CN115403709A - Flame-retardant polypropylene foam plastic and preparation method thereof - Google Patents
Flame-retardant polypropylene foam plastic and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
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- 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
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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Abstract
The invention discloses a flame-retardant polypropylene foam plastic and a preparation method thereof, belonging to the technical field of foam plastics and comprising the following raw materials in parts by weight: 85-90 parts of polypropylene resin, 10-15 parts of fluororubber, 5-7 parts of flame-retardant monomer, 0.6-0.8 part of antioxidant and 3-4 parts of foaming agent; in the preparation method, the composite material is prepared by the polypropylene resin, the fluororubber, the flame-retardant monomer and the antioxidant, and then the composite material and the foaming agent are mixed and foamed to obtain the flame-retardant polypropylene foam plastic. According to the invention, a certain amount of fluororubber is added, so that the foaming quality and the cell structure are improved, and the mechanical property of the polypropylene foam plastic is improved; the polypropylene foam plastic is endowed with the characteristics of lasting, stability, environmental protection and high-efficiency flame retardance by adding the synthesized flame-retardant monomer; the polypropylene foam plastic has wider application space.
Description
Technical Field
The invention belongs to the technical field of foamed plastics, and particularly relates to flame-retardant polypropylene foamed plastic and a preparation method thereof.
Background
EPP is an abbreviation of expanded polypropylene (Expandoldpypypylene) and is an abbreviation of a new type of foam. EPP is a polypropylene plastic foaming material, is a high-crystallization polymer/gas composite material with excellent performance, and becomes the environment-friendly novel compression-resistant buffering heat-insulating material with the fastest growth due to the unique and superior performance. EPP is also an environment-friendly material and can be recycled. Compared with EPS (expanded polystyrene), EPP has higher mechanical strength, and the application scene of the foamed plastic is greatly expanded.
Although the polypropylene foaming material has excellent performance, the polypropylene foaming material belongs to flammable materials because the limiting oxygen index (LOI value) is only 18, and the polypropylene foaming material is especially a high-rate foaming product (the density is lower than 30 kg/m) 3 ) Is more easily ignited, which not only limits its range of use. However, most of the building materials and heat insulation materials used in the market at present use halogen-containing flame retardants for improving flame retardant performance, and although certain flame retardant effect can be achieved, a large amount of toxic gases and a large amount of dense smoke are released in the combustion process, which does not meet the requirements of environmental protection and flame retardance.
Although environment-friendly flame-retardant components are adopted in the prior art, for example, a chinese patent with patent application publication No. CN106566076A discloses a flame-retardant polypropylene expanded bead and a production process thereof, the flame-retardant polypropylene expanded bead comprises a polypropylene substrate and a flame-retardant system, and the flame-retardant system comprises the following components in parts by weight: nano silicon dioxide: 6.7-6.9 parts of fumed silica: 2.5-2.7 parts of methyl hydrogen silicone oil: 91-93 parts of hydroxy polydimethylsiloxane: 0.5-0.7 parts of compatilizer: 0.5-0.7 part of coupling agent: 1.1-1.3 parts of flatting agent: 1.5-1.7 parts of mixed rare earth chloride: 0.3-0.5 part. The flame-retardant system disclosed in the technical scheme can effectively improve the flame-retardant performance of the polypropylene foaming beads, and the LOI is increased to 31%, but the flame-retardant material is complex and various, the effective component is an inorganic substance, the compatibility with a polypropylene matrix is low, and the uniform dispersion in the polypropylene matrix is difficult to realize.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides flame-retardant polypropylene foam plastic and a preparation method thereof.
According to the invention, a certain amount of fluororubber is added, so that the mechanical properties of the polypropylene foam plastic are improved while the foaming quality and the cellular structure are improved; the polypropylene foam plastic is endowed with the lasting, stable, environment-friendly and efficient flame-retardant characteristic by adding the synthesized flame-retardant monomer; the polypropylene foam plastic has wider application space.
The purpose of the invention can be realized by the following technical scheme:
the flame-retardant polypropylene foam plastic comprises the following raw materials in parts by weight: 85-90 parts of polypropylene resin, 10-15 parts of fluororubber, 5-7 parts of flame-retardant monomer, 0.6-0.8 part of antioxidant and 3-4 parts of foaming agent;
the preparation method of the flame-retardant polypropylene foam plastic comprises the following steps:
firstly, mixing polypropylene resin, fluororubber, a flame-retardant monomer and an antioxidant, and then carrying out melt extrusion in a double-screw extruder to obtain a composite material, wherein the temperatures of first zone to eighth zone of the double-screw extruder are respectively 160 ℃, 180 ℃, 200 ℃, 220 ℃, 230 ℃, 220 ℃, 200 ℃, the head temperature is 180 ℃, and the screw rotating speed is 450r/min;
and secondly, uniformly mixing the composite material and the foaming agent, adding the mixture into a foaming injection molding machine, wherein the temperatures from a hopper to a nozzle of the injection molding machine are respectively 160 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃ and 190 ℃, and preparing the polypropylene foamed plastic.
The density of the obtained polypropylene foam is 120-300kg/m 3 Can replace wood and paper boxes;
the fluororubber has excellent chemical resistance, weather resistance and flame retardance; the fluororubber is added into the polypropylene foaming material, on one hand, the introduction of the fluororubber increases the melt viscoelasticity and the tensile viscosity of the composite material, which is beneficial to stabilizing the cell structure in the foaming process, inhibiting the rapid growth of cells, and reducing the conditions of cell deformation, cell combination and cell collapse; the fluororubber has heterogeneous nucleation effect, reduces nucleation energy barrier, obviously improves nucleation rate, forms a large amount of foaming points competing for limited gas, and limits the growth of foam cells, so that the fluororubber can improve foaming quality and foam cell structure; on the other hand, the rubber particles are used as an elastomer, so that the tensile property and the impact property can be improved, and the mechanical property of the polypropylene foam plastic is improved.
Further, the antioxidant is any one of a compound antioxidant B215, a phenol antioxidant 1010, a phosphite antioxidant Irgafos168 and a thioester antioxidant DSTP.
Furthermore, the foaming agent is azodicarbonamide, the efficiency of generating foam by gas released by the azodicarbonamide is high, the gas release speed is high, the gas is not easy to lose control, and the foaming agent is a substance with low toxicity.
Further, the flame retardant monomer is prepared by the following steps:
s1, adding 3-methylthiopropanal, p-phenylenediamine and ethanol into a three-neck flask provided with a stirrer and a reflux condenser, heating, carrying out reflux reaction for 12 hours at a constant temperature of 85 ℃, after the reaction is finished, spin-drying the solvent ethanol, and then carrying out column chromatography purification to obtain an intermediate 1; the dosage ratio of the 3-methylthiopropanal to the p-phenylenediamine to the ethanol is 1mmol;
aldehyde group on 3-methylthiopropanal molecule and-NH on p-phenylenediamine molecule 2 And (3) carrying out chemical reaction to generate Schiff base, wherein the molar ratio of the Schiff base to the p-phenylenediamine is controlled to be close to 1 (the p-phenylenediamine is slightly excessive), and under the action of a steric hindrance, the p-phenylenediamine only has-NH at one end 2 Participate in the reaction to obtain intermediate 1, and the reaction process is as follows:
s2, adding DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), the intermediate 1 and a DMF (dimethyl formamide) solvent into a three-neck flask provided with a stirrer and a reflux condenser, continuously introducing nitrogen for protection, heating the system to 90 ℃ under stirring, keeping the temperature for 50-60min (so that all particle substances are dissolved), heating to 130 ℃ for reaction for 8h, finishing the reaction, pouring a large amount of distilled water into the system after the product is cooled to room temperature to precipitate in an ice water bath, performing suction filtration under reduced pressure, repeatedly washing the crude product (filter cake) with petroleum ether for 3 times, and drying the crude product in a vacuum oven at 80 ℃ for 12h to obtain an intermediate 2; the dosage ratio of DOPO, intermediate 1 and DMF is 21.6 g;
the-C = N-on the intermediate 1 and the P-H on the DOPO molecule are subjected to addition reaction to generate an intermediate 2, and the reaction process is as follows:
s3, in N 2 Acrylic acid, triethylamine (acid-binding agent) and dichloromethane were added to a three-necked flask under protection, and then intermediate 2 and DIC (N, N-diisopropylcarbodiimide) were added thereto at room temperature under N 2 Stirring and reacting for 3 hours under protection, after the reaction is finished, distilling under reduced pressure to remove a solvent dichloromethane, then adding distilled water into the product, adjusting the pH value of the mixed solution to 8.0 by using potassium carbonate, extracting the mixture by using ethyl acetate, taking an organic layer, washing the organic layer by using a saturated NaCl solution, drying by using anhydrous magnesium sulfate, removing most of the solvent by reduced pressure rotary evaporation, and separating by using a silica gel column chromatography to obtain a flame-retardant monomer; the ratio of the amounts of acrylic acid, intermediate 2, triethylamine, DIC, dichloromethane and distilled water used was 1.0 mmol;
-NH on intermediate 2 by Triethylamine and DIC 2 Reacts with-COOH on acrylic acid molecules to generate a flame-retardant monomer, and the reaction process is as follows:
the obtained flame-retardant monomer contains phosphate groups, nitrogen-containing groups, sulfur-containing groups and benzene rings, the phosphate groups can generate phosphoric acid under heating, the dehydration and carbonization of a copolymer matrix (polypropylene) and the benzene rings are promoted in a condensed phase, the nitrogen-containing groups are decomposed under heating to release nitrogen-containing flame-retardant gas, the flammable volatile matter is diluted in a gas phase, and the sulfur-containing groups can accelerate the isomerization of a macromolecular matrix to generate a large amount of CO 2 The Fries rearrangement progress of the catalytic matrix is promoted to form carbon; therefore, the obtained flame-retardant monomer has multiple-effect flame-retardant components, has a halogen-free effect, and can realize environment-friendly and efficient flame-retardant effects; it is further noted that the flame retardant monomer has terminal C = C, so that the flame retardant monomer can participate in the polymerization process of polypropylene and fluororubber during the melt blending process, and the flame retardant monomer is combined with the matrix in a chemical bond block mode, thereby improving the flame retardant monomer and the matrixThe bonding force of the flame retardant improves the defects that the traditional flame retardant is easy to migrate and exude in the copolymer; the addition of the flame-retardant monomer enables the polypropylene foam to have the characteristics of stability, durability, environmental protection and high-efficiency flame retardance.
The invention has the beneficial effects that:
1. in order to improve the quality of the foam cells of the polypropylene foam, a certain amount of fluororubber is added, and the fluororubber has excellent chemical resistance, weather resistance and flame retardance; the fluororubber is added into the polypropylene foaming material, on one hand, the introduction of the fluororubber increases the melt viscoelasticity and the tensile viscosity of the composite material, which is beneficial to stabilizing the cell structure in the foaming process, inhibiting the rapid growth of cells, and reducing the conditions of cell deformation, cell combination and cell collapse; the fluororubber has heterogeneous nucleation effect, reduces nucleation energy barrier, obviously improves nucleation rate, forms a large amount of foaming points to compete limited gas, and limits the growth of foam cells, so that the fluororubber can improve foaming quality and cell structure; on the other hand, the rubber particles are used as an elastomer, so that the tensile property and the impact property can be improved, and the mechanical property of the polypropylene foam plastic is improved;
2. in order to improve the flame retardant property of the polypropylene foam plastic, a synthetic flame retardant monomer is added, the flame retardant monomer contains phosphate ester groups, nitrogen-containing groups, sulfur-containing groups and benzene rings, the phosphate ester groups can generate phosphoric acid when being heated, the dehydration and the char formation of a copolymer matrix (polypropylene) and the benzene rings are promoted in a condensed phase, the nitrogen-containing groups are decomposed by heating to release nitrogen-containing nonflammable gas, flammable volatile matters are diluted in a gas phase, and the sulfur-containing groups can accelerate the isomerization of a macromolecular matrix to generate a large amount of CO 2 The Fries rearrangement progress of the catalytic matrix is promoted to form carbon; therefore, the obtained flame-retardant monomer has multiple-effect flame-retardant components, has a halogen-free effect, and can realize environment-friendly and efficient flame-retardant effects; it is further noted that the flame retardant monomer contains terminal C = C, so that the flame retardant monomer can participate in the polymerization process of polypropylene and fluororubber during melt blending, and the flame retardant monomer is combined with the matrix in a chemical bond block mode, thereby improving the binding force of the flame retardant monomer and the matrix, and overcoming the defects that the traditional flame retardant is easy to migrate and exude in the copolymer(ii) a The addition of the flame-retardant monomer enables the polypropylene foam to have the characteristics of stability, durability, environmental protection and high-efficiency flame retardance.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing a flame-retardant monomer:
s1, adding 10mmol of 3-methylthiopropanal, 10.5mmol of p-phenylenediamine and 200mL of ethanol into a three-neck flask provided with a stirrer and a reflux condenser, heating, carrying out reflux reaction at the constant temperature of 85 ℃ for 12 hours, after the reaction is finished, spin-drying the solvent ethanol, and then carrying out column chromatography purification to obtain an intermediate 1;
s2, adding 21.6g of DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and 19.4g of intermediate 1 and 150mL of DMF solvent into a three-neck flask provided with a stirrer and a reflux condenser, continuously introducing nitrogen for protection, heating the system to 90 ℃ firstly under stirring, preserving the temperature for 50min (completely dissolving the particle substances), heating to 130 ℃ for reaction for 8h, finishing the reaction, pouring a large amount of distilled water into the three-neck flask after the product is cooled to room temperature to precipitate in an ice water bath, carrying out vacuum filtration, repeatedly washing the crude product (filter cake) for 3 times by using petroleum ether, and drying in a vacuum oven at 80 ℃ for 12h to obtain an intermediate 2;
s3, in N 2 10mmol of acrylic acid, 30mmol of triethylamine (acid-binding agent) and 200mL of dichloromethane were added to a three-necked flask under protection, 4.5g of intermediate 2 and 10.5mmol of DIC (N, N-diisopropylcarbodiimide) were added thereto, and the mixture was cooled to room temperature under N-diisopropylcarbodiimide 2 Stirring and reacting for 3h under protection, after the reaction is finished, distilling under reduced pressure to remove a solvent dichloromethane, then adding 400mL of distilled water into the product, adjusting the pH value of the mixed solution to 8.0 by potassium carbonate, extracting the mixture by ethyl acetate, taking an organic layer, and using saturated NaCl, washing the solution, drying the solution by anhydrous magnesium sulfate, removing most of solvent by reduced pressure rotary evaporation, and separating by silica gel column chromatography to obtain the flame-retardant monomer.
Example 2
Preparing a flame-retardant monomer:
s1, adding 20mmol of 3-methylthiopropanal, 21mmol of p-phenylenediamine and 400mL of ethanol into a three-neck flask provided with a stirrer and a reflux condenser, heating, carrying out reflux reaction at a constant temperature of 85 ℃ for 12 hours, after the reaction is finished, drying the solvent ethanol in a spinning mode, and then carrying out column chromatography purification to obtain an intermediate 1;
s2, adding 43.2g of DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and 38.8g of intermediate 1 and 300mL of DMF (dimethyl formamide) solvent into a three-neck flask provided with a stirrer and a reflux condenser, continuously introducing nitrogen for protection, heating the system to 90 ℃ firstly under stirring, keeping the temperature for 60min (completely dissolving the particle substances), heating to 130 ℃ for reaction for 8h, finishing the reaction, pouring a large amount of distilled water into the three-neck flask after the product is cooled to room temperature to precipitate in an ice water bath, carrying out vacuum filtration, repeatedly washing the crude product (filter cake) for 3 times by using petroleum ether, and drying in a vacuum oven at 80 ℃ for 12h to obtain an intermediate 2;
s3, in N 2 20mmol of acrylic acid, 60mmol of triethylamine (acid-binding agent) and 400mL of dichloromethane were added to a three-necked flask under protection, 9g of intermediate 2 and 21mmol of DIC (N, N-diisopropylcarbodiimide) were added thereto, and the mixture was cooled to room temperature under N-dichloromethane 2 Stirring and reacting for 3 hours under protection, after the reaction is finished, distilling under reduced pressure to remove a solvent dichloromethane, then adding 800mL of distilled water into the product, adjusting the pH value of the mixed solution to 8.0 by using potassium carbonate, extracting the mixture by using ethyl acetate, taking an organic layer, washing the organic layer by using a saturated NaCl solution, drying anhydrous magnesium sulfate, removing most of the solvent by reduced pressure rotary distillation, and separating by using a silica gel column chromatography to obtain the flame-retardant monomer.
Example 3
The flame-retardant polypropylene foam plastic comprises the following raw materials in parts by weight: 85 parts of polypropylene resin, 15 parts of fluororubber, 5 parts of flame-retardant monomer prepared in example 1, 0.6 part of composite antioxidant B215 and 3 parts of azodicarbonamide;
the preparation method of the flame-retardant polypropylene foam plastic comprises the following steps:
firstly, mixing polypropylene resin, fluororubber, the flame-retardant monomer prepared in the embodiment 1 and a composite antioxidant B215, and then carrying out melt extrusion in a double-screw extruder to obtain a composite material, wherein the temperatures of first to eighth zones of the double-screw extruder are respectively 160 ℃, 180 ℃, 200 ℃, 220 ℃, 230 ℃, 220 ℃, 200 ℃, the head temperature is 180 ℃, and the screw rotation speed is 450r/min;
and secondly, uniformly mixing the composite material and the azodicarbonamide, adding the mixture into a foaming injection molding machine, wherein the temperatures of the injection molding machine from a hopper to a nozzle are respectively 160 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃ and 190 ℃, and preparing the polypropylene foamed plastic.
Example 4
The flame-retardant polypropylene foam plastic comprises the following raw materials in parts by weight: 87.5 parts of polypropylene resin, 12.5 parts of fluororubber, 6 parts of flame-retardant monomer prepared in example 2, 0.7 part of phenolic antioxidant and 3.5 parts of azodicarbonamide;
the preparation method of the flame-retardant polypropylene foam plastic comprises the following steps:
step one, mixing polypropylene resin, fluororubber, the flame-retardant monomer prepared in the embodiment 2 and a phenolic antioxidant 1010, and then carrying out melt extrusion in a double-screw extruder to obtain a composite material, wherein the temperatures of the first zone to the eighth zone of the double-screw extruder are respectively 160 ℃, 180 ℃, 200 ℃, 220 ℃, 230 ℃, 220 ℃, 200 ℃, the machine head temperature is 180 ℃, and the screw rotating speed is 450r/min;
and secondly, uniformly mixing the composite material and the azodicarbonamide, adding the mixture into a foaming injection molding machine, wherein the temperatures from a hopper to a nozzle of the injection molding machine are respectively 160 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃ and 190 ℃, and preparing the polypropylene foam plastic.
Example 5
The flame-retardant polypropylene foam plastic comprises the following raw materials in parts by weight: 90 parts of polypropylene resin, 10 parts of fluororubber, 7 parts of the flame-retardant monomer prepared in the embodiment 1, 0.8 part of phosphite antioxidant Irgafos and 4 parts of azodicarbonamide;
the preparation method of the flame-retardant polypropylene foam plastic comprises the following steps:
firstly, mixing polypropylene resin, fluororubber, the flame-retardant monomer prepared in the embodiment 1 and phosphite antioxidant Irgafos168, and then carrying out melt extrusion in a double-screw extruder to obtain a composite material, wherein the temperatures of first to eighth zones of the double-screw extruder are respectively 160 ℃, 180 ℃, 200 ℃, 220 ℃, 230 ℃, 220 ℃, 200 ℃, the head temperature is 180 ℃, and the screw rotation speed is 450r/min;
and secondly, uniformly mixing the composite material and the azodicarbonamide, adding the mixture into a foaming injection molding machine, wherein the temperatures of the injection molding machine from a hopper to a nozzle are respectively 160 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃ and 190 ℃, and preparing the polypropylene foamed plastic.
The polypropylene foams obtained in examples 3 to 5 were cut into test specimens and subjected to the following property tests:
mechanical properties: the tensile property is tested according to GB/T1040.1-2018, the temperature is 25 ℃, and the tensile rate is 50mm/min; the impact performance is tested according to GB/T1843-2008, and the notch depth is 2mm;
the flame retardant property is as follows: according to GB/T2406-2008, adopting an oxygen index tester and according to GB8332-2008 'horizontal combustion method of foam plastic combustion performance test method' adopting a vertical and horizontal UL-94 combustion tester;
the results obtained are shown in the following table:
| example 3 | Example 4 | Example 5 | |
| Tensile strength/MPa | 24.8 | 23.9 | 24.5 |
| Elongation at break/% | 56.7 | 56.0 | 56.4 |
| Notched impact strength/kJ · m -2 | 3.69 | 3.55 | 3.63 |
| Oxygen index/% | 34.7 | 33.9 | 34.5 |
| Horizontal combustion rating | HF-2 | HF-2 | HF-2 |
As can be seen from the data in the table, the polypropylene foam plastic obtained by the invention has good mechanical property and flame retardant property.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (10)
1. The flame-retardant polypropylene foam plastic is characterized by comprising the following raw materials in parts by weight: 85-90 parts of polypropylene resin, 10-15 parts of fluororubber, 5-7 parts of flame-retardant monomer, 0.6-0.8 part of antioxidant and 3-4 parts of foaming agent.
2. The flame-retardant polypropylene foam plastic according to claim 1, wherein the antioxidant is any one of a compound antioxidant B215, a phenolic antioxidant 1010, a phosphite antioxidant Irgafos168 and a thioester antioxidant DSTP.
3. The flame retarded polypropylene foam according to claim 1 wherein said blowing agent is azodicarbonamide.
4. The flame retardant polypropylene foam according to claim 1, wherein the flame retardant monomer is prepared by the steps of:
s1, adding 3-methylthiopropanal, p-phenylenediamine and ethanol into a three-neck flask with a stirrer and a reflux condenser, heating, carrying out reflux reaction for 12 hours at a constant temperature of 85 ℃, after the reaction is finished, spin-drying the solvent ethanol, and then carrying out column chromatography purification to obtain an intermediate 1;
s2, adding DOPO, the intermediate 1 and a DMF solvent into a three-neck flask provided with a stirrer and a reflux condenser tube, continuously introducing nitrogen for protection, heating the system to 90 ℃ under stirring, preserving heat for 50-60min, heating to 130 ℃ for reaction for 8h, finishing the reaction, cooling the product to room temperature, pouring a large amount of distilled water into an ice water bath to precipitate, performing vacuum filtration, repeatedly washing the crude product with petroleum ether for 3 times, and drying in a vacuum oven at 80 ℃ for 12h to obtain an intermediate 2;
s3, in N 2 Acrylic acid, triethylamine and dichloromethane were added to a three-necked flask under protection, then intermediate 2 and DIC were added, and the mixture was cooled to room temperature under N 2 Stirring and reacting for 3h under protection, and after the reaction is finished, performing post-treatment to obtain the flame-retardant monomer.
5. The flame-retardant polypropylene foam according to claim 4, wherein the ratio of the amounts of 3-methylthiopropanal, p-phenylenediamine and ethanol used in step S1 is 1mmol.
6. The flame-retardant polypropylene foam according to claim 4, wherein the ratio of the amounts of DOPO, intermediate 1 and DMF in step S2 is 21.6 g.
7. The flame retardant polypropylene foam according to claim 4, wherein the post-treatment in step S3 comprises: distilling under reduced pressure to remove solvent dichloromethane, adding distilled water into the product, adjusting pH value of the mixed solution to 8.0 with potassium carbonate, extracting the mixture with ethyl acetate, taking an organic layer, washing with saturated NaCl solution, drying with anhydrous magnesium sulfate, removing most of solvent by rotary evaporation under reduced pressure, and separating by silica gel column chromatography to obtain the flame-retardant monomer.
8. The flame-retardant polypropylene foam according to claim 4, wherein the ratio of the amounts of acrylic acid, intermediate 2, triethylamine, DIC, methylene chloride and distilled water used in step S3 is 1.0 mmol.
9. The method for preparing the flame-retardant polypropylene foam according to claim 1, comprising the steps of:
firstly, mixing polypropylene resin, fluororubber, a flame-retardant monomer and an antioxidant, and then carrying out melt extrusion in a double-screw extruder to obtain a composite material;
and secondly, uniformly mixing the composite material and a foaming agent, and adding the mixture into a foaming injection molding machine for foaming to prepare the polypropylene foam plastic.
10. The process for producing the flame-retarded polypropylene foam according to claim 9, wherein the temperatures of the first to eighth zones of the twin-screw extruder are 160 ℃, 180 ℃, 200 ℃, 220 ℃, 230 ℃, 220 ℃, 200 ℃, the head temperature is 180 ℃ and the screw rotation speed is 450r/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116606488A (en) * | 2023-06-12 | 2023-08-18 | 深圳市好年璟科技有限公司 | Wear-resistant rubber-plastic composite material |
| CN119463040A (en) * | 2025-01-14 | 2025-02-18 | 湖南省新基源新材料科技有限公司 | A method for preparing hydrophobically modified polypropylene plastic |
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| CN104194152A (en) * | 2014-08-27 | 2014-12-10 | 江门市道生工程塑料有限公司 | Halogen-free flame-retardant polypropylene composite material and preparation method thereof |
| CN110698600A (en) * | 2019-10-14 | 2020-01-17 | 湖南工学院 | Preparation method and application of bulk flame-retardant polypropylene graft |
| CN110734609A (en) * | 2019-12-05 | 2020-01-31 | 万华化学（宁波）有限公司 | High-toughness oil-resistant polypropylene composite material and preparation method thereof |
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| CN104194152A (en) * | 2014-08-27 | 2014-12-10 | 江门市道生工程塑料有限公司 | Halogen-free flame-retardant polypropylene composite material and preparation method thereof |
| CN110698600A (en) * | 2019-10-14 | 2020-01-17 | 湖南工学院 | Preparation method and application of bulk flame-retardant polypropylene graft |
| CN110734609A (en) * | 2019-12-05 | 2020-01-31 | 万华化学（宁波）有限公司 | High-toughness oil-resistant polypropylene composite material and preparation method thereof |
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| CN116606488A (en) * | 2023-06-12 | 2023-08-18 | 深圳市好年璟科技有限公司 | Wear-resistant rubber-plastic composite material |
| CN116606488B (en) * | 2023-06-12 | 2024-05-17 | 深圳市好年璟科技有限公司 | Wear-resistant rubber-plastic composite material |
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