CN1031120A - Rare-earth modification technology of polybexamethylene adipamide fibre - Google Patents
Rare-earth modification technology of polybexamethylene adipamide fibre Download PDFInfo
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- CN1031120A CN1031120A CN 87108196 CN87108196A CN1031120A CN 1031120 A CN1031120 A CN 1031120A CN 87108196 CN87108196 CN 87108196 CN 87108196 A CN87108196 A CN 87108196A CN 1031120 A CN1031120 A CN 1031120A
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- earth
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Abstract
Poly-adipoyl is diamines fiber rare-earth modification technology, be with the mixture of rare earth chloride, rare earth oxide and organic RE or single component in poly-adipoyl diamines fiber production with diamines diamines copolycondensation; Or evenly mix with poly-adipoyl, hexanedioic acid, generate polymer-modified, the poly-adipoyl of making a kind of modification through spinning, drawing-off diamines fiber again.This fiber has good dyeability, antistatic property and fire resistance, has good physical property simultaneously.The used rare earth of the present invention is the compound of element lanthanum, cerium, praseodymium, neodymium.The cost of this fiber and fibrillation are very close, but economic benefit and obvious social benefit.
Description
The invention belongs to synthetic fiber molecule modification field.
By the molecular structure decision, poly fibre has three defectives.One, because poly fibre end amido content is few, hydrogen bond is many, so dye-uptake is low, dyeing is uneven, can not criticize and dye, the dyeing rank only is 2.5 grades and the dyestuff consumption is big, dyeing expense height; Its two because poly fibre is carbon, hydrogen, the oxygen atom macromolecular compound with covalent bonds, Gu hydrophobicity strong, static is serious, sheet resistance is 10
14Europe, genus insulator; Its three because low, the limited oxygen index of its decomposition temperature is 22%, therefore belong to combustible material.
In order to address the aforementioned drawbacks, generally adopt single method to handle.As when dyeing, adopt levelling agent to help and dye; When dying long filament and filament yarn fabric, must first sample dye, marking is made in batches again or is criticized and dye in batches.Beijing Socks Factory adds rare earth chloride under certain condition in the dyestuff, makes itself and fiber complexing during dyeing.Promptly utilize the rolling action of rare earth to provide and dye seat.This method does not have the effect of polymer modification and the weight ratio that maximum complexing amount is 0.06%(rare earth and polymer); In the production (or textile dyeing, afterwards arrangement) of poly fibre, add antistatic additive, be intended to eliminate static; In textile dyeing or back arrangement, add fire retardant so that poly fibre and fabric have fire resistance.Above-mentioned any processing method all can not fundamentally be eliminated dyeing, static and the inflammable disadvantage of poly fibre simultaneously.
The objective of the invention is, a kind of rare-earth modification technology of polybexamethylene adipamide fibre is provided.This technology makes fiber and textile dyeing is even, the saving dyestuff; Have antistatic and fire resistance.Its physical index also reaches or is better than the standard of like product.
The present invention is that the compound with rare earth (lanthanum, cerium, praseodymium, neodymium) carries out physics and chemical treatment, then it is joined the polycondensation step of poly fibre Direct Spinning production line, make itself and the complexing of polyhexamethylene adipamide diamines fiber molecule, make a kind of polymer-modified.Make a kind of poly fibre of modification again through spinning, drawing-off.Or when spinning indirectly, add and make its even distribution, promptly make a kind of modification poly fibre through the spinning drawing-off again.
Its specific practice and principle are:
Mixture or single component (general designation modifier) and hexamethylene diamine, adipic acid copolycondensation with rare earth chloride, fatty acid rare earth; Or mix with polyhexamethylene adipamide, generate polymer-modified.Reaction equation is as follows:
Except that above-mentioned complex reaction, the sat linkage of generation and the oxygen atom of carbonyl also can react; Also have part not react, then there be (do not influencing under the fibrous physics index situation, can have proper proportion to exist with form of mixtures) in the form with mixture.
Facts have proved: rare earth chloride and polyhexamethylene adipamide polymer reaction exist with form complexed mostly, and fatty acid rare earth and polyhexamethylene adipamide polymer reaction exist with the covalent bond form mostly.The latter's reaction equation is as follows:
HO
OC（CH
2）
4COHN（CH
2）
6-NH
H+RE-R-COOH
→HO
OC（CH
2）
4COHN（CH
2）
6-NH〕
nOC-R-RE-H
2O
In the formula:
The RE-rare earth
R-（CH-CH）-
Poly fibre after the modification is owing to the existence of rare earth, and dying seat has increased; Again because of rare earth has " hyperchromic effect ", so even dyeing, save dyestuff.
Rare earth is the very strong material of a kind of water imbibition, so the poly fibre after the modification has increased moisture percentage and electric conductivity.
Poly fibre has anti-flammability after the rare earth chloride modification.This is that chlorine then can generate firing-difficult matter matter with combustible because generate hydrogen, oxygen, carbon monoxide etc. during the high polymer decomposes.
Rare-earth modifier can add when the polycondensation of Direct Spinning, also can be when spinning indirectly and polymer phase mix into.It adds implantation site such as accompanying drawing institute formula on the poly fibre production line.That is:
1, when salt is allocated and hexamethylene diamine, adipate feed intake simultaneously;
2, after giving reaction, before the flash distillation and give any position that can add of reaction main evaporator inlet and all can;
In pelletizing, sneak into when 3, spinning indirectly.
Adding rare-earth modifier on the polycondensation line, is to finish with injecting systems, promptly adds with existing equipment in the flow process.
The compound method of rare-earth modifier:
The present invention uses rare earth chloride, rare earth oxide and organic RE.Its compound method is respectively:
1, rare earth chloride makes its concentration at 15-40% with deionized water (or redistilled water) dissolving, and add acidic materials (as phosphoric acid lipid) control pH value at 4-6(to prevent in polycondensation, producing chain termination).
2, rare earth oxide is water insoluble, adds with solid form.Add fashionable need and carry out milled processed, requiring granularity is 10
-5～10
-6Centimetre.
3, organic RE is a liquid, can directly add, and will pH value be controlled at 3-5 with acidic materials (as phosphoric acid lipid) before adding.
When adding rare earth, must meet the following conditions:
1, adds at polycondensation step, except that the control pH value, also will satisfy the reaction time.Its reaction time accounts for the over half of total reaction time.So not only can guarantee to react but also can fully mix, it is evenly distributed.
2, when spinning indirectly, add, should guarantee to mix; During screw spinning, mix back pelletizing moisture content and should be lower than 0.04%.
3, production technology also will be done suitable adjustment, and promptly spinning temperature is answered corresponding downward modulation; The every increase by 0.05% of modifier, 1.5-2 ℃ of spinning temperature downward modulation.General spinning temperature is 280-290 ℃.
The addition of rare-earth modifier of the present invention is the 0.06%-1.2% of polymer weight, and optimum range is 0.1%-0.6%.
The present invention has carried out repeatedly lab scale, has also carried out industrial production test on the polyhexamethylene adipamide production line, and product has been carried out performance test.Its technical indicator actual measurement is as follows:
Physical index: (on average)
Fracture strength 4.2g/D
Extension at break 30.5%
Regain 5.0%
The dyeing index:
Dye-uptake (on average) 90%
3.5～4 grades of dye uniformities
The static index:
Sheet resistance 10 Europe
3.5 seconds half-life
750 volts of friction voltages
Fire-retardant index:
Limited oxygen index 26%
After flame time 3.5 seconds
Long 75 centimetres of charcoal
Advantage of the present invention and benefit are in the poly fibre production line, to add the certain proportion rare earth and can make modified fibre.This fiber has good dyeability, antistatic property and fire resistance.Has excellent physical and mechanical performance simultaneously.The cost of this fiber and fibrillation are very approaching, but economic benefit and obvious social benefit.
Description of drawings
Accompanying drawing is a process chart of the present invention
Embodiment 1
Equipment and the condition used
15 kilograms of V15 batch condensation polymerization reactor production capacity/time
The V-type composite spinning machine spins 1500 meters/minute of speed
Modifier addition 0.5%(and weight of material ratio)
Phosphoric acid fat addition 0.8%(and rare-earth modifier weight ratio)
Compound modifier is fully mixed with the material pelletizing.
Material molecular weight quite stable in the enforcement, reaction condition and common silk are produced basically identical.Current 100 kilograms of the co-spun yarns of implementing, its dyeability, antistatic property and fire resistance all reach design objective: 4 grades of dye uniformities, sheet resistance 5 * 10 Europe, limited oxygen index 26%.
Embodiment 2
Use equipment and condition
10 kilograms of Vc401 extruder production capacity/time
The Vc421 spinning machine spins 1300 meters/minute of speed
960 meters/minute tractions of Vc443 hauling machine multiple 2.7033
Rare-earth modifier addition 0.5%(and weight of material ratio)
Phosphoric acid fat addition 0.8%(and rare-earth modifier weight ratio)
Compound modifier is fully mixed with the material pelletizing.
Except that spinning temperature was reduced on request, other process conditions did not have big variation in the enforcement, production status and common spinning no significant difference.Polymer molecular weight does not have degraded, and flowability improves, and spinning is produced smoothly, strand moisture absorption increasing, color and luster is good, the back processing effect is good.The physical mechanical index of spun fiber reaches the technical indicator of common silk; Antistatic index and fire-retardant index all reach the index of embodiment 1.During implementing, this produces 500 kilograms of modified fibres.
Claims (6)
1, rare-earth modification technology of polybexamethylene adipamide fibre, it is characterized in that modifier comprises rare earth chloride, rare earth oxide and organic RE, with its mixture or single component with weight of material 0.06～1.2%, optimum range be 0.1～0.6% be expelled to the salt allotment, give reaction back flash distillation before, give and reacting to any one position that can add between evaporator inlet, be added in the pelletizing when spinning indirectly.
2, the rare-earth modification technology of narrating according to claim 1 is characterized in that the rare earth element that uses comprises the compound of lanthanum, cerium, praseodymium, neodymium.
3, the rare-earth modification technology of narrating according to claim 1 is characterized in that rare earth chloride with deionized water dissolving, concentration 15-40%, pH value 4-6, and the rare earth oxide granularity is 10
5-10
6Centimetre, organic RE is liquid, pH value 3-5, is acidic materials (as the phosphoric acid fat etc.) in order to the material of adjusting rare earth chloride, organic RE pH value.
4, the rare-earth modification technology of narrating according to claim 1, it is characterized in that the reaction time that adds rare-earth modifier when polycondensation should account for the over half of total reaction time, adding will guarantee to mix when spinning indirectly, and screw spinning mixes back pelletizing moisture should be lower than 0.04%.
5, the rare-earth modification technology of narrating according to claim 1, it is characterized in that adding the modifier production technology will adjust thereupon, promptly whenever adds 1.5-2.0 ℃ of rare-earth modifier 0.05%, spinning temperature downward modulation, and spinning temperature is advisable with 280-290 ℃.
6, the rare-earth modification technology of narrating according to claim 1 is characterized in that the work of injection rare-earth modifier on the poly fibre production line, is finished by the injecting systems in the production line
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87108196 CN1009661B (en) | 1987-12-26 | 1987-12-26 | Rare-earth modification technology of polybexamethylene adipamide fibre |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87108196 CN1009661B (en) | 1987-12-26 | 1987-12-26 | Rare-earth modification technology of polybexamethylene adipamide fibre |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1031120A true CN1031120A (en) | 1989-02-15 |
| CN1009661B CN1009661B (en) | 1990-09-19 |
Family
ID=4816401
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87108196 Expired CN1009661B (en) | 1987-12-26 | 1987-12-26 | Rare-earth modification technology of polybexamethylene adipamide fibre |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1009661B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1306079C (en) * | 2004-09-23 | 2007-03-21 | 北京大学 | Rere-earth compound modified polyurethane fibre and preparing process thereof |
-
1987
- 1987-12-26 CN CN 87108196 patent/CN1009661B/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1306079C (en) * | 2004-09-23 | 2007-03-21 | 北京大学 | Rere-earth compound modified polyurethane fibre and preparing process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1009661B (en) | 1990-09-19 |
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