CN101805496A - Novel halogen-free flame-retardant reinforcing polyester alloy (ETP) - Google Patents
Novel halogen-free flame-retardant reinforcing polyester alloy (ETP) Download PDFInfo
- Publication number
- CN101805496A CN101805496A CN 201010127798 CN201010127798A CN101805496A CN 101805496 A CN101805496 A CN 101805496A CN 201010127798 CN201010127798 CN 201010127798 CN 201010127798 A CN201010127798 A CN 201010127798A CN 101805496 A CN101805496 A CN 101805496A
- Authority
- CN
- China
- Prior art keywords
- halogen
- free flame
- etp
- retardant
- polyester alloy
- 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.)
- Pending
Links
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A novel halogen-free flame-retardant reinforcing polyester alloy (ETP) is characterized in that the prescription (weight percent) of raw materials comprises the following main materials and auxiliary materials, wherein the main materials comprise (1) 40-50% of polyethylene glycol terephthalate (PET) and (2) 15-20% of polytrimethylene terephthalate (PTT), and the auxiliary materials comprise (1) 12-20% of halogen-free flame retardant (PDPTP), (2) 0.2% of antioxidant 1010/168, (3) 0.4-0.6% of lubricating agent (TAF), (4) 1-3% of nucleating agent (nano-bentonite), (5) 2-4% of crystallization accelerating agent (polyether), and (6) 10-30% of reinforcing agent (alkali-free glass fiber). The polyester alloy is prepared by taking PET/PTT polyester as main material, taking PDPTP as halogen-free flame retardant, using polymerizing technology, crystallization accelerating technology and nucleating technology, adding auxiliary material, and using a double-screw extruder for plastifying and pelleting. Through the synergistic effect of each component of the system and the unique processing technique, the product has excellent comprehensive performance; the environmental index meets European Union RoHS, IEC halogenation-free and Reach requirements; the flame-retardant grade reaches to UL94, 0.8mm V-0 level; the leakage tracking index (CTI) reaches to 425V; the test temperature of scorching wire reaches to 750 DEG C; both the intensity and the toughness can meet the requirement of products in electronic industry.
Description
Technical field
The present invention relates to the modified polymer material field, be specifically related to a kind of novel halogen-free flame-retardant reinforcing polyester alloy (ETP) and preparation method thereof.This material has been realized complete non-halogen aspect environmental protection, mechanical property, flame retardant properties, electric property excellence, and the shaping efficiency height is widely used in industry and fields such as electric, automobile, household electrical appliance.
Background technology
PET is a kind of crystalline high polymer with higher melt temperature (Tm) and second-order transition temperature (Tg), it occurs early, cheap, although have high rigidity, high strength and good dimensional stability, overall characteristics such as thermotolerance, be widely used and synthon, fields such as film, but because the rigidity of PET makes its crystallization velocity slower, the injection moulding difficulty is very limited its application.For many years, improve the crystallization rate of PET, improve its processing characteristics is one of main direction of PET modification always; PBT then has good moulding processability and over-all properties, but owing to cost an arm and a leg, has limited its application; And a kind of new polyester material that PTT is a twentieth century just to be occurred the end of the nineties has the physicals of PET, and aspect processing, melt crystallization speed is near PBT, and shaping efficiency is faster than PET.Therefore PTT has development prospect by feat of high-performance that has PET concurrently and PBT good processing properties.In addition, this kind polyester material major part is to need through strengthening flame-retardant modifiedly, just can be used for industry and fields such as electric, household electrical appliance, IT, automobile, medical treatment and sports apparatus.
All the time, the fire retardant that is used for modifying plastics is based on bromo-antimony compound system, this system good flame retardation effect, addition are low, little to the mechanical property influence of material, but it can produce toxic substances such as hydrogen halide, dioxin in the process of combustion decomposition, all can cause greatly harm to people's health and environment.To the electrical property of material influence very big (as CTI), and in the course of processing easy bloom, easily stifled venting port has corrosive nature to mould.Along with the whole world particularly developed country such as America and Europe environmental protection and public safety are required progressively to improve, a lot of in the world well-known electronic enterprises, IT industry (as Dell, Sony, Samsung, LG, Sony-Ericson, association, Benq etc.) all require non-halogen to the fire-retardant parts in its product, and all to have proposed the deadline be the end of the year 2009.International Power committee (IEC) has also put into effect non-halogen standard, requires in the material Cl and Br distinguish must not and surpass 900PPm, and the two content must not amount to above 1500PPm.So fire retardant material is non-halogen extremely urgent.But common several halogen-free flame retardantss all have all drawbacks, and range of application is very limited.As the conventional red phosphorus fire retardant, good flame retardation effect, little to the material mechanical performance influence, but can only do black product.The oxyhydroxide fire retardant will reach flame retardant effect, needs heavy addition, and is very big, also inadvisable to the mechanical property influence of material.Also useful phosphorus-nitrogen combustion inhibitor interworking, but flame retardant effect is very poor, does not reach the UL94 0.8mm V-0 level of electric industry universal demand.
The halogen-free flameproof modification of polyester engineering plastics is a difficult problem always, especially most widely used PBT, PC material, and world-famous puzzle promptly enables to make especially, and cost also is several times of halogen flame retardant.My department looks for another way the advantage combination of PET and PTT, through a large amount of tests, utilize nanometer to become nuclear technique and crystallization promotion technology, select best prescription, PET and the slow problem of PTT crystallization have been solved, in conjunction with the halogen-free flame retardants of independent development, produce a kind of novel halogen-free flame-retardant reinforcing polyester alloy with low cost (ETP) through special process, can replace the higher fire retardant PBT with no halogen of price, materials such as PC, PA.This product good mechanical performance, good electrical property; Do not influence color matching, the environmental protection aspect meets ROHS of European Union and Reach statutory standard, satisfies the non-halogen standard of IEC fully, excellent combination property, and cost performance is high, is domestic initiation.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, provide a kind of cost lower, environmental protection index can satisfy the non-halogen and Reach laws and regulations requirement of the RoHS of European Union, IEC, flame retardant resistance reaches U.S. UL94 0.8mm V-0 level, halogen-free flame-retardant reinforcing polyester alloy (ETP) material of mechanical property, electric property excellence.Fire retardant PBT with no halogen, materials such as PC, PA that the alternative price of this material is higher, and good forming effect do not influence color matching, can be widely used in fields such as electric, automobile, household electrical appliance, are good industrialization application technology.
Another object of the present invention provides the preparation method of above-mentioned novel halogen-free flame-retardant reinforcing polyester alloy (ETP).
For achieving the above object, the technical solution used in the present invention is:
1. a novel halogen-free flame-retardant reinforcing polyester alloy (ETP), composition of raw materials (weight percentage) is:
Major ingredient:
(1) polyethylene terephthalate (PET) 40～50%;
(2) Poly(Trimethylene Terephthalate) (PTT) 15～20%;
Auxiliary material:
(1) halogen-free flame retardants
PDPTP 12～20％；
(2) oxidation inhibitor
Oxidation inhibitor 101 0.2%;
Oxidation inhibitor 168 0.2%;
(3) lubricant
TAF 0.4～0.6％；
(4) nucleator
Nano-bentonite 1～3%;
(5) crystallization promoter
Polyethers 2～4%;
(6) toughener
Alkali free glass fibre 10～30%.
2. the preparation method is as follows:
(1) resin drying: with PET and PTT resin 90～120 ℃ dry 4～8 hours down, moisture controlled is below 0.03%, dry back is standby;
(2) main ingredient mixes: with dried PET, PTT, with halogen-free flame retardants, oxidation inhibitor, lubricant, nucleator, crystallization promoter mixing stirring, each component fully is uniformly dispersed;
(3) melt extrude: above-mentioned compound is sent in the twin screw extruder, when melt extruding, introduced alkali free glass fibre, fully plasticizing, kneading, mixing melt extrude temperature in 200 ~ 250 ℃ of scopes.
(4) granulation and aftertreatment:, handle the back packing through vibratory screening apparatus, magnetic separation again and get product with material tie rod, cooling, the air-dry back granulation of extruding.
Related content in the technique scheme is explained as follows:
(1) in the such scheme, described halogen-free flame retardants PDPTP is poly-thio-phenyl phosphonic acids (9, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphono) penylene ester;
(2) in the such scheme, described lubricant TAF is the modification ethylene bis stearamide;
(3) in the such scheme, described nucleator is a nano-bentonite, is a kind of layered silicate wilkinite of 20～70 nanometers;
(4) in the such scheme, described preparation method's (2) step main ingredient mixes, and adopts homogenizer to mix stirring, better effects if under the rotating speed more than 1000 rev/mins.
Products characteristics of the present invention:
1) this product good flame retardation effect, flame retardant resistance reach U.S. UL94 0.8mm V-0 level.
2) this product has good processing properties, and flowability is much better than common modified poly ester engineering plastics, can be used to prepare large-scale, thin-walled, complex component.
3) this product good electrical property, anti creepage trace index (CTI) reaches 425V.
4) this product glowing filament (GWIT) test temperature reaches 750 ℃.
5) do not influence color matching fully.
6) this product environmental protection grade height can satisfy ROHS of European Union and Reach statutory standard, and not containing halide (F, Cl, Br, I), satisfies the non-halogen standard of IEC.
7) this product mechanical property excellence, the intensity height, good toughness can be used for producing the structural part of multiple electric, household electrical appliance and automobile.
Description of drawings
Accompanying drawing 1 is process flow sheet of the present invention.
Embodiment
Referring to shown in Figure 1, the preparation method is as follows:
(1) resin drying: with PET and PTT resin 90～120 ℃ dry 4～8 hours down, moisture controlled is below 0.03%, dry back is standby;
(2) main ingredient mixes: with dried PET, PTT, with halogen-free flame retardants, oxidation inhibitor, lubricant, nucleator, crystallization promoter mixing stirring, each component fully is uniformly dispersed;
(3) melt extrude: above-mentioned compound is sent in the twin screw extruder, when melt extruding, introduced alkali free glass fibre, fully plasticizing, kneading, mixing melt extrude temperature in 200 ~ 250 ℃ of scopes.
(4) granulation and aftertreatment:, handle the back packing through vibratory screening apparatus, magnetic separation again and get product with material tie rod, cooling, the air-dry back granulation of extruding.
According to above-mentioned preparation method:
Embodiment 1
Novel halogen-free flame-retardant reinforcing polyester alloy (ETP) prescription (weight percentage):
Major ingredient:
(1) polyethylene terephthalate (PET) 48%;
(2) Poly(Trimethylene Terephthalate) (PTT) 16%;
Auxiliary material:
(1) halogen-free flame retardants
PDPTP 20％；
(2) oxidation inhibitor
Antioxidant 1010 0.2%;
Oxidation inhibitor 168 0.2%;
(3) lubricant
TAF 0.4％；
(4) nucleator
Nano-bentonite 2%;
(5) crystallization promoter
Polyethers 4%;
(6) toughener
Alkali free glass fibre 10%.
This embodiment performance is as follows: tensile strength=121Mpa, notched Izod impact strength=60J/m, flexural strength=180Mpa, fire-retardant UL94 V0 level.
Embodiment 2
Novel halogen-free flame-retardant reinforcing polyester alloy (ETP) prescription (weight percentage):
Major ingredient:
(1) polyethylene terephthalate (PET) 40%;
(2) Poly(Trimethylene Terephthalate) (PTT) 15%;
Auxiliary material:
(1) halogen-free flame retardants
PDPTP 12％；
(2) oxidation inhibitor
Antioxidant 1010 0.2%;
Oxidation inhibitor 168 0.2%;
(3) lubricant
TAF 0.6％；
(4) nucleator
Nano-bentonite 1%;
(5) crystallization promoter
Polyethers 2%;
(6) toughener
Alkali free glass fibre 30%.
This embodiment performance is as follows: tensile strength=132Mpa, notched Izod impact strength=75J/m, flexural strength=212Mpa, fire-retardant UL94 V0 level.
Embodiment 3
Novel halogen-free flame-retardant reinforcing polyester alloy (ETP) prescription (weight percentage):
Major ingredient:
(1) polyethylene terephthalate (PET) 45%;
(2) Poly(Trimethylene Terephthalate) (PTT) 16%;
Auxiliary material:
(1) halogen-free flame retardants
PDPTP 14％；
(2) oxidation inhibitor
Antioxidant 1010 0.2%;
Oxidation inhibitor 168 0.2%;
(3) lubricant
TAF 0.5％；
(4) nucleator
Nano-bentonite 2%;
(5) crystallization promoter
Polyethers 3%;
(6) toughener
Alkali free glass fibre 20%.
This embodiment performance is as follows: tensile strength=126Mpa, notched Izod impact strength=68J/m, flexural strength=195Mpa, fire-retardant UL94 V0 level.
The foregoing description only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the personage who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalences that spirit is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (5)
1. a novel halogen-free flame-retardant reinforcing polyester alloy (ETP) is characterized in that:
Composition of raw materials (weight percentage) is:
Major ingredient:
(1) polyethylene terephthalate (PET) 40～50%;
(2) Poly(Trimethylene Terephthalate) (PTT) 15～20%;
Auxiliary material:
(1) halogen-free flame retardants
PDPTP 12～20％；
(2) oxidation inhibitor
Antioxidant 1010 0.2%;
Oxidation inhibitor 168 0.2%;
(3) lubricant
TAF 0.4～0.6％；
(4) nucleator
Nano-bentonite 1～3%;
(5) crystallization promoter
Polyethers 2～4%;
(6) toughener
Alkali free glass fibre 10～30%.
2. novel halogen-free flame-retardant reinforcing polyester alloy according to claim 1 (ETP) is characterized in that described halogen-free flame retardants PDPTP is poly-thio-phenyl phosphonic acids (9, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphono) penylene ester.
3. novel halogen-free flame-retardant reinforcing polyester alloy according to claim 1 (ETP) is characterized in that described lubricant TAF is the modification ethylene bis stearamide.
4. novel halogen-free flame-retardant reinforcing polyester alloy according to claim 1 (ETP) is characterized in that described nucleator is a nano-bentonite, is a kind of layered silicate wilkinite of 20～70 nanometers.
5. novel halogen-free flame-retardant reinforcing polyester alloy according to claim 1 (ETP), it is characterized in that: the preparation method is as follows:
(1) resin drying: with PET and PTT resin 90～120 ℃ dry 4～8 hours down, moisture controlled is below 0.03%, dry back is standby;
(2) main ingredient mixes: with dried PET, PTT, with halogen-free flame retardants, oxidation inhibitor, lubricant, nucleator, crystallization promoter mixing stirring, each component fully is uniformly dispersed;
(3) melt extrude: above-mentioned compound is sent in the twin screw extruder, when melt extruding, introduced alkali free glass fibre, fully plasticizing, kneading, mixing melt extrude temperature in 200 ~ 250 ℃ of scopes.
(4) granulation and aftertreatment:, handle the back packing through vibratory screening apparatus, magnetic separation again and get product with material tie rod, cooling, the air-dry back granulation of extruding.
Related content among the above-mentioned preparation method is explained as follows:
(2) step main ingredient mixes described in the above-mentioned preparation method, adopts homogenizer to mix stirring, better effects if under the rotating speed more than 1000 rev/mins.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010127798 CN101805496A (en) | 2010-03-19 | 2010-03-19 | Novel halogen-free flame-retardant reinforcing polyester alloy (ETP) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010127798 CN101805496A (en) | 2010-03-19 | 2010-03-19 | Novel halogen-free flame-retardant reinforcing polyester alloy (ETP) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101805496A true CN101805496A (en) | 2010-08-18 |
Family
ID=42607459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010127798 Pending CN101805496A (en) | 2010-03-19 | 2010-03-19 | Novel halogen-free flame-retardant reinforcing polyester alloy (ETP) |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101805496A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955636A (en) * | 2010-10-12 | 2011-01-26 | 江苏安格特新材料科技有限公司 | Yellowing resistant reinforced thermoplastic polyester (PET) and preparation method thereof |
| CN102585459A (en) * | 2012-03-12 | 2012-07-18 | 苏州萃智新技术开发有限公司 | Novel halogen-free flame-retardant enhanced polyester alloy (ETP) |
| CN103435980A (en) * | 2013-07-26 | 2013-12-11 | 金发科技股份有限公司 | Antistatic halogen-free flame-retardant reinforced PET/PTT alloy material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789329A (en) * | 2005-12-13 | 2006-06-21 | 苏州市凯米克新材料有限公司 | High-performance reinforced fire-retardant polyster engineering plastic |
| CN101092507A (en) * | 2007-05-21 | 2007-12-26 | 苏州兰特纳米材料科技有限公司 | Enganced environmental protective flame retardant polyester alloy (ETP) |
-
2010
- 2010-03-19 CN CN 201010127798 patent/CN101805496A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789329A (en) * | 2005-12-13 | 2006-06-21 | 苏州市凯米克新材料有限公司 | High-performance reinforced fire-retardant polyster engineering plastic |
| CN101092507A (en) * | 2007-05-21 | 2007-12-26 | 苏州兰特纳米材料科技有限公司 | Enganced environmental protective flame retardant polyester alloy (ETP) |
Non-Patent Citations (1)
| Title |
|---|
| 《中国塑料》 20091231 邓义 等 阻燃剂PDPTP在PET中的阻燃机理研究 第65-71页 第23卷, 第12期 2 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955636A (en) * | 2010-10-12 | 2011-01-26 | 江苏安格特新材料科技有限公司 | Yellowing resistant reinforced thermoplastic polyester (PET) and preparation method thereof |
| CN102585459A (en) * | 2012-03-12 | 2012-07-18 | 苏州萃智新技术开发有限公司 | Novel halogen-free flame-retardant enhanced polyester alloy (ETP) |
| CN103435980A (en) * | 2013-07-26 | 2013-12-11 | 金发科技股份有限公司 | Antistatic halogen-free flame-retardant reinforced PET/PTT alloy material and preparation method thereof |
| CN103435980B (en) * | 2013-07-26 | 2015-11-18 | 金发科技股份有限公司 | A kind of anti-static halogen-free flame-retardant REINFORCED PET/PTT alloy material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102850661A (en) | Halogen-free flame-retardant PP/polyester alloy and preparation method thereof | |
| CN102070884B (en) | Fire resistant glass fiber reinforced polyethylene terephthalate/polybutylece terephthalate alloy and preparation method thereof | |
| CN101659779B (en) | Halogen-free flame-retardant ABS resin and preparation method thereof | |
| CN100425652C (en) | High-performance reinforced fire-retardant polyster engineering plastic | |
| CN103087518B (en) | Glass-fiber-reinforced halogen-free flame-retardant nylon 46 composite material and preparation method thereof | |
| CN102070885B (en) | Halogen-free flame-retardant glass fiber reinforced polyester terephthalate (PET)/poly butylenes terephthalate (PBT) alloy and preparation method thereof | |
| CN102382465A (en) | Halogen-free flame retarding strengthened PA66 material and preparation method thereof | |
| CN102816414A (en) | High heat-resistant fire-retardant reinforced polyethylene terephthalate (PET) composition and preparation method thereof | |
| CN101798447A (en) | PBT (Polybutylece Terephthalate) special halogen and phosphorus free inflaming retarding plasticizing mother particle and preparation method thereof | |
| CN104693701A (en) | Low-warpage halogen-free flame-retardant glass fiber reinforced PBT/AS alloy and preparation method thereof | |
| CN101092507A (en) | Enganced environmental protective flame retardant polyester alloy (ETP) | |
| CN101805496A (en) | Novel halogen-free flame-retardant reinforcing polyester alloy (ETP) | |
| CN104861583A (en) | High-performance flame retardation PTT/PETG composite material | |
| CN104629307A (en) | Flame retardant reprocessed plastic with recycled PC and ABS | |
| CN104672809A (en) | Toughened reinforced environment-friendly flame-retardant PBT/PET (polybutylene terephthalate/polyethylene terephthalate) alloy | |
| CN103131147A (en) | High heat wire inflaming retarding enhancement polybutylece terephthalate (PBT) material and manufacturing method thereof | |
| CN103073854A (en) | Polyester composition, preparation method and applications thereof | |
| CN104419141A (en) | Glass fiber reinforced halogen-free flame retardant and antistatic PBT/PET alloy | |
| CN104725794A (en) | Glass-fiber-reinforced flame-retardant PBT-PET alloy | |
| CN104341728A (en) | Glass fiber enhanced flame retardant modified regenerated PET (polyethylene terephthalate)/PBT (polybutylene terephthalate) composite material | |
| CN104513467A (en) | Polycarbonate (PC) blended alloy material | |
| CN102585459A (en) | Novel halogen-free flame-retardant enhanced polyester alloy (ETP) | |
| CN106084685A (en) | A kind of low floating fine high fire-retardance PBT material and preparation method thereof | |
| CN110819010A (en) | Halogen-free flame-retardant polypropylene material with ultrahigh specific gravity and preparation method thereof | |
| CN104861614A (en) | Halogen-free flame-retardant antistatic enhanced modified PC and PET composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20100818 |