CN116675978A - PA6/ABS/OMMT nanocomposite and preparation method thereof - Google Patents
PA6/ABS/OMMT nanocomposite and preparation method thereof Download PDFInfo
- Publication number
- CN116675978A CN116675978A CN202210162998.XA CN202210162998A CN116675978A CN 116675978 A CN116675978 A CN 116675978A CN 202210162998 A CN202210162998 A CN 202210162998A CN 116675978 A CN116675978 A CN 116675978A
- Authority
- CN
- China
- Prior art keywords
- abs
- ommt
- parts
- dispersion system
- caprolactam
- 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.)
- Pending
Links
- 229910017059 organic montmorillonite Inorganic materials 0.000 title claims abstract description 57
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims abstract description 52
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 229920001971 elastomer Polymers 0.000 claims abstract description 10
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005060 rubber Substances 0.000 claims abstract description 9
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 59
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 58
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 58
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 15
- 238000005520 cutting process Methods 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- 239000012190 activator Substances 0.000 claims description 7
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- MOMGDEWWZBKDDR-UHFFFAOYSA-M sodium;3,4,5,6-tetrahydro-2h-azepin-7-olate Chemical compound [Na+].O=C1CCCCC[N-]1 MOMGDEWWZBKDDR-UHFFFAOYSA-M 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- QISSLHPKTCLLDL-UHFFFAOYSA-N N-Acetylcaprolactam Chemical compound CC(=O)N1CCCCCC1=O QISSLHPKTCLLDL-UHFFFAOYSA-N 0.000 claims description 4
- 238000007906 compression Methods 0.000 claims description 4
- 230000006835 compression Effects 0.000 claims description 4
- FEFQUIPMKBPKAR-UHFFFAOYSA-N 1-benzoylazepan-2-one Chemical compound C=1C=CC=CC=1C(=O)N1CCCCCC1=O FEFQUIPMKBPKAR-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 238000001125 extrusion Methods 0.000 abstract description 18
- 239000000956 alloy Substances 0.000 abstract description 17
- 229910045601 alloy Inorganic materials 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002131 composite material Substances 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000009210 therapy by ultrasound Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract 1
- 229920002292 Nylon 6 Polymers 0.000 description 51
- 238000011065 in-situ storage Methods 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 230000009471 action Effects 0.000 description 7
- 238000010008 shearing Methods 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 6
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 3
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- -1 polyamide 6 monomer Chemical compound 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000012653 anionic ring-opening polymerization Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical class C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
- C08G69/18—Anionic polymerisation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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 application discloses a PA6/ABS/OMMT nano composite material and a reactive extrusion preparation method thereof, wherein the raw materials comprise 100 parts of caprolactam, 5-50 parts of ABS high rubber powder, 0.5-30 parts of organic modified montmorillonite, 0.1-10 parts of catalyst and 0.01-10 parts of activating agent. Pre-dispersing OMMT in molten caprolactam monomer; then dissolving ABS in the pre-dispersion solution, and uniformly mixing; and adding a catalyst and an activating agent, adding the dispersion system into a reaction extruder after water removal is finished, and extruding and granulating to obtain the PA6/ABS/OMMT nanocomposite. The method of the application adopts ultrasonic treatment to disperse OMMT in molten caprolactam monomer, and then carries out reactive extrusion in a liquid feeding mode, so that OMMT can be uniformly dispersed in PA6/ABS alloy, and the industrial preparation of high-toughness high-strength PA6/ABS/OMMT nanocomposite is realized. Compared with commercial PA6/ABS (Barblend/N NM-11) alloy, the composite material has obviously improved strength, toughness, heat resistance and the like, and further widens the application of the composite material in automobile interior trim and electronic and mechanical shells.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to a PA6/ABS/OMMT nanocomposite and a preparation method thereof.
Background
Nylon 6 (PA 6) is one of the most widely used engineering plastics at present, and has the advantages of high melting point, good wear resistance and fatigue resistance, and the like; meanwhile, the defects of low modulus, poor impact performance and the like are also present. Acrylonitrile-butadiene-styrene (ABS) is a versatile thermoplastic with the advantages of light weight, impact resistance, dimensional stability, etc., and at the same time, it has outstanding strength and toughness, and resists thermal deformation. The actual properties of ABS depend to a large extent on the blending ratio of the three main components. The acrylonitrile component imparts good chemical resistance and thermal stability to the copolymer; the butadiene component is responsible for toughness and impact strength; styrene imparts excellent rigidity and processability. By varying the composition of these three components, ABS products of different processability, toughness and heat resistance can be prepared.
The PA6/ABS alloy combines the excellent mechanical property and thermal property of PA6 and the processing property and impact property of ABS, and has been widely applied to industries such as automobiles, electronic appliances and the like. Compared with the traditional rubber or elastomer toughened PA6, the PA6/ABS alloy has effectively balanced toughness and rigidity, good heat resistance, processability and dimensional stability. However, the current process for preparing PA6/ABS alloys is reactive compatibilization, i.e. the groups of the specially functionalized graft or block copolymers react with the terminal carboxylic or amine groups of PA6 and are compatible with the styrene-acrylonitrile copolymer (SAN) in ABS, thereby improving the compatibility of PA6 and ABS.
Chinese patent application No. 200510025573.0, 200510025572.6, 200510112126.9, 200610036823.5, 200810039826.3 reports a method for preparing PA6/ABS alloy by reactive compatibilization, involving reactive compatibilizers mainly SMA (styrene-maleic anhydride copolymer), ABS-g-MAH (maleic anhydride grafted ABS), SEBS-g-MAH (maleic anhydride grafted hydrogenated styrene-butadiene-styrene triblock copolymer). Foreign researchers reported compatibilization of PA6/ABS alloys by imidizing acrylic acid (IA), glycidyl methacrylate-methyl methacrylate copolymers (GMA/MMA). However, the reactive compatibilizers of the graft or block structure generally have poor mechanical properties and have adverse factors of side reaction, influence by mixing conditions and high price. In addition, there have been studies reporting in situ compatibilization methods, i.e., copolymerization with PA6 by alkaline hydrolysis of the nitrile groups in ABS to improve the compatibility of the two. However, the PA6/ABS alloy obtained by casting polymerization has low notch impact strength and is difficult to meet the application requirements. Moreover, the method can only carry out polymerization in a batch mode, and is difficult to realize industrialized production.
Disclosure of Invention
In view of the above, the present application provides a PA6/ABS/OMMT nanocomposite and a preparation method thereof, so as to solve the technical problems presented in the above background art, and the preparation process is simple and can be continuously produced, and the compatibility of the composite is greatly improved.
In order to achieve the above purpose, the present application provides the following technical solutions:
the application discloses a preparation method of a PA6/ABS/OMMT nanocomposite, which comprises the following steps:
(1) Adding OMMT into molten caprolactam (namely polyamide 6 monomer, CL for short) for ultrasonic dispersion to obtain a first dispersion system;
(2) Adding ABS into the first dispersion system under stirring at 140-160 ℃ to obtain a second dispersion system; the CL ring-opening polymerization requires a proper temperature, and too high or too low is unfavorable for polymerization, resulting in a decrease in CL conversion.
(3) Stirring at 140-160 ℃, adding a catalyst into the second dispersion liquid, performing vacuum dewatering, cooling to below 120 ℃, and adding an activating agent to obtain a third dispersion system; the catalyst can initiate the anionic ring-opening polymerization reaction of CL, and the addition of the activator can accelerate the polymerization reaction rate; it should be noted in particular that the CL anionic polymerization by the catalyst and initiator is carried out in a subsequent reaction extruder, since the reaction requires a specific temperature. Firstly adding a catalyst to prepare caprolactam sodium anions so as to initiate subsequent polymerization reaction; the activator is added after vacuum water removal so as not to be consumed by trace water in the system.
(4) And adding the third dispersion system into a feeding section of a reaction extruder, extruding and molding by a screw after passing through a compression section and a metering section, and cooling, cutting and granulating to obtain the PA6/ABS/OMMT nanocomposite.
In the activation environment of CL anion polymerization, the alkaline hydrolysis product is subjected to grafting reaction with PA6, and the grafting product can improve the compatibility of ABS and PA6 and the interface effect of the grafting product, so that rubber particles in the ABS are uniformly dispersed in the PA6, and the above is in-situ polymerization-reaction. The first dispersion system is to uniformly disperse OMMT in melted CL, so that CL small molecules are dispersed in the sheet layer of OMMT; the second dispersion is prepared by dissolving ABS in OMMT/CL solution; the third dispersion system is prepared by adding a catalyst, reacting with caprolactam to generate caprolactam sodium anions, removing water, and adding an activating agent to initiate subsequent CL anion polymerization.
As a further scheme of the application: in the step (1), the ultrasonic dispersion is carried out in a cell pulverizer for 10-90min.
As a further scheme of the application: in the step (3), the temperature of a feeding section of a screw of the reaction extruder is 80-140 ℃, the temperature of a compression section is 140-200 ℃, the temperature of a metering section is 200-260 ℃, the temperature of a machine head is 220-240 ℃, and the rotating speed of the screw is 50-300r/min.
As a further scheme of the application: 100 parts of caprolactam, 5-50 parts of ABS, 0.5-30 parts of OMMT, 0.1-10 parts of catalyst and 0.01-10 parts of activator.
As a further scheme of the application: the OMMT is at least one of phyllosilicate nano montmorillonite and organically modified montmorillonite.
As a further scheme of the application: the ABS is an acrylonitrile-butadiene-styrene copolymer with rubber content of 50-80 wt%.
As a further scheme of the application: the catalyst is at least one selected from alkaline earth metal, sodium hydroxide, sodium caprolactam, lithium hydride and potassium hydroxide.
As a further scheme of the application: the activator is at least one selected from N-acetyl caprolactam, N-benzoyl caprolactam, 2, 4-toluene diisocyanate and 2-phenyl methane diisocyanate.
The application also discloses a PA6/ABS/OMMT nanocomposite which is prepared by the preparation method according to any one of the above.
Compared with the prior art, the application has the beneficial effects that:
1. the application adopts an in-situ polymerization-reaction extrusion process, can realize continuous production, has the characteristics of high efficiency, low cost and the like, and is suitable for continuously producing PA6/ABS/OMMT nano composite materials.
2. According to the method, through an in-situ polymerization-reaction extrusion process, through alkaline hydrolysis of cyano groups in ABS, copolymerization reaction is carried out with PA6 in reaction extrusion, so that the compatibility of the ABS and the PA6 is improved, the interface effect of the ABS is improved, the ABS is uniformly dispersed in a PA6 monomer without addition of a compatilizer, and the PA6/ABS high-toughness alloy with improved compatibility is obtained.
According to the method, OMMT is dispersed in a fused CL monomer by adopting an ultrasonic treatment method, then in-situ intercalation-reaction extrusion is adopted, CL small molecules are dispersed in an OMMT lamellar by utilizing low viscosity and strong polarity of CL, then ring-opening polymerization of CL is carried out in the reaction extrusion process, and the interlayer spacing of OMMT is increased by a PA6 macromolecular chain, so that the OMMT lamellar is well dispersed in the alloy, the strength and heat resistance of the PA6/ABS alloy are obviously improved, and the application field of the composite material is further widened.
Drawings
FIG. 1 is a graph showing the results of a scan of the loss factor (tan (delta)) of a PA6/ABS/OMMT nanocomposite as a function of temperature; wherein tan (delta) is the molecular viscoelastic behavior of a dynamic mechanical behavior capable of characterizing a polymer under practical use conditions, the temperature at the tan (delta) peak corresponding to the glass transition temperature;
FIG. 2 is a TEM photograph of a PA6/ABS/OMMT nanocomposite, wherein the OMMT amount (phr) (a-0.5; b-1;c-2;d-3).
Detailed Description
In order that the application may be readily understood, a more particular description of the application will be rendered by reference to specific embodiments that are illustrated below. This application may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
Specific information of the raw materials used in the following examples and comparative examples are as follows:
ABS, the rubber content is 58wt%, the rubber content is higher, and the toughening effect of the composite material can be improved; ABS181H produced by Korea Jinhu petrochemical company is selected;
caprolactam, industrial grade, manufacturer is China petrochemical group Co., ltd;
OMMT, organic modified montmorillonite, manufactured by Zhejiang Feng Hong New Material Co., ltd, with the brand of DK-5;
the catalyst, analytical grade sodium hydroxide, manufacturer is national medicine group chemical reagent company; analytical grade sodium caprolactam is manufactured by Shanghai Ala Biochemical technology Co., ltd; analytical grade potassium hydroxide, manufacturer is national medicine group chemical reagent company;
activator, 2, 4-toluene diisocyanate, analytical grade, manufacturer is Shanghai Ala Biochemical technology Co., ltd; 2-phenyl methane diisocyanate, technical grade, manufacturer is Wanhua chemical group Co., ltd; n-acetyl caprolactam, analytical grade, manufacturer is Guangdong Weng Jiang chemical agent Co., ltd;
all materials are commercially available conventional and commonly used products.
It will be appreciated that the above raw material reagents are only examples of some embodiments of the application, so that the technical solution of the application is more clear, and it is not represented that the application can only employ the above reagents, and the scope of the claims is in particular. In addition, "parts" described in examples and comparative examples refer to parts by weight unless otherwise specified.
Any range recited in the application includes any numerical value between the endpoints and any sub-range of any numerical value between the endpoints or any numerical value between the endpoints.
Example 1
(1) 100 parts of caprolactam is put into a 2L three-neck flask to be heated and melted, then 2 parts of OMMT is added, and ultrasonic dispersion is carried out for 10 minutes, thus obtaining a mixed first dispersion system;
(2) Heating to 140 ℃, and stirring and dissolving 10 parts of ABS into the first dispersion system under mechanical stirring to obtain a second dispersion system;
(3) Adding 10 parts of sodium hydroxide into the second dispersion system, removing water in vacuum at 140 ℃ for 30min, cooling to 110 ℃, then adding 0.1 part of 2, 4-toluene diisocyanate, and shaking uniformly to obtain a third dispersion system;
(4) Placing the third dispersion system into an extruder charging tank, starting the extruder, regulating and controlling the flow of the charging tank, uniformly flowing out and entering the extruder, and performing reactive extrusion under the shearing action of a screw; wherein the rotating speed of the extruder is 50r/min;
(5) And cooling the extruded material in a cold water bath, and then sending the cooled material into a cutting machine for cutting and granulating to obtain the PA6/ABS/OMMT nanocomposite.
Example 2
(1) 100 parts of caprolactam is put into a 2L three-neck flask to be heated and melted, then 10 parts of OMMT is added, and ultrasonic dispersion is carried out for 20 minutes, thus obtaining a mixed first dispersion system;
(2) Heating to 140 ℃, and stirring and dissolving 20 parts of ABS into the first dispersion system under mechanical stirring to obtain a second dispersion system;
(3) Adding 10 parts of sodium caprolactam into the second dispersion system, removing water in vacuum at 160 ℃ for 30min, cooling to 110 ℃, then adding 5 parts of 2-phenyl methane diisocyanate and shaking uniformly to obtain a third dispersion system;
(4) Placing the third dispersion system into an extruder charging tank, starting the extruder, regulating and controlling the flow of the charging tank, uniformly flowing out and entering the extruder, and performing reactive extrusion under the shearing action of a screw; wherein the rotating speed of the extruder is 150r/min;
(5) And cooling the extruded material in a cold water bath, and then sending the cooled material into a cutting machine for cutting and granulating to obtain the PA6/ABS/OMMT nanocomposite.
Example 3
(1) 100 parts of caprolactam is put into a 2L three-neck flask to be heated and melted, then 20 parts of OMMT is added, and ultrasonic dispersion is carried out for 60 minutes, thus obtaining a mixed first dispersion system;
(2) Heating to 140 ℃, and stirring and dissolving 30 parts of ABS into the first dispersion system under mechanical stirring to obtain a second dispersion system;
(3) Adding 5 parts of potassium hydroxide into the second dispersion system, carrying out vacuum dehydration at 150 ℃ for 40min, cooling to 110 ℃, then adding 15 parts of N-acetyl caprolactam, and shaking uniformly to obtain a third dispersion system;
(4) Placing the third dispersion system into an extruder charging tank, starting the extruder, regulating and controlling the flow of the charging tank, uniformly flowing out and entering the extruder, and performing reactive extrusion under the shearing action of a screw; wherein the rotating speed of the extruder is 300r/min;
(5) And cooling the extruded material in a cold water bath, and then sending the cooled material into a cutting machine for cutting and granulating to obtain the PA6/ABS/OMMT nanocomposite.
Example 4
(1) 100 parts of caprolactam is put into a 2L three-neck flask to be heated and melted, then 5 parts of OMMT is added, and ultrasonic dispersion is carried out for 30 minutes, thus obtaining a mixed first dispersion system;
(2) Heating to 160 ℃, and stirring and dissolving 15 parts of ABS into the first dispersion system under mechanical stirring to obtain a second dispersion system;
(3) Adding 2 parts of sodium hydroxide into the second dispersion system, carrying out vacuum dehydration at 160 ℃ for 40min, cooling to 110 ℃, then adding 1 part of 2-phenyl methane diisocyanate, and shaking uniformly to obtain a third dispersion system;
(4) Placing the third dispersion system into an extruder charging tank, starting the extruder, regulating and controlling the flow of the charging tank, uniformly flowing out and entering the extruder, and performing reactive extrusion under the shearing action of a screw; wherein the rotating speed of the extruder is 200r/min;
(5) And cooling the extruded material in a cold water bath, and then sending the cooled material into a cutting machine for cutting and granulating to obtain the PA6/ABS/OMMT nanocomposite.
Example 5
(1) 100 parts of caprolactam is put into a 2L three-neck flask to be heated and melted, then 20 parts of OMMT is added, and ultrasonic dispersion is carried out for 120 minutes, so as to obtain a mixed first dispersion system;
(2) Heating to 140 ℃, and stirring and dissolving 30 parts of ABS into the first dispersion system under mechanical stirring to obtain a second dispersion system;
(2) Adding 5 parts of sodium caprolactam into the second dispersion system, vacuum dewatering at 160 ℃ for 60min, cooling to 100 ℃, then adding 10 parts of 2, 4-toluene diisocyanate and shaking uniformly to obtain a third dispersion system;
(3) Placing the third dispersion system into an extruder charging tank, starting the extruder, regulating and controlling the flow of the charging tank, uniformly flowing out and entering the extruder, and performing reactive extrusion under the shearing action of a screw; wherein the rotating speed of the extruder is 100r/min;
(4) And cooling the extruded material in a cold water bath, and then sending the cooled material into a cutting machine for cutting and granulating to obtain the PA6/ABS/OMMT nanocomposite.
Comparative example 1
(1) 100 parts of caprolactam is put into a 2L three-neck flask to be heated and melted, 2 parts of sodium hydroxide is added, vacuum dehydration is carried out for 40min at 160 ℃, the temperature is reduced to 110 ℃, and then 1 part of 2-phenyl methane diisocyanate is added and uniformly shaken;
(2) The dispersion system is put into a charging tank of an extruder, the extruder is started, the flow of the charging tank is regulated and controlled, the dispersion system flows out of the extruder at a constant speed and enters the extruder, and the reaction extrusion is carried out under the shearing action of a screw rod; wherein the rotating speed of the extruder is 200r/min;
(3) And cooling the extruded material in a cold water bath, and then sending the cooled material into a cutting machine for cutting and granulating to obtain pure PA6.
(4) 5 parts of OMMT and 15 parts of ABS are added into 100 parts of PA6, the mixture is mixed at high speed for 10 minutes, then the mixture is extruded in an extruder, the temperature setting and the rotating speed of the extruder are the same as those of the embodiment 4, and the PA6/ABS/OMMT nano composite material prepared by a melt blending process is obtained after extrusion granulation.
Referring to fig. 1, PA6 used in the alloy was prepared by reactive extrusion, and the glass transition temperatures of PA6 and SAN (styrene-acrylonitrile copolymer) in the melt-blended alloy were 50.6 ℃ and 112.8 ℃, respectively, while the glass transition temperatures of PA6 and SAN in the in-situ reacted alloy were 52.4 ℃ and 109.5 ℃, respectively. The difference in glass transition temperatures of SAN and PA6 in the melt-blended alloy (made from comparative example 1) was equal to 62.2 ℃ and greater than the difference in glass transition temperatures of both in-situ alloys (57 ℃ C.). This is because the in situ reaction improves the compatibility of ABS and PA6 to some extent, so that the glass transition temperatures of the two are close to each other, consistent with the conclusions reported in the literature.
Referring to FIG. 2, the black lines in FIG. 2 are OMMT, and the spherical particles are rubber particles in ABS. It can be seen from the figure that OMMT is mainly dispersed in the PA6 matrix, which is determined by the wetting coefficient of montmorillonite in multicomponent blends. At levels of 0.5phr and 1phr, OMMT gives better exfoliation in the matrix, uniformly dispersed in the form of flakes in PA6. The PA6/ABS/OMMT nanocomposite prepared by the in-situ reaction extrusion process can obtain better montmorillonite dispersion effect, because the organically modified OMMT interlayer spacing is increased, CL monomers are easy to enter, intercalation polymerization is carried out in the ring-opening polymerization process of reaction extrusion to form a lamellar structure, and meanwhile, the lamellar structure is easier to be peeled off under the strong shearing action of double screws. As OMMT usage continues to increase, montmorillonite dispersion decreases, mostly in an intercalated form in PA6, and particles aggregate. At 3phr, OMMT distributes the rubber particles in the vicinity of the band and has a build-up phenomenon, with more severe agglomeration. Probably because OMMT aggregates during the dispersion of ABS/CL solution, CL did not enter OMMT intercalation before reaction, and a large amount of OMMT aggregates occurred in PA6 matrix after reaction extrusion was completed.
The PA6/ABS/OMMT nanocomposites prepared in examples 1-5 were subjected to performance testing, and the test results are shown in Table 1.
Table 1 alloy material property comparison
| Nanocomposite type | Manufacturer (S) | Tensile Strength (MPa) | Notched impact Strength (J/m) | Elongation at break (%) |
| Example 1 | / | 57 | 386 | 43 |
| Example 2 | / | 64 | 429 | 48 |
| Example 3 | / | 70 | 515 | 57 |
| Example 4 | / | 72 | 730 | 85 |
| Example 5 | / | 76 | 672 | 62 |
| Comparative example 1 | / | 56 | 114 | 17 |
| HNB0270G6 | Jinhu Rili | 100 | 130 | 5 |
| Terblend/N NM-11 | Basoff' s | 43 | 650 | 40 |
Note that: the tensile strength test standard is ASTM D-638; the notched impact strength test standard is ASTM-D-256; the test standard for elongation at break is ASTM D-638.
Although the present disclosure describes embodiments, not every embodiment is described in terms of a single embodiment, and such description is for clarity only, and one skilled in the art will recognize that the embodiments described in the disclosure as a whole may be combined appropriately to form other embodiments that will be apparent to those skilled in the art.
Therefore, the above description is not intended to limit the scope of the application; all changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Claims (9)
1. The preparation method of the PA6/ABS/OMMT nanocomposite is characterized by comprising the following steps:
(1) Adding OMMT into molten caprolactam to carry out ultrasonic dispersion to obtain a first dispersion system;
(2) Adding ABS into the first dispersion system under stirring at 140-160 ℃ to obtain a second dispersion system;
(3) Stirring at 140-160 ℃, adding a catalyst into the second dispersion liquid, performing vacuum dewatering, cooling to below 120 ℃, and adding an activating agent to obtain a third dispersion system;
(4) And adding the third dispersion system into a feeding section of a reaction extruder, extruding and molding by a screw after passing through a compression section and a metering section, and cooling, cutting and granulating to obtain the PA6/ABS/OMMT nanocomposite.
2. The method according to claim 1, wherein in the step (1), the ultrasonic dispersion is performed in a cell pulverizer for 10 to 90 minutes.
3. The method according to claim 1, wherein in the step (3), the temperature of the feeding section of the screw of the reaction extruder is 80-140 ℃, the temperature of the compression section is 140-200 ℃, the temperature of the metering section is 200-260 ℃, the temperature of the head is 220-240 ℃, and the rotating speed of the screw is 50-300r/min.
4. The preparation method according to claim 1, wherein 100 parts of caprolactam, 5-50 parts of ABS, 0.5-30 parts of OMMT, 0.1-10 parts of catalyst and 0.01-10 parts of activator are calculated in parts by weight.
5. The method according to claim 1, wherein the OMMT is at least one of a layered silicate nano montmorillonite and an organically modified montmorillonite.
6. The method according to claim 1, wherein the ABS is an acrylonitrile-butadiene-styrene copolymer having a rubber content of 50 to 80 wt%.
7. The method according to claim 1, wherein the catalyst is at least one selected from alkaline earth metals, sodium hydroxide, sodium caprolactam, lithium hydride, and potassium hydroxide.
8. The method according to claim 1, wherein the activator is at least one selected from the group consisting of N-acetyl caprolactam, N-benzoyl caprolactam, 2, 4-toluene diisocyanate, and 2-phenyl methane diisocyanate.
9. PA6/ABS/OMMT nanocomposite, characterized in that it is produced by the preparation method according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210162998.XA CN116675978A (en) | 2022-02-22 | 2022-02-22 | PA6/ABS/OMMT nanocomposite and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210162998.XA CN116675978A (en) | 2022-02-22 | 2022-02-22 | PA6/ABS/OMMT nanocomposite and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116675978A true CN116675978A (en) | 2023-09-01 |
Family
ID=87777492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210162998.XA Pending CN116675978A (en) | 2022-02-22 | 2022-02-22 | PA6/ABS/OMMT nanocomposite and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116675978A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004536160A (en) * | 2001-02-16 | 2004-12-02 | ロディア エンジニアリング プラスティックス ソシエテ ア レスポンサビリテ リミテー | Thermoplastic polymer composition based on polyamide |
| CN1982373A (en) * | 2005-12-12 | 2007-06-20 | 上海杰事杰新材料股份有限公司 | Production of peel montmorillonite/casting nylon nano-composite material |
| CN101735604A (en) * | 2009-12-25 | 2010-06-16 | 杭州鸿雁电器有限公司 | Montmorillonoid modified Pa6/ABS alloy material and preparation method thereof |
| CN104672443A (en) * | 2014-12-11 | 2015-06-03 | 张蕾 | Method for preparing nylon 6/nano-montmorillonite composite material |
| CN109320898A (en) * | 2018-10-11 | 2019-02-12 | 吉林建筑大学 | Nano montmorillonite modified PA6/ABS alloy and preparation method |
-
2022
- 2022-02-22 CN CN202210162998.XA patent/CN116675978A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004536160A (en) * | 2001-02-16 | 2004-12-02 | ロディア エンジニアリング プラスティックス ソシエテ ア レスポンサビリテ リミテー | Thermoplastic polymer composition based on polyamide |
| CN1982373A (en) * | 2005-12-12 | 2007-06-20 | 上海杰事杰新材料股份有限公司 | Production of peel montmorillonite/casting nylon nano-composite material |
| CN101735604A (en) * | 2009-12-25 | 2010-06-16 | 杭州鸿雁电器有限公司 | Montmorillonoid modified Pa6/ABS alloy material and preparation method thereof |
| CN104672443A (en) * | 2014-12-11 | 2015-06-03 | 张蕾 | Method for preparing nylon 6/nano-montmorillonite composite material |
| CN109320898A (en) * | 2018-10-11 | 2019-02-12 | 吉林建筑大学 | Nano montmorillonite modified PA6/ABS alloy and preparation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102391431B (en) | Nylon toughener and preparation method and application thereof | |
| CN112724571B (en) | Regenerated alloy material based on chemical and physical common modification and preparation method thereof | |
| CN105038200A (en) | Multiple-composite-toughened nylon-6 composite material, composite toughening agent and preparation method thereof | |
| CN106478939A (en) | A kind of nano composite material of Graphene/nylon/elastomer and preparation method thereof | |
| DE102004059241A1 (en) | Impact-modified thermoplastic molding compositions based on vinylaromatic copolymers and polyamide | |
| CN102020807A (en) | High-performance environment-friendly polypropylene blending material and preparation method thereof | |
| Zhao et al. | Preparation of super-toughened PA6 with submicron-sized ABS by in situ reactive extrusion method | |
| CN101759924A (en) | Preparation method of nanometer calcium carbonate filling modified polypropylene automotive interior material | |
| CN114276641B (en) | Regenerated HIPS/PP alloy material based on in-situ compatibilization and chain extension and preparation method thereof | |
| CN108285598B (en) | Polyvinyl chloride processing aid master batch with toughening function and preparation method thereof | |
| CN116675978A (en) | PA6/ABS/OMMT nanocomposite and preparation method thereof | |
| CN102051046A (en) | PA (polyamide)/ABS (Acrylonitrile Butadiene Styrene) composite material and preparation method thereof | |
| CN103910921A (en) | High density polyethylene (HDPE) alloy and preparation method thereof | |
| CN106947233B (en) | A kind of PC/PA6/ graphene composite material and preparation method thereof | |
| Fu et al. | Super-tough poly (butylene terephthalate) based blends by modification with core-shell structured polyacrylic nanoparticles | |
| CN102634195B (en) | Super-tough green nylon 11 alloy and preparation method of super-tough green nylon 11 alloy | |
| CN111187446A (en) | Method for recycling waste HIPS (high impact polystyrene) | |
| CN1125098C (en) | Process for preparation of rubber-reinforced styrene resin | |
| CN115055145B (en) | HIPS resin production process system and preparation method thereof | |
| CN114106506B (en) | PP/PA6 porous composite material and preparation method thereof | |
| CN106893251B (en) | A kind of high-performance ABS/PA6/ graphene composite material and preparation method thereof | |
| CN110776695B (en) | Antistatic polypropylene composition and preparation method thereof | |
| CN111019240B (en) | Polypropylene composite material for injection molding foaming and preparation method thereof | |
| CN110372822B (en) | Compatilizer and preparation method and application thereof | |
| CN104045964B (en) | A kind of chemical method for toughening of waste and old ABS plastic |
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 |