WO2022089469A1 - 一种聚合型磷硅协同阻燃剂及其制备方法和应用 - Google Patents
一种聚合型磷硅协同阻燃剂及其制备方法和应用 Download PDFInfo
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- WO2022089469A1 WO2022089469A1 PCT/CN2021/126626 CN2021126626W WO2022089469A1 WO 2022089469 A1 WO2022089469 A1 WO 2022089469A1 CN 2021126626 W CN2021126626 W CN 2021126626W WO 2022089469 A1 WO2022089469 A1 WO 2022089469A1
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Classifications
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Definitions
- the present application relates to the field of flame retardants, for example, a polymeric phosphosilicate synergistic 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 phosphorous-silicon synergistic flame retardant and a preparation method and application thereof.
- the polymerized phosphorus-silicon synergistic flame retardant can directly provide excellent flame retardant additives for polymer materials;
- the polymerized phosphorus-silicon synergistic flame retardant provided by the present application has high content of phosphorus and silicon elements, and simultaneously exerts the advantages of the two elements. Flame retardant performance, the synergistic flame retardant of the two elements can achieve the effect of no dripping and extremely low smoke generation when the added system is burned, and only a small amount of addition can achieve excellent flame retardant performance;
- the preparation process of the phosphorus-silicon synergistic flame retardant is simple, resource-saving and environmentally friendly.
- the embodiment of the present application provides a polymerized phosphorus-silicon synergistic flame retardant, and the structure of the flame retardant is shown in formula 1:
- R 1 to R 5 and R are arbitrary groups satisfying their chemical environment
- X and Y are arbitrary groups satisfying their chemical environment, n ⁇ 1, m ⁇ 1.
- n can be 1, 5, 10, 20, 50, 80, 100, 150, 200, or 500, etc.
- the provided polymeric phosphorus-silicon synergistic flame retardant has more excellent flame retardant effect than the flame retardant or phosphorus nitrogen flame retardant containing only phosphorus element.
- a flame retardant containing both phosphorus and silicon is a composite flame retardant, and phosphorus and silicon belong to different components, resulting in poor compatibility with added substances, especially polymer materials.
- the very stable phosphorus-silicon synergistic flame retardant of the present application is a polymeric flame retardant, which has good compatibility with polymer materials such as epoxy resin, silicone resin and polyester resin, and contains reactive groups. , which can be combined with polymer materials through chemical bonds, further improving the flame retardant properties of polymer materials, and further improving the mechanical properties, heat resistance and water resistance of polymer materials.
- the provided polymeric phosphorus-silicon synergistic flame retardant has relatively high content of silicon and phosphorus, the residue generated after combustion will form a porous self-supporting ceramic body, which can be used in extremely high Maintains structural integrity at temperature, resulting in non-drip burning effects.
- the R 1 to R 5 each independently preferably include H, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted Any one of unsubstituted heteroaryl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkoxy, substituted or unsubstituted aryloxy or substituted or unsubstituted heteroaryloxy or A combination of at least two.
- the R 1 to R 5 independently preferably include C1-C12 substituted or unsubstituted alkyl, C3-C12 substituted or unsubstituted cycloalkyl, C6-C12 substituted or unsubstituted Substituted aryl, C5-C12 substituted or unsubstituted heteroaryl, C1-C12 substituted or unsubstituted alkoxy, C3-C12 substituted or unsubstituted cycloalkoxy, C6-C12 substituted or unsubstituted Any one or a combination of at least two of aryloxy or C5-C12 substituted or unsubstituted heteroaryloxy.
- 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 C6-C12 aryloxy group, such as a 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 X preferably includes any one of absence, imine group, O or S.
- the Y preferably includes any one of absence, imino group, O or S.
- the R preferably includes any one of an absent, substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, an amide group or an ester group.
- 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 arylene group is preferably a C6-C12 substituted or unsubstituted arylene group, such as a C7, C8, C9, C10 or C11 substituted or unsubstituted arylene group.
- the embodiment of the present application provides a preparation method of the above-mentioned polymerized phosphorus-silicon synergistic flame retardant, the method comprising: preparing a compound containing silicon element and a phosphorus-containing compound through a polymerization reaction.
- the compound containing silicon element preferably includes any one or a combination of at least two of substituted or unsubstituted silane, polysilane or polysiloxane.
- the polysilane preferably includes a polymer obtained by self-polymerization of silane or copolymerization of silane and a chain extender.
- the polysiloxane preferably comprises a polymer obtained from the self-polymerization of siloxane or the copolymerization of siloxane and a chain extender.
- the silane is preferably C1-C12 substituted or unsubstituted alkylsilane, C3-C12 substituted or unsubstituted cycloalkylsilane, C6-C12 substituted or unsubstituted arylsilane, or C5-C12 substituted or unsubstituted arylsilane Substituted heteroarylsilane, C1-C12 substituted or unsubstituted alkoxy, C3-C12 substituted or unsubstituted cycloalkoxy, C6-C12 substituted or unsubstituted aryloxy or C5-C12 substituted or unsubstituted Substituted heteroaryloxy.
- C1 ⁇ C12 substituted or unsubstituted alkylsilane can be C2, C3, C4, C5, C6, C7, C8, C9, C10 or C11 substituted or unsubstituted alkylsilane;
- C3-C12 substituted or unsubstituted cycloalkylsilane can be C4, C5, C6, C7, C8, C9, C10 or C11 substituted or unsubstituted cycloalkylsilane;
- C6-C12 substituted or unsubstituted aryl silane can be C7, C8, C9, C10 or C11 substituted or unsubstituted aryl silane;
- C5-C12 substituted or unsubstituted heteroaryl silane can be C6, C7, C8, C9, C10 or C11 substituted or unsubstituted heteroaryl silane;
- C1-C12 substituted or unsubstituted alkoxysilanes such as C2, C3, C4, C5, C6, C7, C8, C9, C10 or C11 substituted or unsubstituted alkoxysilanes;
- C3-C12 cycloalkoxysilane such as C4, C5, C6, C7, C8, C9, C10 or C11 substituted or unsubstituted cycloalkoxysilane;
- C6-C12 aryloxysilanes such as C7, C8, C9, C10 or C11 substituted or unsubstituted aryloxysilanes;
- C5-C12 heteroaryloxysilanes for example, can be substituted or unsubstituted heteroaryloxysilanes of C6, C7, C8, C9, C10 or C11.
- the phosphorus-containing compounds preferably include phosphoric acid compounds and their derivatives, phosphorous acid compounds and their derivatives, hypophosphorous acid compounds and their derivatives, phosphate compounds and their derivatives , phosphite compounds and their derivatives, hypophosphite compounds and their derivatives, phosphate compounds and their derivatives, phosphite compounds and their derivatives, hypophosphite compounds and their derivatives, and Any one or a combination of at least two of DOPO compounds and derivatives thereof.
- the metal elements in phosphate compounds and their derivatives, phosphite compounds and their derivatives, hypophosphite compounds and their derivatives may be alkaline earth metal elements, transition metal elements, group IIIA metal elements, IVA Any one or a combination of at least two of Group 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 preparation method preferably includes obtaining a silicon-containing compound containing a hydroxyl group and a phosphorus-containing compound containing an ester group through a polymerization reaction, and passing a silicon-containing compound containing an alkoxy group and a phosphorus-containing compound containing a hydroxyl group through a polymerization reaction.
- the silicon-containing compound containing an amino group and the phosphorus-containing compound containing an ester group obtained by a polymerization reaction are obtained by a polymerization reaction.
- the above preparation method is only a simple enumeration of the preparation method adopted in this application, and other polymerization reactions can also be used for the preparation of the flame retardant provided in this application.
- the embodiment of the present application provides an application of the above-mentioned phosphorus-silicon synergistic flame retardant, and the application field of the phosphorus-silicon synergistic flame retardant includes any one or at least one of thermoplastic resins, thermosetting resins or photocurable resins combination of the two.
- the examples of this application disclose a polymerized phosphorus-silicon synergistic flame retardant.
- the phosphorus-silicon synergistic flame retardant has high content of phosphorus and silicon elements, and only needs a small amount of addition to have excellent flame retardant performance.
- the phosphor-silicon synergistic flame retardant can exert the flame retardant properties of the two elements, and can achieve the effect of no dripping and extremely low smoke generation when the added system is burned;
- the embodiment of the present application discloses a polymeric phosphorus-silicon synergistic flame retardant.
- the polymeric phosphorus-silicon synergistic flame retardant has a wide range of applications and is suitable for use as various thermosetting resins, photocurable resins and thermoplastic resins ;
- the embodiment of the present application discloses a polymeric phosphorus-silicon synergistic flame retardant, which can be applied to thermosetting resins, light-curing resins and thermoplastic resins to obtain no migration, no precipitation, Does not pollute the use environment, permanent flame retardant effect;
- the examples of this application disclose a polymerized phospho-silicon synergistic flame retardant.
- the polymerized phospho-silicon is synergistically added to thermosetting resins, light-curing resins and thermoplastic resins, and the prepared resin composition has excellent mechanical properties, resistance to Thermal properties, electrical properties and flame retardant properties, flame retardant properties (UL-94) up to V-0 level;
- the examples of this application disclose a polymerized flame retardant, which is added to thermosetting resins, light-curing resins and thermoplastic resins, and the prepared resin composition has excellent anti-drip performance through ceramization.
- GB/T The anti-drip level in the 20284-2006 test can reach the d0 level, that is, no dripping;
- the embodiment of this application discloses a polymeric phosphor-silicon synergistic flame retardant.
- the polymeric phosphor-silicon synergistic flame retardant can be obtained by self-polymerization or copolymerization and is used in thermosetting resins, light-curing resins, etc. In resins and thermoplastic resins, it has the effect of no migration, no precipitation, no pollution to the use environment, and permanent flame retardant effect.
- This embodiment provides a polymeric phosphorus-silicon synergistic flame retardant, the structure of which is shown in formula 2:
- This embodiment provides a polymeric phosphorus-silicon synergistic flame retardant, the structure of which is shown in formula 3:
- the preparation method of the compound shown in formula 3 is as follows: dissolve 1 mol of trimethyl phosphate and 1 mol of vinylmethyldimethoxysilane in 100 mL of DMSO, add 1 mol of diethyltriamine and 0.01 mol of DMAP, and react at 170° C. 3h, 190°C for 3h and 210°C for 3h, after the solvent is separated by distillation, the product is purified to obtain the compound shown in formula 3.
- This embodiment provides a polymeric phosphorus-silicon synergistic flame retardant, the structure of which is shown in formula 4:
- the preparation method of the compound shown in formula 4 is as follows: dissolving 1 mol of triethyl phosphate in 100 mL of cyclohexanone, adding 1 mol of polymethylphenylsiloxane (polymerization degree of 50) and 0.01 mol of dibutyltin oxide, and adding 1 mol of dibutyl tin oxide at 190 mol. The reaction is carried out at °C for 3 hours, at 200 °C for 3 hours and at 210 °C for 3 hours. After separating the solvent by distillation, the product is purified to obtain the compound shown in formula 4.
- the hydrogen nuclear magnetic resonance spectrum test shows that the compound prepared by the above preparation method has the CH peak of CH 2 at 4.08-4.01, and the OH peak without hydroxyl group appears, which proves that triethyl phosphate and polymethylphenylsiloxane have been polymerized. reaction.
- This embodiment provides a polymeric phosphorus-silicon synergistic flame retardant, the structure of which is shown in formula 5:
- the preparation method of the compound shown in formula 5 is as follows: 1 mol of trimethyl phosphate is dissolved in 100 mL of NMP, 1 mol of polytrifluoropropylmethylsiloxane (polymerization degree 30), 1 mol of ethylene glycol and 0.01 mol of dibutyl oxide are added. The tin was reacted at 170°C for 5h, 185°C for 3h and 200°C for 2h. After separating the solvent by distillation, the product was purified to obtain the compound shown in formula 5.
- the hydrogen nuclear magnetic resonance spectrum test shows that the compound prepared by the above preparation method has the CH peak of CH 3 at 3.81 ⁇ 3.75, and the OH peak without hydroxyl group appears, which proves that the trimethyl phosphate and polytrifluoropropyl methyl siloxane and Ethylene glycol polymerized.
- This embodiment provides a polymeric phosphorus-silicon synergistic 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 trimethyl phosphate in 100 mL of cyclohexanone, add 1 mol of polydiethylsiloxane (polymerization degree 20), 1 mol of ethylene glycol and 0.01 mol of dibutyltin oxide , followed by reaction at 160°C for 3h, 175°C for 2h and 190°C for 2h. After separating the solvent by distillation, the product was purified to obtain the compound shown in formula 6.
- the hydrogen nuclear magnetic resonance spectrum test shows that the compound prepared by the above preparation method has the CH peak of CH 3 at 3.82-3.75, and the OH peak without hydroxyl group appears, which proves that trimethyl phosphate and polydiethyl siloxane and ethylene glycol A polymerization reaction has occurred.
- the performance of the above epoxy resin cured products a-c is tested.
- the test method of flexural 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
- the smoke density test method is GB/T 8627-2007.
- Table 1 The test results are shown in Table 1.
- the polymeric phosphor-silicon synergistic flame retardant provided in Example 1 of this application is pre-mixed with epoxy resin
- the polymeric flame retardant provided in this application is pre-mixed with the cured epoxy resin.
- the resin has good compatibility, and at the same time, because the polymerized flame retardant provided by the present application contains reactive groups, it can react with the epoxy resin, which further improves the description of the flame retardant and the epoxy resin.
- Phosphorus-silicon synergistic flame retardant makes the epoxy resin have the characteristics of no dripping and low smoke when burning, which not only improves the flame retardant performance of the epoxy resin, but also improves the mechanical properties of the epoxy resin.
- MCA and APP cannot react with epoxy resin molecules, so they do not contribute to the mechanical properties of epoxy resin, and their added amount is large, but the flame retardant effect is limited.
- the properties of the silicone resins a-c 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
- the flame retardancy test method is UL- 94.
- the anti-drip test method is GB/T 20284-2006, and the test condition for water resistance is immersion in boiling water for 2 hours. The test results are shown in Table 2.
- the polymeric phosphorus-silicon synergistic flame retardant provided in Example 1 of the present application has a similar structure to trimethylethoxysiloxane and tetraethoxysiloxane, and is similar to silicon Resin molecules have good compatibility and provide excellent flame retardant properties for silicone resins, which make silicone resins have the characteristics of no dripping and low smoke during combustion, and can also improve the mechanical properties of silicone resins.
- the flame retardant properties and mechanical properties similar to those in Example 7 cannot be achieved.
- Example 2 25 parts by weight of the flame retardant prepared in Example 2 was mixed with 15 parts by weight of methyl methacrylate, 15 parts by weight of butyl methacrylate, 11 parts by weight of ethyl acrylate, and 1 part by weight of methacrylic acid. parts, 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.
- Cross-linked acrylic resin composition a 25 parts by weight of the flame retardant prepared in Example 2 was mixed with 15 parts by weight of methyl methacrylate, 15 parts by weight of butyl methacrylate, 11 parts by weight of ethyl acrylate, and 1 part by weight of methacrylic acid. parts, 13 parts by weight of hydroxypropyl acrylate, 45 parts by weight of tri
- the compressive strength, tensile strength, water resistance and flame retardancy of the acrylic resin compositions a-e prepared above were tested, and the results are shown in Table 3.
- 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 dripping resistance test method is GB/T 20284-2006.
- the smoke density test method is ASTM E1354-94.
- the water resistance is that after the acrylic resin composition after the compressive strength test is soaked in boiling water for 2 hours, the compressive strength test is performed again.
- the polymeric phosphor-silicon synergistic flame retardant provided in Example 2 of the present application has good compatibility with the acrylic resin group, and can also pass through the unsaturated group on the acrylic resin monomer.
- a polymerization reaction occurs, thereby further improving the compatibility of the polymerized phosphor-silicon synergistic flame retardant provided in Example 2 with the acrylic resin molecule, improving the flame retardant performance of the acrylic resin, so that the acrylic resin has no dripping and low emission during combustion. Smoke characteristics, while also improving the mechanical properties of acrylic resin.
- the prepared acrylic resin composition has more excellent flame retardant properties and mechanical properties.
- Example 2 15 parts by weight of the flame retardant prepared in Example 2 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 , 0.6 parts by weight of antioxidant 1010, 34 parts by weight of glass fiber and 0.8 parts by weight of bis-stearic acid amide, mixed to prepare nylon composite material a.
- 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 b.
- 30 parts by weight of decabromodiphenylethane is mixed 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, antioxidant 0.6 parts by weight of agent 1010, 34 parts by weight of glass fiber and 0.8 parts by weight of bis-stearic acid amide, mixed to prepare nylon composite material d.
- the flame retardancy test method is UL- 94.
- the anti-drip test method is GB/T 20284-2006, and the smoke density test method is ASTM E1354-94. The results are shown in Table 4.
- Example 3 18 parts by weight of the polymeric phosphorus-silicon synergistic flame retardant provided in Example 3, 100 parts by weight of 2,2'-bis(4-hydroxyphenyl)propane polycarbonate, polytetrafluoroethylene (anti-drip agent) 0.5 parts by weight, 0.5 parts by weight of light stabilizer 944, mixed to prepare polycarbonate plastic a.
- the tensile properties, Izod impact strength and flame retardant properties of polycarbonate plastics a-c provided in Example 10 and Comparative Examples 13 and 14 were tested, the tensile properties were tested according to GB/T14884-2008, and the Izod impact strength was tested according to GB/T1843-2008 is tested, the flame retardancy test method is UL-94, the anti-drip test method is GB/T 20284-2006, and the smoke density test method is GB/T 8627-2007.
- Table 5 The results are shown in Table 5.
- the polymeric phosphor-silicon synergistic flame retardant provided in Example 3 of the present application because of its good compatibility with polycarbonate plastics, can not only provide good performance for polycarbonate plastics.
- the high flame retardant properties make polycarbonate plastics have the characteristics of no dripping and low smoke when burning, and 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 Example 10, but also have limited flame retardant effect due to poor compatibility and are not beneficial to the mechanical properties of polycarbonate plastics. Influence.
- the PPS plastic a was prepared by mixing 17.5 parts by weight of the polymeric phosphorus-silicon synergistic flame retardant provided in Example 4, 100 parts by weight of PPS, 10 parts by weight of talc, 8 parts by weight of polyvinyl acetate, and 5 parts by weight of zirconia.
- the PPS used is linear PPS with a molecular weight of about 50,000 and a melt index of 30 g/min.
- PPS plastic b 20 parts by weight of APP flame retardant, 100 parts by weight of PPS, 10 parts by weight of talc, 8 parts by weight of polyvinyl acetate, and 5 parts by weight of zirconia were mixed to prepare PPS plastic b.
- the PPS used is linear PPS with a molecular weight of about 50,000 and a melt index of 30 g/min.
- PPS plastic c 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 c.
- the PPS used is 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-c provided in Example 11 and Comparative Examples 15 and 16 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, the anti-drip test method is GB/T 20284-2006, and the smoke density test method is GB/T 8627-2007.
- Table 6 The results are shown in Table 6.
- the polymeric phosphosilicate flame retardant provided in Example 4 of the present application has good compatibility with PPS, which can not only improve the flame retardant performance of PPS plastic, but also make PPS plastic have no The characteristics of dripping and low smoke can also improve the mechanical properties of PPS plastics.
- 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.
- the tensile properties, Izod impact strength and flame retardant properties of the PBT plastics a-c provided in Example 12 and Comparative Examples 17 and 18 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, the anti-drip test method is GB/T 20284-2006, and the smoke density test method is GB/T 8627-2007.
- Table 7 The results are shown in Table 7.
- the polymeric phosphor-silicon synergistic flame retardant provided in Example 2 of the present application is directly added into the PBT plastic system.
- the polymeric phosphorus-silicon synergistic flame retardant can further self-polymerize, so as to be more uniformly dispersed in the PBT plastic, which can not only improve the flame retardant performance of the PBT plastic, but also make the PBT plastic have the characteristics of no dripping and low smoke when burning.
- the mechanical properties of PBT plastics can be improved.
- PPA and MCA as additive flame retardants 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.
- 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 b.
- the tensile properties, Izod impact strength and flame retardant properties of the PPO plastics a-c provided in Example 13 and Comparative Examples 19 and 20 were tested, the tensile properties were tested according to GB/T14884-2008, and the Izod impact strength was tested according to GB /T1843-2008, the flame retardancy test method is UL-94, the anti-drip test method is GB/T 20284-2006, and the smoke density test method is GB/T 8627-2007.
- Table 8 The results are shown in Table 8.
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Abstract
本文公布一种聚合型磷硅协同阻燃剂及其制备方法和应用,所述聚合型磷硅协同阻燃剂与被添加体系具有优异的相容性,且具有优异的阻燃性能,制备工艺简单,节约资源且绿色环保。
Description
本申请涉及阻燃剂领域,例如一种聚合型磷硅协同阻燃剂及其制备方法和应用。
传统的阻燃技术一般分为卤素阻燃和无卤素阻燃。
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。
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。
发明内容
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。
本申请提供一种聚合型磷硅协同阻燃剂及其制备方法和应用。所述聚合型磷硅协同阻燃剂可直接为高分子材料提供优异的阻燃添加剂;本申请提供的聚 合型磷硅协同阻燃剂的磷元素和硅元素含量高,同时发挥两种元素的阻燃性能,两种元素的协同阻燃,可以达到被添加体系在燃烧时无滴落以及发烟量极低的效果,且仅需少量添加即可达到优异的阻燃性能;本申请提供的磷硅协同阻燃剂制备工艺简单,节约资源且绿色环保。
本申请实施例提供一种聚合型磷硅协同阻燃剂,所述阻燃剂结构如式1所示:
其中,R
1~R
5以及R为满足其化学环境的任意基团,X和Y为满足其化学环境的任意基团,n≥1,m≥1。
其中,m可以是1、5、10、20、50、80、100、150、200或500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。
本申请中,提供的聚合型磷硅协同阻燃剂,相比于只含有磷元素的阻燃剂或磷氮阻燃剂具有更为优异的阻燃效果。现有技术中,同时含有磷元素和硅元素的阻燃剂为复合阻燃剂,磷元素和硅元素属于不同的组份,导致其与被添加物质,尤其是聚合物材料的相容性差。而本申请挺稳定磷硅协同阻燃剂,为聚合型阻燃剂,其与聚合物材料如环氧树脂、硅树脂以及聚酯树脂等具有良好的相容性,且其含有反应性基团,可以通过化学键与聚合物材料结合,在进一步提高聚合物材料阻燃性能的同时,进一步提高了聚合物材料的机械性能、耐热性能以及耐水性能等。
本申请中,由于提供的聚合型磷硅协同阻燃剂中,硅元素和磷元素的含量较高,在燃烧后生成的残余物会生成多孔性的自支撑的陶瓷体,可以在极高的温度下保持结构的完整性,从而起到燃烧无滴落的效果。
作为本申请优选的技术方案,所述R
1~R
5分别独立地优选的包括H、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。
作为本申请优选的技术方案,所述R
1~R
5分别独立地优选的包括C1~C12取代或未取代的烷基、C3~C12取代或未取代的环烷基、C6~C12取代或未取代的芳香基、C5~C12取代或未取代的杂芳基、C1~C12取代或未取代的烷氧基、C3~C12取代或未取代的环烷氧基、C6~C12取代或未取代的芳香氧基或C5~C12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。
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;
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;
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;
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;
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;
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;
取代或未取代的芳香氧基优选为C6~C12芳香氧基,例如可以是C7、C8、C9、C10或C11的取代或未取代的芳香氧基;
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。
作为本申请优选的技术方案,所述X优选的包括不存在、亚胺基、O或S中的任意一种。
优选地,所述Y优选的包括不存在、亚胺基、O或S中的任意一种。
作为本申请优选的技术方案,所述R优选的包括不存在、取代或未取代的亚烷基、取代或未取代的亚芳基、酰胺基或者酯基中的任意一种。
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;
取代或未取代的亚芳基优选为C6~C12的取代或未取代的亚芳基,例如可以是C7、C8、C9、C10或C11的取代或未取代的亚芳基。
本申请实施例提供一种上述聚合型磷硅协同阻燃剂的制备方法,所述方法包括:含有硅元素的化合物与含磷化合物通过聚合反应制备得到。
作为本申请优选的技术方案,所述含有硅元素的化合物优选的包括取代或未取代的硅烷、聚硅烷或聚硅氧烷中的任意一种或至少两种组合。
优选地,所述聚硅烷优选的包括硅烷自聚或硅烷与扩链剂共聚所得到的聚合物。
优选地,所述聚硅氧烷优选的包括硅氧烷自聚或硅氧烷与扩链剂共聚所得到的聚合物。
其中,所述硅烷优选为C1~C12取代或未取代的烷基硅烷、C3~C12取代或未取代的环烷基硅烷、C6~C12取代或未取代的芳香基硅烷或C5~C12取代或未取代的杂芳基硅烷、C1~C12取代或未取代的烷氧基、C3~C12取代或未取代的环烷氧基、C6~C12取代或未取代的芳香氧基或C5~C12取代或未取代的杂芳氧基。
其中,C1~C12取代或未取代的烷基硅烷可以是C2、C3、C4、C5、C6、C7、C8、C9、C10或C11的取代或未取代的烷基硅烷;
C3~C12取代或未取代的环烷基硅烷可以是C4、C5、C6、C7、C8、C9、C10或C11的取代或未取代的环烷基硅烷;
C6~C12取代或未取代的芳香基硅烷可以是C7、C8、C9、C10或C11的取代或未取代的芳香基硅烷;
C5~C12取代或未取代的杂芳基硅烷可以是C6、C7、C8、C9、C10或C11的取代或未取代的杂芳基硅烷;
C1~C12的取代或未取代的烷氧基硅烷,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硅烷;
C3~C12的环烷氧基硅烷,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硅烷;
C6~C12芳香氧基硅烷,例如可以是C7、C8、C9、C10或C11的取代或未取代的芳香氧基硅烷;
C5~C12杂芳氧基硅烷,例如可以是C6、C7、C8、C9、C10或C11的取代或未取代的杂芳氧基硅烷。
作为本申请优选的技术方案,所述含磷化合物优选的包括磷酸类化合物及其衍生物、亚磷酸类化合物及其衍生物、次磷酸类化合物及其衍生物、磷酸盐 类化合物及其衍生物、亚磷酸盐类化合物及其衍生物、次磷酸盐类化合物及其衍生物、磷酸酯类化合物及其衍生物、亚磷酸酯类化合物及其衍生物、次磷酸酯类化合物及其衍生物以及DOPO类化合物及其衍生物中的任意一种或至少两种的组合。
其中,磷酸盐类化合物及其衍生物、亚磷酸盐类化合物及其衍生物、次磷酸盐类化合物及其衍生物中的金属元素可以是碱土金属元素、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。
其中,碱土金属元素可以是Be、Mg、Ca、Sr、Ba或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;
IIIA族金属元素可以是Al、Ga、In或Tl;
IVA族金属元素可以是Ge、Sn或Pb;
VA族金属元素可以是Sb或Bi;
VIA族金属元素可以是Po。
作为本申请优选的技术方案,所述制备方法优选地包括含有羟基的含硅化合物与含有酯基的含磷化合物通过聚合反应得到、含有烷氧基的含硅化合物与含有羟基的含磷化合物通过聚合反应得到或含有氨基的含硅化合物与含有酯基的含磷化合物通过聚合反应得到。上述制备方法仅为对本申请采用的制备方法的简单列举,其他聚合反应也可以用于本申请提供的阻燃剂的制备。
本申请实施例提供一种上述磷硅协同阻燃剂的应用,所述磷硅协同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。
与相关技术相比,本申请实施例至少具有以下有益效果:
(1)本申请实施例公开一种聚合型磷硅协同阻燃剂,所述磷硅协同阻燃剂磷元素和硅元素含量高,仅需少量添加具备优异的阻燃性能,同时所述聚合型磷硅协同阻燃剂可以发挥两种元素的阻燃性能,可以达到被添加体系在燃烧时无滴落以及发烟量极低的效果;
(2)本申请实施例公开一种聚合型磷硅协同阻燃剂,所述聚合型磷硅协同阻燃剂应用范围广,适合于用作各种热固性树脂、光固化树脂和热塑型树脂;
(3)本申请实施例公开一种聚合型磷硅协同阻燃剂,所述聚合型磷硅协同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;
(4)本申请实施例公开一种聚合型磷硅协同阻燃剂,聚合型磷硅协同添加于热固性树脂、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机械性能、耐热性能、电性能和阻燃性能,阻燃性能(UL-94)达V-0级别;
(5)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,通过陶瓷化使得制备得到的树脂组合物具有优异的抗滴落性能,GB/T 20284-2006测试中的抗滴落等级可达到d0等级,即无滴落;
(6)本申请实施例公开一种聚合型磷硅协同阻燃剂,所述聚合型磷硅协同阻燃剂通过自聚或共聚等反应可以得到聚合型阻燃剂应用于热固性树脂、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。
在阅读并理解了详细描述后,可以明白其他方面。
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。
实施例1
本实施例提供一种聚合型磷硅协同阻燃剂,其结构如式2所示:
式2所示化合物的制备方法为:将1mol亚磷酸二甲酯以及1mol二羟基二苯基硅烷溶于100mL NMP,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2h,180℃反应2h以及200℃下反应2h,采用蒸馏分离溶剂后,对产物进行提纯得到式2所示化合物。软化点为133℃,n=10。
1H NMR(CDCl
3,500MHz):δ7.56~7.48(m,2H,Ar-H),7.45~7.39(m,4H,Ar-H),7.35~7.28(m,4H,Ar-H),6.72~6.67(s,H,P-H)3.81~3.73(t,2H,CH
2),3.59~3.52(d,2H,CH
2),1.82~1.75(m,2H,CH
2)。
实施例2
本实施例提供一种聚合型磷硅协同阻燃剂,其结构如式3所示:
式3所示化合物的制备方法为:将1mol磷酸三甲酯以及1mol乙烯基甲基二甲氧基硅烷溶于100mL DMSO,加入1mol二乙基三胺以及0.01mol DMAP,依次在170℃下反应3h,190℃反应3h以及210℃下反应3h,采用蒸馏分离溶剂后,对产物进行提纯得到式3所示化合物。软化点为135℃,n=8。
1H NMR(CDCl
3,500MHz):δ5.45~5.37(t,H,HC=C
H
2),5.32~5.25(m,H,
HC=CH
2),5.19~5.11(t,2H,HC=C
H
2),3.81~3.75(s,3H,CH
3),2.79~2.72(m,4H,CH
2),2.70~2.62(m,4H,CH
2),2.30~2.22(t,2H,NH),2.21~2.15(m,H,NH),2.08~2.01(t,H,NH),0.23~0.15(s,3H,CH
3)。
实施例3
本实施例提供一种聚合型磷硅协同阻燃剂,其结构如式4所示:
式4所示化合物的制备方法为:将1mol磷酸三乙酯溶于100mL环己酮、加入1mol聚甲基苯基硅氧烷(聚合度50)以及0.01mol二丁基氧化锡,依次在190℃下反应3h,200℃反应3h以及210℃下反应3h,采用蒸馏分离溶剂后,对产物进行提纯得到式4所示化合物。
核磁共振氢谱测试表明,上述制备方法制备得到的化合物在4.08~4.01出现 CH
2的C-H峰,且无羟基的O-H峰出现,证明磷酸三乙酯与聚甲基苯基硅氧烷发生了聚合反应。软化点为149℃,m=6。
实施例4
本实施例提供一种聚合型磷硅协同阻燃剂,其结构如式5所示:
式5所示化合物的制备方法为:将1mol磷酸三甲酯溶于100mL NMP、加入1mol聚三氟丙基甲基硅氧烷(聚合度30)、1mol乙二醇以及0.01mol二丁基氧化锡,依次在170℃下反应5h,185反应3h以及200℃下反应2h,采用蒸馏分离溶剂后,对产物进行提纯得到式5所示化合物。
核磁共振氢谱测试表明,上述制备方法制备得到的化合物在3.81~3.75出现CH
3的C-H峰,且无羟基的O-H峰出现,证明磷酸三甲酯与聚三氟丙基甲基硅氧烷以及乙二醇发生了聚合反应。软化点为143℃,m=6。
实施例5
本实施例提供一种聚合型磷硅协同阻燃剂,其结构如式6所示:
式6所示化合物的制备方法为:将1mol磷酸三甲酯溶于100mL环己酮、加入1mol聚二乙基硅氧烷(聚合度20)、1mol乙二醇以及0.01mol二丁基氧化锡,依次在160℃下反应3h,175反应2h以及190℃下反应2h,采用蒸馏分离溶剂后,对产物进行提纯得到式6所示化合物。
核磁共振氢谱测试表明,上述制备方法制备得到的化合物在3.82~3.75出现CH
3的C-H峰,且无羟基的O-H峰出现,证明磷酸三甲酯与聚二乙基硅氧烷以及乙二醇发生了聚合反应。软化点为128℃,m=8。
环氧树脂中的应用
实施例6
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,与实施例2所示阻燃剂20重量份混合,180℃下固化2h,得到环氧树脂固化物a-e。
对比例1
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,180℃下固化2h,得到环氧树脂固化物b。
对比例2
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,180℃下固化2h,得到环氧树脂固化物c。
对上述环氧树脂固化物a-c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,烟密度测试方法为GB/T 8627-2007。测试结果表1所示。
表1
从表1的测试结果可以看出,本申请实施例1提供的聚合型磷硅协同阻燃剂,其与环氧树脂预先混合,本申请提供的聚合型阻燃剂其与固化后的环氧树脂具有良好的相容性,同时由于本申请提供的聚合型阻燃剂包含反应基团,可 以与环氧树脂发生反应,进一步提高了阻燃剂与环氧树脂的形容性。磷硅协同阻燃,使得环氧树脂在燃烧时具备无滴落以及低发烟的特性,在提高环氧树脂阻燃性能的同时,还提高了环氧树脂的机械性能。而MCA以及APP作为添加型阻燃剂不能与环氧树脂分子发生反应,因此对环氧树脂的机械性能没有贡献,且其添加量大,而起到的阻燃效果有限。
硅树脂的应用:
实施例7
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,与50重量份实施例1制备得到的聚合型磷硅协同阻燃剂混合,并在20℃下固化5h,制备得到硅树脂a。
对比例3
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b。
对比例4
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c。
对上述得到的硅树脂a-c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,抗滴落测试方法为GB/T 20284-2006,耐水性能的测试条件为沸水中浸泡2h。测试结果如表2所示。
表2
根据表2的测试结果可以看出,本申请实施例1提供的聚合型磷硅协同阻燃剂与三甲基乙氧基硅氧烷以及四乙氧基硅氧烷具有相似的结构,与硅树脂分子具有良好的相容性,为硅树脂提供优异的阻燃性能,使得硅树脂在燃烧时具备无滴落以及低发烟的特性,同时还可以提高硅树脂的机械性能。而在不添加实施例1提供的聚合型磷硅协同阻燃剂,以及使用APP作为阻燃剂时,均不能达到与实施例7相近的阻燃性能和机械性能。
不饱和树脂中的应用:
实施例8
本实施例中,分别将实施例2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。
对比例5
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b。
对比例6
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c。
对比例7
本对比例中,将十溴二苯乙烷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。
对比例8
本对比例中,将四溴双酚A 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e。
对上述制备得到的丙烯酸树脂组合物a-e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3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,抗滴落测试方法为GB/T 20284-2006,烟密度测试方法为ASTM E1354-94。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。
表3
根据表3的测试结果可以看出,本申请实施例2提供的聚合型磷硅协同阻燃剂与丙烯酸树脂组具有良好的相容性,还可以通过与丙烯酸树脂单体上的不饱和基团发生聚合反应,从而进一步提高实施例2提供的聚合型磷硅协同阻燃剂与丙烯酸树脂分子的相容性,提高丙烯酸树脂的阻燃性能,使得丙烯酸树脂在燃烧时具备无滴落以及低发烟的特性,同时还提高了丙烯酸树脂机械性能。与同样添加量的现有阻燃剂相比,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。
尼龙复合材料中的应用:
实施例9
在本实施例中,将实施例2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。
对比例9
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b。
对比例10
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c。
对比例11
在本实施例中,将十溴二苯乙烷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。
对比例12
在本实施例中,将四溴双酚A 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e。
对实施例9以及对比例9-12制备得到的尼龙复合材料a-e的抗压强度(GB/T15231-2008)、抗拉强度(ASTM C1557-2003(2008)),阻燃性测试方法为UL-94,抗滴落测试方法为GB/T 20284-2006,烟密度测试方法为ASTM E1354-94。结果如表4所示。
表4
根据表4的测试结果可以看出,本申请提供的聚合型磷硅协同阻燃剂在添加入尼龙复合材料体系后,对于添加量更多的现有阻燃剂而言MCA和APP,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,使得尼龙复合材料在燃烧时具备无滴落以及低发烟的特性。
聚碳酸酯塑料中的应用
实施例10
将实施例3提供的聚合型磷硅协同阻燃剂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。
对比例13
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c。
对比例14
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d。
对实施例10以及对比例13和14提供的聚碳酸酯塑料a-c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,烟密度测试方法为GB/T 8627-2007。其结果如表5所示。
表5
从表5的测试结果可以看出,本申请实施例3提供的聚合型磷硅协同阻燃剂,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,使得聚碳酸酯塑料在燃烧时具备无滴落以及低发烟的特性,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10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。
PPS塑料中的应用
实施例11
将实施例4提供的聚合型磷硅协同阻燃剂17.5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。使用的PPS为分子量为5万左右的线性PPS,熔融指数为30g/min。
对比例15
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b。使用的PPS为分子量为5万左右的线性PPS,熔融指数为30g/min。
对比例16
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c。使用的PPS为分子量为5万左右的线性PPS,熔融指数为30g/min。
对实施例11以及对比例15和16提供的PPS塑料a-c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,烟密度测试方法为GB/T 8627-2007。其结果如表6所示。
表6
从表6的测试结果看出,本申请实施例4提供的聚合型磷硅阻燃剂与PPS具有良好的相容性,不仅可以提高PPS塑料的阻燃性能,使得PPS塑料在燃烧时具备无滴落以及低发烟的特性,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。
PBT塑料中的应用
实施例12
将实施例2提供的聚合型磷硅协同阻燃剂15.4重量份,偶氮二异丁腈0.05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,混合熔炼制备得到PBT塑料a。
对比例17
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b。
对比例18
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c。
对实施例12以及对比例17和18提供的PBT塑料a-c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,烟密度测试方法为GB/T 8627-2007。其结果如表7所示。
表7
从表7的测试结果看出,本申请实施例2提供的聚合型磷硅协同阻燃剂直接添加进入PBT塑料体系中,在塑料炼胶过程中,在加入的少量引发剂的作用,所述聚合型磷硅协同阻燃剂可以进一步自聚,从而更加均匀分散于PBT塑料中,不仅可以提高PBT塑料的阻燃性能,使得PBT塑料在燃烧时具备无滴落以及低发烟的特性,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。
PPO塑料中的应用
实施例13
在本实施例中,将实施例5提供的聚合型阻燃剂20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。
对比例19
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b。
对比例20
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c。
对实施例13以及对比例19和20提供的PPO塑料a-c的拉拉伸性能、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,烟密度测试方法为GB/T 8627-2007。其结果如表8所示。
表8
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。
Claims (13)
- 根据权利要求1所述的阻燃剂,其中,所述R 1~R 5分别独立地包括H、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。
- 根据权利要求2所述的阻燃剂,其中,所述R 1~R 5分别独立地包括C1~C12取代或未取代的烷基、C3~C12取代或未取代的环烷基、C6~C12取代或未取代的芳香基、C5~C12取代或未取代的杂芳基、C1~C12取代或未取代的烷氧基、C3~C12取代或未取代的环烷氧基、C6~C12取代或未取代的芳香氧基或C5~C12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。
- 根据权利要求1-3任一项所述的阻燃剂,其中,所述X包括不存在、亚胺基、O或S中的任意一种。
- 根据权利要求1-4任一项所述的阻燃剂,其中,所述Y包括不存在、亚胺基、O或S中的任意一种。
- 根据权利要求1-5任一项所述的阻燃剂,其中,所述R包括不存在、取代或未取代的亚烷基、取代或未取代的亚芳基、酰胺基或者酯基中的任意一种。
- 一种权利要求1-6任一项所述的聚合型磷硅协同阻燃剂的制备方法,其包括:含有硅元素的化合物与含磷化合物通过聚合反应制备得到。
- 根据权利要求7所述的制备方法,其中,所述含有硅元素的化合物包括取代或未取代的硅烷、聚硅烷或聚硅氧烷中的任意一种或至少两种组合。
- 根据权利要求8所述的制备方法,其中,所述聚硅烷包括硅烷自聚或硅烷与扩链剂共聚所得到的聚合物。
- 根据权利要求8所述的制备方法,其中,所述聚硅氧烷包括硅氧烷自聚或硅氧烷与扩链剂共聚所得到的聚合物。
- 根据权利要求7-10任一项所述的制备方法,其中,所述含磷化合物包括磷酸类化合物及其衍生物、亚磷酸类化合物及其衍生物、次磷酸类化合物及其衍生物、磷酸盐类化合物及其衍生物、亚磷酸盐类化合物及其衍生物、次磷酸盐类化合物及其衍生物、磷酸酯类化合物及其衍生物、亚磷酸酯类化合物及其衍生物、次磷酸酯类化合物及其衍生物以及DOPO类化合物及其衍生物中的任意一种或至少两种的组合。
- 根据权利要求7所述的制备方法,其中,所述制备方法包括含有羟基的含硅化合物与含有酯基的含磷化合物通过聚合反应得到、含有烷氧基的含硅化合物与含有羟基的含磷化合物通过聚合反应得到或含有氨基的含硅化合物与含有酯基的含磷化合物通过聚合反应得到。
- 一种权利要求1-6任一项所述的聚合型阻燃剂的应用,其中,所述磷硅协同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。
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