CN112961362A - Polymeric flame retardant and preparation method and application thereof - Google Patents
Polymeric flame retardant and preparation method and application thereof Download PDFInfo
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- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
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Abstract
The invention provides a polymeric flame retardant, and a preparation method and application thereof.
Description
Technical Field
The invention belongs to the field of flame retardants, and relates to a polymeric flame retardant, and a preparation method and application 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, antimony trioxide and other combustion-supporting additives which are harmful to organisms and not friendly to the environment 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 traditional halogen-free flame retardant method is generally to add a large amount of salt flame retardant such as ammonium polyphosphate, melamine cyanurate, piperazine pyrophosphate or 2-ethyl aluminium hypophosphite, phosphate ester compounds such as trimethyl phosphate or triphenyl phosphate, and metal hydroxide containing crystal water such as aluminum hydroxide or magnesium hydroxide into a material system to achieve the purpose of flame retardant. 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, and the flame retardance, the mechanical property and the heat resistance of the material are further damaged.
Disclosure of Invention
In order to solve the technical problems, the application provides a polymeric flame retardant, a preparation method and an application thereof, the polymeric flame retardant can directly provide an excellent flame retardant additive for a high polymer material, and the flame retardant provided by the invention has the advantages of simple preparation process, resource saving and environmental protection.
One of the purposes of the invention is to provide a polymeric flame retardant, which has a structure shown in a formula 1:
wherein M is a metal element, R1、R2、R3R, X and Y are any group satisfying the chemical environment, m is 0-3, n is not less than 1.
Where m can be 0, 1, 2, 3, etc., and n can be 1, 5, 10, 20, 50, 80, 100, 150, 200, 500, etc., but is not limited to the recited values, and other values not recited within the above numerical ranges are also applicable.
The polymeric flame retardant provided by the invention has high phosphorus content, has good compatibility with high polymer materials, can stably exert the flame retardant property, and does not have precipitation or migration phenomenon for a long time. Meanwhile, reactive groups can be introduced into the polymeric flame retardant molecules through different chemical reactions, and enter the polymer material molecules through crosslinking of the reactive groups, so that stable flame retardant performance is provided, and the mechanical performance of the polymer material is enhanced.
As a preferred embodiment of the present invention, R is1～R3Each independently preferably comprises H, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkoxy, substituted or unsubstitutedAny one or a combination of at least two of the cycloalkoxy group, the substituted or unsubstituted aryloxy group, or the substituted or unsubstituted heteroaryloxy group of (a).
Among them, the substituted or unsubstituted alkyl group is preferably a substituted or unsubstituted alkyl group having C1 to C12, and may be, for example, a substituted or unsubstituted alkyl group having C2, C3, C4, C5, C6, C7, C8, C9, C10, or C11;
the substituted or unsubstituted cycloalkyl group is preferably a cycloalkyl group having C3 to C12, and may be, for example, a substituted or unsubstituted cycloalkyl group having C4, C5, C6, C7, C8, C9, C10, or C11;
the substituted or unsubstituted aromatic group is preferably a C5-C12 aromatic group, and may be, for example, a substituted or unsubstituted aromatic group of C6, C7, C8, C9, C10 or C11;
the substituted or unsubstituted heteroaryl group is preferably a C5 to C12 heteroaryl group, and may be, for example, a substituted or unsubstituted heteroaryl group of C6, C7, C8, C9, C10, or C11;
the substituted or unsubstituted alkoxy group is preferably a substituted or unsubstituted alkoxy group having C1 to C12, and may be, for example, a substituted or unsubstituted alkoxy group having C2, C3, C4, C5, C6, C7, C8, C9, C10, or C11;
the substituted or unsubstituted cycloalkoxy group is preferably a C3 to C12 cycloalkoxy group, and may be, for example, a C4, C5, C6, C7, C8, C9, C10 or C11 substituted or unsubstituted cycloalkoxy group;
the substituted or unsubstituted aromatic oxy group is preferably a C5 to C12 aromatic oxy group, and may be, for example, a substituted or unsubstituted aromatic oxy group of C6, C7, C8, C9, C10, or C11;
the substituted or unsubstituted heteroaryloxy group is preferably a C5 to C12 heteroaryloxy group, and may be, for example, a substituted or unsubstituted heteroaryloxy group of 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～R3Does not react with the reactants under the reaction conditionsThe other groups react.
As a preferred embodiment of the present invention, R preferably includes any one or a combination of at least two of a group containing a nitrogen element, a group containing a silicon element, a group containing an oxygen element, a group containing a sulfur element, or a group containing a phosphorus element.
Preferably, said R preferably comprises-O-, -O-R4-O-or-NH-R5-NH-wherein R is any one or a combination of at least two4And R5Any group that satisfies its chemical environment.
As a preferred embodiment of the present invention, R is4And R5Each independently preferably includes any one of a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group, or a combination of at least two thereof.
Among them, the substituted or unsubstituted alkylene group is preferably a substituted or unsubstituted alkylene group having C1 to C12, and may be, for example, a substituted or unsubstituted alkylene group having C2, C3, C4, C5, C6, C7, C8, C9, C10, or C11;
the substituted or unsubstituted cycloalkylene group is preferably a cycloalkylene group having C3 to C12, and may be, for example, a substituted or unsubstituted cycloalkylene group having C4, C5, C6, C7, C8, C9, C10, or C11;
the substituted or unsubstituted arylene group is preferably a C5 to C12 arylene group, and may be, for example, a substituted or unsubstituted arylene group of C6, C7, C8, C9, C10 or C11;
the substituted or unsubstituted heteroarylene is preferably a C5-C12 heteroarylene, which may be, for example, a substituted or unsubstituted heteroarylene of C6, C7, C8, C9, C10, or C11.
Preferably, said R is4And R5Each independently preferably includes any one or a combination of at least two of a substituted or unsubstituted alkylene group in which at least one carbon atom is substituted with a silicon atom, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group.
Among them, the substituted or unsubstituted alkylene group in which at least one carbon atom is substituted with a silicon atom is preferably a substituted or unsubstituted alkylene group of C1 to C12, and may be, for example, a substituted or unsubstituted alkylene group of C2, C3, C4, C5, C6, C7, C8, C9, C10, or C11;
the substituted or unsubstituted cycloalkylene group in which at least one carbon atom is substituted with a silicon atom is preferably a cycloalkylene group of C3 to C12, and may be, for example, a substituted or unsubstituted cycloalkylene group of C4, C5, C6, C7, C8, C9, C10, or C11;
the substituted or unsubstituted arylene group in which at least one carbon atom is substituted with a silicon atom is preferably a C5 to C12 arylene group, and may be, for example, a substituted or unsubstituted arylene group of C6, C7, C8, C9, C10, or C11;
the substituted or unsubstituted heteroarylene group in which at least one carbon atom is substituted with a silicon atom is preferably a C5 to C12 heteroarylene group, and may be, for example, a substituted or unsubstituted heteroarylene group of C6, C7, C8, C9, C10, or C11.
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.
As a preferred technical scheme of the invention, X and Y respectively and independently preferably comprise a reactive end capping group or an inert end capping group.
In a preferred embodiment of the present invention, the reactive group contained in the reactive end capping group includes 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.
In the invention, various reactive groups can be introduced into the molecule of the polymeric flame retardant through chemical reaction, for example, groups containing active hydrogen are introduced, and the molecule of the polymeric flame retardant can be introduced into the molecule of the epoxy resin; unsaturated groups (such as vinyl groups) can be introduced to introduce polymeric flame retardant molecules into unsaturated resins (such as acrylic resins); the introduction of amino or epoxy groups can introduce polymeric flame retardant molecules into polyamide molecules, so that the flame retardant property and the mechanical property of the high polymer material are further improved.
Another object of the present invention is to provide a method for preparing the polymeric flame retardant, the method comprising:
prepared by polymerization of an acid salt of a metal M, preferably with a compound containing at least two functional groups;
preferably, the compound is further reacted with an end-capping compound containing X and/or Y.
In the present invention, the acid salt of the metal M is preferably an acid phosphate of the metal M; the compound having at least two functional groups is preferably a compound having at least two hydroxyl groups, at least two amino groups, or at least one hydroxyl group and one amino group, and the compound may be a compound containing a silicon element, a compound containing a sulfur element, a compound containing a phosphorus element, or the like.
The invention also provides an application of the polymeric flame retardant, which is characterized in that the application field of the polymeric flame retardant comprises any one or a 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 polymeric flame retardant, which has wide application range and is suitable for being used as various thermosetting resins, light-cured resins and thermoplastic resins;
(2) the invention discloses a polymeric 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;
(3) the invention discloses a polymeric 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;
(4) the invention discloses a polymeric flame retardant which is added into thermosetting resin, light-cured resin and thermoplastic resin, the prepared resin composition has excellent anti-dripping performance, and the anti-dripping grade in GB/T20284 + 2006 test can reach d0 grade, namely no dripping.
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 polymeric flame retardant, which has a structure shown in formula 2:
the preparation method of the compound shown in the formula 2 comprises the following steps: dissolving 1mol of manganese dihydrogen phosphate in 100mL of DMF, adding 1mol of 1, 3-propylene glycol and 0.01mol of dibutyltin oxide, reacting for 3h at 150 ℃, reacting for 3h at 170 ℃ and reacting for 3h at 190 ℃, separating the solvent by distillation, mixing the obtained product with 0.95mol of methanol, adding 0.1mol of epichlorohydrin after the methanol completely reacts, and purifying the product after the reaction is finished to obtain the compound shown in the formula 2.
1H NMR(CDCl3,500MHz):δ4.11～4.05(t，2H，CH2)，3.71～3.63(s，6H，CH3)，3.45～3.37(t，2H，CH2)，1.89～1.82(m，2H，CH2)。
No hydroxyl hydrogen peak appears in the result of the nuclear magnetic resonance hydrogen spectrum, which proves that the hydroxyl of the manganese dihydrogen phosphate has all the corresponding reactions. The softening point was 132 ℃.
ICP test of the obtained flame retardant shows that the manganese element, the phosphorus element and the carbon element exist simultaneously in the obtained compound, and the molar ratio of the manganese element to the phosphorus element to the carbon element is 1:2: 5.
Example 2
The embodiment provides a polymeric flame retardant, which has a structure shown in formula 3:
the preparation method of the compound shown in the formula 3 comprises the following steps: dissolving 1.5mol of sodium dihydrogen phosphate and 0.5mol of molybdenum trichloride in 100mL of NMP, adding 0.5mol of ethylenediamine and 0.01mol of DMAP, reacting at 160 ℃ for 2.5h, at 175 ℃ for 2.5h and at 190 ℃ for 2.5h in sequence, separating the solvent by distillation, reacting the obtained product with 2.05mol of allyl alcohol, and purifying the product after the reaction is finished to obtain the compound shown in the formula 3.
1H NMR(CDCl3,500MHz):δ6.02～5.95(m，2H，HC＝CH2)，5.41～5.36(t，2H，HC＝CH 2)，5.28～5.21(t，2H，HC＝CH 2)，4.59～4.52(d，4H，CH2)，2.83～2.75(m，4H，CH2)，2.30～2.22(t，2H，NH)。
No hydroxyl hydrogen peak appears in the result of the nuclear magnetic resonance hydrogen spectrum, which proves that the hydroxyl groups of the barium dihydrogen phosphate all have corresponding reaction. The softening point of the product was 137 ℃.
Example 3
The embodiment provides a polymeric flame retardant, which has a structure shown in formula 4:
the preparation method of the compound shown in the formula 4 comprises the following steps: dissolving 1mol of zinc dihydrogen phosphate in 100mL of DMSO, adding 1mol of 1, 4-cyclohexanediamine and 0.01mol of DMAP, reacting for 3h at 190 ℃, reacting for 3h at 210 ℃ and reacting for 3h at 230 ℃, separating the solvent by distillation, reacting the obtained product with 3mol of epichlorohydrin, acidifying after the reaction is finished, washing to neutrality, and purifying the product to obtain the compound shown in formula 4.
1H NMR(CDCl3,500MHz):δ4.13～4.06(t，4H，CH2)，3.72～3.65(t，2H，OH)，3.53～3.46(m，4H，CH2)，2.58～2.52(m，2H，CH)，2.30～2.22(d，2H，NH)，2.01～1.95(m，4H，CH2)，1.75～1.69(m，2H，CH2)，1.62～1.55(m，2H，CH2)，1.51～1.44(m，2H，CH2)，1.36～1.30(m，2H，CH2)。
The result of the nuclear magnetic resonance hydrogen spectrum shows that the peak of hydroxyl hydrogen is 3.72-3.65, which is different from the chemical shift of hydroxyl hydrogen on phosphoric acid, and the hydroxyl groups of zinc dihydrogen phosphate all have corresponding reaction. The softening point of the product was 153 ℃.
Example 4
The embodiment provides a polymeric flame retardant, which has a structure shown in formula 5:
the preparation method of the compound shown in the formula 5 comprises the following steps: dissolving 1mol of manganese dihydrogen phosphate in 100mL of cyclohexanone, adding 1mol of 1, 3-propylene glycol and 0.01mol of dibutyltin oxide, reacting for 3h at 160 ℃, 3h at 180 ℃ and 3h at 200 ℃ in sequence, separating the solvent by distillation, mixing the obtained product with 1.99mol of ethanol, and purifying the product after the ethanol completely reacts to obtain the compound shown in the formula 5.
1H NMR(CDCl3,500MHz):δ4.12～4.06(t，2H，CH2)，3.70～3.62(s，6H，CH3)，3.43～3.35(t，2H，CH2)，2.33～2.27(d，H，NH)，1.88～1.81(m，2H，CH2)。
No hydroxyl hydrogen peak appears in the result of the nuclear magnetic resonance hydrogen spectrum, which proves that the hydroxyl groups of the monocalcium phosphate all have corresponding reaction. The softening point of the product was 145 ℃.
Example 5
The embodiment provides a polymeric flame retardant, which has a structure shown in formula 6:
the preparation method of the compound shown in the formula 6 comprises the following steps: dissolving 1mol of manganese dihydrogen phosphate in 100mL of DMF, adding 1mol of gamma-aminopropyl trimethoxy silane, 0.01mol of DMAP and 0.05mol of dibutyltin oxide, reacting for 1.5h at 180 ℃, 1.5h at 200 ℃ and 1.5h at 220 ℃ in sequence, separating the solvent by distillation, mixing the obtained product with 1.99mol of methanol, and purifying the product after the methanol completely reacts to obtain the compound shown in the formula 6.
1H NMR(CDCl3,500MHz):δ3.83～3.76(s，6H，CH3)，3.62～3.55(s，6H，CH3)，2.53～2.46(m，2H，CH2)，2.35～2.28(d，H，NH)，1.59～1.53(m，2H，CH2)，0.68～0.59(t，2H，CH2)。
No hydroxyl hydrogen peak appears in the result of the nuclear magnetic resonance hydrogen spectrum, which proves that the hydroxyl of the magnesium dihydrogen phosphate has all the corresponding reactions. The softening point of the product was 131 ℃.
Example 6
The embodiment provides a polymeric flame retardant, which has a structure shown in formula 7:
the preparation method of the compound shown in the formula 7 comprises the following steps: dissolving 1mol of aluminum dihydrogen phosphate in 100mL of NMP, adding 1mol of diethyl triamine and 0.01mol of DMAP, reacting for 3h at 180 ℃, reacting for 3h at 200 ℃ and reacting for 3h at 220 ℃, mixing the obtained product with 3.99mol of methanol, and purifying the product after the methanol completely reacts to obtain the compound shown in the formula 7.
1H NMR(CDCl3,500MHz):δ3.95～3.87(m，4H，CH2)，3.83～3.77(s，12H，CH3)，2.30～2.23(d，H，NH)。
No hydroxyl hydrogen peak appears in the result of the nuclear magnetic resonance hydrogen spectrum, which proves that the hydroxyl groups of the aluminum dihydrogen phosphate have all the corresponding reactions. The softening point of the product was 149 ℃.
Application in polycarbonate plastics
Example 7
In this example, polycarbonate plastics a to f were prepared by separately mixing 18 parts by weight of the polymeric flame retardant provided in examples 1 to 6, 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 1
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 light stabilizer to prepare polycarbonate plastic g.
Comparative example 2
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 h.
The polycarbonate plastics a-h provided in example 7 and comparative examples 1 and 2 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, the flame retardant properties were tested according to UL-94, and the anti-drip test method was GB/T20284-. The results are shown in Table 1.
TABLE 1
As can be seen from the test results in Table 1, the polymeric flame retardants provided in examples 1-6 of the present invention, due to their 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 retardants provided in examples 1 to 6, 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 8
In this example, PPS plastics a to f were prepared by separately mixing 18 parts by weight of the polymeric flame retardant provided in examples 1 to 6, 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.
Comparative example 3
In this comparative example, PPS plastic g was prepared by mixing 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. 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 4
In this comparative example, PPS plastic h 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-h provided by the example 8 and the comparative examples 3 and 4 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, the flame retardant property is UL-94, and the anti-dripping property is GB/T20284-. The results are shown in Table 2.
TABLE 2
The test results in Table 2 show that the flame retardants provided in examples 1-6 of the present invention have good compatibility with PPS, and not only can improve the flame retardant properties 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 9
In this example, 15 parts by weight of the polymeric 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 provided in examples 1 to 6 were independently mixed to prepare PBT plastics a to f.
Comparative example 5
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 g.
Comparative example 6
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 a PBT plastic h.
The PBT plastics a-h provided by the example 9 and the comparative examples 5 and 6 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, the flame retardant property is UL-94, and the anti-dripping test method is GB/T20284-. The results are shown in Table 3.
TABLE 3
| Tensile strength/MPa | Impact Strength/J/m | Flame retardancy/UL-94 | Drip rating | |
| PBT Plastic a | 131 | 138 | V-0 | d0 |
| PBT Plastic b | 123 | 132 | V-0 | d0 |
| PBT Plastic c | 135 | 141 | V-0 | d0 |
| PBT Plastic d | 128 | 137 | V-0 | d0 |
| PBT Plastic e | 125 | 135 | V-0 | d0 |
| PBT Plastic d | 130 | 138 | V-0 | d0 |
| PBT Plastic g | 111 | 115 | V-1 | d1 |
| PBT plastic h | 106 | 110 | V-1 | d1 |
The test results in Table 3 show that the flame retardant provided by the embodiments 1-6 of the invention has good compatibility with PBT, and can improve the flame retardant property of PBT plastic and the mechanical property of 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.
Application of PPO plastic
Example 10
In this example, 15 parts by weight of the polymeric flame retardant provided in examples 1 to 6, 100 parts by weight of PPO, 10103.5 parts by weight of antioxidant, 15 parts by weight of titanium dioxide, 10 parts by weight of SEBS, and 5 parts by weight of graft PP were independently mixed to prepare PPO plastics a-f.
Comparative example 7
In the comparative example, 25 parts by weight of PPA flame retardant, 100 parts by weight of PPO, 10103.5 parts by weight of antioxidant, 15 parts by weight of titanium dioxide, 10 parts by weight of SEBS and 5 parts by weight of grafted PP are mixed to prepare PPO plastic g.
Comparative example 8
In the comparative example, 25 parts by weight of MCA flame retardant, 100 parts by weight of PPO, 10103.5 parts by weight of antioxidant, 15 parts by weight of titanium dioxide, 10 parts by weight of SEBS and 5 parts by weight of grafted PP are mixed to prepare the PPO plastic h.
The PPO plastics a-h provided by the example 10 and the comparative examples 7 and 8 are tested for tensile property, cantilever beam impact strength and flame retardant property, wherein the tensile property is tested according to GB/T14884-2008, the cantilever beam impact strength is tested according to GB/T1843-2008, the flame retardant property is UL-94, and the anti-dripping test method is GB/T20284-. The results are shown in Table 4.
TABLE 4
The test results in table 4 show that the flame retardants provided in examples 1 to 6 of the present invention have good compatibility with PPO, and not only can improve the flame retardant property of PPO plastics, but also can improve the mechanical properties of PPO plastics. Compared with PPA and MCA which are additive flame retardants, the PPA and MCA have poor compatibility with PPO, not only are the addition amount of the PPA and MCA large, but also the flame retardant performance is general, and the PPO plastic has no beneficial effect on the mechanical performance.
Application in epoxy resin
Example 11
In this example, 100 parts by weight of bisphenol A epoxy resin having an epoxy equivalent of 360/eq and 6 parts by weight of dicyandiamide were mixed with 20 parts by weight of the flame retardant described in example 3 or 4, respectively, and cured at 185 ℃ for 1.5 hours to obtain epoxy resin cured products a and b.
Comparative example 9
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 was added and cured at 185 ℃ for 1.5 hours to obtain an epoxy resin cured product c.
Comparative example 10
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 185 ℃ for 1.5 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, the flame retardance test method is UL-94, and the anti-dripping test method is GB/T20284-2006. The test results are shown in Table 5.
TABLE 5
From the test results in table 5, it can be seen that the flame retardant provided by the present application, after being added into an epoxy resin system, has more excellent flame retardant performance and mechanical properties of the epoxy resin cured product prepared with the same addition amount of the conventional flame retardant. And the polymeric flame retardant provided by the embodiment 3 of the application has hydroxyl groups, and can react with the epoxy group at the tail end of the epoxy resin, so that the compatibility of the flame retardant and an epoxy resin system is further improved, and the polymeric flame retardant has more beneficial performance.
Application of the silicone resin:
example 12
In this example, 114 parts by weight of trimethylethoxysiloxane, 186 parts by weight of tetraethoxysiloxane and 50 parts by weight of sodium nonahydrate were mixed with 50 parts by weight of the flame retardant prepared in example 5 or 6, respectively, and cured at 20 ℃ for 5 hours to prepare silicone resins a and b.
Comparative example 11
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 c.
Comparative example 12
In this comparative example, 114 parts by weight of trimethylethoxysiloxane, 186 parts by weight of tetraethoxysiloxane, 50 parts by weight of sodium nonahydrate, and 30 parts by weight of APP were mixed and cured at 20 ℃ for 5 hours to prepare a silicone resin d.
The performance of the obtained silicone resins a-d 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, the test condition of water resistance is soaking in boiling water for 2h, and the test method of anti-dripping is GB/T20284-2006. The test results are shown in table 6.
TABLE 6
According to the test results in table 6, after the flame retardant provided by the present application is added into a silicone resin system, the prepared silicone resin has more excellent flame retardant performance and mechanical properties for the existing flame retardant with the same addition amount. The flame retardant containing silicon element prepared in the example 5 has better compatibility with the silicone resin, so that the performance of the silicone resin is further improved.
Use in unsaturated resins:
example 13
In this example, 25 parts by weight of the flame retardant prepared in example 2 or 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, respectively, to prepare crosslinking type acrylic resin compositions a and b.
Comparative example 13
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 c.
Comparative example 14
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 d.
The acrylic resin compositions a to d prepared as described above were tested for compressive strength, tensile strength, water resistance and flame retardancy, and the results are shown in table 7. 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 2h, and then the compressive strength test is carried out again, and the anti-dripping test method is GB/T20284-.
TABLE 7
According to the test results in table 7, it can be seen that the flame retardant provided by the present application, after being added into an acrylic resin composition system, has more excellent flame retardant performance and mechanical properties for the same added amount of the existing flame retardant. In example 2, the provided flame retardant has an unsaturated group, and can react with the unsaturated group in the acrylic resin in the process of preparing the acrylic resin, so that the flame retardant is combined with acrylic resin molecules, and the compatibility of the flame retardant and an acrylic resin system is further increased, so that the flame retardant has better performance compared with the polymeric flame retardant without the unsaturated group in example 4.
The application of the nylon composite material is as follows:
example 14
In this example, 15 parts by weight of the flame retardant prepared in example 1 or 5 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 an antioxidant, 34 parts by weight of glass fiber, and 0.8 part by weight of bisstearamide to prepare nylon composites a and b.
Comparative example 15
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, 34 parts by weight of glass fiber, and 0.8 part by weight of bisstearamide to prepare nylon composite c.
Comparative example 16
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, 34 parts by weight of glass fiber, and 0.8 part by weight of bisstearamide were mixed to prepare a nylon composite d.
The nylon composites a-d prepared in example 14 and comparative examples 15 and 16 were tested for compressive strength (GB/T15231-2008), tensile strength (ASTM C1557-2003(2008)), and flammability, and for anti-dripping test method GB/T20284-.
TABLE 8
According to the test results in table 8, after the flame retardant provided by the application is added into a nylon composite system, the prepared nylon composite has more excellent flame retardant performance and mechanical performance for the existing flame retardant with the same addition amount.
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 polymeric flame retardant is characterized in that the polymeric flame retardant has a structure shown in formula 1:
wherein M is a metal element, R1、R2、R3R, X and Y are any group satisfying the chemical environment, m is 0-3, n is not less than 1.
2. The polymeric flame retardant of claim 1, wherein each of R1-R3 independently preferably comprises 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.
3. A polymeric flame retardant according to claim 2, wherein R is1～R3Each independently preferably comprises an inert group.
4. A polymeric flame retardant according to any of claims 1-3, wherein R preferably comprises any one or a combination of at least two of a nitrogen-containing group, a silicon-containing group, a sulfur-containing group, an oxygen-containing group, or a phosphorus-containing group;
preferably, said R preferably comprises-O-, -O-R4-O-or-NH-R5-NH-wherein R is any one or a combination of at least two4And R5Any group that satisfies its chemical environment.
5. A polymeric flame retardant according to claim 4, wherein R is4And R5Each independently preferably includes any one of a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group, or a combination of at least two thereof;
preferably, said R is4And R5Each independently preferably comprises a substituted or unsubstituted alkylene group having at least one carbon atom substituted with a silicon atom, substituted or unsubstitutedAny one or a combination of at least two of a substituted cycloalkylene, a substituted or unsubstituted arylene, or a substituted or unsubstituted heteroarylene.
6. A polymeric flame retardant according to any of claims 1-5, wherein M comprises any one of 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.
7. A polymeric flame retardant according to any of claims 1 to 6, wherein X and Y each independently preferably comprise a reactive end cap or an inert end cap.
8. A polymeric flame retardant according to claim 7, wherein the reactive end capping group comprises reactive groups preferably comprising any one or a combination of at least two of hydroxyl, amine, unsaturated, carboxyl, epoxy, ester, anhydride, methoxy, isocyanate or cyano groups.
9. A method of preparing a polymeric flame retardant of any of claims 1-8, comprising:
prepared by polymerization of an acid salt of a metal M, preferably with a compound containing at least two functional groups;
preferably, the compound is further reacted with an end-capping compound containing X and/or Y.
10. Use of a polymeric flame retardant according to any of claims 1 to 8, wherein the polymeric flame retardant is used in the field of applications comprising any one or a combination of at least two of thermoplastic resins, thermosetting resins or photocurable resins.
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| WO2022089468A1 (en) * | 2020-10-29 | 2022-05-05 | 广东广山新材料股份有限公司 | Polymeric flame retardant, preparation method therefor and use thereof |
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