CN111484521B - Phosphorus-containing acrylate flame retardant and preparation method and application thereof - Google Patents

Phosphorus-containing acrylate flame retardant and preparation method and application thereof Download PDF

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CN111484521B
CN111484521B CN202010336771.3A CN202010336771A CN111484521B CN 111484521 B CN111484521 B CN 111484521B CN 202010336771 A CN202010336771 A CN 202010336771A CN 111484521 B CN111484521 B CN 111484521B
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flame retardant
phosphorus
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acrylate flame
soft foam
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马超
周峰
胡伟兆
汪碧波
宋磊
胡源
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University of Science and Technology of China USTC
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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
    • C07F9/28—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
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
    • 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
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4075—Esters with hydroxyalkyl compounds
    • 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
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4084—Esters with hydroxyaryl compounds
    • 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
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5304—Acyclic saturated phosphine oxides or thioxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

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Abstract

The invention discloses a phosphorus-containing acrylate flame retardant and a preparation method and application thereof, wherein the phosphorus-containing acrylate flame retardant has the following structural general formula:
Figure DDA0002466886010000011
wherein R is1、R3Selected from hydrogen or methyl, R2Selected from methyl, ethyl, propyl, butyl or phenyl. The flame retardant is liquid and is added into the polyurethane flexible foam, so that the production process of the polyurethane flexible foam is not influenced. After foaming, the double bonds are polymerized to form a cross-linked network by heating, so that the flame retardance of the soft foam can be improved, the flame retardant can not be separated out from the polymer, and the compression strength of the soft foam can be improved.

Description

Phosphorus-containing acrylate flame retardant and preparation method and application thereof
Technical Field
The invention belongs to the field of flame retardant synthesis and flame-retardant polymer materials, and particularly relates to a phosphorus-containing acrylate flame retardant, and a preparation method and application thereof.
Background
The open-cell structure of the flexible polyurethane foam further deteriorates its flame retardancy, and the oxygen index of the ordinary flexible foam is only about 17%, which is a flammable material. Although additive flame retardants have the advantages of low impact on the production process, ease of use, and low cost, they are prone to precipitation in polymers, which affects the long-term use of materials. For polyurethane flexible foams, liquid flame retardants are more suitable for their production process, and improving the compressive strength of the flexible foams is beneficial to improving the supporting ability of the flexible foams as materials for cushions, headrests, mattresses and the like.
The acrylate is easily polymerized under the action of a free radical initiator, and a network structure can be formed after the multifunctional acrylate is polymerized. The polymer chain segments in the cross-linked network are restricted in movement and do not precipitate in the matrix. And the network structure and the crosslinking density can be conveniently adjusted by adjusting the structure and the addition amount of the monomer, so that the mechanical property of the material is controlled. Therefore, the phosphorus-containing acrylate flame retardant is added into the polyurethane flexible foam, and is heated and polymerized to form a cross-linked network after foaming, so that the flame retardance can be improved, the problem of precipitation can be solved, and the compression strength of the flexible foam can be improved.
Disclosure of Invention
The invention aims to solve the problems that an additive flame retardant is easy to separate out, a liquid flame retardant is needed in a soft foam production process, and the compression strength of soft foam is improved, and provides a phosphorus-containing acrylate flame retardant, and a preparation method and application thereof. According to the invention, the phosphorus-containing acrylate flame retardant and the free radical initiator are added into the raw materials of the polyurethane soft foam, and the mixture is heated and polymerized to form a cross-linked network after foaming, so that the flame retardance of the soft foam can be improved, the problem of precipitation of the flame retardant can be solved, and the compression strength of the soft foam can be improved.
The phosphorus-containing acrylate flame retardant has the following structural general formula:
Figure BDA0002466884000000011
wherein R is1、R3Selected from hydrogen or methyl, R2Selected from methyl, ethyl, propyl, butyl or phenyl.
The preparation method of the phosphorus-containing acrylate flame retardant comprises the following steps:
mixing hydroxymethylphosphonic acid diester or trimethylolpropane phosphine oxide with a polymerization inhibitor, an acid-binding agent and a solvent, then dropwise adding an acyl chloride compound under an ice bath condition, and reacting at room temperature for 1-24 hours after dropwise adding is finished; after the reaction is finished, washing the reaction product by dilute hydrochloric acid and sodium bicarbonate water solution in sequence, and removing the solvent from the organic phase by reduced pressure distillation to obtain the target product.
The hydroxymethyl phosphonic diester is selected from one of hydroxymethyl phosphonic acid dimethyl ester, hydroxymethyl phosphonic acid diethyl ester, hydroxymethyl phosphonic acid dipropyl ester, hydroxymethyl phosphonic acid dibutyl ester and hydroxymethyl phosphonic acid diphenyl ester.
The polymerization inhibitor is selected from one or more of phenol, p-methoxyphenol, an antioxidant 1010 and 2, 4-dimethyl-6-tert-butylphenol; the addition amount of the polymerization inhibitor is 0-0.01 time of the mass of the acyl chloride compound.
The acid-binding agent is selected from one or more of triethylamine, tripropylamine, tributylamine, N-dimethylaniline and N, N-diethylaniline; the addition amount of the acid-binding agent is 1 to 1.5 times of the molar weight of the acyl chloride compound.
The solvent is selected from one or more of dichloromethane, trichloromethane, carbon tetrachloride, 1, 2-dichloroethane and chlorobenzene; the addition amount of the solvent is 5 to 30 times of the mass of the acyl chloride compound.
The acyl chloride compound is acryloyl chloride or methacryloyl chloride; the molar ratio of the acyl chloride compound to the hydroxyl contained in the phosphorus-containing compound is 1:1-1.5: 1. Phosphorus-containing compounds are referred to as bis-hydroxymethylphosphonic acid or tris-hydroxymethylphosphine oxide.
The application of the phosphorus-containing acrylate flame retardant is that the phosphorus-containing acrylate flame retardant is added into the raw materials of the polyurethane soft foam, and the foaming and the heating polymerization form a cross-linked network, so that the flame retardance of the soft foam can be improved, the problem of precipitation of the flame retardant is solved, and the compression strength of the soft foam can be improved. Specifically, a free radical initiator is dissolved into a flame retardant, then the mixture is added into the raw materials of the general polyurethane flexible foam, and after the foaming is finished, the mixture is heated for 1 to 48 hours at the temperature of between 60 and 150 ℃.
The free radical initiator is selected from one or more of azodiisobutyronitrile and dibenzoyl peroxide. The addition amount of the initiator is 0.001-0.05 times of the mass of the flame retardant.
The addition amount of the flame retardant is 0.05-0.3 time of the total mass of the flame-retardant polyurethane flexible foam.
Further, the flame retardant is formed by compounding a compound shown in a formula I and a compound shown in a formula II, and the mass ratio is 0-10:1, preferably 1: 1.
The diester of hydroxymethylphosphonic acid and the tris can be purchased commercially or synthesized by reference to literature, for example: journal of Polymer Science, Part A: Polymer Chemistry,2012,50(12): 2432-.
The addition of the phosphorus-containing acrylate liquid flame retardant (containing the initiator) does not influence the production process of the polyurethane flexible foam, and is beneficial to the application of the flame retardant and the polyurethane flexible foam. The flame retardants are polymerized to form a cross-linked network structure through heat treatment after foaming, and the macromolecular chain segments of the cross-linked structure are limited in movement and cannot be separated out from the polymer. And the addition of the flame retardant containing three acrylate groups can obtain a polyacrylate network with high crosslinking density after free radical polymerization, and the higher strength of the polyacrylate network improves the compression strength of the soft foam.
The invention has the beneficial effects that:
1. the flame retardant is liquid, and does not influence the production process of the soft foam.
2. The soft foam prepared by the invention can improve the flame retardance, the flame retardant can not be separated out from the soft foam, and the compression strength can be improved.
Detailed Description
The process of the invention is further illustrated by the following specific examples, except that the diesters of hydroxymethylphosphonic acid and tris-hydroxyphenylphosphine oxide are synthesized according to the literature and the other starting materials are commercially available.
Example 1:
adding 45.6g of dimethyl hydroxymethylphosphonate, 47g of triethylamine and 500mL of dichloromethane into a flask, then dropwise adding 33.7g of acryloyl chloride in an ice bath, and reacting for 12 hours at room temperature after dropwise adding is finished; washing twice by dilute hydrochloric acid, washing once by sodium bicarbonate water solution, and evaporating an organic phase to obtain a light yellow liquid product, wherein the structural formula is as follows:
Figure BDA0002466884000000031
example 2:
adding 45.6g of dimethyl hydroxymethylphosphonate, 47g of triethylamine and 500mL of dichloromethane into a flask, then dropwise adding 38.9g of methacryloyl chloride in an ice bath, and reacting for 12 hours at room temperature after dropwise adding is finished; washing twice by dilute hydrochloric acid, washing once by sodium bicarbonate water solution, and evaporating an organic phase to obtain a yellow liquid product, wherein the structural formula is as follows:
Figure BDA0002466884000000032
example 3:
adding 86g of diphenyl hydroxymethylphosphonate, 47g of triethylamine, 0.05g of p-methoxyphenol and 500mL of dichloromethane into a flask, dropwise adding 33.7g of acryloyl chloride in an ice bath, and reacting at room temperature for 12 hours after dropwise adding; washing twice by dilute hydrochloric acid, washing once by sodium bicarbonate water solution, and evaporating an organic phase to obtain a yellow liquid product, wherein the structural formula is as follows:
Figure BDA0002466884000000033
example 4:
15g of trishydroxymethyl phosphine oxide, 39g of triethylamine, 0.0648g of 2, 4-dimethyl-6-tert-butylphenol and 300mL of methylene chloride were charged in a flask, and then 35g of acryloyl chloride was added dropwise while cooling on ice. After completion of the dropwise addition, the reaction was carried out at room temperature for 12 hours. Washing twice by dilute hydrochloric acid, washing once by sodium bicarbonate water solution, and evaporating an organic phase to obtain a dark yellow liquid product, wherein the structural formula is as follows:
Figure BDA0002466884000000041
example 5:
AIBN was dissolved in the flame retardant obtained in examples 1 and 4, polyether polyol 330, A33, dibutyltin dilaurate, silicone oil and distilled water were added, after stirring and mixing uniformly, TDI 80/20 was added, after high-speed stirring, the mixture was poured into a closed mold for foaming, and after foaming was completed, the mixture was heated at 120 ℃ for 12 hours. The formulations and properties of the soft foams obtained are shown in the following table:
Figure BDA0002466884000000042
gel content: measured after soaking in tetrahydrofuran for 24 hours
Compressive strength: compressive stress at 50% strain
From the above test results, it can be seen that the prepared flame-retardant flexible polyurethane foam has a high gel content (hardly separated), better flame retardancy (LOI) and higher compressive strength, compared to the flexible polyurethane foam without the addition of the phosphorous acrylate.

Claims (3)

1. The application of the phosphorus-containing acrylate flame retardant is characterized in that:
the phosphorus-containing acrylate flame retardant is added into the raw materials of the polyurethane soft foam, and is heated and polymerized to form a cross-linked network after foaming, so that the flame retardance of the soft foam can be improved, the problem of precipitation of the flame retardant is solved, and the compression strength of the soft foam can be improved; dissolving a free radical initiator into a phosphorus-containing acrylate flame retardant, adding the phosphorus-containing acrylate flame retardant into the raw materials of the general polyurethane soft foam, and heating the mixture for 1 to 48 hours at the temperature of between 60 and 150 ℃ after the foaming is finished; the addition amount of the phosphorus-containing acrylate flame retardant is 0.05-0.3 time of the total mass of the polyurethane flexible foam;
the structural general formula of the phosphorus-containing acrylate flame retardant is as follows:
Figure FDA0003061570110000011
wherein R is1、R3Selected from hydrogen or methyl, R2Selected from methyl, ethyl, propyl, butyl or phenyl.
2. Use according to claim 1, characterized in that:
the free radical initiator is selected from one or more of azodiisobutyronitrile and dibenzoyl peroxide; the addition amount of the free radical initiator is 0.001-0.05 times of the mass of the phosphorus-containing acrylate flame retardant.
3. Use according to claim 1, characterized in that:
the phosphorus-containing acrylate flame retardant is formed by compounding a compound shown as a formula I and a compound shown as a formula II in a mass ratio of 0-10: 1.
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