CN114085467B - Low-odor low-floating-fiber reinforced AS composite material and preparation method and application thereof - Google Patents

Abstract

The invention discloses a low-odor and low-floating-fiber reinforced AS composite material, and a preparation method and application thereof, wherein the AS composite material comprises the following components in parts by weight: 45-80 parts of AS resin, 10-35 parts of glass fiber, 5-15 parts of wollastonite mineral fiber, 1-5 parts of expandable polymer microsphere, 1-5 parts of compatilizer and 0.1-3 parts of auxiliary agent. By using wollastonite mineral fiber to replace part of glass fiber, the floating fiber exposure can be obviously improved without affecting the mechanical property of the composition, and the dimensional stability is good; the added expandable polymer microspheres are heated and expanded in the injection molding process, so that the plastics are helped to generate uniform micropore structures, and the risk of floating fibers is effectively reduced, and the odor of the composition is effectively reduced; the finally prepared reinforced AS composite material has good dimensional stability, low odor, good product appearance and high mechanical property, and can be widely applied to preparing household appliances and automobile products.

Description

Low-odor low-floating-fiber reinforced AS composite material and preparation method and application thereof

Technical Field

The invention belongs to the technical field of modified plastic processing, and particularly relates to a low-odor and low-floating-fiber reinforced AS composite material, and a preparation method and application thereof.

Background

Styrene-acrylonitrile resin (abbreviated AS resin) is a hard and transparent material, and styrene in the component imparts its hard, transparent and easy-to-process properties; the acrylonitrile component imparts chemical and thermal stability.

Glass fibers are typically incorporated into AS resin systems to increase their strength and resistance to thermal deformation and to reduce the coefficient of thermal expansion. However, due to the addition of the glass fiber, each component has anisotropy, so that the appearance of the product is easy to generate defects such as floating fiber exposure and the like during molding; at present, the problems are mainly solved by reducing the retention length of the glass fiber, but the glass fiber can play a role of filling rather than reinforcing, so that the improvement effect on the overall mechanical property of the material is not obvious.

Moreover, the odor of the glass fiber reinforced AS composite material is usually large, on one hand, the AS resin has more micromolecular impurities in the manufacturing process, the odor is more unpleasant, and the total carbon emission is higher; on the other hand, various compatibilizers are often added in the preparation process of the glass fiber reinforced AS composite material, and unpleasant odors are emitted to different degrees. Patent CN1699460a mentions that the odor solution generated by the process cleavage of resin raw materials, stabilizers, mineral fillers is the addition of nano zinc oxide and nano titanium dioxide. However, these additives generally have a great influence on the mechanical properties of AS alloy materials.

In addition, the reinforced AS compound is generally applied to large-scale workpieces, such AS through-flow of an air conditioner, and poor dimensional stability not only can influence the assembly of the workpieces, but also can cause problems of abnormal sound and the like in the use of the subsequent air conditioner, thereby influencing the experience of users.

In summary, the defects of exposed floating fiber, over-high odor, poor dimensional stability and the like limit the application of the reinforced AS composite material in the fields of automobiles, household appliances and the like. Therefore, developing a low odor, low floating fiber reinforced AS composite material with good dimensional stability has great research significance and application market.

Disclosure of Invention

In order to solve the defects that the floating fiber of the reinforced AS composite material is exposed, the odor is too high, the dimensional stability is poor and the like in the prior art, the invention provides a low-odor low-floating fiber reinforced AS composite material which has good dimensional stability, low odor, good product appearance and good mechanical property; the odor grade is less than or equal to 3, the floating fiber grade is less than or equal to 2, the shrinkage rate is less than or equal to 0.15%, the flexural modulus is more than or equal to 8400MPa, and the fiber can be widely applied to the fields of household appliances, automobiles and the like.

Another object of the present invention is to provide a method for preparing the low odor, low fiber float reinforced AS composite described above.

Another object of the present invention is to provide an application of the low odor, low floating fiber reinforced AS composite material in the preparation of automobiles and home appliances.

In order to achieve the aim of the invention, the invention adopts the following technical scheme:

the low-odor low-floating fiber reinforced AS composite material comprises the following components in parts by weight: 45-80 parts of AS resin, 10-35 parts of glass fiber, 5-15 parts of wollastonite mineral fiber, 1-5 parts of expandable polymer microsphere, 1-5 parts of compatilizer and 0.1-3 parts of auxiliary agent.

In the invention, the low odor and low floating fiber reinforced AS composite material performance improvement is realized by the following modes:

(1) The wollastonite mineral fiber is used for replacing a part of glass fiber, so that the thermal deformation temperature and the dimensional stability are improved while the mechanical property is maintained, the floating fiber exposure can be solved to a certain extent, and the cost can be reduced.

(2) The volume of the expandable polymer microsphere adopted in the invention is greatly expanded by 80-100 times after heating, so as to form a closed-cell hollow structure. The expandable polymer microspheres are heated and expanded in the injection molding process, so that the AS resin is helped to generate a uniform microporous structure, the fluidity of plastics can be improved while the density is reduced, and the temperature of each part of the injection molding part in the molding and cooling processes is more uniform, so that the risk of floating fibers is effectively reduced. In addition, a large number of holes in the micropore structure can adsorb any small molecules generating smell or other volatile matters, so that the smell of the composite material can be effectively reduced.

(3) In the processing process of the resin composite system, the expandable polymer microspheres are mixed with wollastonite mineral fibers, and uniform air holes can be formed in the wollastonite mineral fibers by utilizing the self closed-pore hollow sphere structure after expansion; the method is equivalent to using microspheres as a cell agent to produce porous wollastonite mineral fibers with uniform pore diameters and controllable sizes, thereby greatly improving the surface fiber floating effect of the composite and greatly reducing the odor of the composite.

According to the invention, the expandable polymer microspheres are adopted, and a certain amount of wollastonite mineral fibers are added, so that the problems of fiber floating and odor of the glass fiber reinforced AS composite material can be effectively solved, and the prepared AS composite material has good dimensional stability, low odor, good product appearance and high mechanical property, and can be widely applied to preparation of household appliances and automobile products.

Preferably, the low odor, low floating fiber reinforced AS composite material comprises the following components in parts by weight: 50-60 parts of AS resin, 20-32 parts of glass fiber, 6-12 parts of wollastonite mineral fiber, 1.5-3 parts of expandable polymer microsphere, 2-4 parts of compatilizer and 0.6-1.5 parts of auxiliary agent.

Preferably, the styrene content in the AS resin is 75wt.% to 85wt.%.

Preferably, the glass fibers are at least one of long glass fibers or chopped glass fibers.

Further preferably, the long glass fibers are alkali-free glass fibers having an average diameter of 10 to 16 μm.

Further preferably, the chopped glass fibers have an average length of 0.2 to 10mm and an average diameter of 8 to 20 μm.

Preferably, the wollastonite mineral fiber has an aspect ratio of 8-15:1. Preferably, the expandable polymeric microspheres have a "core-shell" structure.

Further preferably, the inner core of the expandable high molecular microsphere is a high molecular polymer, and the outer shell is a thermoplastic outer shell.

More preferably, the high molecular polymer is a polymer obtained by polymerizing at least one of the following monomers: acrylonitrile, vinyl acetate or acrylic monomers.

More preferably, the thermoplastic shell is a methacrylate; further preferably at least one of methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate or epoxypropyl methacrylate.

Preferably, the D50 particle size of the expandable polymeric microspheres is 15-40 μm.

Preferably, the compatibilizing agent is a maleic anhydride grafted ABS blend.

Further preferably, the compatibilizer has a melt index of 1 to 5g/10min at 200℃under 5kg according to ASTM D-1238-2010 test standard.

Preferably, the auxiliary agent is at least one of a heat stabilizer, a light stabilizer and a lubricant.

Further preferably, the heat stabilizer is at least one of hindered phenols, phosphites or thioesters.

Further preferably, the light stabilizer is at least one of a hindered amine or an ultraviolet absorber.

Further preferably, the lubricant is at least one of stearates, metal soaps or amides.

The invention also provides a preparation method of the low-odor low-floating-fiber reinforced AS composite material, which comprises the following steps:

uniformly mixing AS resin, expandable polymer microspheres, a compatilizer and an auxiliary agent, placing the mixture in a main feeding port, adding glass fiber and wollastonite mineral fiber from a side feeding port, carrying out melt blending, extruding and granulating to obtain the low-odor and low-floating fiber reinforced AS composite material.

Preferably, the melt extrusion conditions are: 180-210 ℃ in the first area, 190-220 ℃ in the second area, 190-230 ℃ in the third area, 190-240 ℃ in the fourth area, 190-240 ℃ in the fifth area, 190-240 ℃ in the sixth area, 190-240 ℃ in the seventh area, 190-240 ℃ in the eighth area, 190-240 ℃ in the ninth area, and 250-600 revolutions per minute of the host machine; the length-diameter ratio of the twin-screw extruder is 40-42:1.

The application of the low-odor and low-floating-fiber reinforced AS composite material in the preparation of automobiles and household appliances is also within the protection scope of the invention.

Compared with the prior art, the invention has the following beneficial effects:

(1) According to the invention, wollastonite mineral fibers are used for replacing part of glass fibers, so that the exposure of floating fibers can be obviously improved without affecting the mechanical properties of the composition, and the dimensional stability is good; the added expandable polymer microspheres are heated and expanded in the injection molding process, so that AS resin is helped to generate a uniform micropore structure, thereby effectively reducing the risk of floating fiber and effectively reducing the odor of the composition; the finally prepared reinforced AS composite material has good dimensional stability, low odor, good product appearance and high mechanical property, and can be widely applied to preparing household appliances and automobile products.

(2) The preparation method of the low-odor low-floating-fiber reinforced AS composite material provided by the invention has the advantages of simple production process and suitability for mass production.

Detailed Description

The invention is further illustrated below with reference to examples. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The experimental procedures in the examples below, without specific details, are generally performed under conditions conventional in the art or recommended by the manufacturer; the raw materials, reagents and the like used, unless otherwise specified, are those commercially available from conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art in light of the above teachings are intended to be within the scope of the invention as claimed.

The reagents selected for each example and comparative example of the present invention are described below:

AS resin:

1. model: NF2200 (styrene content 75 wt.%) manufacturer: taiwan;

2. model: 310TR (styrene content 80 wt.%) manufacturer: korean brocade lake;

3. model: SAN350 (styrene content 70 wt.%) manufacturer: korean brocade lake;

glass fiber:

1. long glass fiber model: ER13-2000-988A (average diameter of glass fibers 13 μm) manufacturer: a boulder group;

2. chopped glass fiber model: ECS-13-4.5 (average length of glass fiber 4.5mm, average diameter 13 μm) manufacturer: shenzhen yataida;

wollastonite mineral fiber:

1. model: AH-0023 (aspect ratio 15:1) manufacturer: jiang Xiao technology;

2. model: AH-0026 (aspect ratio 8:1) manufacturer: jiang Xiao technology;

3. model: SYW-XA 180 (aspect ratio 10:1) manufacturer: the Siyuan mining industry in New city of Jiangxi;

4. model: SYW-XA800 (aspect ratio 30:1) manufacturer: the Siyuan mining industry in New city of Jiangxi;

expandable polymeric microspheres:

1. model: DU1901M-2LG (D50 particle size 20 μm) manufacturer: quick thought technology (Shanghai) Inc.;

2. model: DU180 (D50 particle size 30 μm) manufacturer: quick thought technology (Shanghai) Inc.; non-expandable polymeric microsphere number: porous polymeric copolymer microsphere (D50 particle size 60 μm) manufacturer: north Korea New Material technology Co.Ltd

And (3) a compatilizer:

model: KT-2, maleic anhydride grafted ABS blend (melt index 3.5g/10min (200 ℃, 5 kg)) manufacturer: shenyang Ketong plastics Co., ltd;

auxiliary agent:

heat stabilizer model: irganox 1010 (hindered phenols) is commercially available;

light stabilizer model: TINUV 770 (hindered amine) is commercially available;

lubricant type: erucamide is commercially available;

the AS composite material of each embodiment and the comparative example is prepared by the following steps:

mixing the components in a high-speed mixer for 3min according to the proportion, and uniformly mixing to obtain a premix; placing the premix into a main feeding port of a double-screw extruder, adding glass fibers and wollastonite mineral fibers from a side feeding port, carrying out melt blending, extruding, granulating and drying to obtain the low-odor low-floating-fiber reinforced AS composite material;

wherein, the conditions of melt blending are: the temperature of the first area is 190 ℃, the temperature of the second area is 200 ℃, the temperature of the third area is 210 ℃, the temperature of the fourth area is 220 ℃, the temperature of the fifth area is 220 ℃, the temperature of the sixth area is 230 ℃, the temperature of the seventh area is 230 ℃, the temperature of the eighth area is 230 ℃, the temperature of the ninth area is 230 ℃, and the rotating speed of a host machine is 400 revolutions per minute; the aspect ratio of the twin screw extruder was 40:1.

The performance test method and standard of the low odor, low floating fiber reinforced AS composite material of each example and comparative example of the invention are AS follows:

(1) Tensile strength: testing according to ASTM-D638-2014;

(2) Bending properties: injection molding the sample into a mechanical spline, testing according to ASTM-D790-2017, and bending at a speed of 2mm/min; (3) heat distortion temperature: testing according to ASTM-D648-2016;

(4) Smell: the higher the rating, the greater the odor, according to the De-Guo automobile VW's PV3900E standard, with a rating of 1-6. Table 1 shows the evaluation of the standard PV3900-2019 for controlling odor in automobiles for mass cars, and the scores are divided into 6 grades.

TABLE 1 evaluation criteria for controlling odor in automobiles by mass automobile

Grade	Evaluation of
		1	Odorless
2	Odorous but no disturbing smell
		3	Has obvious smell but no disturbing smell
4	Having a disturbing odour
		5	Has strong disturbing smell
6	With intolerable odour

(5) Fiber floating condition: the composite was injection molded into a panel, the same part (square with length of 15cm and width of 10 cm) of each square was selected, and after about 100-fold amplification by a two-dimensional image measuring instrument, the number of float fibers was calculated, and the float fiber grade was classified into 5 grades in table 2:

TABLE 2 float fiber grading

Fiber grade of float	Number of floating fibers	Determination of
			Level 1	<10	Smooth surface and no floating fiber
Level 2	10-20	Slightly floating fiber
			3 grade	20-40	General floating fiber
Grade 4	40-60	Obvious floating fiber
			Grade 5	>60	Severe float fiber

The floating fiber grade is 1-3, which indicates that the floating fiber is good and can meet the use requirement.

(3) Shrinkage ratio: the test was performed according to ISO 2577-2007.

Examples 1 to 12

This example provides a series of low odor, low fiber float reinforced AS composites with the formulations shown in Table 3.

Table 3 examples 1-12 formulations (parts)

Comparative examples 1 to 5

This comparative example provides a series of AS composites with the formulations shown in Table 4.

Table 4 formulations (parts) of comparative examples 1 to 5

The results of the performance test on the AS composites of each example and comparative example according to the above-mentioned method are shown in table 5.

Table 5 results of performance tests of examples and comparative examples

As can be seen from Table 5, the low odor, low floating fiber reinforced AS composite materials prepared in examples 1-12 of the present invention all have good dimensional stability, low odor, good product appearance and good mechanical properties; the AS composite material prepared has an odor grade less than or equal to 3, a floating fiber grade less than or equal to 2, a shrinkage rate less than or equal to 0.15%, and a flexural modulus greater than or equal to 8400MPa.

As can be seen from the performance test data of comparative examples 1 to 5, the wollastonite mineral fiber is not added in comparative example 1, but the smell thereof is inferior to that of example 1, it is grade 4, and the floating fiber is serious; in comparative example 2, the mechanical properties are drastically deteriorated by adding an excessive amount of wollastonite mineral fiber, since the excessive amount of wollastonite mineral fiber plays a role of filling but not reinforcing; in comparative example 3, the odor is poor and the floating fiber is serious without adding expandable polymer microspheres; comparative example 4, without wollastonite mineral fiber and expandable polymeric microspheres, shows that the corresponding properties, odor and fiber float are all the most severe, and from the comparative data, the expandable polymeric microspheres and wollastonite have synergistic effect on the reduction of odor and improvement of fiber float; in comparative example 5, the addition of non-expandable microspheres not only increased the odor and the fiber suspension, but also had some decay in mechanical properties.

In conclusion, the wollastonite mineral fiber is used for replacing part of glass fiber, so that the exposure of the floating fiber can be obviously improved, the buckling deformation of a finished piece can be reduced, the mechanical property of the composition is not affected, and the dimensional stability is good; the added polymer microspheres are heated and expanded in the injection molding process, so that the plastics are helped to generate uniform micropore structures, the risk of floating fiber is effectively reduced, and the odor of the composition is effectively reduced; the finally prepared reinforced AS composite material has good dimensional stability, low odor, good product appearance and high mechanical property, and can be widely applied to preparing household appliances and automobile products.

Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.

Claims (9)

1. The low-odor low-floating-fiber reinforced AS composite material is characterized by comprising the following components in parts by weight: 45-80 parts of AS resin, 10-35 parts of glass fiber, 5-15 parts of wollastonite mineral fiber, 1-5 parts of expandable polymer microsphere, 1-5 parts of compatilizer and 0.1-3 parts of auxiliary agent,

the length-diameter ratio of the wollastonite mineral fiber is 8-15:1.

2. The low odor, low float fiber reinforced AS composite of claim 1, wherein said low odor, low float fiber reinforced AS composite comprises the following components in parts by weight: 50-60 parts of AS resin, 20-32 parts of glass fiber, 6-12 parts of wollastonite mineral fiber, 1.5-3 parts of expandable polymer microsphere, 2-4 parts of compatilizer and 0.6-1.5 parts of auxiliary agent.

3. The low odor, low float fiber reinforced AS composite of claim 1, wherein said AS resin has a styrene content of 75wt.% to 85wt.%.

4. The low odor, low float fiber reinforced AS composite of claim 1, wherein said glass fibers are at least one of long glass fibers or chopped glass fibers.

5. The low odor, low fiber float reinforced AS composite of claim 1 wherein said expandable polymeric microspheres have a D50 particle size of 15-40 μm.

6. The low odor, low float fiber reinforced AS composite of claim 1, wherein said compatibilizer is a maleic anhydride grafted ABS blend.

7. The low odor, low float fiber reinforced AS composite of claim 1, wherein said auxiliary agent is at least one of a heat stabilizer, a light stabilizer, or a lubricant.

8. The method for preparing the low-odor and low-floating-fiber reinforced AS composite material according to any one of claims 1 to 7, which is characterized by comprising the following steps:

uniformly mixing AS resin, expandable polymer microspheres, a compatilizer and an auxiliary agent, placing the mixture in a main feeding port, adding glass fiber and wollastonite mineral fiber from a side feeding port, carrying out melt blending, extruding and granulating to obtain the low-odor and low-floating fiber reinforced AS composite material.

9. Use of the low odor, low fiber suspension reinforced AS composite material according to any one of claims 1 to 7 for the preparation of automobiles and household appliances.