CN115197493A - Anti-biological fouling material and preparation method and application thereof - Google Patents
Anti-biological fouling material and preparation method and application thereof Download PDFInfo
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- CN115197493A CN115197493A CN202211013965.5A CN202211013965A CN115197493A CN 115197493 A CN115197493 A CN 115197493A CN 202211013965 A CN202211013965 A CN 202211013965A CN 115197493 A CN115197493 A CN 115197493A
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- biofouling
- parts
- auxiliary agent
- antioxidant
- hydrochloride
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- 239000000463 material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 51
- 239000011347 resin Substances 0.000 claims abstract description 51
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 44
- -1 polyhexamethylene guanidine hydrochloride Polymers 0.000 claims abstract description 24
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 23
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 23
- 239000011159 matrix material Substances 0.000 claims abstract description 19
- 229910017059 organic montmorillonite Inorganic materials 0.000 claims abstract description 17
- 239000003963 antioxidant agent Substances 0.000 claims description 39
- 230000003078 antioxidant effect Effects 0.000 claims description 38
- 229920002413 Polyhexanide Polymers 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 17
- 239000004595 color masterbatch Substances 0.000 claims description 13
- 239000004611 light stabiliser Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000000071 blow moulding Methods 0.000 claims description 10
- 229920001903 high density polyethylene Polymers 0.000 claims description 10
- 239000004700 high-density polyethylene Substances 0.000 claims description 10
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 10
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 230000006750 UV protection Effects 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000003337 fertilizer Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 10
- 230000003373 anti-fouling effect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- ORECYURYFJYPKY-UHFFFAOYSA-N n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine;2,4,6-trichloro-1,3,5-triazine;2,4,4-trimethylpentan-2-amine Chemical compound CC(C)(C)CC(C)(C)N.ClC1=NC(Cl)=NC(Cl)=N1.C1C(C)(C)NC(C)(C)CC1NCCCCCCNC1CC(C)(C)NC(C)(C)C1 ORECYURYFJYPKY-UHFFFAOYSA-N 0.000 description 7
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 6
- YHCGGLXPGFJNCO-UHFFFAOYSA-N 2-(2H-benzotriazol-4-yl)phenol Chemical compound OC1=CC=CC=C1C1=CC=CC2=C1N=NN2 YHCGGLXPGFJNCO-UHFFFAOYSA-N 0.000 description 6
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 229910021389 graphene Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- YXHRTMJUSBVGMX-UHFFFAOYSA-N 4-n-butyl-2-n,4-n-bis(2,2,6,6-tetramethylpiperidin-4-yl)-2-n-[6-[(2,2,6,6-tetramethylpiperidin-4-yl)amino]hexyl]-1,3,5-triazine-2,4-diamine Chemical compound N=1C=NC(N(CCCCCCNC2CC(C)(C)NC(C)(C)C2)C2CC(C)(C)NC(C)(C)C2)=NC=1N(CCCC)C1CC(C)(C)NC(C)(C)C1 YXHRTMJUSBVGMX-UHFFFAOYSA-N 0.000 description 5
- 241000195493 Cryptophyta Species 0.000 description 5
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011253 protective coating Substances 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- 241000238586 Cirripedia Species 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- ZTOTXIJTXLDCFH-UHFFFAOYSA-N O(P(OCCCCCCCCCCCCCCCCCC)OP(O)O)CCCCCCCCCCCCCCCCCC.OCC(CO)(CO)CO Chemical compound O(P(OCCCCCCCCCCCCCCCCCC)OP(O)O)CCCCCCCCCCCCCCCCCC.OCC(CO)(CO)CO ZTOTXIJTXLDCFH-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000010288 cold spraying Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229940075559 piperine Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2248—Oxides; Hydroxides of metals of copper
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Abstract
The invention relates to an anti-biofouling material, a preparation method and application thereof, wherein the anti-biofouling material comprises matrix resin, an anti-biofouling auxiliary agent and other auxiliary agents; the anti-biofouling auxiliary agent comprises polyhexamethylene guanidine hydrochloride, organic montmorillonite and nano cuprous oxide. The anti-biofouling material disclosed by the invention has long-acting and excellent anti-biofouling performance and can meet the offshore application of water surface photovoltaics.
Description
Technical Field
The invention relates to the technical field of anti-biological fouling materials, in particular to an anti-biological fouling material and a preparation method and application thereof.
Background
At present, water surface photovoltaics on the market are mainly applied to inland lake surfaces, a large amount of algae, barnacles and shellfish organisms are attached to the surface of a floating body in offshore application, after various organisms are attached in a large amount, the buoyancy of a water surface photovoltaic floating body system is reduced, and in order to reduce the attachment phenomenon of the large amount of algae organisms, an anti-biological fouling material for offshore application of the water surface photovoltaics needs to be developed.
CN109207984A discloses a preparation method of a corrosion-resistant, antibacterial and anti-biofouling multifunctional metal-based protective coating. The method comprises the steps of firstly synthesizing nano silver on a graphene oxide-OH functional group in situ through a chemical reaction, reducing to obtain graphene/nano silver composite powder, then carrying out ball milling on the graphene/nano silver composite powder and metal powder to form metal/graphene/nano silver composite powder, then carrying out stress relief annealing under the protection of inert gas, and finally depositing the composite powder into a protective coating by adopting a cold spraying technology. The method disclosed by the invention can change the distribution state of the graphene/nano silver in the metal-based composite coating by adjusting the chemical reaction conditions, the particle size distribution of the metal powder, the weight ratio of the metal/graphene/nano silver and the ball milling time, so that the multifunctional metal-based protective coating with good corrosion resistance, antibacterial property and anti-biological fouling property is prepared.
Currently, although there have been many studies on anti-biofouling materials, there are certain limitations in terms of long-term effectiveness and effectiveness, such as the anti-biofouling materials are easily released, require regular maintenance, etc.
In conclusion, it is important to develop an anti-biofouling material with a long lasting fouling reduction.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide an anti-biofouling material, a preparation method and application thereof, wherein the anti-biofouling material has long acting and excellent anti-biofouling performance and can meet the requirements of offshore application of surface photovoltaics.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an anti-biofouling material comprising a matrix resin, an anti-biofouling aid and other aids;
the anti-biofouling auxiliary agent comprises polyhexamethylene guanidine hydrochloride, organic montmorillonite and nano cuprous oxide.
In the invention, the anti-biofouling material has long-acting and excellent anti-biofouling property, and can meet the offshore application of surface photovoltaics. The anti-biofouling auxiliary agent comprises polyhexamethylene guanidine hydrochloride, organic montmorillonite and nano cuprous oxide, wherein the polyhexamethylene guanidine hydrochloride and the organic montmorillonite are compounded to enhance the positive charge of the surface of a polymer, while the algae cells in the offshore area are negatively charged, so that the algae cells can form flocs through electrostatic attraction, and the algae removal effect is further achieved; and by compounding cuprous oxide, some marine microorganisms which do not form flocs are killed and disinfected through the toxicity of cuprous oxide, and the three are used in a synergistic manner to achieve a better anti-biofouling effect.
In the present invention, the other auxiliary is an auxiliary other than the anti-biofouling auxiliary.
Preferably, the anti-biofouling aid further comprises a compatible resin.
Preferably, the anti-biofouling auxiliary agent comprises the following components in parts by weight:
in the present invention, the compatible resin is present in an amount of 50 to 70 parts by weight, for example, 52 parts, 54 parts, 56 parts, 58 parts, 60 parts, 62 parts, 64 parts, 66 parts, 68 parts, etc.
The parts by weight of the polyhexamethylene guanidine hydrochloride are 15-30 parts, such as 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts and the like.
The weight portion of the organic montmorillonite is 5-10 portions, such as 6 portions, 7 portions, 8 portions, 9 portions and the like.
The weight parts of the nano cuprous oxide are 5-20 parts, such as 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts and the like.
Preferably, the polyhexamethylene guanidine hydrochloride comprises a combination of polyhexamethylene guanidine hydrochloride and polyhexamethylene biguanide hydrochloride.
In the present invention, the polyhexamethyleneguanidine hydrochloride is preferably a combination of polyhexamethylenebiguanide hydrochloride and polyhexamethylenebiguanide hydrochloride because: only single polyhexamethylene guanidine hydrochloride is selected to cause higher use concentration, and the compounded polyhexamethylene guanidine hydrochloride can reduce the proportion of single components, achieve the same antifouling effect and reduce the use cost.
Preferably, the mass ratio of the polyhexamethylene biguanide hydrochloride to the polyhexamethylene biguanide hydrochloride is 1: (0.6-1.5), wherein 0.6-1.5 can be 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, etc.
In the invention, the mass ratio of the polyhexamethylene biguanide hydrochloride to the polyhexamethylene biguanide hydrochloride is controlled to be 1: (0.6-1.5) because: the proportion of the polyhexamethylene biguanide hydrochloride is too high, the antifouling effect cannot be obviously improved, and the cost of the compounded auxiliary agent is increased.
Preferably, the compatible resin comprises a linear low density polyethylene resin.
Preferably, the linear low density polyethylene resin has a melt index of 1.5 to 3.5g/10min, such as 1.6g/10min, 1.8g/10min, 2g/10min, 2.2g/10min, 2.4g/10min, 2.6g/10min, 2.8g/10min, 3g/10min, 3.2g/10min, 3.4g/10min, etc., at 190 ℃ and 2.16 kg.
Preferably, the nano cuprous oxide particle size is 30-500nm, such as 50nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm and the like.
Preferably, the anti-biofouling material comprises the following components in parts by weight:
85-95 parts of matrix resin
2-10 parts of anti-biological fouling auxiliary agent
0.05-0.65 part of other auxiliary agents.
In the present invention, the base resin is 85 to 95 parts by weight, for example, 86 parts, 88 parts, 90 parts, 92 parts, 94 parts, and the like.
The anti-biofouling aid is 2-10 parts by weight, such as 4 parts, 6 parts, 8 parts and the like.
The weight portion of the other auxiliary agent is 0.05-0.65 portion, such as 0.1 portion, 0.2 portion, 0.3 portion, 0.4 portion, 0.5 portion, 0.6 portion and the like.
Preferably, the matrix resin comprises high density polyethylene.
Preferably, the high density polyethylene has a melt index of 5-12g/10min, such as 6g/10min, 7g/10min, 8g/10min, 9g/10min, 10g/10min, 11g/10min, etc., at 190 ℃ and 21.6 kg.
Preferably, the other auxiliary agents comprise an antioxidant and/or an anti-ultraviolet auxiliary agent.
Preferably, the antioxidant comprises a combination of primary and secondary antioxidants.
Preferably, the mass ratio of the primary antioxidant to the secondary antioxidant is 1: (0.5-2), wherein 0.5-2 can be 0.6, 0.8, 1, 1.2, 1.4, 1.6, 1.8, etc.
Preferably, the primary antioxidant comprises any one or a combination of at least two of antioxidant 2246, antioxidant bisphenol a, or antioxidant 1010, where typical but non-limiting combinations include: a combination of antioxidant 2246 and antioxidant bisphenol A, a combination of antioxidant bisphenol A and antioxidant 1010, a combination of antioxidant 2246, antioxidant bisphenol A and antioxidant 1010, and the like.
In the present invention, the antioxidant 2246 refers to 2,2' -methylenebis (4-methyl-6-tert-butylphenol), and the antioxidant 1010 refers to pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
Preferably, the secondary antioxidant comprises any one or a combination of at least two of antioxidant 618, antioxidant 6280 or antioxidant DLDP, wherein typical but non-limiting combinations include: a combination of antioxidant 618 and antioxidant 6280, a combination of antioxidant 6280 and antioxidant DLDP, a combination of antioxidant 618, antioxidant 6280 and antioxidant DLDP, and the like.
In the present invention, the antioxidant 618 is pentaerythritol distearyl diphosphite, the antioxidant 6280 is dipentaerythritol diphosphite, and the antioxidant DLDP is dilauryl thiodipropionate.
Preferably, the ultraviolet resistance aid includes a combination of an ultraviolet absorber, a light stabilizer and a light shielding agent.
Preferably, the uv absorber comprises any one of 2-hydroxybenzophenone, 2-hydroxyphenylbenzotriazole or a hindered benzoate salt, or a combination of at least two thereof, wherein typical but non-limiting combinations include: combinations of 2-hydroxybenzophenone and 2-hydroxyphenylbenzotriazole, combinations of 2-hydroxyphenylbenzotriazole and hindered benzoate, combinations of 2-hydroxybenzophenone, 2-hydroxyphenylbenzotriazole and hindered benzoate, and the like.
Preferably, the light stabilizer comprises any one of Chimassorb944, chimassorb 2020, or HALS 770, or a combination of at least two thereof, wherein typical but non-limiting combinations include: combinations of Chimassorb944 and Chimassorb 2020, combinations of Chimassorb 2020 and HALS 770, combinations of Chimassorb944, chimassorb 2020, and HALS 770, and the like.
In the present invention, chimassorb944 refers to a light stabilizer 944, poly [ [6- [ (1, 3-tetramethylbutyl) amine ] -1,3, 5-triazine-2, 4-diyl ] [ (2, 6-tetramethyl-4-piper-ine ]; chimassorb 2020 and HALS 770 are hindered amine light stabilizers.
Preferably, the ultraviolet light shielding aid includes titanium dioxide and/or carbon black.
Preferably, the antioxidant is present in an amount of 0.1 to 0.5 parts by weight, such as 0.2 parts, 0.3 parts, 0.4 parts, etc.
Preferably, the weight part of the ultraviolet resistance auxiliary agent is 0.05-0.15 part, such as 0.06 part, 0.07 part, 0.08 part, 0.09 part, 0.10 part, 0.11 part, 0.12 part, 0.13 part, 0.14 part and the like.
Preferably, in the anti-ultraviolet auxiliary agent, the mass ratio of the ultraviolet absorbent, the light stabilizer and the light shielding agent is 1: (1-3): (1-3), wherein 1-3 may be 1.2, 1.4, 1.6, 1.8, 2, 2.2, 2.4, 2.6, 2.8, etc., and the light stabilizer and the light-shielding agent may be added in the same amount or in different amounts.
Preferably, the anti-biofouling material further comprises a color masterbatch.
Preferably, the color masterbatch is 4-10 parts by weight, such as 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, and the like.
In a second aspect, the present invention provides a method of preparing an anti-biofouling material according to the first aspect, the method comprising the steps of:
(1) Mixing polyhexamethylene guanidine hydrochloride, organic montmorillonite and nano cuprous oxide, and extruding and granulating to obtain the anti-biological fouling assistant;
(2) And mixing the matrix resin, the anti-biofouling additive and other additives, and performing blow molding processing to obtain the anti-biofouling material.
In the invention, the anti-biological fouling assistant and other materials are blended and processed into a whole, so that the long-acting decontamination effect can be achieved, and the surface coating mode is superior to that of the surface coating mode.
Preferably, in step (1), the temperature of the extrusion granulation is 160 to 210 ℃, for example 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃ and the like.
Preferably, in the step (1), the mixed raw materials further comprise a compatible resin.
Preferably, in step (2), the temperature of the blow molding process is 170 to 210 ℃, such as 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃ and the like.
Preferably, in the step (2), the mixed raw materials further comprise a color master batch.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) Mixing compatible resin, polyhexamethylene guanidine hydrochloride, organic montmorillonite and nano cuprous oxide, and extruding and granulating at 160-210 ℃ to obtain the anti-biological fouling auxiliary agent;
(2) Mixing matrix resin, an anti-biofouling auxiliary agent, other auxiliary agents and color master batches, and carrying out blow molding processing at 170-210 ℃ to obtain the anti-biofouling material.
In a third aspect, the present invention provides the use of an anti-biofouling material according to the first aspect in biofouling with a marine organism.
Compared with the prior art, the invention has the following beneficial effects:
(1) In the invention, the anti-biofouling material has long-acting and excellent anti-biofouling property, and can meet the offshore application of surface photovoltaics.
(2) The anti-biofouling material has excellent anti-biofouling property, the initial anti-biofouling organism removal efficiency is over 86 percent, and after 120 days, the anti-biofouling organism removal efficiency is over 82 percent.
(3) In the invention, compatible resin is arranged in the anti-biofouling auxiliary agent, and the mass ratio of the polyhexamethylene biguanide hydrochloride to the polyhexamethylene biguanide hydrochloride is 1: (0.6-1.5) the initial anti-fouling organism removal efficiency of the formed anti-biofouling material is above 89% and after 120 days the anti-fouling organism removal efficiency is above 83%.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
In the present invention, purchase information of part of raw materials in each embodiment is as follows:
high density polyethylene: HDPE, available in Daqing petrochemical, having a trade mark of B4506, and having a melt index of 5-12g/10min at 190 ℃ and 21.6 kg;
linear low density polyethylene: LLDPE purchased from Letian chemical, having a brand EM-400 and a melt index of 1.5-3.5g/10min at 190 ℃ under 2.16 kg;
polyhexamethylene biguanide hydrochloride: PHMG available from Liangshi chemical Co., ltd;
polyhexamethylene biguanide hydrochloride: PHMB, available from LISOURCE INDUSTRIES, FORCHI;
organic montmorillonite: purchased from Zhejiang Fenghong New materials GmbH, with a particle size of 200 meshes;
inorganic montmorillonite: purchased from Zhejiang Fenghong New materials GmbH, with a particle size of 200 mesh.
Example 1
The embodiment provides an anti-biofouling material, which comprises the following components in parts by weight:
in this example, the matrix resin is high density polyethylene; the antioxidant is prepared from the following components in percentage by mass of 1:1 (primary antioxidant 1010) and a secondary antioxidant (antioxidant 618); the anti-ultraviolet auxiliary agent is prepared from the following components in a mass ratio of 1:2:2 (equal mass of 2-hydroxybenzophenone and 2-hydroxyphenylbenzotriazole), a light stabilizer (equal mass of Chimassorb944 and 2020), and a light-shielding agent (titanium dioxide).
The anti-biofouling auxiliary agent comprises the following components in parts by weight:
in this example, the compatible resin is a linear low density polyethylene resin; the polyhexamethylene guanidine hydrochloride is prepared from the following raw materials in a mass ratio of 1:1 and polyhexamethylene biguanide hydrochloride; the average grain diameter of the nano cuprous oxide is 30nm.
The anti-biofouling material is prepared by a method comprising the steps of:
(1) Mixing compatible resin, polyhexamethylene guanidine hydrochloride, organic montmorillonite and nano cuprous oxide, and extruding and granulating at 180 ℃ to obtain the anti-biological fouling auxiliary agent;
(2) Mixing matrix resin, an anti-biological fouling assistant, an antioxidant, an anti-ultraviolet assistant and color master batches, and carrying out blow molding processing at 200 ℃ to obtain the anti-biological fouling material.
Example 2
The embodiment provides an anti-biofouling material, which comprises the following components in parts by weight:
in this example, the matrix resin is high density polyethylene; the antioxidant is prepared from the following components in percentage by mass of 1:1 (primary antioxidant 1010) and a secondary antioxidant (antioxidant 618); the anti-ultraviolet auxiliary agent is prepared from the following components in a mass ratio of 1:2:2 (equal mass of 2-hydroxybenzophenone and 2-hydroxyphenylbenzotriazole), a light stabilizer (equal mass of Chimassorb944 and 2020), and a light-shielding agent (titanium dioxide).
The anti-biofouling auxiliary agent comprises the following components in parts by weight:
in this example, the compatible resin is a linear low density polyethylene resin; the mass ratio of the polyhexamethylene guanidine hydrochloride is 1:1 and polyhexamethylene biguanide hydrochloride; the average grain diameter of the nano cuprous oxide is 100nm.
The anti-biofouling material is prepared by a method comprising the steps of:
(1) Mixing compatible resin, polyhexamethylene guanidine hydrochloride, organic montmorillonite and nano cuprous oxide, and extruding and granulating at 160 ℃ to obtain the anti-biological fouling auxiliary agent;
(2) Mixing matrix resin, an anti-biological fouling assistant, an antioxidant, an anti-ultraviolet assistant and color master batches, and carrying out blow molding processing at 210 ℃ to obtain the anti-biological fouling material.
Example 3
The embodiment provides an anti-biofouling material, which comprises the following components in parts by weight:
in this example, the matrix resin is high density polyethylene; the antioxidant is prepared from the following components in percentage by mass of 1:1 (primary antioxidant, bisphenol a) and secondary antioxidant (antioxidant DLDP); the anti-ultraviolet auxiliary agent is prepared from the following components in percentage by mass of 1:2:2 (a) a combination of a uv absorber (hindered benzoate), a light stabilizer (Chimassorb 944) and a light-shielding agent (carbon black).
The anti-biofouling auxiliary agent comprises the following components in parts by weight:
in this example, the compatible resin is a linear low density polyethylene resin; the mass ratio of the polyhexamethylene guanidine hydrochloride is 1:1 and polyhexamethylene biguanide hydrochloride; the average grain diameter of the nano cuprous oxide is 300nm.
The anti-biofouling material is prepared by a method comprising the steps of:
(1) Mixing compatible resin, polyhexamethylene guanidine hydrochloride, organic montmorillonite and nano cuprous oxide, and extruding and granulating at 210 ℃ to obtain the anti-biological fouling assistant;
(2) Mixing matrix resin, an anti-biofouling auxiliary agent, an antioxidant, an anti-ultraviolet auxiliary agent and color master batches, and carrying out blow molding processing at 210 ℃ to obtain the anti-biofouling material.
Example 4
The embodiment provides an anti-biofouling material, which comprises the following components in parts by weight:
in this example, the matrix resin was high density polyethylene; the antioxidant is prepared from the following components in percentage by mass: 1 (antioxidant 2246) and a secondary antioxidant (antioxidant 6280); the anti-ultraviolet auxiliary agent is prepared from the following components in a mass ratio of 1:2:2 (2), a light stabilizer (HALS 770) and a light-shielding agent (titanium dioxide).
The anti-biofouling auxiliary agent comprises the following components in parts by weight:
in this example, the compatible resin is a linear low density polyethylene resin; the polyhexamethylene guanidine hydrochloride is prepared from the following raw materials in a mass ratio of 1:1 and polyhexamethylene biguanide hydrochloride; the average grain diameter of the nano cuprous oxide is 500nm.
The anti-biofouling material is prepared by a method comprising the steps of:
(1) Mixing compatible resin, polyhexamethylene guanidine hydrochloride, organic montmorillonite and nano cuprous oxide, and extruding and granulating at 160 ℃ to obtain the anti-biological fouling auxiliary agent;
(2) Mixing matrix resin, an anti-biofouling auxiliary agent, an antioxidant, an anti-ultraviolet auxiliary agent and color master batches, and carrying out blow molding processing at 170 ℃ to obtain the anti-biofouling material.
Example 5
This example is different from example 1 in that the anti-biofouling aid does not include a compatible resin, and the anti-biofouling material is obtained by mixing the compatible resin as a separate component with a base resin, the anti-biofouling aid, an antioxidant, an anti-uv aid, and a color masterbatch, and the rest is the same as example 1.
Examples 6 to 9
Examples 6 to 9 are different from example 1 in that the mass ratio of polyhexamethylene biguanide hydrochloride to polyhexamethylene biguanide hydrochloride is 1:0.6 (example 6), 1:1.5 (example 7), 1:0.4 (example 8) and 1:1.8 (example 9), the rest is the same as example 1.
Comparative example 1
This comparative example is different from example 1 in that polyhexamethyleneguanidine hydrochloride is replaced with an equal mass of polyhexamethyleneguanidine phosphate, and the rest is the same as example 1.
Comparative example 2
The comparative example is different from example 1 in that organic montmorillonite is replaced by inorganic montmorillonite of equal mass, and the rest is the same as example 1.
Comparative example 3
The comparative example is different from example 1 in that nano cuprous oxide is replaced by nano silver of the same mass, and the rest is the same as example 1.
Performance test
The anti-biofouling materials described in examples 1-9 and comparative examples 1-3 were tested as follows:
anti-fouling organism removal efficiency: culturing 100mg/L of marine microorganism suspension through a culture dish, adding an anti-fouling material, and calculating the anti-fouling organism removal rate by the anti-fouling organism concentration at intervals of 3 days (test 1), 14 days (test 2), 60 days (test 3) and 120 days (test 4), wherein the calculation formula is as follows:
the test results are summarized in table 1.
TABLE 1
Analysis of the data in table 1 shows that the anti-biofouling material of the present invention has excellent anti-biofouling properties, the initial anti-biofouling organism removal efficiency is above 86%, and after 120 days, the anti-biofouling organism removal efficiency is above 82%; in the invention, compatible resin is arranged in the anti-biofouling auxiliary agent, and the mass ratio of the polyhexamethylene biguanide hydrochloride to the polyhexamethylene biguanide hydrochloride is 1: (0.6-1.5) the formed anti-biofouling material has an initial anti-fouling organism removal efficiency of more than 89% and after a period of 120 days the anti-fouling organism removal efficiency is more than 83%.
As can be seen from the analysis of comparative examples 1 to 3 and example 1, comparative examples 1 to 3 are not the same as example 1, and the anti-biofouling material formed by the synergistic effect of the polyhexamethylene guanidine hydrochloride, the organic montmorillonite and the nano cuprous oxide in the anti-biofouling auxiliary agent has excellent anti-biofouling performance.
As can be seen from the analysis of example 5 and example 1, the performance of example 5 is inferior to that of example 1, and the compatibility resin is arranged in the anti-biofouling assistant, so that the performance of the formed anti-biofouling material is better.
As can be seen from the analysis of examples 6 to 9, examples 8 to 9 are inferior in performance to examples 6 to 7, and it was confirmed that the mass ratio of polyhexamethylene biguanide hydrochloride to polyhexamethylene biguanide hydrochloride was in the range of 1: (0.6-1.5), the formed anti-biofouling material has better performance.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. An anti-biofouling material comprising a matrix resin, an anti-biofouling aid and other aids;
the anti-biofouling auxiliary agent comprises polyhexamethylene guanidine hydrochloride, organic montmorillonite and nano cuprous oxide.
2. The anti-biofouling material of claim 1, wherein the anti-biofouling aid further comprises a compatible resin;
preferably, the anti-biofouling aid comprises the following components in parts by weight:
3. the anti-biofouling material of claim 1 or 2, wherein the polyhexamethyleneguanidine hydrochloride comprises a combination of polyhexamethylenebiguanide hydrochloride and polyhexamethylenebiguanide hydrochloride;
preferably, the mass ratio of the polyhexamethylene biguanide hydrochloride to the polyhexamethylene biguanide hydrochloride is 1: (0.6-1.5);
preferably, the compatible resin comprises a linear low density polyethylene resin;
preferably, the linear low density polyethylene resin has a melt index of 1.5 to 3.5g/10min at 190 ℃ and 2.16 kg;
preferably, the particle size of the nano cuprous oxide is 30-500nm.
4. The anti-biofouling material of claim 1, comprising the following components in parts by weight:
85-95 parts of matrix resin
2-10 parts of anti-biological fouling auxiliary agent
0.05 to 0.65 portion of other auxiliary agents.
5. The anti-biofouling material of claim 1, wherein the matrix resin comprises high density polyethylene;
preferably, the high-density polyethylene has a melt index of 5-12g/10min at 190 ℃ and 21.6 kg;
preferably, the other auxiliary agents comprise an antioxidant and/or an anti-ultraviolet auxiliary agent;
preferably, the ultraviolet resistance aid includes a combination of an ultraviolet absorber, a light stabilizer and a light shielding agent.
6. The anti-biofouling material of claim 5, wherein the antioxidant is present in an amount of 0.1-0.5 parts by weight;
preferably, the weight portion of the anti-ultraviolet auxiliary agent is 0.05-0.15;
preferably, the anti-biofouling material further comprises a color masterbatch;
preferably, the weight part of the color master batch is 4-10 parts.
7. A method for the preparation of an anti-biofouling material according to any one of claims 1 to 6, comprising the steps of:
(1) Mixing polyhexamethylene guanidine hydrochloride, organic montmorillonite and nano cuprous oxide, and extruding and granulating to obtain the anti-biological fouling assistant;
(2) And mixing the matrix resin, the anti-biofouling auxiliary agent and other auxiliary agents, and performing blow molding processing to obtain the anti-biofouling material.
8. The method for preparing the compound fertilizer according to claim 7, wherein in the step (1), the temperature of the extrusion granulation is 160-210 ℃;
preferably, in the step (1), the mixed raw materials further comprise a compatible resin;
preferably, in the step (2), the temperature of the blow molding process is 170-210 ℃;
preferably, in the step (2), the mixed raw materials further comprise a color master batch.
9. The method according to claim 7 or 8, characterized in that it comprises the steps of:
(1) Mixing compatible resin, polyhexamethylene guanidine hydrochloride, organic montmorillonite and nano cuprous oxide, and extruding and granulating at 160-210 ℃ to obtain the anti-biological fouling auxiliary agent;
(2) Mixing matrix resin, the anti-biofouling additive, other additives and the color master batch, and carrying out blow molding processing at 170-210 ℃ to obtain the anti-biofouling material.
10. Use of an anti-biofouling material according to any one of claims 1 to 6 in biofouling of a marine organism.
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