formaldehyde solution is 37%, and the mass concentration of the p-toluenesulfonic acid solution is 20% -40%.
Preferably, the mass ratio of the starch to the furfuryl alcohol to the formaldehyde is 1 (0.5-1) to 0.2-0.4.
(2) Preparation of thermosetting starch/furfuryl alcohol foam: and (2) adding a foaming agent into the SF resin obtained in the step (1), uniformly mixing, injecting into a mold, foaming and curing to obtain the SF foam material.
Preferably, the foaming agent is selected from at least one of AC foaming agent and diethyl ether.
Preferably, the foaming agent is added and simultaneously a foam stabilizer is also added, and the foam stabilizer is selected from at least one of tween, a silicone foam stabilizer and a polyurethane foam stabilizer.
Preferably, the mass ratio of the SF resin to the foam stabilizer to the foaming agent is 3 (0-1): 1.
Preferably, the foaming and curing temperature is 60-80 ℃ and the time is 12-15 h.
The invention has the beneficial effects that:
the invention provides a thermosetting starch/furfuryl alcohol foam material, which is obtained by copolycondensation reaction of unmodified starch, furfuryl alcohol and formaldehyde. Wherein, the unmodified starch has low price and wide source; the furfuryl alcohol is from processing residues of agricultural and forestry crops such as corn, wheat and sugarcane, has stable furan rings and hydroxymethyl, and has good reactivity and heat stability. The furfuryl alcohol and the starch can react at normal temperature, so that the hydroxyl content of the starch can be reduced, and the thermal stability and the mechanical strength of the starch can be improved; meanwhile, a small amount of formaldehyde is added in the reaction process to react with free hydroxyl of the starch, so that the degree of polycondensation of the starch and the furfuryl alcohol can be increased, the content of the free hydroxyl of the starch is reduced, the viscosity of the starch is finally reduced, and the processing and forming of the starch-based material are facilitated. The raw materials are all derived from biomass materials and are natural and renewable. Compared with pure starch-based foam materials, the foam material obtained by the invention has better thermal stability and compressive strength.
Drawings
FIG. 1 is a flow chart of the process for preparing thermosetting starch/furfuryl alcohol foam of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Embodiments of the present invention relate to a thermosetting starch/furfuryl alcohol foam material obtained by a copolycondensation reaction of raw materials including starch and furfuryl alcohol. In one embodiment of the invention, the mass ratio of the starch to the furfuryl alcohol is 1 (0.5-1).
The invention improves the thermal stability of the starch-based foam material by introducing furfuryl alcohol with better thermal stability to react with starch. In a preferred scheme, the content of free hydroxyl can be further reduced by adding a small amount of formaldehyde to react with the free hydroxyl of the starch, so that the viscosity of the starch-based foam material is reduced. The raw materials adopted by the invention are mostly from biomass materials, and starch does not need to be modified, such as heat treatment, surface ultraviolet crosslinking and chemical modification of the starch, and the preparation process is simple. The obtained starch-based foam material has better hardness, compressive strength and heat resistance.
The invention also relates to a preparation method of the foam material, and the flow chart of the method is shown in figure 1, and the method comprises the following steps:
(1) preparation of thermosetting starch/furfuryl alcohol resin
(i) Mixing starch with water, adding NaOH to adjust the pH value to 9-10, then adding water and stirring to obtain paste, wherein the purpose of the step is to expand and degrade the starch;
in one embodiment of the invention, the starch is selected from at least one of corn starch, tapioca starch, wheat starch, potato starch, sweet potato starch, bean starch and rice starch. The mass ratio of the starch to the water is 1 (1-2). The starch is native starch, and modified starch such as acid hydrolyzed starch, esterified starch, oxidized starch, etherified starch or cross-linked starch can also be used. Since the cost of modified starch is higher than that of native starch, native starch is preferably used as the raw material in the present invention.
In one embodiment of the invention, NaOH is added in the form of an aqueous solution, and the mass concentration of the sodium hydroxide solution is 20-40%.
(ii) (ii) mixing the paste obtained in the step (i) with furfuryl alcohol and formaldehyde, adding p-toluenesulfonic acid to adjust the pH value to 2-3, and then stirring for 2-3 h at 50-70 ℃;
furfuryl alcohol is a renewable material as it can be obtained from biomass materials such as corn, wheat processing residues; and the furfuryl alcohol contains stable furan rings and hydroxymethyl, and can react with starch and formaldehyde to improve the mechanical strength and the thermal property of the foam. Thus, the present invention selects furfuryl alcohol to make starch-based foams.
In one embodiment of the invention, the mass ratio of the starch to the furfuryl alcohol is 1 (0.5-1). The addition amount of the furfuryl alcohol cannot be too large because the cost is higher than that of the starch, and the excessive addition amount is easy to generate self-polycondensation, so that the furfuryl alcohol cannot react with the starch; if the furfuryl alcohol is added in an excessively small amount, the reaction effect is not obtained.
In one embodiment of the invention, the stirring reaction is carried out under the water bath condition, namely, the stirring is carried out for 2-3 hours in the water bath at the temperature of 50-70 ℃. The purpose of heating and stirring is to carry out the pre-polycondensation reaction of the starch, the furfuryl alcohol and the formaldehyde. The principle of the prepolycondensation reaction is as follows: under the condition of strong acid, the carbon atom at the ortho position of the furfuryl alcohol furan epoxy atom and the hydroxyl at the end group of the starch are subjected to condensation reaction. Meanwhile, formaldehyde reacts with hydroxymethyl of a Starch side chain and hydroxymethyl of Furfuryl alcohol, and the two can be further condensed to obtain thermosetting Starch/Furfuryl alcohol resin, SF resin for short (the resin is obtained by polycondensation of Starch and Furfuryl alcohol, so that the resin is called SF resin).
The formaldehyde is used as a cross-linking agent and has the function of polymerizing starch and furfuryl alcohol to a certain extent to generate cross-linking, so that an insoluble cross-linked polymer is obtained. The p-toluenesulfonic acid is a strong non-oxidizing acid and is used for adjusting the pH value of the reaction system. Non-oxidizing strong acids are used in order to reduce the degradation of the polymer molecules, and an increase in oxidizing strength promotes the degradation of the polymer.
The reaction of the above starch, furfuryl alcohol and formaldehyde is shown below:
in one embodiment of the invention, formaldehyde and p-toluenesulfonic acid are added in the form of aqueous solution, the mass concentration of the formaldehyde solution is 37%, and the mass concentration of the p-toluenesulfonic acid solution is 20% -40%.
In one embodiment of the invention, the mass ratio of the starch, the furfuryl alcohol and the formaldehyde is 1 (0.5-1) to 0.2-0.4.
(2) Preparation of thermosetting starch/furfuryl alcohol foam: and (2) adding a foaming agent into the SF resin obtained in the step (1), uniformly mixing, injecting into a mold, carrying out copolycondensation reaction, foaming and curing, and obtaining an SF foam material, namely the thermosetting starch/furfuryl alcohol foam material.
The foaming agent may be at least one selected from the group consisting of an AC foaming agent and diethyl ether, and functions to reduce the surface tension of the liquid and form fine pores in the polymer. Preferably, the foaming agent is added and simultaneously the foam stabilizer is also added, and the foam stabilizer is at least one selected from Tween, an organic silicon foam stabilizer and a polyurethane foam stabilizer and is used for emulsifying a foam material, stabilizing foam and adjusting foam holes.
In one embodiment of the invention, the mass ratio of the SF resin to the foam stabilizer to the foaming agent is 3 (0-1): 1.
In one embodiment of the invention, the foaming and curing temperature is 60-80 ℃ and the time is 12-15 h, so that the starch and the furfuryl alcohol are subjected to a polycondensation reaction, and the principle of the polycondensation reaction is as shown above. And simultaneously, curing under the action of a foaming agent and a foam stabilizer to obtain the thermosetting starch/furfuryl alcohol foam material.
More than 90% of the raw materials of the invention come from biomass materials and are natural and renewable. Compared with pure starch-based foam and modified starch-based foam, the thermosetting starch/furfuryl alcohol foam material provided by the invention has better compressive strength and hardness, and is simple in preparation process and lower in cost.
Example 1
(1) Preparation of thermosetting starch/furfuryl alcohol resin
(i) Mixing corn starch with the purity of 90-95% and distilled water according to the mass ratio of 1:1, stirring for 5 minutes, adding NaOH aqueous solution with the mass concentration of 30% to adjust the pH value to 9, then continuously adding distilled water and stirring to obtain paste;
(ii) (ii) transferring the paste obtained in the step (i) into a three-neck flask, adding furfuryl alcohol and a 37% formaldehyde aqueous solution, adding a 30% p-toluenesulfonic acid aqueous solution to adjust the pH value to 2, and stirring for 2 hours in a water bath at 60 ℃ to obtain SF resin;
the mass ratio of the starch to the furfuryl alcohol to the formaldehyde is 1:0.5: 0.2.
(2) Stirring the SF resin obtained in the step (1) for 3 minutes, adding a foaming agent and a foam homogenizing agent, uniformly mixing, and injecting into a rectangular mold with the size of 15 multiplied by 10 multiplied by 5 cm. And placing the mould in an oven at 60 ℃ for foaming and curing for 12h to obtain the thermosetting starch/furfuryl alcohol foam material.
The foaming agent is an AC foaming agent, and the foam stabilizer is Tween 80. The mass ratio of the SF resin to the foam stabilizer to the foaming agent is 3:1: 1.
The reaction conditions in examples 2 to 7 and comparative examples 1 to 3 were changed, and the specific settings are shown in Table 1.
TABLE 1
| Examples | Modified reaction conditions |
| Example 2 | Step (ii) of(1) In the preparation method, the mass ratio of the starch, the furfuryl alcohol and the formaldehyde is 1:1: 0.2. |
| Example 3 | In the step (1), the mass ratio of the starch, the furfuryl alcohol and the formaldehyde is 1:0.3: 0.2. |
| Example 4 | In the step (1), the mass ratio of the starch, the furfuryl alcohol and the formaldehyde is 1:1.5: 0.2. |
| Example 5 | In the step (1), the mass ratio of the starch, the furfuryl alcohol and the formaldehyde is 1:0.5: 0.1. |
| Example 6 | In the step (1), the mass ratio of the starch, the furfuryl alcohol and the formaldehyde is 1:0.5: 0.5. |
| Example 7 | In the step (2), the mass ratio of the SF resin, the foam stabilizer and the foaming agent is 3:0: 1. |
| Comparative example 1 | In the step (1), furfuryl alcohol is replaced by benzyl alcohol. |
| Comparative example 2 | In the step (1), formaldehyde is not added. |
| Comparative example 3 | In the step (1), the aqueous solution of p-toluenesulfonic acid is replaced by an aqueous hydrochloric acid solution of the same concentration. |
The parameters of examples 2 to 7 and comparative examples 1 to 3 were the same as those of example 1 except for the parameters described in table 1.
Comparative example 4
The preparation method of the starch-based foam by using ungelatinized starch comprises the following steps: in the step (1), starch and water are directly mixed to obtain paste, and then furfuryl alcohol and formaldehyde are added for subsequent reaction. Namely, the procedure was the same as in example 1 except that NaOH was not added in step (1).
Comparative example 5
The preparation method adopts modified starch-based foam, wherein the modified starch is carboxymethyl starch, and comprises the following steps: 50mL of distilled water is placed in a 250mL three-neck flask, 25g of NaOH aqueous solution with the mass concentration of 30% is added, 50g of starch and 5g of chloroacetic acid are added while stirring, the stirring is continued to uniformly mix the substances, and the three-neck flask is placed in a 55 ℃ water bath and stirred for 5 hours. After the reaction is finished, reducing the temperature of the system, and adjusting the pH value of the reaction system to 6-7. And then carrying out suction filtration, washing the precipitate with distilled water, and drying to obtain the carboxymethyl starch. The subsequent preparation of SF resin and thermosetting starch/furfuryl alcohol foam using the carboxymethyl starch was the same as in example 1.
The starch-based foams prepared in the above examples and comparative examples were tested for mechanical properties and thermal stability. The compressive strength and modulus of elasticity tests of the foams were carried out according to GBT15048-1996, including tests carried out using a general-purpose tester (AG-50KN, Shimadzu, Japan) and an indenter of 50 KN. The samples were cut to dimensions of 30X 1.5mm and compression tested at a constant loading rate of 2.0 mm/min.
The thermal stability of the foam was checked using a TGA 5500 analyzer (TA instruments, USA) comprising transferring 5-8mg of sample powder into a platinum pan, testing under a nitrogen flow at a heating rate of 10 ℃/min, the test temperature rising from room temperature to 800 ℃, resulting in mass loss at 300 ℃ and 500 ℃. The results of the above tests are shown in Table 2.
TABLE 2
As can be seen from table 2, examples 2 and 4 increased the amount of furfuryl alcohol added as compared to example 1. The addition amount of furfuryl alcohol in example 2 is still within the range of the invention, and the measured compressive strength, elastic modulus and heat resistance are partially improved compared with those in example 1, which shows that the performance is not greatly improved by increasing the amount of furfuryl alcohol; on the basis of the above, the performance of the foam is reduced by continuously increasing the addition amount of furfuryl alcohol.
Example 3 the furfuryl alcohol addition was reduced and all properties measured were lower than in example 1. The reason is that the furfuryl alcohol is added in an excessively small amount, the starch contains more hydroxyl groups, and the viscosity is excessively high, so that the performance of the foam material is deteriorated.
Example 5 the amount of formaldehyde added was reduced and the measured properties were lower than those of example 1; comparative example 2 no formaldehyde was added and the performance degradation was more pronounced. Example 6 increased the amount of formaldehyde added and the properties measured were slightly higher than those of example 1, indicating that formaldehyde acted as a crosslinking agent.
Example 7, without the addition of a foam stabilizer, also showed a decrease in performance compared to example 1.
Compared with example 1, each performance of comparative example 1 is reduced, which indicates that benzyl alcohol can not replace furfuryl alcohol; comparative example 3 also has lower performance than example 1 because hydrochloric acid is oxidizing and promotes polymer degradation and cannot replace p-toluenesulfonic acid.
Compared with the example 1, the performance of the comparative example 4 is reduced, which shows that the starch is treated by NaOH to achieve the gelatinization effect, and the number of functional groups participating in the reaction is increased; comparative example 5 compared with example 1, the properties of the two are similar, which shows that the invention adopts furfuryl alcohol and formaldehyde to modify starch, and the performance of the obtained foam material is equivalent to that of modified starch foam. In contrast, the preparation cost of the starch foam material is greatly reduced.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. A thermosetting starch/furfuryl alcohol foam material, characterised in that it is obtained by copolycondensation of starting materials comprising starch and furfuryl alcohol.
2. A process for the preparation of the foam according to claim 1, characterized in that it comprises the following steps:
(1) preparation of thermosetting starch/furfuryl alcohol resin:
(i) mixing starch with water, adding NaOH to adjust the pH value to 9-10, then adding water and stirring to obtain paste;
(ii) mixing the paste with furfuryl alcohol and formaldehyde, adding p-toluenesulfonic acid to adjust the pH value to 2-3, and stirring at 50-70 ℃ for 2-3 hours to obtain SF resin;
(2) preparation of thermosetting starch/furfuryl alcohol foam: and (2) adding a foaming agent into the SF resin obtained in the step (1), uniformly mixing, injecting into a mold, foaming and curing to obtain the SF foam material.
3. The method according to claim 2, wherein in step (i), the starch is selected from at least one of corn starch, tapioca starch, wheat starch, potato starch, sweet potato starch, bean starch and rice starch.
4. The method according to claim 2, wherein in the step (i), the mass ratio of the starch to the water is 1 (1-2).
5. The method according to claim 2, wherein in step (i), the NaOH is added in the form of an aqueous solution, and the mass concentration of the sodium hydroxide solution is 20-40%.
6. The method according to claim 2, wherein in the step (ii), the mass ratio of the starch to the furfuryl alcohol is 1 (0.5-1).
7. The method according to claim 2, wherein in the step (ii), the formaldehyde and the p-toluenesulfonic acid are added in the form of aqueous solutions, the mass concentration of the formaldehyde solution is 37%, and the mass concentration of the p-toluenesulfonic acid solution is 20% -40%.
8. The method as claimed in claim 2, wherein in step (ii), the mass ratio of the starch, the furfuryl alcohol and the formaldehyde is 1 (0.5-1) to (0.2-0.4).
9. The method according to claim 2, wherein in step (2), the foaming agent is selected from at least one of an AC foaming agent and diethyl ether;
and/or adding a foaming agent and a foam stabilizer, wherein the foam stabilizer is at least one selected from tween, an organic silicon foam stabilizer and a polyurethane foam stabilizer;
and/or the mass ratio of the SF resin to the foam stabilizer to the foaming agent is 3 (0-1) to 1.
10. The method according to claim 2, wherein in the step (2), the foaming and curing temperature is 60-80 ℃ and the time is 12-15 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110737468.9A CN113462004B (en) | 2021-06-30 | 2021-06-30 | Thermosetting starch/furfuryl alcohol foam material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110737468.9A CN113462004B (en) | 2021-06-30 | 2021-06-30 | Thermosetting starch/furfuryl alcohol foam material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113462004A true CN113462004A (en) | 2021-10-01 |
| CN113462004B CN113462004B (en) | 2022-07-08 |
Family
ID=77878236
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110737468.9A Active CN113462004B (en) | 2021-06-30 | 2021-06-30 | Thermosetting starch/furfuryl alcohol foam material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113462004B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116925344A (en) * | 2023-09-08 | 2023-10-24 | 西南林业大学 | Porous triazinyl sulfur-containing polyamide material, and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1485995A (en) * | 1973-11-09 | 1977-09-14 | Bolidt License Nv | Process for the manufacture of non-inflammable synthetic foams |
| US20140116698A1 (en) * | 2012-10-26 | 2014-05-01 | Halliburton Energy Services, Inc. | Wellbore Servicing Fluids Comprising Foamed Materials and Methods of Making and Using Same |
| CN104163904A (en) * | 2014-03-05 | 2014-11-26 | 西南林业大学 | Tannin-based biomass foam material and preparation method thereof |
| CN108276541A (en) * | 2017-12-29 | 2018-07-13 | 天津宁康科技有限公司 | A kind of the casting low formaldehyde furane resins of low furfuryl alcohol and its production method |
| CN109608701A (en) * | 2018-12-07 | 2019-04-12 | 上海耐特复合材料制品有限公司 | A kind of thermoplastic starch based foam material and preparation method |
| CN110684316A (en) * | 2019-11-12 | 2020-01-14 | 江阴市威腾铝箔合成材料有限公司 | Low-thermal-conductivity phenolic foam material and preparation method thereof |
-
2021
- 2021-06-30 CN CN202110737468.9A patent/CN113462004B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1485995A (en) * | 1973-11-09 | 1977-09-14 | Bolidt License Nv | Process for the manufacture of non-inflammable synthetic foams |
| US20140116698A1 (en) * | 2012-10-26 | 2014-05-01 | Halliburton Energy Services, Inc. | Wellbore Servicing Fluids Comprising Foamed Materials and Methods of Making and Using Same |
| CN104163904A (en) * | 2014-03-05 | 2014-11-26 | 西南林业大学 | Tannin-based biomass foam material and preparation method thereof |
| CN108276541A (en) * | 2017-12-29 | 2018-07-13 | 天津宁康科技有限公司 | A kind of the casting low formaldehyde furane resins of low furfuryl alcohol and its production method |
| CN109608701A (en) * | 2018-12-07 | 2019-04-12 | 上海耐特复合材料制品有限公司 | A kind of thermoplastic starch based foam material and preparation method |
| CN110684316A (en) * | 2019-11-12 | 2020-01-14 | 江阴市威腾铝箔合成材料有限公司 | Low-thermal-conductivity phenolic foam material and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| ABINADER GEORGES，等: ""Effect of formulation and process on the extrudability of starch-based foam cushions"", 《INDUSTRIAL CROPS AND PRODUCTS》, vol. 115, 31 December 2018 (2018-12-31), pages 306 - 314 * |
| TIANYU JIANG，等: ""Starch-based biodegradable materials: challenges and opportunities"", 《ADVANCED INDUSTRIAL AND ENGINEERING POLYMER RESEARCH》, vol. 3, no. 1, 31 December 2020 (2020-12-31), pages 8 - 18, XP055864646, DOI: 10.1016/j.aiepr.2019.11.003 * |
| 李进兴，等: ""3种试剂对单宁/呋喃泡沫塑料的改性研究"", 《西北林学院学报》, vol. 35, no. 3, 31 December 2020 (2020-12-31), pages 218 - 223 * |
| 金龙飞，等: ""混合脲醛树脂发泡材料的研究"", 《华中师范大学学报(自然科学版)》, vol. 36, no. 3, 30 September 2002 (2002-09-30), pages 316 - 318 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116925344A (en) * | 2023-09-08 | 2023-10-24 | 西南林业大学 | Porous triazinyl sulfur-containing polyamide material, and preparation method and application thereof |
| CN116925344B (en) * | 2023-09-08 | 2023-11-17 | 西南林业大学 | Porous triazinyl sulfur-containing polyamide material, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113462004B (en) | 2022-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Farhat et al. | Polysaccharides and lignin based hydrogels with potential pharmaceutical use as a drug delivery system produced by a reactive extrusion process | |
| CN110408180B (en) | Lignin-starch combined master batch compounded biodegradable polyester material and preparation method thereof | |
| CN104559097B (en) | A kind of plasticizing polylactic acid and preparation method thereof | |
| Gustini et al. | Green and selective polycondensation methods toward linear sorbitol‐based polyesters: enzymatic versus organic and metal‐based catalysis | |
| CN113462004B (en) | Thermosetting starch/furfuryl alcohol foam material and preparation method thereof | |
| Bräuer et al. | Preparation and thermoplastic processing of modified plant proteins | |
| Zhou et al. | Degradable photo-crosslinked starch-based films with excellent shape memory property | |
| Amaraweera et al. | Preparation and characterization of dual-modified cassava starch-based biodegradable foams for sustainable packaging applications | |
| CN113292865A (en) | Plant fiber-based composite material and preparation method and application thereof | |
| Castanho et al. | Developing thermoplastic corn starch composites filled with brewer's spent grain for applications in biodegradable films | |
| Peng et al. | Melt-processing, moisture-resistance and strength retention properties of supercritical CO 2-processed thermoplastic starch resins. | |
| Liu et al. | Cross-linked poly (ester urethane)/starch composite films with high starch content as sustainable food-packaging materials: Influence of cross-link density | |
| CN112795038B (en) | Preparation method of flexible bio-based film material and product thereof | |
| CN111574755B (en) | Biodegradable plastic and preparation method thereof | |
| Hou et al. | Preparation and characterization on the eco-friendly corn starch based adhesive of with salient water resistance, mildew resistance | |
| CN104497512B (en) | Method for preparing degradable material modified polylactic acid polymer | |
| CN114456565B (en) | Carbon dioxide-based polylactic acid copolymer modified cellulose material and preparation method thereof | |
| EP2483335A1 (en) | Xyloglucan films | |
| Stocker et al. | Modulating superabsorbent polymer properties by adjusting the amphiphilicity | |
| Guleria et al. | Preparation of starch-based biocomposites reinforced with mercerized lignocellulosic fibers: Evaluation of their thermal, morphological, mechanical, and biodegradable properties | |
| CN113388043B (en) | Thermosetting starch-based plastic and preparation method thereof | |
| CN116285015A (en) | Waterproof starch-based biodegradable plastic and preparation method thereof | |
| KR101417413B1 (en) | A method for manufacturing natural fiber poly lactic acid composite materials | |
| S. Castro et al. | Synthesis and evaluation of the incorporation of sisal fiber cellulose in the polymeric matrix of starch from jackfruit seed (Artocarpus heterophyllus Lam.) using thermogravimetry | |
| CN111662485B (en) | Degradable plastic containing lignin-carbohydrate and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230925 Address after: 830000 Factory Building 7, Comprehensive Bonded Zone, No. 9 Tunping North Road, Urumqi Economic and Technological Development Zone (Toutunhe District), Xinjiang Uygur Autonomous Region Patentee after: Xinjiang Zhonggao Green Biotechnology Co.,Ltd. Address before: 401120 No.107 dataguzhong Road, Xiantao street, Yubei District, Chongqing Patentee before: Chongqing Super Star Technology Co.,Ltd. Effective date of registration: 20230925 Address after: 401120 No.107 dataguzhong Road, Xiantao street, Yubei District, Chongqing Patentee after: Chongqing Super Star Technology Co.,Ltd. Address before: 650000 Bailong Temple 300, Kunming City, Yunnan Province Patentee before: SOUTHWEST FORESTRY University |
|
| TR01 | Transfer of patent right |