CN1887841A - Improved process of producing heat resistant nylon salt - Google Patents
Improved process of producing heat resistant nylon salt Download PDFInfo
- Publication number
- CN1887841A CN1887841A CN 200510027200 CN200510027200A CN1887841A CN 1887841 A CN1887841 A CN 1887841A CN 200510027200 CN200510027200 CN 200510027200 CN 200510027200 A CN200510027200 A CN 200510027200A CN 1887841 A CN1887841 A CN 1887841A
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- CN
- China
- Prior art keywords
- diamine
- nylon
- nylon salt
- salt
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000003839 salts Chemical class 0.000 title claims abstract description 36
- 239000004677 Nylon Substances 0.000 title claims abstract description 35
- 229920001778 nylon Polymers 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000004985 diamines Chemical class 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000007796 conventional method Methods 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000010009 beating Methods 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- -1 carbon diamines Chemical class 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 claims description 3
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- 150000001412 amines Chemical class 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 2
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000003756 stirring Methods 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 5
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 230000003472 neutralizing effect Effects 0.000 description 4
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000007520 diprotic acids Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920006115 poly(dodecamethylene terephthalamide) Polymers 0.000 description 1
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Polyamides (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The improved process of producing heat resistant nylon salt includes the following steps: (1) mixing aromatic dibasic acid with water in 2-5 times weight to pulp and heating to 60-105 deg.c; (2) dissolving diamine in water in 1-2 times weight and heating to 60-100 deg.c; (3) mixing the materials obtained in the two foregoing steps in the same molar ratio and reacting at 60-95 deg.c until the reaction end point of pH 7.0-7.2; and (4) cooling to 20-40 deg.c for crystallizing and collecting nylon salt in conventional method. The process is simple, and has short operation period, low power consumption, mild reaction condition, environment friendship, low cost and capacity of effectively controlling the content of free acid and free amine in nylon salt product.
Description
Technical field
The present invention relates to a kind of production method of salt of high temperature resistant nylon.
Technical background
Nylon resin (PA) has excellent mechanical mechanics property, wear-resisting, self-lubricating, oil resistant, heatproof etc., is domestic and international application engineering plastics the most widely, first of the row five large-engineering plastics.
High temperature resistant nylon such as PA46, PA6T, PA9T, PA12T etc. have the character of the difficult ratio of some general nylon, 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 shows excellent performance.
Nylon has two kinds on AABB type and AB type usually, and its difference is be used for that the monomer of synthetic nylon forms different, and the former is a monomer with the salt (nylon salt) of diprotic acid and diamine, and the latter mainly is monomer with the lactan.
The manufacturing usual method of nylon salt is that diprotic acid and diamine are formed solution respectively in ethanol or other organic solvents, in the reactor that a band stirs, make it to neutralize fully then, after separate, dry and obtain.These methods all have free acid or shortcomings such as amine content height and energy consumption height in solvent recuperation problem, the difficult control of neutralization reaction, the nylon salt.
Summary of the invention
The present invention aims to provide a kind of method of improved production heat resistant nylon salt, to overcome the shortcoming of traditional method.
Method of the present invention comprises the steps:
(1) aromatic acid is mixed making beating with the water of 2～5 times of weight, be heated to 60～105 ℃, standby;
(2) diamine is dissolved in the water of 1～2 times of weight, is heated to 60～100 ℃, standby;
(3) with two kinds of raw materials of step (1) and step (2) according to etc. mol ratio in hybrid reaction, temperature of reaction is controlled at 60～95 ℃, reaction end is pH 7.0～7.2;
(4) crystallisation by cooling under 20～40 ℃ temperature then, adopt conventional method to collect the nylon wet salt, this salt can be directly used in the polymerization of polymeric amide, as the dried salt of need, can be with nylon wet salt drying, drying temperature is 40～110 ℃, can obtain the nylon salt finished product of white powder, and the molecular formula of nylon salt is:
-OOC(C
6H
4)COO
-+H
3N(CH
2)
nNH
3 +；
N=6～16 wherein.
The aromatic acid of one of raw material of production nylon salt of the present invention is:
Or its mixing acid.
Be used to prepare the diamine of nylon salt among the present invention, molecular formula is H
2N (CH
2)
nNH
2, n=6～16 wherein, typical diamine comprises hexanediamine, nonamethylene diamine, decamethylene diamine, 11 carbon diamines, 12 carbon diamines, 13 carbon diamines, 14 carbon diamines.
The hybrid reaction of step (3), preferably adopt a kind of static mixing reactor, the structure of this reactor all has detailed description in relevant chemical engineering handbook, comprise shell of reactor and setting inner member in the enclosure, shell of reactor is provided with the import of the aromatic acid and the diamine aqueous solution, and an end is a reacting product outlet.The aromatic acid and the diamine aqueous solution is the thorough mixing making beating under the effect of inner member, and reacts.
Adopt method of the present invention to prepare described nylon salt, production technique is simplified, and shortens operational cycle and energy consumption, the reaction conditions gentleness, and environmental friendliness, production cost falls, and can control the free acid and the unhindered amina content of nylon salt effectively.
Description of drawings
Fig. 1 is the static mixing reactor structural representation.
Embodiment
As seen from Figure 1, static mixing reactor comprises shell of reactor 1 and the inner member 2 that is arranged in the shell 1, and shell of reactor is provided with aromatic dicarboxylic aqueous acid import 3 and diamine aqueous solution import 4, one ends are reacting product outlet 5.
Embodiment 1
The 166.13Kg terephthalic acid is added in the making beating still, add the deionized water of 2 times of weight again, be heated to 100 ℃ while stirring.The 116.21Kg hexanediamine is joined in 1 times of deionized water simultaneously, under 80 ℃ of temperature condition, dissolve.Simultaneously two kinds of solution are sent into mixing tank with volume pump respectively, after enter neutralizing well, 90 ℃ of neutral temperatures of control, PH 7.1～7.2.Reactant enters crystallizer and cools off by refrigerated water, makes temperature reduce to 25 ℃, and forms crystallization.Material is put into whizzer, obtain wet nylon 6T salt 266.25Kg after the separation, yield 94.3%.284.9 ℃ of the fusing points of nylon salt, free acid content 0.15%, unhindered amina content 0.21%.
The 166.13Kg m-phthalic acid is added in the making beating still, add the deionized water of 2 times of weight again, be heated to 100 ℃ while stirring.The 116.21Kg hexanediamine is joined in 1 times of deionized water simultaneously respectively, under 80 ℃ of temperature condition, dissolve.Simultaneously two kinds of solution are sent into mixing tank with volume pump, after enter neutralizing well, 90 ℃ of neutral temperatures of control, PH 7.1～7.2.Reactant enters crystallizer and cools off by refrigerated water, makes temperature reduce to 25 ℃, and forms crystallization.Material is put into whizzer, obtain wet nylon 6I salt 263.14Kg after the separation, yield 93.2%.265.2 ℃ of the fusing points of nylon salt, free acid content 0.17%, unhindered amina content 0.19%.
Embodiment 3
The mixing acid of 166.13Kg terephthalic acid and m-phthalic acid is added in the making beating still, add the deionized water of 2 times of weight again, be heated to 100 ℃ while stirring.The 116.21Kg hexanediamine is joined in 1 times of deionized water simultaneously respectively, under 80 ℃ of temperature condition, dissolve.Simultaneously two kinds of solution are sent into mixing tank with volume pump, after enter neutralizing well, 90 ℃ of neutral temperatures of control, PH 7.1～7.2.Reactant enters crystallizer and cools off by refrigerated water, makes temperature reduce to 25 ℃, and forms crystallization.Material is put into whizzer, obtain wet nylon 6T/6I salt 264.83Kg after the separation, yield 93.8%.281.5 ℃ of the fusing points of nylon salt, free acid content 0.10%, unhindered amina content 0.18%.
The 166.13Kg m-phthalic acid is added in the making beating still, add the deionized water of 2 times of weight again, be heated to 100 ℃ while stirring.The 4158.31Kg nonamethylene diamine is joined in 1 times of deionized water simultaneously respectively, under 80 ℃ of temperature condition, dissolve.Simultaneously two kinds of solution are sent into mixing tank with volume pump, after enter neutralizing well, 90 ℃ of neutral temperatures of control, PH 7.1～7.2.Reactant enters crystallizer and cools off by refrigerated water, makes temperature reduce to 25 ℃, and forms crystallization.Material is put into whizzer, obtain wet nylon 9 T salt 310.16Kg after the separation, yield 95.6%.273.9 ℃ of the fusing points of nylon salt, free acid content 0.20%, unhindered amina content 0.14%.
The 166.13Kg terephthalic acid is added in the making beating still, add the deionized water of 2 times of weight again, be heated to 100 ℃ while stirring.The 116.21Kg hexanediamine is joined in 1 times of deionized water simultaneously, under 80 ℃ of temperature condition, dissolve.Simultaneously two kinds of solution are sent in the neutralization reactor of band stirring with volume pump respectively, 90 ℃ of control neutral temperatures, PH 7.1～7.2, residence time 1h.Reactant cools off by refrigerated water, makes temperature reduce to 25 ℃, and forms crystallization.Material is put into whizzer, obtain wet nylon 6T salt 260.25Kg after the separation, yield 92.2%.281.9 ℃ of the fusing points of nylon salt, free acid content 0.35%, unhindered amina content 0.40%.
Claims (7)
1. the method for an improved production heat resistant nylon salt is characterized in that, comprises the steps:
(1) aromatic acid is mixed making beating with water, be heated to 60～105 ℃, standby;
(2) diamine is dissolved in the water, is heated to 60～100 ℃, standby;
(3) with two kinds of raw material hybrid reactions of step (1) and step (2), temperature of reaction is controlled at 60～95 ℃, and reaction end is pH 7.0～7.2;
(4) crystallisation by cooling under 20～40 ℃ temperature then adopts conventional method to collect the nylon wet salt or with nylon wet salt drying, can obtain the nylon salt finished product of white powder, and the molecular formula of nylon salt is:
-OOC(C
6H
4)COO
-+H
3N(CH
2)
nNH
3 +；
N=6～16 wherein.
2. method according to claim 1 is characterized in that, aromatic acid is mixed making beating with the water of 2～5 times of weight.
3. method according to claim 1 is characterized in that, diamine is dissolved in the water of 1～2 times of weight.
4. method according to claim 1 is characterized in that, with two kinds of raw materials of step (1) and step (2) according to etc. mol ratio in mixing reactor, react.
5. according to each described method of claim 1～4, it is characterized in that aromatic acid is:
Or
Or its mixing acid.
6. according to each described method of claim 1～4, it is characterized in that, diamine, molecular formula is H
2N (CH
2)
nNH
2, n=6～16 wherein.
7. method according to claim 6 is characterized in that, diamine select oneself diamines, nonamethylene diamine, decamethylene diamine, 11 carbon diamines, 12 carbon diamines, 13 carbon diamines or 14 carbon diamines.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100272007A CN100447123C (en) | 2005-06-28 | 2005-06-28 | Improved process of producing heat resistant nylon salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100272007A CN100447123C (en) | 2005-06-28 | 2005-06-28 | Improved process of producing heat resistant nylon salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1887841A true CN1887841A (en) | 2007-01-03 |
| CN100447123C CN100447123C (en) | 2008-12-31 |
Family
ID=37577122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100272007A Active CN100447123C (en) | 2005-06-28 | 2005-06-28 | Improved process of producing heat resistant nylon salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100447123C (en) |
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 |
| CN103724209A (en) * | 2014-01-16 | 2014-04-16 | 郑州大学 | Preparation method of long-carbon-chain semi-aromatic nylon salt |
| CN104530421A (en) * | 2015-01-05 | 2015-04-22 | 无锡殷达尼龙有限公司 | Semi-aromatic polyamide preparation method |
| 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 |
| CN113461537A (en) * | 2021-06-30 | 2021-10-01 | 江苏扬农化工集团有限公司 | Method for continuously synthesizing nylon salt solution by using microchannel reactor |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH684756A5 (en) * | 1992-12-24 | 1994-12-15 | Inventa Ag | Molding of transparent copolyamides. |
| CN100406495C (en) * | 2003-08-07 | 2008-07-30 | 上海杰事杰新材料股份有限公司 | Process for producing long carbon chain nylon salt |
-
2005
- 2005-06-28 CN CNB2005100272007A patent/CN100447123C/en active Active
Cited By (7)
| 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 |
| CN103724209A (en) * | 2014-01-16 | 2014-04-16 | 郑州大学 | Preparation method of long-carbon-chain semi-aromatic nylon salt |
| 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 |
| CN104530421A (en) * | 2015-01-05 | 2015-04-22 | 无锡殷达尼龙有限公司 | Semi-aromatic polyamide preparation method |
| CN113461537A (en) * | 2021-06-30 | 2021-10-01 | 江苏扬农化工集团有限公司 | Method for continuously synthesizing nylon salt solution by using microchannel reactor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100447123C (en) | 2008-12-31 |
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