CN114058115B - Antibacterial and antiviral high-impact polypropylene composition and preparation method and application thereof - Google Patents
Antibacterial and antiviral high-impact polypropylene composition and preparation method and application thereof Download PDFInfo
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- CN114058115B CN114058115B CN202111016934.0A CN202111016934A CN114058115B CN 114058115 B CN114058115 B CN 114058115B CN 202111016934 A CN202111016934 A CN 202111016934A CN 114058115 B CN114058115 B CN 114058115B
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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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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C08L2205/24—Crystallisation aids
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Abstract
The invention discloses an antibacterial and antiviral high impact polypropylene composition, and a preparation method and application thereof, wherein the composition comprises the following components in parts by weight: 34-80 parts of high-crystalline polypropylene resin; 5-20 parts of high melt strength polypropylene resin; 5-20 parts of inorganic filler; 10-25 parts of an elastomer; 0.1 to 1 part of alpha crystal form nucleating agent; 0.1 to 0.3 part of antibacterial agent; the melting enthalpy of the high-crystalline polypropylene resin is more than or equal to 100J/g; the enthalpy of fusion is determined according to GB/T19466.3-2004; the melt strength of the high melt strength polypropylene resin is more than or equal to 20cN. The polypropylene composition prepared by blending the high-crystallization polypropylene resin, the high-melt-strength polypropylene resin, the alpha-crystal nucleating agent and the antibacterial agent can reduce the addition amount of the antibacterial agent under the condition of reaching 99% of antibacterial effect and 90% of antiviral effect, can realize high impact strength, and meets the requirement of automotive interior parts on impact strength.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an antibacterial and antiviral high impact polypropylene composition, a preparation method and application thereof.
Background
The polypropylene has the advantages of wide source, low density, excellent mechanical property, fatigue resistance, yield, low price and the like, and is widely applied to automobile interior parts, such as instrument panels, door panels, upright posts and the like. With the development of the automobile industry, whether the internal environment of the automobile is healthy or not is more and more paid attention to consumers, and particularly, more and more people who develop sharing travel can indirectly contact other people through automobile interiors. In combination with the influence of new coronavirus epidemic situation in 2020-2021, it is necessary to provide a polypropylene modified material with better antibacterial and antiviral effects, so as to meet the requirements of antibacterial and antiviral requirements of automobiles in the current large environment, meet the requirements of automobile interior trim part test outline, and provide a healthier and safer driving environment for passengers.
The traditional method for improving the antibacterial property of the automotive interior material is realized by adding an antibacterial agent, and the antibacterial effect is required to be realized by 99 percent, wherein the addition amount of the antibacterial agent is more than 0.5 part, for example, chinese patent (CN 111471234A) discloses a durable anti-aging antibacterial polypropylene composite material for automotive interior and a preparation method thereof, and the addition amount of the antibacterial agent is 0.6-1.2 parts; when the addition amount is more than 0.6 part, 99% of antibacterial effect can be realized, and the main problem is that the antibacterial agent usually only acts on the surface of the material, and the antibacterial agent is uniformly distributed in a material matrix at the same time through modification processing by a material melt blending mode, so that the actual addition amount is larger than the actual antibacterial agent which can act on the surface, the antibacterial agent is usually quite expensive, and the impact performance of the polypropylene material can be reduced by adding the excessive antibacterial agent.
Disclosure of Invention
The invention provides an antibacterial and antiviral high-impact polypropylene composition, which aims to overcome the defects that a large amount of antibacterial agents are required to be added in automobile interior decoration to realize high antibacterial effect and the addition of a large amount of antibacterial agents can reduce impact strength.
Another object of the present invention is to provide a method for preparing the antibacterial and antiviral high impact polypropylene composition.
It is another object of the present invention to provide the use of said antibacterial and antiviral high impact polypropylene composition.
In order to achieve the above purpose, the invention adopts the following technical scheme:
an antibacterial and antiviral high impact polypropylene composition comprises the following components in parts by weight:
the melting enthalpy of the high-crystalline polypropylene resin is more than or equal to 100J/g; the enthalpy of fusion is determined according to GB/T19466.3-2004;
the melt strength of the high melt strength polypropylene resin is more than or equal to 20cN.
The melt strength is tested by a melt tensile rheometer, the test temperature is 200 ℃, and the tensile acceleration is 60mm/s 2 。
The inventors found that the distribution of the internal antimicrobial agent can be reduced by a smaller proportion of amorphous regions in the highly crystalline polypropylene resin; the branched chain of the high melt strength polypropylene resin is longer, the occupied free volume is more, the distribution of the antibacterial agent in the matrix can be obviously reduced, and better antibacterial and antiviral effects are achieved by more distribution on the surface. The alpha crystal form nucleating agent induces and initiates an alpha crystal form structure (the alpha crystal form structure is relatively compact) in the polypropylene resin, so that the distribution of the antibacterial agent in a system is further reduced, and the antibacterial agent has high antiviral and antibacterial effects under the condition of low addition amount of the antibacterial agent. Therefore, the high melt strength polypropylene resin, the high crystallization polypropylene resin, the alpha crystal form nucleating agent and the antibacterial agent selected by the invention are blended, so that the effects of high antivirus and high antibacterial can be realized under the condition of less antibacterial agent content, and the requirement of the automobile interior product on the impact strength can be met.
Preferably, the high melt strength polypropylene resin has a melt strength of 30cN or more.
Further studies by the inventors have found that at melt strengths greater than 30cN, the proportion of branching is greater and more free volume is occupied.
Preferably, the high melt strength polypropylene resin has a melt strength of 40cN or less.
Preferably, the high crystalline polypropylene resin has a melting enthalpy of 207J/g or less, as determined according to GB/T19466.3-2004.
Preferably, the alpha crystal form nucleating agent is one or more of aromatic acid metal soap alpha crystal form nucleating agent, sorbitol alpha crystal form nucleating agent, rosin alpha crystal form nucleating agent or organic phosphate alpha crystal form nucleating agent.
Preferably, the alpha-form nucleating agent is a sorbitol alpha-form nucleating agent.
The sorbitol alpha crystal form nucleating agent has good compatibility with polypropylene, excellent nucleating effect and higher nucleating efficiency, the formed alpha crystal form has few defects and more uniform distribution, and the formed compact, complete and uniform alpha crystal has a displacement effect, so that the distribution of the antibacterial agent in the matrix is further reduced.
Preferably, the antibacterial agent is one or more of a silver ion antibacterial agent, a zinc ion antibacterial agent or a nano zinc oxide antibacterial agent.
Preferably, the antimicrobial agent is a silver ion antimicrobial agent.
More preferably, the silver ion antibacterial agent is a zirconium phosphate carrier silver ion antibacterial agent.
Preferably, the elastomer is an ethylene-butene copolymer and/or an ethylene-octene copolymer.
Preferably, the inorganic filler is talc and/or calcium carbonate.
Preferably, the inorganic filler has a D50 particle size of 1 to 10. Mu.m.
The preparation method of the antibacterial and antiviral high impact polypropylene composition comprises the following steps:
s1, mixing high-crystalline polypropylene resin, high-melt-strength polypropylene resin, inorganic filler, elastomer, alpha-crystal nucleating agent and antibacterial agent uniformly to obtain premix;
s2, melting, extruding, granulating and drying the premix in the step S1 to obtain the antibacterial and antiviral high impact polypropylene composition.
An automotive interior product contains the antibacterial and antiviral high impact polypropylene composition.
The product has high antiviral and antibacterial effects, and the impact strength of the product meets the requirements of automotive interior products.
Compared with the prior art, the invention has the beneficial effects that:
the polypropylene composition prepared by blending the high-crystallization polypropylene resin, the high-melt-strength polypropylene resin, the alpha-crystal nucleating agent and the antibacterial agent can reduce the dosage of the antibacterial agent under the condition of 99% of antibacterial efficiency and 90% of antiviral efficiency, and has high impact strength, thereby meeting the requirement of the polypropylene composition on the impact strength in the automotive interior parts.
Detailed Description
Technical solutions in the embodiments of the present invention will be clearly and completely described below, but the embodiments of the present invention are not limited thereto.
The reagents, methods and apparatus employed in the present invention, unless otherwise specified, are all conventional in the art.
The following examples and comparative examples were prepared from the following raw materials:
high crystalline polypropylene resin a: the fusion enthalpy was 102J/g, BX3900, SK chemical Co., ltd;
high crystalline polypropylene resin B: the melting enthalpy is 123/g, H9018, lanzhou petrochemical Co., ltd;
high crystalline polypropylene resin C: melting enthalpy is 151J/g, HJ4045, and Korean is oiled;
common crystalline polypropylene resin: melting enthalpy is 70J/g, M60RHC, china petroleum sea-level refining;
high melt strength polypropylene resin B: melt strength 31cn, wb135hms, northern european chemical;
high melt strength polypropylene resin C: melt strength 34cn, wb130hms, northern european chemical;
high melt strength polypropylene resin D: melt strength 36cn, wb140hms, northern european chemical;
ordinary melt strength polypropylene resin: melt strength of 7cN, WE100HMS, nordic chemical industry
Inorganic filler a: talcum powder with D50 particle size of 4.0 μm, TYT-3000A, available from additive chemical industry Co., ltd;
inorganic filler B: calcium carbonate with a D50 particle size of 1.6 μm, AC-MLT04, dongguan Mei Litai chemical Co., ltd;
inorganic filler C: talcum powder, the D50 particle size is 11 mu m, HY-TA10, sea-borne powder;
elastomer a: ethylene-butene copolymer, POE 8150, dow chemical limited;
elastomer B: ethylene-octene copolymer, POE 8842, dow chemical limited;
alpha crystal form nucleating agent a: sorbitol alpha crystal form nucleating agent, TM-3, shanxi chemical institute;
alpha crystal form nucleating agent B: organic phosphate alpha crystal form nucleating agent, NA-21, ai Dike limited;
alpha crystal form nucleating agent C: aromatic acid metal soap alpha-crystal form nucleating agent, MTK-122, japan DIC company;
alpha crystal form nucleating agent D: rosin alpha crystal form nucleating agent, KM-1600, japan Sichuan chemical Co., ltd;
beta crystal form nucleating agent: rare earth beta nucleating agent, WBG-II, guangdong British Linna Co., ltd;
antimicrobial agent a: zirconium phosphate carrier silver ion antibacterial agent, P203, langyi materials limited;
antimicrobial agent B: glass carrier silver ion antibacterial agent, B130 langyi new materials limited;
antimicrobial agent C: zinc ion antibacterial agent, B201, langyi new materials limited;
antimicrobial agent D: nanometer zinc oxide, JDGQP-004, jinda nanometer technology Co., ltd;
the polypropylene compositions of examples and comparative examples were prepared by the following method comprising the steps of:
s1, mixing high-crystallization polypropylene resin, high-melt-strength polypropylene resin, inorganic filler, elastomer, alpha-crystal nucleating agent and antibacterial agent in a high-speed mixer for 3min, and uniformly mixing to obtain premix;
s2, placing the premix in the step S1 into a main feeding port of a double-screw extruder for melting, extruding, granulating and drying to obtain the antibacterial and antiviral high-impact polypropylene composition, wherein the extrusion processing temperature is 100-220 ℃, and the host rotation speed is 500 revolutions per minute; the length-diameter ratio of the double-screw extruder is 48:1.
Detailed test mode of melting enthalpy and melt strength: the melting enthalpy test adopts DSC as an instrument, 8-10mg of sample is taken according to GB/T19466 standard, the test condition is that the temperature is increased from 30 ℃ to 200 ℃, the heating rate is 10 ℃/min, and the melting enthalpy of the corresponding material is obtained by integrating melting peaks; the melt strength is tested by a melt tensile rheometer, the test temperature is 200 ℃, and the tensile acceleration is 60mm/s 2 。
Examples 1 to 6
Examples 1-6 provide a series of antibacterial and antiviral high impact polypropylene compositions with specific component contents as shown in table 1.
TABLE 1 content (parts) of Components of examples 1 to 6
Examples 7 to 15
Examples 7-15 provide a series of antibacterial and antiviral high impact polypropylene compositions with specific component contents as shown in Table 2.
TABLE 2 content (parts) of Components of examples 7 to 15
Examples 16 to 17 and comparative examples 1 to 4
Examples 16-17 and comparative examples 1-4 provide a series of polypropylene compositions with specific component levels as shown in Table 3.
TABLE 3 component contents (parts) of examples 16 to 17 and comparative examples 1 to 4
Performance testing
The notched impact strength of the cantilever beam is tested according to the ISO 180-2019 standard;
the antibacterial experiment is tested according to ISO 22196-2011 standard;
antiviral tests were tested according to the ISO 21702-2019 standard.
Table 4 data for examples and comparative examples
In comparative examples 1 to 3, the use of the ordinary crystalline polypropylene resin, the ordinary melt strength polypropylene resin or the beta-form nucleating agent does not achieve 99% or more of the antibacterial effect and 90% or more of the antiviral effect, and in comparative example 4, the use of the ordinary crystalline polypropylene resin in total adds 0.6 part of the antibacterial agent, the 99% antibacterial effect and 90% antiviral effect still cannot be achieved, and the toughness is greatly reduced.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (6)
1. An antibacterial and antiviral high impact polypropylene composition is characterized by comprising the following components in parts by weight:
34-80 parts of high-crystalline polypropylene resin;
5-20 parts of high melt strength polypropylene resin;
5-20 parts of inorganic filler;
10-25 parts of an elastomer;
0.1-1 part of alpha crystal form nucleating agent;
0.1-0.3 parts of an antibacterial agent;
the melting enthalpy of the high-crystalline polypropylene resin is more than or equal to 100J/g; the enthalpy of fusion is determined according to GB/T19466.3-2004;
the alpha crystal form nucleating agent is one or more of aromatic acid metal soap alpha crystal form nucleating agent, sorbitol alpha crystal form nucleating agent, rosin alpha crystal form nucleating agent or organic phosphate alpha crystal form nucleating agent;
the antibacterial agent is one or more of silver ion antibacterial agent, zinc ion antibacterial agent or nano zinc oxide antibacterial agent;
the elastomer is an ethylene-butene copolymer and/or an ethylene-octene copolymer;
the high melt strength polypropylene resin is identified as WB135HMS, WB130HMS or WB140HMS.
2. The antibacterial and antiviral high impact polypropylene composition according to claim 1, wherein said high crystalline polypropylene resin has a melting enthalpy of 207J/g or less, said melting enthalpy being determined according to GB/T19466.3-2004.
3. The antimicrobial antiviral high impact polypropylene composition according to claim 1, wherein said alpha-form nucleating agent is sorbitol alpha-form nucleating agent.
4. The antibacterial and antiviral high impact polypropylene composition according to claim 1, wherein said inorganic filler is talc and/or calcium carbonate.
5. The method for preparing the antibacterial and antiviral high impact polypropylene composition according to any one of claims 1 to 4, comprising the steps of:
s1, mixing high-crystalline polypropylene resin, high-melt-strength polypropylene resin, inorganic filler, elastomer, alpha-crystal nucleating agent and antibacterial agent uniformly to obtain premix;
s2, melting, extruding, granulating and drying the premix in the step S1 to obtain the antibacterial and antiviral high impact polypropylene composition.
6. An automotive interior article characterized by being prepared from the antibacterial and antiviral high impact polypropylene composition according to any one of claims 1 to 4.
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| CN115109379B (en) * | 2022-06-10 | 2023-12-22 | 中广核俊尔(浙江)新材料有限公司 | Antibacterial polypropylene composite material with short molding cycle, and preparation method and application thereof |
| CN115216092B (en) * | 2022-07-29 | 2024-04-30 | 横店集团得邦工程塑料有限公司 | Low-temperature-resistant reinforced halogen-free flame-retardant PP/HMSPP composite material and preparation method thereof |
| CN115521537A (en) * | 2022-10-14 | 2022-12-27 | 宿迁联宏新材料有限公司 | Formula and preparation method of efficient antibacterial calcium carbonate master batch |
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| KR101338569B1 (en) * | 2005-05-12 | 2013-12-12 | 다우 글로벌 테크놀로지스 엘엘씨 | Thermoformed, extruded sheeting with reduced gloss |
| WO2009057131A2 (en) * | 2007-05-29 | 2009-05-07 | Reliance Industries Limited | Polyolefin composition having high melt strength |
| EP2338931A1 (en) * | 2009-12-23 | 2011-06-29 | Borealis AG | Blown grade showing superior stiffness, transparency and processing behaviour |
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