CN114736231B - 一种有机硅改性焦性没食子酸杀菌剂及其制备方法 - Google Patents
一种有机硅改性焦性没食子酸杀菌剂及其制备方法 Download PDFInfo
- Publication number
- CN114736231B CN114736231B CN202210430410.4A CN202210430410A CN114736231B CN 114736231 B CN114736231 B CN 114736231B CN 202210430410 A CN202210430410 A CN 202210430410A CN 114736231 B CN114736231 B CN 114736231B
- Authority
- CN
- China
- Prior art keywords
- pyrogallic acid
- bactericide
- modified
- pyrogallic
- preparation
- 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
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 37
- 239000003899 bactericide agent Substances 0.000 title claims abstract description 30
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 18
- 239000010703 silicon Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- -1 silicon modified pyrogallic acid Chemical class 0.000 title claims description 11
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical class OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims abstract description 75
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000002390 rotary evaporation Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 17
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 17
- SWGZAKPJNWCPRY-UHFFFAOYSA-N methyl-bis(trimethylsilyloxy)silicon Chemical compound C[Si](C)(C)O[Si](C)O[Si](C)(C)C SWGZAKPJNWCPRY-UHFFFAOYSA-N 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims 2
- 229910015900 BF3 Inorganic materials 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 230000001954 sterilising effect Effects 0.000 abstract description 13
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 9
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical class OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 6
- 244000005700 microbiome Species 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 4
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 4
- 235000010703 Modiola caroliniana Nutrition 0.000 description 4
- 244000038561 Modiola caroliniana Species 0.000 description 4
- 239000008294 cold cream Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 229920001817 Agar Polymers 0.000 description 3
- 241000222122 Candida albicans Species 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 239000008272 agar Substances 0.000 description 3
- 229940095731 candida albicans Drugs 0.000 description 3
- 239000001963 growth medium Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- YBGZDTIWKVFICR-JLHYYAGUSA-N Octyl 4-methoxycinnamic acid Chemical compound CCCCC(CC)COC(=O)\C=C\C1=CC=C(OC)C=C1 YBGZDTIWKVFICR-JLHYYAGUSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003139 biocide Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229940074391 gallic acid Drugs 0.000 description 2
- 235000004515 gallic acid Nutrition 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000000475 sunscreen effect Effects 0.000 description 2
- 239000000516 sunscreening agent Substances 0.000 description 2
- 239000012137 tryptone Substances 0.000 description 2
- CUNWUEBNSZSNRX-RKGWDQTMSA-N (2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol;(z)-octadec-9-enoic acid Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O CUNWUEBNSZSNRX-RKGWDQTMSA-N 0.000 description 1
- TYYHDKOVFSVWON-UHFFFAOYSA-N 2-butyl-2-methoxy-1,3-diphenylpropane-1,3-dione Chemical compound C=1C=CC=CC=1C(=O)C(OC)(CCCC)C(=O)C1=CC=CC=C1 TYYHDKOVFSVWON-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 239000004166 Lanolin Substances 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003619 algicide Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229960005193 avobenzone Drugs 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- PKPOVTYZGGYDIJ-UHFFFAOYSA-N dioctyl carbonate Chemical compound CCCCCCCCOC(=O)OCCCCCCCC PKPOVTYZGGYDIJ-UHFFFAOYSA-N 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 235000019388 lanolin Nutrition 0.000 description 1
- 229940039717 lanolin Drugs 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003641 microbiacidal effect Effects 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
- 229940124561 microbicide Drugs 0.000 description 1
- 229960001679 octinoxate Drugs 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229960005078 sorbitan sesquioleate Drugs 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- ZQTYRTSKQFQYPQ-UHFFFAOYSA-N trisiloxane Chemical compound [SiH3]O[SiH2]O[SiH3] ZQTYRTSKQFQYPQ-UHFFFAOYSA-N 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
- C07F7/0878—Si-C bond
- C07F7/0879—Hydrosilylation reactions
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
- A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
- A01N31/16—Oxygen or sulfur directly attached to an aromatic ring system with two or more oxygen or sulfur atoms directly attached to the same aromatic ring system
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Pest Control & Pesticides (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明公开了一种有机硅改性焦性没食子酸杀菌剂及其制备方法,首先焦性没食子酸与烯丙基缩水甘油醚制得焦性没食子酸中间体,再将中间体和七甲基三硅氧烷反应,制得有机硅焦性没食子酸杀菌剂。通过将有机硅和具有杀菌性能的焦性没食子酸结合起来,利用碳碳不饱和双键引入有机硅分子,制备得到的杀菌剂在表面铺展性好,具有良好的表面张力和杀菌效果。
Description
技术领域
本发明属于杀菌剂领域,涉及天然衍生物杀菌剂领域,特别是一种有机硅改性焦性没食子酸杀菌剂及其制备方法。
背景技术
杀菌剂又称杀生剂、杀菌灭藻剂、杀微生物剂等,通常是指能有效地控制或杀死水系统中的微生物——细菌、真菌和藻类的化学制剂。在国际上,通常是作为防治各类病原微生物的药剂的总称。现代工业的迅速发展对工业材料的性质和功能不断提出更高要求,工业杀菌剂的适用领域已经从纺织、木材、纸张、石油制品、胶黏剂、涂料等一直扩大到塑料、玻璃、陶瓷金属乃至航天部件等,工业中几乎所有的领域都离不开杀菌剂。随着绿色环保理念的普遍接受,新型高效的杀菌剂,尤其是天然基衍生杀菌剂的开发一直是杀菌剂领域的追求。
发明内容
发明目的:本发明所要解决的技术问题是针对现有技术的不足,提供具有降低表面张力能力、杀菌效果好的含三硅氧烷的焦性没食子酸杀菌剂及其制备方法。通过较低表面张力为其在需要杀菌的体系界面有很好的铺展和渗透作用,进而提高杀菌性能。
为了实现上述目的,本发明采取的技术方案如下:
一种有机硅改性焦性没食子酸杀菌剂的制备方法,包括如下步骤:
(1)焦性没食子酸中间体的合成:
将焦性没食子酸溶于二氧六环中,加入三氟化硼乙醚,加热碱化,在氮气氛围下滴加烯丙基缩水甘油醚,加热反应一段时间后冷却旋蒸除去溶剂和未反应烯丙基缩水甘油醚,反应方程式如下:
(2)有机硅改性处理:
以二氧六环为溶剂,氯铂酸为催化剂,在氮气氛围下滴加七甲基三硅氧烷到步骤(1)得到的焦性没食子酸中间体中,进行硅氢加成反应,反应结束后旋蒸除去溶剂和未反应七甲基三硅氧烷即得,反应方程式如下:
优选地,步骤(1)中,所述焦性没食子酸、三氟化硼乙醚、烯丙基缩水甘油醚三者的反应摩尔比为1:(0.001~2):(1~3)。
优选地,步骤(1)中,所述加热碱化的温度为65~95℃,时间为0.5~1.5h。
优选地,步骤(1)中,加热反应的温度为65~95℃,反应时间为6~24h。
优选地,步骤(1)中,旋蒸温度为45~100℃。
优选地,步骤(2)中,氯铂酸在反应体系中的质量浓度为15~35ppm。
优选地,步骤(2)中,焦性没食子酸中间体和七甲基三硅氧烷反应摩尔比为1:(0.8~3.4)。
优选地,步骤(2)中,硅氢加成反应的温度为65~80℃,反应时间为4~8h。
优选地,步骤(2)中,旋蒸温度为45~100℃。
进一步地,本发明还要求保护上述制备方法制备得到的有机硅改性焦性没食子酸杀菌剂。
有益效果:
本发明首先焦性没食子酸与烯丙基缩水甘油醚制得焦性没食子酸中间体,再将中间体和七甲基三硅氧烷反应,制得有机硅焦性没食子酸杀菌剂。通过将有机硅和具有杀菌性能的焦性没食子酸结合起来,利用碳碳不饱和双键引入有机硅结构,制备得到的杀菌剂有较低的表面张力24.96mN/m,铺展性好,有良好的杀菌效果。
附图说明
下面结合附图和具体实施方式对本发明做更进一步的具体说明,本发明的上述和/或其他方面的优点将会变得更加清楚。
图1为实施例1制备的焦性没食子酸,焦性没食子酸中间体和有机硅改性焦性没食子酸的红外光谱图。
杀菌性能依据标准QB/T 2738-2005日化产品抗菌抑菌效果的评价方法和ISO9252:1989(E)微生物检测规范—平板计数法进行试验,在样品中加入定量细菌培养液,在一定时间后对其进行微生物检测。用无菌吸管吸取适量样品,在胰蛋白胨琼脂培养基里均匀混合,然后将蛋白胨琼脂培养基在35℃下培养48h,取出观察微生物在琼脂平板上的生长情况,进行读数。
具体实施方式
根据下述实施例,可以更好地理解本发明。
实施例1
1.称取1.26g(0.01mol)焦性没食子酸,溶于15g二氧六环中,升温至80℃搅拌至完全溶解,向焦性没食子酸溶液中加入50μL三氟化硼乙醚(0.004mol三氟化硼乙醚),在80℃下碱化1h,接通氮气,称取1.14g(0.01mol)烯丙基缩水甘油醚和2.5g二氧六环混合,以1滴/2-3s的速度滴加至反应体系,滴加完毕后继续反应8h得到紫色溶液,冷却至室温,取紫红色液体在45-99℃之间旋蒸,除去二氧六环及未反应完全的烯丙基缩水甘油醚。
2.将旋蒸后的焦性没食子酸中间体溶于30g二氧六环中,升温至85℃,加入30ppm(占原料和溶剂总质量)的氯铂酸于上述二氧六环溶液中,以1滴1-2s速度加入2.22g(0.01mol)七甲基三硅氧烷,滴加结束后升温至80℃反应8h后冷却至室温结束反应后于45~99℃之间旋蒸,除去二氧六环及未反应完全的七甲基三硅氧烷。得有机硅改性焦性没食子酸化合物。
实施例1中焦性没食子酸中间体,有机硅改性焦性没食子酸和焦性没食子酸的红外光谱图如图1所示,对于焦性没食子酸中间体来说,在2960cm-1和2870cm-1处出现了甲基的伸缩振动峰,在1260cm-1处的环氧键伸缩振动峰消失,证明焦性没食子酸中间体的成功合成。对于有机硅改性焦性没食子酸,1257cm-1和843cm-1出现了碳硅键伸缩振动峰,在2152cm-1处无硅氢键伸缩振动峰证明有机硅改性焦性没食子酸的成功合成。
将实施例1得到的有机硅改性焦性没食子酸、焦性没食子酸原料,分别配置成0.1%wt的水溶液,用BYZ自动表面张力仪分别测定表面张力,结果见表1。
表1表面张力测试结果
试样 | 表面张力(mN/M) |
0.1%焦性没食子酸水溶液 | 69.85 |
0.1%有机硅改性焦性没食子酸水液 | 24.96 |
由表1可见焦性没食子酸接入有机硅基团后形成的有机硅改性焦性没食子酸比焦性没食子酸本身有更大降低表面张力的能力。
实施例2
1.称取1.26g(0.01mol)焦性没食子酸,溶于15g异丙醇中,升温至80℃搅拌至完全溶解,向焦性没食子酸溶液中加入100μL三氟化硼乙醚(0.008mol三氟化硼乙醚),在80℃下碱化1h,接通氮气,称取2.28g(0.02mol)烯丙基缩水甘油醚和2.5g二氧六环混合,以1滴/2-3s的速度滴加至反应体系,滴加完毕后继续反应8h得到紫色溶液,冷却至室温,取紫红色液体在45-99℃之间旋蒸,除去异丙醇及未反应完全的烯丙基缩水甘油醚。
2.将旋蒸后的焦性没食子酸中间体溶于30g异丙醇中,升温至85℃,加入35ppm(占原料和溶剂总质量)的氯铂酸于上述二氧六环溶液中,以1滴1-2s速度加入4.45g(0.02mol)七甲基三硅氧烷,滴加结束后升温至70℃反应6h后冷却至室温结束反应后于45~90℃之间旋蒸,除去异丙醇及未反应完全的七甲基三硅氧烷。
实施例2中有机硅改性焦性没食子酸的杀菌性结果如表2所示。
表2
从表2可以看出:与对照组相比,合成的有机硅改性焦性没食子酸对金黄葡萄球菌、大肠杆菌和白念珠菌的杀菌率都在99.8%以上。
实施例3
1.称取1.26g(0.01mol)焦性没食子酸,溶于15g二氧六环中,升温至80℃搅拌至完全溶解,向焦性没食子酸溶液中加入50μL三氟化硼乙醚(0.012mol三氟化硼乙醚),在80℃下碱化1h,接通氮气,称取3.52g(0.03mol)烯丙基缩水甘油醚和2.5g二氧六环混合,以1滴/2-3s的速度滴加至反应体系,滴加完毕后继续反应7h得到紫色溶液,冷却至室温,取紫红色液体在45-99℃之间旋蒸,除去二氧六环及未反应完全的烯丙基缩水甘油醚。
2.将旋蒸后的焦性没食子酸中间体溶于30g二氧六环中,升温至85℃,加入25ppm(占原料和溶剂总质量)的氯铂酸于上述二氧六环溶液中,以1滴1-2s速度加入6.67g(0.03mol)七甲基三硅氧烷,滴加结束后升温至65℃反应7h后冷却至室温结束反应后于45~80℃之间旋蒸,除去二氧六环及未反应完全的七甲基三硅氧烷。得有机硅改性焦性没食子酸目标化合物。
将实施例3制备得到的产物和原料焦性没食子酸分别用于油包水型的冷霜配方中,添加量均为0.1%。冷霜基本配方如下:蜂蜡16.00%;羊毛脂12.00%;白油34.00%;
实施例3制备得到的有机硅改性焦性没食子酸(或焦性没食子酸)0.1%;以及水37.9%。结果见表3。
表3
测试微生物 | 焦性没食子酸杀菌率 | 有机硅改性焦性没食子酸杀菌率 |
金黄葡萄球菌 | 10.27% | 99.97% |
大肠杆菌 | 9.28% | 99.92% |
白念珠菌 | 12.67% | 99.95% |
从表3可以看出,在测试的冷霜配方中,有机硅改性没食子酸比原料没食子酸本身杀菌率很大程度的提高。
实施例4
1.称取1.26g(0.01mol)焦性没食子酸,溶于15g二氧六环中,升温至80℃搅拌至完全溶解,向焦性没食子酸溶液中加入50μL三氟化硼乙醚(0.004mol三氟化硼乙醚),在80℃下碱化1h,接通氮气,称取1.14g(0.01mol)烯丙基缩水甘油醚和2.5g二氧六环混合,以1滴/2-3s的速度滴加至反应体系,滴加完毕后继续反应8h得到紫色溶液,冷却至室温,取紫红色液体在45-99℃之间旋蒸,除去二氧六环及未反应完全的烯丙基缩水甘油醚。
2.将旋蒸后的焦性没食子酸中间体溶于30g二氧六环中,升温至85℃,加入20ppm(占原料和溶剂总质量)的氯铂酸于上述二氧六环溶液中,以1滴1-2s速度加入2.22g(0.01mol)七甲基三硅氧烷,滴加结束后升温至70℃反应8h后冷却至室温结束反应后于45~70℃之间旋蒸,除去二氧六环及未反应完全的七甲基三硅氧烷,得有机硅改性焦性没食子酸杀菌剂。
实施例4合成的用于防晒配方体系当中,并对与焦性没食子酸原料杀菌性进行对比。防晒配方如下:
环五聚二甲基硅氧烷10.0%;硅油PMX-200 10.0%;甲氧基肉桂酸辛酯(UV-A)8.0%;钛白粉6.0%;碳酸二辛酯5.0%;丁基甲氧基二苯酰甲烷3.0%;甘油3.0%;NMF-503.0%;丁二醇2.0%;乳化剂EM 90 2.0%;山梨糖醇酐倍半油酸酯1.5%;氧化锌0.5%;硬脂酸镁0.50%;维生素E 0.5%;杀菌剂0.1%;水加水至100%。
上述配方中的杀菌剂是实施例4合成的有机硅改性焦性没食子酸,或焦性没食子酸,杀菌实验结果见表4。
表4
测试微生物 | 焦性没食子酸杀菌率 | 有机硅改性焦性没食子酸杀菌率 |
金黄葡萄球菌 | 8.56% | 99.99% |
大肠杆菌 | 8.37% | 99.98% |
白念珠菌 | 7.65% | 99.89% |
从表4可以看出,在测试的冷霜配方中,有机硅改性没食子酸比原料没食子酸本身杀菌率很大程度的提高。
实施例5
1.称取1.26g(0.01mol)焦性没食子酸,溶于15g二氧六环中,升温至80℃搅拌至完全溶解,向焦性没食子酸溶液中加入50μL三氟化硼乙醚(0.004mol三氟化硼乙醚),在80℃下碱化1h,接通氮气,称取1.14g(0.01mol)烯丙基缩水甘油醚和2.5g二氧六环混合,以1滴/2-3s的速度滴加至反应体系,滴加完毕后继续反应7h得到紫色溶液,冷却至室温,取紫红色液体在45-99℃之间旋蒸,除去二氧六环及未反应完全的烯丙基缩水甘油醚。
2.将旋蒸后的焦性没食子酸中间体溶于30g二氧六环中,升温至85℃,加入15ppm(占原料和溶剂总质量)的氯铂酸于上述二氧六环溶液中,以1滴1-2s速度加入4.45g(0.02mol)七甲基三硅氧烷,滴加结束后升温至80℃反应6h后冷却至室温结束反应后于45~60℃之间旋蒸,除去二氧六环及未反应完全的七甲基三硅氧烷。
本发明提供了一种有机硅改性焦性没食子酸杀菌剂及其制备方法的思路及方法,具体实现该技术方案的方法和途径很多,以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。本实施例中未明确的各组成部分均可用现有技术加以实现。
Claims (9)
1.一种有机硅改性焦性没食子酸杀菌剂的制备方法,其特征在于,包括如下步骤:
(1)焦性没食子酸中间体的合成:
将焦性没食子酸溶于二氧六环中,加入三氟化硼乙醚,加热碱化,在氮气氛围下滴加烯丙基缩水甘油醚,加热至65~95℃,反应6~24 h后冷却旋蒸除去溶剂和未反应烯丙基缩水甘油醚;
(2)有机硅改性处理:
以二氧六环为溶剂,氯铂酸为催化剂,在氮气氛围下滴加七甲基三硅氧烷到步骤(1)得到的焦性没食子酸中间体中,进行硅氢加成反应,反应结束后旋蒸除去溶剂和未反应七甲基三硅氧烷即得。
2.根据权利要求1所述的有机硅改性焦性没食子酸杀菌剂的制备方法,其特征在于,步骤(1)中,所述焦性没食子酸、三氟化硼乙醚、烯丙基缩水甘油醚三者的反应摩尔比为1:0.001~2:1~3。
3.根据权利要求1所述的有机硅改性焦性没食子酸杀菌剂的制备方法,其特征在于,步骤(1)中,所述加热碱化的温度为65~95 ℃,时间为0.5~1.5 h。
4.根据权利要求1所述的有机硅改性焦性没食子酸杀菌剂的制备方法,其特征在于,步骤(1)中,旋蒸温度为45~100 ℃。
5.根据权利要求1所述的有机硅改性焦性没食子酸杀菌剂的制备方法,其特征在于,步骤(2)中,氯铂酸在反应体系中的质量浓度为15~35 ppm。
6.根据权利要求1所述的有机硅改性焦性没食子酸杀菌剂的制备方法,其特征在于,步骤(2)中,焦性没食子酸中间体和七甲基三硅氧烷反应摩尔比为1:0.8~3.4。
7.根据权利要求1所述的有机硅改性焦性没食子酸杀菌剂的制备方法,其特征在于,步骤(2)中,硅氢加成反应的温度为65~80℃,反应时间为4~8 h。
8.根据权利要求1所述的有机硅改性焦性没食子酸杀菌剂的制备方法,其特征在于,步骤(2)中,旋蒸温度为45~100 ℃。
9.权利要求1~8中任意一项制备方法制备得到的有机硅改性焦性没食子酸杀菌剂。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210430410.4A CN114736231B (zh) | 2022-04-22 | 2022-04-22 | 一种有机硅改性焦性没食子酸杀菌剂及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210430410.4A CN114736231B (zh) | 2022-04-22 | 2022-04-22 | 一种有机硅改性焦性没食子酸杀菌剂及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114736231A CN114736231A (zh) | 2022-07-12 |
CN114736231B true CN114736231B (zh) | 2022-10-28 |
Family
ID=82283308
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210430410.4A Active CN114736231B (zh) | 2022-04-22 | 2022-04-22 | 一种有机硅改性焦性没食子酸杀菌剂及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114736231B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115386020A (zh) * | 2022-09-30 | 2022-11-25 | 南京智茂新材料科技有限公司 | 一种有机硅改性菊粉表面活性剂制备方法及应用 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107494553B (zh) * | 2017-09-11 | 2020-09-11 | 西华大学 | 一种没食子酸衍生的农用杀菌剂及用途 |
CN109265673B (zh) * | 2018-09-26 | 2020-03-31 | 南京林业大学 | 一种有机硅改性聚醚多元醇及其制备方法和应用 |
CN113024818B (zh) * | 2021-03-01 | 2022-07-08 | 浙江润禾有机硅新材料有限公司 | 一种高纯度低副产的聚醚改性硅氧烷的制备方法 |
-
2022
- 2022-04-22 CN CN202210430410.4A patent/CN114736231B/zh active Active
Also Published As
Publication number | Publication date |
---|---|
CN114736231A (zh) | 2022-07-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN114736231B (zh) | 一种有机硅改性焦性没食子酸杀菌剂及其制备方法 | |
CN101812086B (zh) | 一种抗菌化合物及其制备方法 | |
DE102006060115A1 (de) | Cyclische Siloxane und deren Verwendung | |
Matei et al. | Synthesis of chitosan oligomers/propolis/silver nanoparticles composite systems and study of their activity against Diplodia seriata | |
EP4292590A2 (en) | Efficient anti-bacterial hydroxy acid ester oligomer | |
CN102286010B (zh) | N-(2-乙酸)水杨酰腙稀土配合物及其制备方法和用途 | |
US20050261418A1 (en) | Crosslinked polymers containing biomass derived materials | |
US5616317A (en) | Polycationic polymer and polycationic microbicidal and algaecidal agent | |
CN109988525B (zh) | 一种档案防霉驱虫胶黏剂 | |
CN114164711A (zh) | 一种制备含有松香基季铵盐抗菌涂料的方法及应用 | |
CN110965143B (zh) | 一种具有抗菌除臭性能的纤维及其制备方法 | |
CN102924496A (zh) | 一种抗菌化合物制备方法 | |
CN111643705B (zh) | 一种精油组合物及其在制备空气清新剂中的应用 | |
US4404014A (en) | Salt-like products of the addition of phenols onto amino organosilane esters and method for the preparation thereof and use as a preservative | |
CN109608392B (zh) | 芪类类似化合物及其制备方法和用途 | |
CN109535065B (zh) | 一种长叶烯基季铵盐类化合物及其合成方法与应用 | |
CN113880780A (zh) | 苯甲脒类衍生物、制备方法及应用 | |
CN113214464B (zh) | 一种抗菌聚酯材料及其制备方法与应用 | |
CN1060235C (zh) | 一种抑菌聚丙烯纤维及其制造方法 | |
JP5435546B2 (ja) | 銀コバルト錯体、および抗菌・抗カビ剤 | |
RU2259369C2 (ru) | 5-арил-1-фенил-4-гетероил-3-гидрокси-3-пирролин-2-оны, проявляющие противомикробную активность | |
US2536750A (en) | Organic mercury compounds and germicidal compositions thereof | |
CN116036344B (zh) | 一种抗感染敷料及其制备方法 | |
CN111925527B (zh) | 长链烷基接枝的季铵化硅酮及其制备方法与应用 | |
CN118058996A (zh) | 一种含对羟基苯甲酸的组合物、制备方法、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 |