CN105330962A - Preparation method of super-tough antibacterial masterbatch with high concentration - Google Patents
Preparation method of super-tough antibacterial masterbatch with high concentration Download PDFInfo
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- CN105330962A CN105330962A CN201510788594.1A CN201510788594A CN105330962A CN 105330962 A CN105330962 A CN 105330962A CN 201510788594 A CN201510788594 A CN 201510788594A CN 105330962 A CN105330962 A CN 105330962A
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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
- C08L23/12—Polypropene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92009—Measured parameter
- B29C2948/92209—Temperature
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- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
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Abstract
The invention discloses a preparation method of super-tough antibacterial masterbatch with high concentration. The antibacterial masterbatch comprises components in parts by mass as follows: 100 parts of a resin carrier, 50-95 parts of an inorganic antibacterial agent, 10-20 parts of a toughening agent, 5-15 parts of inorganic powder and 5-15 parts of an auxiliary. According to the preparation method, the components are mixed uniformly and then melted, extruded and granulated by a twin-screw extruder, the super-tough antibacterial masterbatch with high concentration is obtained, then the resin carrier is added in proportion, the mixture is mixed uniformly, melted, extruded and granulated, and super-tough antibacterial plastic sections are obtained. The antibacterial masterbatch is prepared by a simple preparation process, has the lasting broad-spectrum antibacterial property, can be widely applied to the fields of toys, spectacle frames and the like and has very high application values.
Description
Technical field
The invention belongs to anti-biotic material preparations and applicatio technical field, be specifically related to a kind of preparation method of super tough high density antibacterial matrices.
Background technology
Plastics have a wide range of applications in life, can increase the germ resistance of plastics by adding antiseptic-germicide, have health self-cleaning function with the various plastics that they are made, and to protection human health, reduce disease, can play an important role.The development and application of antibacterial matrices has become the important technology content of this development field, and high density antibacterial matrices is conducive to the process for processing of antibacterial plastic product, and greatly can reduce production cost, and therefore development rapidly.
Antiseptic-germicide comprises organic and inorganic antiseptic, and wherein organic antibacterial agent poor heat resistance, is easily hydrolyzed, and validity period is short, and security is poor.The advantages such as inorganic antiseptic relies on good heat resistance, antibacterial timeliness is long, security is high are used widely.Conventional inorganic antiseptic comprises silver system, copper system and zinc system.Such as, Chinese patent CN1699459A discloses a kind of silver-carrying nano oxide compound antibacterial polypropylene water-feeding pipes and preparation method thereof, but silver-series antibacterial agent chemical stability is poor, by ambient light according to etc. after effect color easily deepen, and price is more expensive.In recent years, copper series antibacterial agent is also used widely, and such as Chinese patent CN103980628A discloses the preparation method that a kind of cupric oxide is the antibiotic plastic of antiseptic-germicide, but copper series antibacterial agent color is comparatively dark, affects the attractive in appearance of product, thus makes it apply to be restricted.Zinc series antibacterial agent, without discoloration problem, is convenient to toning, low price, and nontoxic, reliable to human-body safety, can be widely used in preparing various plastics.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides a kind of preparation method of super tough high density antibacterial matrices, with resin matrix, inorganic powder antiseptic-germicide, toughner, inorganic powder and auxiliary agent for raw material, by melt extruding, granulation obtains the finished product.Antibacterial matrices preparation technology in the present invention is simple, has the antibacterial and anti-mold effect of durable broad spectrum, has very high using value.
A preparation method for super tough high density antibacterial matrices, is characterized in that, comprise the following steps:
(1) load weighted resin matrix, inorganic antiseptic, toughner, inorganic powder and auxiliary agent are fully mixed, proportioning is resin carrier 100 parts, inorganic antiseptic 50-95 part, toughner 10-20 part, inorganic powder 5-15 part, auxiliary agent 5-15 part;
(2) raw material fully mixed is added twin screw extruder, through melt extruding, granulation process, then the mother particles of antibacterial plastics of preparation is placed in the dry 3-5h of baking oven of 60-80 DEG C;
(3) fully mixing antibacterial matrices and resin matrix, proportioning is 5-7:100, melt extrudes, granulation obtains super tough antibiotic plastic section.
Inorganic powder antiseptic-germicide used is Zinc oxide powder, and purity is greater than 98%, initial particle is at 20-50nm.
Toughner used is polyolefin elastomer or thermoplastic elastomer, POE.
The auxiliary agent used is oxidation inhibitor and lubricant, wherein, oxidation inhibitor is three (2,4-di-tert-butyl-phenyl) phosphorous acid ester (168), four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (1010), N, the combination of one or more in N '-inferior hexyl-1.6-two [(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid amide] (1098); Lubricant is the combination of one or more in whiteruss, Zinic stearas, polyethylene wax.
Inorganic powder used is titanium dioxide, silicon-dioxide, calcium carbonate.
Plastic substrate used is polyethylene, polypropylene.
The invention provides a kind of preparation method of super tough high density antibacterial matrices, take zinc oxide as antiseptic-germicide, add thermoplastic elastomer and inorganic powder raising toughness, the antibacterial matrices of the tough high density of preparation excess of export, can be widely used in the association area such as toy for children, spectacle frame.
The super tough high density antibacterial matrices adopting the inventive method to prepare has following advantage:
(1) because nano-scale oxidized zinc powder has excellent germ resistance, prepared antibacterial matrices and section reach more than 99% to the antibiotic rate of the bacterium colony such as intestinal bacteria, streptococcus aureus;
(2) the super tough high density antibacterial matrices prepared of the present invention and section thereof have broad-spectrum antimicrobial effect, can suppress, eliminating bacteria and fungi, can be widely used in the field such as toy for children, spectacle frame, have very high using value.
Embodiment
Below by embodiment, the present invention is specifically described.Following examples, only for the invention will be further described, can not be interpreted as limiting the scope of the invention, the adjustment that professional and technical personnel's content according to the present invention in this field is made, and still belong to protection scope of the present invention.
Embodiment one:
Take acrylic resin 100 parts, whiteruss 6 parts, 0.15 part, oxidation inhibitor, zinc oxide antiseptic-germicide 55 parts, POE15 part, titanium dioxide 5.5 parts, then it is fully mixed, process with twin screw extruder, the temperature in each district of twin screw extruder is: 140 DEG C, a district, two 150 DEG C, districts, three 180 DEG C, districts, four 180 DEG C, districts, five 185 DEG C, districts, six 190 DEG C, districts, seven 190 DEG C, districts, eight 195 DEG C, districts, nine 190 DEG C, districts, head 190 DEG C, rate of feeding: 14, forcing machine rotating speed: 180rpm, after granulation, 60 DEG C of dry 4h.By this master batch and acrylic resin according to 5:95 ratio melt blending, extrude, granulation, forcing machine each section of temperature is 150 ~ 195 DEG C, prepares the antibacterial section that ZnO content is 1.5wt%, and tests its correlated performance.
Embodiment two:
Take acrylic resin 100 parts, whiteruss 7 parts, 0.2 part, oxidation inhibitor, zinc oxide antiseptic-germicide 85 parts, POE12 part, titanium dioxide 8.5 parts, then it is fully mixed, process with twin screw extruder, the temperature in each district of twin screw extruder is: 140 DEG C, a district, two 150 DEG C, districts, three 180 DEG C, districts, four 185 DEG C, districts, five 190 DEG C, districts, six 190 DEG C, districts, seven 195 DEG C, districts, eight 195 DEG C, districts, nine 195 DEG C, districts, head 190 DEG C, rate of feeding: 15, forcing machine rotating speed: 220rpm, after granulation, 80 DEG C of dry 3h.By this master batch and acrylic resin according to 5:100 ratio melt blending, extrude, granulation, forcing machine each section of temperature is 150 ~ 195 DEG C, prepares the antibacterial section that ZnO content is 1.9wt%, and tests its correlated performance.
Embodiment three:
Take acrylic resin 100 parts, whiteruss 9 parts, 0.2 part, oxidation inhibitor, zinc oxide antiseptic-germicide 92 parts, POE15 part, titanium dioxide 13 parts, then it is fully mixed, process with twin screw extruder, the temperature in each district of twin screw extruder is: 150 DEG C, a district, two 155 DEG C, districts, three 180 DEG C, districts, four 185 DEG C, districts, five 185 DEG C, districts, six 190 DEG C, districts, seven 190 DEG C, districts, eight 195 DEG C, districts, nine 195 DEG C, districts, head 190 DEG C, rate of feeding: 15, forcing machine rotating speed: 200rpm, after granulation, 80 DEG C of dry 4h.By this master batch and acrylic resin according to 5:100 ratio melt blending, extrude, granulation, prepare the antibacterial section that ZnO content is 1.9wt%, and test its correlated performance.
Embodiment four:
Take acrylic resin 100 parts, polyethylene wax 10 parts, 0.5 part, oxidation inhibitor, zinc oxide antiseptic-germicide 160 parts, POE30 part, titanium dioxide 20 parts, then it is fully mixed, process with twin screw extruder, the temperature in each district of twin screw extruder is: 150 DEG C, a district, two 155 DEG C, districts, three 180 DEG C, districts, four 185 DEG C, districts, five 185 DEG C, districts, six 190 DEG C, districts, seven 190 DEG C, districts, eight 195 DEG C, districts, nine 195 DEG C, districts, head 190 DEG C, rate of feeding: 15, forcing machine rotating speed: 200rpm, after granulation, 80 DEG C of dry 5h.By this master batch and acrylic resin according to 4:96 ratio melt blending, extrude, granulation, prepare the antibacterial section that ZnO content is 2wt%, and test its correlated performance.
The performance test results of the antibiotic plastic section in table 1 embodiment
In the present invention, antibacterial detection is according to GB GB21510-2008 material anti-microbial property experimental technique---and film applicator coating is tested; Tensile strength, elongation at break adopt GB/T1040.2-2006 standard to test, and specimen size is 150mm*10mm*4mm; Flexural strength adopts GB/T9341-2000 standard to test, and specimen size is 80mm*10mm*4mm; Shock strength adopts GB/T1943-2007 standard to test, and specimen size is 60mm*10mm*4mm.As can be seen from case study on implementation and table 1, by ratio and the composition of each component in adjustment formula, high density antibacterial matrices can be prepared, and the section of high tenacity antibiotic plastic can be prepared.
Claims (6)
1. a preparation method for super tough high density antibacterial matrices, is characterized in that, comprise the following steps:
(1) load weighted resin matrix, inorganic antiseptic, toughner, inorganic powder and auxiliary agent are fully mixed, proportioning is resin carrier 100 parts, inorganic antiseptic 50-95 part, toughner 10-20 part, inorganic powder 5-15 part, auxiliary agent 5-15 part;
(2) raw material fully mixed is added twin screw extruder, through melt extruding, granulation process, then the mother particles of antibacterial plastics of preparation is placed in the dry 3-5h of baking oven of 60-80 DEG C;
(3) fully mixing antibacterial matrices and resin matrix, proportioning is 5-7:100, melt extrudes, granulation obtains super tough antibiotic plastic section.
2. the preparation method of a kind of super tough high density antibacterial matrices according to claim 1, it is characterized in that, inorganic powder antiseptic-germicide used is Zinc oxide powder, and purity is greater than 98%, initial particle is at 20-50nm.
3. the preparation method of a kind of super tough high density antibacterial matrices according to claim 1, it is characterized in that, toughner used is polyolefin elastomer or thermoplastic elastomer, POE.
4. the preparation method of a kind of super tough high density antibacterial matrices according to claim 1, it is characterized in that, the auxiliary agent used is oxidation inhibitor and lubricant, wherein, oxidation inhibitor is three (2,4-di-tert-butyl-phenyl) phosphorous acid ester (168), four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (1010), N, the combination of one or more in N '-inferior hexyl-1.6-two [(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid amide] (1098); Lubricant is the combination of one or more in whiteruss, Zinic stearas, polyethylene wax.
5. the preparation method of a kind of super tough high density antibacterial matrices according to claim 1, it is characterized in that, inorganic powder used is titanium dioxide, silicon-dioxide, calcium carbonate.
6. the preparation method of a kind of super tough high density antibacterial matrices according to claim 1, it is characterized in that, plastic substrate used is polyethylene, polypropylene.
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694176A (en) * | 2016-02-18 | 2016-06-22 | 惠州市环美盛新材料有限公司 | Antibacterial reinforced HDPE (high-density polyethylene) pipeline functional master batch and method for preparing same |
| CN106633279A (en) * | 2016-11-07 | 2017-05-10 | 上海纳米技术及应用国家工程研究中心有限公司 | Antibacterial PE masterbatch for preservative film and application |
| CN106854380A (en) * | 2016-12-19 | 2017-06-16 | 钦州市科学技术开发中心 | A kind of mother particles of antibacterial plastics and preparation method thereof |
| CN108395679A (en) * | 2017-09-22 | 2018-08-14 | 浙江中迪纺织新材料科技有限公司 | A kind of high molecular polymer antibacterial plastic concentrate and preparation method thereof based on one-D nano zinc oxide |
| CN108411399A (en) * | 2017-09-22 | 2018-08-17 | 浙江中迪纺织新材料科技有限公司 | A kind of bed necessaries prepared by the polyester antibacterial plastic concentrate based on 1-dimention nano Ag/C composite materials |
| CN108410141A (en) * | 2017-09-22 | 2018-08-17 | 浙江中迪纺织新材料科技有限公司 | A kind of high molecular polymer antibacterial plastic concentrate and preparation method thereof based on 1-dimention nano Ag/C composite materials |
| CN108641181A (en) * | 2018-05-15 | 2018-10-12 | 北京金天化塑胶有限公司 | A kind of toughening type master batch and preparation method thereof |
| CN108976565A (en) * | 2018-08-10 | 2018-12-11 | 阜南县鲲鹏塑业科技有限公司 | A kind of dedicated antibacterial of household electrical appliances plastic shell prevents old noise reduction masterbatch |
| CN109535550A (en) * | 2018-10-31 | 2019-03-29 | 安徽春辉仪表线缆集团有限公司 | A kind of watermeter shell antibiotic aging-resistant PP composite material |
| CN109721844A (en) * | 2018-12-29 | 2019-05-07 | 上海普利特复合材料股份有限公司 | A kind of high antibacterial low distributes automobile-used modified polypropylene composite material and preparation method thereof |
| CN110551335A (en) * | 2019-09-19 | 2019-12-10 | 苏州润步新材料有限公司 | Antibacterial masterbatch and preparation method thereof |
| CN111605098A (en) * | 2019-02-22 | 2020-09-01 | 斯坦德瑞琪色彩（苏州）有限公司 | Color master batch with antibacterial hydrophilic softening function, non-woven fabric and preparation method thereof |
| CN111621090A (en) * | 2020-05-20 | 2020-09-04 | 博富科技股份有限公司 | Master batch with algae inhibiting function and preparation method thereof |
| CN111944249A (en) * | 2020-08-24 | 2020-11-17 | 安徽联科水基材料科技有限公司 | Transparent GPPS (general purpose polystyrene) antibacterial functional master batch and preparation method thereof |
| CN112679822A (en) * | 2020-12-17 | 2021-04-20 | 厦门翔鹭化纤股份有限公司 | Preparation method and application of antibacterial polyethylene master batch |
| CN115368839A (en) * | 2022-09-13 | 2022-11-22 | 上海优珀斯材料科技有限公司 | Antiviral and antibacterial PE self-adhesive protective film and manufacturing method and application thereof |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694176A (en) * | 2016-02-18 | 2016-06-22 | 惠州市环美盛新材料有限公司 | Antibacterial reinforced HDPE (high-density polyethylene) pipeline functional master batch and method for preparing same |
| CN105694176B (en) * | 2016-02-18 | 2019-02-19 | 惠州市环美盛新材料有限公司 | A kind of antibacterial enhancing HDPE function pipeline masterbatch and preparation method thereof |
| CN106633279A (en) * | 2016-11-07 | 2017-05-10 | 上海纳米技术及应用国家工程研究中心有限公司 | Antibacterial PE masterbatch for preservative film and application |
| CN106854380A (en) * | 2016-12-19 | 2017-06-16 | 钦州市科学技术开发中心 | A kind of mother particles of antibacterial plastics and preparation method thereof |
| CN108411399A (en) * | 2017-09-22 | 2018-08-17 | 浙江中迪纺织新材料科技有限公司 | A kind of bed necessaries prepared by the polyester antibacterial plastic concentrate based on 1-dimention nano Ag/C composite materials |
| CN108410141A (en) * | 2017-09-22 | 2018-08-17 | 浙江中迪纺织新材料科技有限公司 | A kind of high molecular polymer antibacterial plastic concentrate and preparation method thereof based on 1-dimention nano Ag/C composite materials |
| CN108395679A (en) * | 2017-09-22 | 2018-08-14 | 浙江中迪纺织新材料科技有限公司 | A kind of high molecular polymer antibacterial plastic concentrate and preparation method thereof based on one-D nano zinc oxide |
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