CN113527552B - 一种修饰二烷基次膦酸官能团的氯球改性方法 - Google Patents
一种修饰二烷基次膦酸官能团的氯球改性方法 Download PDFInfo
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- CN113527552B CN113527552B CN202110774839.0A CN202110774839A CN113527552B CN 113527552 B CN113527552 B CN 113527552B CN 202110774839 A CN202110774839 A CN 202110774839A CN 113527552 B CN113527552 B CN 113527552B
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- 239000000460 chlorine Substances 0.000 title claims abstract description 62
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 62
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 60
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical group O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002715 modification method Methods 0.000 title claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 32
- 150000001804 chlorine Chemical class 0.000 claims abstract description 21
- 125000000524 functional group Chemical group 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 17
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- 238000000926 separation method Methods 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- -1 amino modified chlorine Chemical class 0.000 claims abstract description 4
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 3
- 125000003368 amide group Chemical group 0.000 claims abstract description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 3
- 238000007342 radical addition reaction Methods 0.000 claims abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
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- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 12
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- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 10
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- 239000003999 initiator Substances 0.000 claims description 6
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
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- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
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- 125000003277 amino group Chemical group 0.000 claims description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 4
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
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- 239000000463 material Substances 0.000 claims description 4
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
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- 229920001577 copolymer Polymers 0.000 claims description 3
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 3
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
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- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 claims description 2
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
- B01D15/206—Packing or coating
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Abstract
本发明公开了一种修饰二烷基次膦酸官能团的氯球改性方法，属于固相萃取分离技术领域。其特征在于首先通过氯球上的氯原子与含有伯胺官能团的化合物进行反应，得到氨基改性的氯球；然后利用氨基与酰氯反应生成的酰胺基团将碳碳双键接枝到氯球表面；再利用碳碳双键与单烷基次膦酸的自由基加成反应得到修饰二烷基次膦酸官能团的改性氯球。本发明公布的修饰二烷基次膦酸官能团的氯球改性方法简单、易于产业化，得到的接枝二烷基次膦酸官能团的改性氯球选择性好、化学稳定性高、饱和吸附量大、不存在萃取剂流失的问题，可广泛用于低浓度稀土富集、稀土深度分离、核级锆铪制备、金属离子除杂等领域。
Description
技术领域
本发明属于固相萃取分离技术领域，尤其是涉及一种氯球的改性及其在低浓度稀土富集、稀土分离、锆铪分离、金属离子除杂等方面的应用。
背景技术
有机磷/膦酸类萃取剂被广泛应用于稀土、镍钴、锆铪等相似元素的溶剂萃取分离，已经商业化的有机磷/膦酸类萃取剂有P204(二(2-乙基己基)磷酸酯),P507(2-乙基己基磷酸单2-乙基己基酯)和Cyanex 272(二(2,4,4-三甲基戊基)次膦酸)。随着烷氧基被烷基取代，其酸性按P204>P507>Cyanex 272顺序递减。酸性越强，萃取稀土离子、钴镍、锆铪的能力越强(萃取性能：P204>P507>Cyanex 272)，但相似元素的分离性能降低(分离性能：P204<P507<Cyanex 272)。
虽然Cyanex 272分离稀土、镍钴、锆铪的性能比P507高，但Cyanex 272的饱和负载量低，易乳化，常产生第三相，给生产带来困难。溶剂萃取法还因萃取剂溶于水相造成萃取剂流失，大量有机废水会造成环境污染，且有机溶剂易燃易爆，造成安全隐患。萃取色层法同时具有溶剂萃取法的高选择性和离子交换法的设备简单、高效性的双重优点，试剂投入量、消耗量和萃取剂的流失都大为减少，不存在萃取过程产生的乳化难题，不会有第三相生成，也避免了有机溶剂的大量使用给环境造成的污染，降低了安全隐患。
用于萃取色层法的树脂是关键。很多学者关注于浸渍树脂，即将萃取剂(如P204、P507、Cyanex 272等)通过范德华力以物理方式吸附于大孔树脂或硅基材料的表面。这种树脂使用过程中萃取剂易于流失，影响了萃淋树脂的稳定性和循环性能。以干法制备的浸渍树脂，吸附在基底材料表面的萃取剂往往不止一层，实际应用过程中往往只有表面的萃取剂起到作用，大量萃取剂无法与金属离子接触而起不到吸附的作用。以湿法制备的浸渍树脂，萃取剂吸附量有限。鲜有将二烷基次膦酸类萃取剂通过化学键连接到基底表面的报道。
发明内容
本发明提供一种修饰二烷基次膦酸官能团的氯球改性方法，其特征在于，首先通过氯球上的氯原子与含有伯胺官能团的化合物进行反应，得到氨基改性的氯球；然后利用氨基与酰氯反应生成的酰胺基团将碳碳双键接枝到氯球表面；再利用碳碳双键与单烷基次膦酸的自由基加成反应得到修饰二烷基次膦酸官能团的改性氯球。
其中氯球为引入了-CH2Cl活性官能团的苯乙烯-二乙烯苯共聚物；R1-NH2为含伯胺的化合物；R2为H或碳原子数为1～8的脂肪族取代基；R3为碳原子数为0～12的脂肪族烷基链；R4为碳原子数为4～12的脂肪族取代基。当R1基团中含有伯胺、仲胺、羟基官能团时，酰氯也可以与这些伯胺、仲胺、羟基官能团反应，从而在氯球表面引入更多的碳碳双键。
所述的含有伯胺官能团的化合物包括但不限于乙胺、丙胺、丁胺、戊胺、己胺、庚胺、辛胺、异辛胺、2-氨基辛烷、壬胺、癸胺、1-氨基十五烷、1,3-二甲基戊胺、2-氨基庚烷、3-氯苄胺、苯胺、苯甲胺、苯乙胺、乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、2-羟基乙胺、1,6-己二胺、N-(3-氨丙基)环己胺。
所述的一种修饰二烷基次膦酸官能团的氯球改性方法，制备步骤如下：
(1)将氯球、含有伯胺官能团的化合物和碱性物质在有机溶剂A中于40～180℃下反应4～24h，经固液分离后得到氨基改性的氯球。其中氯球与含有伯胺官能团的化合物质量比为10:1～1:10,氯球与碱性物质的质量比为20:1～1:10；
(2)向步骤(1)中所得的氨基改性的氯球中加入其体积0.5～20倍的水和/或有机溶剂B，并加入碱性物质，碱性物质与表面接枝氨基的氯球材料的质量比为0.05～2：1；
(3)将具有碳碳双键的酰氯用有机溶剂B溶解，酰氯与有机溶剂B的体积比为1:0.5～10，于0～50℃缓慢滴加到步骤(2)所得的含有氨基改性的氯球和碱性物质的混合体系中，酰氯与表面接枝氨基的氯球的质量比为0.05～3：1，滴加完毕后再反应0～10h，得到表面接枝碳碳双键的氯球。其中酰氯与碱性物质的摩尔比为1:0.5～2；
(4)将步骤(3)所得的表面接枝碳碳双键的氯球与单烷基次膦酸、酸、引发剂和有机溶剂C于80～150℃下反应8～48h,经固液分离得到表面修饰二烷基次膦酸官能团的氯球。
所述的碱性物质为三乙胺、吡啶、碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾、氢氧化钠或氢氧化钾中的一种或一种以上。
所述的有机溶剂A为1,4-二氧六环、正丁醇、正辛醇、异辛醇、N,N-二甲基甲酰胺、甲苯或二甲苯中的一种或一种以上。
所述的有机溶剂B为乙醚、石油醚、四氢呋喃、1,4-二氧六环、正辛烷、环己烷、磺化煤油、N,N-二甲基甲酰胺、甲苯或二甲苯其中的一种或一种以上。
所述的有机溶剂C为正辛烷、环己烷、石油醚、磺化煤油、四氢呋喃、1,4-二氧六环、正丁醇、正辛醇、异辛醇、癸醇、N,N-二甲基甲酰胺、甲苯或二甲苯其中的一种或一种以上。
所述的酸为醋酸、硫酸、盐酸中的一种或一种以上。
所述的引发剂为叔丁基过氧化氢、异丙苯过氧化氢、过氧化二叔丁基、过氧化二异丙苯、过氧化二苯甲酰、过氧化十二酰、过氧化叔戊酸叔丁酯、过氧化苯甲酸叔丁酯、过氧化二碳酸二异丙酯、过氧化二碳酸二乙基己酯、过氧化二碳酸二环己酯、过氧化二碳酸二苯氧乙酯、偶氮二异丁腈中的一种或一种以上。
所述的表面接枝碳碳双键的氯球与单烷基次膦酸的质量比为5:1～1:5，单烷基次膦酸与酸的摩尔比为5:1～1:2，引发剂质量为单烷基次膦酸质量的0.1～25％。
本发明提供一种修饰二烷基次膦酸官能团的氯球改性方法。苯乙烯-二乙烯苯共聚物机械强度高，化学稳定性好，耐酸碱，是理想的吸附树脂基底材料。氯球比表面积大、具有一定的粒度，用氯球改性的树脂可直接填充在工业级别的离子交换色谱柱中，用于金属离子分离。二烷基次膦酸官能团对稀土、锆铪、镍钴等相似元素具有良好的分离性能，将二烷基次膦酸官能团通过化学键接枝到氯球的表面，不存在萃取剂流失的问题，稳定性好，循环使用性能好，选择性好，产业化应用前景广阔。
附图说明
构成本申请的一部分的附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。在附图中：
图1为本发明制备路线示意图，
图2修饰二烷基次膦酸官能团的氯球结构示意图(实施例1)，
图3修饰二烷基次膦酸官能团的氯球结构示意图(实施例2)，
图4修饰二烷基次膦酸官能团的氯球结构示意图(实施例3)。
具体实施方式
以下结合实施例进一步说明本发明的方法。本发明的实施例用于解释本发明，并不构成对本发明的不当限定。
实施例1
(1)氨基改性氯球：称取10.2g干燥的氯球，加入150mL甲苯溶胀18h，加入12.9g正己胺和10.6g三乙胺，于80℃反应18h。降至室温，过滤，用乙醇洗涤2次、水洗至滤液呈中性，乙醇再洗涤1次后真空干燥，得到氨基改性氯球。
(2)含有C＝C双键的酰氯的制备：向18.1g十一烯酸中加入15.2g氯化亚砜，于80℃反应2h，降至室温，通过旋转蒸发仪除去过量氯化亚砜，加入40mL无水乙醚，得到十一烯酰氯的乙醚溶液。
(3)氯球接枝C＝C双键：取12.0g氨基改性的氯球，加入50mL无水乙醚和8.2g三乙胺，于常温下通过恒压漏斗缓慢加入十一酰氯的乙醚溶液，滴加完毕后反应4h。过滤，用去离子水洗涤至滤液呈中性，乙醇洗涤，室温晾干。
(4)接枝C＝C双键的氯球与单(2,3-二甲基丁基)次膦酸反应：取15.0g接枝C＝C双键的氯球、1.2g冰醋酸、5.68g单(2,3-二甲基丁基)次膦酸、0.55g过氧化二叔丁基和20mL正辛烷，回流反应8h,补加过氧化二叔丁基0.35g,再反应8h,再补加过氧化二叔丁基0.35g,再反应12h。降至室温，用乙醇洗涤4次后，于室温晾干，得到修饰二烷基次膦酸官能团的改性氯球(结构示意图如图2所示)。
实施例2
(1)氨基改性氯球：称取20.8g干燥的氯球，加入200mL 1,4-二氧六环溶胀12h，加入18.2g二乙烯三胺和17.6g无水碳酸钠，回流反应12h。降至室温，过滤，用乙醇洗涤2次、水洗至滤液呈中性，乙醇再洗涤1次后室温晾干，得到氨基改性氯球。
(2)氯球接枝C＝C双键：取25.0g氨基改性的氯球，加入50mL四氢呋喃和20.2g饱和碳酸氢钠溶液，于常温下通过恒压漏斗缓慢加入含有42.2g十一酰氯的四氢呋喃溶液，滴加完毕后反应6h。过滤，用去离子水洗涤至滤液呈中性，乙醇洗涤后，室温晾干。
(3)接枝C＝C双键的氯球与单己基次膦酸反应：取25.0g接枝C＝C双键的氯球、20mL异辛醇、1.2mL浓硫酸、18.2g单己基次膦酸和0.80g过氧化二苯甲酰，120℃反应8h,补加过氧化二苯甲酰0.42g,再反应8h,再补加过氧化二苯甲酰0.42g,再反应8h。降至室温，用乙醇洗涤4次后，室温晾干，得到修饰二烷基次膦酸官能团的改性氯球(结构示意图如图3所示)。
实施例3
(1)氨基改性氯球：称取5.2g干燥的氯球，加入80mL N,N-二甲基甲酰胺溶胀10h，加入8.4g 1,6-己二胺和6.6g氢氧化钠，回流反应8h。降至室温，过滤，用乙醇洗涤3次、水洗至滤液呈中性，乙醇再洗涤1次后室温晾干，得到氨基改性氯球。
(2)含有C＝C双键的酰氯的制备：向8.1g 5-己烯酸中加入9.2g氯化亚砜，于80℃反应2.5h，降至室温，通过旋转蒸发仪除去过量氯化亚砜，加入20mL干燥的1,4-二氧六环，得到5-己烯酰氯的1,4-二氧六环溶液。
(3)氯球接枝C＝C双键：取5.6g氨基改性的氯球，加入20mL环己烷和6.2g碳酸钾溶液，于常温下通过恒压漏斗缓慢加入5-己烯酰氯的1,4-二氧六环溶液，滴加完毕后反应8h。过滤，用去离子水洗涤至滤液呈中性，乙醇洗涤2次后，室温晾干。
(4)接枝C＝C双键的氯球与单(2,4,4-三甲基戊基)次膦酸反应：取6.8g接枝C＝C双键的氯球、15mL癸醇、0.5mL浓盐酸、12.0g单(2,4,4-三甲基戊基)次膦酸和0.80g过氧化二碳酸二异丙酯，90℃反应6h,补加过氧化二碳酸二异丙酯0.64g,再反应6h,再补加过氧化二碳酸二异丙酯0.64g,再反应8h。降至室温，用乙醇洗涤4次后，室温晾干，得到修饰二烷基次膦酸官能团的改性氯球(结构示意图如图4所示)。
Claims (10)
1.一种修饰二烷基次膦酸官能团的氯球改性方法，其特征在于，首先通过氯球上的氯原子与含有伯胺官能团的化合物进行反应，得到氨基改性的氯球；然后利用氨基与酰氯反应生成的酰胺基团将碳碳双键接枝到氯球表面；再利用碳碳双键与单烷基次膦酸的自由基加成反应得到修饰二烷基次膦酸官能团的改性氯球；制备路线为：
其中氯球为引入了-CH2Cl活性官能团的苯乙烯-二乙烯苯共聚物；R1-NH2为含伯胺的化合物；R2为H或碳原子数为1～8的脂肪族取代基；R3为碳原子数为0～12的脂肪族烷基链；R4为碳原子数为4～12的脂肪族取代基；当R1基团中含有伯胺、仲胺、羟基官能团时，酰氯也可以与这些伯胺、仲胺、羟基官能团反应，从而在氯球表面引入更多的碳碳双键。
2.如权利要求1所述的一种修饰二烷基次膦酸官能团的氯球改性方法，其特征在于所述的含有伯胺官能团的化合物包括但不限于乙胺、丙胺、丁胺、戊胺、己胺、庚胺、辛胺、异辛胺、2-氨基辛烷、壬胺、癸胺、1-氨基十五烷、1,3-二甲基戊胺、2-氨基庚烷、3-氯苄胺、苯胺、苯甲胺、苯乙胺、乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、2-羟基乙胺、1,6-己二胺、N-(3-氨丙基)环己胺。
3.如权利要求1所述的一种修饰二烷基次膦酸官能团的氯球改性方法，其特征在于，具体制备步骤如下：
(1)将氯球、含有伯胺官能团的化合物和碱性物质在有机溶剂A中于40～180℃下反应4～24h，经固液分离后得到氨基改性的氯球；其中氯球与含有伯胺官能团的化合物质量比为10:1～1:10,氯球与碱性物质的质量比为20:1～1:10；
(2)向步骤(1)中所得的氨基改性的氯球中加入其体积0.5～20倍的水和/或有机溶剂B，并加入碱性物质，碱性物质与表面接枝氨基的氯球材料的质量比为0.05～2：1；
(3)将具有碳碳双键的酰氯用有机溶剂B溶解，酰氯与有机溶剂B的体积比为1:0.5～10，于0～50℃缓慢滴加到步骤(2)所得的含有氨基改性的氯球和碱性物质的混合体系中，酰氯与表面接枝氨基的氯球的质量比为0.05～3：1，滴加完毕后再反应0～10h，得到表面接枝碳碳双键的氯球； 其中酰氯与碱性物质的摩尔比为1:0.5～2；
(4)将步骤(3)所得的表面接枝碳碳双键的氯球与单烷基次膦酸、酸、引发剂和有机溶剂C于80～150℃下反应8～48h,经固液分离得到表面修饰二烷基次膦酸官能团的氯球。
4.根据权利要求3所述的一种修饰二烷基次膦酸官能团的氯球改性方法，其特征在于，所述的碱性物质为三乙胺、吡啶、碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾、氢氧化钠或氢氧化钾中的一种或一种以上。
5.根据权利要求3所述的一种修饰二烷基次膦酸官能团的氯球改性方法，其特征在于，步骤(1)中所述的有机溶剂A为1,4-二氧六环、正丁醇、正辛醇、异辛醇、N,N-二甲基甲酰胺、甲苯或二甲苯中的一种或一种以上。
6.根据权利要求3所述的一种修饰二烷基次膦酸官能团的氯球改性方法，其特征在于，步骤(2)～(3)中所述的有机溶剂B为乙醚、石油醚、四氢呋喃、1,4-二氧六环、正辛烷、环己烷、磺化煤油、N,N-二甲基甲酰胺、甲苯或二甲苯其中的一种或一种以上。
7.根据权利要求3所述的一种修饰二烷基次膦酸官能团的氯球改性方法，其特征在于，步骤(4)中所述的有机溶剂C为正辛烷、环己烷、石油醚、磺化煤油、四氢呋喃、1,4-二氧六环、正丁醇、正辛醇、异辛醇、癸醇、N,N-二甲基甲酰胺、甲苯或二甲苯其中的一种或一种以上。
8.根据权利要求3所述的一种修饰二烷基次膦酸官能团的氯球改性方法，其特征在于，步骤(4)中所述的酸为醋酸、硫酸、盐酸中的一种或一种以上。
9.根据权利要求3所述的一种修饰二烷基次膦酸官能团的氯球改性方法，其特征在于，步骤(4)中所述的引发剂为叔丁基过氧化氢、异丙苯过氧化氢、过氧化二叔丁基、过氧化二异丙苯、过氧化二苯甲酰、过氧化十二酰、过氧化叔戊酸叔丁酯、过氧化苯甲酸叔丁酯、过氧化二碳酸二异丙酯、过氧化二碳酸二乙基己酯、过氧化二碳酸二环己酯、过氧化二碳酸二苯氧乙酯、偶氮二异丁腈中的一种或一种以上。
10.根据权利要求3所述的一种修饰二烷基次膦酸官能团的氯球改性方法，其特征在于，步骤(4)中所述的表面接枝碳碳双键的氯球与单烷基次膦酸的质量比为5:1～1:5，单烷基次膦酸与酸的摩尔比为5:1～1:2，引发剂质量为单烷基次膦酸质量的0.1～25％。
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