CN114085467A - Low-odor and 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 AS well AS 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 partial glass fiber, the exposure of floating fiber can be obviously improved without influencing the mechanical property of the composition, and the dimensional stability is good; the added expandable polymer microspheres are heated to expand in the injection molding process, so that the plastic is helped to generate a uniform microporous structure, the risk of fiber floating is effectively reduced, and the smell 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 preparation of household appliances and automobile products.

Description

Low-odor and 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 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 composition imparts the characteristics of hardness, transparency and easy processing; the acrylonitrile component imparts chemical and thermal stability to the composition.

Glass fibers are generally added to 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, the components have anisotropy, so that the appearance of a product is easy to have the defects of exposed floating fibers and the like during molding; these problems are currently mainly solved by reducing the retention length of the glass fibers, but this in turn causes the glass fibers to act more as fillers than reinforcements, and the improvement effect on the overall mechanical properties of the material is not significant.

Moreover, the glass fiber reinforced AS composite material has a large odor, on one hand, in the process of manufacturing the AS resin, more small molecular impurities exist, the odor is more unpleasant, and the total carbon emission is higher; on the other hand, various compatilizers are often added in the preparation process of the glass fiber reinforced AS composite material, and the bad smell is emitted to different degrees. Patent CN1699460A mentions that resin raw materials, stabilizers, mineral fillers and processing cracking generate odor solution by adding nano zinc oxide and nano titanium dioxide. However, these additives generally have a great influence on the mechanical properties of the AS alloy material.

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

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

Disclosure of Invention

In order to overcome the defects that the exposure of floating fibers of a reinforced AS composite material cannot be ensured, the odor is too high, the dimensional stability is poor and the like in the prior art, the invention provides the low-odor low-floating-fiber reinforced AS composite material, and the AS composite material has good dimensional stability, low odor, good product appearance and good mechanical property; the odor grade is less than or equal to 3 grades, the floating fiber grade is less than or equal to 2 grades, the shrinkage rate is less than or equal to 0.15 percent, and the flexural modulus is more than or equal to 8400MPa, so that the composite material can be widely applied to the fields of household appliances, automobiles and the like.

The invention also aims to provide a preparation method of the low-odor low-floating-fiber reinforced AS composite material.

The invention also aims to provide application of the low-odor low-floating-fiber reinforced AS composite material in preparation of automobiles and household electrical appliances.

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

a low-odor and 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.

According to the invention, the performance improvement of the low-odor and low-floating-fiber reinforced AS composite material is realized by the following components:

(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 problem of exposed floating fiber can be solved to a certain extent, and the cost can be reduced.

(2) The expandable polymer microspheres adopted in the invention expand by 80-100 times after being heated, so as to form a closed-cell hollow structure. The expandable polymer microspheres expand by heating in the injection molding process, help AS resin generate a uniform microporous structure, reduce the density and improve the flowability of the plastic, so that the temperature of each part of an injection molding part is more uniform in the molding and cooling processes, and the risk of fiber floating is effectively reduced. In addition, a large number of holes contained in the microporous structure can adsorb any small molecules generating odor or other volatile matters, so that the odor 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 a closed-pore hollow sphere structure of the expanded expandable polymer microspheres; the method is equivalent to the method for producing the porous wollastonite mineral fiber with uniform pore diameter and controllable size by using the microsphere as a cell agent, 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 fiber is 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 size 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 and 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 content of styrene in the AS resin is 75 wt.% to 85 wt.%.

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 and have 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 length-diameter ratio of the wollastonite mineral fiber is 8-15: 1. Preferably, the expandable polymeric microspheres have a "core-shell" structure.

Further preferably, the core of the expandable polymeric microsphere is a polymeric compound, and the shell is a thermoplastic 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; more preferably at least one of methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and glycidyl methacrylate.

Preferably, the D50 particle size of the expandable polymer microsphere is 15-40 μm.

Preferably, the compatibilizer is a maleic anhydride grafted ABS blend.

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

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 a stearate, a metal soap, or an amide.

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

and (2) uniformly mixing the AS resin, the expandable polymer microspheres, the compatilizer and the auxiliary agent, placing the mixture into a main feeding port, adding the glass fiber and the wollastonite mineral fiber from a side feeding port, carrying out melt blending, and carrying out extrusion granulation to obtain the low-odor and low-floating-fiber reinforced AS composite material.

Preferably, the melt extrusion conditions are: the first zone temperature is 180-; the length-diameter ratio of the double-screw extruder is 40-42: 1.

The application of the low-odor low-floating-fiber reinforced AS composite material in the preparation of automobiles and household electrical 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 influencing the mechanical property of the composition, and the dimensional stability is good; the added expandable polymer microspheres are heated to expand in the injection molding process, so that the AS resin is helped to generate a uniform microporous structure, the risk of fiber floating is effectively reduced, and the smell 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 preparation of household appliances and automobile products.

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

Detailed Description

The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.

The reagents selected for the examples and comparative examples of the present invention are illustrated below:

AS resin:

1. the model is as follows: NF2200 (styrene content 75 wt.%): taiwan taiwanese;

2. the model is as follows: 310TR (styrene content 80 wt.%): korea brocade lake;

3. the model is as follows: SAN350 (styrene content 70 wt.%): korea brocade lake;

glass fiber:

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

2. type of chopped glass fiber: ECS-13-4.5 (average length of glass fibers 4.5mm, average diameter 13 μm) manufacturer: shenzhen ya Taida;

wollastonite mineral fiber:

1. the model is as follows: AH-0023 (aspect ratio 15: 1): jiangxi Oyt science and technology;

2. the model is as follows: AH-0026 (aspect ratio of 8: 1): jiangxi Oyt science and technology;

3. the model is as follows: SYW-XA 180 (aspect ratio 10:1) manufacturer: the West New City thought distant mining industry;

4. the model is as follows: SYW-XA800 (aspect ratio 30:1) manufacturer: the West New City thought distant mining industry;

expandable polymeric microspheres:

1. the model is as follows: DU1901M-2LG (D50 particle size 20 μm) manufacturer: fast-thinking technologies (shanghai) ltd;

2. the model is as follows: DU180(D50 particle size 30 μm) manufacturer: fast-thinking technologies (shanghai) ltd; the type of the non-expandable polymer microsphere is as follows: porous polymer copolymer microspheres (D50 particle size 60 μm) manufacturer: suzhou Beike Material science and technology Co., Ltd

A compatilizer:

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

auxiliary agent:

the types of the heat stabilizer are as follows: irganox 1010 (hindered phenol) is commercially available;

light stabilizer types: TINUV 770 (hindered amines) are commercially available;

the type of the lubricant is as follows: erucamide is commercially available;

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

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

wherein the conditions of melt blending are as follows: the temperature of a first zone is 190 ℃, the temperature of a second zone is 200 ℃, the temperature of a third zone is 210 ℃, the temperature of a fourth zone is 220 ℃, the temperature of a fifth zone is 220 ℃, the temperature of a sixth zone is 230 ℃, the temperature of a seventh zone is 230 ℃, the temperature of an eighth zone is 230 ℃, the temperature of a ninth zone is 230 ℃, and the rotating speed of a main engine is 400 revolutions per minute; the length-diameter ratio of the twin-screw extruder is 40: 1.

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

(1) tensile strength: testing was performed according to ASTM-D638-2014;

(2) bending property: the sample is injected and molded into a mechanical sample strip, and the mechanical sample strip is tested according to ASTM-D790-2017, wherein the bending speed is 2 mm/min; (3) heat distortion temperature: testing was performed according to ASTM-D648-2016;

(4) odor: according to the standard of VW's PV3900E of Germany popular automobile company, the evaluation is carried out on a 1-6 grade, and the higher the grade is, the larger the smell is. Table 1 shows the evaluation contents of the standards PV3900-2019 for controlling the odor in the automobiles of the public automobiles, and the scores are divided into 6 grades.

TABLE 1 evaluation criteria for controlling odor in automobiles by popular automobiles

Grade	Evaluation of
		1	Has no odor
2	Odorous, but non-interfering, odors
		3	Has obvious smell but no interfering smell
4	Has interfering odor
		5	Has strong interfering smell
6	Has intolerable odor

(5) Fiber floating condition: the compound was injection molded into color plaques, the same portions of each square plaque (squares 15cm long by 10cm wide) were selected, placed approximately 100 times with a two-dimensional image measuring instrument, the number of floating fibers was calculated, and the floating fiber grades were classified into 5 grades in table 2:

TABLE 2 Floating fiber rating

Float fiber grade	Number of floating fibers	Determination
			Level 1	<10	Smooth surface and no floating fiber
Stage 2	10-20	Light micro-floating fiber
			Grade 3	20-40	General floating fiber
4 stage	40-60	Apparent floating fiber
			Grade 5	>60	Severely floated fibrils

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

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

Examples 1 to 12

This example provides a series of low odor, low fiber-floating reinforced AS composites having the formulation shown in Table 3.

TABLE 3 examples 1 to 12 formulations (parts)

Comparative examples 1 to 5

This comparative example provides a series of AS composites having the formulation shown in Table 4.

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

The results of the performance test of the AS composite materials of each example and comparative example according to the above-mentioned method are shown in Table 5.

TABLE 5 results of Performance test of each example and comparative example

As can be seen from Table 5, the low-odor and low-floating-fiber reinforced AS composite materials prepared in the embodiments 1 to 12 of the invention have good dimensional stability, low odor, good product appearance and good mechanical properties; the odor grade of the prepared AS composite material is less than or equal to 3 grades, the floating fiber grade is less than or equal to 2 grades, the shrinkage rate is less than or equal to 0.15 percent, and the flexural modulus is more than or equal to 8400 MPa.

From the performance test data of comparative examples 1-5, it can be seen that wollastonite mineral fiber is not added in comparative example 1, although the mechanical property is similar to that of example 1, the odor is poor and is grade 4, and the floating fiber is serious; in comparative example 2, the mechanical properties are rapidly deteriorated due to the addition of excessive wollastonite mineral fibers, which play a role in filling but not reinforcing; in comparative example 3, expandable polymer microspheres are not added, so that the odor is poor and the fiber floating is serious; comparative example 4 without wollastonite mineral fiber and expandable polymer microsphere, the corresponding performance, odor and floating fiber are most serious, and the expandable polymer microsphere and wollastonite are found to have synergistic effect on the odor reduction and the floating fiber improvement from the performance comparison data; in comparative example 5, the addition of non-expandable microspheres not only resulted in a more severe odor and fiber floating, but also in some attenuation of mechanical properties.

In conclusion, the wollastonite mineral fiber is used for replacing part of glass fiber, so that the exposure of floating fiber can be obviously improved, the warping deformation of a workpiece is reduced without influencing the mechanical property of the composition, and the dimensional stability is good; the added polymer microspheres are heated to expand in the injection molding process, so that the plastic is helped to generate a uniform microporous structure, the risk of fiber floating is effectively reduced, and the smell 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 preparation of household appliances and automobile products.

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 (10)

1. The low-odor and 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.

2. The low odor, low fiber-bloom reinforced AS composite of claim 1 wherein the low odor, low fiber-bloom 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 fiber-floating reinforced AS composite of claim 1, wherein the amount of styrene in the AS resin is from 75 wt.% to 85 wt.%.

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

5. The low odor, low fiber-floating reinforced AS composite of claim 1 wherein the wollastonite mineral fibers have an aspect ratio of 8 to 15: 1.

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

7. The low odor, low fiber-floating reinforced AS composite of claim 1 wherein the compatibilizer is a maleic anhydride grafted ABS blend.

8. The low odor, low fiber bleed reinforced AS composite of claim 1 wherein said adjunct is at least one of a heat stabilizer, a light stabilizer, or a lubricant.

9. The method for preparing the low-odor and low-floating-fiber reinforced AS composite material AS claimed in any one of claims 1 to 8, comprising the steps of:

and (2) uniformly mixing the AS resin, the expandable polymer microspheres, the compatilizer and the auxiliary agent, placing the mixture into a main feeding port, adding the glass fiber and the wollastonite mineral fiber from a side feeding port, carrying out melt blending, and carrying out extrusion granulation to obtain the low-odor and low-floating-fiber reinforced AS composite material.

10. Use of the low odor, low fiber-floating reinforced AS composite material of any one of claims 1 to 8 in the preparation of automotive and household electrical products.