CN107118296B - 一种具有可控薄荷醇包覆量的高分子树脂复合微球及其制备方法 - Google Patents
一种具有可控薄荷醇包覆量的高分子树脂复合微球及其制备方法 Download PDFInfo
- Publication number
- CN107118296B CN107118296B CN201610893255.4A CN201610893255A CN107118296B CN 107118296 B CN107118296 B CN 107118296B CN 201610893255 A CN201610893255 A CN 201610893255A CN 107118296 B CN107118296 B CN 107118296B
- Authority
- CN
- China
- Prior art keywords
- menthol
- controllable
- added
- complex microsphere
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/08—Copolymers of styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
Abstract
本发明提供了一种具有可控薄荷醇包覆量的高分子树脂复合微球及其制备方法。本发明通过在合成自由基聚合法合成高分子微球的过程中加入薄荷醇,直接通过单体的溶解作用将薄荷醇溶解在单体中,然后通过油‑水界面聚合,实现薄荷醇的可控包覆,并获得尺寸均匀的功能微球。该复合微球具有薄荷醇分布均匀、包覆量可控、锁香能力强的优势,可用于薄荷香烟制品,实现薄荷醇香烟等的薄荷醇缓慢释放的目的,极大地改善在香烟的生产、贮存以及运输过程中香味不稳定,容易流失等缺点。本发明方法简单,原料易得,适于放大生产。
Description
技术领域
本发明属于先进功能纳米复合材料的技术领域,具体涉及一种具有可控薄荷醇包覆量的高分子树脂复合微球及制备方法。
背景技术
薄荷醇又名薄荷脑是一种天然香精,可以从许多天然植物中提取。薄荷醇作为清凉剂被广泛应用于食品、香水等产品中。此外,由于薄荷醇具有良好的药理作用,医药上广泛将薄荷醇作为刺激药,内服可用于治疗头痛及鼻、咽、喉炎症;外用于皮肤或粘膜,具有清凉止痒作用等。在产品制备过程中,薄荷脑清凉剂往往是作为添加剂直接溶解或机械混合于一定的基质中使用的,其保存稳定性差,在使用过程中释放速度过快,耐久性差。在现代医药和药剂的研发方面,许多药物如抗肿瘤药物、强刺激性的药物等都需要进行微包囊化处理,对药物进行封装,发展具有缓释功能,达到持久释放和治疗目的。在发展薄荷清凉剂产品方面,同样需要开发新型制备工艺来提高其使用性能。孙鹏宇等人采用明胶乳状液和乙基纤维素作为包衣剂制备了缓释型胶囊薄荷醇。王璐等人采用脂肪作为壁材,制备了缓释型风味微胶囊化薄荷油产品。但是,这些微包囊制备步骤较多,而且薄荷醇的释放速率较难控制。高分子聚合物材料具有分子量可控、交联程度可控、亲疏水性可调节等特点,同时其分子网络易于修饰、骨架机械稳定性高,十分适合于包覆薄荷醇,通过一定的工艺将薄荷醇清凉剂包覆在高分子聚合物中,有利于提高薄荷醇的挥发稳定性,提高清凉剂产品的品质。(Xu,C.J.;Yu,D.Q.Acta Chim.Sinica 1976,34,275.Yang,Z.X.;Gong,Y.K.ActaChim.Sinica 2011,69,508.Li,Z.Q.;Jian,J.;Cao,X.L.;Song,X.W.;Wu,F.P.ActaChim.Sinica 2010,68,181.Xia,K.J.;Sheng,R.L.;Zhu,Y.D.;Li,H.;Luo,T.;Xu,Y.H.;Cao,A.M.Acta Chim.Sinica 2010,68,1130.Augustin,M.A.;Sanguansri,L.;Margetts,C.Food Australia,2001,53,220.Sun,P.Y.M.S.Thesis,Jiangnan University,Wuxi,2013.Sun,P.Y.;Zeng,M.M.;He,Z.Y.;Qin,F.;Chen,J.Food and Fermentation Industry,2013,15,84.Wang,L.;Xiao,G.;Xu,S.Y.Food and Fermentation Industry,2000,26,28.)
无皂乳液聚合由于在聚合过程中完全不加或仅加入微量乳化剂(其浓度小于临界胶束浓度CMC),因而可以得到表面洁净、单一分散的乳胶粒,同时避免了乳化剂对环境的污染。与传统的乳液聚合相比,无皂乳液聚合产物具有3个特点:(1)免去了去乳化剂的后处理,产品可直接使用;(2)聚合物乳胶粒的表面洁净,从而避免了乳化剂对聚合物产品电性能、光性能、表面性质、耐水性及成膜性等的不良影响;(3)所得到的聚合物乳胶粒子的粒径单分散性好,且较常规乳液聚合的粒子大。(蔡晓音,王直刚.无皂乳液聚合体系稳定性的研究与发展[J].炼油与化工,2005,16(3):10-12)
发明内容
本发明的目的在于提供一种具有可控薄荷醇包覆量的高分子树脂复合微球及其制备方法。
本发明所提供的具有可控薄荷醇包覆量的高分子树脂复合微球(小球),是一种以丰富的高分子网络为包覆位点,通过氢键将薄荷醇均匀地包覆在高分子树脂微球中。
本发明提出的一种具有可控薄荷醇包覆量的高分子树脂复合微球的制备方法,由以下步骤制得:首先在反应容器中加入一定量的去离子水,加入适量的单体(如有共聚单体,也一并加入),加入一定量的薄荷醇。通氮气,排出体系中的氧气。之后,将温度升高至引发剂分解温度,注入引发剂的水溶液,反应开始。若反应温度较高,须配备回流冷凝装置。反应一段时间后,可以通过离心、抽滤、板框压滤机压滤等手段将树脂微球分离出来,用水洗涤三次后,可除尽残余单体。最后得到的就是可控薄荷醇包覆量的高分子树脂复合微球。
本发明中,所述的薄荷醇是左旋薄荷醇。
本发明中,高分子复合微球是由丙烯酸、甲基丙烯酸、丙烯酸甲酯、甲基丙烯酸甲酯、苯乙烯、甲基丙烯酰氧乙基三甲基氯化铵等单体中的一种均聚或多种共聚所得。
本发明中,所述的引发剂是2,2'-偶氮二异丁腈米二盐酸盐(AIBA)、过硫酸钾、过硫酸铵、异丙苯过氧化氢、过氧化二苯甲酰、偶氮二异丁腈、过氧化氢和亚铁盐、过硫酸盐和亚铁盐、过硫酸盐和硫代硫酸盐等。
本发明中,所制得的可控薄荷醇包覆量的高分子树脂复合微球的粒径为80nm-2μm,薄荷醇的重量百分比在5%-50wt%范围内可调。优选粒径为500nm-900nm,薄荷醇的重量百分比在20%-30wt%范围内.如若在高温条件下使薄荷醇挥发,便得到具有丰富微孔网络的高分子树脂复合微球。
本发明中,去除残余单体的方法是将得到的包覆有薄荷醇的高分子树脂复合微球分散在去离子水中,搅拌,通过离心分离、板框压滤机压滤或抽滤的方法除去溶有残余单体的水得到树脂复合微球,如此重复操作3次。
本发明通过在合成自由基聚合法合成高分子微球的过程中加入薄荷醇,直接通过单体的溶解作用将薄荷醇溶解在单体中,然后通过油-水界面聚合,实现薄荷醇的可控包覆,并获得尺寸均匀的功能微球。该复合微球具有薄荷醇分布均匀、包覆量可控、锁香能力强的优势,可用于薄荷香烟制品,实现薄荷醇香烟等的薄荷醇缓慢释放的目的,极大地改善在香烟的生产、贮存以及运输过程中香味不稳定,容易流失等缺点。本发明方法简单,原料易得,适于放大生产。
附图说明:
图1:包覆薄荷醇的聚甲基丙烯酸微球微球的扫描电镜照片(A)和包覆薄荷醇的聚甲基丙烯酸树脂微球的透射电镜照片(B)
具体实施方式
以下对本发明进一步描述:
实施例1:
在1000mL三口烧瓶中,加入380mL去离子水,机械搅拌,搅拌速度为200rpm,加入35mL甲基丙烯酸甲酯(MMA),5mL丙烯酸,加入3.5mL二甲基丙烯酸乙二醇酯(EGDMA),继续搅拌10min后,称取20g薄荷醇加入到三口烧瓶中。在体系中通入氮气除氧,半个小时后,将温度升高至75℃,等温度升高至75℃并且稳定后,向体系注射20ml的2,2'-偶氮二异丁基脒二盐酸盐(AIBA)水溶液(含AIBA 4g),触发聚合反应。反应24h以后,停止加热,继续搅拌至整个体系冷却至室温。通过离心或抽滤或板框压滤器压滤的方法收集包覆薄荷醇的高分子树脂微球,用水洗涤三遍。得到的薄荷醇/高分子树脂复合微球粒径为300nm,薄荷醇的负载量为33%。
实施例2:
在1000mL三口烧瓶中,加入400mL去离子水,机械搅拌,搅拌速度为200rpm,加入45mL苯乙烯单体,加入5mL二乙烯基苯(DVB),继续搅拌10min后,称取10g薄荷醇加入,称取0.5g过氧化二苯甲酰加入反应体系。在体系中通入氮气除氧,半个小时后,将温度升高至70℃,触发聚合反应。反应24h以后,停止加热,继续搅拌至整个体系冷却至室温。通过离心或抽滤或板框压滤器压滤的方法收集包覆薄荷醇的高分子树脂微球,用水洗涤三遍。得到的薄荷醇/高分子树脂复合微球具有良好的分散性,可以稳定分散在三醋酸甘油酯等溶剂中,微球粒径为900nm,薄荷醇负载量为18%。
实施例3:
在1000mL三口烧瓶中,加入400mL去离子水,机械搅拌,搅拌速度为200rpm,加入25mL丙烯酸甲酯(MA)和10mL甲基丙烯酸(MAA),加入5mL二甲基丙烯酸乙二醇酯(EGDMA),继续搅拌10min后,称取25g薄荷醇加入,称取1g偶氮二异丁腈(AIBN)加入反应体系。在体系中通入氮气除氧,半个小时后,将温度升高至65℃,触发聚合反应。反应24h以后,停止加热,继续搅拌至整个体系冷却至室温。通过离心或抽滤或板框压滤器压滤的方法收集包覆薄荷醇的高分子树脂微球,用水洗涤三遍。得到的薄荷醇/高分子树脂复合微球具有良好的分散性,可以稳定分散在三醋酸甘油酯等溶剂中,微球粒径1.8μm,薄荷醇负载量为39%。
实施例4:
在1000mL三口烧瓶中,加入380mL去离子水,机械搅拌,搅拌速度为200rpm,加入5mL甲基丙烯酸甲酯(MMA)和25mL甲基丙烯酰氧乙基三甲基氯化铵(MTC),加入5mL二甲基丙烯酸乙二醇酯(EGDMA),继续搅拌10min后,称取30g薄荷醇加入到三口烧瓶中。在体系中通入氮气除氧,半个小时后,将温度升高至75℃,等温度升高至75℃并且稳定后,向体系注射20ml的过硫酸铵水溶液(含过硫酸铵3g),触发聚合反应。反应24h以后,停止加热,继续搅拌至整个体系冷却至室温。通过离心或抽滤或板框压滤器压滤的方法收集包覆薄荷醇的高分子树脂微球,用水洗涤三遍。得到的薄荷醇/高分子树脂复合微球具有良好的分散性,可以稳定分散在三醋酸甘油酯等溶剂中,微球粒径80nm,薄荷醇负载量为43%。
实施例5:
在1000mL三口烧瓶中,加入380mL去离子水,机械搅拌,搅拌速度为200rpm,加入25mL甲基丙烯酸甲酯(MMA)和5mL甲基丙烯酸(MA),加入3mL二甲基丙烯酸乙二醇酯(EGDMA),继续搅拌10min后,称取10g薄荷醇加入到三口烧瓶中。在体系中通入氮气除氧,半个小时后,向体系注射10ml的过硫酸铵水溶液(含过硫酸铵1g),之后向体系注射10mL的硫酸亚铁水溶液(含硫酸亚铁1.1g),触发聚合反应。反应24h以后,通过离心或抽滤或板框压滤器压滤的方法收集包覆薄荷醇的高分子树脂微球,用水洗涤三遍。得到的薄荷醇/高分子树脂复合微球具有良好的分散性,可以稳定分散在三醋酸甘油酯等溶剂中,微球粒径500nm,薄荷醇负载量为24%。
复合高分子微球的扫描电子显微镜照片和透射电子显微镜照片见图1。
Claims (2)
1.一种具有可控薄荷醇包覆量的高分子树脂微球的制备方法,其特征在于:在合成高分子微球的过程中,于单体引入反应体系之后,加入可溶于单体的薄荷醇,之后加入引发剂,启动无皂乳液聚合聚合反应;聚合过程中,由于氢键作用薄荷醇分子能够均匀地包覆到高分子网络中,即得到具有可控薄荷醇包覆量的高分子树脂复合微球;
其中,高分子是线型高分子或体型高分子;
单体是甲基丙烯酸甲酯、丙烯酸、甲基丙烯酸、丙烯酸甲酯、苯乙烯、甲基丙烯酰氧乙基三甲基氯化铵中的一种或几种;
引发剂是偶氮二异丁腈、2,2’-偶氮二异丁基脒二盐酸盐、过氧化二苯甲酰、过硫酸钾、过硫酸铵、异丙苯过氧化氢、过氧化氢和亚铁盐、过硫酸盐和亚铁盐、过硫酸盐和硫代硫酸盐;
在15℃~80℃的温度条件下均可合成;
交联剂是二乙烯基苯(DVB)或二甲基丙烯酸乙二醇酯(EGDMA);
在整个反应体系中,单体质量比在1%~15%,交联剂用量为0.05%~3%,引发剂用量为0.02%~1.5%,薄荷醇用量为0.7%~10%,其余为水;
所得到的微球是单分散的,具有均匀的粒径,粒径在500nm~900nm范围内可控;
所使用的薄荷醇为左旋薄荷醇;
薄荷醇的包覆量以重量百分比计,在20%-30%范围内可调;
去除残余单体的方法是将得到的包覆有薄荷醇的高分子树脂复合微球分散在去离子水中,搅拌,通过离心分离、板框压滤机压滤或抽滤的方法除去溶有残余单体的水得到树脂复合微球,如此重复操作3次。
2.根据权利要求1所述的具有可控薄荷醇包覆量的高分子树脂微球的制备方法,其特征在于:
在1000mL三口烧瓶中,加入380mL去离子水,机械搅拌,搅拌速度为200rpm,加入35mL甲基丙烯酸甲酯(MMA),5mL丙烯酸,加入3.5mL二甲基丙烯酸乙二醇酯,继续搅拌10min后,称取20g薄荷醇加入到三口烧瓶中;在体系中通入氮气除氧,半个小时后,将温度升高至75℃,等温度升高至75℃并且稳定后,向体系注射20ml的2,2'-偶氮二异丁基脒二盐酸盐、含AIBA4g的水溶液,触发聚合反应;反应24h以后,停止加热,继续搅拌至整个体系冷却至室温;通过离心或抽滤或板框压滤器压滤的方法收集包覆薄荷醇的高分子树脂微球,用水洗涤三遍,得到的薄荷醇/高分子树脂复合微球。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610893255.4A CN107118296B (zh) | 2016-10-13 | 2016-10-13 | 一种具有可控薄荷醇包覆量的高分子树脂复合微球及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610893255.4A CN107118296B (zh) | 2016-10-13 | 2016-10-13 | 一种具有可控薄荷醇包覆量的高分子树脂复合微球及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107118296A CN107118296A (zh) | 2017-09-01 |
CN107118296B true CN107118296B (zh) | 2019-11-01 |
Family
ID=59717831
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610893255.4A Active CN107118296B (zh) | 2016-10-13 | 2016-10-13 | 一种具有可控薄荷醇包覆量的高分子树脂复合微球及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107118296B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023202969A1 (en) * | 2022-04-20 | 2023-10-26 | Basf Se | Antibacterial polymer and process of preparing the same |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101309746A (zh) * | 2005-08-22 | 2008-11-19 | 塔格拉生物科技有限公司 | 单层和多层微胶囊的制备方法 |
CN102746450A (zh) * | 2012-07-25 | 2012-10-24 | 浙江理工大学 | 一种自粘性的长效缓释精油微胶囊及其制备方法和应用 |
CN103442727A (zh) * | 2011-02-11 | 2013-12-11 | Zx制药有限责任公司 | 多微粒l-薄荷醇制剂及相关方法 |
CN105854745A (zh) * | 2016-04-15 | 2016-08-17 | 广州秘理普植物技术开发有限公司 | 一种通过聚合物预包覆制备微胶囊的方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4456882B2 (ja) * | 2004-01-29 | 2010-04-28 | 三洋化成工業株式会社 | 熱膨張性マイクロカプセル |
JP2005213379A (ja) * | 2004-01-29 | 2005-08-11 | Sanyo Chem Ind Ltd | 熱膨張性マイクロカプセル |
-
2016
- 2016-10-13 CN CN201610893255.4A patent/CN107118296B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101309746A (zh) * | 2005-08-22 | 2008-11-19 | 塔格拉生物科技有限公司 | 单层和多层微胶囊的制备方法 |
CN103442727A (zh) * | 2011-02-11 | 2013-12-11 | Zx制药有限责任公司 | 多微粒l-薄荷醇制剂及相关方法 |
CN102746450A (zh) * | 2012-07-25 | 2012-10-24 | 浙江理工大学 | 一种自粘性的长效缓释精油微胶囊及其制备方法和应用 |
CN105854745A (zh) * | 2016-04-15 | 2016-08-17 | 广州秘理普植物技术开发有限公司 | 一种通过聚合物预包覆制备微胶囊的方法 |
Also Published As
Publication number | Publication date |
---|---|
CN107118296A (zh) | 2017-09-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107550921B (zh) | 一种纳米颗粒-高分子可注射复合水凝胶双载药体系及其制备方法 | |
CN103588920B (zh) | 单分散多孔聚合物纳米微囊的新型制备方法 | |
CN1423661A (zh) | 包括有气味组分的聚合纳米粒子 | |
CN102010488B (zh) | 一种温敏性可降解微水凝胶及其制备和应用 | |
CN107854449A (zh) | 一种具有药物控释性能的纳米复合微球及其制备方法和应用 | |
CN104558421A (zh) | 一种具有pH/温度响应性的接枝纤维素药用分子制备方法 | |
CN105646891A (zh) | 一种两亲性三元分子刷聚合物及其构筑的蠕虫状单分子胶束 | |
CN103304733A (zh) | 一种可降解环境响应性聚合物纳米水凝胶的制备方法和应用 | |
CN103965421A (zh) | 一种具有核壳结构的温敏性两亲嵌段共聚物的制备方法及其产品 | |
CN106519152B (zh) | 一种聚合物纳米粒子、复合水凝胶及其制备方法 | |
CN103483601B (zh) | 一种聚合物纳米微球的制备方法 | |
CN102603962B (zh) | 一种表面功能化的多孔异形微球的制备方法 | |
CN107118296B (zh) | 一种具有可控薄荷醇包覆量的高分子树脂复合微球及其制备方法 | |
CN105085939B (zh) | 三维结构且具有电刺激和pH响应的聚吡咯/海藻酸盐凝胶的制备及双重控制药物释放 | |
CN105859958A (zh) | 智能型树枝化聚合物、其纳米凝胶及其制备方法 | |
CN106947026A (zh) | 一种利用双表面活性剂制备单分散聚苯乙烯微球的方法 | |
CN103191441B (zh) | 一种刺激响应型酯化纳米纤维素前药缓释材料的制备方法 | |
CN104721140B (zh) | 具有靶向可控释药和栓塞效应的两亲离子型载药囊泡的制备方法 | |
CN1331590C (zh) | 一种制备中空微胶囊的方法 | |
CN102617772B (zh) | 一种用于重金属离子水处理的聚苯乙烯微球的制备方法 | |
CN101457007B (zh) | 一种多头型聚合物复合微球及其制备方法 | |
CN102936390B (zh) | 胶原蛋白-g-聚合物/Ag多孔纳米抗菌薄膜材料及制备方法 | |
CN104193905A (zh) | 一种通过raft聚合诱导大分子自组装制备颗粒乳化剂的方法 | |
CN104288123A (zh) | 一种负载干扰素微胶囊的制备方法 | |
CN109078008A (zh) | 氧化石墨烯药物载体中空微胶囊的制备及应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |