CN112442076A - 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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CN112442076A
CN112442076A CN201910803190.3A CN201910803190A CN112442076A CN 112442076 A CN112442076 A CN 112442076A CN 201910803190 A CN201910803190 A CN 201910803190A CN 112442076 A CN112442076 A CN 112442076A
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flame retardant
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潘庆崇
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Guangdong Guangshan New Materials Co ltd
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    • 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
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    • 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
    • C07F9/4009—Esters containing the structure (RX)2P(=X)-alk-N...P (X = O, S, Se)
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    • 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
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    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
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    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
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    • C08K5/5333—Esters of phosphonic acids
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    • 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
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

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Abstract

The invention relates to a reactive flame retardant, a preparation method and application thereof.

Description

Reactive flame retardant and preparation method and application thereof
Technical Field
The invention belongs to the field of high polymer materials, and relates to a reactive flame retardant, and a preparation method and application thereof.
Background
Electronic products represented by mobile phones, computers, video cameras, and electronic game machines, home and office electric products represented by air conditioners, refrigerators, television images, audio products, and various products used in other fields are required to have flame retardancy and heat resistance for safety in most of the products.
In the traditional technology, inorganic flame-retardant substances such as aluminum hydroxide hydrate, magnesium hydroxide hydrate and other metal hydroxides containing crystal water are generally added into a material system, and organic flame-retardant substances with higher halogen content such as brominated bisphenol A, brominated bisphenol A epoxy resin and the like are added into the material system, so that the product reaches the required flame-retardant performance or grade. To improve the flame retardancy of these organic halogen-containing chemicals, inorganic flame retardant substances such as antimony trioxide, which are not environmentally friendly, are often added to the system.
The halogen-containing flame retardant substances can generate non-degradable or difficultly degradable toxic substances (such as dioxin organic halogen chemical substances) during combustion, pollute the environment and influence the health of human beings and animals.
The halogen-free flame retardant in the prior art has the defects of poor identity with a flame retardant main body, poor water resistance, poor operability, non-uniform flame retardant effect and the like.
Disclosure of Invention
In order to solve the technical problems, the invention provides a reactive flame retardant, a preparation method and an application thereof.
In order to achieve the technical effect, the invention adopts the following technical scheme:
the invention aims to provide a reactive flame retardant, which is obtained by reacting a compound shown in a formula I with a compound containing an unsaturated group to remove at least one molecule of R '-O-R';
Figure BDA0002182892450000021
wherein X is a group VI element or is absent, R1And R2Each independently is any group which satisfies the chemical environment, R' comprises any one of hydrogen and isotope thereof and substituted or unsubstituted alkyl, aryl or heteroaryl, a, b and c are each independently integers which are more than or equal to 0, and a + b + c is less than or equal to 3;
wherein, R' comprises any one of hydrogen and isotopes thereof, and substituted or unsubstituted alkyl, cycloalkyl, aryl or heteroaryl.
Wherein a may be 0,1,2 or 3, b may be 0,1,2 or 3, and c may be 1,2 or 3.
As a preferred embodiment of the present invention, R is1And R2Each independently preferably includes any one of a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryloxy group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted cycloalkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, a substituted or unsubstituted alkylmercapto group, a substituted or unsubstituted arylmercapto group, or a substituted or unsubstituted heteroarylmercapto group.
As a preferred embodiment of the present invention, R preferably includes any one of substituted or unsubstituted alkylene, cycloalkylene, arylene, heteroarylene, alkylenecycloalkyl, alkylenearyl, alkyleneheteroaryl, cycloalkylenearyl, cycloalkyleneheteroaryl, or aryleneheteroaryl.
In a preferred embodiment of the present invention, X is O or S.
As a preferable technical solution of the present invention, the unsaturated group includes any one of a carbon-carbon double bond, a carbon-carbon triple bond, a carbon-oxygen double bond, a carbon-sulfur double bond, or a carbon-nitrogen double bond.
In the present invention, the substituted or unsubstituted alkyl group is preferably a substituted or unsubstituted alkyl group having from C1 to C12 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, or C11).
The substituted or unsubstituted cycloalkyl group is preferably a cycloalkyl group of C3 to C12 (e.g., C4, C5, C6, C7, C8, C9, C10, or C11).
The substituted or unsubstituted aryl group is preferably an aryl group of C6 to C13 (e.g., C7, C8, C9, C10, C11, or C12).
The substituted or unsubstituted heteroaryl group is preferably a C4-C12 (e.g., C5, C6, C7, C8, C9, C10, or C11) substituted or unsubstituted heteroaryl group.
The substituted or unsubstituted alkoxy group is preferably a C1 to C12 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, or C11) substituted or unsubstituted alkoxy group.
The substituted or unsubstituted cycloalkoxy group is preferably a C3 to C12 (e.g., C4, C5, C6, C7, C8, C9, C10, or C11) substituted or unsubstituted cycloalkoxy group.
The substituted or unsubstituted aryloxy group is preferably a C6-C13 (e.g., C7, C8, C9, C10, C11, or C12) substituted or unsubstituted aryloxy group.
The substituted or unsubstituted heteroaryloxy group is preferably a C4 to C12 (e.g., C5, C6, C7, C8, C9, C10, or C11) substituted or unsubstituted heteroaryloxy group.
The substituted or unsubstituted alkylamino group is preferably a substituted or unsubstituted alkylamino group having at least one carbon atom selected from the group consisting of C1 to C12 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, and C11).
The substituted or unsubstituted cycloalkylamino group is preferably a C3 to C12 (e.g., C4, C5, C6, C7, C8, C9, C10, or C11) substituted or unsubstituted cycloalkylamino group.
The substituted or unsubstituted arylamino group is preferably a C6-C13 (e.g., C7, C8, C9, C10, C11, or C12) substituted or unsubstituted arylamino group.
The substituted or unsubstituted heteroaralmino group is preferably a C4-C12 (e.g., C5, C6, C7, C8, C9, C10, or C11) substituted or unsubstituted heteroaralmino group.
The substituted or unsubstituted arylalkylamino group is preferably a C7-C12 (e.g., C8, C9, C10, or C11) substituted or unsubstituted arylalkylamino group.
The substituted or unsubstituted heteroarylalkylamino group is preferably a C7-C13 (e.g., C8, C9, C10, C11, or C12) substituted or unsubstituted heteroarylalkylamino group.
Substituted or unsubstituted alkylmercapto groups C1 to C12 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, or C11).
The substituted or unsubstituted arylmercapto group is preferably a substituted or unsubstituted arylmercapto group having from C6 to C13 (e.g., C7, C8, C9, C10, C11, or C12).
The substituted or unsubstituted heteroarylmercapto group is preferably a C4 to C12 (e.g., C5, C6, C7, C8, C9, C10, or C11) substituted or unsubstituted heteroarylmercapto group.
The substituted or unsubstituted alkylene group is preferably an alkylene group having from C1 to C12 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, or C11).
The substituted or unsubstituted cycloalkylene group is preferably a cycloalkylene group of C3 to C12 (e.g., C4, C5, C6, C7, C8, C9, C10, or C11).
The substituted or unsubstituted arylene group is preferably an arylene group having from C6 to C13 (e.g., C7, C8, C9, C10, C11, or C12).
The substituted or unsubstituted heteroarylene is preferably a C5-C13 (e.g., C6, C7, C8, C9, C10, C11, or C12) substituted or unsubstituted heteroarylene.
The substituted or unsubstituted alkylenearyl group is preferably a C7-C13 (e.g., C8, C9, C10, C11, or C12) substituted or unsubstituted alkylenearylene group.
The substituted or unsubstituted cycloalkylene group is preferably a substituted or unsubstituted cycloalkylene group of C4 to C12 (e.g., C5, C6, C7, C8, C9, C10, or C11).
Substituted or unsubstituted alkyleneheteroaryl groups C6 to C12 (e.g., C7, C8, C9, C10, or C11).
Substituted or unsubstituted cycloalkylenearyl groups C9 to C12 (e.g., C10 or C11).
Substituted or unsubstituted cycloalkyleneheteroaryl of substituted or unsubstituted cycloalkyleneheteroaryl C9 to C12 (e.g., C10 or C11).
Substituted or unsubstituted aryleneheteroaryl of C11 to C12 of substituted or unsubstituted aryleneheteroaryl.
The term "substituted" as used herein means that any one or more hydrogen atoms on the designated atom is replaced with a substituent selected from the designated group, provided that the designated atom does not exceed a normal valence and that the result of the substitution is a stable compound. When the substituent is an oxo group or a keto group (i.e., ═ O), then 2 hydrogen atoms on the atom are substituted. The ketone substituent is absent on the aromatic ring.
The second object of the present invention is to provide a method for preparing the above reactive flame retardant, the method comprising:
the compound shown in the formula I reacts with the compound containing unsaturated groups to remove at least one molecule of R '-O-R' to prepare the compound.
The invention also aims to provide application of the flame retardant, and the reactive flame retardant is used for preparing engineering plastics, molding materials and composite materials.
As a preferred technical scheme of the invention, the reactive flame retardant is used for preparing polyester compositions, unsaturated resin compositions and acrylic resin compositions.
As a preferable technical scheme of the invention, the reactive flame retardant is used for preparing high polymer materials.
Preferably, the polymer material includes any one of polyester, unsaturated resin or acrylic resin.
In the invention, the provided reactive flame retardant is applied to a high polymer material, and can be added as a monomer as a fragment of the high polymer material when the high polymer material is prepared; or the reactive flame retardant is prepared into a high molecular compound firstly, then the high molecular compound is added into a high molecular material, for example, the reactive flame retardant containing unsaturated groups provided by the invention is subjected to free radical polymerization reaction to prepare the high molecular compound, and then the high molecular compound is added into the high molecular material as a flame retardant additive.
As the preferable technical scheme of the invention, the reactive flame retardant is used for preparing acrylic and ethylene propylene rubber.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the reactive flame retardant provided by the invention has excellent flame retardant property and excellent compatibility with a flame retardant main body, and is excellent in operability, water resistance and electrical property, and the preparation method saves resources and is green and environment-friendly;
(2) the reactive flame retardant provided by the invention can be used in various fields such as engineering plastics, epoxy resin curing agents, phenolic resins, unsaturated resins, polyurethane and the like, and can greatly improve the flame retardant property of the material;
(3) by using the reactive flame retardant provided by the invention as an additive, the flame retardance of the acrylic resin can reach V-0, and the acrylic resin has excellent tensile property;
(4) the unsaturated resin composition prepared by using the reactive flame retardant provided by the invention as an additive has the flame retardance reaching V-0 and excellent mechanical properties;
(5) by using the reactive flame retardant provided by the invention as an additive, the flame retardance of the ABS composition can reach V-0, and the ABS composition has excellent tensile property and bending property;
(6) the flame retardant of the nylon composition prepared by using the reactive flame retardant provided by the invention as an additive can reach V-0 in flame retardance and has excellent mechanical properties.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a reactive flame retardant, which has a structure shown in formula II:
Figure BDA0002182892450000071
the synthesis method of the compound shown in the formula II comprises the following steps: dissolving 1mol of diethyl hydroxymethyl phosphite in 50mL of chloroform, adding 1.2mol of 3-aminopropene, adding 0.01mol of potassium carbonate and 0.01mol of potassium iodide, heating, refluxing, mechanically stirring, reacting for 8 hours, purifying by a physical method after the reaction is finished, and drying to obtain the compound shown in the formula II.
1H NMR(CDCl3,500MHz):δ5.83～5.77(m，H，CH2＝CH)，5.25～5.15(t，2H，CH 2＝CH)，4.22～4.15(m，4H，CH2)，3.28～3.21(t，2H，CH2)，2.97～2.91(d，2H，CH2)，2.35～2.30(m，H，NH)，1.39～1.33(s，6H，CH3)。
Example 2
The present embodiment provides a reactive flame retardant, which has a structure shown in formula III:
Figure BDA0002182892450000072
the synthesis method of the compound shown in the formula III comprises the following steps: dissolving 1mol of hydroxymethyl dimethyl phosphite in 50mLDMF, adding 1.2mol of hydroxyethyl methacrylate and 0.1mol of sodium hydroxide, heating, refluxing, mechanically stirring and reacting for 12 hours, purifying by adopting a physical method after the reaction is finished, and drying to obtain the compound shown in the formula III.
1H NMR(CDCl3,500MHz):δ6.51～6.42(t，2H，CH 2＝CH)，4.31～4.25(t，2H，CH2)，3.85～3.78(s，2H，CH2)，3.68～3.62(s，6H，CH3)，3.61～3.65(t，2H，CH2)，2.08～2.02(s，3H，CH3)。
Example 3
The present embodiment provides a reactive flame retardant, which has a structure as shown in formula IV:
Figure BDA0002182892450000081
the synthesis method of the compound shown in the formula IV comprises the following steps: dissolving 1mol of diethyl phosphite in 50mL of chloroform, adding 1.2mol of ethylene oxide and 2mL of hydrochloric acid (1mol/L), mechanically stirring at room temperature for reaction for 2h, after the reaction is finished, removing the solvent by rotary evaporation to obtain a solid, washing the obtained solid with water for 5 times, and drying to obtain the diethyl hydroxyethyl phosphite. Dissolving 1mol of diethyl hydroxyethyl phosphite in 50mL of chloroform, adding 1.1mol of 1-hydroxy-3-cyclohexene and 0.01mol of sodium ethoxide, reacting for 8h under a reflux condition, purifying by adopting a physical method after the reaction is finished, and drying to obtain the compound shown in the formula IV.
1H NMR(CDCl3,500MHz):δ5.62～5.55(m，2H，CH＝CH)，4.22～4.15(m，4H，CH2)，3.58～3.51(t，2H，CH2)，3.07～3.01(m，H，CH)，2.25～2.18(t，H，CH2)，2.06～2.01(m，H，CH2)，1.98～1.90(m，5H，CH2)，1.71～1.66(m，H，CH)，1.39～1.33(t，6H，CH3)。
Example 4
The present embodiment provides a reactive flame retardant, which has a structure shown in formula V:
Figure BDA0002182892450000091
the synthesis method of the compound shown in the formula V comprises the following steps: dissolving 1mol of diethyl hydroxymethyl phosphite in 50mL of chloroform, adding 1.2mol of p-hydroxystyrene and 0.01mol of sodium ethoxide, reacting for 12h under the reflux condition, purifying by adopting a physical method after the reaction is finished, and drying to obtain the compound shown in the formula V.
1H NMR(CDCl3,500MHz):7.69～7.63(m，2H，Ar-H)，7.12～7.05(m，2H，Ar-H)，6.65～6.49(m，H，CH2＝CH)，5.73～5.66(t，H，CH 2＝CH)，5.19～5.12(t，H，CH 2＝CH)，4.39～4.32(t，2H，CH2)，4.22～4.15(m，4H，CH2)，1.39～1.33(t，6H，CH3)。
Example 5
The present embodiment provides a reactive flame retardant, which has a structure as shown in formula VI:
Figure BDA0002182892450000092
the synthesis method of the compound shown in the formula VI comprises the following steps: dissolving 1mol of hydroxymethyl dimethyl phosphite in 50mL of chloroform, adding 1.2mol of 3-amino-3-methyl-1-butyne, adding 0.01mol of sodium methoxide, heating, refluxing, mechanically stirring, reacting for 12h, purifying by a physical method after the reaction is finished, and drying to obtain the compound shown in the formula VI.
1H NMR(CDCl3,500MHz):3.78～3.72(t，H，NH)，3.65～3.58(s，6H，CH3)，3.06～3.00(d，2H，CH2)，2.91～2.85(s，H，CH)，1.39～1.32(s，6H，CH3)。
The application of the acrylic resin adhesive comprises the following steps:
example 6
In this example, 25 parts by weight of the reactive flame retardant prepared in example 1 was mixed with 125 parts by weight of methyl methacrylate, MBS 17, 13 parts by weight of methacrylic acid, 15 parts by weight of chloroprene rubber, 2 parts by weight of 1, 4-hydroquinone and 6 parts by weight of dicumyl peroxide to prepare an acrylic resin adhesive a.
Example 7
In this example, 25 parts by weight of the reactive flame retardant prepared in example 2 was mixed with 125 parts by weight of methyl methacrylate, MBS 17, 13 parts by weight of methacrylic acid, 15 parts by weight of chloroprene rubber, 2 parts by weight of 1, 4-hydroquinone and 6 parts by weight of dicumyl peroxide to prepare an acrylic resin adhesive b.
Example 8
In this example, 25 parts by weight of the reactive flame retardant prepared in example 3 was mixed with 125 parts by weight of methyl methacrylate, MBS 17, 13 parts by weight of methacrylic acid, 15 parts by weight of chloroprene rubber, 2 parts by weight of 1, 4-hydroquinone and 6 parts by weight of dicumyl peroxide to prepare an acrylic resin adhesive c.
Example 9
In this example, 25 parts by weight of the reactive flame retardant prepared in example 4 was mixed with 125 parts by weight of methyl methacrylate, MBS 17, 13 parts by weight of methacrylic acid, 15 parts by weight of chloroprene rubber, 2 parts by weight of 1, 4-hydroquinone and 6 parts by weight of dicumyl peroxide to prepare an acrylic resin adhesive d.
Example 10
In this example, an acrylic resin adhesive e was prepared by mixing 25 parts by weight of the reactive flame retardant prepared in example 5 with 125 parts by weight of methyl methacrylate, MBS 17, 13 parts by weight of methacrylic acid, 15 parts by weight of chloroprene rubber, 2 parts by weight of 1, 4-hydroquinone and 6 parts by weight of dicumyl peroxide.
Comparative example 1
In the comparative example, 25 parts by weight of the reactive flame retardant prepared from the red phosphorus capsule was mixed with 125 parts by weight of methyl methacrylate, 17 parts by weight of MBS, 13 parts by weight of methacrylic acid, 15 parts by weight of chloroprene rubber, 2 parts by weight of 1, 4-hydroquinone and 6 parts by weight of dicumyl peroxide to prepare the acrylic resin adhesive f.
Comparative example 2
In the comparative example, 25 parts by weight of a reactive flame retardant prepared from triphenyl phosphate was mixed with 125 parts by weight of methyl methacrylate, MBS 17, 13 parts by weight of methacrylic acid, 15 parts by weight of chloroprene rubber, 2 parts by weight of 1, 4-hydroquinone and 6 parts by weight of dicumyl peroxide to prepare an acrylic resin adhesive g.
The acrylic adhesives prepared in examples 6 to 10 and comparative examples 1 and 2 were tested for their performance and the results are shown in table 1. Wherein, the test method of the tensile shear strength is GB/T7124-.
TABLE 1
Figure BDA0002182892450000111
Figure BDA0002182892450000121
As can be seen from the test results of Table 1, examples 6-10, which used the reactive flame retardants prepared in examples 1-5 as additives, could achieve V-0 flame retardancy of acrylic resin adhesives and have excellent tensile properties, while comparative examples 1 and 2, which used red phosphorus and triphenyl phosphate as flame retardant additives, respectively, gave acrylic resin adhesives having inferior tensile properties to examples 6-10 and acrylic resin adhesives using triphenyl phosphate having V-1 flame retardancy.
Use in unsaturated resins:
example 11
In this example, 40 parts by weight of the reactive flame retardant prepared in example 3 was mixed with 15 parts by weight of methyl methacrylate, 15 parts by weight of butyl methacrylate, 11 parts by weight of ethyl acrylate, 1 part by weight of methacrylic acid, 13 parts by weight of hydroxypropyl acrylate, 45 parts by weight of trifluoroethyl methacrylate, 2 parts by weight of benzoyl peroxide, 70 parts by weight of xylene, 20 parts by weight of methyl ethyl ketone and 10 parts by weight of cyclohexanone to prepare a crosslinked acrylic resin composition a.
Example 12
In this example, 40 parts by weight of the reactive flame retardant prepared in example 1 was mixed with 15 parts by weight of methyl methacrylate, 15 parts by weight of butyl methacrylate, 11 parts by weight of ethyl acrylate, 1 part by weight of methacrylic acid, 13 parts by weight of hydroxypropyl acrylate, 45 parts by weight of trifluoroethyl methacrylate, 2 parts by weight of benzoyl peroxide, 70 parts by weight of xylene, 20 parts by weight of methyl ethyl ketone and 10 parts by weight of cyclohexanone to prepare a crosslinked acrylic resin composition b.
Example 13
In this example, 40 parts by weight of the reactive flame retardant prepared in example 2 was mixed with 15 parts by weight of methyl methacrylate, 15 parts by weight of butyl methacrylate, 11 parts by weight of ethyl acrylate, 1 part by weight of methacrylic acid, 13 parts by weight of hydroxypropyl acrylate, 45 parts by weight of trifluoroethyl methacrylate, 2 parts by weight of benzoyl peroxide, 70 parts by weight of xylene, 20 parts by weight of methyl ethyl ketone and 10 parts by weight of cyclohexanone to prepare a crosslinked acrylic resin composition c.
Example 14
In this example, 40 parts by weight of the reactive flame retardant prepared in example 3 was mixed with 15 parts by weight of methyl methacrylate, 15 parts by weight of butyl methacrylate, 11 parts by weight of ethyl acrylate, 1 part by weight of methacrylic acid, 13 parts by weight of hydroxypropyl acrylate, 45 parts by weight of trifluoroethyl methacrylate, 2 parts by weight of benzoyl peroxide, 70 parts by weight of xylene, 20 parts by weight of methyl ethyl ketone and 10 parts by weight of cyclohexanone to prepare a crosslinked acrylic resin composition d.
Example 15
In this example, 40 parts by weight of the reactive flame retardant prepared in example 4 was mixed with 15 parts by weight of methyl methacrylate, 15 parts by weight of butyl methacrylate, 11 parts by weight of ethyl acrylate, 1 part by weight of methacrylic acid, 13 parts by weight of hydroxypropyl acrylate, 45 parts by weight of trifluoroethyl methacrylate, 2 parts by weight of benzoyl peroxide, 70 parts by weight of xylene, 20 parts by weight of methyl ethyl ketone and 10 parts by weight of cyclohexanone to prepare a crosslinked acrylic resin composition e.
Comparative example 3
In this example, 40 parts by weight of APP was mixed with 15 parts by weight of methyl methacrylate, 15 parts by weight of butyl methacrylate, 11 parts by weight of ethyl acrylate, 1 part by weight of methacrylic acid, 13 parts by weight of hydroxypropyl acrylate, 45 parts by weight of trifluoroethyl methacrylate, 2 parts by weight of benzoyl peroxide, 70 parts by weight of xylene, 20 parts by weight of methyl ethyl ketone and 10 parts by weight of cyclohexanone to prepare a crosslinked acrylic resin composition f.
Comparative example 4
In this example, a crosslinking type acrylic resin composition g was prepared by mixing 40 parts by weight of MCA with 15 parts by weight of methyl methacrylate, 15 parts by weight of butyl methacrylate, 11 parts by weight of ethyl acrylate, 1 part by weight of methacrylic acid, 13 parts by weight of hydroxypropyl acrylate, 45 parts by weight of trifluoroethyl methacrylate, 2 parts by weight of benzoyl peroxide, 70 parts by weight of xylene, 20 parts by weight of methyl ethyl ketone and 10 parts by weight of cyclohexanone.
The acrylic resin compositions prepared in examples 11 to 15 and comparative examples 3 and 4 were tested for compressive strength, tensile strength, thermal conductivity, water resistance and flammability, and the results are shown in Table 2. The method for testing the compression resistance adopts GB/T20467-2008, the method for testing the tensile strength adopts GB/T6344-2008, and the method for testing the flame resistance is UL-94. The water resistance is that the acrylic resin composition after the compressive strength test is soaked in boiling water for 2 hours and then the compressive strength test is carried out again.
TABLE 2
Figure BDA0002182892450000141
Figure BDA0002182892450000151
As can be seen from the test results of Table 2, the acrylic resin compositions prepared in examples 11-15 using the reactive flame retardants provided in examples 1-5 as additives exhibited flame retardancy up to V-0 and excellent mechanical properties, while the acrylic resin compositions prepared in comparative examples 3 and 4 using APP and MCA as flame retardant additives exhibited flame retardancy of V-1 and decreased mechanical properties as compared to those of examples 11-15.
Use in ABS compositions:
example 16
121H 80 parts of ABS resin, 10 parts of the reactive flame retardant prepared in example 1,2 parts of montmorillonite, 2 parts of high rubber powder, 10101 parts of antioxidant and 1 part of EBS are uniformly mixed and then extruded in a double-screw extruder to obtain the ABS resin composition a, wherein the temperature of a first zone of the double-screw extruder is 180 ℃, the temperature of a second zone of the double-screw extruder is 190 ℃, the temperature of a third zone of the double-screw extruder is 195 ℃, the temperature of a fourth zone of the double-screw extruder is 200 ℃, the temperature of a machine head of the double-screw extruder is 205 ℃, and the rotating speed of the double-screw extruder is 150 rpm.
Example 17
121H 80 parts of ABS resin, 10 parts of the reactive flame retardant prepared in example 2, 2 parts of montmorillonite, 2 parts of high rubber powder, 10101 parts of antioxidant and 1 part of EBS are uniformly mixed and then extruded in a double-screw extruder to obtain an ABS resin composition b, wherein the temperature of a first zone of the double-screw extruder is 180 ℃, the temperature of a second zone of the double-screw extruder is 190 ℃, the temperature of a third zone of the double-screw extruder is 195 ℃, the temperature of a fourth zone of the double-screw extruder is 200 ℃, the temperature of a machine head of the double-screw extruder is 205 ℃, and the rotating speed of the double-screw extruder is 150 rpm.
Example 18
121H 80 parts of ABS resin, 10 parts of the reactive flame retardant prepared in example 3, 2 parts of montmorillonite, 2 parts of high rubber powder, 10101 parts of antioxidant and 1 part of EBS are uniformly mixed and then extruded in a double-screw extruder to obtain an ABS resin composition v, wherein the temperature of a first zone of the double-screw extruder is 180 ℃, the temperature of a second zone is 190 ℃, the temperature of a third zone is 195 ℃, the temperature of a fourth zone is 200 ℃, the temperature of a machine head is 205 ℃, and the rotating speed is 150 rpm.
Example 19
121H 80 parts of ABS resin, 10 parts of the reactive flame retardant prepared in example 4, 2 parts of montmorillonite, 2 parts of high rubber powder, 10101 parts of antioxidant and 1 part of EBS are uniformly mixed and then extruded in a double-screw extruder to obtain an ABS resin composition d, wherein the temperature of a first zone of the double-screw extruder is 180 ℃, the temperature of a second zone of the double-screw extruder is 190 ℃, the temperature of a third zone of the double-screw extruder is 195 ℃, the temperature of a fourth zone of the double-screw extruder is 200 ℃, the temperature of a machine head of the double-screw extruder is 205 ℃, and the rotating speed of the double-screw extruder is 150 rpm.
Example 20
121H 80 parts of ABS resin, 10 parts of the reactive flame retardant prepared in example 5, 2 parts of montmorillonite, 2 parts of high rubber powder, 10101 parts of antioxidant and 1 part of EBS are uniformly mixed and then extruded in a double-screw extruder to obtain an ABS resin composition e, wherein the temperature of a first zone of the double-screw extruder is 180 ℃, the temperature of a second zone of the double-screw extruder is 190 ℃, the temperature of a third zone of the double-screw extruder is 195 ℃, the temperature of a fourth zone of the double-screw extruder is 200 ℃, the temperature of a machine head of the double-screw extruder is 205 ℃, and the rotating speed of the double-screw extruder is 150 rpm.
Comparative example 5
Mixing 121H 80 parts of ABS resin, 15 parts of red phosphorus capsules, 2 parts of montmorillonite, 2 parts of high rubber powder, 10101 parts of antioxidant and 1 part of EBS uniformly, and extruding the mixture with a double-screw extruder to obtain an ABS resin composition f, wherein the temperature of a first area of the double-screw extruder is 180 ℃, the temperature of a second area of the double-screw extruder is 190 ℃, the temperature of a third area of the double-screw extruder is 195 ℃, the temperature of a fourth area of the double-screw extruder is 200 ℃, the temperature of a machine head of the double-screw extruder is 205 ℃, and the rotating speed of the double-screw extruder is 150.
Comparative example 6
Uniformly mixing 121H 80 parts of ABS resin, 20 parts of MCA, 2 parts of montmorillonite, 2 parts of high rubber powder, 10101 parts of antioxidant and 1 part of EBS, and extruding in a double-screw extruder to obtain an ABS resin composition g, wherein the temperature of a first zone of the double-screw extruder is 180 ℃, the temperature of a second zone of the double-screw extruder is 190 ℃, the temperature of a third zone of the double-screw extruder is 195 ℃, the temperature of a fourth zone of the double-screw extruder is 200 ℃, the temperature of a machine head of the double-screw extruder is 205 ℃, and the rotating speed of the double-screw extruder is 150 rpm.
The ABS compositions prepared in examples 16-20 and comparative examples 5 and 6 were tested for tensile strength, flexural strength, melt index and flame retardant properties, and the results are shown in Table 3. Wherein the test method of tensile strength is ASTM D638, the test method of flexural strength is ASTM D790, the test method of melt index is ASTM D1238, and the test method of flame retardancy is UL-94.
TABLE 3
Figure BDA0002182892450000171
Figure BDA0002182892450000181
As can be seen from the test results in Table 3, the ABS compositions prepared in examples 16-20 using the reactive flame retardants prepared in examples 1-5 respectively have excellent flame retardant properties, flame retardancy up to V-0 level, and excellent mechanical properties. Whereas comparative examples 5 and 6 used red phosphorus capsules and MCA as flame retardant additives, respectively, the ABS compositions prepared were inferior in mechanical properties to examples 16-20, and the flame retardant properties of comparative example 6 were only V-1 grade.
The application of the nylon composition comprises the following steps:
example 21
A nylon composition comprises, by weight, 6680 parts of nylon, 15 parts of long-chain nylon, 15 parts of alkali-free glass fiber, 10 parts of the reactive flame retardant prepared in example 1, 15 parts of talcum powder, 1 part of cuprous iodide, 1 part of silicone powder and 1 part of black master batch. The raw materials are blended and then extruded in a double-screw extruder to obtain the nylon composition a.
Wherein the temperature of the first zone of the double-screw extruder is 210 ℃, the temperature of the second zone is 220 ℃, the temperature of the third zone is 235 ℃, the temperature of the fourth zone is 250 ℃, the temperature of the machine head is 260 ℃, and the rotating speed is 400 rpm.
Example 22
A nylon composition comprises, by weight, 6680 parts of nylon, 15 parts of long-chain nylon, 15 parts of alkali-free glass fiber, 10 parts of the reactive flame retardant prepared in example 2, 15 parts of talcum powder, 1 part of cuprous iodide, 1 part of silicone powder and 1 part of black master batch. The raw materials are blended and then extruded in a double-screw extruder to obtain the nylon composition b.
Wherein the temperature of the first zone of the double-screw extruder is 210 ℃, the temperature of the second zone is 220 ℃, the temperature of the third zone is 235 ℃, the temperature of the fourth zone is 250 ℃, the temperature of the machine head is 260 ℃, and the rotating speed is 400 rpm.
Example 23
A nylon composition comprises, by weight, 6680 parts of nylon, 15 parts of long-chain nylon, 15 parts of alkali-free glass fiber, 10 parts of the reactive flame retardant prepared in example 3, 15 parts of talcum powder, 1 part of cuprous iodide, 1 part of silicone powder and 1 part of black master batch. The raw materials are blended and then extruded in a double-screw extruder to obtain the nylon composition c.
Wherein the temperature of the first zone of the double-screw extruder is 210 ℃, the temperature of the second zone is 220 ℃, the temperature of the third zone is 235 ℃, the temperature of the fourth zone is 250 ℃, the temperature of the machine head is 260 ℃, and the rotating speed is 400 rpm.
Example 24
A nylon composition comprises, by weight, 6680 parts of nylon, 15 parts of long-chain nylon, 15 parts of alkali-free glass fiber, 10 parts of the reactive flame retardant prepared in example 4, 15 parts of talcum powder, 1 part of cuprous iodide, 1 part of silicone powder and 1 part of black master batch. The raw materials are blended and then extruded in a double-screw extruder to obtain the nylon composition d.
Wherein the temperature of the first zone of the double-screw extruder is 210 ℃, the temperature of the second zone is 220 ℃, the temperature of the third zone is 235 ℃, the temperature of the fourth zone is 250 ℃, the temperature of the machine head is 260 ℃, and the rotating speed is 400 rpm.
Example 25
A nylon composition comprises, by weight, 6680 parts of nylon, 15 parts of long-chain nylon, 15 parts of alkali-free glass fiber, 10 parts of the reactive flame retardant prepared in example 5, 15 parts of talcum powder, 1 part of cuprous iodide, 1 part of silicone powder and 1 part of black master batch. The raw materials are blended and then extruded in a double-screw extruder to obtain the nylon composition e.
Wherein the temperature of the first zone of the double-screw extruder is 210 ℃, the temperature of the second zone is 220 ℃, the temperature of the third zone is 235 ℃, the temperature of the fourth zone is 250 ℃, the temperature of the machine head is 260 ℃, and the rotating speed is 400 rpm.
Comparative example 7
The nylon composition comprises nylon 6680 parts by weight, long-chain nylon 15 parts by weight, alkali-free glass fiber 15 parts by weight, MBS 20 parts by weight, talcum powder 15 parts by weight, cuprous iodide 1 part by weight, silicone powder 1 part by weight and black master 1 part by weight. The raw materials are blended and then extruded in a double-screw extruder to obtain the nylon composition f.
Wherein the temperature of the first zone of the double-screw extruder is 210 ℃, the temperature of the second zone is 220 ℃, the temperature of the third zone is 235 ℃, the temperature of the fourth zone is 250 ℃, the temperature of the machine head is 260 ℃, and the rotating speed is 400 rpm.
Comparative example 8
A nylon composition comprises nylon 6680 parts by weight, long-chain nylon 15 parts by weight, alkali-free glass fiber 15 parts by weight, APP 20 parts by weight, talcum powder 15 parts by weight, cuprous iodide 1 part by weight, silicone powder 1 part by weight and black master 1 part by weight. The raw materials are blended and then extruded in a double-screw extruder to obtain a nylon composition g.
Wherein the temperature of the first zone of the double-screw extruder is 210 ℃, the temperature of the second zone is 220 ℃, the temperature of the third zone is 235 ℃, the temperature of the fourth zone is 250 ℃, the temperature of the machine head is 260 ℃, and the rotating speed is 400 rpm.
The nylon compositions prepared in examples 21 to 25 and comparative examples 7 and 8 were tested for tensile strength, elongation, flexural strength and flame retardant properties, and the results are shown in Table 4. Wherein the test method of tensile strength and elongation is IOS 527, the test method of bending strength is IOS 178, and the test method of flame retardance is UL-94.
TABLE 4
Figure BDA0002182892450000201
Figure BDA0002182892450000211
As can be seen from the test results in Table 4, the reactive flame retardants prepared in examples 1-5 were used in examples 21-25, respectively, and the prepared nylon compositions have excellent flame retardant properties, flame retardancy up to V-0 level, and excellent mechanical properties. While comparative examples 7 and 8 use MBS and APP as flame retardant additives, respectively, the mechanical properties of the prepared nylon compositions are inferior to those of examples 21-25, and the flame retardant properties are only V-1 grade.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. A reactive flame retardant is characterized in that the flame retardant is obtained by reacting a compound shown in a formula I with a compound containing an unsaturated group to remove at least one molecule of R '-O-R';
Figure FDA0002182892440000011
wherein X is a group VI element or is absent, R1And R2Each independently is any group which satisfies the chemical environment, R' comprises any one of hydrogen and isotope thereof and substituted or unsubstituted alkyl, cycloalkyl, aryl or heteroaryl, a, b and c are each independently integers which are more than or equal to 0, and a + b + c is more than or equal to 3;
wherein, R' comprises any one of hydrogen and isotopes thereof, and substituted or unsubstituted alkyl, cycloalkyl, aryl or heteroaryl.
2. The flame retardant of claim 1, wherein R is1And R2Each independently preferably comprises a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryloxy group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted cycloalkylamino groupAnd a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, a substituted or unsubstituted alkylmercapto group, a substituted or unsubstituted arylmercapto group, or a substituted or unsubstituted heteroarylmercapto group.
3. The flame retardant of claim 1 or 2, wherein R preferably comprises any one of substituted or unsubstituted alkylene, cycloalkylene, arylene, heteroarylene, alkylenecycloalkyl, alkylenearyl, alkyleneheteroaryl, cycloalkylenearyl, cycloalkyleneheteroaryl, or aryleneheteroaryl.
4. The flame retardant of any one of claims 1-3, wherein X is O or S.
5. The flame retardant of any one of claims 1-4, wherein said unsaturated group comprises any one of a carbon-carbon double bond, a carbon-carbon triple bond, a carbon-oxygen double bond, a carbon-sulfur double bond, or a carbon-nitrogen double bond.
6. A method for preparing the flame retardant of any one of claims 1-5, comprising: the compound shown in the formula I reacts with the compound containing unsaturated groups to remove at least one molecule of R '-O-R' to prepare the compound.
7. Use of the reactive flame retardant according to any of claims 1 to 5 for the preparation of engineering plastics, shaped materials and composites.
8. Use of a reactive flame retardant according to any of claims 1 to 5 for the preparation of polyester compositions, unsaturated resin compositions and acrylic resin compositions.
9. Use of a reactive flame retardant according to any of claims 1 to 5 for the preparation of a polymeric material;
preferably, the polymer material includes any one of polyester, unsaturated resin or acrylic resin.
10. Use of a reactive flame retardant according to any of claims 1 to 5 for the preparation of acrylic and ethylene-propylene rubbers.
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US20130296473A1 (en) * 2010-12-14 2013-11-07 Cheil Industries Inc. Flame-Retardant Polycarbonate Resin Composition with Scratch Resistance
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