CN111057359B - CNT (carbon nanotube) composite branched acrylate with core-shell structure and weather-resistant antistatic low-temperature-resistant polycarbonate material - Google Patents

CNT (carbon nanotube) composite branched acrylate with core-shell structure and weather-resistant antistatic low-temperature-resistant polycarbonate material Download PDF

Info

Publication number
CN111057359B
CN111057359B CN201911277577.6A CN201911277577A CN111057359B CN 111057359 B CN111057359 B CN 111057359B CN 201911277577 A CN201911277577 A CN 201911277577A CN 111057359 B CN111057359 B CN 111057359B
Authority
CN
China
Prior art keywords
core
cnt
acrylate
shell structure
shell
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201911277577.6A
Other languages
Chinese (zh)
Other versions
CN111057359A (en
Inventor
吴剑波
麻一明
徐禄波
王旭
孙剑
范方虹
蒋祥鸳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningbo Jianfeng New Material Co ltd
Original Assignee
Ningbo Dopda Polymer Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningbo Dopda Polymer Co ltd filed Critical Ningbo Dopda Polymer Co ltd
Priority to CN201911277577.6A priority Critical patent/CN111057359B/en
Publication of CN111057359A publication Critical patent/CN111057359A/en
Application granted granted Critical
Publication of CN111057359B publication Critical patent/CN111057359B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • C08K2201/001—Conductive additives
    • 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
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/002—Physical properties
    • C08K2201/004—Additives being defined by their length
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • 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
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/53—Core-shell polymer

Abstract

The invention relates to a CNT composite branched core-shell structure acrylate and a weather-resistant antistatic low-temperature-resistant polycarbonate material, belonging to the technical field of high polymer materials. The CNT composite branched core-shell structure acrylate comprises an acrylate core, a polymethyl methacrylate shell covering the acrylate core, a branched monomer grafted on the polymethyl methacrylate shell, and a carbon nano tube connected with the branched monomer.

Description

CNT (carbon nanotube) composite branched acrylate with core-shell structure and weather-resistant antistatic low-temperature-resistant polycarbonate material
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to a CNT composite branched core-shell structure acrylate and a weather-resistant antistatic low-temperature-resistant polycarbonate material.
Background
The Polycarbonate (PC) isA non-crystalline resin which is a transparent glass in a melt and a solidified state and has excellent optical properties and surface gloss. The molecular structure of the polycarbonate is composed of a main chain benzene ring structure and an ester group structure, the polycarbonate is a material with rigidity and toughness, the flexural modulus can reach more than 2400MPa, and the IZOD notch impact at normal temperature is 60-90 KJ/cm2(ii) a The thermal property and the flame retardant property of the polycarbonate are excellent, the thermal deformation temperature of pure polycarbonate plastic is about 130 ℃, the ball pressure is 125 ℃, and the GWFI of a glow wire can reach 850 ℃; the composite performance of the composite material can be called as warping in engineering plastics, and the composite material is widely applied to the fields of optics, plates, automobile parts, bulletproof glass, electronics and electricity, smart phones, household articles, appliances, power tools, medical care equipment, office facilities, plastic containers, leisure and safety protection articles, films, modification and the like.
According to statistics, the global polycarbonate consumption in 2018 reaches over 400 million tons, and the increase of 3-5% per year is expected to be kept; in 2018, the consumption of Chinese polycarbonate reaches over 180 million tons, and the increase of 7-10% per year is expected to be kept. The enormous consumption, resulting in the enormous volume of polycarbonate PCR, has caused serious troubles to our lives and environment. At present, the modification and application of polycarbonate PCR recycling granulation and regenerated polycarbonate granules have been researched and applied in China. However, the research of modifying the direct crushing material of the polycarbonate PCR into the weather-resistant antistatic low-temperature-resistant material lacks corresponding technology and method.
The non-crystallinity of polycarbonate causes poor notched impact strength in low temperature environments, seriously affecting and limiting its use in low temperature environments or cold regions. The prior low-temperature resistant polycarbonate material comprises a conventional toughened polycarbonate material and a polycarbonate-organic silicon block copolymer, and can meet the application scene of a low-temperature environment. However, the conventional toughened polycarbonate material in the existing market is generally toughened by high rubber powder, and modification of weather resistance is less considered, so that the conventional toughened polycarbonate material is often insufficient in aging resistance, and a new material or a regenerated material particle is generally used as a raw material in a formula, so that the economic cost is high, and the application range of the conventional toughened polycarbonate material is limited to a certain extent; the polycarbonate-organic silicon block copolymer is a polymerization modifier, needs to be synthesized by petroleum-based chemical monomers, is a material which cannot be obtained by renewable resources, has the defects of environmental protection and higher cost.
The surface resistivity of polycarbonate is high, 1015Above Ohm/sq, the polycarbonate product is easy to generate static electricity during production, packaging, transportation and use, the production process is affected, dust is easy to absorb during use, and even fire or explosion can be caused.
The patent application document (CN109401265) discloses a weather-resistant and low-temperature-resistant polycarbonate packaging material and a preparation method thereof, wherein polycarbonate is used as a raw material, and 3-12 parts of a toughening agent, 0.1-1.2 parts of a weather-resistant agent, 1-2 parts of a flame retardant, 0.1-0.3 part of an antioxidant and 0.1-0.3 part of a lubricant are used as auxiliary materials, so that the polycarbonate material with the notch impact strength of-40 ℃ of 30-40J/m and the weather resistance test delta E of 7-11.6 is obtained in the embodiment, but the antistatic function research of the material is not involved; the patent application document (CN108912645A) discloses a low-temperature-resistant conductive polycarbonate blending material and a preparation method thereof, and particularly discloses a conductive master batch of CNT compounded SiPC, and then the conductive master batch is blended with polycarbonate to prepare a low-temperature-resistant conductive material, wherein the low-temperature-resistant performance of the material is provided by a SiPC base material, the weight ratio of the SiPC master batch to the polycarbonate is preferably (1-50): 99-50), and further preferably (40-50): 60-50), which shows that the low-temperature impact performance of the material is inevitably reduced along with the reduction of the content of the SiPC in the composite material.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides a CNT composite branched core-shell structure acrylate for polycarbonate, which can effectively toughen polycarbonate, improve the low temperature resistance of the polycarbonate and effectively improve the antistatic performance of the polycarbonate.
The purpose of the invention can be realized by the following technical scheme:
the CNT composite branched core-shell structure acrylate comprises a core-shell structure acrylate consisting of an acrylate core and a polymethyl methacrylate shell covering the acrylate core, a branched monomer grafted on the polymethyl methacrylate shell, and a Carbon Nano Tube (CNT) connected with the branched monomer.
Preferably, the branched monomer is at least one of acrylate, methacrylic acid, glycidyl methacrylate, maleic acid and acrylamide.
Preferably, the particle size of the core-shell structure acrylate is 250-350nm, the tube diameter of the CNT is 1-5 nm, and the length of the CNT is 0.1-3 μm.
According to the invention, by matching the particle size of the acrylate with the core-shell structure and the pipe diameter and length of the CNT, the CNT has a smaller steric effect when being grafted to a branched monomer, and can be quickly and efficiently subjected to grafting reaction; if the diameter and length of the CNT are too large, grafting can be affected.
The CNT is preferably an aminated multi-walled carbon nanotube of Ishikaki technologies, Inc., Beijing Dekko.
Preferably, the CNT composite branched core-shell structure acrylate is used as a toughening conductive agent of polycarbonate.
The common acrylate with the core-shell structure is an acrylate copolymer taking acrylate as a core and polymethyl methacrylate as a shell, and can be used as a toughening agent of polycarbonate; the Carbon Nano Tube (CNT) is used as a one-dimensional nano material, has light weight, perfect connection of a hexagonal structure, excellent mechanical, electrical and chemical properties, and particularly excellent conductive performance, and can effectively improve the antistatic performance of polycarbonate when being applied to the polycarbonate. However, the existing common core-shell structure acrylate has poor binding force with polycarbonate, and CNT serving as hard particles is not easy to enter a polycarbonate system, so that the further improvement of the performance of modified polycarbonate is limited.
The CNT composite branched core-shell structure acrylate is subjected to branching and CNT composite functionalization treatment on the basis of common core-shell structure acrylate. The invention grafts the branching monomer with carboxyl (-COOH) on the surface of the common acrylate core-shell structure body, and the carboxyl (-COOH) on the branching monomer and the hydroxyl (-OH) at the tail end of the polycarbonate molecule can carry out polycondensation reaction in the preparation process, thereby forming strongerThe bonding force greatly improves the interface effect of the branched core-shell structure acrylate and the polycarbonate matrix; meanwhile, the surface of the CNT contains amino (-NH)2) The modified polycarbonate can react with carboxyl of a branched monomer to complete a grafting reaction, CNT is grafted on branched core-shell structure acrylic acid, and the CNT can better enter a polycarbonate system by taking the branched core-shell structure acrylic acid as a carrier, so that the modified polycarbonate achieves better physical and conductivity properties.
Another objective of the present invention is to provide a preparation method of CNT composite branched core-shell structure acrylate, which comprises the following steps:
s1, adding butyl acrylate, allyl methacrylate, an anionic emulsifier, an initiator and a crosslinking agent into deionized water for heating reaction to prepare a core-layer emulsion;
s2, preparing a shell emulsion from a branched monomer, CNT, methyl methacrylate and an anionic emulsifier;
s3, mixing the core-layer emulsion and the shell emulsion, adding an initiator and deionized water for heating reaction, and filtering, washing and drying a reaction product to obtain the CNT composite branched core-shell structure acrylate.
Preferably, in the step S1, the weight ratio of the butyl acrylate, the allyl methacrylate, the anionic emulsifier, the initiator, the cross-linking agent and the deionized water is (50-500): 0.01-0.1): 0.5-5): 0.1-2): 10-100.
Preferably, the anionic emulsifier in steps S1 and S2 includes one or more of sodium stearate, sodium lauryl sulfate or calcium dodecylbenzenesulfonate.
Preferably, the initiator in steps S1 and S3 includes potassium persulfate, sodium bisulfite, or ammonium persulfate.
Preferably, the crosslinking agent is 1, 4-butanediol diacrylate.
Preferably, the heating reaction in step S1 is carried out at 50-100 deg.C while mechanically stirring at 50-500 rpm
Preferably, the heating method of the heating reaction in step S1 is water bath heating.
Preferably, the weight ratio of the branched monomer, CNT, methyl methacrylate and anionic emulsifier in step S2 is (0.01-0.2): (5-60): (30-100): (1-5).
Preferably, the weight ratio of the core-layer emulsion, the shell-layer emulsion, the initiator and the deionized water in the step S3 is (5-60): (3-15): (0.05-0.2): (1-3).
Preferably, the temperature of the heating reaction in step S3 is 70 to 100 ℃.
According to the invention, the branched monomer and the CNT are introduced into the shell emulsion, so that the branched monomer with carboxyl (-COOH) is grafted on the surface of the acrylate core-shell structure, and meanwhile, the amino (-NH2) on the surface of the CNT can react with the carboxyl of the branched monomer to complete the grafting reaction, so that the CNT is grafted on the branched monomer. Carboxyl (-COOH) on the branched monomer and hydroxyl (-OH) at the tail end of a polycarbonate molecule have better affinity in the preparation process, so that stronger binding force is formed, and the interface effect of the branched core-shell structure acrylate and the polycarbonate matrix is greatly improved; the CNT takes branched acrylic acid with a core-shell structure as a carrier and can better enter a polycarbonate system, so that the modified polycarbonate achieves good physical and conductive properties.
The third purpose of the invention is to provide a weather-resistant antistatic low-temperature-resistant polycarbonate material, which comprises the following components:
Figure BDA0002313057800000051
preferably, the PC substrate is a recycled PC chip, or a mixture of a recycled PC chip and at least one of recycled PC pellets and virgin PC pellets.
Preferably, the regenerated PC fragments are crushed fragments of waste PC parts, the regenerated PC granules are particle type materials obtained by granulating the waste PC parts serving as raw materials, and the waste PC parts comprise water bottles, plate leftover materials, sheets, records and other PC parts which are made of PC materials; the brand new PC granules are particle materials prepared by a phosgene method, a semi-phosgene method or a non-phosgene method.
Preferably, the fluidity of the regenerated PC chips, the regenerated PC granules and the brand-new PC granules is 3-80 g/10 min.
Preferably, the chain extender is a polymer containing an epoxy functional group, and each molecule of the chain extender contains 1-20 active groups of epoxy groups.
The chain extender can perform a linking reaction with carboxyl and hydroxyl on polycarbonate molecules, so that the weight average molecular weight of the polycarbonate material is improved, the flowability of the material is reduced, and the properties of the material, such as impact strength, tensile strength, modulus and the like, are improved.
Preferably, the ultraviolet absorber is at least one of benzophenones, benzotriazoles, salicylates, and triazines.
Preferably, the primary antioxidant is a hindered phenol compound or a secondary aromatic amine compound, and includes at least one of 4, 4 '-thiobis- (6-tert-butyl-3-methylphenol) (antioxidant 300), alkylated monophenol, alkylated bisphenol, alkylated polyphenol, thiobisphenol, phenyl-beta-naphthylamine, diphenylamine, and N, N' -diphenyl-p-phenylenediamine.
Preferably, the secondary antioxidant is at least one of dilauryl thiodipropionate (DLTP), phosphite, disulfide, thioether, thiol, and bisphenyloxalyl diamine.
Preferably, the compatibilizer is at least one of PS-g-MAH, SEBS-g-MAH and PE-g-MAH.
Preferably, the processing aid is at least one of toner, white oil, silicone oil, elastomers, silanes, and phthalates.
The fourth purpose of the invention is to provide a preparation method of the weather-resistant antistatic low-temperature-resistant polycarbonate material, which comprises the following steps:
(1) sorting, crushing, cleaning/drying, color selecting and detecting waste PC parts to obtain regenerated PC fragments as a PC base material, or mixing at least one of the regenerated PC fragments, regenerated PC granules and brand-new PC granules as the PC base material, wherein the regenerated PC granules are particle type materials prepared by extruding and granulating the regenerated PC fragments, and the brand-new PC granules are particle type materials prepared by preparing the particle type materials by a phosgene method, a semi-phosgene method or a non-phosgene method;
(2) uniformly mixing a PC substrate, CNT composite branched core-shell structure acrylate, a chain extender, an ultraviolet absorber, an antioxidant, an auxiliary antioxidant, a compatilizer and a processing aid to form a mixture;
(3) and melting, mixing, extruding and granulating the mixture by using a double-screw extruder.
Preferably, in the step (1), the sorting is completed by manual operation and infrared spectrum sorting; the crushing is carried out in a crusher, and the block diameter of the crushed pieces is controlled to be less than or equal to 10 mm; the cleaning/drying is carried out in a powerful cleaning machine, the impurity content of the cleaned broken pieces is less than or equal to 200ppm, and the drying temperature is 90-120 ℃; the color sorting is carried out by adopting a photoelectric color sorter, and the impurity content of the crushed pieces after the color sorting is less than or equal to 100 ppm; the detection is to adopt lamp box visual, spectrometer, MI tester and tensile tester to detect and evaluate the material physical properties.
Preferably, the mixing process in the step (2) is carried out in a high-speed stirrer, and the mixing time is 5-10 min.
Preferably, in the step (3), the length-diameter ratio of the twin-screw extruder is 40:1, the extrusion temperature is 170-290 ℃, and the screw rotation speed is 300-500 rpm.
The weather-resistant antistatic low-temperature-resistant polycarbonate material takes the regenerated PC fragments as a basic raw material, or is matched with regenerated PC granules and brand new PC granules to form a compound modified PC base material, on one hand, the polycarbonate material is a process for recycling PC plastic wastes, and on the other hand, the recycling process of common waste PC products is as follows: the method comprises the steps of waste PC products, sorting, crushing, cleaning/drying, regenerating PC fragments, feeding by an extruder, cooling, granulating, homogenizing, regenerating PC granules and modifying, wherein the regenerated PC fragments are directly adopted for modification, namely the recycling process of the waste PC products is shortened as follows: the method comprises the steps of sorting, crushing, cleaning, drying, breaking PC and modifying the waste PC products, wherein the process of recycling PC broken pieces is shortened by half compared with the process of recycling PC granules, and the PC is a polymer which is particularly sensitive to hot water and oxygen and is easy to break chains in a molten state, so that the performance of the PC is lost to a certain extent, generally 10-20% after being granulated by a screw.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, branching and CNT compounding functionalization treatment is carried out on the basis of core-shell structure acrylate, so that the CNT compound branched core-shell structure acrylate has a better interface effect than common core-shell structure acrylate and polycarbonate, the toughness and low temperature resistance of modified polycarbonate are effectively improved, and the modified polycarbonate has a conductive function, and CNT can better enter a polycarbonate system by taking branched core-shell structure acrylic acid as a carrier, so that the physical and chemical properties and the conductive performance of the modified polycarbonate can be better improved;
(2) the invention uses polycarbonate PCR (post-consumer recycled product) as a raw material, adopts a modification technology, and enables the polycarbonate material to have the performances of ultraviolet aging resistance, static resistance and low-temperature impact strength, so that the regenerated polycarbonate can be used in cell phone shells, cell phone sheaths, intelligent door lock shells, interphones and other products used in a low-temperature environment; the invention directly takes the regenerated PC fragments as the raw material of the polycarbonate material for modification, shortens the recycling process of the waste polycarbonate and realizes the high-performance utilization of the polycarbonate PCR.
Drawings
FIG. 1 is a weather resistance test characterization of specific examples and comparative examples of the present application.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
Example 1
The preparation method of the CNT composite branched core-shell structure acrylate of the embodiment comprises the following steps:
s1, adding butyl acrylate, allyl methacrylate, an anionic emulsifier sodium stearate, an initiator potassium persulfate and a cross-linking agent 1, 4-butanediol diacrylate into deionized water, heating the butyl acrylate, the allyl methacrylate, the sodium stearate, the potassium persulfate, the 1, 4-butanediol diacrylate and the deionized water in a weight ratio of 150:0.06:2:0.7:0.7:45 in a water bath to 70 ℃ for reaction, and mechanically stirring at a speed of 200rpm during the reaction to prepare a core layer emulsion;
s2, stirring and mixing a branched monomer methacrylic acid (the branched monomer is at least one of acrylate, methacrylic acid, glycidyl methacrylate, maleic acid and acrylamide), CNT, methyl methacrylate and sodium stearate to fully disperse the CNT in a solution to prepare a shell emulsion, wherein the weight ratio of the branched monomer, the CNT, the methyl methacrylate and the sodium stearate is 0.05:20:60:1.3, the CNT is an aminated multi-walled carbon nanotube of Beijing Deke island gold science and technology Limited, the tube diameter range is 1-5 nm, and the length range is 0.1-3 mu m;
s3, mixing the core-layer emulsion and the shell emulsion, adding potassium persulfate and deionized water, heating to 85 ℃ for reaction, wherein the weight ratio of the core-layer emulsion to the shell-layer emulsion to the initiator to the deionized water is 20:5:0.09:2, and filtering, washing and drying the obtained reaction product to obtain the CNT composite branched core-shell structure acrylate.
The CNT composite branched core-shell structure acrylate prepared in the embodiment comprises an acrylate core, a polymethyl methacrylate shell coated with the acrylate core, a branched monomer grafted on the polymethyl methacrylate shell, and a CNT connected with the branched monomer, wherein the diameter of the polymethyl methacrylate shell is 300 nm.
Example 2
The preparation method of the CNT composite branched core-shell structure acrylate of the embodiment comprises the following steps:
s1, adding butyl acrylate, allyl methacrylate, anionic emulsifier lauryl sodium sulfate, initiator potassium persulfate and cross-linking agent 1, 4-butanediol diacrylate into deionized water, heating the butyl acrylate, the allyl methacrylate, the lauryl sodium sulfate, the potassium persulfate, the 1, 4-butanediol diacrylate and the deionized water in a weight ratio of 200:0.05:3:0.5:0.5:50 in a water bath to 65 ℃ for reaction, and mechanically stirring the mixture at the same time of the reaction at a stirring speed of 100rpm to prepare a core layer emulsion;
s2, stirring and mixing a branched monomer of glycidyl methacrylate, CNT, methyl methacrylate and sodium dodecyl sulfate to fully disperse the CNT in a solution to prepare a shell emulsion, wherein the weight ratio of the branched monomer to the CNT to the methyl methacrylate to the sodium dodecyl sulfate is 0.07:30:50:1.5, the CNT is an aminated multi-walled carbon nanotube of Beijing Deke island gold science and technology Limited, the tube diameter range is 1-5 nm, and the length range is 0.1-3 mu m;
s3, mixing the core-layer emulsion and the shell emulsion, adding potassium persulfate and deionized water, heating to 70 ℃ for reaction, wherein the weight ratio of the core-layer emulsion to the shell-layer emulsion to the initiator to the deionized water is 30:5:0.1:2, and filtering, washing and drying the obtained reaction product to obtain the CNT composite branched core-shell structure acrylate.
The CNT composite branched core-shell structure acrylate prepared in the embodiment comprises an acrylate core, a polymethyl methacrylate shell coated with the acrylate core, a branched monomer grafted on the polymethyl methacrylate shell, and CNT connected with the branched monomer, wherein the diameter of the polymethyl methacrylate shell is 280 nm.
Example 3
The preparation method of the CNT composite branched core-shell structure acrylate of the embodiment comprises the following steps:
s1, adding butyl acrylate, allyl methacrylate, an anionic emulsifier calcium dodecyl benzene sulfonate, an initiator potassium persulfate and a cross-linking agent 1, 4-butanediol diacrylate into deionized water, heating the butyl acrylate, the allyl methacrylate, the calcium dodecyl benzene sulfonate, the potassium persulfate, the 1, 4-butanediol diacrylate and the deionized water in a weight ratio of 300:0.07:2.5:0.6:0.6:50 in a water bath to 80 ℃ for reaction, and mechanically stirring at a stirring speed of 250rpm while reacting to prepare a core layer emulsion;
s2, stirring and mixing a branched monomer, namely maleic acid, CNT, methyl methacrylate and calcium dodecyl benzene sulfonate, so that the CNT is fully dispersed in a solution to prepare a shell emulsion, wherein the weight ratio of the branched monomer, the CNT, the methyl methacrylate and the calcium dodecyl benzene sulfonate is 0.06:20:70:2.0, the CNT is an aminated multi-walled carbon nanotube of Beijing Deke island science and technology Limited, the tube diameter range is 1-5 nm, and the length range is 0.1-3 mu m;
s3, mixing the core-layer emulsion and the shell emulsion, adding potassium persulfate and deionized water, heating to 90 ℃ for reaction, wherein the weight ratio of the core-layer emulsion to the shell-layer emulsion to the initiator to the deionized water is 40:5:0.13:2, and filtering, washing and drying the obtained reaction product to obtain the CNT composite branched core-shell structure acrylate.
The CNT composite branched core-shell structure acrylate prepared in the embodiment comprises an acrylate core, a polymethyl methacrylate shell coated with the acrylate core, a branched monomer grafted on the polymethyl methacrylate shell, and a CNT connected with the branched monomer, wherein the diameter of the polymethyl methacrylate shell is 330 nm.
Examples 4 to 9
The preparation method of the weather-resistant antistatic low-temperature-resistant polycarbonate material in the embodiment comprises the following steps:
(1) the raw materials were prepared according to the components and their parts by weight in table 1, respectively,
table 1: component formula of weather-resistant antistatic low-temperature-resistant polycarbonate material in embodiment 4-9 of the application
Figure BDA0002313057800000111
The regenerated PC fragments in Table 1 are prepared by adopting waste PC parts (water bottles, plate leftover materials, sheets, records and the like made of PC materials) through sorting, crushing, cleaning/drying, color sorting and detection, and the sorting is finished by adopting manual operation and infrared spectrum sorting; the crushing is carried out in a crusher, and the block diameter of the crushed pieces is controlled to be less than or equal to 10 mm; cleaning/drying in a powerful cleaning machine, wherein the impurity content of the cleaned broken pieces is less than or equal to 200ppm, and the drying temperature is 90-120 ℃; the color selection is carried out by adopting a photoelectric color selector, and the impurity content of the crushed pieces after the color selection is less than or equal to 100 ppm; the detection is to adopt a lamp box to visually detect, a spectrometer, an MI tester and a tensile tester to detect and evaluate the physical properties of the material;
the regenerated PC granules in Table 1 are particle-type materials prepared by extruding and granulating regenerated PC chips, and the brand-new PC granules are particle-type materials prepared by a phosgene method, a semi-phosgene method or a non-phosgene method; the fluidity of the regenerated PC fragments, the regenerated PC granules and the brand-new PC granules is 30g/10 min;
the CNT composite branched core-shell structure acrylate in table 1 was the CNT composite branched core-shell structure acrylate prepared in example 1.
(2) Mixing a PC substrate, CNT composite branched core-shell structure acrylate, a chain extender, an ultraviolet absorber, an antioxidant, an auxiliary antioxidant, a compatilizer and a processing aid in a high-speed mixer for 8min to form a uniform mixture;
(3) and (2) carrying out melt mixing extrusion granulation on the mixture by adopting a double-screw extruder, wherein the length-diameter ratio of the double-screw extruder is 40:1, the rotating speed of a screw is 380rpm, and the temperature of the screw is 210 ℃ in a first zone, 230 ℃ in a second zone, 250 ℃ in a third zone, 250 ℃ in a fourth zone and 220 ℃ in a fifth zone.
Example 10
The polycarbonate material with weather resistance, antistatic property and low temperature resistance is prepared by adopting the CNT composite branched core-shell structure acrylate prepared in the embodiment 2 and the components, the formula and the preparation method in the embodiment 4.
Example 11
The polycarbonate material with weather resistance, antistatic property and low temperature resistance is prepared by adopting the CNT composite branched core-shell structure acrylate prepared in the embodiment 3 and the components, the formula and the preparation method in the embodiment 4.
Comparative example 1
The modified polycarbonate is prepared by adopting the same amount of common core-shell structure acrylate (namely, the core-shell structure acrylate is prepared according to the method in the embodiment 1, but no branching monomer and CNT are added in the preparation process, and the prepared core-shell structure acrylate has no grafting branching monomer and CNT on the surface) to replace CNT composite branched core-shell structure acrylate, and simultaneously, the same amount of CNT is directly added into the polycarbonate to prepare the modified polycarbonate according to the method in the embodiment 4.
Comparative example 2
A reference sample of a commercially available conventional polycarbonate, having the designation koshichu 2805.
The polycarbonate products of inventive examples 4-11 and comparative examples 1-2 were characterized according to ASTM standards, and the density, melt flow rate, tensile strength, tensile rate, flexural modulus, flexural strength, notched impact and heat distortion temperature were as given in Table 2 under the test conditions and test methods, with the results as given in Table 2; the weather resistance test was characterized according to ASTM D-4459, and the results are shown in FIG. 1.
Table 2: examination and Properties of polycarbonate products in examples and comparative examples of the present invention
Figure BDA0002313057800000131
In conclusion, the invention carries out antistatic, UV resistant and toughening modification on the polycarbonate PCR, so that the surface resistivity of the material reaches 103～9Ohm/sq, the low-temperature impact performance is obviously improved, and the IZOD notch impact strength of more than or equal to 40J/m can be kept at the temperature of minus 30 ℃, which is more than 2.5 times of that of common PC at the temperature of minus 30 ℃. Meanwhile, the weather resistance of the material is greatly improved, weather resistance tests are carried out under the same conditions, after 1000 hours, the weather resistance test data delta E of the modified polycarbonate material is less than or equal to 2, and the delta E of the common polycarbonate material in the comparative example 2 is close to 6.5.
According to the invention, the polycarbonate plastic PCR fragments are used as raw materials, on one hand, the plastic waste is recycled, the environment protection effect is achieved, and the manufacturing cost of the final material is reduced from the raw materials; on the other hand, polycarbonate plastic PCR broken materials which are not granulated are directly adopted as raw materials for modification, so that the whole process is shortened, the manufacturing cost is reduced, and the material performance of the original base material is protected.
In other embodiments or alternatives of the present invention, when the melt-kneading extrusion granulation is performed using a twin-screw extruder, the temperature of the screw may be 220 ℃ in the first zone, 240 ℃ in the second zone, 250 ℃ in the third zone, 250 ℃ in the fourth zone, 220 ℃ in the fifth zone, or 200 ℃ in the first zone, 230 ℃ in the second zone, 240 ℃ in the third zone, 240 ℃ in the fourth zone, 220 ℃ in the fifth zone, or 210 ℃ in the first zone, 240 ℃ in the second zone, 260 ℃ in the third zone, 260 ℃ in the fourth zone, 220 ℃ in the fifth zone, or 220 ℃ in the first zone, 250 ℃ in the second zone, 260 ℃ in the third zone, 260 ℃ in the fourth zone, 220 ℃ in the fifth zone.
The technical scope of the invention claimed by the embodiments of the present application is not exhaustive, and new technical solutions formed by equivalent replacement of single or multiple technical features in the technical solutions of the embodiments are also within the scope of the invention claimed by the present application; in all the embodiments of the present invention, which are listed or not listed, each parameter in the same embodiment only represents an example (i.e., a feasible embodiment) of the technical solution, and there is no strict matching and limiting relationship between the parameters, wherein the parameters may be replaced with each other without departing from the axiom and the requirements of the present invention, unless otherwise specified.
The technical means disclosed by the scheme of the invention are not limited to the technical means disclosed by the technical means, and the technical scheme also comprises the technical scheme formed by any combination of the technical characteristics. While the foregoing is directed to embodiments of the present invention, it will be appreciated by those skilled in the art that various changes may be made in the embodiments without departing from the principles of the invention, and that such changes and modifications are intended to be included within the scope of the invention.

Claims (6)

1. The CNT composite branched core-shell structure acrylate comprises a core-shell structure acrylate formed by an acrylate core and a polymethyl methacrylate shell covering the acrylate core, and is characterized by also comprising a branched monomer grafted on the polymethyl methacrylate shell and a Carbon Nano Tube (CNT) connected with the branched monomer;
the branched monomer comprises at least one of acrylate, methacrylic acid, glycidyl methacrylate, maleic acid and acrylamide;
the particle size of the core-shell structure acrylate is 250-350nm, the tube diameter range of the CNT is 1-5 nm, and the length range of the CNT is 0.1-3 mu m;
the preparation method of the CNT composite branched core-shell structure acrylate comprises the following steps:
s1, adding butyl acrylate, allyl methacrylate, an anionic emulsifier, an initiator and a crosslinking agent into deionized water for heating reaction to prepare a core-layer emulsion;
s2, preparing a shell emulsion from a branched monomer, CNT, methyl methacrylate and an anionic emulsifier;
s3, mixing the core-layer emulsion and the shell emulsion, adding an initiator and deionized water for heating reaction, and filtering, washing and drying a reaction product to obtain the CNT composite branched core-shell structure acrylate;
in the step S1, the weight ratio of butyl acrylate, allyl methacrylate, anionic emulsifier, initiator, cross-linking agent and deionized water is (50-500): (0.01-0.1): (0.5-5): (0.1-2): 10-100%, the temperature of the heating reaction is 50-100 ℃, the heating reaction is carried out while mechanical stirring is carried out, and the stirring speed is 50-500 rpm.
2. The CNT composite branched core-shell structured acrylate according to claim 1, wherein the weight ratio of the branched monomer, the CNT, the methyl methacrylate and the anionic emulsifier in step S2 is (0.01-0.2): (5-60): (30-100): (1-5).
3. The CNT composite branched core-shell structure acrylate according to claim 1, wherein the weight ratio of the core-layer emulsion, the shell-layer emulsion, the initiator and the deionized water in step S3 is (5-60): (3-15): (0.05-0.2): (1-3), wherein the temperature of the heating reaction is 70-100 ℃.
4. The weather-resistant antistatic low-temperature-resistant polycarbonate material is characterized by comprising the following components:
64-96 parts of PC base material
1.0-20 parts of CNT (carbon nanotube) composite branched core-shell structure acrylate
0.1-4.0 parts of chain extender
0.1 to 1.0 part of ultraviolet absorber
0.1-0.5 part of primary antioxidant
0.1-0.5 part of auxiliary antioxidant
0.5 to 9.0 parts of compatibilizer
0.1-1.0 part of processing aid;
the CNT composite branched core-shell structure acrylate is the CNT composite branched core-shell structure acrylate of claim 1.
5. The weather-resistant, antistatic and low temperature resistant polycarbonate material of claim 4, wherein the PC substrate is recycled PC chips, or a mixture of recycled PC chips and at least one of recycled PC pellets and brand new PC pellets.
6. The weather-resistant antistatic low-temperature-resistant polycarbonate material as claimed in claim 5, wherein the regenerated PC chips are crushed chips of waste PC parts, the regenerated PC granules are particle-type materials obtained by granulating waste PC parts as raw materials, and the waste PC parts comprise water bottles, plate leftover materials, sheets, records and other PC parts made of PC materials; the brand new PC granules are particle materials prepared by a phosgene method, a semi-phosgene method or a non-phosgene method.
CN201911277577.6A 2019-12-11 2019-12-11 CNT (carbon nanotube) composite branched acrylate with core-shell structure and weather-resistant antistatic low-temperature-resistant polycarbonate material Active CN111057359B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911277577.6A CN111057359B (en) 2019-12-11 2019-12-11 CNT (carbon nanotube) composite branched acrylate with core-shell structure and weather-resistant antistatic low-temperature-resistant polycarbonate material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911277577.6A CN111057359B (en) 2019-12-11 2019-12-11 CNT (carbon nanotube) composite branched acrylate with core-shell structure and weather-resistant antistatic low-temperature-resistant polycarbonate material

Publications (2)

Publication Number Publication Date
CN111057359A CN111057359A (en) 2020-04-24
CN111057359B true CN111057359B (en) 2022-03-04

Family

ID=70300949

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911277577.6A Active CN111057359B (en) 2019-12-11 2019-12-11 CNT (carbon nanotube) composite branched acrylate with core-shell structure and weather-resistant antistatic low-temperature-resistant polycarbonate material

Country Status (1)

Country Link
CN (1) CN111057359B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101421338A (en) * 2006-04-14 2009-04-29 阿克马法国公司 Conductive carbon nanotube-polymer composite
CN103923252A (en) * 2014-04-21 2014-07-16 中国科学技术大学 Thermoplastic elastomer and preparation method thereof
CN105418835A (en) * 2016-01-12 2016-03-23 河北工业大学 Preparing method for core-shell structure functionality acrylate polymer particles for toughening polycarbonate
CN105418836A (en) * 2016-01-12 2016-03-23 河北工业大学 Preparation method of acrylate polymer/nanometer silicon dioxide composite particles for polycarbonate toughening
CN108543505A (en) * 2018-04-24 2018-09-18 中广核俊尔新材料有限公司 A kind of compound particle and preparation method thereof with multiple nucleocapsid

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060100368A1 (en) * 2004-11-08 2006-05-11 Park Edward H Elastomer gum polymer systems

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101421338A (en) * 2006-04-14 2009-04-29 阿克马法国公司 Conductive carbon nanotube-polymer composite
CN103923252A (en) * 2014-04-21 2014-07-16 中国科学技术大学 Thermoplastic elastomer and preparation method thereof
CN105418835A (en) * 2016-01-12 2016-03-23 河北工业大学 Preparing method for core-shell structure functionality acrylate polymer particles for toughening polycarbonate
CN105418836A (en) * 2016-01-12 2016-03-23 河北工业大学 Preparation method of acrylate polymer/nanometer silicon dioxide composite particles for polycarbonate toughening
CN108543505A (en) * 2018-04-24 2018-09-18 中广核俊尔新材料有限公司 A kind of compound particle and preparation method thereof with multiple nucleocapsid

Also Published As

Publication number Publication date
CN111057359A (en) 2020-04-24

Similar Documents

Publication Publication Date Title
CN101880450B (en) High-fog-degree and high-transparency LED lamp tube material and preparation method thereof
CN111592667B (en) Reinforced antibacterial artificial granite waste residue-based plastic master batch and preparation method thereof
CN101925653A (en) Alicyclic epoxy resin composition, cured product thereof, production method thereof, and rubbery polymer-containing resin composition
CN113652062B (en) PBT/PC alloy with stable mechanical property, preparation method and product thereof
CN101117433B (en) Elastomer-containing polycarbonate-based blending material and method for making same
CN101709142A (en) High-toughness halogen-free flame-retardanting reclaimed polycarbonate compound and preparation method thereof
CN102702633B (en) In-situ fiber-forming toughened regenerated polystyrene material and preparation method
CN108676341A (en) PC/PMMA/PETG ternary-alloy materials and preparation method thereof
KR101000658B1 (en) Recycling polyethyleneterephthalate composite and manufacturing method of thereof
CN111518334A (en) Method for recycling and preparing modified polypropylene composite material from waste polypropylene pipeline
JP4803616B2 (en) Method for recycling plastic waste material and method for producing plastic molded body
CN113583396A (en) PBT composition resistant to cyclic injection molding, preparation method and product thereof
CN1702116A (en) Nylon / acrylonitrile-butadiene-styrene terpolymer resin alloy materials
CN103360732A (en) Alloy for recovering polyethylene glycol terephthalate/acrylonitrile-butadiene-styrene copolymer and preparation method thereof
CN111057359B (en) CNT (carbon nanotube) composite branched acrylate with core-shell structure and weather-resistant antistatic low-temperature-resistant polycarbonate material
CN111647260B (en) PC/ABS alloy for tail lamp housing and preparation method thereof
CN102993623A (en) Preparation method for novel ABS/PC/PMMA (alkyl benzo sulfonate/poly carbonate/polymethyl methacrylate) alloy
CN105237996B (en) Recycled polycarbonate reinforced and toughened through isomeric crosslinking method and preparation method of recycled polycarbonate
CN113150480A (en) High-black high-brightness spraying-free scratch-resistant super-weather-resistant PMMA/ASA alloy material
CN105237983A (en) Halogen-free flame retardant PC composite and preparation method thereof
CN113698750B (en) Polycarbonate material with good appearance and high recovery ratio and preparation method and application thereof
CN112745630B (en) Super-tough high-fluidity regenerated ABS/PA6 composite material and preparation method and application thereof
CN114479333A (en) Low-creep high-toughness cycloolefin copolymer composite material and preparation method thereof
Zhang et al. Toughening of PBT/PC blends with epoxy functionalized core-shell modifiers
CN114685899A (en) High-temperature-resistant scratch-resistant polypropylene composite material and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20220609

Address after: 315000 No.29 Hehai Road, Binhai New Area, Fenghua Economic Development Zone, Ningbo City, Zhejiang Province

Patentee after: Ningbo Jianfeng New Material Co.,Ltd.

Address before: Room 801, No.17, building 17, Zhongwu Science Park, Panhuo street, Yinzhou District, Ningbo City, Zhejiang Province, 315104

Patentee before: Ningbo dopda polymer Co.,Ltd.

TR01 Transfer of patent right
EE01 Entry into force of recordation of patent licensing contract

Application publication date: 20200424

Assignee: Zhejiang Hi Carbon Cabin Network Technology Co.,Ltd.

Assignor: Ningbo Jianfeng New Material Co.,Ltd.

Contract record no.: X2023980049430

Denomination of invention: A CNT composite branched core-shell structure acrylic ester and weather resistant, anti-static, and low-temperature resistant polycarbonate material

Granted publication date: 20220304

License type: Common License

Record date: 20231201

EE01 Entry into force of recordation of patent licensing contract