CN103881087B - High temperature resistant nylon/PTT/PEIP/PBIP copolymer and its preparation method and application - Google Patents
High temperature resistant nylon/PTT/PEIP/PBIP copolymer and its preparation method and application Download PDFInfo
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- CN103881087B CN103881087B CN201410108188.1A CN201410108188A CN103881087B CN 103881087 B CN103881087 B CN 103881087B CN 201410108188 A CN201410108188 A CN 201410108188A CN 103881087 B CN103881087 B CN 103881087B
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Abstract
The invention discloses a kind of high temperature resistant nylon/PTT/PEIP/PBIP copolymer and its preparation method and application, its preparation method comprises the following steps: get tri-kinds of resins of PTT, PEIP and PBIP and diamine and be dissolved in solvent, 190～290 DEG C, polymerisation 4～10h under 1.5～2.5MPa pressure, obtains high temperature resistant nylon/PTT/PEIP/PBIP copolymer; Wherein, the molar ratio of PTT, PEIP, PBIP and diamine is (30～60): (15～30): (15～30): (70～99). This copolymer not only has good processing fluidity and impact strength, has good resistance to elevated temperatures simultaneously.
Description
Technical field
The present invention relates to a kind of high temperature resistant nylon and its preparation method and application, specifically a kind of high temperature resistantNylon/PTT (PTT)/polyethylene glycol isophthalate (PEIP)/poly-isophthalicDioctyl phthalate butanediol ester (PBIP) copolymer and its preparation method and application.
Background technology
Polyamide, is commonly called as nylon, is the engineering plastics that a class has good physical and mechanical properties. Aliphatic Buddhist nunDragon, as PA6, PA66, has excellent mechanical strength, heat resistance, chemical proofing, mar proofAnd self lubricity, its application has comprised electronic apparatus, automobile component, furniture, building materials and fiber,Through becoming one of important engineering plastics.
In the last few years, along with the development of industrial situation, little at industry requirement equipment such as electronics, electrical equipment, informationType, high performance, further improve the requirement of material, and environment for use is harsher. Particularly along withThe development of surface mounting technique (SMT), the various elements such as connector, switch, relay, capacitor are sameTime install, connect in the circuit board, promoted electronic component miniaturization, densification, construction costs than beforeProduct reduce by 20～30%. But, adopting SMT technology, each electric elements and wiring board are wanted simultaneously redIn external heating device, heat, to making soldering resistance and the dimensional stability of material of various elements and circuit base plateHave higher requirement. For reducing environmental pollution, existing advocating energetically used lead-free scolding tin. In the pastLead-copper-silver soldering tin, fusing point is 215 DEG C, fusing point material has than before improved 30 DEG C, at this moment PA6, PA66Heat resistance just can not meet the demands. Therefore developing the material that heat resistance is higher just becomes inevitable.
High temperature resistant nylon used is the PA46 of DSM the most widely at present, but because PA46 is still fatFamily's nylon, at high temperature resistant and still too late aromatic series or semi-aromatic nylon of mechanical properties. Semi-aromaticNylon is diamines and aliphatic diacid or the diamines with aromatic rings, and the polyamide of preparing through polycondensation, isOne in aromatic polyamide. Owing to having imported aromatic rings in polyamide molecular backbone, thereby improveHeat resistance and mechanical property, reduced water absorption rate, and have more suitable cost performance, is between general workThe high resin of heat resistance between engineering plastics and thermostability engineering plastic PEEK, is mainly used in automobile and electronics electricityDevice industry. Along with the continuous progress of science and technology, the market demand is in rising trend. Therefore, obtain now sending out very greatlyThe semi-aromatic nylon of exhibition mainly contains PA6T, PA9T, PA10T and PA12T, and they all have general nylonThe character of difficult analogy, as good stability of the dimension, heat-resisting, high rigidity, agent of low hygroscopicity and good chemical resistanceCan etc. Patent about PA6T is existing a lot, as US4022756, and GB1526329, US4113708,US4246395，US4663166，US4863991，US560167，JP02251352，JP034317，JP03161507 and JP0408730 etc. have all reported the preparation method of PA6T. But nylon 6T, especially pure resin,Cause processing fluidity poor because fusing point has exceeded its decomposition temperature, processing characteristics is bad, therefore must addThe 3rd monomer is to reduce fusing point. And nylon 6T also has the shortcomings such as impact strength is not high, and toughness is lower.
The technology of existing production semi-aromatic nylon, great majority are by improving polymerization temperature, getting rid of polycondensation productMicromolecular water is realized the raising of polymer molecular weight. And in these measures, heighten on the one hand polymerization temperature meetingCause the generation of side reaction, also can improve reaction pressure, with the also corresponding raising of requirement of equipment; On the other handIn getting rid of byproduct of reaction water, due to the very high unreacted diamine of the temperature part of also can volatilizing,Cause the proportional imbalance of polymerization single polymerization monomer, have a strong impact on the performance of polymer.
Can first monomer be made to nylon salt by neutralization reaction, then be synthesized by polycondensation semiaromatic by nylon saltNylon. So in theory can ensure the molar ratio balance of polymerization single polymerization monomer. But have because polymerization is highTemperature nylon most of diamines and the solubility of dicarboxylic acid monomer in water used is all very low, so at salifyProcess in reaction end be difficult to judgement. In actual production process, the salify that also can first system be heated up,Separate again, purify, the dry nylon salt that obtains, but increased again like this loaded down with trivial details of cost and production technology.
Patent CN102660019A, the CN102634012 of JinFa Science Co., Ltd,CN102660018 discloses similar technical scheme, related to PETG (PET),Polybutylene terephthalate (PBT) (PBT) and three kinds of polyester of PEN (PEN), finalObtain 6T and 6N (according to different 10T, 10N, 12T, the 12N of also can be of used diamines) one orThe experimental program of its blend, its object is introduces main chain preparation half virtue by the phenyl ring of terephthalic acid (TPA) (T)Fragrant nylon, not high enough, the poor fluidity of its impact strength, high temperature resistant relatively poor compared with the present invention.
Do not have at present by preparing high temperature resistant nylon/PTT/PEIP/PBIP copolymer and improve materials processing mobilityMaterials processing mobility, raising impact strength are improved the relevant report of fragility.
Summary of the invention
For the shortcoming that overcomes prior art is with not enough, the object of the present invention is to provide a kind of high temperature resistant nylon/PTT (PTT)/polyethylene glycol isophthalate (PEIP)/poly-M-phthalic acidButanediol ester (PBIP) copolymer, this copolymer not only has good processing fluidity and impact strength,There is good resistance to elevated temperatures simultaneously.
Another object of the present invention is to provide the preparation of above-mentioned high temperature resistant nylon/PTT/PEIP/PBIP copolymerMethod.
A further object of the present invention is to provide the purposes of above-mentioned high temperature resistant nylon/PTT/PEIP/PBIP copolymer.
In order to reach above object, technical scheme of the present invention is as follows:
A kind of high temperature resistant nylon/PTT/PEIP/PBIP copolymer, it is obtained by following preparation method: get PTT,Tri-kinds of resins of PEIP and PBIP and diamine are dissolved in solvent, and 190～290 DEG C, polymerization under 1.5～2.5MPa pressureReaction 4～10h, obtains high temperature resistant nylon/PTT/PEIP/PBIP copolymer; Wherein, PTT, PEIP, PBIPWith the molar ratio of diamine be (30～60): (15～30): (15～30): (70～99).
Described high temperature resistant nylon/PTT/PEIP/PBIP copolymer, the composition that comprises following molar percentage:
High-temperature nylon: 68～90%
PTT：1～30％
PEIP：1～15％
PBIP:1～15%, wherein high-temperature nylon is, PTT, PEIP, PBIP react with diamine generateHigh-temperature nylon unit.
Preferably, described high temperature resistant nylon/PTT/PEIP/PBIP copolymer, comprises following molar percentageComposition:
High-temperature nylon: 80～90%
PTT：3～13％
PEIP：1～6％
PBIP:1～6%, wherein high-temperature nylon is, PTT, PEIP, PBIP react the height generating with diamineTemperature nylon unit.
The fusing point of described high temperature resistant nylon/PTT/PEIP/PBIP copolymer is 280～306 DEG C.
In the present invention, described diamines is straight chain aliphatic diamine or cycloalphatic diamine.
In the present invention, described aliphatic diamine is: ethylenediamine, propane diamine, butanediamine, hexamethylene diamine,Octamethylenediamine, nonamethylene diamine, decamethylene diamine, 11 carbon diamines, 12 carbon diamines or 14 carbon diamines.
Described cycloalphatic diamine is 4,4 '-diaminourea-dicyclohexyl methyl hydride (PACM), 4,4 '-diaminourea-dicyclohexyl propane (PACP) or 3,3-dimethyl-4,4-diaminourea-dicyclohexyl methyl hydride (MACM).
A kind of preparation method of high temperature resistant nylon/PTT/PEIP/PBIP copolymer, comprises following steps:
Get PTT (PTT), polyethylene glycol isophthalate (PEIP) and poly-betweenThree kinds of resins of benzene dicarboxylic acid butanediol ester (PBIP) and diamine are dissolved in solvent, and 190～290 DEG C, 1.5～2.5Polymerisation 4～10h under MPa pressure, obtains high temperature resistant nylon/PTT/PEIP/PBIP copolymer; Wherein,The molar ratio of PTT, PEIP, PBIP and diamine is (30～60): (15～30): (15～30):(70～99)。
In preparation method of the present invention, described solvent is alcoholic solution, dimethyl formamide, 1-METHYLPYRROLIDONEOr dimethyl sulfoxide (DMSO).
Above-mentioned high temperature resistant nylon/PTT/PEIP/PBIP copolymer can be used for moulding high temperature resistant fuel tank, the oil of Dai GangPipe, lubricating cup etc.
High temperature resistant nylon/PTT/PEIP/PBIP copolymer of the present invention have good heat resistance be becauseIn backbone structure, introduced PTT, its reaction principle is as follows:
It is because in structure that high temperature resistant nylon/PTT/PEIP/PBIP copolymer of the present invention has good toughnessIntroduced PEIP and PBIP, its reaction principle is as follows:
Pressure described in the present invention is gauge pressure.
Good effect of the present invention is: its corresponding phenyl ring homopolymers of copolymer of the present invention is compared, realExecute mode easier, require relatively lowly to what establish experimental facilities, add PTT, PEIP and PBIP not onlyCan reduce the cost of material, make the heat resistance of high-temperature nylon be kept simultaneously. Prepared resistance to heightTemperature nylon/PTT/PEIP/PBIP copolymer not only has good heat resistance, and toughness, materials processing is simultaneously flowedProperty is also better.
Detailed description of the invention
Further describe the present invention below in conjunction with embodiment, but therefore the present invention is not subject to any limitSystem.
In the embodiment of the present invention, the correlated performance parameter of product is measured in accordance with the following methods:
Heat resistance (fusing point): (GB/T1634), adopt DSC test.
Notched Izod impact strength: (GB_T1043)
Melt index: (GBT3682)
The component of product can be by infrared spectrum measurement.
Embodiment 1～3:
In the 20L polymeric kettle of being furnished with electric mixer, add PTT, PEIP, PBIP, 1,6-hexamethylene diamine and secondAlcohol, heats up after carbon dioxide purges. Under agitation temperature is raised to 220 DEG C, and pressure rises to 2.0MPa, starts to protectPress. Control still internal pressure by moisture in eliminating reaction system constant, after pressurize reaction 8h, start step-down,After being down to constant temperature normal pressure, keep 1h discharging, obtain high temperature resistant nylon/PTT/PEIP/PBIP copolymer, its specificsCan see the following form:
Table: the performance of copolymer contrast table of embodiment and comparative example
As can be seen from the table, high temperature resistant nylon/PTT/PEIP/PBIP copolymer of the present invention and high temperature resistant nylon/ PBT/PET copolymer is compared, and has better heat resistance and toughness, and mobile performance is also good.
Claims (5)
1. high temperature resistant nylon/PTT/PEIP/PBIP copolymer, is characterized in that, its preparation method comprisesFollowing steps: get tri-kinds of resins of PTT, PEIP and PBIP and diamine and be dissolved in solvent, 190～290 DEG C,Polymerisation 4～10h under 1.5～2.5MPa pressure, obtains high temperature resistant nylon/PTT/PEIP/PBIP copolymer;Wherein, the molar ratio of PTT, PEIP, PBIP and diamine is (30～60): (15～30): (15～30):(70～99)。
2. high temperature resistant nylon/PTT/PEIP/PBIP copolymer according to claim 1, is characterized in that,Described diamines is straight chain aliphatic diamine or cycloalphatic diamine.
3. high temperature resistant nylon/PTT/PEIP/PBIP copolymer according to claim 2, is characterized in that,Described straight chain aliphatic diamine is: ethylenediamine, propane diamine, butanediamine, hexamethylene diamine, octamethylenediamine, the ninth of the ten Heavenly StemsDiamines, decamethylene diamine, 11 carbon diamines, 12 carbon diamines or 14 carbon diamines; Described is alicyclicDiamine is 4,4 '-diaminourea-dicyclohexyl methyl hydride, 4,4 '-diaminourea-dicyclohexyl propane or 3,3-dimethyl-4,4-diaminourea-dicyclohexyl methyl hydride.
4. the preparation of the high temperature resistant nylon/PTT/PEIP/PBIP copolymer described in any one in claim 1-3Method, is characterized in that, comprises following steps:
Get tri-kinds of resins of PTT, PEIP and PBIP and diamine and be dissolved in solvent, 190～290 DEG C, 1.5～2.5MPaPolymerisation 4～10h under pressure, obtains high temperature resistant nylon/PTT/PEIP/PBIP copolymer; Wherein, PTT,The molar ratio of PEIP, PBIP and diamine is (30～60): (15～30): (15～30): (70～99).
5. preparation method according to claim 4, is characterized in that, described solvent is alcoholic solution, twoNMF, 1-METHYLPYRROLIDONE or dimethyl sulfoxide (DMSO).
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| CN109776349B (en) | 2017-11-15 | 2022-02-22 | 财团法人工业技术研究院 | Diamine compound, diamine diacid salt, and method for forming copolymer |
| TWI705986B (en) * | 2017-11-15 | 2020-10-01 | 財團法人工業技術研究院 | Diamine compound, diamine-diacid salt, copolymer and method for manufacturing the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6458439B1 (en) * | 1996-05-17 | 2002-10-01 | The Valspar Corporation | Extrusion coating compositions and method |
| CN102634012A (en) * | 2012-05-09 | 2012-08-15 | 金发科技股份有限公司 | Heat resisting polyamide/PEN (polyethylene naphthalate)/PET (polyethylene terephthalate) copolymer and manufacturing method and application of heat resisting polyamide/PEN/PET copolymer |
| CN102660019A (en) * | 2012-05-09 | 2012-09-12 | 金发科技股份有限公司 | High temperature-resistant nylon/ polybutylece terephthalate (PBT)/polyethylene terephthalate (PET) copolymer, and preparation method and application thereof |
| CN102660020A (en) * | 2012-05-09 | 2012-09-12 | 金发科技股份有限公司 | High-temperature resistant nylon/PEN/PBT/PET copolymer and preparation method thereof |
| CN102660018A (en) * | 2012-05-09 | 2012-09-12 | 金发科技股份有限公司 | High temperature-resistant nylon/polyethylenenaphthalate (PEN) /polyethylene glycol terephthalate (PBT) copolymer, and preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6458439B1 (en) * | 1996-05-17 | 2002-10-01 | The Valspar Corporation | Extrusion coating compositions and method |
| CN102634012A (en) * | 2012-05-09 | 2012-08-15 | 金发科技股份有限公司 | Heat resisting polyamide/PEN (polyethylene naphthalate)/PET (polyethylene terephthalate) copolymer and manufacturing method and application of heat resisting polyamide/PEN/PET copolymer |
| CN102660019A (en) * | 2012-05-09 | 2012-09-12 | 金发科技股份有限公司 | High temperature-resistant nylon/ polybutylece terephthalate (PBT)/polyethylene terephthalate (PET) copolymer, and preparation method and application thereof |
| CN102660020A (en) * | 2012-05-09 | 2012-09-12 | 金发科技股份有限公司 | High-temperature resistant nylon/PEN/PBT/PET copolymer and preparation method thereof |
| CN102660018A (en) * | 2012-05-09 | 2012-09-12 | 金发科技股份有限公司 | High temperature-resistant nylon/polyethylenenaphthalate (PEN) /polyethylene glycol terephthalate (PBT) copolymer, and preparation method and application thereof |
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