CN103073854A - Polyester composition, preparation method and applications thereof - Google Patents

Polyester composition, preparation method and applications thereof Download PDF

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Publication number
CN103073854A
CN103073854A CN2012103003267A CN201210300326A CN103073854A CN 103073854 A CN103073854 A CN 103073854A CN 2012103003267 A CN2012103003267 A CN 2012103003267A CN 201210300326 A CN201210300326 A CN 201210300326A CN 103073854 A CN103073854 A CN 103073854A
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CN
China
Prior art keywords
polymer blend
weight
polyester
flame retardant
fire retardant
Prior art date
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Pending
Application number
CN2012103003267A
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Chinese (zh)
Inventor
陈锐
陈大华
蔡彤旻
艾军伟
陈伟
付学俊
陈锋
朱文
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Kingfa Science and Technology Co Ltd
Shanghai Kingfa Science and Technology Co Ltd
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Kingfa Science and Technology Co Ltd
Shanghai Kingfa Science and Technology Co Ltd
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Application filed by Kingfa Science and Technology Co Ltd, Shanghai Kingfa Science and Technology Co Ltd filed Critical Kingfa Science and Technology Co Ltd
Priority to CN2012103003267A priority Critical patent/CN103073854A/en
Publication of CN103073854A publication Critical patent/CN103073854A/en
Pending legal-status Critical Current

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    • B29C47/92

Abstract

The present invention discloses a polyester composition, a preparation method and applications thereof. The polyester composition comprises the following substances, by weight, (a) 30-80 parts of a polyester, (b) 10-30 parts of a fire retardation agent, wherein the fire retardation agent comprises a phosphorus fire retardation agent and a nitrogen fire retardation agent, (c) 0-10 parts of an optional toughener, (d) 0.01-1 part of an antioxidant, and (e) 0.01-2 parts of a lubricant. The polyester composition adopts the halogen-free fire retardation agent, does not contain red phosphorus, is an environment-friendly polyester composition, and has characteristics of good fire retardation and good fluidity, wherein fluidity of the polyester composition is more than 2 times the fluidity of the common polyester so as to conveniently process, the formed product has a good surface, and fiber floating is not obvious.

Description

A kind of polymer blend, preparation method and application thereof
Technical field
The present invention relates to field of polymer technology, particularly a kind of polymer blend and application thereof.
Background technology
In recent years, the demand of flame-retardant PBT in electronic apparatus and other industrial circle is increasing.The plastics that PBT compares other have outstanding performance characteristics: shaping speed is fast, electrical property is excellent, flame retardant properties is strong, chemical proofing, physical strength are high.Traditional flame-retardant PBT generally adopts bromide fire retardant and stibium trioxide composite, and this flame-retardant system can produce a large amount of smog and discharge poisonous corrosive hydrogen halides gas when burning.In the face of more and more stricter environmental requirement, and electronic apparatus, automobile, machinery instrument lamp industry are to an urgent demand of bittern-free flame-proof material, EU Committee has promulgated " using some objectionable impurities instruction about restriction in electronic electric equipment " (RoHs instruction) in 2003, the instruction regulation was from 1 day July in 2006, and the electronic and electrical equipment that enters EU market bans use of the 6 class objectionable impuritiess that comprise Polybrominated biphenyl (PBB), Poly Brominated Diphenyl Ethers (PBDE).Therefore the research of bittern-free flame-proof material has been obtained the great attention of various countries, the market requirement of product is also more urgent.
In addition, present halogen-free antiflaming polyester, its poor fluidity is unfavorable for processing, and floating obviously fine, product surface is poor.
Summary of the invention
In sum, for overcoming the above problems, the present invention is necessary to provide a kind of polymer blend and application thereof, and its flame retardant properties is good, and mobile high, product surface is good after the moulding, and is floating fine not obvious.
Further, also be necessary to provide a kind of preparation method of above-mentioned polymer blend.
Further, also be necessary to provide a kind of application of above-mentioned polymer blend.
The technical solution adopted in the present invention is: a kind of polymer blend comprises following material by weight:
(a) polyester 30-80 part;
(b) fire retardant 10-30 part;
Described fire retardant comprises phosphorus flame retardant and nitrogenated flame retardant, and described phosphorus flame retardant is material shown in (I) formula:
(Ⅰ),
Wherein, described R1 and R2 are the straight or branched alkyl, and M is Mg, Ca, and Al, Zn, Li, Na or K, m are 1-4;
Described nitrogenated flame retardant is selected from trimeric cyanamide or melamine phosphate.
Wherein, described fire retardant also comprises nitrogenated flame retardant, and described nitrogenated flame retardant is selected from trimeric cyanamide or melamine phosphate.
Wherein, comprise phosphorus flame retardant 6-27 weight part in the described fire retardant.
Wherein, described polymer blend also comprises following material by weight, (c) optional toughner 0-10 part, (d) oxidation inhibitor 0.01-1 part, (e) lubricant 0.01-2 part.
Wherein, formed by following material by weight:
(a) polyester 30-80 part;
(b) fire retardant 10-30 part;
(c) optional toughner 0-10 part; Preferred 1-5 part;
(d) oxidation inhibitor 0.01-1 part;
(e) lubricant 0.01-2 part.
Wherein, described polyester is selected from one or more in poly terephthalic acid Isosorbide-5-Nitrae cyclohexanedimethanoester ester, polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate) (PTT), polybutylene terephthalate (PBT), PEN, poly-naphthalic acid propylene glycol ester or the PBN.
The ring-type PBT oligopolymer (CBT) that described polyester also comprises, described ring-type PBT oligopolymer are material shown in (II) formula:
(Ⅱ)。
Ring-type PBT oligopolymer is a kind of cyclic low molecular weight PBT oligopolymer, this oligopolymer has large ring oligomerization ester structure, can improve the flowability of polymer blend, described ring-type PBT oligopolymer is as raw material take PBT, with catalyzer oligopolymer with the short chain of PBT cracking in solution, and be closed into ring-type, obtain ring-type PBT oligopolymer.
Wherein, the weight part of described ring-type PBT oligopolymer is 1-10 part.
The weight-average molecular weight of the ring-type PBT oligopolymer described in the present invention is below 1500, and its weight-average molecular weight is preferably below 1300.
In above-mentioned polymer blend, the weight part of described (a) polyester can be 30-35,35-40,45-50,50-60,60-70 or 70-80 part;
Described (b) fire retardant, its weight part can be 10-12,12-15,15-18,18-20,20-25 or 25-30 part; Described fire retardant comprises phosphorus flame retardant, and described phosphorus flame retardant is material shown in (I) formula:
(Ⅰ);
Wherein, described R1 and R2 are the straight or branched alkyl, and M is metal, can be Mg, Ca, Al, Zn, Li, Na, K etc.M is 1-4.Described phosphorus flame retardant can be three (diethyl phospho acid) aluminium, two (diethyl phospho acid) zinc, four (diethyl Hypophosporous Acid, 50) titanium, described fire retardant can also comprise nitrogenated flame retardant, described nitrogenated flame retardant is selected from trimeric cyanamide or melamine phosphate, wherein, to account for the weight percentage of described (b) fire retardant be 60%-90% to described phosphorus flame retardant.
Described (c) toughner is selected from one or more of ethylene-methyl methacrylate butyl ester-glycidyl acrylate terpolymer, ethylene-methyl acrylate copolymer, and its weight part can be 0-1,1-5 or 5-10 part;
The scope interval value of above (a) and (b), (c) can arbitrary combination, and in addition, (d) weight part of oxidation inhibitor is 0.01-1 part; (e) weight part of lubricant is 0.01-2 part; (f) weight part of processing aid is 0.1-1 part.
Wherein, comprise that also mineral filler counts 5-50 part by weight, its weight part also can be 10-15,15-20,20-25,25-30,30-35,35-40,40-50 part.
Wherein, described mineral filler is preferably glass fibre, is particularly preferably alkali-free glass fiber.
Wherein, described toughner is selected from one or more of ethylene-methyl methacrylate butyl ester-glycidyl acrylate terpolymer, ethylene-methyl acrylate copolymer.
Wherein, described oxidation inhibitor is selected from one or more of Hinered phenols antioxidant, phosphite antioxidant and organosulfur oxidation inhibitor.
Wherein, described lubricant is the pentaerythritol stearate series lubricant agent.
Wherein, above-mentioned polymer blend also comprises the processing aid of 0.1-1 part by weight.
A kind of preparation method of above-mentioned polymer blend:
With (a) polyester 30-80 part; (b) fire retardant 10-30 part; (c) optional toughner 0-10 part, (d) oxidation inhibitor 0.01-1 part, (e) lubricant 0.01-2 part blending extrusion obtains polymer blend.
A kind of application of above-mentioned polymer blend, described polymer blend is used for field of electronics.
Beneficial effect of the present invention:
Polymer blend of the present invention, used fire retardant is Halogen, and do not contain red phosphorus, it is a kind of environmentally friendly polymer blend, its flame retardant properties is good, can reach the 1.6mm thickness V-0 flame retardant rating of UL94, and good fluidity, be convenient to processing, in addition, polyester of the present invention comprises ring-type PBT oligopolymer, the polymer blend flowing property of described ring-type PBT oligopolymer modification has reached more than the twice of conventional polyester, by improving flowability, even mould complex-shaped or that wall thickness is very little also can well be filled each corner of mould, make things convenient for component manufacturer to make accurate product and the large-scale product of thin-walled with low injection pressure.Another beneficial effect of the present invention is that surface floating fiber is improved obviously, and product surface is good.
Embodiment
Below in conjunction with some embodiments the present invention is described further.Specific embodiment is for further describing the present invention, non-limiting protection scope of the present invention.
Below the used material of the present invention is carried out following explanation.
Polyethylene terephthalate (PET), its limiting viscosity 0.83dl/g, density 1.35g/cm 3
Poly(Trimethylene Terephthalate) (PTT), limiting viscosity 0.92dl/g, density 1.35g/cm 3
Polybutylene terephthalate (PBT), limiting viscosity 1.0dl/g, density 1.31 g/cm 3
CBT: ring-type PBT oligopolymer, from the CBT100 of Cyclics company.
Other material among the embodiment all comes from the market can purchase available material.
The present invention carries out following test to the polymer blend of halogen-free flameproof:
Tensile strength: testing standard ISO 527/2-93, test at the Zwick electronic universal tester;
Flexural strength: testing standard ISO 178-2005, test at the Zwick electronic universal tester;
Modulus in flexure: testing standard ISO 178-2005, test at the Zwick electronic universal tester;
The socle girder notch shock: testing standard ISO 180-2000, test at the Zwick electronic universal tester;
Melt index: testing standard ISO 1133,260 ℃ of test conditions, 2.16kg;
Flame retardant rating: testing standard UL94.
Surface floating fiber: use the method for injection moulding to be injection molded into model, the floating fibre on model surface and slickness and self-defining five grades " a large amount of cloudings, a small amount of clouding, micro-clouding, smooth, glossy " standard jig compares, thereby obtain the surface floating fiber of five grades, five grades are designated as respectively 1 grade, 2 grades, 3 grades, 4 grades, 5 grades, five grade difference corresponding " a large amount of cloudings, a small amount of clouding, micro-clouding, smooth, glossy ", the larger presentation surface of grade numeral is better, and floating fibre is more not serious.
Below be illustrated in the mode of specific embodiment, described raw material is weight part.
Embodiment 1-13
The PBT/PET/PTT resin is lower dry 4 ~ 6 hours at 120 ~ 140 ℃, moisture controlled is less than 0.03%, PBT/PET/PTT resin after the drying treatment, fire retardant, toughner, oxidation inhibitor, lubricant are added in the reactor by the weight part shown in the table 1, carry out that homogenizer mixes or enter premixing machine by the metering feeding device separately.(2) the said mixture material is sent in the twin screw extruder, regulating the feeding rotating speed is 250-350rpm, in twin screw extruder, add alkali-free glass fiber, the temperature of each of dual-screw-stem machine section extruder temperature from the charging opening to the head is respectively 220 ℃, 230 ℃, 240 ℃, 250 ℃, 240 ℃, 230 ℃, 230 ℃, 220 ℃, 220 ℃, screw speed 250-350rpm, the length-to-diameter ratio of twin screw extruder is 75, under the conveying and shearing action of twin screw extruder, abundant fusion plastification, mediate mixing, extrude through head, tie rod, cooling, pelletizing, dry, packing namely obtains halogen-free flame-retarded polyester composition at last.The halogen-free flame-retarded polyester composition that obtains is carried out respectively tensile strength, flexural strength, modulus in flexure, socle girder notch shock, melt index, flame retardant rating and surface floating fiber grade measure respectively, the results are shown in Table 1 for it.
Comparative Examples 1-9
The PBT/PET/PTT resin is lower dry 4 ~ 6 hours at 120 ~ 140 ℃, moisture controlled is less than 0.03%, PBT/PET/PTT resin after the drying treatment, fire retardant, toughner, oxidation inhibitor, lubricant are added in the reactor by the weight part shown in the table 2, carry out that homogenizer mixes or enter premixing machine by the metering feeding device separately.(2) the said mixture material is sent in the twin screw extruder, regulating the feeding rotating speed is 250-350rpm, in twin screw extruder, add alkali-free glass fiber, the temperature of each of dual-screw-stem machine section extruder temperature from the charging opening to the head is respectively 220 ℃, 230 ℃, 240 ℃, 250 ℃, 240 ℃, 230 ℃, 230 ℃, 220 ℃, 220 ℃, screw speed 250-350rpm, the length-to-diameter ratio of twin screw extruder is 75, under the conveying and shearing action of twin screw extruder, abundant fusion plastification, mediate mixing, extrude through head, tie rod, cooling, pelletizing, dry, packing namely obtains halogen-free flame-retarded polyester composition at last.The halogen-free flame-retarded polyester composition that obtains is carried out respectively tensile strength, flexural strength, modulus in flexure, socle girder notch shock, melt index, flame retardant rating and surface floating fiber grade measure respectively, the results are shown in Table 2 for it.
Can find out from embodiment 1-4 and Comparative Examples 1-4, in polymer blend, add nitrogenated flame retardant such as trimeric cyanamide, so that its flame retardant properties of polymer blend of the present invention is greatly improved.
Can find out from comparing of embodiment 5-9 and Comparative Examples 5-9, added CBT among the embodiment in the polymer blend, the melt index of polymer blend can reach more than the twice of polymer blend in the Comparative Examples among the embodiment, its flowability can well be improved, and surface floating fiber is improved significantly, can obtain smooth glossiness surface.
Simultaneously, relative with Comparative Examples 1-4 from embodiment 10-13, also can find out added CBT in the polymer blend after, the melt index of polymer blend can reach more than the twice of polymer blend in the Comparative Examples, its flowability can well be improved, and surface floating fiber is improved significantly, can obtain smooth glossiness surface.
The above only is embodiments of the invention; be not so limit claim of the present invention; every equivalent transformation that utilizes description of the present invention to do, or directly or indirectly be used in other relevant technical fields, all in like manner be included in the scope of patent protection of the present invention.

Claims (10)

1. polymer blend comprises following material by weight:
(a) polyester 30-80 part;
(b) fire retardant 10-30 part;
Described fire retardant comprises phosphorus flame retardant and nitrogenated flame retardant, and described phosphorus flame retardant is material shown in (I) formula:
(Ⅰ),
Wherein, described R1 and R2 are the straight or branched alkyl, and M is Mg, Ca, and Al, Zn, Li, Na or K, m are 1-4;
Described nitrogenated flame retardant is selected from trimeric cyanamide or melamine phosphate.
2. polymer blend according to claim 1 is characterized in that:
Comprise phosphorus flame retardant 6-27 weight part in the described fire retardant.
3. polymer blend according to claim 1 is characterized in that:
Described polymer blend also comprises following material by weight, (c) optional toughner 0-10 part, (d) oxidation inhibitor 0.01-1 part, (e) lubricant 0.01-2 part.
4. polymer blend according to claim 1 is characterized in that:
Formed by following material by weight:
(a) polyester 30-80 part;
(b) fire retardant 10-30 part;
(c) optional toughner 0-10 part;
(d) oxidation inhibitor 0.01-1 part;
(e) lubricant 0.01-2 part.
5. each described polymer blend according to claim 1-4 is characterized in that:
Described polyester is selected from one or more in poly terephthalic acid Isosorbide-5-Nitrae cyclohexanedimethanoester ester ester, polyethylene terephthalate, Poly(Trimethylene Terephthalate), polybutylene terephthalate, PEN, poly-naphthalic acid propylene glycol ester or the PBN;
The ring-type PBT oligopolymer that described polyester also comprises, described ring-type PBT oligopolymer are material shown in (II) formula:
(Ⅱ)。
6. polymer blend according to claim 5 is characterized in that:
The weight part of described ring-type PBT oligopolymer is 1-10 part.
7. polymer blend according to claim 5 is characterized in that:
Comprise that also mineral filler counts 5-50 part by weight.
8. polymer blend according to claim 5 is characterized in that:
Described toughner is selected from one or more of ethylene-methyl methacrylate butyl ester-glycidyl acrylate terpolymer, ethylene-methyl acrylate copolymer.
9. the preparation method of each described polymer blend of claim 1-8 is characterized in that:
With (a) polyester 30-80 part; (b) fire retardant 10-30 part; (c) optional toughner 0-10 part; (d) oxidation inhibitor 0.01-1 part; (e) lubricant 0.01-2 part blending extrusion obtains polymer blend.
10. the application of each described polymer blend of claim 1-8 is characterized in that: described polymer blend is used for field of electronics.
CN2012103003267A 2012-08-22 2012-08-22 Polyester composition, preparation method and applications thereof Pending CN103073854A (en)

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Application Number Priority Date Filing Date Title
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105440601A (en) * 2015-12-21 2016-03-30 东莞市美塑塑料科技有限公司 PBT/PCT synthesis material
WO2019100471A1 (en) * 2017-11-22 2019-05-31 南通展鹏塑料有限公司 Pp-pe-pen three-matrix resin composite material
WO2022088597A1 (en) * 2020-10-30 2022-05-05 金发科技股份有限公司 Low-smoke high-toughness halogen-free flame-retardant pbt/ptt composite, preparation method therefor and use thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101479313A (en) * 2005-07-15 2009-07-08 赛克利克斯公司 Macrocyclic polyester oligomers as carriers and/or flow modifier additives for thermoplastics
CN102264816A (en) * 2008-12-30 2011-11-30 沙伯基础创新塑料知识产权有限公司 Glass fiber reinforced polyester compositions, methods of manufacture, and articles thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101479313A (en) * 2005-07-15 2009-07-08 赛克利克斯公司 Macrocyclic polyester oligomers as carriers and/or flow modifier additives for thermoplastics
CN102264816A (en) * 2008-12-30 2011-11-30 沙伯基础创新塑料知识产权有限公司 Glass fiber reinforced polyester compositions, methods of manufacture, and articles thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105440601A (en) * 2015-12-21 2016-03-30 东莞市美塑塑料科技有限公司 PBT/PCT synthesis material
WO2019100471A1 (en) * 2017-11-22 2019-05-31 南通展鹏塑料有限公司 Pp-pe-pen three-matrix resin composite material
WO2022088597A1 (en) * 2020-10-30 2022-05-05 金发科技股份有限公司 Low-smoke high-toughness halogen-free flame-retardant pbt/ptt composite, preparation method therefor and use thereof

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Application publication date: 20130501