CN104479306A - Halogen-free and non-phosphorus flame retardance PBT (Polybutylece Terephthalate) resin and preparation method thereof - Google Patents
Halogen-free and non-phosphorus flame retardance PBT (Polybutylece Terephthalate) resin and preparation method thereof Download PDFInfo
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- CN104479306A CN104479306A CN201410789130.8A CN201410789130A CN104479306A CN 104479306 A CN104479306 A CN 104479306A CN 201410789130 A CN201410789130 A CN 201410789130A CN 104479306 A CN104479306 A CN 104479306A
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Abstract
The invention provides halogen-free and non-phosphorus flame retardance PBT (Polybutylece Terephthalate) resin. The halogen-free and non-phosphorus flame retardance PBT resin is prepared from the following components: 70 to 95 parts of PBT, 1 to 10 parts of flexibilizer, 5 to 25 parts of halogen-free flame retardant, 0.5 to 2 parts of synergistic flame retardant, and 0.1 to 0.5 part of initiator. The invention also discloses a preparation method of the resin above. According to the halogen-free and non-phosphorus flame retardance PBT resin and the preparation method, the component ratio is optimized; all components fuse mutually and work together to enable the flame retardance of the halogen-free and non-phosphorus flame retardance PBT resin to reach UL94 V-0 level which is similar to the flame retardance of halogen-containing flame retardance products; the halogen-free and non-phosphorus flame retardance PBT resin is environmentally friendly, safe, and outstanding in electric insulation performance and mechanical performance; meanwhile, the raw materials and the preparation process are simple, the cost is decreased; the halogen-free and non-phosphorus flame retardance PBT resin can be widely applied to preparation of fittings of household appliance, electronic, automobile and other products.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of halogen-free phosphorus-free inflaming retarding PBT resin and preparation method thereof.
Background technology
Flame-retardant PBT resin not only has the good chemical resistant properties physical property of the splendid dimensional precision of high rigidity, high strength and stability and low warpage properties affects minimum good surface quality, easy-formation feature by water-intake rate, is widely used in various electric equipment products and auto parts machinery.Current flame-retardant PBT fire retardant nearly 95% used is halogen containing flame-retardant, because brominated flame-retardant efficiency is high, consumption is few, little to the performance impact of material, and it is moderate, its usefulness/cost ratio other fire retardants non-can be equal to, and therefore 70% ~ 80% all use this based flame retardant in China's electric series products for export.But bromide fire retardant is subject to the puzzlement of dioxin problem in recent years, a large amount of flue dust and corrosive gases can be generated with its (bromo-antimony system) fire-retardant macromolecular material when thermo-cracking and burning simultaneously, current European Union and Japan oneself in succession put into effect that it is forbidden by decree to and use this type of fire retardant.
Melamine cyanurate (MCA) is a kind of nitrogenous halogen-free environment-friendly type flame-proof agent, has and uses the feature such as economic, efficient, excellent electrical property and mechanical property, nondiscoloration, low cigarette, low-corrosiveness.Its low toxicity, to user's safety, good with Environmental compatibility simultaneously, thermostability is good, be particularly suitable for not filled nylon material, fire retardant material can be made to reach UL94V-0, its fire retardant mechanism walks heat to reach by Flashmelt dropping zone the flame retardant effect certainly put out.But for PBT resin material, the physical and mechanical properties adding the PBT resin of not only deterioration of MCA, and can wick effect be there is, slow down melting drippage during material combustion, the V2 even flame retardant rating of HB can only be accomplished, which greatly limits the range of application of MCA in PBT.
Summary of the invention
The object of the invention is to overcome in prior art not enough, a kind of halogen-free phosphorus-free inflaming retarding PBT resin and preparation method thereof is provided, PBT resin utilizes melamine cyanurate do fire retardant, compound synergistic flame retardant and initiator synergy, make its flame retardant properties reach UL94V0 grade.This material has environmental protection, safety, electrical insulation capability excellence, mechanical property advantages of higher, can significantly reduce the cost of flame-retardant PBT resin.
First aspect of the present invention is to provide a kind of halogen-free phosphorus-free inflaming retarding PBT resin, and according to weight parts, its component comprises:
Polybutylene terephthalate (PBT) is obtained through polycondensation with BDO (BDO) by terephthalic acid (PTA) or dimethyl terephthalate (DMT) (DMT).The geometrical regularity of PBT main chain and rigid element make polymkeric substance have high physical strength, outstanding chemical reagent resistance, thermotolerance and excellent electrical property; Molecular structure is symmetrical, meets the requirement of closely piling up, thus makes this polymkeric substance have crystallinity and the high-melting-point of height.Because PBT at a lower temperature can crystallization rapidly, so moulding processability is good, shaping cycle is short, can be made into complex-shaped product or thin wall parts.
Wherein, the molecular weight of described polybutylene terephthalate is 10000 ~ 200000.
Wherein, described halogen-free flame retardants is melamine cyanurate (MCA).
Wherein, toughner has the analog assistant reducing matrix material fragility and improve matrix material shock resistance, and the chemical structure of the material that those skilled in the art are toughness reinforcing is as required different, can be selected from the toughner of respective type.
Preferably, toughner described in the present invention is thermoplastic polyester elastomer (TPEE), and because TPEE has the block structure similar with PBT, toughening effect is good and don't affect the flame retardant effect of material.
Wherein, synergistic flame retardant, for improving the flame retardant effect of halogen-free flame retardants, reduces the consumption of halogen-free flame retardants.Main based on nitrogen system, phosphorus series compound and metal hydroxides, also comprise nitrogen phosphorus intumescent system, graphite expansion system.Such as melamine phosphate (APP), polyphosphoric acid amine (MP), hexaaniline cyclotriphosphazene, three O-Phenylene Diamine basic ring three phosphonitriles, triphenylenyl-1-amido-2-oxygen basic ring three phosphonitrile, nanometer ATH, polyvinyl alcohol etc.
Preferably, synergistic flame retardant described in the present invention is polyvinyl alcohol, and it has excellent incarbonization in flame-retardant system of the present invention.
Wherein, initiator refers to that easy decomposes becomes a compounds of free radical, can cause rapidly for flame-retardant system and cause material molecule splitting of chain, thus accelerated material melting dropping zone walks heat, reach the effect from putting out, such as lauroyl peroxide, isopropyl benzene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2,3-dimethyl-2,3-diphenyl butanes (bicummyl) etc.
Preferably, initiator described in the present invention is 2,3-dimethyl-2,3-diphenyl butane (bicummyl).
Contriver is surprised to find, and polyvinyl alcohol and bicummyl are used in conjunction with each other, and has excellent flame retardant synergism in the MCA flame-retardant system of PBT, can certainly the putting out of accelerate combustion material, and improves flame retardant effect.
Preferably, according to weight parts, the component of halogen-free phosphorus-free inflaming retarding PBT resin comprises:
The component of halogen-free phosphorus-free inflaming retarding PBT resin of the present invention can also comprise other auxiliary agents conventional in matrix material preparation, such as oxidation inhibitor, lubricant, dispersion agent, anti ultraviolet agent and tinting material etc.
Preferably, described halogen-free phosphorus-free inflaming retarding PBT resin comprises other auxiliary agents 0.5 ~ 2 part, is more preferably 1 part.
Should be understood that, consumption those skilled in the art of described antioxidant, lubricant, dispersion agent, anti ultraviolet agent and tinting material etc. can add as one sees fit according to the knowledge grasped, and are not specifically limited in the present invention.
Described antioxidant, lubricant, dispersion agent, anti ultraviolet agent and tinting material etc. all can adopt the material that polymeric material field is conventional, are not particularly limited in the present invention.Antioxidant is as four [methyl-β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, the β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid, N; N'-pair-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine, 1,3; 5-tri-(the 4-tertiary butyl-3-hydroxyl-2; 6-dimethyl benzyl)-1,3,5-triazines-2; 4; 6 (1H, 3H, 5H)-triketones etc.Lubricant is as Zinic stearas, n-butyl stearate, amine hydroxybenzene, ethylenebisstearamide, glyceryl monostearate etc.Dispersion agent is as whiteruss, oxidized polyethlene wax, methyl hydroxystearate, polydimethylsiloxane etc.Tinting material as: carbon black, titanium dioxide white, iron oxide brown, ultramarine blue, permanent bordeaux, phthalein are dark green.
Second aspect of the present invention is to provide the preparation method of the halogen-free phosphorus-free inflaming retarding PBT resin described in the present invention first aspect, comprises the following steps:
Step 1, takes each component by weight, mixes;
Step 2, is placed in Double-screw machine by mixture, through melt extruding, and granulation, both.
Preferably, the screw slenderness ratio of described Double-screw machine is 28 ~ 44, processing condition are: district's temperature 210 ~ 230 DEG C, two district's temperature 220 ~ 240 DEG C, three district's temperature 230 ~ 250 DEG C, four district's temperature 220 ~ 240 DEG C, head temperature is 230 ~ 260 DEG C, the barrel residence time is 0.5 ~ 2 minute, melt pressure 10 ~ 20MPa.
The present invention utilizes melamine cyanurate to do on the basis of fire retardant in PBT resin, compound synergistic flame retardant and initiator cooperative flame retardant, can greatly improve its flame retardant properties, especially polyvinyl alcohol is adopted to be used in conjunction with each other as synergistic flame retardant and initiator bicummyl, excellent flame retardant synergism is had in the MCA flame-retardant system of PBT, can certainly the putting out of accelerate combustion material, improve flame retardant effect.The flame retardant properties of halogen-free phosphorus-free inflaming retarding PBT resin provided by the invention reaches UL94V0 grade, the flame retardant properties of the Halogen flame retardant products that matches in excellence or beauty, Environmental Safety, and has excellent electrical insulation capability and mechanical property etc.Simply, cost is very cheap, significantly reduces the cost of flame-retardant PBT resin, can be widely used in household electrical appliances, electronics, the product accessories etc. such as automobile for raw material of the present invention and preparation technology simultaneously.
Embodiment
Below in conjunction with embodiment, the present invention is described in further details, to understand the present invention better.
In embodiment and comparative example, employ following material:
PBT is provided by Nantong Zhong Lan company, trade names 1100
TPEE is provided by Changchun, Taiwan company, trade names 1155
MCA is provided by Nantong Yi Te company, trade names MCA-25
Polyvinyl alcohol is provided by Kuraray company, trade names PVA217
Bicummyl is provided by Sheng Lai Coulter Corp of the U.S.
Other auxiliary agent is common commercial oxidation inhibitor, lubricant, dispersion agent, anti ultraviolet agent, tinting material etc.As 1010 of vapour Bagong department, the OP wax of Clariant Corporation, the EBS of KAO. Corp. SA, the R69 etc. of E.I.Du Pont Company.
Embodiment 1
With reference to table 1, a kind of halogen-free phosphorus-free inflaming retarding PBT resin, according to weight parts, it comprises following component:
Take raw material by the weight ratio of each component to join high-speed mixer and mix; Mixture is placed in dual-screw-stem machine, through melt extruding, granulation.Wherein, the screw slenderness ratio of described Double-screw machine is 28 ~ 44, processing condition are: district's temperature 210 ~ 230 DEG C, two district's temperature 220 ~ 240 DEG C, three district's temperature 230 ~ 250 DEG C, four district's temperature 220 ~ 240 DEG C, head temperature is 230 ~ 260 DEG C, the barrel residence time is 0.5 ~ 2 minute, melt pressure 10 ~ 20MPa.
Embodiment 2
A kind of halogen-free phosphorus-free inflaming retarding PBT resin, its constituent species is identical with embodiment 1, and its difference is, the proportioning of the component of the halogen-free phosphorus-free inflaming retarding PBT resin of the present embodiment is different from embodiment 1, specifically arranges in table 1 the 3rd.
Embodiment 3
A kind of halogen-free phosphorus-free inflaming retarding PBT resin, its constituent species is identical with embodiment 1, and its difference is, the proportioning of the component of the halogen-free phosphorus-free inflaming retarding PBT resin of the present embodiment is different from embodiment 1, specifically arranges in table 1 the 4th.
Embodiment 4
A kind of halogen-free phosphorus-free inflaming retarding PBT resin, its constituent species is identical with embodiment 1, and its difference is, the proportioning of the component of the halogen-free phosphorus-free inflaming retarding PBT resin of the present embodiment is different from embodiment 1, specifically arranges in table 1 the 5th.
Comparative example 1
This comparative example is with the difference of embodiment 1, and component is different with proportioning, specifically arranges in table 1 the 6th.
Comparative example 2
This comparative example is with the difference of embodiment 1, and component is different with proportioning, specifically arranges in table 1 the 7th.
The component of table 1 embodiment 1 ~ 4 and comparative example 1 ~ 2 and proportioning (weight part)
Performance evaluation:
The halogen-free phosphorus-free inflaming retarding PBT resin that Example 1 ~ 4 and comparative example 1 ~ 2 provide, detect density, mechanical property and flame retardant properties etc., detected result is as shown in table 2, and wherein, detection method is as follows:
By the material in the convection oven of 110 DEG C dry 3 ~ 6 hours completing granulation, then dried material is carried out injection molding sample preparation on injection moulding machine, injection molding die temperance control is at 90 DEG C.Tensile strength test is undertaken by ASTM D638 standard, and specimen size is 180 × 12.7 × 3.2mm, and draw speed is 50mm/min; Bending property test is undertaken by ASTM D790 standard, and specimen size is 128 × 13 × 3.2, and rate of bending is 3mm/min, and span is 64mm; Cantilever beam impact strength is undertaken by ASTM D256 standard, and specimen size is 63.5 × 12.7 × 4.2mm, and notch size is 1/5th of sample thickness; Flame retardant rating is undertaken by UL94 testing standard, and specimen size is 128mm × 13mm × 1.6mm.
The performance test results of table 2 halogen-free phosphorus-free inflaming retarding PBT resin
As shown in Table 2, halogen-free phosphorus-free inflaming retarding PBT resin 0.8mm flame retardant rating prepared by the present invention's four embodiments all reaches V0, and comparative example 1 is HB, and comparative example 2 is V2; And the 1.6mm flame retardant rating of embodiment 1 ~ 3 reaches V0, and embodiment 4 is because toughner adds, and the too many wick effect that easily produces causes flame retardant rating to decline, but also can reach V2, is much better than comparative example 1 (HB) and comparative example 2 (HB); Illustrate that halogen-free phosphorus-free inflaming retarding PBT resin of the present invention has splendid flame retardant effect.Contrast from embodiment 2 and contrast 1 and 2, polyvinyl alcohol and bicummyl have the synergistic fire retardation of excellence, and it is not good to be used alone its flame retardant effect.In addition, tensile strength of the present invention is 46 ~ 54Mpa, and flexural strength is 78 ~ 95Mpa, and notched Izod impact strength is 3.5 ~ 6.6, has good mechanical property.
Product performance of the present invention reach the performance requirement to plastic material such as household electrical appliances accessory, electronic product accessory completely, and material is not halogen-containing, in use can not release obnoxious flavour because of the decomposition of its material, pollution-free to large G&W etc., its cost is even lower than Halogen fire retardant material, has broad application prospects.
Be described in detail specific embodiments of the invention above, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and substituting also all among category of the present invention.Therefore, equalization conversion done without departing from the spirit and scope of the invention and amendment, all should contain within the scope of the invention.
Claims (10)
1. a halogen-free phosphorus-free inflaming retarding PBT resin, is characterized in that, according to weight parts, its component comprises:
2. halogen-free phosphorus-free inflaming retarding PBT resin according to claim 1, is characterized in that, the molecular weight of described polybutylene terephthalate is 10000 ~ 200000.
3. halogen-free phosphorus-free inflaming retarding PBT resin according to claim 1, is characterized in that, described toughner is thermoplastic polyester elastomer.
4. halogen-free phosphorus-free inflaming retarding PBT resin according to claim 1, is characterized in that, described halogen-free flame retardants is melamine cyanurate.
5. halogen-free phosphorus-free inflaming retarding PBT resin according to claim 1, is characterized in that, described synergistic flame retardant is polyvinyl alcohol.
6. halogen-free phosphorus-free inflaming retarding PBT resin according to claim 1, is characterized in that, described initiator is 2,3-dimethyl-2,3-diphenyl butane.
7. halogen-free phosphorus-free inflaming retarding PBT resin according to claim 1, is characterized in that, according to weight parts, its component comprises:
8. the halogen-free phosphorus-free inflaming retarding PBT resin according to claim 1 or 7, is characterized in that, its component also comprises other auxiliary agents 0.5 ~ 2 part.
9. halogen-free phosphorus-free inflaming retarding PBT resin according to claim 8, is characterized in that, other auxiliary agents described are one or more in oxidation inhibitor, lubricant, dispersion agent, anti ultraviolet agent and tinting material.
10., as a preparation method for the halogen-free phosphorus-free inflaming retarding PBT resin in claim 1 ~ 9 as described in any one, it is characterized in that, comprise the following steps:
Step 1, takes each raw material by weight, mixes;
Step 2, is placed in Double-screw machine by mixture, through melt extruding, and granulation, both.
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| CN201410789130.8A CN104479306A (en) | 2014-12-17 | 2014-12-17 | Halogen-free and non-phosphorus flame retardance PBT (Polybutylece Terephthalate) resin and preparation method thereof |
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| CN201410789130.8A CN104479306A (en) | 2014-12-17 | 2014-12-17 | Halogen-free and non-phosphorus flame retardance PBT (Polybutylece Terephthalate) resin and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250702A (en) * | 2018-03-01 | 2018-07-06 | 苏州维洛克电子科技有限公司 | Sheet material of flame retardant polyester containing carbamide and preparation method thereof |
| CN108285546A (en) * | 2018-03-01 | 2018-07-17 | 苏州维洛克电子科技有限公司 | A kind of fire retardant mylar and preparation method thereof of without phosphorus Halogen |
| CN112759894A (en) * | 2020-12-30 | 2021-05-07 | 广州敬信高聚物科技有限公司 | High-temperature-resistant TPEE/ETFE composite material and preparation method thereof |
-
2014
- 2014-12-17 CN CN201410789130.8A patent/CN104479306A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250702A (en) * | 2018-03-01 | 2018-07-06 | 苏州维洛克电子科技有限公司 | Sheet material of flame retardant polyester containing carbamide and preparation method thereof |
| CN108285546A (en) * | 2018-03-01 | 2018-07-17 | 苏州维洛克电子科技有限公司 | A kind of fire retardant mylar and preparation method thereof of without phosphorus Halogen |
| CN112759894A (en) * | 2020-12-30 | 2021-05-07 | 广州敬信高聚物科技有限公司 | High-temperature-resistant TPEE/ETFE composite material and preparation method thereof |
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