CN108570205B - Flame-retardant styrene composition and preparation method thereof - Google Patents

Abstract

The invention discloses a flame-retardant styrene composition and a preparation method thereof, wherein the flame-retardant styrene composition comprises the following components: 65-90 parts of ABS resin; 3-8 parts of organic brominated flame retardant; 5-30 parts of P-series flame retardant master batch; 1-5 parts of flame-retardant synergist. According to the invention, bromine-phosphorus (Br-P) flame retardants are compounded, so that the stable V-2 flame-retardant grade flame-retardant ABS material can be obtained under the condition of lower usage amount of the flame retardants, the addition amount of the flame retardants in the flame-retardant ABS material is reduced by half compared with that of the traditional V-2 flame-retardant ABS, the cost can be reduced by 30-40%, and the thermal stability and the mechanical properties of the composition can be maximally maintained.

Description

Flame-retardant styrene composition and preparation method thereof

Technical Field

The invention belongs to the field of high polymer materials, and particularly relates to a flame-retardant styrene composition and a preparation method thereof.

Background

The ABS resin is a yellowish solid, has the density of about 1.04 g/cm3, organically integrates the performances of three different materials of acrylonitrile, butadiene and styrene, and has the advantages of formability, rigidity, toughness, excellent comprehensive performance and wide application. ABS is suitable for household electrical appliance products, such as television shells, refrigerator linings, dust collectors and the like, and plastic products for instruments, telephones and automobile industries.

However, ABS also has some defects, such as low weather resistance and heat resistance, and in order to overcome these defects, many kinds of modified ABS materials have been produced. Flame retardant ABS is one of the major classes, which was developed to address the disadvantage of the easy burning of conventional ABS resins. According to the test standards of UL94-2015 for vertical burning, the flame retardant ratings can be classified from low to high as V-2, V-1 and V-0. The flame retardant rating is not necessarily as high as possible and needs to be determined according to the specific requirements of the product. In certain application conditions, plastics with low flame retardant grades are rather better. For example, in some electronic appliances, where the material is required to have arc ignition resistance, it is more desirable to use a V-2 grade material because it does not form conductive coke under the electrical action, thereby reducing the possibility of fire. In recent years, in office system (OA) industry, flat panel television industry and the like, the shell of a workpiece has V-2 flame retardant requirement.

Brominated flame retardants are commonly added in the industry to improve the flame retardant performance of materials, but the brominated flame retardants have poor stability due to the fact that the addition amount is large, so that the stability of the materials is poor, and the cost is high. For example, patent CN201410234773 discloses a preparation method of high-fluidity high-flame-retardant high-toughness ABS, which adopts blending of ABS resin and compound flame-retardant composition, and the prepared flame-retardant ABS has good flame-retardant effect, but general thermal stability and higher cost.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide a flame-retardant styrene composition which is low in cost and good in stability.

The invention is realized by the following technical scheme:

the flame-retardant styrene composition comprises the following components in parts by weight:

65-90 parts of ABS resin;

3-8 parts of organic brominated flame retardant;

5-30 parts of P-series flame retardant master batch;

1-5 parts of flame-retardant synergist.

The ABS resin is acrylonitrile-butadiene-styrene copolymer, and the weight content of butadiene in the ABS resin is 14-28% based on the total weight of the ABS resin; the melt flow rate of the ABS resin is 3-10 g/10min under the condition of 200 ℃/5 kg.

The organic bromine flame retardant is at least one of tetrabromobisphenol A bis (2, 3-dibromopropyl) ether or tetrabromobisphenol S bis (2, 3-dibromopropyl) ether.

The P-series flame retardant master batch is a master batch taking ABS resin as a carrier, and the weight content of the P-series flame retardant is 20-40% based on the total weight of the P-series flame retardant master batch.

The P-based flame retardant is at least one selected from triphenyl phosphate, bisphenol A bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate), tricresyl phosphate, trixylenyl phosphate, propylbenzene-based phosphate and butylbenzene-based phosphate.

The mass ratio of the organic bromine flame retardant to the P flame retardant master batch is 1: 5-4: 5.

the flame-retardant synergist is at least one of antimony trioxide or antimonate.

According to the actual performance requirements, the flame-retardant styrene composition also comprises 0.1 to 0.5 part of antioxidant, 0.1 to 1 part of acid absorption aid and 0.1 to 1 part of lubricant in parts by weight.

The antioxidant is one or more of hindered phenol antioxidant, phosphite antioxidant, amine antioxidant, sulfur-containing antioxidant or metal salt antioxidant, such as antioxidant 1010 and antioxidant 168;

the acid absorbent is one or a mixture of more of magnesium stearate, calcium stearate, zinc stearate, magnesium hydroxide, high-activity magnesium oxide or hydrotalcite;

the lubricant is one or a mixture of more of silicone lubricant, amide lubricant (such as Ethylene Bis Stearamide (EBS)) and stearic acid lubricant, polyolefin lubricant or ester lubricant.

The preparation method of the flame-retardant styrene composition comprises the following steps:

a. weighing the raw materials in parts by weight;

b. all the raw materials are added into a high-speed mixer to be mixed for 1-2 minutes;

c. and then adding the mixed raw materials into a double-screw extruder for extrusion granulation, wherein the speed of the extruder is 50-100 revolutions per minute, and the temperature is 180-200 ℃.

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

(1) according to the invention, bromine-phosphorus (Br-P) flame retardants are compounded, so that the stable V-2 flame-retardant grade flame-retardant ABS material can be obtained under the condition of lower usage amount of the flame retardants;

(2) according to the invention, a proper type of brominated flame retardant is selected for ABS, and a V-2 flame retardant effect can be obtained only by a small amount, compared with the conventional flame retardants commonly used in ABS, such as tribromotriazine, tetrabromobisphenol A and the like, the equivalent flame retardant effect can be achieved, and the addition amount of the later flame retardant is more than one time of that of the former flame retardant;

(3) the V-2 level flame retardant composition prepared by the invention has stable flame retardance and low cost, and the addition amount of the flame retardant in the composition is reduced by half compared with that of the traditional V-2 level flame retardant ABS, so that the cost can be reduced by 30-40%;

(4) the addition amount of the brominated flame retardant having slightly poor relative stability is greatly reduced, and the thermal stability and mechanical properties of the composition are also maintained to the maximum.

Detailed Description

The following examples are given to specifically describe the present invention, but are not limited thereto.

The raw materials used in the examples and comparative examples are now described below, but are not limited to these materials:

ABS resin, the weight content of butadiene in ABS resin is 14-28% based on the total weight of ABS resin; the melt flow rate of the ABS resin is 3-10 g/10min under the condition of 200 ℃/5kg, and 6000P produced by Taida chemical industry Co., Ltd is selected;

organic brominated flame retardants: tetrabromobisphenol A bis (2, 3-dibromopropyl) ether, produced by Shandong Brother science and technology Co., Ltd;

tetrabromobisphenol S bis (2, 3-dibromopropyl) ether, produced by Shandong Brother science and technology Co., Ltd;

the P-series flame retardant master batch is self-made by the golden hair technology and is prepared by extruding and granulating 20 weight percent of bisphenol A bis (diphenyl phosphate) and 80 weight percent of ABS resin by a double screw; bisphenol a bis (diphenyl phosphate), produced by jingle (hunan) chemical limited;

the flame retardant synergist is antimony trioxide, which is produced by Huachang antimony industry company;

the antioxidant is a mixture prepared by compounding an antioxidant 1010 and an antioxidant 168 produced by Shanghai Ciba refining company according to the weight ratio of 1: 2;

the acid absorbent is made of high-activity magnesium oxide and is produced by Japan and Co;

the lubricant is Ethylene Bis Stearamide (EBS) provided by Beijing Kodafeng commercial Co., Ltd;

the tris (tribromophenoxy) triazine is FR-245 produced by Israel dead sea bromine company;

the tetrabromobisphenol A is FR-1524 produced by Israel dead sea bromine company.

Examples 1 to 17 and comparative examples 1 to 3:

weighing the raw materials according to the proportion shown in the table 2, adding all the raw materials into a high-speed mixer, mixing for 1-2 minutes, adding the mixed raw materials into a double-screw extruder, and extruding and granulating to obtain the flame-retardant styrene composition. Wherein the speed of the extruder is 50-100 r/min, and the temperature is 180-200 ℃. The compositions prepared in the above examples and comparative examples were injection molded into test standard bars according to standard dimensions, and then subjected to performance tests according to the test standards shown in Table 1; the performance test data for each sample is shown in table 3.

TABLE 1 Performance test methods

Performance index	Test conditions	Test method
			Melt index	200℃/5kg	ISO 1133
Tensile strength/elongation at break	50mm/min	ISO 527
			Thermal stability	23℃	Respectively putting the materials inAt 220 deg.C under normal process conditions, and at 220 deg.C After 5min, injection molding was carried out to obtain a 100mm by 100mm square plate, and the two square plates were compared Color difference value △ E of the panel (the larger the △ E, the worse the thermal stability)
IZOD notched impact strength	23℃	ISO 180
			Density of	23℃	ISO 1183
Flame rating test	2.5mm	UL94

TABLE 2 concrete proportions (in parts by weight) of the components in the examples and comparative examples

	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Examples 1	Examples 2	Examples 3	Examples 4
									ABS 6000P	84	84	84	84	84	84	84	84
Tetrabromobisphenol S bis (2, 3-dibromopropane) Alkyl) ethers	14				4	6	8	1.5
									FR-245		4		14
FR-1524			4
									P-series flame retardant master batch		10	10		10	8	6	12.5
Antimony trioxide	2	2	2	2	2	2	2	2
									Antioxidant agent	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5
Acid absorbent	0.4	0.4	0.4	0.4	0.4	0.4	0.4	0.4
									Lubricant agent	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5

TABLE 2

	Example 5	Example 6	Example 7
				ABS 6000P	65	76	89
Tetrabromobisphenol S bis (2, 3-dibromopropyl) ether
				Tetrabromobisphenol A bis (2, 3-dibromopropyl) ether	3	6	8
P-series flame retardant master batch	30	15	5
				Antimony trioxide	2	2	2
Antioxidant agent	0.5	0.5	0.5
				Acid absorbent	0.4	0.4	0.4
Lubricant agent	0.5	0.5	0.5

TABLE 3 Performance test data for each of the examples and comparative examples

Performance index	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Example 1	Example 2	Example 3
								Melt index (200 ℃/5kg, g- 10min)	11	8	9	8	9	9	10
Tensile Strength (mPa)	40	39	37	38	38	37	35
								Elongation at Break (%)	6	17	9	7	15	12	11
Thermal stability/△ E	0.8	0.4	0.7	0.7	0.2	0.2	0.4
								IZOD notched impact strength (KJ/m 2)	9	19	17	16	19	16	14
Density (g/cm 3)	1.08	1.07	1.07	1.08	1.07	1.08	1.08
								Flame retardant rating (2.5 mm, Class)	V-2	V-2 fail	V-2 fail	V-2	V-2	V-2	V-2

TABLE 3

Performance index	Example 4	Example 5	Example 6	Example 7
					Melt index (200 ℃/5kg, g/10min)	10	15	12	10
Tensile Strength (mPa)	36	32	34	36
					Elongation at Break (%)	10	16	17	13
Thermal stability/△ E	0.3	0.3	0.3	0.4
					IZOD notched impact strength (KJ/m 2)	15	14	15	14
Density (g/cm 3)	1.06	1.08	1.08	1.08
					Flame retardant rating (2.5 mm, Class)	V-2	V-2	V-2	V-2

As can be seen from the results in Table 3, the composition prepared by compounding the bromine-phosphorus (Br-P) flame retardant and selecting the proper bromine flame retardant has stable flame retardant performance and balanced fluidity, mechanical property and thermal stability.

Claims (8)

1. The flame-retardant styrene composition is characterized by comprising the following components in parts by weight:

65-90 parts of ABS resin;

3-8 parts of organic brominated flame retardant;

5-30 parts of P-series flame retardant master batch;

1-5 parts of flame-retardant synergist;

the organic bromine flame retardant is at least one of tetrabromobisphenol A bis (2, 3-dibromopropyl) ether or tetrabromobisphenol S bis (2, 3-dibromopropyl) ether;

the P-series flame retardant master batch is a master batch taking ABS resin as carrier resin, and the weight content of the P-series flame retardant is 20-40% based on the total weight of the P-series flame retardant master batch.

2. The flame retardant styrene composition of claim 1, wherein the ABS resin is an acrylonitrile-butadiene-styrene copolymer, and the weight content of butadiene in the ABS resin is 14-28% based on the total weight of the ABS resin; the melt flow rate of the ABS resin is 3-10 g/10min under the condition of 200 ℃/5 kg.

3. The flame-retardant styrene composition according to claim 1, wherein the P-based flame retardant is at least one selected from the group consisting of triphenyl phosphate, bisphenol A bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate), tricresyl phosphate, trixylenyl phosphate, propylbenzene-based phosphate and butylbenzene-based phosphate.

4. The flame-retardant styrene composition according to claim 1, wherein the mass ratio of the organic bromine-based flame retardant to the P-based flame retardant master batch is 1: 5-4: 5.

5. the flame retardant styrene composition as claimed in claim 1, wherein the flame retardant synergist is at least one of antimony trioxide or antimonate.

6. The flame-retardant styrene composition according to claim 1, further comprising 0.1 to 0.5 part by weight of an antioxidant, 0.1 to 1 part by weight of an acid absorption aid, and 0.1 to 1 part by weight of a lubricant.

7. The flame-retardant styrene composition of claim 6, wherein the antioxidant is one or more of hindered phenol antioxidant, phosphite antioxidant, amine antioxidant, sulfur-containing antioxidant or metal salt antioxidant; the acid absorbent is one or a mixture of more of magnesium stearate, calcium stearate, zinc stearate, magnesium hydroxide, high-activity magnesium oxide or hydrotalcite; the lubricant is one or a mixture of more of a silicone lubricant, an amide lubricant, a stearic acid lubricant, a polyolefin lubricant or an ester lubricant.

8. The method for preparing a flame retardant styrene composition according to any one of claims 1 to 7, comprising the steps of:

a. weighing the raw materials in parts by weight;

b. all the raw materials are added into a high-speed mixer to be mixed for 1-2 minutes;

c. and then adding the mixed raw materials into a double-screw extruder for extrusion granulation, wherein the speed of the extruder is 50-100 revolutions per minute, and the temperature is 180-200 ℃.