CN113387830A - Bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent and preparation method thereof - Google Patents
Bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent and preparation method thereof Download PDFInfo
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- C07C235/32—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings
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- C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
- C07D295/125—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/13—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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Abstract
The invention discloses a bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent and a preparation method thereof, wherein polyphosphoric acid is utilizedThe high flame-retardant efficiency of ammonium endows the integrated auxiliary agent with high flame-retardant efficiency, and C is recycled2‑10Any one of aliphatic diamine, polyethylene polyamine, piperazine and derivatives thereof is used as a bridge, after ammonium polyphosphate is introduced into a bio-based small molecular structure which contains carboxyl at the end group and contains a phenol structure in the structure and is derived from plant extracts in a chemical bonding mode, the ammonium polyphosphate is endowed with a function of resisting thermo-oxidative aging while the high flame retardant efficiency of the ammonium polyphosphate is maintained, in addition, the modified ammonium polyphosphate and the bio-based small molecule containing the phenol structure form a brand-new novel auxiliary agent with a bifunctional characteristic in a chemical bonding mode, the problem of mechanical property deterioration caused by poor multi-phase composite interface compatibility when a small molecular antioxidant and a flame retardant are respectively added can be avoided, and the problem of easy precipitation caused by poor compatibility of the small molecular antioxidant and a matrix is also avoided.
Description
Technical Field
The invention relates to the technical field of flame-retardant anti-aging high polymer materials, in particular to a bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent and a preparation method thereof.
Background
The polymer material with excellent comprehensive performance is widely applied to various fields such as building materials, household appliances, automobiles, high-speed rails, airplanes and the like. However, most of the polymers belong to flammable materials, the heat release rate in the combustion process is high, the flame propagation speed is high, a large amount of dense smoke and toxic gas are usually generated, and great threat is caused to life and property safety. Meanwhile, the aging of the high molecular material can occur in part of the using environment, and especially in some large-scale equipment, the aging of high molecular material parts can easily cause the functional failure of mechanical equipment, thereby causing serious potential safety hazard.
In order to improve the flame retardancy of the polymer material, a flame retardant may be introduced into the polymer base material. According to the relationship between the flame retardant and the base material, the flame retardant can be divided into an additive type and a reactive type, and the flame retardance of the high polymer material is mainly focused on the additive type flame retardant direction at present. The additive type flame retardant is characterized in that a flame retardant is added into a base material in a physical melt blending mode, so that the flame retardant property of the base material is endowed. In the additive flame retardant, ammonium polyphosphate and a modified series thereof are typical high-efficiency intumescent flame retardant systems, have high flame retardant efficiency, but have single functionality, and mainly play a positive role in flame retardance.
In order to improve the aging resistance of the polymer material, various aging aids, such as hindered phenol antioxidants, hindered amine light stabilizers, etc., must be added to the substrate. Most of high molecular materials have large polarity difference with the micromolecular antiaging agent, so the compatibility is not good, and the micromolecular antiaging agent is easy to separate out, generates a white frost phenomenon and causes the material to lose the antiaging effect; on the other hand, poor compatibility between the anti-aging agent and the polymer substrate and other additives can easily cause the mechanical properties of the polymer material to be reduced.
Aiming at the problems (ammonium polyphosphate is single in function, micromolecule anti-aging agents are easy to precipitate and lose efficacy, and the high polymer composite material is poor in comprehensive performance due to poor multiphase compatibility), if the ammonium polyphosphate and the anti-aging agents can be chemically bonded to form the flame-retardant anti-aging dual-function integrated auxiliary agent, the functions of the ammonium polyphosphate and the anti-aging agents can be fully exerted, the problem of mechanical property deterioration caused by poor multiphase composite interface compatibility can be solved, and the defect that the micromolecule anti-aging agents are easy to precipitate can be overcome. Therefore, the design and preparation of the flame-retardant anti-aging function integrated auxiliary agent have important practical significance.
Disclosure of Invention
The invention aims to provide a flame-retardant anti-aging bifunctional integrated auxiliary agent and a preparation method thereof, wherein the bifunctional integrated auxiliary agent can endow polyolefin materials with good flame retardance and good thermal oxidation aging resistance.
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the present invention, there is provided a bio-based flame retardant anti-aging dual-function integrated auxiliary, which has the following general structural formula:
wherein R is1Is polyethylene polyamine, piperazine and its derivative, C2-10Any one of the aliphatic diamines of (a); r2The terminal group containing carboxyl and the structure containing phenolBio-based small molecules of plant extracts,
Preferably, R is2Including but not limited to any of the following structures:
preferably, said C is2-10The aliphatic diamine of (a) is any one of the following structures:
preferably, the piperazine is:
the derivative of piperazine is any one of the following structures: 2, 3-diphenylpiperazine, 2-phenylpiperazine, N-aminoethylpiperazine.
Preferably, the polyethylene polyamine is any one of the following structures: diethylenetriamine, triethylene tetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine.
The invention also provides a preparation method of the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent, which comprises the following steps:
adding a mixed solvent of water and ethanol into a reactor in a nitrogen atmosphere, stirring for 20-40 min, and adding R1Injecting the mixture into a reactor, stirring for 8-12 min, adding ammonium polyphosphate into the reactor, heating to a first reaction temperature, stirring for reaction for 3-6 h, detecting whether ammonia exists by using pH test paper after the reaction is finished, and determining that the reaction is finished if the two pH values are both 8-9 within a 10-minute interval; is connected withTo obtain a solution of the product A by cooling the reaction mixture to room temperature; then, R is added2Adding the mixture into the solution of the product A, heating to a second reaction temperature, stirring and reacting for 8-12 h, and generating a precipitate; and then, carrying out suction filtration, washing and drying to constant weight to obtain solid powder, namely the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent.
Preferably, the volume ratio of water to ethanol in the mixed solvent of water and ethanol is 25-50: 1; the R is1The mass volume ratio of the mixed solvent to the mixed solvent is 40-65 g: 1L; the R is1The mass ratio of the ammonium polyphosphate to the ammonium polyphosphate is 8-13: 16-21; the R is2The mass ratio of the ammonium polyphosphate to the ammonium polyphosphate is 6-11: 16-21.
Preferably, the first reaction temperature is 80-100 ℃; the second reaction temperature is 60-90 ℃.
The invention also provides flame-retardant polyolefin prepared by the bio-based flame-retardant anti-aging bifunctional integrated auxiliary agent, which is prepared by melting and blending the following components in parts by weight:
70-80 parts of polypropylene and 20-30 parts of bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent, wherein the limiting oxygen index LOI of the flame-retardant polypropylene is 27.5-35.5%, and the vertical combustion UL-94 grade is V-2 grade to V-0 grade; the tensile strength, the elongation at break and the change rate of the impact strength are all 1-5% after thermal-oxidative aging for 168 hours.
The invention also provides flame-retardant polyolefin prepared by the bio-based flame-retardant anti-aging bifunctional integrated auxiliary agent, which is prepared by melting and blending the following components in parts by weight:
65-75 parts of polyethylene and 25-35 parts of bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent, wherein the limiting oxygen index LOI of the flame-retardant polyethylene is 26.0-33.5%, and the vertical combustion UL-94 grade is V-2 grade to V-0 grade; the tensile strength, the elongation at break and the change rate of the impact strength are all 1-5% after thermal-oxidative aging for 168 hours.
The invention at least comprises the following beneficial effects:
(1) compared with the prior art, the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent disclosed by the invention can realize flame retardance of a high polymer material, can endow the high polymer material with a good thermal oxidation aging resistant effect, and adds a new kind to the functional auxiliary agent in the field of high polymer materials.
(2) The invention also provides a preparation method of the bio-based flame-retardant anti-aging bifunctional integrated auxiliary agent, the method firstly prepares the amine compound modified ammonium polyphosphate, and the modified ammonium polyphosphate not only maintains the original high flame-retardant efficiency of the ammonium polyphosphate, but also provides a reaction site for the chemical introduction of an anti-aging structure. The introduction of the bio-based micromolecule structure which has a terminal group containing carboxyl and contains a phenol structure and is derived from plant extracts endows modified ammonium polyphosphate with a function of resisting thermal oxidation aging while maintaining high flame-retardant efficiency, and simultaneously, because the modified ammonium polyphosphate and the bio-based micromolecules containing the phenol structure form a brand-new novel auxiliary agent with a bifunctional characteristic in a chemical bonding mode, the problem of mechanical property deterioration caused by poor compatibility of a multiphase composite interface when the micromolecule antioxidant and the flame retardant are respectively added can be avoided, and the problem of easy precipitation caused by poor compatibility of the micromolecule antioxidant and a substrate is also avoided. Therefore, the flame retardance and the thermal-oxidative aging resistance of the polyolefin-based material can be simultaneously realized finally by adding a single auxiliary agent.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIG. 1 is an infrared spectrum of the bio-based flame-retardant anti-aging bifunctional integrated auxiliary agent prepared in example 1 of the present invention.
FIG. 2 is an X-ray photoelectron energy spectrum of the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent prepared in example 1 of the present invention.
The specific implementation mode is as follows:
the present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
In the preparation method, the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent is prepared by two steps of ammonium polyphosphate, amine compounds and a bio-based micromolecule structure which contains carboxyl at the end group and is derived from plant extracts and contains a phenol structure in the structure, and is characterized in that the high flame-retardant efficiency of the ammonium polyphosphate is utilized to endow the integrated auxiliary agent with high flame-retardant efficiency, and C is utilized2-10One of aliphatic diamine, polyethylene polyamine, piperazine and derivatives thereof is used as a bridge, and after a bio-based small molecular structure which contains carboxyl at the end group and contains a phenol structure in the structure and is derived from plant extracts is introduced into ammonium polyphosphate in a chemical bonding mode, the ammonium polyphosphate is endowed with the function of resisting thermo-oxidative aging while maintaining high flame retardant efficiency; according to the method, the amine compound modified ammonium polyphosphate is prepared in the first step, and the modified ammonium polyphosphate not only maintains the original high flame retardant efficiency of the ammonium polyphosphate, but also provides a reaction site for chemical introduction of an anti-aging structure. In the second step, the biological-based small molecular structure which contains carboxyl at the end group and phenol structure in the structure and is derived from plant extracts is introduced, so that the modified ammonium polyphosphate has the function of resisting thermo-oxidative aging while the high flame retardant efficiency of the modified ammonium polyphosphate is maintained. Because the modified ammonium polyphosphate and the bio-based micromolecular structure form a brand-new novel auxiliary agent with the bifunctional characteristic in a chemical bonding mode, the problem of mechanical property deterioration caused by poor compatibility of a multiphase composite interface when the micromolecular antioxidant and the flame retardant are respectively added can be avoided, and the problem that the micromolecular antioxidant is easy to separate out caused by poor compatibility with a matrix is also avoided. Therefore, the flame retardance and the thermal-oxidative aging resistance of the polyolefin material can be finally realized by adding a single auxiliary agent.
It is worth noting that the limiting oxygen index test results of the following examples are tested according to GB/T2406-; the thermal-oxidative aging resistance is carried out according to the test procedure GB/T16422.2-2014.
Example 1:
a preparation method of a bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent comprises the following steps:
pouring 1000mL of mixed solvent with the volume ratio of water to ethanol being 50/1 into a three-neck flask with a stirrer under the nitrogen atmosphere, stirring for half an hour, injecting 40g of ethylenediamine into the flask, and stirring for about 10 minutes; then, 80g of ammonium polyphosphate was added to the flask and the mixture was heated to the set reaction temperature of 80 ℃; after stirring and reacting for 3h, detecting whether ammonia exists by using pH test paper, and if the two pH values are both 8-9 within a 10-minute interval, determining that the reaction is finished; next, the reaction mixture was cooled to room temperature to obtain a solution of product a;
adding 30g of gallic acid into the solution of the product A, stirring and reacting for 8h at 60 ℃, and generating precipitate; then carrying out suction filtration, washing with water and drying to constant weight to obtain solid powder, namely the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent;
the flame-retardant polyolefin is prepared by adopting the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent, and is formed by melting and molding the following components in parts by mass (the molding conditions are that polypropylene as a base material and the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent are placed in a torque rheometer to be melted and blended, the temperature is 180 ℃, the rotating speed is 110rpm, the blending time is 10min, a vertical combustion, limiting oxygen index and mechanical test sample strip is molded by a micro injection molding machine, the injection molding temperature is 195 ℃, the mold temperature is room temperature, the injection molding pressure is 700bar, the injection molding time is 10s, and the holding pressure is 600 bar):
70 parts of polypropylene and 30 parts of a bio-based flame-retardant anti-aging bifunctional integrated auxiliary agent;
the experimental results show that: the addition amount of the bio-based flame-retardant anti-aging bifunctional integrated auxiliary agent prepared in example 1 is 30%, the oxygen index of the constructed polypropylene material is 35.5% when the polypropylene content is 70%, and the change rates of the tensile strength, the elongation at break and the impact strength after 168 hours of thermo-oxidative aging are respectively 1%, 2% and 3% according to the UL-94V 0 standard, which are superior to the corresponding change rates of 4%, 6% and 4% of the constructed material of the product A without the introduction of gallic acid under the same conditions.
FIG. 1 is an infrared spectrum of 1630cm for the bio-based flame-retardant anti-aging bifunctional integrated auxiliary agent prepared in example 1 of the present invention, as can be seen from FIG. 1-1Infrared characteristic absorption peak at-C ═ O, 1540cm-1An infrared characteristic absorption peak of-NH-, wherein the structure is from an amido bond formed by ethylenediamine modified APP and gallic acid; 3400 and 3030cm-1Is NH4 +The infrared characteristic absorption peak of (1), the structure is from NH on APP4 +；2826cm-1And 2881cm-1Is represented by-CH2-CH2Characteristic absorption Peak in the Infrared ray of-1539 cm-1Is NH3 +(ii) an infrared characteristic absorption peak of; the analysis shows that the flame-retardant and anti-aging bifunctional integrated auxiliary agent is successfully prepared.
FIG. 2 is an X-ray photoelectron energy spectrum of the flame-retardant anti-aging bifunctional integration aid prepared in example 1 of the present invention, and it can be seen from FIG. 2 that the actual element types and the theoretical element types of the prepared bifunctional integration aid are consistent, further illustrating the successful preparation of the aid.
Example 2:
a preparation method of a bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent comprises the following steps:
pouring 1000mL of mixed solvent with water and ethanol in a volume ratio of 45/1 into a three-neck flask with a stirrer under nitrogen atmosphere, stirring for half an hour, injecting 45g of 1, 2-propanediamine into the flask, stirring for about 10 minutes, then adding 85g of ammonium polyphosphate into the flask, heating the mixture to a set reaction temperature of 90 ℃, stirring for reaction for 4 hours, detecting whether ammonia gas exists by using a pH test paper, if the two pH values are 8-9 within a 10-minute interval, determining that the reaction is finished, and then cooling the reaction mixture to room temperature to obtain a solution of a product A.
And adding 35g of caffeic acid into the solution of the product A, stirring and reacting for 9h at 70 ℃, precipitating, then carrying out suction filtration, washing with water, and drying to constant weight to obtain solid powder, namely the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent.
The flame-retardant polyolefin is prepared by adopting the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent, and is formed by melting and molding the following components in parts by mass (the molding conditions are that polypropylene as a base material and the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent are placed in a torque rheometer to be melted and blended, the temperature is 180 ℃, the rotating speed is 110rpm, the blending time is 10min, a vertical combustion, limiting oxygen index and mechanical test sample strip is molded by a micro injection molding machine, the injection molding temperature is 195 ℃, the mold temperature is room temperature, the injection molding pressure is 700bar, the injection molding time is 10s, and the holding pressure is 600 bar):
75 parts of polypropylene and 25 parts of a bio-based flame-retardant anti-aging bifunctional integrated auxiliary agent;
the experimental results show that: the addition amount of the flame-retardant anti-aging bifunctional integrated auxiliary agent prepared in example 2 is 25%, the oxygen index of the material constructed when the polypropylene content is 75% is 30.0%, and the tensile strength, elongation at break and change rate of impact strength after 168 hours of thermal-oxidative aging are respectively 3%, 3% and 4% according to the V0 standard of UL-94, which are superior to the corresponding change rates of 5%, 6% and 5% of the material constructed under the same conditions of the product A without caffeic acid.
Example 3:
a preparation method of a bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent comprises the following steps:
pouring 1000mL of mixed solvent with water and ethanol in a volume ratio of 40/1 into a three-necked flask with a stirrer under nitrogen atmosphere, stirring for half an hour, injecting 50g of 1, 4-butanediamine into the flask, stirring for about 10 minutes, then adding 90g of ammonium polyphosphate into the flask, heating the mixture to a set reaction temperature of 95 ℃, stirring for reaction for 4 hours, detecting whether ammonia gas exists by using a pH test paper, if the two pH values are 8-9 within a 10-minute interval, determining that the reaction is finished, and then cooling the reaction mixture to room temperature to obtain a solution of a product A.
Adding 40g of p-coumaric acid into the solution of the product A, stirring and reacting for 10 hours at 80 ℃, precipitating, then carrying out suction filtration, washing and drying to constant weight, and obtaining solid powder, namely the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent.
The flame-retardant polyolefin is prepared by the bio-based flame-retardant anti-aging bifunctional integrated auxiliary agent, and is prepared by melting and blending the following components in parts by weight:
80 parts of polypropylene and 20 parts of a bio-based flame-retardant anti-aging bifunctional integrated auxiliary agent;
the experimental results show that: the addition amount of the flame-retardant and anti-aging bifunctional integrated auxiliary agent prepared in example 3 is 20%, the oxygen index of the constructed material is 27.5% when the polypropylene content is 80%, and the tensile strength, the elongation at break and the change rate of the impact strength after 168 hours of thermal-oxidative aging are respectively 3%, 4% and 5% according to the V2 standard of UL-94, which are superior to 5%, 7% and 6% of the corresponding change rates of the constructed material of the product A without introducing p-coumaric acid under the same conditions.
Example 4:
a preparation method of a bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent comprises the following steps:
pouring 1000mL of mixed solvent with water and ethanol in a volume ratio of 35/1 into a three-neck flask with a stirrer under nitrogen atmosphere, stirring for half an hour, injecting 55g of pentamethylene diamine into the flask, stirring for about 10 minutes, then adding 95g of ammonium polyphosphate into the flask, heating the mixture to a set reaction temperature of 95 ℃, stirring for reaction for 5 hours, detecting whether ammonia gas exists by using a pH test paper, if the two pH values are 8-9 within an interval of 10 minutes, determining that the reaction is finished, and then cooling the reaction mixture to room temperature to obtain a solution of a product A.
Adding 45g of ferulic acid into the solution of the product A, stirring and reacting for 10h at 80 ℃, precipitating, then carrying out suction filtration, washing with water, and drying to constant weight to obtain solid powder, namely the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent.
The flame-retardant polyolefin is prepared by adopting the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent, and is formed by melting and molding the following components in parts by mass (the molding conditions are as follows: the matrix material polyethylene and the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent are placed in a torque rheometer to be melted and blended, the temperature is 180 ℃, the rotating speed is 110rpm, the blending time is 10min, a vertical combustion, limiting oxygen index and mechanical test sample strip is molded by a micro injection molding machine, the injection molding temperature is 195 ℃, the mold temperature is room temperature, the injection molding pressure is 700bar, the injection molding time is 10s, and the holding pressure is 600 bar):
65 parts of polyethylene and 35 parts of a bio-based flame-retardant anti-aging bifunctional integrated auxiliary agent;
the experimental results show that: the addition amount of the bio-based flame-retardant anti-aging dual-function integrated auxiliary agent prepared in the embodiment 4 is 35%, the oxygen index of the material constructed when the polyethylene is 65% is 33.5%, and the change rates of the tensile strength, the elongation at break and the impact strength after the thermal-oxidative aging is 168 hours are respectively 1%, 2% and 4% according to the V0 standard of UL-94, which are superior to the corresponding change rates of the material constructed by the product A without ferulic acid which are 3%, 4% and 5% under the same conditions.
Example 5:
a preparation method of a bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent comprises the following steps:
1000mL of a mixed solvent of water and ethanol at a ratio of 30/1 was poured into a three-necked flask equipped with a stirrer under a nitrogen atmosphere, and after stirring for half an hour, 60g of piperazine was charged into the flask and stirred for about 10 minutes. Then, adding 100g of ammonium polyphosphate into a flask, heating the mixture to a set reaction temperature of 100 ℃, stirring for reaction for 5 hours, detecting whether ammonia gas exists or not by using a pH test paper, if the two pH values are 8-9 within an interval of 10 minutes, determining that the reaction is finished, and then cooling the reaction mixture to room temperature to obtain a solution of a product A.
Adding 50g of sinapic acid into the solution of the product A, stirring and reacting for 11h at 90 ℃, precipitating, then carrying out suction filtration, washing with water, and drying to constant weight to obtain solid powder, namely the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent.
The flame-retardant polyolefin is prepared by adopting the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent, and is formed by melting and molding the following components in parts by mass (the molding conditions are as follows: the matrix material polyethylene and the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent are placed in a torque rheometer to be melted and blended, the temperature is 180 ℃, the rotating speed is 110rpm, the blending time is 10min, a vertical combustion, limiting oxygen index and mechanical test sample strip is molded by a micro injection molding machine, the injection molding temperature is 195 ℃, the mold temperature is room temperature, the injection molding pressure is 700bar, the injection molding time is 10s, and the holding pressure is 600 bar):
70 parts of polyethylene and 30 parts of bio-based flame-retardant anti-aging dual-functional integrated auxiliary;
the experimental results show that: the addition amount of the flame-retardant and anti-aging dual-function integrated auxiliary agent prepared in example 5 is 30%, the oxygen index of the material constructed when the polyethylene is 70% is 30.0%, and the change rates of the tensile strength, the elongation at break and the impact strength after 168 hours of thermal-oxidative aging are respectively 2%, 4% and 5% according to the V0 standard of UL-94, which are superior to the corresponding change rates of the material constructed by the product A without the introduction of sinapic acid, such as 4%, 6% and 6%.
Example 6:
a preparation method of a bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent comprises the following steps:
pouring 1000mL of mixed solvent with water and ethanol in a volume ratio of 25/1 into a three-neck flask with a stirrer under nitrogen atmosphere, stirring for half an hour, injecting 65g of decamethylenediamine into the flask, stirring for about 10 minutes, then adding 105g of ammonium polyphosphate into the flask, heating the mixture to a set reaction temperature of 100 ℃, stirring for reaction for 6 hours, detecting whether ammonia gas exists by using a pH test paper, if the two pH values are 8-9 within an interval of 10 minutes, determining that the reaction is finished, and then cooling the reaction mixture to room temperature to obtain a solution of a product A.
Adding 55g of syringic acid into the solution of the product A, stirring and reacting for 12h at 90 ℃, precipitating, then carrying out suction filtration, washing with water, and drying to constant weight to obtain solid powder, namely the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent.
The flame-retardant polyolefin is prepared by adopting the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent, and is formed by melting and molding the following components in parts by mass (the molding conditions are as follows: the matrix material polyethylene and the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent are placed in a torque rheometer to be melted and blended, the temperature is 180 ℃, the rotating speed is 110rpm, the blending time is 10min, a vertical combustion, limiting oxygen index and mechanical test sample strip is molded by a micro injection molding machine, the injection molding temperature is 195 ℃, the mold temperature is room temperature, the injection molding pressure is 700bar, the injection molding time is 10s, and the holding pressure is 600 bar):
75 parts of polyethylene and 25 parts of bio-based flame-retardant anti-aging dual-functional integrated auxiliary;
the experimental results show that: the addition amount of the bio-based flame-retardant anti-aging dual-function integrated auxiliary agent prepared in the embodiment 6 is 25%, the oxygen index of the material constructed when the polyethylene is 75% is 26.0%, and the change rates of the tensile strength, the elongation at break and the impact strength after 168 hours of thermo-oxidative aging are respectively 4%, 4% and 5% according to the V2 standard of UL-94, which are superior to the corresponding change rates of the material constructed by the product A without the syringic acid under the same conditions, such as 6%, 6% and 7%.
Example 7:
a preparation method of a bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent comprises the following steps:
1000mL of a mixed solvent of water and ethanol at a ratio of 35/1 was poured into a three-necked flask equipped with a stirrer under a nitrogen atmosphere, and after stirring for half an hour, 50g of triethylenetetramine was poured into the flask and stirred for about 10 minutes. Then, adding 100g of ammonium polyphosphate into a flask, heating the mixture to a set reaction temperature of 100 ℃, stirring for reaction for 5 hours, detecting whether ammonia gas exists or not by using a pH test paper, if the two pH values are 8-9 within an interval of 10 minutes, determining that the reaction is finished, and then cooling the reaction mixture to room temperature to obtain a solution of a product A.
Adding 50g of sinapic acid into the solution of the product A, stirring and reacting for 11h at 90 ℃, precipitating, then carrying out suction filtration, washing with water, and drying to constant weight to obtain solid powder, namely the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent.
The flame-retardant polyolefin is prepared by adopting the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent, and is formed by melting and molding the following components in parts by mass (the molding conditions are that polypropylene as a base material and the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent are placed in a torque rheometer to be melted and blended, the temperature is 180 ℃, the rotating speed is 110rpm, the blending time is 10min, a vertical combustion, limiting oxygen index and mechanical test sample strip is molded by a micro injection molding machine, the injection molding temperature is 195 ℃, the mold temperature is room temperature, the injection molding pressure is 700bar, the injection molding time is 10s, and the holding pressure is 600 bar):
75 parts of polypropylene and 25 parts of a bio-based flame-retardant anti-aging bifunctional integrated auxiliary agent;
the experimental results show that: the addition amount of the flame-retardant and anti-aging bifunctional integrated auxiliary agent prepared in example 7 is 25%, the oxygen index of the constructed material is 32.0% when the polypropylene content is 75%, and the change rates of the tensile strength, the elongation at break and the impact strength after 168 hours of thermal-oxidative aging are respectively 2%, 4% and 5% according to the V0 standard of UL-94, which are superior to the corresponding change rates of 4%, 6% and 6% of the constructed material of the product A without sinapic acid under the same conditions.
Example 8:
a preparation method of a bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent comprises the following steps:
pouring 1000mL of mixed solvent with water and ethanol in a volume ratio of 40/1 into a three-necked flask with a stirrer under nitrogen atmosphere, stirring for half an hour, injecting 55g N-aminoethylpiperazine into the flask, stirring for about 10 minutes, adding 95g of ammonium polyphosphate into the flask, heating the mixture to a set reaction temperature of 95 ℃, stirring for reaction for 5 hours, detecting whether ammonia gas exists by using a pH test paper, if the two pH values are 8-9 within a 10-minute interval, determining that the reaction is finished, and cooling the reaction mixture to room temperature to obtain a solution of a product A.
Adding 50g of syringic acid into the solution of the product A, stirring and reacting for 10 hours at 80 ℃, precipitating, then carrying out suction filtration, washing with water, and drying to constant weight to obtain solid powder, namely the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent.
The flame-retardant polyolefin is prepared by adopting the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent, and is formed by melting and molding the following components in parts by mass (the molding conditions are as follows: the matrix material polyethylene and the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent are placed in a torque rheometer to be melted and blended, the temperature is 180 ℃, the rotating speed is 110rpm, the blending time is 10min, a vertical combustion, limiting oxygen index and mechanical test sample strip is molded by a micro injection molding machine, the injection molding temperature is 195 ℃, the mold temperature is room temperature, the injection molding pressure is 700bar, the injection molding time is 10s, and the holding pressure is 600 bar):
65 parts of polyethylene and 35 parts of a bio-based flame-retardant anti-aging bifunctional integrated auxiliary agent;
the experimental results show that: the addition amount of the bio-based flame-retardant anti-aging bifunctional integrated auxiliary agent prepared in the embodiment 8 is 35%, the oxygen index of the material constructed when the polyethylene is 65% is 33.5%, and the change rates of the tensile strength, the elongation at break and the impact strength after 168 hours of thermo-oxidative aging are respectively 1%, 2% and 2% according to the V0 standard of UL-94, which are 3%, 4% and 4% better than the corresponding change rates of the material constructed by the product A without the syringic acid under the same conditions.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (10)
1. The bio-based flame-retardant anti-aging bifunctional integrated auxiliary is characterized in that the structural general formula of the auxiliary is as follows:
wherein R is1Is polyethylene polyamine, piperazine and its derivative, C2-10Any one of the aliphatic diamines of (a); r2Containing carboxyl as end group and containing benzene in structureA phenol structure derived from a bio-based small molecule of a plant extract.
2. The bio-based flame-retardant anti-aging bifunctional integrated auxiliary agent as claimed in claim 1, wherein R is2Including but not limited to any of the following structures:
3. the bio-based flame-retardant anti-aging bifunctional integrated auxiliary agent as claimed in claim 1, wherein C is2-10The aliphatic diamine of (a) is any one of the following structures:
4. the bio-based flame-retardant anti-aging bifunctional integrated auxiliary agent as claimed in claim 1, wherein the piperazine is:
the derivative of piperazine is any one of the following structures: 2, 3-diphenylpiperazine, 2-phenylpiperazine, N-aminoethylpiperazine.
5. The bio-based flame-retardant anti-aging bifunctional integrated auxiliary agent as claimed in claim 1, wherein the polyethylene polyamine is any one of the following structures: diethylenetriamine, triethylene tetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine.
6. The preparation method of the bio-based flame-retardant anti-aging bifunctional integrated auxiliary agent as claimed in claim 1, comprising the following steps:
adding a mixed solvent of water and ethanol into a reactor in a nitrogen atmosphere, stirring for 20-40 min, and adding R1Injecting the mixture into a reactor, stirring for 8-12 min, adding ammonium polyphosphate into the reactor, heating to a first reaction temperature, stirring for reaction for 3-6 h, detecting whether ammonia exists by using pH test paper after the reaction is finished, and determining that the reaction is finished if the two pH values are both 8-9 within a 10-minute interval; next, the reaction mixture was cooled to room temperature to obtain a solution of product a; then, R is added2Adding the mixture into the solution of the product A, heating to a second reaction temperature, stirring and reacting for 8-12 h, and generating a precipitate; and then, carrying out suction filtration, washing and drying to constant weight to obtain solid powder, namely the bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent.
7. The preparation method of the bio-based flame-retardant anti-aging bifunctional integrated auxiliary agent as claimed in claim 6, wherein the volume ratio of water to ethanol in the mixed solvent of water and ethanol is 25-50: 1; the R is1The mass volume ratio of the mixed solvent to the mixed solvent is 40-65 g: 1L; the R is1The mass ratio of the ammonium polyphosphate to the ammonium polyphosphate is 8-13: 16-21; the R is2The mass ratio of the ammonium polyphosphate to the ammonium polyphosphate is 6-11: 16-21.
8. The preparation method of the bio-based flame-retardant anti-aging bifunctional integrated auxiliary agent as claimed in claim 6, wherein the first reaction temperature is 80-100 ℃; the second reaction temperature is 60-90 ℃.
9. The flame-retardant polyolefin prepared by the bio-based flame-retardant anti-aging bifunctional integrated auxiliary agent as defined in claim 1 is characterized in that the flame-retardant polyolefin is prepared by melt blending the following components in parts by weight:
70-80 parts of polypropylene and 20-30 parts of bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent, wherein the limiting oxygen index LOI of the flame-retardant polypropylene is 27.5-35.5%, and the vertical combustion UL-94 grade is V-2 grade to V-0 grade; the tensile strength, the elongation at break and the change rate of the impact strength are all 1-5% after thermal-oxidative aging for 168 hours.
10. The flame-retardant polyolefin prepared by the bio-based flame-retardant anti-aging bifunctional integrated auxiliary agent as defined in claim 1 is characterized in that the flame-retardant polyolefin is prepared by melt blending the following components in parts by weight:
65-75 parts of polyethylene and 25-35 parts of bio-based flame-retardant anti-aging dual-functional integrated auxiliary agent, wherein the limiting oxygen index LOI of the flame-retardant polyethylene is 26.0-33.5%, and the vertical combustion UL-94 grade is V-2 grade to V-0 grade; the tensile strength, the elongation at break and the change rate of the impact strength are all 1-5% after thermal-oxidative aging for 168 hours.
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