CN104130404A - Chain-end modified polyamide 6 and preparation method and application thereof - Google Patents
Chain-end modified polyamide 6 and preparation method and application thereof Download PDFInfo
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- CN104130404A CN104130404A CN201410353083.2A CN201410353083A CN104130404A CN 104130404 A CN104130404 A CN 104130404A CN 201410353083 A CN201410353083 A CN 201410353083A CN 104130404 A CN104130404 A CN 104130404A
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- 0 C*C(C)(C)[N+]([N-]*C)=O Chemical compound C*C(C)(C)[N+]([N-]*C)=O 0.000 description 4
- FLPCBNNMLCZWTH-UHFFFAOYSA-N CNC(CN=C)=C Chemical compound CNC(CN=C)=C FLPCBNNMLCZWTH-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses chain-end modified polyamide 6 and a preparation method and an application thereof. The preparation method comprises the following steps: caprolactam is used as a raw material; after melt polymerization, an end modifier is added; a mixture obtained is added into a saturated calcium chloride/methanol solution to carry out a reaction so as to obtain a chain-end rigid group-modified polyamide 6 solution; a precipitation treatment is carried out by the use of a methanol aqueous solution so as to obtain chain-end rigid group-modified polyamide 6; fusion of the chain-end modified polyamide 6 is carried out through a screw extruder; after fusion, the chain-end modified polyamide 6 is extruded from a spinneret plate after passing through a metering pump and a spinning assembly; and cooling forming, stretching and coiling are successively carried out to finally obtain chain-end modified polyamide 6 fiber. Breaking strength of the fiber reaches 690-750 MPa, and young modulus reaches 4.1-4.8 MPa. Based on polyamide 6, rigid group-modified polyamide 6 is introduced to a synthesis end to form a rigid chain-end structure which is convenient for hauling and tension stiffening of a flexible molecular chain, and finally the strength-improved polyamide 6 fiber is obtained.
Description
Technical field
The present invention relates to Polymer Synthesizing and fiberizing stretching technique field, the polyamide 6 that particularly a kind of chain end is modified synthesizes and fibre manufacture.
Background technology
The degree of orientation that improves macromolecular chain by stretching action is the key that improves fibre property.Normal fat polyamide fiber as tynex be flexible chain structure, molecular chain be difficult for orientation, so the actual value of mechanical property and theoretical value have a long way to go.Aromatic polyamide fibre has rigid structure, and molecular chain is easily orientated, and is successfully to realize one of industrialized high-performance fiber kind, in national defence, field of aerospace and daily life, there is very important purposes, but its production requirement is high, processing condition harshness, cost is high.
Conventional synthon high performance is current fashion trend.For the raising of conventional synthon performance, can realize by improving the modes such as molecular weight, change spinning mode, raising draw ratio, particle enhancing, wherein, making macromolecular chain have orientation by stretching is the main path that realizes fiber high performance.But due to factors such as the entanglement of the intermolecular interaction of tynex and melt-spinning molecular chain, hindered the stretch orientation of fiber, current solution is to adopt as raising tensile fiber multiples such as the solvent spinning stretching methods of high temperature lower area stretching method, gel spinning super drawing method, shielding hydrogen bond.But above-mentioned drawing process, in actually operating, need to be prepared the polymer of ultra-high molecular weight, or will change existing conventional spinning technique and equipment, therefore, the progress of not making a breakthrough property also up to now, has affected the high performance of tynex.
Summary of the invention
The present invention is directed to the limitation that prior art exists aspect fiber polymer chain stretch orientation method, provide one can effectively change molecule chain end structure, obtain having modified polyamide 6, the preparation method of enhanced drawing effect, and taking it as raw material, be applied to the functional daiamid-6 fiber of preparation.
The technical scheme that realizes the object of the invention is to provide the terminal modified polyamide 6 of a kind of chain, and its structure is:
；
Wherein, X
1and X
2for functional group or the molecular chain with functional group, X
1with X
2identical or different; Ar
1and Ar
2for phenyl ring, condensed ring or heterocycle, Ar
1identical or different with Ar.
In technical solution of the present invention, described functional group is the one in amino or carbonyl.Described heterocycle is thiophene ring, coughs up and encircle or pyrrole ring.
A preparation method for the terminal modified polyamide 6 of chain as above, its step is as follows:
1,, taking hexanolactam as raw material, adding mass percent is the end-capping reagent of 0～5 wt%, melt polymerization, and described end-capping reagent is diacid or diamines, and obtaining the end of the chain is the polymerization technology for polyamide 6 thing of amino or carboxyl, and the solution solvent viscosity ratio of polymkeric substance is 2.10～3.00;
2,, in the polymkeric substance obtaining in step 1, adding mass percent is end modified dose of 1～5wt%, obtains mixture; Described end modified dose for containing phenyl ring, condensed ring or heterocycle, and with the compound of functional group; Mixture is joined in saturated calcium chloride/methanol solution, obtain the solution that mass concentration is 2～8 wt %; Be fully to stir under the condition of 50～100 DEG C in temperature, reaction 10～30h, obtains the polyamide 6 solution that end of the chain rigid radical is modified;
3, the methanol aqueous solution taking mass percent as 10～80 wt % is precipitating agent, and the polyamide 6 solution that step 2 is obtained carries out precipitating processing, and precipitating thing extracts through alcohol wash, obtains the polyamide 6 that end of the chain rigid radical is modified.
Described end modified dose is aniline, benzylamine, naphthylamines, phenylformic acid, diphenyl acetic acid, naphthylacetic acid or PA.
Technical solution of the present invention also comprises the preparation method of the terminal modified daiamid-6 fiber of a kind of chain, after polyamide 6 terminal modified chain is dry, by screw extrusion press melting, after volume pump, filament spinning component, extrude from spinning jet, through cooling forming, stretching, coiling, obtain the terminal modified daiamid-6 fiber of a kind of chain again.
The preparation method's of the terminal modified daiamid-6 fiber of above-mentioned chain a preferred version is: the temperature of screw extrusion press melting is 255～275 DEG C, and total draw ratio is 5～20 times, and draft temperature is 20～150 DEG C.
The breaking tenacity of the terminal modified daiamid-6 fiber of chain that technical solution of the present invention provides is 690～750MPa, and Young's modulus is 4.1～4.8MPa.
Because the two ends of molecular chain are the important impetus in stretching, therefore, under drawing force effect, bring into play chain end draw, can make numerous and disorderly flexible molecule chain stretch in order, thereby improve mechanical property.The present invention is taking polyamide 6 as basis, and synthetic end is introduced the polyamide 6 of rigid radical, forms the stiff chain end structure of being convenient to flexible molecule chain haulage enhanced drawing effect, finally obtains the daiamid-6 fiber that intensity improves.
Compared with prior art, the beneficial effect that the present invention has is:
1, rigid radical is modified macromolecular chain end by the present invention, has the productive rate of preparation high, and environmental protection, without advantages such as catalyzer;
2, the present invention, with conventional spinning and stretching mode, obtains the high daiamid-6 fiber of molecular chain orientation degree, realizes the high performance of conventional fibre;
3, end of the chain draw not only can improve draw ratio, and can effectively weaken the obstacle of molecule chain end defect to fiber high performance.
Brief description of the drawings
Fig. 1 is that the polyamide 6 modified by naphthylamines of molecular chain two ends prepared by the embodiment of the present invention is in D2SO4
1h nuclear magnetic resonance map.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment 1
The preparation of polyamide 6: taking hexanolactam as basic raw material, taking 6-aminocaprolc acid as initiator, 260 DEG C of melt polymerizations, control vacuum tightness 600Pa, and reaction 5h, obtains the raw material polyamide 6 that relative viscosity of end-blocking is not 2.83, stand-by after extracting, being dried;
Stiff chain is terminal modified: prepare saturated calcium chloride/methanol solution, by polyamide 6 first with end modified dose of naphthylacetic acid in mass ratio (99:1) after mixing, dissolve in saturated calcium chloride methanol solution, obtain concentration and be 5% polyamide 6 solution, temperature constant magnetic stirring 10h at 50 DEG C.Then using the methanol aqueous solution of concentration 50% as precipitation agent, the above-mentioned solution of precipitating, and precipitating thing is carried out to alcohol wash extraction, this process circulation three times, last vacuum-drying; Again the above-mentioned polyamide 6 being dried and end modified dose of benzylamine are dissolved in to saturated calcium chloride/methanol solution after (99:1) mixing in mass ratio, obtain concentration and be 5% polyamide 6 solution, temperature constant magnetic stirring 10h at 50 DEG C, the same methanol aqueous solution using concentration 50% is as precipitation agent, precipitating reaction soln, and precipitating thing is carried out to alcohol wash extraction, this process circulation three times, last vacuum-drying, obtains the polyamide 6 of the different base group modifications in molecular chain two ends of relative viscosity 2.90.
The polyamide 6 of the different base group modifications in molecular chain two ends that the present embodiment obtains, its chemical structure is:
。
By dried polyamide 6, by screw extrusion press melting, melt temperature is 260 DEG C, through volume pump, filament spinning component, from the extrusion moulding of single hole spinning jet, obtains nascent fibre.
Then polyamide 6 to the different base group modifications in two ends carries out two sections of stretch processings to nascent fibre, and first paragraph at room temperature carries out cold stretching, stretches 2.5 times; Second segment carries out thermal stretch at 150 DEG C of heating jackets, stretches 3 times, obtains a kind of polyamide 6 monofilament of rigid tip base traction orientation.
This fiber carries out Mechanics Performance Testing and orientation degree test at filament stretch instrument and wide-angle x-ray diffraction respectively, and result ginseng is shown in Table 1.
Embodiment 2:
The preparation of polyamide 6: taking hexanolactam as basic raw material, hexanodioic acid is end-capping reagent, taking 6-aminocaprolc acid as initiator, 260 DEG C of melt polymerizations, control vacuum tightness 600Pa, reaction 5h, obtain the polyamide 6 of relative viscosity 2.75, carboxy blocking, stand-by after extracting, being dried;
Stiff chain is terminal modified: prepare saturated calcium chloride/methanol solution, by the polyamide 6 of above-mentioned dry carboxy blocking and end modified dose of naphthylamines in mass ratio (98:2) after mixing, dissolve in saturated calcium chloride/methanol solution, obtain concentration and be 5% polyamide 6 solution, temperature constant magnetic stirring 15h at 50 DEG C.Then using the methanol aqueous solution of concentration 50% as precipitation agent, precipitating reaction soln, and precipitating thing is carried out to alcohol wash extraction, this process circulation three times, last vacuum-drying, obtains the polyamide 6 of the identical base group modification of both-end of relative viscosity 2.78.
The polyamide 6 of the identical base group modification in molecular chain two ends that the present embodiment obtains, its chemical structure is:
。
Referring to accompanying drawing 1, it is the polyamide 6 of the identical base group modification in molecular chain two ends prepared of the present embodiment
1h nuclear magnetic resonance map (400MHz, D2SO4, ppm).In Fig. 1, chemical shift δ=3.45, corresponding to the hydrogen on the CH2 of vicinity-NH; δ=2.62, corresponding to the hydrogen on the CH2 of vicinity-CO; δ=1.65, corresponding to the hydrogen on the CH2 of vicinity-NHCH2; δ=1.36, corresponding to the hydrogen on the CH2 of vicinity-NHCH2 CH2; δ=8.92, corresponding to polyamide 6 repeated structural unit-hydrogen on NH; δ=7.55～7.98,8.60, corresponding to naphthalene ring hydrogen.As can be seen here, by the enforcement of technical solution of the present invention, successfully made the polyamide 6 with rigid tip base.
By dried polyamide 6, by screw extrusion press melting, melt temperature is 260 DEG C, through volume pump, filament spinning component, from the extrusion moulding of single hole spinning jet, obtains nascent fibre
Nascent fibre is carried out to two sections of stretch processings, and first paragraph at room temperature carries out cold stretching, stretches 3 times; Second segment carries out thermal stretch at 150 DEG C, stretches 3 times, obtains a kind of polyamide 6 monofilament of rigid tip base traction orientation.
This fiber carries out Mechanics Performance Testing and orientation degree test at filament stretch instrument and wide-angle x-ray diffraction respectively, and result is as shown in table 1.
Table 1
| Fiber sample | Draw ratio | Elongation at break/% | Breaking tenacity/MPa | Young's modulus/GPa | Orientation degree/% |
| Polyamide 6 | 5.6 | 26 | 560 | 2.62 | 61.33 |
| Embodiment 1 | 7.5 | 22 | 739 | 4.18 | 75.42 |
| Embodiment 2 | 9 | 17 | 698 | 4.46 | 82.78 |
Claims (10)
1. the terminal modified polyamide 6 of chain, is characterized in that its structure is:
；
Wherein, X
1and X
2for functional group or the molecular chain with functional group, X
1with X
2identical or different; Ar
1and Ar
2for phenyl ring, condensed ring or heterocycle, Ar
1identical or different with Ar.
2. the terminal modified polyamide 6 of a kind of chain according to claim 1, is characterized in that: described functional group is the one in amino or carbonyl.
3. the terminal modified polyamide 6 of a kind of chain according to claim 1, is characterized in that: described heterocycle is thiophene ring, coughs up and encircle or pyrrole ring.
4. a preparation method for the terminal modified polyamide 6 of chain as claimed in claim 1, is characterized in that comprising the following steps:
(1), taking hexanolactam as raw material, adding mass percent is the end-capping reagent of 0～5 wt%, melt polymerization, and described end-capping reagent is diacid or diamines, and obtaining the end of the chain is the polymerization technology for polyamide 6 thing of amino or carboxyl, and the solution solvent viscosity ratio of polymkeric substance is 2.10～3.00;
(2), in the polymkeric substance obtaining in step (1), adding mass percent is end modified dose of 1～5wt%, obtains mixture; Described end modified dose for containing phenyl ring, condensed ring or heterocycle, and with the compound of functional group; Mixture is joined in saturated calcium chloride/methanol solution, obtain the solution that mass concentration is 2～8 wt %; Be fully to stir under the condition of 50～100 DEG C in temperature, reaction 10～30h, obtains the polyamide 6 solution that end of the chain rigid radical is modified;
(3) methanol aqueous solution taking mass percent as 10～80 wt % is precipitating agent, and the polyamide 6 solution that step (2) is obtained carries out precipitating processing, and precipitating thing extracts through alcohol wash, obtains the polyamide 6 that end of the chain rigid radical is modified.
5. the preparation method of the terminal modified polyamide 6 of a kind of chain according to claim 4, is characterized in that: described functional group is the one in amino or carboxyl.
6. the preparation method of the terminal modified polyamide 6 of a kind of chain according to claim 2, is characterized in that: described heterocycle is thiophene ring, cough up ring or pyrrole ring.
7. the preparation method of the terminal modified polyamide 6 of a kind of chain according to claim 2, is characterized in that: described end modified dose is aniline, benzylamine, naphthylamines, phenylformic acid, diphenyl acetic acid, naphthylacetic acid or PA.
8. the preparation method of the terminal modified daiamid-6 fiber of a chain, it is characterized in that: after polyamide 6 terminal modified chain is dry, by screw extrusion press melting, after volume pump, filament spinning component, extrude from spinning jet, through cooling forming, stretching, coiling, obtain the terminal modified daiamid-6 fiber of a kind of chain again.
9. the preparation method of the terminal modified daiamid-6 fiber of a kind of chain according to claim 8, is characterized in that: the temperature of screw extrusion press melting is 255～275 DEG C, and total draw ratio is 5～20 times, and draft temperature is 20～150 DEG C.
10. the terminal modified daiamid-6 fiber of a kind of chain obtaining by claim 8 or 9 preparation methods, is characterized in that: the breaking tenacity of described fiber is 690～750MPa, and Young's modulus is 4.1～4.8MPa.
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|---|---|---|---|
| CN201410353083.2A CN104130404B (en) | 2014-07-23 | 2014-07-23 | The terminal modified polyamide 6 of a kind of chain, preparation method and application |
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| CN201410353083.2A CN104130404B (en) | 2014-07-23 | 2014-07-23 | The terminal modified polyamide 6 of a kind of chain, preparation method and application |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108368645A (en) * | 2015-12-23 | 2018-08-03 | 艾德凡斯化学公司 | Bi-end-blocking polyamide for high speed spinning application |
| CN112094406A (en) * | 2020-08-31 | 2020-12-18 | 聊城鲁西聚酰胺新材料科技有限公司 | Nylon 6 production process and system and product thereof |
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| US4528361A (en) * | 1983-12-19 | 1985-07-09 | Standard Oil Company (Indiana) | Copolymers of hydroxymethylbenzoic acid and lactam |
| WO2002079300A1 (en) * | 2001-03-30 | 2002-10-10 | Basf Aktiengesellschaft | Wetfast polyamide fiber with high amino end group content |
| CN101768265A (en) * | 2010-01-13 | 2010-07-07 | 苏州大学 | Modified nylon and preparation method thereof |
| CN102493016A (en) * | 2011-12-21 | 2012-06-13 | 苏州大学 | Porous superfine polyamide 6 fully-drawn yarn, preparation method thereof, and equipment thereof |
| CN102653594A (en) * | 2011-03-02 | 2012-09-05 | 骏马化纤股份有限公司 | Block type high-temperature-resistant copolyamide and preparation method thereof |
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2014
- 2014-07-23 CN CN201410353083.2A patent/CN104130404B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4528361A (en) * | 1983-12-19 | 1985-07-09 | Standard Oil Company (Indiana) | Copolymers of hydroxymethylbenzoic acid and lactam |
| WO2002079300A1 (en) * | 2001-03-30 | 2002-10-10 | Basf Aktiengesellschaft | Wetfast polyamide fiber with high amino end group content |
| CN101768265A (en) * | 2010-01-13 | 2010-07-07 | 苏州大学 | Modified nylon and preparation method thereof |
| CN102653594A (en) * | 2011-03-02 | 2012-09-05 | 骏马化纤股份有限公司 | Block type high-temperature-resistant copolyamide and preparation method thereof |
| CN102493016A (en) * | 2011-12-21 | 2012-06-13 | 苏州大学 | Porous superfine polyamide 6 fully-drawn yarn, preparation method thereof, and equipment thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108368645A (en) * | 2015-12-23 | 2018-08-03 | 艾德凡斯化学公司 | Bi-end-blocking polyamide for high speed spinning application |
| CN108368645B (en) * | 2015-12-23 | 2021-02-09 | 艾德凡斯化学公司 | Double-end-capped polyamides for high-speed spinning applications |
| CN112094406A (en) * | 2020-08-31 | 2020-12-18 | 聊城鲁西聚酰胺新材料科技有限公司 | Nylon 6 production process and system and product thereof |
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| CN104130404B (en) | 2016-11-02 |
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Effective date of registration: 20190409 Address after: 310026 Fifteenth Section of Reclamation in Linjiang Industrial Park, Xiaoshan District, Hangzhou City, Zhejiang Province Patentee after: Zhejiang Hengyi polyamide Co., Ltd. Address before: No. 8, Xiangcheng District Ji Xue Road, Suzhou, Jiangsu Patentee before: Soochow University |
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