WO2022089468A1 - Polymeric flame retardant, preparation method therefor and use thereof - Google Patents

Polymeric flame retardant, preparation method therefor and use thereof Download PDF

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Publication number
WO2022089468A1
WO2022089468A1 PCT/CN2021/126625 CN2021126625W WO2022089468A1 WO 2022089468 A1 WO2022089468 A1 WO 2022089468A1 CN 2021126625 W CN2021126625 W CN 2021126625W WO 2022089468 A1 WO2022089468 A1 WO 2022089468A1
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flame retardant
substituted
group
unsubstituted
weight
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PCT/CN2021/126625
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French (fr)
Chinese (zh)
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潘庆崇
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广东广山新材料股份有限公司
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Publication of WO2022089468A1 publication Critical patent/WO2022089468A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the present application relates to the field of flame retardants, such as a polymeric flame retardant and its preparation method and application.
  • Traditional flame retardant technology is generally divided into halogen flame retardant and halogen-free flame retardant.
  • halogen flame retardant methods are generally made by reacting molecules containing halogen and reactive groups with other materials to obtain halogen flame retardant materials, or using decabromodiphenyl ethane without reactive groups.
  • the halogen flame retardant is directly added to the material to achieve the purpose of flame retardant.
  • antimony trioxide and other combustion aids that are harmful to organisms and unfriendly to the environment in the flame retardant system.
  • Halogen-containing flame retardant substances will produce non-degradable or refractory dioxin-like organic halogen chemicals and accumulate when they are decomposed or burned by heat, polluting the environment, affecting the growth and development of organisms and human health.
  • the traditional halogen-free flame retardant method is generally to add a large amount of salt flame retardants such as ammonium polyphosphate, melamine cyanurate, piperazine pyrophosphate or 2-ethyl aluminum hypophosphite into the material system, and such as triphosphate.
  • salt flame retardants such as ammonium polyphosphate, melamine cyanurate, piperazine pyrophosphate or 2-ethyl aluminum hypophosphite
  • Phosphate compounds such as methyl ester or triphenyl phosphate, and metal hydroxides containing crystal water such as aluminum hydroxide or magnesium hydroxide are used to achieve the purpose of flame retardancy.
  • the present application provides a polymeric flame retardant and a preparation method and application thereof.
  • the polymeric flame retardant can directly provide excellent flame retardant additives for polymer materials, and the flame retardant provided by the present application has a simple preparation process, is resource-saving, and is environmentally friendly.
  • the embodiment of the present application provides a polymeric flame retardant, and the structure of the polymeric flame retardant is shown in Formula 1:
  • M is a metal element
  • n can be 0, 1, 2, or 3, etc.
  • n can be 1, 5, 10, 20, 50, 80, 100, 150, 200, or 500, etc., but it is not limited to the listed values. The same applies to other non-recited values in the range.
  • the provided polymeric flame retardant not only has a high content of phosphorus element, but also has good compatibility with polymer materials, and can stably exert its flame retardant performance without precipitation or migration for a long time.
  • reactive groups can be introduced into the polymerized flame retardant molecules through different chemical reactions, and the reactive groups can be cross-linked into the polymer material molecules, which can provide stable flame retardant performance and enhance the mechanical properties of polymer materials. .
  • the R 1 to R 3 preferably independently include H, hydroxyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, Any of substituted or unsubstituted heteroaryl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkoxy, substituted or unsubstituted aryloxy, or substituted or unsubstituted heteroaryloxy one or a combination of at least two.
  • the substituted or unsubstituted alkyl group is preferably a C1-C12 substituted or unsubstituted alkyl group, such as C2, C3, C4, C5, C6, C7, C8, C9, C10 or C11 substituted or unsubstituted the alkyl group;
  • the substituted or unsubstituted cycloalkyl is preferably a C3-C12 cycloalkyl, such as a C4, C5, C6, C7, C8, C9, C10 or C11 substituted or unsubstituted cycloalkyl;
  • the substituted or unsubstituted aryl group is preferably a C5-C12 aryl group, such as a substituted or unsubstituted aryl group of C6, C7, C8, C9, C10 or C11;
  • the substituted or unsubstituted heteroaryl is preferably a C5-C12 heteroaryl, such as a substituted or unsubstituted heteroaryl of C6, C7, C8, C9, C10 or C11;
  • the substituted or unsubstituted alkoxy groups are preferably C1-C12 substituted or unsubstituted alkoxy groups, such as C2, C3, C4, C5, C6, C7, C8, C9, C10 or C11 substituted or unsubstituted alkoxy;
  • the substituted or unsubstituted cycloalkoxy is preferably a C3-C12 cycloalkoxy, such as a C4, C5, C6, C7, C8, C9, C10 or C11 substituted or unsubstituted cycloalkoxy;
  • the substituted or unsubstituted aryloxy group is preferably a C5-C12 aryloxy group, such as a C6, C7, C8, C9, C10 or C11 substituted or unsubstituted aryloxy group;
  • the substituted or unsubstituted heteroaryloxy group is preferably a C5-C12 heteroaryloxy group, such as a C6, C7, C8, C9, C10 or C11 substituted or unsubstituted heteroaryloxy group.
  • the R 1 to R 3 each independently preferably include an inert group.
  • R 1 to R 3 are inert groups.
  • R 1 to R 3 do not react with other groups in the reactants under the reaction conditions.
  • the R preferably includes a group containing nitrogen, a group containing silicon, a group containing oxygen, a group containing sulfur or a group containing phosphorus. any one or a combination of at least two.
  • the R preferably includes any one or a combination of at least two of -O-, -OR 4 -O- or -NH-R 5 -NH-, wherein R 4 and R 5 satisfy their chemical any group of the environment.
  • the R 4 and R 5 each independently preferably include a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted arylene group or a substituted or unsubstituted alkylene group. or any one or a combination of at least two of the unsubstituted heteroarylene groups.
  • the substituted or unsubstituted alkylene is preferably a C1-C12 substituted or unsubstituted alkylene, such as C2, C3, C4, C5, C6, C7, C8, C9, C10 or C11 substituted or unsubstituted alkylene;
  • the substituted or unsubstituted cycloalkylene is preferably a C3-C12 cycloalkylene, such as a C4, C5, C6, C7, C8, C9, C10 or C11 substituted or unsubstituted cycloalkylene;
  • the substituted or unsubstituted arylene group is preferably a C5-C12 arylene group, such as a substituted or unsubstituted arylene group of C6, C7, C8, C9, C10 or C11;
  • the substituted or unsubstituted heteroarylene group is preferably a C5-C12 heteroarylene group, for example, a substituted or unsubstituted heteroarylene group which may be C6, C7, C8, C9, C10 or C11.
  • said R 4 and R 5 each independently preferably include a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene group in which at least one carbon atom is replaced by a silicon atom Any one or a combination of at least two of arylene or substituted or unsubstituted heteroarylene.
  • the substituted or unsubstituted alkylene group in which at least one carbon atom is replaced by a silicon atom is preferably a C1-C12 substituted or unsubstituted alkylene group, such as C2, C3, C4, C5, C6, C7, C8, C9, C10 or C11 substituted or unsubstituted alkylene;
  • the substituted or unsubstituted cycloalkylene group in which at least one carbon atom is replaced by a silicon atom is preferably a C3-C12 cycloalkylene group, for example, it can be substituted by C4, C5, C6, C7, C8, C9, C10 or C11 or unsubstituted cycloalkylene;
  • the substituted or unsubstituted arylene group in which at least one carbon atom is replaced by a silicon atom is preferably a C5-C12 arylene group, such as a C6, C7, C8, C9, C10 or C11 substituted or unsubstituted arylene group ;
  • the substituted or unsubstituted heteroarylene group in which at least one carbon atom is replaced by a silicon atom is preferably a C5-C12 heteroarylene group, such as a substituted or unsubstituted arylene group of C6, C7, C8, C9, C10 or C11 Heteroaryl.
  • the M includes any one or a combination of at least two of alkaline earth metal elements, transition metal elements, group IIIA metal elements, group IVA metal elements, group VA metal elements or group VIA metal elements .
  • the alkaline earth metal element can be Be, Mg, Ca, Sr, Ba or Ra;
  • Transition metal elements 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, lanthanide or actinide, etc.;
  • Group IIIA metal elements can be Al, Ga, In or Tl;
  • Group IVA metal elements can be Ge, Sn or Pb;
  • Group VA metal element can be Sb or Bi
  • the group VIA metal element may be Po.
  • the X and Y each independently preferably include a reactive end-capping group or an inert end-capping group.
  • the reactive group contained in the reactive end-capping group includes a hydroxyl group, an amine group, an unsaturated group, a carboxyl group, an epoxy group, an ester group, an acid anhydride, an isocyanate group or a cyano group. Any one or a combination of at least two.
  • a variety of reactive groups can be introduced into the polymerized flame retardant molecules through chemical reactions, such as the introduction of groups containing active hydrogen, the polymerized flame retardant molecules can be introduced into the epoxy resin molecules; the introduction of unsaturated Groups (such as vinyl) can introduce polymeric flame retardant molecules into unsaturated resins (such as acrylic resins); introducing amino or epoxy groups can introduce polymeric flame retardant molecules into polyamide molecules, further improving Flame retardant properties and mechanical properties of polymer materials.
  • unsaturated Groups such as vinyl
  • unsaturated resins such as acrylic resins
  • introducing amino or epoxy groups can introduce polymeric flame retardant molecules into polyamide molecules, further improving Flame retardant properties and mechanical properties of polymer materials.
  • the embodiment of the present application provides a preparation method of the above-mentioned polymeric flame retardant, and the preparation method includes:
  • the acid salt of metal M is preferably prepared by polymerization reaction with a compound containing at least two functions;
  • it is prepared by reacting with an end-capping compound containing X and/or Y.
  • the acid salt of metal M is preferably the acid phosphate of metal M;
  • the compound containing at least two functions is preferably a compound containing at least two hydroxyl groups, at least two amino groups or at least one hydroxyl group and one amino group,
  • the compound may be a silicon element-containing compound, a sulfur element-containing compound, a phosphorus element-containing compound, or the like.
  • the embodiment of the present application provides an application of the above-mentioned polymeric flame retardant, and the application field of the polymeric flame retardant includes any one or at least two of thermoplastic resins, thermosetting resins or photocurable resins The combination.
  • thermosetting resins thermosetting resins
  • photocurable resins thermoplastic resins
  • thermosetting resins thermosetting resins
  • photocurable resins thermoplastic resins
  • prepared resin composition has excellent mechanical properties, heat resistance, electrical properties and flame retardant properties.
  • thermosetting resins thermosetting resins
  • light-curing resins thermoplastic resins
  • the prepared resin composition has excellent anti-dripping properties.
  • the anti-drip rating of d0 can reach the d0 level, that is, no dripping.
  • This embodiment provides a polymeric flame retardant, the structure of which is shown in formula 2:
  • the preparation method of the compound shown in formula 2 is as follows: dissolving 1 mol of manganese dihydrogen phosphate in 100 mL of DMF, adding 1 mol of 1,3-propanediol and 0.01 mol of dibutyltin oxide, and reacting at 150 °C for 3 hours, 170 °C for 3 hours and The reaction was carried out at 190° C. for 3 hours. After separating the solvent by distillation, the obtained product was mixed with 0.95 mol of methanol. After the methanol was completely reacted, 0.1 mol of epichlorohydrin was added. After the reaction, the product was purified to obtain the compound shown in formula 2.
  • This embodiment provides a polymeric flame retardant, the structure of which is shown in formula 3:
  • the preparation method of the compound shown in formula 3 is as follows: dissolving 1.5mol sodium dihydrogen phosphate and 0.5mol molybdenum trichloride in 100mL NMP, adding 0.5mol ethylenediamine and 0.01mol DMAP, and reacting at 160 ° C for 2.5h, 175 The reaction was carried out at °C for 2.5 h and at 190 °C for 2.5 h. After separating the solvent by distillation, the obtained product was reacted with 2.05 mol of allyl alcohol. After the reaction, the product was purified to obtain the compound shown in formula 3.
  • This embodiment provides a polymeric flame retardant, the structure of which is shown in formula 4:
  • the preparation method of the compound shown in formula 4 is as follows: dissolve 1 mol of zinc dihydrogen phosphate in 100 mL of DMSO, add 1 mol of 1,4-cyclohexanediamine and 0.01 mol of DMAP, and react at 190°C for 3h, 210°C for 3h and 230°C in turn. The reaction was carried out at °C for 3 h, and after separating the solvent by distillation, the obtained product was reacted with 3 mol of epichlorohydrin, acidified after the reaction, washed with water until neutral, and the product was purified to obtain the compound shown in formula 4.
  • This embodiment provides a polymeric flame retardant, the structure of which is shown in formula 5:
  • the preparation method of the compound shown in formula 5 is as follows: dissolve 1 mol of manganese dihydrogen phosphate in 100 mL of cyclohexanone, add 1 mol of 1,3-propanediol and 0.01 mol of dibutyl tin oxide, and react at 160 °C for 3 hours and 180 °C in turn. The reaction was carried out for 3 hours and 200° C. for 3 hours, and after the solvent was separated by distillation, the obtained product was mixed with 1.99 mol of ethanol, and after the ethanol was completely reacted, the product was purified to obtain the compound shown in formula 5.
  • This embodiment provides a polymeric flame retardant, the structure of which is shown in formula 6:
  • the preparation method of the compound shown in formula 6 is as follows: dissolve 1 mol of manganese dihydrogen phosphate in 100 mL of DMF, add 1 mol of ⁇ -aminopropyltrimethoxysilane, 0.01 mol of DMAP and 0.05 mol of dibutyltin oxide, and react at 180° C. 1.5h, 200°C for 1.5h and 220°C for 1.5h. After separating the solvent by distillation, the obtained product was mixed with 1.99mol methanol. After methanol was completely reacted, the product was purified to obtain the compound shown in formula 6.
  • This embodiment provides a polymeric flame retardant, the structure of which is shown in formula 7:
  • the preparation method of the compound shown in formula 7 is as follows: dissolve 1 mol of aluminum dihydrogen phosphate in 100 mL of NMP, add 1 mol of diethyltriamine and 0.01 mol of DMAP, and react at 180 °C for 3 hours, 200 °C for 3 hours and 220 °C in turn. In 3h, the obtained product was mixed with 3.99 mol of methanol, and after the methanol was completely reacted, the product was purified to obtain the compound shown in formula 7.
  • Example 7 The tensile properties, Izod impact strength and flame retardant properties of polycarbonate plastics a-h provided in Example 7 and Comparative Examples 1 and 2 were tested.
  • the tensile properties were tested according to GB/T14884-2008, and the Izod impact strength was tested according to GB/T1843-2008 for testing, the flame retardancy test method is UL-94, and the anti-drip test method is GB/T 20284-2006.
  • the results are shown in Table 1.
  • PPS plastics a-f 18 parts by weight of the polymeric flame retardant provided in Examples 1-6, 100 parts by weight of PPS, 10 parts by weight of talc, 8 parts by weight of polyvinyl acetate, 5 parts by weight of zirconia, Mixed to prepare PPS plastics a-f.
  • the PPS used was linear PPS with a molecular weight of about 50,000 and a melt index of 30 g/min.
  • PPS plastic g 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 g.
  • the PPS used was linear PPS with a molecular weight of about 50,000 and a melt index of 30 g/min.
  • PPS plastic h 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 were mixed to prepare PPS plastic h.
  • the PPS used was linear PPS with a molecular weight of about 50,000 and a melt index of 30 g/min.
  • the tensile properties, Izod impact strength and flame retardant properties of the PPS plastics a-h provided in Example 8 and Comparative Examples 3 and 4 were tested, the tensile properties were tested according to GB/T14884-2008, and the Izod impact strength was tested according to GB/ T1843-2008 for testing, the flame retardancy test method is UL-94, and the anti-drip test method is GB/T 20284-2006.
  • the results are shown in Table 2.
  • the tensile properties, Izod impact strength and flame retardant properties of the PBT plastics a-h provided in Example 9 and Comparative Examples 5 and 6 were tested, the tensile properties were tested according to GB/T14884-2008, and the Izod impact strength was tested according to GB/ T1843-2008 for testing, the flame retardancy test method is UL-94, and the anti-drip test method is GB/T 20284-2006.
  • the results are shown in Table 3.
  • PPA flame retardant 25 parts by weight of PPA flame retardant, 100 parts by weight of PPO, 3.5 parts by weight of antioxidant 1010, 15 parts by weight of titanium dioxide, 10 parts by weight of SEBS, and 5 parts by weight of grafted PP were mixed to prepare PPO plastic g.
  • the tensile properties, Izod impact strength and flame retardant properties of the PPO plastics a-h provided in Example 10 and Comparative Examples 7 and 8 were tested, the tensile properties were tested according to GB/T14884-2008, and the Izod impact strength was tested according to GB/ T1843-2008 for testing, the flame retardancy test method is UL-94, and the anti-drip test method is GB/T 20284-2006.
  • the results are shown in Table 4.
  • the performance of the above epoxy resin cured products a-d is tested.
  • the test method of bending strength adopts GB/T 9341-2008
  • the test method of impact strength adopts GB/T 1843-2008
  • the breakdown voltage adopts GB/T 1408.1-2006.
  • the flame retardancy test method is UL-94
  • the anti-drip test method is GB/T 20284-2006.
  • Table 5 The test results are shown in Table 5.
  • the properties of the silicone resins a-d obtained above are tested, the tensile strength and elongation test methods are GB/T 1701-2001, the shear strength test method is GB/T 1700-2001, and the flame retardancy test method is UL- 94.
  • the test condition of water resistance is immersion in boiling water for 2h, and the test method of anti-dropping is GB/T 20284-2006. The test results are shown in Table 6.
  • Example 2 or 4 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, and 11 parts by weight of methacrylic acid. 1 part by weight, 13 parts by weight of hydroxypropyl acrylate, 45 parts by weight of trifluoroethyl methacrylate, 2 parts by weight of benzoyl peroxide, 70 parts by weight of xylene, 20 parts by weight of methyl ethyl ketone, and 10 parts by weight of cyclohexanone
  • the cross-linked acrylic resin compositions a and b were prepared by mixing.
  • the compressive strength, tensile strength, water resistance and flame retardancy of the acrylic resin compositions a-d prepared above were tested, and the results are shown in Table 7.
  • the compression test method adopts GB/T 20467-2008
  • the tensile strength test method adopts GB/T 6344-2008
  • the flame retardancy test method is UL-94.
  • the water resistance is to soak the acrylic resin composition after the compressive strength test in boiling water for 2 hours, and then conduct the compressive strength test again.
  • the anti-dropping test method is GB/T 20284-2006.
  • the flame retardant of the prepared acrylic resin composition is Performance and mechanical properties are more excellent.
  • Example 2 because the flame retardant provided by it has unsaturated groups, it can react with the unsaturated groups in the acrylic resin in the process of preparing the acrylic resin, thereby combining with the acrylic resin molecules, further increasing the flame retardant.
  • the compatibility of the agent with the acrylic resin system so compared with the polymeric flame retardant without unsaturated groups in Example 4, it has better performance.
  • Example 15 parts by weight of the flame retardant prepared in Example 1 or 5 was mixed with 81 parts by weight of nylon 610, 23 parts by weight of nylon 66, 0.7 parts by weight of vinyltriethoxysilane, and 12 parts by weight of magnesium hydroxide. parts by weight, 0.6 parts by weight of antioxidant 1010, 34 parts by weight of glass fiber and 0.8 part by weight of bis-stearic acid amide are mixed to prepare nylon composite materials a and b.
  • APP 30 parts by weight of APP are combined with 81 parts by weight of nylon 610, 23 parts by weight of nylon 66, 0.7 parts by weight of vinyltriethoxysilane, 12 parts by weight of magnesium hydroxide, and 0.6 parts by weight of antioxidant 1010 , 34 parts by weight of glass fiber and 0.8 part by weight of bis-stearic acid amide, and mixed to prepare nylon composite material c.
  • the compressive strength (GB/T15231-2008), tensile strength (ASTM C1557-2003 (2008)) and flammability of the nylon composite materials a-d prepared in Example 14 and Comparative Examples 15 and 16 were tested, and the drip resistance was tested.
  • the test method is GB/T 20284-2006, and the results are shown in Table 8.

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Abstract

A polymeric flame retardant, a preparation method therefor and the use thereof. The polymeric flame retardant has excellent compatibility with an added polymer system and has excellent flame retardancy. The preparation process thereof is simple, resource-saving and environmentally friendly.

Description

[根据细则37.2由ISA制定的发明名称]　聚合型阻燃剂及其制备方法和应用[Title of invention formulated by ISA in accordance with Rule 37.2] Polymeric flame retardant, method for its preparation and application 技术领域technical field
本申请涉及阻燃剂领域，例如一种聚合型阻燃剂及其制备方法和应用。The present application relates to the field of flame retardants, such as a polymeric flame retardant and its preparation method and application.
背景技术Background technique
传统的阻燃技术一般分为卤素阻燃和无卤素阻燃。Traditional flame retardant technology is generally divided into halogen flame retardant and halogen-free flame retardant.
现有技术中，卤素阻燃的方式一般为将含有卤素和反应性基团的分子与其它材料一起反应制得有卤阻燃材料，或使用如十溴二苯乙烷等不含反应基团的卤素阻燃剂直接添加到材料中，达到阻燃的目的。同时，为了提高阻燃效果，还经常需要在阻燃体系中添加三氧化二锑等对生物体有害、对环境不友好的助燃助剂。含卤阻燃物质在受热分解或燃烧时会产生无降解性或难降解的高毒性二噁英类有机卤素化学物质并积累，污染环境、影响生物体的生长发育以及人类的健康。In the prior art, halogen flame retardant methods are generally made by reacting molecules containing halogen and reactive groups with other materials to obtain halogen flame retardant materials, or using decabromodiphenyl ethane without reactive groups. The halogen flame retardant is directly added to the material to achieve the purpose of flame retardant. At the same time, in order to improve the flame retardant effect, it is often necessary to add antimony trioxide and other combustion aids that are harmful to organisms and unfriendly to the environment in the flame retardant system. Halogen-containing flame retardant substances will produce non-degradable or refractory dioxin-like organic halogen chemicals and accumulate when they are decomposed or burned by heat, polluting the environment, affecting the growth and development of organisms and human health.
传统的无卤阻燃方式一般为向材料体系中大量添加如聚磷酸铵、三聚氰胺氰尿酸盐、焦磷酸哌嗪或2-乙基次磷酸铝类的盐类阻燃剂，和如磷酸三甲酯或磷酸三苯酯类的磷酸酯类化合物，以及如氢氧化铝或氢氧化镁类的含结晶水的金属氢氧化物的方式来达到阻燃的目的。向阻燃材料体系中需大量添加上述阻燃剂，不仅造成严重的资源浪费，降低或者损害材料的力学性能、耐水性能、耐热性能以及电性能，同时因上述阻燃成分的迁移、析出，会对使用环境和自然环境造成污染，还会对材料的阻燃性能、力学性能以及耐热性能造成进一步损害。The traditional halogen-free flame retardant method is generally to add a large amount of salt flame retardants such as ammonium polyphosphate, melamine cyanurate, piperazine pyrophosphate or 2-ethyl aluminum hypophosphite into the material system, and such as triphosphate. Phosphate compounds such as methyl ester or triphenyl phosphate, and metal hydroxides containing crystal water such as aluminum hydroxide or magnesium hydroxide are used to achieve the purpose of flame retardancy. It is necessary to add a large amount of the above flame retardants to the flame retardant material system, which not only causes serious waste of resources, reduces or damages the mechanical properties, water resistance, heat resistance and electrical properties of the material, but also causes the migration and precipitation of the above flame retardant components. It will cause pollution to the use environment and natural environment, and will further damage the flame retardant properties, mechanical properties and heat resistance properties of the material.
发明内容SUMMARY OF THE INVENTION
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的 保护范围。The following is an overview of the topics detailed in this article. This summary is not intended to limit the scope of protection of the claims.
本申请提供一种聚合型阻燃剂及其制备方法和应用。所述聚合型阻燃剂可直接为高分子材料提供优异的阻燃添加剂，本申请提供的阻燃剂制备工艺简单，节约资源且绿色环保。The present application provides a polymeric flame retardant and a preparation method and application thereof. The polymeric flame retardant can directly provide excellent flame retardant additives for polymer materials, and the flame retardant provided by the present application has a simple preparation process, is resource-saving, and is environmentally friendly.
本申请实施例提供一种聚合型阻燃剂，所述聚合型阻燃剂结构如式1所示：The embodiment of the present application provides a polymeric flame retardant, and the structure of the polymeric flame retardant is shown in Formula 1:
Figure PCTCN2021126625-appb-000001
Figure PCTCN2021126625-appb-000001
其中，M为金属元素，R 1、R 2、R 3、R、X以及Y为满足其化学环境的任意基团，m＝0～3，n≥1。 Wherein, M is a metal element, R 1 , R 2 , R 3 , R, X, and Y are any groups satisfying their chemical environment, m=0-3, and n≥1.
其中，m可以是0、1、2或3等，n可以是1、5、10、20、50、80、100、150、200或500等，但并不仅限于所列举的数值，上述各数值范围内其他未列举的数值同样适用。Wherein, m can be 0, 1, 2, or 3, etc., and n can be 1, 5, 10, 20, 50, 80, 100, 150, 200, or 500, etc., but it is not limited to the listed values. The same applies to other non-recited values in the range.
本申请中，提供的聚合型阻燃剂不仅磷元素含量高，与高分子材料还具有良好的相容性，可以稳定发挥其阻燃性能，长期不会出现析出或迁移现象。同时，可以通过不同的化学反应在聚合型阻燃剂分子中引入反应基团，通过反应基团交联进入高分子材料分子中，在提供稳定阻燃性能稳定同时，增强高分子材料的机械性能。In the present application, the provided polymeric flame retardant not only has a high content of phosphorus element, but also has good compatibility with polymer materials, and can stably exert its flame retardant performance without precipitation or migration for a long time. At the same time, reactive groups can be introduced into the polymerized flame retardant molecules through different chemical reactions, and the reactive groups can be cross-linked into the polymer material molecules, which can provide stable flame retardant performance and enhance the mechanical properties of polymer materials. .
作为本申请优选的技术方案，所述R 1～R 3分别独立地优选的包括H、羟基、取代或未取代的烷基、取代或未取代的环烷基、取代或未取代的芳香基、取代或未取代的杂芳基、取代或未取代的烷氧基、取代或未取代的环烷氧基、取代 或未取代的芳香氧基或取代或未取代的杂芳氧基中的任意一种或至少两种的组合。 As a preferred technical solution of the present application, the R 1 to R 3 preferably independently include H, hydroxyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, Any of substituted or unsubstituted heteroaryl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkoxy, substituted or unsubstituted aryloxy, or substituted or unsubstituted heteroaryloxy one or a combination of at least two.
其中，取代或未取代的烷基优选为C1～C12的取代或未取代的烷基，例如可以是C2、C3、C4、C5、C6、C7、C8、C9、C10或C11的取代或未取代的烷基；Wherein, the substituted or unsubstituted alkyl group is preferably a C1-C12 substituted or unsubstituted alkyl group, such as C2, C3, C4, C5, C6, C7, C8, C9, C10 or C11 substituted or unsubstituted the alkyl group;
取代或未取代的环烷基优选为C3～C12的环烷基，例如可以是C4、C5、C6、C7、C8、C9、C10或C11的取代或未取代的环烷基；The substituted or unsubstituted cycloalkyl is preferably a C3-C12 cycloalkyl, such as a C4, C5, C6, C7, C8, C9, C10 or C11 substituted or unsubstituted cycloalkyl;
取代或未取代的芳香基优选为C5～C12芳香基，例如可以是C6、C7、C8、C9、C10或C11的取代或未取代的芳香基；The substituted or unsubstituted aryl group is preferably a C5-C12 aryl group, such as a substituted or unsubstituted aryl group of C6, C7, C8, C9, C10 or C11;
取代或未取代的杂芳基优选为C5～C12杂芳基，例如可以是C6、C7、C8、C9、C10或C11的取代或未取代的杂芳基；The substituted or unsubstituted heteroaryl is preferably a C5-C12 heteroaryl, such as a substituted or unsubstituted heteroaryl of C6, C7, C8, C9, C10 or C11;
取代或未取代的烷氧基优选为C1～C12的取代或未取代的烷氧基，例如可以是C2、C3、C4、C5、C6、C7、C8、C9、C10或C11的取代或未取代的烷氧基；The substituted or unsubstituted alkoxy groups are preferably C1-C12 substituted or unsubstituted alkoxy groups, such as C2, C3, C4, C5, C6, C7, C8, C9, C10 or C11 substituted or unsubstituted alkoxy;
取代或未取代的环烷氧基优选为C3～C12的环烷氧基，例如可以是C4、C5、C6、C7、C8、C9、C10或C11的取代或未取代的环烷氧基；The substituted or unsubstituted cycloalkoxy is preferably a C3-C12 cycloalkoxy, such as a C4, C5, C6, C7, C8, C9, C10 or C11 substituted or unsubstituted cycloalkoxy;
取代或未取代的芳香氧基优选为C5～C12芳香氧基，例如可以是C6、C7、C8、C9、C10或C11的取代或未取代的芳香氧基；The substituted or unsubstituted aryloxy group is preferably a C5-C12 aryloxy group, such as a C6, C7, C8, C9, C10 or C11 substituted or unsubstituted aryloxy group;
取代或未取代的杂芳氧基优选为C5～C12杂芳氧基，例如可以是C6、C7、C8、C9、C10或C11的取代或未取代的杂芳氧基。The substituted or unsubstituted heteroaryloxy group is preferably a C5-C12 heteroaryloxy group, such as a C6, C7, C8, C9, C10 or C11 substituted or unsubstituted heteroaryloxy group.
作为本申请优选的技术方案，所述R 1～R 3分别独立地优选的包括惰性基团。 As a preferred technical solution of the present application, the R 1 to R 3 each independently preferably include an inert group.
本申请中，R 1～R 3为惰性基团优选为在合成式1所示化合物的过程中，R 1～R 3在该反应条件下不与反应物中的其他基团反应。 In the present application, R 1 to R 3 are inert groups. Preferably, in the process of synthesizing the compound represented by formula 1, R 1 to R 3 do not react with other groups in the reactants under the reaction conditions.
作为本申请优选的技术方案，所述R优选地包括包括含有氮元素的基团、含有硅元素的基团、含有氧元素的基团、含有硫元素的基团或含有磷元素的基 团中的任意一种或至少两种的组合。As a preferred technical solution of the present application, the R preferably includes a group containing nitrogen, a group containing silicon, a group containing oxygen, a group containing sulfur or a group containing phosphorus. any one or a combination of at least two.
优选地，所述R优选的包括-O-，-O-R 4-O-或-NH-R 5-NH-中的任意一种或至少两种的组合，其中R 4和R 5为满足其化学环境的任意基团。 Preferably, the R preferably includes any one or a combination of at least two of -O-, -OR 4 -O- or -NH-R 5 -NH-, wherein R 4 and R 5 satisfy their chemical any group of the environment.
作为本申请优选的技术方案，所述R 4和R 5分别独立地优选的包括取代或未取代的亚烷基、取代或未取代的亚环烷基、取代或未取代的亚芳基或取代或未取代的亚杂芳基中的任一种或至少两种的组合。 As a preferred technical solution of the present application, the R 4 and R 5 each independently preferably include a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted arylene group or a substituted or unsubstituted alkylene group. or any one or a combination of at least two of the unsubstituted heteroarylene groups.
其中，取代或未取代的亚烷基优选为C1～C12的取代或未取代的亚烷基，例如可以是C2、C3、C4、C5、C6、C7、C8、C9、C10或C11的取代或未取代的亚烷基；Wherein, the substituted or unsubstituted alkylene is preferably a C1-C12 substituted or unsubstituted alkylene, such as C2, C3, C4, C5, C6, C7, C8, C9, C10 or C11 substituted or unsubstituted alkylene;
取代或未取代的亚环烷基优选为C3～C12的亚环烷基，例如可以是C4、C5、C6、C7、C8、C9、C10或C11的取代或未取代的亚环烷基；The substituted or unsubstituted cycloalkylene is preferably a C3-C12 cycloalkylene, such as a C4, C5, C6, C7, C8, C9, C10 or C11 substituted or unsubstituted cycloalkylene;
取代或未取代的亚芳基优选为C5～C12亚芳基，例如可以是C6、C7、C8、C9、C10或C11的取代或未取代的亚芳基；The substituted or unsubstituted arylene group is preferably a C5-C12 arylene group, such as a substituted or unsubstituted arylene group of C6, C7, C8, C9, C10 or C11;
取代或未取代的亚杂芳基优选为C5～C12亚杂芳基，例如可以是C6、C7、C8、C9、C10或C11的取代或未取代的亚杂芳基。The substituted or unsubstituted heteroarylene group is preferably a C5-C12 heteroarylene group, for example, a substituted or unsubstituted heteroarylene group which may be C6, C7, C8, C9, C10 or C11.
优选地，所述R 4和R 5分别独立地优选的包括至少一个碳原子被硅原子所取代的取代或未取代的亚烷基、取代或未取代的亚环烷基、取代或未取代的亚芳香基或取代或未取代的亚杂芳基中的任一种或至少两种的组合。 Preferably, said R 4 and R 5 each independently preferably include a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene group in which at least one carbon atom is replaced by a silicon atom Any one or a combination of at least two of arylene or substituted or unsubstituted heteroarylene.
其中，至少一个碳原子被硅原子所取代的取代或未取代的亚烷基优选为C1～C12的取代或未取代的亚烷基，例如可以是C2、C3、C4、C5、C6、C7、C8、C9、C10或C11的取代或未取代的亚烷基；Wherein, the substituted or unsubstituted alkylene group in which at least one carbon atom is replaced by a silicon atom is preferably a C1-C12 substituted or unsubstituted alkylene group, such as C2, C3, C4, C5, C6, C7, C8, C9, C10 or C11 substituted or unsubstituted alkylene;
至少一个碳原子被硅原子所取代的取代或未取代的亚环烷基优选为C3～C12的亚环烷基，例如可以是C4、C5、C6、C7、C8、C9、C10或C11的 取代或未取代的亚环烷基；The substituted or unsubstituted cycloalkylene group in which at least one carbon atom is replaced by a silicon atom is preferably a C3-C12 cycloalkylene group, for example, it can be substituted by C4, C5, C6, C7, C8, C9, C10 or C11 or unsubstituted cycloalkylene;
至少一个碳原子被硅原子所取代的取代或未取代的亚芳基优选为C5～C12亚芳基，例如可以是C6、C7、C8、C9、C10或C11的取代或未取代的亚芳基；The substituted or unsubstituted arylene group in which at least one carbon atom is replaced by a silicon atom is preferably a C5-C12 arylene group, such as a C6, C7, C8, C9, C10 or C11 substituted or unsubstituted arylene group ;
至少一个碳原子被硅原子所取代的取代或未取代的亚杂芳基优选为C5～C12亚杂芳基，例如可以是C6、C7、C8、C9、C10或C11的取代或未取代的亚杂芳基。The substituted or unsubstituted heteroarylene group in which at least one carbon atom is replaced by a silicon atom is preferably a C5-C12 heteroarylene group, such as a substituted or unsubstituted arylene group of C6, C7, C8, C9, C10 or C11 Heteroaryl.
作为本申请优选的技术方案，所述M包括碱土金属元素、过渡金属元素、IIIA族金属元素、IVA族金属元素、VA族金属元素或VIA族金属元素中的任意一种或至少两种的组合。As a preferred technical solution of the present application, the M includes any one or a combination of at least two of alkaline earth metal elements, transition metal elements, group IIIA metal elements, group IVA metal elements, group VA metal elements or group VIA metal elements .
其中，碱土金属元素可以是Be、Mg、Ca、Sr、Ba或Ra；Wherein, the alkaline earth metal element can be Be, Mg, Ca, Sr, Ba or Ra;
过渡金属元素可以是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、镧系元素或锕系元素等；Transition metal elements 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, lanthanide or actinide, etc.;
IIIA族金属元素可以是Al、Ga、In或Tl；Group IIIA metal elements can be Al, Ga, In or Tl;
IVA族金属元素可以是Ge、Sn或Pb；Group IVA metal elements can be Ge, Sn or Pb;
VA族金属元素可以是Sb或Bi；Group VA metal element can be Sb or Bi;
VIA族金属元素可以是Po。The group VIA metal element may be Po.
作为本申请优选的技术方案，所述X和Y分别独立地优选的包括反应性封端基或惰性封端基。As a preferred technical solution of the present application, the X and Y each independently preferably include a reactive end-capping group or an inert end-capping group.
作为本申请优选的技术方案，所述反应性封端基含有的反应性基团包括羟基、胺基、不饱和基团、羧基、环氧基、酯基、酸酐、异氰酸酯基或氰基中的任意一种或至少两种的组合。As a preferred technical solution of the present application, the reactive group contained in the reactive end-capping group includes a hydroxyl group, an amine group, an unsaturated group, a carboxyl group, an epoxy group, an ester group, an acid anhydride, an isocyanate group or a cyano group. Any one or a combination of at least two.
本申请中，可以在聚合型阻燃剂分子中通过化学反应引入多种反应基团， 如引入含有活性氢的基团，可以将聚合型阻燃剂分子引入环氧树脂分子中；引入不饱基团(如乙烯基)可以将聚合型阻燃剂分子引入不饱和树脂中(如丙烯酸树脂)；引入氨基或环氧基团可以将将聚合型阻燃剂分子引入聚酰胺分子中，进一步提高高分子材料的阻燃性能以及机械性能。In this application, a variety of reactive groups can be introduced into the polymerized flame retardant molecules through chemical reactions, such as the introduction of groups containing active hydrogen, the polymerized flame retardant molecules can be introduced into the epoxy resin molecules; the introduction of unsaturated Groups (such as vinyl) can introduce polymeric flame retardant molecules into unsaturated resins (such as acrylic resins); introducing amino or epoxy groups can introduce polymeric flame retardant molecules into polyamide molecules, further improving Flame retardant properties and mechanical properties of polymer materials.
本申请实施例提供一种上述聚合型阻燃剂的制备方法，所述制备方法包括：The embodiment of the present application provides a preparation method of the above-mentioned polymeric flame retardant, and the preparation method includes:
使用金属M的酸式盐优选地与至少含有两官能的化合物进行聚合反应制备得到；The acid salt of metal M is preferably prepared by polymerization reaction with a compound containing at least two functions;
优选地，再与含有X和/或Y的封端化合物进行反应制备得到。Preferably, it is prepared by reacting with an end-capping compound containing X and/or Y.
本申请中，金属M的酸式盐优选为金属M的酸式磷酸盐；至少含有两官能的化合物优选为至少含有两个羟基、含有至少两个氨基或含有至少一个羟基和一个氨基的化合物，所述化合物可以是含有硅元素的化合物、含有硫元素的化合物或含有磷元素的化合物等。In this application, the acid salt of metal M is preferably the acid phosphate of metal M; the compound containing at least two functions is preferably a compound containing at least two hydroxyl groups, at least two amino groups or at least one hydroxyl group and one amino group, The compound may be a silicon element-containing compound, a sulfur element-containing compound, a phosphorus element-containing compound, or the like.
本申请实施例提供一种上述聚合型阻燃剂的应用，所述聚合型阻燃剂的应用领域包括热塑型树脂、热固型树脂或光固型树脂中的任意一种或至少两种的组合。The embodiment of the present application provides an application of the above-mentioned polymeric flame retardant, and the application field of the polymeric flame retardant includes any one or at least two of thermoplastic resins, thermosetting resins or photocurable resins The combination.
与相关技术相比，本申请实施例至少具有以下有益效果：Compared with the related art, the embodiments of the present application have at least the following beneficial effects:
(1)本申请实施例公开一种聚合型阻燃剂，所述阻燃剂应用范围广，适合于用作各种热固性树脂、光固化树脂和热塑型树脂；(1) The examples of this application disclose a polymeric flame retardant, which has a wide range of applications and is suitable for use as various thermosetting resins, photocurable resins and thermoplastic resins;
(2)本申请实施例公开一种聚合型阻燃剂，所述阻燃剂可应用于热固性树脂、光固化树脂和热塑性树脂中，得到不迁移、不析出、不污染使用环境，永久阻燃的效果；(2) The examples of this application disclose a polymeric flame retardant, which can be applied to thermosetting resins, light-curing resins and thermoplastic resins to obtain permanent flame retardant properties that do not migrate, separate out, and pollute the use environment. Effect;
(3)本申请实施例公开一种聚合型阻燃剂，添加于热固性树脂、光固化树脂和热塑性树脂中，制备得到的树脂组合物优异的机械性能、耐热性能、电性 能和阻燃性能(UL-94)达V-0级别；(3) The examples of this application disclose a polymeric flame retardant, which is added to thermosetting resins, photocurable resins and thermoplastic resins, and the prepared resin composition has excellent mechanical properties, heat resistance, electrical properties and flame retardant properties. (UL-94) up to V-0 level;
(4)本申请实施例公开一种聚合型阻燃剂，添加于热固性树脂、光固化树脂和热塑性树脂中，制备得到的树脂组合物具有优异的抗滴落性能，GB/T20284-2006测试中的抗滴落等级可达到d0等级，即无滴落。(4) The examples of this application disclose a polymeric flame retardant, which is added to thermosetting resins, light-curing resins and thermoplastic resins, and the prepared resin composition has excellent anti-dripping properties. In the test of GB/T20284-2006 The anti-drip rating of d0 can reach the d0 level, that is, no dripping.
在阅读并理解了详细描述后，可以明白其他方面。Other aspects will become apparent upon reading and understanding the detailed description.
具体实施方式Detailed ways
为便于理解本申请，本申请列举实施例如下。本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。In order to facilitate the understanding of the present application, the present application lists the following examples. It should be understood by those skilled in the art that the embodiments are only for helping the understanding of the present application, and should not be regarded as a specific limitation of the present application.
实施例1Example 1
本实施例提供一种聚合型阻燃剂，其结构如式2所示：This embodiment provides a polymeric flame retardant, the structure of which is shown in formula 2:
Figure PCTCN2021126625-appb-000002
Figure PCTCN2021126625-appb-000002
式2所示化合物的制备方法为：将1mol磷酸二氢锰溶于100mL DMF，加入1mol 1,3-丙二醇以及0.01mol二丁基氧化锡，依次在150℃下反应3h，170℃反应3h以及190℃下反应3h，采用蒸馏分离溶剂后，将得到的产物与0.95mol甲醇混合，待甲醇完全反应后加入0.1mol环氧氯丙烷，反应结束后对产物进行提纯得到式2所示化合物。The preparation method of the compound shown in formula 2 is as follows: dissolving 1 mol of manganese dihydrogen phosphate in 100 mL of DMF, adding 1 mol of 1,3-propanediol and 0.01 mol of dibutyltin oxide, and reacting at 150 °C for 3 hours, 170 °C for 3 hours and The reaction was carried out at 190° C. for 3 hours. After separating the solvent by distillation, the obtained product was mixed with 0.95 mol of methanol. After the methanol was completely reacted, 0.1 mol of epichlorohydrin was added. After the reaction, the product was purified to obtain the compound shown in formula 2.
1H NMR(CDCl 3,500MHz):δ4.11～4.05(t，2H，CH 2)，3.71～3.63(s，6H，CH 3)，3.45～3.37(t，2H，CH 2)，1.89～1.82(m，2H，CH 2)。 1 H NMR (CDCl 3 , 500MHz): δ 4.11-4.05 (t, 2H, CH 2 ), 3.71-3.63 (s, 6H, CH 3 ), 3.45-3.37 (t, 2H, CH 2 ), 1.89- 1.82 (m, 2H, CH2 ).
核磁共振氢谱的结果中无羟基氢峰出现，证明磷酸二氢锰的羟基均已发生 相应反应。软化点为132℃，n＝12。There is no hydroxyl hydrogen peak in the results of H NMR spectrum, which proves that the hydroxyl groups of manganese dihydrogen phosphate have all reacted accordingly. The softening point was 132°C, n=12.
对得到的阻燃剂进行ICP测试发现，所得化合物中锰元素、磷元素以及碳元素同时存在，且锰元素、磷元素以及碳元素的摩尔比为1:2:5。ICP test on the obtained flame retardant found that manganese, phosphorus and carbon elements coexisted in the obtained compound, and the molar ratio of manganese, phosphorus and carbon elements was 1:2:5.
实施例2Example 2
本实施例提供一种聚合型阻燃剂，其结构如式3所示：This embodiment provides a polymeric flame retardant, the structure of which is shown in formula 3:
Figure PCTCN2021126625-appb-000003
Figure PCTCN2021126625-appb-000003
式3所示化合物的制备方法为：将1.5mol磷酸二氢钠与0.5mol三氯化钼溶于100mL NMP，加入0.5mol乙二胺以及0.01mol DMAP，依次在160℃下反应2.5h，175℃反应2.5h以及190℃下反应2.5h，采用蒸馏分离溶剂后，将得到的产物与2.05mol丙烯醇反应，反应结束后对产物进行提纯得到式3所示化合物。The preparation method of the compound shown in formula 3 is as follows: dissolving 1.5mol sodium dihydrogen phosphate and 0.5mol molybdenum trichloride in 100mL NMP, adding 0.5mol ethylenediamine and 0.01mol DMAP, and reacting at 160 ° C for 2.5h, 175 The reaction was carried out at ℃ for 2.5 h and at 190 ℃ for 2.5 h. After separating the solvent by distillation, the obtained product was reacted with 2.05 mol of allyl alcohol. After the reaction, the product was purified to obtain the compound shown in formula 3.
1H NMR(CDCl 3,500MHz):δ6.02～5.95(m，2H， HC＝CH 2)，5.41～5.36(t，2H，HC＝C H 2)，5.28～5.21(t，2H，HC＝C H 2)，4.59～4.52(d，4H，CH 2)，2.83～2.75(m，4H，CH 2)，2.30～2.22(t，2H，NH)。 1 H NMR (CDCl 3 , 500MHz): δ 6.02-5.95 (m, 2H, H C=CH 2 ), 5.41-5.36 (t, 2H, HC= CH 2 ), 5.28-5.21 (t, 2H, HC= CH2 ), 4.59-4.52 (d, 4H, CH2 ), 2.83-2.75 (m, 4H, CH2 ) , 2.30-2.22 (t, 2H, NH).
核磁共振氢谱的结果中无羟基氢峰出现，证明磷酸二氢钠的羟基均已发生相应反应。产物的软化点为137℃，n＝6。There is no hydroxyl hydrogen peak in the results of H NMR spectrum, which proves that the hydroxyl groups of sodium dihydrogen phosphate have all reacted accordingly. The softening point of the product was 137°C, n=6.
实施例3Example 3
本实施例提供一种聚合型阻燃剂，其结构如式4所示：This embodiment provides a polymeric flame retardant, the structure of which is shown in formula 4:
Figure PCTCN2021126625-appb-000004
Figure PCTCN2021126625-appb-000004
式4所示化合物的制备方法为：将1mol磷酸二氢锌溶于100mL DMSO，加入1mol 1,4-环己二胺以及0.01mol DMAP，依次在190℃下反应3h，210℃反应3h以及230℃下反应3h，采用蒸馏分离溶剂后，将得到的产物与3mol环氧氯丙烷反应，反应结束后酸化，水洗至中性对产物进行提纯得到式4所示化合物。The preparation method of the compound shown in formula 4 is as follows: dissolve 1 mol of zinc dihydrogen phosphate in 100 mL of DMSO, add 1 mol of 1,4-cyclohexanediamine and 0.01 mol of DMAP, and react at 190°C for 3h, 210°C for 3h and 230°C in turn. The reaction was carried out at ℃ for 3 h, and after separating the solvent by distillation, the obtained product was reacted with 3 mol of epichlorohydrin, acidified after the reaction, washed with water until neutral, and the product was purified to obtain the compound shown in formula 4.
1H NMR(CDCl 3,500MHz):δ4.13～4.06(t，4H，CH 2)，3.72～3.65(t，2H，OH)，3.53～3.46(m，4H，CH 2)，2.58～2.52(m，2H，CH)，2.30～2.22(d，2H，NH)，2.01～1.95(m，4H，CH 2)，1.75～1.69(m，2H，CH 2)，1.62～1.55(m，2H，CH 2)，1.51～1.44(m，2H，CH 2)，1.36～1.30(m，2H，CH 2)。 1 H NMR (CDCl 3 , 500MHz): δ 4.13-4.06 (t, 4H, CH 2 ), 3.72-3.65 (t, 2H, OH), 3.53-3.46 (m, 4H, CH 2 ), 2.58-2.52 (m, 2H, CH), 2.30-2.22 (d, 2H, NH), 2.01-1.95 (m, 4H, CH 2 ), 1.75-1.69 (m, 2H, CH 2 ), 1.62-1.55 (m, 2H , CH 2 ), 1.51-1.44 (m, 2H, CH 2 ), 1.36-1.30 (m, 2H, CH 2 ).
核磁共振氢谱的结果羟基氢峰为3.72～3.65与磷酸上的羟基氢的化学位移不同，证明磷酸二氢锌的羟基均已发生相应反应。产物的软化点为153℃，n＝10。The results of H NMR spectrum showed that the peak of hydroxyl hydrogen was 3.72-3.65, which was different from the chemical shift of hydroxyl hydrogen on phosphoric acid, which proved that the hydroxyl groups of zinc dihydrogen phosphate had all reacted accordingly. The softening point of the product was 153°C, n=10.
实施例4Example 4
本实施例提供一种聚合型阻燃剂，其结构如式5所示：This embodiment provides a polymeric flame retardant, the structure of which is shown in formula 5:
Figure PCTCN2021126625-appb-000005
Figure PCTCN2021126625-appb-000005
式5所示化合物的制备方法为：将1mol磷酸二氢锰溶于100mL环己酮，加入1mol 1,3-丙二醇以及0.01mol二丁基氧化锡，依次在160℃下反应3h，180℃反应3h以及200℃下反应3h，采用蒸馏分离溶剂后，将得到的产物与1.99mol乙醇混合，待乙醇完全反应后对产物进行提纯得到式5所示化合物。The preparation method of the compound shown in formula 5 is as follows: dissolve 1 mol of manganese dihydrogen phosphate in 100 mL of cyclohexanone, add 1 mol of 1,3-propanediol and 0.01 mol of dibutyl tin oxide, and react at 160 °C for 3 hours and 180 °C in turn. The reaction was carried out for 3 hours and 200° C. for 3 hours, and after the solvent was separated by distillation, the obtained product was mixed with 1.99 mol of ethanol, and after the ethanol was completely reacted, the product was purified to obtain the compound shown in formula 5.
1H NMR(CDCl 3,500MHz):δ4.12～4.06(t，2H，CH 2)，3.70～3.62(s，6H，CH 3)，3.43～3.35(t，2H，CH 2)，2.33～2.27(d，H，NH)，1.88～1.81(m，2H，CH 2)。 1 H NMR (CDCl 3 , 500MHz): δ 4.12-4.06 (t, 2H, CH 2 ), 3.70-3.62 (s, 6H, CH 3 ), 3.43-3.35 (t, 2H, CH 2 ), 2.33- 2.27 (d, H, NH), 1.88-1.81 (m, 2H, CH2 ).
核磁共振氢谱的结果中无羟基氢峰出现，证明磷酸二氢锰的羟基均已发生相应反应。产物的软化点为145℃，n＝12。There is no hydroxyl hydrogen peak in the results of H NMR spectrum, which proves that the hydroxyl groups of manganese dihydrogen phosphate have all reacted accordingly. The softening point of the product was 145°C, n=12.
实施例5Example 5
本实施例提供一种聚合型阻燃剂，其结构如式6所示：This embodiment provides a polymeric flame retardant, the structure of which is shown in formula 6:
Figure PCTCN2021126625-appb-000006
Figure PCTCN2021126625-appb-000006
式6所示化合物的制备方法为：将1mol磷酸二氢锰溶于100mL DMF，加 入1molγ-胺丙基三甲氧基硅烷以及0.01mol DMAP以及0.05mol二丁基氧化锡，依次在180℃下反应1.5h，200℃反应1.5h以及220℃下反应1.5h，采用蒸馏分离溶剂后，将得到的产物与1.99mol甲醇混合，待甲醇完全反应后对产物进行提纯得到式6所示化合物。The preparation method of the compound shown in formula 6 is as follows: dissolve 1 mol of manganese dihydrogen phosphate in 100 mL of DMF, add 1 mol of γ-aminopropyltrimethoxysilane, 0.01 mol of DMAP and 0.05 mol of dibutyltin oxide, and react at 180° C. 1.5h, 200°C for 1.5h and 220°C for 1.5h. After separating the solvent by distillation, the obtained product was mixed with 1.99mol methanol. After methanol was completely reacted, the product was purified to obtain the compound shown in formula 6.
1H NMR(CDCl 3,500MHz):δ3.83～3.76(s，6H，CH 3)，3.62～3.55(s，6H，CH 3)，2.53～2.46(m，2H，CH 2)，2.35～2.28(d，H，NH)，1.59～1.53(m，2H，CH 2)，0.68～0.59(t，2H，CH 2)。 1 H NMR (CDCl 3 , 500MHz): δ 3.83-3.76 (s, 6H, CH 3 ), 3.62-3.55 (s, 6H, CH 3 ), 2.53-2.46 (m, 2H, CH 2 ), 2.35- 2.28 (d, H, NH), 1.59-1.53 (m, 2H, CH2 ), 0.68-0.59 (t, 2H, CH2 ).
核磁共振氢谱的结果中无羟基氢峰出现，证明磷酸二氢锰的羟基均已发生相应反应。产物的软化点为131℃，n＝8。There is no hydroxyl hydrogen peak in the results of H NMR spectrum, which proves that the hydroxyl groups of manganese dihydrogen phosphate have all reacted accordingly. The softening point of the product was 131°C, n=8.
实施例6Example 6
本实施例提供一种聚合型阻燃剂，其结构如式7所示：This embodiment provides a polymeric flame retardant, the structure of which is shown in formula 7:
Figure PCTCN2021126625-appb-000007
Figure PCTCN2021126625-appb-000007
式7所示化合物的制备方法为：将1mol磷酸二氢铝溶于100mL NMP，加入1mol二乙基三胺以及0.01mol DMAP，依次在180℃下反应3h，200℃反应3h以及220℃下反应3h，将得到的产物与3.99mol甲醇混合，待甲醇完全反应后对产物进行提纯得到式7所示化合物。The preparation method of the compound shown in formula 7 is as follows: dissolve 1 mol of aluminum dihydrogen phosphate in 100 mL of NMP, add 1 mol of diethyltriamine and 0.01 mol of DMAP, and react at 180 °C for 3 hours, 200 °C for 3 hours and 220 °C in turn. In 3h, the obtained product was mixed with 3.99 mol of methanol, and after the methanol was completely reacted, the product was purified to obtain the compound shown in formula 7.
1H NMR(CDCl 3,500MHz):δ3.95～3.87(m，4H，CH 2)，3.83～3.77(s，12H，CH 3)，2.30～2.23(d，H，NH)。 1 H NMR (CDCl 3 , 500 MHz): δ 3.95-3.87 (m, 4H, CH 2 ), 3.83-3.77 (s, 12H, CH 3 ), 2.30-2.23 (d, H, NH).
核磁共振氢谱的结果中无羟基氢峰出现，证明磷酸二氢铝的羟基均已发生相应反应。产物的软化点为149℃，n＝8。There is no hydroxyl hydrogen peak in the results of H NMR spectrum, which proves that the hydroxyl groups of aluminum dihydrogen phosphate have all reacted accordingly. The softening point of the product was 149°C, n=8.
聚碳酸酯塑料中的应用Applications in polycarbonate plastics
实施例7Example 7
在本实施例中，分别独立地将实施例1-6提供的聚合型阻燃剂18重量份，与2,2'-双(4-羟基苯基)丙烷聚碳酸酯100重量份，聚四氟乙烯(抗滴落剂)0.5重量份，光稳定剂944 0.5重量份，混合制备聚碳酸酯塑料a-f。In this example, 18 parts by weight of the polymeric flame retardant provided in Examples 1-6, 100 parts by weight of 2,2'-bis(4-hydroxyphenyl)propane polycarbonate, 100 parts by weight of polytetrafluoroethylene 0.5 parts by weight of vinyl fluoride (anti-drip agent) and 0.5 parts by weight of light stabilizer 944 were mixed to prepare polycarbonate plastics a-f.
对比例1Comparative Example 1
在本对比例中，将APP阻燃剂20重量份，与2,2'-双(4-羟基苯基)丙烷聚碳酸酯100重量份，聚四氟乙烯(抗滴落剂)0.5重量份，光稳定剂944 0.5重量份，混合制备聚碳酸酯塑料g。In this comparative example, 20 parts by weight of APP flame retardant, 100 parts by weight of 2,2'-bis(4-hydroxyphenyl) propane polycarbonate, and 0.5 part by weight of polytetrafluoroethylene (anti-drip agent) , Light stabilizer 944 0.5 parts by weight, mixed to prepare polycarbonate plastic g.
对比例2Comparative Example 2
在本对比例中，将MCA阻燃剂20重量份，与2,2'-双(4-羟基苯基)丙烷聚碳酸酯100重量份，聚四氟乙烯(抗滴落剂)0.5重量份，光稳定剂944 0.5重量份，混合制备聚碳酸酯塑料h。In this comparative example, 20 parts by weight of MCA flame retardant, 100 parts by weight of 2,2'-bis(4-hydroxyphenyl) propane polycarbonate, and 0.5 part by weight of polytetrafluoroethylene (anti-drip agent) , 0.5 parts by weight of light stabilizer 944, mixed to prepare polycarbonate plastic h.
对实施例7以及对比例1和2提供的聚碳酸酯塑料a-h的拉伸性能、悬臂梁冲击强度以及阻燃性能进行测试，拉伸性能根据GB/T14884-2008进行测试，悬臂梁冲击强度根据GB/T1843-2008进行测试，阻燃性测试方法为UL-94，抗滴落测试方法为GB/T 20284-2006。其结果如表1所示。The tensile properties, Izod impact strength and flame retardant properties of polycarbonate plastics a-h provided in Example 7 and Comparative Examples 1 and 2 were tested. The tensile properties were tested according to GB/T14884-2008, and the Izod impact strength was tested according to GB/T1843-2008 for testing, the flame retardancy test method is UL-94, and the anti-drip test method is GB/T 20284-2006. The results are shown in Table 1.
表1Table 1
Figure PCTCN2021126625-appb-000008
Figure PCTCN2021126625-appb-000008
Figure PCTCN2021126625-appb-000009
Figure PCTCN2021126625-appb-000009
从表1的测试结果可以看出，本申请实施例1-6提供的聚合型阻燃剂，由于其与聚碳酸酯塑料具有良好的相容性，其不仅可以为聚碳酸酯塑料提供良好的阻燃性能，还可以提高聚碳酸酯塑料的机械性能。而常规的添加型阻燃剂MCA和APP不仅添加量高于实施例1-6提供的聚合型阻燃剂，由于相容性差，导致其阻燃效果有限，且对聚碳酸酯塑料的机械性能没有有益影响。It can be seen from the test results in Table 1 that the polymeric flame retardants provided in Examples 1-6 of the present application, because of their good compatibility with polycarbonate plastics, can not only provide good performance for polycarbonate plastics Flame retardant properties can also improve the mechanical properties of polycarbonate plastics. The conventional additive flame retardants MCA and APP are not only added in higher amounts than the polymeric flame retardants provided in Examples 1-6, but also have a limited flame retardant effect due to poor compatibility. No beneficial effect.
PPS塑料中的应用Application of PPS plastic
实施例8Example 8
在本实施例中，分别独立地将实施例1-6提供的聚合型阻燃剂18重量份，PPS 100重量份，滑石粉10重量份，聚醋酸乙烯8重量份，氧化锆5重量份，混合制备得到PPS塑料a-f。使用的PPS为分子量为5万左右的线性PPS，熔融指数为30g/min。In this example, 18 parts by weight of the polymeric flame retardant provided in Examples 1-6, 100 parts by weight of PPS, 10 parts by weight of talc, 8 parts by weight of polyvinyl acetate, 5 parts by weight of zirconia, Mixed to prepare PPS plastics a-f. The PPS used was linear PPS with a molecular weight of about 50,000 and a melt index of 30 g/min.
对比例3Comparative Example 3
在本对比例中，将APP阻燃剂20重量份，PPS 100重量份，滑石粉10重量份，聚醋酸乙烯8重量份，氧化锆5重量份，混合制备得到PPS塑料g。使用的PPS为分子量为5万左右的线性PPS，熔融指数为30g/min。In this 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 g. The PPS used was linear PPS with a molecular weight of about 50,000 and a melt index of 30 g/min.
对比例4Comparative Example 4
在本对比例中，将MCA阻燃剂20重量份，PPS 100重量份，滑石粉10重量份，聚醋酸乙烯8重量份，氧化锆5重量份，混合制备得到PPS塑料h。使用的PPS为分子量为5万左右的线性PPS，熔融指数为30g/min。In this comparative example, 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 were mixed to prepare PPS plastic h. The PPS used was linear PPS with a molecular weight of about 50,000 and a melt index of 30 g/min.
对实施例8以及对比例3和4提供的PPS塑料a-h的拉伸性能、悬臂梁冲击强度以及阻燃性能进行测试，拉伸性能根据GB/T14884-2008进行测试，悬臂梁冲击强度根据GB/T1843-2008进行测试，阻燃性测试方法为UL-94，抗滴落测试方法为GB/T 20284-2006。其结果如表2所示。The tensile properties, Izod impact strength and flame retardant properties of the PPS plastics a-h provided in Example 8 and Comparative Examples 3 and 4 were tested, the tensile properties were tested according to GB/T14884-2008, and the Izod impact strength was tested according to GB/ T1843-2008 for testing, the flame retardancy test method is UL-94, and the anti-drip test method is GB/T 20284-2006. The results are shown in Table 2.
表2Table 2
   拉伸强度/MPaTensile strength/MPa 冲击强度/J/mImpact strength/J/m 阻燃性/UL-94Flame retardancy/UL-94 滴落物等级Drip grade
PPS塑料aPPS plastic a 125125 6767 V-0V-0 d0d0
PPS塑料bPPS plastic b 122122 6363 V-0V-0 d0d0
PPS塑料cPPS plastic c 131131 7575 V-0V-0 d0d0
PPS塑料dPPS plastic d 126126 6969 V-0V-0 d0d0
PPS塑料ePPS plastic e 123123 6262 V-0V-0 d0d0
PPS塑料dPPS plastic d 128128 7272 V-0V-0 d0d0
PPS塑料gPPS plastic g 7272 6060 V-1V-1 d1d1
PPS塑料hPPS plastic h 7070 5858 V-1V-1 d1d1
从表2的测试结果看出，本申请实施例1-6提供的阻燃剂与PPS具有良好的相容性，不仅可以提高PPS塑料的阻燃性能，还可以提高PPS塑料的机械性能。与之相比，作为添加型阻燃剂的PPA以及MCA与PPS的相容性差，不仅添加量较大，且阻燃性能一般，对PPS塑料的机械性能也没有有益影响。It can be seen from the test results in Table 2 that the flame retardants provided in Examples 1-6 of the present application have good compatibility with PPS, which can not only improve the flame retardant properties of PPS plastics, but also improve the mechanical properties of PPS plastics. In contrast, PPA and MCA, which are additive flame retardants, have poor compatibility with PPS. Not only are they added in large amounts, but their flame retardant properties are average, and they have no beneficial effect on the mechanical properties of PPS plastics.
PBT塑料中的应用Application of PBT plastic
实施例9Example 9
在本实施例中，分别独立地将实施例1-6提供的聚合型阻燃剂15重量份，PBT 100重量份，POE 5重量份，碳酸钙2重量份，单硬脂酸甘油酯5重量份，玻璃纤维10重量份，混合制备得到PBT塑料a-f。In this example, 15 parts by weight of the polymeric flame retardant provided in Examples 1-6, 100 parts by weight of PBT, 5 parts by weight of POE, 2 parts by weight of calcium carbonate, and 5 parts by weight of glycerol monostearate parts, 10 parts by weight of glass fiber, mixed to prepare PBT plastics a-f.
对比例5Comparative Example 5
在本对比例中，将APP阻燃剂20重量份，PBT 100重量份，POE 5重量份，碳酸钙2重量份，单硬脂酸甘油酯5重量份，玻璃纤维10重量份，混合制备得到PBT塑料g。In this 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 glycerol monostearate, and 10 parts by weight of glass fiber were mixed to prepare PBT plastic g.
对比例6Comparative Example 6
在本对比例中，将MCA阻燃剂20重量份，PBT 100重量份，POE 5重量 份，碳酸钙2重量份，单硬脂酸甘油酯5重量份，玻璃纤维10重量份，混合制备得到PBT塑料h。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 glycerol monostearate, and 10 parts by weight of glass fiber were mixed to prepare PBT plastic h.
对实施例9以及对比例5和6提供的PBT塑料a-h的拉伸性能、悬臂梁冲击强度以及阻燃性能进行测试，拉伸性能根据GB/T14884-2008进行测试，悬臂梁冲击强度根据GB/T1843-2008进行测试，阻燃性测试方法为UL-94，抗滴落测试方法为GB/T 20284-2006。其结果如表3所示。The tensile properties, Izod impact strength and flame retardant properties of the PBT plastics a-h provided in Example 9 and Comparative Examples 5 and 6 were tested, the tensile properties were tested according to GB/T14884-2008, and the Izod impact strength was tested according to GB/ T1843-2008 for testing, the flame retardancy test method is UL-94, and the anti-drip test method is GB/T 20284-2006. The results are shown in Table 3.
表3table 3
   拉伸强度/MPaTensile strength/MPa 冲击强度/J/mImpact strength/J/m 阻燃性/UL-94Flame retardancy/UL-94 滴落物等级Drip grade
PBT塑料aPBT plastic a 131131 138138 V-0V-0 d0d0
PBT塑料bPBT plastic b 123123 132132 V-0V-0 d0d0
PBT塑料cPBT plastic c 135135 141141 V-0V-0 d0d0
PBT塑料dPBT plastic d 128128 137137 V-0V-0 d0d0
PBT塑料ePBT plastic e 125125 135135 V-0V-0 d0d0
PBT塑料dPBT plastic d 130130 138138 V-0V-0 d0d0
PBT塑料gPBT plastic g 111111 115115 V-1V-1 d1d1
PBT塑料hPBT plastic h 106106 110110 V-1V-1 d1d1
从表3的测试结果看出，本申请实施例1-6提供的阻燃剂与PBT具有良好的相容性，不仅可以提高PBT塑料的阻燃性能，还可以提高PBT塑料的机械性能。与之相比，作为添加型阻燃剂的PPA以及MCA与PBT的相容性差，不仅添加量较大，且阻燃性能一般，对PBT塑料的机械性能也没有有益影响。It can be seen from the test results in Table 3 that the flame retardants provided in Examples 1-6 of the present application have good compatibility with PBT, which can not only improve the flame retardant properties of PBT plastics, but also improve the mechanical properties of PBT plastics. In contrast, as additive flame retardants, PPA and MCA have poor compatibility with PBT, not only the addition amount is large, but also the flame retardant performance is average, and it has no beneficial effect on the mechanical properties of PBT plastics.
PPO塑料中的应用Application of PPO plastics
实施例10Example 10
在本实施例中，分别独立地将实施例1-6提供的聚合型阻燃剂15重量份，PPO 100重量份，抗氧剂1010 3.5重量份，钛白粉15重量份，SEBS 10重量份，枝接PP 5重量份，混合制备得到PPO塑料a-f。In this example, 15 parts by weight of polymeric flame retardant, 100 parts by weight of PPO, 3.5 parts by weight of antioxidant 1010, 15 parts by weight of titanium dioxide, 10 parts by weight of SEBS, 5 parts by weight of PP were grafted and mixed to obtain PPO plastics a-f.
对比例7Comparative Example 7
在本对比例中，将PPA阻燃剂25重量份，PPO 100重量份，抗氧剂1010 3.5重量份，钛白粉15重量份，SEBS 10重量份，枝接PP 5重量份，混合制备得到PPO塑料g。In this comparative example, 25 parts by weight of PPA flame retardant, 100 parts by weight of PPO, 3.5 parts by weight of antioxidant 1010, 15 parts by weight of titanium dioxide, 10 parts by weight of SEBS, and 5 parts by weight of grafted PP were mixed to prepare PPO plastic g.
对比例8Comparative Example 8
在本对比例中，将MCA阻燃剂25重量份，PPO 100重量份，抗氧剂1010 3.5重量份，钛白粉15重量份，SEBS 10重量份，枝接PP 5重量份，混合制备得到PPO塑料h。In this comparative example, 25 parts by weight of MCA flame retardant, 100 parts by weight of PPO, 3.5 parts by weight of antioxidant 1010, 15 parts by weight of titanium dioxide, 10 parts by weight of SEBS, and 5 parts by weight of grafted PP were mixed to prepare PPO plastic h.
对实施例10以及对比例7和8提供的PPO塑料a-h的拉伸性能、悬臂梁冲击强度以及阻燃性能进行测试，拉伸性能根据GB/T14884-2008进行测试，悬臂梁冲击强度根据GB/T1843-2008进行测试，阻燃性测试方法为UL-94，抗滴落测试方法为GB/T 20284-2006。其结果如表4所示。The tensile properties, Izod impact strength and flame retardant properties of the PPO plastics a-h provided in Example 10 and Comparative Examples 7 and 8 were tested, the tensile properties were tested according to GB/T14884-2008, and the Izod impact strength was tested according to GB/ T1843-2008 for testing, the flame retardancy test method is UL-94, and the anti-drip test method is GB/T 20284-2006. The results are shown in Table 4.
表4Table 4
   拉伸强度/MPaTensile strength/MPa 冲击强度/J/mImpact strength/J/m 阻燃性/UL-94Flame retardancy/UL-94 滴落物等级Drip grade
PPO塑料aPPO plastic a 9292 105105 V-0V-0 d0d0
PPO塑料bPPO plastic b 8787 9393 V-0V-0 d0d0
PPO塑料cPPO plastic c 9696 108108 V-0V-0 d0d0
PPO塑料dPPO plastic d 8888 101101 V-0V-0 d0d0
PPO塑料ePPO plastic e 9090 103103 V-0V-0 d0d0
PPO塑料fPPO plastic f 9393 106106 V-0V-0 d0d0
PPO塑料gPPO plastic g 7373 9292 V-1V-1 d1d1
PPO塑料hPPO plastic h 7575 9797 V-1V-1 d1d1
从表4的测试结果看出，本申请实施例1-6提供的阻燃剂与PPO具有良好的相容性，不仅可以提高PPO塑料的阻燃性能，还可以提高PPO塑料的机械性能。与之相比，作为添加型阻燃剂的PPA以及MCA与PPO的相容性差，不仅添加量较大，且阻燃性能一般，对PPO塑料的机械性能也没有有益影响。It can be seen from the test results in Table 4 that the flame retardants provided in Examples 1-6 of the present application have good compatibility with PPO, which can not only improve the flame retardant properties of PPO plastics, but also improve the mechanical properties of PPO plastics. In contrast, PPA and MCA, which are additive flame retardants, have poor compatibility with PPO. Not only are they added in large amounts, but their flame retardant properties are average, and they have no beneficial effect on the mechanical properties of PPO plastics.
环氧树脂中的应用Application of epoxy resin
实施例11Example 11
本实施例中，将环氧当量为360/eq的双酚A型环氧树脂100重量份，双腈胺6重量份，分别与实施例3或4所示阻燃剂20重量份混合，185℃下固化1.5h，得到环氧树脂固化物a和b。In this example, 100 parts by weight of bisphenol A epoxy resin with an epoxy equivalent of 360/eq and 6 parts by weight of bis-nitrile amine were mixed with 20 parts by weight of the flame retardant shown in Example 3 or 4 respectively, 185 parts by weight. Cured at ℃ for 1.5h to obtain epoxy resin cured products a and b.
对比例9Comparative Example 9
本对比例中，将环氧当量为360/eq的环氧树脂100重量份，加入6重量份双腈胺，再加入30重量份APP，185℃下固化1.5h，得到环氧树脂固化物c。In this comparative example, 100 parts by weight of epoxy resin with an epoxy equivalent of 360/eq was added with 6 parts by weight of bisnitrile amine, and then 30 parts by weight of APP was added, and cured at 185 ° C for 1.5 hours to obtain epoxy resin cured product c .
对比例10Comparative Example 10
本对比例中，将环氧当量为360/eq的环氧树脂100重量份，加入6重量份双腈胺，再加入30重量份MCA，185℃下固化1.5h，得到环氧树脂固化物d。In this comparative example, 100 parts by weight of epoxy resin with an epoxy equivalent of 360/eq was added with 6 parts by weight of bis-nitrile amine, and then 30 parts by weight of MCA was added, and cured at 185 ° C for 1.5 hours to obtain epoxy resin cured product d .
对上述环氧树脂固化物a-d的性能进行测试，弯曲强度的测试方法采用GB/T 9341-2008，抗冲击强度测试方法采用GB/T 1843-2008，击穿电压采用GB/T  1408.1-2006，阻燃性测试方法为UL-94，抗滴落测试方法为GB/T 20284-2006。测试结果表5所示。The performance of the above epoxy resin cured products a-d is tested. The test method of bending strength adopts GB/T 9341-2008, the test method of impact strength adopts GB/T 1843-2008, and the breakdown voltage adopts GB/T 1408.1-2006. The flame retardancy test method is UL-94, and the anti-drip test method is GB/T 20284-2006. The test results are shown in Table 5.
表5table 5
Figure PCTCN2021126625-appb-000010
Figure PCTCN2021126625-appb-000010
从表5的测试结果可以看出，本申请提供的阻燃剂在添加入环氧树脂体系后，对于同样添加量的现有阻燃剂而言，制备得到的环氧树脂固化物的阻燃性能以及机械性能均更为优异。且本申请实施例3提供的聚合型阻燃剂由于其具有羟基，可与环氧树脂中末端的环氧基团反应，进一步增加了该阻燃剂与环氧树脂体系的相容性，因此其具有更加有益的性能。It can be seen from the test results in Table 5 that after the flame retardant provided by the present application is added to the epoxy resin system, for the existing flame retardant of the same addition amount, the flame retardant properties of the prepared epoxy resin cured product Performance and mechanical properties are better. And the polymerized flame retardant provided in Example 3 of this application can react with the epoxy group at the end of the epoxy resin due to its hydroxyl group, which further increases the compatibility of the flame retardant with the epoxy resin system. Therefore, It has more beneficial properties.
硅树脂的应用：Application of silicone resin:
实施例12Example 12
本实施例中，将114重量份三甲基乙氧基硅氧烷、186重量份四乙氧基硅氧烷以及50重量份九水硅酸钠，分别与50重量份实施例5或6制备得到的阻燃剂混合，并在20℃下固化5h，制备得到硅树脂a和b。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 prepared with 50 parts by weight of Example 5 or 6, respectively. The obtained flame retardants were mixed and cured at 20° C. for 5 hours to prepare silicone resins a and b.
对比例11Comparative Example 11
本对比例中，将114重量份三甲基乙氧基硅氧烷、186重量份四乙氧基硅氧烷以及50重量份九水硅酸钠混合，并在20℃下固化5h，制备得到硅树脂c。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°C for 5 hours to prepare Silicone c.
对比例12Comparative Example 12
本对比例中，将114重量份三甲基乙氧基硅氧烷、186重量份四乙氧基硅氧烷、50重量份九水硅酸钠以及30重量份APP混合，并在20℃下固化5h，制备得到硅树脂d。In this comparative example, 114 parts by weight of trimethylethoxysiloxane, 186 parts by weight of tetraethoxysiloxane, 50 parts by weight of sodium silicate nonahydrate and 30 parts by weight of APP were mixed, and the mixture was heated at 20°C. After curing for 5 hours, silicone resin d was prepared.
对上述得到的硅树脂a-d的性能进行测试，拉伸强度和伸长率的测试方法采用GB/T 1701-2001，剪切强度测试方法采用GB/T 1700-2001，阻燃性测试方法为UL-94，耐水性能的测试条件为沸水中浸泡2h，抗滴落测试方法为GB/T 20284-2006。测试结果如表6所示。The properties of the silicone resins a-d obtained above are tested, the tensile strength and elongation test methods are GB/T 1701-2001, the shear strength test method is GB/T 1700-2001, and the flame retardancy test method is UL- 94. The test condition of water resistance is immersion in boiling water for 2h, and the test method of anti-dropping is GB/T 20284-2006. The test results are shown in Table 6.
表6Table 6
Figure PCTCN2021126625-appb-000011
Figure PCTCN2021126625-appb-000011
Figure PCTCN2021126625-appb-000012
Figure PCTCN2021126625-appb-000012
根据表6的测试结果可以看出，本申请提供的阻燃剂在添加入硅树脂体系后，对于同样添加量的现有阻燃剂而言，制备得到的硅树脂的阻燃性能以及机械性能均更为优异。由于实施例5中制备得到的含有硅元素的阻燃剂，其与硅树脂的相容性更好，因此进一步提高了硅树脂的性能。According to the test results in Table 6, it can be seen that after the flame retardant provided by the present application is added into the silicone resin system, for the existing flame retardant with the same addition amount, the flame retardant properties and mechanical properties of the prepared silicone resin are more excellent. Since the silicon-containing flame retardant prepared in Example 5 has better compatibility with the silicone resin, the performance of the silicone resin is further improved.
不饱和树脂中的应用：Applications in unsaturated resins:
实施例13Example 13
本实施例中，分别将实施例2或4制备的阻燃剂25重量份，与甲基丙烯酸甲酯15重量份、甲基丙烯酸丁酯15重量份、丙烯酸乙酯11重量份、甲基丙烯酸1重量份、丙烯酸羟丙酯13重量份、甲基丙烯酸三氟乙酯45重量份、过氧化苯甲酰2重量份、二甲苯70重量份、丁酮20重量份以及环己酮10重量份混合制备交联型丙烯酸树脂组合物a和b。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, and 11 parts by weight of methacrylic acid. 1 part by weight, 13 parts by weight of hydroxypropyl acrylate, 45 parts by weight of trifluoroethyl methacrylate, 2 parts by weight of benzoyl peroxide, 70 parts by weight of xylene, 20 parts by weight of methyl ethyl ketone, and 10 parts by weight of cyclohexanone The cross-linked acrylic resin compositions a and b were prepared by mixing.
对比例13Comparative Example 13
本对比例中，将APP 30重量份，与甲基丙烯酸甲酯15重量份、甲基丙烯 酸丁酯15重量份、丙烯酸乙酯11重量份、甲基丙烯酸1重量份、丙烯酸羟丙酯13重量份、甲基丙烯酸三氟乙酯45重量份、过氧化苯甲酰2重量份、二甲苯70重量份、丁酮20重量份以及环己酮10重量份混合制备交联型丙烯酸树脂组合物c。In this comparative example, 30 parts by weight of APP were 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, and 13 parts by weight of hydroxypropyl acrylate. parts by weight, 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 cross-linked acrylic resin composition c .
对比例14Comparative Example 14
本对比例中，将MCA 30重量份，与甲基丙烯酸甲酯15重量份、甲基丙烯酸丁酯15重量份、丙烯酸乙酯11重量份、甲基丙烯酸1重量份、丙烯酸羟丙酯13重量份、甲基丙烯酸三氟乙酯45重量份、过氧化苯甲酰2重量份、二甲苯70重量份、丁酮20重量份以及环己酮10重量份混合制备交联型丙烯酸树脂组合物d。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, and 13 parts by weight of hydroxypropyl acrylate. parts, 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 cross-linked acrylic resin composition d .
对上述制备得到的丙烯酸树脂组合物a-d的抗压强度、抗拉强度、耐水性能以及阻燃性能进行测试，结果如表7所示。其中抗压的测试方法采用GB/T 20467-2008，抗拉强度测试方法采用GB/T 6344-2008，阻燃性测试方法为UL-94。耐水性能为将抗压强度测试后的丙烯酸树脂组合物在沸水中浸泡2h后，再次进行抗压强度测试，抗滴落测试方法为GB/T 20284-2006。The compressive strength, tensile strength, water resistance and flame retardancy of the acrylic resin compositions a-d prepared above were tested, and the results are shown in Table 7. The compression test method adopts GB/T 20467-2008, the tensile strength test method adopts GB/T 6344-2008, and the flame retardancy test method is UL-94. The water resistance is to soak the acrylic resin composition after the compressive strength test in boiling water for 2 hours, and then conduct the compressive strength test again. The anti-dropping test method is GB/T 20284-2006.
表7Table 7
Figure PCTCN2021126625-appb-000013
Figure PCTCN2021126625-appb-000013
Figure PCTCN2021126625-appb-000014
Figure PCTCN2021126625-appb-000014
根据表7的测试结果可以看出，本申请提供的阻燃剂在添加入丙烯酸树脂组合物体系后，对于同样添加量的现有阻燃剂而言，制备得到的丙烯酸树脂组合物的阻燃性能以及机械性能更为优异。实施例2中由于其提供的阻燃剂具有不饱和基团，在制备丙烯酸树脂的过程中可与丙烯酸树脂中的不饱和基团发生反应，从而与丙烯酸树脂分子结合，进一步增加了该阻燃剂与丙烯酸树脂体系的相容性，因此与实施例4不具有不饱和基团的聚合型阻燃剂相比，其具有更好的性能。According to the test results in Table 7, it can be seen that after the flame retardant provided by the present application is added to the acrylic resin composition system, for the existing flame retardant of the same addition amount, the flame retardant of the prepared acrylic resin composition is Performance and mechanical properties are more excellent. In Example 2, because the flame retardant provided by it has unsaturated groups, it can react with the unsaturated groups in the acrylic resin in the process of preparing the acrylic resin, thereby combining with the acrylic resin molecules, further increasing the flame retardant. The compatibility of the agent with the acrylic resin system, so compared with the polymeric flame retardant without unsaturated groups in Example 4, it has better performance.
尼龙复合材料中的应用：Applications in nylon composites:
实施例14Example 14
在本实施例中，将实施例1或5制备得到的阻燃剂15重量份，与尼龙610 81重量份、尼龙66 23重量份、乙烯基三乙氧基硅烷0.7重量份、氢氧化镁12重量份、抗氧剂1010 0.6重量份、玻璃纤维34重量份以及双硬脂酸酰胺0.8重量份，混合制备得到尼龙复合材料a和b。In this example, 15 parts by weight of the flame retardant prepared in Example 1 or 5 was mixed with 81 parts by weight of nylon 610, 23 parts by weight of nylon 66, 0.7 parts by weight of vinyltriethoxysilane, and 12 parts by weight of magnesium hydroxide. parts by weight, 0.6 parts by weight of antioxidant 1010, 34 parts by weight of glass fiber and 0.8 part by weight of bis-stearic acid amide are mixed to prepare nylon composite materials a and b.
对比例15Comparative Example 15
在本实施例中，将APP 30重量份，与尼龙610 81重量份、尼龙66 23重量份、乙烯基三乙氧基硅烷0.7重量份、氢氧化镁12重量份、抗氧剂1010 0.6重量份、玻璃纤维34重量份以及双硬脂酸酰胺0.8重量份，混合制备得到尼龙复 合材料c。In this embodiment, 30 parts by weight of APP are combined with 81 parts by weight of nylon 610, 23 parts by weight of nylon 66, 0.7 parts by weight of vinyltriethoxysilane, 12 parts by weight of magnesium hydroxide, and 0.6 parts by weight of antioxidant 1010 , 34 parts by weight of glass fiber and 0.8 part by weight of bis-stearic acid amide, and mixed to prepare nylon composite material c.
对比例16Comparative Example 16
在本实施例中，将MCA 30重量份，与尼龙610 81重量份、尼龙66 23重量份、乙烯基三乙氧基硅烷0.7重量份、氢氧化镁12重量份、抗氧剂1010 0.6重量份、玻璃纤维34重量份以及双硬脂酸酰胺0.8重量份，混合制备得到尼龙复合材料d。In this example, 30 parts by weight of MCA, 81 parts by weight of nylon 610, 23 parts by weight of nylon 66, 0.7 parts by weight of vinyltriethoxysilane, 12 parts by weight of magnesium hydroxide, and 0.6 parts by weight of antioxidant 1010 , 34 parts by weight of glass fiber and 0.8 part by weight of bis-stearic acid amide, and mixed to prepare nylon composite material d.
对实施例14以及对比例15和16制备得到的尼龙复合材料a-d的抗压强度(GB/T15231-2008)、抗拉强度(ASTM C1557-2003(2008))以及燃烧性进行测试，抗滴落测试方法为GB/T 20284-2006，结果如表8所示。The compressive strength (GB/T15231-2008), tensile strength (ASTM C1557-2003 (2008)) and flammability of the nylon composite materials a-d prepared in Example 14 and Comparative Examples 15 and 16 were tested, and the drip resistance was tested. The test method is GB/T 20284-2006, and the results are shown in Table 8.
表8Table 8
Figure PCTCN2021126625-appb-000015
Figure PCTCN2021126625-appb-000015
根据表8的测试结果可以看出，本申请提供的阻燃剂在添加入尼龙复合材料体系后，对于同样添加量的现有阻燃剂而言，制备得到的尼龙复合材料的阻 燃性能以及机械性能更为优异。According to the test results in Table 8, it can be seen that after the flame retardant provided by this application is added to the nylon composite material system, for the existing flame retardant of the same added amount, the flame retardant properties of the prepared nylon composite material and Mechanical properties are more excellent.
申请人声明，本申请通过上述实施例来说明本申请的详细工艺设备和工艺流程，但本申请并不局限于上述详细工艺设备和工艺流程，即不意味着本申请必须依赖上述详细工艺设备和工艺流程才能实施。所属技术领域的技术人员应该明了，对本申请的任何改进，对本申请产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本申请的保护范围和公开范围之内。The applicant declares that this application illustrates the detailed process equipment and process flow of the application through the above-mentioned embodiments, but the application is not limited to the above-mentioned detailed process equipment and process flow, that is, it does not mean that the application must rely on the above-mentioned detailed process equipment and process flow. Process flow can be implemented. Those skilled in the art should understand that any improvement to the application, the equivalent replacement of each raw material of the product of the application, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the application.

Claims (11)

  1. 一种聚合型阻燃剂，其中，所述聚合型阻燃剂结构如式1所示：A polymeric flame retardant, wherein the structure of the polymeric flame retardant is shown in formula 1:
    Figure PCTCN2021126625-appb-100001
    Figure PCTCN2021126625-appb-100001
    其中，M为金属元素，R 1、R 2、R 3、R、X以及Y为满足其化学环境的任意基团，m＝0～3，n≥1。 Wherein, M is a metal element, R 1 , R 2 , R 3 , R, X, and Y are any groups satisfying their chemical environment, m=0-3, and n≥1.
  2. 根据权利要求1所述的聚合型阻燃剂，其中，所述R1～R3分别独立地包括H、羟基、取代或未取代的烷基、取代或未取代的环烷基、取代或未取代的芳香基、取代或未取代的杂芳基、取代或未取代的烷氧基、取代或未取代的环烷氧基、取代或未取代的芳香氧基或取代或未取代的杂芳氧基中的任意一种或至少两种的组合。The polymeric flame retardant according to claim 1, wherein the R1 to R3 independently comprise 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 any one or a combination of at least two.
  3. 根据权利要求2所述的聚合型阻燃剂，其中，所述R 1～R 3分别独立地包括惰性基团。 The polymeric flame retardant according to claim 2, wherein each of the R 1 to R 3 independently includes an inert group.
  4. 根据权利要求1-3任一项所述的聚合型阻燃剂，其中，所述R包括含有氮元素的基团、含有硅元素的基团、含有硫元素的基团、含有氧元素的基团或含有磷元素的基团中的任意一种或至少两种的组合；The polymerizable flame retardant according to any one of claims 1 to 3, wherein the R includes a nitrogen-containing group, a silicon-containing group, a sulfur-containing group, and an oxygen-containing group any one or a combination of at least two of the group or the group containing phosphorus element;
    优选地，所述R包括-O-，-O-R 4-O-或-NH-R 5-NH-中的任意一种或至少两种的组合，其中R 4和R 5为满足其化学环境的任意基团。 Preferably, the R includes any one or a combination of at least two of -O-, -OR 4 -O- or -NH-R 5 -NH-, wherein R 4 and R 5 are suitable for their chemical environment any group.
  5. 根据权利要求4所述的聚合型阻燃剂，其中，所述R 4和R 5分别独立地包括取代或未取代的亚烷基、取代或未取代的亚环烷基、取代或未取代的亚芳基或取代或未取代的亚杂芳基中的任一种或至少两种的组合； The polymeric flame retardant according to claim 4, wherein said R 4 and R 5 each independently comprise substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene, substituted or unsubstituted any one or a combination of at least two of arylene or substituted or unsubstituted heteroarylene;
    优选地，所述R 4和R 5分别独立地包括至少一个碳原子被硅原子所取代的取代或未取代的亚烷基、取代或未取代的亚环烷基、取代或未取代的亚芳香基或取代或未取代的亚杂芳基中的任一种或至少两种的组合。 Preferably, said R 4 and R 5 each independently comprise a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted arylene group in which at least one carbon atom is replaced by a silicon atom any one or a combination of at least two of substituted or unsubstituted heteroarylene groups.
  6. 根据权利要求1-5任一项所述的聚合型阻燃剂，其中，所述M包括碱土金属元素、过渡金属元素、IIIA族金属元素、IVA族金属元素、VA族金属元素或VIA族金属元素中的任意一种或至少两种的组合。The polymeric flame retardant according to any one of claims 1-5, wherein the M comprises 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 Any one or a combination of at least two of the elements.
  7. 根据权利要求1-6任一项所述的聚合型阻燃剂，其中，所述X和Y分别独立地包括反应性封端基或惰性封端基。The polymeric flame retardant according to any one of claims 1-6, wherein the X and Y each independently comprise a reactive end-capping group or an inert end-capping group.
  8. 根据权利要求7所述的聚合型阻燃剂，其中，所述反应性封端基含有的反应性基团包括羟基、胺基、不饱和基团、羧基、环氧基、酯基、酸酐、甲氧基、异氰酸酯基或氰基中的任意一种或至少两种的组合。The polymerizable flame retardant according to claim 7, wherein the reactive groups contained in the reactive end capping groups include hydroxyl groups, amine groups, unsaturated groups, carboxyl groups, epoxy groups, ester groups, acid anhydrides, Any one or a combination of at least two of methoxy, isocyanate or cyano.
  9. 一种权利要求1-8任一项所述的聚合型阻燃剂的制备方法，其包括：A preparation method of the polymeric flame retardant according to any one of claims 1-8, comprising:
    使用金属M的酸式盐与至少含有两官能的化合物进行聚合反应制备得到。It is prepared by the polymerization reaction of an acid salt of metal M and a compound containing at least two functions.
  10. 根据权利要求9所述的聚合型阻燃剂的制备方法，还包括：The preparation method of polymeric flame retardant according to claim 9, further comprises:
    再与含有X和/或Y的封端化合物进行反应制备得到。It can be prepared by reacting with the end-capping compound containing X and/or Y.
  11. 一种权利要求1-8任一项所述的聚合型阻燃剂的应用，其中，所述聚合型阻燃剂的应用领域包括热塑型树脂、热固型树脂或光固型树脂中的任意一种或至少两种的组合。An application of the polymeric flame retardant according to any one of claims 1-8, wherein the application field of the polymeric flame retardant includes a thermoplastic resin, a thermosetting resin or a photocurable resin. Any one or a combination of at least two.
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