CN113667254A - High-stability broad-spectrum antibacterial PMMA \ ASA alloy material based on molecular on-line self-assembly technology and preparation method thereof - Google Patents
High-stability broad-spectrum antibacterial PMMA \ ASA alloy material based on molecular on-line self-assembly technology and preparation method thereof Download PDFInfo
- Publication number
- CN113667254A CN113667254A CN202110909915.4A CN202110909915A CN113667254A CN 113667254 A CN113667254 A CN 113667254A CN 202110909915 A CN202110909915 A CN 202110909915A CN 113667254 A CN113667254 A CN 113667254A
- Authority
- CN
- China
- Prior art keywords
- pmma
- raw material
- mixed raw
- asa
- molecular
- 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
Links
- 229920003229 poly(methyl methacrylate) Polymers 0.000 title claims abstract description 81
- 239000004926 polymethyl methacrylate Substances 0.000 title claims abstract description 81
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 37
- 239000000956 alloy Substances 0.000 title claims abstract description 35
- 238000005516 engineering process Methods 0.000 title claims abstract description 27
- 238000001338 self-assembly Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 71
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 50
- 239000011347 resin Substances 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims abstract description 42
- 238000002156 mixing Methods 0.000 claims abstract description 30
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000001125 extrusion Methods 0.000 claims abstract description 16
- 230000003115 biocidal effect Effects 0.000 claims abstract description 14
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims abstract description 13
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 229920001897 terpolymer Polymers 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims abstract description 9
- 230000008018 melting Effects 0.000 claims abstract description 9
- 239000013543 active substance Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims description 23
- 238000012545 processing Methods 0.000 claims description 16
- 238000012360 testing method Methods 0.000 claims description 15
- 238000005303 weighing Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000002834 transmittance Methods 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229920002413 Polyhexanide Polymers 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 claims description 3
- -1 Polytetrafluoroethylene Polymers 0.000 claims description 3
- 150000004283 biguanides Chemical group 0.000 claims description 3
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 239000011258 core-shell material Substances 0.000 claims description 2
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical compound O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 claims description 2
- 229920002877 acrylic styrene acrylonitrile Polymers 0.000 abstract description 51
- 230000000694 effects Effects 0.000 abstract description 5
- 230000000843 anti-fungal effect Effects 0.000 abstract description 4
- 229940121375 antifungal agent Drugs 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 4
- 238000005232 molecular self-assembly Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract description 2
- YAAQEISEHDUIFO-UHFFFAOYSA-N C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 Chemical compound C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 YAAQEISEHDUIFO-UHFFFAOYSA-N 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 230000002779 inactivation Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000002861 polymer material Substances 0.000 description 6
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 241000222122 Candida albicans Species 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 3
- 241000293871 Salmonella enterica subsp. enterica serovar Typhi Species 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 229940095731 candida albicans Drugs 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 3
- 241000228245 Aspergillus niger Species 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 241000079253 Byssochlamys spectabilis Species 0.000 description 1
- 241001515917 Chaetomium globosum Species 0.000 description 1
- 241000606507 Talaromyces pinophilus Species 0.000 description 1
- 241000223261 Trichoderma viride Species 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000001046 anti-mould Effects 0.000 description 1
- 239000002546 antimould Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000000707 layer-by-layer assembly Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions 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; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to a PMMA \ ASA alloy material with high stability and broad-spectrum antibiosis based on a molecular on-line self-assembly technology and a preparation method thereof, and the PMMA \ ASA alloy material is specifically composed of the following raw materials in parts by weight: 40-80 parts of polymethyl methacrylate resin, 15-30 parts of acrylonitrile-styrene-acrylate terpolymer, 1-5 parts of guanidine polymer antibacterial agent, 0.5-3 parts of isothioketone antibacterial agent and 1-3 parts of auxiliary dispersing agent. According to the invention, the online molecular self-assembly of active substances of the isothioketone antibacterial agent with excellent antibacterial performance and the guanidine polymer antibacterial agent with excellent antifungal performance is realized through a tandem type double-stage extrusion modification process method, and then the active substances are subjected to secondary online melting and mixing with a PMMA resin matrix, an auxiliary dispersing agent and the like. The polar group-based molecular self-assembly technology can ensure high activity, broad spectrum and stability of the antibacterial system, and the adopted double-stage online melt extrusion process can well avoid unstable conditions of inactivation, degradation, failure and the like of the active antibacterial system caused by water cooling or external environment contact.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a PMMA \ ASA alloy material with high stability and broad-spectrum antibiosis based on a molecular online self-assembly technology and a preparation method thereof.
Background
In recent years, with the continuous development and improvement of modern society and living standard, the concept of green, environmental protection and healthy living continues to be deeply mastered, and the requirement of people on the health degree of working and living environments is higher and higher, which puts a brand new demand on the high performance and high functionality of the current polymer materials, and the antibacterial plastics are a typical example of the functionalized polymer materials.
Polymethyl methacrylate (PMMA resin for short) is a thermoplastic polymer material with a flexible long molecular chain structure, and the relative molecular mass of the polymethyl methacrylate can be 200 ten thousand or even higher. The molecular chain structure endows the PMMA material with good tensile resistance, heat resistance and excellent notch impact resistance; more importantly, as an amorphous polymer material, PMMA resin has good transmittance performance, and the crystal structure in the PMMA material can be further reduced and the transmittance can be improved to a very high level of 93-95% through a special polymerization process and a post-treatment of the PMMA material, so that the PMMA material can replace the traditional silicate glass.
However, because of the larger branched chain structure of PMMA, the melt viscosity is high, the processing difficulty is high, the extrusion speed is slow, and PMMA \ ASA alloying treatment becomes a widely applied technical scheme and product. Although the ASA resin can solve the PMMA processing problem to some extent after being added, the PMMA/ASA processing method has certain difficulty in antibacterial treatment. Although the organic antibacterial agent has obvious advantages in the aspects of broad spectrum, stability and durability, the characteristics of no high temperature resistance and no shear resistance in the melt blending process are technical difficulties to be solved, so that in the existing PMMA antibacterial scheme, CN201911012396.0 adopts the surface coating treatment of the antibacterial coating, but the loss of the surface coating in the use process easily causes the loss of the antibacterial performance of the material, and the long-term antibacterial stability is not good; CN201911012396.0 adopts an inorganic nano silver antibacterial agent system with higher high temperature resistance and shearing resistance, and although the processing performance is stable, the broad spectrum of the inorganic antibacterial agent is not good. Therefore, few organic antibacterial agent systems with broad-spectrum antibacterial property, high stability and excellent processing resistance which are suitable for the high-viscosity PMMA system are available, and higher technical requirements are provided for the construction and melt blending processing of the antibacterial agent system of the PMMA/ASA alloy.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a PMMA \ ASA alloy material with high stability and broad-spectrum antibiosis based on a molecular online self-assembly technology, aiming at the current situation that inorganic antibacterial agents are mostly used or surface coating treatment is adopted in the prior PMMA antibacterial treatment technical scheme and the current situations that the processing technology and the method are not high in innovation and applicability, the active substances of an organic antibacterial system are subjected to online molecular self-assembly through a tandem type double-stage extrusion modification process method, and then are subjected to secondary online melting, mixing and dispersion with a PMMA resin matrix, a dispersion aid and the like, so that the PMMA \ ASA alloy material with excellent distribution condition and stable antibacterial performance is obtained.
The purpose of the invention is realized by the following technical scheme:
a PMMA \ ASA alloy material with high stability and broad-spectrum antibiosis based on a molecular on-line self-assembly technology is characterized in that: the feed comprises the following raw materials in parts by weight:
further, the PMMA resin is polymethyl methacrylate with high flow and high light transmittance, the melt index MFR of the PMMA resin is more than or equal to 15g/10min under the test conditions of 230 ℃ and 3.8kg, and the light transmittance is more than or equal to 93%.
Further, the ASA terpolymer is high impact resistant ASA superfine powder resin with acrylate rubber phase content of 45-50%, and the average particle size (D98) is 3-5 um.
Furthermore, the guanidine polymer antibacterial agent is polyhexamethylene biguanide hydrochloride, which is a cationic oligomer with a molecular chain containing 22 biguanide units;
furthermore, the isothiazolinone antibacterial agent is an aqueous solution of methylisothiazolinone antibacterial agent (MIT), and the content of effective active substances is more than or equal to 80%.
Further, it is characterized in that: the dispersing agent is acrylate modified Polytetrafluoroethylene (PTFE) powder with a core-shell structure, and the content of acrylate is 8-15%.
The second purpose of the invention is to provide a PMMA \ ASA alloy material with high stability and broad-spectrum antibiosis based on a molecular on-line self-assembly technology, which is characterized by comprising the following steps:
(1) weighing ASA terpolymer, guanidine polymer antibacterial agent and isothioketone antibacterial agent according to the weight parts, and uniformly mixing to obtain a mixed raw material A; weighing PMMA resin and an auxiliary dispersing agent according to the weight parts, and uniformly mixing to obtain a mixed raw material B:
(2) fully drying the mixed raw material A, then placing the dried mixed raw material A into a main feeding bin of a tightly meshed co-rotating double-screw extruder, adding the dried mixed raw material A into a machine barrel of the extruder through a feeding screw, and conveying the isothioketone antibacterial agent aqueous solution into the machine barrel of the extruder through a high-precision liquid metering pump through a feeding hole of a second barrel; the diameter of the used twin-screw extruder is 35mm, the length-diameter ratio L/D is 56, and the temperature of each subarea from the feed inlet to the head outlet of the main machine barrel is set as follows: 160 ℃, 200 ℃, 210 ℃, 215 ℃, 220 ℃ and the rotation speed of a main engine is 200 r/min;
(3) fully drying the mixed raw material B, then placing the dried mixed raw material B into a main feeding bin of a reciprocating single-screw extruder with high temperature control precision, and adding the dried mixed raw material B into a machine barrel of the extruder through a feeding screw; the diameter of the single screw extruder used was 44mm, the length-diameter ratio L/D was 40, and the temperatures of the respective zones from the feed port to the head outlet of the main barrel were set as follows: 190 deg.C, 220 deg.C, 230 deg.C, 235 deg.C, 230 deg.C, 225 deg.C, 230 deg.C, and the rotation speed of the main engine is 300 rpm; and (3) switching a double-screw extruder used for processing the mixed raw material A at the position of a fourth section of cylinder in the middle section of the single-screw extruder to realize secondary on-line melting and blending of the ASA resin melt and the PMMA resin melt, and obtaining the PMMA \ ASA alloy material with high stability and broad-spectrum antibacterial performance based on the molecular on-line self-assembly technology after the processes of extrusion, granulation, drying and the like.
Compared with the prior art, the invention has the following beneficial effects:
1. firstly, a two-stage extrusion blending modification scheme of a close-meshed double-screw extruder and a reciprocating single-screw extruder in a double-machine tandem type is adopted; in a first-order double-screw extruder, ASA resin with high processing fluidity is used as a matrix, and a stable and durable networked organic antibacterial agent molecular system is formed through the electrostatic self-assembly effect between positive ions and negative ions, so that a good basis is provided for ensuring the subsequent further dispersion and extrusion in a PMMA matrix.
2. And then, a double-screw series structure of an extruder is utilized, the ASA resin system in a molten state is directly introduced into a single-screw extruder barrel of a second stage, and the molten-state direct mixing is realized with PMMA and the dispersion aid, so that the activity loss of the antibacterial agent caused by cooling and granulating the ASA resin is effectively avoided, the good interphase compatibility between PMMA and ASA is better utilized, and the secondary distribution and dispersion of the antibacterial agent system are realized.
3. The antibacterial PMMA \ ASA alloy material obtained by the technical scheme of the invention not only can better exert the viscosity reduction and toughening effects of the ASA resin, but also can obviously reduce the apparent viscosity number eta of the PMMA alloy material and improve the normal-temperature and low-temperature notch impact strength of the material in different ranges; more importantly, an antibacterial system with uniform distribution, good broad spectrum and lasting and stable effect is successfully constructed in a PMMA/ASA two-phase system based on an intermolecular ion self-assembly technology of an antibacterial agent, high antibacterial property on four different strains such as escherichia coli, staphylococcus aureus, salmonella typhi, candida albicans and the like is still maintained after the surface of the material is subjected to simulated washing for 100 times, the overall antibacterial rate of the material is still maintained above 98%, and the resistance of the material to 5 mixed mould strains such as aspergillus niger and the like reaches the highest level of 0 after 28d long-period antifungal test, so that excellent, stable and broad-spectrum antibacterial property is shown.
Detailed Description
The invention is further illustrated by the following specific examples, which are intended to be illustrative only and not limiting.
The raw materials used in the embodiment of the invention are as follows:
PMMA-1: polymethyl methacrylate 7N, melt index MFR of 18g/10min at 230 ℃ under 3.8kg test conditions, light transmittance of 95%, Windgesso, Germany
PMMA-2: polymethyl methacrylate HT25X, melt index MFR of 6g/10min at 230 ℃ under 3.8kg, light transmission 90%, Disman, Netherlands.
ASA resin: the superfine acrylic resin powder SH-B63 contains 48% of acrylate, and is white powder with the average particle size (D98) of 3.5 um.
Guanidine polymer antibacterial agent: polyhexamethylene biguanide hydrochloride (PHMB) in the form of a white or yellowish powder having a biguanide unit number of 16 in the molecular chain, rochon biotechnology limited, hangzhou.
Isothiophenone antibacterial agents: methylisothiazolinone antibacterial agent (MIT), transparent clear solution with active substance content of 89%, Nanjing Tianshi Landun Biotech Co.
Silver ion antibacterial agent: the silver-zinc composite mildew-proof antibacterial agent KP-J67 is white powder, the particle size (D50) of the silver-zinc composite mildew-proof antibacterial agent KP-J67 is 2.5um, the effective silver-zinc content is 9.99-10.01%, and the Foshan science and technology company Limited.
Auxiliary dispersing agent: acrylate-modified Polytetrafluoroethylene (PTFE) powder METABLEN a3000 having an acrylate content of 12%, manufactured by mitsubishi yang corporation of japan.
And (3) product performance testing:
apparent viscosity number test: according to the rheometer method, the screw diameter is 26mm, the length-diameter ratio is 30 and the mixing temperature is 230 ℃ when the screw diameter is measured on a RHEOCORD 90 type torque rheometer of HAAKE company, Germany.
Notch impact test: the test is carried out on a simple beam impact tester according to ISO179-1 standard, the notch of a sample strip is A type, and the test is carried out under the conditions of normal temperature (23 ℃), low temperature (-10 ℃) and extremely low temperature (-40 ℃).
And (3) antibacterial property test: cutting a standard test sample plate with the size of 50 multiplied by 3.2mm, and simulating to wash the surface of the test sample plate 100 times according to the method shown in AATCC 100-; then, the antibacterial rates of four different strains, namely escherichia coli, staphylococcus aureus, salmonella typhi, candida albicans and the like, are tested in a standard environment of 23 ℃ and 50% RH according to a standard method of JIS Z2801.
And (3) anti-mold test: a standard test sample plate with the size of 50 multiplied by 3.2mm is cut, the 28d anti-mould grade of the standard sample plate is tested according to the standard method of ISO846-2019, and the detection strains are mixed solution of five moulds, such AS Aspergillus niger ATCC 6275, Penicillium pinophilum ATCC11797, Paecilomyces variotii AS 3.4253, Trichoderma viride 3.3987, and Chaetomium globosum ATCC 6205.
Example 1
Weighing ASA terpolymer and guanidine polymer antibacterial agent according to the data of example 1 shown in Table 1, and uniformly mixing to obtain a mixed raw material A; and weighing PMMA resin and the auxiliary dispersing agent according to the weight parts, and uniformly mixing to obtain a mixed raw material B.
Fully drying the mixed raw material A, then placing the dried mixed raw material A into a main feeding bin of a tightly meshed co-rotating double-screw extruder, adding the dried mixed raw material A into a machine barrel of the extruder through a feeding screw, and conveying the isothioketone antibacterial agent aqueous solution into the machine barrel of the extruder through a high-precision liquid metering pump through a feeding hole of a second barrel; the diameter of the used twin-screw extruder is 35mm, the length-diameter ratio L/D is 56, and the temperature of each subarea from the feed inlet to the head outlet of the main machine barrel is set as follows: 160 ℃, 200 ℃, 210 ℃, 215 ℃, 220 ℃ and the rotation speed of a main engine is 200 r/min.
Fully drying the mixed raw material B, then placing the dried mixed raw material B into a main feeding bin of a reciprocating single-screw extruder with high temperature control precision, and adding the dried mixed raw material B into a machine barrel of the extruder through a feeding screw; the diameter of the single screw extruder used was 44mm, the length-diameter ratio L/D was 40, and the temperatures of the respective zones from the feed port to the head outlet of the main barrel were set as follows: 190 deg.C, 220 deg.C, 230 deg.C, 235 deg.C, 230 deg.C, 225 deg.C, 230 deg.C, and the rotation speed of the main engine is 300 rpm; and (3) switching a double-screw extruder used for processing the mixed raw material A at the position of a fourth section of cylinder in the middle section of the single-screw extruder to realize secondary on-line melting and blending of the ASA resin melt and the PMMA resin melt, and obtaining the PMMA \ ASA alloy material with high stability and broad-spectrum antibacterial performance based on the molecular on-line self-assembly technology after the processes of extrusion, granulation, drying and the like.
Example 2
Weighing ASA terpolymer and guanidine polymer antibacterial agent according to the data of example 2 shown in Table 1, and mixing uniformly to obtain a mixed raw material A; and weighing PMMA resin and the auxiliary dispersing agent according to the weight parts, and uniformly mixing to obtain a mixed raw material B.
Fully drying the mixed raw material A, then placing the dried mixed raw material A into a main feeding bin of a tightly meshed co-rotating double-screw extruder, adding the dried mixed raw material A into a machine barrel of the extruder through a feeding screw, and conveying the isothioketone antibacterial agent aqueous solution into the machine barrel of the extruder through a high-precision liquid metering pump through a feeding hole of a second barrel; the diameter of the used twin-screw extruder is 35mm, the length-diameter ratio L/D is 56, and the temperature of each subarea from the feed inlet to the head outlet of the main machine barrel is set as follows: 160 ℃, 200 ℃, 210 ℃, 215 ℃, 220 ℃ and the rotation speed of a main engine is 200 r/min.
Fully drying the mixed raw material B, then placing the dried mixed raw material B into a main feeding bin of a reciprocating single-screw extruder with high temperature control precision, and adding the dried mixed raw material B into a machine barrel of the extruder through a feeding screw; the diameter of the single screw extruder used was 44mm, the length-diameter ratio L/D was 40, and the temperatures of the respective zones from the feed port to the head outlet of the main barrel were set as follows: 190 deg.C, 220 deg.C, 230 deg.C, 235 deg.C, 230 deg.C, 225 deg.C, 230 deg.C, and the rotation speed of the main engine is 300 rpm; and (3) switching a double-screw extruder used for processing the mixed raw material A at the position of a fourth section of cylinder in the middle section of the single-screw extruder to realize secondary on-line melting and blending of the ASA resin melt and the PMMA resin melt, and obtaining the PMMA \ ASA alloy material with high stability and broad-spectrum antibacterial performance based on the molecular on-line self-assembly technology after the processes of extrusion, granulation, drying and the like.
TABLE 1 formulation table (unit: gram) of highly stable, broad spectrum antibacterial PMMA \ ASA alloy material
Example 3
Weighing ASA terpolymer and guanidine polymer antibacterial agent according to the data of example 3 shown in Table 1, and mixing uniformly to obtain a mixed raw material A; and weighing PMMA resin and the auxiliary dispersing agent according to the weight parts, and uniformly mixing to obtain a mixed raw material B.
Fully drying the mixed raw material A, then placing the dried mixed raw material A into a main feeding bin of a tightly meshed co-rotating double-screw extruder, adding the dried mixed raw material A into a machine barrel of the extruder through a feeding screw, and conveying the isothioketone antibacterial agent aqueous solution into the machine barrel of the extruder through a high-precision liquid metering pump through a feeding hole of a second barrel; the diameter of the used twin-screw extruder is 35mm, the length-diameter ratio L/D is 56, and the temperature of each subarea from the feed inlet to the head outlet of the main machine barrel is set as follows: 160 ℃, 200 ℃, 210 ℃, 215 ℃, 220 ℃ and the rotation speed of a main engine is 200 r/min.
Fully drying the mixed raw material B, then placing the dried mixed raw material B into a main feeding bin of a reciprocating single-screw extruder with high temperature control precision, and adding the dried mixed raw material B into a machine barrel of the extruder through a feeding screw; the diameter of the single screw extruder used was 44mm, the length-diameter ratio L/D was 40, and the temperatures of the respective zones from the feed port to the head outlet of the main barrel were set as follows: 190 deg.C, 220 deg.C, 230 deg.C, 235 deg.C, 230 deg.C, 225 deg.C, 230 deg.C, and the rotation speed of the main engine is 300 rpm; and (3) switching a double-screw extruder used for processing the mixed raw material A at the position of a fourth section of cylinder in the middle section of the single-screw extruder to realize secondary on-line melting and blending of the ASA resin melt and the PMMA resin melt, and obtaining the PMMA \ ASA alloy material with high stability and broad-spectrum antibacterial performance based on the molecular on-line self-assembly technology after the processes of extrusion, granulation, drying and the like.
Example 4
Weighing ASA terpolymer and guanidine polymer antibacterial agent according to the data of example 4 shown in Table 1, and mixing uniformly to obtain a mixed raw material A; and weighing PMMA resin and the auxiliary dispersing agent according to the weight parts, and uniformly mixing to obtain a mixed raw material B.
Fully drying the mixed raw material A, then placing the dried mixed raw material A into a main feeding bin of a tightly meshed co-rotating double-screw extruder, adding the dried mixed raw material A into a machine barrel of the extruder through a feeding screw, and conveying the isothioketone antibacterial agent aqueous solution into the machine barrel of the extruder through a high-precision liquid metering pump through a feeding hole of a second barrel; the diameter of the used twin-screw extruder is 35mm, the length-diameter ratio L/D is 56, and the temperature of each subarea from the feed inlet to the head outlet of the main machine barrel is set as follows: 160 ℃, 200 ℃, 210 ℃, 215 ℃, 220 ℃ and the rotation speed of a main engine is 200 r/min.
Fully drying the mixed raw material B, then placing the dried mixed raw material B into a main feeding bin of a reciprocating single-screw extruder with high temperature control precision, and adding the dried mixed raw material B into a machine barrel of the extruder through a feeding screw; the diameter of the single screw extruder used was 44mm, the length-diameter ratio L/D was 40, and the temperatures of the respective zones from the feed port to the head outlet of the main barrel were set as follows: 190 deg.C, 220 deg.C, 230 deg.C, 235 deg.C, 230 deg.C, 225 deg.C, 230 deg.C, and the rotation speed of the main engine is 300 rpm; and (3) switching a double-screw extruder used for processing the mixed raw material A at the position of a fourth section of cylinder in the middle section of the single-screw extruder to realize secondary on-line melting and blending of the ASA resin melt and the PMMA resin melt, and obtaining the PMMA \ ASA alloy material with high stability and broad-spectrum antibacterial performance based on the molecular on-line self-assembly technology after the processes of extrusion, granulation, drying and the like.
Example 5
Weighing ASA terpolymer and guanidine polymer antibacterial agent according to the data of comparative example 5 shown in Table 1, and mixing uniformly to obtain a mixed raw material A; and weighing PMMA resin and the auxiliary dispersing agent according to the weight parts, and uniformly mixing to obtain a mixed raw material B.
Fully drying the mixed raw material A, then placing the dried mixed raw material A into a main feeding bin of a tightly meshed co-rotating double-screw extruder, adding the dried mixed raw material A into a machine barrel of the extruder through a feeding screw, and conveying the isothioketone antibacterial agent aqueous solution into the machine barrel of the extruder through a high-precision liquid metering pump through a feeding hole of a second barrel; the diameter of the used twin-screw extruder is 35mm, the length-diameter ratio L/D is 56, and the temperature of each subarea from the feed inlet to the head outlet of the main machine barrel is set as follows: 160 ℃, 200 ℃, 210 ℃, 215 ℃, 220 ℃ and the rotation speed of a main engine is 200 r/min.
Fully drying the mixed raw material B, then placing the dried mixed raw material B into a main feeding bin of a reciprocating single-screw extruder with high temperature control precision, and adding the dried mixed raw material B into a machine barrel of the extruder through a feeding screw; the diameter of the single screw extruder used was 44mm, the length-diameter ratio L/D was 40, and the temperatures of the respective zones from the feed port to the head outlet of the main barrel were set as follows: 190 deg.C, 220 deg.C, 230 deg.C, 235 deg.C, 230 deg.C, 225 deg.C, 230 deg.C, and the rotation speed of the main engine is 300 rpm; and (3) switching a double-screw extruder used for processing the mixed raw material A at the position of a fourth section of cylinder in the middle section of the single-screw extruder to realize secondary on-line melting and blending of the ASA resin melt and the PMMA resin melt, and obtaining the PMMA \ ASA alloy material with high stability and broad-spectrum antibacterial performance based on the molecular on-line self-assembly technology after the processes of extrusion, granulation, drying and the like.
Comparative example 1
Weighing PMMA resin, ASA terpolymer, silver ion antibacterial agent and dispersion aid according to comparative example 1 in Table 1, and uniformly mixing to obtain a mixed raw material.
Fully drying the mixed raw materials, then placing the dried mixed raw materials into a main feeding bin of a reciprocating single-screw extruder with high temperature control precision, and adding the dried mixed raw materials into a machine barrel of the extruder through a feeding screw; the diameter of the single screw extruder used was 44mm, the length-diameter ratio L/D was 40, and the temperatures of the respective zones from the feed port to the head outlet of the main barrel were set as follows: 190 deg.C, 220 deg.C, 230 deg.C, 235 deg.C, 230 deg.C, 225 deg.C, 230 deg.C, and the rotation speed of the main engine is 300 rpm. The PMMA \ ASA alloy material is obtained after the processes of extrusion, granulation, drying and the like.
TABLE 2 test results of formula table of highly stable, broad spectrum antimicrobial PMMA \ ASA alloy material
It can be known from the components and test data of each example and comparative example in tables 1 and 2 that PMMA has high viscosity, and the molecules of the added antibacterial agent are difficult to uniformly disperse and distribute, for example, although ASA resin with high content (25%) is added in comparative example 1, the apparent viscosity of the alloy material is still as high as 176pa.s due to high intrinsic viscosity, thereby causing the fluctuation of the antibacterial rate of the PMMA/ASA alloy material and the condition of low antifungal grade (grade 1 b), while in examples 1 and 4, the PMMA resin has low viscosity, and the antibacterial performance of the alloy material is also affected due to low usage (15%) of ASA resin.
Further comparing the types and the use amounts of the antibacterial agents, the guanidine polymer antibacterial agent/isothioketone antibacterial agent which are two antibacterial agent systems compounded by self-assembly based on strong interaction ionic bonds have obvious advantages in both antibacterial stability, broad spectrum and antifungal grade. The alloy material adopting the traditional first-order extrusion mixing and silver ion antibacterial agent in the comparative example 1 has low antibacterial rate (95-97%) and the anti-mold grade is only a lower grade 1b, while the anti-mold grade in the examples 3 and 5 can reach the highest grade 0 level, the antibacterial rate on four strains (escherichia coli, staphylococcus aureus, salmonella typhi and candida albicans) is all kept above 99%, and the antibacterial agent in the example 5 is more than 99.7%.
Of course, such excellent resistanceThe bacterial performance benefits from the matching performance and high efficiency of the composite antibacterial agent system, and on the other hand, the bacterial performance also benefits from the good interface compatibility of a PMMA/ASA two-phase system, which is also seen from the apparent viscosity number of the material and the normal-temperature and low-temperature notch impact performance, examples 3 and 5 with better antibacterial performance have obviously lower apparent viscosity number (about 90 Pa.s) and more balanced and stable normal-temperature and low-temperature notch impact resistance performance, and the highest notch impact strength of the low-temperature (-30) of example 5 can reach 17kJ/m2。
The PMMA/ASA alloy material with high stability and broad spectrum antibiosis based on the molecular on-line self-assembly technology and the preparation method thereof utilize a series two-stage extrusion processing technology which is highly matched with PMMA processing characteristics and a high-efficiency and stable molecular self-assembly antibacterial system, realize the stable, high-efficiency and broad spectrum antibiosis characteristics of the PMMA/ASA alloy system, completely conform to the new trend of high performance and high functionalization of the current polymer material, and have very wide application prospects in the fields of automobile interior and exterior decoration, outer shells of household appliances and medical appliances, food packaging containers and the like.
Claims (7)
1. A PMMA \ ASA alloy material with high stability and broad-spectrum antibiosis based on a molecular on-line self-assembly technology is characterized in that: the feed comprises the following raw materials in parts by weight:
2. the PMMA \ ASA alloy material with high stability and broad spectrum antibiosis based on the molecular on-line self-assembly technology as claimed in claim 1, is characterized in that: the PMMA resin is polymethyl methacrylate with high flow and high light transmittance, the melt index MFR of the PMMA resin is more than or equal to 15g/10min under the test conditions of 230 ℃ and 3.8kg, and the light transmittance is more than or equal to 93%.
3. The PMMA \ ASA alloy material with high stability and broad spectrum antibiosis based on the molecular on-line self-assembly technology as claimed in claim 1, is characterized in that: the ASA terpolymer is high impact resistance ASA superfine powder resin with the acrylate rubber phase content of 45-50%, and the average particle size (D98) is 3-5 um.
4. The PMMA \ ASA alloy material with high stability and broad spectrum antibiosis based on the molecular on-line self-assembly technology as claimed in claim 1, is characterized in that: the guanidine polymer antibacterial agent is polyhexamethylene biguanide hydrochloride, and is a cationic oligomer with a molecular chain containing 22 biguanide units.
5. The PMMA \ ASA alloy material with high stability and broad spectrum antibiosis based on the molecular on-line self-assembly technology as claimed in claim 1, is characterized in that: the isothiazolinone antibacterial agent is an aqueous solution of methylisothiazolinone antibacterial agent (MIT), and the content of effective active substances is more than or equal to 80%.
6. The PMMA \ ASA alloy material with high stability and broad spectrum antibiosis based on the molecular on-line self-assembly technology as claimed in claim 1, is characterized in that: the dispersing agent is acrylate modified Polytetrafluoroethylene (PTFE) powder with a core-shell structure, and the content of acrylate is 8-15%.
7. The preparation method of the PMMA \ ASA alloy material with high stability and broad spectrum antibiosis based on the molecule online self-assembly technology as claimed in any one of claims 1-6, characterized in that the method comprises the following steps:
(1) weighing ASA terpolymer and guanidine polymer antibacterial agent according to the weight parts, and uniformly mixing to obtain a mixed raw material A; weighing PMMA resin and the auxiliary dispersing agent according to the weight parts, and uniformly mixing to obtain a mixed raw material B;
(2) fully drying the mixed raw material A, then placing the dried mixed raw material A into a main feeding bin of a tightly meshed co-rotating double-screw extruder, adding the dried mixed raw material A into a machine barrel of the extruder through a feeding screw, and conveying the isothioketone antibacterial agent aqueous solution into the machine barrel of the extruder through a high-precision liquid metering pump through a feeding hole of a second barrel; the diameter of the used twin-screw extruder is 35mm, the length-diameter ratio L/D is 56, and the temperature of each subarea from the feed inlet to the head outlet of the main machine barrel is set as follows: 160 ℃, 200 ℃, 210 ℃, 215 ℃, 220 ℃ and the rotation speed of a main engine is 200 r/min;
(3) fully drying the mixed raw material B, then placing the dried mixed raw material B into a main feeding bin of a reciprocating single-screw extruder with high temperature control precision, and adding the dried mixed raw material B into a machine barrel of the extruder through a feeding screw; the diameter of the single screw extruder used was 44mm, the length-diameter ratio L/D was 40, and the temperatures of the respective zones from the feed port to the head outlet of the main barrel were set as follows: 190 deg.C, 220 deg.C, 230 deg.C, 235 deg.C, 230 deg.C, 225 deg.C, 230 deg.C, and the rotation speed of the main engine is 300 rpm; and (3) switching a double-screw extruder used for processing the mixed raw material A at the position of a fourth section of cylinder in the middle section of the single-screw extruder to realize secondary on-line melting and blending of the ASA resin melt and the PMMA resin melt, and obtaining the PMMA \ ASA alloy material with high stability and broad-spectrum antibacterial performance based on the molecular on-line self-assembly technology after the processes of extrusion, granulation, drying and the like.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110909915.4A CN113667254A (en) | 2021-08-09 | 2021-08-09 | High-stability broad-spectrum antibacterial PMMA \ ASA alloy material based on molecular on-line self-assembly technology and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110909915.4A CN113667254A (en) | 2021-08-09 | 2021-08-09 | High-stability broad-spectrum antibacterial PMMA \ ASA alloy material based on molecular on-line self-assembly technology and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113667254A true CN113667254A (en) | 2021-11-19 |
Family
ID=78541954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110909915.4A Pending CN113667254A (en) | 2021-08-09 | 2021-08-09 | High-stability broad-spectrum antibacterial PMMA \ ASA alloy material based on molecular on-line self-assembly technology and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113667254A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114656762A (en) * | 2022-04-15 | 2022-06-24 | 佛山市顺德区美的洗涤电器制造有限公司 | Antibacterial transparent material, preparation method thereof, water storage container and dish washing machine |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524858A (en) * | 2012-07-03 | 2014-01-22 | 合肥中科绿色家电科技有限公司 | Antibacterial coloring composition and preparation method thereof |
-
2021
- 2021-08-09 CN CN202110909915.4A patent/CN113667254A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524858A (en) * | 2012-07-03 | 2014-01-22 | 合肥中科绿色家电科技有限公司 | Antibacterial coloring composition and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 中国材料研究学会 等: "《中国战略性新兴产业 新材料 环境工程材料》", 中国轻工业出版社, pages: 760 - 499 * |
| 唐国栋 等: "PMMA/ASA合金的制备及其性能研究", 《塑料工业》, vol. 38, no. 10, 31 October 2010 (2010-10-31), pages 28 - 31 * |
| 杨忠久: "《硬质塑木复合低发泡产品生产技术和基础知识》", 30 November 2018, 江西科学技术出版社, pages: 215 - 216 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114656762A (en) * | 2022-04-15 | 2022-06-24 | 佛山市顺德区美的洗涤电器制造有限公司 | Antibacterial transparent material, preparation method thereof, water storage container and dish washing machine |
| CN114656762B (en) * | 2022-04-15 | 2023-08-22 | 佛山市顺德区美的洗涤电器制造有限公司 | Antibacterial transparent material, preparation method thereof, water storage container and dish-washing machine |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110343327A (en) | A kind of chitosan loaded nanometer silver antimicrobial polypropylene material and preparation method thereof | |
| CN103497490B (en) | A kind of PET composite material and preparation method thereof | |
| CN109082007A (en) | A kind of high-strength antibiotic polypropylene plastic and preparation method | |
| CN113667254A (en) | High-stability broad-spectrum antibacterial PMMA \ ASA alloy material based on molecular on-line self-assembly technology and preparation method thereof | |
| CN114213755B (en) | Hydrophobic durable antibacterial polypropylene composite material and preparation method thereof | |
| CN105086245A (en) | PVC (polyvinyl chloride) plastic wood board and preparation method thereof | |
| CN113801457A (en) | Efficient antibacterial polycarbonate composite material and preparation method thereof | |
| KR101765374B1 (en) | Transparent thermoplastic resin composition, method for preparing the resin composition and molded article produced therefrom | |
| CN109486464B (en) | Antibacterial thermoplastic polyurethane net film for clothing and preparation method thereof | |
| CN103396643A (en) | Modifier-containing polyacrylate grafted vinyl chloride composite resin composition | |
| CN115678278B (en) | PPS composite material and preparation method and application thereof | |
| CN106589889A (en) | High-performance polycarbonate composite material and preparation method and application thereof | |
| CN107245214B (en) | High-efficiency anti-mildew AES resin composition and preparation method thereof | |
| CN115637016A (en) | Antibacterial ABS alloy material and preparation method and application thereof | |
| CN105924728B (en) | A kind of antibiotic plastic and preparation method thereof | |
| KR20090095099A (en) | A preparing method of thermoplastic polyurethane(tpu) composite for increasing bonding strength of tpu film | |
| WO2022214057A1 (en) | Plastic composition and use thereof, plastic part, preparation method therefor and use thereof | |
| CN110951220B (en) | High-performance thermoplastic elastomer capable of injection-molding and bonding polyformaldehyde and preparation method thereof | |
| CN111040439B (en) | Polyamide material with excellent wear resistance, and preparation method and application thereof | |
| CN113234298A (en) | High-performance LDPE ionic polymer and preparation method thereof | |
| CN101709145A (en) | Halogen-free glass fiber enhanced nylon 66 material and manufacturing process thereof | |
| CN108530859B (en) | Preparation method of particle reinforced rubber reinforced composite material | |
| CN110643121A (en) | High-heat-resistance metal silver spraying-free ASA material and preparation method thereof | |
| CN104371172A (en) | Antibacterial and antistatic medical material and preparation method thereof | |
| KR102478645B1 (en) | Thermoplastic resin composition with antimicrobial activity and metal-like texture and molded article comprising the same |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211119 |