WO2022089468A1 - Ignifugeant polymère, son procédé de préparation et son utilisation - Google Patents

Ignifugeant polymère, son procédé de préparation et son utilisation Download PDF

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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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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/fr

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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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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un ignifugeant polymère, son procédé de préparation et son utilisation. L'ignifugeant polymère présente une excellente compatibilité avec un système polymère ajouté et a une excellente ininflammabilité. Son procédé de préparation est simple, économe en ressources et respectueux de l'environnement.
PCT/CN2021/126625 2020-10-29 2021-10-27 Ignifugeant polymère, son procédé de préparation et son utilisation WO2022089468A1 (fr)

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CN112961184A (zh) * 2020-10-29 2021-06-15 广东广山新材料股份有限公司 一种反应型阻燃剂、聚合型阻燃剂及其制备方法和应用
CN112961362A (zh) * 2020-10-29 2021-06-15 广东广山新材料股份有限公司 一种聚合型阻燃剂及其制备方法和应用
CN115819783B (zh) * 2022-09-26 2023-08-22 山东天一化学股份有限公司 含P、N、Si的高度支化大分子阻燃剂及其制备方法

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