CN110498814B - 一种含磷含硅的有机无机内杂化活性单体合成方法和应用 - Google Patents
一种含磷含硅的有机无机内杂化活性单体合成方法和应用 Download PDFInfo
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- CN110498814B CN110498814B CN201910717739.7A CN201910717739A CN110498814B CN 110498814 B CN110498814 B CN 110498814B CN 201910717739 A CN201910717739 A CN 201910717739A CN 110498814 B CN110498814 B CN 110498814B
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- 239000000178 monomer Substances 0.000 title claims abstract description 39
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 30
- 239000011574 phosphorus Substances 0.000 title claims abstract description 30
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 30
- 239000010703 silicon Substances 0.000 title claims abstract description 30
- 238000010189 synthetic method Methods 0.000 title claims abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 21
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006844 Kabachnik-Fields reaction Methods 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 238000010025 steaming Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 9
- 239000012044 organic layer Substances 0.000 claims description 9
- 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 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003063 flame retardant Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 claims description 5
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 7
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 12
- 238000002390 rotary evaporation Methods 0.000 description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000004108 freeze drying Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
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- WCRLEERDBIOKHS-UHFFFAOYSA-N C(C(=C)C)(=O)O.C(C1CO1)C(C(=O)O)=C Chemical compound C(C(=C)C)(=O)O.C(C1CO1)C(C(=O)O)=C WCRLEERDBIOKHS-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
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- 230000003115 biocidal effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 238000007334 copolymerization reaction Methods 0.000 description 1
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- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
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- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
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- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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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
- C07F9/657163—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 the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—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 the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
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- C08F212/02—Monomers containing only one unsaturated aliphatic radical
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/10—Esters
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- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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- C08L33/04—Homopolymers or copolymers of esters
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Abstract
本发明公开了一种含磷含硅有机或无机内杂化活性单体合成方法和应用。利用Kabachnik‑Fields反应,以3‑氨丙基三乙氧基硅烷、4‑羟基苯甲醛和DOPO为原料,可以制备出含磷、硅的酚类中间体,再将该酚类中间体与甲基丙烯酰氯在溶剂和缚酸剂存在的条件下反应,经提纯可制备含活性双键的磷、硅有机或无机内杂化活性单体,所合成有机/无机内杂化活性单体,其元素组成可精确控制,可被用于制备功能性有机/无机杂化聚合物,以及制备阻燃、防腐、耐热、耐候的改性材料。
Description
技术领域
本发明涉及一种含磷含硅的有机无机内杂化活性单体合成方法和应用。
背景技术
有机/无机杂化材料是一种新型复合材料,其兼具了有机材料的质轻、易加工、可进行分子水平的设计和无机材料的刚性大、抗氧化性好、耐热性优良等优点,近年来得到迅速发展。有机/无机内杂化单体的结构特点在于分子中同时具备含杂原子的基团及可聚合双键,并以化学键接的方式将硅、磷、氟等元素与碳、氢、氧、氮等元素结合,在分子水平上实现有机元素与无机元素的协同作用;同时,双键具有反应活性,利用有机/无机内杂化单体可以制备出序列结构、分子量及分子量分布可调的有机/无机内杂化聚合物。基于上述优点,有机/无机内杂化材料在防腐、抗菌、隔热、耐磨、耐老化等材料领域均有着广泛的应用。
有研究表明,通过自由基共聚法,调整共聚单体的比例,可制备一种磷、硅比例可调的聚合型阻燃剂,该阻燃剂有望应用于其他常见聚合物材料。但该有机/无机杂化材料需要通过聚合反应来实现,方法较为复杂,且各元素比例无法进行更为精准的控制。
发明内容
本发明的目的是提供一种含磷含硅的有机无机内杂化活性单体合成方法和应用。
本发明解决上述问题的技术方案之一在于:提供了一种含磷含硅的有机无机内杂化活性单体合成方法,活性单体以3-氨丙基三乙氧基硅烷(KH550)、4-羟基苯甲醛和DOPO为原料,经过Kabachnik-Fields反应得到酚类中间体化合物,再将其与甲基丙烯酰氯在溶剂和缚酸剂存在的条件下反应,过滤除去反应产生的缚酸剂盐,通过洗涤、旋蒸和干燥对粗产物进行提纯后得到含活性双键的磷硅内杂化单体。该方法包括如下步骤:
(1)酚类中间体化合物的合成:将9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物、3-氨丙基三乙氧基硅烷、4-羟基苯甲醛加入第一溶剂中,通过Kabachnik-Fields反应,反应的温度为30~80℃,反应的时间为8~12h,产物以洗涤用溶剂沉淀后得到酚类中间体化合物;
在本发明一较佳实施例中,反应方程式如下:
(2)含活性双键的磷硅内杂化单体的合成:将步骤(1)得到的酚类中间体化合物与甲基丙烯酰氯在第二溶剂和缚酸剂存在的条件下反应,反应的温度为0~50℃,反应的时间为4~8h;过滤除去反应产生的缚酸剂盐,通过洗涤、旋蒸和干燥对粗产物进行提纯后得到含活性双键的磷硅有机或无机内杂化单体;
在本发明一较佳实施例中,反应方程式如下:
在步骤(1)中,所述9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物、3-氨丙基三乙氧基硅烷、4-羟基苯甲醛和第一溶剂的配比为1g:0.5~1.5mL:0.3~0.8g:1~30mL;所述第一溶剂为氯仿、乙醇、甲醇、四氢呋喃、丙酮、乙腈中的一种;所述洗涤用溶剂为甲醇。
在步骤(2)中,所述甲基丙烯酰氯与溶剂的配比为1g:1~20mL,所述酚类中间体化合物、甲基丙烯酰氯和缚酸剂的质量比为1∶0.3~2.0∶0.3~2.0;所述第二溶剂为甲苯、乙酸乙酯、四氢呋喃、N,N-二甲基甲酰胺、二氯甲烷、二甲基亚砜中的一种;所述缚酸剂为吡啶、三乙胺、碳酸氢钠、碳酸钠、氢氧化钠中的一种。
在本发明一较佳实施例中,步骤(2)中对粗产物依次用NaOH溶液、蒸馏水、饱和NaCl水溶液洗涤若干次,将其有机层用无水MgSO4干燥,通过旋蒸、干燥后即得到产物。
本发明解决上述问题的又一技术方案在于:提供了上述一种含磷含硅有机或无机内杂化活性单体合成方法在制备阻燃、防腐、耐热、耐候的功能性材料中的应用。
在本发明一较佳实施例中,将合成的含磷含硅有机或无机内杂化活性单体制备功能性有机或无机杂化聚合物,再作为添加剂对基体进行改性得到阻燃、防腐、耐热、耐候的功能性材料,所述基体包括环氧树脂、PMMA、PSt、ABS、PA、PBT、PET、PC、PP。
本发明与现有技术相比具有如下优点:
(1)本发明通过分子结构设计,合成一种含磷、硅有机/无机内杂化活性单体,在分子中协同引入两种杂元素,并精确控制内杂化单体元素组成;利用3-氨丙基三乙氧基硅烷(KH550)、4-羟基苯甲醛和DOPO为原料,经过Kabachnik-Fields反应得到酚类中间体化合物,再将其与甲基丙烯酰氯在溶剂和缚酸剂存在的条件下反应,过滤除去反应产生的缚酸剂盐,通过洗涤、旋蒸和干燥对粗产物进行提纯后得到含活性双键的磷、硅有机/无机内杂化单体,该内杂化单体合成方法简单,且元素组成精准可控。
(2)本发明的目标产物为含元素组成可精确控制的磷、硅内杂化单体,在结构方面,该单体以化学键接的方式将硅、磷元素与碳、氢、氧、氮等元素结合,在分子水平上实现有机元素与无机元素的协同作用,且含可聚合的活性双键,可以制备出序列结构、分子量及分子量分布可调的有机/无机内杂化聚合物,硅氧烷基团的引入,可以有利于该功能单体偶联在其它基体或填料表面;在功能方面,无机元素的引入可以提高单纯有机物的耐热、耐候与阻隔性能,有机无机内杂化单体有利于增强聚合物涂层材料等与无机基体之间的相容性,突破了聚合物与无机纳米粒子在组成、表面特性、微观尺寸等方面的差异,磷、硅元素具有协同阻燃性能,可在制备阻燃、防腐、耐热、耐候等高分子材料中应用。
具体实施方式
实施例1
在接有冷凝管的1000mL的圆底烧瓶中加入11.68mL KH550(50mmol),6.7g 4-羟基苯基甲醛(55mmol),11.9g DOPO(55mmol)和300mL氯仿,在50℃下搅拌反应12h。反应结束后,旋蒸将反应液浓缩至约50mL,随后将其缓慢滴入冰的甲醇中,沉淀。减压抽滤,并用甲醇洗涤三次后,冻干得到白色固体。
在250mL单口圆底烧瓶中依次加入27.1g(0.05mol)事先合成的酚类中间体化合物、10.1g(0.10mol)的三乙胺和100mL的二氯甲烷,置于5℃的条件下,缓慢滴入10.5g(0.10mol)甲基丙烯酰氯,滴加完毕后继续搅拌反应8h。反应结束后过滤除去三乙胺盐酸盐,依次用3%NaOH溶液、蒸馏水、饱和NaCl水溶液洗涤数次。有机层用无水MgSO4干燥,通过旋蒸、干燥后即得到产物。
实施例2
在接有冷凝管的1000mL的圆底烧瓶中加入11.68mL KH550(50mmol),4.9g 4-羟基苯基甲醛(40mmol),11.9g DOPO(55mmol)和300mL氯仿,在50℃下搅拌反应12h。反应结束后,旋蒸将反应液浓缩至约50mL,随后将其缓慢滴入冰的甲醇中,沉淀。减压抽滤,并用甲醇洗涤三次后,冻干得到白色固体。
在250mL单口圆底烧瓶中依次加入27.1g(0.05mol)事先合成的酚类中间体化合物、10.1g(0.10mol)的三乙胺和100mL的二氯甲烷,置于5℃的条件下,缓慢滴入10.5g(0.10mol)甲基丙烯酰氯,滴加完毕后继续搅拌反应8h。反应结束后过滤除去三乙胺盐酸盐,依次用3%NaOH溶液、蒸馏水、饱和NaCl水溶液洗涤数次。有机层用无水MgSO4干燥,通过旋蒸、干燥后即得到产物。
实施例3
在接有冷凝管的1000mL的圆底烧瓶中加入11.68mL KH550(50mmol),4.9g 4-羟基苯基甲醛(40mmol),11.9g DOPO(55mmol)和300mL乙醇,在50℃下搅拌反应12h。反应结束后,旋蒸将反应液浓缩至约50mL,随后将其缓慢滴入冰的甲醇中,沉淀。减压抽滤,并用甲醇洗涤三次后,冻干得到白色固体。
在250mL单口圆底烧瓶中依次加入27.1g(0.05mol)事先合成的酚类中间体化合物、10.1g(0.10mol)的三乙胺和100mL的二氯甲烷,置于5℃的条件下,缓慢滴入10.5g(0.10mol)甲基丙烯酰氯,滴加完毕后继续搅拌反应8h。反应结束后过滤除去三乙胺盐酸盐,依次用3%NaOH溶液、蒸馏水、饱和NaCl水溶液洗涤数次。有机层用无水MgSO4干燥,通过旋蒸、干燥后即得到产物。
实施例4
在接有冷凝管的1000mL的圆底烧瓶中加入11.68mL KH550(50mmol),6.7g 4-羟基苯基甲醛(55mmol),11.9g DOPO(55mmol)和300mL氯仿,在70℃下搅拌反应8h。反应结束后,旋蒸将反应液浓缩至约50mL,随后将其缓慢滴入冰的甲醇中,沉淀。减压抽滤,并用甲醇洗涤三次后,冻干得到白色固体。
在250mL单口圆底烧瓶中依次加入27.1g(0.05mol)事先合成的酚类中间体化合物、10.1g(0.10mol)的三乙胺和100mL的二氯甲烷,置于5℃的条件下,缓慢滴入10.5g(0.10mol)甲基丙烯酰氯,滴加完毕后继续搅拌反应8h。反应结束后过滤除去三乙胺盐酸盐,依次用3%NaOH溶液、蒸馏水、饱和NaCl水溶液洗涤数次。有机层用无水MgSO4干燥,通过旋蒸、干燥后即得到产物。
实施例5
在接有冷凝管的1000mL的圆底烧瓶中加入11.68mL KH550(50mmol),6.7g 4-羟基苯基甲醛(55mmol),11.9g DOPO(55mmol)和300mL氯仿,在50℃下搅拌反应12h。反应结束后,旋蒸将反应液浓缩至约50mL,随后将其缓慢滴入冰的甲醇中,沉淀。减压抽滤,并用甲醇洗涤三次后,冻干得到白色固体。
在250mL单口圆底烧瓶中依次加入27.1g(0.05mol)事先合成的酚类中间体化合物、7.5g(0.75mol)的三乙胺和100mL的二氯甲烷,置于5℃的条件下,缓慢滴入10.5g(0.10mol)甲基丙烯酰氯,滴加完毕后继续搅拌反应8h。反应结束后过滤除去三乙胺盐酸盐,依次用3%NaOH溶液、蒸馏水、饱和NaCl水溶液洗涤数次。有机层用无水MgSO4干燥,通过旋蒸、干燥后即得到产物。
实施例6
在接有冷凝管的1000mL的圆底烧瓶中加入11.68mL KH550(50mmol),6.7g 4-羟基苯基甲醛(55mmol),11.9g DOPO(55mmol)和300mL氯仿,在50℃下搅拌反应12h。反应结束后,旋蒸将反应液浓缩至约50mL,随后将其缓慢滴入冰的甲醇中,沉淀。减压抽滤,并用甲醇洗涤三次后,冻干得到白色固体。
在250mL单口圆底烧瓶中依次加入27.1g(0.05mol)事先合成的酚类中间体化合物、7.5g(0.75mol)的三乙胺和100mL的二氯甲烷,置于10℃的条件下,缓慢滴入10.5g(0.10mol)甲基丙烯酰氯,滴加完毕后继续搅拌反应5h。反应结束后过滤除去三乙胺盐酸盐,依次用3%NaOH溶液、蒸馏水、饱和NaCl水溶液洗涤数次。有机层用无水MgSO4干燥,通过旋蒸、干燥后即得到产物。
实施例7
在接有冷凝管的1000mL的圆底烧瓶中加入11.68mL KH550(50mmol),6.7g 4-羟基苯基甲醛(55mmol),11.9g DOPO(55mmol)和300mL氯仿,在50℃下搅拌反应12h。反应结束后,旋蒸将反应液浓缩至约50mL,随后将其缓慢滴入冰的甲醇中,沉淀。减压抽滤,并用甲醇洗涤三次后,冻干得到白色固体。
在250mL单口圆底烧瓶中依次加入27.1g(0.05mol)事先合成的酚类中间体化合物、4.0g(0.10mol)的氢氧化钠和100mL的二氯甲烷,置于5℃的条件下,缓慢滴入10.5g(0.10mol)甲基丙烯酰氯,滴加完毕后继续搅拌反应8h。反应结束后,依次用3%NaOH溶液、蒸馏水、饱和NaCl水溶液洗涤数次。有机层用无水MgSO4干燥,通过旋蒸、干燥后即得到产物。
实施例8
将得到含磷含硅的内杂化活性单体产物,与甲基丙烯酸(丙烯酸)缩水甘油酯(GMA),偶氮二异丁腈(AIBN)加入反应瓶中,经过通氮气体鼓泡除掉溶剂中的氧气后,在70℃下,搅拌反应24h。反应结束后,浓缩反应液,用甲醇沉淀2~3次,得到聚合物添加剂。先将不同量的聚合物添加剂加入环氧E51基体中,加热至90℃,待其完全溶解后加入计算量的固化剂,继续搅拌至固化剂完全溶解。趁热倒入铝模中,经过120℃加热4h,140℃加热2h,180℃加热2h三步固化程序后,自然冷却,得到以该含磷含硅的内杂化活性单体聚合的聚合物添加剂改性环氧基体的样条。该环氧制品测试性能见表1:
表1
实施例9
在装有机械搅拌三颈瓶中,加入上述所制备的含磷含硅的内杂化活性单体产物、甲基丙烯酸甲酯(MMA)和引发剂AIBN逐步加热至80℃,保温搅拌,当预聚物有一定粘度时,则移去热源,冷却至50℃左右,立即将预聚浆液注入模具中。将注有浆液的模具放入50℃烘箱内低温聚合12h,当成柔软透明固体时,升温至100℃下继续聚合2h,使之反应完全,然后再冷却至室温。
实施例10
在装有机械搅拌三颈瓶中加入上述所制备含磷含硅的内杂化活性单体产物、苯乙烯、引发剂AIBN以及甲苯,在25℃下搅拌至混合,在N2气氛保护下将反应混合物升温至95℃,反应6h后将反应物冷却至25℃,过滤分离出溶剂,得到改性聚苯乙烯材料。
以上所述,仅为本发明较佳实施例而已,故不能依此限定本发明实施的范围,即依本发明专利范围及说明书内容所作的等效变化与修饰,皆应仍属本发明涵盖的范围内。
Claims (10)
1.一种含磷含硅有机或无机内杂化活性单体合成方法,其特征在于,包括如下步骤:
(1)酚类中间体化合物的合成:将9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物、3-氨丙基三乙氧基硅烷、4-羟基苯甲醛加入第一溶剂中,通过Kabachnik-Fields反应,反应的温度为30~80℃,反应的时间为8~12h,产物以洗涤用溶剂沉淀后得到酚类中间体化合物;
(2)含活性双键的磷硅内杂化单体的合成:将步骤(1)得到的酚类中间体化合物与甲基丙烯酰氯在第二溶剂和缚酸剂存在的条件下反应,反应的温度为0~50℃,反应的时间为4~8h;过滤除去反应产生的缚酸剂盐,通过洗涤、旋蒸和干燥对粗产物进行提纯后得到含活性双键的磷硅有机或无机内杂化单体,其结构式如下:
2.根据权利要求1所述的一种含磷含硅有机或无机内杂化活性单体合成方法,其特征在于:在步骤(1)中,所述9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物、3-氨丙基三乙氧基硅烷、4-羟基苯甲醛和第一溶剂的配比为1g:0.5~1.5mL:0.3~0.8g:1~30mL。
3.根据权利要求1所述的一种含磷含硅有机或无机内杂化活性单体合成方法,其特征在于:在步骤(1)中,所述第一溶剂为氯仿、乙醇、甲醇、四氢呋喃、丙酮、乙腈中的一种。
4.根据权利要求1所述的一种含磷含硅有机或无机内杂化活性单体合成方法,其特征在于:在步骤(1)中,所述洗涤用溶剂为甲醇。
5.根据权利要求1所述的一种含磷含硅有机或无机内杂化活性单体合成方法,其特征在于:在步骤(2)中,所述甲基丙烯酰氯与溶剂的配比为1g:1~20mL,所述酚类中间体化合物、甲基丙烯酰氯和缚酸剂的质量比为1∶0.3~2.0∶0.3~2.0。
6.根据权利要求1所述的一种含磷含硅有机或无机内杂化活性单体合成方法,其特征在于:在步骤(2)中,所述第二溶剂为甲苯、乙酸乙酯、四氢呋喃、N,N-二甲基甲酰胺、二氯甲烷、二甲基亚砜中的一种。
7.根据权利要求1所述的一种含磷含硅有机或无机内杂化活性单体合成方法,其特征在于:在步骤(2)中,所述缚酸剂为吡啶、三乙胺、碳酸氢钠、碳酸钠、氢氧化钠中的一种。
8.根据权利要求1所述的一种含磷含硅有机或无机内杂化活性单体合成方法,其特征在于:在步骤(2)中,对粗产物依次用NaOH溶液、蒸馏水、饱和NaCl水溶液洗涤若干次,将其有机层用无水MgSO4干燥,通过旋蒸、干燥后即得到产物。
9.如权利要求1~8任一项所述的一种含磷含硅有机或无机内杂化活性单体合成方法在制备阻燃材料中的应用。
10.根据权利要求9所述的应用,其特征在于:将合成的含磷含硅有机或无机内杂化活性单体制备功能性有机或无机杂化聚合物,再作为添加剂对基体进行改性得到阻燃材料,所述基体包括环氧树脂、ABS、PA、PBT、PET、PC、PP、PMMA、PSt。
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