CN104530634B - Environment-friendly type regenerates ABS flame-proof modified compositions and preparation method and application at high proportion - Google Patents

Abstract

ABS flame-proof modified compositions and its preparation and application are regenerated at high proportion the invention discloses a kind of environment-friendly type, and the formula of regeneration ABS flame-proof modified compositions is 70 parts of r ABS, high rigidity ABS resin 30, environmentally friendly bromide fire retardant：10 25 parts；Antimony system fire retarding synergist：01 parts；Phosphorous flame-retardant synergist：15 parts；Toughener：5 15 parts；Compatilizer：13 parts；Inorganic particle：15 parts；Wherein, the environmentally friendly bromide fire retardant is three (tribromo phenyl) cyanurates.The present invention also provides the preparation method and applications of above-mentioned regeneration ABS flame-proof modified compositions.R ABS materials of the present invention remain to keep higher mechanical property and fire resistance after flame-retardant modified, while having extremely low cost.It is adapted to the popularization and application in each needs flame retardant area such as household electrical appliance, communications and transportation, communication.

Description

Environment-friendly high-ratio recycled ABS flame-retardant modified composition and its preparation method and application

technical field

The invention relates to the technical field of modified ABS, in particular to an environment-friendly high-ratio recycled ABS (Recycled ABS, r-ABS for short) flame retardant modified composition, and a preparation method and application of the composition.

Background technique

ABS resin is a terpolymer composed of styrene, butadiene and acrylonitrile. It combines the high fluidity of styrene, the rubber toughness of butadiene and the chemical resistance of acrylonitrile. It has excellent processing performance, Low temperature resistance, electrical insulation, chemical corrosion resistance, high gloss and excellent electroplating performance, as well as good creep resistance, high dimensional stability, small molding shrinkage, etc., are widely used in military industry, automobiles, electronic appliances, etc. The field of application is very wide.

A large number of applications of ABS in the above-mentioned fields, especially in the past five years, a large number of electronic products such as (TV, washing machine, refrigerator, air conditioner, computer) produced by using ABS resin are in a peak period of renewal and elimination, resulting in a huge amount of recycled ABS spare parts The focus of material manufacturers is to reduce the cost of products by using recycled ABS. However, in addition to ABS resin, the plastic materials used in electronic and electrical products may also contain PP, PC, PE and other plastics and their modified compositions, so they may also contain some inorganic powder, metal impurities and other unknown components. , In addition, rinsing is required in the process of recycling ABS resin, which may also introduce certain elements, such as Cl elements, etc. during the rinsing process. The components of the above non-ABS resin may be an important factor that deteriorates the performance of the recycled ABS resin. On the other hand, due to the structural characteristics of the ABS resin itself, the light aging effect of the ABS product during use makes the rubber phase in it double. The bond is saturated, and then forms the cross-linking of the chain segment, which reduces the rubber phase, thus reducing the impact resistance of the ABS resin. At the same time, the photoaging effect causes the chain segments of the ABS resin to break, and the molecular weight of the polymer decreases, resulting in a decrease in the elastic modulus and tensile strength of the material, and a decrease in the heat distortion temperature. Further, the photochemical reaction of ABS produces a large number of new substances, such as aldehydes, ketones and peroxides, and the appearance of carbonyl structures causes the yellowing of ABS, and peroxides are sensitive to ultraviolet rays, and their existence further aggravates the deterioration of ABS resins. photoaging and performance deterioration. The combined results of the above two factors have led to a significant deterioration in the performance of ABS resins, increasing the difficulty of its subsequent modification.

Therefore, scientific workers have carried out a lot of in-depth research on the improvement of the performance of recycled ABS resin, such as Wang Jikui and others in the article "Research on the performance of ABS recycled materials" ("Shanghai Plastics", 2005, Vol.9, No.3: 16-19) proposed that adding special toughening agent in r-ABS can improve the impact resistance of r-ABS. In the patent document whose publication number is CN1646280, a method for restoring the physical properties of r-ABS by adding ABS resin is disclosed. This method can only be regarded as a partial recycling of r-ABS, and has no effect on the performance of r-ABS itself. Any change is only achieved by sacrificing the performance of ABS resin, and the improvement of its performance is closely related to the proportion of ABS resin added. In the article "Performance Improvement of Recycled ABS Resin" ("Polymer Materials Science and Engineering", 2011, Vol.27, No.3:62-66), Zhang Hongmei and others proposed the compound modification of high rubber powder/inorganic nanoparticles According to the scheme, adding 5%-8% high-grade rubber powder and 2%-3% inorganic nanoparticles can greatly improve the toughness of recycled ABS resin, while taking into account the rigidity, strength and heat resistance of the material. In the patent document with the authorization number CN103254561B, the toughness of recycled ABS is improved through the method of toughening with high rubber powder. This method only realizes the application in fields that do not require high material usage through toughening a single performance.

The above literature only proposed some modification methods for the lack of performance in one aspect of r-ABS, such as toughening, strengthening and other modifications, or by compounding with ABS resin to improve the performance of r-ABS resin, or to reduce the use requirements To achieve the purpose of recycling recycled ABS. The above-mentioned improvement plan is based on the performance improvement of r-ABS resin itself, but there is no way to use r-ABS resin in the field of modified ABS resin, especially in the field of flame-retardant ABS modification. The main reason is that it does not target r-ABS. The root cause of performance degradation - that is, the influence of impurities and the structural changes caused by the use process, etc., proposes targeted improvement methods.

Contents of the invention

The primary purpose of the present invention is to provide an environment-friendly high-ratio r-ABS flame-retardant modified composition, which has excellent mechanical properties, stable flame-retardant and extremely low cost.

Another object of the present invention is to provide the preparation method and application of the above-mentioned r-ABS flame retardant modified composition.

To achieve the above object, the present invention adopts the following technical solutions:

The environmentally friendly high-ratio recycled ABS flame-retardant modified composition is composed of the following raw materials in parts by weight:

in,

The environmentally friendly brominated flame retardant is tris(tri-bromophenyl)cyanurate.

The antimony-based flame retardant synergist is at least one of the following substances: antimony trioxide, colloidal antimony pentoxide, antimony trichloride, and antimony pentachloride.

The phosphorus-based flame retardant synergist can be at least one of the following substances: m-phenylene tetraphenyl bisphosphate, bisphenol A bis (diphenyl phosphate), m-phenylene tetrakis (xylene base) bisphosphate, m-phenylene tetrakis (xylyl) bisphosphate oligomer, triphenyl phosphate, diphenyl (xylene) phosphate, diphenyl cumyl phosphate, diphenyl isooctyl phosphate ester, diphenylisodecyl phosphate, tris(cresyl) phosphate, tris(xylene) phosphate, phenyl tert-butylphenyl phosphate, alkylphenyl bisphosphate, cycloalkyl-containing bisphosphate, Biphenyl bis (diphenyl) phosphate, triethyl phosphate, tributyl phosphate, triisooctyl phosphate, tris (2-butoxyethyl) phosphate, 1-oxo-4-hydroxymethyl- 2,6,7-trioxa-1-phosphabicyclo(2,2,2)octane, tris(1-oxo-2,6,7-trioxa-1-phosphabicyclo[2.2. 2] Octane-methylene-4) phosphate, 2,2-dimethyl-1,3-propanediol-di(neopentyl glycol) bisphosphate.

The toughening agent can be one or a mixture of styrene toughening agents, chlorinated polyethylene toughening agents and ABS high rubber powder.

The compatibilizer is one or more of SBS, SEBS, ABS-G-MAH, SMA700 and PP-G-MAH.

The inorganic powder is composed of one or more of silicon-containing inorganic compounds such as sodium aluminosilicate, montmorillonite, kaolin, feldspar powder, wollastonite, mica powder, magnesium silicate and calcium silicate. become.

The preparation method of the above-mentioned environmentally friendly high-ratio recycled ABS flame-retardant modified composition comprises the following steps:

a. The regenerated ABS, the high-rigidity ABS, the environmentally friendly brominated flame retardant, the antimony-based flame-retardant synergist, the phosphorus-based flame-retardant synergist, and the toughening agent , the compatibilizer and the inorganic powder are added into a mixer and mixed to obtain a mixture; wherein, the environmentally friendly brominated flame retardant is three (tri-bromophenyl) cyanurate;

b. Add the above mixture into a twin-screw extruder, and under the shearing, mixing and conveying of the screws, melt, extrude, granulate, and dry to obtain an environmentally friendly high-ratio recycled ABS flame-retardant modified composition ; Wherein, the screw temperature of each section of the extruder is controlled between 180-230°C, the aspect ratio of the twin-screw extruder is 25-40, and the screw speed is 200-800 rpm.

The environment-friendly high-ratio recycled ABS flame retardant modified composition of the invention can be widely used in various fields requiring flame retardant, such as household appliances, transportation, and communication.

The present invention has following beneficial effect:

1) The flame retardant grade of the environment-friendly high-ratio recycled ABS flame retardant modified composition described in the present invention can reach UL94V-2-V-0@1.5mm-3.0mm, and the impact strength is kept above 15kJ/ ^m2 , The melt index is above 40g/10min, and other mechanical properties are good, and it also has excellent heat resistance.

2) The preparation method of the environment-friendly high-proportion recycled ABS flame-retardant modified composition of the present invention is simple, easy to process, and low in cost, and is very suitable for various fields that require flame retardancy, such as household appliances, transportation, and communications.

detailed description

The following is a further description of the environment-friendly high-ratio recycled ABS flame-retardant modified composition, preparation method and application of the present invention in conjunction with some specific implementation methods. The specific examples are to further describe the present invention in detail, without limiting the protection scope of the present invention.

The environment-friendly high-ratio recycled ABS flame-retardant modified composition according to the present invention was prepared according to the standard sample to perform the performance tests listed in Table 1 below.

Table 1 Performance tests and their standards

In all the embodiments provided by the present invention, the raw materials provided can be purchased from the market. in,

The r-ABS resin is made of recycled ABS from Panasonic refrigerator panels in Japan;

The high-rigidity ABS resin is ABS AG15A1 from Taiwan Taiwan Chemical Co., Ltd.

The bromotriazine is FR-245 from Israel Dead Sea Bromine Company;

The toughening agent is HR181 from Korea Kumho Company;

The antimony-based flame retardant synergist is S-05N from Yunnan Muli Antimony Industry Co., Ltd.;

Phosphorus-based flame retardant synergist-1 uses bisphenol A bis(diphenyl phosphate) WSFR-BDP-N2 from Zhejiang Wansheng Company;

Phosphorus-based flame retardant synergist-2 uses m-phenylene tetraphenyl bisphosphate WSFR-RDP from Zhejiang Wansheng Company;

The compatibilizer is PP-G-MAH from Nanjing Sutai Company

The inorganic powder is NYAD MD400 from NYCO, USA

Embodiment 1-4, comparative example 1-4

According to the parts by weight listed in Table 2, each component is added into a high-speed mixer for uniform mixing, and then the above-mentioned mixture is sent into a twin-screw extruder for kneading, extrusion, stranding, water cooling, and pelletizing; wherein, The length-diameter ratio of the twin-screw extruder is 25-40; the temperature of the screw barrel is set as follows: the temperature of the first zone is 180°C, the temperature of the second zone is 190°C, the temperature of the third zone is 200°C, the temperature of the fourth zone is 210°C, and the temperature of the fifth zone is 220°C , the temperature of the sixth zone is 220°C, the temperature of the seventh zone is 220°C, the temperature of the eighth zone is 220°C, the temperature of the ninth zone is 220°C, the temperature of the tenth zone is 220°C, the temperature of the head is 230°C; the screw speed is 200-800 rpm.

The environment-friendly high-ratio recycled ABS flame-retardant modified composition prepared by the above method was tested according to the standard preparation of each performance test listed in Table 1 and the data were recorded in Table 2.

Table 2

From the above table 2, comparing Examples 1-4 with Comparative Examples 1-4, it can be seen that the r-ABS of Comparative Example 1 is compared with the ABS AG15A1 in Comparative Example 2, and each mechanical property has a significant If the same flame retardant modification method is adopted as shown in Comparative Example 3 and Comparative Example 4, the performance of the flame retardant ABS prepared in Comparative Example 4 is excellent, but the performance of the flame retardant ABS prepared in Comparative Example 3 is better than that of r-ABS It is further deteriorated, especially the impact property is as low as 4kJ/m ² , such a low impact property has almost no use value for the flame retardant ABS composition. However, the formula design of the environment-friendly high-ratio recycled ABS flame-retardant modified composition described in Examples 1-4 can still produce excellent flame-retardant properties when the r-ABS addition ratio is as high as 70 parts. Balanced performance, excellent flow performance and extremely low cost at the same time. According to the different requirements for flame retardant performance, select the appropriate formula, and prepare the corresponding environmentally friendly high-proportion recycled ABS flame retardant modified composition, which can be used in various fields that require flame retardant, such as household appliances, transportation, and communications.

Claims (9)

1. The environment-friendly high-proportion regenerated ABS flame-retardant modified composition is characterized in that: the composite material consists of the following raw materials in parts by weight:

2. the environment-friendly high-proportion recycled ABS flame-retardant modified composition according to claim 1, characterized in that: the environment-friendly brominated flame retardant is tris (tri-bromophenyl) cyanurate.

3. The environment-friendly high-proportion recycled ABS flame-retardant modified composition according to claim 1, characterized in that: the antimony flame-retardant synergist is at least one of the following substances: antimony trioxide, colloidal antimony pentoxide, antimony trichloride, antimony pentachloride.

4. The environment-friendly high-proportion recycled ABS flame-retardant modified composition according to claim 1, characterized in that: the phosphorus flame-retardant synergist is at least one of the following substances: m-phenylene tetraphenyl diphosphate, bisphenol A bis (diphenyl phosphate), m-phenylene tetraxylyl diphosphate oligomer, triphenyl phosphate, diphenyl (xylene) phosphate, diphenyl isopropyl phenyl phosphate, diphenyl isooctyl phosphate, diphenyl isodecyl phosphate, tri (toluene) phosphate, tri (xylene) phosphate, phenyl tert-butylphenyl phosphate, alkylphenyl diphosphate, cycloalkyl-containing diphosphate, diphenyl bis (diphenyl) phosphate, triethyl phosphate, tributyl phosphate, triisooctyl phosphate, tris (2-butoxyethyl) phosphate, 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo (2, 2, 2) octane, tris (1-oxo-2, 6, 7-trioxa-1-phosphabicyclo [2.2.2] octane-methylene-4) phosphate, 2-dimethyl-1, 3-propanediol-bis (neopentyl glycol) diphosphate.

5. The environment-friendly high-proportion recycled ABS flame-retardant modified composition according to claim 1, characterized in that: the toughening agent is one or a mixture of more of a styrene toughening agent, a chlorinated polyethylene toughening agent and ABS high rubber powder.

6. The environment-friendly high-proportion recycled ABS flame-retardant modified composition according to claim 1, characterized in that: the compatilizer is one or more of SBS, SEBS, ABS-G-MAH, SMA700 and PP-G-MAH.

7. The environment-friendly high-proportion recycled ABS flame-retardant modified composition according to claim 1, characterized in that: the inorganic powder is formed by compounding one or more of silicon-containing inorganic compounds of sodium aluminosilicate, montmorillonite, kaolin, feldspar powder, wollastonite, mica powder, magnesium silicate and calcium silicate.

8. The environment-friendly high-proportion recycled ABS flame-retardant modified composition as recited in any of claims 1 to 7, characterized in that: the method is applied to the fields of household appliances, transportation and communication.

9. The preparation method of the environment-friendly high-proportion recycled ABS flame-retardant modified composition as claimed in any one of claims 1 to 7, characterized in that: the method comprises the following steps:

a. proportionally adding the regenerated ABS, the high-rigidity ABS, the environment-friendly brominated flame retardant, the antimony flame retardant synergist, the phosphorus flame retardant synergist, the toughening agent, the compatilizer and the inorganic powder into a mixer to be mixed to obtain a mixture; wherein the environment-friendly brominated flame retardant is tris (tri-bromophenyl) cyanurate;

b. adding the mixture into a double-screw extruder, and carrying out melting, extrusion, granulation and drying under the shearing, mixing and conveying of screws to obtain an environment-friendly high-proportion regenerated ABS flame-retardant modified composition; wherein, the temperature of each section of screw of the extruder is controlled between 180 ℃ and 230 ℃, the length-diameter ratio of the double-screw extruder is 25-40, and the rotating speed of the screw is 200 ℃ and 800 r/min.