CN114479403B - Flame-retardant antibacterial polymer alloy material and preparation method and application thereof - Google Patents
Flame-retardant antibacterial polymer alloy material and preparation method and application thereof Download PDFInfo
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- CN114479403B CN114479403B CN202011159068.6A CN202011159068A CN114479403B CN 114479403 B CN114479403 B CN 114479403B CN 202011159068 A CN202011159068 A CN 202011159068A CN 114479403 B CN114479403 B CN 114479403B
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 134
- 239000003063 flame retardant Substances 0.000 title claims abstract description 131
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- LUYIHWDYPAZCNN-UHFFFAOYSA-N 2-butyl-1,2-benzothiazol-3-one Chemical compound C1=CC=C2C(=O)N(CCCC)SC2=C1 LUYIHWDYPAZCNN-UHFFFAOYSA-N 0.000 claims description 8
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical compound O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 claims description 7
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- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 claims description 6
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- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the field of high polymer materials, and in particular relates to a flame-retardant antibacterial polymer alloy material, which is prepared by taking a polymer alloy as a matrix material and adding an antibacterial flame-retardant auxiliary agent, an optional melting auxiliary agent, an antioxidant and the like. The alloy material has the greatest characteristics that the material comprehensive performance, especially the low-temperature impact performance, is improved by utilizing a special processing means while the flame retardant and antibacterial performance of the material are improved, and the problem that the flame retardant and antibacterial impact performance cannot be simultaneously improved is effectively solved. The manufacturing process provided by the invention has the advantages of simple process, energy conservation and environmental friendliness, and can be widely applied to the fields with high requirements on flame retardance and low-temperature impact performance.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a flame-retardant antibacterial polymer alloy material, and a preparation method and application thereof.
Background
In recent years, with the improvement of the living standard of people and the enhancement of the consciousness of sanitation, the demand for various antibacterial material products, which occupy a great proportion, is increasing, and various kinds of living products, including refrigerators, air conditioners, various food containers, packaging bags, washing machines, toy products, dust collectors, etc., are using various kinds of thermoplastic antibacterial plastics.
PBT, the chemical name polybutylene terephthalate, has evolved rapidly since its commercial production. There are many factories in China to use PBT plastics. As one of five engineering plastics, PBT is favored by people in the characteristics of good physical and mechanical properties, good electrical properties, easy molding and processing, and the like. The PBT resin can be applied to various potentiometer products matched with various industries in the fields of aerospace, communication, post and telecommunications, military industry, energy, traffic, household appliances, instruments and the like. With the development of the automobile industry, the electronic industry and the electric industry, the development of the PBT has a broad prospect. PBT has good processing fluidity and impact resistance, but mechanical properties and heat resistance are not ideal enough, thereby limiting the application of PBT. However, the buckling deformation of the PBT plastic part is more prominent, so that the correct use of the PBT is affected, and the PBT resin is easy to crystallize and is difficult to avoid the buckling phenomenon basically.
Polycarbonate (PC) is a high polymer with excellent advantages of high heat resistance, high impact, good glossiness, good transparency, good dimensional stability and the like, but has the defects of easy stress cracking, poor processing fluidity, poor solvent resistance, notch sensitivity and the like, thereby restricting the application of PC in the field of engineering plastics.
The PC and PBT resin are used for blending to prepare the alloy, so that the performances of the PC and the PBT resin are complementary. The PC/PBT alloy has the excellent properties of both, on one hand, the heat resistance and the mechanical property of the PBT can be improved, and on the other hand, the melt strength of the PC can be reduced, the processing property can be improved, and the stress sensitivity of a product can be reduced. Therefore, PC/PBT alloy has been widely used in the fields of automobiles, machinery, home appliances, communication tools, office equipment and the like.
The polycarbonate is not easy to burn, and can reach V-2 grade in UL-94 vertical burning test, but the flame retardant property of PC/PBT alloy is reduced after the PBT is blended with PBT resin due to the flammability of the PBT, and the PC/PBT alloy cannot be rated (NR, no Rating) in UL-94 test, so that the PC/PBT alloy can be applied to fields with higher flame retardant requirements such as automobiles, electronics, electrics, machinery and the like through flame retardant modification.
When the PC/PBT alloy material is prepared, the toughening auxiliary agent of the material is added in the traditional method, the mutual melting of the materials is enhanced, the toughness of the material and the defects of the two complementary materials are improved, particularly, the transesterification of the material is easy to occur between the PC/PBT materials, the physical properties of the material are greatly influenced, and after the flame retardance of the material is modified, a compatilizer and a toughening agent are additionally added to improve the interaction between the auxiliary agent and a base material, so that the toughness of the alloy is improved. Patent CN104530634A, patent CN107057322a and patent CN107325518A all solve the contradiction between flame retardance and material toughness by this method. The strength, toughness and functions of the PC/PBT material application guide material are very important, and the flame-retardant and antibacterial alloy material can greatly help the application of the material to be widened in the application of electric appliances, so that the quality of life in daily life and working environment can be further improved. In addition, the halogen-free flame retardant, the material compatilizer and the low-temperature toughening agent are high in price, and the development of the materials is limited.
The novel antibacterial product which is developed in nineties of the last century and has broad spectrum, high efficiency, no toxicity and no irritation is widely applied to the fields of textile, agriculture, food, sanitation and the like. The preparation of the antibacterial plastic is mainly realized by adding a certain amount of antibacterial agent in the granulating process. The types of antibacterial agents are various, mainly comprise two major types of inorganic antibacterial agents and organic antibacterial agents, and guanidine salt polymer antibacterial agents are commonly used. Currently, the varieties of guanidine salt polymers mainly include polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine propionate, polyhexamethylene (bis) guanidine stearate, other inorganic or organic salts of polyhexamethylene (bis) guanidine, polyoxyethylene guanidine, and the like. Since the guanidine salt polymer has excellent solubility in water, the guanidine salt polymer is mostly used in the form of an aqueous solution, as a bactericide for water treatment in japanese patent publication No. JP05209195A, US patent publication No. US4891423a, chinese patent publication No. CN101156586 a. In addition, the guanidine salt polymer also has good thermal stability, and the thermal decomposition temperature is higher and can reach 280 ℃, so that the guanidine salt polymer can be used as an additive to be applied to plastics, fibers and rubber products to obtain antibacterial products. However, most guanidine salt polymers are very water-soluble, and are difficult to prepare into powder samples, which limits their application in the plastic, rubber and fiber fields. Chinese patent publication No. CN101037503a discloses a method for preparing powdered guanidine salt polymer product, wherein guanidine salt polymer is separated from aqueous solution by ion-separation exchange membrane to obtain powder sample; however, the method for preparing the guanidine salt polymer powder has the defects of harsh conditions and complex process.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a high-efficiency processing method for preparing a flame-retardant and antibacterial polymer alloy material, and the obtained flame-retardant and antibacterial polymer alloy material has the characteristics of good fluidity and good physical properties, and can be continuously produced in a large scale.
One of the purposes of the invention is to provide a flame-retardant and antibacterial polymer alloy material, which comprises a blended matrix material and an antibacterial and flame-retardant auxiliary agent, wherein the matrix material comprises at least two of polycarbonate, polyester, acrylonitrile-butadiene-styrene polymer and polyamide; the antibacterial flame retardant auxiliary agent is at least one selected from isothiazolinone antibacterial agents and phosphate flame retardants.
In the flame-retardant antibacterial polymer alloy material, when the matrix material is two polymers, the weight ratio of the two polymers is 10:90-90:10; the amount of the antibacterial flame retardant auxiliary is 1-30 parts by weight, preferably 5-20 parts by weight, based on 100 parts by weight of the matrix material; in the antibacterial flame retardant auxiliary, the dosage ratio of the phosphate compound to the isothiazolinone compound is 100 (0.5-10), preferably 100 (1-5);
In the flame-retardant antibacterial polymer alloy material, the polyester comprises at least one of polybutylene terephthalate and polyethylene terephthalate; the melt index of the polycarbonate is 1-30 g/10min, preferably 6-15 g/10min; the polyamide is nylon 6.
In the alloy material, the isothiazolinone antibacterial agent is at least one selected from n-octyl isothiazolinone, n-butyl-1, 2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one, preferably at least one selected from n-octyl isothiazolinone, n-butyl-1, 2-benzisothiazolin-3-one and 1, 2-benzisothiazolin-3-one. Among the isothiazolinone antibacterial agents, N-octyl isothiazolinone (N-octyl-4-isothiazolin-3-ketone, OIT) is prepared by cyclization of di-N-octyl dipropionamide in the presence of a chlorinating agent, OIT is an oil-soluble sterilization preservative, has good inhibition capability on fungi, bacteria, mold and enzyme bacteria, is low in toxicity and long-acting, does not contain formaldehyde, has no peculiar smell, is strong in sterilization capability, has strong mold killing capability, has an effect obviously superior to that of a traditional mildew preventive, is a new generation product of the traditional paint film mildew preventive, is harmless to the environment, can be naturally degraded into non-toxic substances, and does not cause environmental pollution; the broad-spectrum bactericide taking n-butyl-1, 2-benzisothiazolin-3-one (BBIT) as an active ingredient has the appearance of reddish brown liquid, effectively inhibits the growth of gram-positive bacteria and gram-negative bacteria, effectively inhibits the growth of mold, saccharomycetes and algae, and has the advantages of low addition amount, high efficiency, stability, long acting, no arsenic and no tin; the 1, 2-benzisothiazolin-3-one (BIT) antibacterial agent is white powder, can increase the melting degree after being heated, belongs to an isothiazolinone compound, has a broad-spectrum antibacterial effect when being used as an antibacterial auxiliary agent commonly used in liquid, and has the active ingredient of heat resistance. In the preparation process of the flame-retardant antibacterial material, the OIT antibacterial material is preferably used as a main antibacterial agent in consideration of the mixing temperature of the material, the appearance of a material part and the application environment of the material, and other liquid antibacterial auxiliary agents can be added.
In the alloy material, the phosphate compound is at least one selected from triphenyl phosphate and oligomers thereof, resorcinol-bis (diphenyl phosphate), bisphenol A-bis (diphenyl phosphate) and resorcinol-bis [ di (2, 6-dimethyl benzene) phosphate ] \hexaphenoxy cyclotriphosphazene), preferably at least one selected from triphenyl phosphate and oligomers thereof, bisphenol A-bis (diphenyl phosphate) and hexaphenoxy cyclotriphosphazene; more preferably at least one of bisphenol A-bis (diphenyl phosphate) (BDP) and hexaphenoxy cyclotriphosphazene.
Most preferably, the isothiazolinone antibacterial agent is selected from n-octyl isothiazolinone compounded bisphenol A-bis (diphenyl phosphate), the phosphate compound is selected from at least one of hexaphenoxy cyclotriphosphazene, the compounds are oily liquid, the materials are easy to mix, and the antibacterial flame retardant auxiliary agent is obtained after even mixing.
In the alloy material, the matrix material is selected from polycarbonate and polybutylene terephthalate, polycarbonate and polyethylene terephthalate, polycarbonate and acrylonitrile-butadiene-styrene polymer or acrylonitrile-butadiene-styrene polymer and nylon 6; preferably, the matrix material is polycarbonate and polybutylene terephthalate; in the matrix material, the weight ratio of the polycarbonate to the polybutylene terephthalate is 60:40-80:20.
Polycarbonate (PC) is a high molecular polymer having a carbonate group in a molecular chain, and can be synthesized from bisphenol a and carbon oxychloride (COCl 2) according to various types of ester groups such as aliphatic, aromatic, aliphatic-aromatic, etc., and a melt transesterification method (synthesis of bisphenol a and diphenyl carbonate by transesterification and polycondensation reaction) is currently widely used, and the polycarbonate resin produced by the melt transesterification method is preferred in the present invention.
Polybutylene terephthalate (PBT) is a common polymer material, and a plurality of factories are producing PBT plastics in China, because PBT resin is easy to crystallize, the occurrence of warping phenomenon is basically difficult to avoid, in order to reduce the warping of PBT, glass fiber or filler is usually added into the PBT material, so that the strength of the material is improved, the yield of the PBT material is reduced, and the mechanical property of the PBT material is reduced; according to the invention, the antibacterial flame retardant auxiliary agent is added into the PC/PBT alloy material to effectively improve the crystallization performance of the material, so that the warping of the PBT is reduced. The PBT material is mainly divided into high, medium and low viscosity according to the viscosity, material manufacturers mainly adopt foreign manufacturers such as eastern Japan, korean LG, german BASF and the like, domestic and medium petrochemical chemical fiber company materials are used as domestic excellent manufacturers, the prepared PBT material is excellent in performance, the prepared plastic product is small in buckling deformation, the requirements for preparing flame-retardant antibacterial materials can be met, and the PBT material can be completely used.
The alloy material further comprises an antistatic agent, wherein the antistatic agent is selected from nonionic antistatic agents, preferably ethoxylated alkylamine compounds; in the antibacterial flame retardant auxiliary, the dosage ratio of the phosphate compound to the antistatic agent is 100: (0.5 to 10), preferably 100: (1-5).
Antistatic agents generally have the characteristics of surfactants, and structurally have both polar and nonpolar groups. The polar groups (i.e., hydrophilic groups) commonly used are: the anions of carboxylic acids, sulfonic acids, sulfuric acids, phosphoric acids, cations of amine salts, quaternary ammonium salts, and groups such as-OH, -O-, and the like, and the commonly used nonpolar groups (i.e., lipophilic or hydrophobic groups) are: alkyl, alkylaryl, etc., depending on the application, there are two types of surface active antistatic agents, i.e., external and internal, external, or topical antistatic agents, applied to the surface of the polymer by spraying, rubbing, or dipping. Such external antistatic agents, while suitable for use in a variety of polymers, have only temporary efficacy and are easily lost by subsequent contact with solvents or abrasion with other materials. The internal antistatic agent is incorporated into the polymer during its processing. As the flame-retardant antibacterial material prepared by the invention is mostly applied to the fields of electric appliances and building materials, the antistatic agent is preferably a solid long-term antistatic auxiliary agent, for example, an ethoxylated alkylamine compound (Gramineae antistatic agent Atmer 163) is a long-term antistatic agent with excellent performance, is suitable for being added into high-end injection products, and is an internal antistatic auxiliary agent. Atmer163 is a water-like clear, low viscosity liquid with efficacy on polyolefins and styrene.
The alloy material also contains at least one of a melting aid and an antioxidant.
Wherein the melting additive is at least one selected from maleic anhydride series, butadiene rubber powder, styrene-butadiene rubber powder and a compatilizer with a shell-core structure. Wherein, the rubber powder component in the melting additive can lead the alloy material to have the characteristics of flame resistance and high-low temperature toughness; in addition, the compatilizer with the shell-core structure can be made of common methyl methacrylate-butadiene-styrene copolymer shell-core structure materials, such as products of Rogowski products MBS, EXL2602, EXL2330 and the like, and the compatilizer can be added into alloy materials to increase the melting effect of the materials, increase the toughness of the alloy materials and reduce the occurrence of transesterification reaction among components in the preparation process of the alloy materials. In the invention, the compatibilizing agent of the shell-core structure is preferably used in an amount of 0.2 to 0.3 parts by weight based on 100 parts by weight of the matrix material.
PC and PBT are used as two common engineering materials in engineering materials, the materials are simpler in mixing, and in the production process of the materials, transesterification reaction is easy to occur between the materials, so that in the mixing processing engineering, the performance of the materials after blending is considered, and the melting influence of the added components of the materials is considered. The invention adds a certain part of rubber powder and other melt-increasing materials into the alloy material, which has promoting effect on adding liquid compatibility effect at the rear section of the screw and locking antibacterial agent at the later stage. According to the invention, after the rubber powder type melting additive is added into the alloy material, the melting effect of the material is further improved, and as the rubber powder is uniformly distributed in the alloy material, the long-term performance of the material in antibacterial, flame-retardant and antistatic properties can be well ensured.
The antioxidant is at least one selected from phosphite antioxidant and hindered phenol antioxidant, and can be selected from common antioxidant products such as antioxidant 168, antioxidant B225, antioxidant 1010, antioxidant 1076 and antioxidant 900; the amount of the melting aid is 1-15 parts by weight, preferably 5-10 parts by weight, based on 100 parts by weight of the matrix material; the dosage of the antioxidant is 0.1 to 0.5 part, preferably 0.3 to 0.5 part. The antioxidant can be a single antioxidant component product or an antioxidant product with an antioxidant supported on an inorganic carrier.
The second object of the present invention is to provide a method for preparing the above flame-retardant antibacterial polymer alloy material, which comprises mixing the components including the base material and the antibacterial flame-retardant auxiliary agent, and then melt blending the mixture to obtain the alloy material, and specifically comprises the following steps: the antibacterial flame retardant auxiliary is firstly mixed and then is melt-blended with the components comprising the matrix material. Wherein the mixing temperature is 50-90 ℃, preferably 70-80 ℃; the melt blending temperature is 210-260 ℃, preferably 235-255 ℃; the melt blending also comprises at least one of a melting aid and an antioxidant.
In the preparation method, the melt blending is performed by a screw extruder, and the antibacterial flame retardant auxiliary agent is added through a liquid feed inlet of the screw extruder; preferably, the antibacterial flame retardant auxiliary is added by a liquid pump, the liquid pump is used for uniformly adding the antibacterial flame retardant auxiliary into the screw extruder, and the adding speed can be set according to actual requirements. The screw blocks at the liquid feed inlet of the screw extruder are combined in an open type material conveying combination mode. In the preparation of the flame-retardant antibacterial polymer alloy material, the auxiliary agent of the liquid is added into the material, and in the process of adding the liquid, the reflux of the material under the pressure of the machine barrel is prevented, so that in the double-screw combined device, the screw combination at the liquid feeding port is in an open material conveying mode, the pressure of the double-screw machine barrel can be released in advance, and the liquid material can be uniformly and stably dispersed in the alloy material. In the alloy material provided by the invention, the antibacterial flame retardant auxiliary agent is an oil-soluble component, and the viscosity of the liquid flame retardant (such as BDP) and the viscosity of the liquid antibacterial auxiliary agent (such as OIT) in the components have a certain difference, so that before the materials are input into a screw, the two materials are required to be heated to a certain degree and kept at a certain temperature, and the materials are mixed and stirred in a heated container, so that the water content in the solution is reduced, the solution is uniformly mixed, and then the mixture is uniformly added into the screw to be extruded and granulated through a liquid pump. The liquid pump of the invention has the function of directly leading the flame-retardant antibacterial liquid to enter the screw machine barrel through the pipeline, and can not generate bridging phenomenon, thereby improving the processing technology of materials.
The invention also aims to provide the application of the flame-retardant antibacterial polymer alloy material or the flame-retardant antibacterial polymer alloy material obtained by the preparation method in the aspect of flame-retardant antibacterial materials. The polymer alloy material prepared by the invention has high flame retardance and high-low temperature impact property. The material can be widely applied to other fields such as automobile charging piles, new energy automobiles, electronics and electrics, and the like, is particularly suitable for being used in cold environments, and can effectively improve the flame retardant and antibacterial functions of material parts.
The invention takes polymer alloy as a matrix material, and adds antibacterial flame retardant auxiliary agent, optional melting additive, antioxidant and the like to prepare the flame retardant antibacterial polymer alloy material. The alloy material has the greatest characteristics that the material comprehensive performance, especially the low-temperature impact performance, is improved by utilizing a special processing means while the flame retardant and antibacterial performance of the material are improved, and the problem that the flame retardant and antibacterial impact performance cannot be simultaneously improved is effectively solved.
The invention prepares the polymer alloy material with high flame retardance, antibiosis, high-low temperature impact property and excellent comprehensive performance by designing the components of the flame retardant antibacterial polymer alloy material and adding the melt-increasing auxiliary agent, the halogen-free flame retardant and the liquid antibacterial agent which integrate toughening and toughening. In the processing process of PBT, the warp deformation is the biggest defect of the PBT material, the warp deformation of the PBT material is effectively overcome, and the warp deformation of the PBT material is also the focus of research in multiple fields. Compared with the traditional processing method for reducing the warp deformation, the processing technology is simpler and more feasible, the flame retardant, antibacterial performance and impact performance of the material are effectively improved through a simple and efficient toughening means and a flame retardant and antibacterial method, and the problem that the halogen-free flame retardant antibacterial and high impact performance of the polymer alloy are contradictory is solved. The alloy material has potential application value in the fields of charging piles and new energy automobiles.
In the prior art, the processing methods of the composite material are more, the processes of twin-screw extrusion, single-screw extrusion, banburying and the like are all common processing means of the alloy material, the methods can expose the defects of serious processing procedures in the process of processing and preparing special materials, and in the traditional processing processes, the flame retardant auxiliary agent is mostly halogen-free flame retardant, the added part is more, the processing process of the alloy material is seriously influenced, and the physical properties of the material can be obviously reduced.
Compared with the prior art, the invention has the following beneficial effects:
1) The invention provides an antibacterial halogen-free flame-retardant polymer alloy material with high and low temperature toughness, which solves the problem that the antibacterial flame-retardant performance and the physical performance of the material cannot be improved simultaneously in the polymer alloy material through structural design and formula optimization;
2) The flame-retardant antibacterial polymer alloy material provided by the invention is a polymer compound with excellent flame retardance, normal and low temperature toughness and excellent comprehensive performance;
3) The preparation method of the flame-retardant antibacterial polymer alloy material provided by the invention is simple, the process is simple and convenient, the operation is easy, the production efficiency is high, the energy is saved, and the environment is protected;
4) The flame-retardant antibacterial polymer alloy material provided by the invention is suitable for the fields of automobiles, electronics, electrics and the like, and is particularly suitable for being used in a humid low-temperature environment.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The test instruments and test conditions used in the examples are as follows:
heating the mixing vessel: beijing plastic mechanical factory
Extrusion equipment: ZSK40 from Keplon, germany.
The raw materials and sources used in the examples are as follows:
Styrene-butadiene rubber powder: beijing chemical institute of China petrochemical industry;
OIT: beijing New family Australia Utility Co., ltd;
BIT: beijing New family Australia Utility Co., ltd;
BDP: beijing and Rui days as a real company;
PC: brand 2805, bayer, germany;
PBT; petrochemical and chemical fiber company for viscosity medium grade
Antistatic agent: 163. british Heda Co Ltd
And (3) a compatilizer: 2602. DOW chemical Co Ltd
And (3) a compatilizer: 2330. DOW chemical Co Ltd
Composite antioxidant: mixing antioxidant 1010 (Basoff), antioxidant 900 (Basoff) and calcium stearate according to mass ratio of 1/3/1.
Example 1
Preparation of liquid material antibacterial flame-retardant auxiliary agent
The antibacterial OIT liquid, antibacterial BIT, antistatic agent 163 were mixed in a heated vessel for ten minutes at a weight ratio of 90:8:2, set at 70 ℃. The flame retardant auxiliary BDP (BDP: OIT dosage ratio is 12:1), the antibacterial OIT liquid, the antibacterial BIT and the antistatic agent 163 are fully mixed to obtain mixed liquid, namely OB16. In the ten-minute mixing heating process, the moisture in the material is fully released, and the final performance of the PC/PBT alloy material can be effectively improved.
Preparation of flame-retardant antibacterial polymer alloy material
The flame-retardant antibacterial polymer alloy material is prepared by adding 20 parts by weight of PC, 80 parts by weight of PBT, 5%wt of a composite antioxidant into a matrix material, 1 part by weight of styrene-butadiene rubber powder, 26022 parts by weight of a compatilizer and 2303 parts by weight of a compatilizer, 10 parts by weight of a combined antibacterial flame-retardant auxiliary OB16, and extruding and granulating by a weightless feeder according to the production efficiency of 50KG per hour, wherein the processing temperature of a double-screw extruder is 235-255 ℃; uniformly and quantitatively adding the antibacterial flame retardant auxiliary mixed liquid OB16 into a screw machine barrel through a liquid pump according to a preset proportion for melt blending extrusion;
And (3) melting and blending the mixed materials through a double-screw extruder, extruding and granulating at the temperature of 225-255 ℃ and the rotating speed of 300r.p.m, drying the extruded granules in a constant-temperature oven at 90 ℃ for 3hr, and injecting the dried granules into a sample with the thickness of 50mm multiplied by 50mm at the injection temperature of 230-255 ℃ for antibacterial test. Part of the sample pieces were immersed in hot water at 50℃for 16 hours before the antibacterial test.
Example 2
Preparation of liquid material antibacterial flame-retardant auxiliary agent
The antibacterial OIT liquid, antibacterial BBIT, antistatic agent 163 in a 90:6:4 weight ratio were mixed in a container with heating for ten minutes, set at a temperature of 70 ℃. The flame retardant auxiliary BDP (BDP: OIT dosage ratio is 12:1), the antibacterial OIT liquid, the antibacterial BIT and the antistatic agent 163 are fully mixed to obtain mixed liquid called OBT2 for short. During the heating process for ten minutes, the moisture in the material is fully released, and the final performance of the polymer alloy material is effectively improved.
Preparation of flame-retardant antibacterial polymer alloy material
The flame-retardant antibacterial polymer alloy material is prepared by adding 20 parts by weight of PC, 80 parts by weight of PBT, 5%wt of a composite antioxidant into a matrix material, 2 parts by weight of styrene-butadiene rubber powder, 26022 parts by weight of a compatilizer, 23303 parts by weight of a compatilizer, 11 parts by weight of a combined antibacterial flame-retardant auxiliary OBT2, extruding and granulating by a weightless feeder according to the production efficiency of 50KG per hour, wherein the processing temperature of a double-screw extruder is 220-255 ℃; and uniformly and quantitatively adding the antibacterial flame retardant auxiliary agent mixed liquid OBT2 into a screw machine barrel through a liquid pump according to a preset proportion to perform melt blending extrusion.
Example 3
Preparation of flame-retardant antibacterial polymer alloy material
The flame-retardant antibacterial polymer alloy material is prepared by adding 60 parts by weight of PC, 40 parts by weight of PBT, 5%wt of composite antioxidant into a matrix material, 3 parts by weight of styrene-butadiene rubber powder, 26023 parts by weight of compatilizer, 2303 parts by weight of compatilizer, 12 parts by weight of combined antibacterial flame-retardant auxiliary agent, extruding and granulating by a weight loss feeder according to the production efficiency of 50KG per hour, wherein the processing temperature of a double-screw extruder is 220-255 ℃; the antibacterial flame retardant auxiliary mixed liquid OB16 is uniformly and quantitatively added into a screw machine barrel through a liquid pump according to a preset proportion to be melt, blended and extruded.
Example 4
Preparation of flame-retardant antibacterial polymer alloy material
The flame-retardant antibacterial polymer alloy material is prepared by adding 60 parts by weight of PC, 40 parts by weight of PBT, 5%wt of a composite antioxidant into a matrix material, 4 parts by weight of styrene-butadiene rubber powder, 26024 parts by weight of a compatilizer, 23304 parts by weight of a compatilizer, 13 parts by weight of a combined antibacterial flame-retardant auxiliary OBT2, extruding and granulating by a weightless feeder according to the production efficiency of 50KG per hour, wherein the processing temperature of a double-screw extruder is 220-255 ℃; and uniformly and quantitatively adding the antibacterial flame retardant auxiliary agent mixed liquid OBT2 into a screw machine barrel through a liquid pump according to a preset proportion to perform melt blending extrusion.
Example 5
Preparation of flame-retardant antibacterial polymer alloy material
The flame-retardant antibacterial polymer alloy material is prepared by adding 20 parts by weight of PC, 80 parts by weight of PBT, 5%wt of composite antioxidant into a matrix material, 5 parts by weight of styrene-butadiene rubber powder, 26025 parts by weight of compatilizer, 23305 parts by weight of compatilizer, 14 parts by weight of combined antibacterial flame-retardant auxiliary agent, extruding and granulating by a weight loss feeder according to the production efficiency of 50KG per hour, wherein the processing temperature of a double-screw extruder is 220-255 ℃; and uniformly and quantitatively adding the antibacterial flame retardant auxiliary mixed liquid OB16 into a screw machine barrel through a liquid pump according to a preset proportion to perform melt blending extrusion.
Comparative example 1
This comparative example is illustrative of a reference PC/PBT composition and method of making the same. The components are weighed and mixed according to the proportion, wherein the PC is 80 parts by weight, the PBT resin is 20 parts by weight, the halogen-free flame retardant TPP is 10 parts by weight, the polyhexamethylene (bis) guanidine hydrochloride antibacterial agent is 3 per mill, the toughening additive is 2602 with a shell-core structure, and the parts by weight are 5 percent, the antioxidant 1010 (BASF company), the antioxidant 168 (BASF company) and the like are respectively 0.2 and 0.1 part by weight. And then adding the mixture into a high-speed stirrer to be uniformly mixed, adding the mixed material into a feeder of a double-screw extruder manufactured by Keplon company, enabling the material to enter the double screw through the feeder, keeping the temperature of the screw between 250 and 300 ℃ in the processing process, and uniformly mixing the materials through melting the screw, wherein the torque is controlled to be about 65%, and the rotating speed is 300rpm.
And (3) melting and blending the mixed materials through a double-screw extruder, extruding and granulating at the temperature of 225-255 ℃ and the rotating speed of 300r.p.m, drying the extruded granules in a constant-temperature oven at 90 ℃ for 3hr, and injecting the dried granules into a sample with the thickness of 50mm multiplied by 50mm at the injection temperature of 230-255 ℃ for antibacterial test. Part of the sample pieces were immersed in hot water at 50℃for 16 hours before the antibacterial test.
Comparative example 2
This comparative example is illustrative of a reference PC/PBT composition and method of making the same. The components are weighed and mixed according to the proportion, wherein 80 parts by weight of PC, 20 parts by weight of PBT resin, 12 parts by weight of halogen-free flame retardant TPP, 2 per mill of polyhexamethylene (bis) guanidine propionate antibacterial agent, 2602 parts by weight of toughening aid with a shell-core structure, and 0.2 and 0.1 part by weight of antioxidant 1010 (BASF company), antioxidant 168 (BASF company) and the like are added. And then adding the mixture into a high-speed stirrer to be uniformly mixed, adding the mixed material into a feeder of a double-screw extruder manufactured by Keplon company, enabling the material to enter the double screw through the feeder, keeping the temperature of the screw between 250 and 300 ℃ in the processing process, and uniformly mixing the materials through melting the screw, wherein the torque is controlled to be about 65%, and the rotating speed is 300rpm.
And (3) melting and blending the mixed materials through a double-screw extruder, extruding and granulating at the temperature of 225-255 ℃ and the rotating speed of 300r.p.m, drying the extruded granules in a constant-temperature oven at 90 ℃ for 3hr, and injecting the dried granules into a sample with the thickness of 50mm multiplied by 50mm at the injection temperature of 230-255 ℃ for antibacterial test. Part of the sample pieces were immersed in hot water at 50℃for 16 hours before the antibacterial test.
Comparative example 3
This comparative example is illustrative of a reference PC/PBT composition and method of making the same. The components are weighed and mixed according to the proportion, wherein the PC is 80 parts by weight, the PBT resin is 20 parts by weight, the halogen-free flame retardant HTCTP parts by weight, the polyhexamethylene (bis) guanidine propionate antibacterial agent is 1 per mill, the toughening additive is 2602 with a shell-core structure, and the components are added with 5% of antioxidant 1010 (BASF company), antioxidant 168 (BASF company) and the like in 0.2 and 0.1 parts by weight respectively. And then adding the mixture into a high-speed stirrer to be uniformly mixed, adding the mixed material into a feeder of a double-screw extruder manufactured by Keplon company, enabling the material to enter the double screw through the feeder, keeping the temperature of the screw between 250 and 300 ℃ in the processing process, and uniformly mixing the materials through melting the screw, wherein the torque is controlled to be about 65%, and the rotating speed is 300rpm.
Comparative example 4
Preparation of flame-retardant antibacterial polymer alloy material
The flame-retardant antibacterial polymer alloy material is prepared by adding 80 parts by weight of PBT, 5 per mill by weight of composite antioxidant into a matrix material, 6 parts by weight of styrene-butadiene rubber powder, 2602 parts by weight of compatilizer, 23306 parts by weight of compatilizer, 15 parts by weight of an antibacterial flame-retardant auxiliary agent, namely, an isothiazolinone compound BIT, into the matrix material, extruding and granulating the mixture by a weight loss feeder according to the production efficiency of 50KG per hour, wherein the added liquid amount is 2% of the capacity of a heating container according to the preset proportion and the granules of PC/PBT. In the experiment, if the addition amount of the liquid exceeds 2%, the flame-retardant antibacterial liquid enters the screw machine barrel, and the bridging phenomenon does not occur, so that the blanking and mixing of the materials are obviously bonded, and the performance of the materials is affected.
Example 6
Antibacterial detection standard and operation steps:
1. Antibacterial test criteria: GB/T31402-2015 plastic surface antibacterial property test method for detecting bacteria: coli (ESCHERICHIA COLI) ATCC 25922, staphylococcus aureus (Staphylococcus aureus) ATCC 6538.
2. An antibacterial test step, namely, testing by referring to an antibacterial plastic detection standard GB/T31402-2015, wherein the specific steps are as follows: and (3) sterilizing the sample to be tested by using 75% ethanol, airing, and diluting the strain into a bacterial suspension with proper concentration by using sterile water for standby. 0.2mL of the bacterial suspension was dropped onto the surface of the sample, and a polyethylene film (4.0 cm. Times.4.0 cm) of 0.1mm thickness was applied thereto to form a uniform liquid film between the sample and the film. The culture was maintained at 37℃for 24 hours with a relative humidity of 90%. The bacterial liquid was washed with sterile water, diluted to an appropriate concentration gradient, 0.1mL of the bacterial liquid was uniformly spread on the prepared sterile agar medium, and cultured at 37℃for 24 hours, and the results were observed. The negative control was replaced with a sterile dish and the other operations were the same.
3. The degree of crosslinking of the guanidine salt antibacterial microspheres is expressed in terms of gel content, as measured by a solvent extraction method. The specific method comprises the following steps: and weighing the sample to be measured W 1, placing the sample to be measured in acetone with 5 times of the weight of the sample to be measured, extracting the sample at 50 ℃ for 30min, and measuring and weighing the sample to be measured W 2 after the extraction is finished, wherein the crosslinking degree is W 2/W1 multiplied by 100%. The content of the soluble matters is (1-W 2/W1) multiplied by 100 percent.
Table 1 results of antibacterial experiments of example 1 and comparative examples 1 to 2
From the above comparison results, it is shown that the guanidine salt composite antibacterial agent still has a better antibacterial effect after the use amount is reduced, and the water resistance after water boiling is reduced, but the antibacterial effect of the antibacterial plastics before and after water boiling (comparative example 1 and comparative example 2) is lower than that of the antibacterial liquid mixing aids (example 1) prepared by the liquid antibacterial aids OIT and BBIT.
Table 2 comparison of the properties of flame retardant PC/PBT products prepared in examples 1 to 6 and comparative examples 1 to 3
As can be seen from Table 2, the conventional toughening methods of comparative examples 1 to 3 have lower toughening efficiency relative to the alloy materials of examples 1 to 6 of the present invention, and in addition, the flame retardant properties of the PC/PBT composition are lowered due to the flammability of the material phase itself of comparative example 2, and the UL-94 test is V-2 grade. However, the addition of the halogen-free flame retardant (comparative example 1) alone greatly affects the toughness of the alloy, and compared with the PC/ABS alloy (comparative example 3), the impact properties at normal temperature and low temperature are respectively reduced by 75.8% and 47.4%. Therefore, the addition of the liquid antibacterial auxiliary agent and the flame retardant not only can greatly influence the interaction among the components of the material, but also can greatly reduce the impact performance of the PC/PBT alloy. In addition, in comparative examples 1 to 2, the flame retardant was difficult to disperse due to poor interaction between the flame retardant and the matrix resin, thereby decreasing the flame retardant efficiency of the flame retardant.
As can be seen from examples 1 to 5, the halogen-free flame retardant PC/PBT prepared by the method has good comprehensive performance, and the PC/PBT alloy with flame retardant performance and high impact performance is prepared by the formula design and the addition of the halogen-free flame retardant and the single-component compatibilizer and toughening agent. The PC/PBT alloy material can reach V-0 grade in UL94 vertical burning test, the self-extinguishing time is less than 10s, the better rigidity of the PC/PBT alloy is maintained, the impact property, especially the low-temperature impact property, can reach 58kJ m -2, which is obviously higher than that of the PC/PBT alloy (19 kJ m -2) modified by flame retardance of the comparative example. In the comparative example 3, HTCTP flame retardant auxiliary agent with better flame retardant market is selected, the material performance and flame retardant effect are better through test performance, and in the use process and the preparation process of the material, the thermal deformation temperature of the flame retardant auxiliary agent is lower, so that great difficulty is brought to the use of the flame retardant auxiliary agent, and the waste generated in the experiment is difficult for the user to continue the experiment.
In the preparation of the flame-retardant antibacterial alloy material, the effects of the flame-retardant auxiliary agent and the antibacterial auxiliary agent and the specific preparation process are adopted, so that the flame-retardant antibacterial alloy material has decisive effects on the performance of the material and the application result of the material. In comparative example 4, a common double-screw processing technology is adopted, a liquid pump is not adopted to add a mixture of antibacterial flame retardant additives, and after different flame retardants and antibacterial agents are adopted to be mixed, bridging phenomenon often occurs to material blanking due to different additives in a material feeding section part, raw materials are prevented from entering an extruder, obvious bonding phenomenon occurs to the materials in the processing process, and the processing and using performances of the materials are affected. In comparative example 4, the flame-retardant and antibacterial material is prepared by a traditional mixing process without adding a liquid pump, and the liquid directly flows out of a feeder in an experiment because of larger liquid addition in the sample preparation, so that the prepared material is inaccurate in adding a liquid auxiliary agent, and the processing process is affected, so that the flame retardance, the antibacterial property and the physical property of the material are obviously reduced. And the materials obtained by the preparation process provided by the invention in examples 1-5 are uniformly mixed, and have better mechanical properties.
Claims (20)
1. A flame retardant antimicrobial polymer alloy material comprising a blended matrix material and an antimicrobial flame retardant aid, wherein the matrix material comprises at least two of polycarbonate, polyester, acrylonitrile-butadiene-styrene polymer, polyamide; the antibacterial flame retardant auxiliary comprises an isothiazolinone antibacterial agent and a phosphate flame retardant; the isothiazolinone compound is at least one selected from n-octyl isothiazolinone, n-butyl-1, 2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one; the phosphate compound is at least one of resorcinol-bis (diphenyl phosphate), bisphenol A-bis (diphenyl phosphate) and resorcinol-bis [ di (2, 6-dimethyl benzene) phosphate ] \hexaphenoxy cyclotriphosphazene); in the antibacterial flame retardant auxiliary agent, the dosage ratio of the phosphate flame retardant to the isothiazolinone antibacterial agent is 100 (1-5);
The alloy material is obtained by mixing the components including the matrix material and the antibacterial flame retardant auxiliary agent and then carrying out melt blending, wherein the melt blending is carried out by a screw extruder, and the antibacterial flame retardant auxiliary agent is added through a liquid feed inlet of the screw extruder.
2. The alloy material according to claim 1, wherein,
When the matrix material is the two polymers, the weight ratio of the two polymers is 10: 90-90: 10; and/or the number of the groups of groups,
The usage amount of the antibacterial flame retardant auxiliary is 1-30 parts by weight based on 100 parts by weight of the matrix material.
3. The alloy material according to claim 2, wherein,
The usage amount of the antibacterial flame retardant auxiliary is 5-20 parts by weight based on 100 parts by weight of the matrix material.
4. The alloy material according to claim 1, wherein,
The polyester is at least one selected from polybutylene terephthalate and polyethylene terephthalate; and/or the number of the groups of groups,
The melt index of the polycarbonate is 1-30 g/10min; and/or the number of the groups of groups,
The polyamide is nylon 6; and/or the number of the groups of groups,
The isothiazolinone compound is at least one selected from n-octyl isothiazolinone, n-butyl-1, 2-benzisothiazolin-3-one and 1, 2-benzisothiazolin-3-one; and/or the number of the groups of groups,
The phosphate compound is at least one selected from bisphenol A-bis (diphenyl phosphate) and hexaphenoxy cyclotriphosphazene.
5. The alloy material according to claim 4, wherein,
The melt index of the polycarbonate is 6-15 g/10min.
6. The alloy material according to claim 4, wherein,
The matrix material is selected from at least one of polycarbonate and polybutylene terephthalate, polycarbonate and polyethylene terephthalate, polycarbonate and acrylonitrile-butadiene-styrene polymer or acrylonitrile-butadiene-styrene polymer and nylon 6.
7. The alloy material according to claim 6, wherein,
The matrix material is selected from the group consisting of polycarbonate and polybutylene terephthalate.
8. The alloy material according to claim 7, wherein,
In the matrix material, the weight ratio of the polycarbonate to the polybutylene terephthalate is 60:40-80:20.
9. The alloy material according to claim 1, wherein,
The antibacterial flame retardant auxiliary agent also contains an antistatic agent; and/or the number of the groups of groups,
The alloy material also contains at least one of a melting aid and an antioxidant.
10. The alloy material according to claim 9, wherein,
The antistatic agent is selected from nonionic antistatic agents; and/or the number of the groups of groups,
The melting additive is at least one selected from maleic anhydride series, butadiene rubber powder, styrene-butadiene rubber powder and a shell-core structure compatilizer; and/or the number of the groups of groups,
The antioxidant is at least one selected from phosphite antioxidants and hindered phenol antioxidants.
11. The alloy material according to claim 10, wherein,
The antistatic agent is selected from ethoxylated alkylamine compounds.
12. The alloy material according to claim 8, wherein,
In the antibacterial flame retardant auxiliary, the dosage ratio of the phosphate compound to the antistatic agent is 100: (0.5-10); and/or the number of the groups of groups,
The amount of the melting aid is 1-15 parts by weight based on 100 parts by weight of the matrix material; and/or the number of the groups of groups,
The amount of the antioxidant is 0.1 to 0.5 part by weight based on 100 parts by weight of the matrix material.
13. The alloy material according to claim 12, wherein,
In the antibacterial flame retardant auxiliary, the dosage ratio of the phosphate compound to the antistatic agent is 100: (1-5); and/or the number of the groups of groups,
The melting additive is used in an amount of 5-10 parts by weight based on 100 parts by weight of the matrix material; and/or the number of the groups of groups,
The amount of the antioxidant is 0.3 to 0.5 part by weight based on 100 parts by weight of the matrix material.
14. A method of preparing a flame retardant antimicrobial polymeric alloy material according to any one of claims 1 to 13, comprising mixing the antimicrobial flame retardant aid first and then melt blending it with components comprising the matrix material to obtain the alloy material.
15. The method of claim 14, wherein the process comprises,
The mixing temperature is 50-90 ℃; and/or the number of the groups of groups,
The melt blending temperature is 210-260 ℃.
16. The method according to claim 15, wherein,
The mixing temperature is 70-80 ℃; and/or the number of the groups of groups,
The melt blending temperature is 235-255 ℃.
17. The method of claim 14, wherein the process comprises,
The melt blending is performed by a screw extruder;
the antibacterial flame retardant auxiliary is added through a liquid feed inlet of the screw extruder.
18. The method of claim 17, wherein the process comprises,
The antibacterial flame retardant auxiliary is added through a liquid pump.
19. The method of claim 17, wherein the process comprises,
The screw blocks at the liquid feed inlet of the screw extruder are combined in an open type material conveying combination mode.
20. Use of a flame retardant and antibacterial polymer alloy material according to any one of claims 1 to 13 or obtained according to the method of preparation of any one of claims 14 to 19 in flame retardant and antibacterial materials.
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