CN100506911C - Super high flowing, white, fire retardant PBT with no halogen, in high thermal stability, and preparation method - Google Patents
Super high flowing, white, fire retardant PBT with no halogen, in high thermal stability, and preparation method Download PDFInfo
- Publication number
- CN100506911C CN100506911C CNB200710019557XA CN200710019557A CN100506911C CN 100506911 C CN100506911 C CN 100506911C CN B200710019557X A CNB200710019557X A CN B200710019557XA CN 200710019557 A CN200710019557 A CN 200710019557A CN 100506911 C CN100506911 C CN 100506911C
- Authority
- CN
- China
- Prior art keywords
- pbt
- thermal stability
- retardant
- weight
- high thermal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
This invention discloses a method for producing white halogen-free flame-retardant PBT with ultrahigh fluidity and high thermal stability. The product is produced mainly from poly (butylene terephthalate), composite flame retardant, alkali-free glass fibers and toughening agent by mixing. The product has ultrahigh fluidity and high thermal stability.
Description
Technical field:
The present invention relates to a kind of fire retardant PBT with no halogen and production method.
Background technology:
For a long time, the fire retardant that enhancing PBT flame-retardant system is continued to use mostly is halogenated flame retardant, owing to can discharge gases such as a large amount of smog and poisonous corrosive hydrogen halides during burning, relate to various disadvantages such as Polybrominated biphenyl and Poly Brominated Diphenyl Ethers, European Union announced WEEE and two instructions of ROHS in 2003, and the toxicity of halogen flame and the arguement of environmental problem are pushed to a new high.Weight can not contain halogenide greater than the plastic components of 25 grams in Sweden even the regulation computer, and Europe also requires not contain bromide.Halogen-free environment-friendly flame-proof PBT Development of Materials becomes inexorable trend.
The fire retardant PBT with no halogen material of the patent documentation report and the marketization mostly is the production of red phosphorus master batch at present.Mainly have the following disadvantages (1) owing to be subjected to the restriction of red phosphorus master batch intrinsic colour, final fire retardant PBT with no halogen material can only be made black or scarlet.(2) because the easy oxidized back of red phosphorus forms phosphoric acid, very easily form " globule " at product surface, electrical property sharply descends, and can't satisfy normal service requirements so common red phosphorus flame-retardant Halogen PBT is long-lasting.(3) red phosphorus flame-retardant Halogen PBT is in user's injection moulding, because the unstable of phosphorus, if brief stay is arranged or produce undesiredly, can produce " flame " phenomenon and produce a large amount of dense smoke.
Document announcement is arranged in addition: the PBT product made from common nitrogen, the compound or common phosphorus flame retardant of phosphorus in fact or do not reach truly flame retardant effect, or is exactly that thermostability is not enough, extrudes in the production foaming easily even decomposes.
Secondly: along with PBT engineering plastics plastic part more and more to the trend of miniaturization, thin-walled property and precise treatment development, market has also proposed new requirement to the comprehensive mechanical performance of PBT material, flowability, stability etc.
Summary of the invention:
The object of the present invention is to provide that a kind of superelevation with super-high fluidity, high thermal stability flows, high thermal stability white halogen-free antiflaming PBT and production method.
Technical solution of the present invention is:
A kind of superelevation flows, high thermal stability white halogen-free antiflaming PBT, it is characterized in that: mainly be made up of weight components:
Polybutylene terephthalate 20～90%
Composite flame-retardant agent 8～50%
Alkali free glass fibre 0～50%
Toughner 0～20%.
Composite flame-retardant agent is made up of A, B, three kinds of components of C, and the weight proportion of three kinds of components is:
A 25～98％
B 1～50％
C 1～25％，
Wherein the A component is one or more organic mixtures that contain phosphine or phosphorus, the B component is one or more nanoclays or other nano inorganic salt or other the oxyhydroxide inorganic combustion inhibitor of silicate, and C is one or more mixtures or other silicon-series five-retardant or the master batch that contains in the superpolymer of siloxanes group.
Composite flame-retardant agent is made up of following three kinds of components by weight percent:
Organic phosphonate 60～68%
Nano kaoline 15～30%
Silicone powder 10～18%.
Composite flame-retardant agent is made up of following three kinds of components by weight percent:
The mixture 55% of organic phosphonate and phosphoric acid ester
Nano imvite 30%
Silicone master batch 15%.
Toughner is the nucleocapsid toughner that contains acrylate, the copolymer that contains acrylate or Ethylene Propylene Terpolymer grafted maleic anhydride and their compound.Toughner is methacrylic ester butadiene styrene terpolymer.Above-mentioned toughner and PBT consistency are fabulous, and toughening effect is good, give product good mechanical integrated performance.
A kind of superelevation flows, the production method of high thermal stability white halogen-free antiflaming PBT, it is characterized in that: comprise the following steps:
Polybutylene terephthalate (PBT) with 20～90% weight dried by the fire 2-5 hour down at 120-150 ℃ earlier, control moisture content＜below 0.05%; Mix by mixer with the composite flame-retardant agent of 8～50% weight subsequently or enter twin screw extruder plasticizing, fusion from the metering feeding device separately respectively, simultaneously add the alkali free glass fibre of 0～50% weight, the toughner of 0～20% weight at twin screw extruder, again through extrude, cool off product;
Wherein the preparation method of composite flame-retardant agent is: earlier fire retardant B is added high-speed mixer and mixing, be warming up to 70-150 ℃ simultaneously, mix the moisture content of removing among the B in 3-10 minute, added the further blending dispersion 2-10 of fire retardant C minute again; It is stand-by after 2-10 minute to add fire retardant A mixing at last.
Adopt the advantage of A+B+C type compound flame retardant to be that they have very big collaborative stabilization mutually: fire retardant A suppresses flame when material combustion, phosphoric acid forms surface barrier, and fused PBT resin is constituted foam layer by foamed gas and carbon source.It and PBT consistency are good, the flame retarding efficiency height.Fire retardant B is inorganic combustion inhibitors such as one or more nanometers, and dispersion effect is fabulous, and issuable drippage also effectively promotes the formation of carbon-coating when just in time eliminating list with A, further improves the flame retardant resistance of product; Fire retardant C has the reduction amount of smoke, reduces the CO productive rate, and the heat when reducing burning produces speed, and have good smoke suppressing, thereby give PBT more excellent flame-retarding characteristic, be a kind of good fire retarding synergist; Particularly A and C cooperate the processing fluidity that has also greatly improved material, give the flowing property of product superelevation.Fire retardant A has fabulous stability, the heat decomposition temperature height; Fire retardant B is inorganicss such as nanometer, and stability is splendid; Fire retardant C stable performance reduces the friction that adds man-hour, has improved the stability of product.Three's mutual synergy has been given halogen-free flameproof, high heat stability and the super-high fluidity of product.
The superelevation of the present invention high thermal stability white halogen-free antiflaming polybutylene terephthalate PBT mixture that flows can also add photostabilizer, oxidation inhibitor, whitening agent, pigment, lubricant etc.Typical photostabilizer is a benzotriazole category: as 2-(2-hydroxyl-uncle's 5-octyl phenyl benzene) and triazole; 2-(2H-benzotriazole-2-yl)-4,6 two (1-methyl isophthalic acid-phenylethyl) phenol; Other all photostabilizers and compound thereof that is applicable to polyester all can; Typical oxidation inhibitor has: tetramethylolmethane four 3-(3,5-di-t-butyl-4 hydroxybenzyl) propionic ester, as vapour crust Irganox1010, ethylene glycol (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester) is as Irganox259,4,4 '-thiobis (the 6-tertiary butyl-3-methylphenol); 3,5 diphosphorous acids three ((2, the 4-di-tert-butyl-phenyl) ester etc.; And the IrganoxB215 of the compound of their various ratios such as vapour crust, B225 or the like; Typical whitening agent has: titanium dioxide: TIO
2, OB:2, two (the 5-tertiary butyl-2-benzoxazolyl) thiophene of 5-:, OB-1:2,2-Er benzoxazole or the like; Pigment is to add according to the color needs; Lubricant reaches other various lubricants that are applicable to PBT and all can as containing the multiple auxiliary agent of high carbon chain interfacial activity mixture.
Superelevation of the present invention high thermal stability white halogen-free antiflaming polybutylene terephthalate (PBT) mixture that flows, adopt three kinds of fire retardant compound cooperative flame retardants to reach not only fire-retardant complementation but also the mobile and stable net effect of superelevation is arranged, three kinds of fire retardants are white or light color, finished product can be made white and other any color, solved in the past and can only make dark product or big owing to addition with red phosphorus with other expanding fire retardant, bad mechanical property, the product flowability is bad, poor stability and product are difficult for reaching fire-retardant or the like problem, realized not only halogen-free environmentalization but also can do very whitely of product, through the test of dependence test mechanisms such as SGS center, Shanghai, do not contain any halogens in this product; And have super good flowability, product melts the body index and can reach more than the 120g/10min under the 1.2Kg condition, and common flame-retardant PBT melts and is generally 8-20g/10min under the body index similarity condition; And product has high thermostability, carries out the thermal weight loss test through Shanghai macromolecular material research and development centre, and heat decomposition temperature reaches 366.6 ℃.And the favorable mechanical performance is arranged, reach common halogen flame retardant The comprehensive performance substantially.Satisfied electronic apparatus fully, household electrical appliances, all demands of halogen-free environmentalizations such as connector, thin-walled property, miniaturization, complicated, stabilization precise injection molding etc.
The invention will be further described below in conjunction with embodiment.
Embodiment:
Embodiment 1:
Polybutylene terephthalate (PBT) with 73.6% weight dries by the fire 2-5 hour (example 2,4,5 hours) down 120-150 ℃ (120 ℃, 135 ℃, 150 ℃ of examples) earlier, control moisture content＜below 0.05%; Mix by mixer with the composite flame-retardant agent of 20% weight subsequently or enter twin screw extruder plasticizing, fusion from the metering feeding device separately respectively, simultaneously add the toughner methacrylic ester butadiene styrene terpolymer of 6% weight and primary antioxidant (1010) tetramethylolmethane four 3-(3 of 0.2% weight at twin screw extruder, 5-di-t-butyl-4 hydroxybenzyl) auxiliary antioxidant (168) tricresyl phosphite ((2 of propionic ester, 0.2% weight, the 4-di-tert-butyl-phenyl) ester, again through routine extrude, tie rod, cooling, pelletizing, all mix, pack product.
Wherein the preparation method of composite flame-retardant agent is: earlier nano kaoline is added high-speed mixer and mixing, be warming up to 70-150 ℃ (70 ℃, 110 ℃, 150 ℃ of examples) simultaneously, mix 3-10 minute (example 3,6,10 minutes) and remove the moisture content in the nano kaoline, add the further blending dispersion 2-10 of silicone minute (example 2,6,10 minutes) again; (example 2,6,10 minutes) back is stand-by to add the organic phosphonate mixing at last 2-10 minute.
Embodiment 2:
Polybutylene terephthalate (PBT) with 49.6% weight dries by the fire 2-5 hour (example 2,4,5 hours) down 120-150 ℃ (120 ℃, 135 ℃, 150 ℃ of examples) earlier, control moisture content＜below 0.05%; Mix by mixer with the composite flame-retardant agent of 16% weight subsequently or enter twin screw extruder from the metering feeding device separately respectively and plastify, fusion, the toughner methacrylic ester butadiene styrene terpolymer that adds 4% weight simultaneously at twin screw extruder, the primary antioxidant of the alkali free glass fibre of 30% weight and 0.2% weight (1010) tetramethylolmethane four 3-(3,5-di-t-butyl-4 hydroxybenzyl) propionic ester, the auxiliary antioxidant of 0.2% weight (168) tricresyl phosphite ((2, the 4-di-tert-butyl-phenyl) ester is extruded through routine again, tie rod, cooling, pelletizing, all mix, pack product.
Wherein the preparation method of composite flame-retardant agent is: earlier nano kaoline is added high-speed mixer and mixing, be warming up to 70-150 ℃ (70 ℃, 110 ℃, 150 ℃ of examples) simultaneously, mix 3-10 minute (example 3,6,10 minutes) and remove the moisture content in the nano kaoline, add the further blending dispersion 2-10 of silicone minute (example 2,6,10 minutes) again; (example 2,6,10 minutes) back is stand-by to add the organic phosphonate mixing at last 2-10 minute.
The product compositions content of embodiment 1,2 and product test index such as following table:
| The matrix material title | Embodiment 1 (not strengthening product) | Embodiment 2 (strengthening product) |
| PBT(％) | 73.6 | 49.6 |
| Organic phosphonate (%) | 13 | 10 |
| Nano kaoline (%) | 4 | 4 |
| Silicone (%) | 3 | 2 |
| Methacrylic ester butadiene styrene terpolymer | 6 | 4 |
| Alkali free glass fibre (%) | 0 | 30 |
| Primary antioxidant (1010) Ji Wusi | 0.2 | 0.2 |
| Alcohol four 3-(3,5-di-t-butyl-4 hydroxybenzyl) propionic ester (%) | ||
| Auxiliary antioxidant (168) tricresyl phosphite ((2, the 4-di-tert-butyl-phenyl) ester (%) | 0.2 | 0.2 |
| Tensile strength (Mpa) | 56 | 90 |
| Flexural strength ((Mpa) | 90 | 150 |
| Notch shock (KJ/m^2) | 6 | 8 |
| Non-notch impacts (KJ/m^2) | 75 | 65 |
| Flame retardant properties (1.6mm) | V-0 | V-0 |
| Melt index (1.2Kg/10min) | 120 | 132 |
| Heat decomposition temperature ℃ (23 ℃, relative humidity: 60%RH) | 364.2 | 366.6 |
Embodiment 3:
Polybutylene terephthalate (PBT) with 85% weight dries by the fire 2-5 hour (example 2,4,5 hours) down 120-150 ℃ (120 ℃, 135 ℃, 150 ℃ of examples) earlier, control moisture content＜below 0.05%; Mix by mixer with the composite flame-retardant agent (silicone of the nano kaoline of the organic phosphonate of 3% weight, 2% weight, 3% weight) of 8% weight subsequently or enter twin screw extruder plasticizing, fusion from the metering feeding device separately respectively, the toughner methacrylic ester butadiene styrene terpolymer that adds simultaneously 7% weight at twin screw extruder, again through routine extrude, tie rod, cooling, pelletizing, all mix, pack product.All the other are with embodiment 1.
Embodiment 4:
Polybutylene terephthalate (PBT) with 25% weight dries by the fire 2-5 hour (example 2,4,5 hours) down 120-150 ℃ (120 ℃, 135 ℃, 150 ℃ of examples) earlier, control moisture content＜below 0.05%; Mix by mixer with the composite flame-retardant agent (silicone of the nano kaoline of the organic phosphonate of 15% weight, 15% weight, 15% weight) of 45% weight subsequently or enter twin screw extruder plasticizing, fusion from the metering feeding device separately respectively, simultaneously add the toughner methacrylic ester butadiene styrene terpolymer of 18% weight, the alkali free glass fibre of 12% weight at twin screw extruder, again through routine extrude, tie rod, cooling, pelletizing, all mix, pack product.All the other are with embodiment 1.
Embodiment 4:
Polybutylene terephthalate (PBT) with 30% weight dries by the fire 2-5 hour (example 2,4,5 hours) down 120-150 ℃ (120 ℃, 135 ℃, 150 ℃ of examples) earlier, control moisture content＜below 0.05%; Mix by mixer with the composite flame-retardant agent of 25% weight subsequently or enter twin screw extruder plasticizing, fusion from the metering feeding device separately respectively, the alkali free glass fibre that adds simultaneously 45% weight at twin screw extruder, again through routine extrude, tie rod, cooling, pelletizing, all mix, pack product.
Above-mentioned composite flame-retardant agent is made up of the component of following three kinds of weight proportions:
The mixture 55% of organic phosphonate and phosphoric acid ester
Nano imvite 30%
Silicone master batch 15%.
The preparation method of composite flame-retardant agent is: earlier nano imvite is added high-speed mixer and mixing, be warming up to 70-150 ℃ (70 ℃, 110 ℃, 150 ℃ of examples) simultaneously, mix 3-10 minute (example 3,6,10 minutes) and remove the moisture content in the nano imvite, add the further blending dispersion 2-10 of silicone master batch minute (example 2,6,10 minutes) again; It is stand-by with 2-10 minute (example 2,6,10 minutes) back of mixture mixing of phosphoric acid ester to add organic phosphonate at last; The weight ratio of organic phosphonate and phosphoric acid ester is 1:1 (or other proper ratio) in the mixture of organic phosphonate and phosphoric acid ester.
Claims (3)
1, mobile, the high thermal stability white halogen-free antiflaming PBT of a kind of superelevation is characterized in that: mainly be made up of weight components:
Polybutylene terephthalate 20～90%
Composite flame-retardant agent 8～50%
Alkali free glass fibre 0～50%
Toughner 0～20%;
Wherein composite flame-retardant agent is one of following two kinds of composite flame-retardant agents:
(1) composite flame-retardant agent is made up of following three kinds of components by weight percent:
Organic phosphonate 60～68%
Nano kaoline 15～30%
Silicone powder 10～18%;
(2) composite flame-retardant agent is made up of following three kinds of components by weight percent:
The mixture 55% of organic phosphonate and phosphoric acid ester
Nano imvite 30%
Silicone master batch 15%.
2, mobile, the high thermal stability white halogen-free antiflaming PBT of superelevation according to claim 1, it is characterized in that: toughner is the nucleocapsid toughner that contains acrylate, the copolymer that contains acrylate or Ethylene Propylene Terpolymer grafted maleic anhydride and their compound.
3, mobile, the high thermal stability white halogen-free antiflaming PBT of superelevation according to claim 1, it is characterized in that: toughner is methacrylic ester butadiene styrene terpolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200710019557XA CN100506911C (en) | 2007-01-09 | 2007-01-09 | Super high flowing, white, fire retardant PBT with no halogen, in high thermal stability, and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200710019557XA CN100506911C (en) | 2007-01-09 | 2007-01-09 | Super high flowing, white, fire retardant PBT with no halogen, in high thermal stability, and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101003666A CN101003666A (en) | 2007-07-25 |
| CN100506911C true CN100506911C (en) | 2009-07-01 |
Family
ID=38703056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200710019557XA Active CN100506911C (en) | 2007-01-09 | 2007-01-09 | Super high flowing, white, fire retardant PBT with no halogen, in high thermal stability, and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100506911C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101608022B (en) * | 2009-07-31 | 2013-07-24 | 东莞市美塑塑料科技有限公司 | Preparation method of fiber glass reinforced halogen-free flame retardant PBT composition and product thereof |
| CN102775747A (en) * | 2012-07-30 | 2012-11-14 | 南通星辰合成材料有限公司 | Antimony-free reinforced flame-retardant polybutylece terephthalate (PBT) environmental-friendly material and preparation method thereof |
| CN103819882B (en) * | 2012-11-16 | 2016-01-13 | 江苏金发科技新材料有限公司 | Halogen-free flame-retardant long fiber glass reinforced PBT matrix material and preparation method thereof |
| CN103087481B (en) * | 2013-01-18 | 2015-02-04 | 广东奇德新材料股份有限公司 | High-strength halogen-free flame retardant PBT (Polybutylece Terephthalate) nano composite material and preparation method thereof |
| CN105385118B (en) * | 2015-11-18 | 2016-11-09 | 南通开普乐工程塑料有限公司 | A kind of high CTI value fire-retardant reinforced PBT composite material |
| CN105838067B (en) * | 2016-06-15 | 2018-06-19 | 广州市合诚化学有限公司 | Halogen-free fire-retarding reinforced polyamide composition and product prepared therefrom |
| CN107446324B (en) * | 2017-08-02 | 2020-01-07 | 广东锦湖日丽高分子材料有限公司 | Inorganic nanoparticle reinforced halogen-free flame-retardant PBT (polybutylene terephthalate) material and preparation method thereof |
-
2007
- 2007-01-09 CN CNB200710019557XA patent/CN100506911C/en active Active
Non-Patent Citations (2)
| Title |
|---|
| 磷硅阻燃剂协同效应及其应用. 张利利，刘安华.塑料工业，第33卷第增刊期. 2005 |
| 磷硅阻燃剂协同效应及其应用. 张利利，刘安华.塑料工业，第33卷第增刊期. 2005 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101003666A (en) | 2007-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100506911C (en) | Super high flowing, white, fire retardant PBT with no halogen, in high thermal stability, and preparation method | |
| CN102604377B (en) | A kind of flame-proofed thermoplastic daiamid composition | |
| CN101717560B (en) | Halogen-free antiflaming polyester molding composition and preparation method thereof | |
| CN102337029B (en) | Halogen-free flame-retardant nylon 66 composite material and preparation method thereof | |
| CN100590146C (en) | Preparation of halogen-free flame-proof nylon 66 having high-mechanical property and composite material | |
| CN100590145C (en) | Method for preparing high machinery performance halogen-free anti-flaming PBT composite and composite material | |
| CN102532693B (en) | High-performance low-smoke halogen-free flame-retardant polypropylene composite material and preparation method thereof | |
| CN101280097A (en) | Nanometer flame-proof polyethylene glycol terephthalate engineering plastics and preparation thereof | |
| CN103044762A (en) | Mineral reinforced halogen-free flame-retardant polypropylene composite material and preparation method thereof | |
| CN103160080B (en) | A kind of halogen-free flame-retardant long fiber glass reinforced PBT composite and preparation method thereof | |
| CN112812366B (en) | Flame-retardant composition and application thereof, PBT composite material and preparation method thereof | |
| CN102850661A (en) | Halogen-free flame-retardant PP/polyester alloy and preparation method thereof | |
| CN101235174A (en) | Environmental protection halogen-free anti-flaming polypropylene composite material and preparation method thereof | |
| CN102558791A (en) | High heat resistance, high gloss, low volatility and rapid prototyping polybutylene terephthalate and preparation method thereof | |
| CN103342880A (en) | High-surface-gloss environment-friendly halogen-free flame-retardant PBT (polybutylene terephthalate) composite material and preparation method thereof | |
| CN104448554A (en) | Highlight high-flexibility polypropylene environment-friendly flame retardant material and preparation method thereof | |
| CN102040810A (en) | Polybutylece terephthalate (PBT) engineering plastics as well as preparation method and application thereof | |
| CN103467934B (en) | A kind of flame retardant polyester composition and preparation method thereof | |
| CN102120881A (en) | Inflaming retarding reinforced polyamide/polyformaldehyde composition and preparation method thereof | |
| CN101864137B (en) | High impact-resistance anti-smoldering polystyrene resin composite and preparation method thereof | |
| CN103881180A (en) | Flame-retardant antistatic bifunctional modified polyethylene composite material and its preparation method | |
| CN103965623A (en) | High-dimensional-stability reinforced flame-retardant cold-resistant composite material and preparation method thereof | |
| CN103131147A (en) | High heat wire inflaming retarding enhancement polybutylece terephthalate (PBT) material and manufacturing method thereof | |
| CN102604340A (en) | PET(polyethylene terephthalate)/PTT(polytrimethylene terephthalate) alloy with high glowing filament and enhanced flame retardance as well as production process of PET/PTT alloy | |
| CN114106522B (en) | Brominated flame-retardant PBT (polybutylene terephthalate) material as well as preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |