CN117487304B - Antibacterial masterbatch based on guanidine salt polymer and preparation method thereof - Google Patents
Antibacterial masterbatch based on guanidine salt polymer and preparation method thereof Download PDFInfo
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 135
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 59
- 229920000642 polymer Polymers 0.000 title claims abstract description 34
- 150000002357 guanidines Chemical class 0.000 title claims abstract description 28
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 126
- 238000002156 mixing Methods 0.000 claims abstract description 35
- 239000004743 Polypropylene Substances 0.000 claims abstract description 23
- 229920001155 polypropylene Polymers 0.000 claims abstract description 23
- 239000000805 composite resin Substances 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 20
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 18
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 15
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 229920000098 polyolefin Polymers 0.000 claims abstract description 12
- 238000001125 extrusion Methods 0.000 claims abstract description 8
- 238000012661 block copolymerization Methods 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 230000002209 hydrophobic effect Effects 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000005543 nano-size silicon particle Substances 0.000 claims description 7
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 230000000845 anti-microbial effect Effects 0.000 claims 1
- 239000004599 antimicrobial Substances 0.000 claims 1
- 238000004383 yellowing Methods 0.000 abstract description 30
- 230000000694 effects Effects 0.000 abstract description 9
- 229920003023 plastic Polymers 0.000 abstract description 4
- 239000004033 plastic Substances 0.000 abstract description 4
- 230000002411 adverse Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 30
- 229920001400 block copolymer Polymers 0.000 description 15
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 13
- 230000002829 reductive effect Effects 0.000 description 12
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 9
- 230000003115 biocidal effect Effects 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- 238000001514 detection method Methods 0.000 description 8
- 230000002349 favourable effect Effects 0.000 description 7
- 125000000542 sulfonic acid group Chemical group 0.000 description 7
- 238000012423 maintenance Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- ZILVNHNSYBNLSZ-UHFFFAOYSA-N 2-(diaminomethylideneamino)guanidine Chemical compound NC(N)=NNC(N)=N ZILVNHNSYBNLSZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- AKGZDINYLOSBTE-UHFFFAOYSA-N [(e)-n'-(diaminomethylideneamino)carbamimidoyl]azanium;chloride Chemical compound Cl.NC(=N)NN=C(N)N AKGZDINYLOSBTE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012039 electrophile Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229960004198 guanidine Drugs 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000008782 xin-kang Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/26—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
-
- 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
- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
-
- 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
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
-
- 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
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The application relates to the technical field of antibacterial compositions, and particularly discloses an antibacterial masterbatch based on a guanidine salt polymer and a preparation method thereof. An antibacterial masterbatch based on a guanidine salt polymer comprises the following raw materials in parts by weight: 76-80 parts of composite resin, 10-20 parts of modified guanidine salt polymer, 2-4 parts of polydimethylsiloxane and 2-4 parts of hydrogenated C6-14 olefin polymer; the composite resin is prepared from linear low-density polyethylene powder and medium-melt index block copolymerization polypropylene powder according to the weight ratio of 1: (1-3) mixing; the preparation method comprises the following steps: premixing, mixing, melt extrusion, and granulating. The antibacterial masterbatch based on the guanidine salt polymer can be used in the fields of preparation of antibacterial plastics and the like, and has the advantage of reducing adverse effects of yellowing of the antibacterial masterbatch on product quality.
Description
Technical Field
The application relates to the technical field of antibacterial compositions, in particular to an antibacterial masterbatch based on guanidine salt polymer and a preparation method thereof.
Background
With the improvement of the living standard of people, the health and sanitation consciousness is continuously enhanced, and the requirements of antibiosis are put on a plurality of plastic products. In the processing of polyethylene or polypropylene products, a certain amount of antibacterial master batch is usually added, so that the prepared product is antibacterial, and the antibacterial master batch is usually prepared by mixing raw materials and granulating.
The types of antibacterial machines in the conventional antibacterial master batches are various, and the antibacterial machines are mainly divided into two major types, namely inorganic antibacterial agents and organic antibacterial agents, wherein guanidine polymers are used as common organic bactericides, and have the advantages of broad spectrum, high efficiency, no toxicity and the like, and the common antibacterial agents include polyhexamethylene biguanidine hydrochloride, polyhexamethylene biguanidine propionate, polyhexamethylene biguanidine stearate, polyoxyethylene guanidine hydrochloride and the like.
The guanidine salt polymer contains an unsaturated structure, and along with the reasons of climate change, environmental pollution and the like, ozone existing in the atmosphere is used as an electrophile, so that electron pairs in the unsaturated structure can be attacked, and unsaturated organic molecules are broken, so that the antibacterial master batch generates a yellowing phenomenon, and the quality of a product prepared from the antibacterial master batch is further influenced.
Disclosure of Invention
In order to reduce adverse effects of yellowing of antibacterial masterbatch on product quality, the application provides an antibacterial masterbatch based on guanidine salt polymer and a preparation method thereof.
In a first aspect, the present application provides an antibacterial masterbatch based on a guanidine salt polymer, which adopts the following technical scheme:
an antibacterial masterbatch based on a guanidine salt polymer comprises the following raw materials in parts by weight:
76-80 parts of composite resin, 10-20 parts of modified guanidine salt polymer, 2-4 parts of polydimethylsiloxane and 2-4 parts of hydrogenated C6-14 olefin polymer;
the composite resin is prepared from linear low-density polyethylene powder and medium-melt index block copolymerization polypropylene powder according to the weight ratio of 1: (1-3) and mixing.
By adopting the technical scheme, the modified guanidinium polymer is taken as an antibacterial component, the polydimethylsiloxane is taken as a dispersing agent, and the hydrogenated C6-14 olefin polymer is added into the antibacterial master batch, so that the hydrogenated C6-14 olefin polymer is not reacted with ozone, and the hydrogenated C6-14 olefin polymer is wrapped on the outer side of the modified guanidinium polymer, so that the ozone is difficult to contact with the modified guanidinium polymer, and the ozone is prevented from attacking an unsaturated structure in the modified guanidinium polymer, so that the yellowing possibility of the modified guanidinium polymer is reduced, the prepared antibacterial master batch is not easy to yellow, and the adverse effect on the prepared polyethylene or polypropylene product is reduced.
The antibacterial master batch is characterized in that the linear low-density polyethylene and the medium-melt index block copolymer polypropylene are compounded to form the composite resin, the linear low-density polyethylene is used as the matrix resin, the processing is easy, and the tensile strength, the penetration resistance and the tear resistance of the linear low-density polyethylene are increased, so that when the antibacterial master batch is added into a product, the penetration resistance of the product is increased, the medium-melt index block copolymer polypropylene is added into the linear low-density polyethylene, the rigidity and the strength are provided for the matrix resin, the medium-melt index block copolymer polypropylene has the wear resistance, and the prepared antibacterial master batch has the wear resistance, so that the antibacterial property can be conveniently and continuously exerted in the prepared product.
Preferably, the modified guanidine salt polymer is modified polyhexamethylene guanidine hydrochloride, and the weight ratio of the modified polyhexamethylene guanidine hydrochloride to the nano silicon dioxide is 100: (1-3).
Preferably, the modified guanidine salt polymer is prepared by the steps of:
the modified polyhexamethylene guanidine hydrochloride is prepared by mixing polyhexamethylene guanidine hydrochloride and nano silicon dioxide according to the weight ratio.
Through adopting above-mentioned technical scheme, mix polyhexamethylene guanidine hydrochloride with nanometer silica, nanometer silica parcel is at polyhexamethylene guanidine hydrochloride surface this moment to separate polyhexamethylene guanidine hydrochloride granule, reduce polyhexamethylene guanidine hydrochloride and the possibility of caking in the in-process of mixing with other raw materials, reduce polyhexamethylene guanidine hydrochloride and ozone contact and the possibility of oxidation yellowing simultaneously, and nanometer silica evenly disperses in the in-process of raw materials mixing, thereby improve the antibiotic master batch ageing resistance and the ability of anti chemical reagent of preparing, improve antibiotic master batch corrosion resistance.
Preferably, the polyhexamethylene guanidine hydrochloride is hydrophobic polyhexamethylene guanidine hydrochloride, the hydrophobic polyhexamethylene guanidine hydrochloride is prepared from guanidine group grafted sulfonic acid groups of the polyhexamethylene guanidine hydrochloride, and the weight ratio of the polyhexamethylene guanidine hydrochloride to naphthalene sulfonic acid is 1: (1.0-1.2).
Preferably, the hydrophobic polyhexamethylene guanidine hydrochloride is prepared by the steps of:
polyhexamethylene guanidine hydrochloride and water are mixed according to the weight ratio of 1: (4-6) mixing at 30-40 ℃, adding naphthalene sulfonic acid, mixing for 3-6h, filtering and drying to obtain the hydrophobic polyhexamethylene guanidine hydrochloride.
Through the technical scheme, the polyhexamethylene guanidine hydrochloride has hydrophilicity, the sulfonic acid group is grafted on the guanidine group, and the guanidine group grafted with the sulfonic acid group has hydrophobicity due to the hydrophobicity of the sulfonic acid group, so that the possibility that the prepared antibacterial master batch contacts with water and is separated from a product when the surface of the antibacterial master batch is antibacterial is reduced, and the antibacterial effect on the product is continuously maintained.
Preferably, the hydrogenated C6-14 olefin polymer is hydrogenated polydecene.
By adopting the technical scheme, the hydrogenated C6-14 olefin polymer is hydrogenated polydecene, and the hydrogenated polydecene has an antioxidation effect, so that the possibility of oxidation of polyhexamethylene guanidine hydrochloride is further reduced, and the hydrogenated polydecene also has an antibiosis effect, so that the hydrogenated polydecene and the polyhexamethylene guanidine hydrochloride cooperate to further improve the antibiosis performance of the antibiosis master batch.
Preferably, the viscosity of the polydimethylsiloxane is 300-400cs.
According to the technical scheme, the polydimethylsiloxane with the viscosity of 300-400cs is selected, at the moment, the polydimethylsiloxane has low viscosity and is in a liquid state, the viscosity of the mixed raw materials is reduced in the process of adding the composite resin and mixing, so that the mixed raw materials are easy to process, simultaneously have the functions of lubrication and coating, and when the mixed raw materials are mixed with the modified polyhexamethylene guanidine hydrochloride, the mixed raw materials are wrapped on the outer side of the modified polyhexamethylene guanidine hydrochloride, and a protective layer is further formed for the polyhexamethylene guanidine hydrochloride, so that the possibility of contact and yellowing of the polyhexamethylene guanidine hydrochloride with ozone is reduced; when the viscosity is more than 400cs, the viscosity of the mixed raw material increases due to the increase of the annual and surface tension of the polydimethylsiloxane, so that the mixed raw material is difficult to extrude; when the viscosity is less than 300cs, the material belongs to dangerous goods, is easy to burn, and further causes the condition of poor product safety.
In a second aspect, the present application provides a method for preparing an antibacterial masterbatch based on a guanidine salt polymer, which adopts the following technical scheme:
a preparation method of antibacterial master batch based on guanidine salt polymer comprises the following steps:
s1, premixing: uniformly mixing the composite resin and the polydimethylsiloxane according to the weight ratio to prepare a premix;
s2, mixing: mixing the premix prepared in the step S1 with the modified guanidine salt polymer, adding hydrogenated C6-14 olefin polymers, and uniformly mixing to prepare a mixture:
s3, melt extrusion: melting the mixture prepared in the step S2 at 160-200 ℃ and extruding at 0.3-0.5MPa to prepare an extruded material;
s4, granulating: cutting the extruded material prepared in the step S3 into particles, and drying at 100-110 ℃ to prepare the antibacterial master batch.
By adopting the technical scheme, the viscosity of the composite resin is regulated by mixing the composite resin and the polydimethylsiloxane, the modified guanidine salt polymer is added into the premix, and the prepared mixture is subjected to melt mixing, extrusion granulation and drying to prepare the antibacterial master batch, and the mixture of the composite resin and the polydimethylsiloxane forms a protective layer on the surface of the modified guanidine salt polymer, so that the yellowing possibility of the modified guanidine salt polymer is reduced.
In summary, the present application has the following beneficial effects:
1. the antibacterial master batch is characterized in that the linear low-density polyethylene and the medium-melt index block copolymer polypropylene are compounded to form the composite resin, the linear low-density polyethylene is used as the matrix resin, the processing is easy, and the tensile strength, the penetration resistance and the tear resistance of the linear low-density polyethylene are increased, so that when the antibacterial master batch is added into a product, the penetration resistance of the product is increased, the medium-melt index block copolymer polypropylene is added into the linear low-density polyethylene, the rigidity and the strength are provided for the matrix resin, the medium-melt index block copolymer polypropylene has the wear resistance, and the prepared antibacterial master batch has the wear resistance, so that the antibacterial property can be conveniently and continuously exerted in the prepared product.
2. The polyhexamethylene guanidine hydrochloride has hydrophilicity, and the sulfonic acid group is grafted on the guanidine group, so that the guanidine group grafted with the sulfonic acid group has hydrophobicity due to the hydrophobicity of the sulfonic acid group, the possibility that the prepared antibacterial master batch contacts with water and is separated from a product when the surface of the antibacterial master batch is antibacterial is reduced, and the antibacterial effect on the product is continuously maintained.
3. Hydrogenated C6-14 olefin polymer is hydrogenated polydecene, and the hydrogenated polydecene has an antioxidation effect, so that the possibility of oxidation of polyhexamethylene guanidine hydrochloride is further reduced, and the hydrogenated polydecene also has an antibiosis effect, so that the hydrogenated polydecene has a synergistic effect with polyhexamethylene guanidine hydrochloride, and the antibiosis performance of the antibiosis master batch is further improved.
Detailed Description
The present application is described in further detail below with reference to examples.
The yellow index detection method and the antibacterial rate detection method of all examples and comparative examples are as follows:
1. yellow index
The yellow index of the antibacterial master batch is detected according to the detection standard of national standard GB/T39822-2021 determination of Plastic yellow index and its variation value, the thickness of the sample is 3mm, and the reproducibility standard deviation is 0.09. The detection environment is as follows: 23 ℃.
2. Antibacterial rate
According to the detection standard of national standard GB/T31402-2015 "method for testing antibacterial property of Plastic surface", staphylococcus aureus with strain number ATCC 6538P and escherichia coli with strain number ATCC 8739 are selected to detect the antibacterial rate of antibacterial master batch, 5 groups of parallel antibacterial samples are set in each example, 10 pieces are used in each group, and the average value is recorded.
All experimental examples and examples herein are commercially available. Wherein the melt index of the medium melt index block polypropylene is 15-17g/10min, the melt index of the high melt index block polypropylene is more than 18g/10min, and the linear low density polyethylene is purchased from Shanghai Peng approximately 218WJ of New materials Co.
Preparation example 1
PREPARATION EXAMPLE 1.1
A preparation method of the hydrophobic polyhexamethylene guanidine hydrochloride comprises the following steps:
10kg of polyhexamethylene guanidine hydrochloride which is purchased from Hubei Xinkang pharmaceutical chemical Co Ltd and has CAS number 57028-96-3 is mixed with 60kg of water, the mixing temperature is 30 ℃, 10kg of naphthalene sulfonic acid is added for mixing for 3 hours, and the mixture is filtered and dried to prepare the hydrophobic polyhexamethylene guanidine hydrochloride.
PREPARATION EXAMPLE 1.2
Unlike preparation example 1.1, the amount of water added in preparation example 1.2 was 50kg, and the amount of naphthalene sulfonic acid added was 11kg.
PREPARATION EXAMPLE 1.3
Unlike preparation example 1.1, the amount of water added in preparation example 1.3 was 40kg, and the amount of naphthalene sulfonic acid added was 12kg.
PREPARATION EXAMPLE 1.4
Unlike preparation 1.2, the mixing temperature was 35℃and the mixing time was 4.5 hours in preparation 1.4.
PREPARATION EXAMPLE 1.5
Unlike preparation 1.2, the mixing temperature was 40℃and the mixing time was 6 hours in preparation 1.5.
PREPARATION EXAMPLE 1.6
Unlike preparation example 1.4, polyhexamethylene guanidine hydrochloride in preparation example 1.6 was purchased from Hubei Wankenkoku chemical Co., ltd, and the CAS number was 57028-96-3.
PREPARATION EXAMPLE 1.7
Unlike preparation 1.4, polyhexamethylene guanidine hydrochloride in preparation 1.7 was purchased from Hubei Yongku technology Co., ltd, and CAS number 57028-96-3.
Preparation example 2
PREPARATION EXAMPLE 2.1
A modified polyhexamethylene guanidine hydrochloride is prepared by the following steps:
20kg of polyhexamethylene guanidine hydrochloride and 0.2kg of nano silica were mixed to prepare modified polyhexamethylene guanidine hydrochloride.
PREPARATION EXAMPLE 2.2
Unlike preparation example 2.1, the nano silica in preparation example 2.2 was added in an amount of 0.4kg.
PREPARATION EXAMPLE 2.3
Unlike preparation example 2.1, the nano silica in preparation example 2.3 was added in an amount of 0.6kg.
PREPARATION EXAMPLES 2.4 to 2.10
Unlike preparation 2.2, preparation 2.4 to 2.10 each replaced polyhexamethylene guanidine hydrochloride with an equivalent amount of hydrophobic polyhexamethylene guanidine hydrochloride from preparation 1.1 to 1.7.
Preparation example 3
PREPARATION EXAMPLE 3.1
A preparation method of the composite resin comprises the following steps:
40kg of linear low-density polyethylene powder and 40kg of medium-melt index block copolymerization polypropylene powder were mixed to prepare a composite resin.
PREPARATION EXAMPLE 3.2
Unlike preparation example 3.1, the amount of the linear low-density polyethylene powder added in preparation example 3.2 was 26kg, and the amount of the medium melt index block copolymer polypropylene powder added was 52kg.
PREPARATION EXAMPLE 3.3
Unlike preparation example 3.1, the amount of the linear low-density polyethylene powder added in preparation example 3.3 was 19.5kg, and the amount of the medium melt index block copolymer polypropylene powder added was 58.5kg.
Examples
Example 1
Example 1.1
An antibacterial masterbatch based on guanidine salt polymer, which is prepared by the following steps:
s1, premixing: 76kg of the composite resin from preparation example 3.1 was uniformly mixed with 2kg of polydimethylsiloxane having a viscosity of 300cs to prepare a premix;
s2, mixing: after mixing the premix prepared in the step S1 with 20kg of modified polyhexamethylene guanidine hydrochloride from preparation example 2.1, 4kg of hydrogenated polydecene was added and mixed uniformly to prepare a mixture:
s3, melt extrusion: melting the mixture prepared in the step S2 at 160 ℃ and extruding at 0.3MPa to prepare an extrusion material;
s4, granulating: cutting the extruded material prepared in the step S3 into particles, and drying at 100 ℃ to prepare the antibacterial master batch.
Examples 1.2 to 1.7
Unlike example 1.1, the proportions of the raw materials in examples 1.2 to 1.7 differ from the melting temperature, as shown in Table 1.
Table 1 examples 1.1-1.7 raw material ratios
Comparative example 1
Unlike example 1.1, comparative example 1 replaced the modified polyhexamethylene guanidine hydrochloride with an equivalent amount of polyhexamethylene guanidine hydrochloride.
Comparative example 2
Unlike example 1.1, hydrogenated polydecene was not added in comparative example 2.
After the antibacterial master batches prepared in examples 1.1 to 1.7 and comparative examples 1 to 2 were left at the same room temperature for 3 months, the antibacterial master batches prepared in examples 1.1 to 1.7 and comparative examples 1 to 2 were examined for yellow index and antibacterial rate, as detailed in Table 2.
TABLE 2 Performance test data tables for examples 1.1-1.7, comparative examples 1-2
As is clear from a combination of tables 1 and 2, the antibacterial master batches obtained in examples 1.1 to 1.7 were each lower in yellow index than comparative example 1, probably due to the addition of the modified polyhexamethylene guanidine hydrochloride in examples 1.1 to 1.7, at which time the polyhexamethylene guanidine hydrochloride was coated with nano silica and formed a protective layer, so that the oxides such as ozone in the atmosphere were hardly contacted with the polyhexamethylene guanidine hydrochloride, and unsaturated structures such as guanidine groups of the polyhexamethylene guanidine hydrochloride were not destroyed, thereby inhibiting yellowing of the polyhexamethylene guanidine hydrochloride and maintaining the antibacterial performance of the polyhexamethylene guanidine hydrochloride.
As a result of examining the effect of hydrogenated polydecene in examples 1.1 to 1.7 and comparative example 2, it was found that the yellow index of the antibacterial master batch obtained in examples 1.1 to 1.7 was lower than that of comparative example 2, and the antibacterial rate of the antibacterial master batch obtained in examples 1.1 to 1.7 was higher than that of comparative example 2, indicating that the addition of hydrogenated polydecene to the raw material was superior in improving yellowing and maintaining antibacterial properties.
As a result of examining the influence of the raw material proportion of the antibacterial master batch in examples 1.1 to 1.3, the antibacterial master batch prepared in example 1.2 is found to be better in surface performance of anti-yellowing and antibacterial properties, which indicates that the raw material proportion of the antibacterial master batch selected in example 1.2 is favorable for reducing the yellowing of the antibacterial master batch on the premise of maintaining the antibacterial properties of the antibacterial master batch.
As a result of examining the influence of the melting temperature and the drying temperature in examples 1.4 to 1.5 by taking example 1.2 as a control, it was found that the antibacterial master batch prepared in example 1.4 exhibited better in terms of yellowing resistance and maintenance of antibacterial properties, which means that the melting temperature and the drying temperature selected in example 1.4 are favorable for reducing yellowing of the antibacterial master batch on the premise of maintaining antibacterial properties of the antibacterial master batch.
As a result of examining the effects of the viscosity and extrusion pressure of the polydimethylsiloxane in examples 1.6 to 1.7 against the control of example 1.4, it was found that the antibacterial master batch prepared in example 1.6 was superior in terms of anti-yellowing and antibacterial property maintenance, probably because the viscosity and extrusion pressure of the polydimethylsiloxane selected in example 1.6 were favorable for reducing the yellowing of the antibacterial master batch on the premise of maintaining the antibacterial property of the antibacterial master batch.
Example 2
Examples 2.1 to 2.2
Unlike example 1.6, the composite resins in examples 2.1-2.2 were equally derived from preparation examples 3.2-3.3.
Comparative example 3
Unlike example 2.1, comparative example 3 replaces linear low density polyethylene powder with an equal amount of low density polyethylene powder.
Comparative example 4
Unlike example 2.1, comparative example 4 replaces the medium melt block copolymer polypropylene powder with an equivalent amount of the high melt block copolymer polypropylene powder.
After the antibacterial master batches prepared in examples 2.1 to 2.2 and comparative examples 3 to 4 were left at the same room temperature for 3 months, the antibacterial master batches prepared in examples 2.1 to 2.2 and comparative examples 3 to 4 were subjected to the detection of yellow index and antibacterial rate, as shown in Table 3.
TABLE 3 Performance test data Table for examples 1.6, examples 2.1-2.2, comparative examples 3-4
As can be seen from table 3, comparing examples 1.6, 2.1-2.2 with comparative examples 3-4 for compounding of the composite resin, it is known from the detection results that the antibacterial master batches prepared in examples 2.1 and 2.2 are superior to the antibacterial master batch prepared in comparative examples 3-4 in terms of yellowing resistance and antibacterial property maintenance, and this is probably due to the fact that the low-density polyethylene powder is selected to replace the linear low-density polyethylene in comparative example 3, so that the compounded composite resin is reduced in acid, alkali and organic solvent resistance, the prepared antibacterial master batch is easy to corrode, the antibacterial property is reduced, and the modified polyhexamethylene guanidine hydrochloride in the antibacterial master batch is exposed to air and is further subjected to oxidative yellowing by ozone and the like; in comparative example 4, the high-melt-index block copolymer polypropylene powder was selected to replace the medium-melt-index block copolymer polypropylene powder, and the aging resistance of the prepared antibacterial master batch was reduced because the aging resistance stability of the high-melt-index block copolymer polypropylene is lower than that of the medium-melt-index block copolymer polypropylene.
As a result of examining the influence of the compounding ratio of the composite resin by taking example 1.6 as a control and examples 2.1 to 2.2, the antibacterial master batch prepared in example 2.1 is found to be better in terms of yellowing resistance and antibacterial property maintenance, which means that the compounding ratio of the linear low-density polyethylene selected in example 2.1 to the medium-melt index block copolymer polypropylene reduces the yellowing of the antibacterial master batch on the premise of maintaining the antibacterial property of the antibacterial master batch.
Example 3
Examples 3.1 to 3.9
Unlike example 2.1, examples 3.1 to 3.9 each replaced the modified polyhexamethylene guanidine hydrochloride with an equivalent amount of modified polyhexamethylene guanidine hydrochloride from preparation examples 2.2 to 2.10.
Comparative example 5
Unlike example 3.3, the modified polyhexamethylene guanidine hydrochloride was replaced in the comparative example with an equivalent amount of hydrophobic polyhexamethylene guanidine hydrochloride from preparation 1.1.
After the antibacterial master batches prepared in examples 3.1 to 3.9 and comparative example 5 were left at the same room temperature for 3 months, the antibacterial master batches prepared in examples 3.1 to 3.9 and comparative example 5 were subjected to yellow index and antibacterial rate detection, as shown in Table 4.
TABLE 4 Performance test data Table for examples 3.1-3.9, comparative example 5
As can be seen from table 4, the antibacterial master batch prepared in examples 3.1 to 3.9 is superior to comparative example 5 in terms of both anti-yellowing and antibacterial property retention, probably because the comparative example 5 replaces the modified polyhexamethylene guanidine hydrochloride with the hydrophobic polyhexamethylene guanidine hydrochloride, the outside of which is not coated with the nano silica powder, so that the hydrophobic polyhexamethylene guanidine hydrochloride is liable to contact with oxidative substances such as ozone in the air and become yellow, and the hydrophobic polyhexamethylene guanidine hydrochloride is not uniformly dispersed by the nano silica during the drying process, so that the antibacterial property of the prepared antibacterial master batch is unstable, and the antibacterial property of the antibacterial master batch is further affected.
Taking example 2.2 as a control, the influence of the raw material proportion of the modified polyhexamethylene guanidine hydrochloride is examined in examples 3.1-3.2, and the result shows that the antibacterial master batch prepared in example 3.1 is better in terms of yellowing resistance, antibacterial property maintenance and the like, which shows that the proportion of the polyhexamethylene guanidine hydrochloride and the nano silicon dioxide selected in example 3.1 is favorable for reducing the yellowing of the antibacterial master batch on the premise of maintaining the antibacterial property of the antibacterial master batch.
As a result of examining the influence of the hydrophobic polyhexamethylene guanidine hydrochloride in examples 3.3 to 3.9 against example 3.1, it was found that the modified polyhexamethylene guanidine hydrochloride was prepared by modifying the hydrophobic polyhexamethylene guanidine hydrochloride in examples 3.3 to 3.9, and the prepared antibacterial master batch was superior to example 3.1 in terms of yellowing resistance and antibacterial property retention, which is probably due to the fact that the hydrophobic polyhexamethylene guanidine hydrochloride has more hydrophobic groups than the structure of the polyhexamethylene guanidine hydrochloride, so that the hydrophobic polyhexamethylene guanidine hydrochloride is not easily dissolved in water during the contact with water and the antibacterial property of the antibacterial master batch is lowered, thereby maintaining the antibacterial property of the antibacterial master batch.
Taking example 3.1 as a control, the influence of the proportion of the hydrophobic polyhexamethylene guanidine hydrochloride to the nano silicon dioxide is examined in examples 3.3-3.5, and the result shows that the antibacterial master batch prepared in example 3.4 is better in terms of yellowing resistance, antibacterial property maintenance and the like, which shows that the proportion of the hydrophobic polyhexamethylene guanidine hydrochloride to the nano silicon dioxide selected in example 3.4 is favorable for reducing the yellowing of the antibacterial master batch on the premise of maintaining the antibacterial property of the antibacterial master batch.
As a result of examining the influence of the mixing temperature and mixing time of the preparation of the hydrophobic polyhexamethylene guanidine hydrochloride in examples 3.6 to 3.7 against the control of example 3.4, it was found that the antibacterial master batch prepared in example 3.6 exhibited superior yellowing resistance and antibacterial property retention, and this suggests that the moderating temperature and mixing time of the preparation of the hydrophobic polyhexamethylene guanidine hydrochloride selected in example 3.6 are favorable for reducing yellowing of the antibacterial master batch on the premise of maintaining antibacterial property of the antibacterial master batch.
As a result of examining the influence of polyhexamethylene guanidine hydrochloride from different manufacturers in examples 3.8-3.9 by taking example 3.6 as a control, it is found that the polyhexamethylene guanidine hydrochloride produced by other manufacturers in examples 3.8 and 3.9 has higher yellowing index than that in example 3.6 and lower antibacterial performance, and the antibacterial master batch prepared in example 3.6 has better performances in terms of resisting yellowing, maintaining antibacterial performance and the like, so that the preparation of modified polyhexamethylene guanidine hydrochloride by the polyhexamethylene guanidine hydrochloride in example 3.6 is favorable for reducing the yellowing of the antibacterial master batch on the premise of maintaining the antibacterial performance of the antibacterial master batch.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (3)
1. An antibacterial masterbatch based on a guanidine salt polymer is characterized by comprising the following raw materials in parts by weight:
76-80 parts of composite resin, 10-20 parts of modified guanidine salt polymer, 2-4 parts of polydimethylsiloxane and 2-4 parts of hydrogenated C6-14 olefin polymer;
the composite resin is prepared from linear low-density polyethylene powder and medium-melt index block copolymerization polypropylene powder according to the weight ratio of 1: (1-3) mixing; the modified guanidine salt polymer is modified polyhexamethylene guanidine hydrochloride, and the weight ratio of the modified polyhexamethylene guanidine hydrochloride to the nano silicon dioxide is 100: (1-3) preparing; the modified guanidine salt polymer is prepared by the following steps:
mixing polyhexamethylene guanidine hydrochloride and nano silicon dioxide according to a weight ratio to prepare modified polyhexamethylene guanidine hydrochloride; the hydrogenated C6-14 olefin polymer is hydrogenated polydecene; the viscosity of the polydimethylsiloxane is 300-400cs.
2. An antimicrobial masterbatch based on a guanidine salt polymer according to claim 1, characterized in that: the polyhexamethylene guanidine hydrochloride is hydrophobic polyhexamethylene guanidine hydrochloride, and the hydrophobic polyhexamethylene guanidine hydrochloride is prepared by the following steps:
polyhexamethylene guanidine hydrochloride and water are mixed according to the weight ratio of 1: (4-6) mixing at 30-40 ℃, adding naphthalene sulfonic acid, mixing for 3-6 hours, filtering and drying to obtain the hydrophobic polyhexamethylene guanidine hydrochloride; and the weight ratio of polyhexamethylene guanidine hydrochloride to naphthalene sulfonic acid is 1: (1.0-1.2).
3. A process for the preparation of an antibacterial masterbatch based on a guanidine salt polymer according to any one of claims 1-2, characterized in that it comprises the following steps:
s1, premixing: uniformly mixing the composite resin and the polydimethylsiloxane according to the weight ratio to prepare a premix;
s2, mixing: mixing the premix prepared in the step S1 with the modified guanidine salt polymer, adding hydrogenated C6-14 olefin polymers, and uniformly mixing to prepare a mixture:
s3, melt extrusion: melting the mixture prepared in the step S2 at 160-200 ℃ and extruding at 0.3-0.5MPa to prepare an extruded material;
s4, granulating: cutting the extruded material prepared in the step S3 into particles, and drying at 100-110 ℃ to prepare the antibacterial master batch.
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