CN103360598A - High molecular weight semi-aromatic nylon and preparation method thereof - Google Patents
High molecular weight semi-aromatic nylon and preparation method thereof Download PDFInfo
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- CN103360598A CN103360598A CN2012100908718A CN201210090871A CN103360598A CN 103360598 A CN103360598 A CN 103360598A CN 2012100908718 A CN2012100908718 A CN 2012100908718A CN 201210090871 A CN201210090871 A CN 201210090871A CN 103360598 A CN103360598 A CN 103360598A
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Abstract
The invention belongs to the technical field of high molecular weight materials, and relates to high molecular weight semi-aromatic nylon and a preparation method thereof. The nylon is prepared from the following components in parts by weight: 30-40 parts of aromatic binary acid, 10-20 parts of aliphatic binary acid, 40-60 parts of aliphatic diamine, 0.1-1 part of an end-capping reagent, 2-8 parts of a flow modifier and 60-80 parts of desalted water. The high polymer prepared by the invention has high molecular weight with the number-average molecular weight of 27000-39000, and is excellent in comprehensive mechanic property, free from impurities and simple in process. Therefore, the polymer obtained can be used for producing products with high mechanical properties.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of semi-aromatic nylon and preparation method thereof.
Background technology
Nylon is as the leading strength in the engineering plastics field, the world, and it occupies important share in use in market.Therefore the exploitation of nylon new variety, the improvement of complete processing, all respects such as the raising of product properties all become the target of always effort of scientific research personnel.In recent years, the requirement to material improved constantly for the electronics processing technology, and the popularization of Lead-Free Soldering Technology has further improved the requirement to the work material heat resistance.And the object that semi-aromatic nylon is high temperature resistant with himself, good stability of the dimension, high strength and the premium propertiess such as high rigidity, agent of low hygroscopicity become the at present continuous focus development research of each manufacture field.Although the special engineering plastics such as polyphenylene sulfide (PPS), polymeric liquid crystal copolymer (LCP), polyimide (PI), polyether-ether-ketone (PEEK) have advantage at aspect of performance, but because of its price high, each enterprise of producer has to seek the engineering plastics of moderate cost, excellent property, so semi-aromatic nylon becomes the primary selection of each producer of enterprise.
For semi-aromatic nylon, the mechanical property that it is good and resistance to elevated temperatures are people's outlines.As everyone knows, the molecular weight of polymkeric substance has important impact to its physical and mechanical properties.People are by a large amount of experiments, find just can demonstrate mechanical strength after polymericular weight must reach a certain numerical value, on the other hand, because there is polymolecularity in the molecular weight of high-molecular weight polymer, so the molecular weight distribution of polymkeric substance affects the performance of material too.But the increase of polyamide molecular weight tends to cause the raising of polymer viscosity, and mobile decline finally caused the processing difficulties of material.Therefore inventing a kind of molecular weight semiaromatic polyamide composition high and good processability is a kind of method that semiaromatic polyamide composition is used in industry that is very beneficial for enlarging.
The disclosed method of Chinese patent CN03127422, although can react at short notice, the preparation of the two lactan of its third component carbonyl that adds is loaded down with trivial details, and the adding of the third component is so that the preparation process of polymeric amide is complicated.And the method for the firm molecular weight polyamide of the disclosed preparation of Chinese patent No.200580026598, needing to use can be at the isocyanic acid of 150-350 ℃ of lower reaction generation, the 3rd component that namely increase is worked to polyamide molecular weight need to generate in reaction, and this just has been doomed the unstable of this reaction.And some patents are arranged when preparation high molecular semi-aromatic nylon, use and prepare first low-molecular weight polymer, after carry out the mode of solid-phase tack producing, although the method can make the higher polymkeric substance of viscosity to a certain extent, loaded down with trivial details technique has increased production cost.
The preparation method of the disclosed high molecular semi-aromatic nylon of this patent is the improvement on traditional technology, can produce at existing installation, has saved cost, can obtain again the semiaromatic polyamide composition of high molecular.
Summary of the invention
The object of the invention is to provides a kind of high molecular semi-aromatic nylon and preparation method thereof for the defective that overcomes prior art.
For achieving the above object, the present invention is by the following technical solutions:
A kind of high molecular semi-aromatic nylon, made by the component that comprises following weight part:
Described aromatic acid is one or more in terephthalic acid or the m-phthalic acid, in order to obtain high-molecular weight polymer, preferred terephthalic acid;
Described aliphatic dibasic acid is selected from the diprotic acid of the straight or branched of 4-12 carbon atom, in order to obtain high-molecular weight polymer, preferred straight chain aliphatic dibasic acid, the wherein preferred Succinic Acid of straight chain aliphatic dibasic acid, pentanedioic acid, hexanodioic acid, suberic acid, nonane diacid, sebacic acid, 11 carbon diacid or dodecanedioic acids, more preferably hexanodioic acid, suberic acid, nonane diacid or sebacic acid.
Described aliphatic diamine is selected from the diamine of the straight or branched of 4-12 carbon atom, in order to obtain high-molecular weight polymer, preferred straight chain aliphatic diamine, the preferred butanediamine of straight chain aliphatic diamine, pentamethylene diamine, hexanediamine, octamethylenediamine, nonamethylene diamine, decamethylene diamine, 11 carbon diamines or 12 carbon diamines, more preferably hexanediamine, octamethylenediamine, nonamethylene diamine or decamethylene diamine.
Described end-capping reagent be selected from can with the organism that contains an active reactive group of carboxyl or amino reaction, as contain carboxyl, amino, hydroxyl isoreactivity group, preferred phenylformic acid, acetic acid, propionic acid, ethamine or benzene methanamine, more preferably phenylformic acid.
Described flow ability modifying agent is selected from silicone compound or macromolecule wax series lubricant agent, preferred silicone compound, the preferred silicone lubricating grease of silicone compound, silicone master batch or silicone lubricant, more preferably silicone master batch.
Described de-salted water is for removing the contained strong electrolyte that is easy to remove or reduce to water to a certain degree.
The mean number average molecular weight of described high molecular semi-aromatic nylon is 27000-39000.
A kind of preparation method of above-mentioned semi-aromatic nylon may further comprise the steps:
(1) takes by weighing each component raw material by said ratio, 30-40 part aromatic acid, 10-20 part straight chain aliphatic dibasic acid, 40-60 straight chain part aliphatic diamine, 0.1-1 part end-capping reagent, 2-8 part flow ability modifying agent and 60-80 part de-salted water are joined in the autoclave;
(2) to the reactor vacuum nitrogen filling, discharge the air in the reactor, close each valve;
(3) reacting by heating still carries out isothermal reaction, keeps the sealing of reaction system;
(4) after isothermal reaction finished, the rising temperature when treating that pressure rises to 1.5-3.0MPa, began to keep constant pressure;
(5) temperature continues to raise, when treating that temperature rises to 300-325 ℃, and the beginning pressure release, the pressure release time is 30-90min, to normal pressure, and holding temperature is no more than 350 ℃;
(6) pass into nitrogen in still, to 0.5-2.0MPa, by pressurization reaction product is emitted from the bottom valve of reactor, reaction product can be passed through the forcing machine granulation, perhaps enters the direct injection moulding of injection moulding machine.
In the described step (3), Heating temperature is 110-150 ℃, and the reaction times is 2-6 hour.
The mensuration of the molecular weight of polymkeric substance is according to Preparation and some properties of Nylon 46 (Jouranl of Polymer Science 15,537-545 (1977)) disclosed method in, measure first the amino content with holding carboxyl of end, then calculate the molecular-weight average of polymkeric substance, in addition, the limiting viscosity of measuring products therefrom with 96% the vitriol oil is [η].
The present invention has following beneficial effect:
The preparation method of high molecular semi-aromatic nylon disclosed in this invention does not adopt the adding of the 3rd monomer, can guarantee the purity of whole polymers and stablizing of performance; Can improve the flowability of high-molecular weight polymer after reaction finishes by adding flow ability modifying agent, guarantee the smoothly discharging of polymkeric substance that obtains, and obtain the product of type; The polymkeric substance that obtains has high molecular, improved greatly its mechanical property, has enlarged the range of application of this polymkeric substance in auto parts machinery, the high temperature resistant component such as electric; Compared with prior art, the method technique is simple, can carry out in original production unit, has reduced production cost.
Embodiment
Below in conjunction with specific embodiments, further set forth the present invention.Following embodiment only is not used in for explanation the present invention and limits the scope of the invention.
Limiting viscosity among the embodiment is measured with following methods: the semi-aromatic nylon sample that will need to test is dissolved in the vitriol oil, obtain concentration and be 0.05,0.1,0.3,0.5 or the polymers soln of 1.0g/dl, at the logarithmic viscosity number h of 25 ℃ of lower each sample solutions of test
Rln
h
rln＝[ln(t/t
0)]/C (dl/g)
In the formula:
t
0The time of flowing through viscometer (second) of expression solvent,
T represents the flushing time (second) of sample solution,
C represents the concentration of sample in the sample solution.
With h
RlnData Extrapolation be the limiting viscosity [η] that can obtain sample in 0 the scope to concentration.
Related umber all calculates by weight in following examples.
Embodiment 1
(1) with 30 parts of terephthalic acids, 20 parts of hexanodioic acids, 55 parts of hexanediamines, 0.8 part of phenylformic acid, 2 parts of silicone lubricating grease, 70 parts of de-salted waters join in the autoclave;
(2) reactor is vacuumized, discharge air in the still, add nitrogen to normal pressure, repeatedly should operate for 3 times, with the air in the thorough discharge reactor, close each valve;
(3) reacting by heating still to 110 ℃ is kept isothermal reaction in 2 hours, keeps the stopping property of reaction system;
(4) after isothermal reaction finished, the rising temperature when treating that pressure rises to 1.5MPa, began to keep constant pressure;
(5) temperature continues to raise, when treating that temperature rises to 300 ℃, and the beginning pressure release, the pressure release time is 30min, to normal pressure, and holding temperature is no more than 350 ℃;
(6) pass into nitrogen in still, to 0.5MPa, by pressurization reaction product is emitted from the bottom valve of reactor, reaction product can be passed through the forcing machine granulation, perhaps enters the direct injection moulding of injection moulding machine;
By measuring end amino and the content of carboxyl end group of products therefrom, the number-average molecular weight that calculates resulting polymers is 27000; Limiting viscosity is [η]=1.25dl/g.
Embodiment 2
(1) with 35 parts of terephthalic acids, 15 parts of suberic acids, 45 parts of fat octamethylenediamines, 0.1 part of phenylformic acid, 4 parts of silicone master batch, 65 parts of de-salted waters join in the autoclave;
(2) reactor is vacuumized, discharge air in the still, add nitrogen to normal pressure, repeatedly should operate for 3 times, with the air in the thorough discharge reactor, close each valve;
(3) reacting by heating still to 130 ℃ is kept isothermal reaction in 4 hours, keeps the stopping property of reaction system;
(4) after isothermal reaction finished, the rising temperature when treating that pressure rises to 2.0MPa, began to keep constant pressure;
(5) temperature continues to raise, when treating that temperature rises to 305 ℃, and the beginning pressure release, the pressure release time is 60min, to normal pressure, and holding temperature is no more than 350 ℃;
(6) pass into nitrogen in still, to 1.0MPa, by pressurization reaction product is emitted from the bottom valve of reactor, reaction product can be passed through the forcing machine granulation, perhaps enters the direct injection moulding of injection moulding machine;
By measuring end amino and the content of carboxyl end group of products therefrom, the number-average molecular weight that calculates resulting polymers is 30000, and limiting viscosity is [η]=1.38dl/g.
Embodiment 3
(1) with 40 parts of terephthalic acids, 15 parts of sebacic acid, 60 parts of decamethylene diamines, 1 part of phenylformic acid, 8 parts of silicone lubricating grease, 80 parts of de-salted waters join in the autoclave;
(2) reactor is vacuumized, discharge air in the still, add nitrogen to normal pressure, repeatedly should operate for 3 times, with the air in the thorough discharge reactor, close each valve;
(3) reacting by heating still to 150 ℃ is kept isothermal reaction in 6 hours, keeps the stopping property of reaction system;
(4) after isothermal reaction finished, the rising temperature when treating that pressure rises to 3.0MPa, began to keep constant pressure;
(5) temperature continues to raise, when treating that temperature rises to 325 ℃, and the beginning pressure release, the pressure release time is 90min, to normal pressure, and holding temperature is no more than 350 ℃;
(6) pass into nitrogen in still, to 1.5MPa, by pressurization reaction product is emitted from the bottom valve of reactor, reaction product can be passed through the forcing machine granulation, perhaps enters the direct injection moulding of injection moulding machine;
By measuring end amino and the content of carboxyl end group of products therefrom, the number-average molecular weight that calculates resulting polymers is 36000, and limiting viscosity is [η]=1.52dl/g.
Embodiment 4
(1) with 30 parts of terephthalic acids, 10 parts of nonane diacids, 40 parts of nonamethylene diamines, 0.3 part of phenylformic acid, 5 parts of silicone master batch, 60 parts of de-salted waters join in the autoclave;
(2) reactor is vacuumized, discharge air in the still, add nitrogen to normal pressure, repeatedly should operate for 3 times, with the air in the thorough discharge reactor, close each valve;
(3) reacting by heating still to 140 ℃ is kept isothermal reaction in 5 hours, keeps the stopping property of reaction system;
(4) after isothermal reaction finished, the rising temperature when treating that pressure rises to 2.5MPa, began to keep constant pressure;
(5) temperature continues to raise, when treating that temperature rises to 310 ℃, and the beginning pressure release, the pressure release time is 50min, to normal pressure, and holding temperature is no more than 350 ℃;
(6) pass into nitrogen in still, to 2.0MPa, by pressurization reaction product is emitted from the bottom valve of reactor, reaction product can be passed through the forcing machine granulation, perhaps enters the direct injection moulding of injection moulding machine;
By measuring end amino and the content of carboxyl end group of products therefrom, the number-average molecular weight that calculates resulting polymers is 39000, and limiting viscosity is [η]=1.62dl/g.
Embodiment 5
(1) with 37 parts of terephthalic acids, 10 parts of hexanodioic acids, 50 parts of nonamethylene diamines, 0.5 part of phenylformic acid, 6 parts of silicone master batch, 75 parts of de-salted waters join in the autoclave;
(2) reactor is vacuumized, discharge air in the still, add nitrogen to normal pressure, repeatedly should operate for 3 times, with the air in the thorough discharge reactor, close each valve;
(3) reacting by heating still to 135 ℃ is kept isothermal reaction in 5 hours, keeps the stopping property of reaction system;
(4) after isothermal reaction finished, the rising temperature when treating that pressure rises to 2.5MPa, began to keep constant pressure;
(5) temperature continues to raise, when treating that temperature rises to 320 ℃, and the beginning pressure release, the pressure release time is 70min, to normal pressure, and holding temperature is no more than 350 ℃;
(6) pass into nitrogen in still, to 1.0MPa, by pressurization reaction product is emitted from the bottom valve of reactor, reaction product can be passed through the forcing machine granulation, perhaps enters the direct injection moulding of injection moulding machine;
By measuring end amino and the content of carboxyl end group of products therefrom, the number-average molecular weight that calculates resulting polymers is 32000, and limiting viscosity is [η]=1.48dl/g.
Embodiment 6
(1) with 33 parts of terephthalic acids, 12 parts of hexanodioic acids, 48 parts of decamethylene diamines, 02 part of phenylformic acid, 7 parts of silicone master batch, 70 parts of de-salted waters join in the autoclave;
(2) reactor is vacuumized, discharge air in the still, add nitrogen to normal pressure, repeatedly should operate for 3 times, with the air in the thorough discharge reactor, close each valve;
(3) reacting by heating still to 150 ℃ is kept isothermal reaction in 6 hours, keeps the stopping property of reaction system;
(4) after isothermal reaction finished, the rising temperature when treating that pressure rises to 3.0MPa, began to keep constant pressure;
(5) temperature continues to raise, when treating that temperature rises to 325 ℃, and the beginning pressure release, the pressure release time is 60min, to normal pressure, and holding temperature is no more than 350 ℃;
(6) pass into nitrogen in still, to 1.5MPa, by pressurization reaction product is emitted from the bottom valve of reactor, reaction product can be passed through the forcing machine granulation, perhaps enters the direct injection moulding of injection moulding machine;
By measuring end amino and the content of carboxyl end group of products therefrom, the number-average molecular weight that calculates resulting polymers is 35000, and limiting viscosity is [η]=1.51dl/g.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not breaking away from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (9)
1. semi-aromatic nylon is characterized in that: made by the component that comprises following weight part:
2. semi-aromatic nylon according to claim 1, it is characterized in that: described aromatic acid is one or more in terephthalic acid or the m-phthalic acid, preferred terephthalic acid.
3. semi-aromatic nylon according to claim 1, it is characterized in that: described aliphatic dibasic acid is selected from the diprotic acid of the straight or branched of 4-12 carbon atom, preferred straight chain aliphatic dibasic acid, further preferred Succinic Acid, pentanedioic acid, hexanodioic acid, suberic acid, nonane diacid, sebacic acid, 11 carbon diacid or dodecanedioic acids, more preferably hexanodioic acid, suberic acid, nonane diacid or sebacic acid.
4. semi-aromatic nylon according to claim 1, it is characterized in that: described aliphatic diamine is selected from the diamine of the straight or branched of 4-12 carbon atom, preferred straight chain aliphatic diamine, further preferred butanediamine, pentamethylene diamine, hexanediamine, octamethylenediamine, nonamethylene diamine, decamethylene diamine, 11 carbon diamines or 12 carbon diamines, more preferably hexanediamine, octamethylenediamine, nonamethylene diamine or decamethylene diamine.
5. semi-aromatic nylon according to claim 1 is characterized in that: described end-capping reagent is selected from and the monobasic organism of carboxyl or amino reaction, preferred phenylformic acid, acetic acid, propionic acid, ethamine or benzene methanamine, more preferably phenylformic acid.
6. semi-aromatic nylon according to claim 1; it is characterized in that: described flow ability modifying agent is selected from silicone compound or macromolecule wax series lubricant agent; preferred silicone compound, further preferred silicone lubricating grease, silicone master batch or silicone lubricant, more preferably silicone master batch.
7. semi-aromatic nylon according to claim 1, it is characterized in that: the mean number average molecular weight of described high molecular semi-aromatic nylon is 27000-39000.
8. the preparation method of arbitrary described semi-aromatic nylon among the claim 1-7 is characterized in that: may further comprise the steps:
(1) takes by weighing each component raw material by proportioning claimed in claim 1,30-40 part aromatic acid, 10-20 part straight chain aliphatic dibasic acid, 40-60 part straight chain part aliphatic diamine, 0.1-1 part end-capping reagent, 2-8 part flow ability modifying agent and 60-80 part de-salted water are joined in the autoclave;
(2) to the reactor vacuum nitrogen filling, discharge the air in the reactor, close each valve;
(3) reacting by heating still carries out isothermal reaction to certain temperature, keeps the stopping property of reaction system;
(4) after isothermal reaction finished, the rising temperature when treating that pressure rises to 1.5-3.0MPa, began to keep constant pressure;
(5) temperature continues to raise, when treating that temperature rises to 300-325 ℃, and the beginning pressure release, the pressure release time is 30-90min, to normal pressure, and holding temperature is no more than 350 ℃;
(6) pass into nitrogen in still, to 0.5-2.0MPa, by pressurization reaction product is emitted from the bottom valve of reactor, reaction product perhaps enters the direct injection moulding of injection moulding machine by the forcing machine granulation.
9. preparation method according to claim 8, it is characterized in that: in the described step (3), Heating temperature is 110-150 ℃, and the reaction times is 2-6 hour.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103936978A (en) * | 2013-05-20 | 2014-07-23 | 金发科技股份有限公司 | Polyamide resin and polyamide composition composed of polyamide resin |
| EP3502165A1 (en) | 2017-12-22 | 2019-06-26 | Rhodia Operations | Process for preparing a copolyamide without encrustation in the autoclave |
| CN113444241A (en) * | 2021-06-28 | 2021-09-28 | 广州辰东新材料有限公司 | Polyamide and preparation method thereof |
| CN114573805A (en) * | 2022-01-19 | 2022-06-03 | 浙江恒逸石化研究院有限公司 | Preparation method of high-barrier transparent flame-retardant copolymerized nylon |
| CN115010922A (en) * | 2022-07-22 | 2022-09-06 | 山东东辰瑞森新材料科技有限公司 | Long-carbon-chain high-temperature-resistant nylon and preparation method and application thereof |
| WO2023284285A1 (en) * | 2021-07-15 | 2023-01-19 | 上海凯赛生物技术股份有限公司 | High-temperature-resistant semi-aromatic copolyimide and preparation method therefor, composition, and molded article |
| US11905370B2 (en) | 2020-11-10 | 2024-02-20 | Zhengzhou University | Method for synthesizing long carbon chain semi-aromatic nylon |
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| CN102070902A (en) * | 2009-11-23 | 2011-05-25 | Ems专利股份公司 | Semi-aromatic moulding masses and their applications |
| CN102311515A (en) * | 2010-07-09 | 2012-01-11 | 新疆石河子中发化工有限责任公司 | Method for feeding materials and controlling temperature in process for producing copolymerization resin by suspension method |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103936978A (en) * | 2013-05-20 | 2014-07-23 | 金发科技股份有限公司 | Polyamide resin and polyamide composition composed of polyamide resin |
| EP3502165A1 (en) | 2017-12-22 | 2019-06-26 | Rhodia Operations | Process for preparing a copolyamide without encrustation in the autoclave |
| WO2019122298A1 (en) | 2017-12-22 | 2019-06-27 | Rhodia Operations | Process for preparing a copolyamide without encrustation in the autoclave |
| US11905370B2 (en) | 2020-11-10 | 2024-02-20 | Zhengzhou University | Method for synthesizing long carbon chain semi-aromatic nylon |
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| WO2023272459A1 (en) * | 2021-06-28 | 2023-01-05 | 广州辰东新材料有限公司 | Polyamide and preparation method therefor |
| WO2023284285A1 (en) * | 2021-07-15 | 2023-01-19 | 上海凯赛生物技术股份有限公司 | High-temperature-resistant semi-aromatic copolyimide and preparation method therefor, composition, and molded article |
| CN114573805A (en) * | 2022-01-19 | 2022-06-03 | 浙江恒逸石化研究院有限公司 | Preparation method of high-barrier transparent flame-retardant copolymerized nylon |
| CN114573805B (en) * | 2022-01-19 | 2024-03-08 | 浙江恒逸石化研究院有限公司 | Preparation method of high-barrier transparent flame-retardant copolymerized nylon |
| CN115010922A (en) * | 2022-07-22 | 2022-09-06 | 山东东辰瑞森新材料科技有限公司 | Long-carbon-chain high-temperature-resistant nylon and preparation method and application thereof |
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