CN101928447B - Halogen-free antiflaming enhanced polybutylene terephthalate composite and preparation method thereof - Google Patents
Halogen-free antiflaming enhanced polybutylene terephthalate composite and preparation method thereof Download PDFInfo
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- CN101928447B CN101928447B CN200910057461.1A CN200910057461A CN101928447B CN 101928447 B CN101928447 B CN 101928447B CN 200910057461 A CN200910057461 A CN 200910057461A CN 101928447 B CN101928447 B CN 101928447B
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Abstract
The invention relates to a halogen-free antiflaming enhanced polybutylene terephthalate composite and a preparation method thereof. The composite is prepared by the following steps: polybutylene terephthalate, flexibilizer, heat stabilizer, processing aid, phosphorus-nitrogenous flame retardant and synergistic effect flame retardant are added in a twin-screw extruder with a diameter ratio of 40-50:1 for fusing, mixing and dispersing, then glass fiber is added, and finally, squeezing granulation is carried out at the temperature of 220-250 DEG C. The flame retardant performance of the composite can reach a grade of 1.6mm UL 94V-0, the mechanical property is equivalent to that of a conventional halogen-containing PBT enhanced material, and the composite meets the halogen-free requirements of electronic and electric industry, information industry and office and household appliance industry on flame retardant materials.
Description
Technical field
The present invention relates to a kind of polybutylene terephthalate composition, be specifically related to a kind of halogen-free flame-proof reinforced poly mutual-phenenyl two acid bromide two alcohol ester composition and method of making the same.
Background technology
Along with the reinforcement of people's environmental consciousness and the appearance of environmental regulation, the macromolecular material Non-halogen Flame Retardant Technology with Halogen and low cigarette characteristic will progressively replace halogen flame-retarded technology.Studied successfully by Celanese company of the U.S. at the initial stage in the 1970's from polybutylene terephthalate (PBT), and with Celanex trade(brand)name listing, subsequently a lot of producers PBT ranks that all put into production.The advantages such as PBT has thermotolerance, weathering resistance, chemical-resistant, electric property excellence, water-absorbent is little, surface is good, be widely used in electric, automobile, machinery, household electrical appliance etc., especially electric industry, and the sector has fire-retardant requirement mostly to material.For a long time, PBT flame-retardant system is mainly halogenated flame retardant (as TDE, brominated epoxy etc.).Along with all of halogenated flame retardant is identified the disadvantageous drawback of environment, European Union announced two instructions of Weee and RoHs in 2003.Various environmental protection instructions are subsequently put into effect successively, and electric in European Union and North America market, information, that office household electric appliances start requirement material is non-halogen.
Fire retardant PBT with no halogen is mainly to select suitable fire retardant: although red phosphorus flame retarding efficiency is high, color is dark, can not meet client's product to versicolor needs, and high temperature process can produce a large amount of acid phosphine gas; Organophosphorus (BDP, TPP etc.) flame retarding efficiency is low, uses addition high, large to the performance impact of material; Inorganic phosphorus is also larger on material property impact when addition is large.
Summary of the invention
The object of this invention is to provide a kind of halogen-free flame-proof reinforced poly mutual-phenenyl two acid bromide two alcohol ester composition, adopt fire retardant compounded technology, carry out composite with BACN phosphazene compound and phosphorus-nitrogen compound, prepare the good PBT mixture of a kind of flame retardant properties, flame retardant properties can reach 1.6mm UL94V-0 level, and mechanical property is suitable with conventional Halogen flame-retardant PBT strongthener.
Polybutylene terephthalate composition of the present invention comprises following raw material, by weight percentage:
Polybutylene terephthalate 40%～50%
Toughner 1%～9%
Thermo-stabilizer 0.5%～2%
Processing aid 0.5%～1%
Phosphor nitrogen combustion inhibitor 10%～18%
Synergistic flame retardant 2%～10%
Glass fibre 26%～30%;
Described toughner is one or more the mixture in ethylene-vinyl acetate random copolymers, ethylene-methyl acrylate random copolymers, ethylene-propylene acid butyl ester random copolymers, ethylene-propylene acid butyl ester-glycidyl methacrylate; In toughner, can react with PBT end group with epoxide group or ester group, be grafted on PBT macromolecular chain, play toughening effect.
Thermo-stabilizer reaches for the free radical of ending processing reaction generation the object that stops degraded; Described thermo-stabilizer is one or more the mixture in mixture class and the calixarene kind thermo-stabilizer of phenols, amine, phosphorous acid esters, half Hinered phenols, acryl functional group and monothioester.
Described phenols thermo-stabilizer is a kind of in dihydroxyphenyl propane, bisphenol-c and 2,6 ditertiary butyl p cresol or more than one mixture.
Described amine thermo-stabilizer is a kind of in diphenyl-para-phenylene diamine, diphenyl-para-phenylene diamine, 4-hydroxy-dodecanoic acid anilide and 4-hydroxyl octadecanoic acid anilide or more than one mixture.
Described phosphorous acid ester type thermal stabilizing agent is a kind of in the pungent diphenyl ester of trisnonyl phenyl phosphite, triphenyl phosphite and phosphorous acid or more than one mixture.
Half described Hinered phenols thermo-stabilizer is 1,3,5-trimethylammonium-2,4, a kind of in 6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, Three methyl Benzene and 2,2 '-methylene bis (4-ethyl-6-tert.-butyl phenol) or more than one mixture.
Described acryl functional group and the mixture type thermal stabilizing agent of monothioester are Tyox B.
Described calixarene kind thermo-stabilizer is to tert-butyl-calix [4] aromatic hydrocarbons, to tert-butyl-calix [6] aromatic hydrocarbons and to a kind of in tert-butyl-calix [8] aromatic hydrocarbons or more than one mixture.
In order to be beneficial to lubricated dispersion, Raw composition of the present invention also comprises processing aid, to play interior lubricated and outer lubrication, thereby reduces the outer friction between molecule internal friction or superpolymer and equipment; Described processing aid is one or more the mixture in low molecule ester class, metal soap, stearic acid complex ester class and amides processing aid.
Described low molecule ester class processing aid is a kind of in butyl stearate, glyceryl monostearate and Tristearoylglycerol or more than one mixture; Described metal soap processing aid is a kind of in calcium stearate, Zinic stearas, Magnesium Stearate and lead stearate or more than one mixture; Described stearic acid complex ester class processing aid is a kind of in Tripolyglycerol monostearates, Polyglycerine monostearate and or more than one mixture; Described amides processing aid is a kind of in amine hydroxybenzene, stearylamide and ethylene bis stearamide or more than one mixture.
Fire retardant of the present invention is selected from one or more the mixture in ammonium polyphosphate, Melamine Polyphosphate and melamine cyanurate; Under high temperature, thereby phosphonium flame retardant can decompose and produces phosphoric acid and can be dehydrated into charcoal reaction, makes fire retardant material generate more coke, and reduces the growing amount of flammable volatile matter, reaches fire-retardant effect.
Described synergistic flame retardant is one or more the mixture in phenoxy phosphazene, three O-Phenylene Diamine basic ring three phosphonitriles and six isopropoxy ring three phosphonitriles; In phosphonitrile synergistic flame retardant molecular chain, contain P-N key, can accelerate catalysis carbon-forming reaction, produce cooperative flame retardant effect.
The present invention also provides a kind of preparation method of halogen-free flame-proof reinforced poly mutual-phenenyl two acid bromide two alcohol ester composition, and its concrete steps are:
Step 1, gets the raw materials ready, by weight percentage:
Polybutylene terephthalate 40%～50%
Toughner 1%～9%
Thermo-stabilizer 0.5%～2%
Processing aid 0.5%～1%
Phosphor nitrogen combustion inhibitor 10%～18%
Synergistic flame retardant 2%～10%
Glass fibre 26%～30%;
Step 2, it is 40-50 that polybutylene terephthalate, toughner, thermo-stabilizer, processing aid, phosphor nitrogen combustion inhibitor and synergistic flame retardant are joined to length-to-diameter ratio: in 1 twin screw extruder, melting mixing is disperseed;
Step 3, glass fibre staple fibre adds from side feeding;
Step 4,220-250 DEG C extrudes, granulation from forcing machine.
In phosphazene compound molecular structure, have two kinds of elements of phosphorus and nitrogen simultaneously, exist very strong fire-retardant synergistic effect between phosphorus nitrogen, and most of phosphonitrile compounds has and have no side effect, thermostability is strong, not the feature of facile hydrolysis; The present invention adopts fire retardant compounded technology, carries out compositely with BACN phosphazene compound and phosphorus-nitrogen compound, has prepared the good PBT mixture of a kind of flame retardant properties, and flame retardant properties can reach 1.6mm UL94V-0 level.
Embodiment
Illustrate the present invention below in conjunction with embodiment.
Embodiment 1
In parts by weight, by 5 parts of 40 parts of PBT, ethylene-vinyl acetate random copolymers, 2, it is 40-50 that 9 parts of 0.5 part of 6-ditertbutylparacresol, 0.5 part of butyl stearate, 15 parts of ammonium polyphosphates and phenoxy phosphazenes join length-to-diameter ratio: in 1 twin screw extruder, melting mixing is disperseed, 30 parts of short glass fibers add from side feeding, at 220-250 DEG C of extruding pelletization, gained pellet is measured its performance after sample preparation, and concrete data are in table 1.
Embodiment 2
In parts by weight, it is 40-50 that 7 parts of 45 parts of PBT, 5 parts of ethylene-methyl acrylate random copolymerss, 0.5 part of bisphenol-c, 0.5 part of calcium stearate, 12 parts of Melamine Polyphosphate and three O-Phenylene Diamine basic ring three phosphonitriles are joined to length-to-diameter ratio: in 1 twin screw extruder, melting mixing is disperseed, 30 parts of short glass fibers add from side feeding, at 220-250 DEG C of extruding pelletization, gained pellet is measured its performance after sample preparation, and concrete data are in table 1.
Embodiment 3
In parts by weight, by 50 parts of PBT, 1 part of ethylene-propylene acid butyl ester random copolymers, 4 parts of 0.5 part, tert-butyl-calix [4] aromatic hydrocarbons, 0.5 part of amine hydroxybenzene, 14 parts of melamine cyanurates and six isopropoxy ring three phosphonitriles are joined to length-to-diameter ratio is 40-50: in 1 twin screw extruder, melting mixing is disperseed, 30 parts of short glass fibers add from side feeding, at 220-250 DEG C of extruding pelletization, gained pellet is measured its performance after sample preparation, and concrete data are in table 1.
Embodiment 4
In parts by weight, it is 40-50 that 7 parts of 50 parts of PBT, 2 parts of ethylene-propylene acid butyl ester-glycidyl methacrylate, 0.5 part of diphenyl-para-phenylene diamine, 0.5 part of Tripolyglycerol monostearates processing aid, 10 parts of Melamine Polyphosphate and phenoxy phosphazenes are joined to length-to-diameter ratio: in 1 twin screw extruder, melting mixing is disperseed, 30 parts of short glass fibers add from side feeding, at 220-250 DEG C of extruding pelletization, gained pellet is measured its performance after sample preparation, and concrete data are in table 1.
Embodiment 5
In parts by weight, it is 40-50 that 5 parts of 50 parts of PBT, 2 parts of ethylene-propylene acid butyl ester random copolymerss, 0.5 part of trisnonyl phenyl phosphite, 0.5 part of glyceryl monostearate, 12 parts of melamine cyanurates and three O-Phenylene Diamine basic ring three phosphonitriles are joined to length-to-diameter ratio: in 1 twin screw extruder, melting mixing is disperseed, 30 parts of short glass fibers add from side feeding, at 220-250 DEG C of extruding pelletization, gained pellet is measured its performance after sample preparation, and concrete data are in table 1.
Embodiment 6
In parts by weight, it is 40-50 that 4 parts of 50 parts of PBT, 3 parts of ethylene-propylene acid butyl ester-glycidyl methacrylate, 0.5 part of stearylamide, 0.5 part of Zinic stearas, 12 parts of Melamine Polyphosphate and six isopropoxy ring three phosphonitriles are joined to length-to-diameter ratio: in 1 twin screw extruder, melting mixing is disperseed, 30 parts of short glass fibers add from side feeding, at 220-250 DEG C of extruding pelletization, gained pellet is measured its performance after sample preparation, and concrete data are in table 1.
The numerical value of tensile strength, elongation at break, flexural strength, modulus in flexure and notch shock is larger, illustrates that its mechanical property is better; The numerical value of heat-drawn wire is larger, illustrates that its resistance toheat is better; Flame retardant properties numerical value is less, illustrates that its flame retardant properties is better.
Mechanical property and the flame retardant properties of table 1 embodiment 1-6 resulting materials
| Embodiment | Tensile strength/MPa (ISO 527) | Elongation at break/% (ISO527) | Flexural strength/MPa (ISO17) | Modulus in flexure/MPa (ISO178) | Notch shock/KJ/m 2 (ISO180) | Heat-drawn wire/DEG C (ISO75) | Flame retardant properties (UL94) |
| 1 | 122 | 3.5 | 202 | 9100 | 12.5 | 211 | 1.6mmV-0 |
| 2 | 130 | 4.1 | 209 | 9500 | 13.1 | 214 | 1.6mmV-0 |
| 3 | 125 | 3.7 | 210 | 9300 | 12.8 | 213 | 1.6mmV-0 |
| 4 | 127 | 3.3 | 208 | 9200 | 14.0 | 216 | 1.6mmV-0 |
| 5 | 123 | 3.9 | 204 | 9070 | 14.2 | 211 | 1.6mmV-0 |
| 6 | 128 | 3.4 | 202 | 9120 | 13.3 | 212 | 1.6mmV-0 |
As shown in Table 1, the composition material that the inventive method makes shows good comprehensive mechanical property, thermal property and flame retardant properties.
Although content of the present invention has been done detailed introduction by above preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention.Read after foregoing those skilled in the art, for multiple amendment of the present invention and substitute will be all apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (5)
1. halogen-free flame-proof reinforced poly mutual-phenenyl two acid bromide two alcohol ester composition, it is characterized in that, said composition is made up of following raw material, in parts by weight: 30 parts of 40 parts of polybutylene terephthalates, 5 parts of ethylene-vinyl acetate random copolymerss, 0.5 part of 2,6 ditertiary butyl p cresol, 0.5 part of butyl stearate, 15 parts of ammonium polyphosphates, 9 parts of phenoxy phosphazenes and short glass fibers.
2. halogen-free flame-proof reinforced poly mutual-phenenyl two acid bromide two alcohol ester composition, it is characterized in that, said composition is made up of following raw material, in parts by weight: 30 parts of 45 parts of polybutylene terephthalates, 5 parts of ethylene-methyl acrylate random copolymerss, 0.5 part of bisphenol-c, 0.5 part of calcium stearate, 12 parts of Melamine Polyphosphate, three 7 parts of O-Phenylene Diamine basic ring three phosphonitriles and short glass fibers.
3. halogen-free flame-proof reinforced poly mutual-phenenyl two acid bromide two alcohol ester composition, it is characterized in that, said composition is made up of following raw material, in parts by weight: 30 parts of 50 parts of polybutylene terephthalates, 2 parts of ethylene-propylene acid butyl ester-glycidyl methacrylate, 0.5 part of diphenyl-para-phenylene diamine, 0.5 part of Tripolyglycerol monostearates processing aid, 10 parts of Melamine Polyphosphate, 7 parts of phenoxy phosphazenes and short glass fibers.
4. halogen-free flame-proof reinforced poly mutual-phenenyl two acid bromide two alcohol ester composition, it is characterized in that, said composition is made up of following raw material, in parts by weight: 30 parts of 50 parts of polybutylene terephthalates, 3 parts of ethylene-propylene acid butyl ester-glycidyl methacrylate, 0.5 part of stearylamide, 0.5 part of Zinic stearas, 12 parts of Melamine Polyphosphate, six 4 parts of isopropoxy ring three phosphonitriles and short glass fibers.
5. a method of preparing the halogen-free flame-proof reinforced poly mutual-phenenyl two acid bromide two alcohol ester composition as described in any one in claim 1-4, is characterized in that, the method comprises the following steps:
Step 1, gets the raw materials ready;
Step 2, it is 40-50 that the raw material except glass fibre is joined to length-to-diameter ratio: in 1 twin screw extruder, melting mixing is disperseed;
Step 3, glass fibre staple fibre adds from side feeding;
Step 4,220-250 DEG C extrudes, granulation from forcing machine.
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| CN200910057461.1A CN101928447B (en) | 2009-06-24 | 2009-06-24 | Halogen-free antiflaming enhanced polybutylene terephthalate composite and preparation method thereof |
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| CN102660071A (en) * | 2012-04-18 | 2012-09-12 | 同济大学 | Polyphosphazene-containing halogen-free eco-friendly flame-retardant polyolefin cable material and preparation method thereof |
| CN102993650B (en) * | 2012-09-27 | 2015-03-25 | 天津金发新材料有限公司 | Polybutylene terephthalate-based thermoplastic elastomer composition, and preparation method and application thereof |
| CN103923444B (en) * | 2014-04-30 | 2015-10-14 | 上海瀚氏模具成型有限公司 | Heat-resisting PBT plastic of automotive upholstery halogen-free flameproof and preparation method thereof |
| CN104945866A (en) * | 2015-06-29 | 2015-09-30 | 株洲时代新材料科技股份有限公司 | PBT (polybutylene terephthalate) molding composition |
| CN106700429A (en) * | 2015-07-24 | 2017-05-24 | 苏州盈茂光电材料股份有限公司 | Process for enhancing PBT bending resistant and grinding performance |
| CN105385119B (en) * | 2015-11-24 | 2016-12-14 | 金发科技股份有限公司 | A kind of fiberglass reinforced fire retardant PBT composition and preparation method thereof |
| CN106751558A (en) * | 2016-11-18 | 2017-05-31 | 无锡明盛纺织机械有限公司 | A kind of engineering plastic materials and preparation method containing bamboo fibre |
| CN113372715B (en) * | 2021-06-23 | 2022-12-16 | 杭州本松新材料技术股份有限公司 | Red phosphorus flame-retardant reinforced nylon composite material and application thereof |
| CN114805775B (en) * | 2022-05-17 | 2024-02-02 | 华润化学材料科技股份有限公司 | Regenerated PET polyester, regenerated flame-retardant PET foaming material and preparation method thereof |
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| CN1599776A (en) * | 2001-11-30 | 2005-03-23 | 宝理塑料株式会社 | Flame-retardant resin composition |
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| CN1980996B (en) * | 2004-06-29 | 2010-11-03 | 三菱工程塑料株式会社 | Flame-retardant polybutylene terephthalate composition and molded product |
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| CN1599776A (en) * | 2001-11-30 | 2005-03-23 | 宝理塑料株式会社 | Flame-retardant resin composition |
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