CN108329741A - 阻燃、抗菌、防水石墨烯改性丙烯酸酯树脂涂料中间产物的制备方法 - Google Patents

阻燃、抗菌、防水石墨烯改性丙烯酸酯树脂涂料中间产物的制备方法 Download PDF

Info

Publication number
CN108329741A
CN108329741A CN201810254267.1A CN201810254267A CN108329741A CN 108329741 A CN108329741 A CN 108329741A CN 201810254267 A CN201810254267 A CN 201810254267A CN 108329741 A CN108329741 A CN 108329741A
Authority
CN
China
Prior art keywords
walnut
water
retardant
antibacterial
fire
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
Application number
CN201810254267.1A
Other languages
English (en)
Inventor
段宝荣
李成
王延青
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN201810254267.1A priority Critical patent/CN108329741A/zh
Publication of CN108329741A publication Critical patent/CN108329741A/zh
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00Coating compositions based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04Homopolymers or copolymers of esters
    • C09D133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12Homopolymers or copolymers of methyl methacrylate
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/14Methyl esters, e.g. methyl (meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02Organic and inorganic ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/32Phosphorus-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/36Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37Thiols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/36Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/39Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/36Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41Compounds containing sulfur bound to oxygen
    • C08K5/42Sulfonic acids; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00Coating compositions based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04Homopolymers or copolymers of esters
    • C09D133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062Copolymers with monomers not covered by C09D133/06
    • C09D133/066Copolymers with monomers not covered by C09D133/06 containing -OH groups
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18Fireproof paints including high temperature resistant paints
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/63Additives non-macromolecular organic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/32Phosphorus-containing compounds
    • C08K2003/321Phosphates
    • C08K2003/322Ammonium phosphate
    • C08K2003/323Ammonium polyphosphate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/014Additives containing two or more different additives of the same subgroup in C08K
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Plant Pathology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

阻燃、抗菌、防水石墨烯改性丙烯酸酯类树脂涂料中间产物的制备方法,将核桃青皮剥离后用水洗净,置于烘箱内40~70℃温度下烘干至恒重,粉碎并过80~100目筛,得核桃青皮粉末,称取核桃青皮粉末及水,加入烯丙基三甲基氯化铵、4‑甲氧基乙酰乙酸甲酯于80~100℃温度下回流煎煮,过滤煎煮液,60~70℃温度下减压浓缩,待浓缩液成水含量在15%~20%的浓膏状至恒重即可,得到核桃青皮提取物浓缩液,并用于丙烯酸酯类树脂中,所得丙烯酸酯类树脂具有抗菌、阻燃和防水性好。

Description

阻燃、抗菌、防水石墨烯改性丙烯酸酯树脂涂料中间产物的制 备方法
本申请是申请号为201610331925.3发明专利申请的分案申请。
技术领域
本发明涉及一种丙烯酸酯类树脂的制备方法,特别涉及阻燃、抗菌、防水丙烯酸酯类树脂的制备方法。
背景技术
青皮是核桃的果皮,保护种子,虽然不能吃,但其也有一定的生物化学作用:经研究,其果皮对5种人类致病细菌有明显的抑制作用,且抑菌效果不同。抑制表皮葡萄球菌效果最好,抑菌率为83.3%;其次为金黄色葡萄球菌、猪霍乱沙门氏菌、肺炎球菌,抑菌率分别为75.4%、70.2%、62.6%;对痢疾志贺氏菌抑菌效果较差,为41.1%。通过对山核桃青果皮挥发物质的分析,共鉴定出24种挥发性成份。
目前,我国丙烯酸树脂的品种已经相对完善,但是与国外先进同行相比,生产规模、工艺控制及部分特殊性能要求的产品还存在一定差距,特别是在工艺控制与质量稳定性方面。因此,我们要在未来几年内,采用更先进的自动化控制系统,确保产品工艺控制能保持一致,从而进一步提高产品质量的稳定性,特别是产品质量力求达到国外厂家的水平,是丙烯酸树脂发展的当务之急,也是根本所在。其中,江苏三木、山东科耀化工、同德化工等企业生产的丙烯酸树脂产品表现良好。
随着市场的竞争日益激烈,通用型丙烯酸树脂的利润在不断下跌,在此情况下,想要丙烯酸产品扩大利润,只有研发高性能的产品,做到人无我有,人有我优。只有这样,才能真正提高产品参与市场的竞争能力,才能提高企业的综合效益。建筑涂料在所有涂料中所占的比例最大。据报道,我国的建筑涂料在丙烯酸涂料中所占的比例为24%,处于世界中等发展水平。目前的年产量在50万吨左右,其中内墙占60%,外墙占25%,其他占15%。
虽然我国目前使用的涂料仍以中低档为主,但我国丙烯酸涂料的品种较齐全,与发达国家相比,差距并不在于涂料的品种,而是原料、生产设备、生产工艺以及生产规模的差距。其中生产规模较大、技术起点较高的企业,生产的产品技术含量高、质量好。
石墨烯是由sp2杂化碳原子相互连接形成单原子层厚度二维蜂窝状晶格结构的碳材料。石墨烯具有优异的电学、力学、热学和机械性能,有望在透明导电膜复合材料、能源、传感器、生物技术、催化材料等领域得到广泛应用。
发明内容
本发明利用烯丙基三甲基氯化铵、4-甲氧基乙酰乙酸甲酯提取核桃青皮粉末的抗菌因子,并将抗菌因子用在丙烯酸酯类单体中,并利用二甲基二硫代氨基甲酸钠、二乙基二硫代氨基甲酸钠、二巯基丙醇、二巯基丙烷磺酸钠对抗菌因子固定,该方法所使用的抗菌剂使用长久。
阻燃、抗菌、防水石墨烯改性丙烯酸酯类树脂涂料制备方法,其特征在于:
(1)核桃青皮提取物浓缩液,其特征在于该方法包括如下步骤:将核桃青皮剥离后用水洗净,置于烘箱内40~70℃温度下烘干至恒重,粉碎并过80~100目筛,得核桃青皮粉 末,称取核桃青皮粉末及水,加入烯丙基三甲基氯化铵、4-甲氧基乙酰乙酸甲酯于80~100℃ 温度下回流煎煮,过滤煎煮液,60~70℃温度下减压浓缩,待浓缩液成水含量在15%~20%的浓膏状至恒重即可,得到核桃青皮提取物浓缩液,其中核桃青皮粉末与水的质量比为1:3;烯丙基三甲基氯化铵、4-甲氧基乙酰乙酸甲酯分别为核桃青皮粉末的5%、2%;
(2)取60mg的石墨烯加入到50mL的N-甲基吡咯烷酮、四丁基氢氧化铵20g、四丁基氢氧化铵0.2g中,超声剥离30min,以2000rpm的速度离心分离,获得石墨烯分散液;
(3)向带有搅拌器、温度计和冷凝管的250ml三口烧瓶中加入水80g、十二烷基苯磺酸钠0.45g、脂肪醇聚氧乙烯醚0.35g、丙烯酸0.4g,升温至60℃,搅拌40min,加入A单体,乳化60min,升温到70℃开始通回流水,升温到80℃滴加用7g水溶解的过硫酸钾溶液8.4g,滴加时间2h,滴加完反应2h,再加入核桃青皮浓缩液0.53g和防水剂0.23g,搅拌反应4h,得核层乳液;所述A单体是由:丙烯酸丁酯4g、甲基丙烯酸甲酯4g、丙烯酸乙酯10.5g混合而成;
(4)向步骤(3)所得核层乳液中同时滴加B单体和用9g水溶解的过硫酸钾溶液11.2g,滴加时间0.5h,滴加完80℃搅拌反应2h,降温到40℃,加结合剂A、3-硝基苯磺酸钠0.25g、脂肪醇聚氧乙烯醚0.225g、石墨烯分散液0.7g和八苯基环四硅氧烷0.6g、聚磷酸铵0.6g,反应时间60min,70℃反应1h,用调pH值至7~8,得所述的阻燃、抗菌、防水石墨烯改性丙烯酸酯类树脂涂料,其中结合剂用量为核桃青皮粉末的重量5%;
所述B单体:甲基丙烯酸甲酯8.0g、丙烯酸羟乙酯7.0g、苯乙烯0.5g混合组成。
所述的结合剂A为二甲基二硫代氨基甲酸钠、二乙基二硫代氨基甲酸钠、二巯基丙醇、二巯基丙烷磺酸钠中的一种;防水剂为3-氨丙基三乙氧基硅烷、3-氨丙基三甲氧基硅烷、乙烯基三乙氧基硅烷、十三氟辛基三乙氧基硅烷中的一种;聚磷酸铵的聚合度在10~20,相对分子质量1000~2000。
本发明的创新点在于:
(1)使用烯丙基三甲基氯化铵可以将核桃青皮粉末中的抗菌因子提取出,同时该抗菌剂颜色浅淡,同时使用4-甲氧基乙酰乙酸甲酯提高水、N-丙基烯丙基氯化铵的提取效率。
(2)本发明提取效率高,毒性小。
(3)二甲基二硫代氨基甲酸钠、二乙基二硫代氨基甲酸钠、二巯基丙醇、二巯基丙烷磺酸钠对核桃青皮粉末进行吸附。
(4)烯丙基三甲基氯化铵购买与百顺(北京)化学科技有限公司。
(5)四丁基氢氧化铵、四丁基氢氧化铵增加石墨烯的分散性。
(6)八苯基环四硅氧烷增加丙烯酸酯类树脂的阻燃性,依靠聚磷酸铵加热成酸,使八苯基环四硅氧烷硅层增加,阻止燃烧进行。
具体实施举例
实例一
(1)核桃青皮提取物浓缩液,其特征在于该方法包括如下步骤:将核桃青皮剥离后用水洗净,置于烘箱内40℃温度下烘干至恒重,粉碎并过80目筛,得核桃青皮粉末,称取核 桃青皮粉末50g及水150g,加入烯丙基三甲基氯化铵2.5g、4-甲氧基乙酰乙酸甲酯1g于80℃温度下回流煎煮,过滤煎煮液,60℃温度下减压浓缩,待浓缩液成水含量在15%~20%的浓膏状至恒重即可,得到核桃青皮提取物浓缩液;
(2)取60mg的石墨烯加入到50mL的N-甲基吡咯烷酮、四丁基氢氧化铵20g、四丁基氢氧化铵0.2g中,超声分散30min,以2000rpm的速度离心分离,获得石墨烯分散液;
(3)向带有搅拌器、温度计和冷凝管的250ml三口烧瓶中加入水80g、十二烷基苯磺酸钠0.45g、脂肪醇聚氧乙烯醚0.35g、丙烯酸0.4g,升温至60℃,搅拌40min,加入A单体,乳化60min,升温到70℃开始通回流水,升温到80℃滴加用7g水溶解的过硫酸钾溶液8.4g,滴加时间2h,滴加完反应2h,再加入核桃青皮浓缩液0.53g和3-氨丙基三乙氧基硅烷0.23g,搅拌反应4h,得核层乳液;所述A单体是由:丙烯酸丁酯4g、甲基丙烯酸甲酯4g、丙烯酸乙酯10.5g混合而成;
(4)向步骤(3)所得核层乳液中同时滴加B单体和用9g水溶解的过硫酸钾溶液11.2g,滴加时间0.5h,滴加完80℃搅拌反应2h,降温到40℃,加二甲基二硫代氨基甲酸钠2.5g、3-硝基苯磺酸钠0.25g、脂肪醇聚氧乙烯醚0.225g、石墨烯分散液0.7g和八苯基环四硅氧烷0.6g、聚磷酸铵0.6g,反应时间60min,70℃反应1h,用调pH值至7~8,得所述的阻燃、抗菌、防水石墨烯改性丙烯酸酯类树脂涂料,其中结合剂用量为核桃青皮粉末的重量5%;
所述B单体:甲基丙烯酸甲酯8.0g、丙烯酸羟乙酯7.0g、苯乙烯0.5g混合组成。
实例二
(1)核桃青皮提取物浓缩液,其特征在于该方法包括如下步骤:将核桃青皮剥离后用水洗净,置于烘箱内70℃温度下烘干至恒重,粉碎并过100目筛,得核桃青皮粉末,称取 核桃青皮粉末60g及水180g,加入烯丙基三甲基氯化铵3g、4-甲氧基乙酰乙酸甲酯1.2g于 100℃温度下回流煎煮,过滤煎煮液,70℃温度下减压浓缩,待浓缩液成水含量15%~20%的浓 膏状至恒重即可,得到核桃青皮提取物浓缩液;
(2)取60mg的石墨烯加入到50mL的N-甲基吡咯烷酮、四丁基氢氧化铵20g、四丁基氢氧化铵0.2g中,超声剥离30min,以2000rpm的速度离心分离,获得石墨烯分散液;
(3)向带有搅拌器、温度计和冷凝管的250ml三口烧瓶中加入水80g、十二烷基苯磺酸钠0.45g、脂肪醇聚氧乙烯醚0.35g、丙烯酸0.4g,升温至60℃,搅拌40min,加入A单体,乳化60min,升温到70℃开始通回流水,升温到80℃滴加用7g水溶解的过硫酸钾溶液8.4g,滴加时间2h,滴加完反应2h,再加入核桃青皮浓缩液0.53g和3-氨丙基三甲氧基硅烷0.23g,搅拌反应4h,得核层乳液;所述A单体是由:丙烯酸丁酯4g、甲基丙烯酸甲酯4g、丙烯酸乙酯10.5g混合而成;
(4)向步骤(3)所得核层乳液中同时滴加B单体和用9g水溶解的过硫酸钾溶液11.2g,滴加时间0.5h,滴加完80℃搅拌反应2h,降温到40℃,加二乙基二硫代氨基甲酸钠3g、3-硝基苯磺酸钠0.25g、脂肪醇聚氧乙烯醚0.225g、石墨烯分散液0.7g和八苯基环四硅氧烷0.6g、聚磷酸铵0.6g,反应时间60min,70℃反应1h,用调pH值至7~8,得所述的阻燃、抗菌、防水石墨烯改性丙烯酸酯类树脂涂料;
所述B单体:甲基丙烯酸甲酯8.0g、丙烯酸羟乙酯7.0g、苯乙烯0.5g混合组成。
实例三
(1)核桃青皮提取物浓缩液,其特征在于该方法包括如下步骤:将核桃青皮剥离后用水洗净,置于烘箱内55℃温度下烘干至恒重,粉碎并过90目筛,得核桃青皮粉末,称取核 桃青皮粉末50g及水150g,加入烯丙基三甲基氯化铵2.5g、4-甲氧基乙酰乙酸甲酯1g于90℃温度下回流煎煮,过滤煎煮液,65℃温度下减压浓缩,待浓缩液成水含量在15%~20%的浓膏状至恒重即可,得到核桃青皮提取物浓缩液;
(2)取60mg的石墨烯加入到50mL的N-甲基吡咯烷酮、四丁基氢氧化铵20g、四丁基氢氧化铵0.2g中,超声分散
30min,以2000rpm的速度离心分离,获得石墨烯分散液;
(3)向带有搅拌器、温度计和冷凝管的250ml三口烧瓶中加入水80g、十二烷基苯磺酸钠0.45g、脂肪醇聚氧乙烯醚0.35g、丙烯酸0.4g,升温至60℃,搅拌40min,加入A单体,乳化60min,升温到70℃开始通回流水,升温到80℃滴加用7g水溶解的过硫酸钾溶液8.4g,滴加时间2h,滴加完反应2h,再加入核桃青皮浓缩液0.53g和乙烯基三乙氧基硅烷0.23g,搅拌反应4h,得核层乳液;所述A单体是由:丙烯酸丁酯4g、甲基丙烯酸甲酯4g、丙烯酸乙酯10.5g混合而成;
(4)向步骤(3)所得核层乳液中同时滴加B单体和用9g水溶解的过硫酸钾溶液11.2g,滴加时间0.5h,滴加完80℃搅拌反应2h,降温到40℃,加二巯基丙醇2.5g、3-硝基苯磺酸钠0.25g、脂肪醇聚氧乙烯醚0.225g、石墨烯分散液0.7g和八苯基环四硅氧烷0.6g、聚磷酸铵0.6g,反应时间60min,70℃反应1h,用调pH值至7~8,得所述的阻燃、抗菌、防水石墨烯改性丙烯酸酯类树脂涂料;
所述B单体:甲基丙烯酸甲酯8.0g、丙烯酸羟乙酯7.0g、苯乙烯0.5g混合组成。
实例四
(1)核桃青皮提取物浓缩液,其特征在于该方法包括如下步骤:将核桃青皮剥离后用水洗净,置于烘箱内40℃温度下烘干至恒重,粉碎并过100目筛,得核桃青皮粉末,称取 核桃青皮粉末30g及水90g,加入烯丙基三甲基氯化铵1.5g、4-甲氧基乙酰乙酸甲酯0.6g于100℃温度下回流煎煮,过滤煎煮液,70℃温度下减压浓缩,待浓缩液成水含量在15%~20%的浓膏状至恒重即可,得到核桃青皮提取物浓缩液;
(2)取60mg的石墨烯加入到50mL的N-甲基吡咯烷酮、四丁基氢氧化铵20g、四丁基氢氧化铵0.2g中,超声分散30min,以2000rpm的速度离心分离,获得石墨烯分散液;
(3)向带有搅拌器、温度计和冷凝管的250ml三口烧瓶中加入水80g、十二烷基苯磺酸钠0.45g、脂肪醇聚氧乙烯醚0.35g、丙烯酸0.4g,升温至60℃,搅拌40min,加入A单体,乳化60min,升温到70℃开始通回流水,升温到80℃滴加用7g水溶解的过硫酸钾溶液8.4g,滴加时间2h,滴加完反应2h,再加入核桃青皮浓缩液0.53g和十三氟辛基三乙氧基硅烷0.23g,搅拌反应4h,得核层乳液;所述A单体是由:丙烯酸丁酯4g、甲基丙烯酸甲酯4g、丙烯酸乙酯10.5g混合而成;
(4)向步骤(3)所得核层乳液中同时滴加B单体和用9g水溶解的过硫酸钾溶液11.2g,滴加时间0.5h,滴加完80℃搅拌反应2h,降温到40℃,加二巯基丙烷磺酸钠1.5g、3-硝基苯磺酸钠0.25g、脂肪醇聚氧乙烯醚0.225g、石墨烯分散液0.7g和八苯基环四硅氧烷0.6g、聚磷酸铵0.6g,反应时间60min,70℃反应1h,用调pH值至7~8,得所述的阻燃、抗菌、防水石墨烯改性丙烯酸酯类树脂涂料;
所述B单体:甲基丙烯酸甲酯8.0g、丙烯酸羟乙酯7.0g、苯乙烯0.5g混合组成。
实例五
(1)核桃青皮提取物浓缩液,其特征在于该方法包括如下步骤:将核桃青皮剥离后用水洗净,置于烘箱内70℃温度下烘干至恒重,粉碎并过100目筛,得核桃青皮粉末,称取 核桃青皮粉末60g及水180g,加入烯丙基三甲基氯化铵3g、4-甲氧基乙酰乙酸甲酯1.2g于 100℃温度下回流煎煮,过滤煎煮液,70℃温度下减压浓缩,待浓缩液成水含量20%的浓膏状 至恒重即可,得到核桃青皮提取物浓缩液;
(2)取60mg的石墨烯加入到50mL的N-甲基吡咯烷酮、四丁基氢氧化铵20g、四丁基氢氧化铵0.2g中,超声剥离30min,以2000rpm的速度离心分离,获得石墨烯分散液;
(3)向带有搅拌器、温度计和冷凝管的250ml三口烧瓶中加入水80g、十二烷基苯磺酸钠0.45g、脂肪醇聚氧乙烯醚0.35g、丙烯酸0.4g,升温至60℃,搅拌40min,加入A单体,乳化60min,升温到70℃开始通回流水,升温到80℃滴加用7g水溶解的过硫酸钾溶液8.4g,滴加时间2h,滴加完反应2h,再加入核桃青皮浓缩液0.53g和3-氨丙基三甲氧基硅烷0.23g,搅拌反应4h,得核层乳液;所述A单体是由:丙烯酸丁酯4g、甲基丙烯酸甲酯4g、丙烯酸乙酯10.5g混合而成;
(4)向步骤(3)所得核层乳液中同时滴加B单体和用9g水溶解的过硫酸钾溶液11.2g,滴加时间0.5h,滴加完80℃搅拌反应2h,降温到40℃,加二乙基二硫代氨基甲酸钠3g、3-硝基苯磺酸钠0.25g、脂肪醇聚氧乙烯醚0.225g、石墨烯分散液0.7g和八苯基环四硅氧烷0.6g、聚磷酸铵0.6g,反应时间60min,70℃反应1h,用调pH值至7~8,得所述的阻燃、抗菌、防水石墨烯改性丙烯酸酯类树脂涂料;
所述B单体:甲基丙烯酸甲酯8.0g、丙烯酸羟乙酯7.0g、苯乙烯0.5g混合组成。聚磷酸铵的聚合度在10~20,相对分子质量1000~2000。
下面通过相关实验数据进一步说明本发明的有益效果:防霉涂料选自于上海意罗涂料有限公司。
表1阻燃、抗菌、防水石墨烯改性丙烯酸酯类树脂涂料所成膜对供试菌种的抗菌率(%)
从表1可以发现,实例1到实例5五所制备的抗菌性涂料对大肠杆菌、金黄色葡萄球菌、黄曲霉均有很好的抗菌效果。
表2阻燃、抗菌、防水石墨烯改性丙烯酸酯类树脂涂料所成膜90天的抗菌率(%)
表3阻燃、抗菌、防水石墨烯改性丙烯酸酯类树脂涂料所成膜360天的抗菌率(%)
从表2和表3可以发现,实例1到实例5所制备的抗菌性涂料抗菌效果缓慢释放,放置90天到360天对大肠杆菌、金黄色葡萄球菌、黄曲霉仍能显示良好的抗菌效果。
本发明具体实施例所涂料制作成膜,膜的阻燃性是通过烟密度法(最大烟密
度、达到最大烟密度时间)、氧指数、垂直燃烧指标(有焰燃烧时间、无焰燃烧时间)来衡量,断裂伸长率表征其力学性能。
表4阻燃、抗菌、防水石墨烯改性丙烯酸酯类树脂涂料的阻燃效果指标
表4各项指标的检测分别依据如下标准:烟密度依据GB8323-2008来测定,氧指数采用GB/T5454-1997《纺织品燃烧性能试验-氧指数法》测定;有焰燃烧时间和无焰燃烧时间 是采用GB/T5455-1997《纺织品燃烧能试验-垂直法》来测定,BMR是江苏国联科技有限公 司。
由表4可知,使用了本发明丙烯酸酯类树脂后,氧指数明显提高,燃烧时间明显缩短。
表5阻燃、抗菌、防水石墨烯改性丙烯酸酯类树脂涂料的阻燃效果指标
防水性采用取适量乳液均匀涂覆于玻璃板上,一定温度下干燥成膜后将玻璃板放入去离子水中浸泡,观察涂膜变蓝、发白、起泡、发皱、脱落的情况,市场聚氨酯选自于江苏朗科环保有限公司。

Claims (7)

1.阻燃、抗菌、防水石墨烯改性丙烯酸酯类树脂涂料中间产物的制备方法,所述中间产物为核桃青皮提取物浓缩液,其特征在于:该方法包括如下步骤:将核桃青皮剥离后用水洗净,置于烘箱内40~70℃温度下烘干至恒重,粉碎并过80~100目筛,得核桃青皮粉末, 称取核桃青皮粉末及水,加入烯丙基三甲基氯化铵、4-甲氧基乙酰乙酸甲酯于80~100℃温 度下回流煎煮,过滤煎煮液,60~70℃温度下减压浓缩,待浓缩液成水含量在15%~20%的浓膏状至恒重即可,得到核桃青皮提取物浓缩液,其中核桃青皮粉末与水的质量比为1:3;烯丙基三甲基氯化铵、4-甲氧基乙酰乙酸甲酯分别为核桃青皮粉末的5%、2%。
2.根据权利要求1所述的制备方法,其特征在于:所述中间产物为石墨烯分散液,其制备过程如下:取60mg的石墨烯加入到50mL的N-甲基吡咯烷酮、四丁基氢氧化铵20g、四丁基氢氧 化铵0.2g中,超声剥离30min,以2000rpm的速度离心分离,获得石墨烯分散液。
3.根据权利要求1所述的制备方法,其特征在于:所述中间产物为核层乳液,其制备过程如下:向带有搅拌器、温度计和冷凝管的250ml三口烧瓶中加入水80g、十二烷基苯磺酸钠0.45g、脂肪醇聚氧乙烯醚0.35g、丙烯酸0.4g,升温至60℃,搅拌40min,加入A单体,乳化60min,升温到70℃开始通回流水,升温到80℃滴加用7g水溶解的过硫酸钾溶液8.4g,滴加时间2h,滴加完反应2h,再加入核桃青皮浓缩液0.53g和防水剂0.23g,搅拌反应4h,得核层乳液;所述A单体是由:丙烯酸丁酯4g、甲基丙烯酸甲酯4g、丙烯酸乙酯10.5g混合而成。
4.一种包括权利要求1-3所述制备方法制得的阻燃、抗菌、防水石墨烯改性丙烯酸酯类树脂涂料,其特征在于:所得核层乳液中同时滴加B单体和用9g水溶解的过硫酸钾溶液11.2g,滴 加时间0.5h,滴加完80℃搅拌反应2h,降温到40℃,加结合剂A、3-硝基苯磺酸钠0.25g、脂肪 醇聚氧乙烯醚0.225g、石墨烯分散液0.7g和八苯基环四硅氧烷0.6g、聚磷酸铵0.6g,反应时 间60min,70℃反应1h,用调pH值至7~8,得所述的阻燃、抗菌、防水石墨烯改性丙烯酸酯类树 脂涂料,其中结合剂用量为核桃青皮粉末的重量5%,
所述B单体:甲基丙烯酸甲酯8.0g、丙烯酸羟乙酯7.0g、苯乙烯0.5g混合组成。
5.根据权利要求4所述的阻燃、抗菌、防水石墨烯改性丙烯酸酯类树脂涂料,所述的结合剂A为二甲基二硫代氨基甲酸钠、二乙基二硫代氨基甲酸钠、二巯基丙醇、二巯基 丙烷磺酸钠中的一种。
6.根据权利要求4所述的阻燃、抗菌、防水石墨烯改性丙烯酸酯类树脂涂料,其特征在于:防水剂为3-氨丙基三乙氧基硅烷、3-氨丙基三甲氧基硅烷、乙烯基三乙氧基硅烷、十三氟辛 基三乙氧基硅烷中的一种。
7.根据权利要求4所述的阻燃、抗菌、防水石墨烯改性丙烯酸酯类树脂涂料,其特征在于:聚 磷酸铵的聚合度在10~20,相对分子质量1000~2000。
CN201810254267.1A 2016-05-18 2016-05-18 阻燃、抗菌、防水石墨烯改性丙烯酸酯树脂涂料中间产物的制备方法 Pending CN108329741A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810254267.1A CN108329741A (zh) 2016-05-18 2016-05-18 阻燃、抗菌、防水石墨烯改性丙烯酸酯树脂涂料中间产物的制备方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610331925.3A CN105820695B (zh) 2016-05-18 2016-05-18 阻燃、抗菌、防水石墨烯改性丙烯酸酯树脂涂料制备方法
CN201810254267.1A CN108329741A (zh) 2016-05-18 2016-05-18 阻燃、抗菌、防水石墨烯改性丙烯酸酯树脂涂料中间产物的制备方法

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN201610331925.3A Division CN105820695B (zh) 2016-05-18 2016-05-18 阻燃、抗菌、防水石墨烯改性丙烯酸酯树脂涂料制备方法

Publications (1)

Publication Number Publication Date
CN108329741A true CN108329741A (zh) 2018-07-27

Family

ID=56529994

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201610331925.3A Active CN105820695B (zh) 2016-05-18 2016-05-18 阻燃、抗菌、防水石墨烯改性丙烯酸酯树脂涂料制备方法
CN201810254267.1A Pending CN108329741A (zh) 2016-05-18 2016-05-18 阻燃、抗菌、防水石墨烯改性丙烯酸酯树脂涂料中间产物的制备方法

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN201610331925.3A Active CN105820695B (zh) 2016-05-18 2016-05-18 阻燃、抗菌、防水石墨烯改性丙烯酸酯树脂涂料制备方法

Country Status (1)

Country Link
CN (2) CN105820695B (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106609058A (zh) * 2016-12-05 2017-05-03 天长市优信电器设备有限公司 一种铝制充电器外壳的绝缘涂层
CN113598199B (zh) * 2021-09-13 2022-05-20 贵州省核桃研究所 一种核桃青皮制备的涂白剂
CN117050629B (zh) * 2023-08-14 2024-02-27 河北宇阳泽丽防水材料有限公司 一种抗菌持久性的水性聚氨酯涂料及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104872195A (zh) * 2015-04-16 2015-09-02 甘肃省分析测试中心 青核桃外果皮提取物及提取方法和用途以及用该提取物制作的种子包衣剂
CN105482601A (zh) * 2015-12-30 2016-04-13 段宝荣 一种建筑抗菌性与阻燃性丙烯酸酯类树脂涂料的制备方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102875723B (zh) * 2012-10-26 2014-04-16 烟台大学 一种阻燃性核壳型丙烯酸类树脂的制备方法
CN105153355A (zh) * 2015-10-29 2015-12-16 南阳理工学院 一种建筑抗菌性与耐光性丙烯酸酯类树脂涂料的制备方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104872195A (zh) * 2015-04-16 2015-09-02 甘肃省分析测试中心 青核桃外果皮提取物及提取方法和用途以及用该提取物制作的种子包衣剂
CN105482601A (zh) * 2015-12-30 2016-04-13 段宝荣 一种建筑抗菌性与阻燃性丙烯酸酯类树脂涂料的制备方法

Also Published As

Publication number Publication date
CN105820695B (zh) 2018-06-01
CN105820695A (zh) 2016-08-03

Similar Documents

Publication Publication Date Title
CN102304316B (zh) 聚丙烯酸酯/纳米ZnO复合涂饰剂及其制备方法
CN102134296B (zh) 氟硅改性水溶性丙烯酸树脂分散体及其用途
CN106478864B (zh) 一种低凝聚物防水乳液及其制备方法
CN102532401B (zh) 一种弹性乳液及其制备方法
CN106479303A (zh) 一种防水抗菌涂料
CN108329741A (zh) 阻燃、抗菌、防水石墨烯改性丙烯酸酯树脂涂料中间产物的制备方法
DE112017000374B4 (de) Ein langsam freisetzendes, vor Schimmelpilzen schützendes und kaseinbasiertes Mikrohohlkugel-Beschichtungsmaterial und ein Verfahren zu dessen Herstellung
CN104017456B (zh) 一种耐光与阻燃性水性丙烯酸酯类树脂涂料的制备方法
CN102146247B (zh) 一种含聚醚改性硅丙柔性树脂的防水涂料及其制备方法
CN101724116A (zh) 一种聚合物乳液及其制备方法
CN101550217A (zh) 一种无皂核壳型硅丙乳液的制备方法
CN103130950B (zh) 一种含氟丙烯酸酯三元共聚物乳液的制备方法
CN109651558B (zh) 一种自交联核壳结构的水性丙烯酸分散体及其制备方法和应用
CN104119544A (zh) 聚全氟乙丙烯浓缩分散液的制备方法
CN102020818B (zh) 丙烯酸酯/硅丙复配乳液的制备方法及其复配乳液
CN108912929A (zh) 阻燃、抗菌性水性核壳丙烯酸酯类树脂涂料和油漆制备方法
CN104087107B (zh) 耐擦洗抗菌防火环保儿童涂料及其制备方法
CN102504087A (zh) 以保护胶体稳定的含硅丙烯酸酯无皂乳液的制备方法
CN109796552A (zh) 一种儿童漆用纯丙乳液及其制备方法
CN104497842A (zh) 一种防静电紫外光固化涂料的制备方法
CN111500097A (zh) 一种环保美术颜料及其制备方法
CN104086686B (zh) 一种具有优异冻融稳定性的苯丙乳液及其制备方法与应用
CN110511323A (zh) 一种改性丙烯酸乳液及其制备方法
CN102732075B (zh) 一种木器腻子及其制备方法
CN109734837A (zh) 一种耐水型k11乳液及其制备方法

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
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20180727