WO2023061493A1 - Flame retardant pc/abs alloy composition, preparation method therefor and application thereof - Google Patents

Abstract

The present invention relates to a flame retardant PC/ABS alloy composition, a preparation method therefor and an application thereof. The flame retardant PC/ABS alloy composition comprises PC, ABS, a non-phosphate ester halogen-free flame retardant, a toughener, a flame retardant synergist and an anti-dripping agent. The flame retardant PC/ABS alloy composition provided in the present invention achieves a suitable molecular weight retention rate during an aging process by means of selection of a non-phosphate ester halogen-free flame retardant and synergistic cooperation of a specific flame retardant synergist, not only having a relatively high flame retardant grade and relatively good mechanical properties, but also having relatively good damp-heat aging stability.

Description

A kind of flame-retardant PC/ABS alloy composition and its preparation method and application technical field

The invention belongs to the field of engineering plastics, and in particular relates to a flame-retardant PC/ABS alloy composition and a preparation method and application thereof.

Background technique

With the development of the industry, the demand for materials is also constantly upgrading. From the perspective of customer needs, materials must follow the development directions of halogen-free environmental protection, thinner walls, and service safety. Halogen-free flame-retardant PC/ABS alloy composition is a very versatile and widely used material. In order to meet the technical update and change requirements of this material in application, especially for harsh service conditions, such as high temperature, high humidity and other environments Among them, the PC composition should have excellent moisture-heat aging stability and ensure sufficient mechanical properties during service. However, due to the fact that the molecular chain of PC is very sensitive to heat and water, the general addition of components will bring about a relatively large negative impact, resulting in accelerated degradation of PC and reduced service stability. The conventional improvement method is generally to add flame retardants or tougheners to supplement the defects, but if there are residues and small molecules such as tougheners in ABS, the addition of flame retardants will also lead to a decline in heat resistance. Further degrade the humidity and heat stability, because the presence of the above external catalytic components will promote the reduction of the molecular weight retention rate of the PC resin during the aging process, and increase the content of tougheners and flame retardants to ensure the maintenance of flame retardancy and impact strength The rate will further deteriorate the humidity and heat aging phenomenon, accelerate the degradation of PC resin, and further reduce the molecular weight retention rate, which cannot provide guarantee for the service safety of mechanical properties, which limits the application of materials in electronics, construction, lighting, new energy, communications and personal portable appliances. etc. applications.

At present, it has been reported to improve the thermo-oxidative aging performance by adding phenolic substances and controlling the content of metal manganese (such as CN105440624A), but the research is mainly on color stability and high gloss, whether it can also improve flame retardancy Stability and mechanical stability are not known. Therefore, it is of great significance to develop a PCABS alloy material with good hygrothermal aging performance in terms of flame retardancy and mechanical properties to expand its application range.

Contents of the invention

The object of the present invention is to overcome the defects or deficiencies in the prior art and provide a flame-retardant PC/ABS alloy composition. The flame-retardant PC/ABS alloy composition provided by the present invention has higher PC molecular weight retention rate and SAN molecular weight retention rate, higher flame-retardant grade and better mechanical properties, and has excellent damp-heat aging stability. After aging treatment, it still has a high flame retardant grade and good mechanical properties, and has a wide application prospect.

Another object of the present invention is to provide a method for preparing the above-mentioned flame-retardant PC/ABS alloy composition.

Another object of the present invention is to provide the application of the above-mentioned flame-retardant PC/ABS alloy composition in the preparation of automotive materials, electrical and electronic, construction, lighting, new energy, communication, and personal portable electrical appliances.

In order to realize the above-mentioned purpose of the invention, the present invention adopts following technical scheme:

A flame-retardant PC/ABS alloy composition, comprising the following components in parts by weight:

The flame retardant synergist is a ring silicide, and the silicon content in the ring silicide is not less than 10%.

In the present invention, the selection of the toughening agent can endow the flame-retardant PC/ABS alloy composition with better mechanical properties. Studies have found that non-phosphate ester halogen-free flame retardants generally do not hydrolyze in the PC/ABS alloy system, and their addition can not only improve the hydrolysis stability, but also further increase the toughness of the material to achieve high toughness. At the same time, this type of flame retardant The agent has excellent heat resistance, which can promote the improvement of moisture and heat stability from both physical and chemical levels. Specifically, on the physical level, non-phosphate ester halogen-free flame retardants have high compatibility with PC resin, and are in a state of physical dispersion in the PC resin matrix, and there is a certain physical barrier at the interface between the two; on the chemical level , The non-phosphate ester halogen-free flame retardant itself does not have an ester structure that is easily hydrolyzed in its molecular chain structure, and groups such as hydroxyl and carboxyl groups do not undergo hydrolysis reactions themselves, and the molecular weight retention rate is stable. However, there are still some limitations in the improvement of its thermal stability.

Further research found that by adding a specific flame retardant synergist cyclic silicide that has a certain compatibility with the resin matrix, physical isolation of water can be achieved, and the residues in ABS, small molecules of tougheners, and flame retardants can be significantly reduced. The negative impact brought about by the addition of polyphenylsiloxane reduces the moisture absorption rate during the heat and humidity aging process, thereby reducing the hydrolytic degradation of PC resin in the external environment; in addition, polyphenylsiloxane can also increase the stability of thin-walled flame retardancy.

Through the synergistic cooperation of specific non-phosphate ester halogen-free flame retardants and specific flame retardant synergists, the flame retardant PC/ABS alloy composition provided by the present invention has a higher PC molecular weight retention rate and SAN molecular weight retention rate, higher Excellent flame retardant grade, better mechanical properties and humidity and heat aging stability. Specifically, after heat and humidity aging treatment, the flame retardancy level can still be maintained at 1.0mm, V-0 level; the tensile strength retention rate is greater than 90%.

Preferably, the flame-retardant PC/ABS alloy composition includes the following components in parts by weight:

Conventional PC, ABS (acrylonitrile-butadiene-styrene copolymer), non-phosphate ester halogen-free flame retardants, toughening agents and anti-dripping agents in this field can be used in the present invention, and its preparation method can also be used in the present invention. for the conventional method.

Preferably, the weight-average molecular weight of the PC is 22000-30000, the content of terminal hydroxyl groups is 0.1-100 ppm, and the content of BPA is 0.05-20 ppm.

The terminal hydroxyl content is determined according to the GB12008.3-1989 standard.

Bisphenol A (BPA) was determined by the following process: passing through a C18 chromatographic column with a fixed column temperature of 40°C, a mobile phase of acetonitrile:methanol at 9:1 (volume ratio), a fixed flow rate of 1mL/min, and a detection wavelength of 280nm by The content was determined by o-cresol internal standard method.

Preferably, the residual monomer content in the ABS is 0.1-300ppm.

The residual monomer content is determined through the following process. The fluidity of the gas phase collected through gas phase thermal desorption at a set temperature enters MS for analysis to determine the composition and content.

Preferably, the non-phosphate ester halogen-free flame retardant is one or more of phenoxycyclotriphosphazene, octaphenylcyclotetraphosphazene or decaphenoxycyclopentaphosphazene.

Preferably, the toughening agent is a silicon-based toughening agent with acrylate as the shell layer, and the content of silica gel in the silicon-based toughening agent is 5-40%.

Preferably, the anti-dripping agent is a fluoropolymer, which may include fibrillation forming or non-fibrillating fluoropolymers, such as polytetrafluoroethylene (PTFE).

Preferably, the ring silicide is one or more of FCA107, 8008 or 400-001.

Preferably, the silicon content in the ring silicide is 10-75%.

The silicon content in the cyclic silicide is measured by the following process: Weigh the silicide with a fixed weight, put it in a muffle furnace with a preset temperature of 700°C for 4 hours, take it out and weigh the ash, and then measure the silicon content by ICP. content.

The preparation method of the above-mentioned flame-retardant PC/ABS alloy composition comprises the following steps: mixing PC, ABS, non-phosphate ester halogen-free flame retardant, toughening agent, flame-retardant synergist and anti-dripping agent, extruding , and granulate to obtain the flame-retardant PC/ABS alloy composition.

Preferably, the preparation method of the above-mentioned flame retardant PC/ABS alloy composition comprises the following steps: mixing PC, ABS, non-phosphate ester halogen-free flame retardant, toughening agent, flame retardant synergist and anti-dripping agent in Stirring and mixing in a high mixer, then melt extruding in a twin-screw extruder, and granulating to obtain the flame-retardant PC/ABS alloy composition.

More preferably, the stirring and mixing speed is 20-50 rpm; the aspect ratio of the twin-screw extruder is 38-52:1, the temperature of the screw barrel is 220-260°C, and the screw speed is 300 ~600 rpm/min.

The application of the above-mentioned flame-retardant PC/ABS alloy composition in the preparation of automotive materials, electronics, construction, lighting, new energy, communications, and personal portable appliances is also within the protection scope of the present invention.

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

The flame-retardant PC/ABS alloy composition of the present invention greatly improves the PC molecular weight retention rate, SAN molecular weight retention rate and humidity-heat aging stability through the selection of non-phosphate ester halogen-free flame retardants and flame-retardant synergists, and has high Excellent flame retardant grade and flame retardant stability, and better mechanical properties and stability.

Detailed ways

The present invention is further set forth below in conjunction with embodiment. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The experimental method that does not indicate specific conditions in the following example embodiment, usually according to the conventional conditions in this field or according to the conditions suggested by the manufacturer; used raw materials, reagents, etc., if no special instructions, are available from commercial channels such as conventional markets Raw materials and reagents obtained. Any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention fall within the scope of the present invention.

The partial reagents that each embodiment of the present invention and comparative examples select are described as follows:

Polycarbonate 1#, S-2000F, Shanghai Mitsubishi Engineering, with an average molecular weight of 23,000, a terminal hydroxyl content of 47ppm, and a BPA content of 12ppm;

Polycarbonate 2#, FN1900, Idemitsu, with an average molecular weight of 22000, a terminal hydroxyl content of 87ppm, and a BPA content of 134ppm;

ABS 1#, 275, Shanghai Gaoqiao, the residual monomer content is 88ppm;

ABS 2#, PA757, Chimei, the residual monomer content is 780ppm;

Non-phosphate ester halogen-free flame retardant 1#, FP-110T, Otsuka, Japan;

Non-phosphate ester halogen-free flame retardant 2#, HPCTP, Weihai Jinwei

Phosphate flame retardant 3#, BDP, Wansheng;

Toughening agent 1#, S-2030, silicon-based toughening agent, Mitsubishi Rayon, the content of silica gel is 30%;

Toughening agent 2#, EM500, non-silicon based toughening agent, LG, silica gel content is 0%;

Anti-dripping agent, TS-30X, Pacific Ocean;

Flame retardant synergist 1#, FCA-107 Dow Corning, silicon content is 16%;

Flame retardant synergist 2#, 8008, Dow Corning, silicon content is 20%;

Flame retardant synergist 3#, SI-PC, LG, silicon content is 2%;

The test methods of each performance of the flame-retardant PC/ABS alloy composition of each embodiment of the present invention and comparative example are as follows:

PC molecular weight retention rate and SAN molecular weight retention rate: Dissolve the composition in tetrahydrofuran (THF) (dissolution time is 24h), configure it to a concentration of 0.5mg/mL, set the temperature of two columns in series at 40°C, and pass through a differential detector The injection volume was fixed at 10 μL, the flow rate was 0.5 mL/min, and the standard substance was polystyrene, and the molecular weights of PC resin and SAN resin were tested by the outflow time. The molecular weight retention rate was obtained by comparing the molecular weight before wet heat aging with the molecular weight after 504 hours of wet heat aging. The higher the molecular weight retention rate, the better the wet heat stability, and vice versa.

Flame retardant grade: The flammability test is carried out in accordance with the regulations of "Tests for Flammability of Plastic Materials, UL94". The flammability rating is based on the burning rate, time to extinguish, ability to resist dips, and whether the dips are burning. Sample used for testing: 125mm length and 13mm width, the thickness of the present invention is selected as 1.0mm when testing, according to the UL94 regulations, the flame retardant grade of the material can be classified into (UL94-HB): V0, V1, V2, 5VA and/or or 5VB. At the same time, after the sample is subjected to a humid heat aging treatment with a temperature of 85°C and a humidity of 85% in a constant temperature and humidity box for 500 hours, its flame retardancy level is determined according to the same conditions;

Tensile strength: According to ASTM D527-2008, tensile specimens were subjected to damp heat aging in a constant temperature and humidity test box with a preset temperature of 85°C and a humidity of 85%. Adjust at a room temperature of 25°C and a humidity of 50% for more than 48 hours, then test and record the results, and compare the performance retention rate before and after aging as the judgment of the damp heat performance. The higher the performance retention rate, the better the damp heat stability. good.

The preparation process of the flame-retardant PC/ABS alloy compositions of the various embodiments of the present invention and comparative examples is as follows: Weigh each component according to the proportion, stir and mix them in a high-mixer, and then melt and extrude them in a twin-screw extruder , Granulating, that is, the flame retardant PC/ABS alloy composition. Wherein, the rotation speed of stirring and mixing is 40 rpm; the aspect ratio of the twin-screw extruder is 40:1, the temperature of the screw barrel is 240° C., and the screw rotation speed is 350 rpm.

Examples 1-10

This embodiment provides a series of flame-retardant PC/ABS alloy compositions, the formulations of which are shown in Table 1.

Table 1 The formula (part) of the flame-retardant PC/ABS alloy composition that embodiment 1～10 provides

Comparative example 1～3

This comparative example provides a series of flame-retardant PC/ABS alloy compositions, the formulations of which are shown in Table 2.

Table 2 Components (parts) of the flame-retardant PC/ABS alloy composition provided by Comparative Examples 1-3

the	Example 1	Comparative example 1	Comparative example 2	Comparative example 3
PC1#	94	94	94	94
ABS 1#	6	6	6	6
Flame retardant 1#	6	/	6	6
Toughener	3	3	3	3
Flame retardant 3#	/	6	/	/
Flame retardant synergist 1#	0.5	0.5	/	/
Flame retardant synergist 3#	/	/	0.5	/
anti-dripping agent	0.5	0.5	0.5	0.5

The properties of the flame-retardant PC/ABS alloy compositions of the examples and comparative examples were measured according to the test method mentioned above, and the test results are shown in Table 3.

Table 3 The performance test results of the flame-retardant PC/ABS alloy compositions of each embodiment and comparative examples

It can be seen from Table 3 that the flame-retardant PC/ABS alloy composition provided by each embodiment of the present invention has a higher PC molecular weight retention rate, a higher SAN molecular weight retention rate, a higher flame-retardant grade, better mechanical properties and better The humidity and heat aging stability, wherein the comprehensive performance of embodiment 1 is the best, the PC molecule retention rate, tensile strength of embodiment 4 and embodiment 5, and the tensile strength retention rate after heat and humidity aging are respectively better than embodiment 2 and 3. The overall performance is better; in Comparative Example 1, due to the addition of a phosphate flame retardant, the esterification reaction of the flame retardant itself strongly promotes the degradation of the PC resin and leads to a chain scission reaction, resulting in a sharp drop in the molecular weight of PC and SAN As a result, the material cannot be used normally after heat and humidity aging, the tensile strength retention rate is only 13%, and the flame retardant grade drops to V-2; due to the low silicon content in the flame retardant synergist used in Comparative Example 2, it is impossible to achieve sufficient time. However, the flame retardant efficiency is not satisfactory for the initial flame retardancy, and the flame retardancy further deteriorates after humid heat aging.

Those skilled in the art will appreciate that the embodiments herein are to help readers understand the principles of the present invention, and it should be understood that the protection scope of the present invention is not limited to such specific statements and embodiments. Those skilled in the art can make various other specific modifications and combinations based on the technical revelations disclosed in the present invention without departing from the essence of the present invention, and these modifications and combinations are still within the protection scope of the present invention.

Claims (10)

1. A kind of flame-retardant PC/ABS alloy composition is characterized in that, comprises the component of following parts by weight:

   

   The flame retardant synergist is a ring silicide, and the silicon content in the ring silicide is not less than 10%.
2. Flame-retardant PC/ABS alloy composition according to claim 1, is characterized in that, comprises the component of following parts by weight:

   
3. The flame-retardant PC/ABS alloy composition according to claim 1, wherein the average molecular weight of the PC is 22000-30000, the content of terminal hydroxyl groups is 0.1-100ppm, and the content of BPA is 0.05-20ppm; The content of the monomer is 0.1-300 ppm.
4. The flame retardant PC/ABS alloy composition according to claim 1, wherein the non-phosphate ester halogen-free flame retardant is phenoxycyclotriphosphazene, octaphenylcyclotetraphosphazene or decaphenoxy One or more of the base cyclopentaphosphazenes.
5. The flame-retardant PC/ABS alloy composition according to claim 1, wherein the silicon-based toughening agent is a silicon-based toughening agent with acrylate as the shell layer.
6. The flame-retardant PC/ABS alloy composition according to claim 1, wherein the silica gel content in the silicon-based toughening agent is 5-40%.
7. The flame-retardant PC/ABS alloy composition according to claim 1, wherein the anti-dripping agent is a fluoropolymer.
8. The flame retardant PC/ABS alloy composition according to claim 1, characterized in that the silicon content in the ring silicide is 10-75%.
9. The preparation method of the flame-retardant PC/ABS alloy composition according to any one of claims 1-8, characterized in that it comprises the following steps: mixing PC, ABS, non-phosphate ester halogen-free flame retardant, toughening agent, flame retardant The synergist and the anti-dripping agent are mixed, extruded and granulated to obtain the flame-retardant PC/ABS alloy composition.
10. The application of the flame-retardant PC/ABS alloy composition described in any one of claims 1 to 8 in the preparation of automotive materials, electronic and electrical appliances, construction, lighting, new energy, communications, and personal portable electrical appliances.