CN102002184B - Enhanced toughened halogen-free flame-retardant polypropylene mixture and preparation method thereof - Google Patents

Enhanced toughened halogen-free flame-retardant polypropylene mixture and preparation method thereof Download PDF

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CN102002184B
CN102002184B CN2010105030857A CN201010503085A CN102002184B CN 102002184 B CN102002184 B CN 102002184B CN 2010105030857 A CN2010105030857 A CN 2010105030857A CN 201010503085 A CN201010503085 A CN 201010503085A CN 102002184 B CN102002184 B CN 102002184B
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retardant
magnesium sulfate
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flame
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CN102002184A (en
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曾幸荣
赖学军
李红强
张海丽
尹昌宇
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South China University of Technology SCUT
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Abstract

The invention discloses an enhanced toughened halogen-free flame-retardant polypropylene mixture and a preparation method thereof. The method comprises the steps of: diluting 0.5-3 parts by weight of surfactants with 20-30 parts by weight of absolute ethyl alcohol, then adding into 100 parts by weight of alkaline magnesium sulfate whiskers, mixing for 15-30 min in a mixer, and then drying in a dryer to obtain the modified alkaline magnesium sulfate whiskers, wherein the alkaline magnesium sulfate whiskers is required to be 10-60 mum in average length and less than 10 mu m in diameter; adding polypropylene resin firstly on an open type warming mill with double-roll temperature of 170-180 DEG C, sequentially adding an antioxidant, a toughened modifier, the modified alkaline magnesium sulfate whiskers, a synergistic flame retardant, a molten-drop prevention modifier and a compatibilization modifier after the polypropylene resin is molten and covers the rolls, and evenly mixing to obtain the enhanced toughened halogen-free flame-retardant polypropylene mixture. The polypropylene mixture prepared in the invention has the advantages of high strength, good toughness, low smoke, no toxicity, no molten drop, remarkable flame retardant property and the like.

Description

A kind of enhancing toughening non-halogen flame-retardant propylene mixture and preparation method thereof
Technical field
It is fire-retardant to the present invention relates to modified resin, particularly relates to the halogen-free polypropylene flame redardant mixture, is specifically related to a kind of enhancing toughening non-halogen flame-retardant propylene mixture.The invention still further relates to and strengthen the toughening non-halogen flame-retardant propylene preparation process of mixture.
Background technology
Vestolen PP 7052 (PP) is widely used in fields such as electronic apparatus, Communication Equipment, automobile, material of construction owing to have advantages such as inexpensive, that mechanical property is excellent, forming process is easy.But, limited its further application because PP self is inflammable.Though traditional halogen containing flame-retardant has good flame retardancy, when burning, can produce a large amount of smog and toxic gas, cause secondary pollution, therefore study halogen-free polypropylene flame redardant and have great importance.
In numerous halogen-free flame retardantss, Marinco H (MTH) and white lake (ATH) are because cheap and easy to get, environmental protection is maximum one type an of consumption.Yet the surface polarity of MTH and ATH is big, flame retarding efficiency is low, reach satisfied flame retardant effect, often will add more than the 50wt%, the mechanical property and the processing characteristics of the material that deteriorated significantly.Therefore, be necessary the halogen-free flame-retardant system that development mechanics performance and flame retardant properties are good.
Alkali magnesium sulfate crystal whisker [MgSO 45Mg (OH) 2XH 2O] (be called for short MHSH) be a kind ofly to have single crystal fibre shape material than big L/D ratio (diameter is 0.5-1.0 μ m; Length is 20-80 μ m); Has very good physicals; It is added to can play flame-retardant smoke inhibition in the polymeric matrix, strengthen toughness reinforcing effect, effect is superior to Marinco H, has broad application prospects.Chinese invention patent application CN200910010635.9 (publication number is CN 101508787A) discloses the method and the article of reinforcing PP material capability with alkali magnesium sulfate crystal whisker; Be Vestolen PP 7052 and the alkali magnesium sulfate crystal whisker with the certain mass umber, melt blending has prepared enhancing PP matrix material in warm-up mill.Its tensile strength and Young's modulus have improved 62.4% and 52.4% than pure PP respectively, but its oxygen index is lower, is merely 22.7%; In addition, its elongation at break declines to a great extent, and is merely 15.1% of pure PP resin, is difficult to satisfy request for utilization.
Summary of the invention
The objective of the invention is to shortcomings such as big to present inorganic combustion inhibitor surface polarity, that flame retarding efficiency is low, addition is big; A kind of enhancing toughening non-halogen flame-retardant propylene mixture is provided; When having improved the system flame retarding efficiency greatly; Keep or improve tensile strength and the shock strength of PP, preparation strengthens the toughening non-halogen flame-retardant propylene mixture.
In order to improve the flame retarding efficiency of MHSH, improve intensity and the toughness of fire-retardant PP simultaneously to PP.The present invention is that main flame retardant, triphenylphosphate (TPP), expanded graphite (EG) and organo montmorillonite (OMMT) are plasticized modifier for synergistic flame retardant, ethylene-vinyl acetate copolymer (EVA) etc. with MHSH; Prepare the halogen-free polypropylene flame redardant mixture of flame retardant properties and good mechanical performance with the PP melt blending, can be widely used in fields such as electric wire, automobile, building materials and household electrical appliances.
The object of the invention is realized through following technical scheme:
1, a kind of enhancing toughening non-halogen flame-retardant propylene preparation process of mixture comprises the steps:
(1) with after the absolute ethyl alcohol dilution of the surface-modifying agent of 0.5~3 mass parts, add in the alkali magnesium sulfate crystal whisker of 100 mass parts with 20~30 mass parts, in mixing machine, mix 15~30 minutes after, in baking oven, dry, obtain the modification alkali magnesium sulfate crystal whisker; Said surface-modifying agent is silane coupling agent or titanate coupling agent; Said alkali magnesium sulfate crystal whisker mean length 10~60 μ m, diameter is less than 10 μ m;
(2) be to add acrylic resin on 170~180 ℃ the open warm-up mill earlier at two roll temperatures; Treat to add oxidation inhibitor, plasticized modifier, modification alkali magnesium sulfate crystal whisker, synergistic flame retardant, anti-molten drop properties-correcting agent and compatibilized modifier successively behind its fusion bag roller, mixing evenly can making strengthens the toughening non-halogen flame-retardant propylene mixture; The mass fraction of each amounts of components is following:
A, acrylic resin 100
B, plasticized modifier 10~40
C, modification alkali magnesium sulfate crystal whisker 30~50
D, synergistic flame retardant 10~25
E, anti-molten drop properties-correcting agent 1~5
F, compatibilized modifier 5~10
Said plasticized modifier is ethene-1-octene copolymer (POE), ethylene-vinyl acetate copolymer (EVA) or linear low density polyethylene (LLDPE);
Said synergistic flame-proof modifier is the expanded graphite (EG) and the triphenylphosphate (TPP) of mass ratio 2: 1~4: 1;
Said anti-molten drop properties-correcting agent is the polytetrafluoroethylene (PTFE) and the organo montmorillonite (OMMT) of mass ratio 1: 4~4: 1;
Said compatibilized modifier is polypropylene grafted maleic anhydride (PP-g-MAH) or glycidyl methacrylate graft polyolefin elastomer POE-g-(GMA-co-St), and percentage of grafting is 0.2%~1.5%.
For further realizing the object of the invention, the rotating speed of the mixing machine of said step (1) is preferably 400~800 rev/mins.
The bake out temperature of the baking oven of said step (1) is preferably 80~100 ℃, and drying time is preferably 4~6 hours.
The percentage of grafting of said compatibilized modifier is preferably 0.5%~1%.
A kind of enhancing toughening non-halogen flame-retardant propylene mixture is by method for preparing.
The present invention compared with prior art has following advantage:
(1) the present invention is a main flame retardant with alkali magnesium sulfate brilliant (MHSH), halogen-free environmental, LSZH, and have the toughness reinforcing effect of enhancing, effect is superior to the magnesium hydroxide flame retardant system.
(2) be synergistic flame retardant with triphenylphosphate (TPP), expanded graphite (EG) and organo montmorillonite (OMMT) etc., improved the flame retarding efficiency of system greatly, lower addition just can make the flame retardant properties of material reach UL94V-0 level, no molten drop.
(3) through surface-treated MHSH and interpolation compatibilized modifier polypropylene grafted maleic anhydride (PP-g-MAH), increased the consistency of fire retardant and PP matrix, help the raising of system over-all properties; Through adding the toughening modifying resin, make system when possessing than high tensile, shock strength and elongation at break also increase.
(4) preparation technology of the present invention is simple, and easy handling has broad application prospects.
Embodiment
Below in conjunction with embodiment the present invention is described further, but embodiments of the invention are not limited to this.
Embodiment 1
With 0.5 mass parts silane coupling agent (KH-560, spark chemical plant, Jiangxi) with 20 mass parts absolute ethyl alcohols (analytical pure, Guangzhou east reddening factory) dilution after; With 100 mass parts alkali magnesium sulfate crystal whisker (MHSH; Trade mark WS-1S, mean length 10~60 μ m, diameter is less than 10 μ m; This digests ltd Yingkou, Shandong prestige) at 400 rev/mins high-speed mixer (JYHG-100W; Source, Jia, Shenzhen City Kechuang plastics machinery ltd) mixed 30 minutes in, baking obtained modification alkali magnesium sulfate crystal whisker (m-MHSH) in 6 hours in 80 ℃ of baking ovens (model LG1008, Shanghai laboratory apparatus factory).
Be to add 100 mass parts Vestolen PP 7052 (melting index is 3.0g/10min, China Petroleum & Chemical Co., Ltd. Maoming Branch for PP, trade mark T30S) on 170 ℃ the open type dual-roller warm-up mill in the roller temperature; 10 mass parts ethylene-vinyl acetate copolymers (EVA, trade mark EVA14-2, vinyl acetate between to for plastic (Vac) content 14%, melting index is 2.0g/10min; Beijing Organic Chemical Plant), treat to add 0.1 mass parts oxidation inhibitor (B215, Switzerland vapour crust fine chemistry industry company) successively, 30 mass parts m-MHSH behind its fusion bag roller; 10 mass parts expanded graphites (EG, trade mark JF550-50N, initial expansion temperature are 200 ℃, expansion multiple is 250; The Beijing ChuangYi Biology Engineering New Materials Co., Ltd), 5 mass parts triphenylphosphates (CP, Tianjin Chemical Reagents Factory No.1), 2 mass parts organo montmorillonite (OMMT; Trade mark 1.44P, U.S. Nanocor company), 1 mass parts polytetrafluorethylepowder powder (PTFE; Trade mark XY-500, the prosperous win commerce and trade in Zhuhai City Development Co., Ltd) and 5 mass parts polypropylene grafted maleic anhydrides (PP-g-MAH, trade mark HS1-008; Percentage of grafting 0.8%, melting index 50.0g/10min, Guangzhou Hecheng Industry Co., Ltd.); Slice after mixing 15 minutes, then vulcanizing press (model XQLB-3508350, Shanghai first machine works) go up in 180 ℃ of following hot pressing, room temperatures cold pressing, slice; Make and strengthen the toughening non-halogen flame-retardant propylene mixture, on omnipotent sampling machine (model HY-W, Chinese Chengde trier factory), make the fire-retardant PP sample that is used to test mechanical property and flame retardant properties again.
Can see that from table 1 the fire-retardant PP mixture that makes is compared with pure PP sample (comparative example 1), when obtaining the excellent flame retardancy ability, have the characteristics of intensity height, good toughness.Wherein, oxygen index brings up to 33.0% from 17.5%, and amplification is up to 88.6%; The vertical combustion rank is hanged down cigarette, no molten drop from the stepless UL94V-0 level that is not increased to; Notched Izod impact strength is from 3.0kJm -2Be increased to 4.5kJm -2, amplification is up to 50%; The also purer PP of tensile strength increases.Prepared fire-retardant PP mixture high comprehensive performance has been expanded the application of PP in fields such as electronic apparatus, communications and transportation and interior decorations greatly.
Compare with traditional magnesium hydroxide flame retardant system (comparative example 2), the prepared fire-retardant PP mixture of the present invention also shows remarkable advantages.In the comparative example 2, the mechanical property and the flame retardant properties of the magnesium hydroxide flame retardant PP system of 50 mass parts Marinco Hs and 100 mass parts polypropylene fusion blend preparation are all relatively poor, and wherein, notched Izod impact strength is merely 1.7kJm -2, elongation at break also is merely 3.0%, and oxygen index is low, is merely 24.5, is difficult to satisfy request for utilization.
Embodiment 2
With 3 mass parts silane coupling agents (KH-560, spark chemical plant, Jiangxi) with 30 mass parts absolute ethyl alcohols (analytical pure, Guangzhou east reddening factory) dilution after; With 100 mass parts alkali magnesium sulfate crystal whisker (MHSH; Trade mark WS-1S, mean length 10~60 μ m, diameter is less than 10 μ m; This digests ltd Yingkou, Shandong prestige) at 800 rev/mins high-speed mixer (JYHG-100W; Source, Jia, Shenzhen City Kechuang plastics machinery ltd) mixed 15 minutes in, baking obtained modification alkali magnesium sulfate crystal whisker (m-MHSH) in 4 hours in 100 ℃ of baking ovens (model LG1008, Shanghai laboratory apparatus factory).
Be to add 100 mass parts Vestolen PP 7052 (melting index is 3.0g/10min, China Petroleum & Chemical Co., Ltd. Maoming Branch for PP, trade mark T30S) on 180 ℃ the open type dual-roller warm-up mill in the roller temperature; 20 mass parts ethene-1-octene copolymer (melting index is 1.2g/10min, Mitsui TAFERM for POE, trade mark DF610); Treat to add 0.1 mass parts oxidation inhibitor (B215, Switzerland vapour crust fine chemistry industry company) successively, 50 mass parts m-MHSH behind its fusion bag roller; 10 mass parts expanded graphites (EG, trade mark JF550-50N, initial expansion temperature are 200 ℃; Expansion multiple is 250, the Beijing ChuangYi Biology Engineering New Materials Co., Ltd), 5 mass parts triphenylphosphate (CPs; Tianjin Chemical Reagents Factory No.1), 2 mass parts organo montmorillonites (OMMT, trade mark 1.44P; U.S. Nanocor company), 3 mass parts polytetrafluorethylepowder powders (PTFE, trade mark XY-500; Zhuhai City prosperous win commerce and trade Development Co., Ltd) and 10 mass parts glycidyl methacrylate graft polyolefin elastomers (melting index is 5.0g/10min for POE-g-(GMA-co-St), percentage of grafting 1.5%; Guangzhou Hecheng Industry Co., Ltd.), slice after mixing 15 minutes, then on vulcanizing press in 185 ℃ of following hot pressing, room temperatures cold pressing, slice; Make and strengthen the toughening non-halogen flame-retardant propylene mixture, on omnipotent sampling machine (model HY-W, Chinese Chengde trier factory), make the fire-retardant PP sample that is used to test mechanical property and flame retardant properties again.
The result is as shown in table 1, can find out, prepared fire-retardant PP mixture has good flame retardant property and mechanical property.Wherein, oxygen index is up to 38.0%, and low cigarette, no molten drop reach the UL94V-0 level; In addition, its tensile strength and notched Izod impact strength are respectively 35.5MPa and 5.5kJm -2, be higher than the 35.5MPa and the 3.0kJm of pure PP (comparative example 1) -2, more be higher than the 27.0MPa and the 1.7kJm of traditional magnesium hydroxide flame retardant PP flame-retardant system (comparative example 2) -2, the prepared fire-retardant PP mixture of this explanation is one and has the flame-retardant system that strengthens toughening effect, expanded the application of PP in fields such as electronic apparatus, communications and transportation and interior decorations greatly.
Embodiment 3
With 2 mass parts titanate coupling agent (NXT-401; Guangzhou precious prosperous chemical materials ltd) with after 30 mass parts absolute ethyl alcohols (analytical pure, east, the Guangzhou reddening factory) dilution, with 100 mass parts alkali magnesium sulfate crystal whisker (MHSH; Trade mark WS-1S; Mean length 10~60 μ m, diameter are less than 10 μ m, and this digests ltd Yingkou, Shandong prestige) at 600 rev/mins high-speed mixer (JYHG-100W; Source, Jia, Shenzhen City Kechuang plastics machinery ltd) mixed 20 minutes in, baking obtained modification alkali magnesium sulfate crystal whisker (m-MHSH) in 5 hours in 90 ℃ of baking ovens.
Be to add 100 mass parts Vestolen PP 7052 on 170 ℃ the open type dual-roller warm-up mill (melting index is 3.0g/10min for PP, trade mark T30S in the roller temperature; China Petroleum & Chemical Co., Ltd. Maoming Branch), 40 mass parts linear low density polyethylenes (LLDPE, trade mark DFDA-7042; Melting index is 2.0g/10min, China Petroleum & Chemical Co., Ltd. Maoming Branch), treat to add 0.1 mass parts oxidation inhibitor (B215 successively behind its fusion bag roller; Switzerland vapour crust fine chemistry industry company), 40 mass parts m-MHSH, 15 mass parts expanded graphite (EG; Trade mark JF550-50N, initial expansion temperature are 200 ℃, and expansion multiple is 250; The Beijing ChuangYi Biology Engineering New Materials Co., Ltd), 5 mass parts triphenylphosphates (CP, Tianjin Chemical Reagents Factory No.1); 1 mass parts organo montmorillonite (OMMT, trade mark 1.44P, U.S. Nanocor company); 4 mass parts polytetrafluorethylepowder powders (PTFE, trade mark XY-500, the prosperous win commerce and trade in Zhuhai City Development Co., Ltd) and 10 mass parts glycidyl methacrylate graft polyolefin elastomer (POE-g-(GMA-co-St); Percentage of grafting 1.5%, melting index are 5.0g/10min, Guangzhou Hecheng Industry Co., Ltd.); Slice after mixing 15 minutes, then vulcanizing press (model XQLB-3508350, Shanghai first machine works) go up in 180 ℃ of following hot pressing, room temperatures cold pressing, slice; Make and strengthen the toughening non-halogen flame-retardant propylene mixture, on omnipotent sampling machine (model HY-W, Chinese Chengde trier factory), make the fire-retardant PP sample that is used to test mechanical property and flame retardant properties again.
The result is as shown in table 1, can find out, prepared fire-retardant PP mixture has good flame retardant property and mechanical property.Wherein, oxygen index is up to 35.5%, and low cigarette, no molten drop reach the UL94V-0 level; In addition, its notched Izod impact strength is 9.7kJm -2, elongation at break is also up to 25.0%, and the prepared fire-retardant PP mixture of this explanation has that intensity is good, toughness is had outstanding performance and the flame retardant properties excellent characteristics, can be widely used in fields such as electric wire.
Embodiment 4
With 1 mass parts titanate coupling agent (NXT-401; Guangzhou precious prosperous chemical materials ltd) with after 30 mass parts absolute ethyl alcohols (analytical pure, east, the Guangzhou reddening factory) dilution, with 100 mass parts alkali magnesium sulfate crystal whisker (MHSH; Trade mark WS-1S; Mean length 10~60 μ m, diameter are less than 10 μ m, and this digests ltd Yingkou, Shandong prestige) at 500 rev/mins high-speed mixer (JYHG-100W; Source, Jia, Shenzhen City Kechuang plastics machinery ltd) mixed 20 minutes in, baking obtained modification alkali magnesium sulfate crystal whisker (m-MHSH) in 5 hours in 100 ℃ of baking ovens.
Be to add 100 mass parts Vestolen PP 7052 (melting index is 3.0g/10min, China Petroleum & Chemical Co., Ltd. Maoming Branch for PP, trade mark T30S) on 170 ℃ the open type dual-roller warm-up mill in the roller temperature; 20 mass parts ethene-1-octene copolymer (melting index is 1.2g/10min, Mitsui TAFERM for POE, trade mark DF610); Treat to add 0.1 mass parts oxidation inhibitor (B215, Switzerland vapour crust fine chemistry industry company) successively, 30 mass parts modification alkali magnesium sulfate crystal whisker m-MHSH, 20 mass parts expanded graphite (EG behind its fusion bag roller; Trade mark JF550-50N, initial expansion temperature are 200 ℃, and expansion multiple is 250; The Beijing ChuangYi Biology Engineering New Materials Co., Ltd), 5 mass parts triphenylphosphates (CP, Tianjin Chemical Reagents Factory No.1); 4 mass parts organo montmorillonites (OMMT, trade mark 1.44P, U.S. Nanocor company); 1 mass parts polytetrafluorethylepowder powder (PTFE, trade mark XY-500, the prosperous win commerce and trade in Zhuhai City Development Co., Ltd) and 10 mass parts glycidyl methacrylate graft polyolefin elastomer (POE-g-(GMA-co-St); Percentage of grafting 1.5%, melting index are 5.0g/10min, Guangzhou Hecheng Industry Co., Ltd.); Slice after mixing 15 minutes, then vulcanizing press (model XQLB-3508350, Shanghai first machine works) go up in 180 ℃ of following hot pressing, room temperatures cold pressing, slice; Make and strengthen the toughening non-halogen flame-retardant propylene mixture, on omnipotent sampling machine (model HY-W, Chinese Chengde trier factory), make the fire-retardant PP sample that is used to test mechanical property and flame retardant properties again.
The result is as shown in table 1, can find out, prepared fire-retardant PP mixture has good flame retardant property and mechanical property.Wherein, oxygen index is up to 41.5%, and the UL94V-0 level is hanged down cigarette, no molten drop; Tensile strength is 28.0MPa, and notched Izod impact strength is 3.3kJm -2, can satisfy the Application for Field that PP has relatively high expectations in some flame retardant propertiess.
Comparative example 1
For the performance characteristics of the outstanding prepared fire-retardant PP mixture of the present invention, with pure PP sample as comparative example.
Be to add 100 mass parts Vestolen PP 7052 earlier on 170 ℃ the open type dual-roller warm-up mill (melting index is 3.0g/10min for PP, trade mark T30S in the roller temperature; China Petroleum & Chemical Co., Ltd. Maoming Branch); Treat to add 0.1 mass parts oxidation inhibitor (B215, Switzerland vapour crust fine chemistry industry company) successively, slice after mixing 15 minutes behind its fusion bag roller; Then at vulcanizing press (model XQLB-3508350; Shanghai first machine works) go up in 180 ℃ of following hot pressing, room temperatures cold pressing, slice, on omnipotent sampling machine (model HY-W, Chinese Chengde trier factory), make the PP sample that is used to test mechanical property and flame retardant properties again.
As shown in table 1, the tensile strength of said PP is 35.0MPa, and notched Izod impact strength is 3.0kJm -2, elongation at break has only 8.0%, oxygen index also is merely 17.5%, can not be through UL94 test, big limitations its range of application.
Comparative example 2
For better explanation advantageous feature of the present invention, with magnesium hydroxide flame retardant PP system commonly used as comparative example.
Be to add 100 mass parts Vestolen PP 7052 earlier on 170 ℃ the open type dual-roller warm-up mill (melting index is 3.0g/10min for PP, trade mark T30S in the roller temperature; China Petroleum & Chemical Co., Ltd. Maoming Branch), treat to add 0.1 mass parts oxidation inhibitor (B215, Switzerland vapour crust fine chemistry industry company) successively behind its fusion bag roller; 50 mass parts Marinco Hs (MTH, FM-70A, particle diameter 1.3-2.0 μ m; The Foshan City Jinge Fire-fighting Materials Co., Ltd); Slice after mixing 15 minutes, then vulcanizing press (model XQLB-3508350, Shanghai first machine works) go up in 180 ℃ of following hot pressing, room temperatures cold pressing, slice; On omnipotent sampling machine (model HY-W, Chinese Chengde trier factory), make the magnesium hydroxide flame retardant PP sample that is used to test mechanical property and flame retardant properties again.
As shown in table 1, the mechanical property and the flame retardant properties of said magnesium hydroxide flame retardant PP mixture are all undesirable.Wherein, tensile strength is 27.0MPa, and notched Izod impact strength is merely 1.7kJm -2, elongation at break also has only 3.0%; Oxygen index also is merely 24.5%, can not molten drop be arranged through the UL94 test, is difficult to reach application requiring.
Comparative example 3
For better explanation alkali magnesium sulfate crystal whisker as the enhancing of fire retardant toughness reinforcing and fire retardation, with the fire-retardant PP system of alkali magnesium sulfate crystal whisker as comparative example.
Be to add 100 mass parts Vestolen PP 7052 earlier on 170 ℃ the open type dual-roller warm-up mill (melting index is 3.0g/10min for PP, trade mark T30S in the roller temperature; China Petroleum & Chemical Co., Ltd. Maoming Branch), treat to add 0.1 mass parts oxidation inhibitor (B215, Switzerland vapour crust fine chemistry industry company) successively behind its fusion bag roller; 50 mass parts alkali magnesium sulfate crystal whiskers (MHSH, trade mark WS-1S, mean length 10~60 μ m; Diameter is less than 10 μ m, and this digests ltd Yingkou, Shandong prestige), slice after mixing 15 minutes; Then at vulcanizing press (model XQLB-3508350; Shanghai first machine works) go up in 180 ℃ of following hot pressing, room temperatures cold pressing, slice, on omnipotent sampling machine (model HY-W, Chinese Chengde trier factory), make the fire-retardant PP sample of alkali magnesium sulfate crystal whisker that is used to test mechanical property and flame retardant properties again.
As shown in table 1, the mechanical property of the fire-retardant PP mixture of said alkali magnesium sulfate crystal whisker and flame retardant properties are superior to magnesium hydroxide flame retardant PP mixture (comparative example 1).Wherein, tensile strength exceeds 33.3%, and notched Izod impact strength exceeds 64.7%; Elongation at break exceeds 133.3%, and oxygen index also is promoted to 26.0% from 24.5%, and this explanation alkali magnesium sulfate crystal whisker is the fire retardant that is superior to Marinco H; Has the enhancing toughening effect; But add alkali magnesium sulfate crystal whisker separately, can not can not satisfy request for utilization through the UL94 test.
Testing method
Mechanics Performance Testing: measure tensile strength and elongation at break according to GB/T1040-92; Measure the notched izod shock strength according to GB/T1843-1996.
Flame retardant properties test: measure LOI according to GB/T 2406-1993; The test of testing vertical flammability is with reference to UL-94 or its flame retardant rating of ASTM D635-77 standard testing
The flame retardant properties and the mechanical property of table 1 halogen-free polypropylene flame redardant mixture
Figure BSA00000297739900081

Claims (5)

1. one kind strengthens the toughening non-halogen flame-retardant propylene preparation process of mixture, it is characterized in that comprising the steps:
(1) with after the absolute ethyl alcohol dilution of the surface-modifying agent of 0.5~3 mass parts, add in the alkali magnesium sulfate crystal whisker of 100 mass parts with 20~30 mass parts, in mixing machine, mix 15~30 minutes after, in baking oven, dry, obtain the modification alkali magnesium sulfate crystal whisker; Said surface-modifying agent is silane coupling agent or titanate coupling agent; Said alkali magnesium sulfate crystal whisker mean length 10~60 μ m, diameter is less than 10 μ m;
(2) be to add acrylic resin on 170~180 ℃ the open warm-up mill earlier at two roll temperatures; Treat to add oxidation inhibitor, plasticized modifier, modification alkali magnesium sulfate crystal whisker, synergistic flame retardant, anti-molten drop properties-correcting agent and compatibilized modifier successively behind its fusion bag roller, mixing evenly can making strengthens the toughening non-halogen flame-retardant propylene mixture; The mass fraction of each amounts of components is following:
A, acrylic resin 100
B, plasticized modifier 10~40
C, modification alkali magnesium sulfate crystal whisker 30~50
D, synergistic flame retardant 10~25
E, anti-molten drop properties-correcting agent 1~5
F, compatibilized modifier 5~10
G, oxidation inhibitor 0.1
Said plasticized modifier is ethene-1-octene copolymer, ethylene-vinyl acetate copolymer or linear low density polyethylene;
Said synergistic flame retardant is the expanded graphite and the triphenylphosphate of mass ratio 2: 1~4: 1;
Said anti-molten drop properties-correcting agent is the tetrafluoroethylene and the organo montmorillonite of mass ratio 1: 4~4: 1;
Said compatibilized modifier is polypropylene grafted maleic anhydride or glycidyl methacrylate graft polyolefin elastomer, and percentage of grafting is 0.2%~1.5%.
2. enhancing toughening non-halogen flame-retardant propylene preparation process of mixture according to claim 1 is characterized in that:
The rotating speed of the mixing machine of said step (1) is 400~800 rev/mins.
3. enhancing toughening non-halogen flame-retardant propylene preparation process of mixture according to claim 1 is characterized in that:
The bake out temperature of the baking oven of said step (1) is 80~100 ℃, and drying time is 4~6 hours.
4. enhancing toughening non-halogen flame-retardant propylene preparation process of mixture according to claim 1 is characterized in that:
The percentage of grafting of said compatibilized modifier is 0.5%~1%.
5. one kind strengthens the toughening non-halogen flame-retardant propylene mixture, it is characterized in that by the said method preparation of claim 1.
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