CN101200543B - Preparation method for improving performance of high-temperature nylon - Google Patents
Preparation method for improving performance of high-temperature nylon Download PDFInfo
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- CN101200543B CN101200543B CN2006101473582A CN200610147358A CN101200543B CN 101200543 B CN101200543 B CN 101200543B CN 2006101473582 A CN2006101473582 A CN 2006101473582A CN 200610147358 A CN200610147358 A CN 200610147358A CN 101200543 B CN101200543 B CN 101200543B
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Abstract
The present invention relates to a preparation method of improving the performance of high temperature nylon. The method includes: long carbon-chain nylon or copolynylon is added into paraphthaloyl acidhexamethylene diamine salt, m-phthalic acryl acidhexamethylene diamine salt, diamide hexamethylene diamine salt and/or hexanolactam reactor and then a proper amount of antioxygen is added; the reactor is firstly vacuumized and then filled with nitrogen with certain pressure; when the temperature begins to rise and the pressure goes up to 2.0 to 3.0MPa, the pressure is maintained; when the temperature reaches 290 to 300 DEG C, the pressure is reduced and the temperature keeps rising; when the temperature is 310 to 330 DEG C, the state of constant temperature and constant pressure is maintained for 20 to 60 minutes for in-situ fusion, condensation and polymerization, thus getting the modified high-temperature nylon. Compared with the prior technology, the present invention, with the characteristics of strong stretching intensity and notch impact strength, is simple, effective and very economical.
Description
Technical field
The present invention relates to a kind of novel preparation and improve the method for high-temperature nylon (HPN) performance, particularly improve the method for tensile strength and notched Izod impact strength.
Background technology
Nylon resin has characteristics such as excellent mechanical mechanics property, wear-resisting, self-lubricating, oil resistant, heatproof, is domestic and international application engineering plastics the most widely.The character of aromatic nylon difficult ratio of aliphatics nylon as PA6T, PA9T, PA12T etc. have some, good as dimensional stability, heat-resisting, high rigidity, agent of low hygroscopicity and good chemical resistance, the application at aspects such as electronics, electric and automobile component demonstrates excellent performance.Existing a lot of about the patent of PA6T, as US4022756, GB1526329, US4113708, US4246395, US4663166, US4863991, WO9210525, US560167, JP02251352, JP034317, JP03161507, JP0408730 etc. have all disclosed the preparation method of PA6T.But nylon PA6T, especially virgin resin, its common shortcoming is crisp, toughness is poor, to such an extent as to stretching and notched Izod impact strength are all poor.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of preparation method who improves performance of high-temperature nylon who improves tensile strength and notched Izod impact strength for the defective that overcomes above-mentioned prior art existence.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method who improves performance of high-temperature nylon, it is characterized in that, this method comprises: long carbon chain nylon or copolymer nylon are added hexamethylene terephthalamide salt, 6I hexamethylene isoterephalamide salt, in the reactor of hexamethylene adipamide salt and/or hexanolactam, add an amount of oxidation inhibitor, vacuumize earlier, feed the nitrogen of certain pressure then, begin to heat up, when pressure rises to 2.0～3.0Mpa, the beginning pressurize, when temperature rises to 290～300 ℃, begin decompression, temperature continues to rise, when temperature is 310～330 ℃, constant temperature normal pressure 20～60 minutes carries out the original position melt phase polycondensation, obtains the modification high-temperature nylon.
Described long carbon chain nylon or copolymer nylon add-on are 1～20wt%.
The carbonatoms of described long carbon chain nylon or copolymer nylon generally surpasses 6, and is best greater than 10.
Described long carbon chain nylon comprises nylon 7, nylon 8, nylon 9, Ni Long11, nylon 12, NYLON610, nylon 612, nylon 1010, nylon 1212, nylon 46.
Described oxidation inhibitor is phosphite ester kind antioxidant, comprise tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, two (2, the 4-di-t-butyl) season tetrol diphosphites, triphenyl phosphite, phosphorous acid benzene di-isooctyl, trisnonylphenyl phosphite etc., add-on is 0.001～2wt%.
Described long carbon chain nylon or copolymer nylon are directly to add in the reactor, prepare the high-temperature nylon multipolymer and high-temperature nylon is carried out modification by the reaction in process.
Compared with prior art, the present invention directly adds the long carbon chain nylon resin in reactor, preparing the HPN multipolymer and HPN is carried out modification by the reaction in process, and do not need with long carbon chain nylon the HPN resin to be carried out modification, is a kind of simple effective and very economical method.
Because the fragility of half aromatics nylon resin own is bigger, toughness is relatively poor, and long carbochain aliphatics nylon itself has toughness preferably, in 6T or 6I salt and 66 salt or hexanolactam, add long carbon chain nylon and carry out the fusion copolymerization, because these long carbon chain nylons or other nylon have the structure similar to nylon 66 or nylon 6, therefore have certain consistency, simultaneously again owing to there be certain being separated, will inevitably cause microfaciesization, separately crystallization.This structure will inevitably cause good toughness, thereby improves the toughness of HPN resin greatly, improves performances such as its stretching and notched Izod impact strength.
Embodiment
Below in conjunction with specific embodiment method involved in the present invention and technology are described.
6T salt is that hexamethylene terephthalamide salt, 6I salt are that 6I hexamethylene isoterephalamide salt, 66 salt are hexamethylene adipamide salt in the following specific embodiment.
Embodiment 1
With 825 gram 6T salt, 525 gram 6I salt, 140 grams, 66 salt, 1000 gram deionized waters, the oxidation inhibitor tricresyl phosphite of 0.001wt% (2, the 4-di-tert-butyl-phenyl) ester and 37.25 gram PA1212 resins add in 5 liters the reactor.Vacuumize earlier, feed the nitrogen of certain pressure then, begin to heat up.When pressure rises to 2.5Mpa, the beginning pressurize.When temperature rises to 290～300 ℃, begin decompression, temperature continues to rise, when temperature is 320 ℃, constant temperature normal pressure 30 minutes.Then discharging in the reactor.The calorifics of resin and mechanical mechanics property index are as follows:
Fusing point: (Tm) 288 ℃ of tensile strengths: 38.3MPa elongation at break: 8.1%
Modulus in flexure: 3019Mpa Izod notched Izod impact strength: 60J/m
Heat-drawn wire: 140 ℃
Embodiment 2
With 825 gram 6T salt, 525 gram 6I salt, 140 grams, 66 salt, 1000 gram deionized waters, an amount of inferior sodium phosphate, oxidation inhibitor and 74.5 restrain in the steel reactor of 5 liters of PA1010 resins addings. and specific operation process is as follows with the calorifics and the mechanical mechanics property index of embodiment 1. resins:
Fusing point: (Tm) 287 ℃ of tensile strengths: 67.6MPa elongation at break: 10.8%
Modulus in flexure: 2910Mpa Izod notched Izod impact strength: 90J/m
Heat-drawn wire: 137 ℃
Embodiment 3
With 825 gram 6T salt, 525 gram 6I salt, 140 grams, 66 salt, 1000 gram deionized waters, an amount of inferior sodium phosphate, oxidation inhibitor and 109 gram PA612 resins add in 5 liters the steel reactor.Specific operation process is with embodiment 1.The calorifics of resin and mechanical mechanics property index are as follows:
Fusing point: (Tm) 285 ℃ of tensile strengths: 91.2MPa elongation at break: 16.4%
Modulus in flexure: 2830Mpa Izod notched Izod impact strength: 152J/m
Heat-drawn wire: 136 ℃
Embodiment 4:
With 825 gram 6T salt, 525 gram 6I salt, 60 lactan of restraining oneself, 1000 gram deionized waters, an amount of inferior sodium phosphate, oxidation inhibitor and 70.5 gram PA1212 resins add in 5 liters the steel reactor. and specific operation process is as follows with the calorifics and the mechanical mechanics property index of embodiment 1. resins:
Fusing point: (Tm) 288 ℃ of tensile strengths: 74.5MPa elongation at break: 11.8%
Modulus in flexure: 3060Mpa Izod notched Izod impact strength: 98J/m
Heat-drawn wire: 137 ℃
Embodiment 5:
With 825 gram 6T salt, 525 gram 6I salt, 60 lactan of restraining oneself, 1000 gram deionized waters, an amount of silicone oil, oxidation inhibitor and 140 gram PA11 resins add in 5 liters the steel reactor. and specific operation process is as follows with the calorifics and the mechanical mechanics property index of embodiment 1. resins:
Fusing point: (Tm) 286 ℃ of tensile strengths: 90.8MPa elongation at break: 19.4%
Modulus in flexure: 2900Mpa Izod notched Izod impact strength: 148J/m
Heat-drawn wire: 130 ℃
Embodiment 6
A kind of preparation method who improves performance of high-temperature nylon, it is characterized in that, this method comprises: the long carbon chain nylon or the copolymer nylon of adding 1% in 6T or 6I salt and 66 salt or hexanolactam, 2wt% antioxidant resin two (2, the 4-di-t-butyl) in the season tetrol diphosphites adding reactor, vacuumize earlier, feed the nitrogen of certain pressure then, begin to heat up, when pressure rises to 2.0Mpa, the beginning pressurize when temperature rises to 290 ℃, begins decompression, temperature continues to rise, when temperature was 310 ℃, constant temperature normal pressure 20 minutes carried out the fusion copolymerization.
Embodiment 7
A kind of preparation method who improves performance of high-temperature nylon is characterized in that, this method comprises: the long carbon chain nylon or the copolymer nylon of adding 20% in 6T or 6I salt and 66 salt or hexanolactam, an amount of antioxidant resin adds in the reactor, vacuumizes earlier, feeds the nitrogen of certain pressure then, begin to heat up, when pressure rises to 3.0Mpa, the beginning pressurize, when temperature rises to 300 ℃, begin decompression, temperature continues to rise, when temperature is 330 ℃, constant temperature normal pressure 60 minutes carries out the fusion copolymerization.
Described oxidation inhibitor is phosphite ester kind antioxidant, also comprises triphenyl phosphite, phosphorous acid benzene di-isooctyl, trisnonylphenyl phosphite etc.
Claims (4)
1. preparation method who improves performance of high-temperature nylon, it is characterized in that, this method comprises: long carbon chain nylon or copolymer nylon are added hexamethylene terephthalamide salt, 6I hexamethylene isoterephalamide salt, in the reactor of hexamethylene adipamide salt and/or hexanolactam, long carbon chain nylon or copolymer nylon are directly to add in the reactor, prepare the high-temperature nylon multipolymer and high-temperature nylon is carried out modification by the reaction in process, long carbon chain nylon or copolymer nylon add-on are 1～20wt%, add an amount of oxidation inhibitor, vacuumize earlier, feed the nitrogen of certain pressure then, begin to heat up, when pressure rose to 2.0～3.0Mpa, the beginning pressurize was when temperature rises to 290～300 ℃, begin decompression, temperature continues to rise, when temperature is 310～330 ℃, and constant temperature normal pressure 20～60 minutes, carry out the original position melt phase polycondensation, obtain the modification high-temperature nylon.
2. a kind of preparation method who improves performance of high-temperature nylon according to claim 1 is characterized in that the carbonatoms of described long carbon chain nylon or copolymer nylon is above 6.
3. a kind of preparation method who improves performance of high-temperature nylon according to claim 1 is characterized in that described long carbon chain nylon comprises nylon 7, nylon 8, nylon 9, Ni Long11, nylon 12, NYLON610, nylon 612, nylon 1010, nylon 1212, nylon 46.
4. a kind of preparation method who improves performance of high-temperature nylon according to claim 1, it is characterized in that, described oxidation inhibitor is phosphite ester kind antioxidant, comprise tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, two (2, the 4-di-t-butyl) season tetrol diphosphites, triphenyl phosphite, phosphorous acid benzene di-isooctyl or trisnonylphenyl phosphite, add-on is 0.001～2wt%.
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| CN101200543B true CN101200543B (en) | 2010-12-08 |
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| CN102465353B (en) * | 2010-11-18 | 2014-04-16 | 上海杰事杰新材料(集团)股份有限公司 | Homopolymerization semi-aromatic polyamide fiber and preparation method thereof |
| CN104774454B (en) * | 2014-01-15 | 2018-02-27 | 上海杰事杰新材料(集团)股份有限公司 | A kind of high temperature resistant nylon PA66T materials and preparation method thereof |
| CN108203508A (en) * | 2016-12-16 | 2018-06-26 | 中国石油化工股份有限公司 | A kind of modified nylon-6 material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6539073B1 (en) * | 2000-02-17 | 2003-03-25 | General Electric Company | Nuclear fuel bundle having spacers captured by a water rod |
| CN1493639A (en) * | 2002-11-02 | 2004-05-05 | 中国石油化工股份有限公司 | Long carbon chain nylon hot melt glue and its synthesis method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6539073B1 (en) * | 2000-02-17 | 2003-03-25 | General Electric Company | Nuclear fuel bundle having spacers captured by a water rod |
| CN1493639A (en) * | 2002-11-02 | 2004-05-05 | 中国石油化工股份有限公司 | Long carbon chain nylon hot melt glue and its synthesis method |
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Denomination of invention: Preparation method for improving performance of high-temperature nylon Effective date of registration: 20191223 Granted publication date: 20101208 Pledgee: Chuzhou economic and Technological Development Corporation Pledgor: Shanghai Jieshijie New Materials (Group) Co., Ltd. Registration number: Y2019980001220 |
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