CN106478727B - Fire retardant Phenylmethoxy silicic acid disulfide group phospha trioxa-l-phosphabicyclo octyl methyl compound and preparation method thereof - Google Patents
Fire retardant Phenylmethoxy silicic acid disulfide group phospha trioxa-l-phosphabicyclo octyl methyl compound and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- -1 octyl methyl compound Chemical class 0.000 title description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 87
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 238000005194 fractionation Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- XXUJHZYMULSBTO-UHFFFAOYSA-N benzylperoxy(trihydroxy)silane Chemical compound C1(=CC=CC=C1)COO[Si](O)(O)O XXUJHZYMULSBTO-UHFFFAOYSA-N 0.000 claims 2
- 125000002619 bicyclic group Chemical group 0.000 claims 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 2
- NQFNREAPSWQXCD-UHFFFAOYSA-N C1C2(COP(=S)(O1)OC2)PO Chemical compound C1C2(COP(=S)(O1)OC2)PO NQFNREAPSWQXCD-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 239000000155 melt Substances 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 238000004508 fractional distillation Methods 0.000 abstract description 13
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000003822 epoxy resin Substances 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 229920000647 polyepoxide Polymers 0.000 abstract description 3
- 229920000728 polyester Polymers 0.000 abstract description 3
- 229920002635 polyurethane Polymers 0.000 abstract description 3
- 239000004814 polyurethane Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 13
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 230000002195 synergetic effect Effects 0.000 description 10
- 239000003610 charcoal Substances 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- MPPXAUXDXZZYHX-UHFFFAOYSA-N 4-methyl-3,5,8-trioxabicyclo[2.2.2]octane Chemical compound O1CC2COC1(C)OC2 MPPXAUXDXZZYHX-UHFFFAOYSA-N 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 150000003457 sulfones Chemical group 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
-
- 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
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
本发明涉及一种阻燃剂苯基甲氧基硅酸双‑1‑硫基磷杂‑2,6,7‑三氧杂双环[2.2.2]辛基‑4‑甲酯化合物及其制备方法,该化合物的结构如下式所示:制备方法为:苯基三甲氧基硅烷和1‑硫基磷杂‑4‑羟甲基‑2,6,7‑三氧杂双环[2.2.2]辛烷在120℃~160℃分馏反应4h~9h,或于有机溶剂中,在80℃~160℃下,反应5h~10h,分馏出甲醇,经纯化处理得苯基甲氧基硅酸双‑1‑硫基磷杂‑2,6,7‑三氧杂双环[2.2.2]辛基‑4‑甲酯。本发明阻燃剂阻燃效能高,成炭效果好,适合用作聚酯、聚氨酯、环氧树脂、不饱和树脂等的阻燃成炭剂,并且生产工艺简单,成本低,易于实现工业化生产。The invention relates to a flame retardant phenylmethoxysilicate bis-1-thiophospha-2,6,7-trioxabicyclo[2.2.2]octyl-4-methyl ester compound and its preparation method, the structure of the compound is shown in the following formula: The preparation method is: phenyltrimethoxysilane and 1-thiophospha-4-hydroxymethyl-2,6,7-trioxabicyclo[2.2.2]octane react by fractional distillation at 120℃~160℃ for 4h ~9h, or in an organic solvent, at 80°C~160°C, react for 5h~10h, fractionally distill methanol, and purify to obtain phenylmethoxysilicate bis-1-thiophospha-2,6, 7‑trioxabicyclo[2.2.2]octyl‑4‑methyl ester. The flame retardant of the present invention has high flame retardant efficiency and good char formation effect, and is suitable for use as a flame retardant char formation agent for polyester, polyurethane, epoxy resin, unsaturated resin, etc., and has simple production process, low cost, and is easy to realize industrial production .
Description
技术领域technical field
本发明涉及一种硅、磷、硫三元素协同阻燃剂苯基甲氧基硅酸双-1-硫基磷杂-2,6,7-三氧杂双环[2.2.2]辛基-4-甲酯化合物及其制备方法,该化合物适合用作聚酯、聚氨酯、环氧树脂、不饱和树脂等的阻燃成炭剂。The invention relates to a synergistic flame retardant of silicon, phosphorus and sulfur three elements phenylmethoxysilicate bis-1-thiophospha-2,6,7-trioxabicyclo[2.2.2]octyl- A 4-methyl ester compound and a preparation method thereof, the compound is suitable for use as a flame-retardant char-forming agent for polyester, polyurethane, epoxy resin, unsaturated resin and the like.
背景技术Background technique
随着人们生活水平的提高及安全防火意识的增强,阻燃剂工业得到了飞速发展,特别是对新型高效无毒阻燃剂的需求更有急迫性。至前对磷系阻燃剂研究较多。由于硅系阻燃剂有良好的热稳定性,有效的防熔体滴落和抑烟性能,而成为目前低烟无毒阻燃材料开发的热点之一。硫元素能改变高分子材料的分解历程,在凝聚相起阻燃作用,并与磷元素有良好的协同增效性,是新开发的阻燃元素。若把硅、磷及硫设计到同一化合物结构内,让其发挥协同阻燃增效作用,可以大幅提高其阻燃效能。With the improvement of people's living standards and the enhancement of safety and fire prevention awareness, the flame retardant industry has developed rapidly, especially the demand for new high-efficiency non-toxic flame retardants is more urgent. So far, there have been many studies on phosphorus-based flame retardants. Due to the good thermal stability, effective anti-melt dripping and smoke suppression performance of silicon-based flame retardants, it has become one of the hot spots in the development of low-smoke non-toxic flame-retardant materials. Sulfur element can change the decomposition process of polymer materials, play a flame-retardant role in the condensed phase, and has good synergistic effect with phosphorus element. It is a newly developed flame-retardant element. If silicon, phosphorus, and sulfur are designed into the same compound structure, allowing them to play a synergistic flame-retardant synergistic effect, the flame-retardant performance can be greatly improved.
本发明公开了以苯基三甲氧基硅烷、1-硫基磷杂-4-羟甲基-2,6,7-三氧杂双环[2.2.2]辛烷为主要原料制备硅、磷、硫三元素协同阻燃剂苯基甲氧基硅酸双-1-硫基磷杂-2,6,7-三氧杂双环[2.2.2]辛基-4-甲酯化合物的方法。本发明阻燃剂具有多重阻燃机理,其中磷元素在燃烧时能生成聚磷酸膜,阻断空气对可燃物的侵袭;硅元素能生成致密的硅炭层,有较好的防熔滴作用;硫元素能改变材料的分解历程,在凝聚相阻燃。三元素协同阻燃能产生优异的阻燃效果。本发明阻燃剂阻燃效能高,成炭效果好,应用范围广,有很好的开发前景。The invention discloses the preparation of silicon, phosphorus, A method for synergistic flame retardant of sulfur trielement with phenylmethoxysilicate bis-1-thiophospha-2,6,7-trioxabicyclo[2.2.2]octyl-4-methyl ester compound. The flame retardant of the present invention has multiple flame retardant mechanisms, in which the phosphorus element can form a polyphosphoric acid film when burning, blocking the air from invading combustibles; the silicon element can form a dense silicon carbon layer, which has a better anti-droplet effect ; Sulfur can change the decomposition process of the material, and flame retardant in the condensed phase. The synergistic flame retardant of three elements can produce excellent flame retardant effect. The flame retardant of the invention has high flame retardant efficiency, good char formation effect, wide application range and good development prospect.
发明内容Contents of the invention
本发明的目的之一在于提出一种硅、磷、硫协同阻燃成炭剂苯基甲氧基硅酸双-1-硫基磷杂-2,6,7-三氧杂双环[2.2.2]辛基-4-甲酯化合物,其阻燃效能高,可克服现有技术中的不足。One of the objectives of the present invention is to propose a silicon, phosphorus, sulfur synergistic flame retardant char-forming agent phenylmethoxysilicate bis-1-thiophospha-2,6,7-trioxabicyclo[2.2. 2] The octyl-4-methyl ester compound has high flame retardant efficiency and can overcome the deficiencies in the prior art.
为实现上述发明目的,本发明采用了如下技术方案:In order to realize the above-mentioned purpose of the invention, the present invention has adopted following technical scheme:
苯基甲氧基硅酸双-1-硫基磷杂-2,6,7-三氧杂双环[2.2.2]辛基-4-甲酯化合物,其特征在于,该化合物的结构如下式所示:Phenylmethoxysilicate bis-1-thiophospha-2,6,7-trioxabicyclo[2.2.2]octyl-4-methyl ester compound is characterized in that the structure of the compound is as follows: Shown:
本发明的另一目的在于提出一种硅、磷、硫协同阻燃剂苯基甲氧基硅酸双-1-硫基磷杂-2,6,7-三氧杂双环[2.2.2]辛基-4-甲酯化合物的制备方法,其工艺简单,设备投资少,易于规模化生产,且原料廉价易得,成本低廉,该方法为:Another object of the present invention is to propose a silicon, phosphorus, sulfur synergistic flame retardant phenylmethoxysilicate bis-1-thiophospha-2,6,7-trioxabicyclo[2.2.2] The preparation method of octyl-4-methyl ester compound has simple process, less investment in equipment, easy large-scale production, and cheap and easy-to-obtain raw materials and low cost. The method is:
在装有搅拌器、温度计和分馏装置的反应器中,氮气赶尽空气,在25℃的温度下,加入一倍摩尔的苯基三甲氧基硅烷和2-4倍摩尔的1-硫基磷杂-4-羟甲基-2,6,7-三氧杂双环[2.2.2]辛烷,升温至120℃~160℃,固体逐渐溶解,最终呈无色透明液体,分馏反应4h~9h,在反应过程中保持反应器内微真空(-0.02Mpa),以便于生成的甲醇及时被分离出来,分馏出定量的甲醇后,降温至40℃左右,再加入产物理论质量克数1~5倍体积毫升数的甲醇或乙醇搅拌分散1h,抽滤,干燥,得白色固体粉末苯基甲氧基硅酸双-1-硫基磷杂-2,6,7-三氧杂双环[2.2.2]辛基-4-甲酯。In a reactor equipped with a stirrer, a thermometer and a fractional distillation device, nitrogen is used to drive out the air, and at a temperature of 25°C, one time mole of phenyltrimethoxysilane and 2-4 times mole of 1-thiophosphorus are added Hetero-4-hydroxymethyl-2,6,7-trioxabicyclo[2.2.2]octane, heat up to 120℃~160℃, the solid gradually dissolves, and finally becomes a colorless transparent liquid, fractionation reaction 4h~9h , keep a slight vacuum (-0.02Mpa) in the reactor during the reaction, so that the generated methanol can be separated in time, after fractional distillation of a certain amount of methanol, the temperature is lowered to about 40°C, and then 1 to 5 grams of the theoretical mass of the product is added. Multiple milliliters of methanol or ethanol was stirred and dispersed for 1 h, suction filtered, and dried to obtain white solid powder phenylmethoxysilicate bis-1-thiophospha-2,6,7-trioxabicyclo[2.2. 2] Octyl-4-methyl ester.
该方法还可为:The method can also be:
在装有搅拌器、温度计和分馏装置的反应器中,氮气赶尽空气,在25℃的温度下,加入1倍摩尔的苯基三甲氧基硅烷、2-4倍摩尔的1-硫基磷杂-4-羟甲基-2,6,7-三氧杂双环[2.2.2]辛烷和相对于1-硫基磷杂-4-羟甲基-2,6,7-三氧杂双环[2.2.2]辛烷质量克数2~6倍体积毫升数的有机溶剂,升温至80℃-160℃回流,分馏反应5h~10h,及时分离出生成的甲醇;分出定量的甲醇后,冷却到25℃,抽滤,再用产物理论质量克数1~2倍体积毫升数的甲醇或乙醇洗涤,抽滤,干燥,得白色固体粉末苯基甲氧基硅酸双-1-硫基磷杂-2,6,7-三氧杂双环[2.2.2]辛基-4-甲酯。In a reactor equipped with a stirrer, a thermometer and a fractional distillation device, nitrogen is used to drive out the air, and at a temperature of 25°C, 1 times the mole of phenyltrimethoxysilane and 2-4 times the mole of 1-thiophosphorus Hetero-4-hydroxymethyl-2,6,7-trioxabicyclo[2.2.2]octane and relative to 1-thiophospha-4-hydroxymethyl-2,6,7-trioxa Bicyclo[2.2.2]octane is an organic solvent whose mass is 2-6 times the volume in milliliters, heated up to 80°C-160°C to reflux, fractionated for 5h-10h, and the generated methanol is separated in time; after the quantitative methanol is separated , cooled to 25°C, filtered with suction, washed with methanol or ethanol with 1 to 2 times the theoretical mass of the product in milliliters, filtered with suction, and dried to obtain bis-1-sulfur phenylmethoxysilicate as a white solid powder Phospha-2,6,7-trioxabicyclo[2.2.2]octyl-4-methyl ester.
如上方法二所述的有机溶剂为乙腈、二氧六环或二乙二醇二甲醚。The organic solvent as described in the second method above is acetonitrile, dioxane or diglyme.
本发明的苯基甲氧基硅酸双-1-硫基磷杂-2,6,7-三氧杂双环[2.2.2]辛基-4-甲酯为白色固体粉末,产品得率为90.2%~93.1%,熔点为169±2℃,分解温度为322±5℃。其适合用作聚酯、聚氨酯、环氧树脂、不饱和树脂等材料的阻燃成炭剂。该苯基甲氧基硅酸双-1-硫基磷杂-2,6,7-三氧杂双环[2.2.2]辛基-4-甲酯的制备工艺原理如下式所示:Bis-1-thiophospha-2,6,7-trioxabicyclo[2.2.2]octyl-4-methyl phenylmethoxysilicate of the present invention is a white solid powder, and the product yield is 90.2%~93.1%, melting point is 169±2℃, decomposition temperature is 322±5℃. It is suitable for use as a flame-retardant char-forming agent for materials such as polyester, polyurethane, epoxy resin, and unsaturated resin. The preparation process principle of the phenylmethoxysilicate bis-1-thiophospha-2,6,7-trioxabicyclo[2.2.2]octyl-4-methyl ester is shown in the following formula:
与现有技术相比,本发明的有益效果在于:Compared with prior art, the beneficial effect of the present invention is:
①本发明苯基甲氧基硅酸双-1-硫基磷杂-2,6,7-三氧杂双环[2.2.2]辛基-4-甲酯含硅、磷、硫三种阻燃元素,其协同阻燃效能高,硅元素具有成炭作用,能有效防止材料受热熔融滴落而产生的二次燃烧,磷元素在燃烧时能生成聚磷酸膜,阻断可燃物与空气,硫元素能改变高分子材料的分解历程,凝聚相阻燃。①Phenylmethoxysilicate bis-1-thiophospha-2,6,7-trioxabicyclo[2.2.2]octyl-4-methyl ester of the present invention contains three kinds of inhibitors of silicon, phosphorus and sulfur Combustible element, its synergistic flame retardant efficiency is high, silicon element has charcoal forming effect, which can effectively prevent the secondary combustion caused by material heating, melting and dripping, phosphorus element can form polyphosphate film when burning, blocking combustibles and air, Sulfur can change the decomposition process of polymer materials, and the condensed phase is flame retardant.
②本发明苯基甲氧基硅酸双-1-硫基磷杂-2,6,7-三氧杂双环[2.2.2]辛基-4-甲酯结构中硅原子上连有两个苯基,具有C-Si键,为有机硅结构,有机硅结构稳定性好、耐水性强,燃烧时更易于生成致密的炭-硅层,阻燃效果更优异。② In the present invention, there are two Phenyl, with a C-Si bond, is an organosilicon structure. The organosilicon structure has good stability and strong water resistance. It is easier to form a dense carbon-silicon layer when it is burned, and the flame retardant effect is more excellent.
③本发明苯基甲氧基硅酸双-1-硫基磷杂-2,6,7-三氧杂双环[2.2.2]辛基-4-甲酯对称性好、物理化学性能稳定,分解温度高,且含有的苯环具有电子结构的多向性,与高分子材料相容性好,有利于改善材料的力学性能,能适应工程材料的高温加工。③ The phenylmethoxysilicate bis-1-thiophospha-2,6,7-trioxabicyclo[2.2.2]octyl-4-methyl ester of the present invention has good symmetry and stable physical and chemical properties. The decomposition temperature is high, and the benzene ring contained has multi-directional electronic structure, and has good compatibility with polymer materials, which is conducive to improving the mechanical properties of materials, and can adapt to high-temperature processing of engineering materials.
④本发明苯基甲氧基硅酸双-1-硫基磷杂-2,6,7-三氧杂双环[2.2.2]辛基-4-甲酯的制备工艺简单,无需添加催化剂不引入杂质,设备简单,成本低廉,适于规模化生产,有很好的应用开发前景。4. The preparation process of phenylmethoxysilicate bis-1-thiophospha-2,6,7-trioxabicyclo[2.2.2]octyl-4-methyl ester of the present invention is simple, without adding a catalyst. Impurities are introduced, the equipment is simple, the cost is low, the method is suitable for large-scale production, and has good application and development prospects.
附图说明Description of drawings
为了进一步说明产品的结构和性能特给出如下附图。In order to further illustrate the structure and performance of the product, the following drawings are given.
图1是苯基甲氧基硅酸双-1-硫基磷杂-2,6,7-三氧杂双环[2.2.2]辛基-4-甲酯的红外光谱图;图1表明,993cm-1处为P-O键的伸缩振动峰,2843cm-1-2968cm-1处是甲基及亚甲基的C-H的伸缩振动峰,3069cm-1处是苯环上C-H的伸缩振动峰,696cm-1处为P=S的特征吸收峰,1021cm-1处为C-O键的伸缩振动峰,811cm-1处为Si-C键的伸缩振动峰,1407cm-1、1542cm-1及1689cm-1处是苯环骨架的特征吸收峰,1103cm-1处为Si-O-C键的特征吸收峰。Fig. 1 is the infrared spectrogram of phenylmethoxysilicate bis-1-thiophospha-2,6,7-trioxabicyclo[2.2.2]octyl-4-methyl ester; Fig. 1 shows, 993cm -1 is the stretching vibration peak of PO bond, 2843cm -1 -2968cm -1 is the stretching vibration peak of methyl and methylene CH, 3069cm -1 is the stretching vibration peak of CH on the benzene ring, 696cm - One is the characteristic absorption peak of P=S, 1021cm -1 is the stretching vibration peak of CO bond, 811cm -1 is the stretching vibration peak of Si-C bond, 1407cm -1 , 1542cm -1 and 1689cm -1 are The characteristic absorption peak of the benzene ring skeleton, and the characteristic absorption peak of the Si-OC bond at 1103cm -1 .
图2是苯基甲氧基硅酸双-1-硫基磷杂-2,6,7-三氧杂双环[2.2.2]辛基-4-甲酯的核磁谱图;图2表明,以氘代二甲基亚砜作溶剂,化学位移δ7.41-7.64处为苯环上氢峰;δ4.64-4.68处为C(CH2O)上与氧相连的亚甲基上氢峰;δ3.64-3.70处为CCH2OSi与氧相连的亚甲基上氢峰,δ3.23-3.28处为CH3O上甲基氢峰;δ2.51处为溶剂氘代二甲基亚砜交换的质子峰。Fig. 2 is the NMR spectrum of phenylmethoxysilicate bis-1-thiophospha-2,6,7-trioxabicyclo[2.2.2]octyl-4-methyl ester; Fig. 2 shows, Using deuterated dimethyl sulfoxide as solvent, the chemical shift δ7.41-7.64 is the hydrogen peak on the benzene ring; δ4.64-4.68 is the hydrogen peak on the methylene connected to oxygen on C(CH 2 O) ; δ3.64-3.70 is the hydrogen peak on the methylene of CCH 2 OSi connected with oxygen, δ3.23-3.28 is the methyl hydrogen peak on CH 3 O; δ2.51 is the solvent deuterated dimethyl methylene Proton peak for sulfone exchange.
图3是苯基甲氧基硅酸双-1-硫基磷杂-2,6,7-三氧杂双环[2.2.2]辛基-4-甲酯的热重图;图3表明,温度为318℃时,产品开始分解;当温度为322左右时,分解速率达峰值,并且伴有强烈的放热;温度达到330℃后,分解第一阶段基本结束,此时的残渣剩率为64%;当温度升高到500℃后,生成的炭层开始缓慢分解,到700℃后,残渣剩率仍有44%。Fig. 3 is the thermogravimetric diagram of bis-1-thiophosphora-2,6,7-trioxabicyclo[2.2.2]octyl-4-methyl ester of phenylmethoxysilicate; Fig. 3 shows, When the temperature is 318°C, the product begins to decompose; when the temperature is around 322°C, the decomposition rate reaches a peak, accompanied by a strong exotherm; when the temperature reaches 330°C, the first stage of decomposition basically ends, and the residual residue rate at this time is 64%; when the temperature rises to 500°C, the generated carbon layer begins to slowly decompose, and after reaching 700°C, the residual rate is still 44%.
具体实施例specific embodiment
以下结合具体实施方式对本发明的技术方案做进一步说明。The technical solution of the present invention will be further described below in combination with specific embodiments.
实施例1 在装有搅拌器、温度计和分馏装置的250ml四口反应瓶中,氮气赶尽瓶内的空气,在25℃的温度下,加入21.56g(0.11mol)1-硫基磷杂-4-羟甲基-2,6,7-三氧杂双环[2.2.2]辛烷和9.91g(0.05mol)苯基三甲氧基硅烷,升温至150℃,固体逐渐溶解,最终呈无色透明液体,分馏反应6h,在反应过程中保持反应器内微真空(-0.02Mpa),以便于生成的甲醇及时被分离出来,分馏出定量的甲醇后,降温至40℃左右,再加入60mL乙醇搅拌分散1h,抽滤,干燥,得白色固体粉末苯基甲氧基硅酸双-1-硫基磷杂-2,6,7-三氧杂双环[2.2.2]辛基-4-甲酯,产率为92.7%。Example 1 In a 250ml four-necked reaction flask equipped with a stirrer, a thermometer and a fractionation device, nitrogen was used to drive out the air in the flask, and at a temperature of 25°C, 21.56g (0.11mol) of 1-thiophospha- 4-Hydroxymethyl-2,6,7-trioxabicyclo[2.2.2]octane and 9.91g (0.05mol) of phenyltrimethoxysilane, heated up to 150°C, the solid gradually dissolved and finally became colorless Transparent liquid, fractionation reaction for 6 hours, keep a slight vacuum (-0.02Mpa) in the reactor during the reaction process, so that the generated methanol can be separated in time, after fractional distillation of a certain amount of methanol, cool down to about 40°C, and then add 60mL of ethanol Stir and disperse for 1 hour, filter with suction, and dry to obtain white solid powder phenylmethoxysilicate bis-1-thiophospha-2,6,7-trioxabicyclo[2.2.2]octyl-4-methanol Esters with a yield of 92.7%.
实施例2 在装有搅拌器、温度计和分馏装置的250ml四口反应瓶中,氮气赶尽瓶内的空气,在25℃的温度下,加入39.23g(0.20mol)1-硫基磷杂-4-羟甲基-2,6,7-三氧杂双环[2.2.2]辛烷和9.91g(0.05mol)苯基三甲氧基硅烷,升温至120℃,固体逐渐溶解,最终呈无色透明液体,分馏反应9h,在反应过程中保持反应器内微真空(-0.02Mpa),以便于生成的甲醇及时被分离出来,分馏出定量的甲醇后,降温至40℃左右,再加入130mL甲醇搅拌分散1h,抽滤,干燥,得白色固体粉末苯基甲氧基硅酸双-1-硫基磷杂-2,6,7-三氧杂双环[2.2.2]辛基-4-甲酯,产率为91.9%。Example 2 In a 250ml four-necked reaction flask equipped with a stirrer, a thermometer and a fractionation device, nitrogen was used to drive out the air in the flask, and at a temperature of 25°C, 39.23g (0.20mol) of 1-thiophospha- 4-Hydroxymethyl-2,6,7-trioxabicyclo[2.2.2]octane and 9.91g (0.05mol) of phenyltrimethoxysilane, heated up to 120°C, the solid gradually dissolved and finally became colorless Transparent liquid, fractional distillation reaction for 9 hours, keep a slight vacuum (-0.02Mpa) in the reactor during the reaction process, so that the generated methanol can be separated in time, after fractional distillation of a certain amount of methanol, cool down to about 40°C, and then add 130mL methanol Stir and disperse for 1 hour, filter with suction, and dry to obtain white solid powder phenylmethoxysilicate bis-1-thiophospha-2,6,7-trioxabicyclo[2.2.2]octyl-4-methanol Esters with a yield of 91.9%.
实施例3 在装有搅拌器、温度计和分馏装置的250ml四口反应瓶中,氮气赶尽瓶内的空气,在25℃的温度下,加入19.61g(0.10mol)1-硫基磷杂-4-羟甲基-2,6,7-三氧杂双环[2.2.2]辛烷和9.91g(0.05mol)苯基三甲氧基硅烷,升温至160℃,固体逐渐溶解,最终呈无色透明液体,分馏反应4h,在反应过程中保持反应器内微真空(-0.02Mpa),以便于生成的甲醇及时被分离出来,分馏出定量的甲醇后,降温至40℃左右,再加入50mL乙醇搅拌分散1h,抽滤,干燥,得白色固体粉末苯基甲氧基硅酸双-1-硫基磷杂-2,6,7-三氧杂双环[2.2.2]辛基-4-甲酯,产率为90.7%。Example 3 In a 250ml four-necked reaction flask equipped with a stirrer, a thermometer and a fractionation device, nitrogen was used to drive out the air in the flask, and at a temperature of 25°C, 19.61g (0.10mol) of 1-thiophospha- 4-Hydroxymethyl-2,6,7-trioxabicyclo[2.2.2]octane and 9.91g (0.05mol) of phenyltrimethoxysilane, heated up to 160°C, the solid gradually dissolved and finally became colorless Transparent liquid, fractional distillation reaction for 4 hours, keep a slight vacuum (-0.02Mpa) in the reactor during the reaction process, so that the generated methanol can be separated in time, after fractional distillation of a certain amount of methanol, cool down to about 40°C, and then add 50mL of ethanol Stir and disperse for 1 hour, filter with suction, and dry to obtain white solid powder phenylmethoxysilicate bis-1-thiophospha-2,6,7-trioxabicyclo[2.2.2]octyl-4-methanol Esters with a yield of 90.7%.
实施例4 在装有搅拌器、温度计和分馏装置的250ml四口反应瓶中,氮气赶尽空气,在25℃的温度下,加入24.51g(0.125mol)1-硫基磷杂-4-羟甲基-2,6,7-三氧杂双环[2.2.2]辛烷和9.91g(0.05mol)苯基三甲氧基硅烷,升温至140℃,固体逐渐溶解,最终呈无色透明液体,分馏反应7h,在反应过程中保持反应器内微真空(-0.02Mpa),以便于生成的甲醇及时被分离出来,分馏出定量的甲醇后,降温至40℃左右,再加入100mL甲醇搅拌分散1h,抽滤,干燥,得白色固体粉末苯基甲氧基硅酸双-1-硫基磷杂-2,6,7-三氧杂双环[2.2.2]辛基-4-甲酯,产率为93.1%。Example 4 In a 250ml four-necked reaction flask equipped with a stirrer, a thermometer and a fractionation device, nitrogen was used to drive out the air, and at a temperature of 25°C, 24.51g (0.125mol) of 1-thiophosphata-4-hydroxyl was added Methyl-2,6,7-trioxabicyclo[2.2.2]octane and 9.91g (0.05mol) of phenyltrimethoxysilane were heated up to 140°C, the solid gradually dissolved, and finally became a colorless transparent liquid. Fractional distillation reaction for 7 hours, keep a slight vacuum (-0.02Mpa) in the reactor during the reaction process, so that the generated methanol can be separated in time, after fractional distillation of a certain amount of methanol, cool down to about 40°C, then add 100mL of methanol and stir to disperse for 1 hour , suction filtration, and drying to obtain bis-1-thiophospha-2,6,7-trioxabicyclo[2.2.2]octyl-4-methyl phenylmethoxysilicate as white solid powder, producing The rate is 93.1%.
实施例5 在装有搅拌器、温度计和分馏装置的250ml四口反应瓶中,氮气赶尽空气,在25℃的温度下,加入29.42g(0.15mol)1-硫基磷杂-4-羟甲基-2,6,7-三氧杂双环[2.2.2]辛烷和9.91g(0.05mol)苯基三甲氧基硅烷,升温至130℃,固体逐渐溶解,最终呈无色透明液体,分馏反应8h,在反应过程中保持反应器内微真空(-0.02Mpa),以便于生成的甲醇及时被分离出来,分馏出定量的甲醇后,降温至40℃左右,再加入120mL乙醇搅拌分散1h,抽滤,干燥,得白色固体粉末苯基甲氧基硅酸双-1-硫基磷杂-2,6,7-三氧杂双环[2.2.2]辛基-4-甲酯,产率为92.3%。Example 5 In a 250ml four-necked reaction flask equipped with a stirrer, a thermometer and a fractionation device, nitrogen was used to drive out the air, and at a temperature of 25°C, 29.42g (0.15mol) of 1-thiophospha-4-hydroxyl was added Methyl-2,6,7-trioxabicyclo[2.2.2]octane and 9.91g (0.05mol) of phenyltrimethoxysilane were heated up to 130°C, the solids gradually dissolved, and finally became a colorless transparent liquid. Fractional distillation reaction for 8 hours, keep a slight vacuum (-0.02Mpa) in the reactor during the reaction process, so that the generated methanol can be separated in time, after fractional distillation of a certain amount of methanol, cool down to about 40°C, then add 120mL ethanol to stir and disperse for 1 hour , suction filtration, and drying to obtain bis-1-thiophospha-2,6,7-trioxabicyclo[2.2.2]octyl-4-methyl phenylmethoxysilicate as white solid powder, producing The rate is 92.3%.
实施例6 在装有搅拌器、温度计和分馏装置的250ml四口反应瓶中,氮气赶尽空气,在25℃的温度下,加入29.42g(0.15mol)1-硫基磷杂-4-羟甲基-2,6,7-三氧杂双环[2.2.2]辛烷、9.91g(0.05mol)苯基三甲氧基硅烷和80mL二乙二醇二甲醚,升温至160℃回流,分馏反应5h,及时分离出生成的甲醇;分出定量的甲醇后,冷却到25℃,抽滤,再用50mL甲醇洗涤,抽滤,干燥,得白色固体粉末苯基甲氧基硅酸双-1-硫基磷杂-2,6,7-三氧杂双环[2.2.2]辛基-4-甲酯,产率为92.3%。Example 6 In a 250ml four-necked reaction flask equipped with a stirrer, a thermometer and a fractionation device, nitrogen was used to drive out the air, and at a temperature of 25°C, 29.42g (0.15mol) of 1-thiophosphata-4-hydroxyl was added Methyl-2,6,7-trioxabicyclo[2.2.2]octane, 9.91g (0.05mol) phenyltrimethoxysilane and 80mL diethylene glycol dimethyl ether, heated to reflux at 160°C, fractionated After reacting for 5 hours, the generated methanol was separated in time; after a certain amount of methanol was separated, it was cooled to 25°C, filtered with suction, washed with 50 mL of methanol, filtered with suction, and dried to obtain white solid powder of phenylmethoxysilicate bis-1 -thiophospha-2,6,7-trioxabicyclo[2.2.2]octyl-4-methyl ester, the yield was 92.3%.
实施例7 在装有搅拌器、温度计和分馏装置的250ml四口反应瓶中,氮气赶尽空气,在25℃的温度下,加入19.61g(0.10mol)1-硫基磷杂-4-羟甲基-2,6,7-三氧杂双环[2.2.2]辛烷、9.91g(0.05mol)苯基三甲氧基硅烷和120mL二氧六环,升温至100℃回流,分馏反应8h,及时分离出生成的甲醇;分出定量的甲醇后,冷却到25℃,抽滤,再用40mL乙醇洗涤,抽滤,干燥,得白色固体粉末苯基甲氧基硅酸双-1-硫基磷杂-2,6,7-三氧杂双环[2.2.2]辛基-4-甲酯,产率为90.2%。Example 7 In a 250ml four-necked reaction flask equipped with a stirrer, a thermometer and a fractionation device, nitrogen was used to drive out the air, and at a temperature of 25°C, 19.61g (0.10mol) of 1-thiophospha-4-hydroxyl was added Methyl-2,6,7-trioxabicyclo[2.2.2]octane, 9.91g (0.05mol) phenyltrimethoxysilane and 120mL dioxane, heated to 100°C and refluxed, fractionated for 8h, Separate the generated methanol in time; after the quantitative methanol is separated, cool to 25°C, filter with suction, wash with 40mL ethanol, filter with suction, and dry to obtain white solid powder phenylmethoxysilicate bis-1-sulfanyl Phospha-2,6,7-trioxabicyclo[2.2.2]octyl-4-methyl ester, the yield is 90.2%.
实施例8 在装有搅拌器、温度计和分馏装置的250ml四口反应瓶中,氮气赶尽空气,在25℃的温度下,加入39.32g(0.20mol)1-硫基磷杂-4-羟甲基-2,6,7-三氧杂双环[2.2.2]辛烷、9.91g(0.05mol)苯基三甲氧基硅烷和100mL乙腈,升温至80℃回流,分馏反应10h,及时分离出生成的甲醇;分出定量的甲醇后,冷却到25℃,抽滤,再用80mL乙醇洗涤,抽滤,干燥,得白色固体粉末苯基甲氧基硅酸双-1-硫基磷杂-2,6,7-三氧杂双环[2.2.2]辛基-4-甲酯,产率为91.3%。Example 8 In a 250ml four-necked reaction flask equipped with a stirrer, a thermometer and a fractionation device, nitrogen was used to drive out the air, and at a temperature of 25°C, 39.32g (0.20mol) of 1-thiophospha-4-hydroxyl was added Methyl-2,6,7-trioxabicyclo[2.2.2]octane, 9.91g (0.05mol) phenyltrimethoxysilane and 100mL acetonitrile, heated to 80°C and refluxed, reacted fractionally for 10h, separated in time The generated methanol; after separating out a certain amount of methanol, cool to 25°C, filter with suction, wash with 80mL ethanol, filter with suction, and dry to obtain white solid powder phenylmethoxysilicate bis-1-thiophospha- The yield of 2,6,7-trioxabicyclo[2.2.2]octyl-4-methyl ester was 91.3%.
本案发明人将上述制备的苯基甲氧基硅酸双-1-硫基磷杂-2,6,7-三氧杂双环[2.2.2]辛基-4-甲酯(PSMDSPE)单独或与三聚氰胺聚磷酸盐(MPP)进行复配应用于阻燃聚对苯二甲酸丁二醇酯(PBT)中。参照:GB/T2406-2008《塑料燃烧性能试验方法-氧指数法》测样品的极限氧指数(LOI)。取PSMDSPE与PBT以不同比例混合均匀或取PSMDSPE、MPP及PBT以不同比例混合均匀,用挤出机挤出,制成直径为3mm的样条,并对其阻燃熔滴性能进行了测试,列出了部分试验结果如表1~2所示:The inventors of the present case prepared the phenylmethoxysilicate bis-1-thiophospha-2,6,7-trioxabicyclo[2.2.2]octyl-4-methyl ester (PSMDSPE) alone or It is compounded with melamine polyphosphate (MPP) and used in flame-retardant polybutylene terephthalate (PBT). Reference: GB/T2406-2008 "Test Method for Combustion Performance of Plastics - Oxygen Index Method" to measure the limiting oxygen index (LOI) of the sample. Take PSMDSPE and PBT mixed uniformly in different proportions or take PSMDSPE, MPP and PBT mixed uniformly in different proportions, extrude with an extruder to make a sample with a diameter of 3mm, and test its flame retardant droplet performance, Some test results are listed as shown in Table 1-2:
表1 PSMDSPE单独阻燃PBT的阻燃性能数据Table 1 Flame retardant performance data of PSMDSPE alone flame retardant PBT
表2 PSMDSPE与MPP复配阻燃PBT的阻燃性能数据Table 2 Flame retardant performance data of PSMDSPE and MPP compound flame retardant PBT
根据表1可以看出,当产物PSMDSPE单独在PBT中的添加量达到10%时,就能延缓阻燃PBT在燃烧时的滴落;当添加量达到20%后,PBT的LOI达28%,属于难燃级别。根据表2可以看出,当PSMDSPE与MPP进行复配在PBT中的加入总量为20%,PSMDSPE与MPP质量比为1∶1时,阻燃PBT的LOI高达34%,且能迅速成炭,有效防止熔融滴落。由此可见,PSMDSPE对PBT材料有很好的阻燃成炭效果,与MPP复配用于PBT中同样表现出协同增效性。According to Table 1, it can be seen that when the addition amount of the product PSMDSPE in PBT alone reaches 10%, it can delay the dripping of flame-retardant PBT when burning; when the addition amount reaches 20%, the LOI of PBT reaches 28%. It belongs to the flame retardant level. According to Table 2, it can be seen that when the total amount of PSMDSPE and MPP compounded in PBT is 20%, and the mass ratio of PSMDSPE and MPP is 1:1, the LOI of flame-retardant PBT is as high as 34%, and it can quickly form charcoal , Effectively prevent molten dripping. It can be seen that PSMDSPE has a good flame-retardant charcoal effect on PBT materials, and it also shows synergistic effect when used in PBT when combined with MPP.
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