FLAME-RETARDANT HIPS MATERIAL AND PREPARATION METHOD THEREOF

Abstract

Disclosed is a flame-retardant HIPS material and a preparation method thereof, comprising the following components: 90 parts to 67 parts of a HIPS resin; 8 parts to 15 parts of a brominated flame retardant; and 3 parts to 7 parts of an auxiliary flame retardant; wherein the auxiliary flame retardant is a 1,3,5-triazine compound. In the present invention, a synergistic compounding of the brominated flame retardant and the auxiliary flame retardant effectively reduces an amount of the brominated flame retardant, and a stable UL 94 (1.5 mm) V-0 flame-retardant class can be achieved. Compared with the existing brominated flame-retardant HIPS, the present invention has a low halogen content, low gas, and high cost performance ratio, which avoids excessive acid gas from forming air lines on the surface of parts, has a good appearance.

Claims

1. A flame-retardant HIPS material, comprising the following components in parts by weight: a HIPS resin of 90 parts to 67 parts; a brominated flame retardant of 10 parts to 15 parts; and an auxiliary flame retardant of 3 parts to 7 parts, wherein the auxiliary flame retardant is a 1,3,5-triazine compound, which is a chemical substance or a derivative having the following structure: ##STR00002## wherein R.sub.1, R.sub.2, R.sub.3 are the same and each independently represents —P(C.sub.6H.sub.5).sub.2, —P(CH.sub.3).sub.2, —PH.sub.2O.sub.4, —PH.sub.2O.sub.2, —SiH.sub.3, —SiCl.sub.3, —SiOH.sub.2, —SiHCl.sub.2, —SiHO.sub.3, —((CH.sub.3).sub.5Si)2O, —NHR, —NR.sub.2, —NCH, —NO.sub.3, —NH.sub.2, —NCO, —N(CH.sub.3) or —N.sub.2Cl.

2. The flame-retardant HIPS material according to claim 1, wherein the HIPS resin is a butadiene-styrene graft copolymer with a rubber content of 7 wt % to 11 wt % based on a total weight of the entire HIPS resin.

3. The flame-retardant HIPS material according to claim 1, wherein the HIPS resin has a melt flow rate of 5 g/min to 15 g/min under a load of 5 kg at 200° C.

4. The flame-retardant HIPS material according to claim 1, wherein the brominated flame retardant is one of or a mixture of more of decabromodiphenyl ethane, brominated epoxy, tetrabromobisphenol A, tris(tribromophenoxy)triazine, octabromoether and imine bromide.

5. The flame-retardant HIPS material according to claim 1, wherein further comprising 1 part to 7 parts of an antimony-based flame-retardant synergist, 0.01 part to 2 parts of an anti-dropping agent, and 0 part to 2 parts of a processing aid in parts by weight.

6. The flame-retardant HIPS material according to claim 5, wherein the antimony-based flame-retardant synergist is one or more of diantimony trioxide, diantimony pentoxide, sodium antimonate and antimony phosphite; the anti-dropping agent is a perfluoropolyolefin or a perfluoropolyolefin coated with styrene-acrylonitrile; and the processing aid is one or more of an antioxidant, a lubricant and an anti-photothermal oxidant.

7. The flame-retardant HIPS material according to claim 1, wherein a phosphorus element weight content is 30 ppm to 3,000 ppm based on a total weight of the flame-retardant HIPS material.

8. The flame-retardant HIPS material according to claim 1, wherein a nitrogen element weight content is 500 ppm to 50,000 ppm based on a total weight of the flame-retardant HIPS material.

9. The flame-retardant HIPS material according to claim 7, wherein a test method of the phosphorus element weight content is: taking 0.4 g to 0.6 g of a sample particle to be tested and placing in a round-bottom flask, adding 10 ml of concentrated H.sub.2SO.sub.4 and 5 ml of H.sub.2O.sub.2, placing on an electric heating plate at 480° C. for digestion until a complete carbonization, which requires 35 minutes to 45 minutes; after carbonization, cooling for 5 minutes, then adding an appropriate amount of H.sub.2O.sub.2, judging whether the carbonization is completed, if not, continuing to add H.sub.2O.sub.2 until the carbonization is completed, then cooling in a 100 ml volumetric flask and adding to a constant volume, filtering, centrifuging to take a supernatant, and then performing an inductively coupled plasma emission spectroscopy test ICP.

10. The flame-retardant HIPS material according to claim 8, wherein a test method of the nitrogen element weight content is: adopting a Kjeldahl nitrogen determination method, adding 1.0 mL of a protein solution with an appropriate concentration in a flask, adding an analysis sample to a bottom of the flask, adding 0.3 g of potassium sulfate-copper sulfate, 2.0 mL of concentrated sulfuric acid, and 1.0 mL of 30.0% hydrogen peroxide in sequence, bringing to boil over low heat until the substance in the flask becomes carbonized and blackened, performing distillation and absorption of an inorganic nitrogen standard sample, performing distillation and absorption of a sample to be tested and a blank sample, after the samples are processed, performing a titration with 0.0100 mol/L of a standard hydrochloric acid solution by using an acid microburette, recording a number of milliliter of the standard hydrochloric acid solution for each titration, and finally calculating the nitrogen element content of the sample to be tested.

11. A preparation method of the flame-retardant HIPS material according to claim 1, comprising the following steps: step a, fully mixing raw materials of each component according to a ratio in a high-speed mixer for 3 minutes to 6 minutes to obtain a mixture; step b, feeding the mixture into a twin-screw extruder through a precisely metered feeding device, with a temperature of each section of a extruder screw being controlled between 170° C. and 220° C., a length-to-diameter ratio of the twin-screw extruder being 30 to 35, and a rotating speed of the screw being 300 revolutions/minute to 800 revolutions/minute, fully melting and mixing the materials under shearing, mixing and conveying of the screw, and then through extrusion, granulation and drying to obtain a flame-retardant HIPS particle; and step c, adding the flame-retardant HIPS particle to an injection machine to mold into a sample strip to be tested, under injection conditions that a barrel temperature is 185° C. to 220° C., an injection pressure is 40 MPa to 60 MPa, and a speed is 40 cm.sup.3/s to 70 cm.sup.3/s.

12. A preparation method of the flame-retardant HIPS material according to claim 2, comprising the following steps: step a, fully mixing raw materials of each component according to a ratio in a high-speed mixer for 3 minutes to 6 minutes to obtain a mixture; step b, feeding the mixture into a twin-screw extruder through a precisely metered feeding device, with a temperature of each section of a extruder screw being controlled between 170° C. and 220° C., a length-to-diameter ratio of the twin-screw extruder being 30 to 35, and a rotating speed of the screw being 300 revolutions/minute to 800 revolutions/minute, fully melting and mixing the materials under shearing, mixing and conveying of the screw, and then through extrusion, granulation and drying to obtain a flame-retardant HIPS particle; and step c, adding the flame-retardant HIPS particle to an injection machine to mold into a sample strip to be tested, under injection conditions that a barrel temperature is 185° C. to 220° C., an injection pressure is 40 MPa to 60 MPa, and a speed is 40 cm.sup.3/s to 70 cm.sup.3/s.

13. A preparation method of the flame-retardant HIPS material according to claim 3, comprising the following steps: step a, fully mixing raw materials of each component according to a ratio in a high-speed mixer for 3 minutes to 6 minutes to obtain a mixture; step b, feeding the mixture into a twin-screw extruder through a precisely metered feeding device, with a temperature of each section of a extruder screw being controlled between 170° C. and 220° C., a length-to-diameter ratio of the twin-screw extruder being 30 to 35, and a rotating speed of the screw being 300 revolutions/minute to 800 revolutions/minute, fully melting and mixing the materials under shearing, mixing and conveying of the screw, and then through extrusion, granulation and drying to obtain a flame-retardant HIPS particle; and step c, adding the flame-retardant HIPS particle to an injection machine to mold into a sample strip to be tested, under injection conditions that a barrel temperature is 185° C. to 220° C., an injection pressure is 40 MPa to 60 MPa, and a speed is 40 cm.sup.3/s to 70 cm.sup.3/s.

14. A preparation method of the flame-retardant HIPS material according to claim 4, comprising the following steps: step a, fully mixing raw materials of each component according to a ratio in a high-speed mixer for 3 minutes to 6 minutes to obtain a mixture; step b, feeding the mixture into a twin-screw extruder through a precisely metered feeding device, with a temperature of each section of a extruder screw being controlled between 170° C. and 220° C., a length-to-diameter ratio of the twin-screw extruder being 30 to 35, and a rotating speed of the screw being 300 revolutions/minute to 800 revolutions/minute, fully melting and mixing the materials under shearing, mixing and conveying of the screw, and then through extrusion, granulation and drying to obtain a flame-retardant HIPS particle; and step c, adding the flame-retardant HIPS particle to an injection machine to mold into a sample strip to be tested, under injection conditions that a barrel temperature is 185° C. to 220° C., an injection pressure is 40 MPa to 60 MPa, and a speed is 40 cm.sup.3/s to 70 cm.sup.3/s.

15. A preparation method of the flame-retardant HIPS material according to claim 5, comprising the following steps: step a, fully mixing raw materials of each component according to a ratio in a high-speed mixer for 3 minutes to 6 minutes to obtain a mixture; step b, feeding the mixture into a twin-screw extruder through a precisely metered feeding device, with a temperature of each section of a extruder screw being controlled between 170° C. and 220° C., a length-to-diameter ratio of the twin-screw extruder being 30 to 35, and a rotating speed of the screw being 300 revolutions/minute to 800 revolutions/minute, fully melting and mixing the materials under shearing, mixing and conveying of the screw, and then through extrusion, granulation and drying to obtain a flame-retardant HIPS particle; and step c, adding the flame-retardant HIPS particle to an injection machine to mold into a sample strip to be tested, under injection conditions that a barrel temperature is 185° C. to 220° C., an injection pressure is 40 MPa to 60 MPa, and a speed is 40 cm.sup.3/s to 70 cm.sup.3/s.

16. A preparation method of the flame-retardant HIPS material according to claim 6, comprising the following steps: step a, fully mixing raw materials of each component according to a ratio in a high-speed mixer for 3 minutes to 6 minutes to obtain a mixture; step b, feeding the mixture into a twin-screw extruder through a precisely metered feeding device, with a temperature of each section of a extruder screw being controlled between 170° C. and 220° C., a length-to-diameter ratio of the twin-screw extruder being 30 to 35, and a rotating speed of the screw being 300 revolutions/minute to 800 revolutions/minute, fully melting and mixing the materials under shearing, mixing and conveying of the screw, and then through extrusion, granulation and drying to obtain a flame-retardant HIPS particle; and step c, adding the flame-retardant HIPS particle to an injection machine to mold into a sample strip to be tested, under injection conditions that a barrel temperature is 185° C. to 220° C., an injection pressure is 40 MPa to 60 MPa, and a speed is 40 cm.sup.3/s to 70 cm.sup.3/s.

17. A preparation method of the flame-retardant HIPS material according to claim 7, comprising the following steps: step a, fully mixing raw materials of each component according to a ratio in a high-speed mixer for 3 minutes to 6 minutes to obtain a mixture; step b, feeding the mixture into a twin-screw extruder through a precisely metered feeding device, with a temperature of each section of a extruder screw being controlled between 170° C. and 220° C., a length-to-diameter ratio of the twin-screw extruder being 30 to 35, and a rotating speed of the screw being 300 revolutions/minute to 800 revolutions/minute, fully melting and mixing the materials under shearing, mixing and conveying of the screw, and then through extrusion, granulation and drying to obtain a flame-retardant HIPS particle; and step c, adding the flame-retardant HIPS particle to an injection machine to mold into a sample strip to be tested, under injection conditions that a barrel temperature is 185° C. to 220° C., an injection pressure is 40 MPa to 60 MPa, and a speed is 40 cm.sup.3/s to 70 cm.sup.3/s.

18. A preparation method of the flame-retardant HIPS material according to claim 8, comprising the following steps: step a, fully mixing raw materials of each component according to a ratio in a high-speed mixer for 3 minutes to 6 minutes to obtain a mixture; step b, feeding the mixture into a twin-screw extruder through a precisely metered feeding device, with a temperature of each section of a extruder screw being controlled between 170° C. and 220° C., a length-to-diameter ratio of the twin-screw extruder being 30 to 35, and a rotating speed of the screw being 300 revolutions/minute to 800 revolutions/minute, fully melting and mixing the materials under shearing, mixing and conveying of the screw, and then through extrusion, granulation and drying to obtain a flame-retardant HIPS particle; and step c, adding the flame-retardant HIPS particle to an injection machine to mold into a sample strip to be tested, under injection conditions that a barrel temperature is 185° C. to 220° C., an injection pressure is 40 MPa to 60 MPa, and a speed is 40 cm.sup.3/s to 70 cm.sup.3/s.

19. A preparation method of the flame-retardant HIPS material according to claim 9, comprising the following steps: step a, fully mixing raw materials of each component according to a ratio in a high-speed mixer for 3 minutes to 6 minutes to obtain a mixture; step b, feeding the mixture into a twin-screw extruder through a precisely metered feeding device, with a temperature of each section of a extruder screw being controlled between 170° C. and 220° C., a length-to-diameter ratio of the twin-screw extruder being 30 to 35, and a rotating speed of the screw being 300 revolutions/minute to 800 revolutions/minute, fully melting and mixing the materials under shearing, mixing and conveying of the screw, and then through extrusion, granulation and drying to obtain a flame-retardant HIPS particle; and step c, adding the flame-retardant HIPS particle to an injection machine to mold into a sample strip to be tested, under injection conditions that a barrel temperature is 185° C. to 220° C., an injection pressure is 40 MPa to 60 MPa, and a speed is 40 cm.sup.3/s to 70 cm.sup.3/s.

20. A preparation method of the flame-retardant HIPS material according to claim 10, comprising the following steps: step a, fully mixing raw materials of each component according to a ratio in a high-speed mixer for 3 minutes to 6 minutes to obtain a mixture; step b, feeding the mixture into a twin-screw extruder through a precisely metered feeding device, with a temperature of each section of a extruder screw being controlled between 170° C. and 220° C., a length-to-diameter ratio of the twin-screw extruder being 30 to 35, and a rotating speed of the screw being 300 revolutions/minute to 800 revolutions/minute, fully melting and mixing the materials under shearing, mixing and conveying of the screw, and then through extrusion, granulation and drying to obtain a flame-retardant HIPS particle; and step c, adding the flame-retardant HIPS particle to an injection machine to mold into a sample strip to be tested, under injection conditions that a barrel temperature is 185° C. to 220° C., an injection pressure is 40 MPa to 60 MPa, and a speed is 40 cm.sup.3/s to 70 cm.sup.3/s.

Description

DESCRIPTION OF THE EMBODIMENTS

[0025] The present invention is further described by specific implementations hereinafter, the following embodiments are preferred implementations of the present invention, but the implementations of the present invention are not limited by the embodiments below.

[0026] Raw materials used in the present invention are as follows, which are all commercially available raw materials.

[0027] HIPS resin, PS 350 K, GPPC CHEMICAL CORPORATION, with a rubber content of 7 wt % to 11 wt %, and a melt flow rate of 5 g/min to 15 g/min under a load of 5 kg at 200° C.;

[0028] Brominated flame retardant:

[0029] decabromodiphenyl ethane, commercially available;

[0030] brominated epoxy, commercially available;

[0031] bromotriazine, commercially available;

[0032] imine bromide, commercially available;

[0033] auxiliary flame retardant 1: R.sub.1, R.sub.2 and R.sub.3 are the same phosphoalkyl group (—P(CH.sub.3).sub.2) or phosphoryl group (—PH.sub.2O.sub.4);

[0034] auxiliary flame retardant 2: R.sub.1, R.sub.2 and R.sub.3 are the same silyl group (—SiH.sub.3) or amino group (—NH.sub.2);

[0035] lubricant: EBS B50, Ruichi Chemical;

[0036] flame-retardant synergist: diantimony trioxide, Yiyang Yincheng Mineral;

[0037] anti-dripping agent, 5935EF, 3M Corporation, USA.

[0038] Test Standards or Methods for Each Performance:

TABLE-US-00002 Test item Unit Executive standard Flame retardancy Class UL 94

Embodiments 1 to 8 and Comparative Examples 1 to 3: Preparation of the Flame-Retardant HIPS Material

[0039] a, raw materials of each component were fully mixed according to a ratio in a high-speed mixer for 3 minutes to 6 minutes to obtain a mixture;

[0040] b, the mixture was fed into a twin-screw extruder through a precisely metered feeding device, with a temperature of each section of the extruder screw was controlled between 170° C. and 220° C., a length-to-diameter ratio of the twin-screw extruder was 30 to 35, and a rotating speed of the screw was 300 revolutions/minute to 800 revolutions/minute, the materials were fully melted and mixed under shearing, mixing and conveying of the screw, and then through extrusion, granulation and drying, a flame-retardant HIPS particle was obtained; and

[0041] c, the flame-retardant HIPS particle was added to an injection machine to mold into a sample strip to be tested, under injection conditions that a barrel temperature was 185° C. to 220° C., an injection pressure was 40 MPa to 60 MPa, and a flow rate was 40 cm.sup.3/s to 70 cm.sup.3/s.

[0042] Performance tests of the flame-retardant HIPS material were carried out, and the data are shown in Table 1.

TABLE-US-00003 TABLE 1 Specific ratios (parts by weight) and test performance results of Embodiments 1 to 8 and Comparative Examples 1 to 3 Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment 1 2 3 4 5 6 7 8 PS 350K 75.8 76.8 75.8 76.8 72.8 73.8 71.8 79.8 Decabromodiphenyl 11 11 8 8 11 ethane Brominated epoxy 3 5 Bromotriazine 3 14 Imine bromide 14 10 Auxiliary flame 4 3 4 7 7 retardant 1 Auxiliary flame 3 3 3 6 6 3 retardant 2 Diantimony 5 5 5 5 5 5 5 5 trioxide EBS B50 1 1 1 1 1 1 1 1 5935EF 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Phosphorus element 800 650 800 40 2850 30 2780 50 weight content (based on the entire flame-retardant HIPS material) ppm Nitrogen element 15310 15100 15200 45000 47000 25000 15310 18200 weight content (based on the entire flame-retardant HIPS material) ppm Flame-retardant V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 class (1.5 mm) Air lines No No No No No No No No Comparative Comparative Comparative Example 1 Example 2 Example 3 PS 350K 76.8 76.8 76.8 Decabromodiphenyl 8 17 15 ethane Brominated epoxy Bromotriazine Imine bromide Auxiliary flame 2 retardant 1 Auxiliary flame retardant 2 Diantimony trioxide 5 5 5 EBS B50 1 1 1 5935EF 0.2 0.2 0.2 Phosphorus element 50 40 150 weight content (based on the entire flame-retardant HIPS material) ppm Nitrogen element 0 0 280 weight content (based on the entire flame-retardant HIPS material) ppm Flame-retardant V-2 V-0 V-0 class (1.5 mm) Air lines No Obvious Light

[0043] It can be seen from comparison of the Embodiments and the Comparative examples in Table 1 that a combined action of the auxiliary flame retardant and different types of brominated flame retardants can achieve a V-0 flame-retardant effect, and the two have a synergistic compounding effect, which effectively reduces an amount of the brominated flame retardant and a cost for flame-retarding. After the compounding, not only the material can reach a stable UL 94 (1.5 mm) V-0 flame-retardant class, but also excessive acid gas forming air lines on the surface of parts is avoided, and a good appearance is obtained.