CN108948274A - 一种毫米级聚合物复合微球的制备方法 - Google Patents
一种毫米级聚合物复合微球的制备方法 Download PDFInfo
- Publication number
- CN108948274A CN108948274A CN201810471609.5A CN201810471609A CN108948274A CN 108948274 A CN108948274 A CN 108948274A CN 201810471609 A CN201810471609 A CN 201810471609A CN 108948274 A CN108948274 A CN 108948274A
- Authority
- CN
- China
- Prior art keywords
- monomer
- polymer composite
- composite microsphere
- polymer
- added
- 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.)
- Pending
Links
- 239000004005 microsphere Substances 0.000 title claims abstract description 74
- 229920000642 polymer Polymers 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 38
- 229920006037 cross link polymer Polymers 0.000 claims abstract description 13
- 239000010954 inorganic particle Substances 0.000 claims abstract description 10
- 238000004090 dissolution Methods 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000008346 aqueous phase Substances 0.000 claims abstract description 4
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 10
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000011010 flushing procedure Methods 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 238000002242 deionisation method Methods 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 229940056319 ferrosoferric oxide Drugs 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 26
- 239000002253 acid Substances 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 230000005764 inhibitory process Effects 0.000 abstract description 4
- 239000003595 mist Substances 0.000 abstract description 4
- 239000003937 drug carrier Substances 0.000 abstract description 2
- 229920002223 polystyrene Polymers 0.000 description 16
- 239000004793 Polystyrene Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000011805 ball Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920006327 polystyrene foam Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 229940117958 vinyl acetate Drugs 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 102400000830 Saposin-B Human genes 0.000 description 1
- 101800001697 Saposin-B Proteins 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011553 magnetic fluid Substances 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- 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
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
-
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
Abstract
本发明公开了一种毫米级聚合物复合微球的制备方法,该方法将非交联聚合物溶解在单体中,得到聚合物单体溶液,然后加入油溶性引发剂,最后加入有机微球或无机颗粒,充分搅拌混合均匀后,采用悬浮聚合法在水相体系中进行聚合,制备毫米级聚合物复合微球;通过选用特定聚合物和相应的单体,并调整它们的种类或用量,以及被包覆的有机微球或无机颗粒的种类或用量,可制备出溶解性质不同、密度可调、粒径可控、机械强度可控、亲疏水可调和结构可控的直径范围在0.5~2.0mm之间的毫米级聚合物复合微球;可广泛应用于酸雾抑制、药物载体、催化剂负载等领域。
Description
技术领域
本发明涉及一种毫米级聚合物复合微球的制备方法,属于聚合物功能材料领域。
背景技术
复合微球由于其独特的结构和性能已经被广泛用于石油运输、药物载体、催化剂加载、磁流体和靶丸等领域。随着科学的发展和生产生活的需要,复合微球的种类日益丰富。其中,为了满足酸雾抑制剂、药物、催化剂加载以及靶丸等领域的需求,复合微球已经备受科学工作者的关注。
目前,制备复合微球的方法主要有分散聚合、悬浮聚合、膜乳化法等,这些方法最终能制备出具有特殊结构和性能(如:多孔、中空、多核、核-壳、密度可调控等)的单分散或宽分散的微米级复合微球。其中,采用传统的悬浮聚合制备的聚合物复合微球粒径分布很宽,要得到粒径集中的单分散的复合微球需要繁琐地分级处理,此外,该方法很难兼容无机材料制备出无机/有机复合微球。采用分散聚合法,亲水性单体和疏水性单体间的交联反应困难,因此制备复合高分子微球的种类受到限制,而且制备的复合微球的最大粒径也是微米级,难以突破毫米级,并且分散介质中含有大量的有机溶剂,对实际生产和应用造成一定的困难。对此,CN105924569A报道了一种采用预聚体悬浮聚合法制备多核包裹型复合微球的方法,该法先把溶有引发剂的单体进行本体预聚合,得到具有一定粘度的预聚物,并快速降温至室温,再把有机微球或无机颗粒加入该预聚物中,充分搅拌混合均匀后,然后把它分散在水相体系中进行悬浮聚合,最终得到多核包裹型复合微球。这种方法能够制备出毫米级的复合微球,但是这种方法本体聚合制备预聚物的粘度和转化率难以准确控制,若使用单体量很大,难以将高温预聚物快速降温,则反应存在一定危险。专利CN101691425A报道了一种利用废旧聚苯乙烯制备吸附性树脂材料的方法,该法先用苯乙烯单体溶解一定量的废旧聚苯乙烯,并以二乙烯基苯为交联剂、过氧化苯甲酰为引发剂、正庚烷为制孔剂、聚乙烯醇为稳定剂,通过聚合交联得到聚苯乙烯交联吸附材料,与其相关的报道还有CN:201110093502.X等;这种方法经济环保,但局限在有机/有机微球材料方面。
此外,乳液溶剂挥发法或膜乳化-乳液溶剂挥发法也是制备复合微球的一种较好的方法,专利CN105037603A、CN105126714A、CN1990522A等对这种方法进行了报道,它主要是用有机溶剂将一种或多种聚合物溶解,制备成有机溶液分散相,再借助孔径均一的多孔质玻璃膜管分散到分散介质中,制得粒径呈单分散稳定的乳状液,再通过抽提、扩散、加热等方法将有机溶剂从乳状液体系中除去,得到单分散高分子复合微球,最后经减压抽滤、离心等操作,即可从悬浮液中分离出聚合物复合微球。该方法在去除有机溶剂时会扩散到大气污染环境,或者要增加溶剂收集处理的工序,增加了生产成本和困难,此外,该类反应装置造价较高。
发明内容
本发明提供了一种过程简单、生产效率高、溶解性和机械性能等可调的毫米级聚合物复合微球的制备方法,本发明方法是将非交联聚合物溶解在单体中,得到聚合物单体溶液,然后加入油溶性引发剂,最后加入有机微球或无机颗粒,充分搅拌混合均匀后,采用悬浮聚合法在水相体系中进行聚合,制备毫米级聚合物复合微球。
该方法操作简单,安全环保,通用性强,并可实现大批量生产,能制备出具有特殊结构和性能(如:多孔、中空、多核、核-壳、密度可调控等)的毫米级聚合物复合微球,并能实现复合微球表面改性、溶解性质、力学性能、粒径、密度和结构等可调,因此更加优越。
在本方法中,通过选用特定聚合物和相应的单体,并调整它们的种类或用量,以及被包覆的有机微球或无机颗粒的种类或用量,可制备出溶解性质不同、密度可调、粒径可控、机械强度可控、亲疏水可调和结构可控的直径在0.5 ~2.0mm之间的毫米级聚合物复合微球;可根据实际需要,采用不同的单体组成可以制备一系列性能不同的聚合物复合微球。例如:选用交联单体时,所制备的微球具有耐高温、耐溶剂、强度高等特点;选用不同的有机微球或无机颗粒,所制备的聚合物复合微球具有易着色、高强度、密度可调等特点。
本发明的具体制备方法如下:
(1) 将非交联聚合物粉碎后,加入单体中使其溶解得到聚合物单体溶液,聚合物单体溶液中非交联聚合物质量浓度为5.0~50.0%,然后加入单体质量1.0~3.0%的油溶性引发剂;
(2) 向步骤(1)中制备的溶液加入其总质量5.0%~50.0%的有机微球或无机颗粒,充分搅拌混合均匀;
(3)将步骤(2)混匀后的聚合物溶液加入到含质量百分比1.0~3.0%聚乙烯醇的去离子水溶液中,聚合物溶液与聚乙烯醇去离子水溶液的质量比为1:3~1:5,在300转/分钟的转速下升温至65~75℃,反应4小时,然后再升温至85℃熟化1小时,经冷却、过滤、冲洗和干燥后得到毫米级聚合物复合微球。
所述聚合物单体溶液中非交联聚合物质量浓度为5.0~50.0%,其粘度在100~50000厘泊之间。
所述溶解非交联聚合物的单体可以是含单个烯键的非交联单体,如:苯乙烯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、醋酸乙烯酯、丙烯酸酯等,也可以是含两个双键的交联单体,如:二乙烯基苯、乙二醇双甲基丙烯酸酯等,溶解聚合物的单体可以是上述单体中的一种或几种混合单体。
所述的有机微球为交联聚合物微球,不能被单体溶液溶解,其粒径在10μm~500μm之间,最好为40μm ~200μm。
所述的机颗粒为碳酸钙、钛白粉、白炭黑、二氧化硅、四氧化三铁、炭黑和二氧化硅中的一种或多种,颗粒粒径在10μm ~100μm之间,最好为20μm ~40μm。
所述油溶性引发剂为偶氮二异丁腈或过氧化苯甲酰。
本发明中使用的胶体保护剂为聚乙烯醇。
本发明所制备的毫米级聚合物复合微球直径在0.5 ~2.0mm之间。
本发明有益效果:
本发明提供了一种通用性好且简便、经济、环保的用于制备毫米级聚合物复合微球的方法;通过控制聚合物单体溶液的浓度,进而控制单体溶液的初始粘度,实现微球的粒径初步控制,再混合有机微球或无机颗粒,可以制备具有溶解性质不同、粒径范围不同、机械强度不同、密度可调、亲疏水可调等特殊性能毫米级聚合物复合微球。同时,本发明制备单体溶液时,除了专门制备的聚合物,也可以选用聚合物废料(如:聚苯乙烯泡沫等)和加工聚合物成品时产生的边角料,把这些固体废料回收,并进行二次循环利用,不仅避免它们污染环境,而且节约资源,带来更大的经济效益。此外,本发明方法,工艺操作简单、安全,可批量化生产。用本发明方法制备的毫米级聚合物复合微球,具有多核、密度可调、粒径可调和力学性能良好等特点,在酸雾抑制、药物、催化剂加载以及靶丸等领域具有广泛的应用前景。
具体实施方式
下面通过实施例对本发明方法作进一步详细说明,但本发明保护范围不局限于所述内容。
实施例1:聚苯乙烯包覆炭黑粉末制备聚合物复合微球,具体配方见表1:
表1:
具体步骤如下:
(1)向一个50mL的烧杯中加入20.00g苯乙烯,再加入聚苯乙烯微球颗粒1.05g,搅拌使其完全溶解,然后加入0.40g偶氮二异丁腈,搅拌混合均匀;
(2)向步骤(1)制备的混合溶液中加入1.06g白炭黑颗粒(粒径范围70~100μm),充分搅拌混合均匀;
(3)向带有回流装置、搅拌器和加热装置的250mL三口反应瓶中,加入100.00g去离子水、1.00g PVA1788,搅拌使其完全溶解,停止搅拌,并加入步骤(2)中制备的混合溶液,在300转/分钟的转速下升温至75℃反应4小时,然后升温至85℃熟化1小时,经冷却、过滤、冲洗和干燥后,得到非交联聚苯乙烯包裹炭黑粉末的多核型复合微球。
制备得到的非交联聚苯乙烯包裹炭黑粉末的多核型复合微球,平均粒径0.5mm,多核结构明显,炭黑粉末均匀分散在聚合物微球内部。
实施例2:聚苯乙烯包覆白炭黑颗粒,制备交联聚合物复合微球;具体配方见表2。
表2:
具体步骤如下:
(1)向一个150mL的烧杯中加入60.00g苯乙烯、15.00g二乙烯基苯、25.00g聚苯乙烯微球颗粒,搅拌使其完全溶解,然后加入0.75g偶氮二异丁腈,搅拌溶解完全;
(2)向步骤(1)制备的聚合物单体溶液中加入15.00g白炭黑(粒径范围10μm ~50μm),充分搅拌,使物料混合均匀;
(3)向带有回流装置、搅拌器和加热装置的1L反应釜中,加入400.00g去离子水、8.00gPVA1788,搅拌使其完全溶解,停止搅拌,加入步骤(2)中制备的混合溶液,在300转/分钟的转速下并升温至70℃反应4小时,然后升温至85℃熟化1小时,经冷却、过滤、冲洗和干燥后,得到交联聚苯乙烯包裹白炭黑的多核型白色复合微球。
制备的聚合物复合微球的平均粒径1.20mm,多核结构明显,白炭黑颗粒均匀分散在聚合物微球内部。
实施例3:采用废弃聚苯乙烯泡沫板包裹四氧化三铁粉末颗粒,制备聚合物复合微球。具体配方见表3;
表3:
具体步骤如下:
(1)取废弃聚苯乙烯泡沫板,洗净晾干,并粉碎成小碎片,向一个100mL的烧杯中加入5.00g乙酸乙烯酯、30.00g苯乙烯、35.00g废弃聚苯乙烯泡沫,搅拌使其完全溶解,然后加入1.05g过氧化二苯甲酰,搅拌溶解完全;
(2)向步骤(1)制备的聚合物混合溶液中加入35.0g四氧化三铁(粒径范围30μm ~60μm),充分搅拌,使物料混合均匀;
(3)向带有回流装置、搅拌器和加热装置的1L反应釜中,加入210.00g去离子水、6.3gPVA1788,搅拌使其完全溶解,停止搅拌,接着加入步骤(2)中制备的混合溶液,保持300转/分钟的转速下并升温至65℃反应4小时,然后升温至85℃熟化1小时,经冷却、过滤、冲洗和干燥后,得到聚苯乙烯/乙酸乙烯酯-苯乙烯共聚物包裹四氧化三铁粉末的复合微球。
制备的聚合物复合微球的平均粒径为2.0mm,多核结构明显,四氧化三铁粉末均匀分散在聚合物微球内部。
实施例4:聚甲基丙烯酸甲酯包覆交联聚苯乙烯中空微球,制备多核型低密度复合微球,具体配方见表4;
表4:
具体步骤如下:
(1)向一个50mL的烧杯中加入20.00g甲基丙烯酸甲酯、16.00g聚甲基丙烯酸甲酯,搅拌使其完全溶解,然后加入0.40g偶氮二异丁腈,搅拌混合均匀;
(2)向步骤(1)中制备的溶液加入3.60g交联聚苯乙烯中空微球,充分搅拌,使物料混合均匀;
(3)向带有回流装置、搅拌器和加热装置的250ml三口反应瓶中,加入150.00g去离子水、2.40g PVA1788,搅拌使其完全溶解,停止搅拌,加入步骤(2)中的混合溶液,在300转/分钟的转速下并升温至70℃反应4小时,然后升温至85℃熟化1小时,经冷却、过滤、冲洗和干燥后,得到非交联聚甲基丙烯酸甲酯包裹交联聚苯乙烯中空微球的多核型低密度复合微球。
制备的聚合物复合微球的平均粒径为2.0mm,核基本被聚集包覆在微球中央,核壳结构明显,把球放于水中浸泡30天,无沉球,说明该多核型低密度复合微球密度低于1g/cm3。可以应用于酸雾抑制、石油运输等行业。
实施例5:聚苯乙烯包埋交联聚甲基丙烯酸甲酯多孔微球和钛白粉,制备聚合物复合微球。具体配方见表5;
表5:
具体步骤如下:
(1)取一个100mL的烧杯,加入4.00g聚苯乙烯、50.0g苯乙烯,搅拌使其完全溶解,然后加入1.00g偶氮二异丁腈,搅拌混合均匀,制得混合单体溶液;
(2)向步骤(1)中制备的溶液加入11.0g交联聚甲基丙烯酸甲酯多孔微球(粒径范围40μm~60μm),充分搅拌,使物料混合均匀;
(3)向带有回流装置、搅拌器和加热装置的500mL三口反应瓶中加入216.00g去离子水,5.40g PVA1788,搅拌使其完全溶解,停止搅拌,并加入步骤(1)中制备的混合单体溶液,保持300转/分钟的转速下并升温至75℃反应4小时,然后再升温至85℃熟化1小时,经冷却、过滤、冲洗和干燥后,得到包埋交交联聚甲基丙烯酸甲酯多孔微球的复合微球。
制备的聚合物复合微球的平均粒径为1.2mm,核基本被聚集包覆在微球中央。把球放于水中浸泡30天,无沉球,说明该多核型低密度复合微球密度低于1g/cm3;可以应用于酸雾抑制等行业。
Claims (6)
1.一种毫米级聚合物复合微球的制备方法,其特征在于:将非交联聚合物溶解在单体中,得到聚合物单体溶液,然后加入油溶性引发剂,最后加入有机微球或无机颗粒,充分搅拌混合均匀后,采用悬浮聚合法在水相体系中进行聚合,制备毫米级聚合物复合微球。
2.根据权利要求1所述的毫米级聚合物复合微球的制备方法,其特征在于,按以下具体步骤进行:
(1)将非交联聚合物粉碎后,加入单体中使其溶解得到聚合物单体溶液,然后加入单体质量1.0~3.0%的油溶性引发剂;
(2)向步骤(1)中制备的溶液加入其总质量1.0%~50.0%的有机微球或无机颗粒,充分搅拌混合均匀;
(3)将步骤(2)混匀后的聚合物溶液加入到含质量百分比1.0~3.0%聚乙烯醇的去离子水溶液中,聚合物溶液与聚乙烯醇去离子水溶液的质量比为1:3~1:5,在300转/分钟的转速下升温至65~75℃,反应4小时,然后再升温至85℃熟化1小时,经冷却、过滤、冲洗和干燥后得到毫米级聚合物复合微球。
3.根据权利要求1或2所述的毫米级聚合物复合微球的制备方法,其特征在于:聚合物单体溶液中非交联聚合物的质量浓度为5.0~50.0%。
4.根据权利要求1或2所述的毫米级聚合物复合微球的制备方法,其特征在于:溶解非交联聚合物的单体为苯乙烯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、醋酸乙烯酯、丙烯酸酯、二乙烯基苯、乙二醇双甲基丙烯酸酯中的一种或任意比几种。
5.根据权利要求1或2所述的毫米级聚合物复合微球的制备方法,其特征在于:有机微球为交联聚合物微球,不能被单体溶液溶解,其粒径在10μm~500μm之间。
6.根据权利要求1或2所述的毫米级聚合物复合微球的制备方法,其特征在于:无机颗粒为碳酸钙、钛白粉、白炭黑、二氧化硅、四氧化三铁、炭黑和二氧化硅中的一种或几种,颗粒粒径在10μm ~100μm之间。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810471609.5A CN108948274A (zh) | 2018-05-17 | 2018-05-17 | 一种毫米级聚合物复合微球的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810471609.5A CN108948274A (zh) | 2018-05-17 | 2018-05-17 | 一种毫米级聚合物复合微球的制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN108948274A true CN108948274A (zh) | 2018-12-07 |
Family
ID=64499185
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810471609.5A Pending CN108948274A (zh) | 2018-05-17 | 2018-05-17 | 一种毫米级聚合物复合微球的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108948274A (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110003517A (zh) * | 2019-04-04 | 2019-07-12 | 河北科技大学 | 一种改性多孔聚苯乙烯磁性微球及其制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102731727A (zh) * | 2011-04-14 | 2012-10-17 | 湖北大学 | 由废旧聚苯乙烯泡沫塑料制造热熔树脂的新工艺 |
CN105924569A (zh) * | 2016-05-16 | 2016-09-07 | 昆明理工大学 | 一种多核包裹型复合微球的制备方法 |
-
2018
- 2018-05-17 CN CN201810471609.5A patent/CN108948274A/zh active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102731727A (zh) * | 2011-04-14 | 2012-10-17 | 湖北大学 | 由废旧聚苯乙烯泡沫塑料制造热熔树脂的新工艺 |
CN105924569A (zh) * | 2016-05-16 | 2016-09-07 | 昆明理工大学 | 一种多核包裹型复合微球的制备方法 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110003517A (zh) * | 2019-04-04 | 2019-07-12 | 河北科技大学 | 一种改性多孔聚苯乙烯磁性微球及其制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105924569B (zh) | 一种多核包裹型复合微球的制备方法 | |
CN104624132B (zh) | 环氧树脂自修复微胶囊及其制备方法 | |
CN101508823B (zh) | 一种室温快速自修复型聚合物复合材料 | |
KR101190383B1 (ko) | 초저밀도 열적 피복 미세구 | |
CN105854745B (zh) | 一种通过聚合物预包覆制备微胶囊的方法 | |
CN107529536B (zh) | 一种弱极性松香基高分子微球及其制备方法和应用 | |
JPH0635483B2 (ja) | 架橋コポリマーの製造方法 | |
JP2020510745A (ja) | 親水性ポリマーを含有する高内相エマルションから調製する多孔性架橋親水性ポリマー材料 | |
JP4714780B2 (ja) | 単孔中空ポリマー微粒子の製造方法 | |
CN106046229A (zh) | 一种相变微球及其制备方法 | |
CN108097182A (zh) | 一种超细环保热膨胀微胶囊及其制备方法 | |
Wang et al. | Preparation and properties of bisphenol A epoxy resin microcapsules coated with melamine–formaldehyde resin | |
CN106349421A (zh) | 一种高分子微球及其制备方法 | |
Wu et al. | One-pot efficient preparation of microcapsules based on photopolymerization for self-healing coatings | |
CN105131163B (zh) | 一种voc吸收剂及其制备方法 | |
EP2283047B1 (en) | Filled nanoparticles | |
CN108948274A (zh) | 一种毫米级聚合物复合微球的制备方法 | |
CN111662412A (zh) | 一种均一粒径高分子微球的制备方法 | |
EP3279284A1 (en) | Heat-expandable microspheres | |
CN105080442A (zh) | 一种包覆异氰酸酯微胶囊的制备方法 | |
CN104874338A (zh) | 石油树脂作壁材原料制备疏水性芯材微胶囊的方法 | |
Lee et al. | Synthesis and characteristics of poly (methyl methacrylate‐co‐methacrylic acid)/poly (methacrylic acid‐co‐N‐isopropylacrylamide) thermosensitive semi‐hollow latex particles and their application to drug carriers | |
CN110721644A (zh) | 一种乙烯基聚合物微胶囊的辐射制备方法 | |
Kim et al. | Morphologies of microparticles of partially neutralized sodium polyacrylate by inverse suspension polymerization | |
CN115417940A (zh) | 一种聚合物多孔微球及其制备方法 |
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 | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181207 |