CN105384776B - 十二烷基硅酸三(膦杂环甲基)酯化合物及其制备方法 - Google Patents
十二烷基硅酸三(膦杂环甲基)酯化合物及其制备方法 Download PDFInfo
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 35
- BMYXFDYLULLPCA-UHFFFAOYSA-N dodecoxy(trihydroxy)silane Chemical compound CCCCCCCCCCCCO[Si](O)(O)O BMYXFDYLULLPCA-UHFFFAOYSA-N 0.000 title claims abstract description 33
- -1 ester compounds Chemical class 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003063 flame retardant Substances 0.000 claims abstract description 27
- 150000002148 esters Chemical class 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 230000002195 synergetic effect Effects 0.000 claims abstract description 7
- 238000010792 warming Methods 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 claims abstract description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 15
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- 238000000034 method Methods 0.000 claims description 10
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- 238000010992 reflux Methods 0.000 claims description 7
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 5
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 claims description 5
- 238000005292 vacuum distillation Methods 0.000 claims description 5
- VRZVPALEJCLXPR-UHFFFAOYSA-N ethyl 4-methylbenzenesulfonate Chemical compound CCOS(=O)(=O)C1=CC=C(C)C=C1 VRZVPALEJCLXPR-UHFFFAOYSA-N 0.000 claims description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical group COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 4
- 150000004702 methyl esters Chemical class 0.000 claims 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 239000003610 charcoal Substances 0.000 abstract description 6
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- 238000004519 manufacturing process Methods 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 10
- 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 class 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 description 9
- 238000000354 decomposition reaction Methods 0.000 description 8
- 241000272517 Anseriformes Species 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 5
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- 230000015572 biosynthetic process Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-DYCDLGHISA-N Deuterium chloride Chemical compound [2H]Cl VEXZGXHMUGYJMC-DYCDLGHISA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
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- 238000009841 combustion method Methods 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
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- 238000000280 densification Methods 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 230000000979 retarding effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
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- 150000003384 small molecules Chemical class 0.000 description 1
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- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
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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
- C07F9/657163—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
- C07F9/657181—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, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
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- 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
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
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- 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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- Life Sciences & Earth Sciences (AREA)
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- General Health & Medical Sciences (AREA)
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Abstract
本发明涉及一种磷硅协同阻燃剂十二烷基硅酸三(膦杂环甲基)酯化合物及其制备方法,该化合物的结构如下式所示:
Description
技术领域
本发明涉及一种阻燃剂十二烷基硅酸三(膦杂环甲基)酯化合物及其制备方法,具体涉及一种阻燃剂十二烷基三(1-氧-1-甲基-4-乙基-1-磷杂-2,6-二氧杂-环己烷基-<4>-甲氧基)硅烷化合物及其制备方法,该化合物含有磷、硅双重阻燃元素,磷硅协同有较高的阻燃效能,适合用作聚酯PBT、PET、聚氨酯、尼龙、聚丙烯等材料的阻燃剂。
背景技术
随着工业的发展和技术的进步,高分子材料品种越来越多,应用也越来越广泛,给人们带来便利的同时由于其易燃性也带来了极大的火灾隐患,这就促进了阻燃剂产业的迅速发展。近年来,随着人们的安全环保意识不断增强,国际上限制使用卤系阻燃剂的呼声越来越高,因此,开发新型无卤阻燃剂成为当前阻燃剂发展的热点。磷系阻燃剂以其无卤、毒性较低、发烟量少、阻燃效率高、环境友好等优点受到了人们的关注,一系列以有机磷为主要成分的新型无卤阻燃剂已经被广泛开发利用;有机硅系阻燃剂以其独特的阻燃效果也逐渐受到了人们的重视。研究表明,若将磷、硅两种阻燃元素设计在同一分子结构中,即能实现分子内阻燃元素的复配,会产生更好的协同增效作用,将会获得性能更为优异的阻燃剂。
本发明公开了一种阻燃剂十二烷基硅酸三(膦杂环甲基)酯化合物及其制备方法。该化合物分子结构中含有磷、硅两种阻燃元素,磷、硅协同阻燃效能高;其拥有磷系阻燃剂和硅系阻燃剂的优点,又表现出较好的成炭性和友好的加工性能,且稳定性好,适用范围广泛,是一种高效、抑烟、无毒的阻燃剂,具有广阔的发展前景。
发明内容
本发明的目的之一在于提出一种磷、硅协同阻燃剂十二烷基硅酸三(膦杂环甲基)酯化合物。其物理化学性能稳定,分解温度高,与高分子材料有较好的相容性,且有成炭防滴落的作用,可克服现有技术中的不足。
为实现上述发明目的,本发明采用了如下技术方案:
一种十二烷基硅酸三(膦杂环甲基)酯化合物,其特征在于,该化合物的结构如下式所示:
本发明的另一目的在于提出一种如上所述十二烷基硅酸三(膦杂环甲基)酯的制备方法,其工艺简单,适合规模化生产,且原料廉价易得,具有良好的开发应用前景,该方法为:
氮气保护下,控制十二烷基三甲氧基硅烷与4-乙基-2,6,7-三氧杂-1-磷杂双环[2.2.2]辛烷(简称:笼状磷酸酯)的摩尔比为1∶3-1∶3.3,再加入催化剂和有机溶剂,升温到140-160℃,保温反应16-22h,冷却到50℃,减压蒸馏除去有机溶剂,冷却到50℃,经纯化处理,得产品十二烷基硅酸三(膦杂环甲基)酯。
该方法为:
氮气保护下,控制十二烷基三甲氧基硅烷与4-乙基-2,6,7-三氧杂-1-磷杂双环[2.2.2]辛烷(简称:笼状磷酸酯)的摩尔比为1∶3-1∶3.3,再加入催化剂,加热至回流,开始反应,随着反应的进行回流温度逐渐升高,在150-190℃,回流和保温反应14-18h,冷却到50℃,经纯化处理,得产品十二烷基硅酸三(膦杂环甲基)酯。
如上所述的有机溶剂为二乙二醇二甲醚、苯甲醚或二甲基甲酰胺(DMF),其用量是有机溶剂的体积毫升数为十二烷基三甲氧基硅烷质量克数的2-5倍。
如上所述的催化剂为硫酸二甲酯、对甲苯磺酸甲酯或对甲苯磺酸乙酯,其用量为十二烷基三甲氧基硅烷质量的4%-7%。
如上所述的纯化处理方法为加入与产品理论质量克数相同体积毫升数的石油醚,搅拌使固体分散于石油醚中,抽滤、烘干。
本发明十二烷基硅酸三(膦杂环甲基)酯为白色固体,其产率为83.8%-88.6%,熔点:126±2℃,分解温度:312±5℃,适合用作聚酯PBT、PET、聚氨酯、尼龙、聚丙烯等材料的阻燃剂。
十二烷基硅酸三(膦杂环甲基)酯的合成工艺原理如下式所示:
与现有技术相比,本发明的创新之处在于:
①本发明十二烷基硅酸三(膦杂环甲基)酯化合物含有磷、硅两种阻燃元素,高温下,磷元素转化为磷酸或聚磷酸能催化促成炭的形成,形成的聚磷酸膜有隔热绝氧作用;硅与碳形成致密的硅炭层,能有效防止熔融滴落的发生。磷、硅从不同的机理协同阻燃,能发挥较高的阻燃效能。
②本发明十二烷基硅酸三(膦杂环甲基)酯化合物分子结构中含有C-P键、C-Si键以及三个六元环结构,这些结构特点使得该化合物物理化学性能稳定,分解温度高,能适应于工程塑料的高温加工;含有长链烷基使得其与材料具有很好的相容性,且分散性好,对材料的力学性能影响较小,同时还赋予产品较好的增塑性。
③本发明十二烷基硅酸三(膦杂环甲基)酯化合物的制备是通过双分子重排反应,将无机磷化合物转变为的有机膦化合物,其热稳定性和阻燃性能都得到了很大的提高。
④本发明十二烷基硅酸三(膦杂环甲基)酯化合物制备方法,没有任何小分子缩去,原子利用率100%,无三废排放,为绿色工艺。
附图说明
为了进一步说明产品的结构和性能特给出如下附图。
图1是十二烷基硅酸三(膦杂环甲基)酯的红外光谱图;图1表明:3021cm-1和2923cm-1(C-H键的伸缩振动);1436cm-1(C-H键的弯曲振动);1250cm-1(P=O键的伸缩振动);1172cm-1(Si-O-C键的伸缩振动);998cm-1(Si-O-C键的弯曲振动);941cm-1(P-O-C键的伸缩振动);794cm-1(Si-C键的伸缩振动)。
图2是十二烷基硅酸三(膦杂环甲基)酯的核磁光谱图;图2表明:氘代氯仿为溶剂,δ0.45-0.53为Si-CH2CH3上与硅相连的亚甲基氢峰;δ0.71-0.75为C-CH2CH3上与碳相连的甲基氢峰;δ0.77-0.84为Si-(CH2)11CH3上与碳相连的甲基氢峰;δ1.10-1.19为C-CH2CH3上与碳相连的亚甲基氢峰;δ1.25-1.36为Si-(CH2)11CH3上与碳相连的亚甲基氢峰;δ1.52-1.76为O=P-CH3上与磷氧相连的甲基氢峰;δ4.03-4.27为Si-OCH2C上与硅氧相连的亚甲基氢峰;δ4.33-4.52为(CH2O)2-P=O(-CH3)膦环上与氧相连的亚甲氧基氢峰;δ7.26为溶剂氘代氯仿交换的质子峰。
具体实施方式
以下结合具体实施例对本发明的技术方案作进一步说明。
实施例1在装有搅拌器、温度计、高效回流冷凝管的250ml四口烧瓶中,用氮气置换掉瓶内空气,加入52.68g(0.325mol)笼状磷酸酯、100ml二乙二醇二甲醚、29.06g(0.10mol)十二烷基三甲氧基硅烷和1.16g硫酸二甲酯,升温到160℃,保温反应16h,减压蒸馏除去二乙二醇二甲醚(回收使用),冷却到50℃,再加入75ml的石油醚,搅拌使固体分散于石油醚中,抽滤、烘干,得白色固体十二烷基硅酸三(膦杂环甲基)酯,产品得率88.6%,其分解温度:312±5℃。
实施例2在装有搅拌器、温度计、高效回流冷凝管的150ml四口烧瓶中,用氮气置换掉瓶内空气,加入53.49g(0.33mol)笼状磷酸酯、29.06g(0.10mol)十二烷基三甲氧基硅烷和1.55g硫酸二甲酯,升温到155℃,回流和保温反应18h,冷却到50℃,再加入75ml的石油醚,搅拌使固体分散于石油醚中,抽滤、烘干,得白色固体十二烷基硅酸三(膦杂环甲基)酯,产品得率87.2%,其分解温度:312±5℃。
实施例3在装有搅拌器、温度计、高效回流冷凝管的200ml四口烧瓶中,用氮气置换掉瓶内空气,加入51.87g(0.32mol)笼状磷酸酯、60ml苯甲醚、29.06g(0.10mol)十二烷基三甲氧基硅烷和1.85g对甲苯磺酸甲酯,升温到150℃,保温反应20h,减压蒸馏除去苯甲醚(回收使用),冷却到50℃,再加入75ml的石油醚,搅拌使固体分散于石油醚中,抽滤、烘干,得白色固体十二烷基硅酸三(膦杂环甲基)酯,产品得率86.0%,其分解温度:312±5℃。
实施例4在装有搅拌器、温度计、高效回流冷凝管的250ml四口烧瓶中,用氮气置换掉瓶内空气,加入48.63g(0.30mol)笼状磷酸酯、90mlDMF、29.06g(0.10mol)十二烷基三甲氧基硅烷和2.0g对甲苯磺酸乙酯,升温到140℃,保温反应22h,减压蒸馏除去DMF(回收使用),冷却到50℃,再加入75ml的石油醚,搅拌使固体分散于石油醚中,抽滤、烘干,得白色固体十二烷基硅酸三(膦杂环甲基)酯,产品得率83.8%,其分解温度:312±5℃。
实施例5在装有搅拌器、温度计、高效回流冷凝管的200ml四口烧瓶中,用氮气置换掉瓶内空气,加入50.25g(0.31mol)笼状磷酸酯、29.06g(0.10mol)十二烷基三甲氧基硅烷和1.9g对甲苯磺酸甲酯,加热到155℃回流,开始反应,随着反应的进行温度逐渐升到190℃,回流和保温反应14h,冷却到50℃,再加入75ml的石油醚,搅拌使固体分散于石油醚中,抽滤、烘干,得白色固体十二烷基硅酸三(膦杂环甲基)酯,产品得率85.4%,其分解温度:312±5℃。
表1制备例主要工艺参数
本案发明人还将上述合成的十二烷基硅酸三(膦杂环甲基)酯应用于聚酯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。取产物磷硅协同阻燃剂十二烷基硅酸三(膦杂环甲基)酯和聚酯PBT以不同重量百分比混合均匀后,用挤出机在230℃下挤出,制成直径为3mm的样条,并对其阻燃性能进行了测试,试验结果如表2所示:
表2十二烷基硅酸三(膦杂环甲基)酯应用于PBT中的阻燃性能数据
由表2可以看出当本发明阻燃剂十二烷基硅酸三(膦杂环甲基)酯添加量达25%时,阻燃PBT的极限氧指数达到30%,具有了良好的阻燃效果,且对其在受热或燃烧时易熔融滴落的缺陷有所改善。因此,本发明阻燃剂有良好的阻燃性能及成炭防滴落性能,应用前景十分广阔。
Claims (4)
1.一种磷硅协同阻燃剂十二烷基硅酸三(膦杂环甲基)酯化合物,其特征在于,该化合物的结构如下式所示:
2.一种磷硅协同阻燃剂十二烷基硅酸三(膦杂环甲基)酯的制备方法,其特征在于,该方法为:
氮气保护下,控制十二烷基三甲氧基硅烷与4-乙基-2,6,7-三氧杂-1-磷杂双环[2.2.2]辛烷的摩尔比为1∶3-1∶3.3,再加入十二烷基三甲氧基硅烷质量4%-7%的硫酸二甲酯、对甲苯磺酸甲酯或对甲苯磺酸乙酯催化剂和有机溶剂,升温到140-160℃,保温反应16-22h,减压蒸馏除去有机溶剂,冷却到50℃,加入与产品理论质量克数相等体积毫升数的石油醚,搅拌使固体分散于石油醚中,抽滤、烘干,得产品十二烷基硅酸三(膦杂环甲基)酯。
3.一种磷硅协同阻燃剂十二烷基硅酸三(膦杂环甲基)酯的制备方法,其特征在于,该方法为:
氮气保护下,控制十二烷基三甲氧基硅烷与4-乙基-2,6,7-三氧杂-1-磷杂双环[2.2.2]辛烷的摩尔比为1∶3-1∶3.3,再加入十二烷基三甲氧基硅烷质量4%-7%的硫酸二甲酯、对甲苯磺酸甲酯或对甲苯磺酸乙酯催化剂,加热至回流,开始反应,随着反应的进行回流温度逐渐升高,在150-190℃,回流和保温反应14-18h,冷却到50℃,加入与产品理论质量克数相等体积毫升数的石油醚,搅拌使固体分散于石油醚中,抽滤、烘干,得产品十二烷基硅酸三(膦杂环甲基)酯。
4.如权利要求2所述十二烷基硅酸三(膦杂环甲基)酯的制备方法,其特征在于:所述的有机溶剂为二乙二醇二甲醚、苯甲醚或二甲基甲酰胺,其用量是有机溶剂的体积毫升数为十二烷基三甲氧基硅烷质量克数的2-5倍。
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