CN109456594B - Polyamide antibacterial masterbatch and its production process - Google Patents
Polyamide antibacterial masterbatch and its production process Download PDFInfo
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- CN109456594B CN109456594B CN201811359220.8A CN201811359220A CN109456594B CN 109456594 B CN109456594 B CN 109456594B CN 201811359220 A CN201811359220 A CN 201811359220A CN 109456594 B CN109456594 B CN 109456594B
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 46
- 229920002647 polyamide Polymers 0.000 title claims abstract description 46
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 45
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000005303 weighing Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 43
- 229960001545 hydrotalcite Drugs 0.000 claims description 43
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 22
- 239000000654 additive Substances 0.000 claims description 17
- 230000000996 additive effect Effects 0.000 claims description 17
- 239000000945 filler Substances 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 17
- 229920002943 EPDM rubber Polymers 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000004744 fabric Substances 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical group CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 claims description 10
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 10
- 239000003242 anti bacterial agent Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 150000004714 phosphonium salts Chemical group 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 8
- -1 3-chloro-2-hydroxypropyl Chemical group 0.000 claims description 7
- LWFBRHSTNWMMGN-UHFFFAOYSA-N 4-phenylpyrrolidin-1-ium-2-carboxylic acid;chloride Chemical compound Cl.C1NC(C(=O)O)CC1C1=CC=CC=C1 LWFBRHSTNWMMGN-UHFFFAOYSA-N 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 230000014759 maintenance of location Effects 0.000 claims description 7
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- LIGACIXOYTUXAW-UHFFFAOYSA-N phenacyl bromide Chemical compound BrCC(=O)C1=CC=CC=C1 LIGACIXOYTUXAW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002203 pretreatment Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- GJDRKHHGPHLVNI-UHFFFAOYSA-N 2,6-ditert-butyl-4-(diethoxyphosphorylmethyl)phenol Chemical compound CCOP(=O)(OCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GJDRKHHGPHLVNI-UHFFFAOYSA-N 0.000 claims description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 3
- SBKRBXBQFDKYSO-UHFFFAOYSA-N (3-tert-butyl-4-hydroxy-5-methylphenyl) propanoate Chemical compound CCC(=O)OC1=CC(C)=C(O)C(C(C)(C)C)=C1 SBKRBXBQFDKYSO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims description 2
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical group OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004033 plastic Substances 0.000 abstract description 8
- 229920003023 plastic Polymers 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 5
- 239000000835 fiber Substances 0.000 abstract description 3
- 230000008952 bacterial invasion Effects 0.000 abstract description 2
- 239000013538 functional additive Substances 0.000 abstract description 2
- 229920006122 polyamide resin Polymers 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 239000004953 Aliphatic polyamide Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 229920003231 aliphatic polyamide Polymers 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- OQLRBFNNEQUJPK-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl)methyl diethyl phosphate Chemical compound CCOP(=O)(OCC)OCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 OQLRBFNNEQUJPK-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 230000005541 medical transmission Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
-
- 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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- 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
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0058—Biocides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
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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)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开了一种聚酰胺抗菌母粒及其生产工艺，所述生产工艺包括以下步骤：(1)按重量份称取各原料；(2)将上述各原料在高速混合器中混合15‑20min，再加入双螺杆挤出机中经熔融挤出、冷却、切粒，即得。本发明聚酰胺抗菌母粒及其生产工艺，生产工艺简单，成本低，各功能添加剂与聚酰胺树脂的相容性好，使得产品的均一性明显改善，不仅具有现有技术中聚酰胺塑料本身的优势，最重要的是能够显著提高聚酰胺纤维的抗菌性能，整体性能优异，保护了塑料制备品免受细菌侵袭，对于聚酰胺材料的应用和进一步推广，具有十分重要的意义。The invention discloses a polyamide antibacterial masterbatch and a production process thereof. The production process comprises the following steps: (1) weighing each raw material by weight; (2) mixing the above-mentioned raw materials in a high-speed mixer for 15-15 20min, then added to the twin-screw extruder, melted, extruded, cooled, and pelletized. The polyamide antibacterial masterbatch and the production process thereof of the invention have the advantages of simple production process, low cost, good compatibility between each functional additive and polyamide resin, so that the uniformity of the product is obviously improved, and not only has the polyamide plastic itself in the prior art The most important thing is that it can significantly improve the antibacterial properties of polyamide fibers, the overall performance is excellent, and the plastic preparations are protected from bacterial invasion, which is of great significance for the application and further promotion of polyamide materials.
Description
Technical Field
The invention relates to the technical field of polymer materials, and particularly relates to a polyamide antibacterial master batch and a production process thereof.
Background
Polyamide (PA) is obtained by polycondensation of a dibasic acid and a diamine or an amino acid, and is a generic name of resins having a repeating amide group in a molecular chain. The polyamide can be prepared by ring-opening polymerization of lactam, or polycondensation of diamine and diacid. The DuPont company in the United states originally developed resins for fibers and was commercialized in 1939. In the 50 th of the 20 th century, injection molded products are developed and produced to replace metals to meet the requirements of light weight and cost reduction of downstream industrial products.
Polyamides can be classified into three groups according to their structures: aliphatic polyamides, aliphatic-aromatic polyamides, and aromatic polyamides. The aliphatic polyamide has many varieties, large yield and wide application, and the nomenclature of the polyamide is mainly determined by the specific carbon atom number of the synthetic monomer. The synthesis of polyamides can be mainly divided into three types: melt polycondensation, interfacial polycondensation, and solid phase polymerization.
Polyamides have good mechanical properties, heat resistance, abrasion resistance, chemical resistance, flame retardancy, and self-lubricity, are easy to process, have a low friction coefficient, and are widely used in the fields of electric and electronic parts, automobiles, furniture, building materials, films, and the like. There are generally two methods for modifying polyamides, one being modification by chemical means, such as copolymerization, grafting, crosslinking, etc.; the other is physical modification, which refers to a modification method in which no chemical change or only a very small degree of chemical reaction occurs in the whole modification process.
With the development and progress of society and the increasing living standard of materials, people have higher requirements on living and working environments, particularly sanitary environments. Because the plastic has the advantages of light weight, no corrosion, good insulation property and the like, the plastic is used in many links of household appliance production. However, in daily life, a considerable part of harmful bacteria are present and multiply on the surface of plastic products, such as: telephones, washing machines, computers, refrigerators, electric switches, etc., and cause various diseases by contact; therefore, in life, people inevitably come into contact with various microorganisms such as bacteria and mold and become a bacterial pollution source and a disease transmission source. But with the increasing awareness of people on health and environmental protection, the antibacterial and mildewproof effects are provided for household electric products which are frequently contacted in daily life.
Disclosure of Invention
In order to meet the requirements, the technical problem to be solved by the invention is to provide a polyamide antibacterial master batch and a production process thereof.
Therefore, the invention provides the following technical scheme:
a production process of polyamide antibacterial masterbatch comprises the following steps:
(1) weighing the raw materials in parts by weight;
(2) mixing the raw materials in a high-speed mixer for 15-20min, adding into a double-screw extruder, and performing melt extrusion, cooling and granulation to obtain the final product.
Further, the production process of the polyamide antibacterial masterbatch comprises the following steps:
(1) weighing the following raw materials in parts by weight: 80-90 parts of polyamide, 2-5 parts of silane coupling agent, 1-2 parts of maleic anhydride grafted compatilizer, 15-25 parts of filler, 1-2 parts of antioxidant, 1-2 parts of N, N' -ethylene bis stearamide and 1-2 parts of antibacterial additive;
(2) stirring and mixing the raw materials in a high-speed mixer at the rotating speed of 400-800r/min for 15-20min, adding the mixture into a double-screw extruder, and performing melt extrusion, cooling and grain cutting to obtain the material.
The polyamide is PA6 or PA 66.
The silane coupling agent is 3-chloropropylmethyldimethoxysilane or 3- (2, 3-glycidoxy) propyltrimethoxysilane.
The maleic anhydride grafted compatilizer is maleic anhydride grafted polypropylene or maleic anhydride grafted polyethylene or maleic anhydride grafted EPDM.
The filler is kaolin, hydrotalcite or palygorskite.
Further, the filler is functionalized hydrotalcite.
The preparation method of the functionalized hydrotalcite comprises the following steps: adding 90-110g of hydrotalcite and 20-40g of 3- (2, 3-epoxypropoxy) propyltrimethoxysilane into 950-1050mL of water, stirring for 2-4h at 40-60 ℃ at the rotating speed of 200-400r/min, filtering by using 500-mesh filter cloth, washing a filter cake for 2-4 times by using distilled water, and drying the obtained product for 20-40h at 40-60 ℃ to obtain pre-treated hydrotalcite; the pretreatment method comprises the following steps of (1) preparing pretreated hydrotalcite, 1-chloro-3-hydroxymethyl-5-epoxypropyl-S-triazinetrione, guanylurea phosphate and water according to the mass ratio of 1: (0.1-0.3): (0.05-0.2): (8-12), stirring and reacting for 3-5h at the rotation speed of 200-.
The antioxidant is triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate or 3, 5-di-tert-butyl-4-hydroxybenzyl diethyl phosphate.
The antibacterial additive is at least one of a quaternary phosphonium salt type halamine antibacterial agent and (3-chloro-2-hydroxypropyl) - (5, 5-dimethylhydantoin-1) methyl-dimethyl ammonium chloride. Further, the antibacterial additive is a quaternary phosphonium salt type halamine antibacterial agent, a (3-chloro-2-hydroxypropyl) - (5, 5-dimethylhydantoin-1) methyl-dimethyl ammonium chloride according to a mass ratio of 1: (0.4-0.6).
The temperature of the first area of the double-screw extruder is 170-185 ℃, the temperature of the second area is 225-245 ℃, the temperature of the third area is 255-275 ℃ and the temperature of the fourth area is 250-270 ℃; the fifth zone is 230 ℃ and 250 ℃, the retention time is 1-2 minutes, and the pressure is 10-15 Mpa.
The invention provides a polyamide antibacterial master batch which is prepared by the production process.
The invention has the beneficial effects that:
the polyamide antibacterial master batch and the production process thereof have the advantages of simple production process, low cost, good compatibility of each functional additive and polyamide resin, obviously improved product uniformity, excellent overall performance, capability of obviously improving the antibacterial performance of polyamide fiber, and protection of plastic preparations from bacterial invasion, and very important significance for application and further popularization of polyamide materials.
Detailed Description
The materials used are described below: the quaternary phosphonium salt type halamine antibacterial agent was prepared as shown in example 1 of chinese patent application No. 201510249967.8. (3-chloro-2-hydroxypropyl) - (5, 5-dimethylhydantoin-1) methyl-dimethylammonium chloride was prepared according to the method shown in example 3 of the chinese patent application No. 201210295496.0. N, N' -ethylene bis stearamide, CAS No.: 110-30-5. Diethyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate, CAS number: 976-56-7. 3-chloropropylmethyldimethoxysilane, CAS number: 18171-19-2. Maleic anhydride grafted EPDM was supplied by Catalph plastics Mill, Dongyuan county, model 9905E. Hydrotalcite is provided by Jingjiang city Kanggao Special plastics science and technology Limited, and has a model of FM300 and a granularity of 300 meshes. 1-chloro-3-hydroxymethyl-5-epoxypropyl-S-triazinetrione was prepared according to the method shown in example 3 of the Chinese patent application No. 201210362485. X. 3- (2, 3-glycidoxy) propyltrimethoxysilane, CAS no: 2530-83-8. Guanylurea phosphate was manufactured by Zhengzhou Guanda chemical products Co., Ltd., model number 2203. PA6 is supplied by DuPont, USA, and is 73G 20L.
Example 1
The production process of the polyamide antibacterial masterbatch comprises the following steps:
(1) weighing the following raw materials in parts by weight: PA 685 parts, 3 parts of 3-chloropropylmethyl dimethoxy silane, 1.5 parts of maleic anhydride grafted EPDM (ethylene-propylene-diene monomer), 20 parts of filler, 1.5 parts of diethyl 3, 5-di-tert-butyl-4-hydroxybenzyl phosphate, 1.5 parts of N, N' -ethylene bis stearamide and 1.5 parts of antibacterial additive;
(2) stirring and mixing the raw materials in a high-speed mixer at the rotating speed of 600r/min for 16min, adding the mixture into a double-screw extruder, performing melt extrusion, cooling the mixture by an air duct, and performing hot cutting by a cutter to obtain 3 x 3mm cylindrical particles, wherein the temperature of a first zone of the double-screw extruder is 175 ℃, the temperature of a second zone of the double-screw extruder is 235 ℃, the temperature of a third zone of the double-screw extruder is 270 ℃, the temperature of a fourth zone of the double-screw extruder is 260 ℃, the temperature of a fifth zone of the double-screw extruder is 240 ℃, the retention time is 1.5 min.
The filler is functionalized hydrotalcite.
The preparation method of the functionalized hydrotalcite comprises the following steps: adding 100g of hydrotalcite and 24g of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into 1000mL of deionized water, stirring for 3h at 50 ℃ at the rotating speed of 300r/min, filtering by adopting 600-mesh filter cloth, washing a filter cake for 3 times by using distilled water, wherein the mass ratio of the filter cake to the water after each washing is 1: 2, drying the obtained product at the temperature of 50 ℃ for 30h to obtain pretreated hydrotalcite; the pretreatment method comprises the following steps of (1) preparing pretreated hydrotalcite, 1-chloro-3-hydroxymethyl-5-epoxypropyl-S-triazinetrione, guanylurea phosphate and water according to the mass ratio of 1: 0.2: 0.08: 10, stirring and reacting for 4 hours at the rotation speed of 300r/min at the temperature of 50 ℃, filtering by using 600-mesh filter cloth, and drying the obtained product for 30 hours at the temperature of 50 ℃ to obtain the functionalized hydrotalcite.
The antibacterial additive is a quaternary phosphonium salt type halamine antibacterial agent.
Example 2
The production process of the polyamide antibacterial masterbatch comprises the following steps:
(1) weighing the following raw materials in parts by weight: PA 685 parts, 3 parts of 3-chloropropylmethyl dimethoxy silane, 1.5 parts of maleic anhydride grafted EPDM (ethylene-propylene-diene monomer), 20 parts of filler, 1.5 parts of diethyl 3, 5-di-tert-butyl-4-hydroxybenzyl phosphate, 1.5 parts of N, N' -ethylene bis stearamide and 1.5 parts of antibacterial additive;
(2) stirring and mixing the raw materials in a high-speed mixer at the rotating speed of 600r/min for 16min, adding the mixture into a double-screw extruder, performing melt extrusion, cooling the mixture by an air duct, and performing hot cutting by a cutter to obtain 3 x 3mm cylindrical particles, wherein the temperature of a first zone of the double-screw extruder is 175 ℃, the temperature of a second zone of the double-screw extruder is 235 ℃, the temperature of a third zone of the double-screw extruder is 270 ℃, the temperature of a fourth zone of the double-screw extruder is 260 ℃, the temperature of a fifth zone of the double-screw extruder is 240 ℃, the retention time is 1.5 min.
The filler is hydrotalcite.
The antibacterial additive is a quaternary phosphonium salt type halamine antibacterial agent.
Example 3
The production process of the polyamide antibacterial masterbatch comprises the following steps:
(1) weighing the following raw materials in parts by weight: PA 685 parts, 3 parts of 3-chloropropylmethyl dimethoxy silane, 1.5 parts of maleic anhydride grafted EPDM (ethylene-propylene-diene monomer), 20 parts of filler, 1.5 parts of diethyl 3, 5-di-tert-butyl-4-hydroxybenzyl phosphate, 1.5 parts of N, N' -ethylene bis stearamide and 1.5 parts of antibacterial additive;
(2) stirring and mixing the raw materials in a high-speed mixer at the rotating speed of 600r/min for 16min, adding the mixture into a double-screw extruder, performing melt extrusion, cooling the mixture by an air duct, and performing hot cutting by a cutter to obtain 3 x 3mm cylindrical particles, wherein the temperature of a first zone of the double-screw extruder is 175 ℃, the temperature of a second zone of the double-screw extruder is 235 ℃, the temperature of a third zone of the double-screw extruder is 270 ℃, the temperature of a fourth zone of the double-screw extruder is 260 ℃, the temperature of a fifth zone of the double-screw extruder is 240 ℃, the retention time is 1.5 min.
The filler is functionalized hydrotalcite.
The preparation method of the functionalized hydrotalcite comprises the following steps: adding 100g of hydrotalcite and 24g of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into 1000mL of deionized water, stirring for 3h at 50 ℃ at the rotating speed of 300r/min, filtering by adopting 600-mesh filter cloth, washing a filter cake for 3 times by using distilled water, wherein the mass ratio of the filter cake to the water after each washing is 1: 2, drying the obtained product at the temperature of 50 ℃ for 30h to obtain pretreated hydrotalcite; the pretreatment of hydrotalcite, 1-chloro-3-hydroxymethyl-5-epoxypropyl-S-triazine trione and water are mixed according to the mass ratio of 1: 0.2: 10, stirring and reacting for 4 hours at the rotation speed of 300r/min at the temperature of 50 ℃, filtering by using 600-mesh filter cloth, and drying the obtained product for 30 hours at the temperature of 50 ℃ to obtain the functionalized hydrotalcite.
The antibacterial additive is a quaternary phosphonium salt type halamine antibacterial agent.
Example 4
The production process of the polyamide antibacterial masterbatch comprises the following steps:
(1) weighing the following raw materials in parts by weight: PA 685 parts, 3 parts of 3-chloropropylmethyl dimethoxy silane, 1.5 parts of maleic anhydride grafted EPDM (ethylene-propylene-diene monomer), 20 parts of filler, 1.5 parts of diethyl 3, 5-di-tert-butyl-4-hydroxybenzyl phosphate, 1.5 parts of N, N' -ethylene bis stearamide and 1.5 parts of antibacterial additive;
(2) stirring and mixing the raw materials in a high-speed mixer at the rotating speed of 600r/min for 16min, adding the mixture into a double-screw extruder, performing melt extrusion, cooling the mixture by an air duct, and performing hot cutting by a cutter to obtain 3 x 3mm cylindrical particles, wherein the temperature of a first zone of the double-screw extruder is 175 ℃, the temperature of a second zone of the double-screw extruder is 235 ℃, the temperature of a third zone of the double-screw extruder is 270 ℃, the temperature of a fourth zone of the double-screw extruder is 260 ℃, the temperature of a fifth zone of the double-screw extruder is 240 ℃, the retention time is 1.5 min.
The filler is functionalized hydrotalcite.
The preparation method of the functionalized hydrotalcite comprises the following steps: adding 100g of hydrotalcite and 24g of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into 1000mL of deionized water, stirring for 3h at 50 ℃ at the rotating speed of 300r/min, filtering by adopting 600-mesh filter cloth, washing a filter cake for 3 times by using distilled water, wherein the mass ratio of the filter cake to the water after each washing is 1: 2, drying the obtained product at the temperature of 50 ℃ for 30h to obtain pretreated hydrotalcite; the pretreatment method comprises the following steps of (1) preparing pretreated hydrotalcite, 1-chloro-3-hydroxymethyl-5-epoxypropyl-S-triazinetrione, guanylurea phosphate and water according to the mass ratio of 1: 0.2: 0.08: 10, stirring and reacting for 4 hours at the rotation speed of 300r/min at the temperature of 50 ℃, filtering by using 600-mesh filter cloth, and drying the obtained product for 30 hours at the temperature of 50 ℃ to obtain the functionalized hydrotalcite.
The antibacterial additive is (3-chloro-2-hydroxypropyl) - (5, 5-dimethylhydantoin-1) methyl-dimethyl ammonium chloride.
Example 5
The production process of the polyamide antibacterial masterbatch comprises the following steps:
(1) weighing the following raw materials in parts by weight: PA 685 parts, 3 parts of 3-chloropropylmethyl dimethoxy silane, 1.5 parts of maleic anhydride grafted EPDM (ethylene-propylene-diene monomer), 20 parts of filler, 1.5 parts of diethyl 3, 5-di-tert-butyl-4-hydroxybenzyl phosphate, 1.5 parts of N, N' -ethylene bis stearamide and 1.5 parts of antibacterial additive;
(2) stirring and mixing the raw materials in a high-speed mixer at the rotating speed of 600r/min for 16min, adding the mixture into a double-screw extruder, performing melt extrusion, cooling the mixture by an air duct, and performing hot cutting by a cutter to obtain 3 x 3mm cylindrical particles, wherein the temperature of a first zone of the double-screw extruder is 175 ℃, the temperature of a second zone of the double-screw extruder is 235 ℃, the temperature of a third zone of the double-screw extruder is 270 ℃, the temperature of a fourth zone of the double-screw extruder is 260 ℃, the temperature of a fifth zone of the double-screw extruder is 240 ℃, the retention time is 1.5 min.
The filler is functionalized hydrotalcite.
The preparation method of the functionalized hydrotalcite comprises the following steps: adding 100g of hydrotalcite and 24g of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into 1000mL of deionized water, stirring for 3h at 50 ℃ at the rotating speed of 300r/min, filtering by adopting 600-mesh filter cloth, washing a filter cake for 3 times by using distilled water, wherein the mass ratio of the filter cake to the water after each washing is 1: 2, drying the obtained product at the temperature of 50 ℃ for 30h to obtain pretreated hydrotalcite; the pretreatment method comprises the following steps of (1) preparing pretreated hydrotalcite, 1-chloro-3-hydroxymethyl-5-epoxypropyl-S-triazinetrione, guanylurea phosphate and water according to the mass ratio of 1: 0.2: 0.08: 10, stirring and reacting for 4 hours at the rotation speed of 300r/min at the temperature of 50 ℃, filtering by using 600-mesh filter cloth, and drying the obtained product for 30 hours at the temperature of 50 ℃ to obtain the functionalized hydrotalcite.
The antibacterial additive is a quaternary phosphonium salt type halamine antibacterial agent, (3-chloro-2-hydroxypropyl) - (5, 5-dimethylhydantoin-1) methyl-dimethyl ammonium chloride according to a mass ratio of 1: 0.5 of a mixture.
Test example 1
The polyamide antibacterial master batches of examples 1 to 5 were subjected to performance tests. Specific results are shown in table 1.
And (3) testing antibacterial performance: the bacterial strain is tested according to the national common people's republic of China light industry Standard QB/T2591-: staphylococcus aureus (ATCC 6538).
And (3) oxygen index test: according to the standard GB/T2406.1-2008.
And (3) low temperature resistance test: placing the polyamide antibacterial master batch at 25 ℃ for 48 hours, and then carrying out tensile strength (the value is marked as A)1) The test was carried out, and the tensile strength (value A) was measured after leaving at-15 ℃ for 48 hours2) Testing, wherein the tensile strength is tested according to the standard GB/T1040.1-2006. The tensile strength decrease rate was calculated as follows. Tensile strength reduction (%) - (A)1-A2)/A1×100。
Table 1: test result table
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. The production process of the polyamide antibacterial masterbatch is characterized by comprising the following steps of:
(1) weighing the following raw materials in parts by weight: 80-90 parts of polyamide, 2-5 parts of silane coupling agent, 1-2 parts of maleic anhydride grafted compatilizer, 15-25 parts of filler, 1-2 parts of antioxidant, 1-2 parts of N, N' -ethylene bis stearamide and 1-2 parts of antibacterial additive;
(2) stirring and mixing the raw materials in a high-speed mixer at the rotating speed of 400-;
the filler is functionalized hydrotalcite; the preparation method of the functionalized hydrotalcite comprises the following steps: adding 90-110g of hydrotalcite and 20-40g of 3- (2, 3-epoxypropoxy) propyltrimethoxysilane into 950-1050mL of water, stirring for 2-4h at 40-60 ℃ at the rotating speed of 200-400r/min, filtering by using 500-mesh filter cloth, washing a filter cake for 2-4 times by using distilled water, and drying the obtained product for 20-40h at 40-60 ℃ to obtain pre-treated hydrotalcite; the pretreatment method comprises the following steps of (1) preparing pretreated hydrotalcite, 1-chloro-3-hydroxymethyl-5-epoxypropyl-S-triazinetrione, guanylurea phosphate and water according to the mass ratio of 1: (0.1-0.3): (0.05-0.2): (8-12), stirring and reacting at the rotation speed of 200-;
the antibacterial additive is a quaternary phosphonium salt type halamine antibacterial agent, (3-chloro-2-hydroxypropyl) - (5, 5-dimethylhydantoin-1) methyl-dimethyl ammonium chloride according to a mass ratio of 1: (0.4-0.6).
2. The process for producing the polyamide antibacterial masterbatch according to claim 1, wherein the polyamide is PA6 or PA 66.
3. The process for producing the polyamide antibacterial masterbatch according to claim 1, wherein the silane coupling agent is 3-chloropropylmethyldimethoxysilane or 3- (2, 3-glycidoxy) propyltrimethoxysilane.
4. The process for producing the polyamide antibacterial masterbatch according to claim 1, wherein the maleic anhydride grafted compatibilizer is maleic anhydride grafted polypropylene or maleic anhydride grafted polyethylene or maleic anhydride grafted EPDM.
5. The process for producing the polyamide antibacterial masterbatch according to claim 1, wherein the antioxidant is triethylene glycol ether-bis (3-t-butyl-4-hydroxy-5-methylphenyl) propionate or diethyl 3, 5-di-t-butyl-4-hydroxybenzylphosphonate.
6. The production process of the polyamide antibacterial masterbatch comprises the following steps:
(1) weighing the following raw materials in parts by weight: PA 685 parts, 3 parts of 3-chloropropylmethyl dimethoxy silane, 1.5 parts of maleic anhydride grafted EPDM (ethylene-propylene-diene monomer), 20 parts of filler, 1.5 parts of diethyl 3, 5-di-tert-butyl-4-hydroxybenzyl phosphate, 1.5 parts of N, N' -ethylene bis stearamide and 1.5 parts of antibacterial additive;
(2) stirring and mixing the raw materials in a high-speed mixer at the rotating speed of 600r/min for 16min, adding the mixture into a double-screw extruder, performing melt extrusion, cooling the mixture by an air duct, and performing hot cutting by a cutter to obtain 3 x 3mm cylindrical particles, wherein the temperature of a first zone of the double-screw extruder is 175 ℃, the temperature of a second zone of the double-screw extruder is 235 ℃, the temperature of a third zone of the double-screw extruder is 270 ℃, the temperature of a fourth zone of the double-screw extruder is 260 ℃, the temperature of a fifth zone of the double-screw extruder is 240 ℃, the retention time is 1.5 minutes;
the filler is functionalized hydrotalcite;
the preparation method of the functionalized hydrotalcite comprises the following steps: adding 100g of hydrotalcite and 24g of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into 1000mL of deionized water, stirring for 3h at 50 ℃ at the rotating speed of 300r/min, filtering by adopting 600-mesh filter cloth, washing a filter cake for 3 times by using distilled water, wherein the mass ratio of the filter cake to the water after each washing is 1: 2, drying the obtained product at the temperature of 50 ℃ for 30h to obtain pretreated hydrotalcite; the pretreatment method comprises the following steps of (1) preparing pretreated hydrotalcite, 1-chloro-3-hydroxymethyl-5-epoxypropyl-S-triazinetrione, guanylurea phosphate and water according to the mass ratio of 1: 0.2: 0.08: 10, mixing, stirring and reacting for 4 hours at the rotation speed of 300r/min at 50 ℃, filtering by using 600-mesh filter cloth, and drying the obtained product for 30 hours at the temperature of 50 ℃ to obtain the functionalized hydrotalcite;
the antibacterial additive is a quaternary phosphonium salt type halamine antibacterial agent, (3-chloro-2-hydroxypropyl) - (5, 5-dimethylhydantoin-1) methyl-dimethyl ammonium chloride according to a mass ratio of 1: 0.5 of a mixture.
7. The polyamide antibacterial masterbatch is characterized by being prepared by the production process of any one of claims 1-6.
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