CN114790260B - High-modulus, high-impact, wear-resistant and heat-resistant intrinsic flame-retardant polydicyclopentadiene engineering material and preparation method thereof - Google Patents
High-modulus, high-impact, wear-resistant and heat-resistant intrinsic flame-retardant polydicyclopentadiene engineering material and preparation method thereof Download PDFInfo
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- CN114790260B CN114790260B CN202210340804.0A CN202210340804A CN114790260B CN 114790260 B CN114790260 B CN 114790260B CN 202210340804 A CN202210340804 A CN 202210340804A CN 114790260 B CN114790260 B CN 114790260B
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
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- H—ELECTRICITY
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
- H01M50/218—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material
- H01M50/22—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material of the casings or racks
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Abstract
The invention discloses a high-modulus, high-impact, wear-resistant, heat-resistant and intrinsic flame-retardant polydicyclopentadiene engineering material and a preparation method thereof. The polydicyclopentadiene engineering material is prepared by taking dicyclopentadiene, 5-norbornene-2-formamide, 5-norbornene-2-methanol, a norbornene-based reaction type flame retardant containing an amido bond and a cage-shaped phosphate structure, a catalyst and an inhibitor as raw materials through a thermal-driven self-propagating technology. The norbornene reaction type flame retardant containing the amido bond and cage-shaped phosphate ester structure is simple in synthesis method and high in yield, and can improve the flame retardance and mechanical properties of the polydicyclopentadiene material. The prepared polydicyclopentadiene material has a limited oxygen index of 42%, a flame retardant rating of UL94V-0 grade and an impact strength of 90kJ/m 2 The Shore hardness exceeds 92HD, the tensile strength reaches 120MPa, the thermal deformation temperature reaches 197 ℃, the abrasion loss is reduced by 92 percent, and the flame retardant property and the mechanical property are excellent.
Description
Technical Field
The invention belongs to the technical field of high polymer materials and engineering, particularly relates to a high-modulus, high-impact, wear-resistant and heat-resistant intrinsic flame-retardant polydicyclopentadiene engineering material, and also relates to a norbornene-based reactive flame retardant containing an amido bond and a cage-shaped phosphate structure.
Background
Polydicyclopentadiene is a high-performance thermosetting engineering material, has the unique advantage of large-area integral molding in the molding process, and is widely applied to the field of manufacturing large-sized parts. However, the polydicyclopentadiene is extremely easy to combust due to the whole hydrocarbon composition, and a large amount of smoke dust and toxic gas are generated in the combustion process due to the structure of the polydicyclopentadiene, so that the application of the polydicyclopentadiene material in the fields of heat resistance and flame retardance is limited, and the wear resistance and the self-lubricating property of the polydicyclopentadiene are insufficient compared with engineering materials such as nylon, polyformaldehyde and the like.
In order to solve the above problems, a great deal of research has been conducted on the high performance of polydicyclopentadiene by domestic and foreign scientists. CN 107828004A discloses a method for improving flame retardant property of polydicyclopentadiene by compounding one or more flame retardants of modified aluminum hydroxide, modified magnesium hydroxide, organosilicon flame retardant, melamine phosphate, phosphate flame retardant and pentaerythritol, but mechanical property and wear resistance of the material are not obviously improved. CN102690483B patent proposes that the impact strength of the prepared flame-retardant polydicyclopentadiene composite material is improved by 25% by blending antimony trioxide, acrylate monomers and dicyclopentadiene, but the limiting oxygen index only reaches 24%, and the flame-retardant property is not obviously improved. In the patent CN 110746530A, alkyl hypophosphite is used as a main flame retardant, ammonium polyphosphate and zinc borate are used as synergistic flame retardants, and the dispersibility of each component is improved through a coupling agent, so that the flame retardant can be stably suspended in a dicyclopentadiene monomer. Compared with the method of directly adding the composite flame retardant to improve the flame retardant property of the polydicyclopentadiene, part of science and technology workers design a reactive flame retardant monomer, and a flame retardant element is introduced into a molecular chain of the polydicyclopentadiene through a chemical bond, so that the purpose of improving the flame retardant property of the polydicyclopentadiene material is achieved. Researchers in patents CN104558326A and CN 104592301A respectively prepare dicyclopentadienyl hexachlorocyclotriphosphazene flame retardant and norbornenyl hexachlorocyclotriphosphazene flame retardant, and copolymerize them with dicyclopentadiene to prepare flame retardant polydicyclopentadiene composite material, respectively, the oxygen index of the prepared material reaches 29.4% and 28.7%, but the strength, modulus and toughness of the material still need to be further improved, and the wear resistance of the material is not involved, and meanwhile, the flame retardant containing halogen is limited in modern industrial popularization and application, and cannot be applied under high-end and severe requirements. In general, the flame retardant property of polydicyclopentadiene cannot be improved by the flame retardant strategy provided by the existing patent, and the high modulus, high impact and wear resistance of the material cannot be realized, and the flame retardant property still needs to be further improved, so that the application of the polydicyclopentadiene engineering material in severe environments such as a high-voltage battery pack shell of a new energy automobile, a cable joint of a high-speed train, an automobile engine support frame and the like is met.
The invention provides a norbornene group reaction type flame retardant containing an amido bond and a cage-shaped phosphate structure, which can be copolymerized with a dicyclopentadiene monomer through a thermal-driven self-propagating technology, and introduces the cage-shaped phosphate and amide structures into a polydicyclopentadiene molecular chain, thereby improving the flame retardant property of the material. Meanwhile, on the basis, 5-norbornene-2-formamide and 5-norbornene-2-methanol are introduced, so that abundant amido bonds and hydroxyl groups exist in the polydicyclopentadiene, a large number of strong non-covalent bond effects such as hydrogen bonds are formed in the polydicyclopentadiene, and the modulus, impact resistance, heat resistance and wear resistance of the polydicyclopentadiene are greatly improved. In addition, the introduction of oxygen-containing substances such as hydroxyl and the like can be used as a carbon source in the combustion process, the carbon forming performance of the polydicyclopentadiene is further improved, and finally the intrinsic flame-retardant polydicyclopentadiene engineering material with high modulus, high impact, wear resistance and heat resistance is prepared.
Disclosure of Invention
The invention aims to provide a high-modulus, high-impact, wear-resistant and heat-resistant intrinsic flame-retardant polydicyclopentadiene engineering material.
The second purpose of the invention is to provide a norbornene-based reactive flame retardant containing an amido bond and a cage-shaped phosphate structure, which solves the problem of flammability of the existing polydicyclopentadiene material and improves the mechanical property of the polydicyclopentadiene material.
The third purpose of the invention is to introduce a large amount of polar groups such as hydroxyl, amido bond and the like into the polydicyclopentadiene structure and construct hydrogen bond through the polar groups so as to improve the wear resistance of the material.
The invention discloses a high-modulus, high-impact, wear-resistant, heat-resistant and intrinsic flame-retardant polydicyclopentadiene engineering material and a preparation method thereof. The polydicyclopentadiene engineering material comprises the following raw materials: dicyclopentadiene, 5-norbornene-2-formamide, 5-norbornene-2-methanol, a norbornene-based reactive flame retardant containing an amide bond and a cage-shaped phosphate structure, a catalyst and an inhibitor. Wherein the mass fraction of dicyclopentadiene is 34.86-77.13%, the mass fraction of 5-norbornene-2-formamide is 6.42-14.49%, the mass fraction of 5-norbornene-2-methanol is 6.25-10.25%, the mass fraction of reactive flame retardant is 10-40%, the mass fraction of catalyst is 0.16-0.26%, and the mass fraction of inhibitor is 0.04-0.14%. The polydicyclopentadiene material has the limiting oxygen index of 42%, the flame retardant grade of UL94V-0 grade and the impact strength of 90kJ/m 2 The Shore hardness exceeds 92HD, the tensile strength reaches 120MPa, the thermal deformation temperature reaches 197 ℃, the abrasion loss is reduced by 92 percent, and the flame retardant property and the mechanical property are excellent.
The specific scheme is as follows:
the invention provides a high-modulus, high-impact, wear-resistant, heat-resistant and intrinsic flame-retardant polydicyclopentadiene engineering material, which has a structural formula shown in (1):
wherein n, m, o, p and q are integers between 100 and 1500; in the structural formula (1), R 1 Is an aliphatic substituent or an aromatic substituent having 1 to 8 carbon atoms, R 2 Is an aliphatic substituent or an aromatic substituent having 1 to 8 carbon atoms;
the sum of the mass percentages of the raw materials for preparing the polydicyclopentadiene engineering material is 100%, and the mass percentages of the raw materials are as follows:
the structural formula of the norbornene-based reaction type flame retardant containing the amido bond and the cage-shaped phosphate structure is shown as (2):
in the structural formula (2), R 1 Is an aliphatic substituent or an aromatic substituent having 1 to 8 carbon atoms, R 2 Is an aliphatic substituent or an aromatic substituent with 1-8 carbon atoms;
the catalyst is a ruthenium catalyst;
the inhibitor is phosphate ester.
Further, the synthesis method of the norbornene-based reactive flame retardant containing the amido bond and the cage-shaped phosphate structure comprises the following steps:
carrying out amidation reaction on norbornene containing monoacyl chloride and monoamine containing a cage-shaped phosphate ester structure under the action of a catalyst, wherein the reaction temperature is 0-120 ℃, the reaction time is 5-24h, and after the reaction is finished, washing, separating and drying the reaction product to obtain the norbornene-based reaction type flame retardant monomer containing the amido bond and the cage-shaped phosphate ester structure.
Further, in the method for synthesizing the norbornene-based reactive flame retardant monomer containing the amide bond and the caged phosphate structure, the catalyst required by the amidation reaction is as follows: pyridine, triethylamine, sodium carbonate, sodium bicarbonate, sodium acetate, N-diisopropylethylamine, N-dimethylaniline, tri-N-butylamine, N-methylmorpholine, 4-N, N-dimethylpyridine, 4-pyrrolidinylpyridine, 1-hydroxybenzotriazole, 1-hydroxy-7-azabenzotriazole, N-hydroxysuccinimide, N-hydroxyphthalimide and N-hydroxy-1, 8-naphthalimide or a mixture of a plurality of the compounds;
the organic solvent used for the amidation reaction is: one of dichloromethane, trichloromethane, toluene, benzene, xylene, acetone, N dimethylformamide, dichloroethane, acetonitrile and hexachloroethane.
Further, a preparation method of the high-modulus, high-impact, wear-resistant, heat-resistant and intrinsic flame-retardant polydicyclopentadiene material comprises the following steps:
(1) Adding the catalyst and the inhibitor into a mixed solution of dicyclopentadiene, 5-norbornene-2-formamide and 5-norbornene-2-methanol in proportion, ultrasonically mixing the mixed solution for 30s-180s under the ice-water bath condition, and then dispersing a norbornene-based reaction type flame retardant containing an amido bond and a cage-shaped phosphate ester structure into the mixed solution containing the catalyst and the inhibitor to obtain a dispersion solution;
(2) And injecting the dispersion liquid into a mold, carrying out local thermal initiation at 135-200 ℃, driving polymerization by polymerization heat released by the dispersion liquid, and copolymerizing to obtain the high-modulus, high-impact, wear-resistant, heat-resistant and intrinsic flame-retardant polydicyclopentadiene material.
Furthermore, the high-modulus, high-impact, wear-resistant and heat-resistant intrinsic flame-retardant polydicyclopentadiene material can be applied to high-voltage battery pack shells of new energy automobiles, cable joints of high-speed trains and automobile engine support frame materials.
The invention has the following beneficial effects:
compared with the prior art, the invention has the beneficial effects that:
1) The invention provides a norbornene-based reactive flame retardant monomer containing an amido bond and a cage-shaped phosphate structure, which can be copolymerized with a dicyclopentadiene monomer through a thermal-driven self-propagating technology, and the cage-shaped phosphate and amide structures are introduced into a polydicyclopentadiene molecular chain, so that the flame retardant property of the material is improved. Specifically, the phosphate can generate strong dehydration substances such as polymetaphosphoric acid and the like in a high-temperature environment, so that the charring of the material in the combustion process is promoted, and the flame retardant property of the material is improved through condensed phase flame retardant. Meanwhile, the flame retardant can generate phosphorous free radicals to capture hydrogen free radicals and hydroxyl free radicals in gas-phase flame and terminate combustion reaction. In addition, amide bonds can form non-combustible gases such as nitrides and the like in the combustion process, the concentration of the combustible gases is diluted, the flame retardant property of the polydicyclopentadiene engineering material is further improved through gas-phase flame retardance, and the efficient intrinsic flame retardance of the polydicyclopentadiene is realized.
2) According to the invention, the norbornene group reaction type flame retardant containing an amido bond and a cage-shaped phosphate ester structure is introduced into a polydicyclopentadiene molecular chain, and simultaneously, the 5-norbornene-2-formamide and the 5-norbornene-2-methanol are introduced, and the introduction of the substances enables the polydicyclopentadiene to have abundant amido bonds and hydroxyl groups, so that a large number of strong noncovalent bond effects such as hydrogen bonds are formed in the material, and the modulus, impact, heat resistance and wear resistance of the polydicyclopentadiene material are greatly improved. In addition, the introduction of substances containing oxygen atoms such as hydroxyl groups and the like can be used as a carbon source in the combustion process of the polydicyclopentadiene, so that the carbon forming performance of the polydicyclopentadiene can be further improved.
3) Compared with the traditional reaction injection molding curing process, the intrinsic flame-retardant polydicyclopentadiene engineering material has simple polymerization process, does not need secondary curing and has simple industrialized process flow.
Drawings
FIG. 1 shows a norbornene-based reactive flame retardant A containing an amide bond and a caged phosphate structure 1 H-NMR spectra
FIG. 2 shows a norbornene-based reactive flame retardant B containing an amide bond and a caged phosphate structure 1 H-NMR spectra
FIG. 3 is a synthetic flow chart of a norbornene-based reactive flame retardant A containing an amido bond and a caged phosphate structure
FIG. 4 is a synthetic flow chart of norbornene-based reactive flame retardant B containing amido bond and caged phosphate structure
Detailed Description
The present invention will be further described with reference to the following embodiments. The scope of the present invention is not limited to the following embodiments, and all the non-essential modifications and changes made to the present invention according to the above disclosure are within the scope of the present invention.
The following examples used the following raw materials:
dicyclopentadiene, 5-norbornene-2-carboxamide and 5-norbornene-2-methanol, preferably Sigma-Aldrich;
the flame retardants A and B are norbornene-based reactive flame retardants synthesized by self in the patent and containing amide bonds and caged phosphate structures, the structural formulas are detailed in examples 1 and 6, and the synthetic raw materials and the catalyst comprise: 5-norbornene-2-carboxylic acid, 2,6, 7-trioxa-1-phosphabicyclo [2.2.2] octane-4-bromomethyl-1-oxide, potassium phthalimide, 4- (1R, 2R, 4R) -bicyclo [2.2.1] hept-5-ene-2-benzoyl chloride, p-aminobenzoic acid, bicyclo [2.2.1] hept-5-ene-2-acetyl chloride, oxalyl chloride, pentaerythritol phosphate, 1-ethyl- (3-dimethylaminopropyl) carbodiimide and 1-hydroxybenzotriazole. Wherein 5-norbornene-2-carboxylic acid, potassium phthalimide, p-aminobenzoic acid, oxalyl chloride, pentaerythritol phosphate, 1-ethyl- (3-dimethylaminopropyl) carbodiimide and 1-hydroxybenzotriazole are preferably the products of Shanghai Arantin Biochemical technology, inc.; 2,6, 7-trioxa-1-phosphabicyclo [2.2.2] octane-4-bromomethyl-1-oxide, preferably Chongqingfuteng pharmaceutical chemical Co., ltd; 4- (1R, 2R, 4R) -bicyclo [2.2.1] hept-5-ene-2-benzoyl chloride is self-made by a laboratory; bicyclo [2.2.1] hept-5-ene-2-acetic acid is preferably a product of Shanghai Michael Biotech Co. The organic solvent used for the synthesis is preferably a product of Shanghai Aladdin Biotechnology GmbH.
Magnesium hydroxide, aluminum hydroxide and zinc borate are inorganic flame retardants, preferably a product of the Jinan Taxing Fine chemical Co., ltd;
melamine, for containing nitrogen additive type flame retardant, preferably Shanghai Aladdin Biotechnology GmbH products;
antimony trioxide is an inorganic auxiliary flame retardant, decabromodiphenyl ether is a halogen-containing flame retardant, and a product of Shanghai Michelle chemical technology Co.
The catalyst is ruthenium catalyst, the inhibitor is phosphite ester, preferably Sigma-Aldrich product;
other production raw materials and processing aids are common commercial industrial products in the field of flame-retardant materials.
Table 1 shows the raw materials and the amounts used in the examples
To prove the effect of the invention, 8 groups of proportion are provided:
table 2 shows the raw materials and the amounts used in each proportion
Example 1
The flame-retardant polydicyclopentadiene material comprises the following raw materials: 77.13wt% of dicyclopentadiene, 6.42wt% of 5-norbornene-2-carboxamide, 6.25wt% of 5-norbornene-2-methanol, 10wt% of flame retardant, 0.16wt% of catalyst and 0.04wt% of inhibitor. Wherein the flame retardant is a norbornene group reaction type flame retardant A containing an amido bond and a cage-shaped phosphate structure.
The structural formula is as follows:
preparation of flame retardant A (FIG. 1 for synthesis scheme):
(1) 0.1mol of 2,6, 7-trioxa-1-phosphabicyclo [2.2.2] octane-4-bromomethyl-1-oxide, 0.14mol of potassium phthalimide and 150ml of N, N-dimethylformamide were stirred under nitrogen at 0 ℃ for 2 hours, then raised to 70 ℃ and reacted for 20 hours. Then cooled to room temperature and washed with deionized water. The solid was collected by filtration to obtain an intermediate 2,6, 7-trioxa-1-phosphabicyclo [2.2.2] octane-4-aminomethyl-1-oxide.
(2) 0.1mol of 4- (1R, 2R, 4R) -bicyclo [2.2.1] heptane-5-ene-2-benzoyl chloride, 0.99mol of the intermediate 2,6, 7-trioxa-1-phosphabicyclo [2.2.2] octane-4-aminomethyl-1-oxide obtained in step (1) and 80ml of pyridine were charged into a 500ml three-necked flask containing 150ml of dichloromethane, and the three-necked flask was connected to a condenser and a nitrogen inlet and outlet. The mixture was first stirred at room temperature for 1 hour, then the temperature was gradually raised to 60 ℃ and the reaction was continued for 12 hours.
(3) After the reaction is finished, extracting, washing, filtering, drying and rotary evaporating the obtained mixed solution, collecting an organic phase, carrying out fast column chromatography on the organic phase by taking the mixed solution of ethyl acetate and petroleum ether as an eluent, enriching the product, and making the product into a product 1 H NMR is carried out to obtain norbornene-based reaction type flame retardant A containing amido bond and cage-shaped phosphate ester structure
Preparing a flame-retardant polydicyclopentadiene engineering material:
(1) Adding 0.16 part of catalyst and 0.04 part of inhibitor into 77.13 parts of dicyclopentadiene, 6.42 parts of 5-norbornene-2-formamide and 6.25 parts of 5-norbornene-2-methanol to obtain a mixed solution in which the catalyst and the inhibitor are dissolved;
(2) Then adding 10 parts of the synthesized flame retardant A into the mixed solution, and ultrasonically dispersing the penicillin bottle filled with the mixed solution in an ice water bath for 60 seconds to obtain a dispersion liquid;
(3) The dispersion is then injected into a preformed mould and after local thermal initiation at 200 ℃, the polymerisation is driven by the heat of polymerisation released by itself. Obtaining the intrinsic flame-retardant polydicyclopentadiene engineering material.
Example 2
The flame-retardant polydicyclopentadiene material comprises the following raw materials: 67.13wt% of dicyclopentadiene, 6.42wt% of 5-norbornene-2-carboxamide, 6.25wt% of 5-norbornene-2-methanol, 20wt% of flame retardant, 0.16wt% of catalyst and 0.04wt% of inhibitor. Wherein the flame retardant is a norbornene-based reaction type flame retardant A containing an amido bond and a cage-shaped phosphate structure.
The preparation process of the flame-retardant polydicyclopentadiene engineering material is the same as that of example 1.
Example 3
The flame-retardant polydicyclopentadiene material comprises the following raw materials: 57.13wt% of dicyclopentadiene, 6.42wt% of 5-norbornene-2-carboxamide, 6.25wt% of 5-norbornene-2-methanol, 30wt% of flame retardant, 0.16wt% of catalyst and 0.04wt% of inhibitor. Wherein the flame retardant is a norbornene-based reaction type flame retardant A containing an amido bond and a cage-shaped phosphate structure.
The preparation process of the flame-retardant polydicyclopentadiene engineering material is the same as that of example 1.
Example 4
The flame-retardant polydicyclopentadiene material comprises the following raw materials: 47.13wt% of dicyclopentadiene, 6.42wt% of 5-norbornene-2-carboxamide, 6.25wt% of 5-norbornene-2-methanol, 40wt% of flame retardant, 0.16wt% of catalyst and 0.04wt% of inhibitor. Wherein the flame retardant is a norbornene-based reaction type flame retardant A containing an amido bond and a cage-shaped phosphate structure.
The preparation process of the flame-retardant polydicyclopentadiene engineering material is the same as that of example 1.
Example 5
The flame-retardant polydicyclopentadiene material comprises the following raw materials: 57.13wt% of dicyclopentadiene, 6.42wt% of 5-norbornene-2-carboxamide, 6.25wt% of 5-norbornene-2-methanol, 30wt% of flame retardant, 0.16wt% of catalyst and 0.04wt% of inhibitor. The flame retardant is a norbornene-based reaction type flame retardant A containing an amido bond and a cage-shaped phosphate structure and pentaerythritol phosphate, and the proportion of the flame retardant A to the pentaerythritol phosphate is that A: pentaerythritol phosphate =2:1.
the preparation process of the flame-retardant polydicyclopentadiene engineering material is the same as that of example 1.
Example 6
The flame-retardant polydicyclopentadiene material comprises the following raw materials: 57.13wt% of dicyclopentadiene, 6.42wt% of 5-norbornene-2-carboxamide, 6.25wt% of 5-norbornene-2-methanol, 30wt% of flame retardant, 0.16wt% of catalyst and 0.04wt% of inhibitor. Wherein the flame retardant is a norbornene group reaction type flame retardant B containing an amido bond and a cage-shaped phosphate structure.
The structural formula is as follows:
preparation of flame retardant B (FIG. 2 for the scheme):
(1) 0.1mol of p-aminobenzoic acid, 0.99mol of pentaerythritol phosphate, 0.15mol of 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine and 0.15mol of 1-hydroxybenzotriazole were added to a 500ml three-necked flask containing 150ml of acetonitrile, and reacted with stirring at 60 ℃ under reflux for 12 hours.
(2) After the reaction is finished, the obtained mixed solution is subjected to extraction, washing, filtration, drying and rotary evaporation, and then the product is enriched to obtain an intermediate with the yield of about 80%.
(3) 0.1mol of bicyclo [2.2.1] hept-5-ene-2-yl chloride, 0.99mol of the intermediate prepared in step (1) and 80ml of triethylamine were added to a 500ml three-necked flask containing 150ml of acetonitrile, the three-necked flask was equipped with a condenser and a nitrogen inlet and outlet, the mixture was stirred at 0 ℃ for 1 hour, and then the temperature was gradually raised to room temperature for about 16 hours.
(4) After the reaction is finished, extracting the obtained mixed solution for multiple times by using dilute hydrochloric acid and saturated sodium chloride solution, filtering, drying and performing rotary evaporation, then enriching the product, collecting an organic phase, performing flash column chromatography on the organic phase by using the mixed solution of dichloromethane and methanol as an eluent, then enriching the product, and preparing the product 1 H NMR to give flame retardant B in about 70% yield
The preparation process of the flame-retardant polydicyclopentadiene engineering material is the same as that of example 1.
Example 7
The flame-retardant polydicyclopentadiene material comprises the following raw materials: 57.13wt% of dicyclopentadiene, 6.42wt% of 5-norbornene-2-carboxamide, 6.25wt% of 5-norbornene-2-methanol, 30wt% of flame retardant, 0.16wt% of catalyst and 0.04wt% of inhibitor. The flame retardant is norbornene-based reactive flame retardants A and B containing amido bonds and a cage-shaped phosphate ester structure, and the proportion of the norbornene-based reactive flame retardants A to B is 1:1.
the preparation process of the flame-retardant polydicyclopentadiene engineering material is the same as that of example 1.
Example 8
The flame-retardant polydicyclopentadiene material comprises the following raw materials: 51.53wt% of dicyclopentadiene, 10.02wt% of 5-norbornene-2-carboxamide, 8.25wt% of 5-norbornene-2-methanol, 30wt% of flame retardant, 0.16wt% of catalyst and 0.04wt% of inhibitor. Wherein the flame retardant is a norbornene group reaction type flame retardant A containing an amido bond and a cage-shaped phosphate structure.
The preparation process of the flame-retardant polydicyclopentadiene engineering material is the same as that of example 1.
Example 9
The flame-retardant polydicyclopentadiene material comprises the following raw materials: 45.49wt% of dicyclopentadiene, 14.06wt% of 5-norbornene-2-carboxamide, 10.25wt% of 5-norbornene-2-methanol, 30wt% of flame retardant, 0.16wt% of catalyst and 0.04wt% of inhibitor. Wherein the flame retardant is a norbornene-based reaction type flame retardant A containing an amido bond and a cage-shaped phosphate structure.
The preparation process of the flame-retardant polydicyclopentadiene engineering material is the same as that of example 1.
Example 10
The flame-retardant polydicyclopentadiene material comprises the following raw materials: 45.49wt% of dicyclopentadiene, 14.06wt% of 5-norbornene-2-carboxamide, 10.25wt% of 5-norbornene-2-methanol, 30wt% of flame retardant, 0.16wt% of catalyst and 0.04wt% of inhibitor. The flame retardant is norbornene-based reaction type flame retardants A and B containing amido bonds and a cage-shaped phosphate ester structure, and the proportion of the norbornene-based reaction type flame retardants A to B is 1:1.
the preparation process of the flame-retardant polydicyclopentadiene engineering material is the same as that of example 1.
Comparative example 1
The basic process and the target structure in the comparative example are the same as those in example 1, but the preparation method is different, and the specific preparation process is as follows:
(1) 0.1mol of 2,6, 7-trioxa-1-phosphabicyclo [2.2.2] octane-4-bromomethyl-1-oxide, 0.14mol of ammonia water, 0.14mol of triethylamine and 150ml of dichloromethane were stirred at 0 ℃ for 2 hours under nitrogen protection, and then warmed to room temperature to react for 20 hours. After the reaction is finished, the obtained mixed solution is washed by dilute hydrochloric acid and saturated salt solution for many times, dried and collected with an organic phase to obtain an intermediate 2,6, 7-trioxa-1-phosphabicyclo [2.2.2] octane-4-aminomethyl-1-oxide.
(2) 0.1mol of 4- (1R, 2R, 4R) -bicyclo [2.2.1] hept-5-ene-2-phenylcarbonyl chloride, 0.99mol of 2,6, 7-trioxa-1-phosphabicyclo [2.2.2] octane-4-aminomethyl-1-oxide, 0.15mol of 1-ethyl- (3-dimethylaminopropyl) carbodiimide and 0.15mol of 1-hydroxybenzotriazole were charged into a 500ml three-necked flask containing 150ml of acetonitrile, and the three-necked flask was connected to a condenser and a nitrogen inlet and outlet. The reaction was maintained at 40 ℃ under nitrogen blanket for about 24 hours.
(3) After the reaction is finished, extracting, washing, filtering, drying and rotary evaporating the obtained mixed solution, collecting an organic phase, carrying out rapid column chromatography on the organic phase by taking the mixed solution of dichloromethane and methanol as an eluent, enriching the product, and preparing the product 1 HNMR, found that the target product could not be obtained.
Comparative example 2
The flame-retardant polydicyclopentadiene material comprises the following raw materials: 99.8wt% dicyclopentadiene, 0wt% 5-norbornene-2-carboxamide, 0wt% 5-norbornene-2-methanol, 0wt% flame retardant, 0.16wt% catalyst, 0.04wt% inhibitor.
The preparation process of the flame-retardant polydicyclopentadiene engineering material of the comparative example is the same as that of example 1.
Comparative example 3
The flame-retardant polydicyclopentadiene material of the comparative example comprises the following raw materials: 81.53wt% of dicyclopentadiene, 10.02wt% of 5-norbornene-2-carboxamide, 8.25wt% of 5-norbornene-2-methanol, 0wt% of flame retardant, 0.16wt% of catalyst and 0.04wt% of inhibitor.
The preparation process of the flame-retardant polydicyclopentadiene engineering material of the comparative example is the same as that of example 1.
Comparative example 4
The flame-retardant polydicyclopentadiene material of the comparative example comprises the following raw materials: 59.78wt% of dicyclopentadiene, 10.02wt% of 5-norbornene-2-carboxamide, 0wt% of 5-norbornene-2-methanol, 30wt% of flame retardant, 0.16wt% of catalyst and 0.04wt% of inhibitor. Wherein the flame retardant is a reactive flame retardant A with an amido bond-containing norbornene caged phosphate structure.
The preparation process of the flame-retardant polydicyclopentadiene engineering material of the comparative example is the same as that of example 1.
Comparative example 5
The flame-retardant polydicyclopentadiene material of the comparative example comprises the following raw materials: 61.55wt% of dicyclopentadiene, 0wt% of 5-norbornene-2-carboxamide, 8.25wt% of 5-norbornene-2-methanol, 30wt% of flame retardant, 0.16wt% of catalyst and 0.04wt% of inhibitor. Wherein the flame retardant is a reactive flame retardant A with an amido bond-containing norbornene caged phosphate structure.
The preparation process of the flame retardant polydicyclopentadiene engineering material of this comparative example is the same as that of example 1.
Comparative example 6
The flame-retardant polydicyclopentadiene material comprises the following raw materials: 51.53wt% of dicyclopentadiene, 10.02wt% of 5-norbornene-2-carboxamide, 8.25wt% of 5-norbornene-2-methanol, 30wt% of flame retardant, 0.16wt% of catalyst and 0.04wt% of inhibitor. Wherein, the flame retardant is an inorganic additive flame retardant of magnesium hydroxide, aluminum hydroxide and zinc borate, and the proportion is 5:5:1.
the preparation process of the flame retardant polydicyclopentadiene engineering material of this comparative example is the same as that of example 1.
Comparative example 7
The flame-retardant polydicyclopentadiene material of the comparative example comprises the following raw materials: 51.53wt% of dicyclopentadiene, 10.02wt% of 5-norbornene-2-carboxamide, 8.25wt% of 5-norbornene-2-methanol, 30wt% of flame retardant, 0.16wt% of catalyst and 0.04wt% of inhibitor. Wherein, the flame retardant is additive flame retardant pentaerythritol phosphate and melamine, and the proportion is 2:1.
the preparation process of the flame-retardant polydicyclopentadiene engineering material of the comparative example is the same as that of example 1.
Comparative example 8
The flame-retardant polydicyclopentadiene material of the comparative example comprises the following raw materials: 51.53wt% of dicyclopentadiene, 10.02wt% of 5-norbornene-2-carboxamide, 8.25wt% of 5-norbornene-2-methanol, 30wt% of flame retardant, 0.16wt% of catalyst and 0.04wt% of inhibitor. Wherein the flame retardant comprises halogen-containing additive flame retardant decabromodiphenyl ether ester and synergistic flame retardant antimony trioxide, and the proportion of the flame retardant is 4:1.
the preparation process of the flame-retardant polydicyclopentadiene engineering material of the comparative example is the same as that of example 1.
Test and results
The materials prepared in the above examples and comparative examples were cut to prepare test specimens, the test method of which was:
heat of polymerization: determination of the Heat of polymerization H of the samples by DSC r . About 10mg of the prepared dicyclopentadiene mixture was added to the crucible, and the sample was cooled to-10 ℃ at a rate of 5 ℃ per minute, held at that temperature for 2 minutes, and then raised to 200 ℃ at a rate of 5 ℃ per minute. After baseline calibration, the heat flow between 20 ℃ and 150 ℃ is integrated over temperature and the heat of polymerization H is calculated r 。
Curing degree: firstly, DSC is used for measuring reaction residual heat H res . Taking about 10mg of cured sample, performing heat-cold-heat circulation at-50 ℃ and 250 ℃ at the rate of 10 ℃ per minute, after baseline calibration, integrating heat flow between 50 ℃ and 150 ℃ with temperature, and calculating to obtain reaction waste heat H res . The degree of cure α is calculated by the following formula:
molecular weight M between crosslinking points c ：M c Calculated according to the following formula:
in the formula, the value of rho is 1g cm -3 R is an ideal gas constant having a value of 8.314 J.mol -1 ·K -1 T is T g +50K，E′ Tg+50K Is T g +50K, storage modulus of the sample.
Tensile strength: tested according to ISO 527-2 standard 1993 at a speed of 50mm/min;
elongation at break: tested according to ISO 527-2 standard 1993, at a speed of 50mm/min;
impact strength: testing according to ISO 180;
hardness: testing according to ISO 7619-973 standard;
heat distortion temperature: testing according to ISO 75-2;
abrasion loss: tested according to ISO 9352;
flame retardant property: testing according to GB/T2408-2008.
TABLE 3 polymerization kinetics, mechanical properties and flame retardant Properties of the flame retardant polydicyclopentadiene engineering materials prepared in examples 1-10
TABLE 4 polymerization kinetics, mechanical properties and flame retardant Properties of the flame retardant polydicyclopentadiene engineering materials prepared in comparative examples 1-8
Tables 1 and 2 show the experimental formulas of examples 1 to 10 and comparative examples 1 to 8, and tables 3 and 4 show the polymerization kinetics, mechanical properties and flame retardant performance indexes of the flame retardant polydicyclopentadiene engineering materials prepared according to examples 1 to 10 and comparative examples 1 to 8.
The polymerization kinetics data for examples 1-10 in Table 3 show that the comonomer incorporation has no significant effect on the heat of polymerization and the degree of cure of the dicyclopentadiene, with the degree of cure of the material exceeding 94%, indicating that the material is still capable of maintaining a high degree of polymerization. The glass transition data of the materials in examples 1-10 show that as the content of the flame retardant is increased and the 5-norbornene-2-formamide and the 5-norbornene-2-methanol are compounded, the glass transition temperature of the polydicyclopentadiene engineering material is increased from 159 ℃ to 225 ℃, and the reason for analyzing the glass transition temperature is that the activity of the norbornene monomer is higher than that of dicyclopentadiene, and the structure has more C = C, so that the crosslinking density of the material is increased, and the glass transition temperature of the material is increased. In addition, the introduction of hydrogen bonds in the dicyclopentadiene strengthens the interaction among molecular chains to reduce the movement capacity of the molecular chains, thereby further improving the glass transition temperature of the material. After testing the mechanical property and the flame retardant property of the material, the introduction of the norbornene-based reactive flame retardant containing an amido bond and a cage-shaped phosphate structure, the 5-norbornene-2-formamide and the 5-norbornene-2-methanol obviously increases the impact strength, the tensile strength, the hardness, the wear resistance and the thermal deformation temperature of the material. Particularly, the LOI value of the material is improved to 42 percent from 18 percent, the heat release rate peak value p HRR is reduced by 81.9 percent, the smoke generation rate peak value p SPR is reduced by 71.4 percent, the fire index FPI is increased by 6 times, and the flame retardant grade of the material reaches UL94V-0 grade. The result shows that the introduction of the norbornene group reaction type flame retardant containing the amido bond and the caged phosphate structure, the 5-norbornene-2-formamide and the 5-norbornene-2-methanol greatly improves the flame retardant property of the polydicyclopentadiene material.
Table 4 shows the results of the data for comparative examples 1-8. In comparative examples 2 to 5, 5-norbornene-2-carboxamide, 5-norbornene-2-methanol and norbornene-based reactive flame retardants containing amide bonds and caged phosphate structures were introduced into polydicyclopentadiene, respectively, and the results show that the introduction of 5-norbornene-2-carboxamide, 5-norbornene-2-methanol or norbornene-based reactive flame retardants containing amide bonds and caged phosphate structures alone can only improve one aspect of performance, and the performance improvement is not significant.
In comparative examples 6 to 8, inorganic flame retardant, intumescent flame retardant and halogen-containing flame retardant were added to polydicyclopentadiene, respectively, and the flame retardant property and mechanical property of the prepared polydicyclopentadiene material were significantly poorer than those in the examples of this patent.
In conclusion, the introduction of the norbornene reaction type flame retardant containing the amido bond and the caged phosphate structure, the 5-norbornene-2-formamide and the 5-norbornene-2-methanol improves the flame retardant property of the polydicyclopentadiene material, improves the mechanical property, the wear resistance and the heat resistance of the polydicyclopentadiene material, and has good application prospect.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention.
Claims (5)
1. A high modulus, high impact, wear-resistant, heat-resistant intrinsic flame-retardant polydicyclopentadiene engineering material is characterized in that:
the structural formula of the polydicyclopentadiene engineering material is shown as (1):
wherein n, m, o, p, q are allIs an integer between 100-1500; in the structural formula (1), R 1 Is an aliphatic substituent or an aromatic substituent having 1 to 8 carbon atoms, R 2 Is an aliphatic substituent or an aromatic substituent having 1 to 8 carbon atoms;
the sum of the mass percentages of the raw materials for preparing the polydicyclopentadiene engineering material is 100%, and the mass percentages of the raw materials are as follows:
the structural formula of the norbornene-based reaction type flame retardant containing the amido bond and the cage-shaped phosphate structure is shown as (2):
in the structural formula (2), R 1 Is an aliphatic substituent or an aromatic substituent having 1 to 8 carbon atoms, R 2 Is an aliphatic substituent or an aromatic substituent having 1 to 8 carbon atoms;
the catalyst is a ruthenium catalyst;
the inhibitor is phosphate ester.
2. The high modulus, high impact, abrasion resistant, heat resistant intrinsic flame retardant polydicyclopentadiene engineering material of claim 1, wherein:
the synthesis method of the norbornene-based reactive flame retardant containing the amido bond and the cage-shaped phosphate structure comprises the following steps:
and carrying out amidation reaction on norbornene containing acyl chloride and monoamine containing a cage-shaped phosphate structure under the action of a catalyst, wherein the reaction temperature is 0-120 ℃, the reaction time is 5-24h, and after the reaction is finished, washing, separating and drying to obtain the norbornene-based reactive flame retardant monomer containing the amido bond and the cage-shaped phosphate structure.
3. The high modulus, high impact, abrasion resistant, heat resistant intrinsic flame retardant polydicyclopentadiene engineering material of claim 2, wherein:
in the method for synthesizing the norbornene-based reactive flame retardant containing the amido bond and the cage-shaped phosphate structure, the catalyst required by the amidation reaction is as follows: pyridine, triethylamine, sodium carbonate, sodium bicarbonate, sodium acetate, N-diisopropylethylamine, N-dimethylaniline, tri-N-butylamine, N-methylmorpholine, 4-N, N-dimethylpyridine, 4-pyrrolidinylpyridine, 1-hydroxybenzotriazole, 1-hydroxy-7-azabenzotriazole, N-hydroxysuccinimide, N-hydroxyphthalimide and N-hydroxy-1, 8-naphthalimide or a mixture of a plurality of the same;
the organic solvent used for the amidation reaction is: one of dichloromethane, trichloromethane, toluene, benzene, xylene, acetone, N dimethylformamide, dichloroethane, acetonitrile, carbon tetrachloride and hexachloroethane.
4. A process for the preparation of a high modulus, high impact, abrasion resistant, heat resistant intrinsic flame retardant polydicyclopentadiene engineering material as claimed in any one of claims 1-3, characterized by the steps of:
(1) Adding the catalyst and the inhibitor into a mixed solution of dicyclopentadiene, 5-norbornene-2-formamide and 5-norbornene-2-methanol in proportion, ultrasonically mixing the mixed solution for 30s-180s under the ice-water bath condition, and then dispersing a norbornene-based reaction type flame retardant containing an amido bond and a cage-shaped phosphate ester structure into the mixed solution containing the catalyst and the inhibitor to obtain a dispersion solution;
(2) And injecting the dispersion liquid into a mold, carrying out local thermal initiation at 135-200 ℃, driving polymerization by polymerization heat released by the dispersion liquid, and copolymerizing to obtain the high-modulus, high-impact, wear-resistant, heat-resistant and intrinsic flame-retardant polydicyclopentadiene engineering material.
5. Use of the flame retardant polydicyclopentadiene engineering material as recited in any one of claims 1 to 3 or the flame retardant polydicyclopentadiene engineering material obtained by the method for producing as recited in claim 4, wherein: the flame-retardant polydicyclopentadiene engineering material is used for high-voltage battery pack shells of new energy automobiles, cable connectors of high-speed trains and automobile engine support frame materials.
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| US4059561A (en) * | 1975-02-07 | 1977-11-22 | Showa Denko Kabushiki Kaisha | Flame-resistant composition containing a norbornene derivative polymer |
| JPH05112678A (en) * | 1991-10-18 | 1993-05-07 | Idemitsu Kosan Co Ltd | Flame-retardant resin composition and electric wire coated therewith |
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| CN113004474A (en) * | 2021-03-10 | 2021-06-22 | 安徽建筑大学 | Multi-walled carbon nanotube/barium titanate/polydicyclopentadiene composite material based on front-end ring-opening metathesis polymerization and preparation method thereof |
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| US4059561A (en) * | 1975-02-07 | 1977-11-22 | Showa Denko Kabushiki Kaisha | Flame-resistant composition containing a norbornene derivative polymer |
| JPH05112678A (en) * | 1991-10-18 | 1993-05-07 | Idemitsu Kosan Co Ltd | Flame-retardant resin composition and electric wire coated therewith |
| CN104592301A (en) * | 2015-01-05 | 2015-05-06 | 张玉清 | Flame retardant, preparation method as well as modified polydicyclopentadiene and preparation method |
| CN113004474A (en) * | 2021-03-10 | 2021-06-22 | 安徽建筑大学 | Multi-walled carbon nanotube/barium titanate/polydicyclopentadiene composite material based on front-end ring-opening metathesis polymerization and preparation method thereof |
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