CN101955635B - Method for preparing halogen-free and flame-retardant polybutylene terephthalate composition - Google Patents
Method for preparing halogen-free and flame-retardant polybutylene terephthalate composition Download PDFInfo
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- CN101955635B CN101955635B CN2010102895569A CN201010289556A CN101955635B CN 101955635 B CN101955635 B CN 101955635B CN 2010102895569 A CN2010102895569 A CN 2010102895569A CN 201010289556 A CN201010289556 A CN 201010289556A CN 101955635 B CN101955635 B CN 101955635B
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Abstract
The invention discloses a method for preparing a halogen-free and flame-retardant polybutylene terephthalate composition. The halogen-free and flame-retardant polybutylene terephthalate composition obtained by performing halogen-free flame retardancy on polybutylece terephthalate by using a halogen-free and flame-retardant system consisting of an aryloxyphosphazene halogen-free flame retardant and a flame retardant synergist has the advantages of high mechanical property, tensile strength of up to 125 MPa, non-notched impact of up to 47 KJ/m2 and capability of reaching level 1.6 mm UL94V-0.
Description
Technical field
The present invention relates to a kind of preparation method of macromolecular material, particularly a kind of halogen-free flameproof polybutylene terephthalate preparation of compositions method.
Background technology
Polybutylene terephthalate is a kind of saturated polyester that is become with butyleneglycol esterification condensation polymerization by terephthalic acid.Because the height geometrical regularity of its molecule and rigid element make polybutylene terephthalate have higher mechanical strength, elasticity, wear resistance, chemical reagent resistance and good electrical property preferably, thereby application is more and more widely in electronic apparatus and each industrial circle.
Though polybutylene terephthalate has above excellent properties,, reasons such as molding shrinkage big, easy firing relatively poor because of its resistance toheat are restricted its application.Therefore need carry out fire-retardant enhancing modified to satisfy application demand widely to polybutylene terephthalate.Traditional fire-retardant polybutylene terephthalate generally adopts bromide fire retardant and stibium trioxide composite, and this flame-retardant system can produce a large amount of smog and discharge deleterious corrosive hydrogen halides gas when burning, and environment and life safety are caused very big injury.In the face of more and more stricter environmental protection and safety requirements; And electronics, electrical equipment, automobile and other industries are to an urgent demand of Halogen, low cigarette, low-poison and combustion-resisting material; Particularly EU Committee's promulgation in 2003 " using some objectionable impurities instruction " (RoHs instruction) about restriction in electronic electric equipment; The instruction regulation was from July 1st, 2006; The electronic and electrical equipment forbidding that gets into European Union market comprises 6 types of objectionable impuritiess of PBBs (PBB), PBDE (PBDE), the therefore non-halogen great attention that obtains industry of fire-retardant polybutylene terephthalate, and the exploitation dynamics is also increasing.At present, the Halogen polybutylene terephthalate mainly adopts red phosphorus to do fire retardant, but doing fire retardant with red phosphorus mainly exists following shortcoming, and the one, product can only be made black or redness, can't prepare the true qualities product; The 2nd, this series products smell when injection moulding is bigger, and mould has red phosphorus and separates out the corrosion mould during injection moulding for a long time.Also useful organic hypophosphite is done Halogen polybutylene terephthalate fire retardant, but because this fire retardant is expensive, market outlook are wideless.Therefore lower, flame retardant properties of cost of development and the good halogen-free flameproof polybutylene terephthalate of processing characteristics certainly will become current development trend.
One Chinese patent application 200510021394.X discloses a kind of high relative discharge tracking index (CTI) value Halogen does not have red phosphorus flame-retardant enhancing polybutylene terephthalate; This fire-retardant enhancing polybutylene terephthalate is through adding alkyl phosphinate, organophosphate and the preparation of Melamine Polyphosphate compound flame retardant; The material that is obtained is when 1.6mm thickness; Flame retardant properties reaches V-0; But the mechanical property of material is not very desirable, and tensile strength is 96MPa, and flexural strength is 130MPa.
A kind of superelevation that discloses one Chinese patent application 200710019557.X flows, high thermal stability white halogen-free antiflaming polybutylene terephthalate and working method.This method mainly adopts organic phosphonate or SULPHOSUCCINIC ACID ESTER and nanoclay and silicone powder to carry out compositional flame-retardant.The material that is obtained is when 1.6mm thickness, and flame retardant properties reaches V-0, and tensile strength also has only 90MPa, flexural strength 150MPa.
Patent US5814690 discloses a kind of with two (diphenyl phosphoester) oligopolymers of Resorcinol or the collaborative fire-retardant polybutylene terephthalate of melamine pyrophosphate of two (diphenyl phosphoester) oligopolymers of dihydroxyphenyl propane.The fire retardant addition of this matrix material big (reaching 40wt%), flame retardant properties is lower, and the mechanical property of materials is also relatively poor.
In sum, the weak point of polybutylene terephthalate halogen-free flame is that high flame resistance and strong mechanical performance can not get both simultaneously at present.
Summary of the invention
The object of the invention is that it is fire-retardant to provide a kind of flame retardant resistance to reach 1.6mm UL94V-0, and the good halogen-free flameproof polybutylene terephthalate preparation of compositions method of mechanical property to the prior art defective.
A kind of halogen-free flameproof polybutylene terephthalate preparation of compositions method is following, below all representes with weight part:
40 parts of-50 parts of polybutylene terephthalates were descended dry 4-6 hour at 120 ℃-140 ℃, and moisture controlled obtains dry good polybutylene terephthalate below 0.02wt%; 1 part of-2 parts of fire retarding synergist, 3 parts of-8 parts of mineral fillers and 0.3 part of-1 part of oxidation inhibitor are added high-speed stirring mixer premix 3-5 minute, obtain Preblend; Again the Preblend that obtains and 40 parts of-50 parts of polybutylene terephthalates that drying is good are added twin screw extruder from main spout respectively; 15 parts of-20 parts of phenoxy phosphazenes and 30 parts of-40 parts of inorganic strengthening agents add the twin screw extruder from the side spout respectively; Temperature setting range from main spout to head is 210-260 ℃, and screw speed is 250-350rpm, fully extrudes after the plasticizing; Pelletizing obtains a kind of halogen-free flameproof polybutylene terephthalate compsn.
The limiting viscosity of used polybutylene terephthalate is 0.5-2.5dl/g among the present invention.
Among the present invention used phenoxy phosphazene a kind of be halogen-free flame retardants, its concrete preparation method is following:
0.72mol phenol is dissolved in 500ml THF (THF) solution, adds 0.72mol sodium hydroxide, the heated and stirred dissolving.0.1mol purified hexachlorocyclotriphosphazene is dissolved among the 150ml THF; And slowly splash in the reaction system through constant pressure funnel, 65 ℃ down behind the reaction 48h, distill out THF; Obtain the khaki color solid; Adopt the zero(ppm) water dipping to clean and remove by products such as unreacted sodium hydroxide, phenol and sodium-chlor, sodium phenylate, recrystallization and drying obtain white powdered product and promptly obtain the phenoxy phosphazene fire retardant in THF then, and productive rate is 93%.
Used fire retarding synergist is zinc borate, zinc oxide or zeolite among the present invention.
Used oxidation inhibitor is 1 among the present invention, 3-benzene diamide-N, N '-two (2,2,6,6-tetramethyl--4-piperidyl), three (2, the 4-DI-tert-butylphenol compounds) phosphorous acid ester or 3,3 '-sulfo-propyl ester bay alcohol ester.
Used inorganic strengthening agent is short glass fiber, wollastonite fibre, steel fiber or boric acid fibre among the present invention, and wherein fiber diameter range is 6-17 μ m.
Used mineral filler is glass flake, flat glass fiber, mica powder, talcum powder, graphite or glass microballon among the present invention, and wherein the median size of glass flake is 0.5mm, and the aspect ratio of flat glass fiber is 4-6, and the mica powder particle diameter is the 300-3000 order.
Adopted a kind of phenoxy phosphazene halogen-free flame retardants and fire retarding synergist to form halogen-free flame-retardant system in a kind of halogen-free flameproof polybutylene terephthalate of the present invention preparation of compositions method polybutylene terephthalate has been carried out halogen-free flameproof; The phenoxy phosphazene halogen-free flame retardants is a kind of organic halogen-free flame retardants; Addition is few, and flame retardant properties is excellent, and good with the polybutylene terephthalate consistency; Little to the polybutylene terephthalate performance impact; Therefore the halogen-free flameproof polybutylene terephthalate compsn good mechanical property that obtains, tensile strength can reach 125MPa, and non-notch impacts can reach 47KJ/m
2, and can reach 1.6mm UL94V-0 grade.
Embodiment
Below in conjunction with embodiment the present invention is described further.
The limiting viscosity of the polybutylene terephthalate that following examples are used is 1.8-2.5dl/g, available from appearance chemical industry engineering plastics factory.
Embodiment 1
40 parts of polybutylene terephthalates were descended dry 4-6 hour at 120 ℃-140 ℃, and moisture controlled obtains dry good polybutylene terephthalate below 0.02wt%; With 1 part of fire retarding synergist zinc borate, 3.7 parts of mineral filler 350 order mica powders and 0.3 part 3,3 '-sulfo-propyl ester bay alcohol ester oxidation inhibitor added high-speed stirring mixer premix 3-5 minute, obtained Preblend; Again the Preblend that obtains and 40 parts of dry good polybutylene terephthalates are added twin screw extruder from main spout respectively; 15 parts of halogen-free flame retardants phenoxy phosphazenes and 40 parts of inorganic strengthening agent spun glass add the twin screw extruder from the side spout respectively; Temperature setting range from main spout to head is 210-260 ℃, and screw speed is 250-350rpm, fully extrudes after the plasticizing; Pelletizing obtains a kind of halogen-free flameproof polybutylene terephthalate compsn.
The parameters test result of a kind of halogen-free flameproof polybutylene terephthalate compsn that this embodiment obtains is seen table 1.
Embodiment 2
50 parts of polybutylene terephthalates were descended dry 4-6 hour at 120 ℃-140 ℃, and moisture controlled obtains dry good polybutylene terephthalate below 0.02wt%; With 1 part of fire retarding synergist zinc borate, 3.7 parts of mineral filler 350 order mica powders and 0.3 part 3,3 '-sulfo-propyl ester bay alcohol ester oxidation inhibitor added high-speed stirring mixer premix 3-5 minute, obtained Preblend; Again the Preblend that obtains and 50 parts of dry good polybutylene terephthalates are added twin screw extruder from main spout respectively; 15 parts of halogen-free flame retardants phenoxy phosphazenes and 30 parts of inorganic strengthening agent spun glass add the twin screw extruder from the side spout respectively; Temperature setting range from main spout to head is 210-260 ℃, and screw speed is 250-350rpm, fully extrudes after the plasticizing; Pelletizing obtains a kind of halogen-free flameproof polybutylene terephthalate compsn
The parameters test result of a kind of halogen-free flameproof polybutylene terephthalate compsn that this embodiment obtains is seen table 1.
Embodiment 3
45 parts of polybutylene terephthalates were descended dry 4-6 hour at 120 ℃-140 ℃, and moisture controlled obtains dry good polybutylene terephthalate below 0.02wt%; With 1 part of fire retarding synergist zinc borate, 8.7 parts of mineral filler flat glass fibers and 0.3 part 3,3 '-sulfo-propyl ester bay alcohol ester oxidation inhibitor added high-speed stirring mixer premix 3-5 minute, obtained Preblend; Again the Preblend that obtains and 45 parts of dry good polybutylene terephthalates are added twin screw extruder from main spout respectively; 15 parts of halogen-free flame retardants phenoxy phosphazenes and 30 parts of inorganic strengthening agent spun glass add the twin screw extruder from the side spout respectively; Temperature setting range from main spout to head is 210-260 ℃, and screw speed is 250-350rpm, fully extrudes after the plasticizing; Pelletizing obtains a kind of halogen-free flameproof polybutylene terephthalate compsn
The parameters test result of a kind of halogen-free flameproof polybutylene terephthalate compsn that this embodiment obtains is seen table 1.
Embodiment 4
42 parts of polybutylene terephthalates were descended dry 4-6 hour at 120 ℃-140 ℃, and moisture controlled obtains dry good polybutylene terephthalate below 0.02wt%; With 1 part of fire retarding synergist zinc borate, 6.7 parts of mineral filler glass flakes and 0.3 part 3,3 '-sulfo-propyl ester bay alcohol ester oxidation inhibitor added high-speed stirring mixer premix 3-5 minute, obtained Preblend; Again the Preblend that obtains and 42 parts of dry good polybutylene terephthalates are added twin screw extruder from main spout respectively; 20 parts of halogen-free flame retardants phenoxy phosphazenes and 30 parts of inorganic strengthening agent spun glass add the twin screw extruder from the side spout respectively; Temperature setting range from main spout to head is 210-260 ℃, and screw speed is 250-350rpm, fully extrudes after the plasticizing; Pelletizing obtains a kind of halogen-free flameproof polybutylene terephthalate compsn
The parameters test result of a kind of halogen-free flameproof polybutylene terephthalate compsn that this embodiment obtains is seen table 1.
Embodiment 5
40 parts of polybutylene terephthalates were descended dry 4-6 hour at 120 ℃-140 ℃, and moisture controlled obtains dry good polybutylene terephthalate below 0.02wt%; With 1 part of fire retarding synergist zinc borate, 5.7 parts of mineral filler 350 order mica powders and 0.3 part 1,3-benzene diamide-N, N '-two (2,2,6,6-tetramethyl--4-piperidyl) oxidation inhibitor added high-speed stirring mixer premix 3-5 minute, obtained Preblend; Again the Preblend that obtains and 40 parts of dry good polybutylene terephthalates are added twin screw extruder from main spout respectively; 15 parts of halogen-free flame retardants phenoxy phosphazenes and 38 parts of inorganic strengthening agent spun glass add the twin screw extruder from the side spout respectively; Temperature setting range from main spout to head is 210-260 ℃, and screw speed is 250-350rpm, fully extrudes after the plasticizing; Pelletizing obtains a kind of halogen-free flameproof polybutylene terephthalate compsn
The parameters test result of a kind of halogen-free flameproof polybutylene terephthalate compsn that this embodiment obtains is seen table 1.
Table 1
| Performance | Testing method | Test condition | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Tensile strength | ISO?527-2 | 10mm/min | Mpa | 125.2 | 108.9 | 121.3 | 107.6 | 120.4 |
| Elongation at break | ISO?527-2 | 10mm/min | MPa | 9.8 | 8.3 | 8.7 | 7.9 | 9 |
| Flexural strength | ISO?178 | 2mm/min | MPa | 160.1 | 139.8 | 158.4 | 140.3 | 157.3 |
| Modulus in flexure | ISO?178 | 2mm/min | MPa | 9245 | 8169 | 8976 | 8134 | 9105 |
| Unnotched impact strength | ISO?180/A | / | KJ/m^2 | 47.1 | 44 | 45.3 | 45.2 | 46.3 |
| Shrinking percentage | ISO?2577 | / | ％ | 0.2-0.5 | 0.3-0.7 | 0.2-0.4 | 0.3-0.6 | 0.2-0.5 |
| Fire-retardant | UL94 | 1.6mm | Class | V-0 | V-0 | V-0 | V-0 | V-0 |
Can find out advantage of the present invention through table 1: it is a kind of halogen-free flame retardants that this product uses phenoxy phosphazene; In addition is the 15wt%-20wt% scope; Not only when flame retardant resistance reaches the UL94V-0 flame retardant rating, kept the excellent mechanical property of halogen-free flameproof glass TR-RFT.Can reach 125MPa through the optimization of C ultimate tensile strength, unnotched impact strength can reach 47KJ/m
2, flame retardant properties still can reach the 1.6mmUL94V-0 grade.
Claims (3)
1. a halogen-free flameproof polybutylene terephthalate preparation of compositions method is characterized in that the preparation method is following, below all representes with weight part:
With 40 parts of-50 parts of polybutylene terephthalates 120
oC-140
oUnder the C dry 4-6 hour, moisture controlled obtained dry good polybutylene terephthalate below 0.02wt%; 1 part of-2 parts of fire retarding synergist, 3 parts of-8 parts of mineral fillers and 0.3 part of-1 part of oxidation inhibitor are added high-speed stirring mixer premix 3-5 minute, obtain Preblend; Again the Preblend that obtains and 40 parts of-50 parts of polybutylene terephthalates that drying is good are added twin screw extruder from main spout respectively; 15 parts of-20 parts of phenoxy phosphazenes and 30 parts of-40 parts of inorganic strengthening agents add the twin screw extruder from the side spout respectively; Temperature setting range from main spout to head is 210-260 ℃, and screw speed is 250-350rpm, fully extrudes after the plasticizing; Pelletizing obtains a kind of halogen-free flameproof polybutylene terephthalate compsn;
Described inorganic strengthening agent is spun glass, wollastonite fibre, steel fiber or boric acid fibre;
Described mineral filler is glass flake, mica, talcum powder, graphite or glass microballon;
Described fire retarding synergist is zinc borate, zinc oxide or zeolite.
2. a kind of halogen-free flameproof polybutylene terephthalate preparation of compositions method according to claim 1 is characterized in that the polybutylene terephthalate limiting viscosity is 0.5-2.5dl/g.
3. a kind of halogen-free flameproof polybutylene terephthalate preparation of compositions method according to claim 1 is characterized in that oxidation inhibitor is 1,3-benzene diamide-N; N '-two (2,2,6; 6-tetramethyl--4-piperidyl) or three (2, the 4-DI-tert-butylphenol compounds) phosphorous acid ester.
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| KR20170007791A (en) | 2014-06-26 | 2017-01-20 | 사빅 글로벌 테크놀러지스 비.브이. | Flame retardant thermally conductive polymer compositions with good flow property and uses thereof |
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