CN102618025A - High-temperature resistant nylon/PEN copolymer and preparation method as well as application thereof - Google Patents
High-temperature resistant nylon/PEN copolymer and preparation method as well as application thereof Download PDFInfo
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- CN102618025A CN102618025A CN2012100936101A CN201210093610A CN102618025A CN 102618025 A CN102618025 A CN 102618025A CN 2012100936101 A CN2012100936101 A CN 2012100936101A CN 201210093610 A CN201210093610 A CN 201210093610A CN 102618025 A CN102618025 A CN 102618025A
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Abstract
The invention discloses a high-temperature resistant nylon/PEN copolymer and a preparation method as well as application thereof. The high-temperature resistant nylon/PEN copolymer is composed of 50-99% of high-temperature nylon and 1-50% of polybutylene terephthalate; the percentage refers to the mole percentage; and diamine is linear chain aliphatic diamine, branched chain aliphatic diamine or alicyclic diamine. Compared with a corresponding benzene ring copolymer, the copolymer provided by the invention has higher barrier performance and heat resistant 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) multipolymer and preparation method thereof and application.
Background technology
Fatty polyamide; Like 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,, required electronics, electrical equipment, associating information device miniaturization, high performance, the requirement of material was further strengthened along with the development of situation.Particularly along with surface mounting technique (Surface Mount Technology; Abbreviation SMT) development; Various electric elements such as junctor, switch, rly., electrical condenser are installed simultaneously, are connected in the circuit board; Promoted electronic component miniaturized, densification, construction costs reduced by 20～30% than former product.But, adopting the SMT technology, each electric elements and circuit base plate want the while in infrared heating device, heat, and the soldering resistance and the dimensional stability of the material of processing each element and wiring board are had higher requirement.For reducing environmental pollution, 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 diamines or dicarboxylicacid and the aliphatic dicarboxylic acid or the diamines of band aromatic nucleus, through the prepared polyamide resin of polycondensation, is a kind of in the aromatic polyamide.Owing in the polymeric amide molecular backbone chain, imported aromatic nucleus; Thereby thermotolerance and mechanical property have been improved; Reduced water-intake rate; And more suitable P/C ratio is arranged, and is the high resin of thermotolerance between general engineering plastic nylon and thermostability engineering plastic PEEK, is 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 is proposed, in batch reactor, aromatic diamine is added drop-wise in the fused aliphatic dicarboxylic acid, 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 a kind of polymeric amide MXD6, preserves polymeric amide under given conditions, even initial polymeric amide is from preparing the back to spending 20 days solid-phase tack producing or the longer time, 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 that the diamine components polycondensation of 6-hexanediamine composition obtains through the dicarboxylic acid component who mainly is made up of terephthalic acid and m-phthalic acid or hexanodioic acid with mainly by 1.The carboxamido-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 and reduced crystallinity of polymer, 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, the method for coming synthesizing polyamides 6T multipolymer through 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, come synthesizing polyamides 6T multipolymer through melt polymerization.Yet when adopting the melt polymerization process 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 causes polymkeric substance tone variation, physical strength reduction and formability to degenerate easily.
Patent US5663284 discloses a kind of method for preparing polyamide 6 T/66 polymkeric substance; Earlier carry out first-stage polymerization having under the condition that water exists, temperature of reaction is lower than melting point polymer; When discharging, keep pressure through make up water in autoclave, prepolymer obtains the high viscosity polymkeric substance through exhaust twin screw extruder fusion tackify.But in order to obtain satisfying the prepolymer of fusion tackify requirement, the prepolymerization temperature is near 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: earlier under the condition that has water to exist; Prepolymer at the synthetic low limiting viscosity of lower temperature; Through the prepolymer of the higher limiting viscosity of solid-phase tack producing prepared in reaction, melt extrude the polymkeric substance that tackify obtains high limiting viscosity through twin screw more then.This route relates to prepolymerization reaction, solid-phase tack producing, fusion tackify polystep reaction, requires complicated production stage and equipment.
Among the patent US6156869, after obtaining prepolymer, can obtain polymeric amide 9T resin through long solid-phase tack producing, this technical requirements prepolymer has higher limiting viscosity.Polymeric amide 9T has higher percent crystallinity, dimensional stability and lower water-intake rate.
In the prior art, obtain the semiaromatic polyamide composition prepolymer of higher limiting viscosity, can realize through the water that improves the prepolymerization temperature or discharge in the prepolymerization reaction system.Raising prepolymerization temperature can cause the generation of side reaction, also can improve reaction pressure, to the also corresponding raising of the requirement of equipment.The water of discharging in the reaction can vapor away unreacted diamine, and the result causes the monomeric unit ratio of prepolymer greatly different with the initial monomers ratio that joins reactor drum, can not guarantee the molar ratio balance of monomer di-carboxylic acid and diamine.
Earlier process salt to monomer, be synthesized by polycondensation the loss that semiaromatic polyamide composition just can be avoided diamine by salt again.Patent US5663284 judges the terminal point of salt-forming reaction through measuring the pH value, uses salt to prepare semiaromatic polyamide composition.
When the synthetic fat polyamide, for the ease of the molar ratio of control di-carboxylic acid, diamine, and remove the impurity in the monomer, the method that salt carries out polycondensation is again processed in employing earlier usually.During preparation fatty polyamide salt, in aqueous solvent or alcohol, carry out neutralization reaction earlier usually, separate then, purify, drying and obtaining.
Do not have at present through preparation high temperature resistant nylon/PEN multipolymer and improve the barrier property of material and the report of resistance toheat.
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 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 multipolymer.
A purpose more of the present invention is to provide the purposes of above-mentioned high temperature resistant nylon/PEN multipolymer.
The object of the invention is realized through following technical proposals:
A kind of high temperature resistant nylon/PEN multipolymer is made up of the high-temperature nylon of 50-99% and the PEN of 1-50%; Described per-cent is molar percentage;
Preferably, above-mentioned high temperature resistant nylon/PEN multipolymer is made up of the high-temperature nylon of 75-99% and the PEN of 1-25%; Described per-cent is molar percentage;
Described high-temperature nylon is to be generated by PEN and diamine reactant;
Described diamines is straight chain aliphatic diamine, side chain aliphatic diamine or cycloalphatic diamine;
Described straight chain aliphatic diamine is 1,4-tetramethylenediamine, 1,6-hexanediamine, 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 1,1,11-11 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.
The fusing point of said high temperature resistant nylon/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 multipolymer may further comprise the steps:
Get to gather (ethylene naphthalate) (PEN) and diamines are dissolved in the solvent, 180～280 ℃ of following polyreaction 6-18h obtain high temperature resistant nylon/PEN multipolymer; The mol ratio of said PEN and diamines is 100: (75-99);
Described solvent is alcoholic solution, N-Methyl pyrrolidone, N, DMSO 99.8MIN., METHYL SULFONYL METHANE., diethylammonium sulfone, diethyl sulfoxide, di-isopropyl sulfone, sulfobenzide, tetramethylene sulfone or tetramethyl-sulfone.
As required, in above-mentioned preparation method, can also add oxidation inhibitor, lubricant, nucleator, fire retardant, tinting material, softening agent, static inhibitor; Also can strengthen the performance of multipolymer through adding spun glass, thomel, mineral filler.
Above-mentioned high temperature resistant nylon/PEN multipolymer can be used for moulding the high temperature resistant obstruct fuel tank of Dai Gang.
High temperature resistant nylon of the present invention/PEN multipolymer has preferably, and barrier property and resistance toheat are because in structure, introduced PEN.Its reaction principle is following:
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.
Description of drawings
Fig. 1 is the infrared spectrogram of embodiment 1 resulting high temperature resistant nylon/PEN multipolymer.
Fig. 2 is the DSC test result figure of embodiment 1 resulting high temperature resistant nylon/PEN multipolymer.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is described in further detail, but embodiment of the present invention is not limited thereto.
The relevant performance perameter of product is measured by following method in the embodiment of the invention:
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 multipolymer may further comprise the steps
In the 20L autoclave pressure of being furnished with magnetic force coupling stirring, prolong, gas phase mouth, charging opening, add PEN, 1, sulfobenzide, heat up behind the nitrogen purging.Under agitation be warmed up to 230 ℃, reacted 12 hours, cooling discharge obtains high temperature resistant nylon/PEN multipolymer.Performance is shown in Table 1 as a result.
Table 1
The multipolymer of getting embodiment 1 carries out infrared analysis, and the result sees Fig. 1.Can find out by Fig. 1, exist a spot of ester group and a large amount of carboxamido-group in the molecular chain of multipolymer.
The multipolymer of getting embodiment 1 has carried out the DSC test, and the result sees Fig. 2.Can find out that by Fig. 2 the fusing point of multipolymer is far above the temperature of fusion of PBT, but be lower than the fusing point of pure PA6T.
The infared spectrum of embodiment 2-4 gained multipolymer and DSC test result and embodiment's 1 is approximate.
Visible from table 1, multipolymer of the present invention is compared with corresponding homopolymer has higher barrier property and resistance toheat.
Embodiment 5-7
The preparation method of a kind of high temperature resistant nylon/PEN multipolymer may further comprise the steps
In the 20L autoclave pressure of being furnished with magnetic force coupling stirring, prolong, gas phase mouth, charging opening, add PEN, 1,6-hexanediamine, sulfobenzide heat up behind the nitrogen purging.Under agitation be warmed up to 230 ℃, reacted 12 hours, cooling discharge obtains high temperature resistant nylon/PEN multipolymer.Performance is shown in Table 2 as a result.
Table 2
Visible from table 2, multipolymer of the present invention is compared with corresponding homopolymer has higher barrier property and resistance toheat.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (8)
1. high temperature resistant nylon/PEN multipolymer is characterized in that: be made up of the high-temperature nylon of 50-99% and the PEN of 1-50%; Described per-cent is molar percentage;
Described high-temperature nylon is to be generated by PEN and diamine reactant.
2. high temperature resistant nylon according to claim 1/PEN multipolymer is characterized in that: described high temperature resistant nylon/PEN multipolymer is made up of the high-temperature nylon of 75-99% and the PEN of 1-25%; Described per-cent is molar percentage.
3. high temperature resistant nylon according to claim 1/PEN multipolymer is characterized in that: described diamines is straight chain aliphatic diamine, side chain aliphatic diamine or cycloalphatic diamine.
4. high temperature resistant nylon according to claim 3/PEN multipolymer is characterized in that:
Described straight chain aliphatic diamine is 1,4-tetramethylenediamine, 1,6-hexanediamine, 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 1,1,11-11 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.
5. high temperature resistant nylon according to claim 1/PEN multipolymer is characterized in that: described high temperature resistant nylon/PEN multipolymer contains oxidation inhibitor, lubricant, nucleator, fire retardant, tinting material, softening agent, static inhibitor, spun glass, thomel or mineral filler.
6. the preparation method of each described high temperature resistant nylon/PEN multipolymer of claim 1-5 is characterized in that may further comprise the steps:
Get to gather (ethylene naphthalate) and diamines are dissolved in the solvent, 180～280 ℃ of following polyreaction 6-18h obtain high temperature resistant nylon/PEN multipolymer; The mol ratio of said PEN and diamines is 100: (75-99).
7. the preparation method of high temperature resistant nylon according to claim 6/PEN multipolymer is characterized in that: described solvent is alcoholic solution, N-Methyl pyrrolidone, N, DMSO 99.8MIN., METHYL SULFONYL METHANE., diethylammonium sulfone, diethyl sulfoxide, di-isopropyl sulfone, sulfobenzide, tetramethylene sulfone or tetramethyl-sulfone.
8. each described high temperature resistant nylon/PEN multipolymer application in high temperature resistant obstruct fuel tank of claim 1-5.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111546736A (en) * | 2020-05-29 | 2020-08-18 | 厦门长塑实业有限公司 | Biaxially oriented polyamide film for vacuum insulation board and preparation method thereof |
| CN111961341A (en) * | 2020-08-25 | 2020-11-20 | 宁波公牛电器有限公司 | Composite material, preparation method thereof, fixing frame and wall switch |
| CN118562124A (en) * | 2024-07-30 | 2024-08-30 | 山东广垠新材料有限公司 | Gas barrier polyamide elastomer material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN118562124A (en) * | 2024-07-30 | 2024-08-30 | 山东广垠新材料有限公司 | Gas barrier polyamide elastomer material and preparation method thereof |
| CN118562124B (en) * | 2024-07-30 | 2024-10-18 | 山东广垠新材料有限公司 | Gas barrier polyamide elastomer material and preparation method thereof |
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