CN102634012B - Heat resisting polyamide/PEN (polyethylene naphthalate)/PET (polyethylene terephthalate) copolymer and manufacturing method and application of heat resisting polyamide/PEN/PET copolymer - Google Patents
Heat resisting polyamide/PEN (polyethylene naphthalate)/PET (polyethylene terephthalate) copolymer and manufacturing method and application of heat resisting polyamide/PEN/PET copolymer Download PDFInfo
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- CN102634012B CN102634012B CN2012101429956A CN201210142995A CN102634012B CN 102634012 B CN102634012 B CN 102634012B CN 2012101429956 A CN2012101429956 A CN 2012101429956A CN 201210142995 A CN201210142995 A CN 201210142995A CN 102634012 B CN102634012 B CN 102634012B
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Abstract
The invention discloses a heat resisting polyamide/PEN (polyethylene naphthalate)/PET (polyethylene terephthalate) copolymer and a manufacturing method and application of the heat resisting polyamide/PEN/PET copolymer. The copolymer consists of 75-90% of high-temperature polyamides, 0.85-23.75% of PEN and 0.05-3.75% of PET; the high-temperature polyamides are high-temperature polyamide units generated by a reaction of PEN and PET with diamine; and diamine is linear chain aliphatic diamine, branched chain alphatic diamine or cycloaliphatic diamine. Compared with a corresponding benzene ring homopolymer, the copolymer provided by the invention has higher barrier performance and heat resistance.
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 (PET) multipolymer and preparation method thereof and application.
Background technology
Fatty polyamide,, as PA6, PA66, have 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 heat in infrared heating device simultaneously, and soldering resistance and the dimensional stability of the material of making each element and wiring board are had higher requirement.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 higher material of thermotolerance just becomes inevitable.
Semiaromatic polyamide composition is with the diamines of aromatic nucleus or dicarboxylic acid and aliphatic dicarboxylic acid or diamines,, through the prepared polyamide resin of polycondensation, is a kind of in aromatic polyamide.Owing to having imported aromatic nucleus in the polymeric amide molecular backbone chain, 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.Develop rapidly along with high-tech, 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 that proposes, in batch reactor, aromatic diamine is added drop-wise in the aliphatic dicarboxylic acid of melting, the water that the system temperature that raises is simultaneously 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, even initial polymeric amide is rear to spending 20 days solid-phase tack producing or the longer time from preparing, the polymeric amide MXD6 Huang degree that makes 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 by the dicarboxylic acid component who mainly is comprised of terephthalic acid and m-phthalic acid or hexanodioic acid and mainly by the diamine components polycondensation of 1,6-hexanediamine composition, is obtained.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, 5-pentamethylene diamine are main raw material, carry 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, keep 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 through the prepolymer of the higher limiting viscosity of solid-phase tack producing reaction preparation, then melt extrude tackify through twin screw and obtain the polymkeric substance of 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 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 separate, purify, drying and obtaining.
Do not have at present by preparing high temperature resistant nylon/PEN/PET multipolymer and improve the barrier property of material and the report of resistance toheat, add PET and can reduce the cost of multipolymer, barrier property and the resistance toheat of material are kept simultaneously.
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/PET 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/PET multipolymer.
A further object of the present invention is to provide the purposes of above-mentioned high temperature resistant nylon/PEN/PET multipolymer.
Purpose of the present invention is achieved through the following technical solutions:
A kind of high temperature resistant nylon/PEN/PET multipolymer is grouped into by the one-tenth of following molar percentage:
High-temperature nylon: 75-99%
PEN：0.85-23.75%
PET：0.05-3.75%；
Described high-temperature nylon is the high-temperature nylon unit that PEN, PET 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/PET 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/PET 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/PET multipolymer comprises the following steps:
Get polyethylene naphthalate (PEN), polyethylene terephthalate (PET) and diamines and be dissolved in solvent, 180 ~ 280 ℃ of lower polyreaction 6-18h, obtain high temperature resistant nylon/PEN/PET multipolymer; The mol ratio of described PEN, PET and diamines is (85-95): (5-15): (75-99);
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/PET 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/PET multipolymer has barrier property and resistance toheat 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 higher barrier property and resistance toheat.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, 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 1-4
The preparation method of a kind of high temperature resistant nylon/PEN/PET multipolymer, comprise the following steps
Add PEN, PET, 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 ℃, reacted 12 hours, cooling discharge, obtain high temperature resistant nylon/PEN/PET 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 and resistance toheat with corresponding homopolymer.
Above-described embodiment is the better 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 the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (7)
1. high temperature resistant nylon/PEN/PET multipolymer, it is characterized in that: its preparation method comprises the following steps: get PEN, PET and diamines and be dissolved in solvent, 180 ~ 280 ℃ of lower polyreaction 6-18h, obtain high temperature resistant nylon/PEN/ PET multipolymer; The mol ratio of described PEN, PET and diamines is (85-95): (5-15): (75-99).
2. high temperature resistant nylon according to claim 1/PEN/PET multipolymer, it is characterized in that: described diamines is straight chain aliphatic diamine, side chain aliphatic diamine or cycloalphatic diamine.
3. high temperature resistant nylon according to claim 2/PEN/PET 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.
4. high temperature resistant nylon according to claim 1/PEN/PET multipolymer, it is characterized in that: described high temperature resistant nylon/PEN/PET multipolymer also comprises more than one in oxidation inhibitor, lubricant, nucleator, fire retardant, tinting material, softening agent, static inhibitor or mineral filler.
5. the preparation method of the described high temperature resistant nylon of claim 1-3 any one/PEN/PET multipolymer, it is characterized in that comprising the following steps: get PEN, PET and diamines and be dissolved in solvent, 180 ~ 280 ℃ of lower polyreaction 6-18h, obtain high temperature resistant nylon/PEN/ PET multipolymer; The mol ratio of described PEN, PET and diamines is (85-95): (5-15): (75-99).
6. the preparation method of high temperature resistant nylon according to claim 5/PEN/PET 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.
7. the described high temperature resistant nylon of the claim 1-4 any one/application of PEN/PET multipolymer in high temperature resistant obstruct fuel tank.
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| CN2012101429956A CN102634012B (en) | 2012-05-09 | 2012-05-09 | Heat resisting polyamide/PEN (polyethylene naphthalate)/PET (polyethylene terephthalate) copolymer and manufacturing method and application of heat resisting polyamide/PEN/PET copolymer |
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| CN2012101429956A CN102634012B (en) | 2012-05-09 | 2012-05-09 | Heat resisting polyamide/PEN (polyethylene naphthalate)/PET (polyethylene terephthalate) copolymer and manufacturing method and application of heat resisting polyamide/PEN/PET copolymer |
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| 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 |
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| US6011125A (en) * | 1998-09-25 | 2000-01-04 | General Electric Company | Amide modified polyesters |
| DE60014529T2 (en) * | 1999-06-29 | 2005-10-27 | M & S Research and Development Co, . Ltd. | Process for the preparation of polyamide resins in the presence of a carboxylic acid activator and / or an inorganic salt in the reaction system |
| CN100349951C (en) * | 2005-11-04 | 2007-11-21 | 东华大学 | Solid phase polymerization process for preparing ethylene telephthalate and aromatic diamine copolymer |
| CN101492535A (en) * | 2008-01-25 | 2009-07-29 | 东丽纤维研究所（中国）有限公司 | Method for preparing block polyester-amide copolymer |
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