CN112961184A - Reactive flame retardant, polymeric flame retardant, and preparation method and application thereof - Google Patents

Reactive flame retardant, polymeric flame retardant, and preparation method and application thereof Download PDF

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CN112961184A
CN112961184A CN202110184292.9A CN202110184292A CN112961184A CN 112961184 A CN112961184 A CN 112961184A CN 202110184292 A CN202110184292 A CN 202110184292A CN 112961184 A CN112961184 A CN 112961184A
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flame retardant
substituted
group
unsubstituted
reactive
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潘庆崇
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Guangdong Guangshan New Materials Co ltd
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    • C07—ORGANIC CHEMISTRY
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—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
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
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    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
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    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
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    • 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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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C08G59/304—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing phosphorus
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/30—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen phosphorus-containing groups
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

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Abstract

The invention provides a reactive flame retardant, a polymeric flame retardant, a preparation method and application thereof, wherein the reactive flame retardant can react with a reactive group in an added system to obtain a required flame retardant component product; the polymeric flame retardant can be obtained through the self-polymerization or copolymerization of the reactive flame retardant, and the excellent flame retardant additive is directly provided for the high polymer material.

Description

Reactive flame retardant, polymeric flame retardant, and preparation method and application thereof
Technical Field
The invention belongs to the field of flame retardants, and relates to a reactive flame retardant, a polymeric flame retardant, and preparation methods and applications thereof.
Background
Conventional flame retardant technologies are generally classified into halogen flame retardants and halogen-free flame retardants.
In the prior art, the halogen flame retardant mode generally comprises the steps of reacting molecules containing halogen and reactive groups with other materials to prepare a halogen flame retardant material, or directly adding a halogen flame retardant without reactive groups, such as decabromodiphenylethane, into the material to achieve the purpose of flame retardance. Meanwhile, in order to improve the flame retardant effect, flame retardant auxiliaries which are harmful to organisms and not friendly to the environment such as antimony trioxide are often added into a flame retardant system. When the halogen-containing flame retardant substance is decomposed or burned by heat, non-degradable or difficultly degradable high-toxicity dioxin organic halogen chemical substances are generated and accumulated, so that the environment is polluted, and the growth and development of organisms and the health of human beings are influenced.
The conventional halogen-free flame retardant method is generally to add a large amount of flame retardant salts such as ammonium polyphosphate, melamine cyanurate, piperazine pyrophosphate or 2-ethyl aluminum hypophosphite, phosphate compounds such as trimethyl phosphate or triphenyl phosphate which are designated as environmental substances by the european union and many countries and regions, and metal hydroxide containing crystal water such as aluminum hydroxide or magnesium hydroxide to the material system to achieve the purpose of flame retardancy. The flame retardant is added into a flame-retardant material system in a large amount, so that not only is serious resource waste caused and the mechanical property, the water resistance, the heat resistance and the electrical property of the material are reduced or damaged, but also the use environment and the natural environment are polluted due to the migration and precipitation of the flame-retardant components, the flame resistance, the mechanical property and the heat resistance of the material are further damaged, and the environment is directly polluted and the human health is influenced by adding the phosphate flame retardant which is designated as an environmental substance.
Disclosure of Invention
In order to solve the technical problems, the invention provides a reactive flame retardant, a polymeric flame retardant, a preparation method and an application thereof, wherein the reactive flame retardant can react with a reactive group in an added system to obtain a required stable flame retardant component product; the polymeric flame retardant can be obtained by the self-polymerization or copolymerization of the reactive flame retardant or the polymerization of the reactive flame retardant and other reactive flame retardants, and the excellent flame retardant additive is directly provided for the high polymer material.
One purpose of the present invention is to provide a reactive flame retardant, which is characterized in that the structure of the reactive flame retardant is as shown in formula 1:
Figure BDA0002942371730000021
wherein M is a metal element, R, R1、R2、R3And R4N is more than or equal to 1, R, R to meet any group of chemical environment1、R2、R3And R4At least one of the groups contains a reactive group, m and q are not less than 0, and m + n + q is 1-5.
Where m can be 0, 1, 2, 3, 4 or 5, etc., n can be 0, 1, 2, 3, 4 or 5, etc., and q can be 0, 1, 2, 3, 4 or 5, etc., but is not limited to the recited values, and other values not recited within the above numerical ranges are also applicable.
According to the reactive flame retardant provided by the invention, the flame retardant molecules can be directly introduced into the system molecules by directly reacting the reactive groups with other reactive groups in the added system, so that the compatibility of the flame retardant and the added system is increased, the problems of precipitation and migration of the flame retardant cannot occur after long-term use, and the flame retardant effect is stable; meanwhile, the reactive flame retardant has high content of flame-retardant elements, and has excellent flame-retardant property only by adding a small amount of the flame-retardant elements; the flame retardant can also modify the added system to improve the mechanical properties of the added system.
In a preferred embodiment of the present invention, the reactive group preferably includes any one or a combination of at least two of a hydroxyl group, an amine group, an unsaturated group, a carboxyl group, an epoxy group, an ester group, an acid anhydride, an isocyanate group, and a cyano group.
As a preferred embodiment of the present invention, R is1And R2Each independently preferably comprises any one or a combination of at least two of H, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.
As a preferred embodiment of the present invention, R is1And R2The compound independently and preferably comprises any one or the combination of at least two of C1-C12 substituted or unsubstituted alkyl, C3-C12 substituted or unsubstituted cycloalkyl, C6-C12 substituted or unsubstituted aryl or substituted or C5-C12 unsubstituted heteroaryl.
Wherein, the substituted or unsubstituted alkyl group of C1-C12 may be a substituted or unsubstituted alkyl group of C2, C3, C4, C5, C6, C7, C8, C9, C10 or C11;
the cycloalkyl of C3-C12 can be substituted or unsubstituted cycloalkyl of C4, C5, C6, C7, C8, C9, C10 or C11;
the C5-C12 aromatic group can be a substituted or unsubstituted aromatic group of C6, C7, C8, C9, C10 or C11;
the heteroaryl group of C5-C12 can be substituted or unsubstituted heteroaryl group of C6, C7, C8, C9, C10 or C11.
R, R is a preferred embodiment of the present invention3And R4Each independently preferably includes any one or a combination of at least two of H, hydroxyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkoxy, substituted or unsubstituted aryloxy, or substituted or unsubstituted heteroaryloxy.
The R, R patent preferably3And R4The aryl group independently and preferably comprises any one or a combination of at least two of C1-C12 substituted or unsubstituted alkyl, C3-C12 substituted or unsubstituted cycloalkyl, C6-C12 substituted or unsubstituted aryl, C5-C12 substituted or unsubstituted heteroaryl, C1-C12 substituted or unsubstituted alkoxy, C3-C12 substituted or unsubstituted cycloalkoxy, C6-C12 substituted or unsubstituted aryloxy, and C5-C12 substituted or unsubstituted heteroaryloxy.
Wherein, the substituted or unsubstituted alkyl group of C1-C12 may be a substituted or unsubstituted alkyl group of C2, C3, C4, C5, C6, C7, C8, C9, C10 or C11;
the cycloalkyl of C3-C12 can be substituted or unsubstituted cycloalkyl of C4, C5, C6, C7, C8, C9, C10 or C11;
the C5-C12 aromatic group can be a substituted or unsubstituted aromatic group of C6, C7, C8, C9, C10 or C11;
the C5-C12 heteroaryl can be substituted or unsubstituted heteroaryl of C6, C7, C8, C9, C10 or C11;
the substituted or unsubstituted alkoxy group having C1 to C12 may be, for example, a substituted or unsubstituted alkoxy group having C2, C3, C4, C5, C6, C7, C8, C9, C10, or C11;
the cycloalkoxy group of C3 to C12 may be, for example, a substituted or unsubstituted cycloalkoxy group of C4, C5, C6, C7, C8, C9, C10 or C11;
the C5-C12 aryloxy group may be, for example, a substituted or unsubstituted aryloxy group of C6, C7, C8, C9, C10 or C11;
the heteroaryloxy group having C5 to C12 may be, for example, a substituted or unsubstituted heteroaryloxy group having C6, C7, C8, C9, C10 or C11.
As a preferred embodiment of the present invention, R is1～R3Each independently preferably comprises an inert group.
In the present invention, R1～R3Preferably, R is an inert group during the synthesis of the compound of formula 11～R3Under which conditions it does not react with other groups in the reactants.
In a preferred embodiment of the present invention, M includes any one or a combination of at least two of an alkaline earth metal element, a transition metal element, a group IIIA metal element, a group IVA metal element, a group VA metal element, and a group VIA metal element.
Wherein the alkaline earth metal element can Be Be, Mg, Ca, Sr, Ba or Ra;
the transition metal element can be Sc, Ti, V, Cr, Mg, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, lanthanides or actinides;
the group IIIA metal element may be Al, Ga, In or Tl;
the group IVA metal element may be Ge, Sn or Pb;
the group VA metal element may be Sb or Bi;
the group VIA metal element may be Po.
Another object of the present invention is to provide a method for preparing the reactive flame retardant, the method comprising: the acid salt of the metal M is prepared by chemical reaction with a compound containing a reactive group.
In the present invention, the chemical reaction may be a substitution reaction, an addition reaction, or the like.
In the present invention, the reactive group-containing compound may be any one or a combination of at least two of an alcohol compound, an ester compound, and an acid glycoside compound containing a reactive group.
Wherein, the reactive group comprises any one or the combination of at least two of hydroxyl, amine group, unsaturated group, carboxyl, epoxy group, ester group, acid anhydride, isocyanate group or cyano.
The alcohol compound may be a C2 to C18 alcohol compound, and may be, for example, a C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, or C17 alcohol.
The ester compound may be an ester compound of C3 to C24, and may be, for example, an ester of C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, or C23;
the acid glycoside compound may be a C3-C24 acid glycoside compound, and may be, for example, a C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, or C23 acid glycoside.
The third purpose of the invention is to provide a polymeric flame retardant, which is prepared from any one of the reactive flame retardants through self-polymerization or copolymerization.
In a preferred embodiment of the present invention, the polymeric flame retardant is prepared by copolymerization of any one of the reactive flame retardants described above with a compound containing a reactive group.
Wherein the compound containing a reactive group preferably includes a flame retardant containing a reactive group or a chain extender containing a reactive group.
In the present invention, the polymeric flame retardant may be synthesized by: when the reactive group of the reactive flame retardant is an unsaturated group, the polymerization flame retardant can be obtained through copolymerization in free radical polymerization. The polymeric flame retardant can be obtained by polymerizing two reactive flame retardants containing hydroxyl and carboxyl through a polycondensation reaction. Or the polymeric flame retardant can be obtained by polymerizing two reactive flame retardants containing amino and carboxyl through polycondensation. Or a compound containing epoxy groups, and a chain extender are copolymerized to obtain the polymeric flame retardant. The polymeric flame retardant can be applied to the field of engineering plastics, such as polycarbonate plastics, PPO plastics, PPS plastics or PBT plastics.
In the invention, the provided polymeric flame retardant can also be obtained by reacting the reactive flame retardant provided by the invention with the existing flame retardant containing reactive groups in the prior art. The flame retardant containing unsaturated groups, provided by the invention, is obtained by free radical polymerization copolymerization with another existing flame retardant containing unsaturated groups. The reactive flame retardant containing carboxyl provided by the invention is copolymerized with another existing flame retardant containing amino or hydroxyl through a polycondensation reaction.
The fourth purpose of the invention is to provide the application of the above-mentioned reaction type and polymerization type flame retardant, and the application field of the flame retardant comprises any one or the combination of at least two of thermoplastic resin, thermosetting resin or light-cured resin.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the invention discloses a reactive flame retardant, which can obtain a flame retardant component through chemical reaction with a reactive group in an added system, and provides excellent flame retardant property for the added system;
(2) the invention discloses a reactive flame retardant, which has wide application range and is suitable for being used as various thermosetting resins, light-cured resins and thermoplastic resins;
(3) the invention discloses a reactive flame retardant which can be applied to thermosetting resin, light-cured resin and thermoplastic resin to obtain the effects of no migration, no precipitation, no pollution to the use environment and permanent flame retardance;
(4) the invention discloses a reactive flame retardant which is added into thermosetting resin, light-cured resin and thermoplastic resin, and the prepared resin composition has excellent mechanical property, heat resistance, electrical property and flame retardant property (UL-94) reaching V-0 level;
(5) the invention discloses a polymeric flame retardant which can be obtained through reactions such as self-polymerization or copolymerization and the like, is applied to thermosetting resin, light-cured resin and thermoplastic resin, and has the effects of no migration, no precipitation, no pollution to the use environment and permanent flame retardance.
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 2:
Figure BDA0002942371730000081
the preparation method of the compound shown in the formula 2 comprises the following steps: dispersing 1mol of titanium hydrogen phosphate in 100mL of cyclohexanone, adding 2mol of isopropanol and 0.01mol of dibutyltin oxide, reacting for 3h at 120 ℃ under reflux, adding 2.2mol of ethylene glycol after the reaction is finished, heating to 135 ℃ and continuing to react for 3h, separating the solvent by distillation, adding 500mL of MIBK into the obtained product, adding 2.2mol of epichlorohydrin, 2mol of potassium hydroxide and 0.01mol of dibutyltin oxide, stirring at 90 ℃ for reaction for 240min, removing unreacted epichlorohydrin, the generated by-product potassium chloride and the solvent by a physical method after the reaction is finished, and purifying the product to obtain the compound shown in the formula 2.
1H NMR(CDCl3,500MHz):δ4.27～4.21(t，4H，CH2)，3.81～3.74(t，4H，CH2)，3.67～3.61(d，2H，CH2)，3.45～3.37(d，2H，CH2)，2.85～2.77(m，2H，CH)，2.63～2.56(d，2H，CH2)，2.42～2.34(t，2H，CH2)。
ICP test of the obtained flame retardant shows that the manganese element and the phosphorus element exist simultaneously in the obtained compound, and the molar ratio of the titanium element to the phosphorus element is 1: 2.
Example 2
The embodiment provides a reactive flame retardant, which has a structure shown in formula 3:
Figure BDA0002942371730000082
the preparation method of the compound shown in the formula 3 comprises the following steps: dispersing 1mol of titanium hydrogen phosphate in 100mL of cyclohexanone, adding 2mol of isopropanol and 0.01mol of dibutyltin oxide, reacting for 3h under the condition of heating at 120 ℃ and refluxing, adding 2.2mol of allyl alcohol after the reaction is finished, continuing to react for 6h, removing unreacted allyl alcohol and solvent by a physical method after the reaction is finished, and purifying the product to obtain the compound shown in the formula 3.
1H NMR(CDCl3,500MHz):δ6.03～5.95(m，2H，HC＝CH2)，5.41～5.36(t，2H，HC＝CH 2)，5.28～5.20(t，2H，HC＝CH 2)，4.58～4.52(d，4H，CH2)。
The obtained flame retardant was subjected to an ICP test, and found that the titanium element and the phosphorus element were present simultaneously in the obtained compound, and the molar ratio of the titanium element to the phosphorus element was 1: 2.
Example 3
The embodiment provides a reactive flame retardant, which has a structure shown in formula 4:
Figure BDA0002942371730000091
the preparation method of the compound shown in the formula 4 comprises the following steps: dispersing 1mol of zinc dihydrogen phosphate in 100mL of DMSO, adding 4mol of isopropanol and 0.01mol of dibutyltin oxide, reacting for 6h under the reflux condition at 110 ℃, separating the solvent by distillation, dispersing the obtained product in toluene, stirring and reacting with 4.2mol of epichlorohydrin, 4mol of potassium hydroxide and 0.01mol of dibutyltin oxide at 80 ℃ for 180min, removing unreacted epichlorohydrin, the generated byproduct potassium chloride and the solvent by a physical method after the reaction is finished, acidifying the product, washing with water to neutrality, and purifying the product to obtain the compound shown in the formula 4.
1H NMR(CDCl3,500MHz):δ4.10～4.02(t，8H，CH2)，3.68～3.60(t，4H，OH)，3.52～3.45(m，8H，CH2)，1.99～1.92(m，8H，CH2)。
ICP test of the obtained flame retardant shows that zinc and phosphorus exist simultaneously in the obtained compound, and the molar ratio of the zinc to the phosphorus is 1: 2.
Example 4
The embodiment provides a reactive flame retardant, which has a structure shown in formula 5:
Figure BDA0002942371730000101
the preparation method of the compound shown in the formula 5 comprises the following steps: dispersing 1mol of manganese dihydrogen phosphate in 100mL of DMSO, adding 4mol of isopropanol and 0.01mol of dibutyltin oxide, reacting for 5h at 120 ℃ under reflux, separating the solvent by distillation, dispersing the obtained product in chloroform, reacting with 2mol of aminopropionic acid and 0.01mol of DMAP, and purifying the product after the reaction is finished to obtain the compound shown in the formula 5.
1H NMR(CDCl3,500MHz):δ11.13～11.05(s，2H，COOH)，4.59～4.52(s，2H，CH)，2.96～2.88(m，4H，CH2)，2.68～2.61(t，4H，CH2)，2.34～2.25(d，2H，NH)，1.31～1.23(d，12H，CH3)。
ICP test of the obtained flame retardant shows that the manganese element and the phosphorus element exist simultaneously in the obtained compound, and the molar ratio of the calcium element to the phosphorus element is 1: 2.
Example 5
The embodiment provides a reactive flame retardant, which has a structure shown in formula 6:
Figure BDA0002942371730000111
the preparation method of the compound shown in the formula 6 comprises the following steps: dispersing 1.5mol of sodium dihydrogen phosphate into 100mL of cyclohexanone, adding 3mol of isopropanol and 0.01mol of dibutyltin oxide, reacting for 2.5h at 130 ℃ under reflux, adding 1.5mol of 3-aminopropyl trihydroxysilane and 0.01mol of dibutyltin oxide, reacting for 6h at 170 ℃, adding molybdenum trichloride until no precipitate is generated after the reaction is finished, carrying out solid-liquid separation to obtain a solid product, mixing the solid product with 5mol of methanol, adding 0.01mol of dibutyltin oxide, reacting for 12h under a heating reflux condition, and purifying the product after the reaction to obtain the compound shown in the formula 6.
1H NMR(CDCl3,500MHz):δ11.96～11.88(s，3H，OH)，5.17～5.07(t，6H，NH2)，3.81～3.73(s，9H，CH3)，3.55～3.47(s，18H，CH3)，2.66～2.60(m，6H，CH2)，1.57～1.50(m，6H，CH2)，0.63～0.55(t，6H，CH2)。
ICP test of the obtained flame retardant shows that molybdenum, phosphorus and silicon exist simultaneously in the obtained compound, and the molar ratio of the molybdenum, the phosphorus and the silicon is 1:3: 3.
Example 6
The embodiment provides a reactive flame retardant, which has a structure shown in formula 7:
Figure BDA0002942371730000121
the preparation method of the compound shown in the formula 7 comprises the following steps: dispersing 1mol of aluminum dihydrogen tripolyphosphate in 100mL of cyclohexanone, adding 2mol of ethylene glycol and 0.01mol of dibutyltin oxide, reacting for 8h at 120 ℃, separating the solvent by distillation, dispersing the obtained product in toluene, stirring and reacting with 2mol of epichlorohydrin, 2mol of potassium hydroxide and 0.01mol of dibutyltin oxide at 80 ℃ for 180min, removing by-products of potassium chloride and the solvent generated by a physical method after the reaction is finished, acidifying the product, washing with water to neutrality, and purifying the product to obtain the compound shown in formula 7.
1H NMR(CDCl3,500MHz):δ4.22～4.15(t，4H，CH2)，3.76～3.68(t，4H，CH2)，3.66～3.58(t，2H，OH)，3.55～3.48(m，4H，CH2)，3.39～3.31(m，4H，CH2)，1.96～1.88(m，4H，CH2)。
ICP test of the obtained flame retardant shows that the aluminum element and the phosphorus element exist simultaneously in the obtained compound, and the molar ratio of the aluminum element to the phosphorus element is 1: 3.
Application in epoxy resin
Example 7
In this example, 100 parts by weight of bisphenol A epoxy resin having an epoxy equivalent of 360/eq was mixed with 20 parts by weight of the reactive flame retardant shown in example 1, and then cured at 180 ℃ for 2 hours with 6 parts by weight of dicyandiamide and 0.2 part by weight of 2-methylimidazole to obtain an epoxy resin cured product a.
Example 8
In this example, 100 parts by weight of bisphenol A epoxy resin having an epoxy equivalent of 360/eq was mixed with 4 parts by weight of dicyandiamide, 0.2 part by weight of 2-methylimidazole and 3 parts by weight of the reactive flame retardant described in example 5, and cured at 120 ℃ for 1.5 hours to obtain epoxy resin cured product b.
Comparative example 1
In this comparative example, 100 parts by weight of an epoxy resin having an epoxy equivalent of 360/eq was added with 6 parts by weight of a dicyandiamide and then 30 parts by weight of APP, followed by curing at 180 ℃ for 2 hours to obtain an epoxy resin cured product c.
Comparative example 2
In this comparative example, 100 parts by weight of an epoxy resin having an epoxy equivalent of 360/eq was added with 6 parts by weight of dicyandiamide, and then 30 parts by weight of MCA was added and cured at 180 ℃ for 2 hours to obtain an epoxy resin cured product d.
The performance of the cured epoxy resin a-d is tested, the bending strength test method adopts GB/T9341-2008, the impact strength test method adopts GB/T1843-2008, the breakdown voltage adopts GB/T1408.1-2006, and the flame retardance test method is UL-94. The test results are shown in Table 1.
TABLE 1
Figure BDA0002942371730000131
As can be seen from the test results in table 1, the reactive flame retardant provided in example 1 of the present invention is pre-mixed with epoxy resin, and then the flame retardant molecules can be grafted into the epoxy resin molecules through a curing reaction, so that the flame retardant property of the epoxy resin is improved, and the mechanical property of the epoxy resin is also improved. The reactive flame retardant provided in embodiment 5 of the present invention has active hydrogen, so that when the reactive flame retardant is added to an epoxy resin system, the amount of the curing agent can be appropriately reduced, and the reactive flame retardant provided in embodiment 5 is grafted to epoxy resin molecules through a curing reaction, thereby improving the flame retardant property and the mechanical property of the epoxy resin. MCA and APP as additive flame retardants cannot react with epoxy resin molecules, so that the MCA and the APP do not contribute to the mechanical properties of the epoxy resin, and the MCA and the APP have a large addition amount and have a limited flame retardant effect.
Application of the silicone resin:
example 9
In this example, 114 parts by weight of trimethylethoxysiloxane, 186 parts by weight of tetraethoxysiloxane and 50 parts by weight of sodium silicate nonahydrate were mixed with 50 parts by weight of the reactive flame retardant prepared in example 5, and cured at 20 ℃ for 5 hours to prepare a silicone resin a.
Comparative example 3
In this comparative example, 114 parts by weight of trimethylethoxysiloxane, 186 parts by weight of tetraethoxysiloxane and 50 parts by weight of sodium silicate nonahydrate were mixed and cured at 20 ℃ for 5 hours to prepare a silicone resin b.
Comparative example 4
In this comparative example, 114 parts by weight of trimethylethoxysiloxane, 186 parts by weight of tetraethoxysiloxane, 50 parts by weight of sodium nonahydrate, and 60 parts by weight of APP were mixed and cured at 20 ℃ for 5 hours to prepare silicone resin c.
The performance of the obtained silicone resins a-c is tested, the test method of tensile strength and elongation adopts GB/T1701-2001, the test method of shear strength adopts GB/T1700-2001, the test method of flame retardance is UL-94, and the test condition of water resistance is soaking in boiling water for 2 h. The test results are shown in table 2.
TABLE 2
Figure BDA0002942371730000151
According to the test results in table 2, it can be seen that the reactive flame retardant provided in example 5 of the present invention has a structure similar to that of trimethylethoxysiloxane and tetraethoxysiloxane, and can be grafted into the silicone resin molecule after the curing reaction, so as to provide excellent flame retardant property for the silicone resin, and simultaneously improve the mechanical properties of the silicone resin. The flame retardant performance and mechanical properties similar to those of example 9 could not be achieved without adding the reactive flame retardant provided in example 5 and using APP as the flame retardant.
Use in unsaturated resins:
example 10
In this example, 25 parts by weight of the 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 a.
Comparative example 5
In this comparative example, 30 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 b.
Comparative example 6
In this comparative example, 30 parts by weight of MCA 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.
The acrylic resin compositions a to c prepared as described above were tested for compressive strength, tensile strength, water resistance and flame retardancy, and the results are shown in table 3. 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 3
Figure BDA0002942371730000171
According to the test results in table 3, it can be seen that the reactive flame retardant provided in example 2 of the present invention can be polymerized with the unsaturated group on the acrylic resin monomer after being added into the acrylic resin composition system, so that the reactive flame retardant provided in example 2 can be linked into the acrylic resin molecule, thereby improving the flame retardant property and the mechanical property of the acrylic resin. Compared with the existing flame retardant with the same addition amount, the prepared acrylic resin composition has more excellent flame retardant performance and mechanical performance.
The application of the nylon composite material is as follows:
example 11
In this example, 15 parts by weight of the flame retardant prepared in example 2, 0.05 part by weight of azobisisobutyronitrile, 61081 parts by weight of nylon, 6623 parts by weight of nylon, 0.7 part by weight of vinyltriethoxysilane, 12 parts by weight of magnesium hydroxide, 10100.6 parts by weight of antioxidant, 55 parts by weight of glass fiber, and 0.8 part by weight of bisstearamide were mixed to prepare a nylon composite a.
Comparative example 7
In this example, 30 parts by weight of APP was mixed with 61081 parts by weight of nylon, 6623 parts by weight of nylon, 0.7 part by weight of vinyltriethoxysilane, 12 parts by weight of magnesium hydroxide, 10100.6 parts by weight of antioxidant, 55 parts by weight of glass fiber, and 0.8 part by weight of bisstearamide to prepare nylon composite b.
Comparative example 8
In this example, 30 parts by weight of MCA, 61081 parts by weight of nylon, 6623 parts by weight of nylon, 0.7 part by weight of vinyltriethoxysilane, 12 parts by weight of magnesium hydroxide, 10100.6 parts by weight of antioxidant, 55 parts by weight of glass fiber, and 0.8 part by weight of bisstearamide were mixed to prepare a nylon composite c.
The nylon composites a-C prepared in example 9 and comparative examples 7 and 8 were tested for compressive strength (GB/T15231-2008), tensile strength (ASTM C1557-2003(2008)), and flammability, and the results are shown in Table 4.
TABLE 4
Figure BDA0002942371730000181
According to the test results in table 4, it can be seen that after the reactive flame retardant provided in example 4 of the present invention is added into a nylon composite system, the flame retardant performance and the mechanical performance of the prepared nylon composite are more excellent for the existing flame retardant added in more MCA and APP.
Application in polycarbonate plastics
Example 12
Dispersing the compounds provided in the embodiments 1 and 4 in DMSO, reacting at 180 ℃ for 2h, 19 ℃ for 2h and 200 ℃ for 2h in sequence, separating the solvent by distillation, and purifying the product to obtain the polymeric flame retardant I.
Polycarbonate plastic a was prepared by mixing 15 parts by weight of a polymeric flame retardant I, 100 parts by weight of 2,2' -bis (4-hydroxyphenyl) propane polycarbonate, 0.5 part by weight of polytetrafluoroethylene (anti-dripping agent), and 9440.5 parts by weight of a light stabilizer.
Comparative example 9
In this comparative example, 20 parts by weight of APP flame retardant was mixed with 100 parts by weight of 2,2' -bis (4-hydroxyphenyl) propane polycarbonate, 0.5 part by weight of polytetrafluoroethylene (anti-dripping agent), and 9440.5 parts by weight of a light stabilizer to prepare polycarbonate plastic c.
Comparative example 10
In this comparative example, 20 parts by weight of MCA flame retardant was mixed with 100 parts by weight of 2,2' -bis (4-hydroxyphenyl) propane polycarbonate, 0.5 part by weight of polytetrafluoroethylene (anti-dripping agent), and 9440.5 parts by weight of a light stabilizer to prepare polycarbonate plastic d.
The polycarbonate plastics a-c provided in example 12 and comparative examples 9 and 10 were tested for tensile properties, Izod impact strength and flame retardancy, the tensile properties being tested according to GB/T14884-2008, the Izod impact strength being tested according to GB/T1843-2008, and the flame retardancy being tested according to UL-94. The results are shown in Table 5.
TABLE 5
Tensile strength/MPa Impact Strength/J/m Flame retardancy/UL-94
Polycarbonate plastic a 81 90 V-0
Polycarbonate plastic b 62 58 V-1
Polycarbonate plastic c 65 63 V-1
From the test results in table 5, it can be seen that the polymeric flame retardant provided in example 12 of the present invention, due to its good compatibility with polycarbonate plastics, can not only provide good flame retardant properties for polycarbonate plastics, but also improve the mechanical properties of polycarbonate plastics. The conventional additive flame retardants MCA and APP are not only higher than the polymeric flame retardant provided in example 12, but also have limited flame retardant effect due to poor compatibility and no beneficial effect on the mechanical properties of the polycarbonate plastic.
Application of PPS plastic
Example 13
In this example, 1mol each of the reactive flame retardants provided in examples 6 and 4 was dispersed in NMP, 0.01mol of dibutyltin oxide was added, and the mixture was reacted at 160 ℃ for 3 hours, 180 ℃ for 3 hours, and 200 ℃ for 3 hours in this order, and the solvent was separated by distillation, and then the product was purified to obtain a polymeric flame retardant II.
15 parts of polymeric flame retardant II, 100 parts of PPS, 10 parts of talcum powder, 8 parts of polyvinyl acetate and 5 parts of zirconia are mixed to prepare PPS plastic a. The PPS used was a linear PPS having a molecular weight of about 5 ten thousand and a melt index of 30 g/min.
Comparative example 11
In the comparative example, 20 parts by weight of APP flame retardant, 100 parts by weight of PPS, 10 parts by weight of talc, 8 parts by weight of polyvinyl acetate, and 5 parts by weight of zirconia were mixed to prepare PPS plastic b. The PPS used was a linear PPS having a molecular weight of about 5 ten thousand and a melt index of 30 g/min.
Comparative example 12
In this comparative example, PPS plastic c was prepared by mixing 20 parts by weight of MCA flame retardant, 100 parts by weight of PPS, 10 parts by weight of talc, 8 parts by weight of polyvinyl acetate, and 5 parts by weight of zirconia. The PPS used was a linear PPS having a molecular weight of about 5 ten thousand and a melt index of 30 g/min.
The PPS plastics a-c provided in example 13 and comparative examples 11 and 12 were tested for tensile properties, Izod impact strength and flame retardant properties, the tensile properties were tested according to GB/T14884-2008, the Izod impact strength was tested according to GB/T1843-2008, and the flame retardant properties were tested according to UL-94. The results are shown in Table 6.
TABLE 6
Tensile strength/MPa Impact Strength/J/m Flame retardancy/UL-94
PPS Plastic a 127 73 V-0
PPS Plastic b 72 60 V-1
PPS Plastic c 70 58 V-1
From the test results in table 6, it is seen that the flame retardant provided in example 13 of the present invention has good compatibility with PPS, and not only can improve the flame retardant property of PPS plastic, but also can improve the mechanical properties of PPS plastic. Compared with the PPA and MCA as additive flame retardants, the PPA and MCA have poor compatibility with PPS, are added in large amount, have general flame retardant performance and have no beneficial effect on the mechanical performance of PPS plastics.
Application of PBT plastic
Example 14
The PBT plastic a is prepared by mixing and melting 15 parts by weight of the reactive flame retardant provided in example 2, 0.05 part by weight of azobisisobutyronitrile, 100 parts by weight of PBT, 5 parts by weight of POE, 2 parts by weight of calcium carbonate, 5 parts by weight of glyceryl monostearate and 10 parts by weight of glass fiber.
Comparative example 13
In the comparative example, 20 parts by weight of APP flame retardant, 100 parts by weight of PBT, 5 parts by weight of POE, 2 parts by weight of calcium carbonate, 5 parts by weight of glyceryl monostearate and 10 parts by weight of glass fiber are mixed to prepare the PBT plastic b.
Comparative example 14
In this comparative example, 20 parts by weight of MCA flame retardant, 100 parts by weight of PBT, 5 parts by weight of POE, 2 parts by weight of calcium carbonate, 5 parts by weight of glyceryl monostearate and 10 parts by weight of glass fiber were mixed to prepare PBT plastic c.
The PBT plastics a-c provided by the example 14 and the comparative examples 13 and 14 are tested for tensile property, Izod impact strength and flame retardant property, wherein the tensile property is tested according to GB/T14884-2008, the Izod impact strength is tested according to GB/T1843-2008, and the flame retardant property is tested according to UL-94. The results are shown in Table 7.
TABLE 7
Tensile strength/MPa Impact Strength/J/m Flame retardancy/UL-94
PBT Plastic a 129 136 V-0
PBT Plastic b 111 115 V-1
PBT Plastic c 106 110 V-1
From the test results in table 7, it is seen that the reactive flame retardant provided in example 2 of the present invention is directly added into a PBT plastic system, and under the action of a small amount of initiator added during the rubber mixing of the plastic, the reactive flame retardant can self-polymerize and thus is uniformly dispersed in the PBT plastic, which not only can improve the flame retardant property of the PBT plastic, but also can improve the mechanical properties of the PBT plastic. Compared with the PPA and MCA used as additive flame retardants, the PBT plastic has poor compatibility with the PPA and MCA, is large in addition amount, has general flame retardant performance, and has no beneficial effect on the mechanical performance of PBT plastics.
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 (11)

1. A reactive flame retardant is characterized in that the structure of the reactive flame retardant is as shown in formula 1:
Figure FDA0002942371720000011
wherein M is a metal element, R, R1、R2、R3And R4N is more than or equal to 1, R, R to meet any group of chemical environment1、R2、R3And R4At least one of the groups contains a reactive group, m and q are not less than 0, and m + n + q is 1-5.
2. The reactive flame retardant of claim 1, wherein the reactive group preferably comprises any one or a combination of at least two of a hydroxyl group, an amine group, an unsaturated group, a carboxyl group, an epoxy group, an ester group, an acid anhydride, a methoxy group, an isocyanate group, or a cyano group.
3. The reactive flame retardant according to claim 1 or 2, wherein R is1And R2Each independently preferably comprises H, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstitutedAny one of heteroaryl groups or a combination of at least two thereof.
4. The reactive flame retardant according to claim 3, wherein R is1And R2The compound independently and preferably comprises any one or the combination of at least two of C1-C12 substituted or unsubstituted alkyl, C3-C12 substituted or unsubstituted cycloalkyl, C6-C12 substituted or unsubstituted aryl or substituted or C5-C12 unsubstituted heteroaryl.
5. The reactive flame retardant of any one of claims 1 to 4, wherein R, R is the reactive flame retardant3And R4Each independently preferably includes any one or a combination of at least two of H, hydroxyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkoxy, substituted or unsubstituted aryloxy, or substituted or unsubstituted heteroaryloxy.
6. The reactive flame retardant of claim 5, wherein said R, R3And R4The aryl group independently and preferably comprises any one or a combination of at least two of C1-C12 substituted or unsubstituted alkyl, C3-C12 substituted or unsubstituted cycloalkyl, C6-C12 substituted or unsubstituted aryl, C5-C12 substituted or unsubstituted heteroaryl, C1-C12 substituted or unsubstituted alkoxy, C3-C12 substituted or unsubstituted cycloalkoxy, C6-C12 substituted or unsubstituted aryloxy, and C5-C12 substituted or unsubstituted heteroaryloxy.
7. The reactive flame retardant according to any one of claims 1 to 6, wherein M comprises any one or a combination of at least two of an alkaline earth metal element, a transition metal element, a group IIIA metal element, a group IVA metal element, a group VA metal element, or a group VIA metal element;
preferably, the M includes any one of manganese, copper, molybdenum, titanium, zinc, aluminum, lithium, cobalt or nickel or a combination of at least two thereof.
8. A method for preparing the reactive flame retardant of any one of claims 1 to 7, wherein the method comprises: the acid salt of the metal M is prepared by chemical reaction with a compound containing a reactive group.
9. A polymeric flame retardant prepared by self-polymerization or copolymerization of the reactive flame retardant of any of claims 1-7.
10. A polymeric flame retardant prepared by copolymerization of the reactive flame retardant of any of claims 1-8 with a compound containing a reactive group.
11. Use of a flame retardant according to any of claims 1-10, wherein the field of application of the flame retardant comprises any one or a combination of at least two of thermoplastic resins, thermosetting resins or photocurable resins.
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