CN114524967A - 一种中空聚合物微球的制备方法 - Google Patents
一种中空聚合物微球的制备方法 Download PDFInfo
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- CN114524967A CN114524967A CN202111566185.9A CN202111566185A CN114524967A CN 114524967 A CN114524967 A CN 114524967A CN 202111566185 A CN202111566185 A CN 202111566185A CN 114524967 A CN114524967 A CN 114524967A
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- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 3
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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
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Abstract
本发明涉及高分子材料技术领域,提供一种中空聚合物微球的制备方法。采用悬浮聚合的方法,在可聚合的单体及交联剂中添加两亲性长链化合物及链转移试剂,通过控制两亲性长链化合物在可聚合单体油相中吸收水分及链转移剂控制可聚合单体的聚合速率调节相分离发生的快慢程度,协同作用,经聚合固定后,可得到中空呈独立空腔的聚合物微球。此法具有合成方法简单,容易控制、便于放大生产等优点,在生物医药检测,石油开采等领域具有潜在的应用价值。
Description
技术领域
本发明涉及高分子材料技术领域,尤其涉及一种中空聚合物微球的制备方法。
背景技术
中空微球是一种中间具有独立壳内空腔的微球,因其特殊的结构,而具有特殊的性质, 可被应用于生物医药检测,微反应器,药物输送、缓释,酶固定化,喷墨,油漆及纸面加工 等领域,近年来正受到科研人员的广泛关注。目前合成中空微球的方法主要有模板法,即在 作为模板的纳/微米微球外表面包裹一层不同材质的壳材料,经过聚合之后除去模板而保留壳 材料以获得中空微球。但此法合成过程繁杂,合成步骤多,且除去模板的方法苛刻,需要高 温煅烧或者有机溶剂溶解模板等,批次稳定性差,不利于大规模生产。
本发明主要内容是采用常规的悬浮聚合方法,即含有可聚合单体的油相在含有稳定剂的 水溶液中,搅拌形成“油滴”,经过引发聚合固定成球形;本发明通过在可聚合油相单体中 添加两亲性长链化合物及链转移试剂,使得“油滴”内部吸收大量水分现成“微胶束”,并 在引发剂引发可聚合单体聚合阶段控制相分离速率,通过两者之间的协同作用,可一步得到 中间带有空腔的聚合物微球材料。
发明内容
因此,针对上述现有技术的不足,本发明的目的在于提供了一种中空聚合物微球的制备 方法,采用悬浮聚合的方法,通过在可聚合的单体中添加两亲性长链化合物及链转移试剂, 经过聚合后可得到一种中间具有独立壳内空腔的中空微球。
一种中空的聚合物微球的制备方法,包括以下步骤:
(1)油相制备:
称取适量的可聚合单体M1、交联剂M2、引发剂I1,两亲性长链物质S1、链转移剂C1于 烧杯中,搅拌均匀,备用;
(2)稳定相制备:
将适量的稳定剂P1加入到去离子水,升温至50~80℃,待稳定剂完全溶解后,即得到 含稳定剂P1的水相溶液;
(3)聚合
称取适量的盐S3于烧杯中,加入去离子水,溶解完全;加入乳化剂S2,分散均匀后,转 移至反应瓶中;将(2)中得到的稳定相转移至反应瓶中,搅拌均匀,将(1)中得到的油相转移至反应瓶中,50-1000rpm搅拌转速下,升温至65-90℃,保温反应8-18h;反应结束 后,降至室温。
(4)清洗
将(3)中得到的聚合物微球,抽滤掉反应液,用甲醇或乙醇或丙酮清洗未反应单体,烘 干可得到中空聚合物微球。
进一步的改进是:所述可聚合单体M1为苯乙烯、甲基苯乙烯、乙基苯乙烯、氯甲基苯乙 烯、丙烯酸甲酯、丙烯酸丙酯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸季戊四醇酯、甲 基丙烯酸缩水甘油酯、丙烯酸缩水甘油酯、甲基丙烯酸丁酯、甲基丙烯酸羟乙酯、丙烯酸羟 乙酯中的任意一种或两种以上的混合物。
进一步的改进是:所述交联剂M2为二乙烯基苯、二甲基丙烯酸乙二醇酯、三乙烯酸甘油 酯、三羟甲基丙基三甲基丙烯酸、季戊四醇三丙烯酸酯、二乙二醇二甲基丙烯酸酯、二缩三 乙二醇二甲基丙烯酸酯、三缩四乙二醇二甲基丙烯酸酯、1,3-丁二醇二甲基丙烯酸酯、1,4- 丁二醇二甲基丙烯酸酯、六亚甲基双甲基丙烯酰胺、三甲基丙烯酸甘油酯、亚甲基丙烯酰胺 中的任意一种或两种以上的混合物。
进一步的改进是:所述引发剂I1为过氧化苯甲酰、偶氮二异丁腈、偶氮二异丁酸二甲酯、 偶氮二异丁基脒中的任意一种或两种以上的混合物。
进一步的改进是:所述两亲性长链物质S1为司盘85、司盘80、司盘65、司盘60、吐温80、 吐温65中的任意一种或两种以上的混合物。
进一步的改进是:所述链转移剂C1为十二硫醇、己硫醇、3-巯基丙酸甲酯、3-巯基丙酸 异辛酯中的任意一种或两种以上的混合物。
进一步的改进是:所述稳定剂P1是聚乙烯醇、聚乙二醇、聚乙烯吡咯烷酮、羟甲基纤维 素、羟丙基纤维素、羟乙基纤维素、羧甲基纤维素、β-环糊精、β-甲基环糊精、羟基磷灰石中的任意一种或两种以上的混合物。
进一步的改进是:所述的盐S3为氯化钠、硫酸钠、硝酸钠、磷酸钠、磷酸氢二钠、磷酸 二氢钠中的任意一种或两种以上的混合物。
进一步的改进是:所述乳化剂S2为离子型乳化剂、非离子型乳化剂中的任意一种或二者 以任意比混合而成。所述离子型乳化剂为烷基苯磺酸盐、烷基磺酸盐、烷基丁二酸酯磺酸盐 或烷基联苯基醚磺酸盐。
进一步的改进是:所述的交联剂M2与单体M1的质量配比为2.5-90∶10。
进一步的改进是:所述的引发剂I1与单体M1及交联剂M2之和的质量配比为0.5-5∶100。
进一步的改进是:所述的两亲性长链物质S1与单体M1及交联剂M2之和的质量配比为 10-60∶100。
进一步的改进是:所述的链转移剂C1与单体M1及交联剂M2之和的质量配比为0.5-20∶100。
进一步的改进是:所述的稳定剂P1与单体M1及交联剂M2之和的质量配比为0.5-5∶100。
进一步的改进是:所述的单体M1及交联剂M2之和与水的质量配比为5-20∶100。
进一步的改进是:所述的盐S3与单体M1及交联剂M2之和与水的质量配比为5-20∶100。
本发明的特点:
通过采用前述技术方案,本发明的有益效果是:
采用悬浮聚合的方法,通过在可聚合的单体中添加两亲性长链化合物及链转移试剂,使 得可聚合单体与稳定相混合后,两亲性长链化合物亲水端可吸收水分,在可聚合单体油相内 形成“微胶束”;当可聚合单体发生聚合的时候,两亲性长链化合物中亲水端吸收的水分被 “挤压”至聚合物主链外周,迫使含水部分互相聚集,形成水相聚集区;此外添加的链转移 剂调节聚合速率,控制相分离发生的快慢,且可调节可聚合单体的聚合度来控制主链分子量 大小;经胶束效应与相分离协同作用,可聚合单体聚合完全后,甲醇或乙醇或丙酮洗去未聚 合单体,烘干微球后,可得到中间是空腔的聚合物微球。此法还具有如下优点:合成方法简 单,容易控制、便于放大生产等优点,在生物医药检测,石油开采等领域具有潜在的应用价 值。
附图说明
图1是实施例2中得到中空聚合物微球的SEM图
具体实施方式
以下将结合具体实施例来详细说明本发明的实施方式,借此对本发明如何应用技术手段 来解决技术问题,并达成技术效果的实现过程能充分理解并据以实施。
若未特别指明,实施例中所采用的技术手段为本领域技术人员所熟知的常规手段,所采 用的试剂和产品也均为可商业获得的。所用试剂的来源、商品名以及有必要列出其组成成分 者,均在首次出现时标明。
实施例一
一种中空聚合物微球的制备方法,包括以下步骤:
(1)油相制备:
称取10g的苯乙烯,10g的二乙烯基苯,0.15g的偶氮二异丁腈,10g的司盘80,0.2g的己硫醇于烧杯中,搅拌均匀,备用。
(2)稳定相制备:
称取50g的去离子水于反应瓶中,继续加入1g的聚乙烯醇,升温至80℃,搅拌至聚乙 烯醇完全溶解,备用。
(3)聚合
称取4g的氯化钠于烧杯中,加入100g的去离子水,加入0.4g的SDS,搅拌至氯化钠完 全溶解,转移至反应瓶中;将上述的稳定相转移至反应瓶中;搅拌均匀;继续将上述的油性 单体转移至反应瓶中,在搅拌220rpm下,体系升温至80℃,保温反应8h;反应结束后,降至室温。
(4)清洗
将上述(3)中聚合物微球,过滤,用10倍量的乙醇清洗,烘干,即得平均粒径为43.3μm的中空聚合物微球。
实施例二
一种中空聚合物微球的制备方法,包括以下步骤:
(1)油相制备:
称取10g的苯乙烯,10g的二乙烯基苯,0.1g的过氧化苯甲酰,10g的司盘80,2g的己硫醇于烧杯中,搅拌均匀,备用。
(2)稳定相制备:
称取50g的去离子水于反应瓶中,继续加入1.5g的羟丙基纤维素,升温至80℃,搅拌 至羟丙基纤维素完全溶解,备用。
(3)聚合
称取4g的氯化钠于烧杯中,加入100g的去离子水,加入0.1g的SDS,搅拌至氯化钠完全溶解,转移至反应瓶中;将上述的稳定相转移至反应瓶中;搅拌均匀;继续将上述的油性单体转移至反应瓶中,在搅拌220rpm下,体系升温至80℃,保温反应8h;反应结束后, 降至室温。
(4)清洗
将上述(3)中聚合物微球,过滤,用10倍量的乙醇清洗,烘干,即得平均粒径为68.3μm的中空聚合物微球。
实施例三
一种中空聚合物微球的制备方法,包括以下步骤:
(1)油相制备:
称取10g的丙烯酸缩水甘油酯,25g的二乙二醇二甲基丙烯酸酯,0.18g的偶氮二异丁腈, 3.5g的司盘80,1.575g的3-巯基丙烯酸异辛酯于烧杯中,搅拌均匀,备用。
(2)稳定相制备:
称取50g的去离子水于反应瓶中,继续加入0.8g的β-环糊精,升温至80℃,搅拌至β-环糊精完全溶解,备用。
(3)聚合
称取1.75g的氯化钠于烧杯中,加入100g的去离子水,加入0.35g的曲拉通X-104,搅拌至氯化钠完全溶解,转移至反应瓶中;将上述的稳定相转移至反应瓶中;搅拌均匀; 继续将上述的油性单体转移至反应瓶中,在搅拌180rpm下,体系升温至80℃,保温反应 10h;反应结束后,降至室温。
(4)清洗
将上述(3)中聚合物微球,过滤,用10倍量的乙醇清洗,烘干,即得平均粒径为26.5μm的中空聚合物微球。
实施例四
一种中空聚合物微球的制备方法,包括以下步骤:
(1)油相制备:
称取10g的甲基苯乙烯,32g的二乙烯基苯,1.47g的偶氮二异丁基脒,4.2g的吐温65, 1.47g的己硫醇于烧杯中,搅拌均匀,备用。
(2)稳定相制备:
称取50g的去离子水于反应瓶中,继续加入0.8g的聚乙烯醇,升温至80℃,搅拌至聚 乙烯醇完全溶解,备用。
(3)聚合
称取1.75g的氯化钠及0.28g的磷酸二氢钠于烧杯中,加入100g的去离子水,加入0.21g 的SDS,搅拌至氯化钠及磷酸二氢钠完全溶解,转移至反应瓶中;将上述的稳定相转移至 反应瓶中;搅拌均匀;继续将上述的油性单体转移至反应瓶中,在搅拌180rpm下,体系升温至75℃,保温反应10h;反应结束后,降至室温。
(4)清洗
将上述(3)中聚合物微球,过滤,用10倍量的乙醇清洗,烘干,即得平均粒径为61.5μm的中空聚合物微球。
实施例五
一种中空聚合物微球的制备方法,包括以下步骤:
(1)油相制备:
称取10g的丙烯酸缩水甘油酯,5g的季戊四醇三丙烯酸酯,0.1g的偶氮二异丁腈,1.5g 的吐温60,1.5g的十二硫醇于烧杯中,搅拌均匀,备用。
(2)稳定相制备:
称取50g的去离子水于反应瓶中,继续加入1.8g的聚乙烯基吡咯烷酮,升温至80℃, 搅拌至聚乙烯基吡咯烷酮完全溶解,备用。
(3)聚合
称取1.15g的硫酸钠于烧杯中,加入100g的去离子水,加入0.15g的曲拉通X-104,搅拌至硫酸钠完全溶解,转移至反应瓶中;将上述的稳定相转移至反应瓶中;搅拌均匀; 继续将上述的油性单体转移至反应瓶中,在搅拌80rpm下,体系升温至80℃,保温反应 8h;反应结束后,降至室温。
(4)清洗
将上述(3)中聚合物微球,过滤,用10倍量的乙醇清洗,烘干,即得平均粒径为58.7μm的中空聚合物微球。
实施例六
一种中空聚合物微球的制备方法,包括以下步骤:
(1)油相制备:
称取10g的丙烯酸缩水甘油酯,10g的二乙烯基苯,0.1g的偶氮二异丁腈,1.5g的司盘 80,0.5g的3-巯基丙酸异辛酯于烧杯中,搅拌均匀,备用。
(2)稳定相制备:
称取50g的去离子水于反应瓶中,继续加入1.5g的聚乙烯醇及0.3g的羟基磷灰石,升 温至80℃,搅拌至聚乙烯醇完全溶解,备用。
(3)聚合
称取1.05g的氯化钠于烧杯中,加入100g的去离子水,加入0.2g的曲拉通X-104,搅拌至氯化钠完全溶解,转移至反应瓶中;将上述的稳定相转移至反应瓶中;搅拌均匀;继 续将上述的油性单体转移至反应瓶中,在搅拌120rpm下,体系升温至80℃,保温反应8h; 反应结束后,降至室温。
(4)清洗
将上述(3)中聚合物微球,过滤,用10倍量的乙醇清洗,烘干,即得平均粒径为64.7μm的中空聚合物微球。
实施例七
一种中空聚合物微球的制备方法,包括以下步骤:
(1)油相制备:
称取10g的苯乙烯,8g的二乙烯基苯,0.1g的偶氮二异丁基脒,1.8g的司盘80,0.5g的3-巯基丙酸异辛酯于烧杯中,搅拌均匀,备用。
(2)稳定相制备:
称取50g的去离子水于反应瓶中,继续加入1.5g的聚乙烯基吡咯烷酮,升温至80℃, 搅拌至聚乙烯基吡咯烷酮完全溶解,备用。
(3)聚合
称取1.45g的硝酸钠于烧杯中,加入100g的去离子水,加入0.2g的曲拉通X-104,搅拌至硝酸钠完全溶解,转移至反应瓶中;将上述的稳定相转移至反应瓶中;搅拌均匀;继 续将上述的油性单体转移至反应瓶中,在搅拌160rpm下,体系升温至60℃,保温反应18h; 反应结束后,降至室温。
(4)清洗
将上述(3)中聚合物微球,过滤,用10倍量的乙醇清洗,烘干,即得平均粒径为82.7μm的中空聚合物微球。
实施例八
一种中空聚合物微球的制备方法,包括以下步骤:
(1)油相制备:
称取10g的丙烯酸缩水甘油酯,90g的二缩三乙二醇二甲基丙烯酸酯,0.5g的过氧化苯 甲酰,10.0g的司盘80,1.5g的3-巯基丙酸异辛酯于烧杯中,搅拌均匀,备用。
(2)稳定相制备:
称取50g的去离子水于反应瓶中,继续加入2.1g的聚乙烯醇,升温至80℃,搅拌至聚 乙烯醇完全溶解,备用。
(3)聚合
称取0.575g的氯化钠于烧杯中,加入100g的去离子水,加入5.0g的曲拉通X-104,搅拌至氯化钠完全溶解,转移至反应瓶中;将上述的稳定相转移至反应瓶中;搅拌均匀; 继续将上述的油性单体转移至反应瓶中,在搅拌360rpm下,体系升温至70℃,保温反应 12h;反应结束后,降至室温。
(4)清洗
将上述(3)中聚合物微球,过滤,用10倍量的乙醇清洗,烘干,即得平均粒径为24.7μm的中空聚合物微球。
实施例九
一种中空聚合物微球的制备方法,包括以下步骤:
(1)油相制备:
称取10g的甲基丙烯酸缩水甘油酯,16g的二缩三乙二醇二甲基丙烯酸酯,0.11g的过 氧化苯甲酰,2.2g的司盘80,0.33g的3-巯基丙酸异辛酯于烧杯中,搅拌均匀,备用。
(2)稳定相制备:
称取50g的去离子水于反应瓶中,继续加入2.1g的聚乙烯醇,升温至80℃,搅拌至聚 乙烯醇完全溶解,备用。
(3)聚合
称取0.63g的氯化钠于烧杯中,加入100g的去离子水,加入0.2g的SDBS,搅拌至氯化钠完全溶解,转移至反应瓶中;将上述的稳定相转移至反应瓶中;搅拌均匀;继续将上 述的油性单体转移至反应瓶中,在搅拌240rpm下,体系升温至65℃,保温反应14h;反 应结束后,降至室温。
(4)清洗
将上述(3)中聚合物微球,过滤,用10倍量的乙醇清洗,烘干,即得平均粒径为8.3μm的中空聚合物微球。
Claims (4)
1.一种中空的聚合物微球的制备方法,其特征在于:包括以下步骤:
(1)油相制备:
称取适量的可聚合单体M1、交联剂M2、引发剂I1,两亲性长链物质S1、链转移剂C1于烧杯中,搅拌均匀,备用;
(2)稳定相制备:
将适量的稳定剂P1加入到去离子水,升温至50~80℃,待稳定剂完全溶解后,即得到含稳定剂P1的水相溶液;
(3)聚合
称取适量的盐S3于烧杯中,加入去离子水,溶解完全;加入乳化剂S2,分散均匀后,转移至反应瓶中;将(2)中得到的稳定相转移至反应瓶中,搅拌均匀,将(1)中得到的油相转移至反应瓶中,50-1000rpm搅拌转速下,升温至65-90℃,保温反应8-18h;反应结束后,降至室温。
(4)清洗
将(3)中得到的聚合物微球,抽滤掉反应液,用甲醇或乙醇或丙酮清洗未反应单体,烘干可得到中空聚合物微球。
2.根据权利要求1所述的一种中空聚合物微球的制备方法,其特征在于:所述的可聚合单体M1为苯乙烯、甲基苯乙烯、乙基苯乙烯、氯甲基苯乙烯、丙烯酸甲酯、丙烯酸丙酯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸季戊四醇酯、甲基丙烯酸缩水甘油酯、丙烯酸缩水甘油酯、甲基丙烯酸丁酯、甲基丙烯酸羟乙酯、丙烯酸羟乙酯中的任意一种或两种以上的混合物。所述交联剂M2为二乙烯基苯、二甲基丙烯酸乙二醇酯、三乙烯酸甘油酯、三羟甲基丙基三甲基丙烯酸、季戊四醇三丙烯酸酯、二乙二醇二甲基丙烯酸酯、二缩三乙二醇二甲基丙烯酸酯、三缩四乙二醇二甲基丙烯酸酯、1,3-丁二醇二甲基丙烯酸酯、1,4-丁二醇二甲基丙烯酸酯、六亚甲基双甲基丙烯酰胺、三甲基丙烯酸甘油酯、亚甲基丙烯酰胺中的任意一种或两种以上的混合物。所述引发剂I1为过氧化苯甲酰、偶氮二异丁腈、偶氮二异丁酸二甲酯、偶氮二异丁基脒中的任意一种或两种以上的混合物。所述两亲性长链物质S1为司盘85、司盘80、司盘65、司盘60、吐温80、吐温65中的任意一种或两种以上的混合物。所述链转移剂C1为十二硫醇、己硫醇、3-巯基丙酸甲酯、3-巯基丙酸异辛酯中的任意一种或两种以上的混合物。所述稳定剂P1是聚乙烯醇、聚乙二醇、聚乙烯吡咯烷酮、羟甲基纤维素、羟丙基纤维素、羟乙基纤维素、羧甲基纤维素、β-环糊精、β-甲基环糊精、羟基磷灰石中的任意一种或两种以上的混合物。所述的盐S3为氯化钠、硫酸钠、硝酸钠、磷酸钠、磷酸氢二钠、磷酸二氢钠中的任意一种或两种以上的混合物。所述乳化剂S2为离子型乳化剂、非离子型乳化剂中的任意一种或二者以任意比混合而成。所述离子型乳化剂为烷基苯磺酸盐、烷基磺酸盐、烷基丁二酸酯磺酸盐或烷基联苯基醚磺酸盐。
3.根据权利要求1所述的一种中空聚合物微球的制备方法,其特征在于:所述的交联剂M2与单体M1的质量配比为2.5-90∶10。所述的引发剂I1与单体M1及交联剂M2之和的质量配比为0.5-5∶100。所述的两亲性长链物质S1与单体M1及交联剂M2之和的质量配比为10-60∶100。所述的链转移剂C1与单体M1及交联剂M2之和的质量配比为0.5-20∶100。所述的稳定剂P1与单体M1及交联剂M2之和的质量配比为0.5-5∶100。所述的单体M1及交联剂M2之和与水的质量配比为5-20∶100。所述的盐S3与单体M1及交联剂M2之和与水的质量配比为5-20∶100。所述的乳化剂S2与单体M1及交联剂M2之和与水的质量配比为0.5-5∶100。
4.根据权利要求1所述的一种中空聚合物微球的制备方法,其特征在于:得到的微球的粒径为:0.5um~200um间。
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CN116478326A (zh) * | 2023-04-23 | 2023-07-25 | 厦门大学 | 一种聚丙烯酸酯微球及其应用 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103421253A (zh) * | 2012-05-17 | 2013-12-04 | 中国石油化工股份有限公司 | 聚苯乙烯空心微球的制备方法及其应用 |
CN107337759A (zh) * | 2016-03-17 | 2017-11-10 | 青岛大学 | 一种单孔中空聚合物微球及其制备方法 |
CN108623734A (zh) * | 2017-03-24 | 2018-10-09 | 南京工业大学 | 一种中空聚合物微球的制备方法 |
CN112341558A (zh) * | 2020-10-29 | 2021-02-09 | 深圳市优宝新材料科技有限公司 | 聚合物微球及其制备方法和润滑脂组合物 |
CN112724336A (zh) * | 2020-12-30 | 2021-04-30 | 王海涛 | 包封有功能芯材的核-壳型聚合物微球的制备方法 |
CN112808189A (zh) * | 2020-12-23 | 2021-05-18 | 西能化工科技(上海)有限公司 | 中空微球及其制备方法 |
-
2021
- 2021-12-20 CN CN202111566185.9A patent/CN114524967A/zh active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103421253A (zh) * | 2012-05-17 | 2013-12-04 | 中国石油化工股份有限公司 | 聚苯乙烯空心微球的制备方法及其应用 |
CN107337759A (zh) * | 2016-03-17 | 2017-11-10 | 青岛大学 | 一种单孔中空聚合物微球及其制备方法 |
CN108623734A (zh) * | 2017-03-24 | 2018-10-09 | 南京工业大学 | 一种中空聚合物微球的制备方法 |
CN112341558A (zh) * | 2020-10-29 | 2021-02-09 | 深圳市优宝新材料科技有限公司 | 聚合物微球及其制备方法和润滑脂组合物 |
CN112808189A (zh) * | 2020-12-23 | 2021-05-18 | 西能化工科技(上海)有限公司 | 中空微球及其制备方法 |
CN112724336A (zh) * | 2020-12-30 | 2021-04-30 | 王海涛 | 包封有功能芯材的核-壳型聚合物微球的制备方法 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116478326A (zh) * | 2023-04-23 | 2023-07-25 | 厦门大学 | 一种聚丙烯酸酯微球及其应用 |
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