CN106750328A - 一种含氟硅聚磷酸酯及其制备方法和应用 - Google Patents
一种含氟硅聚磷酸酯及其制备方法和应用 Download PDFInfo
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- CN106750328A CN106750328A CN201611037133.1A CN201611037133A CN106750328A CN 106750328 A CN106750328 A CN 106750328A CN 201611037133 A CN201611037133 A CN 201611037133A CN 106750328 A CN106750328 A CN 106750328A
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- epoxy resin
- fluorine silicon
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- polyphosphate
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- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229920000388 Polyphosphate Polymers 0.000 title claims abstract description 31
- 239000001205 polyphosphate Substances 0.000 title claims abstract description 31
- 235000011176 polyphosphates Nutrition 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003822 epoxy resin Substances 0.000 claims abstract description 49
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 49
- 239000000126 substance Substances 0.000 claims abstract description 6
- -1 cyclic phosphate Ester Chemical class 0.000 claims description 33
- 229910019142 PO4 Inorganic materials 0.000 claims description 25
- 239000010452 phosphate Substances 0.000 claims description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 22
- 238000007711 solidification Methods 0.000 claims description 22
- 230000008023 solidification Effects 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- KGQCLZJFUIPDGS-UHFFFAOYSA-N dioxaphospholane Chemical compound C1CPOO1 KGQCLZJFUIPDGS-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 239000002210 silicon-based material Substances 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 claims description 6
- VNOMEAQPOMDWSR-UHFFFAOYSA-N 2,2,2-trifluoro-1-phenylethanol Chemical class FC(F)(F)C(O)C1=CC=CC=C1 VNOMEAQPOMDWSR-UHFFFAOYSA-N 0.000 claims description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims description 5
- CSUFEOXMCRPQBB-UHFFFAOYSA-N 1,1,2,2-tetrafluoropropan-1-ol Chemical compound CC(F)(F)C(O)(F)F CSUFEOXMCRPQBB-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000009267 minimal disease activity Effects 0.000 claims description 4
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims description 4
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 3
- NLSXASIDNWDYMI-UHFFFAOYSA-N triphenylsilanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)C1=CC=CC=C1 NLSXASIDNWDYMI-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229930185605 Bisphenol Natural products 0.000 claims 1
- 239000004593 Epoxy Substances 0.000 claims 1
- XZVCHVOJRIFBBU-UHFFFAOYSA-N O1POCC1.[O] Chemical compound O1POCC1.[O] XZVCHVOJRIFBBU-UHFFFAOYSA-N 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 13
- 239000011574 phosphorus Substances 0.000 abstract description 13
- 239000003063 flame retardant Substances 0.000 abstract description 11
- 229910052710 silicon Inorganic materials 0.000 abstract description 7
- 239000010703 silicon Substances 0.000 abstract description 7
- 239000003610 charcoal Substances 0.000 abstract description 6
- 239000010410 layer Substances 0.000 abstract description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 abstract description 5
- 239000011737 fluorine Substances 0.000 abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- ZHQXROVTUTVPGO-UHFFFAOYSA-N [F].[P] Chemical compound [F].[P] ZHQXROVTUTVPGO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 239000011241 protective layer Substances 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 238000002485 combustion reaction Methods 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000002240 furans Chemical class 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical group [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 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 description 1
- 229920001634 Copolyester Polymers 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
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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Abstract
本发明公开了一种含氟硅聚磷酸酯及其制备方法和应用,其化学式结构为:其中,R1为R2为n=10~100。本发明的含氟硅聚磷酸酯利用磷氟硅元素进行阻燃,磷元素能够催化体系形成富磷炭层,起到保护层的作用从而阻止环氧树脂的进一步分解;含有硅的环氧树脂在燃烧过程中会形成含有二氧化硅的炭层,增强炭层结构,进一步提高炭层的保护作用;氟元素的引入能提高环氧树脂的热稳定性,从而提高体系的阻燃性能。
Description
技术领域
本发明属于有机阻燃材料技术领域,具体涉及一种含氟硅聚磷酸酯及其制备方法和应用。
背景技术
大部分的高分子材料都具有易燃的特性,许多火灾的发生是高分子材料的燃烧造成的,给人们的生活带来极大的危害。为了改善高分子材料的阻燃性能,阻燃剂的应用也随之兴起,制备出一种高效的阻燃剂以提高材料的阻燃性能,亦或是在提高阻燃性能的同时赋予材料新性能的研究,仍然是一个富有挑战的课题。
CN201410680503.8公开了一种磷硅复合阻燃剂,其利用笼状七苯基三硅磷倍半硅氧烷应用于硅橡胶的阻燃,发挥了磷系阻燃剂与硅系阻燃剂的优势,起到防熔滴、隔热抑烟的作用。CN201210094955.9公开了一种磷硅氟阻燃共聚酯薄膜,通过缩聚得到磷硅氟共聚酯切片,最后经过加工得到阻燃性能达到VTM-0级的薄膜。然而,大部分的阻燃剂仍然存在着与基体树脂相容性差的缺陷,而且阻燃剂对基体改性的功能单一,无法扩展阻燃剂与高分子材料的应用领域。
发明内容
本发明的目的在于提供一种含氟硅聚磷酸酯。
本发明的另一目的在于提供上述含氟硅聚磷酸酯的制备方法。
本发明的再一目的在于提供上述含氟硅聚磷酸酯的应用。
本发明的技术方案如下:
一种含氟硅聚磷酸酯,其化学式结构为:
其中,R1为
R2为n=10~100。
上述含氟硅聚磷酸酯的制备方法,包括如下步骤:
(1)在冰浴下向反应容器中依次加入含硅化合物、三乙胺和第一有机溶剂,再缓慢滴加2-氯-2-氧-1,3,2-二氧磷杂环戊烷,室温反应4~12h,接着过滤除去三乙胺盐酸盐,将所得滤液用水反复淬洗,取有机相用无水硫酸镁干燥,抽滤,最后旋蒸除去溶剂得含硅环状磷酸酯单体;上述含硅化合物为三甲基硅醇、三苯基硅醇或氨丙基笼型聚倍半硅氧烷(NH2-POSS);2-氯-2-氧-1,3,2-二氧磷杂环戊烷和第一有机溶剂的质量比为1∶5~50;含硅化合物、三乙胺和2-氯-2-氧-1,3,2-二氧磷杂环戊烷的摩尔比为1∶1~2∶1~2;
(2)在步骤(1)所得的含硅环状磷酸酯单体中加入含氟化合物、异辛酸亚锡和第二有机溶剂,然后升温至35℃~80℃,反应6~12h,最后将溶剂旋干,即得所述含氟硅聚磷酸酯;上述含氟化合物为3,5-双(三氟甲基)苄醇或四氟丙醇;含硅环状磷酸酯单体与第二有机溶剂的质量比为1∶5~50;含硅环状磷酸酯单体、含氟化合物何异辛酸亚锡的摩尔比为1∶0.01~0.05:0.002~0.01。
在本发明的一个优选实施方案中,所述第一有机溶剂为二氯甲烷、甲苯或乙酸乙酯。
在本发明的一个优选实施方案中,所述第二有机溶剂为二氯甲烷、三氯甲烷或四氢呋喃中。
上述含氟硅聚磷酸酯在制备阻燃性环氧树脂中的应用。
在本发明的一个优选实施方案中,具体为:取环氧树脂预聚体升温至70~110℃,在其中加入2~90wt%的含氟硅聚磷酸酯,搅拌至呈均一透明的状态,接着按化学计量比加入固化剂4,4-二氨基二苯甲烷(DDM)直至完全溶解,然后倒入铝制模具中,设置升温程序进行固化得到阻燃性环氧树脂。
进一步优选的,所述环氧树脂预聚体为E51双酚A型环氧树脂。
进一步优选的,所述环氧树脂预聚体与固化剂4,4-二氨基二苯甲烷的质量比为8∶2.02。
进一步优选的,所述升温程序为:120℃固化4h,140℃固化2h,180℃固化2h。
本发明的有益效果是:
1、本发明的含氟硅聚磷酸酯中环状磷酸酯开环聚合所得的大分子提高了体系中的含磷量;
2、本发明的含氟硅聚磷酸酯利用磷氟硅元素进行阻燃,磷元素能够催化体系形成富磷炭层,起到保护层的作用从而阻止环氧树脂的进一步分解;含有硅的环氧树脂在燃烧过程中会形成含有二氧化硅的炭层,增强炭层结构,进一步提高炭层的保护作用;氟元素的引入能提高环氧树脂的热稳定性,从而提高体系的阻燃性能;
3、本发明的含氟硅聚磷酸酯中引入了氟、硅元素,因这两种元素的原子特殊性,不仅能提高环氧树脂的阻燃性能,还能降低环氧树脂的表面能,使材料表现出疏水的性质;
4、本发明的制备方法通过合成不同环状磷酸酯单体,或改变引发环状磷酸酯的单羟基化合物种类,可以调整体系中的磷硅氟比例;
5、本发明的制各方法利用环状磷酸酯开环聚合的特点,制备出磷、硅、氟一体的大分子阻燃剂,应用于环氧树脂的阻燃,对提高环氧树脂阻燃性能并实现功能化有着显著的作用。
附图说明
图1为实施例1中含氟硅聚磷酸酯的结构式;
图2为纯环氧树脂与实施例1制得的阻燃性环氧树脂的水接触角对比图,上图为纯环氧树脂,下图为实施例1制得的阻燃性环氧树脂。
具体实施方案
以下通过具体实施方式结合附图对本发明的技术方案进行进一步的说明和描述。
下述实施例中,环氧树脂预聚体为E51双酚A型环氧树脂。
实施例1
(1)在冰浴下向单口瓶中依次加入8.00g(9.14mmol)氨丙基笼型聚倍半硅氧烷(NH2-POSS)、1.12g(11.06mmol)三乙胺和25mL二氯甲烷,再用注射器缓慢滴加1.96g(13.75mmol)2-氯-2-氧-1,3,2-二氧磷杂环戊烷,室温反应8h;接着过滤除去三乙胺盐酸盐,将所得滤液用水反复淬洗,取有机相用无水硫酸镁干燥,抽滤,旋蒸除去溶剂得含硅的环状磷酸酯单体。
(2)取6.08g(6.20mmol)步骤(1)中所得含硅环状磷酸酯单体于单口瓶中,加入13.60mg(0.10mmol)四氟丙醇、20.00mg(0.04mmol)异辛酸亚锡和10mL四氢呋喃,升温至80℃,反应6h,反应结束后将溶剂旋干,得到含氟硅聚磷酸酯(如图1所示)。
(3)称取20g环氧树脂预聚体升温至90℃,加入2.78g的步骤(2)中所得含氟硅聚磷酸酯,搅拌至呈均一透明的状态,接着加入5.05gDDM直至完全溶解,然后倒入铝制模具中,120℃固化4h,140℃固化2h,180℃固化2h,得到阻燃性环氧树脂。
根据GB/T 2406-2009测得上述阻燃性环氧树脂的氧指数为32.4%。
根据GB/T 30693-2014测得上述阻燃性环氧树脂的水接触角为87.7°(如图2所示)。
实施例2
(1)含硅环状磷酸酯单体的合成同实施例1。
(2)含氟硅聚磷酸酯的合成同实施例1。
(3)称取20g环氧树脂预聚体升温至90℃,加入6.26g的步骤(2)中所得含氟硅聚磷酸酯,搅拌至混合物呈均一透明的状态,加入5.05gDDM直至完全溶解,倒入铝制模具中,120℃固化4h,140℃固化2h,180℃固化2h得到阻燃性环氧树脂。
根据GB/T 2406-2009测得上述阻燃性环氧树脂的氧指数为33.1%。
根据GB/T 30693-2014测得上述阻燃性环氧树脂的水接触角为90.5°。
实施例3
(1)含硅环状磷酸酯单体的制备同实施例1。
(2)取6.08g(6.20mmol)步骤(1)中所得含硅环状磷酸酯单体于单口瓶中,加入24.41mg(0.10mmol)3,5-双(三氟甲基)苄醇、20.00mg(0.04mmol)异辛酸亚锡和10mL四氢呋喃,升温至80℃,反应6h,反应结束后将溶剂旋干,得到含氟硅聚磷酸酯。
(3)称取20g环氧树脂预聚体升温至90℃,加入2.78g的步骤(2)中所得含氟硅聚磷酸酯,搅拌至呈均一透明的状态,接着加入5.05gDDM直至完全溶解,然后倒入铝制模具中,120℃固化4h,140℃固化2h,180℃固化2h得到阻燃性环氧树脂。
根据GB/T 2406-2009测得上述阻燃性环氧树脂的氧指数为30.9%。
根据GB/T 30693-2014测得上述阻燃性环氧树脂的水接触角为87.9°。
实施例4
(1)含硅环状磷酸酯单体的制备同实施例3。
(2)含氟硅聚磷酸酯的制备同实施例3。
(3)称取20g环氧树脂预聚体升温至90℃,加入2.78g的步骤(2)中所得含氟硅聚磷酸酯,搅拌至呈均一透明的状态,接着加入5.05gDDM直至完全溶解,然后倒入铝制模具中,120℃固化4h,140℃固化2h,180℃固化2h得到阻燃性环氧树脂。
根据GB/T 2406-2009测得上述阻燃性环氧树脂的氧指数为32.7%。
根据GB/T 30693-2014测得上述阻燃性环氧树脂的水接触角为91.6°。
实施例5
(1)在冰浴下向单口瓶中依次加入1.03g(9.14mmol)三甲基硅醇、1.12g(11.06mmol)三乙胺和20mL二氯甲烷,再用注射器缓慢滴加1.96g(13.75mmol)2-氯-2-氧-1,3,2-二氧磷杂环戊烷,反应8h;接着过滤除去三乙胺盐酸盐,将所得滤液用水反复淬洗三次,取有机相用无水硫酸镁干燥,抽滤,旋蒸除去溶剂得含氟或含硅的环状磷酸酯单体含硅环状磷酸酯单体。
(2)取6.08g(6.20mmol)步骤(1)中所得含硅环状磷酸酯单体于单口瓶中,加入24.41mg(0.10mmol)3,5-双(三氟甲基)苄醇、20.00mg(0.04mmol)异辛酸亚锡和10mL四氢呋喃,升温至80℃,反应6h,反应结束后将溶剂旋干,得到含氟硅聚磷酸酯。
(3)称取20g环氧树脂预聚体升温至90℃,加入2.78g的步骤(2)中所得含氟硅聚磷酸酯,搅拌至混合物呈均一透明的状态,加入5.05gDDM直至完全溶解,倒入铝制模具中,120℃固化4h,140℃固化2h,180℃固化2h得到阻燃性环氧树脂。
根据GB/T 2406-2009测得上述阻燃性环氧树脂的氧指数为32.5%。
根据GB/T 30693-2014测得上述阻燃性环氧树脂的水接触角为89.7°。
本领域普通技术人员可知,本发明的技术方案在下述范围内变化时,仍然能够得到与上述实施例相同或相近的技术效果,仍然属于本发明的保护范围:
一种含氟硅聚磷酸酯,其化学式结构为:
其中,R1为
R2为n=10~100。
上述含氟硅聚磷酸酯的制备方法,包括如下步骤:
(1)在冰浴下向反应容器中依次加入含硅化合物、三乙胺和第一有机溶剂,再缓慢滴加2-氯-2-氧-1,3,2-二氧磷杂环戊烷,室温反应4~12h,接着过滤除去三乙胺盐酸盐,将所得滤液用水反复淬洗,取有机相用无水硫酸镁干燥,抽滤,最后旋蒸除去溶剂得含硅环状磷酸酯单体;上述含硅化合物为三甲基硅醇、三苯基硅醇或氨丙基笼型聚倍半硅氧烷(NH2-POSS);2-氯-2-氧-1,3,2-二氧磷杂环戊烷和第一有机溶剂的质量比为1∶5~50;含硅化合物、三乙胺和2-氯-2-氧-1,3,2-二氧磷杂环戊烷的摩尔比为1∶1~2∶1~2;
(2)在步骤(1)所得的含硅环状磷酸酯单体中加入含氟化合物、异辛酸亚锡和第二有机溶剂,然后升温至35~80℃,反应6~12h,最后将溶剂旋干,即得所述含氟硅聚磷酸酯;上述含氟化合物为3,5-双(三氟甲基)苄醇或四氟丙醇;含硅环状磷酸酯单体与第二有机溶剂的质量比为1∶5~50;含硅环状磷酸酯单体、含氟化合物何异辛酸亚锡的摩尔比为1∶0.01~0.05∶0.002~0.01。
所述第一有机溶剂为二氯甲烷、甲苯或乙酸乙酯。所述第二有机溶剂为二氯甲烷、三氯甲烷或四氢呋喃。
上述含氟硅聚磷酸酯在制备阻燃性环氧树脂中的应用。具体为:取环氧树脂预聚体升温至70~110℃,在其中加入2~90wt%的含氟硅聚磷酸酯,搅拌至呈均一透明的状态,接着按化学计量比加入固化剂4,4-二氨基二苯甲烷(DDM)直至完全溶解,然后倒入铝制模具中,设置升温程序进行固化得到阻燃性环氧树脂。
以上所述,仅为本发明的较佳实施例而已,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 (9)
1.一种含氟硅聚磷酸酯,其特征在于:其化学式结构为:
其中,R1为 R2为n=10~100。
2.如权利要求1所述的一种含氟硅聚磷酸酯的制备方法,其特征在于:包括如下步骤:
(1)在冰浴下向反应容器中依次加入含硅化合物、三乙胺和第一有机溶剂,再缓慢滴加2-氯-2-氧-1,3,2-二氧磷杂环戊烷,室温反应4~12h,接着过滤除去三乙胺盐酸盐,将所得滤液用水反复淬洗,取有机相用无水硫酸镁干燥,抽滤,最后旋蒸除去溶剂得含硅环状磷酸酯单体;上述含硅化合物为三甲基硅醇、三苯基硅醇或氨丙基笼型聚倍半硅氧烷;2-氯-2-氧-1,3,2-二氧磷杂环戊烷和第一有机溶剂的质量比为1∶5~50;含硅化合物、三乙胺和2-氯-2-氧-1,3,2-二氧磷杂环戊烷的摩尔比为1∶1~2∶1~2;
(2)在步骤(1)所得的含硅环状磷酸酯单体中加入含氟化合物、异辛酸亚锡和第二有机溶剂,然后升温至35~80℃,反应6~12h,最后将溶剂旋干,即得所述含氟硅聚磷酸酯;上述含氟化合物为3,5-双(三氟甲基)苄醇或四氟丙醇;含硅环状磷酸酯单体与第二有机溶剂的质量比为1∶5~50;含硅环状磷酸酯单体、含氟化合物何异辛酸亚锡的摩尔比为1∶0.01~0.05∶0.002~0.01。
3.如权利要求2所述的制备方法,其特征在于:所述第一有机溶剂为二氯甲烷、甲苯或乙酸乙酯。
4.如权利要求2所述的制备方法,其特征在于:所述第二有机溶剂为二氯甲烷、三氯甲烷或四氢呋喃。
5.权利要求1所述的含氟硅聚磷酸酯在制备阻燃性环氧树脂中的应用。
6.如权利要求5所述的应用,其特征在于:具体为:取环氧树脂预聚体升温至70~110℃,在其中加入2~90wt%的含氟硅聚磷酸酯,搅拌至呈均一透明的状态,接着按化学计量比加入固化剂4,4-二氨基二苯甲烷(DDM)直至完全溶解,然后倒入铝制模具中,设置升温程序进行固化得到阻燃性环氧树脂。
7.如权利要求6所述的应用,其特征在于:所述环氧树脂预聚体为E51双酚A型环氧树脂。
8.如权利要求6所述的应用,其特征在于:所述环氧树脂预聚体与固化剂4,4-二氨基二苯甲烷的质量比为8∶2.02。
9.如权利要求6所述的应用,其特征在于:所述升温程序为:120℃固化4h,140℃固化2h,180℃固化2h。
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Cited By (7)
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WO2018095357A1 (zh) * | 2016-11-23 | 2018-05-31 | 厦门大学 | 一种含氟硅聚磷酸酯及其制备方法和应用 |
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CN115873258B (zh) * | 2023-02-24 | 2023-05-26 | 开贝科技(苏州)有限公司 | 一种改性聚磷酸酯及其制备方法和应用 |
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US20190284344A1 (en) | 2019-09-19 |
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