CN116515116B - 一种笼型低聚倍半硅氧烷阻燃剂 - Google Patents
一种笼型低聚倍半硅氧烷阻燃剂 Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 46
- 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 title claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 10
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 4
- IDHDPWUDFGNQJM-UHFFFAOYSA-N azido dihydrogen phosphate Chemical compound P(=O)(O)(O)ON=[N+]=[N-] IDHDPWUDFGNQJM-UHFFFAOYSA-N 0.000 claims abstract description 3
- IBZUISWMZGLPKG-UHFFFAOYSA-N phosphoric acid azide Chemical compound [N-]=[N+]=[N-].OP(O)(O)=O IBZUISWMZGLPKG-UHFFFAOYSA-N 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 229910019142 PO4 Inorganic materials 0.000 claims description 13
- 239000010452 phosphate Substances 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 125000005997 bromomethyl group Chemical group 0.000 claims description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 9
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 8
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- 238000000034 method Methods 0.000 claims description 7
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 6
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 claims description 5
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- UIWJXEAMDJCNOV-UHFFFAOYSA-N 1-chloro-3-(chloromethyl)-2,4,5,6-tetrafluorobenzene Chemical group FC1=C(F)C(Cl)=C(F)C(CCl)=C1F UIWJXEAMDJCNOV-UHFFFAOYSA-N 0.000 claims description 3
- MMHHBAUIJVTLFZ-UHFFFAOYSA-N 2-(bromomethyl)-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)CBr MMHHBAUIJVTLFZ-UHFFFAOYSA-N 0.000 claims description 3
- AYORTOFSIKLNIK-UHFFFAOYSA-N 1-n-[2-(dimethylamino)ethyl]-2-n,2-n-dimethylpropane-1,2-diamine Chemical compound CN(C)C(C)CNCCN(C)C AYORTOFSIKLNIK-UHFFFAOYSA-N 0.000 claims description 2
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- 239000010703 silicon Substances 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
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- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000000502 dialysis Methods 0.000 description 4
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
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- 239000003795 chemical substances by application Substances 0.000 description 3
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- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 description 3
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
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- 239000008367 deionised water Substances 0.000 description 2
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- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
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- 238000007792 addition Methods 0.000 description 1
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/395—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing phosphorus
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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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
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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Abstract
本发明公开了一种笼型低聚倍半硅氧烷阻燃剂,包括:1)制备炔基多面体低聚倍半硅氧烷;2)制备叠氮磷酸酯;3)炔基多面体低聚倍半硅氧烷与叠氮磷酸酯进行叠氮‑炔环点击反应制备笼型低聚倍半硅氧烷阻燃剂;本发明提供的笼型低聚倍半硅氧烷阻燃剂,其酸源、气源、炭源、硅源集于一个分子结构内,使用方便,热稳定性高,制备方法简单,具有广阔的应用前景。
Description
技术领域
本发明属于膨胀型阻燃剂领域,具体涉及一种笼型低聚倍半硅氧烷阻燃剂。
背景技术
随着时代的发展,高分子材料在许多邻域都得到了广泛的应用。但其易燃性却使得火灾事故频发,造成大量人员伤亡和财产损失。现有阻燃剂虽然能提升各类高分子材料的阻燃性能,但提升效果有限且对高分子材料的其它性能影响严重,再加上人们环保呼声的日益高涨以及国家对阻燃标准的日趋完善,新型阻燃剂的研发变得尤为重要。
与其它阻燃剂相比,膨胀型阻燃剂拥有更大的发展潜力,其主要是由酸源、气源、炭源三部分组成,燃烧过程中酸源分解与炭源发生酯化反应,然后脱水交联,同时在气源的帮助下形成一层均匀致密的膨胀炭层,从而起到隔热、隔氧、抑烟和防止融滴的作用,但传统膨胀型阻燃剂的成炭速度慢、炭层结构酥,对材料的加工性能影响较大。而本文提出的含磷含氮含硅膨胀型阻燃剂,其是将酸源、炭源、气源、硅源以化学合成的方式结合成一个大分子,相对传统膨胀型阻燃剂阻燃效率更高,再加上硅源的引入,使形成的膨胀炭层结构均一致密,能更好的隔绝热量、抑制烟气。
发明内容
本发明的目的是针对传统膨胀型阻燃剂阻燃效率低、对材料的加工性能影响较大的不足之处,提供一种新的笼型低聚倍半硅氧烷阻燃剂。
本发明的次要目的是提供上述笼型低聚倍半硅氧烷阻燃剂的制备方法。
本发明的另一目的是提供上述笼型低聚倍半硅氧烷阻燃剂的应用。
本发明提供的笼型低聚倍半硅氧烷阻燃剂具有如下分子结构:
所述式(I)中,为含磷基团,选自/> R’为/>
本发明提供一种笼型低聚倍半硅氧烷阻燃剂含有聚倍半硅氧烷(POSS),具有良好的热稳定性和防熔滴作用,通过引入磷、氮元素,三者可实现协同增效。
本发明提供的笼型低聚倍半硅氧烷阻燃剂的制备方法是:
(1)制备炔基多面体低聚倍半硅氧烷(POSS-Alkyne)
以二氯甲烷为溶剂,1-羟基苯并三唑(HOBT)为酰胺基保护剂,1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐(EDC·HCl)为脱水剂,5-乙炔酸键合到氨基多面体低聚倍半硅氧烷(POSS-NH2)上,得到POSS-Alkyne。
(2)制备叠氮磷酸酯(AZ)
以DMF为溶剂,叠氮化钠在常温下与含溴磷酸酯反应,制备叠氮磷酸酯(AZ);
所述含溴磷酸酯为2-溴乙基膦酸二乙酯或溴甲基笼状磷酸酯;
进一步的,溴甲基笼状磷酸酯具有如下分子结构:
溴甲基笼状磷酸酯制备方法是:以二氧六环为溶剂,2-(溴甲基)-2-(羟甲基)-1,3-丙二醇与三氯氧磷在加热环境下进行反应至没有氯化氢放出,得到溴甲基笼状磷酸酯。
(3)Click反应制备笼型低聚倍半硅氧烷阻燃剂
以DMSO为溶剂,在N,N,N’,N’,N”-五甲基二亚乙基三胺(PMDETA)、CuBr为催化体系下,POSS-Alkyne与AZ进行叠氮-炔环点击反应,制备笼型低聚倍半硅氧烷阻燃剂。
本发明具有如下优点和有益效果:
(1)本发明提供的笼型低聚倍半硅氧烷阻燃剂,其酸源、气源、炭源、硅源集于一个分子结构内,使用方便,热稳定性高。
(2)本发明提供的笼型低聚倍半硅氧烷阻燃剂制备方法简单,制备过程不产生环境污染。
附图说明
图1为实施例1制备的POSS-Alkyne、POSS-CPA的1H-NMR谱图(采用BrukerAV-400核磁共振仪测定,溶剂为CDCl3(TMS内标))。
图2为实施例2制备的POSS-Alkyne、POSS-NP的1H-NMR谱图(采用BrukerAV-400核磁共振仪测定,溶剂为CDCl3(TMS内标))。
具体实施方式
下面结合具体实施例对本发明做进一步详细说明,但实施例并不对本发明做任何形式的限定。除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1
(1)制备POSS-Alkyne
称取5-乙炔酸(5.35g,0.05mol)、HOBT(5.16g,0.04mol)、POSS-NH2(5.01g,5.68mmol)加入三口烧瓶中,加入200mL除水二氯甲烷使其充分溶解,在氮气保护下,室温搅拌30min,然后将溶于50mL二氯甲烷的EDC·HCl(18.30g,0.8388mmol)缓慢滴加到上述混合溶液中,室温反应48h。反应结束后,旋蒸浓缩反应液,然后倒入水/甲醇(V/V=1/4)的混合溶液中沉淀析出,用去离子水冲洗后干燥得到POSS-Alkyne固体粉末,产率为88.2%。
(2)制备CPA-AZ
在装有冷凝装置、氯化氢吸收装置的三口烧瓶中加入2-(溴甲基)-2-(羟甲基)-1,3-丙二醇(6.21g,0.03mol)和三氯氧磷(4.78g,0.03mol),并加入100mL二氧六环室温下充分搅拌溶解,逐步升温至90℃(10℃/10min),搅拌反应至没有氯化氢放出,停止反应。反应液冷却后过滤,用乙醇洗涤5遍后烘干得白色固体粉末,为溴甲基笼状磷酸酯(CPA-Br),产率82.5%
称量CPA-Br(5.68g,0.02mol)、叠氮化钠(1.67g,0.03mol)放入圆底烧瓶中,加入20mLDMF搅拌溶解后,室温下反应12h后旋蒸除去溶剂得到白色粉末。重新以氯仿溶解,加入水和甲醇的混合溶剂(V水/V甲醇=2:1)洗涤3遍,取有机相旋蒸干燥得到白色固体粉末,产率为62.4%。
(3)制备笼型低聚倍半硅氧烷阻燃剂(POSS-CPA)
在反应管中加入POSS-Alkyne(3.84g,2.35mmol)、CPA-AZ(3.86g,18.8mmol)、CuBr(0.03g,0.24mmol),冷冻-抽真空-解冻-通氮气3次后注射加入PMDETA(0.08g,0.47mmol)和20mL DMSO,置于70℃油浴锅中反应72h后注射加入四氢呋喃,所得反应液过中性Al2O3柱以除去催化剂,剩余溶液转移至截留分子量为3kDa的透析袋中,在500mLTHF中透析3d以除去未反应的聚合物和溶剂。透析后,溶液在冰乙醚中沉淀,干燥后得到POSS-CPA,产率72.6%。
实施例2
(1)制备POSS-Alkyne
称取5-乙炔酸(5.35g,0.05mol)、HOBT(5.16g,0.04mol)、POSS-NH2(5.01g,5.68mmol)加入三口烧瓶中,加入200mL除水二氯甲烷使其充分溶解,在氮气保护下,室温搅拌30min,然后将溶于50mL二氯甲烷的EDC·HCl(18.30g,0.8388mmol)缓慢滴加到上述混合溶液中,室温反应48h。反应结束后,旋蒸浓缩反应液,然后倒入水/甲醇(V/V=1/4)的混合溶液中沉淀析出,用去离子水冲洗后干燥得到POSS-Alkyne固体粉末,产率为88.2%。
(2)制备AZP
称量2-溴乙基膦酸二乙酯(5.04g,0.02mol)、叠氮化钠(1.34g,0.02mol)放入圆底烧瓶中,加入20mLDMF搅拌溶解后,室温下反应12h后旋蒸除去溶剂,以二氯甲烷为洗脱剂,经硅胶柱层析纯化,干燥得到AZP,产率为72.3%。
(3)制备含磷氮硅膨胀型阻燃剂(POSS-NP)
在反应管中加入POSS-Alkyne(2.32g,1.42mmol)、AZP(2.35g,11.36mmol)、CuBr(0.02g,0.14mmol),冷冻-抽真空-解冻-通氮气3次后注射加入PMDETA(0.05g,0.28mmol)和15mLDMSO,置于70℃油浴锅中反应72h后注射加入四氢呋喃,所得反应液过中性Al2O3柱以除去催化剂,剩余溶液转移至截留分子量为3kDa的透析袋中,在THF中透析3d以除去未反应的聚合物和溶剂。透析后,溶液在冰乙醚中沉淀,干燥后得到POSS-NP,产率65.2%。
实施例3
将实施例1和实施例2制备的阻燃剂置于60℃真空烘箱中干燥24h后置于球磨罐中,采用QM-3SP2行星式球磨机(南京大学仪器厂)进行高能球磨,球料比10:1,球磨转速3600r/min,球磨时间为12h。
将甲基乙烯基硅橡胶与气相白炭黑在30℃捏合机中捏合均匀后,加入阻燃剂,在双辊开炼机上室温开炼成片;加入硫化剂混炼均匀,放置24h后在平板硫化机上制片,硫化温度为120℃,硫化时间为5min,在200℃烘箱中二次硫化2h。
配方如下:甲基乙烯基硅橡胶100份,气相白炭黑30份,阻燃剂20份、硫化剂2份。
得到阻燃橡胶两份,分别为样品1(实施例1阻燃剂)和样品2(实施例1阻燃剂)。
对得到的阻燃硅橡胶进行如下性能测试,结果列于表1。
垂直燃烧测试按GB/T13488-1992测试。
拉伸强度和伸长率按GB/T528-1998测试,拉伸速度为500mm/min;
撕裂强度按GB/T529-1999测试,拉伸速度为500mm/min。
邵尔A型硬度按GB/T531-1999测定。
表1
对比例1橡胶配方:甲基乙烯基硅橡胶100份,气相白炭黑30份,硫化剂2份,硫化温度为120℃,硫化时间为5min。
以上所述的实施例对本发明的技术方案进行了详细说明,应理解的是以上所述仅为本发明的具体实施例,并不用于限制本发明,凡在本发明的原则范围内所做的任何修改、补充或类似方式替代等,均应包含在本发明的保护范围之内。
Claims (5)
1.一种笼型低聚倍半硅氧烷阻燃剂,其特征在于,具有式(I)结构:
所述式(I)中,为含磷基团,选自/>或R’为/>
2.一种如权利要求1所述的笼型低聚倍半硅氧烷阻燃剂的制备方法,其特征在于:
(1)制备炔基多面体低聚倍半硅氧烷(POSS-Alkyne)
以二氯甲烷为溶剂,1-羟基苯并三唑(HOBT)为酰胺基保护剂,1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐(EDC·HCl)为脱水剂,5-乙炔酸键合到氨基多面体低聚倍半硅氧烷(POSS-NH2)上,得到POSS-Alkyne;
(2)制备叠氮磷酸酯(AZ)
以DMF为溶剂,叠氮化钠在常温下与含溴磷酸酯反应,制备叠氮磷酸酯(AZ);
所述含溴磷酸酯为2-溴乙基膦酸二乙酯或溴甲基笼状磷酸酯;
溴甲基笼状磷酸酯具有如下分子结构:
(3)Click反应制备笼型低聚倍半硅氧烷阻燃剂
以DMSO为溶剂,在N,N,N’,N’,N”-五甲基二亚乙基三胺(PMDETA)、CuBr为催化体系下,POSS-Alkyne与AZ进行叠氮-炔环点击反应,制备笼型低聚倍半硅氧烷阻燃剂。
3.根据权利要求2所述的一种笼型低聚倍半硅氧烷阻燃剂的制备方法,其特征在于,所述溴甲基笼状磷酸酯制备方法是:以二氧六环为溶剂,2-(溴甲基)-2-(羟甲基)-1,3-丙二醇与三氯氧磷在加热环境下进行反应至没有氯化氢放出,得到溴甲基笼状磷酸酯。
4.根据权利要求2所述的一种笼型低聚倍半硅氧烷阻燃剂的制备方法,其特征在于:所述步骤(1)5-乙炔酸、POSS-NH2、HOBT、EDC·HCl的投料摩尔比例为8.4:1:6.5:16.5。
5.根据权利要求2所述的一种笼型低聚倍半硅氧烷阻燃剂的制备方法,其特征在于:所述步骤(3)POSS-Alkyne、AZ、CuBr、PMDETA的反应投料摩尔比为1:8:0.1:0.2。
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