CN101880235A - Preparation method of long-chain semi-aromatic nylon salt - Google Patents
Preparation method of long-chain semi-aromatic nylon salt Download PDFInfo
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- CN101880235A CN101880235A CN2010102126519A CN201010212651A CN101880235A CN 101880235 A CN101880235 A CN 101880235A CN 2010102126519 A CN2010102126519 A CN 2010102126519A CN 201010212651 A CN201010212651 A CN 201010212651A CN 101880235 A CN101880235 A CN 101880235A
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Abstract
The invention discloses a preparation method of long-chain semi-aromatic nylon salt. The method comprises the following steps: firstly, respectively dissolving aromatic dibasic acid and long-chain diamine in an organic solvent under the temperature of 60-80 DEG C, then slowly adding the long-chain diamine into aromatic dibasic acid solution to carry out neutral reaction under the temperature of 60-80 DEG C, adjusting pH value to 7.2-7.4, cooling, separating, washing with the organic solvent, and drying to obtain the long-chain semi-aromatic nylon salt. The long-chain semi-aromatic nylon salt prepared by the invention has higher purity, the speed of the neutral reaction can be controlled, and simultaneously the molar ratio of dibasic acid and diamine can be controlled; the neutral reaction temperature of the organic solvent selected by the invention is lower, the obtained long-chain semi-aromatic nylon salt can be partially dissolved in the organic solvent at the neutral reaction temperature, and is not dissolved in the organic solvent under normal temperature, so as to be convenient to adjust the pH value, separate and purify; and the used organic solvent can be used circularly.
Description
Technical field
The present invention relates to a kind of preparation production method of long-chain semi-aromatic nylon salt.
Background technology
Nylon has good physical strength, wear resistance, self lubricity and erosion resistance preferably, is widely used in fields such as electronic apparatus, automotive industry, engineering machinery, fiber, is one of important engineering plastics, and output occupies first of the five large-engineering plastics.
In recent years in order to satisfy more high performance requirement in fields such as electronics, electrical equipment, automobiles, the particularly popularization that develops and do not have lead-tin soldering rapidly of surface mounting technology, make PBT and PA66 not to meet the demands, high temperature resistant nylon PA46, PA6T, HTN and PA9T, PA10T, PA12T etc. are developed in succession.
When nylon was synthetic, for the ease of the molar ratio of control diprotic acid, diamine, nylon salt was made in employing earlier usually, and then carries out the method for polycondensation.The method for making of conventional nylon salt is that diprotic acid and diamine carry out neutralization reaction in water or alcohol solvent, and it is dry to separate then, purify.It is solvent with water that patent CN1887841A discloses a kind of, and first water aromatic dibasic acid, long-chain diamine respectively mixes making beating, carries out neutralization reaction then, judges the method for preparing semi-aromatic nylon salt of salify terminal point with the pH value.It is the method that solvent prepares semi-aromatic nylon salt with N-Methyl pyrrolidone or dimethyl formamide that patent CN101456804A discloses a kind of.
Have following problem in the existing nylon salt technology of preparing: 1. when preparing semi-aromatic nylon salt with water or ethanol as solvent, aromatic acid, nylon salt solubleness in these solvents is less, is difficult to obtain the nylon salt of the mol ratio that requires; 2. selecting dimethyl formamide or N-Methyl pyrrolidone is solvent when preparing semi-aromatic nylon salt, because prepared nylon salt is insoluble to solvent in the neutralization reaction temperature range, causes reaction end to be difficult to judge.
Summary of the invention
The present invention is directed to the deficiencies in the prior art the method for the long-chain semi-aromatic nylon salt of a kind of controlled diprotic acid and diamine mol ratio is provided.Carry out in organic solvent in this preparation process, this solvent can dissolve aromatic dibasic acid and long-chain diamine preferably, and preparation aramid fiber salt part can be dissolved in 60～80 ℃ of solvents under the temperature, is insoluble to this solvent under the normal temperature.
Method of the present invention comprises the steps:
(1) aromatic acid is dissolved in 60～80 ℃ the organic solvent, standby;
(2) the long-chain diamine is dissolved in 60～80 ℃ the organic solvent, standby;
(3) step (2) gained long-chain diamine solution is slowly joined in the solution of (1) gained 60～80 ℃ of temperature with under stirring, after reinforced the finishing, between pH value to 7.2～7.4 with long-chain diamine solution regulation system;
(4) then step (3) reactant is continued reaction after 0.5 hour material be cooled to room temperature (～25 ℃), through centrifugation, organic solvent washing, be drying to obtain white powder long-chain semi-aromatic nylon salt.
Aromatic dibasic acid is dissolved in the organic solvent of 1～1.5 times of weight in the above step, and the long-chain diamine is dissolved in the organic solvent of 0.8～1 times of weight, and organic solvent is a dimethyl sulfoxide (DMSO).
The used aromatic dibasic acid of the present invention is: terephthalic acid, m-phthalic acid, 4,4-biphenyl dicarboxylic acid, 2, one or more in the 6-naphthalic acid.
The used long-chain diamine of the present invention is: 1,1,11-11 carbon diamines, 1,12-12 carbon diamines, 1,13-13 carbon diamines, 1,14-14 carbon diamines, 1, one or more in the 15-15 carbon diamines.
Be that long-chain diamine solution slowly joins in the aromatic dibasic acid solution in the step of the present invention (3), after long-chain diamine solution added, regulating pH behind the reaction 1h was 7.2～7.4 o'clock, is judged to be the salt-forming reaction terminal point; The used salt-forming reaction still of step (3) is the reactor of common normal pressure, stirring and controllable temperature.
The used organic solvent of the present invention has solvability preferably to aromatic dibasic acid and long-chain diamine, because the long-chain semi-aromatic nylon salt that makes is dissolved in the organic solvent dimethyl sulfoxide (DMSO) 60～80 ℃ of lower sections, be beneficial to and regulate the pH value, judge the salt-forming reaction terminal point; Reduce to room temperature (～25 ℃) long-chain semi-aromatic nylon salt when temperature and from organic solvent, be precipitated out, be convenient to the separation and the purifying of long-chain semi-aromatic nylon salt.
Compared with prior art, the present invention has following advantage:
1, preparation nylon salt method of the present invention, reaction process is controlled, and is with pH value method control reaction end, effectively simple;
2, the organic solvent selected for use of the present invention can dissolve aromatic dibasic acid and long-chain diamine, and this solvent can be partly dissolved nylon salt under 60～80 ℃ of temperature, does not dissolve nylon salt under the normal temperature, can be easy to the nylon salt that generates separate, purifying;
3, neutralization reaction temperature of the present invention is lower, cuts down the consumption of energy;
4, the organic solvent of the present invention's use can recycle.
Embodiment
Embodiment 1
1.661Kg (10mol) terephthalic acid is dissolved in 70 ℃ the 1.661Kg dimethyl sulfoxide solvent; Again the decamethylene diamine of 1.723Kg (10mol) is dissolved in 70 ℃ the 1.378Kg dimethyl sulfoxide solvent; Earlier terephthaldehyde's acid solution is added in the reactor, start stirring, keep 70 ℃ of temperature, then decamethylene diamine solution is joined in the reactor gradually, behind reinforced the finishing, behind the reaction 1h, after regulating pH to 7.2～7.4, reduce to room temperature (～25 ℃) after reacting 0.5h again, centrifugation, wash, be drying to obtain 10T salt 3.196Kg, productive rate 94.3%.
Embodiment 2
1.661Kg (10mol) m-phthalic acid is dissolved in 60 ℃ the 1.661Kg dimethyl sulfoxide solvent; Again the decamethylene diamine of 1.723Kg (10mol) is dissolved in 70 ℃ the 1.378Kg dimethyl sulfoxide solvent; Earlier m-phthalic acid solution is added in the reactor, start stirring, keep 60 ℃ of temperature, then decamethylene diamine solution is joined in the reactor gradually, behind reinforced the finishing, behind the reaction 1h, after regulating pH to 7.2～7.4, reduce to room temperature (～25 ℃) after reacting 0.5h again, centrifugation, wash, be drying to obtain 10I salt 3.264Kg, productive rate 96.4%.
Embodiment 3
1.942Kg (10mol) is dissolved in phenylene-diacetic acid in 75 ℃ the 2.531Kg dimethyl sulfoxide solvent; Again the decamethylene diamine of 1.723Kg (10mol) is dissolved in 70 ℃ the 1.378Kg dimethyl sulfoxide solvent; Earlier phenylene-diacetic acid solution is added in the reactor, start stirring, keep 70 ℃ of temperature, then decamethylene diamine solution is joined in the reactor gradually, behind reinforced the finishing, behind the reaction 1h, after regulating pH to 7.2～7.4, reduce to room temperature (～25 ℃) after reacting 0.5h again, centrifugation, wash, be drying to obtain 10P salt 3.384Kg, productive rate 97.1%.
Embodiment 4
With 2.422Kg (10mol) 4, the 4-biphenyl dicarboxylic acid is dissolved in 80 ℃ the 3.633Kg dimethyl sulfoxide solvent; Again with 1 of 2.424Kg (10mol), 15-15 carbon diamines are dissolved in 80 ℃ the 2.424Kg dimethyl sulfoxide solvent; Earlier 4,4-biphenyl dicarboxylic acid solution adds in the reactor, starts stirring, keeps 80 ℃ of temperature, then 1,15-15 carbon diamine solution join in the reactor gradually, behind reinforced the finishing, behind the reaction 1h, after regulating pH to 7.2～7.4, reduce to room temperature (～25 ℃) after reacting 0.5h again, centrifugation, wash, be drying to obtain 15B salt 4.461Kg, productive rate 95.6%.
Embodiment 5
With 2.162Kg (10mol) 2, the 6-naphthalic acid is dissolved in 70 ℃ the 2.323Kg dimethyl sulfoxide solvent; Again with 1 of 2.424Kg (10mol), 15-15 carbon diamines are dissolved in 70 ℃ the 2.424Kg dimethyl sulfoxide solvent; Earlier 2,6-naphthalic acid solution adds in the reactor, starts stirring, keeps 80 ℃ of temperature, then 1,15-15 carbon diamine solution join in the reactor gradually, behind reinforced the finishing, behind the reaction 1h, after regulating pH to 7.2～7.4, reduce to room temperature (～25 ℃) after reacting 0.5h again, centrifugation, wash, be drying to obtain 15N salt 4.195Kg, productive rate 95.2%.
The above; only be the specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, anyly is familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain that claim was defined.
Claims (6)
1. the preparation method of a long-chain semi-aromatic nylon salt is characterized in that, comprises the steps:
(1) aromatic acid is dissolved in 60～80 ℃ the organic solvent, standby;
(2) the long-chain diamine is dissolved in 60～80 ℃ the organic solvent, standby;
(3) step (2) gained long-chain diamine solution is under agitation slowly joined in the solution of (1) gained, behind reaction 1h under 60～80 ℃ of temperature, between pH value to 7.2～7.4 with long-chain diamine solution regulation system;
(4) then the reaction mass of step (3) gained is continued 0.5 hour postcooling of reaction to room temperature (～25 ℃), through centrifugation, organic solvent washing, be drying to obtain white powder long-chain semi-aromatic nylon salt.
2. the preparation method of long-chain semi-aromatic nylon salt according to claim 1 is characterized in that, aromatic dibasic acid is dissolved in the organic solvent of 1～1.5 times of weight.
3. the preparation method of long-chain semi-aromatic nylon salt according to claim 1 and 2, it is characterized in that described aromatic dibasic acid is: terephthalic acid, to phenylene-diacetic acid, m-phthalic acid, 4,4-biphenyl dicarboxylic acid, 2, one or more in the 6-naphthalic acid.
4. the preparation method of long-chain semi-aromatic nylon salt according to claim 1 is characterized in that, described long-chain diamine is dissolved in the organic solvent of 0.8～1 times of weight.
5. according to the preparation method of claim 1 or 4 described long-chain semi-aromatic nylon salts, it is characterized in that described long-chain diamine is: 1,10-decamethylene diamine, 1,11-11 carbon diamines, 1,12-12 carbon diamines, 1,13-13 carbon diamines, 1,14-14 carbon diamines, 1, one or more in the 15-15 carbon diamines.
6. the preparation method of long-chain semi-aromatic nylon salt according to claim 1 is characterized in that, described organic solvent is a dimethyl sulfoxide (DMSO).
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| CN2010102126519A CN101880235A (en) | 2010-06-30 | 2010-06-30 | Preparation method of long-chain semi-aromatic nylon salt |
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| CN2010102126519A CN101880235A (en) | 2010-06-30 | 2010-06-30 | Preparation method of long-chain semi-aromatic nylon salt |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613495A (en) * | 2013-11-18 | 2014-03-05 | 江门市德众泰工程塑胶科技有限公司 | Preparation method of long-carbon chain semi-aromatic nylon salt |
| CN103613505A (en) * | 2013-11-18 | 2014-03-05 | 江门市德众泰工程塑胶科技有限公司 | Method for synthesizing semi-aromatic nylon salt by using mixed solvent |
| CN105777553A (en) * | 2014-12-17 | 2016-07-20 | 上海凯赛生物技术研发中心有限公司 | Preparation method of nylon salt |
| CN105924358A (en) * | 2016-05-19 | 2016-09-07 | 株洲时代新材料科技股份有限公司 | Preparation method of nylon salts |
| CN108285532A (en) * | 2018-01-16 | 2018-07-17 | 郑州大学 | A kind of preparation method of 65 salt of nylon |
| WO2021083300A1 (en) * | 2019-11-01 | 2021-05-06 | 昆山博科化学有限公司 | High-carbon alkane diamine terephthalate, preparation method therefor and application thereof |
-
2010
- 2010-06-30 CN CN2010102126519A patent/CN101880235A/en active Pending
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| 《化工新型材料》 20090430 王文志 等 新型长碳链半芳香尼龙的合成与表征 40-41，103 1-6 第37卷, 第4期 * |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613495A (en) * | 2013-11-18 | 2014-03-05 | 江门市德众泰工程塑胶科技有限公司 | Preparation method of long-carbon chain semi-aromatic nylon salt |
| CN103613505A (en) * | 2013-11-18 | 2014-03-05 | 江门市德众泰工程塑胶科技有限公司 | Method for synthesizing semi-aromatic nylon salt by using mixed solvent |
| CN103613505B (en) * | 2013-11-18 | 2015-05-20 | 江门市德众泰工程塑胶科技有限公司 | Method for synthesizing semi-aromatic nylon salt by using mixed solvent |
| CN105777553A (en) * | 2014-12-17 | 2016-07-20 | 上海凯赛生物技术研发中心有限公司 | Preparation method of nylon salt |
| CN105924358A (en) * | 2016-05-19 | 2016-09-07 | 株洲时代新材料科技股份有限公司 | Preparation method of nylon salts |
| CN108285532A (en) * | 2018-01-16 | 2018-07-17 | 郑州大学 | A kind of preparation method of 65 salt of nylon |
| CN108285532B (en) * | 2018-01-16 | 2020-04-03 | 郑州大学 | Preparation method of nylon 65 salt |
| WO2021083300A1 (en) * | 2019-11-01 | 2021-05-06 | 昆山博科化学有限公司 | High-carbon alkane diamine terephthalate, preparation method therefor and application thereof |
| CN112759522A (en) * | 2019-11-01 | 2021-05-07 | 昆山博科化学有限公司 | High-carbon-chain alkane diamine terephthalate and preparation method and application thereof |
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Application publication date: 20101110 |