CN111499791B - Application of multi-random copolymer in improving phase structure and phase stability of polyester/styrene resin alloy - Google Patents
Application of multi-random copolymer in improving phase structure and phase stability of polyester/styrene resin alloy Download PDFInfo
- Publication number
- CN111499791B CN111499791B CN202010404537.XA CN202010404537A CN111499791B CN 111499791 B CN111499791 B CN 111499791B CN 202010404537 A CN202010404537 A CN 202010404537A CN 111499791 B CN111499791 B CN 111499791B
- Authority
- CN
- China
- Prior art keywords
- monomer
- styrene
- phase
- styrene resin
- acrylonitrile
- 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
Links
Images
Classifications
-
- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
- C08F212/10—Styrene with nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an application of a polynary random copolymer in improving the phase structure and the phase stability of a polyester/styrene resin alloy or an application of the polynary random copolymer in preparing the polyester/styrene resin alloy; the polynary random copolymer is formed by copolymerizing aromatic vinyl monomers, acrylonitrile monomers and glycidyl methacrylate. The special compatibilizer for polyester/styrene resin alloy provided by the invention is blended with other raw materials, extruded and granulated, so that the polyester/styrene resin alloy with excellent phase structure and phase stability can be prepared simply, effectively and conveniently, at low cost, and the alloy has special effects brought by the phase stability, such as repeatable processing, excellent multi-axial impact property, low notch sensitivity and the like while maintaining excellent mechanical properties, thereby widening the application field of the alloy.
Description
Technical Field
The invention relates to a special compatilizer for improving phase state distribution and stability of polyester/styrene resin alloy and application thereof.
Background
The polymer alloy material has the advantages of two polymers, and is more and more concerned by researchers, for example, the PC/ABS alloy has the comprehensive characteristics of PC and ABS, so that the fluidity is improved compared with PC, the processing performance is improved, the sensitivity of a product to stress is reduced, and the heat stability is more excellent compared with ABS. Therefore, the optical fiber can be applied to the fields of household appliances, office equipment, communication equipment, photographic equipment, medical instruments, buildings, lighting appliances, aerospace, electronic computers, optical fibers and the like. Especially, the high-strength and high-heat-resistance parts such as automobile inner decorations, outer decorations, automobile lamps and the like are widely applied.
In recent years, the market of PC/ABS has been kept more than 10% more, and with the development of industries such as automobiles and home appliances, people have increasingly demanded more beautiful and higher performance polyester/styrene resins, and a new generation of high performance polyester/styrene resin alloy series materials are required to have not only excellent mechanical properties, but also new series of properties including phase distribution structure and phase stability, no spraying, ultra-low gloss, chemical resistance, and the like.
In addition, as plastic products are widely applied in various industrial fields, the accompanying plastic wastes are increasing, which causes huge waste of energy and serious pollution caused by non-biodegradability of plastics. Therefore, the recycling of waste plastics is more and more emphasized by people. Among them, polyethylene terephthalate (PET) is a widely recycled material. At present, PET (R-PET) recycled materials mainly come from the recycling of bottle flakes, have poor performance and are mainly used for alloys, fillers of polyester short fibers, polyester reinforced wood-plastic composite materials and the like.
The ABS and PET can be blended to prepare alloy with excellent performance, and the alloy has the advantages of both ABS and PET, not only widens the application field of recycled materials, but also can overcome some inherent performance defects of ABS and reduce the price, is a material with great prospect, and has wide application in household appliances such as televisions, printers, copiers and other OA products.
Generally, polyester/styrene-based resin alloys have a high processing temperature and a large difference in solubility parameters between polyester and styrene-based resin, and are prone to phase separation. Although the compatibility of PC/ABS is good, the ester group of PC is easy to be attacked and degraded by active groups such as hydroxyl under the condition of long thermal history or strong shearing, so that the re-aggregation of the dispersed phase is easy to occur in the processing process or the recycling process; the prior art for solving the compatibility problem of polyester/styrene resin generally adds a compatilizer. Common and literature reports are: isocyanates, oxazolines, epoxies and anhydrides. The acid anhydrides and epoxy products are produced industrially, but the applications of chain extension, toughening and the like are more, such as ADR-4370 of BASF, AX8900 of Acomata company, PTW of Dupont and the like, but no reports of relevant compatilizers on the aspects of phase state improvement and phase state stability exist.
Therefore, how to obtain a compatilizer capable of improving the phase state distribution and stability of the polyester/styrene resin alloy becomes an important problem, and the compatilizer is used for stably, simply and effectively improving the phase state structure and the phase state stability of the polyester/styrene resin, improving the mechanical property of the alloy and being the key for preparing the high-performance polyester/styrene resin alloy.
Disclosure of Invention
Compared with the prior art, the method has the advantages of simplicity, effectiveness, convenience in use, low cost and the like.
The purpose of the invention can be realized by the following technical scheme:
the use of a random multipolymer in the preparation of polyester/styrene resin alloy.
The application of the polynary random copolymer in improving the phase structure and phase stability of polyester/styrene resin alloy.
The polyester/styrene resin alloy with phase state distribution structure and phase state stability is prepared from polyester, styrene resin, a compatilizer and an auxiliary agent; the compatibilizer is a random multipolymer.
The preparation method of the polyester/styrene resin alloy with the phase distribution structure and the phase stability comprises the steps of putting the polyester, the styrene resin, the compatilizer and the auxiliary agent into a high-speed mixer, mixing, discharging, and then extruding and granulating by using a screw extruder to obtain the polyester/styrene resin alloy with the phase distribution structure and the phase stability. For example, polyester, styrene resin, a compatilizer and an auxiliary agent are placed into a high-speed mixer to be mixed for 1-5 minutes at the temperature of 25-90 ℃, discharged and extruded and granulated by a screw extruder, the extrusion processing temperature is 220-260 ℃, the rotation speed of the screw is 180-600 rpm, the rotation speed of the high-speed mixer is 2000rpm, and the length-diameter ratio of the double-screw extruder is 34-40, so that the polyester/styrene resin alloy with a phase distribution structure and phase stability is obtained.
In the invention, the multi-component random copolymer is used as a compatilizer in the preparation of polyester/styrene resin alloy; or in improving the phase structure and phase stability of the polyester/styrene resin alloy. The polynary random copolymer used as the compatilizer is formed by copolymerizing an aromatic vinyl monomer, an acrylonitrile monomer and a methacrylate monomer; in the aromatic vinyl monomer and the acrylonitrile monomer, the weight percentage of the aromatic vinyl monomer is 50 to 90 percent, and the balance is the acrylonitrile monomer; the amount of the methacrylate monomer is 0.1 to 15 percent of the sum of the weight of the aromatic vinyl monomer and the acrylonitrile monomer. Furthermore, in the aromatic vinyl monomer and the acrylonitrile monomer, the weight percentage of the aromatic vinyl monomer is 60 to 80 weight percent, and the balance is the acrylonitrile monomer; the amount of the methacrylate monomer is 0.1 to 10% by weight, preferably 0.2 to 2% by weight, based on the sum of the aromatic vinyl monomer and the acrylonitrile monomer. The multi-element random copolymer is added into polyester/styrene resin alloy as a compatilizer to improve the phase distribution and phase stability of the alloy.
In the invention, the weight percentage of the compatilizer is 0.5-15% of the sum of the weight of the polyester, the weight of the styrene resin and the weight of the compatilizer. The special compatilizer for polyester/styrene resin alloy is simply and effectively prepared by blending with other raw materials and extruding and granulating in the preparation process, is convenient to use, and has excellent phase distribution structure and phase stability while maintaining excellent mechanical property at low cost.
In the invention, the auxiliary agent is selected conventionally, for example, the auxiliary agent is an antioxidant and/or a lubricant, the auxiliary agent does not comprise a compatilizer and a conductive agent, and the dosage of the auxiliary agent is added according to the actual situation, for example, 0.1-1 wt% of the antioxidant and 0.1-0.5 wt% of the lubricant, based on the weight sum of the polyester, the styrene resin and the compatilizer.
In the polyester, the styrene resin and the compatilizer, the weight percentage of the polyester is 30-90%, the weight percentage of the compatilizer is 0.5-15%, and the balance is the styrene resin. The embodiment can confirm that the special compatilizer for improving the phase distribution and stability of the polyester/styrene resin alloy can obtain the alloy with excellent phase distribution structure and phase stability by simple addition on the premise of ensuring the mechanical property of the polyester/styrene resin alloy; particularly, in the polyester/styrene resin alloy, the content of polyester can be adjusted within the range of 30-90%, and the application range is wide.
In the invention, the polyester can be one of polycarbonate, polyethylene terephthalate and polybutylene terephthalate; the styrene resin is one or more of ABS, SAN, ASA and AES, and can be prepared by a bulk method or an emulsion method.
In the invention, the weight average molecular weight of the polynary random copolymer is 20000-100000, and the melt index of 235 ℃/2.16kg is 30-120 g/10 min.
In the present invention, the aromatic vinyl monomer includes a styrenic monomer such as a styrene monomer, an α -methylstyrene monomer, an α -chlorostyrene monomer or a p-methylstyrene monomer; the acrylonitrile monomer comprises acrylonitrile monomer or alpha-methacrylonitrile monomer; the methacrylate can be one or more of methyl methacrylate and glycidyl methacrylate. More preferably, the multi-component random copolymer is selected as the compatilizer, wherein the content of GMA is 0.1 wt% -10 wt%, preferably 0.2 wt% -2 wt%, the mechanical property of the polyester/styrene resin material can be improved to the maximum extent, and the phase structure and the phase stability of the polyester/styrene resin are improved.
Compared with the prior art, the invention has the following beneficial effects:
the compatilizer and the polymer have good coextrusion thermal stability, the problems of precipitation or difficult migration to an interface to reduce the reactivity and the like can be avoided, the content of the reactive functional group is proper, and the occurrence of black spots or gel phenomenon can be easily controlled; is completely thermodynamically compatible with styrenic resins, and does not have the problem of phase separation. The use is convenient, no mother granulation is needed, and no secondary pollution exists; the multi-component random copolymer has high reaction activity, high use efficiency, one third to one half of use cost lower than similar purpose commodities in the market, and excellent cost performance. The application is wide: provides a simple method for improving the phase structure and considering the mechanical property for the recycled polyester/styrene resin.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a comparison of scanning electron micrographs of alloys prepared in examples 5-8;
FIG. 2 is a comparison of multi-axial impact for example 5 and example 8;
FIG. 3 is a comparison of the phase stability (TEM) of the near gate versus the far gate of the injection molded articles of examples 5 and 6;
FIG. 4 is a comparison of the impact performance of the injection molded articles of examples 5 and 6 for near and far gates;
FIG. 5 is a comparison of phase stability of comparative example 5 and example 3 over multiple extrusions;
FIG. 6 is a comparative micrograph of examples 9 to 13.
Detailed Description
The invention discloses a polynary random copolymer used as a compatilizer, which is copolymerized by an aromatic vinyl monomer, an acrylonitrile monomer and a methacrylate monomer; the specific preparation method can be selected according to the prior art, such as:
taking 760g of aromatic vinyl monomer, 240g of acrylonitrile monomer and 10g of methacrylate monomer in example 2 as an example, 500g of aromatic vinyl monomer, 180g of acrylonitrile monomer, 5g of methacrylate monomer and 1500g of deionized water are mixed, stirred and reacted at 70 ℃ for 1 hour, then the rest of the mixture of aromatic vinyl monomer, acrylonitrile monomer and methacrylate monomer is dripped, dropwise addition is completed within 1 hour, reaction is continued for 1 hour, then temperature is raised to 90 ℃ for curing for 1 hour, and discharging, filtering, washing and drying are carried out to obtain the multi-random copolymer which is used as a special compatilizer for improving phase distribution and stability of polyester/styrene resin alloy.
The compatibilizer preparation in the examples below was carried out as such and the raw material additions were adjusted in proportion.
The polyester/styrene resin alloy with phase state distribution structure and phase state stability is prepared from polyester, styrene resin, a compatilizer and an auxiliary agent; the compatibilizer is a random multipolymer. The adjuvants are of conventional choice, such as antioxidants and/or lubricants.
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
Examples 1 to 4
According to the raw material composition ratio of table 1, a special compatilizer for improving the phase distribution and stability of polyester/styrene resin alloy is prepared, and examples 1-4 and 14 are consistent with comparative example 1-2 (the preparation method is consistent with the examples, and the addition is adjusted conventionally). The compatilizers are used for preparing polyester/styrene resin alloys so as to research the improvement of the phase state and the phase state stability of the alloys.
Examples 5 to 9
PC resin is PCI250WP (relative number average molecular weight is 22000 g/mol, glass transition temperature is 140 ℃) from Japan emperor company; the ABS resin is prepared from Korean Jinhu petrochemical P/D190 (with a relative weight average molecular weight of 120000 g/mol, butadiene content of 50 wt%, acrylonitrile content of 15 wt%, and styrene content of 35 wt%).
Putting the components into a high-speed mixer according to a certain proportion, mixing for 3 minutes, discharging, and then extruding and granulating by using a screw extruder, wherein the processing temperature is 220-260 ℃, and the screw revolution is 300 r/min; the speed of the high-speed mixer was 2000rpm, the length-diameter ratio of the twin-screw extruder was 36.
The particles prepared according to the embodiments 5 to 8 are prepared into sheets through conventional injection molding, wherein the sheets are respectively a sample 1 to a sample 4, the samples are subjected to liquid nitrogen cooling and brittle fracture, then a rubber phase is etched, and the cross section is observed through a scanning electron microscope, and the result is shown in a figure 1, so that the blank samples without the compatilizer in the embodiment 2 and the comparative examples 1 and 2 can improve the phase structure, but in comparison, under the condition of the same components, the PC/ABS taking the embodiment 2 as the compatilizer has a finer dispersed phase structure. In combination with the mechanical property data of table 3, a more excellent phase structure also means more excellent mechanical properties, in particular impact strength, although the rubber component is higher in the components of examples 7, 8, the results show that the impact properties of example 5 are more excellent, which benefits mainly from the optimization of the phase structure. The sheet obtained by replacing example 2 in example 5 with example 3 and keeping the rest unchanged (example 15) had an Izod impact strength of 748J/m; the sheet obtained by replacing example 2 in example 5 with example 1 was found to have a decrease in Izod impact strength of 808J/m.
The optimization of the phase state of the invention not only shows advantages on the conventional mechanical property, but also can play a special role in some special application occasions, please see figure 2, the multi-axial impact result shows the destructiveness of the impact, the multi-axial impact result has specificity, the conventional impact property is high, the multi-axial impact property is not necessarily good, and the performance advantages of the invention are obvious. In the multi-axial impact test (ASTM D1709), the sample of example 5 using example 2 as a compatibilizer showed better passage due to the change in phase structure, while examples 6-8 each showed some failure, specifically, 52.2J total energy, total brittleness, 55.3J total energy, 50% toughness, 54.8J total energy, 70% toughness, 56.4J total energy, 100% toughness of example 8; this difference allows the use of PC/ABS alloys in higher grade safety materials.
The injection molded articles of examples 5 and 6 are different in phase structure, and the scanning electron microscope of fig. 3 is combined to sample the injection molded articles of examples 5 and 6 at the position near the gate and the position far from the gate, and the injection molded articles are sliced and analyzed for phase structure by transmission electron microscope to observe the phase stability. In order to illustrate the influence of the compatilizer on the stability of the metallurgical phase distribution, the injection molding part with the length of 30 cm and the width of the standard width of a notch impact sample strip is prepared by adopting a large mold through conventional injection molding, and the sample strip closest to the sprue and the sample strip farthest from the sprue are respectively taken for testing; it can be seen that in the injection mold, the phase structure in example 6 is unstable due to the existence of the shear-tensile force field, and a certain degree of phase agglomeration obviously occurs to the phase structure at the position far from the gate relative to the position near the gate, so that the uniformity of the dispersed phase is reduced; the phase at the far gate position of example 5 still maintained a very good phase structure. This is also directly reflected in the impact strength, as shown in FIG. 4, the distance gate of example 5 reached 831J/m, while the distance gate and near gate sheet of example 6 had a larger performance difference, and it was also found that the distance gate/near gate sheet of example 8 had a larger performance difference than that of example 6. It is mentioned here that the preparation of the samples of the examples of the invention, except for the preparation of the sample length, were of a size consistent with the standard test bars.
It can be seen that the special compatibilizer for improving the phase distribution and stability of polyester/styrene resin alloy disclosed by the invention has more efficient performance, in fig. 5, the phase stability is compared and researched by combining repeated extrusion and granulation, namely, after the first extrusion granulation by a screw extruder, the particles are put into the extruder again to continue granulation, namely secondary extrusion, the above circulation is repeated, the particles obtained by different extrusion times are injected according to the same conventional method, the transmission electron microscope TEM of the alloy sheet is tested, as can be seen from the figure, after the extrusion processing for a plurality of times, the phase of example 3 undergoes some degree of dispersed phase aggregation due to multiple heat-shear history, while example 5 still maintains a better phase structure, so the mechanical properties are more excellent, see table 4, which is a sheet test after conventional injection molding of particles, and the test method is as above.
Examples 9 to 12
The PET resin is selected from a recycled material (with the intrinsic viscosity of 0.65) of a commercially available bottle chip; the ABS resin was selected from Korean Jinhu petrochemical P/D190 (with a relative weight average molecular weight of 120000 g/mol, butadiene content of 50 wt%, acrylonitrile content of 15 wt%, and styrene content of 35 wt%) and Taiwan chemical SAN resin NF2200 (with a relative weight average molecular weight of 120000 g/mol, acrylonitrile content of 24 wt%, and styrene content of 76 wt%) in Taiwan.
Putting the components into a high-speed mixer according to a certain proportion, mixing for 3 minutes, discharging, and then extruding and granulating by using a screw extruder, wherein the processing temperature is 220-260 ℃, and the screw revolution is 500 r/min; the speed of the high-speed mixer was 2000rpm, the length-diameter ratio of the twin-screw extruder was 36.
The particles prepared according to examples 9-13 were subjected to microscopic morphology observation and mechanical property test, respectively, after being conventionally injection molded into sheets, and the cross-sectional SEM morphology is shown in fig. 6. As can be seen from FIG. 6, the phase states of examples 9-11 are superior to those of examples 12, 13, which are related to the structure of the compatibilizer chosen, similar to the results obtained for the two compatibilizers of example 2 compared to comparative example 1 in the PC/ABS system.
This is also true in the PET/ABS system, so example 13 is the worst, as seen from the phase structure. While the phase homogeneity of example 12 is still acceptable, the dispersed phase has a large particle size and the compatibilizer used therein also has GMA functionality, which may be related to MMA in the structure, and this affects the reactivity of GMA due to the presence of MMA, thereby causing a difference in phase. Table 6 shows the mechanical property test data, the test method is as above. The compatibilizer (number average molecular weight 25000) in CN106189167A example was used in place of example 2 in inventive example 10, and the remainder was unchanged to obtain a sheet having a notched impact strength (1/8 inch) of 178J/m; the compatilizer prepared in the prior CN105462149A example 4 is used for replacing the example 2 in the invention example 10, and the rest is unchanged, so that the notch impact strength (1/8 inch) of the obtained sheet is 141J/m; the existing ADR-4370 compatilizer is used for replacing the example 2 in the example 10 of the invention, and the rest is unchanged, so that the notch impact strength (1/8 inch) of the obtained sheet is 152J/m.
In conclusion, the method is simple and feasible, and by taking the multi-component random copolymer as the compatilizer, adding a proper proportion and selecting a proper functional group content, the mechanical property of the polyester/styrene resin material can be effectively improved, and the phase structure of the polyester/styrene resin and the phase stability in the processing process are improved. The multi-element random copolymer has the advantages that the dispersed phase particle size is finer, the deformation is smaller, and the distribution is more uniform through chemical reaction, so that the alloy material can absorb more energy when being acted by external force, and the performance advantages of improving the impact strength, reducing the notch sensitivity and the like are shown. The polybasic random copolymer can be directly mixed with polyester and styrene resin, does not need to be mastered, is easy to use, has low addition amount, and is a method for obtaining high-performance polyester/styrene resin alloy.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (5)
1. The polyethylene terephthalate/styrene resin alloy with phase state distribution structure and phase state stability is prepared from polyethylene terephthalate, styrene resin, a compatilizer and an auxiliary agent; the compatilizer is a polynary random copolymer, and is characterized in that the polynary random copolymer is formed by copolymerizing an aromatic vinyl monomer, an acrylonitrile monomer and a methacrylate monomer; the weight percentage of the aromatic vinyl monomer in the aromatic vinyl monomer and the acrylonitrile monomer is 60 to 80 percent, and the rest is the acrylonitrile monomer; the amount of the methacrylate monomer is 1 percent of the sum of the weight of the aromatic vinyl monomer and the acrylonitrile monomer; the aromatic vinyl monomer is a styrene monomer, an alpha-methyl styrene monomer, an alpha-chlorostyrene monomer or a p-methyl styrene monomer; the acrylonitrile monomer is an acrylonitrile monomer or an alpha-methacrylonitrile monomer; the methacrylate is glycidyl methacrylate; the polyethylene terephthalate/styrene resin composite material comprises, by weight, 30-90% of polyethylene terephthalate, 2% of a compatibilizer and the balance of styrene resin; the weight average molecular weight of the polynary random copolymer is 20000-100000.
2. The polyethylene terephthalate/styrene-based resin alloy having a phase distribution structure and phase stability according to claim 1, wherein the PET resin has an intrinsic viscosity of 0.65; the styrene resin is ABS resin and SAN resin.
3. The polyethylene terephthalate/styrene-based resin alloy with phase distribution structure and phase stability according to claim 2, wherein the ABS resin has a relative weight average molecular weight of 120000 g/mol, and wherein the butadiene content is 50 wt%, the acrylonitrile content is 15 wt%, and the styrene content is 35 wt%; the SAN resin had a relative weight average molecular weight of 120000 g/mol, with an acrylonitrile content of 24% by weight and a styrene content of 76% by weight.
4. The polycarbonate/styrene resin alloy with the phase state distribution structure and the phase state stability is prepared from polycarbonate, styrene resin, a compatilizer and an auxiliary agent; the compatilizer is a polynary random copolymer, and is characterized in that the polynary random copolymer is formed by copolymerizing an aromatic vinyl monomer, an acrylonitrile monomer and a methacrylate monomer; the weight percentage of the aromatic vinyl monomer in the aromatic vinyl monomer and the acrylonitrile monomer is 60 to 80 percent, and the rest is the acrylonitrile monomer; the amount of the methacrylate monomer is 1 percent of the sum of the weight of the aromatic vinyl monomer and the acrylonitrile monomer; the aromatic vinyl monomer is a styrene monomer, an alpha-methyl styrene monomer, an alpha-chlorostyrene monomer or a p-methyl styrene monomer; the acrylonitrile monomer is an acrylonitrile monomer or an alpha-methacrylonitrile monomer; the methacrylate is glycidyl methacrylate; the polycarbonate has a relative number average molecular weight of 22000 g/mol and a glass transition temperature of 140 ℃; the styrene resin is ABS resin; in the polycarbonate, the styrene resin and the compatilizer, the weight percentage of the polycarbonate is 30-90%, the weight percentage of the compatilizer is 1%, and the balance is the styrene resin; the relative weight-average molecular weight of the ABS resin is 120000 g/mol, wherein the weight percentage content of butadiene is 50%, the weight percentage content of acrylonitrile is 15%, and the weight percentage content of styrene is 35%; the weight average molecular weight of the polynary random copolymer is 20000-100000.
5. The polycarbonate/styrenic resin alloy having a phase distribution structure and phase stability according to claim 4, wherein the auxiliary agent is an antioxidant and/or a lubricant.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010404537.XA CN111499791B (en) | 2020-05-13 | 2020-05-13 | Application of multi-random copolymer in improving phase structure and phase stability of polyester/styrene resin alloy |
PCT/CN2020/097305 WO2021227201A1 (en) | 2020-05-13 | 2020-06-20 | Use of multi-element random copolymer in improving phase state structure and phase state stability of polyester/styrenic resin alloy |
KR1020227043721A KR20230009980A (en) | 2020-05-13 | 2020-06-20 | Application of multi-membered random copolymers to improve the state structure and state stability of polyester/styrenic resin alloys |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010404537.XA CN111499791B (en) | 2020-05-13 | 2020-05-13 | Application of multi-random copolymer in improving phase structure and phase stability of polyester/styrene resin alloy |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111499791A CN111499791A (en) | 2020-08-07 |
CN111499791B true CN111499791B (en) | 2021-10-29 |
Family
ID=71868339
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010404537.XA Active CN111499791B (en) | 2020-05-13 | 2020-05-13 | Application of multi-random copolymer in improving phase structure and phase stability of polyester/styrene resin alloy |
Country Status (3)
Country | Link |
---|---|
KR (1) | KR20230009980A (en) |
CN (1) | CN111499791B (en) |
WO (1) | WO2021227201A1 (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104877326A (en) * | 2015-05-14 | 2015-09-02 | 上海日之升新技术发展有限公司 | Special compatilizer for improving hydrolysis heat stability of PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene) alloy and alloy |
CN106189167A (en) * | 2016-07-22 | 2016-12-07 | 佳易容相容剂江苏有限公司 | Efficient anti-static PC/ABS composite and preparation method thereof |
CN108929515A (en) * | 2017-05-27 | 2018-12-04 | 金发科技股份有限公司 | A kind of preparation method of ABS/ polyester alloy composition |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6153307A (en) * | 1998-07-30 | 2000-11-28 | Nova Chemicals Inc. | Compatibilizer and laminates containing said compatibilizer |
US20100152348A1 (en) * | 2006-04-06 | 2010-06-17 | David Abecassis | Nanocompatibilized novel polymer blends |
CN101974218B (en) * | 2010-11-12 | 2012-07-11 | 大河宝利材料科技(苏州)有限公司 | Special plastic/acrylonitrile butadiene styrene (PC/ABS) alloy for notebook computer shell |
CN102181122B (en) * | 2011-01-27 | 2013-07-10 | 上海锦湖日丽塑料有限公司 | ABS (acrylonitrile-butadiene-styrene)/regenerated PET (polyethylene terephthalate) resin composition and preparation method thereof |
CN102719073A (en) * | 2012-07-03 | 2012-10-10 | 上海锦湖日丽塑料有限公司 | Electroplating poly carbonate (PC)/acrylonitrile butadiene styrene (ABS) alloy composition and preparation method thereof |
CN104341732A (en) * | 2013-07-30 | 2015-02-11 | 青岛欣展塑胶有限公司 | High-performance toughened flame retardant PET (polyethylene terephthalate)/ABS (acrylonitrile-butadiene-styrene) alloy and preparation method |
CN104725797B (en) * | 2015-03-27 | 2017-01-18 | 北京石油化工学院 | Method for preparing flame-retardant plastic composite material |
CN104974463A (en) * | 2015-07-31 | 2015-10-14 | 重庆友强高分子材料有限公司 | High-glossiness heat-resistant ABS/PET (acrylonitrile-butadiene-styrene/polyethylene terephthalate) bottle chip composite material and preparation method thereof |
CN105419291B (en) * | 2015-12-24 | 2017-07-21 | 上海锦湖日丽塑料有限公司 | High PC/ABS alloys of a kind of weld bond good appearance intensity and preparation method thereof |
CN108314869B (en) * | 2018-02-12 | 2020-09-29 | 金发科技股份有限公司 | ASA/polyester alloy material and preparation method and application thereof |
CN109504057A (en) * | 2018-10-30 | 2019-03-22 | 广东格瑞新材料股份有限公司 | A kind of antistatic PC-ABS alloy material and preparation method thereof |
-
2020
- 2020-05-13 CN CN202010404537.XA patent/CN111499791B/en active Active
- 2020-06-20 WO PCT/CN2020/097305 patent/WO2021227201A1/en active Application Filing
- 2020-06-20 KR KR1020227043721A patent/KR20230009980A/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104877326A (en) * | 2015-05-14 | 2015-09-02 | 上海日之升新技术发展有限公司 | Special compatilizer for improving hydrolysis heat stability of PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene) alloy and alloy |
CN106189167A (en) * | 2016-07-22 | 2016-12-07 | 佳易容相容剂江苏有限公司 | Efficient anti-static PC/ABS composite and preparation method thereof |
CN108929515A (en) * | 2017-05-27 | 2018-12-04 | 金发科技股份有限公司 | A kind of preparation method of ABS/ polyester alloy composition |
Non-Patent Citations (1)
Title |
---|
苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯对PC/ABS性能的影响;段浩等;《上海塑料》;20150515(第1期);59-62 * |
Also Published As
Publication number | Publication date |
---|---|
CN111499791A (en) | 2020-08-07 |
WO2021227201A1 (en) | 2021-11-18 |
KR20230009980A (en) | 2023-01-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101851345B (en) | Chain extension method of engineering resin and reclaimed material thereof | |
CN101029168B (en) | PC/ABS alloy and its production | |
CN101735579A (en) | High-performance recovered PET/ABS alloy | |
CN108929515B (en) | Preparation method of ABS/polyester alloy composition | |
CN103205104A (en) | Preparation method of POSS (Polyhedral Oligomeric Silsesquioxane) hybridized polylactic acid/polycarbonate alloy | |
CN112679921B (en) | Ionomer composite nucleating agent for PET extrusion foaming and preparation method and application thereof | |
CN111073192B (en) | Lampshade and preparation method thereof | |
ZA200505640B (en) | Solid concentrate composition for polymeric chain extension | |
CN102746632B (en) | Polycarbonate/ABS (acrylonitrile, butadiene and styrene) resin plastic alloy | |
CN108676341A (en) | PC/PMMA/PETG ternary-alloy materials and preparation method thereof | |
CN105754303A (en) | PC/PBT/PET alloy and preparation method thereof | |
CN102942736B (en) | High-glass fiber content reinforced polypropylene material and preparation method thereof | |
CN112442251B (en) | ABS composite material and preparation method and application thereof | |
CN109867918B (en) | Contact antibacterial material with excellent performance and preparation method thereof | |
CN111499791B (en) | Application of multi-random copolymer in improving phase structure and phase stability of polyester/styrene resin alloy | |
CN106939112B (en) | High-gloss HIPS/recycled PET bottle flake composite material and preparation method thereof | |
CN1927932A (en) | Modified polypropylene, preparing process and application thereof | |
CN101497734A (en) | High-performance low-cost ABS/PET alloy material | |
CN109867917B (en) | Tough PET (polyethylene terephthalate) antibacterial composite material and preparation method thereof | |
CN110791072A (en) | Regenerated modified PC/PET alloy and preparation method thereof | |
CN112679900B (en) | High-performance AES/recovered PET/recovered PCTG composite material and preparation method and application thereof | |
CN106995600B (en) | High-reflection low-light-transmission polycarbonate material and preparation method thereof | |
CN105385094A (en) | Low-gloss ABS resin composition and preparation method thereof | |
CN117903530B (en) | Polypropylene modified master batch, modified polypropylene containing same and preparation method and application thereof | |
CN111484721A (en) | Low-temperature impact resistant PC/ABS composite material and preparation method 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 |