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CN112552346B - Hexachlorocyclotriphosphazene derivative, preparation method and application thereof, polydicyclopentadiene composite material and preparation method thereof - Google Patents

Hexachlorocyclotriphosphazene derivative, preparation method and application thereof, polydicyclopentadiene composite material and preparation method thereof Download PDF

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CN112552346B
CN112552346B CN202011565042.1A CN202011565042A CN112552346B CN 112552346 B CN112552346 B CN 112552346B CN 202011565042 A CN202011565042 A CN 202011565042A CN 112552346 B CN112552346 B CN 112552346B
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hexachlorocyclotriphosphazene
polydicyclopentadiene
derivative
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flame retardant
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CN112552346A (en
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余志强
林清怀
郭二茹
任伟
张玉清
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Xiamen Naike Site Automobile Technology Co ltd
AMOY INSTITUTE OF TECHNOVATION
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AMOY INSTITUTE OF TECHNOVATION
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
    • C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
    • C07F9/65814—Cyclic phosphazenes [P=N-]n, n>=3 n = 3 or 4
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    • C08F132/00—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F132/08—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L2201/02—Flame or fire retardant/resistant

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Abstract

The invention relates to a hexachlorocyclotriphosphazene derivative, a preparation method and application thereof, a polydicyclopentadiene composite material and a preparation method thereof, and belongs to the technical field of flame retardance. The hexachlorocyclotriphosphazene derivative has a structure shown in a formula I. The hexachlorocyclotriphosphazene derivative has a structure shown as a formula I, wherein R is C 8 ‑C 18 Chain alkyl. C introduced into the hexachlorocyclotriphosphazene derivative 8 ‑C 18 The chain alkyl can obviously improve the compatibility of hexachlorocyclotriphosphazene derivative and polydicyclopentadiene matrix, so that the hexachlorocyclotriphosphazene derivative has good solubility in dicyclopentadiene. When the hexachlorocyclotriphosphazene derivative is used as the polydicyclopentadiene flame retardant, good flame retardant property can be achieved and the mechanical property of the polydicyclopentadiene composite material can be maintained to a large extent under relatively low addition, meanwhile, migration and precipitation of the flame retardant are reduced, and the flame retardant property of the polydicyclopentadiene composite material is more stable.

Description

Hexachlorocyclotriphosphazene derivative, preparation method and application thereof, polydicyclopentadiene composite material and preparation method thereof
Technical Field
The invention relates to a hexachlorocyclotriphosphazene derivative, a preparation method and application thereof, a polydicyclopentadiene composite material and a preparation method thereof, and belongs to the technical field of flame retardance.
Background
Polydicyclopentadiene (PDCPD) is a thermosetting engineering plastic with excellent comprehensive mechanical properties, and has wide application in the fields of transportation, chemical industry, electrical equipment, sports equipment and the like. However, with the improvement of the safety performance requirements of materials at home and abroad, the application of the polydicyclopentadiene is limited by the inflammability characteristic of the polydicyclopentadiene. It is therefore desirable to add various flame retardants to improve the flame retardant properties of polydicyclopentadiene materials. However, polydicyclopentadiene is usually prepared by a two-component catalytic system, and the catalytic system has higher sensitivity to water, oxygen, active functional groups and the like and is easy to deactivate. In addition, the polydicyclopentadiene is prepared by adopting a reaction injection molding process, so that the viscosity of a polymerization system is not easy to be excessively large. It is therefore important to select and prepare flame retardants suitable for polydicyclopentadiene systems.
Hexachlorocyclotriphosphazene is a flame retardant containing chlorine, nitrogen and phosphorus elements at the same time, and can form a flame-retardant synergistic system, so that the flame-retardant effect is good. Hexachlorocyclotriphosphazene has certain solubility in dicyclopentadiene monomer, and can better improve the flame retardant property of polydicyclopentadiene, but has poor compatibility with polydicyclopentadiene matrix, so that the mechanical property of the polydicyclopentadiene flame retardant composite material is obviously reduced. Chinese patent documents CN104558326A and CN104592301A respectively disclose hexachlorocyclotriphosphazene derivatives with cyclopentadienyl groups and norbornene groups, and the hexachlorocyclotriphosphazene derivatives are used as flame retardants for modification of polydicyclopentadiene, so that the solubility of the flame retardants can be improved, and meanwhile, good mechanical properties are maintained, but the hexachlorocyclotriphosphazene derivatives are relatively complex to prepare, the yield is relatively low, and the cost of the hexachlorocyclotriphosphazene derivatives for flame retardance of polydicyclopentadiene is increased.
Disclosure of Invention
The invention aims to provide a hexachlorocyclotriphosphazene derivative with good compatibility with polydicyclopentadiene, which can reduce the cost of flame-retardant polydicyclopentadiene as a flame retardant.
The invention also provides a preparation method and application of the hexachlorocyclotriphosphazene derivative, and polydicyclopentadiene taking the hexachlorocyclotriphosphazene as a flame retardant and a preparation method thereof.
In order to achieve the above object, the hexachlorocyclotriphosphazene derivative of the present invention adopts the following technical scheme:
a hexachlorocyclotriphosphazene derivative having a structure as shown in formula I:
in the formula I, R is C 8 -C 18 Chain alkyl.
C introduced into hexachlorocyclotriphosphazene derivative of the invention 8 -C 18 The chain alkyl can significantly improve the compatibility of the hexachlorocyclotriphosphazene derivative with the polydicyclopentadiene matrix, so that the hexachlorocyclotriphosphazene derivative has good solubility in dicyclopentadiene. Therefore, when the hexachlorocyclotriphosphazene derivative is used as the polydicyclopentadiene flame retardant, good flame retardant property can be achieved and the mechanical property of the polydicyclopentadiene composite material can be maintained to a large extent under relatively low addition amount, meanwhile, migration and precipitation of the flame retardant are reduced, and the flame retardant property of the polydicyclopentadiene composite material is more stable.
C 8 -C 18 The chain alkyl group may be branched C 8 -C 18 Chain alkyl groups, also C without branching 8 -C 18 Chain alkyl. Preferably, in formula I, R is C without branching 8 -C 18 Chain alkyl.
Preferably, R is C 8 -C 12 Chain alkyl.
The technical scheme adopted by the preparation method of the hexachlorocyclotriphosphazene derivative is as follows:
the preparation method of the hexachlorocyclotriphosphazene derivative comprises the following steps: c is C 8 -C 18 Chain alkaneThe reaction of the thioglycoland hexachlorocyclotriphosphazene in organic solvent is carried out under the action of acid binding agent.
The preparation method of the hexachlorocyclotriphosphazene derivative of the invention adopts C 8 -C 18 The preparation method takes chain alkyl mercaptan and hexachlorocyclotriphosphazene as reaction raw materials to react at 25-50 ℃, has the characteristics of simple process, mild reaction conditions, high yield (more than 92.5%), low cost and the like, and is easy to popularize and apply in industrialization.
Preferably, the temperature of the reaction is 25 to 50 ℃. The reaction is preferably carried out at 25 to 50℃for a period of 5 to 10 hours.
Preferably, the reaction is carried out in an inert atmosphere. The system was stirred during the reaction.
Preferably, the acid binding agent is an organic amine; the organic amine is one or any combination of triethylamine, pyridine and N, N-dimethylpropylamine.
Preferably, the organic solvent is one or any combination of tetrahydrofuran, dichloromethane, cyclohexane and toluene.
The preparation method of the hexachlorocyclotriphosphazene derivative further comprises the following steps: and (3) carrying out solid-liquid separation on the system after the reaction is finished, removing the organic solvent in the liquid phase obtained by the solid-liquid separation to obtain a crude product, and purifying the crude product.
Preferably, C 8 -C 18 The chain alkyl mercaptan and hexachlorocyclotriphosphazene react in organic solvent under the action of acid-binding agent, specifically C 8 -C 18 Adding the organic solution of chain alkyl mercaptan into the organic solution of hexachlorocyclotriphosphazene and acid binding agent, and controlling the temperature to be 25-50 ℃ after adding to react. The addition is preferably dropwise. The C is 8 -C 18 The organic solution of chain alkyl mercaptan is C 8 -C 18 The chain alkyl mercaptan is obtained by dissolving the chain alkyl mercaptan in an organic solvent. The organic solution of the hexachlorocyclotriphosphazene and the acid binding agent is obtained by dissolving the hexachlorocyclotriphosphazene and the acid binding agent in an organic solvent. The hexachlorocyclotriphosphazene and the acid binding agent are protected by inert atmosphere in the process of dissolving in an organic solvent. Preferably, hexachlorocyclotriphosphazene derivatives are preparedThe inert atmosphere in the preparation method is preferably a nitrogen atmosphere.
Preferably, the purification comprises the steps of: washing the crude product with water, dissolving the washed organic phase with organic solvent for purification, adding desiccant for drying, separating to remove the desiccant, and removing the organic solvent. The organic solvent is removed in the purification process to obtain the hexachlorocyclotriphosphazene derivative product with higher purity, and the hexachlorocyclotriphosphazene derivative product is colorless transparent viscous liquid. The drying agent is one or any combination of anhydrous magnesium sulfate and anhydrous sodium sulfate. The organic solvent for purification is preferably ethyl acetate.
Preferably, the hexachlorocyclotriphosphazene is mixed with C 8 -C 18 The molar ratio of chain alkyl mercaptan is 1:1.
Preferably, the mol ratio of the hexachlorocyclotriphosphazene to the acid binding agent is 1:2-3.
The application of the hexachlorocyclotriphosphazene derivative as the polydicyclopentadiene flame retardant adopts the following technical scheme:
the hexachlorocyclotriphosphazene derivative is applied as polydicyclopentadiene flame retardant.
The technical scheme adopted by the polydicyclopentadiene composite material is as follows:
a polydicyclopentadiene composite material, comprising polydicyclopentadiene and a flame retardant; the flame retardant is the hexachlorocyclotriphosphazene derivative.
The polydicyclopentadiene composite material disclosed by the invention has stable and good flame retardant performance and simultaneously can maintain good mechanical properties by taking the hexachlorocyclotriphosphazene derivative as a flame retardant.
Preferably, the mass percentage of hexachlorocyclotriphosphazene derivative in the polydicyclopentadiene composite material is 10-20%.
The preparation method of the polydicyclopentadiene composite material adopts the following technical scheme:
the preparation method of the polydicyclopentadiene composite material comprises the following steps: the component A and the component B are subjected to reaction injection molding under the protection of inert atmosphere, and the product is obtained; the component A consists of the hexachlorocyclotriphosphazene derivative, dicyclopentadiene, a flame retardant synergist and a main catalyst; the component B consists of the hexachlorocyclotriphosphazene derivative, dicyclopentadiene, a flame retardant synergist and a cocatalyst.
The preparation method of the polydicyclopentadiene composite material has simple process, and the types and the use amounts of the adopted flame retardant synergist, the adopted cocatalyst and the adopted main catalyst as well as the reaction temperature and the reaction time can be determined according to the existing reaction injection molding process of the polydicyclopentadiene composite material.
Preferably, the mass percentage of the hexachlorocyclotriphosphazene derivative in the component A and the component B is 10-20 percent.
Preferably, the temperature of the reaction injection molding is 70 ℃. The temperature of the reaction injection molding is the temperature of the mold during the molding process. The mold was kept warm for 10 minutes at the temperature of the reaction injection molding. The flame retardant synergist is preferably antimony trioxide.
Preferably, the preparation method of the component A comprises the following steps: under the protection of inert atmosphere, dissolving the hexachlorocyclotriphosphazene derivative in dicyclopentadiene, adding a flame retardant synergist, uniformly mixing, and then adding a main catalyst to form a component A. The component B is prepared by adopting a method comprising the following steps: under the protection of inert atmosphere, dissolving the hexachlorocyclotriphosphazene derivative in dicyclopentadiene, adding a flame retardant synergist, mixing uniformly, and adding a cocatalyst to form the component B. The inert atmosphere used in the preparation of component A and component B is preferably a nitrogen atmosphere.
Preferably, the main catalyst is a 2, 6-di-tert-butyl-4-methylphenol-tungsten complex of the formula W (OPhCH) 3 (C(CH 3 ) 3 ) 2 ) 3 Cl 3 . Preferably, the cocatalyst is diethyl aluminum monochloride, triisobutyl aluminum or triethyl aluminum, more preferably diethyl aluminum monochloride.
Preferably, the molar ratio of procatalyst to dicyclopentadiene in component A is 1:1500. The molar ratio of the cocatalyst to the main catalyst was 50:1. The mass ratio of the component A to the component B is 1:1.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of hexachlorocyclotriphosphazene derivative prepared in example 2;
FIG. 2 is a nuclear magnetic resonance spectrum of hexachlorocyclotriphosphazene derivatives prepared in example 2.
Detailed Description
The technical scheme of the invention is further described below in connection with the specific embodiments.
Examples 1 to 3 below are examples of hexachlorocyclotriphosphazene derivatives, examples 4 to 6 are methods for producing hexachlorocyclotriphosphazene derivatives, example 7 is an example of polydicyclopentadiene composite material, and examples 8 to 10 are examples of methods for producing polydicyclopentadiene composite material.
Example 1
The hexachlorocyclotriphosphazene derivative of this example has the following structure:
example 2
The hexachlorocyclotriphosphazene derivative of this example has the following structure:
example 3
The hexachlorocyclotriphosphazene derivative of this example has the following structure:
example 4
This example is a process for the preparation of hexachlorocyclotriphosphazene derivatives of example 1 comprising the steps of:
1) Sequentially adding 5.21g (15 mmol) of hexachlorocyclotriphosphazene, 45mL of tetrahydrofuran and 3.04g (30 mmol) of triethylamine into a 250mL three-neck flask, and introducing nitrogen to dissolve the hexachlorocyclotriphosphazene to obtain an organic solution of the hexachlorocyclotriphosphazene;
2.19g (15 mmol) of n-octanethiol is dissolved in 45mL of tetrahydrofuran to obtain an organic solution of n-octanethiol, and the organic solution of n-octanethiol is transferred into a 100mL constant pressure dropping funnel;
2) Dropwise adding an organic solution of n-octyl mercaptan into an organic solution of hexachlorocyclotriphosphazene at room temperature under magnetic stirring, transferring into a water bath at 50 ℃ for continuous reaction for 5 hours after the dropwise adding is finished, cooling to room temperature, filtering to remove triethylamine hydrochloride, and then evaporating filtrate to remove tetrahydrofuran (recycling) to obtain a crude product;
3) Then adding a small amount of deionized water into the crude product to wash twice, adding 30mL of ethyl acetate into the washed organic phase to dissolve, then adding anhydrous magnesium sulfate to dry, standing for 1h, filtering, and then evaporating the filtrate to remove the ethyl acetate, thereby obtaining colorless transparent viscous liquid, namely n-octyl thio pentachlorocyclotriphosphazene (namely hexachlorocyclotriphosphazene derivative of example 1), and the yield is 92.5%.
Example 5
This example is a process for the preparation of hexachlorocyclotriphosphazene derivatives of example 2 comprising the steps of:
1) Sequentially adding 5.21g (15 mmol) of hexachlorocyclotriphosphazene, 45mL of tetrahydrofuran and 3.04g (30 mmol) of triethylamine into a 250mL three-neck flask, and introducing nitrogen to dissolve the hexachlorocyclotriphosphazene to obtain an organic solution of the hexachlorocyclotriphosphazene;
3.04g (15 mmol) of dodecyl mercaptan was dissolved in 45mL of tetrahydrofuran to obtain an organic solution of dodecyl mercaptan, and the organic solution of dodecyl mercaptan was transferred to a 100mL constant pressure dropping funnel;
2) Dropping organic solution of hexachlorocyclotriphosphazene into organic solution of dodecyl mercaptan under magnetic stirring at room temperature, transferring into water bath at 50 ℃ for continuous reaction for 5 hours after the dropping, cooling to room temperature, filtering to remove triethylamine hydrochloride, and then steaming filtrate to remove tetrahydrofuran (recycling) to obtain crude product;
3) Then adding a small amount of deionized water into the crude product to wash twice, adding 30mL of ethyl acetate into the washed organic phase to dissolve, then adding anhydrous magnesium sulfate to dry, standing for 1h, filtering, and then evaporating the filtrate to remove the ethyl acetate, thereby obtaining colorless transparent viscous liquid, namely dodecyl thio pentachlorocyclotriphosphazene (namely hexachlorocyclotriphosphazene derivative of example 2), and the yield is 96.3%.
The hexachlorocyclo three derivative prepared in the embodiment is subjected to structural characterization, wherein a nuclear magnetic hydrogen spectrum is shown in figure 1, and a nuclear magnetic phosphorus spectrum is shown in figure 2. From fig. 1 and 2, it can be confirmed that the hexachlorocyclotriphosphazene derivative prepared in example 5 is dodecylthio pentachlorocyclotriphosphazene.
Example 6
This example is a process for the preparation of hexachlorocyclotriphosphazene derivatives of example 3 comprising the steps of:
1) Sequentially adding 5.21g (15 mmol) of hexachlorocyclotriphosphazene, 45mL of tetrahydrofuran and 3.04g (30 mmol) of triethylamine into a 250mL three-neck flask, and introducing nitrogen to dissolve the hexachlorocyclotriphosphazene to obtain an organic solution of the hexachlorocyclotriphosphazene;
4.30g (15 mmol) of octadecyl mercaptan was dissolved in 45mL of tetrahydrofuran to give an organic solution of octadecyl mercaptan, and the organic solution of octadecyl mercaptan was transferred to a 100mL constant pressure dropping funnel;
2) Dripping an organic solution of octadecyl mercaptan into an organic solution of hexachlorocyclotriphosphazene at room temperature under magnetic stirring, transferring into a water bath at 50 ℃ for continuous reaction for 5 hours after the dripping is finished, cooling to room temperature, filtering to remove triethylamine hydrochloride, and then steaming filtrate to remove tetrahydrofuran (recycling) to obtain a crude product;
3) Then adding a small amount of deionized water into the crude product to wash twice, adding 30mL of ethyl acetate into the washed organic phase to dissolve, then adding anhydrous magnesium sulfate to dry, standing for 1h, filtering, and then evaporating the filtrate to remove the ethyl acetate, thereby obtaining colorless transparent viscous liquid, namely octadecylthio pentachlorocyclotriphosphazene (namely hexachlorocyclotriphosphazene derivative of example 3), and the yield is 95.8%.
Example 7
This example is a polydicyclopentadiene composite flame-retardant with any one of the hexachlorocyclotriphosphazene derivatives of examples 1 to 3 as a flame retardant. The mass percent of the hexachlorocyclotriphosphazene derivative in the polydicyclopentadiene composite material in any one of the embodiments 1-3 is 10 percent or 15 percent or 20 percent. The polydicyclopentadiene composite material of the present example can be prepared by the following preparation methods of examples 8 to 16 according to the specific hexachlorocyclotriphosphazene derivative used and the mass percentage of hexachlorocyclotriphosphazene derivative used in the polydicyclopentadiene composite material.
Example 8
This example is a method for preparing a hexachlorocyclotriphosphazene derivative flame retardant polydicyclopentadiene composite of example 1, comprising the steps of:
1) Under the protection of nitrogen, adding 10 parts by weight of n-octyl thio pentachlorocyclotriphosphazene into 86 parts by weight of liquid dicyclopentadiene to be dissolved, adding 4 parts by weight of antimonous oxide, and homogenizing for 10 minutes by adopting a high-speed homogenizer to prepare dispersion;
2) Taking two equal weight dispersion solutions, adding a main catalyst 2, 6-di-tert-butyl-4-methylphenol-tungsten complex into one of the dispersion solutions, uniformly mixing to obtain a component A, and adding a cocatalyst diethyl aluminum chloride into the other dispersion solution, uniformly mixing to obtain a component B; the mol ratio of the main catalyst to dicyclopentadiene in the component A is 1:1500; the molar ratio of the cocatalyst in the component B to the main catalyst in the component A is 50:1;
3) And (3) at 50 ℃, mixing the component A and the component B according to the mass ratio of 1:1 by a reaction injection molding machine, then injecting into a mold at 70 ℃, preserving heat for 10min, and then opening the mold to obtain the n-octyl thio pentachlorocyclotriphosphazene flame-retardant polydicyclopentadiene composite material.
Example 9
This example is a method for preparing a hexachlorocyclotriphosphazene derivative flame retardant polydicyclopentadiene composite of example 1, comprising the steps of:
1) Under the protection of nitrogen, adding 15 parts by weight of n-octyl thio pentachlorocyclotriphosphazene into 81 parts by weight of liquid dicyclopentadiene to be dissolved, adding 4 parts by weight of antimonous oxide, and homogenizing for 10 minutes by adopting a high-speed homogenizer to prepare dispersion;
2) Taking two equal weight dispersion solutions, adding a main catalyst 2, 6-di-tert-butyl-4-methylphenol-tungsten complex into one of the dispersion solutions, uniformly mixing to obtain a component A, and adding a cocatalyst diethyl aluminum chloride into the other dispersion solution, uniformly mixing to obtain a component B; the mol ratio of the main catalyst to dicyclopentadiene in the component A is 1:1500; the molar ratio of the cocatalyst in the component B to the main catalyst in the component A is 50:1;
3) And (3) at 50 ℃, mixing the component A and the component B according to the mass ratio of 1:1 by a reaction injection molding machine, then injecting into a mold at 70 ℃, preserving heat for 10min, and then opening the mold to obtain the n-octyl thio pentachlorocyclotriphosphazene flame-retardant polydicyclopentadiene composite material.
Example 10
This example is a method for preparing a hexachlorocyclotriphosphazene derivative flame retardant polydicyclopentadiene composite of example 1, comprising the steps of:
1) Under the protection of nitrogen, adding 20 parts by weight of n-octyl thio pentachlorocyclotriphosphazene into 76 parts by weight of liquid dicyclopentadiene to be dissolved, adding 4 parts by weight of antimonous oxide, and homogenizing for 10 minutes by adopting a high-speed homogenizer to prepare dispersion;
2) Taking two equal weight dispersion solutions, adding a main catalyst 2, 6-di-tert-butyl-4-methylphenol-tungsten complex into one of the dispersion solutions, uniformly mixing to obtain a component A, and adding a cocatalyst diethyl aluminum chloride into the other dispersion solution, uniformly mixing to obtain a component B; the mol ratio of the main catalyst to dicyclopentadiene in the component A is 1:1500; the molar ratio of the cocatalyst in the component B to the main catalyst in the component A is 50:1;
3) And (3) at 50 ℃, mixing the component A and the component B according to the mass ratio of 1:1 by a reaction injection molding machine, then injecting into a mold at 70 ℃, preserving heat for 10min, and then opening the mold to obtain the n-octyl thio pentachlorocyclotriphosphazene flame-retardant polydicyclopentadiene composite material.
Example 11
This example is a method for preparing a hexachlorocyclotriphosphazene derivative flame retardant polydicyclopentadiene composite of example 2, comprising the steps of:
1) Under the protection of nitrogen, adding 10 parts by weight of dodecyl sulfur pentachlorocyclotriphosphazene into 86 parts by weight of liquid dicyclopentadiene to be dissolved, adding 4 parts by weight of antimonous oxide, and homogenizing for 10 minutes by adopting a high-speed homogenizer to prepare dispersion;
2) Taking two equal weight dispersion solutions, adding a main catalyst 2, 6-di-tert-butyl-4-methylphenol-tungsten complex into one of the dispersion solutions, uniformly mixing to obtain a component A, and adding a cocatalyst diethyl aluminum chloride into the other dispersion solution, uniformly mixing to obtain a component B; the mol ratio of the main catalyst to dicyclopentadiene in the component A is 1:1500; the molar ratio of the cocatalyst in the component B to the main catalyst in the component A is 50:1;
3) And (3) at 50 ℃, mixing the component A and the component B according to the mass ratio of 1:1 by a reaction injection molding machine, then injecting into a mold at 70 ℃, preserving heat for 10min, and then opening the mold to obtain the dodecyl thio pentachlorocyclotriphosphazene flame-retardant polydicyclopentadiene composite material.
Example 12
This example is a method for preparing a hexachlorocyclotriphosphazene derivative flame retardant polydicyclopentadiene composite of example 2, comprising the steps of:
1) Under the protection of nitrogen, adding 15 parts by weight of dodecyl sulfur pentachlorocyclotriphosphazene into 81 parts by weight of liquid dicyclopentadiene to be dissolved, adding 4 parts by weight of antimonous oxide, and homogenizing for 10 minutes by adopting a high-speed homogenizer to prepare dispersion;
2) Taking two equal weight dispersion solutions, adding a main catalyst 2, 6-di-tert-butyl-4-methylphenol-tungsten complex into one of the dispersion solutions, uniformly mixing to obtain a component A, and adding a cocatalyst diethyl aluminum chloride into the other dispersion solution, uniformly mixing to obtain a component B; the mol ratio of the main catalyst to dicyclopentadiene in the component A is 1:1500; the molar ratio of the cocatalyst in the component B to the main catalyst in the component A is 50:1;
3) And (3) at 50 ℃, mixing the component A and the component B according to the mass ratio of 1:1 by a reaction injection molding machine, then injecting into a mold at 70 ℃, preserving heat for 10min, and then opening the mold to obtain the dodecyl thio pentachlorocyclotriphosphazene flame-retardant polydicyclopentadiene composite material.
Example 13
This example is a method for preparing a hexachlorocyclotriphosphazene derivative flame retardant polydicyclopentadiene composite of example 2, comprising the steps of:
1) Under the protection of nitrogen, adding 20 parts by weight of dodecyl sulfur pentachlorocyclotriphosphazene into 76 parts by weight of liquid dicyclopentadiene to be dissolved, adding 4 parts by weight of antimonous oxide, and homogenizing for 10 minutes by adopting a high-speed homogenizer to prepare dispersion;
2) Taking two equal weight dispersion solutions, adding a main catalyst 2, 6-di-tert-butyl-4-methylphenol-tungsten complex into one of the dispersion solutions, uniformly mixing to obtain a component A, and adding a cocatalyst diethyl aluminum chloride into the other dispersion solution, uniformly mixing to obtain a component B; the mol ratio of the main catalyst to dicyclopentadiene in the component A is 1:1500; the molar ratio of the cocatalyst in the component B to the main catalyst in the component A is 50:1;
3) And (3) at 50 ℃, mixing the component A and the component B according to the mass ratio of 1:1 by a reaction injection molding machine, then injecting into a mold at 70 ℃, preserving heat for 10min, and then opening the mold to obtain the dodecyl thio pentachlorocyclotriphosphazene flame-retardant polydicyclopentadiene composite material.
Example 14
This example is a method for preparing a hexachlorocyclotriphosphazene derivative flame retardant polydicyclopentadiene composite of example 3, comprising the steps of:
1) Under the protection of nitrogen, adding 10 parts by weight of octadecyl thio pentachlorocyclotriphosphazene into 86 parts by weight of liquid dicyclopentadiene to be dissolved, adding 4 parts by weight of antimonous oxide, and homogenizing for 10 minutes by adopting a high-speed homogenizer to prepare dispersion;
2) Taking two equal weight dispersion solutions, adding a main catalyst 2, 6-di-tert-butyl-4-methylphenol-tungsten complex into one of the dispersion solutions, uniformly mixing to obtain a component A, and adding a cocatalyst diethyl aluminum chloride into the other dispersion solution, uniformly mixing to obtain a component B; the mol ratio of the main catalyst to dicyclopentadiene in the component A is 1:1500; the molar ratio of the cocatalyst in the component B to the main catalyst in the component A is 50:1;
3) And (3) at 50 ℃, mixing the component A and the component B according to the mass ratio of 1:1 by a reaction injection molding machine, then injecting into a mold at 70 ℃, preserving heat for 10min, and then opening the mold to obtain the octadecyl thio pentachlorocyclotriphosphazene flame-retardant polydicyclopentadiene composite material.
Example 15
This example is a method for preparing a hexachlorocyclotriphosphazene derivative flame retardant polydicyclopentadiene composite of example 3, comprising the steps of:
1) Under the protection of nitrogen, adding 15 parts by weight of octadecyl thio pentachlorocyclotriphosphazene into 81 parts by weight of liquid dicyclopentadiene to be dissolved, adding 4 parts by weight of antimonous oxide, and homogenizing for 10 minutes by adopting a high-speed homogenizer to prepare dispersion;
2) Taking two equal weight dispersion solutions, adding a main catalyst 2, 6-di-tert-butyl-4-methylphenol-tungsten complex into one of the dispersion solutions, uniformly mixing to obtain a component A, and adding a cocatalyst diethyl aluminum chloride into the other dispersion solution, uniformly mixing to obtain a component B; the mol ratio of the main catalyst to dicyclopentadiene in the component A is 1:1500; the molar ratio of the cocatalyst in the component B to the main catalyst in the component A is 50:1;
3) And (3) at 50 ℃, mixing the component A and the component B according to the mass ratio of 1:1 by a reaction injection molding machine, then injecting into a mold at 70 ℃, preserving heat for 10min, and then opening the mold to obtain the octadecyl thio pentachlorocyclotriphosphazene flame-retardant polydicyclopentadiene composite material.
Example 16
This example is a method for preparing a hexachlorocyclotriphosphazene derivative flame retardant polydicyclopentadiene composite of example 3, comprising the steps of:
1) Under the protection of nitrogen, adding 20 parts by weight of octadecyl thio pentachlorocyclotriphosphazene into 76 parts by weight of liquid dicyclopentadiene to be dissolved, adding 4 parts by weight of antimonous oxide, and homogenizing for 10 minutes by adopting a high-speed homogenizer to prepare dispersion;
2) Taking two equal weight dispersion solutions, adding a main catalyst 2, 6-di-tert-butyl-4-methylphenol-tungsten complex into one of the dispersion solutions, uniformly mixing to obtain a component A, and adding a cocatalyst diethyl aluminum chloride into the other dispersion solution, uniformly mixing to obtain a component B; the mol ratio of the main catalyst to dicyclopentadiene in the component A is 1:1500; the molar ratio of the cocatalyst in the component B to the main catalyst in the component A is 50:1;
3) And (3) at 50 ℃, mixing the component A and the component B according to the mass ratio of 1:1 by a reaction injection molding machine, then injecting into a mold at 70 ℃, preserving heat for 10min, and then opening the mold to obtain the octadecyl thio pentachlorocyclotriphosphazene flame-retardant polydicyclopentadiene composite material.
Comparative example 1
The polydicyclopentadiene composite material of the comparative example is prepared by a method comprising the following steps:
1) Under the protection of nitrogen, adding 10 parts by weight of hexachlorocyclotriphosphazene and 4 parts by weight of antimonous oxide into 86 parts by weight of liquid dicyclopentadiene, and then adding into a high-speed homogenizer for homogenizing for 10 minutes to prepare dispersion;
2) Taking two equal weight dispersion solutions, adding a main catalyst 2, 6-di-tert-butyl-4-methylphenol-tungsten complex into one of the dispersion solutions, uniformly mixing to obtain a component A, adding a cocatalyst diethyl aluminum chloride into the other dispersion solution, and uniformly mixing to obtain a component B; the mol ratio of the main catalyst to dicyclopentadiene in the component A is 1:1500; the molar ratio of the cocatalyst in the component B to the main catalyst in the component A is 50:1;
3) And (3) at 50 ℃, mixing the component A and the component B according to the mass ratio of 1:1 by a reaction injection molding machine, then injecting into a mold at 70 ℃, preserving heat for 10min, and then opening the mold to obtain the hexachlorocyclotriphosphazene flame-retardant polydicyclopentadiene composite material.
Comparative example 2
The polydicyclopentadiene composite material of the comparative example is prepared by a method comprising the following steps:
1) Under the protection of nitrogen, adding 15 parts by weight of hexachlorocyclotriphosphazene and 4 parts by weight of antimonous oxide into 81 parts by weight of liquid dicyclopentadiene, and then adding into a high-speed homogenizer for homogenizing for 10 minutes to prepare dispersion;
2) Taking two equal weight dispersion solutions, adding a main catalyst 2, 6-di-tert-butyl-4-methylphenol-tungsten complex into one of the dispersion solutions, uniformly mixing to obtain a component A, adding a cocatalyst diethyl aluminum chloride into the other dispersion solution, and uniformly mixing to obtain a component B; the mol ratio of the main catalyst to dicyclopentadiene in the component A is 1:1500; the molar ratio of the cocatalyst in the component B to the main catalyst in the component A is 50:1;
3) And (3) at 50 ℃, mixing the component A and the component B according to the mass ratio of 1:1 by a reaction injection molding machine, then injecting into a mold at 70 ℃, preserving heat for 10min, and then opening the mold to obtain the hexachlorocyclotriphosphazene flame-retardant polydicyclopentadiene composite material.
Comparative example 3
The polydicyclopentadiene composite material of the comparative example is prepared by a method comprising the following steps:
1) Under the protection of nitrogen, adding 20 parts by weight of hexachlorocyclotriphosphazene and 4 parts by weight of antimonous oxide into 76 parts by weight of liquid dicyclopentadiene, and then adding into a high-speed homogenizer for homogenizing for 10 minutes to prepare dispersion;
2) Taking two equal weight dispersion solutions, adding a main catalyst 2, 6-di-tert-butyl-4-methylphenol-tungsten complex into one of the dispersion solutions, uniformly mixing to obtain a component A, adding a cocatalyst diethyl aluminum chloride into the other dispersion solution, and uniformly mixing to obtain a component B; the mol ratio of the main catalyst to dicyclopentadiene in the component A is 1:1500; the molar ratio of the cocatalyst in the component B to the main catalyst in the component A is 50:1;
3) And (3) at 50 ℃, mixing the component A and the component B according to the mass ratio of 1:1 by a reaction injection molding machine, then injecting into a mold at 70 ℃, preserving heat for 10min, and then opening the mold to obtain the hexachlorocyclotriphosphazene flame-retardant polydicyclopentadiene composite material.
Experimental example 1
The mechanical properties and flame retardant properties of the flame retardant polydicyclopentadiene composite materials prepared in examples 8 to 16 and comparative examples 1 to 3 were tested in this experimental example, wherein the tensile strength test was performed according to GB/T1040.1-2006, the impact strength test was performed according to GB/T1843-2008, the limiting oxygen index test was performed according to GB/T2406.2-2009, and the vertical combustion test was performed according to GB/T2408-2008, and the results are shown in Table 1.
TABLE 1 mechanical Properties and flame retardant Property detection results of flame retardant polydicyclopentadiene composite materials prepared in examples 8 to 10 and comparative example 1
As can be seen from Table 1, when the addition amount of the flame retardant is 10% and 15%, the mechanical properties of the hexachlorocyclotriphosphazene flame-retardant polydicyclopentadiene composite material are better than those of the hexachlorocyclotriphosphazene flame-retardant polydicyclopentadiene composite material, and the flame-retardant property is also greatly improved. Compared with the hexachlorocyclotriphosphazene flame-retardant polydicyclopentadiene composite material, the hexachlorocyclotriphosphazene derivative flame-retardant polydicyclopentadiene composite material has the same vertical combustion grade, but the oxygen index and the mechanical property are obviously improved, and the hexachlorocyclotriphosphazene derivative has better flame-retardant property and mechanical property when being used as the flame retardant for flame-retardant polydicyclopentadiene.

Claims (14)

1. The application of hexachlorocyclotriphosphazene derivative as polydicyclopentadiene flame retardant is characterized in that: the hexachlorocyclotriphosphazene derivative has a structure shown in a formula I:
in the formula I, R is C 8 -C 18 Chain alkyl.
2. Use of hexachlorocyclotriphosphazene derivatives according to claim 1 as polydicyclopentadiene flame retardants, characterized in that: in the formula I, R is C without branched chain 8 -C 18 Chain alkyl.
3. Use of hexachlorocyclotriphosphazene derivatives according to claim 1 as polydicyclopentadiene flame retardants, characterized in that: the preparation method of the hexachlorocyclotriphosphazene derivative comprises the following steps: c is C 8 -C 18 The chain alkyl mercaptan and hexachlorocyclotriphosphazene react in an organic solvent under the action of an acid binding agent.
4. Use of hexachlorocyclotriphosphazene derivatives according to claim 3 as polydicyclopentadiene flame retardants, characterized in that: the temperature of the reaction is 25-50 ℃.
5. Use of hexachlorocyclotriphosphazene derivatives according to claim 3 as polydicyclopentadiene flame retardants, characterized in that: the acid binding agent is organic amine; the organic amine is one or any combination of triethylamine, pyridine and N, N-dimethylpropylamine.
6. Use of hexachlorocyclotriphosphazene derivatives according to claim 3 as polydicyclopentadiene flame retardants, characterized in that: further comprises: and (3) carrying out solid-liquid separation on the system after the reaction is finished, removing the organic solvent in the liquid phase obtained by the solid-liquid separation to obtain a crude product, and purifying the crude product.
7. A polydicyclopentadiene composite material, characterized in that: comprises polydicyclopentadiene and a flame retardant; the flame retardant is a hexachlorocyclotriphosphazene derivative, and the hexachlorocyclotriphosphazene derivative has a structure shown in a formula I:
in the formula I, R is C 8 -C 18 Chain alkyl.
8. According to the weightsThe polydicyclopentadiene composite of claim 7, wherein: in the formula I, R is C without branched chain 8 -C 18 Chain alkyl.
9. The polydicyclopentadiene composite according to claim 7, wherein: the preparation method of the hexachlorocyclotriphosphazene derivative comprises the following steps: c is C 8 -C 18 The chain alkyl mercaptan and hexachlorocyclotriphosphazene react in an organic solvent under the action of an acid binding agent.
10. The polydicyclopentadiene composite according to claim 9, wherein: the temperature of the reaction is 25-50 ℃.
11. The polydicyclopentadiene composite according to claim 9, wherein: the acid binding agent is organic amine; the organic amine is one or any combination of triethylamine, pyridine and N, N-dimethylpropylamine.
12. The polydicyclopentadiene composite according to claim 9, wherein: further comprises: and (3) carrying out solid-liquid separation on the system after the reaction is finished, removing the organic solvent in the liquid phase obtained by the solid-liquid separation to obtain a crude product, and purifying the crude product.
13. The polydicyclopentadiene composite according to claim 7, wherein: the mass percentage of hexachlorocyclotriphosphazene derivative in the polydicyclopentadiene composite material is 10-20%.
14. A method for preparing the polydicyclopentadiene composite material according to any one of claims 7 to 13, wherein: the method comprises the following steps: the component A and the component B are subjected to reaction injection molding under the protection of inert atmosphere, and the product is obtained; the component A consists of the hexachlorocyclotriphosphazene derivative, dicyclopentadiene, a flame retardant synergist and a main catalyst; the component B consists of the hexachlorocyclotriphosphazene derivative, dicyclopentadiene, a flame retardant synergist and a cocatalyst.
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