CN111116989B - Reactive flame retardant and preparation method and application thereof - Google Patents

Reactive flame retardant and preparation method and application thereof Download PDF

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CN111116989B
CN111116989B CN201911353327.6A CN201911353327A CN111116989B CN 111116989 B CN111116989 B CN 111116989B CN 201911353327 A CN201911353327 A CN 201911353327A CN 111116989 B CN111116989 B CN 111116989B
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flame retardant
catalyst
solvent
reactive flame
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台启龙
胡颐阳
何明山
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Suzhou Hexumei Technology Co ltd
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    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4025—Esters of poly(thio)phosphonic acids
    • 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 disclosesA reactive flame retardant, a preparation method and an application thereof, wherein the structural formula of the reactive flame retardant is shown as the following formula (I); the preparation method comprises the following steps: mixing methyl dimethyl phosphate, terephthalaldehyde and a catalyst with a solvent, reacting in nitrogen or inert atmosphere, and performing post-treatment to obtain the reactive flame retardant; the catalyst is at least one selected from xylene, 2, 3-dichlorotoluene and trimethylbenzene; the solvent is selected from tetrahydrofuran and/or acetonitrile. The preparation method disclosed by the invention is simple, mild in condition, easy to control and high in product purity, and the prepared reactive flame retardant has the advantages of novel structure, high flame retardant efficiency, environmental friendliness and low toxicity; especially has excellent flame retardant property in an epoxy resin matrix.
Figure DDA0002335221820000011

Description

Reactive flame retardant and preparation method and application thereof
Technical Field
The invention belongs to the technical field of flame retardants, and particularly relates to a reactive flame retardant and a preparation method and application thereof.
Background
The epoxy resin is a thermosetting synthetic resin with excellent performance, is colorless and semitransparent thermosetting light general plastic, has extremely excellent mechanical and chemical properties, and is widely developed and applied in various fields such as adhesives, coatings, electronic and electrical materials, engineering plastics, composite materials and the like. However, the largest drawback in the application of epoxy resins is flammability, which is a problem of most high molecular materials. Due to flammability, the application range of epoxy resins is greatly limited. Therefore, the research on the flame retardant property of the epoxy resin is of great significance for expanding the application of the epoxy resin in various fields.
In recent years, the most popular problem in the flame retardant academia is the environmental pollution caused by halogen-containing materials, and a suitable novel flame retardant is sought to replace the halogen-containing flame retardant. With the research and analysis on the combustion products of materials, a large number of researchers believe that a small amount of dioxin or dibenzofuran is released when a halogen-containing flame retardant is combusted, which is also an important reason why plastic products of the halogen-containing flame retardant cannot be recycled or destroyed. Since there is currently no adequate replacement for all halogen-containing flame retardants, and at the same time, europe and japan have generally banned the use of halogen-containing flame retardants, which has resulted in some manufacturers being in double consideration of "environmental issues" and cost issues, and the use of flame retardants has been discontinued. Thus, manufacturers' practice to reduce manufacturing costs and "respond to environmental regulations" has resulted in serious fire hazards, allowing for the continued burning of non-flame retarded devices with a minimal ignition source. The use of halogen-free flame retardants is promoted by the fact that treatment specifications related to electronic and electric waste gas equipment have been promulgated in Europe and specify that halogen-containing waste needs to be specially treated.
Increasingly, flame retardant research for epoxy resins tends towards non-halogenation of flame retardants. The research of halogen is replaced by other flame retardant elements, the research of high-efficiency, low-toxicity and low-smoke halogen-free environment-friendly flame retardant and novel flame retardant polyolefin materials becomes a research hotspot of scholars at home and abroad, the flame retardant synthesized by DMMP and derivatives thereof becomes one of new flame retardant research directions due to the advantages of no halogen, no toxicity, no migration, long-lasting flame retardant property and the like, and has wide development prospect in the flame retardant application of high polymer materials, but 3 problems are urgently needed to be solved in the development and application of DMMP and derivatives thereof:
1. the research of enhancing the synergistic flame retardant effect of other non-halogen elements in DMMP and derivatives thereof;
2. expanding the types and application fields of DMMP and derivatives thereof;
3. the synthesis process of DMMP and the derivatives thereof is simplified, and the cost is reduced, so that the DMMP has better market competitiveness.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a reactive flame retardant and a preparation method thereof, the preparation method is simple, the condition is mild, the control is easy, the purity of the product is high, and the prepared reactive flame retardant has the advantages of novel structure, high flame retardant efficiency, environmental protection and low toxicity.
In order to solve the above technical problems, the technical solution is specifically adopted as follows:
a reactive flame retardant has a structural formula shown as the following formula (I):
Figure BDA0002335221800000021
the reactive flame retardant has a novel structure, and the carbon-phosphorus structure can better activate an acid source and a carbon source, accelerate the generation of reaction and form a more compact and compact carbon layer structure; when the flame retardant is further mixed with a resin matrix, such as epoxy resin, the C-O bond can form pi-pi bonds with the resin matrix, so that the flame retardant is more easily dissolved in the resin matrix, and the prepared epoxy resin composite material has good mechanical properties.
The invention also discloses a preparation method of the reactive flame retardant, which comprises the following steps:
mixing methyl dimethyl phosphate, terephthalaldehyde, a catalyst and a solvent, reacting in nitrogen or inert atmosphere, and performing post-treatment to obtain the reactive flame retardant;
the catalyst is selected from at least one of xylene, 2, 3-dichlorotoluene and trimethylbenzene;
the solvent is selected from tetrahydrofuran and/or acetonitrile.
The synthesis of the reactive flame retardant is carried out according to the following reaction formula:
Figure BDA0002335221800000031
the preparation process of the invention takes dimethyl methyl phosphate (DMMP) and Terephthalaldehyde (TDCA) as raw materials, screens proper catalyst and solvent, and prepares the target flame retardant with high yield.
In consideration of loss amount and side reaction in synthesis, the dimethyl methyl phosphate and the terephthalaldehyde are preferably fed in a molar ratio of 3-5: 1.
in order to ensure that the substrate can be completely dissolved in the solvent, the molar volume ratio of the methyl dimethyl phosphate to the solvent is preferably 1 mol: (80-100) mL; further preferably, the molar volume ratio is 1 mol: (80-85) mL.
In order to ensure the catalytic efficiency of the catalyst, the molar volume ratio of the dimethyl methyl phosphate to the catalyst is preferably 1 mol: (5-15) mL; further preferably, the molar volume ratio is 1 mol: 10 mL.
Aiming at the specific reaction taking dimethyl methylphosphonate and terephthalaldehyde as raw materials, a special catalyst and a special solvent variety are screened.
Tests show that the types of the catalysts are particularly important for the preparation process, and xylene, 2, 3-dichlorotoluene and trimethylbenzene are preferably used as the catalysts, so that the target product can be prepared with high yield.
When toluene, which is a common benzene solvent, is used as a catalyst for the reaction, the yield of the target product is greatly reduced.
Further preferred is xylene, which has been found by experiments to produce the highest yields of the desired product relative to other catalyst types using xylene as catalyst.
Further experiments show that the type of the solvent is particularly important for the preparation process, and tetrahydrofuran and acetonitrile are preferably used as the solvent, so that the target product can be prepared with high yield.
And when petroleum ether, which is a common organic solvent with similar performance to tetrahydrofuran and acetonitrile, is used as a solvent for the reaction, part of target products can be dissolved in the petroleum ether, and the extraction is difficult, so that the yield is seriously influenced.
The further preferred solvent is tetrahydrofuran, and experiments show that the target product is prepared by using tetrahydrofuran as the solvent in the highest yield compared with other solvent types. In tests, the inventor also unexpectedly finds that the flame-retardant epoxy resin composite material prepared by using the target product flame retardant has relatively higher mechanical properties by using tetrahydrofuran as a solvent.
The reaction temperature is 50-120 ℃, and the reaction time is 3-10 h.
The post-treatment comprises filtering, washing and drying; wherein the washing treatment adopts alcohol solvent such as methanol and ethanol, preferably ethanol.
Preferably:
the catalyst is selected from xylene;
the solvent is selected from tetrahydrofuran;
the feeding molar ratio of the dimethyl methylphosphonate to the terephthalaldehyde is 3: 1;
the molar volume ratio of the dimethyl methyl phosphate to the catalyst is 1 mol: 10 mL.
Tests show that the flame retardant prepared by adopting the specific raw materials has the highest yield, and the epoxy resin composite material further prepared by using the flame retardant not only has excellent flame retardant property, but also has excellent mechanical property and low conductivity.
The reaction type flame retardant prepared by the process has excellent flame retardant efficiency, is particularly suitable for preparing flame retardant epoxy resin, and tests prove that the flame retardant has extremely high flame retardant efficiency in the epoxy resin, can reach the flame retardant level of UL941.6mmV-0 at a lower content, and has an oxygen index as high as 31; more importantly, the C-O group in the flame retardant can be combined with the epoxy resin matrix through pi-pi bonds, so that the flame retardant is uniformly dispersed in the matrix resin, the prepared epoxy resin composite material has good mechanical property, hydrolysis is inhibited, and the conductivity is reduced.
Compared with the prior art, the invention has the following advantages:
1. the invention discloses a novel efficient flame retardant, wherein a carbon-phosphorus structure can better activate an acid source and a carbon source, accelerate the generation of reaction, form a more compact and compact carbon layer structure, can reach the flame retardant grade of UL941.6mmV-0 at a lower content, and has an oxygen index as high as 31; has the advantages of low toxicity and environmental protection, and is beneficial to the sustainable development.
2. The invention discloses a preparation process of the novel efficient flame retardant, which can prepare a target product at high yield under the action of a specific catalyst and a solvent, and has the advantages of simple preparation method, mild conditions, easy control and convenient post-treatment.
3. The novel efficient flame retardant and the epoxy resin are compounded to prepare the composite material, so that excellent flame retardant performance is obtained, meanwhile, the composite material is ensured to have excellent mechanical property due to the C-O bond in the structure of the flame retardant, and the conductivity is also remarkably reduced.
Drawings
FIG. 1 is a nuclear magnetic resonance phosphorous spectrum of the flame retardant prepared in example 1;
FIG. 2 is an infrared spectrum of a flame retardant prepared in example 1;
FIG. 3 is a NMR hydrogen spectrum of the flame retardant prepared in example 1.
Detailed Description
For the purpose of illustrating the technical content, the constructional features, the achieved objects and the effects of the invention in detail, reference will be made to the following detailed description of the embodiments in conjunction with the accompanying drawings.
Example 1
A100 mL three-necked flask equipped with a reflux condenser, a thermometer and a stirring rod was charged with 25mL of tetrahydrofuran as a solvent, 3mL of xylene was added thereto, the mixture was heated to 80 ℃ and stirred uniformly, and then 16.4g of TDCA (0.1mol) and 37.2g of DMMP (0.3mol) were added thereto, followed by addition of N2The reaction is carried out for 5h under the atmosphere and at the temperature of 80 ℃. After the reaction was completed, the mixture was filtered, washed, and dried to obtain a flame retardant as a white solid with a yield of 91%. The nuclear magnetic phosphorus spectrum, the infrared spectrum and the nuclear magnetic hydrogen spectrum of the obtained product are respectively shown in FIG. 1, FIG. 2 and FIG. 3. Observation of the above figures can prove that the target product has the structure shown in formula (I).
22 parts of the flame retardant prepared in this example were mixed with 78 parts of EP (model 4926) and compounded in a 190 ℃ twin-screw extruder.
With reference to the American standard ASTM D618, the composite material is made into UL941.6mm standard bars in an injection molding machine and subjected to standard tests on a horizontal and vertical combustion meter and an oxygen index tester. The flame retardant rating of the specimens tested was: UL941.6mm V-0 rating, oxygen index 31.
According to the national standard GB/T1040.1-2018, the composite material is made into a dumbbell type tensile standard sample bar in an injection molding machine, and standard test is carried out on a tensile tester. The test shows that the tensile strength of the sample strip is 32.14MPa, and the bending strength is 37.85 MPa.
10g of the above composite was added to 50mL of deionized water, and the conductivity was measured to be 3200. mu.s/cm.
Comparative example 1
The flame retardant was prepared by the same procedure as in example 1 except that the catalyst was replaced with toluene from xylene.
The comparative example was tested to produce a flame retardant yield of only 64%.
Comparative example 2
The preparation process of the flame retardant was the same as in example 1 except that the solvent was replaced with petroleum ether from tetrahydrofuran.
The test shows that the yield of the comparative example is greatly reduced to 25 percent, which proves that petroleum ether can not be used as a solvent.
Example 2
A250 mL three-necked flask equipped with a reflux condenser, a thermometer and a stirring rod was charged with 62.5mL of acetonitrile as a solvent, 7.5mL of xylene was added thereto, the mixture was heated to 80 ℃ and stirred uniformly, and then 41g of TDCA (0.25mol) and 93g of DMMP (0.75mol) were added thereto, followed by adding N2The reaction is carried out for 5h under the atmosphere and at the temperature of 80 ℃. After the reaction was completed, the mixture was filtered, washed, and dried to obtain a flame retardant as a white solid with a yield of 79%.
22 parts of the flame retardant obtained in this example were mixed with 78 parts of EP (model 4926) and compounded in a 190 ℃ twin-screw extruder.
The composite material is made into an UL941.6mm standard sample strip in an injection molding machine, and standard test is carried out on a horizontal and vertical combustion instrument and an oxygen index tester. The flame retardant rating of the specimens tested was: UL941.6mm V-0 rating, oxygen index 30.
The composite material is made into a dumbbell type tensile standard sample strip in an injection molding machine, and standard test is carried out on a tensile tester. The test shows that the tensile strength of the sample strip is 26.87MPa, and the bending strength is 29.53 MPa.
10g of the composite was added to 50mL of deionized water and the conductivity was tested to be 3200. mu.s/cm.
Example 3
250mL of tetrahydrofuran was added as a solvent to a 1000mL three-necked flask equipped with a reflux condenser, a thermometer and a stirring rod, 30mL of trimethylbenzene was added thereto, and the mixture was heatedAfter stirring uniformly at 80 ℃, 164g (1mol) of TDCA and 372g of DMMP (3mol) are added, and the mixture is stirred in the presence of N2The reaction is carried out for 5h under the atmosphere and at the temperature of 80 ℃. After the reaction was completed, the mixture was filtered, washed, and dried to obtain a white solid with a yield of 84%.
22 parts of the flame retardant obtained in this example were mixed with 78 parts of EP (model 4926) and compounded in a 190 ℃ twin-screw extruder.
The composite material is made into an UL941.6mm standard sample strip in an injection molding machine, and standard test is carried out on a horizontal and vertical combustion instrument and an oxygen index tester. The flame retardant rating of the specimens tested was: UL941.6mm V-0 rating, oxygen index 30.
The composite material is made into a dumbbell type tensile standard sample strip in an injection molding machine, and standard test is carried out on a tensile tester. The test shows that the tensile strength of the sample strip is 31.14MPa, and the bending strength is 35.85 MPa.
10g of the composite was added to 50ml of deionized water and the conductivity was measured to be 3200. mu.s/cm.
Comparative example 3
22 parts of DMMP were mixed with 78 parts of EP (model 4926) and compounded on a 190 ℃ twin-screw extruder.
The composite material is made into an UL941.6mm standard sample strip in an injection molding machine, and standard test is carried out on a horizontal and vertical combustion instrument and an oxygen index tester. The flame retardant rating of the specimens tested was: UL941.6mm V-2 rating, oxygen index 24.
The composite material is made into a dumbbell type tensile standard sample strip in an injection molding machine, and standard test is carried out on a tensile tester. The test shows that the tensile strength of the sample strip is 23.94MPa, and the bending strength is 25.65 MPa.
10g of the composite was added to 50mL of deionized water and tested for conductivity of 4500 uS/cm.
The novel efficient flame retardant disclosed by the invention contains phosphorus which is a flame retardant element, can participate in the solidification of polyolefin, has the characteristics of high flame retardant efficiency, no halogen, low smoke, low toxicity and the like, accords with the current concept of protecting the ecological environment, and reduces the generation of toxic gas and corrosive gas in the combustion process.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (4)

1. A method for preparing a reactive flame retardant is characterized by comprising the following steps:
mixing methyl dimethyl phosphate, terephthalaldehyde, a catalyst and a solvent, reacting in nitrogen or inert atmosphere, and performing post-treatment to obtain the reactive flame retardant;
the catalyst is selected from at least one of dimethylbenzene and trimethylbenzene;
the solvent is selected from tetrahydrofuran;
the feeding molar ratio of the dimethyl methylphosphonate to the terephthalaldehyde is 3-5: 1;
the molar volume ratio of the dimethyl methyl phosphate to the solvent is 1 mol: (80-100) mL;
the molar volume ratio of the dimethyl methyl phosphate to the catalyst is 1 mol: (5-15) mL;
the reaction temperature is 50-120 ℃, and the reaction time is 3-10 h;
the post-treatment comprises filtering, washing and drying.
2. The method of claim 1, wherein the catalyst is selected from xylene.
3. The method for producing a reactive flame retardant according to claim 1 or 2, characterized in that:
the feeding molar ratio of the dimethyl methylphosphonate to the terephthalaldehyde is 3: 1;
the molar volume ratio of the dimethyl methyl phosphate to the catalyst is 1 mol: 10 mL.
4. Use of a reactive flame retardant prepared according to the process of claim 1 in the preparation of a flame retardant epoxy resin.
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