CN108503963A - A kind of high antimicrobial form polypropylene color masterbatch and preparation method thereof - Google Patents
A kind of high antimicrobial form polypropylene color masterbatch and preparation method thereof Download PDFInfo
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- CN108503963A CN108503963A CN201810407830.4A CN201810407830A CN108503963A CN 108503963 A CN108503963 A CN 108503963A CN 201810407830 A CN201810407830 A CN 201810407830A CN 108503963 A CN108503963 A CN 108503963A
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- 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
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- 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
- C08J3/223—Packed additives
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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
- C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
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- 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
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2433/12—Homopolymers or copolymers of methyl methacrylate
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- C—CHEMISTRY; METALLURGY
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- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The invention discloses a kind of high antimicrobial form polypropylene color masterbatchs, are made of the raw material of following weight parts：Modified polypropene 60 90, inorganic pigment 20 30, composite dispersing agent 23, polymethyl methacrylate 10 15, bamboo charcoal fiber 20 30, phenolic antioxidant 1,010 12, Nano-meter CaCO330.5‑1；Polypropylene color masterbatch provided by the invention contains bamboo charcoal fiber, antibiotic rate is up to 90% or more, ultraviolet ray transmissivity is low, anti-aging property is strong, when the coloring applied to polypropylene articles, have many advantages, such as that good dispersion, uniform coloring, colour stability are high, concentration is high, dosage is few and on plasthetics mechanical performance without influencing.
Description
Technical field
The invention belongs to technical field of polymer materials more particularly to a kind of high antimicrobial form polypropylene color masterbatch and its preparations
Method.
Background technology
The color method of production plasthetics mainly has toner coloring, dyeing that grain coloring and Masterbatch is drawn to colour three kinds of sides
Method.Directly use toner coloring when, coloring it is very simple, but its disadvantage be pigment in transport, storage, weighing, mixed
Cheng Zhonghui is flown upward, and is generated pollution, is seriously affected environment, and it is not easy to control to easy to produce color dot, aberration.Dyeing draws grain to colour
Melt blending coloring is carried out using mixing facilities such as double screw extruder after plastic material and toner are mixed, with using toner
Form and aspect ratio draws grain coloring effect to have large increase, but plastic cement need to undergo and heat twice, not only increase production cost, and
The mechanical performance of product is compromised to a certain extent.When being coloured using Masterbatch, pigment is by pre-processing and being dispersed in
In vector resin, the dispersion performance and coloration efficiency of pigment are substantially increased, there is easy to operate, of low cost, pollution is few etc.
Advantage.
It is that the pigment of super quantity is uniformly attached to tree as colorant, carrier, dispersant three parts that Masterbatch, which is mainly organized,
Prepared by fat polymer compound, selected by resin to colorant have good wetting and peptizaiton, and
There is good compatibility with by coloured material.
Country's Masterbatch product structure is single at present, kind is not complete, and universal product accounts for very big proportion, and plastics need to colour
When coloured using monochromatic Masterbatch, need to add Anti-static electricity color master batch when antistatic property, addition resistance when needing flame retardant property
Fire Masterbatch.The method for adding single master batch to need to add when having high requirement to vector resin comprehensive performance
Thus the Masterbatch of a variety of different roles to consume a large amount of vector resin, and brings antioxidant in process to consume
The shortcomings of amount is high, downstream processing and forming component is more, complex process, following Masterbatch will be towards multifunction, high color content
It is continued to develop with the direction of high technology content.
With the continuous improvement of people's living standards, pursuit itself living environment of people more is clean comfortable, and pass through
It often appears in people at one's side, is in direct contact the plastic products of human body, the anti-microbial property of its own is to creating clean healthy life
Environment living plays an important roll, and anti-microbial property is more efficient, can more reduce disease incident, improve people's living environment, protection
Health provides a kind of poly- with anti-microbial property for this purpose, the present invention essential Masterbatch from plastic formula is set about
Propylene Masterbatch and preparation method thereof.
Invention content
The present invention overcomes prior art deficiencies, provide a kind of high antimicrobial form polypropylene color masterbatch and preparation method thereof.
The present invention is achieved by the following technical solutions：
A kind of high antimicrobial form polypropylene color masterbatch, is made of the raw material of following weight parts：
Modified polypropene 60-90, inorganic pigment 20-30, composite dispersing agent 2-3, polymethyl methacrylate 10-15, bamboo
Carbon fibe 20-30, phenolic antioxidant 10101-2, nm level CaCO_3 0.5-1.
It is 2 in mass ratio that the composite dispersing agent, which is by dispersant YY -5023, polyethylene wax, titanate coupling agent,：2：
1 ratio is formulated.
The inorganic pigment be titanium dioxide, carbon black, cadmium yellow, lead chromate yellow, cadmium red, iron oxide red, iron oxide yellow, barba hispanica,
One kind in cobalt blue, iron oxide brown, chrome oxide green or arbitrary combination, grain size are 0.5-10 μm.
The grain size of the bamboo charcoal fiber is 100-300 μm.
A kind of high antimicrobial form polypropylene color masterbatch preparation method, includes the following steps：
(1) by polypropylene by electron accelerator irradiation, the energy rank of electron accelerator is 3-5MeV, and irradiation dose is
10-20KGy, polypropylene and propylene after irradiation are 40-60 by weight：1 ratio mixing, obtains modified polypropene；
(2) by above-mentioned modified polypropene and composite dispersing agent, polymethyl methacrylate, bamboo charcoal fiber, phenolic antioxidant
1010, nm level CaCO_3 mixes by weight proportion, stirs 10-15 minutes, is mixed under the mixing speed of 1000-1200r/min
Close material；
(3) inorganic pigment is sent into autoclave, carbon dioxide is added, the pressure adjusted in autoclave is
60-90MPa, temperature are 100-150 DEG C, and carbon dioxide is made to become supercritical fluid；
(4) it being stirred using magnetic stirring apparatus, inorganic pigment is completely dissolved in supercritical fluid after 3-5 hours, then
The mixture in step (2) is added, continues stirring 20-30 hours, maintains temperature-resistant reduction pressure to 1-5MPa, continues to stir
It 10-15 hours, is deflated by gas bleeder valve, thick color masterbatch is taken out after cooling；
(5) by above-mentioned thick color masterbatch by melting, extrusion, pelletizing, the polypropylene colorant that particle size is 1-10mm is obtained
Grain.
Compared with prior art, it is an advantage of the invention that：
The present invention accumulates big feature using polypropylene surface, it is made to be come into full contact with oxygen, reaches and accelerates in high energy electron
When device irradiates, inhibit crosslinking with radiation, radiation cleavage is made to be reacted to main radioreaction, is made and contains a large amount of non-peroxide activities
The polypropylene powder of group, is melted with the Polyfunctional monomer containing unsaturated bond, and acquisition is grafted with Polyfunctional monomer
Modified polypropene powder so that non-polar polypropylene and the compatibility of polar toner, antioxidant, filler have obtained greatly changing
It is kind.
The bamboo charcoal fiber of honeycomb microporous structure is mixed with auxiliary agents such as carrier, dispersants, is covered in manufactured mixture
Big and small large number of elliptical shaped apertures.Inorganic pigment is dissolved in supercritical carbon dioxide fluid, then with it is porous
Mixture mixing, penetrated into mixture after numerous hole after it, by decompression expansion, micron-sized inorganic pigment can be gradual
It is deposited in mixture, the recyclable recycling of carbon dioxide of releasing.
Supercritical carbon dioxide fluid viscosity is low, diffusion property coefficient is big, diffusion boundary layer is small, the inorganic face of unimolecule of dissolving
Material can be rapidly soaked into gap in mixture, and coloration efficiency is far above traditional handicraft, substantially reduce the production cycle, and
Color is uniform, aberration is smaller, colour stability greatly improves.
Using dispersant YY -5023, the dispersant of polyethylene wax, titanate coupling agent composition, Masterbatch can be improved
Melt flow rate (MFR) increases counter balance torque, shortens the time reached needed for peak torque, is obtained within the shortest time ideal
Dispersion effect, and reduce dispersant dosage, reduce production cost.
Polypropylene color masterbatch provided by the invention contains bamboo charcoal fiber, and antibiotic rate is up to 90% or more, ultraviolet ray transmissivity
Low, anti-aging property is strong, when the coloring applied to polypropylene articles, has good dispersion, uniform coloring, colour stability
It is high, concentration is high, dosage is few and on plasthetics mechanical performance without influencing the advantages that.
Specific implementation mode
With reference to embodiment, present invention is further described in detail：
Embodiment：
A kind of high antimicrobial form polypropylene color masterbatch, is made of the raw material of following weight parts：
60 parts of modified polypropene, 20 parts of inorganic pigment, 2 parts of composite dispersing agent, 10 parts of polymethyl methacrylate, bamboo charcoal are fine
20 parts of dimension, 10101 parts of phenolic antioxidant, 0.5 part of nm level CaCO_3.
It is 2 in mass ratio that the composite dispersing agent, which is by dispersant YY -5023, polyethylene wax, titanate coupling agent,：2：
1 ratio is formulated.
The inorganic pigment is titanium dioxide, and grain size is 0.5 μm.
The grain size of the bamboo charcoal fiber is 100 μm.
A kind of high antimicrobial form polypropylene color masterbatch preparation method, includes the following steps：
(1) by polypropylene by electron accelerator irradiation, the energy rank of electron accelerator is 5MeV, and irradiation dose is
20KGy, polypropylene and propylene after irradiation are 50 by weight：1 ratio mixing, obtains modified polypropene；
(2) by above-mentioned modified polypropene and composite dispersing agent, polymethyl methacrylate, bamboo charcoal fiber, phenolic antioxidant
1010, nm level CaCO_3 mixes by weight proportion, is stirred 15 minutes under the mixing speed of 1000r/min, obtains mixture；
(3) inorganic pigment is sent into autoclave, carbon dioxide is added, the pressure adjusted in autoclave is
60MPa, temperature are 130 DEG C, and carbon dioxide is made to become supercritical fluid；
(4) it is stirred using magnetic stirring apparatus, inorganic pigment is completely dissolved in supercritical fluid after 5 hours, then is added
Enter the mixture in step (2), continue stirring 20 hours, maintains temperature-resistant reduction pressure to 2MPa, continue stirring 15 hours,
It is deflated by gas bleeder valve, thick color masterbatch is taken out after cooling；
(5) by above-mentioned thick color masterbatch by melting, extrusion, pelletizing, the polypropylene color masterbatch that particle size is 2mm is obtained.
Comparative example：
Weigh the raw material of following weight parts：60 parts of modified polypropene, 20 parts of titanium dioxide, 2 parts of polyethylene wax, polymethyl
10 parts of sour methyl esters, 10101 parts of phenolic antioxidant, 0.5 part of nm level CaCO_3 are uniformly mixed, are heated to 50 DEG C, utilize magnetic agitation
Device high-speed stirred 3 hours, then with double screw extruder melting, squeeze out, be granulated, obtain particle size be 2mm Masterbatch.
Embodiment and Masterbatch made from comparative example are tested for the property, as shown in the table：
As can be seen from the above table, the Masterbatch aberration of production technology according to the invention production is small, strong coloring force, and melt is viscous
Degree is preferable, has excellent color fastness.And after adding bamboo charcoal fiber, the Masterbatch of preparation exists to the bacteriostasis rate of Escherichia coli
99% or more, there is potent anti-microbial property.
The above embodiment is merely an example for clearly illustrating the present invention, and is not the embodiment party to the present invention
The restriction of formula.For those skilled in the art, other differences can be made on the basis of the above description
The variation or variation of form.There is no necessity and possibility to exhaust all the enbodiments.And these belong to the essence of the present invention
The obvious changes or variations that god extends out are among protection scope of the present invention and the open scope.
Claims (5)
1. a kind of high antimicrobial form polypropylene color masterbatch, it is characterised in that be made of the raw material of following weight parts：
Modified polypropene 60-90, inorganic pigment 20-30, composite dispersing agent 2-3, polymethyl methacrylate 10-15, bamboo charcoal are fine
Tie up 20-30,1010 1-2 of phenolic antioxidant, nm level CaCO_3 0.5-1.
2. a kind of high antimicrobial form polypropylene color masterbatch as described in claim 1, which is characterized in that the composite dispersing agent is
It is 2 in mass ratio by dispersant YY -5023, polyethylene wax, titanate coupling agent：2：1 ratio is formulated.
3. a kind of high antimicrobial form polypropylene color masterbatch as described in claim 1, which is characterized in that the inorganic pigment is titanium
In white powder, carbon black, cadmium yellow, lead chromate yellow, cadmium red, iron oxide red, iron oxide yellow, barba hispanica, cobalt blue, iron oxide brown, chrome oxide green
A kind of or arbitrary combination, grain size are 0.5-10 μm.
4. a kind of high antimicrobial form polypropylene color masterbatch as described in claim 1, which is characterized in that the grain of the bamboo charcoal fiber
Diameter is 100-300 μm.
5. a kind of high antimicrobial form polypropylene color masterbatch preparation method, which is characterized in that include the following steps：
(1) by polypropylene by electron accelerator irradiation, the energy rank of electron accelerator is 3-5MeV, irradiation dose 10-
20KGy, polypropylene and propylene after irradiation are 40-60 by weight：1 ratio mixing, obtains modified polypropene；
(2) by above-mentioned modified polypropene and composite dispersing agent, polymethyl methacrylate, bamboo charcoal fiber, phenolic antioxidant 1010,
Nm level CaCO_3 mixes by weight proportion, is stirred 10-15 minutes under the mixing speed of 1000-1200r/min, obtains mixture；
(3) inorganic pigment is sent into autoclave, carbon dioxide is added, it is 60- to adjust the pressure in autoclave
90MPa, temperature are 100-150 DEG C, and carbon dioxide is made to become supercritical fluid；
(4) it is stirred using magnetic stirring apparatus, inorganic pigment is completely dissolved in supercritical fluid after 3-5 hours, is added
Mixture in step (2) continues stirring 20-30 hours, maintains temperature-resistant reduction pressure to 1-5MPa, continues to stir 10-
It 15 hours, is deflated by gas bleeder valve, thick color masterbatch is taken out after cooling；
(5) by above-mentioned thick color masterbatch by melting, extrusion, pelletizing, the polypropylene color masterbatch that particle size is 1-10mm is obtained.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111117069A (en) * | 2019-12-31 | 2020-05-08 | 广东顺威赛特工程塑料开发有限公司 | Enhanced polypropylene composite material and preparation method thereof |
| CN112321855A (en) * | 2020-12-03 | 2021-02-05 | 上海金发科技发展有限公司 | Quaternary compound color master batch and preparation method thereof |
| CN113502601A (en) * | 2021-07-19 | 2021-10-15 | 葛飞 | Environment-friendly anti-mite non-woven fabric and preparation method thereof |
| CN113980387A (en) * | 2021-11-17 | 2022-01-28 | 无锡市长虹化塑色粒有限公司 | Antibacterial microporous color master batch |
| CN115747990A (en) * | 2022-11-24 | 2023-03-07 | 山东南山智尚科技股份有限公司 | Peroxide crosslinking modified ultra-dispersed color master batch for stock solution coloring superfine fiber and preparation method and application thereof |
| CN115926222A (en) * | 2022-12-29 | 2023-04-07 | 深圳市富程威科技股份有限公司 | PTFE raw material tape and preparation method and application thereof |
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| CN105291295A (en) * | 2015-11-16 | 2016-02-03 | 东莞市普凯塑料科技有限公司 | Lamelliferous color master batch and manufacturing method thereof |
| CN107746466A (en) * | 2017-11-07 | 2018-03-02 | 成都新柯力化工科技有限公司 | A kind of environment-friendly type preparation method of plastic color master grain |
| CN107868263A (en) * | 2017-12-04 | 2018-04-03 | 深圳市博彩新材料科技有限公司 | Modified polypropene Masterbatch and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2006021598A1 (en) * | 2004-07-27 | 2006-03-02 | Iqap Colorpoint, S.A. | Pigment preparation for colouring polymers |
| CN105291295A (en) * | 2015-11-16 | 2016-02-03 | 东莞市普凯塑料科技有限公司 | Lamelliferous color master batch and manufacturing method thereof |
| CN107746466A (en) * | 2017-11-07 | 2018-03-02 | 成都新柯力化工科技有限公司 | A kind of environment-friendly type preparation method of plastic color master grain |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111117069A (en) * | 2019-12-31 | 2020-05-08 | 广东顺威赛特工程塑料开发有限公司 | Enhanced polypropylene composite material and preparation method thereof |
| CN112321855A (en) * | 2020-12-03 | 2021-02-05 | 上海金发科技发展有限公司 | Quaternary compound color master batch and preparation method thereof |
| CN112321855B (en) * | 2020-12-03 | 2022-11-18 | 上海金发科技发展有限公司 | Quaternary compound color master batch and preparation method thereof |
| CN113502601A (en) * | 2021-07-19 | 2021-10-15 | 葛飞 | Environment-friendly anti-mite non-woven fabric and preparation method thereof |
| CN113980387A (en) * | 2021-11-17 | 2022-01-28 | 无锡市长虹化塑色粒有限公司 | Antibacterial microporous color master batch |
| CN115747990A (en) * | 2022-11-24 | 2023-03-07 | 山东南山智尚科技股份有限公司 | Peroxide crosslinking modified ultra-dispersed color master batch for stock solution coloring superfine fiber and preparation method and application thereof |
| CN115926222A (en) * | 2022-12-29 | 2023-04-07 | 深圳市富程威科技股份有限公司 | PTFE raw material tape and preparation method and application thereof |
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Application publication date: 20180907 |