CN1353129A - Preparation method of copolymerized nylon 613 or 1013 - Google Patents
Preparation method of copolymerized nylon 613 or 1013 Download PDFInfo
- Publication number
- CN1353129A CN1353129A CN 01131592 CN01131592A CN1353129A CN 1353129 A CN1353129 A CN 1353129A CN 01131592 CN01131592 CN 01131592 CN 01131592 A CN01131592 A CN 01131592A CN 1353129 A CN1353129 A CN 1353129A
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- Prior art keywords
- salt
- hours
- hexanediamine
- initiator
- molecular weight
- 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
- 239000004677 Nylon Substances 0.000 title claims abstract description 16
- 229920001778 nylon Polymers 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- HCUZVMHXDRSBKX-UHFFFAOYSA-N 2-decylpropanedioic acid Chemical compound CCCCCCCCCCC(C(O)=O)C(O)=O HCUZVMHXDRSBKX-UHFFFAOYSA-N 0.000 claims description 10
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- -1 Glacial acetic acid Chemical compound 0.000 claims description 2
- 229960000583 acetic acid Drugs 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 150000007524 organic acids Chemical group 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract 2
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000005453 pelletization Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
Landscapes
- Polyamides (AREA)
Abstract
The invention relates to a process for preparing copolymer nylon 613 or 1013, which comprises dissolving hexanediamine or decanediamine and tridecanedioic acid in ethanol, stirring and mixing at 40-120 deg.C for 2-6 h, neutralizing, precipitating, filtering, washing with alcohol, drying to obtain 613 salt or 1013 salt, adding 613 salt or 1013 salt, molecular weight regulator, initiator and anti-aging agent into a polymerization reactor, or directly adding hexanediamine or decanediamine and tridecanedioic acid, molecular weight regulator, initiator and anti-aging agent into a polymerization reactor, heating to 210-290 deg.C, reacting at 0.4-2.5 MPa (gauge pressure) for 2-10 h, and then decompressing to 0-0.05 MPa (gauge pressure) for 0.5-2 h to obtain the product. The copolymer nylon 613 or 1013 prepared by the method of the invention has the performance similar to nylon 11,12,612, better flexibility, stronger solubility resistance, lower cost and strong market competitiveness, and can be widely applied to the automobile, the electrical and electronic industries and the like.
Description
Technical field
The present invention relates to the preparation method of multipolymer nylon 613 or 1013.
Background technology
Nylon 613 or 1013 excellent performances, soft, transparent, water-intake rate and water absorbability are very low, and good fluidity is processed easyly, and shrinking percentage is little, can be used for plastics, film, fiber and transition pipeline.It can substitute Ni Long11 aspect a lot, and 12,612, can be widely used in automobile, Electrical and Electronic industry etc.In industry such as automotive paints, be used as transition pipeline or flexible pipe and pneumatic or water conservancy drift stop etc., also be used for the component of sheath, electronic audio frequency and the video equipment of cable and wire, noiseless gear etc.Be used as gun stock, caisson etc. on the military project.Also be widely used in space industry.Aspect sports goods, can make skiing and nailed climbing boots and articles for use etc.At present, also there are not the development and the production of this product both at home and abroad.
Multipolymer nylon 613 or 1013, performance and Ni Long11,12,612 is approaching, and flexibility is better, dissolubility resistent is stronger, and cost is also lower, and the market competitiveness is strong.
Summary of the invention
The method that the present invention prepares multipolymer nylon 613 or 1013 is as follows:
1) hexanediamine or decamethylene diamine are dissolved in the ethanol with undecane dicarboxylic acid, 40 ℃～mixed more than 120 ℃ 2 hours～6 hours, carry out neutralization reaction, generate and to salt out, refilter, alcohol washes, dry 613 salt or 1013 salt join 613 salt or 1013 salt, molecular weight regulator, initiator, anti-aging agent in the polymeric kettle again; Perhaps directly hexanediamine or the same undecane dicarboxylic acid of decamethylene diamine, molecular weight regulator, initiator, anti-aging agent are joined in the polymeric kettle;
2) be warming up to 210 ℃～290 ℃, under 0.4MPa～2.5MPa (gauge pressure) pressure, reacted 2 hours～10 hours, be decompressed to 0 then～-0.05Mpa (gauge pressure) reaction promptly got product in 0.5 hour～2 hours.
3) each proportioning raw materials is as follows: unit is parts by weight
By 613 salt or 1013 salt 100
Initiator 2～15
Molecular weight regulator 0.01～0.5
Anti-aging agent 0.01～0.5
Wherein initiator is distilled water or deionized water.The add-on of initiator is crossed reaction at least and is not carried out; Cross at most and when reaction, consume too much energy, prolonged the reaction times simultaneously because of boiling off a large amount of water.The add-on of initiator makes a living salifiable 2～15%.
Molecular weight regulator is organic acid or organic amines such as hexanediamine, benzylamine such as Glacial acetic acid, hexanodioic acid, phenylformic acid.Its objective is in order to make chainpropagation stop the molecular weight of controlling polymers.
Anti-aging agent is DMP, 124,168,1098,1010.Its objective is in order to prevent raw material oxidized in reaction process.
The mol ratio of undecane dicarboxylic acid and hexanediamine or decamethylene diamine was the best with 1: 1;
When preparation 613 salt or 1013 salt, the alcoholic acid add-on just in time is dissolved as suitable with starting monomer, crosses monomer dissolving at least not exclusively, makes reaction insufficient, causes monomer wasted; Cross and make part salt be dissolved in uncrystallizable separating out in the ethanol at most, in filtration procedure, cause product loss.
By the nylon 613 of the present invention's preparation or 1013 performance and Ni Long11,12,612 performance index contrast sees Table 1.
Table 1 nylon 613 or 1013 and Ni Long11,12,612 performance index contrast
The preparation of specific embodiment nylon 613:
Embodiment 1:
585.33g hexanediamine, 996g undecane dicarboxylic acid and 1620g ethanolic soln were joined in the there-necked flask back flow reaction 2 hours, be cooled to room temperature and pour in the beaker crystallization into and separate out, use washing with alcohol, dry 613 salt;
1500g exsiccant 613 salt, 132g water, 5g hexanodioic acid, 4gDMP are joined in the reactor, be warming up to 230 ℃, reaction is 10 hours under 0.4MPa pressure, after the release, in gauge pressure be-0.05MPa under reaction 0.5 hour, pressurization discharging, cooling, Cast Strip, pelletizing, dry product.Every performance index of product see Table 2.
Embodiment 2～3
Change temperature of reaction, wherein the temperature of reaction of embodiment 2 is 250 ℃, and the temperature of reaction of embodiment 3 is 270 ℃, and other conditions are with embodiment 1.Every performance index of product see Table 2.
Embodiment 4～5:
Change reaction pressure, wherein the reaction pressure of embodiment 4 is 1.5Mpa, and the reaction pressure of embodiment 5 is 2.5Mpa, and other conditions are with embodiment 1.Every performance index of product see Table 2.
Embodiment 6～8:
Change the reaction times, wherein the reaction times of embodiment 6 is 8 hours, and the reaction times of embodiment 7 is 6 hours, and the reaction times of embodiment 8 is 2 hours, and other conditions are with embodiment 1.Every performance index of product see Table 2.
Embodiment 9～11:
Change the consumption of water, the water consumption of embodiment 9, embodiment 10, embodiment 11 is respectively 108g, 50g, 26g, and other conditions are with embodiment 1.Every performance index of product see Table 2.
Embodiment 12:
458.75g hexanediamine, 964.47g undecane dicarboxylic acid, 108g water, 5g hexanodioic acid, 4gDMP are joined in the reactor, be warming up to 230 ℃, reaction is 10 hours under 0.4MPa pressure, after the release be in gauge pressure-0.05MPa under the reaction 0.5 hour, the pressurization discharging, cooling, Cast Strip, pelletizing, the dry product that gets.Every performance index of product see Table 2.
The performance index of the nylon 613 that table 2: embodiment 1～12 is prepared
The preparation of nylon 1013:
| Embodiment | Proportion | Notched Izod impact strength KJ/m 2 | Tensile strength Mpa | Elongation at break % | Flexural strength MPa | Modulus in flexure MPa | Heat-drawn wire ℃ (1.82MPa) | Fusing point ℃ |
| ?1 | ?1.0555 | ?11.4 | ?51.2 | ?241.9 | ?69.1 | ?1715 | ??64.5 | ??210.2 |
| ?2 | ?1.0591 | ?10.1 | ?50.2 | ?253.8 | ?72.4 | ?1774 | ??65.2 | ??213.1 |
| ?3 | ?1.0562 | ?11.8 | ?51.3 | ?235.2 | ?71.5 | ?1798 | ??62.8 | ??209.6 |
| ?4 | ?1.0558 | ?12.10 | ?50.8 | ?247.8 | ?72.5 | ?1812 | ??63.1 | ??211.5 |
| ?5 | ?1.0572 | ?12.15 | ?52.4 | ?255.7 | ?71.8 | ?1809 | ??62.9 | ??208.8 |
| ?6 | ?1.0554 | ?10.4 | ?522 | ?245.9 | ?69.8 | ?1765 | ??63.5 | ??212.5 |
| ?7 | ?1.0561 | ?11.6 | ?51.2 | ?243.8 | ?71.4 | ?1794 | ??65.6 | ??208.9 |
| ?8 | ?1.0572 | ?10.8 | ?52.3 | ?255.2 | ?72.3 | ?1791 | ??63.8 | ??210.5 |
| ?9 | ?1.0568 | ?11.9 | ?51.8 | ?257.8 | ?70.5 | ?1822 | ??64.1 | ??212.5 |
| ?10 | ?1.0569 | ?12.1 | ?51.4 | ?238.7 | ?72.8 | ?1829 | ??65.9 | ??211.5 |
| ?11 | ?1.0590 | ?12.3 | ?52.7 | ?245.7 | ?71.2 | ?1709 | ??66.4 | ??209.2 |
| ?12 | ?1.0587 | ?11.5 | ?53.3 | ?245.3 | ?72.6 | ?1728 | ??64.9 | ??212.3 |
Embodiment 13:
678.88g decamethylene diamine, 996g undecane dicarboxylic acid and 1620g ethanolic soln were joined in the there-necked flask back flow reaction 2 hours, be cooled to room temperature and pour in the beaker crystallization into and separate out, use washing with alcohol, dry 1013 salt;
1630g exsiccant 1013 salt, 132g water, 5g hexanodioic acid, 4gDMP are joined in the reactor, be warming up to 240 ℃, reaction is 8 hours under 0.5MPa pressure, after the release in gauge pressure be-reacted 0.5 hour under the 0.05MPa, the pressurization discharging, cooling, Cast Strip, pelletizing, the dry product that gets.Every performance index of product see Table 3.
Embodiment 14～15
Change temperature of reaction, wherein the temperature of reaction of embodiment 14 is 245 ℃, and the temperature of reaction of embodiment 15 is 275 ℃, and other conditions are with embodiment 13.Every performance index of product see Table 3.
Embodiment 16～17:
Change reaction pressure, wherein the reaction pressure of embodiment 16 is 1.5Mpa, and the reaction pressure of embodiment 17 is 2.5Mpa, and other conditions are with embodiment 13.Every performance index of product see Table 3.
Embodiment 18～20:
Change the reaction times, the reaction times of embodiment 18, embodiment 19, embodiment 20 was respectively 10 hours, 6 hours, 4 hours, and other conditions are with embodiment 13.Every performance index of product see Table 3.
Embodiment 21～23:
Change the consumption of water, the water consumption of embodiment 21, embodiment 22, embodiment 23 is respectively 128g, 70g, 35g, and other conditions are with embodiment 13.Every performance index of product see Table 3.
Embodiment 24:
655.33g decamethylene diamine, 930.12g undecane dicarboxylic acid, 145g water, 5g hexanodioic acid, 4gDMP are joined in the reactor, be warming up to 240 ℃, reaction is 8 hours under 0.5MPa pressure, after the release be in gauge pressure-0.05MPa under the reaction 0.5 hour, the pressurization discharging, cooling, Cast Strip, pelletizing, the dry product that gets.Every performance index of product see Table 3.
The performance index of the nylon 1013 that table 3 embodiment 13～24 is prepared
| Embodiment | Proportion | Notched Izod impact strength KJ/m 2 | Tensile strength Mpa | Elongation at break % | Flexural strength MPa | Modulus in flexure MPa | Heat-drawn wire ℃ (1.82MPa) | Fusing point ℃ |
| 13 | 1.0238 | 14.2 | 55.8 | 335.3 | 52.7 | 1215 | 55.1 | 193.1 |
| 14 | 1.0120 | 13.8 | 56.1 | 328.5 | 53.4 | 1187 | 55.3 | 192.5 |
| 15 | 1.0157 | 14.2 | 56.9 | 373.2 | 53.8 | 1235 | 54.8 | 189.4 |
| 16 | 1.0182 | 14.6 | 55.7 | 345.1 | 51.2 | 1247 | 56.1 | 193.2 |
| 17 | 1.0135 | 15.1 | 57.2 | 381.3 | 54.1 | 1301 | 54.9 | 191.8 |
| 18 | 1.0136 | 14.7 | 56.8 | 345.3 | 54.7 | 1275 | 54.6 | 192.1 |
| 19 | 1.0130 | 15.5 | 57.1 | 326.5 | 52.4 | 1167 | 54.7 | 192.8 |
| 20 | 1.0137 | 14.8 | 55.6 | 353.2 | 57.8 | 1265 | 56.8 | 190.4 |
| 21 | 1.0132 | 15.6 | 58.7 | 365.1 | 53.2 | 1347 | 56.3 | 193.3 |
| 22 | 1.0125 | 14.4 | 56.2 | 371.3 | 53.1 | 1321 | 54.3 | 193.8 |
| 23 | 1.0133 | 14.9 | 59.4 | 375.1 | 54.2 | 1267 | 56.5 | 192.2 |
| 24 | 1.0138 | 15.2 | 58.2 | 391.3 | 55.1 | 1351 | 57.9 | 192.8 |
Claims (3)
1, multipolymer nylon 613 or 1013 preparation method is characterized in that:
1) hexanediamine or decamethylene diamine are dissolved in the ethanol with undecane dicarboxylic acid, 40 ℃～mixed more than 120 ℃ 2 hours～6 hours, carry out neutralization reaction, generate and to salt out, refilter, alcohol washes, dry 613 salt or 1013 salt join 613 salt or 1013 salt, molecular weight regulator, initiator, anti-aging agent in the polymeric kettle again; Perhaps directly hexanediamine or the same undecane dicarboxylic acid of decamethylene diamine, molecular weight regulator, initiator, anti-aging agent are joined in the polymeric kettle;
2) be warming up to 210 ℃～290 ℃, under 0.4MPa～2.5MPa (gauge pressure) pressure, reacted 2 hours～10 hours, be decompressed to 0 then～-0.05Mpa (gauge pressure) reaction promptly got product in 0.5 hour～2 hours;
3) each proportioning raw materials is as follows: unit is parts by weight
By 613 salt or 1013 salt 100
Initiator 2～15
Molecular weight regulator 0.01～0.5
Anti-aging agent 0.01～0.5.
2, method according to claim 1 is characterized in that initiator is distilled water or deionized water; Molecular weight regulator is organic acid or organic amines such as hexanediamine, benzylamine such as Glacial acetic acid, hexanodioic acid, phenylformic acid; Anti-aging agent is DMP, 124,168,1098,1010.
3, method according to claim 1 and 2 is characterized in that the mol ratio of undecane dicarboxylic acid and hexanediamine or decamethylene diamine was the best with 1: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01131592 CN1132872C (en) | 2001-11-29 | 2001-11-29 | Process for preparing copolymerized nylon 613 or 1013 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01131592 CN1132872C (en) | 2001-11-29 | 2001-11-29 | Process for preparing copolymerized nylon 613 or 1013 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1353129A true CN1353129A (en) | 2002-06-12 |
| CN1132872C CN1132872C (en) | 2003-12-31 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01131592 Expired - Fee Related CN1132872C (en) | 2001-11-29 | 2001-11-29 | Process for preparing copolymerized nylon 613 or 1013 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1132872C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100564425C (en) * | 2004-03-01 | 2009-12-02 | 山东东辰工程塑料有限公司 | Preparation process of nylon 612 |
| CN104945619A (en) * | 2015-06-29 | 2015-09-30 | 苏州荣昌复合材料有限公司 | Preparation method of modified engineering plastic |
| CN107573502A (en) * | 2017-08-09 | 2018-01-12 | 浙江理工大学 | A kind of preparation method of long carbon chain nylon 1211 |
| CN111057233A (en) * | 2019-12-29 | 2020-04-24 | 无锡殷达尼龙有限公司 | Copolymerized semi-aromatic polyamide and preparation method thereof |
-
2001
- 2001-11-29 CN CN 01131592 patent/CN1132872C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100564425C (en) * | 2004-03-01 | 2009-12-02 | 山东东辰工程塑料有限公司 | Preparation process of nylon 612 |
| CN104945619A (en) * | 2015-06-29 | 2015-09-30 | 苏州荣昌复合材料有限公司 | Preparation method of modified engineering plastic |
| CN107573502A (en) * | 2017-08-09 | 2018-01-12 | 浙江理工大学 | A kind of preparation method of long carbon chain nylon 1211 |
| CN107573502B (en) * | 2017-08-09 | 2020-05-08 | 浙江理工大学 | Preparation method of long carbon chain nylon 1211 |
| CN111057233A (en) * | 2019-12-29 | 2020-04-24 | 无锡殷达尼龙有限公司 | Copolymerized semi-aromatic polyamide and preparation method thereof |
| CN111057233B (en) * | 2019-12-29 | 2023-05-05 | 无锡殷达尼龙有限公司 | Copolymerized semi-aromatic polyamide and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1132872C (en) | 2003-12-31 |
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