CN111499791A

CN111499791A - Application of multi-random copolymer in improving phase structure and phase stability of polyester/styrene resin alloy

Info

Publication number: CN111499791A
Application number: CN202010404537.XA
Authority: CN
Inventors: 段浩; 朱从山; 司胜仁
Original assignee: Jiayirong Polymer Shanghai Co ltd
Current assignee: Jiayirong Polymer Shanghai Co ltd
Priority date: 2020-05-13
Filing date: 2020-05-13
Publication date: 2020-08-07
Anticipated expiration: 2040-05-13
Also published as: CN111499791B; WO2021227201A1; KR20230009980A

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

Application of multi-random copolymer in improving phase structure and phase stability of polyester/styrene resin alloy

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 invention, the aromatic vinyl monomer comprises a styrene monomer, such as a styrene monomer, α -methyl styrene monomer, α -chlorostyrene monomer or p-methyl styrene monomer, the acrylonitrile monomer comprises an acrylonitrile monomer or α -methacrylonitrile monomer, the methacrylate can be one or more of methyl methacrylate and glycidyl methacrylate, more preferably, a polynary random copolymer is selected as a compatilizer, wherein the content of GMA is 0.1-10 wt%, preferably 0.2-2 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 120000g/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 120000g/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 120000g/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

1. The application of the polynary random copolymer in preparing polyester/styrene resin alloy or the application of the polynary random copolymer in improving the phase structure and the phase stability of the polyester/styrene resin alloy is characterized in that the polynary random copolymer is formed by copolymerizing aromatic vinyl monomers, acrylonitrile monomers and methacrylate monomers.

2. Use according to claim 1, wherein the polyester/styrene based resin alloy is prepared from polyester, styrene based resin, compatibilizer, and auxiliaries.

3. The use of claim 1, wherein the aromatic vinyl monomer comprises a styrene monomer, the acrylonitrile monomer comprises an acrylonitrile monomer or α -methacrylonitrile monomer, and the methacrylate is one or more of methyl methacrylate and glycidyl methacrylate.

4. The use according to claim 1, wherein the weight percentage of the aromatic vinyl monomer in the aromatic vinyl monomer and the acrylonitrile monomer is 50 to 90 wt%, 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.

5. The use according to claim 1, wherein the polyester is one of polycarbonate, polyethylene terephthalate, polybutylene terephthalate; the styrene resin is one or more of ABS, SAN, ASA and AES.

6. 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 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.

7. The polyester/styrene resin alloy with phase distribution structure and phase stability of claim 6, wherein the weight percentage of the aromatic vinyl monomer in the aromatic vinyl monomer and the acrylonitrile monomer is 50 wt% to 90 wt%, 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.

8. The polyester/styrene resin alloy with the phase distribution structure and the phase stability as claimed in claim 6, wherein the polyester, the styrene resin and the compatibilizer comprise 30-90 wt% of the polyester, 0.5-15 wt% of the compatibilizer and the balance of the styrene resin.

9. A polybasic random copolymer obtained 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.

10. The polynary random copolymer as claimed in claim 9, wherein the aromatic vinyl monomer comprises a styrene monomer, the acrylonitrile monomer comprises an acrylonitrile monomer or α -methacrylonitrile monomer, and the methacrylate is one or more of methyl methacrylate and glycidyl methacrylate.