CN112778368A - Dialkyl phosphinate containing active epoxy group and preparation and application thereof - Google Patents

Dialkyl phosphinate containing active epoxy group and preparation and application thereof Download PDF

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CN112778368A
CN112778368A CN202110006998.6A CN202110006998A CN112778368A CN 112778368 A CN112778368 A CN 112778368A CN 202110006998 A CN202110006998 A CN 202110006998A CN 112778368 A CN112778368 A CN 112778368A
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flame retardant
epoxy group
active epoxy
dialkyl
dialkylphosphinate
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CN112778368B (en
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李金忠
陈章明
雷华
杨建伟
王家凯
曹俊华
王海峰
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Jiangsu Liside New Materials Co ltd
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    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C07F9/65502—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a three-membered ring
    • C07F9/65505—Phosphonic acids containing oxirane groups; esters thereof
    • 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
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract

The invention discloses a dialkyl phosphinate containing active epoxy groups, a preparation method thereof, and application of the dialkyl phosphinate as a flame retardant and a flame retardant material. The structure is shown in any one of the following formulas (I) and (II):
Figure DDA0002883884330000011
in the formulae (I), (II), R1、R2Are each independently selected from C1‑C24Alkyl, cycloalkyl, aryl or alkenyl of R3Independently selected from C1‑C10Linear or branched alkylene of, or C6‑C10Is an arylene, alkylarylene or arylalkylene group, m is an integer of 1 to 3, and n is an integer of 1 to 3. The preparation method comprises the following steps: with metal dialkylphosphinate and halogenated epoxyThe product is obtained by reaction of raw materials. The invention has the advantages that: simultaneously has two structures of dialkyl phosphinic acid and epoxy active group; active epoxy groups, which can be used to prepare alcohols, esters and epoxy resins; can be used as a flame retardant, alone or in combination with other flame retardants.

Description

Dialkyl phosphinate containing active epoxy group and preparation and application thereof
Technical Field
The invention relates to the field of dialkyl phosphinates, in particular to a dialkyl phosphinate containing active epoxy groups and preparation and application thereof.
Background
The organic phosphate is a main variety of organic phosphorus series, and is mainly obtained by reacting phosphoric acid, phosphorous acid, methyl phosphonic acid and the like with alcohol. Common organic phosphates are triethyl phosphate, trimethyl phosphite, dimethyl methylphosphonate, diethyl ethylphosphonate, and the like.
Less organophosphates of hypophosphorous acid are reported, less esters of dialkylphosphinic acids are reported, and dialkylphosphinic esters containing epoxy groups are not reported. Hypophosphorous acid and derivatives thereof have been widely used due to their good flame retardant properties. However, many metal salts of hypophosphorous acid and its derivatives (such as patent technologies disclosed in CN1660857A and CN 106967116A) are used, and these metal salt compounds have no reactivity and are usually added into a polymer matrix in the form of a filler in a large amount, while reactive flame retardants can react with the matrix polymer, so that the flame retardant structure enters into the polymer molecular chain, and therefore, the flame retardant efficiency is higher, and the amount of the flame retardant can be greatly reduced. In addition, salt compounds are usually solid powders, which are not suitable for some applications requiring transparency. Therefore, it is necessary to develop a flame retardant which is reactive and liquid.
The dialkyl phosphinic acid group has better flame retardant property, the epoxy group has the reactivity of continuous ring-opening reaction, the combination of the dialkyl phosphinic acid group and the epoxy group can exert the two characteristics of flame retardant property and epoxy activity, and the compound is different from metal salt and is usually liquid at normal temperature. Therefore, the flame retardant has the advantages of reaction activity, liquid and flame retardant function.
Disclosure of Invention
Aiming at the technical problems and the defects in the field, the invention provides the dialkyl phosphinate containing the active epoxy group, compared with metal salt flame retardants of hypophosphorous acid and derivatives thereof, the dialkyl phosphinate containing the active epoxy group has the advantages of high flame retardant efficiency, capability of meeting transparent application requirements and the like when being liquid; and the molecule contains two P-C bonds at the same time, which does not belong to the chemicals for the key monitoring of the International banning chemical organization, and the production, the popularization and the use are convenient.
An active epoxy group-containing dialkylphosphinic ester compound, which has the structure shown in any one of the following formulas (I) and (II):
Figure BDA0002883884310000021
in the formulae (I), (II), R1、R2Are each independently selected from C1-C24Alkyl (including alkanyl, etc.), cycloalkyl, aryl or alkenyl, R3Independently selected from C1-C10Linear or branched alkylene of, or C6-C10Is an arylene, alkylarylene or arylalkylene group, m is an integer of 1 to 3, and n is an integer of 1 to 3.
R1、R2Respectively include but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, phenyl, alkenyl, and the like.
R3Including but not limited to: methylene, ethylene, phenylene, and the like.
The present invention provides a novel organophosphate compound, which has not been reported in the literature, and has two core characteristic structures, i.e., a dialkylphosphinic acid structure and an epoxy structure, in the structural formula. The dialkyl hypophosphorous acid structure has good flame retardance, while the epoxy structure has reactivity, and can perform ring-opening reaction with various organic groups to form alcohol or ester, or be used as a monomer of epoxy resin for preparing epoxy resin polymers. Meanwhile, the structural compound is usually liquid and does not influence the transparency of the material when applied to the polymer.
When R is1，R2Are both ethyl and R3When m is 1 and n is 1, the structure of the dialkyl phosphinic acid ester containing the active epoxy group is shown as the following formula (III):
Figure BDA0002883884310000031
when R is1Is ethyl, R2Is butyl, R3When m is 1 and n is 1, the structure of the dialkyl phosphinic acid ester containing the active epoxy group is shown as the following formula (IV):
Figure BDA0002883884310000032
when R is1Is methyl, R2Is ethyl, R3When m is 1 and n is 1, the structure of the dialkyl phosphinic acid ester containing the active epoxy group is shown as the following formula (V):
Figure BDA0002883884310000033
when R is1Is ethyl, R2Is phenyl, R3When m is 1 and n is 1, the structure of the dialkyl phosphinic acid ester containing the active epoxy group is shown as the following formula (VI):
Figure BDA0002883884310000034
when R is1，R2Are both ethyl and R3An active epoxy group-containing dialkylphosphinate compound described by the formula (I) wherein m is 1 and n is 1(VII) is as follows:
Figure BDA0002883884310000041
the invention also provides a preparation method of the dialkyl phosphinic acid ester containing the active epoxy group, which comprises the following steps: taking dialkyl metal phosphinate and halogenated epoxy compound as raw materials, and reacting to obtain the dialkyl phosphinate containing the active epoxy group;
the reaction process is as follows:
Figure BDA0002883884310000042
wherein, M is a metal element and is selected from one or more of sodium, potassium, calcium, magnesium, aluminum, zinc and barium, X is selected from one or more of fluorine, chlorine, bromine and iodine, and k is the valence number of the metal element M.
In the above reaction process, the metal dialkylphosphinate participates in the reaction in the form of a solid, the halogenated epoxy compound is a liquid, and the reaction is a liquid-solid reaction.
The above reaction process may be carried out under the action of a catalyst, preferably a phase transfer catalyst, including cationic polyalkyl quaternary ammonium salt compounds, cationic halogenated polyalkyl quaternary ammonium salt compounds, anionic alkyl sulfate compounds, alkyl benzene sulfonate, nonionic surfactant, quaternary phosphonium salt, etc. Preferred catalysts include: polyalkyl ammonium chloride, polyalkyl ammonium bromide, alkyl sulfate, alkyl sulfonate, alkyl benzene sulfonate, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, alkyl phosphate, polyglycol, polyol, etc. The above reaction process can be selected to be carried out for a long time without adding a catalyst, or one or more of the catalysts can be added, so that the reaction is accelerated.
Preferably, the reaction temperature is 40-200 ℃, the pressure is 0-5MPa, and the time is 0.1-20 hours.
After the reaction is finished, the dialkyl phosphinate compound containing epoxy groups with high purity can be obtained by post-treatment processes such as filtration, distillation and the like.
The synthesis process may be carried out batchwise or continuously. The continuous process may be carried out using a series of reaction apparatus, such as a pipe reactor.
The invention also provides the application of the dialkyl phosphinate containing active epoxy groups in preparation or serving as a flame retardant.
The person skilled in the art can use the dialkylphosphinic acid ester of the invention as a flame retardant alone or in combination with other flame retardants according to the actual need. Other flame retardants described herein include (1) phosphate flame retardants such as phosphate flame retardants, triethyl phosphate (TEP), tributyl phosphate (TBP), trioctyl phosphate, triphenyl phosphate (TPP), trixylyl phosphate (TXP), tris (2-chloroisopropyl) phosphate (TCPP), tris (2-chloroethyl) phosphate (TCEP), 3-tris (dichloropropyl) phosphate (TDCPP); dimethyl methylphosphonate (DMMP); diethyl ethylphosphonate (DEEP), etc. (2) nitrogen-containing flame retardants such as ammonium polyphosphate, melamine cyanurate, melamine polyphosphate, piperazine phosphate, piperazine pyrophosphate, etc. (3) alkyl phosphinates such as aluminum diethylphosphinate, aluminum ethylbutylphosphinate, aluminum dibutylphosphinate, etc.; (4) inorganic flame retardants, such as aluminum hydroxide, zinc oxide, tin oxide, and the like, are selected in different amounts depending on the epoxy application system. Typically, the flame retardant is used in an amount of between 1 and 35 wt%. Optionally, the flame retardant is used in an amount between 1 and 25 wt%.
The invention also provides application of the dialkyl phosphinate containing active epoxy groups in preparation of flame retardant materials, wherein the flame retardant materials comprise at least one of epoxy materials, polyester, polyurethane materials, flame-retardant carbon fiber materials, flame-retardant glass fiber materials and alcohol compounds.
The epoxy material can adopt the dialkyl phosphinate of the invention as a reactive flame retardant to participate in the synthesis of epoxy resin.
In the present invention, C1-C24And the like refer to the number of carbon atoms contained in the group.
In the present invention, the "alkyl group" is a group formed by losing any one hydrogen atom on the molecule of the alkane compound. The alkane compound includes straight-chain alkane, branched alkane, etc. The term "aryl" is used analogously.
In the present invention, the "alkylene group" is a group formed by losing any two hydrogen atoms on the molecule of the alkane compound. The alkane compound comprises straight-chain alkane and branched-chain alkane. The term "arylene" is used analogously.
Compared with the prior art, the invention has the main advantages that:
1. the flame retardant has two characteristic structures, namely dialkyl phosphinic acid and active epoxy group in a molecule.
2. The dialkyl phosphinate contains active epoxy groups without ring opening, can be added into an epoxy resin system, simultaneously participates in reaction and is combined in an epoxy compound, has reaction activity, and can react into a polymer molecular chain, so that the dosage of a flame retardant is greatly reduced.
3. The dialkyl phosphinate of the invention can be used for preparing flame-retardant epoxy materials, and the flame retardant is used alone or mixed with other flame retardants. The epoxy material containing the flame retardant has good flame retardant property.
4. The dialkylphosphinate compounds of the present invention are generally liquid and do not affect the transparency of the matrix material.
5. The dialkyl phosphinate compound can also be used for preparing phosphorus-containing alcohol and ester compounds with a flame retardant function.
Drawings
FIG. 1 is a schematic representation of the NMR spectra of the product obtained in example 1 of the present invention;
FIG. 2 is a schematic diagram of the NMR spectrum of the product obtained in example 1 of the present invention;
FIG. 3 is a schematic nuclear magnetic resonance phosphorus spectrum of sodium diethylhypophosphite used as a raw material in example 1 of the present invention;
FIG. 4 is a schematic nuclear magnetic resonance hydrogen spectrum of sodium diethylhypophosphite used as a raw material in example 1 of the present invention;
FIG. 5 is a schematic diagram showing the NMR spectrum of epichlorohydrin used as a raw material in example 1 of the present invention;
FIG. 6 is a DSC graph of a mixture of the compound of formula (III) of example 2 and an epoxy resin curing agent DDS.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Unless otherwise specified, the starting materials were all purchased commercially.
Nuclear Magnetic Resonance (NMR) testing: the model used was AVANCE DMX 400MHz, Bruker, Switzerland; the test method comprises the following steps:
1h NMR in CDCl3As a solvent, tetramethylsilane as an internal standard;
31p NMR, using deuterated chloroform as a solvent, using 85% phosphoric acid as an external standard, and scanning 64 times;
by passing31P NMR and1h NMR can determine the molecular structure of the prepared compound.
In the following examples, the yield was calculated as: (product weight/product theoretical weight). times.100%.
Example 1 preparation of a Compound having the Structure in formula (III)
Figure BDA0002883884310000071
288g (2mol) of sodium diethylphosphinate, 6.0g of catalyst polyalkylammonium bromide and 600g of epoxy chloropropane are added into a pressure kettle provided with a stirrer and a thermometer, stirring is started, nitrogen is introduced for replacement for three times, the temperature is increased to 110-120 ℃, vacuum is started after stirring is carried out for 10 hours under the condition of heat preservation, and the unreacted epoxy chloropropane is removed. The product was filtered, distilled and purified to obtain 338g of finished liquid product with a conversion rate of 95%.
The obtained product was characterized by NMR-P spectrum and NMR-H spectrum, and the results are shown in FIG. 1 (phosphorus spectrum nuclear magnetic) and FIG. 2 (hydrogen spectrum nuclear magnetic). As can be seen by comparison with FIG. 3 (phosphorus nuclear magnetic spectrum of sodium diethylhypophosphite), in FIG. 1, the peak shifted by 60 to 65ppm represents the structure of diethylhypophosphite, and the newly synthesized compound contains the structure of diethylhypophosphite but is slightly shifted from that of sodium diethylhypophosphite. By comparing the hydrogen spectrum nuclear magnetization of FIG. 2 with that of FIGS. 4 and 5, it can be found that the peak between the offsets 3.7 to 4.3 in FIG. 2 represents the new structure (P-O-CH)2) The peaks with offsets of 0.9 to 1.8 represent the hydrogen of the two ethyl groups attached to the phosphorus atom and the peaks with offsets of 2.4 to 2.9 represent the epoxy group structure. The resulting compound is shown to be an epoxy group-containing dialkylphosphinate ester represented by formula (III), which achieves the object of the present invention.
Use of dialkyl phosphinates containing epoxy active groups
Example 2 preparation of flame retardant epoxy Material
1) Reaction of a Compound of formula (III) with DDS
The compound of formula (III) prepared in example 1 and an epoxy resin curing agent DDS are uniformly mixed according to a certain proportion, a small amount of samples are taken to test a DSC curve, and the reaction of the compound of formula (III) and the DDS is judged according to an exothermic peak in the DSC curve. The DSC curve obtained from the test is shown in figure 6.
From the results, the DSC curve of DDS alone shows that DDS has a melting point peak at 179.3 ℃ as being a solid, which is an endothermic process; the exothermic peak of the compound (diethyl phosphinic acid glycidyl ester) with the structure (III) at 218.3 ℃ shows that the compound with the structure (III) generates ring-opening reaction and releases heat; whereas on the DSC curve of the mixture of compound of structure (III) and DDS there are two exothermic peaks, namely 210.0 ℃ and 264.1 ℃, which are clearly different compared to the exothermic peaks of the compound of structure (III) alone: the first is that the exothermic peak is advanced and is shifted from 218 ℃ to 210 ℃; secondly, the heat release is obviously different, the self-opening ring heat release of the compound with the structure (III) alone is 0.04623mW/mg, while the heat release of the mixture of the compound with the structure (III) and the DDS is 0.2142mW/mg, and the heat release is obviously larger than that of the compound with the structure (III) alone. These results demonstrate that the compound of structure (III) reacts with DDS, showing its reactivity.
2) Preparation of flame-retardant epoxy material
The dialkyl phosphinate prepared in the embodiment 1 of the invention is added into epoxy resin, and the specific operation process is as follows:
dissolving a curing agent DDS and butanone in a cup, adding the DDS and butanone into epoxy resin E-44, adding the diethyl hypophosphorous acid glycidyl ester obtained in the example 1, stirring and dispersing for 1 minute, pouring the mixture into a tetrafluoro mold, removing butanone at the vacuum temperature of 40 ℃ for 1 hour, heating to 120 ℃ for 1 hour and heating to 180 ℃ for 1 hour, cooling, and discharging the vacuum to obtain a sample plate with the thickness of 2 mm. The specific formulation is shown in table 1.
Comparative example 1
The same as example 2, except that the system was not charged with the glycidyl diethylphosphinate obtained in example 1, the specific formulation composition was as shown in Table 1, and the oxygen index results were as shown in Table 2.
Comparative example 2
The formulation is as in example 2, except that the flame retardant in example 2 is replaced with aluminum diethylphosphinate, the specific formulation composition is shown in Table 1, and the oxygen index results are shown in Table 2.
TABLE 1 epoxy master preparation formulation
Name of raw materials Example 2 Comparative example 1 Comparative example 2
Epoxy resin (g) 50 50 50
Example 1 Dialkylphosphinic acid ester (g) 5 0 0
Aluminum diethyl phosphinate (g) 0 0 5
Curing agent DDS (g) 15 15 15
Butanone (g) 45 45 45
The raw materials were prepared and made into panels according to the formulation of table 1, and the panels were cut into strips of 120 × 10 × 2mm, and each five strips were tested for oxygen index control, which is a method of characterizing the flame retardant properties of the material, with higher oxygen index indicating better flame retardant properties of the material. The results are shown in Table 2.
TABLE 2 limiting oxygen index test results
Test item Example 2 Comparative example 1 Comparative example 2
Oxygen Index (LOI) 33 18 27
According to application results, the limit oxygen index of the epoxy resin is greatly improved compared with that of the epoxy resin without the flame retardant by adding 5g (accounting for 10 percent of the epoxy resin content) into the system and is improved to 33 from 18, and compared with the conventional additive type aluminum dialkylphosphinate (no reaction activity, powder) flame retardant, under the condition that the adding amount is the same, the oxygen index is only improved to 27, the flame retardant performance is inferior to that of the epoxy group-containing dialkylphosphinate, and the epoxy group-containing dialkylphosphinate has higher flame retardant performance than that of a hypophosphite flame retardant.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.

Claims (10)

1. An active epoxy group-containing dialkyl phosphinate, characterized by having the structure shown in any one of the following formulas (I) and (II):
Figure FDA0002883884300000011
in the formulae (I), (II), R1、R2Are each independently selected from C1-C24Alkyl, cycloalkyl, aryl or alkenyl of R3Independently selected from C1-C10Linear or branched alkylene of, or C6-C10Is an arylene, alkylarylene or arylalkylene group, m is an integer of 1 to 3, and n is an integer of 1 to 3.
2. The active epoxy group-containing dialkylphosphinate of claim 1, having the structure of formula (III):
Figure FDA0002883884300000012
3. the active epoxy group-containing dialkylphosphinate of claim 1, having the structure represented by the following formula (IV):
Figure FDA0002883884300000021
4. the active epoxy group-containing dialkylphosphinate of claim 1, having the structure represented by the following formula (V):
Figure FDA0002883884300000022
5. the active epoxy group-containing dialkylphosphinate of claim 1, having the structure of formula (VI):
Figure FDA0002883884300000023
6. the active epoxy group-containing dialkylphosphinate of claim 1, having the structure represented by formula (VII):
Figure FDA0002883884300000024
7. the method for preparing an active epoxy group-containing dialkylphosphinic ester according to any one of claims 1 to 6, comprising: taking dialkyl metal phosphinate and halogenated epoxy compound as raw materials, and reacting to obtain the dialkyl phosphinate containing the active epoxy group;
the reaction process is as follows:
Figure FDA0002883884300000031
wherein, M is a metal element and is selected from one or more of sodium, potassium, calcium, magnesium, aluminum, zinc and barium, X is selected from one or more of fluorine, chlorine, bromine and iodine, and k is the valence number of the metal element M.
8. The process according to claim 7, wherein the reaction is carried out at a temperature of 40 to 200 ℃ and a pressure of 0 to 5MPa for a period of 0.1 to 20 hours.
9. Use of the dialkyl phosphinate compound containing active epoxy groups according to any one of claims 1 to 6 in the preparation or as a flame retardant.
10. The use of the dialkyl phosphinate containing active epoxy groups according to any one of claims 1 to 6 in the preparation of flame retardant materials, wherein the flame retardant materials comprise at least one of epoxy materials, polyesters, polyurethane materials, flame retardant carbon fiber materials, flame retardant glass fiber materials, and alcohol compounds.
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CN112778368B (en) 2022-08-23

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