CN115819899A - Styrene composition with fiber point effect and preparation method thereof - Google Patents
Styrene composition with fiber point effect and preparation method thereof Download PDFInfo
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- CN115819899A CN115819899A CN202211672488.3A CN202211672488A CN115819899A CN 115819899 A CN115819899 A CN 115819899A CN 202211672488 A CN202211672488 A CN 202211672488A CN 115819899 A CN115819899 A CN 115819899A
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Abstract
The invention discloses a styrene composition with a fiber point effect and a preparation method thereof, belonging to the field of engineering plastics. According to the styrene composition product with the fiber point effect, the specific high-melting-point semi-aromatic high-temperature nylon is used as the fiber point, and after the specific type of compatilizer is matched, the fiber point has certain compatibility with a resin matrix, so that the product has a good shearing resistance effect and a good temperature resistance effect, the product has a complete service cycle, can be effectively separated from the resin system during a recovery stage, achieves the effect of high recovery rate, and has high commercial value. The invention also discloses a preparation method of the product and application of the product in preparation of electric appliances and office appliances.
Description
Technical Field
The invention relates to the technical field of engineering plastics, in particular to a styrene composition with a fiber point effect and a preparation method thereof.
Background
Polystyrene (PS) resin has the characteristics of easy processing, excellent dimensional stability, high impact strength and higher rigidity, particularly High Impact Polystyrene (HIPS) resin can be subjected to injection molding, extrusion, thermoforming, rotational molding, blow molding, foam molding and the like, and is widely applied to the product fields of household appliances, electronic appliances, office equipment and the like.
In order to obtain special appearance design effects such as artificial flocking, marble stripe and the like for various groups of resin products including PS resin, natural fibers or chemical fiber dots/fiber wool are introduced into a system as fiber dots in the prior art, for example, in the technical scheme disclosed in CN109486160A, natural green tea powder subjected to surface treatment by organic siloxane is taken as the fiber dots to obtain the artificial flocking surface effect, but the green tea powder is very weak in temperature resistance, easy to degrade and short in service cycle; in the technical scheme disclosed in CN112480544A, cellulose is used as fiber points to obtain the flocking-like effect of the glass fiber reinforced PP material, but the cellulose is easily carbonized and discolored during the processing process, which affects the appearance and mechanical toughness performance.
Meanwhile, the fiber point component is actually an additional 'impurity' component for a system of a resin product, and when the service cycle of the product is complete, the fiber points also have certain influence on the recovery of the product: the technical scheme disclosed in CN114605744A is to obtain nano-filled polypropylene with good touch by using maleic anhydride grafted and modified PET fiber points, but the temperature resistance and shear resistance of the PET fiber points are not high enough, and the problem that the fiber points of complex parts cannot be separated after subsequent recovery cannot be solved.
Disclosure of Invention
Based on the defects in the prior art, the invention aims to provide a styrene composition with a fiber point effect, wherein a specific high-melting-point semi-aromatic high-temperature nylon is used as a fiber point in the product, and after a specific kind of compatilizer is matched, the fiber point has certain compatibility with a resin matrix, so that the product has a good shear resistant effect and a good temperature resistant effect, and can be effectively separated from the resin system in a recovery stage, so that the high-recovery effect is achieved, and the styrene composition has a high commercial value.
In order to achieve the purpose, the invention adopts the technical scheme that:
a styrene composition with a fiber point effect comprises the following components in parts by weight:
80-95 parts of polystyrene resin, 2-5 parts of compatilizer, 3-7 parts of flexibilizer, 0.3-1 part of weather resistant agent and 0.5-5 parts of fiber point;
the fiber point is semi-aromatic high-temperature nylon, and the melting point is more than or equal to 300 ℃;
the compatilizer is at least one of maleic anhydride grafted SEBS copolymer (maleic anhydride grafted hydrogenated polystyrene-polyethylene-polybutylene-polystyrene copolymer) and styrene-maleic anhydride copolymer.
In current resin processing product, the fibrous point that brings the appearance design effect actually belongs to "impurity" composition to the base resin in the resin product, the introduction of this component can cause certain weakening influence to the toughness of product, lead to the resistant shear effect of product not good, traditional fibrous point component does not possess the temperature toleration simultaneously, this leads to the fibrous point can take place to melt even fuse with the resin base body in slow in-process in processing and use, not only influenced appearance design's effect, and when the product was in the recovery stage, the fibrous point can't be followed the resin base body and separated out, the recycle rate of resin base body and fibrous point itself has been reduced.
Based on the situation, the inventor introduces semi-aromatic high-temperature nylon with high melting point into a polystyrene resin matrix as a fiber point, the component has good high-temperature resistance, has a large difference with the melting point of the polystyrene resin, cannot be slowly fused, has the characteristic of easy recovery for the whole product, and can realize component separation only by simple melt extrusion and filtration.
In addition, the selection of the compatilizer is more critical for the product, and the main reason is that the compatilizer can improve the compatibility between the fiber points and the components such as the polystyrene resin, the toughening agent, the weather resisting agent and the like, so that the temperature resistance of the fiber points in the product is better, meanwhile, the fiber points can not generate too large negative influence on the toughness of the polystyrene resin, but if the compatibility between the fiber points and the polystyrene resin is too good, the fiber points and the matrix resin are distributed too uniformly and are difficult to separate in the melt extrusion filtration stage of product recovery, and the recoverability is remarkably reduced, so that the inventor conducts screening, and when the maleic anhydride grafted SEBS copolymer and the styrene-maleic anhydride copolymer are used as the compatilizer, the shearing resistance, the temperature resistance and the recoverability of the product can be both matched with the fiber points.
Preferably, the styrene-maleic anhydride copolymer has a maleic anhydride content of 20 to 25%, and the maleic anhydride graft SEBS copolymer has a maleic anhydride graft ratio of 1 to 2%.
Preferably, the semi-aromatic high temperature nylon is at least one of poly (paraphenylene terephthalamide) (PA 10T) and poly (hexamethylene terephthalamide) (PA 6T).
Although the content of the semi-aromatic high-temperature nylon as the fiber point is less, the physical and chemical properties of the semi-aromatic high-temperature nylon directly influence the service performance and appearance performance of the product. Through screening, compared with other high-melting-point nylons with the temperature of more than 300 ℃, the PA10T and the PA6T can enable the product to have better shearing resistance and fiber point temperature resistance after introducing the components of the product. In addition, PA10T also has bio-based property, and the environment-friendly property of recycling the component is higher. Meanwhile, when the semi-aromatic high-temperature nylon is used as fiber points, the appearance, the size and the color of the fiber points can be adjusted according to the requirement of the appearance effect of a product, the prepared styrene composition product has the dot or sheet fiber point effect, has enough fiber point length, and has different particle visual effects from those of green tea powder and the like adopted in the existing products.
Preferably, the average particle diameter of the fiber dots is 0.3 to 1.0mm.
Preferably, the polystyrene resin has a melt flow rate of 3 to 8g/10min at 200 ℃ under a load of 5kg according to the determination standards of ISO 1133-1-2011 plastic- -thermoplastic melt mass flow rate and melt volume flow rate.
More preferably, the polystyrene resin is high impact polystyrene.
More preferably, the high impact polystyrene is a mixture of virgin high impact polystyrene having a melt flow rate of 4 to 8g/10min at 200 ℃ under a 5kg load and recycled high impact polystyrene having a melt flow rate of 3 to 5g/10min at 200 ℃ under a 5kg load.
In the styrene composition product of the present invention, in order to ensure the toughness of the product, it is preferable to use HIPS resin with low fluidity and high impact resistance as the matrix resin, wherein in order to increase the environmental protection and environmental friendliness of the product, a new material and a reclaimed material with similar melt flow rate can be selected and matched with each other.
Preferably, the toughening agent is a styrene-butadiene-styrene block copolymer, and the butadiene content is more than or equal to 60%; the weather-resistant agent is a mixture of a hindered amine light stabilizer and a benzotriazole ultraviolet light absorber.
Preferably, the components of the fiber point effect styrene composition also comprise 0 to 4 parts of processing aid.
More preferably, the processing aid is at least one of an antioxidant and a lubricant.
More preferably, the antioxidant is at least one of hindered phenol antioxidants and phosphite antioxidants, and the lubricant is at least one of amide lubricants, silicone lubricants, stearic acid lubricants and organic wax lubricants.
Another object of the present invention is to provide a method for preparing the styrene composition having the fiber point effect, comprising the steps of:
and after uniformly mixing all the components, putting the components into a double-screw extruder for melting, blending, extruding, performing vacuum extraction treatment, and then granulating and drying to obtain the styrene composition with the fiber point effect.
Preferably, the preparation method of the fiber dots comprises the following steps: melting the semi-aromatic high-temperature nylon in a double-screw extruder, adding color powder for coloring, extruding and granulating, and then grinding into punctiform or flaky fiber dots. The preparation method of the product has simple operation steps, and the produced product has high quality and high purity, is convenient to use and recycle, and can realize industrial mass production.
Preferably, the processing temperature of the double-screw extruder in the melt blending extrusion stage is set to be 120-230 ℃, the processing temperature of a first zone and a second zone is set to be 120-190 ℃, the processing temperature of a third zone to a fifth zone is set to be 180-230 ℃, and the processing temperature of a sixth zone to a tenth zone is set to be 190-230 ℃; the screw rotation speed is set to 350-450 rpm.
The invention also aims to provide application of the styrene composition with the fiber point effect in preparing electric appliances and office appliances.
Generally speaking, plastic part products related in the fields of electric appliances and office appliances have higher requirements on appearance design, which is also the reason that plastic products containing fiber points are popular in the fields, and the styrene composition with the fiber point effect not only has good appearance fiber point effect, but also has good shearing resistance and temperature resistance, and the stability of the fiber points is higher; after the product has a complete service cycle, the resin matrix and the fiber points can be separated and recovered by a simple recovery means, the practicability, the economic benefit and the environmental protection are far higher than those of the existing products of the same type, and the product has higher commercial value.
The styrene composition with the fiber point effect has the beneficial effects that the styrene composition with the fiber point effect is provided, the specific high-melting-point semi-aromatic high-temperature nylon is used as the fiber point in the product, and after the compatilizer of a specific type is matched, the fiber point has certain compatibility with a resin matrix, so that the product has a good shearing resistance effect and a good temperature resistance effect, the product can be effectively separated from the resin system in a recycling stage after the service cycle of the product is complete, the high-recovery effect is achieved, and the commercial value is high.
Detailed Description
In order to better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples and comparative examples, which are intended to be understood in detail, but not intended to limit the invention. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of protection of the present invention. The experimental reagents and instruments involved in the practice of the present invention are, unless otherwise specified, common reagents and instruments.
Examples 1 to 11
The styrene composition having the fiber point effect and the preparation method thereof according to the present invention have the following components as shown in table 1.
The preparation method of the styrene composition comprises the following steps:
after uniformly mixing all the components, putting the components into a double-screw extruder for melt blending and extrusion, performing vacuum extraction treatment by adopting a double-vacuumizing system to remove generated small molecular gas, and performing underwater granulation and vacuum drying to obtain the styrene composition with the fiber point effect.
The preparation method of the fiber dots comprises the following steps: melting the semi-aromatic high-temperature nylon in a double-screw extruder, adding color powder for coloring, extruding and granulating, and then grinding into punctiform or flaky fiber dots.
The processing temperature of the double-screw extruder in the melt blending extrusion stage is set to be 120-230 ℃, the processing temperature of a first zone and a second zone is set to be 120-190 ℃, the processing temperature of a third zone to a fifth zone is set to be 180-230 ℃, and the processing temperature of a sixth zone to a tenth zone is set to be 190-230 ℃; the screw rotation speed is set to 350-450 rpm.
Comparative examples 1 to 6
The comparative examples differ from the examples only in the type and ratio of the components, as shown in Table 2.
In the components described in the examples and comparative examples,
HIPS new material resin: PS350K produced by petrochemical engineering of national georges has a melt flow rate of 5g/10min at 200 ℃ under a load of 5 kg;
HIPS recycled resin: LRHPS-BCWA1134 (KS), produced by Guangdong gold hair technology, having a melt flow rate of 4g/10min at 200 ℃ under a 5kg load;
a toughening agent: GLOBALPRENE 3566, a styrene-butadiene-styrene block copolymer produced by luo chang chemical industry, having a butadiene content of about 60%;
1 part of compatilizer: SZ23110, a styrene-maleic anhydride copolymer produced by Polyscope, having a maleic anhydride content of 23%;
a compatilizer 2: globalprene 9901 produced by Liangrong chemical industry, and a maleic anhydride grafted SEBS copolymer, wherein the grafting rate of the maleic anhydride is 1.6 percent;
compatilizer 3: SEBS 7551 produced by lugore chemical industry, styrene-ethylene-butylene-styrene block copolymer;
a compatilizer 4: the toughening compatilizer has an excellent and easily produced SBG-001 and butadiene-GMA core-shell structure;
fiber point 1: vicnyl 600P and PA10T resin produced by the special engineering plastics Co., ltd, the melting point of which is 316 ℃;
fiber point 2: vicyl 400P and PA6T resin produced by Zhuhaiwantong special engineering plastics Limited have the melting point of 308 ℃;
fiber point 3: the melting point of the Genestar N1001A and PA9T resin produced by Coly is 300 ℃;
fiber point 4: XTR31S and PA4T resin produced by Tesmann, the melting point is 320 ℃;
fiber point 5: the melting point of SB500 and PET modified resin produced by chemical industry is 260 ℃;
weather resisting agent: a mixture compounded by a commercially available hindered amine light stabilizer and a benzotriazole ultraviolet light absorber according to the mass ratio of 1;
antioxidant: a mixture compounded by a commercially available hindered phenol antioxidant and a phosphite antioxidant according to the mass ratio of 1;
lubricant: commercially available vinyl bis stearamide;
the component materials used in the examples of the present invention and the comparative examples were all commercially available materials unless otherwise specified, and the component materials used in the respective parallel experiments were the same. The fiber dots used in the examples and comparative examples of the present invention were prepared by melting, coloring, extruding, granulating, and finally grinding the corresponding resins into dots or sheets having an average particle size of 0.5mm, through the above-mentioned steps of preparing the fiber dots, before preparing the styrene composition product.
TABLE 1
TABLE 2
Effect example 1
In order to verify the properties of the styrene compositions of the fiber point effect of the present invention, the following property tests were performed on each of the examples and comparative examples, and the specific steps were as follows:
(1) Notched impact strength test: testing the impact strength of a cantilever notch of each product according to ISO 180-2000, wherein the test notch is an A-type notch;
(2) Fiber point temperature resistance test: respectively carrying out injection molding on each product at the injection molding temperature of 240-250 ℃ at the speed of 50mm/s and 300mm/s to form a color plate, and testing the average length of fiber points on the surface of the color plate by using a fiber length distribution tester, wherein the retention (%) of the average length is calculated according to the formula: (average length of 300 mm/s/average length of 50 mm/s). Times.100%.
(3) Fiber point separation rate test during recovery: crushing the injection-molded products (including but not limited to sample strips, color plates and other products) of each product into sheets by a crusher, performing single-screw melt extrusion filtration, setting the melting temperature at 200-230 ℃, filtering by using a 100-200 mesh filter screen, weighing the weight of the products before and after filtration, and obtaining the separation rate of fiber points, wherein the calculation formula of the separation rate (%) is as follows: (weight of product before filtration-weight of product after filtration)/weight of product before filtration ÷ weight of fiber point in the product formulation × 100%.
The test results are shown in tables 3 and 4.
TABLE 3
TABLE 4
| Test items | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 |
| Notched impact Strength (KJ/m) 2 ) | 13.7 | 6.8 | 8.2 | 12.3 | 8 | 9.3 |
| Fiber point average length retention (%) | -- | 88.1 | 92.5 | 95.8 | 63.9 | 95.5 |
| Fiber point separation Rate% | -- | 96.1 | 95.2 | 73.5 | 25.1 | 68.8 |
As can be seen from tables 3 and 4, the products obtained in the examples all have a good combination of properties: the notch impact strength can reach 10KJ/m 2 As described above, the average length retention rate of the fiber dots can reach 90% or more, and the separation rate of the fiber dots during recovery can reach 90% or more, and it can be seen from examples 4 and 9 to 11 that the solution of the present invention can achieve the expected product effect by using the semi-aromatic high temperature nylon with a high melting point as the fiber dots, and the best use effect of PA10T and PA6T can be obtained. As can be seen from example 2, comparative example 1 and comparative example 2, at an appropriate content, the introduction of the fiber point has no great influence on the toughness of the resulting styrene composition, but if the content is excessive, the toughness of the product is lowered and the product is not shear-resistant; from comparative examples 3 and 4, when the semi-aromatic high temperature nylon is selected as the fiber point component, the compatilizer matched with the semi-aromatic high temperature nylon is very important, compatibility among product components and recovery efficiency of fiber points and resin in the product need to be considered, and improper selection can cause obvious reduction of product toughness or deterioration of fiber point separation efficiency during product recovery; as can be seen from comparative example 6, even if a proper kind of compatibilizer is selected, if the content is excessively increased, the fibrous dots and the matrix resin are likely to be causedThe combination degree of the components is too high, so that the separation and recovery effects of the subsequent process are influenced; as can be seen from the comparative example 5, the conventional commonly used PET fiber point cannot meet good temperature resistance and recovery performance, and meanwhile, the component has a large influence on the toughness of the matrix resin in the product, so that the semi-aromatic high-temperature nylon fiber point can be perfectly replaced.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. The styrene composition with the fiber point effect is characterized by comprising the following components in parts by weight:
80-95 parts of polystyrene resin, 2-5 parts of compatilizer, 3-7 parts of flexibilizer, 0.3-1 part of weather resistant agent and 0.5-5 parts of fiber point;
the fiber point is semi-aromatic high-temperature nylon, and the melting point is more than or equal to 300 ℃;
the compatilizer is at least one of maleic anhydride grafted SEBS copolymer and styrene-maleic anhydride copolymer.
2. The fiber point-effect styrene composition according to claim 1, wherein the semi-aromatic high temperature nylon is at least one of poly (decamethylene terephthalamide) and poly (hexamethylene terephthalamide).
3. The fiber point effect styrene composition according to claim 1, wherein the polystyrene resin has a melt flow rate of 3 to 8g/10min at 200 ℃ under a load of 5 kg.
4. The fiber point effect styrenic composition of claim 3 wherein the polystyrene resin is a high impact polystyrene and the high impact polystyrene is a blend of virgin high impact polystyrene having a melt flow rate of 4 to 8g/10min at 200 ℃ under a 5kg load and recycled high impact polystyrene having a melt flow rate of 3 to 5g/10min at 200 ℃ under a 5kg load.
5. The fiber point effect styrene composition of claim 1, wherein the toughening agent is a styrene-butadiene-styrene block copolymer having a butadiene content of 60% or more; the weather-resistant agent is a mixture of a hindered amine light stabilizer and a benzotriazole ultraviolet light absorber.
6. The fiber point-effect styrene composition according to claim 1, wherein the fiber point-effect styrene composition further comprises 0 to 4 parts of a processing aid; the processing aid is at least one of an antioxidant and a lubricant.
7. A method for preparing a fiber point effect styrene composition according to any one of claims 1 to 6, comprising the steps of:
and after uniformly mixing all the components, putting the components into a double-screw extruder for melting, blending, extruding, performing vacuum extraction treatment, and then granulating and drying to obtain the styrene composition with the fiber point effect.
8. The method for preparing a fiber point effect styrene composition according to claim 7, wherein the twin-screw extruder is set to have a processing temperature of 120 to 230 ℃ in the melt-blending extrusion stage, wherein the processing temperatures of the first zone and the second zone are set to be 120 to 190 ℃, the processing temperatures of the third zone to the fifth zone are set to be 180 to 230 ℃, and the processing temperatures of the sixth zone to the tenth zone are set to be 190 to 230 ℃; the screw rotation speed is set to 350-450 rpm.
9. Use of the fiber point effect styrene composition according to any one of claims 1 to 6 for the preparation of electrical appliances and office equipment.
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