CN102660018B - High temperature-resistant nylon/polyethylenenaphthalate (PEN) /polyethylene glycol terephthalate (PBT) copolymer, and preparation method and application thereof - Google Patents
High temperature-resistant nylon/polyethylenenaphthalate (PEN) /polyethylene glycol terephthalate (PBT) copolymer, and preparation method and application thereof Download PDFInfo
- Publication number
- CN102660018B CN102660018B CN 201210143111 CN201210143111A CN102660018B CN 102660018 B CN102660018 B CN 102660018B CN 201210143111 CN201210143111 CN 201210143111 CN 201210143111 A CN201210143111 A CN 201210143111A CN 102660018 B CN102660018 B CN 102660018B
- Authority
- CN
- China
- Prior art keywords
- pen
- diamine
- pbt
- high temperature
- resistant nylon
- 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.)
- Expired - Fee Related
Links
Abstract
The invention discloses a high temperature-resistant nylon/polyethylenenaphthalate (PEN) /polyethylene glycol terephthalate (PBT) copolymer, and a preparation method and application thereof. The copolymer consists of 70 to 99 percent of high-temperature nylon, 0.5 to 15 percent of PEN and 0.5 to 15 percent of PBT, wherein the high-temperature nylon is a high-temperature nylon unit generated by reacting the PEN, the PBT and diamine; and the diamine is straight-chain aliphatic diamine, branched-chain aliphatic diamine or alicyclic diamine. Compared with the corresponding benzene ring homopolymers, the copolymer has the advantages of high obstruction performance, heat-resistant performance, impact resistance, flowing performance and electrical performance.
Description
Technical field
The invention belongs to the modified plastics field, be specifically related to a kind of high temperature resistant nylon/PEN (PEN)/polyethylene terephthalate (PBT) multipolymer and preparation method thereof and application.
Background technology
Fatty polyamide, as PA6, PA66, there is excellent physical strength, thermotolerance, chemical proofing, wearability and self lubricity, and frictional coefficient is low, its Application Areas comprises electronic apparatus, trolley part, furniture, building materials and fiber, has become one of most important engineering plastics.
In the last few years, along with the development of situation, required electronics, electrical equipment, associating information device miniaturization, high performance, the requirement of material was further strengthened.Particularly along with surface mounting technique (Surface Mount Technology, abbreviation SMT) development, the various electric elements such as junctor, switch, rly., electrical condenser are installed simultaneously, are connected in the circuit board, promoted electronic component miniaturization, densification, construction costs reduced by 20～30% than former product.But, adopting the SMT technology, each electric elements and circuit base plate are wanted in infrared heating device, heat, and soldering resistance and the dimensional stability of the material of making each element and wiring board are had higher requirement simultaneously.For environmental contamination reduction, existing advocating energetically used lead-free scolding tin.The fusing point of lead in the past-soldering tin is at 183 ℃, and novel scolding tin is tin-copper-silver soldering tin, and fusing point is 215 ℃, and fusing point material has than before improved 30 ℃, and at this moment the thermotolerance of PA6, PA66 just can not meet the demands.Therefore developing the material that thermotolerance is higher just becomes inevitable.
Semiaromatic polyamide composition is with the diamines of aromatic nucleus or dicarboxylic acid and aliphatic dicarboxylic acid or diamines, and the prepared polyamide resin through polycondensation is a kind of in aromatic polyamide.Owing in the polymeric amide molecular backbone chain, having imported aromatic nucleus, thereby thermotolerance and mechanical property have been improved, reduced water-intake rate, and more suitable P/C ratio is arranged, be the high resin of thermotolerance between general engineering plastic nylon and thermostability engineering plastic PEEK, be mainly used in automobile and electric and electronic industry.Along with high-tech, develop rapidly, its application has new breakthrough and progress, and the market requirement is in rising trend.
Patent JP57200420, JP58111829, EP1074585A1, CN1624021A disclose the preparation method of polymeric amide MXD6.In the method proposed, in batch reactor, aromatic diamine is added drop-wise in the aliphatic dicarboxylic acid of melting, the water that the system temperature that simultaneously raises is removed the condensation generation carries out polyreaction.CN1451677A has described the solid-phase tack producing method of polymeric amide MXD6 a kind of, preserves under given conditions polymeric amide, though initial polymeric amide from the preparation to spend 20 days solid-phase tack producing or the longer time, the polymeric amide MXD6 Huang degree made is very low.
Because the fusing point of polyamide 6 T has exceeded its decomposition temperature, must add the 3rd monomer to reduce fusing point.Polyamide 6 T multipolymer is dicarboxylic acid component by mainly being comprised of terephthalic acid and m-phthalic acid or hexanodioic acid and is mainly obtained by the diamine components polycondensation of 1,6-hexanediamine composition.The amide group concentration of polyamide 6 T multipolymer is higher, can cause chemical proofing, water absorption resistance, the melt-processed less stable of polymkeric substance.Add the 3rd a large amount of monomers to reduce the degree of crystallinity of polymkeric substance, also can cause thermotolerance, chemical proofing, water absorption resistance and the dimensional stability of polymkeric substance to descend.
Patent US5516882, US5981692 and US962628 have described with terephthalic acid, m-phthalic acid, 1,6-hexanodioic acid, 1,6-hexanediamine and 2-methyl isophthalic acid, the 5-pentamethylene diamine is main raw material, carrys out the method for synthesizing polyamides 6T multipolymer by the high-temperature fusion polymerization more than 300 ℃.Patent US6140459 has described with terephthalic acid, 1, and 6-hexanediamine and another kind of aliphatic long-chain di-carboxylic acid are raw material, by melt polymerization, carry out synthesizing polyamides 6T multipolymer.Yet while adopting melt polymerization to prepare semiaromatic polyamide composition, the secondary polymerization reaction temperature can surpass the fusing point of polymkeric substance, and overstand at high temperature, the DeR of various side reactions and polymkeric substance is violent, the phenomenon that easily causes polymkeric substance tone variation, physical strength reduction and formability to degenerate.
Patent US5663284 discloses a kind of method for preparing polyamide 6 T/66 polymkeric substance, first having that water exists, temperature of reaction carries out first-stage polymerization under lower than the condition of melting point polymer, maintain pressure by make up water in autoclave when discharging, prepolymer obtains high viscosity polymer by vented twin-screw extruder melting tackify.But, in order to obtain meeting the prepolymer of melting tackify requirement, the prepolymerization temperature has approached the fusing point of polymkeric substance, to improve the limiting viscosity of prepolymer.
In the prior art, patent US6133406 has proposed a kind of polymerization technique of semiaromatic polyamide composition: first under the condition that has water to exist, prepolymer at the synthetic low limiting viscosity of lower temperature, then prepare the prepolymer of higher limiting viscosity through the solid-phase tack producing reaction, then melt extrude through twin screw the polymkeric substance that tackify obtains high limiting viscosity.This route relates to prepolymerization, solid-phase tack producing, melting tackify polystep reaction, requires complicated production stage and equipment.
In patent US6156869, after obtaining prepolymer, can obtain the polyamide 9T resin by long solid-phase tack producing, this technical requirements prepolymer has higher limiting viscosity.Polyamide 9T has higher degree of crystallinity, dimensional stability and lower water-intake rate.
In the prior art, obtain the semiaromatic polyamide composition prepolymer of higher limiting viscosity, can realize by the water that improves the prepolymerization temperature or discharge in the prepolymerization system.Raising prepolymerization temperature can cause the generation of side reaction, also can improve reaction pressure, to the also corresponding raising of requirement of equipment.The water of discharging in reaction can vapor away unreacted diamine, and result causes the monomeric unit ratio of prepolymer and the initial monomers ratio that joins reactor greatly different, can not guarantee the molar ratio balance of monomer di-carboxylic acid and diamine.
First monomer is made to salt, then be synthesized by polycondensation semiaromatic polyamide composition by salt and just can avoid the loss of diamine.Patent US5663284 judges the terminal of salt-forming reaction by measuring the pH value, with salt, prepare semiaromatic polyamide composition.
When the synthetic fat polyamide, for the ease of controlling the molar ratio of di-carboxylic acid, diamine, and remove the impurity in monomer, common employing is first made salt and is carried out the method for polycondensation again.While preparing fatty polyamide salt, usually first carry out neutralization reaction in aqueous solvent or alcohol, then separated, purify, drying and obtaining.
Do not have at present by preparing high temperature resistant nylon/PEN/PBT multipolymer and improve the barrier property of material and the report of resistance toheat, shock resistance, streamer performance and electrical property.
Summary of the invention
For the shortcoming and deficiency that overcome prior art, primary and foremost purpose of the present invention is to provide a kind of high temperature resistant nylon/PEN/PBT multipolymer, and this multipolymer has barrier property and resistance toheat preferably.
Another object of the present invention is to provide the preparation method of above-mentioned high temperature resistant nylon/PEN/PBT multipolymer.
A further object of the present invention is to provide the purposes of above-mentioned high temperature resistant nylon/PEN/PBT multipolymer.
Purpose of the present invention is achieved through the following technical solutions:
A kind of high temperature resistant nylon/PEN/PBT multipolymer is grouped into by the one-tenth of following molar percentage:
High-temperature nylon: 70-99%
PEN：0.5-15%
PBT：0.5-15%；
Described high-temperature nylon is the high-temperature nylon unit that PEN, PBT and diamine reactant generate;
Described diamines is straight chain aliphatic diamine, side chain aliphatic diamine or cycloalphatic diamine;
Described straight chain aliphatic diamine is Putriscine, 1,6-hexanediamine, 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 1，10-diaminodecane, 1,11-11 carbon diamines or 1,12-, 12 carbon diamines;
Described side chain aliphatic diamine is the 2-methyl isophthalic acid, 5-pentamethylene diamine, 3-methyl isophthalic acid, 5-pentamethylene diamine, 2,4-dimethyl-1,6-hexanediamine, 2,2,4-trimethylammonium-1,6-hexanediamine, 2,4,4-trimethylammonium-1,6-hexanediamine, 2-methyl isophthalic acid, 8-octamethylenediamine or 5-methyl isophthalic acid, 9-nonamethylene diamine;
Described cycloalphatic diamine is cyclohexane diamine, methylcyclohexane diamines or 4,4 '-diamino-dicyclohexyl methane.
Described high temperature resistant nylon/PEN/PBT multipolymer can also comprise oxidation inhibitor, lubricant, nucleator, fire retardant, tinting material, softening agent, static inhibitor; Also can strengthen the performance of multipolymer by adding glass fibre, carbon fiber, mineral filler.
The fusing point of described high temperature resistant nylon/PEN/PBT multipolymer is 270-330 ℃, and solution solvent viscosity ratio η is 1.5-2.5, and content of carboxyl end group is 15-100mol/t, and terminal amino group content is 15-100mol/t.
The preparation method of above-mentioned high temperature resistant nylon/PEN/PBT multipolymer comprises the following steps:
Get polyethylene naphthalate (PEN), polybutylene terephthalate (PBT) and diamines and be dissolved in solvent, 180 ~ 280 ℃ of lower polyreaction 6-18h, obtain high temperature resistant nylon/PEN/PBT multipolymer; The mol ratio of described PEN, PBT and diamines is 50: 50: (70-99);
Described solvent is alcoholic solution, N-Methyl pyrrolidone, dimethyl formamide, dimethyl sulfoxide (DMSO), dimethyl sulfone, diethyl sulfone, diethyl sulfoxide, di-isopropyl sulfone, sulfobenzide, tetramethylene sulfone or tetramethyl-sulfone.
Above-mentioned high temperature resistant nylon/PEN/PBT multipolymer can be used for moulding the high temperature resistant obstruct fuel tank of Dai Gang.
It is because introduced PEN in structure that high temperature resistant nylon of the present invention/PEN/PBT multipolymer has barrier property and resistance toheat preferably.Its reaction principle is as follows:
It is because introduced PBT in structure that high temperature resistant nylon of the present invention/PBT multipolymer has shock resistance, streamer and electrical property preferably.Its reaction principle is as follows:
The present invention has following advantage and effect with respect to prior art:
Its corresponding phenyl ring homopolymer of multipolymer of the present invention is compared, and has barrier property, resistance toheat, shock resistance, streamer and electrical property preferably.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
In the embodiment of the present invention, the relevant performance perameter of product is measured by the following method:
Thermotolerance is pressed GB 1035-1970 and is measured;
OTR oxygen transmission rate is pressed GBT 19789-2005 and is measured.
Fusing point Tm is by Perkin Elmer DSC-6 analysis-e/or determining.
The component of product is by infrared measurement.
Embodiment 1-5
The preparation method of a kind of high temperature resistant nylon/PEN/PBT multipolymer, comprise the following steps
Add PEN, PBT, 1，10-diaminodecane, sulfobenzide in being furnished with the 20L autoclave pressure of magnetic coupling stirring, prolong, gas phase mouth, charging opening, heating up after nitrogen purging.Under agitation be warmed up to 230 ℃, react 12 hours, cooling discharge, obtain high temperature resistant nylon/PEN/PBT multipolymer.Performance is shown in Table 1 as a result.
Table 1
As seen from Table 1, multipolymer of the present invention is compared and is had higher barrier property, resistance toheat, shock resistance, streamer and electrical property with corresponding homopolymer.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (2)
1. the preparation method of high temperature resistant nylon/PEN/PBT multipolymer, it is characterized in that comprising the following steps: get PEN, PBT and diamines and be dissolved in solvent, 180 ~ 280 ℃ of lower polyreaction 6-18h, obtain high temperature resistant nylon/PEN/PBT multipolymer; The mol ratio of described PEN, PBT and diamines is 50:50:(70-99).
2. the preparation method of high temperature resistant nylon according to claim 1/PEN/PBT multipolymer, it is characterized in that: described solvent is alcoholic solution, N-Methyl pyrrolidone, dimethyl formamide, dimethyl sulfoxide (DMSO), dimethyl sulfone, diethyl sulfone, diethyl sulfoxide, di-isopropyl sulfone, sulfobenzide, tetramethylene sulfone or tetramethyl-sulfone.
3, the preparation method of high temperature resistant nylon according to claim 1/PEN/PBT multipolymer is characterized in that: described diamines is straight chain aliphatic diamine, side chain aliphatic diamine or cycloalphatic diamine.
4, the preparation method of high temperature resistant nylon according to claim 3/PEN/PBT multipolymer is characterized in that:
Described straight chain aliphatic diamine is Putriscine, 1,6-hexanediamine, 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 1，10-diaminodecane, 1,11-11 carbon diamines or 1,12-, 12 carbon diamines;
Described side chain aliphatic diamine is the 2-methyl isophthalic acid, 5-pentamethylene diamine, 3-methyl isophthalic acid, 5-pentamethylene diamine, 2,4-dimethyl-1,6-hexanediamine, 2,2,4-trimethylammonium-1,6-hexanediamine, 2,4,4-trimethylammonium-1,6-hexanediamine, 2-methyl isophthalic acid, 8-octamethylenediamine or 5-methyl isophthalic acid, 9-nonamethylene diamine;
Described cycloalphatic diamine is cyclohexane diamine, methylcyclohexane diamines or 4,4 '-diamino-dicyclohexyl methane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210143111 CN102660018B (en) | 2012-05-09 | 2012-05-09 | High temperature-resistant nylon/polyethylenenaphthalate (PEN) /polyethylene glycol terephthalate (PBT) copolymer, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210143111 CN102660018B (en) | 2012-05-09 | 2012-05-09 | High temperature-resistant nylon/polyethylenenaphthalate (PEN) /polyethylene glycol terephthalate (PBT) copolymer, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102660018A CN102660018A (en) | 2012-09-12 |
| CN102660018B true CN102660018B (en) | 2013-12-25 |
Family
ID=46769614
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210143111 Expired - Fee Related CN102660018B (en) | 2012-05-09 | 2012-05-09 | High temperature-resistant nylon/polyethylenenaphthalate (PEN) /polyethylene glycol terephthalate (PBT) copolymer, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102660018B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103881087B (en) * | 2014-03-21 | 2016-05-25 | 山东广垠新材料有限公司 | High temperature resistant nylon/PTT/PEIP/PBIP copolymer and its preparation method and application |
| US10793673B2 (en) | 2015-11-10 | 2020-10-06 | Iowa State University Research Foundation, Inc. | Bioadvantaged nylon: polycondensation of 3-hexenedioic acid with hexamethylenediamine |
| WO2024025814A1 (en) * | 2022-07-28 | 2024-02-01 | Iowa State University Research Foundation, Inc. | Biobased copolymers of poly(ethylene terephthalate) with superior thermomechanical properties |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4501879A (en) * | 1984-03-26 | 1985-02-26 | Eastman Kodak Company | Polyesteramides and containers having improved gas barrier properties formed therefrom |
| TW336248B (en) * | 1996-02-05 | 1998-07-11 | Eastman Kodak Co | Polyester/polyesteramide blends the invention relates to polyester/polyesteramide blends |
| CN101456949B (en) * | 2007-12-14 | 2012-01-18 | 金发科技股份有限公司 | Semi-aromatic polyamide and preparation method thereof |
-
2012
- 2012-05-09 CN CN 201210143111 patent/CN102660018B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102660018A (en) | 2012-09-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101759853B (en) | Method for preparing semi-aromatic polyamide | |
| CN101492534B (en) | Process for preparing semi-aromatic polyamides | |
| CN101456949B (en) | Semi-aromatic polyamide and preparation method thereof | |
| US8440756B2 (en) | Flame-retardant polyamide resin composition | |
| SG176237A1 (en) | Polyamide resin | |
| CN104387581B (en) | The preparation method of semiaromatic copolyamide resin and resin | |
| JP3986889B2 (en) | Polyamide composition | |
| CN101772528B (en) | E/E connector and polymer composition used therein | |
| US6414064B1 (en) | Polyamide resin composition | |
| CN103154087B (en) | Molded polyamide resin article | |
| US20030023008A1 (en) | Polyamide composition | |
| CN102660019B (en) | High temperature-resistant nylon/ polybutylece terephthalate (PBT)/polyethylene terephthalate (PET) copolymer, and preparation method and application thereof | |
| CN103865058B (en) | A kind of polyamide and preparation method thereof and Amilan polyamide resin composition | |
| JP6130400B2 (en) | Method for preparing halogen-free flame retardant polyamide composition | |
| CN101759851B (en) | Semi-aromatic polyamide and preparation method thereof | |
| CN105283509A (en) | Polyamide resin composition and molded article produced therefrom | |
| TW201130886A (en) | Copolymerized polyamide | |
| CN102660020B (en) | High-temperature resistant nylon/PEN/PBT/PET copolymer and preparation method thereof | |
| CN101759852B (en) | Preparation method of semi-aromatic polyamide | |
| CN102660018B (en) | High temperature-resistant nylon/polyethylenenaphthalate (PEN) /polyethylene glycol terephthalate (PBT) copolymer, and preparation method and application thereof | |
| CN109749080A (en) | Semi-aromatic polyamide resin and preparation method thereof | |
| CN101503512A (en) | Semi-aromatic polyamide and preparation thereof | |
| CN102604081A (en) | High-temperature resistant nylon/ polyethylene terephthalate (PET) copolymer, preparation method and application thereof | |
| CN102634012B (en) | Heat resisting polyamide/PEN (polyethylene naphthalate)/PET (polyethylene terephthalate) copolymer and manufacturing method and application of heat resisting polyamide/PEN/PET copolymer | |
| WO2016058991A1 (en) | Polymers featuring enhanced flow |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131225 Termination date: 20190509 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |