WO2020073781A1 - 一种注塑材料及其制备方法 - Google Patents

一种注塑材料及其制备方法 Download PDF

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WO2020073781A1
WO2020073781A1 PCT/CN2019/106746 CN2019106746W WO2020073781A1 WO 2020073781 A1 WO2020073781 A1 WO 2020073781A1 CN 2019106746 W CN2019106746 W CN 2019106746W WO 2020073781 A1 WO2020073781 A1 WO 2020073781A1
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guanidine
injection molding
molding material
methacrylate
antibacterial
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PCT/CN2019/106746
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English (en)
French (fr)
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刘及响
赵云瑞
李郁聪
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桂林新先立抗菌材料有限公司
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Publication of WO2020073781A1 publication Critical patent/WO2020073781A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • This application belongs to the field of plastic materials. Specifically, this application provides an injection molding material and a preparation method thereof, in which the antibacterial masterbatch is polymerized using a non-toxic / non-irritating polyol and a guanidine salt.
  • Plastic products occupy a very important position in people's daily life and industrial and agricultural production. Many plastic products such as water pipes and daily-use containers will come into frequent contact with people or people's drinking water and food, and plastic materials are easily occupied and contaminated by bacteria , Especially in a humid and organic environment, the plastic surface often breeds a lot of bacteria. Therefore, there are increasingly higher requirements for plastic antibacterial properties in the plastics field. Adding antibacterial agents to plastics and preparing antibacterial plastics can effectively solve this problem.
  • Inorganic antibacterial agents are mainly silver ions and zinc ions. Due to the complicated preparation process, products often have unstable properties and their antifungal properties Often flawed.
  • Organic antibacterial agents mainly include quaternary ammonium salts, ethers, phenols, thiazoles, diphenyl ether compounds, etc. It is characterized by fast sterilization speed and wide antibacterial spectrum, but its heat and water resistance and chemical resistance are poor. The effective period of antibacterial is short, and the above-mentioned problems are particularly serious when used in plastics such as pipes and household containers that are frequently exposed to hot water and detergent.
  • the inventors previously polymerized polyamines and guanidine salts to obtain an antibacterial masterbatch and obtained the Chinese patent CN1111556C.
  • the masterbatch was actually used in plastics, fibers, coatings, etc., and achieved good practice. effect.
  • the masterbatch has a good anti-fungal effect, it has the same problem of insufficient water and washing resistance as most organic antibacterial agents (the water solubility of the guanidine structure makes this problem more pronounced), and existing such as CN1111556C
  • Antimicrobial masterbatches mostly use toxic / irritating raw materials such as polyamines.
  • the waste water generated is not environmentally friendly and the residues may be irritating to human skin if they are in long-term contact with the human body (such as for daily use containers).
  • the inventors further improved the polymer antibacterial agent containing a guanidine structure of CN1111556C, and prepared a new type of antibacterial polymer by polymerizing a polyhydric alcohol and a guanidine salt.
  • the polymer maintained the antibacterial performance similar to that of CN1111556C Achieved a significant increase in heat resistance, water resistance, and detergent resistance, making it more suitable for the preparation of plastic materials that are frequently exposed to water and detergents, such as pipes and household containers, and uses non-toxic / non-irritating polyols As a raw material, it is more environmentally friendly than polyamines, and is more suitable for the preparation of daily containers and pipes.
  • the present application provides an injection molding material, which includes an antibacterial polymer formed by polymerizing a polyhydric alcohol or a polyamine and a guanidinium salt.
  • the antibacterial polymer is formed by polymerizing a polyhydric alcohol and a guanidine salt, and has the following structure:
  • X is selected from acrylate group, methacrylate group, crotonate group, undecylenate group, ethyl acrylate group, propyl acrylate group or hydroxypropyl methacrylate group Ester group.
  • the antibacterial polymer is prepared by the following method: the polyol and the guanidine salt are mixed in a molar ratio of 1: 0.8-1.8. Add to the reactor, adjust the pH to acidic under the protection of nitrogen, heat to 120-180 °C, react for 1-4 hours, and then add 5% -25% by weight of polyol and guanidine salt containing active unsaturated double bond C3- The C20 compound undergoes esterification or ring-opening condensation reaction, and the reaction is terminated after 10 to 120 minutes.
  • the molar ratio of polyol to guanidine salt is 1: 1 to 1.5.
  • the polyhydric alcohol is selected from ethylene glycol, propylene glycol, butylene glycol, pentanediol, 1,6-hexanediol, 1,10-decanediol
  • the guanidine salt is selected from guanidine carbonate, guanidine hydrochloride, guanidine nitrate, Guanidine sulfate, guanidine phosphate, guanidine acetate
  • C3-C20 compounds containing active unsaturated double bonds are selected from acrylic acid, methacrylic acid, epoxyethyl acrylate, glycidyl acrylate, epoxybutyl acrylate, methacrylic acid ring Oxypropyl ester, epoxy ethyl methacrylate, epoxy butyl methacrylate, methyl methacrylate, ethyl methacrylate, butyl acrylate, ethyl acrylate, 2-hydroxyethyl acrylate, acrylic acid- 2-hydroxy
  • preparation method specifically includes:
  • preparation method specifically includes:
  • the molecular weight of the product is about 8300, the thermal decomposition temperature is about 340 °C, and the infrared spectrum shows the characteristic absorption peak.
  • the molecular weight of the product is about 11500, the thermal decomposition temperature is about 360 °C, and the infrared spectrum shows the characteristic absorption peak.
  • injection molding materials are completed by the cooperative enterprise; the antibacterial masterbatch of CN1111556C is prepared according to Example 1 in this publication; the antibacterial masterbatch of this application is prepared according to the method of Example 1 (1.1); PP-R resin raw material particles, A Phenyl silicone oil, polypropylene wax (molecular weight 12000), talc powder (3000 mesh) are all conventional types purchased from Ningbo Zhenhai Better Plastic Co., Ltd. and Shanghai Yuxi Industrial Co., Ltd .; the injection molding machine is Yujiang YJ88 Horizontal injection molding machine.
  • the specific preparation process is as follows: 100 parts by weight of PP-R resin raw material particles are added to the mixer, 0.2 parts by weight of methylphenyl silicone oil is added at 200 rpm, and after continuous mixing for 5 minutes, 1 part by weight of talc and 0.3 parts by weight are added in sequence. Polypropylene wax and optional 3 parts by weight of the antibacterial masterbatch / CN1111556C antibacterial masterbatch of this application, continue to mix for 5 minutes and then loaded into the injection molding machine to produce antibacterial injection materials °C, 220 °C, 210 °C).
  • the main physical properties of materials 1-3 relative density 0.905-0.908, tensile strength 35.7-36.4MPa, elongation at break 400-430%, bending strength 25.2-26.7MPa, Vicat softening point (1kg, 120 °C / h) 150-153 °C, heat distortion temperature (0.45MPa) 97-98 °C.
  • Material 1-1 Material 1 is soaked in hot water at 70 ° C for 48 hours and dried;
  • Material 1-2 Material 1 Plastic tablets are added to the drum-type washing machine with the recommended amount of washing liquid (blue moon, unscented), pre-soaked for 12 hours, and washed 50 times (approximately 1 each time) at 30 °C Hours), rinse and dry;
  • Material 2-1 Material 2 is soaked in hot water at 70 ° C for 48 hours and dried;
  • Material 2-2 Material 2 plastic sheet is added to the drum-type washing machine with the recommended amount of laundry detergent (blue moon, no fragrance), pre-washed and soaked for 12 hours, then washed 50 times (approximately 1 each time) at 30 °C Hours), rinse and dry;
  • the physical properties of the treated materials 1 and 2 did not change significantly compared with that before the treatment.
  • the antibacterial performance test was carried out by the Antibacterial Material Testing Center of the Institute of Physics and Chemistry of the Chinese Academy of Sciences. The experiment basically followed the People ’s Republic of China National Light Industry Standard QB / T2591-2003.
  • Detection of bacteria and Candida albicans the sterilized polyethylene film was covered with The plastic samples were eluted after 24 hours of incubation. After 48 hours of incubation (72 hours of Candida albicans), live bacteria were counted according to the method of GB4789.2 to calculate the antibacterial rate.
  • Detection of mold Spread the plastic sheet on the plate medium and spray the mold spore suspension evenly. After 28 days of cultivation, the area covered by mold growth is detected.
  • Bacterial test objects include: Staphylococcus aureus ATCC 6538, Escherichia coli ATCC 2592, 2 and the fungus Candida albicans (ATCC) 10231, fungal test objects include: Aspergillus niger ( Aspergillusniger) ATCC 6275, ballet shell (Chaetoomium globsum) ATCC 6205,
  • the above-mentioned properties of the injection molding material of the present application make it particularly advantageous in the preparation of water pipes, daily-use containers such as basins, bathtubs, and barrels, and it can better maintain antibacterial ability after long-term use.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

本发明提供了一种注塑材料及其制备方法，其中的抗菌母料由多元醇与胍盐聚合而成，具有以下式（I）结构：抗菌母料制备方法中使用无毒无刺激的多元醇为原料对环境和人体友好。

Description

一种注塑材料及其制备方法 一 技术领域
本申请属于塑料材料领域，具体的本申请提供了一种注塑材料及其制备方法，其中的抗菌母料使用无毒/无刺激的多元醇与胍盐聚合而成。
二 背景技术
塑料制品在人们的日常生活和工农业生产中占十分重要的地位，许多塑料制品如水管、日用容器等会与人或人的饮水与食物频繁接触，而塑料材料容易被细菌所占据和污染，特别是在潮湿且有机物丰富的日用环境中塑料表面经常会滋生大量细菌。因此塑料领域有塑料抗菌性能有越来越高的要求。向塑料中添加抗菌剂，制备抗菌塑料能够有效解决此问题的主要手段。
目前，常用的塑料抗菌剂中，天然抗菌剂由于价格和稳定性的原因无法广泛应用；无机抗菌剂主要为银离子和锌离子，由于其制备工艺复杂产品往往性能不稳定，而且其抗真菌性能往往有缺陷。有机抗菌剂主要有季铵盐类、醚类、苯酚类、噻唑类、联苯醚类化合物等，其特点是杀菌速度快、抗菌谱广，但其耐热耐水耐化学品性能差，产品的抗菌有效期短，上述问题在用于频繁接触热水和洗涤剂的管道和日用容器类塑料时特别严重。
发明人先前将多元胺与胍盐聚合，获得了一种抗菌母料并取得了中国专利CN1111556C，随后的应用中，该母料被实际用于塑料、纤维、涂料等方面，取得了良好的实际效果。但该母料虽然抗霉菌效果良好，但与大多数有机抗菌剂一样存在耐水耐洗涤性能不足的问题(胍结构的水溶性使这一问题更为显著)，而且包括CN1111556C在内的现有此类抗菌母料多采用有毒/刺激性的原料如多元胺，产生的污水废料对环保不利且残留物与人体长期接触(如用于日用容器)可能会对人体皮肤有刺激。含胍结构的聚合物抗菌剂存在进一步改进的需求。
三 发明内容
针对上述问题，发明人进一步改进了CN1111556C的含胍结构的聚合物抗菌剂，使用多元醇与胍盐聚合制备了新型抗菌聚合物，该聚合物在保持类似CN1111556C抗菌聚合物抗菌性能的前提下，实现了耐热、耐水、耐洗涤剂能力的显著提高，使得其更适合用于经常接触水和洗涤剂的塑料材料，如管道、日用容器的制备，而且采用无毒/无刺激的多元醇作为原料，对环境比多元胺更为友好，更适合制备日用容器和管道。
一方面，本申请提供了一种注塑材料，其中包括抗菌聚合物，所述抗菌聚合物由多元醇 或多元胺与胍盐聚合而成。
进一步地，该抗菌聚合物由多元醇与胍盐聚合而成，具有以下结构：
Figure PCTCN2019106746-appb-000001
其中n＝5-10，m＝50-150；Y -为选自Cl -、NO 3 -、HCO 3 -、CH 3COO -、HSO 4 -或H 2PO 4 -阴离子；X为含1-5个活性不饱和双键的C5-C20酯基或醚基；Z为H或X。
进一步地，该抗菌聚合物中，X选自丙烯酸酯基、甲基丙烯酸酯基、丁烯酸酯基、十一碳烯酯基、丙烯酸乙酯基、丙烯酸丙酯基或甲基丙烯酸羟基丙酯基。
进一步地，该抗菌聚合物按以下方法制备：将多元醇与胍盐以摩尔比1：0.8-1.8的比例混合。加入反应器中，氮气保护下，调pH至酸性，加热至120-180℃，反应1-4小时，而后再加入多元醇和胍盐重量5％-25％的含活性不饱和双键的C3-C20化合物，进行酯化或开环缩合反应，10-120分钟后，结束反应。
进一步地，多元醇与胍盐的摩尔比为1：1-1.5。
进一步地，多元醇选自乙二醇、丙二醇、丁二醇、戊二醇、1，6-己二醇、1，10-癸二醇；胍盐选自碳酸胍、盐酸胍、硝酸胍、硫酸胍、磷酸胍、乙酸胍；含活性不饱和双键的C3-C20化合物选自丙烯酸、甲基丙烯酸、丙烯酸环氧乙酯、丙烯酸环氧丙酯、丙烯酸环氧丁酯、甲基丙烯酸环氧丙酯、甲基丙烯酸环氧乙酯、甲基丙烯酸环氧丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸丁酯、丙烯酸乙酯、丙烯酸-2-羟基乙酯、丙烯酸-2-羟基丙酯、甲基丙烯酸环氧丙酯、甲基丙烯酸-2-羟基丙酯、马来酸酐、富马酸酯、衣康酸。
进一步地，制备方法具体包括：
取乙二醇124g，硝酸胍260g，加入反应釜中，混合均匀，氮气保护下，以盐酸调pH为5，加热至120℃，反应3h，再加入丙烯酸30g，进行酯化反应1h，结束反应
进一步地，制备方法具体包括：
取1，6-己二醇118g，盐酸胍100g，加入反应釜中，混合均匀，氮气保护下，以盐酸调pH为3，加热至150℃，反应2h，再加入丙烯酸环氧丙烷20g，进行酯化反应2h，结束反应。
四 具体实施方式
实施例1 本申请抗菌母料的制备
1.1取乙二醇124g，硝酸胍260g，加入反应釜中，混合均匀，氮气保护下，以盐酸调pH为5，加热至120℃，反应3h，再加入丙烯酸30g，进行酯化反应1h，结束反应。造粒。
产品分子量约8300，热分解温度约340℃，红外图谱显示应有的特征吸收峰。
1.2取1，6-己二醇118g，盐酸胍100g，加入反应釜中，混合均匀，氮气保护下，以盐酸调pH为3，加热至150℃，反应2h，再加入丙烯酸环氧丙烷20g，进行酯化反应2h，结束反应。造粒。
产品分子量约11500，热分解温度约360℃，红外图谱显示应有的特征吸收峰。
实施例2 注塑材料的制备
注塑材料具体制备由合作企业完成；CN1111556C的抗菌母料按照该公开文本中的实施例1制备；本申请的抗菌母料按照实施例1(1.1)的方法制备；PP-R树脂原料颗粒、甲基苯基硅油、聚丙烯蜡(分子量12000)、滑石粉(3000目)均为购自宁波市镇海百特思塑化有限公司和上海雨汐实业有限公司的常规种类；注塑机为煜江YJ88卧式注塑机。
具体制备过程为：将100重量份的PP-R树脂原料颗粒加入到混合机中，200rmp下加入0.2重量份甲基苯基硅油，继续混合5分钟后依次加入1重量份滑石粉、0.3重量份聚丙烯蜡和可选的3重量份本申请抗菌母料/CN1111556C抗菌母料，继续混合5分钟后装入注塑机，制得抗菌注塑材料(注塑机四个区域工作温度依次为200℃、210℃、220℃、210℃)。
材料1：加入本申请抗菌母料；
材料2：加入CN1111556C抗菌母料；
材料3：不加入抗菌母料；
材料1-3的主要物理性能：相对密度0.905-0.908、拉伸强度为35.7-36.4MPa、断裂伸长率400-430％、弯曲强度为25.2-26.7MPa、维卡软化点(1kg、120℃/h)150-153℃、热变形温度(0.45MPa)97-98℃。
为检测本申请抗菌注塑材料的耐热和耐洗涤性能，对材料1和2进行进一步处理：
材料1-1：材料1经70℃热水浸泡48小时，干燥；
材料1-2：材料1塑料片在滚筒式洗衣机中加入说明书推荐量的洗衣液(蓝月亮，无香型)，预洗浸泡12小时后，以普通程序30℃洗涤50次(每次约1小时)，漂洗干净，干燥；
材料2-1：材料2经70℃热水浸泡48小时，干燥；
材料2-2：材料2塑料片在滚筒式洗衣机中加入说明书推荐量的洗衣液(蓝月亮，无香型)，预洗浸泡12小时后，以普通程序30℃洗涤50次(每次约1小时)，漂洗干净，干燥；
处理后的材料1和2相比处理前各项物理性能没有明显变化。
实施例3 注塑材料抗菌性能检测
抗菌性能检测由中国科学院理化所抗菌材料检测中心进行，实验基本遵循中华人民共和国国轻工行业标准QB/T2591-2003，检测细菌和白色念珠菌：将灭菌后的聚乙烯薄膜平铺覆盖于塑料样品上，培养24小时后洗脱，培养48小时后(白色念珠菌72小时)按照GB 4789.2的方法活菌计数，计算抗菌率。检测霉菌：将塑料片平铺于平板培养基上，均匀喷洒霉菌孢子悬液，培养28日后检测霉菌生长覆盖面积。
细菌测试对象包括：金黄色葡萄球菌(Staphylococcus aureus)ATCC 6538、大肠埃希氏菌(Escherichia coli)ATCC 2592，2并加入真菌白色念珠菌(Canidia Albicans)ATCC 10231，霉菌测试对象包括：黑曲霉(Aspergillus niger)ATCC 6275、球毛壳(Chaetoomium globsum)ATCC 6205、
表1 注塑材料的抗细菌/白色念珠菌性能
Figure PCTCN2019106746-appb-000002
*参照QB/T2591-2003标准，90％以下即不能称为有抗菌作用。
表2.注塑材料的抗霉菌性能
样品编号 黑曲霉长霉等级 球毛壳长霉等级
材料1 0级 0级
材料2 0级 0级
材料3 无抗菌作用 无抗菌作用
材料1-1 0级 0级
材料1-2 0级 0级
材料2-1 0级 无抗菌作用
材料2-2 无抗菌作用 无抗菌作用
*霉菌生长覆盖面积大于10％(2级)即不能称为有抗菌作用。
以上实验数据显示，本申请抗菌母料的抗菌性能与CN1111556C抗菌母料相似，但耐受热水浸泡和洗涤能力明显强于CN1111556C抗菌母料，高强度热水和洗涤处理后抗细菌霉菌性能几无变化，而CN1111556C在热水处理后抗细菌霉菌性能都有降低，高强度洗涤处理后，更是丧失了大部分抗细菌性能和几乎全部抗霉菌性能。
另外的实验表明，含实施例1(1.2)抗菌聚合物的注塑材料机械和抗菌性能与含实施例1(1.1)的近似，同时制成的材料也具有类似的耐受热水浸泡和洗涤能力(为节约时间和费用未委托进行完整检测)。
本申请注塑材料的上述性能使得其在制备水管，日用容器如盆、浴缸、桶时特别有优势，能在长时间使用后较好的保持抗菌能力。
上述实施例中的注塑材料配方仅是为了举例列出，其余注塑材料颗粒，辅料与本申请抗菌母料配合的技术方案的抗菌效果可以从实施例2、3合理预期，并且这些技术方案也在本申请公开和要求保护的范围内。

Claims (8)

  1. 一种注塑材料，其特征在于其中包括抗菌聚合物，所述抗菌聚合物由多元醇或多元胺与胍盐聚合而成。
  2. 权利要求1的注塑材料，其中的抗菌聚合物由多元醇与胍盐聚合而成，具有以下结构：
    Figure PCTCN2019106746-appb-100001
    其中n＝5-10，m＝50-150；Y -为选自Cl -、NO 3 -、HCO 3 -、CH 3COO -、HSO 4 -或H 2PO 4 -阴离子；X为含1-5个活性不饱和双键的C5-C20酯基或醚基；Z为H或X。
  3. 权利要求2的注塑材料，其中的抗菌聚合物中，X选自丙烯酸酯基、甲基丙烯酸酯基、丁烯酸酯基、十一碳烯酯基、丙烯酸乙酯基、丙烯酸丙酯基或甲基丙烯酸羟基丙酯基。
  4. 权利要求3的注塑材料，其中的抗菌聚合物按以下方法制备：将多元醇与胍盐以摩尔比1：0.8-1.8的比例混合。加入反应器中，氮气保护下，调pH至酸性，加热至120-180℃，反应1-4小时，而后再加入多元醇和胍盐重量5％-25％的含活性不饱和双键的C3-C20化合物，进行酯化或开环缩合反应，10-120分钟后，结束反应。
  5. 权利要求4的注塑材料，其中抗菌聚合物的制备中，多元醇与胍盐的摩尔比为1：1-1.5。
  6. 权利要求5的注塑材料，其中抗菌聚合物的制备中，多元醇选自乙二醇、丙二醇、丁二醇、戊二醇、1，6-己二醇、1，10-癸二醇；胍盐选自碳酸胍、盐酸胍、硝酸胍、硫酸胍、磷酸胍、乙酸胍；含活性不饱和双键的C3-C20化合物选自丙烯酸、甲基丙烯酸、丙烯酸环氧乙酯、丙烯酸环氧丙酯、丙烯酸环氧丁酯、甲基丙烯酸环氧丙酯、甲基丙烯酸环氧乙酯、甲基丙烯酸环氧丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸丁酯、丙烯酸乙酯、丙烯酸-2-羟基乙酯、丙烯酸-2-羟基丙酯、甲基丙烯酸环氧丙酯、甲基丙烯酸-2-羟基丙酯、马来酸酐、富马酸酯、衣康酸。
  7. 权利要求4的注塑材料，其中抗菌聚合物的制备方法具体包括：
    取乙二醇124g，硝酸胍260g，加入反应釜中，混合均匀，氮气保护下，以盐酸调pH为5，加热至120℃，反应3h，再加入丙烯酸30g，进行酯化反应1h，结束反应。
  8. 权利要求4的注塑材料，其中抗菌聚合物的制备方法具体包括：
    取1，6-己二醇118g，盐酸胍100g，加入反应釜中，混合均匀，氮气保护下，以盐酸调pH为3，加热至150℃，反应2h，再加入丙烯酸环氧丙烷20g，进行酯化反应2h，结束反应。
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