CN104098839B - A kind of toughening flame-proof HOPP (PPH) constituent and preparation method thereof - Google Patents

Abstract

A kind of toughening flame-proof HOPP (PPH) constituent, in parts by weight, the component of this constituent includes: HOPP (PPH) 56-68；Inorganic toughener calcium carbonate 5-15；Inorganic combustion inhibitor melamine coated ammonium polyphosphate 18-31；Inorganic combustion inhibitor magnesium hydroxide 5-15；Rare earth titanium coupling agent 1-8；Antioxidant titanium dioxide 0.05-0.6；Antiager hindered amine 0.1-1.The preparation method of this toughening flame-proof HOPP (PPH) constituent is in 180～210 DEG C of extruding pelletizations or to stir prepared toughening flame-proof HOPP (PPH) the various section bar of rear direct extrusion molding or special-shaped blank with extruder.This constituent is ageing-resistant, light stability strong, and on a small quantity efficiently, smoke-free and tasteless is harmless, and fire-retardant rank reaches UL94 V-0 level, good flame retardation effect and environmental protection, is suitable for widely using.

Description

A kind of toughening flame-proof HOPP (PPH) constituent and preparation method thereof

Technical field

The present invention relates to a kind of PP composite material, relate in particular to a kind of toughening flame-proof HOPP (PPH) constituent and preparation method thereof.

Background technology

Polypropylene is a kind of general-purpose plastics, is widely used in electrotechnical, electronic industry.But, owing to polypropylene belongs to combustible material, its oxygen index (OI) (LOI) only has about 18, it is necessary to adds fire retardant and improves its fire resistance.But, after adding a large amount of fire retardant in polypropylene, the mechanical performance of material is often subject to large effect, and especially impact property declines rapidly, and impact strength substantially reduces.The method being usually used in flexibilized polypropylene material is to add appropriate thermoplastic elastomer (TPE), such as POE (polyolefin elastomer), SBS (styrene butadiene styrene block copolymer (SBS)), EPDM (ethylene propylene diene rubber) etc., the interpolation of elastomer can be greatly improved the toughness of thermoplastic resin, but the reduction of material stiffness and the change of chemical property can be caused again, it is difficult to realize making the toughness of material be improved under the premise of not other performance of loss material simultaneously.

HOPP (PPH) resin is a kind of macromolecular material, has the physical and chemical performances such as toughness is better, resistance to impact is high, thermostability is strong, acid and alkali resistance, saline solution function admirable.Also heat-proof water is degraded, is absent from internal stress problem of Cracking, these original characteristics of HOPP (PPH), enable it to for making hard high-pressure bottle and the molded parts etc. of apparatus, descaling bath, soda acid storage tank and automobile, being widely used to household appliances shell, steel rolling, chemical industry, building and built-in, sealing appliance, household supplies, toy and other a lot of consumer goodss, purposes is extremely extensive.

In recent years, safety and environmental protection problem increasingly causes the extensive attention in the whole world, therefore, the fire resistance of HOPP (PPH) and the security requirement of fire retardant is more and more higher, having halogen fire retardant to be eliminated gradually, halogen-free flame retardants arises at the historic moment, and demonstrates powerful vitality.In Non-halogen Flame Retardant Technology, add inorganic compound such as aluminium hydroxide and prepare refractory polypropylene composite in polypropylene, owing to addition is excessive, account for more than the 40% of mixture, result causes constituent poor processability, the mechanical properties decrease of goods so that it is purposes is restricted, this technology is seldom applied；Existing utilize in the fire-retardant technology of APP, have select improper due to synergist or proportioning is unreasonable, cause the weight fraction of additive to exceed the weight fraction of base material, the physical and chemical performance of base material all caused great adverse effect, has the suspicion that a presumptuous guest usurps the role of the host；Some emphasis fire resistances and ignore mechanical property, cause toughness of material to be substantially reduced；During some selection additives, it does not have noting the decomposition temperature of adding ingredient, result employs the decomposition temperature adding ingredient lower than base material processing temperature, causes adding ingredient to decompose in advance in the course of processing, can not get due mechanical property and flame retardant effect.Etc., all can not meet the requirement for HOPP (PPH) toughness of material of the specific uses such as the load that is hit (descaling bath as large-scale in rustless steel continuous rolling production line (tank)), particularly the reduction of toughness of material is extremely serious for the impact of welding performance, is not suitable with the requirement of the main equipment of welding forming.The mechanical property being improved material by polypropylene material and glass fiber impregnated compound having, then belong to technological problems, when not at the row that the present invention is comparable.

Such as publication number is that the Chinese patent of CN101280086A discloses a kind of special material for environment-friendly flame-proof polypropylene and preparation method thereof, wherein polypropylene weight mark 68%, weight of additive mark 32% time, flame retardant grade is V-2 level；When polypropylene weight mark 50%, weight of additive mark 50%, flame retardant grade is V-1 level；Only polypropylene weight mark drop to 35%, weight of additive mark up to 65 time, flame retardant grade can be only achieved V-0 level, and its section Example mechanical property is as shown in table 1:

Table 1:

From table 1 it follows that along with the increase of weight of additive mark, toughness (impact strength) degradation of material, the impact strength of embodiment 6 only has the 51% of embodiment 4.

Such as publication number is that the Chinese patent of CN1712444A discloses a kind of Halogen-Free Flame-Retardant Polypropylene And Preparation Method again, the one of which ammonium polyphosphate flame retardant wherein used is coated with by Melmex, it is known that, formaldehyde resin can discharge toxic gas, contaminated environment when burning；The fire retardant aluminium hydroxide decomposition temperature used again is 200 DEG C, lower than the processing temperature of HOPP (PPH), is not suitable for HOPP (PPH) material；Though it addition, this technology does not announce the data of material mechanical performance, but total consumption of its aluminium hydroxide and magnesium hydroxide is more than 20%, the mechanical property of material especially toughness can be produced considerable influence.

Such as publication number is that the Chinese patent of CN100376628C discloses a kind of refractory polypropylene composite again, and the dimethyl siloxane of its use has higher heat conductivity (being 3 times of calcium carbonate) not to be adapted at directly using in flame-retardant formulations very much；Again " heat decomposition temperature of titanate coupling agent is 211.8 DEG C (synthesis and applied researcies see Harbin University of Science and Technology Zhao Zhen Zhang Wenlong novel rare-earth coupling agent) ", barrel temperature >=240 DEG C in man-hour, the additive of uncomfortable cooperation HOPP (PPH) is added lower than HOPP；Its notch impact strength is only 3kj/m again², the requirement for HOPP (PPH) toughness of material of the specific uses such as the load that is hit (descaling bath as large-scale in rustless steel continuous rolling production line (tank)) can not be met far away.

In sum, on prior art basis, how to reduce additive amount, keep or improve the mechanical property particularly toughness of HOPP (PPH) to greatest extent, also have sizable Improvement space.

Summary of the invention

It is an object of the invention to provide a kind of toughening flame-proof HOPP (PPH) constituent and preparation method thereof, solve in conventional art to sacrifice the problem that toughness exchanges fire resistance for, by reasonable disposition efficient flame-retarding agent and the synergist with combination property, a kind of toughening flame-proof HOPP (PPH) constituent of preparation, to meet the specific use objective demands to fire-retardant HOPP (PPH) mechanical property such as load (descaling bath as large-scale in rustless steel continuous rolling production line (tank)) that are hit.

For achieving the above object, present invention employs techniques below scheme:

A kind of toughening flame-proof HOPP (PPH) constituent, in parts by weight, the component of this constituent includes:

Wherein, described melamine coated ammonium polyphosphate is that tripolycyanamide forms melamine coated ammonium polyphosphate fire retardant in APP surface modification, described calcium carbonate is the powder of granularity 800 order, described antiager hindered amine is benzoic acid (2, 2, 6, 6-tetramethyl-4-hydroxy piperidine) ester, decanedioic acid double, two (2, 2, 6, 6-tetramethyl-4-hydroxy piperidine) ester, nitrilo three [acetic acid (2, 2, 6, 6-tetramethyl-4-hydroxy piperidine) ester] and N, N '-bis-(2, 2, 6, 6-tetramethyl-piperidyl) in hexamethylene diamine any one, described toughener rare earth titanium coupling agent is the rare earth titanium coupling agent of rare earth and titanate esters complexation reaction synthesis.

The preparation method that present invention additionally comprises a kind of toughening flame-proof HOPP (PPH) constituent, this preparation method comprises the steps:

(1) according to the component proportion of arbitrary described toughening flame-proof HOPP (PPH) constituent of claim 1-5；

(2) calcium carbonate, magnesium hydroxide and titanium dioxide are respectively dried 6 hours at 130 DEG C；

(3) add rare earth titanium coupling agent in high speed mixer at 60 DEG C high-speed stirred 20 minutes, be sufficiently mixed and be evenly coated；

(4) melamine coated ammonium polyphosphate and hindered amine are put in the mixture that step (3) is formed, be modulated into homogeneous mixture, then HOPP (PPH) is put into wherein, stir；

(5) prepare fire-retardant toughened homopolymerization polypropylene particulate material with extruder in 180～210 DEG C of extrusions, cooling, pelletizing, or stir prepared toughening flame-proof HOPP (PPH) the various section bar of rear direct extrusion molding or special-shaped blank.

In the present invention, inorganic combustion inhibitor melamine coated ammonium polyphosphate, the combination of inorganic combustion inhibitor magnesium hydroxide are added to after in HOPP (PPH), under the effect of rare earth titanium coupling agent, good with HOPP (PPH) compatibility, and do not change the Main Mechanical of HOPP (PPH), after the fire retardation of said composition starts from polypropylene processing temperature, before degradation temperature, and continue in whole degradation process；Additionally, said composition is ageing-resistant, light stability strong, on a small quantity efficiently, smoke-free and tasteless is harmless, and fire-retardant rank reaches UL94V-0 level, good flame retardation effect and environmental protection, is suitable for widely using.

Detailed description of the invention:

Below the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under not making creative work premise, broadly fall into the scope of protection of the invention.

The new technical scheme that toughening flame-proof HOPP (PPH) constituent of the present invention is mainly formulated from the viewpoint of toughness reinforcing, fire-retardant, synergistic three, toughening flame-proof HOPP (PPH) constituent includes (in parts by weight):

In said components, described calcium carbonate is the powder of granularity 800 order, learns through test, and the toughening effect of granularity 800 order of calcium carbonate is best.

In said components, described melamine coated ammonium polyphosphate is that tripolycyanamide forms melamine coated ammonium polyphosphate fire retardant in APP surface modification, described antiager hindered amine is benzoic acid (2, 2, 6, 6-tetramethyl-4-hydroxy piperidine) ester, decanedioic acid double, two (2, 2, 6, 6-tetramethyl-4-hydroxy piperidine) ester, nitrilo three [acetic acid (2, 2, 6, 6-tetramethyl-4-hydroxy piperidine) ester] and N, N '-bis-(2, 2, 6, 6-tetramethyl-piperidyl) in hexamethylene diamine any one, described toughener rare earth titanium coupling agent is the rare earth titanium coupling agent of rare earth and titanate esters complexation reaction synthesis.

In the composition, inorganic combustion inhibitor melamine coated ammonium polyphosphate and inorganic combustion inhibitor magnesium hydroxide play a role according to temperature step formula, melamine coated ammonium polyphosphate starts, at 250 DEG C, play a role (exceeding HOPP [PPH] processing temperature about 40 DEG C), magnesium hydroxide starts play a role collaborative with melamine coated ammonium polyphosphate at 340 DEG C, is below the decomposition temperature of HOPP (PPH).Further, the addition of melamine coated ammonium polyphosphate is enough to make oxygen index (OI) reach 33 under the combined effect of synergist, substantially exceeds the requirement of flame retardant grade oxygen index (OI) >=27.Along with being gradually increasing of temperature, magnesium hydroxide starts to play a role, and is equivalent to the reinforcements that transfer, and flame retardant effect will be made to be greatly enhanced.

Titanate coupling agent is after rare earth modified, and its heat decomposition temperature is brought up to 262 DEG C by 211.8 DEG C, far above the processing temperature of HOPP (PPH)；Titanate coupling agent, for thermoplastic polymer and dry filler, has good coupling effect；This kind of coupling agent can use formula: ROO (4-n) Ti (OX-R ' Y) n (n=2,3) to represent；Wherein RO-is hydrolyzable lower alkyloxy, can react with mineral surfaces hydroxyl, thus reaching the purpose of chemical coupling；OX-can be pyrophosphoryl oxygen base, carboxyl, alkoxyl, sulfonic group, phosphorio etc., selects pyrophosphoryl oxygen base here, and pyrophosphoryl oxygen base has fire-retardant, antirust and strengthens bonding performance.Having higher characteristic through rare earth modified rare earth titanium coupling agent than titanate coupling agent, the initiation temperature such as raising material, the activation to inorganic rigid particle are strengthened to 91% (synthesis and applied research see Harbin University of Science and Technology Zhao Zhen Zhang Wenlong novel rare-earth coupling agent) etc. by 87%；

Titanium dioxide, after rare-earth coupling agent surface treatment, has antioxidant effect, also has fire-retardant synergistic effect, this is because after adding titanium dioxide (anatase titanium dioxide), one is that titanium dioxide makes material surface energy density reduce；Two is the transmission that titanium dioxide can stop heat；Three titanium dioxide when being higher temperature can be absorbed amount of heat by anatase titanium dioxide to the crystal conversion of rutile-type.

And APP Heat stability is good, in neutrality, mix also not chemically reactive mutually with any addO-on therapy.

The flame retardant effect of fire-retardant HOPP (PPH) and the effect of synergist have important relationship, but synergist can not add too much, in order to avoid the mechanical property of HOPP (PPH) is caused significant impact, so, the synergist with combination property should be selected, to reduce consumption, simultaneously, the present invention puts forth effort to solve the toughness reinforcing problem of HOPP (PPH), therefore first selects the synergist that toughening effect is good.It is toughness reinforcing, fire retardation mechanism is as follows:

Reuse rare earth titanium coupling agent (content of rare earth≤0.5%), improve fire retardant dispersion in the material, improve products machinery performance especially impact strength and toughness.

According to the report in application item (country's high-tech research development plan 863 problem Funded Projects) paper in rigid inorganic filler toughening Pp System of Guangzhou Inst of Chemistry, Chinese Academy of Sciences researcher (doctoral advisor) the Chen Ming rare-earth coupling agent just presided over:

" polypropylene (PP) has good physical and mechanical properties, processing characteristics and electrical insulation capability etc., is that a kind of density is little, the commodity polymer material of high comprehensive performance.Macromolecular material is filled inorganic particulate, is obtain there is one of most effective and generally the least expensive approach of the macromolecule modified material of some special performance.But, conventional inorganic particulate, being typically all the polar substances that surface can be significantly high, specific surface area is big, and between the non-polar polypropylene matrix that surface can be low, performance difference is very big, at the method compound tense adopting melt-processed, the two is because of poor compatibility so that inorganic particulate cannot be infiltrated by PP melt and easily self assemble is agglomerating, poor dispersion, and bonding interface is poor, cause that the impact strength of complex, elongation at break, processing rheological property etc. sharply decline.

Rare earth compound is the material that a class performance is peculiar, adds a small amount of rare earth and beyond thought special performance often occurs, thus have the title of " industry monosodium glutamate " in some systems.Newly synthesized rare-earth modifier WOT can be used as the surface conditioning agent of inorganic particulate, after inorganic particulate is processed, can improve the dispersibility in PP matrix, improves impact property and the mobility of complex.Described herein utilize this rare earth treating agent WOT to process different inorganic particulate, be mixed with treatment effect during complex with polypropylene fusion.

(1) rare-earth coupling agent can significantly modify the surface property of various inorganic particulate.

(2) rare-earth coupling agent processes the processing flowability that can improve various inorganic particulate compound PP system.

(3) mechanical property tests shows, the CaCO3 processed with 2.5% rare-earth coupling agent can make the notch impact strength of PP complex bring up to about 2 times of pure PP under certain condition, shows obvious inorganic particle toughened effect；But for toughening effect, WOT is more notable to the improvement effect of Mg (OH) 2, BaSO4.

(4) SEM observes and shows with viscosity experiment, rare-earth coupling agent processes and makes CaCO3, Mg (OH) 2 and BaSO4 disperse in the base to be more uniformly distributed, from fracture submicroscopic structure, after the particle unsticking processed, on interface, matrix creates a large amount of plastic deformation, and in untreated particle-filled system, after particle unsticking, leaving behind smooth cavity, plastic-less deformation occurs."

All introducing according to another a lot of technical data, the effect of rare-earth coupling agent is: improve filler dispersibility；Improve goods processing flowability；Improve products machinery performance especially impact strength and toughness；Reduce goods water absorption rate and oil factor.

And exactly fire retardant dispersion in the material is except affecting toughness, it also it is the key factor determining its flame retardant effect.Through us it is demonstrated experimentally that rare earth titanium coupling agent has goodish toughness reinforcing, flame retardant synergism.Its result of the test is in Table 2:

Table 2 (fix other proportionings and only change rare earth titanium coupling agent addition):

From table, data can be seen that, when rare earth titanium coupling agent addition reaches the 3-6% of total amount, is reasonable economic and ecologic effets, and significantly breaching its quantity in prior art is the addition of the 2-5% of inorganic particulate.Its impact strength fully meets the needs of the main equipments such as rustless steel continuous rolling production line descaling bath (tank).

The preparation process of above-mentioned toughening flame-proof HOPP (PPH) constituent is:

(1) according to the component proportion of arbitrary described toughening flame-proof HOPP (PPH) constituent of claim 1-4；

(2) calcium carbonate, magnesium hydroxide and titanium dioxide are respectively dried 6 hours at 130 DEG C；

(3) add rare earth titanium coupling agent in high speed mixer at 60 DEG C high-speed stirred 20 minutes, be sufficiently mixed and be evenly coated；

(4) melamine coated ammonium polyphosphate, titanium dioxide and hindered amine are put in the mixture that step (3) is formed, be modulated into homogeneous mixture, then HOPP (PPH) is put into wherein, stir；

(5) prepare fire-retardant toughened homopolymerization polypropylene particulate material with extruder in 180～210 DEG C of extrusions, cooling, pelletizing, or stir rear direct extrusion molding and prepare fire-retardant toughened HOPP (PPH) various section bar or special-shaped blank.

Due to the addition of rational synergist, toughener, various additive dispersion in the material is made to be greatly improved, so that composite material direct extrusion molding is possibly realized.So, much electricity, manpower and mechanical wear can be saved, also effectively reduce the number of times that is heated of material, it is therefore prevented that aging, performance degradation even qualitative change.

Fire-retardant toughened HOPP (PPH) the constituent performance prepared according to inventive formulation and method is as follows:

Oxygen index (OI): 33%；

Flammability: UL94V-0；

Hot strength: 30.5-31.8MPa；

Bending strength: 48.1-50.1MPa；

Impact strength: 48.8-50.9KJ/m2；

Relative density: 0.98-1.05；

Outward appearance: Lycoperdon polymorphum Vitt white, blue, microcomputer color etc..

Specific embodiment:

Implement practical application of the present invention or test result is as follows, but the invention is not restricted to following illustration.

Embodiment 1

Composition (kg): HOPP (PPH) 1000, calcium carbonate 80, melamine coated ammonium polyphosphate 349, magnesium hydroxide 159, rare earth titanium coupling agent 71, titanium dioxide 3.2, hindered amine 4.8.

Method: after above material is pressed the full and uniform mixing of preceding method, with extruder direct extrusion molding prepare toughening flame-proof HOPP (PPH) 30,40,90,120mm heavy-gauge sheeting；Then, be machined, the technique such as welding prepares certain steel enterprise rustless steel cold continuous rolling descaling bath electrode supporting framework, records sheet forming performance as follows:

Oxygen index (OI): 33.1%；

Flammability: UL94V-0；

Melt index (MI): 2.5g/10min；

Outward appearance: blue Lycoperdon polymorphum Vitt；

Operating temperature 90 DEG C, continuous operation 14500h.

Its mechanical property is in Table 3.

Embodiment 2

Weigh HOPP (PPH) 50000g, calcium carbonate 5000, melamine coated ammonium polyphosphate 17460g, magnesium hydroxide 7937g, rare earth titanium coupling agent 3571g, titanium dioxide 159g, hindered amine 238g.

Method: after above material is pressed the full and uniform mixing of preceding method, moulds bar pelletizing after cooling by extruder extrusion and prepares toughening flame-proof HOPP (PPH) particulate material；Then, extruded machine extrusion molding 10mm heavy-gauge sheeting.Its mechanical property is in Table 3.

Embodiment 3

Weigh HOPP (PPH) 50000g, calcium carbonate 4000, melamine coated ammonium polyphosphate 17460g, magnesium hydroxide 7937g, rare earth titanium coupling agent 3175g, titanium dioxide 159g, hindered amine 238g.

Method: after above material is pressed the full and uniform mixing of preceding method, moulds bar pelletizing after cooling by extruder extrusion and prepares toughening flame-proof HOPP (PPH) particulate material；Then, extruded machine extrusion molding 10mm heavy-gauge sheeting.Its mechanical property is in Table 3.

Embodiment 4

Weigh HOPP (PPH) 50000g, calcium carbonate 6000, melamine coated ammonium polyphosphate 17460g, magnesium hydroxide 7937g, rare earth titanium coupling agent 3968g, titanium dioxide 159g, hindered amine 238g.

Method: after above material is pressed the full and uniform mixing of preceding method, moulds bar pelletizing after cooling by extruder extrusion and prepares toughening flame-proof HOPP (PPH) particulate material；Then, extruded machine extrusion molding 10mm heavy-gauge sheeting.Its mechanical property is in Table 3.

Embodiment 5

Weigh HOPP (PPH) 50000g, calcium carbonate 6000, melamine coated ammonium polyphosphate 17460g, magnesium hydroxide 9524g, rare earth titanium coupling agent 3968g, titanium dioxide 159g, hindered amine 238g.

Method: after above material is pressed the full and uniform mixing of preceding method, moulds bar pelletizing after cooling by extruder extrusion and prepares toughening flame-proof HOPP (PPH) particulate material；Then, through injection machine injection moulding 200 × 100 × 10mm test block.Its mechanical property is in Table 3.

Table 3:

As can be seen from Table 3, toughening flame-proof HOPP (PPH) constituent of the present invention is compared with existing poly internal olefins mixture, the performances such as impact strength, hot strength, bending strength all significantly improve, and flame retardant rating is high, meet the specific use requirement to fire-retardant HOPP (PPH) mechanical property.

The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention.

Claims (6)

1. toughening flame-proof HOPP (PPH) constituent, it is characterised in that: in parts by weight, the component of this constituent includes:

2. toughening flame-proof HOPP (PPH) constituent according to claim 1, it is characterised in that: described melamine coated ammonium polyphosphate is that tripolycyanamide forms melamine coated ammonium polyphosphate fire retardant in APP surface modification.

3. toughening flame-proof HOPP (PPH) constituent according to claim 1 and 2, it is characterised in that: described calcium carbonate is the powder of granularity 800 order.

4. toughening flame-proof HOPP (PPH) constituent according to claim 1, it is characterized in that: described antiager hindered amine is benzoic acid (2,2,6,6-tetramethyl-4-hydroxy piperidine) ester, decanedioic acid double; two (2,2,6,6-tetramethyl-4-hydroxy piperidine) ester, nitrilo three [acetic acid (2,2,6,6-tetramethyl-4-hydroxy piperidine) ester] and N, N '-bis-(2,2,6,6-tetramethyl-piperidyls) in hexamethylene diamine any one or a few.

5. toughening flame-proof HOPP (PPH) constituent according to claim 1, it is characterised in that: toughener rare earth titanium coupling agent is the rare earth titanium coupling agent of rare earth and titanate esters complexation reaction synthesis.

6. the preparation method of toughening flame-proof HOPP (PPH) constituent, it is characterised in that this preparation method comprises the steps:

(1) according to the component proportion of arbitrary described toughening flame-proof HOPP (PPH) constituent of claim 1-5；

(2) calcium carbonate, magnesium hydroxide and titanium dioxide are respectively dried 6 hours at 130 DEG C；

(3) add rare earth titanium coupling agent in high speed mixer at 60 DEG C high-speed stirred 20 minutes, be sufficiently mixed and be evenly coated；

(4) melamine coated ammonium polyphosphate and hindered amine are put in the mixture that step (3) is formed, be modulated into homogeneous mixture, then HOPP (PPH) is put into wherein, stir；

(5) prepare toughening flame-proof HOPP particulate material with extruder in 180～210 DEG C of extrusions, cooling, pelletizing, or stir prepared toughening flame-proof HOPP (PPH) the various section bar of rear direct extrusion molding or special-shaped blank.