CN102532709A - Flame retardant polypropylene composition for salivating method sheet materials and manufacture method thereof - Google Patents
Flame retardant polypropylene composition for salivating method sheet materials and manufacture method thereof Download PDFInfo
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- CN102532709A CN102532709A CN2011104473072A CN201110447307A CN102532709A CN 102532709 A CN102532709 A CN 102532709A CN 2011104473072 A CN2011104473072 A CN 2011104473072A CN 201110447307 A CN201110447307 A CN 201110447307A CN 102532709 A CN102532709 A CN 102532709A
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Abstract
The invention discloses a flame retardant polypropylene composition for salivating method sheet materials. The flame retardant polypropylene composition is characterized by consisting of the following ingredients in parts by mass: 100 mass parts of polypropylene, 30 to 50 mass parts of phosphoric flame retardant copolymers, 5 to 8 mass parts of additive flame retardants, 5 to 8 mass parts of tougheners, 1 to 5 mass parts of flame retardant synergistic agents and 0.1 to 1 mass part of antioxidants. A preparation method of the flame retardant polypropylene composition comprises the steps that: the phosphoric flame retardant copolymers are prepared; all ingredients of the composition are put into a mixing machine to be uniformly mixed, then, the melt extrusion is carried out by an extruding machine, in addition, the melt temperature is controlled to be 160 to 200 DEG C, the bar pulling and the grain cutting are carried out, and the flame retardant polypropylene composition for the salivating method sheet materials is prepared. The flame retardant polypropylene composition has good compatibility with polypropylene base bodies, the influence on the mechanical performance and the thermal performance of the material is small, and the flame retardant performance and the tearing resistance performance of the polypropylene material are particularly improved. The flame retardant polypropylene composition can be widely applied to the insulation manufacture in the fields of electronic appliances, office electric appliances, vehicles, instrument apparatuses and the like.
Description
Technical field
The invention belongs to macromolecular material, relate to a kind of hydrostomia method sheet material with flame-proof polypropelene composition and method of manufacture thereof.Flame-proof polypropelene composition of the present invention can be widely used in the electronic apparatus of high flame retardant requirement, the insulating material manufacturing in the fields such as household electrical appliances, vehicle, instrument of handling official business.
Background technology
Vestolen PP 7052 (PP) is a kind of hemicrystalline material, density 0.90 g/cm
3～0.91g/cm
3Be the lightest a kind of in the general-purpose plastics, have mechanical electric performance and anti-high-frequency insulation property preferably, hardly suction; Do not receive humidity effect; Contact with most chemical and not have an effect, bigger shortcoming is that tear resistance is poor, and the Vestolen PP 7052 after modification can be widely used in automotive industry, household electric appliances, plastic pipe industry, mechanical means part etc.Because of the defective of polypropylene material, also be difficult to satisfy some Application Areas to high requests such as flame retardant properties, tear resistances, therefore various polypropylene fire retardant study on the modification is in the ascendant.
At present; China is electron donor with the new type of phosphate compounds; To break away from aromatic ester, fatty ester, the ether compound electron donor that foreign patent covers; Structure through the adjustment phosphate compounds; The copolymerization performance of adjustment catalyzer and chain structure, particle physics packed structures, aggregated structure and firm, the tough performance of polypropylene alloy; Set up the complete polypropylene alloy technology of preparing and the technology of independent intellectual property right; In anti-flaming polypropylene material, be widely used in the product of suitability for industrialized production, halogen flame (chloride or brominated flame-retardant is like tetrabromo-bisphenol, decabromodiphynly oxide, Brominated Polystyrene, pentabromotoluene and hexabromocyclododecane etc.) commonly used uses as outer additive flame retardant; But use that there is environmental pollution in this based flame retardant, the crystalline p p sheet flame retardant properties is not high and defective such as tearing toughness difference, can't satisfy the requirement of the green technology barrier of developed country such as European Union and the area dependent instruction of issue (is " about in electronic electric equipment, limiting some objectionable impurities instruction ", REACH i.e. " about chemical registration, assessment mandate and the rules that limit " etc. like RoHS).
Summary of the invention
The object of the invention is intended to overcome above-mentioned deficiency of the prior art, provide a kind of be easy to produce and have environmental protection, good flame-retardance can, the hydrostomia method sheet material of good mechanical electric property is with flame-proof polypropelene composition and method of manufacture thereof.
Content of the present invention is: hydrostomia method sheet material is used flame-proof polypropelene composition, it is characterized in that: by Vestolen PP 7052 100 mass parts, phosphorus containing fire retardant copolyester thing 30～50 mass parts, additive flame retardant 5～8 mass parts, toughner 5～8 mass parts, fire retarding synergist 1～5 mass parts and oxidation inhibitor 0.1～1 mass parts feed composition mix and to form;
Said Vestolen PP 7052 is commercially available various polypropylene particles;
Said additive flame retardant is three (1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclos [2; 2; 2] octane-4-methylene radical) SULPHOSUCCINIC ACID ESTER, 1-oxygen-4-methylol-2,6,7-trioxa-1-phospha dicyclo [2; 2,2] mixture of one or more in octane (PEPA), dimethyl methyl phosphonate (DMMP), triaryl phosphine oxide, the ammonium polyphosphate compounds such as (APP);
Said toughner is one or both in polyolefin elastomer (POE), the styrene-ethylene-butylene-styrene segmented copolymer (SEBS);
Said fire retarding synergist is any in permanent white, nano-aluminum hydroxide, nano-calcium carbonate, nano imvite, the talcum powder;
Said oxidation inhibitor is that the mass ratio of three (2,4-two trimethylphenylmethane bases) phosphorous acid ester and four [3-(3,5-di-t-butyl-4-phenylor) propionic acid] quaternary amyl alcohol ester is the mixture of 2:1;
Said phosphorus containing fire retardant copolyester thing follows these steps to preparation:
A, in reactor A, be that 30% ydrogen peroxide 50 mixes with mass ratio 1:2.5～5 with MALEIC ANHYDRIDE and weight percent concentration, in 40～60 ℃ of reactions 20～40 minutes down; Be warmed up to 95～100 ℃ again; Under stirring and refluxing, drip vinyl acetate continuously, added in 2 hours; Keep back flow reaction after 2 hours again, vacuum decompression removes and anhydrates, and makes vinyl acetate-maleic anhydride copolymer (VAMA), and is subsequent use;
The mol ratio of said MALEIC ANHYDRIDE and vinyl acetate is 2～3:1;
B, the DOPOMA with 350～700 mass parts, 1000～1600 mass parts terepthaloyl moietie, 0.2～0.8 mass parts of catalyst add in the reactor B; Be warming up to 60～100 ℃ under stirring; Slowly progressively temperature reaction under agitation then, and in 1～1.5 hour, temperature of reaction is risen to 200 ℃ by 100 ℃; Be warming up to 220 ℃ and insulation again; Vinyl acetate-the maleic anhydride copolymer (VAMA) of 380～800 mass parts that under agitation again step a made joins in the reactor B; Be warming up to 230～250 ℃ again, under pressure 0.1～0.2MPa, react and finished in 1～2 hour; Under 230～250 ℃ of temperature, pressure 50～100Pa condition, distill then and removed terepthaloyl moietie and the water that unreacted or transesterify go out in 1～2 hour, make the phosphorus containing fire retardant copolyester thing;
The chemistry of said DOPOMA is by name 9, and the 10-dihydro-9-oxy is assorted-affixture of 10-phospho hetero phenanthrene-10-oxide compound and toxilic acid, chemical structural formula is:
The said hydrostomia method of content of the present invention sheet material is characterized in that comprising the following steps: with the method for manufacture of flame-proof polypropelene composition
First step: preparation phosphorus containing fire retardant copolyester thing:
A, in reactor A, be that 30% ydrogen peroxide 50 mixes with mass ratio 1:2.5～5 with MALEIC ANHYDRIDE and weight percent concentration, in 40～60 ℃ of reactions 20～40 minutes down; Be warmed up to 95～100 ℃ again; Under stirring and refluxing, drip vinyl acetate continuously, added in 2 hours; Keep back flow reaction after 2 hours again, vacuum decompression removes and anhydrates, and makes vinyl acetate-maleic anhydride copolymer (VAMA), and is subsequent use;
The mol ratio of said MALEIC ANHYDRIDE and vinyl acetate is 2～3:1;
B, the DOPOMA with 350～700 mass parts, 1000～1600 mass parts terepthaloyl moietie, 0.2～0.8 mass parts of catalyst add in the reactor B; Be warming up to 60～100 ℃ under stirring; Slowly progressively temperature reaction under agitation then, and in 1～1.5 hour, temperature of reaction is risen to 200 ℃ by 100 ℃; Be warming up to 220 ℃ and insulation again; Vinyl acetate-the maleic anhydride copolymer (VAMA) of 380～800 mass parts that under agitation again step a made joins in the reactor B; Be warming up to 230～250 ℃ again, under pressure 0.1～0.2MPa, react and finished in 1～2 hour; Under 230～250 ℃ of temperature, pressure 50～100Pa condition, distill then and removed terepthaloyl moietie and the water that unreacted or transesterify go out in 1～2 hour, make the phosphorus containing fire retardant copolyester thing;
The chemistry of said DOPOMA is by name 9, and the 10-dihydro-9-oxy is assorted-affixture of 10-phospho hetero phenanthrene-10-oxide compound and toxilic acid, chemical structural formula is:
Second step: be equipped with hydrostomia method sheet material and use the flame-proof polypropelene composition raw material:
Phosphorus containing fire retardant copolyester thing 30～50 mass parts, additive flame retardant 5～8 mass parts, toughner 5～8 mass parts, fire retarding synergist 1～5 mass parts and oxidation inhibitor 0.1～1 mass parts by Vestolen PP 7052 100 mass parts, first step make are got each feed composition;
Said Vestolen PP 7052 is commercially available various polypropylene particles;
Said additive flame retardant is three (1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclos [2; 2; 2] octane-4-methylene radical) SULPHOSUCCINIC ACID ESTER, 1-oxygen-4-methylol-2,6,7-trioxa-1-phospha dicyclo [2; 2,2] mixture of one or more in octane (PEPA), dimethyl methyl phosphonate (DMMP), triaryl phosphine oxide, the ammonium polyphosphate compounds such as (APP);
Said toughner is one or both in polyolefin elastomer (POE), the styrene-ethylene-butylene-styrene segmented copolymer (SEBS);
Said fire retarding synergist is any in permanent white, nano-aluminum hydroxide, nano-calcium carbonate, nano imvite, the talcum powder;
Said oxidation inhibitor is that the mass ratio of three (2,4-two trimethylphenylmethane bases) phosphorous acid ester and four [3-(3,5-di-t-butyl-4-phenylor) propionic acid] quaternary amyl alcohol ester is the mixture of 2:1;
Third step: drop in the mixing machine each feed composition of the said formula ratio of second step evenly mixed; Melt extruding and control melt temperature through forcing machine again is 160～200 ℃; After the tie rod pelletizing, promptly make hydrostomia method sheet material and use the flame-proof polypropelene composition product.
Said forcing machine is preferably twin screw extruder.
Another content of the present invention is: described flame-proof polypropelene composition is used to adopt the hydrostomia method to produce the fire-retardant polypropylene sheet product of electrician's purposes.
Compared with prior art, the present invention has following characteristics and beneficial effect:
(1) the present invention's phosphorus containing fire retardant copolyester thing of adopting response type is as one of major ingredient of anti-flaming polypropylene material; When its high temperature in forcing machine is mixed; Carboxyl and oh group have been participated in further reaction or they and SULPHOSUCCINIC ACID ESTER and have been reacted; It is cancellated than macromole to have formed partial interpenetrating, thereby in polypropylene material, plays the effect of skeleton, has solved existing the polypropylene material low and fire-retardant not high drawback of tearing toughness at low temperatures; And, make the insulating property requirement that to satisfy electric product because of having reduced the carboxyl that has neither part nor lot in reaction and the quantity of oh group;
(2) adopt the present invention, through adding a spot of additive flame retardant,, consolidated the final flame retardant properties of the articles of sheet material that the flame-proof polypropelene composition that adopts application of the present invention produces more basically not under the prerequisite of impact polypropylene bulk material performance;
(3) the present invention has realized the pliability of articles of sheet material through adding toughner polyolefin elastomer (POE), styrene-ethylene-butylene-styrene segmented copolymer (SEBS), makes it to be easy to more the following process and the use of articles of sheet material;
(4) adopt the present invention, reached the purpose that improves the polypropylene flame redardant over-all properties, realized the halogen-free flameproof mode of polypropylene material, meet requirements of green environmental protection;
(5) flame-proof polypropelene composition of the present invention has good electric property, and is applicable to the electric insulation film field of waiting, practical.
Embodiment
Embodiment given below intends so that the present invention is described further; But can not be interpreted as it is restriction to protection domain of the present invention; The technician in this field to some nonessential improvement and adjustment that the present invention makes, still belongs to protection scope of the present invention according to the content of the invention described above.
First part: the preparation of phosphorus containing fire retardant copolyester thing (embodiment 1～12)
Embodiment 1:
The first step: in reactor A, MALEIC ANHYDRIDE is mixed with mass ratio 1:2.5 with the ydrogen peroxide 50 of concentration 30%, reacted 20 minutes down, heat up 95～100 ℃ again, under stirring and refluxing, drip vinyl acetate continuously, added in 2 hours in 40～60 ℃; Keep back flow reaction to finish after 2 hours, vacuum decompression removes and anhydrates, and it is subsequent use to obtain vinyl acetate-maleic anhydride copolymer (VAMA).The mol ratio of MALEIC ANHYDRIDE and Vinyl Acetate Monomer is 2:1.
Second step: DOPOMA, 1000kg terepthaloyl moietie, the 0.2kg catalyzer of 600kg are added in the reactor B; Be warming up to 60～100 ℃ under stirring; Slowly progressively temperature reaction under agitation then, temperature rises to 200 ℃ of 1 hour time spent of reaction end by 100 ℃, is warming up to 220 ℃ and insulation again; Under agitation condition, again the first step synthetic 380kg vinyl acetate-maleic anhydride copolymer (VAMA) is joined in the reactor B; Be warming up to 230～250 ℃ again, under pressure 0.1～0.2Mpa, react and finished in 2 hours; Distillation removal in 1 hour unreacted or transesterify go out under 230～250 ℃ of temperature, pressure 50～100Pa condition terepthaloyl moietie and water obtain the phosphorus containing fire retardant copolyester thing.
Embodiment 2:
The first step: in reactor A, MALEIC ANHYDRIDE is mixed with mass ratio 1:3 with the ydrogen peroxide 50 of concentration 30%, reacted 40 minutes down, heat up 95～100 ℃ again, under stirring and refluxing, drip vinyl acetate continuously, added in 2 hours in 40～60 ℃; Keep back flow reaction to finish after 2 hours, vacuum decompression removes and anhydrates, and it is subsequent use to obtain vinyl acetate-maleic anhydride copolymer (VAMA).The mol ratio of MALEIC ANHYDRIDE and Vinyl Acetate Monomer is 3:1.
Second step: DOPOMA, 1200kg terepthaloyl moietie, the 0.28kg catalyzer of 700kg are added in the reactor B; Be warming up to 60～100 ℃ under stirring; Slowly progressively temperature reaction under agitation then, temperature rises to 200 ℃ of 1.5 hours times spent of reaction end by 100 ℃, is warming up to 220 ℃ and insulation again; Under agitation condition, again the first step synthetic 580kg vinyl acetate-maleic anhydride copolymer (VAMA) is joined in the reactor B; Be warming up to 230～250 ℃ again, under pressure 0.1～0.2Mpa, react and finished in 1 hour; Distillation removal in 2 hours unreacted or transesterify go out under 230～250 ℃ of temperature, pressure 50～100Pa condition terepthaloyl moietie and water obtain the phosphorus containing fire retardant copolyester thing.
Embodiment 3:
The first step: in reactor A, MALEIC ANHYDRIDE is mixed with mass ratio 1:3.5 with the ydrogen peroxide 50 of concentration 30%, reacted 30 minutes down, heat up 95～100 ℃ again, under stirring and refluxing, drip vinyl acetate continuously, added in 2 hours in 40～60 ℃; Keep back flow reaction to finish after 2 hours, vacuum decompression removes and anhydrates, and it is subsequent use to obtain vinyl acetate-maleic anhydride copolymer (VAMA).The mol ratio of MALEIC ANHYDRIDE and Vinyl Acetate Monomer is 2.4:1.
Second step: DOPOMA, 1600kg terepthaloyl moietie, the 0.4kg catalyzer of 350kg are added in the reactor B; Be warming up to 60～100 ℃ under stirring; Slowly progressively temperature reaction under agitation then, temperature rises to 200 ℃ of 1.2 hours times spent of reaction end by 100 ℃, is warming up to 220 ℃ and insulation again; Under agitation condition, again the first step synthetic 800kg vinyl acetate-maleic anhydride copolymer (VAMA) is joined in the reactor B; Be warming up to 230～250 ℃ again, under pressure 0.1～0.2Mpa, react and finished in 2 hours; Distillation removal in 1.5 hours unreacted or transesterify go out under 230～250 ℃ of temperature, pressure 50～100Pa condition terepthaloyl moietie and water obtain the phosphorus containing fire retardant copolyester thing.
Embodiment 4:
The first step: in reactor A, MALEIC ANHYDRIDE is mixed with mass ratio 1:4 with the ydrogen peroxide 50 of concentration 30%, reacted 35 minutes down, heat up 95～100 ℃ again, under stirring and refluxing, drip vinyl acetate continuously, added in 2 hours in 40～60 ℃; Keep back flow reaction to finish after 2 hours, vacuum decompression removes and anhydrates, and it is subsequent use to obtain vinyl acetate-maleic anhydride copolymer (VAMA).The mol ratio of MALEIC ANHYDRIDE and Vinyl Acetate Monomer is 2.6:1.
Second step: DOPOMA, 1500kg terepthaloyl moietie, the 0.6kg catalyzer of 550kg are added in the reactor B; Be warming up to 60～100 ℃ under stirring; Slowly progressively temperature reaction under agitation then, temperature rises to 200 ℃ of 1.3 hours times spent of reaction end by 100 ℃, is warming up to 220 ℃ and insulation again; Under agitation condition, again the first step synthetic 600kg vinyl acetate-maleic anhydride copolymer (VAMA) is joined in the reactor B; Be warming up to 230～250 ℃ again, under pressure 0.1～0.2Mpa, react and finished in 1.5 hours; Distillation removal in 1 hour unreacted or transesterify go out under 230～250 ℃ of temperature, pressure 50～100Pa condition terepthaloyl moietie and water obtain the phosphorus containing fire retardant copolyester thing.
Embodiment 5:
The first step: in reactor A, MALEIC ANHYDRIDE is mixed with mass ratio 1:5 with the ydrogen peroxide 50 of concentration 30%, reacted 25 minutes down, heat up 95～100 ℃ again, under stirring and refluxing, drip vinyl acetate continuously, added in 2 hours in 40～60 ℃; Keep back flow reaction to finish after 2 hours, vacuum decompression removes and anhydrates, and it is subsequent use to obtain vinyl acetate-maleic anhydride copolymer (VAMA).The mol ratio of MALEIC ANHYDRIDE and Vinyl Acetate Monomer is 2.8:1.
Second step: DOPOMA, 1300kg terepthaloyl moietie, the 0. 8kg catalyzer of 450kg are added in the reactor B; Be warming up to 60～100 ℃ under stirring; Slowly progressively temperature reaction under agitation then, temperature rises to 200 ℃ of 1 hour time spent of reaction end by 100 ℃, is warming up to 220 ℃ and insulation again; Under agitation condition, again the first step synthetic 700kg vinyl acetate-maleic anhydride copolymer (VAMA) is joined in the reactor B; Be warming up to 230～250 ℃ again, under pressure 0.1～0.2Mpa, react and finished in 2 hours; Distillation removal in 1 hour unreacted or transesterify go out under 230～250 ℃ of temperature, pressure 50～100Pa condition terepthaloyl moietie and water obtain the phosphorus containing fire retardant copolyester thing.
Embodiment 6:
The phosphorus containing fire retardant copolyester thing follows these steps to preparation:
A, in reactor A, be that 30% ydrogen peroxide 50 mixes with mass ratio 1:3.7 with MALEIC ANHYDRIDE and weight percent concentration, in 40～60 ℃ of reactions 30 minutes down; Be warmed up to 95～100 ℃ again; Under stirring and refluxing, drip vinyl acetate continuously, added in 2 hours; Keep back flow reaction after 2 hours again, vacuum decompression removes and anhydrates, and makes vinyl acetate-maleic anhydride copolymer (VAMA), and is subsequent use.The mol ratio of MALEIC ANHYDRIDE and vinyl acetate is 2.5:1.
B, 520 mass parts (can be kilogram; DOPOMA afterwards together), 1300 mass parts terepthaloyl moietie, 0.5 mass parts of catalyst add in the reactor B; Be warming up to 60～100 ℃ under stirring; Slowly progressively temperature reaction under agitation then, and in 1.2 hours, temperature of reaction is risen to 200 ℃ by 100 ℃; Be warming up to 220 ℃ and insulation again; Vinyl acetate-the maleic anhydride copolymer (VAMA) of 590 mass parts that under agitation again step a made joins in the reactor B; Be warming up to 230～250 ℃ again, under pressure 0.1～0.2MPa, react and finished in 1.5 hours; Terepthaloyl moietie and the water that unreacted or transesterify go out was removed in distillation in 1.5 hours under 230～250 ℃ of temperature, pressure 50～100Pa condition then, made the phosphorus containing fire retardant copolyester thing.
Embodiment 7:
The phosphorus containing fire retardant copolyester thing follows these steps to preparation:
A, in reactor A, be that 30% ydrogen peroxide 50 mixes with mass ratio 1:2.5 with MALEIC ANHYDRIDE and weight percent concentration, in 40～60 ℃ of reactions 20 minutes down; Be warmed up to 95～100 ℃ again; Under stirring and refluxing, drip vinyl acetate continuously, added in 2 hours; Keep back flow reaction after 2 hours again, vacuum decompression removes and anhydrates, and makes vinyl acetate-maleic anhydride copolymer (VAMA), and is subsequent use.The mol ratio of MALEIC ANHYDRIDE and vinyl acetate is 2:1.
B, 350 mass parts (can be kilogram; DOPOMA afterwards together), 1000 mass parts terepthaloyl moietie, 0.2 mass parts of catalyst add in the reactor B; Be warming up to 60～100 ℃ under stirring; Slowly progressively temperature reaction under agitation then, and in 1 hour, temperature of reaction is risen to 200 ℃ by 100 ℃; Be warming up to 220 ℃ and insulation again; The 380 mass parts vinyl acetate-maleic anhydride copolymers (VAMA) that under agitation again step a made join in the reactor B; Be warming up to 230～250 ℃ again, under pressure 0.1～0.2MPa, react and finished in 1 hour; Terepthaloyl moietie and the water that unreacted or transesterify go out was removed in distillation in 1 hour under 230～250 ℃ of temperature, pressure 50～100Pa condition then, made the phosphorus containing fire retardant copolyester thing.
Embodiment 8:
The phosphorus containing fire retardant copolyester thing follows these steps to preparation:
A, in reactor A, be that 30% ydrogen peroxide 50 mixes with mass ratio 1:5 with MALEIC ANHYDRIDE and weight percent concentration, in 40～60 ℃ of reactions 40 minutes down; Be warmed up to 95～100 ℃ again; Under stirring and refluxing, drip vinyl acetate continuously, added in 2 hours; Keep back flow reaction after 2 hours again, vacuum decompression removes and anhydrates, and makes vinyl acetate-maleic anhydride copolymer (VAMA), and is subsequent use.The mol ratio of MALEIC ANHYDRIDE and vinyl acetate is 3:1.
B, 700 mass parts (can be kilogram; DOPOMA afterwards together), 1600 mass parts terepthaloyl moietie, 0.8 mass parts of catalyst add in the reactor B; Be warming up to 60～100 ℃ under stirring; Slowly progressively temperature reaction under agitation then, and in 1.5 hours, temperature of reaction is risen to 200 ℃ by 100 ℃; Be warming up to 220 ℃ and insulation again; The 800 mass parts vinyl acetate-maleic anhydride copolymers (VAMA) that under agitation again step a made join in the reactor B; Be warming up to 230～250 ℃ again, under pressure 0.1～0.2MPa, react and finished in 2 hours; Terepthaloyl moietie and the water that unreacted or transesterify go out was removed in distillation in 2 hours under 230～250 ℃ of temperature, pressure 50～100Pa condition then, made the phosphorus containing fire retardant copolyester thing.
Embodiment 9:
The phosphorus containing fire retardant copolyester thing follows these steps to preparation:
A, in reactor A, be that 30% ydrogen peroxide 50 mixes with mass ratio 1:2.5～5 with MALEIC ANHYDRIDE and weight percent concentration, in 40～60 ℃ of reactions 20～40 minutes down; Be warmed up to 95～100 ℃ again; Under stirring and refluxing, drip vinyl acetate continuously, added in 2 hours; Keep back flow reaction after 2 hours again, vacuum decompression removes and anhydrates, and makes vinyl acetate-maleic anhydride copolymer (VAMA), and is subsequent use.The mol ratio of MALEIC ANHYDRIDE and vinyl acetate is 2～3:1.
B, 350～700 mass parts (can be kilogram; DOPOMA afterwards together), 1000～1600 mass parts terepthaloyl moietie, 0.2～0.8 mass parts of catalyst add in the reactor B; Be warming up to 60～100 ℃ under stirring; Slowly progressively temperature reaction under agitation then, and in 1～1.5 hour, temperature of reaction is risen to 200 ℃ by 100 ℃; Be warming up to 220 ℃ and insulation again; 380～800 mass parts vinyl acetate-maleic anhydride copolymers (VAMA) that under agitation again step a made join in the reactor B; Be warming up to 230～250 ℃ again, under pressure 0.1～0.2MPa, react and finished in 1～2 hour; Under 230～250 ℃ of temperature, pressure 50～100Pa condition, distill then and removed terepthaloyl moietie and the water that unreacted or transesterify go out in 1～2 hour, make the phosphorus containing fire retardant copolyester thing.
Embodiment 10:
The phosphorus containing fire retardant copolyester thing follows these steps to preparation:
A, in reactor A, be that 30% ydrogen peroxide 50 mixes with mass ratio 1:3 with MALEIC ANHYDRIDE and weight percent concentration, in 40～60 ℃ of reactions 25 minutes down; Be warmed up to 95～100 ℃ again; Under stirring and refluxing, drip vinyl acetate continuously, added in 2 hours; Keep back flow reaction after 2 hours again, vacuum decompression removes and anhydrates, and makes vinyl acetate-maleic anhydride copolymer, and is subsequent use.The mol ratio of MALEIC ANHYDRIDE and vinyl acetate is 2.3:1.
B, the DOPOMA with 400 mass parts, 1200 mass parts terepthaloyl moietie, 0.3 mass parts of catalyst add in the reactor B; Be warming up to 60～100 ℃ under stirring; Slowly progressively temperature reaction under agitation then, and in 1.2 hours, temperature of reaction is risen to 200 ℃ by 100 ℃; Be warming up to 220 ℃ and insulation again; The 450 mass parts vinyl acetate-maleic anhydride copolymers (VAMA) that under agitation again step a made join in the reactor B; Be warming up to 230～250 ℃ again, under pressure 0.1～0.2MPa, react and finished in 1.2 hours; Terepthaloyl moietie and the water that unreacted or transesterify go out was removed in distillation in 1.2 hours under 230～250 ℃ of temperature, pressure 50～100Pa condition then, made the phosphorus containing fire retardant copolyester thing.
Embodiment 11:
The phosphorus containing fire retardant copolyester thing follows these steps to preparation:
A, in reactor A, be that 30% ydrogen peroxide 50 mixes with mass ratio 1:4 with MALEIC ANHYDRIDE and weight percent concentration, in 40～60 ℃ of reactions 35 minutes down; Be warmed up to 95～100 ℃ again; Under stirring and refluxing, drip vinyl acetate continuously, added in 2 hours; Keep back flow reaction after 2 hours again, vacuum decompression removes and anhydrates, and makes vinyl acetate-maleic anhydride copolymer, and is subsequent use.The mol ratio of MALEIC ANHYDRIDE and vinyl acetate is 2.8:1.
B, the DOPOMA with 600 mass parts, 1400 mass parts terepthaloyl moietie, 0.6 mass parts of catalyst add in the reactor B; Be warming up to 60～100 ℃ under stirring; Slowly progressively temperature reaction under agitation then, and in 1.4 hours, temperature of reaction is risen to 200 ℃ by 100 ℃; Be warming up to 220 ℃ and insulation again; The 600 mass parts vinyl acetate-maleic anhydride copolymers (VAMA) that under agitation again step a made join in the reactor B; Be warming up to 230～250 ℃ again, under pressure 0.1～0.2MPa, react and finished in 1.8 hours; Terepthaloyl moietie and the water that unreacted or transesterify go out was removed in distillation in 1 hour under 230～250 ℃ of temperature, pressure 50～100Pa condition then, made the phosphorus containing fire retardant copolyester thing.
Embodiment 12:
The phosphorus containing fire retardant copolyester thing follows these steps to preparation:
A, in reactor A, be that 30% ydrogen peroxide 50 mixes with mass ratio 1:4.5 with MALEIC ANHYDRIDE and weight percent concentration, in 40～60 ℃ of reactions 40 minutes down; Be warmed up to 95～100 ℃ again; Under stirring and refluxing, drip vinyl acetate continuously, added in 2 hours; Keep back flow reaction after 2 hours again, vacuum decompression removes and anhydrates, and makes vinyl acetate-maleic anhydride copolymer, and is subsequent use.The mol ratio of MALEIC ANHYDRIDE and vinyl acetate is 2.6:1.
B, the DOPOMA with 550 mass parts, 1500 mass parts terepthaloyl moietie, 0.5 mass parts of catalyst add in the reactor B; Be warming up to 60～100 ℃ under stirring; Slowly progressively temperature reaction under agitation then, and in 1 hour, temperature of reaction is risen to 200 ℃ by 100 ℃; Be warming up to 220 ℃ and insulation again; The 400 mass parts vinyl acetate-maleic anhydride copolymers that under agitation again step a made join in the reactor B; Be warming up to 230～250 ℃ again, under pressure 0.1～0.2MPa, react and finished in 1 hour; Terepthaloyl moietie and the water that unreacted or transesterify go out was removed in distillation in 1 hour under 230～250 ℃ of temperature, pressure 50～100Pa condition then, made the phosphorus containing fire retardant copolyester thing.
Second section: hydrostomia method sheet material is formed (embodiment 13～23) with flame-proof polypropelene composition:
Embodiment 13:
Hydrostomia method sheet material is used flame-proof polypropelene composition; It is characterized in that: by Vestolen PP 7052 100 mass parts, phosphorus containing fire retardant copolyester thing 40 mass parts (can be kilogram, back with), additive flame retardant 6.5 mass parts, toughner 6.5 mass parts, fire retarding synergist 3 mass parts and oxidation inhibitor 0.5 mass parts feed composition mix and form.
Additive flame retardant is three (1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclos [2; 2; 2] octane-4-methylene radical) SULPHOSUCCINIC ACID ESTER, 1-oxygen-4-methylol-2,6,7-trioxa-1-phospha dicyclo [2; 2,2] mixture of one or more in the compounds such as octane, dimethyl methyl phosphonate, triaryl phosphine oxide, ammonium polyphosphate.
Toughner is one or both in polyolefin elastomer, the styrene-ethylene-butylene-styrene segmented copolymer.
Fire retarding synergist is any in permanent white, nano-aluminum hydroxide, nano-calcium carbonate, nano imvite, the talcum powder.
Oxidation inhibitor is that the mass ratio of three (2,4-two trimethylphenylmethane bases) phosphorous acid ester and four [3-(3,5-di-t-butyl-4-phenylor) propionic acid] quaternary amyl alcohol ester is the mixture of 2:1;
The phosphorus containing fire retardant copolyester thing is any that makes among the embodiment 1-12;
Vestolen PP 7052 is commercially available polypropylene particles.
Embodiment 14:
Hydrostomia method sheet material is used flame-proof polypropelene composition; It is characterized in that: by Vestolen PP 7052 100 mass parts (can be kilogram, back with), phosphorus containing fire retardant copolyester thing 30 mass parts, additive flame retardant 5 mass parts, toughner 5 mass parts, fire retarding synergist 1 mass parts and oxidation inhibitor 0.1 mass parts feed composition mix and form.
Other omits with embodiment 13.
Embodiment 15:
Hydrostomia method sheet material is used flame-proof polypropelene composition; It is characterized in that: by Vestolen PP 7052 100 mass parts (can be kilogram, back with), phosphorus containing fire retardant copolyester thing 50 mass parts, additive flame retardant 8 mass parts, toughner 8 mass parts, fire retarding synergist 5 mass parts and oxidation inhibitor 1 mass parts feed composition mix and form.
Other omits with embodiment 13.
Embodiment 16:
Hydrostomia method sheet material is used flame-proof polypropelene composition; It is characterized in that: by Vestolen PP 7052 100 mass parts (can be kilogram, back with), phosphorus containing fire retardant copolyester thing 30～50 mass parts, additive flame retardant 5～8 mass parts, toughner 5～8 mass parts, fire retarding synergist 1～5 mass parts and oxidation inhibitor 0.1～1 mass parts feed composition mix and form.
Other omits with embodiment 13.
Embodiment 17-23:
Hydrostomia method sheet material is used flame-proof polypropelene composition; It is characterized in that: by Vestolen PP 7052 100 mass parts (can be kilogram, back with), phosphorus containing fire retardant copolyester thing 30～50 mass parts, additive flame retardant 5～8 mass parts, toughner 5～8 mass parts, fire retarding synergist 1～5 mass parts and oxidation inhibitor 0.1～1 mass parts feed composition mix and form.
The concrete mass parts consumption of each feed composition sees the following form among each embodiment:
Other omits with embodiment 13.
Third part: hydrostomia method sheet material is with the manufacturing (embodiment 24～33) of flame-proof polypropelene composition:
Embodiment: 24:
A kind of hydrostomia method sheet material comprises the following steps: with the method for manufacture of flame-proof polypropelene composition
First step: preparation phosphorus containing fire retardant copolyester thing, with embodiment 1;
Second step: be equipped with hydrostomia method sheet material and use the flame-proof polypropelene composition raw material:
Press Vestolen PP 7052 100 mass parts and (can be kilogram; The back with), embodiment 1 phosphorus containing fire retardant copolyester thing 50 mass parts, additive flame retardant three (the 1-oxo-1-phospha-2 that make; 6; 7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene radical) SULPHOSUCCINIC ACID ESTER 5 mass parts, toughner polyolefin elastomer (POE) 8 mass parts, fire retarding synergist nano-aluminum hydroxide 2 mass parts and oxidation inhibitor 0.1 mass parts are got each feed composition;
Third step: drop in the mixing machine each feed composition of the said formula ratio of second step evenly mixed; Melt extruding and control melt temperature through forcing machine again is 160～200 ℃; After the tie rod pelletizing, promptly make hydrostomia method sheet material and use the flame-proof polypropelene composition product.
Embodiment: 25:
A kind of hydrostomia method sheet material comprises the following steps: with the method for manufacture of flame-proof polypropelene composition
First step: preparation phosphorus containing fire retardant copolyester thing, with embodiment 1;
Second step: be equipped with hydrostomia method sheet material and use the flame-proof polypropelene composition raw material:
Press Vestolen PP 7052 100 mass parts and (can be kilogram; The back with), embodiment 1 phosphorus containing fire retardant copolyester thing 50 mass parts, the additive flame retardant 1-oxygen-4-methylol-2 that make; 6; 7-trioxa-1-phospha dicyclo [2,2,2] octanes (PEPA) 8 mass parts, toughner styrene-ethylene-butylene-styrene segmented copolymer (SEBS) 6 mass parts, fire retarding synergist permanent white 3 mass parts and oxidation inhibitor 0.2 mass parts are got each feed composition;
Third step: drop in the mixing machine each feed composition of the said formula ratio of second step evenly mixed; Melt extruding and control melt temperature through forcing machine again is 160～200 ℃; After the tie rod pelletizing, promptly make hydrostomia method sheet material and use the flame-proof polypropelene composition product.
Embodiment: 26:
A kind of hydrostomia method sheet material comprises the following steps: with the method for manufacture of flame-proof polypropelene composition
First step: preparation phosphorus containing fire retardant copolyester thing, with embodiment 2;
Second step: be equipped with hydrostomia method sheet material and use the flame-proof polypropelene composition raw material:
Press phosphorus containing fire retardant copolyester thing 45 mass parts, additive flame retardant dimethyl methyl phosphonate (DMMP) 8 mass parts, toughner polyolefin elastomer (POE) 7 mass parts, fire retarding synergist nano-calcium carbonate 3 mass parts and oxidation inhibitor 0.1 mass parts that Vestolen PP 7052 100 mass parts (can be kilogram, back with), embodiment 2 make and get each feed composition;
Third step: drop in the mixing machine each feed composition of the said formula ratio of second step evenly mixed; Melt extruding and control melt temperature through forcing machine again is 160～200 ℃; After the tie rod pelletizing, promptly make hydrostomia method sheet material and use the flame-proof polypropelene composition product.
Embodiment: 27:
A kind of hydrostomia method sheet material comprises the following steps: with the method for manufacture of flame-proof polypropelene composition
First step: preparation phosphorus containing fire retardant copolyester thing, with embodiment 2;
Second step: be equipped with hydrostomia method sheet material and use the flame-proof polypropelene composition raw material:
Press phosphorus containing fire retardant copolyester thing 45 mass parts, additive flame retardant triaryl phosphine oxide 8 mass parts, toughner styrene-ethylene-butylene-styrene segmented copolymer (SEBS) 6 mass parts, fire retarding synergist nano imvite 4 mass parts and oxidation inhibitor 0.2 mass parts that Vestolen PP 7052 100 mass parts (can be kilogram, back with), embodiment 2 make and get each feed composition;
Third step: drop in the mixing machine each feed composition of the said formula ratio of second step evenly mixed; Melt extruding and control melt temperature through forcing machine again is 160～200 ℃; After the tie rod pelletizing, promptly make hydrostomia method sheet material and use the flame-proof polypropelene composition product.
Embodiment: 28:
A kind of hydrostomia method sheet material comprises the following steps: with the method for manufacture of flame-proof polypropelene composition
First step: preparation phosphorus containing fire retardant copolyester thing, with embodiment 3;
Second step: be equipped with hydrostomia method sheet material and use the flame-proof polypropelene composition raw material:
Press phosphorus containing fire retardant copolyester thing 40 mass parts, additive flame retardant (quality is than the mixture of triaryl phosphine oxide: ammonium polyphosphate=3:1) 5 mass parts, toughner polyolefin elastomer (POE) 6 mass parts, fire retarding synergist talcum powder 1 mass parts and oxidation inhibitor 0.1 mass parts that Vestolen PP 7052 100 mass parts (can be kilogram, back with), embodiment 3 make and get each feed composition;
Third step: drop in the mixing machine each feed composition of the said formula ratio of second step evenly mixed; Melt extruding and control melt temperature through forcing machine again is 160～200 ℃; After the tie rod pelletizing, promptly make hydrostomia method sheet material and use the flame-proof polypropelene composition product.
Embodiment: 29:
A kind of hydrostomia method sheet material comprises the following steps: with the method for manufacture of flame-proof polypropelene composition
First step: preparation phosphorus containing fire retardant copolyester thing, with embodiment 3;
Second step: be equipped with hydrostomia method sheet material and use the flame-proof polypropelene composition raw material:
(quality is than polyolefin elastomer: the mixture of styrene-ethylene-butylene-styrene segmented copolymer=1:1) 7 mass parts, fire retarding synergist nano imvite 5 mass parts and oxidation inhibitor 0.2 mass parts are got each feed composition to press phosphorus containing fire retardant copolyester thing 40 mass parts that Vestolen PP 7052 100 mass parts (can be kilogram, back with), embodiment 3 make, additive flame retardant (quality is than the mixture of triaryl phosphine oxide: dimethyl methyl phosphonate=4:1) 6 mass parts, toughner;
Third step: drop in the mixing machine each feed composition of the said formula ratio of second step evenly mixed; Melt extruding and control melt temperature through forcing machine again is 160～200 ℃; After the tie rod pelletizing, promptly make hydrostomia method sheet material and use the flame-proof polypropelene composition product.
Embodiment: 30:
A kind of hydrostomia method sheet material comprises the following steps: with the method for manufacture of flame-proof polypropelene composition
First step: preparation phosphorus containing fire retardant copolyester thing, with embodiment 4;
Second step: be equipped with hydrostomia method sheet material and use the flame-proof polypropelene composition raw material:
(quality is than triaryl phosphine oxide: the mixture of dimethyl methyl phosphonate: ammonium polyphosphate=5:2:3) (quality is than polyolefin elastomer: the mixture of styrene-ethylene-butylene-styrene segmented copolymer=1:3) 5 mass parts, fire retarding synergist nano-aluminum hydroxide 2 mass parts and oxidation inhibitor 0.1 mass parts are got each feed composition for 7 mass parts, toughner to press phosphorus containing fire retardant copolyester thing 35 mass parts that Vestolen PP 7052 100 mass parts (can be kilogram, back with), embodiment 4 make, additive flame retardant;
Third step: drop in the mixing machine each feed composition of the said formula ratio of second step evenly mixed; Melt extruding and control melt temperature through forcing machine again is 160～200 ℃; After the tie rod pelletizing, promptly make hydrostomia method sheet material and use the flame-proof polypropelene composition product.
Embodiment: 31:
A kind of hydrostomia method sheet material comprises the following steps: with the method for manufacture of flame-proof polypropelene composition
First step: preparation phosphorus containing fire retardant copolyester thing, with embodiment 4;
Second step: be equipped with hydrostomia method sheet material and use the flame-proof polypropelene composition raw material:
Press Vestolen PP 7052 100 mass parts and (can be kilogram; The back with), embodiment 4 phosphorus containing fire retardant copolyester thing 35 mass parts, additive flame retardant (mass ratio three (the 1-oxo-1-phospha-2 that make; 6; 7-trioxa-l-phosphabicyclo [2; 2,2] mixture of SULPHOSUCCINIC ACID ESTER: dimethyl methyl phosphonate=4:1 octane-4-methylene radical)) (quality is than polyolefin elastomer: the mixture of styrene-ethylene-butylene-styrene segmented copolymer=2:1) 5 mass parts, fire retarding synergist nano-calcium carbonate 3 mass parts and oxidation inhibitor 0.2 mass parts are got each feed composition for 8 mass parts, toughner;
Third step: drop in the mixing machine each feed composition of the said formula ratio of second step evenly mixed; Melt extruding and control melt temperature through forcing machine again is 160～200 ℃; After the tie rod pelletizing, promptly make hydrostomia method sheet material and use the flame-proof polypropelene composition product.
Embodiment: 32:
A kind of hydrostomia method sheet material comprises the following steps: with the method for manufacture of flame-proof polypropelene composition
First step: preparation phosphorus containing fire retardant copolyester thing, with embodiment 5;
Second step: be equipped with hydrostomia method sheet material and use the flame-proof polypropelene composition raw material:
Press Vestolen PP 7052 100 mass parts and (can be kilogram; The back with), embodiment 5 phosphorus containing fire retardant copolyester thing 30 mass parts, additive flame retardant (mass ratio three (the 1-oxo-1-phospha-2 that make; 6; 7-trioxa-l-phosphabicyclo [2; 2,2] SULPHOSUCCINIC ACID ESTER octane-4-methylene radical): the mixture of triaryl phosphine oxide: dimethyl methyl phosphonate=4:1:2) (quality is than polyolefin elastomer: the mixture of styrene-ethylene-butylene-styrene segmented copolymer=3:1) 8 mass parts, fire retarding synergist talcum powder 4 mass parts and oxidation inhibitor 0.1 mass parts are got each feed composition for 6 mass parts, toughner;
Third step: drop in the mixing machine each feed composition of the said formula ratio of second step evenly mixed; Melt extruding and control melt temperature through forcing machine again is 160～200 ℃; After the tie rod pelletizing, promptly make hydrostomia method sheet material and use the flame-proof polypropelene composition product.
Embodiment: 33:
A kind of hydrostomia method sheet material comprises the following steps: with the method for manufacture of flame-proof polypropelene composition
First step: preparation phosphorus containing fire retardant copolyester thing, with embodiment 5;
Second step: be equipped with hydrostomia method sheet material and use the flame-proof polypropelene composition raw material:
(quality is than polyolefin elastomer: the mixture of styrene-ethylene-butylene-styrene segmented copolymer=1:4) 8 mass parts, fire retarding synergist permanent white 3 mass parts and oxidation inhibitor 0.2 mass parts are got each feed composition to press phosphorus containing fire retardant copolyester thing 30 mass parts that Vestolen PP 7052 100 mass parts (can be kilogram, back with), embodiment 5 make, additive flame retardant (quality is than the mixture of triaryl phosphine oxide: ammonium polyphosphate=1:3) 5 mass parts, toughner;
Third step: drop in the mixing machine each feed composition of the said formula ratio of second step evenly mixed; Melt extruding and control melt temperature through forcing machine again is 160～200 ℃; After the tie rod pelletizing, promptly make hydrostomia method sheet material and use the flame-proof polypropelene composition product.
In the foregoing description 24-33: said oxidation inhibitor is that the mass ratio of three (2,4-two trimethylphenylmethane bases) phosphorous acid ester and four [3-(3,5-di-t-butyl-4-phenylor) propionic acid] quaternary amyl alcohol ester is the mixture of 2:1.
In the foregoing description 24-33: said forcing machine is twin screw extruder preferably.
In the foregoing description: said Vestolen PP 7052 is commercially available various polypropylene particles.
In the foregoing description: described flame-proof polypropelene composition is used to adopt the hydrostomia method to produce the fire-retardant polypropylene sheet product of electrician's purposes.
Following table is to adopt the film that compsn produces of embodiment 24～33 prescriptions and the performance table of comparative example:
Annotate: comparative example has the halogen flame-proof polypropelene composition to be produced film by commercially available pure addition type.
In the foregoing description: each raw material that is adopted is the commercially available prod.
In the foregoing description: in the percentage that is adopted, do not indicate especially, be quality (weight) percentage; Said quality (weight) part can all be gram or kilogram.
In the foregoing description: the processing parameter in each step (temperature, time, concentration etc.) and each amounts of components numerical value etc. are scope, and any point is all applicable.
The not concrete same prior art of narrating of technology contents in content of the present invention and the foregoing description.
The invention is not restricted to the foregoing description, content of the present invention is said all can implement and have said good result.
Claims (4)
1. hydrostomia method sheet material is used flame-proof polypropelene composition, it is characterized in that: by Vestolen PP 7052 100 mass parts, phosphorus containing fire retardant copolyester thing 30～50 mass parts, additive flame retardant 5～8 mass parts, toughner 5～8 mass parts, fire retarding synergist 1～5 mass parts and oxidation inhibitor 0.1～1 mass parts feed composition mix and to form;
Said additive flame retardant is three (1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclos [2; 2; 2] octane-4-methylene radical) SULPHOSUCCINIC ACID ESTER, 1-oxygen-4-methylol-2,6,7-trioxa-1-phospha dicyclo [2; 2,2] mixture of one or more in the compounds such as octane, dimethyl methyl phosphonate, triaryl phosphine oxide, ammonium polyphosphate;
Said toughner is one or both in polyolefin elastomer, the styrene-ethylene-butylene-styrene segmented copolymer;
Said fire retarding synergist is any in permanent white, nano-aluminum hydroxide, nano-calcium carbonate, nano imvite, the talcum powder;
Said oxidation inhibitor is that the mass ratio of three (2,4-two trimethylphenylmethane bases) phosphorous acid ester and four [3-(3,5-di-t-butyl-4-phenylor) propionic acid] quaternary amyl alcohol ester is the mixture of 2:1;
Said phosphorus containing fire retardant copolyester thing follows these steps to preparation:
A, in reactor A, be that 30% ydrogen peroxide 50 mixes with mass ratio 1:2.5～5 with MALEIC ANHYDRIDE and weight percent concentration, in 40～60 ℃ of reactions 20～40 minutes down; Be warmed up to 95～100 ℃ again; Under stirring and refluxing, drip vinyl acetate continuously, added in 2 hours; Keep back flow reaction after 2 hours again, vacuum decompression removes and anhydrates, and makes vinyl acetate-maleic anhydride copolymer, and is subsequent use; The mol ratio of said MALEIC ANHYDRIDE and vinyl acetate is 2～3:1;
B, the DOPOMA with 350～700 mass parts, 1000～1600 mass parts terepthaloyl moietie, 0.2～0.8 mass parts of catalyst add in the reactor B; Be warming up to 60～100 ℃ under stirring; Slowly progressively temperature reaction under agitation then, and in 1～1.5 hour, temperature of reaction is risen to 200 ℃ by 100 ℃; Be warming up to 220 ℃ and insulation again; Vinyl acetate-the maleic anhydride copolymer of 380～800 mass parts that under agitation again step a made joins in the reactor B; Be warming up to 230～250 ℃ again, under pressure 0.1～0.2MPa, react and finished in 1～2 hour; Under 230～250 ℃ of temperature, pressure 50～100Pa condition, distill then and removed terepthaloyl moietie and the water that unreacted or transesterify go out in 1～2 hour, make the phosphorus containing fire retardant copolyester thing;
The chemistry of said DOPOMA is by name 9, and the 10-dihydro-9-oxy is assorted-affixture of 10-phospho hetero phenanthrene-10-oxide compound and toxilic acid, chemical structural formula is:
。
2. by the method for manufacture of the said hydrostomia method of claim 1 sheet material, it is characterized in that comprising the following steps: with flame-proof polypropelene composition
First step: preparation phosphorus containing fire retardant copolyester thing:
A, in reactor A, be that 30% ydrogen peroxide 50 mixes with mass ratio 1:2.5～5 with MALEIC ANHYDRIDE and weight percent concentration, in 40～60 ℃ of reactions 20～40 minutes down; Be warmed up to 95～100 ℃ again; Under stirring and refluxing, drip vinyl acetate continuously, added in 2 hours; Keep back flow reaction after 2 hours again, vacuum decompression removes and anhydrates, and makes vinyl acetate-maleic anhydride copolymer, and is subsequent use; The mol ratio of said MALEIC ANHYDRIDE and vinyl acetate is 2～3:1;
B, the DOPOMA with 350～700 mass parts, 1000～1600 mass parts terepthaloyl moietie, 0.2～0.8 mass parts of catalyst add in the reactor B; Be warming up to 60～100 ℃ under stirring; Slowly progressively temperature reaction under agitation then, and in 1～1.5 hour, temperature of reaction is risen to 200 ℃ by 100 ℃; Be warming up to 220 ℃ and insulation again; Vinyl acetate-the maleic anhydride copolymer of 380～800 mass parts that under agitation again step a made joins in the reactor B; Be warming up to 230～250 ℃ again, under pressure 0.1～0.2MPa, react and finished in 1～2 hour; Under 230～250 ℃ of temperature, pressure 50～100Pa condition, distill then and removed terepthaloyl moietie and the water that unreacted or transesterify go out in 1～2 hour, make the phosphorus containing fire retardant copolyester thing;
The chemistry of said DOPOMA is by name 9, and the 10-dihydro-9-oxy is assorted-affixture of 10-phospho hetero phenanthrene-10-oxide compound and toxilic acid, chemical structural formula is:
Second step: be equipped with hydrostomia method sheet material and use the flame-proof polypropelene composition raw material:
Phosphorus containing fire retardant copolyester thing 30～50 mass parts, additive flame retardant 5～8 mass parts, toughner 5～8 mass parts, fire retarding synergist 1～5 mass parts and oxidation inhibitor 0.1～1 mass parts by Vestolen PP 7052 100 mass parts, first step make are got each feed composition;
Said additive flame retardant is three (1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclos [2; 2; 2] octane-4-methylene radical) SULPHOSUCCINIC ACID ESTER, 1-oxygen-4-methylol-2,6,7-trioxa-1-phospha dicyclo [2; 2,2] mixture of one or more in the compounds such as octane, dimethyl methyl phosphonate, triaryl phosphine oxide, ammonium polyphosphate;
Said toughner is one or both in polyolefin elastomer, the styrene-ethylene-butylene-styrene segmented copolymer;
Said fire retarding synergist is any in permanent white, nano-aluminum hydroxide, nano-calcium carbonate, nano imvite, the talcum powder;
Said oxidation inhibitor is that the mass ratio of three (2,4-two trimethylphenylmethane bases) phosphorous acid ester and four [3-(3,5-di-t-butyl-4-phenylor) propionic acid] quaternary amyl alcohol ester is the mixture of 2:1;
Third step: drop in the mixing machine each feed composition of the said formula ratio of second step evenly mixed; Melt extruding and control melt temperature through forcing machine again is 160～200 ℃; After the tie rod pelletizing, promptly make hydrostomia method sheet material and use the flame-proof polypropelene composition product.
3. by the method for manufacture of the said hydrostomia method of claim 2 sheet material with flame-proof polypropelene composition, it is characterized in that: said forcing machine is a twin screw extruder.
4. use flame-proof polypropelene composition by the said hydrostomia method of claim 1 sheet material, it is characterized in that: described flame-proof polypropelene composition is used to adopt the hydrostomia method to produce the fire-retardant polypropylene sheet product of electrician's purposes.
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| CN103881233B (en) * | 2014-02-26 | 2016-10-19 | 上海金发科技发展有限公司 | A kind of high rigidity height heat-proof impact-resistant fires white polypropylene flame redardant-nylon composite and preparation method thereof |
| CN104527866A (en) * | 2014-12-04 | 2015-04-22 | 苏州欣航微电子有限公司 | Waterproof and heat insulation type liquid crystal display panel of motorcycle |
| CN110526943A (en) * | 2019-08-14 | 2019-12-03 | 上海工程技术大学 | A kind of high content of phosphorus hydrolysis fire retardant and preparation method thereof |
| CN110564114A (en) * | 2019-08-14 | 2019-12-13 | 上海工程技术大学 | Preparation method of flame-retardant material |
| CN110526943B (en) * | 2019-08-14 | 2022-02-08 | 上海工程技术大学 | High-phosphorus-content hydrolysis-resistant flame retardant and preparation method thereof |
| CN112175310A (en) * | 2020-10-16 | 2021-01-05 | 张雪飞 | Phosphorus-containing flame-retardant rigid polypropylene material and preparation method thereof |
| CN115141428A (en) * | 2022-04-21 | 2022-10-04 | 温州鑫泰新材料股份有限公司 | Heat-conducting halogen-free flame-retardant insulating polypropylene film and preparation method thereof |
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