CN113354876A - Preparation method of single-component multi-source integrated halogen-free flame retardant based on biomass - Google Patents
Preparation method of single-component multi-source integrated halogen-free flame retardant based on biomass Download PDFInfo
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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
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/04—Starch derivatives, e.g. crosslinked derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/02—Esters
- C08B31/06—Esters of inorganic acids
- C08B31/066—Starch phosphates, e.g. phosphorylated starch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a preparation method of a single-component multi-source integrated halogen-free flame retardant based on biomass, aiming at obtaining a single-component integrated chemical intumescent flame retardant by taking a biomass material as a carbon source carrier and introducing an acid source and a gas source into the structure of the biomass material. On the basis of fully utilizing cheap and renewable biomass materials, the traditional use mode of mixing multi-source components is simplified, and the flame retardant efficiency of the biomass is obviously improved. By surface modification of the biomass-based flame retardant, the problem of poor compatibility of the biomass material and the polymer material is effectively solved, and the problem that the flame retardant is easy to separate out in a humid environment is solved. The flame retardant prepared by the method has the advantages of simple method, wide raw material source, low manufacturing cost, excellent performance, good flame retardant effect and the like, is harmless to the environment and human body, realizes effective utilization and conversion of natural resources, and improves the added value of biomass materials, so the flame retardant has better application potential.
Description
Technical Field
The invention belongs to the technical field of flame retardant materials, and particularly relates to a preparation method of a biomass-based single-component multi-source integrated halogen-free flame retardant.
Background
With the continuous development of science and technology, the production and living standards of people are continuously improved, and various organic polymer materials are more and more widely applied and occupy an extremely important position in national economy and people's life. However, conventional organic polymer materials are generally flammable and include polystyrene, polyethylene, polypropylene, ABS, polyvinyl acetate, and the like. The materials have high flame propagation speed, high heat release rate and high heat value during combustion, are not easy to extinguish, are accompanied by release of dense smoke and toxic gas, and form great threat to the life and property safety of people. While the traditional halogen-containing flame retardant has the advantages of high flame retardant efficiency and small addition amount, toxic gases such as hydrogen halide and the like released during combustion can cause secondary damage to life; in addition, the waste halogen-containing flame retardant product has a biological enrichment effect in an isolated environment, and potential personal injury and serious environmental pollution are caused. Therefore, from the perspective of flame retardant efficiency, human safety and environmental protection, the development of efficient, harmless, low-smoke, low-toxicity, green and environment-friendly flame retardants is a necessary trend in the development of flame retardant field.
The halogen-free intumescent flame retardant is a halogen-free flame retardant taking phosphorus and nitrogen as main components. The dense and expanded carbon layer structure generated on the surface of the polymer in the heating process of the acid source, the carbon source and the gas source effectively limits and isolates mass transfer and heat transfer in a combustion area, and further realizes a condensed phase flame-retardant process. The halogen-free intumescent flame retardant has the advantages of high flame retardance, no melting and dripping, low smoke, no toxicity, no corrosive gas generation and the like, and has better resistance to flame. Therefore, the halogen-free intumescent flame retardant basically overcomes the defects of the traditional halogen-containing flame retardant technology. However, excessive consumption of petrochemical resources has caused petroleum-based polyhydroxycarbon source materials to become increasingly expensive and non-renewable; the compounding of multi-source components of the chemical expansion flame-retardant system can also cause certain adverse effects on the processing and preparation of flame-retardant polymers. For this reason, the development of high performance, clean and sustainable integral halogen-free intumescent flame retardant systems has become a new goal and challenge in the flame retardant field.
The products output by agriculture, forestry and fishery contain rich biomass resources, and the biomass materials mainly comprise polysaccharide compounds and derivatives thereof, and have the characteristics of wide sources, no toxicity, environmental protection, biodegradability, low price, renewability and the like. In addition, most of the biomass materials have a polyhydroxy macromolecular chemical structure, are similar to a charring agent pentaerythritol in a traditional chemical expansion flame-retardant system, have double characteristics of good charring capability and easy modification, and are important candidates for replacing petroleum-based charring agents. Therefore, the biomass material is combined with a high-performance flame retardant technology to prepare the high-performance, clean and efficient halogen-free flame retardant, so that the method inevitably becomes an important development direction in the fields of environmental protection and sustainable flame retardance, and has far-reaching research significance, good application value and social benefit.
Disclosure of Invention
The invention aims to provide a preparation method of a biomass-based single-component multi-source integrated halogen-free flame retardant.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a biomass-based single-component multi-source integrated halogen-free flame retardant comprises the following steps:
preparation of biomass-based flame retardants:
a. slowly adding 5 g of biomass material into a phosphoric acid source under stirring, wherein the mass ratio is 1:3-5, and uniformly stirring at a stirring speed of 50-200 r/min until the biomass material and the phosphoric acid source become transparent viscous liquid A;
b. transferring the liquid A into a 100 ml reaction kettle with a tetrafluoroethylene lining, and placing the reaction kettle in a 100-DEG dry box for reaction for 1-3 hours to obtain a biomass-based flame retardant intermediate B;
c. 15 g of amine-based gas source powder is ultrasonically dispersed in 50 ml of deionized water and then transferred into a 250 ml three-neck flask with mechanical stirring at the speed of 300-350 r/m and heated to 95-100 ℃. Then, the biomass-based flame retardant intermediate B was dropwise added over a period of about 20 to 30 minutes. After the dropwise addition is finished, the constant-temperature reaction is continued for 0.5 to 1 hour;
d. when the system is cooled to room temperature, carrying out vacuum filtration on the obtained product, repeatedly washing the product for 3-5 times by using deionized water and absolute ethyl alcohol, and collecting a filter cake;
e. and (3) placing the filter cake in a constant-temperature vacuum drying oven at 60-80 ℃ for drying for 24 hours to finally obtain the dry biomass-based flame retardant.
-hydrophobic surface modification of biomass-based flame retardants:
a. adding 10 g of biomass-based flame retardant powder into 50 ml of an absolute ethyl alcohol solution of 5-10% by mass of organosilane, stirring for 0.5-1 hour, transferring the system into a 100 ml reaction kettle with a tetrafluoroethylene liner, and placing the reaction kettle in a constant-temperature drying oven at 70-80 ℃ for reaction for 1-3 hours to obtain a modified product dispersion liquid;
b. when the system is cooled to room temperature, carrying out vacuum filtration on the modified product dispersion liquid, repeatedly washing for 3-5 times by using absolute ethyl alcohol, and collecting a filter cake;
c. placing the filter cake in a constant-temperature vacuum drying oven at 60-70 ℃ for drying for 24 hours to finally obtain a dry biomass-based flame retardant; and obtaining the uniform flame retardant powder with the particle size of 100-200 meshes by mechanical grinding.
Preparation of flame-retardant thermoplastic polymer systems:
a. sequentially adding the modified biomass-based flame retardant and the thermoplastic polymer into an internal mixer or a double-screw extruder according to a certain proportion, setting the melt blending temperature of the equipment at 180-200 ℃, the rotating speed of a screw or a rotor at 40-60 r/min, and the melt blending time at 10-15 min to obtain the flame-retardant polymer;
b. and (3) placing the flame-retardant polymer in a flat vulcanizing instrument, setting the hot-pressing temperature to be 190-200 ℃, setting the hot-pressing pressure to be 10-15MPa, setting the hot-pressing time to be 10-15 minutes, and cutting the flat sample into a sample strip size suitable for the flame-retardant test requirement by adopting electric saw cutting equipment.
Compared with the prior art, the invention has the beneficial effects that:
the polyhydroxy biomass material is used as a carrier, an acid source and a gas source are introduced into the structure of the biomass material through chemical reaction among characteristic groups, and the biomass-based hydrophobic and sustainable single-component multisource integrated halogen-free intumescent flame retardant is prepared through surface modification of silane. Compared with the traditional chemical intumescent flame retardant, the biomass-based flame retardant prepared by the method overcomes the problems that the halogen-free flame retardant is easy to be affected with damp and migrate out, has poor compatibility with polymers, is compounded by multiple components and the like, and utilizes the unique char-forming and intumescent capabilities of the biomass-based flame retardant to further effectively improve the efficiency of the biomass material for flame retarding the polymers.
The flame retardant mechanism of the single-component multi-source integrated halogen-free intumescent flame retardant comprises the following steps:
in the case of a fire, the surface polymer material of the flame-retardant polymer system is melted under the induction of heat, the flame retardant particles in the matrix begin to be enriched on the surface polymer layer, and when the temperature is further increased, various units in the flame retardant particle component begin to interact: under the acid catalysis of the acid source, strong esterification reaction occurs between the carbon source and the acid source to generate compact and continuous residues; meanwhile, the gas source unit in the matrix decomposes to release a large amount of inert gas, the inert gas is released from the interior of the matrix, one part of the inert gas is released to the surface of the polymer before the carbon layer is formed, oxygen in a combustion area can be diluted, the gas-phase flame-retardant process is achieved, the other part of the inert gas cannot break through the blockade of the carbon layer after the carbon layer is formed, and then a carbon skeleton which is compact in surface, continuous and expandable and firm in the interior is formed on the surface of the polymer, so that the influence of flame on the matrix in the polymer can be effectively isolated, the combustion path is cut off, and the condensed phase expansion flame-retardant effect is achieved.
The method for preparing the single-component multi-source integrated halogen-free intumescent flame retardant based on the biomass material has the advantages of simplicity in operation, strong reproducibility, low cost, environmental friendliness, rich raw materials, wide application range, strong practicability and the like.
Drawings
Figure 1. water contact angle test, left panel for unmodified starch based flame retardant, right panel for modified starch based flame retardant.
FIG. 2 is a photograph of water resistance, the left of which is an unmodified starch-based flame retardant, and the right of which is a modified starch-based flame retardant.
FIG. 3 is an interfacial SEM photograph of (a) a polypropylene/starch-based flame retardant and (b) a polypropylene/modified starch-based flame retardant.
Fig. 4 is a photograph of a thermal expansion, the left being a starch-based flame retardant and the right being a starch-based flame retardant that expands upon heating at 600 degrees.
FIG. 5 flame retardant performance testing of flame retardant systems.
Detailed Description
The following examples are given for further details:
example 1:
preparation of starch-based flame retardants:
a. slowly adding 5 g of soluble starch into concentrated phosphoric acid under stirring, wherein the mass ratio is 1:3, and uniformly stirring at a stirring speed of 100 revolutions per minute until the soluble starch and the concentrated phosphoric acid become transparent viscous liquid A;
b. transferring the liquid A into a 100 ml reaction kettle with a polytetrafluoroethylene lining, and placing the reaction kettle in a 100-DEG drying oven for reaction for 1 hour to obtain a starch-based flame retardant intermediate B;
c. 15 g of melamine were dispersed ultrasonically in 50 ml of deionized water and then transferred to a 250 ml three-necked flask with mechanical stirring at 300 rpm and heated to 95 ℃. Then, the starch-based flame retardant intermediate B was dropwise added over a period of about 20 minutes. After the dropwise addition is finished, the constant-temperature reaction is continued for 0.5 hour;
d. when the system is cooled to room temperature, carrying out vacuum filtration on the obtained product, repeatedly washing the product for 3 times by using deionized water and absolute ethyl alcohol, and collecting a filter cake;
e. and (3) drying the filter cake in a constant-temperature vacuum drying oven at 60 ℃ for 24 hours to finally obtain the dried starch-based flame retardant.
-hydrophobic surface modification of starch-based flame retardants:
a. taking 15 g of starch-based flame retardant powder, adding the starch-based flame retardant powder into 75 ml of an absolute ethanol solution of polymethyltriethoxysilane with the mass fraction of 5%, stirring for 0.5 hour, transferring the system into a 100 ml reaction kettle with a polytetrafluoroethylene lining, and placing the reaction kettle in a constant-temperature drying oven at 70 ℃ for reaction for 1 hour to obtain a modified product dispersion liquid;
b. when the system is cooled to room temperature, carrying out vacuum filtration on the modified product dispersion liquid, repeatedly washing for 3 times by using absolute ethyl alcohol, and collecting a filter cake;
c. putting the filter cake into a constant-temperature vacuum drying oven at 60 ℃ for drying for 24 hours to finally obtain a dry starch-based flame retardant; and obtaining the uniform flame retardant powder with the particle size of 100-200 meshes by mechanical grinding.
Preparation of starch-based flame retardant polypropylene systems:
a. sequentially adding 15 g of modified starch-based flame retardant and 50 g of polypropylene into an internal mixer, setting the melt blending temperature of equipment to be 180 ℃, the rotating speed of a rotor to be 40 revolutions per minute, and the melt blending time to be 10 minutes to obtain flame-retardant polypropylene;
b. and (3) placing the flame-retardant polypropylene into a flat vulcanizing instrument, setting the hot-pressing temperature to be 190 ℃, setting the hot-pressing pressure to be 10MPa, setting the hot-pressing time to be 10 minutes, and cutting the flat sample into a sample strip size suitable for the flame-retardant test requirement by adopting electric saw cutting equipment.
Example 2:
preparation of starch-based flame retardants:
a. slowly adding 5 g of starch into concentrated phosphoric acid under stirring, wherein the mass ratio is 1:5, and uniformly stirring at the stirring speed of 200 revolutions per minute until the starch and the concentrated phosphoric acid become transparent viscous liquid A;
b. transferring the liquid A into a 100 ml reaction kettle with a polytetrafluoroethylene lining, and placing the reaction kettle in a 100-DEG drying oven for reaction for 3 hours to obtain a starch-based flame retardant intermediate B;
c. 15 g of melamine were dispersed ultrasonically in 50 ml of deionized water and then transferred to a 250 ml three-necked flask with mechanical stirring at 350 rpm and heated to 100 ℃. Then, the starch-based flame retardant intermediate B was dropwise added over a period of about 30 minutes. After the dropwise addition is finished, the constant-temperature reaction is continued for 1 hour;
d. when the system is cooled to room temperature, carrying out vacuum filtration on the obtained product, repeatedly washing the product for 5 times by using deionized water and absolute ethyl alcohol, and collecting a filter cake;
e. and (3) placing the filter cake in a constant-temperature vacuum drying oven at 80 ℃ for drying for 24 hours to finally obtain the dried starch-based flame retardant.
-hydrophobic surface modification of starch-based flame retardants:
a. taking 15 g of starch-based flame retardant powder, adding the starch-based flame retardant powder into 75 ml of anhydrous ethanol solution of polymethyltriethoxysilane with the mass fraction of 10%, stirring for 1 hour, transferring the system into a 100 ml reaction kettle with a polytetrafluoroethylene lining, and placing the reaction kettle in a constant-temperature drying oven at 80 ℃ for reaction for 3 hours to obtain a modified product dispersion liquid;
b. when the system is cooled to room temperature, carrying out vacuum filtration on the modified product dispersion liquid, repeatedly washing the product dispersion liquid for 5 times by using absolute ethyl alcohol, and collecting a filter cake;
c. putting the filter cake into a constant-temperature vacuum drying oven at 70 ℃ for drying for 24 hours to finally obtain a dry starch-based flame retardant; and obtaining the uniform flame retardant powder with the particle size of 100-200 meshes by mechanical grinding.
Preparation of starch-based flame retardant polypropylene systems:
a. sequentially adding 15 g of modified starch-based flame retardant and 50 g of polypropylene into an internal mixer, setting the melt blending temperature of equipment to be 200 ℃, setting the rotating speed of a rotor to be 60 revolutions per minute, and setting the melt blending time to be 15 minutes to obtain flame-retardant polypropylene;
b. and (3) placing the flame-retardant polypropylene into a flat vulcanizing instrument, setting the hot-pressing temperature to be 200 ℃, setting the hot-pressing pressure to be 15MPa and the hot-pressing time to be 15 minutes, and cutting the flat sample into a sample strip size suitable for the flame-retardant test requirement by adopting electric saw cutting equipment.
Example 3:
-preparation of cellulose-based flame retardant:
a. slowly adding 5 g of hydroxyethyl cellulose into pyrophosphoric acid under stirring, wherein the mass ratio is 1:3, and uniformly stirring at a stirring speed of 100 revolutions per minute until the hydroxyethyl cellulose and the pyrophosphoric acid become transparent viscous liquid A;
b. transferring the liquid A into a 100 ml reaction kettle with a polytetrafluoroethylene lining, and placing the reaction kettle in a 100-DEG drying oven for reaction for 1 hour to obtain a cellulose-based flame retardant intermediate B;
c. 15 g of melamine were dispersed ultrasonically in 50 ml of deionized water and then transferred to a 250 ml three-necked flask with mechanical stirring at 300 rpm and heated to 95 ℃. Then, the cellulose-based flame retardant intermediate B was dropwise added over a period of about 20 minutes. After the dropwise addition is finished, the constant-temperature reaction is continued for 0.5 hour;
d. when the system is cooled to room temperature, carrying out vacuum filtration on the obtained product, repeatedly washing the product for 3 times by using deionized water and absolute ethyl alcohol, and collecting a filter cake;
e. and (3) placing the filter cake in a constant-temperature vacuum drying oven at 60 ℃ for drying for 24 hours to finally obtain the dry cellulose-based flame retardant.
-hydrophobic surface modification of cellulose-based flame retardants:
a. taking 15 g of cellulose-based flame retardant powder, adding the cellulose-based flame retardant powder into 75 ml of an anhydrous ethanol solution of polymethyltriethoxysilane with the mass fraction of 5%, stirring for 0.5 hour, transferring the system into a 100 ml reaction kettle with a polytetrafluoroethylene lining, and placing the reaction kettle in a constant-temperature drying oven at 70 ℃ for reaction for 1 hour to obtain a modified product dispersion liquid;
b. when the system is cooled to room temperature, carrying out vacuum filtration on the modified product dispersion liquid, repeatedly washing for 3 times by using absolute ethyl alcohol, and collecting a filter cake;
c. placing the filter cake in a constant-temperature vacuum drying oven at 60 ℃ for drying for 24 hours to finally obtain a dry cellulose-based flame retardant; and obtaining the uniform flame retardant powder with the particle size of 100-200 meshes by mechanical grinding.
Preparation of a cellulose-based flame retardant polypropylene system:
a. sequentially adding 15 g of modified cellulose-based flame retardant and 50 g of polypropylene into an internal mixer, setting the melt blending temperature of equipment to be 180 ℃, setting the rotating speed of a rotor to be 40 revolutions per minute, and setting the melt blending time to be 10 minutes to obtain flame-retardant polypropylene;
b. and (3) placing the flame-retardant polypropylene into a flat vulcanizing instrument, setting the hot-pressing temperature to be 190 ℃, setting the hot-pressing pressure to be 10MPa and the hot-pressing time to be 10 minutes, and cutting the flat sample into a sample strip size suitable for the flame-retardant test requirement by adopting electric saw cutting equipment.
Example 4:
preparation of starch-based flame retardants:
a. slowly adding 5 g of soluble starch into concentrated phosphoric acid under stirring, wherein the mass ratio is 1:3, and uniformly stirring at a stirring speed of 100 revolutions per minute until the soluble starch and the concentrated phosphoric acid become transparent viscous liquid A;
b. transferring the liquid A into a 100 ml reaction kettle with a polytetrafluoroethylene lining, and placing the reaction kettle in a drying oven at 100 ℃ for reaction for 1 hour to obtain a starch-based flame retardant intermediate B;
c. 15 g of melamine cyanurate were dispersed ultrasonically in 50 ml of deionized water and then transferred to a 250 ml three-necked flask with mechanical stirring at 300 rpm and heated to 95 ℃. Then, the starch-based flame retardant intermediate B was dropwise added over a period of about 20 minutes. After the dropwise addition is finished, the constant-temperature reaction is continued for 0.5 hour;
d. when the system is cooled to room temperature, carrying out vacuum filtration on the obtained product, repeatedly washing the product for 3 times by using deionized water and absolute ethyl alcohol, and collecting a filter cake;
e. and (3) drying the filter cake in a constant-temperature vacuum drying oven at 60 ℃ for 24 hours to finally obtain the dried starch-based flame retardant.
-hydrophobic surface modification of starch-based flame retardants:
a. taking 15 g of starch-based flame retardant powder, adding the starch-based flame retardant powder into 75 ml of an absolute ethanol solution of polymethyltriethoxysilane with the mass fraction of 5%, stirring for 0.5 hour, transferring the system into a 100 ml reaction kettle with a polytetrafluoroethylene lining, and placing the reaction kettle in a constant-temperature drying oven at 70 ℃ for reaction for 1 hour to obtain a modified product dispersion liquid;
b. when the system is cooled to room temperature, carrying out vacuum filtration on the modified product dispersion liquid, repeatedly washing for 3 times by using absolute ethyl alcohol, and collecting a filter cake;
c. placing the filter cake in a constant-temperature vacuum drying oven at 60 ℃ for drying for 24 hours to finally obtain a dry biomass-based flame retardant; and obtaining the uniform flame retardant powder with the particle size of 100-200 meshes by mechanical grinding.
Preparation of starch-based flame retardant polypropylene systems:
a. sequentially adding 10 g of modified starch-based flame retardant and polypropylene into an internal mixer, setting the melt blending temperature of equipment to be 180 ℃, the rotating speed of a rotor to be 40 r/min, and the melt blending time to be 10 min to obtain flame-retardant polypropylene;
b. and (3) placing the flame-retardant polypropylene into a flat vulcanizing instrument, setting the hot-pressing temperature to be 190 ℃, setting the hot-pressing pressure to be 10MPa and the hot-pressing time to be 10 minutes, and cutting the flat sample into a sample strip size suitable for the flame-retardant test requirement by adopting electric saw cutting equipment.
Example 5:
preparation of starch-based flame retardants:
a. slowly adding 5 g of soluble starch into polyphosphoric acid under stirring, wherein the mass ratio is 1:3, and uniformly stirring at a stirring speed of 100 revolutions per minute until the two become transparent viscous liquid A;
b. transferring the liquid A into a 100 ml reaction kettle with a polytetrafluoroethylene lining, and placing the reaction kettle in a 100-DEG drying oven for reaction for 1 hour to obtain a starch-based flame retardant intermediate B;
c. 15 g of melamine were dispersed ultrasonically in 50 ml of deionized water and then transferred to a 250 ml three-necked flask with mechanical stirring at 300 rpm and heated to 95 ℃. Then, the starch-based flame retardant intermediate B was dropwise added over a period of about 20 minutes. After the dropwise addition is finished, the constant-temperature reaction is continued for 0.5 hour;
d. when the system is cooled to room temperature, carrying out vacuum filtration on the obtained product, repeatedly washing the product for 3 times by using deionized water and absolute ethyl alcohol, and collecting a filter cake;
e. and (3) drying the filter cake in a constant-temperature vacuum drying oven at 60 ℃ for 24 hours to finally obtain the dried starch-based flame retardant.
-hydrophobic surface modification of starch-based flame retardants:
a. taking 15 g of starch-based flame retardant powder, adding the starch-based flame retardant powder into 75 ml of an anhydrous ethanol solution of epoxy resin modified organic silicon resin with the mass fraction of 5%, stirring for 0.5 hour, transferring the system into a 100 ml reaction kettle with a polytetrafluoroethylene lining, and placing the reaction kettle in a constant-temperature drying oven at 70 ℃ for reaction for 1 hour to obtain a modified product dispersion liquid;
b. when the system is cooled to room temperature, carrying out vacuum filtration on the modified product dispersion liquid, repeatedly washing for 3 times by using absolute ethyl alcohol, and collecting a filter cake;
c. placing the filter cake in a constant-temperature vacuum drying oven at 60 ℃ for drying for 24 hours to finally obtain a dry biomass-based flame retardant; and obtaining the uniform flame retardant powder with the particle size of 100-200 meshes by mechanical grinding.
Preparation of starch-based flame retardant polypropylene systems:
a. sequentially adding 15 g of modified starch-based flame retardant and 50 g of polypropylene into an internal mixer, setting the melt blending temperature of equipment to be 180 ℃, the rotating speed of a screw or a rotor to be 40 r/min, and the melt blending time to be 10 min to obtain a flame-retardant polymer;
b. and (3) placing the flame-retardant polypropylene into a flat vulcanizing instrument, setting the hot-pressing temperature to be 190 ℃, setting the hot-pressing pressure to be 10MPa and the hot-pressing time to be 10 minutes, and cutting the flat sample into a sample strip size suitable for the flame-retardant test requirement by adopting electric saw cutting equipment.
Example 6:
-preparation of cellulose-based flame retardant:
a. slowly adding 5 g of hydroxyethyl cellulose into pyrophosphoric acid under stirring, wherein the mass ratio is 1:3, and uniformly stirring at a stirring speed of 100 revolutions per minute until the hydroxyethyl cellulose and the pyrophosphoric acid become transparent viscous liquid A;
b. transferring the liquid A into a 100 ml reaction kettle with a polytetrafluoroethylene lining, and placing the reaction kettle in a drying oven at 100 ℃ for reaction for 1 hour to obtain a cellulose-based flame retardant intermediate B;
c. 15 g of melamine were dispersed ultrasonically in 50 ml of deionized water and then transferred to a 250 ml three-necked flask with mechanical stirring at 300 rpm and heated to 95 ℃. Then, the cellulose-based flame retardant intermediate B was dropwise added over a period of about 20 minutes. After the dropwise addition is finished, the constant-temperature reaction is continued for 0.5 hour;
d. when the system is cooled to room temperature, carrying out vacuum filtration on the obtained product, repeatedly washing the product for 3 times by using deionized water and absolute ethyl alcohol, and collecting a filter cake;
e. and (3) placing the filter cake in a constant-temperature vacuum drying oven at 60 ℃ for drying for 24 hours to finally obtain the dry cellulose-based flame retardant.
-hydrophobic surface modification of cellulose-based flame retardants:
a. taking 15 g of cellulose-based flame retardant powder, adding the cellulose-based flame retardant powder into 75 ml of an anhydrous ethanol solution of polymethyltriethoxysilane with the mass fraction of 5%, stirring for 0.5 hour, transferring the system into a 100 ml reaction kettle with a polytetrafluoroethylene lining, and placing the reaction kettle in a constant-temperature drying oven at 70 ℃ for reaction for 1 hour to obtain a modified product dispersion liquid;
b. when the system is cooled to room temperature, carrying out vacuum filtration on the modified product dispersion liquid, repeatedly washing for 3 times by using absolute ethyl alcohol, and collecting a filter cake;
c. placing the filter cake in a constant-temperature vacuum drying oven at 60 ℃ for drying for 24 hours to finally obtain a dry cellulose-based flame retardant; and obtaining the uniform flame retardant powder with the particle size of 100-200 meshes by mechanical grinding.
-preparation of a cellulose-based flame retardant low density polyethylene system:
a. sequentially adding 15 g of cellulose-based flame retardant and 50 g of low-density polyethylene into an internal mixer, setting the melt blending temperature of equipment to be 180 ℃, setting the rotating speed of a rotor to be 40 revolutions per minute, and setting the melt blending time to be 10 minutes to obtain the flame-retardant low-density polyethylene;
b. and (2) placing the flame-retardant low-density polyethylene in a flat vulcanizing machine, setting the hot-pressing temperature to be 190 ℃, setting the hot-pressing pressure to be 10MPa, setting the hot-pressing time to be 10 minutes, and cutting the flat sample into a sample strip size suitable for the flame-retardant test requirement by adopting electric saw cutting equipment.
Claims (6)
1. A preparation method of a biomass-based single-component multi-source integrated halogen-free flame retardant is characterized by comprising the following steps:
preparation of biomass-based flame retardants:
a. slowly adding 5 g of biomass material into a phosphoric acid source under stirring, wherein the mass ratio is 1:3-5, and uniformly stirring at a stirring speed of 50-200 r/min until the biomass material and the phosphoric acid source become transparent viscous liquid A;
b. transferring the liquid A into a 100 ml reaction kettle with a tetrafluoroethylene lining, and placing the reaction kettle in a 100-DEG dry box for reaction for 1-3 hours to obtain a biomass-based flame retardant intermediate B;
c. ultrasonically dispersing 15 g of amine-based gas source powder in 50 ml of deionized water, then transferring the mixture into a 250 ml three-neck bottle with mechanical stirring, stirring at the speed of 300-350 r/m, heating to 95-100 ℃, then dropwise adding the biomass-based flame retardant intermediate B, wherein the dropwise adding process lasts for about 20-30 minutes, and after the dropwise adding is finished, continuing the constant-temperature reaction for 0.5-1 hour;
d. when the system is cooled to room temperature, carrying out vacuum filtration on the obtained product, repeatedly washing the product for 3-5 times by using deionized water and absolute ethyl alcohol, and collecting a filter cake;
e. placing the filter cake in a constant-temperature vacuum drying oven at 60-80 ℃ for drying for 24 hours to finally obtain a dry biomass-based flame retardant;
-hydrophobic surface modification of biomass-based flame retardants:
adding 10 g of biomass-based flame retardant powder into 50 ml of an absolute ethyl alcohol solution of 5-10% by mass of organosilane, stirring for 0.5-1 hour, transferring the system into a 100 ml reaction kettle with a tetrafluoroethylene liner, and placing the reaction kettle in a constant-temperature drying box at 70-80 ℃ for reaction for 1-3 hours to obtain a modified product dispersion liquid;
b. when the system is cooled to room temperature, carrying out vacuum filtration on the modified product dispersion liquid, repeatedly washing for 3-5 times by using absolute ethyl alcohol, and collecting a filter cake;
c. putting the filter cake into a constant-temperature vacuum drying oven at 60-70 ℃ for drying for 24 hours to finally obtain a dry biomass-based flame retardant; and obtaining uniform flame retardant powder with the particle size of 100-200 meshes by mechanical grinding,
preparation of flame-retardant thermoplastic polymer systems:
sequentially adding the modified biomass-based flame retardant and the thermoplastic polymer into an internal mixer or a double-screw extruder according to a certain proportion, setting the melt blending temperature of the equipment at 180-200 ℃, the rotating speed of a screw or a rotor at 40-60 r/min, and the melt blending time at 10-15 min to obtain the flame-retardant polymer;
and (3) placing the flame-retardant polymer in a flat vulcanizing instrument, setting the hot-pressing temperature to be 190-200 ℃, setting the hot-pressing pressure to be 10-15MPa, setting the hot-pressing time to be 10-15 minutes, and cutting the flat sample into a sample strip size suitable for the flame-retardant test requirement by adopting electric saw cutting equipment.
2. The preparation method of the biomass-based single-component multisource integrated halogen-free flame retardant according to claim 1, wherein the biomass material comprises any one of soluble starch, cyclodextrin, cellulose acetate, hydroxyethyl cellulose, gum arabic, sodium alginate, xanthan gum, xylan, hemicellulose, carrageenan or konjac glucomannan.
3. The preparation method of the biomass-based single-component multi-source integrated halogen-free flame retardant according to claim 1, wherein the phosphoric acid source comprises any one of phosphoric acid, pyrophosphoric acid and polyphosphoric acid.
4. The preparation method of the biomass-based single-component multi-source integrated halogen-free flame retardant according to claim 1, wherein the amine-based gas source comprises any one of melamine, dicyandiamide, urea or melamine cyanurate.
5. The preparation method of the biomass-based single-component multisource integrated halogen-free flame retardant as claimed in claim 1, wherein the organosilane modifier comprises any one of methyltriethoxysilane, polymethyltriethoxysilane, dimethyldiethoxysilane, vinyltriethoxysilane, n-octyltriethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, trimethylchlorosilane, epoxy resin modified silicone resin, acrylic resin modified silicone resin, and methylphenyl silicone resin.
6. The preparation method of the biomass-based single-component multisource integrated halogen-free flame retardant according to claim 1, wherein the thermoplastic polymer comprises any one of low-density polyethylene, polypropylene, polystyrene, thermoplastic polyurethane, ABS, EVA and PET.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114957493A (en) * | 2022-07-19 | 2022-08-30 | 太原科技大学 | Preparation method and application of starch-based stiffening flame retardant special for PBAT (Poly (butylene adipate-co-terephthalate)) |
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| US20140249255A1 (en) * | 2013-03-04 | 2014-09-04 | Ricoh Company, Ltd. | Flame retardant resin composition and molded product |
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| US20140249255A1 (en) * | 2013-03-04 | 2014-09-04 | Ricoh Company, Ltd. | Flame retardant resin composition and molded product |
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| ZAIHANG ZHENG等: ""Fabrication of cellulose-based halogen-free flame retardant and its synergistic effect with expandable graphite in polypropylene"", 《CARBOHYDRATE POLYMERS》 * |
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| CN114957493A (en) * | 2022-07-19 | 2022-08-30 | 太原科技大学 | Preparation method and application of starch-based stiffening flame retardant special for PBAT (Poly (butylene adipate-co-terephthalate)) |
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