CN101760012A - Method for preparing high-ductility nylon in-situ alloy - Google Patents
Method for preparing high-ductility nylon in-situ alloy Download PDFInfo
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- CN101760012A CN101760012A CN200810207969A CN200810207969A CN101760012A CN 101760012 A CN101760012 A CN 101760012A CN 200810207969 A CN200810207969 A CN 200810207969A CN 200810207969 A CN200810207969 A CN 200810207969A CN 101760012 A CN101760012 A CN 101760012A
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Abstract
The invention relates to a method for preparing high-ductility nylon in-situ alloy. The high-ductility nylon in-situ alloy is prepared by cyclic lactam monomers which are polymerized under the existence of polytetrahydrofuran. The preparation method is that a screw extruder is used to extrude the mixture obtained after the reaction of the cyclic lactam monomers, the polytetrahydrofuran, anion initiator and cocatalyst. Compared with the prior art, the invention has the advantages the compatibility between nylon and the ductility-enhancing polytetrahydrofuran is good, the ductility enhancing effect is obvious, the polymerization and the ductility enhancement are conducted simultaneously during preparation and the mass production can be realized.
Description
Technical field
The present invention relates to the preparation method of macromolecular material, relate in particular to a kind of preparation method of high-ductility nylon in-situ alloy.
Background technology
Nylon is the engineering plastics of a class partially crystalline, have excellent comprehensive performances such as higher physical strength, thermotolerance, good wear-resisting and self lubricity, good barrier and chemical proofing, be widely used in fields such as automobile, machinofacture and electronic apparatus.But pure nylon has significant disadvantages, and is big as water-intake rate, and made product size stability is bad, often causes the mechanical engagement deviation, and wearing and tearing increase the weight of; Relatively more responsive to breach, requiring the occasion of HI high impact, the use of nylon products usually is restricted.Therefore, the important component part of the toughening modifying of nylon research becoming modified nylon.
Method at the toughening nylon modification mainly is to come tenacity increased nylon with rubber and thermoplastic elastomer at present, and rubber mainly contains terpolymer EP rubber (EPDM), nitrile rubber, styrene-butadiene rubber(SBR) etc.; Thermoplastic elastomer mainly contains styrene-butadiene-styrene multipolymer (SBS), SIS/SEBS (SEBS), ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid (EAA) multipolymer etc.Because the consistency of these components and nylon matrix is poor, often needs rubber or elastomerics are carried out functional modification.Dupont company has at first developed Zytel ST series, adopts grafting maleic anhydride with ethylene propylene terpolymer (EPDM-MA) tenacity increased nylon, has prepared the nylon alloy of resistance to low temperature excellence.U.S. Pat 4,174,358 have reported that also a kind of usefulness contains the method for the rubber of reactive group (as EPDM-MA, EPDM-AA etc.) tenacity increased nylon.European patent EP 348,000 has been reported the method with grafting maleic anhydride with ethylene propylene terpolymer and styrene-maleic anhydride copolymer while toughened Nylon 6.Chinese patent CN1,158,333 have reported with the method for nano carboxy styrene-butadiene rubber(SBR) tenacity increased nylon, nano carboxy styrene-butadiene rubber(SBR) are dispersed in the monomer of polyamide, by the toughness reinforcing nylon nano matrix material of melt polymerization process.These above-mentioned methods, though reached the purpose of toughening nylon to a certain extent, but because thermoplastic elastic body and nylon itself do not have consistency, so the dispersion of thermoplastic elastic body in nylon matrix will have influence on the effect of modification to a great extent.And use the thermoplastic elastic body tenacity increased nylon, and often required toughner addition is bigger, and this can make other performances of nylon seriously descend to a certain extent.
Summary of the invention
Purpose of the present invention is exactly in order to overcome the defective that above-mentioned prior art exists, the preparation method of the good high-ductility nylon in-situ alloy of a kind of toughner and nylon matrix consistency to be provided.
Purpose of the present invention can be achieved through the following technical solutions: a kind of preparation method of high-ductility nylon in-situ alloy, it is characterized in that, this high-ductility nylon in-situ alloy is obtained by the polymerization in the presence of polytetrahydrofuran of cyclic lactames monomer, its preparation method is the utilization screw extrusion press, cyclic lactames monomer, polytetrahydrofuran, anionic initiator and promotor one reacted extrude, comprise the steps:
A mixes raw material by following proportioning (weight part):
(A) cyclic lactames monomer 75-95 weight part,
(B) polytetrahydrofuran 5-25 weight part,
(C) anionic initiator 0.01-5 weight part,
(D) promotor 0.01-5 weight part,
(E) can comprise oxidation inhibitor, stablizer, toughner, tinting material 0-10 weight part;
B extrudes said mixture through screw extrusion press.
Described screw extrusion press comprises single screw extrusion machine, twin screw extruder or multiple screw extruder; The length-to-diameter ratio of forcing machine is in the 15-100 scope, and rotating speed is 10-600 rev/min, and controllable temperature adopts a plurality of charging openings between 30-500 ℃, and additional side is to drawing-in device, liquid quantitative feeding device, vacuum pumping hardware.
Described cyclic lactames monomer comprises one or more of butyrolactam, hexanolactam, spicy inner formyl amine, caprinolactam and laurolactam.
Described polytetrahydrofuran is a molecular weight greater than 1000 polytetrahydrofuran.
Described anionic initiator is the compound with lactan anion structure.
Described promotor is the compound that contains two above groups in acid anhydrides, acyl chlorides, the isocyanic ester, as tolylene diisocyanate, '-diphenylmethane diisocyanate, p-phthaloyl chloride, m-phthaloyl chloride or pyromellitic dianhydride etc.
The essentially consist of described high-ductility nylon in-situ alloy is: (A) cyclic lactames monomer 75-95 weight part; (B) polytetrahydrofuran 5-25 weight part; (C) anionic initiator 0.01-5 weight part; (D) promotor 0.01-5 weight part; (E) can comprise oxidation inhibitor, stablizer, toughner, tinting material 0-10 weight part.
Compare with existing toughening nylon technology, the present invention adopts the reactive extrusion technology single stage method to make the nylon in-situ alloy of high tenacity.Product nylon of the present invention and toughner polytetrahydrofuran consistency is good, toughening effect is obvious, polymerization and increase-volume are carried out simultaneously in preparation process, can realize producing in enormous quantities.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
By mass percentage, 5 parts of polytetrahydrofurans under agitation are dissolved in 95 parts of fused caprolactam monomers, 45min dewaters under vacuum, the tolylene diisocyanate that adds 0.32 part stirs 30min, together add the sodium caprolactam(ate) of mixed solution and 0.40 part in the twin screw extruder, the extruder barrel temperature is 160-280 ℃, and reinforced frequency is 5Hz, and screw speed is 75rpm.80 ℃ of vacuum-dryings of goods of extruding after 24 hours, are made the standard batten through injection moulding machine, and its mechanical property is as shown in table 1.
Embodiment 2
By mass percentage, 15 parts of polytetrahydrofurans under agitation are dissolved in 85 parts of fused butyrolactam monomers, 30min dewaters under vacuum, the p-phthaloyl chloride that adds 0.52 part stirs 48min, together add the butyrolactam sodium of mixed solution and 0.83 part in the twin screw extruder, the extruder barrel temperature is 160-280 ℃, and reinforced frequency is 3.5Hz, and screw speed is 60rpm.80 ℃ of vacuum-dryings of goods of extruding after 24 hours, are made the standard batten through injection moulding machine, and its mechanical property is as shown in table 1.
Embodiment 3
By mass percentage, 25 parts of polytetrahydrofurans under agitation are dissolved in 75 parts of fused laurolactam monomers, 60min dewaters under vacuum, the '-diphenylmethane diisocyanate that adds 1.3 parts stirs 56min, together add the laurolactam sodium of mixed solution and 2.5 parts in the single screw extrusion machine, the extruder barrel temperature is 160-280 ℃, and reinforced frequency is 3.5Hz, and screw speed is 75rpm.80 ℃ of vacuum-dryings of goods of extruding after 24 hours, are made the standard batten through injection moulding machine, and its mechanical property is as shown in table 1.
Embodiment 4
By mass percentage, 11 parts of polytetrahydrofurans under agitation are dissolved in 89 parts of fused spicy inner formyl amine monomers, 55min dewaters under vacuum, the m-phthaloyl chloride that adds 2.8 parts stirs 65min, together add the spicy inner formyl amine sodium of mixed solution and 5 parts in the three-screw extruder, the extruder barrel temperature is 160-280 ℃, and reinforced frequency is 5Hz, and screw speed is 75rpm.80 ℃ of vacuum-dryings of goods of extruding after 24 hours, are made the standard batten through injection moulding machine, and its mechanical property is as shown in table 1.
Embodiment 5
By mass percentage, 8 parts of polytetrahydrofurans under agitation are dissolved in 92 parts of fused caprinolactam monomers, 45min dewaters under vacuum, the pyromellitic dianhydride that adds 5 parts stirs 30min, together add the caprinolactam sodium of mixed solution and 3.98 parts in the twin screw extruder, the extruder barrel temperature is 160-280 ℃, and reinforced frequency is 3.5Hz, and screw speed is 60rpm.80 ℃ of vacuum-dryings of goods of extruding after 24 hours, are made the standard batten through injection moulding machine, and its mechanical property is as shown in table 1.
The mechanical property of table 1 high-ductility nylon in-situ alloy
| Embodiment | ??1 | ??2 | ??3 | ??4 | ??5 |
| Tensile strength (MPa) | ??55 | ??47 | ??28 | ??32 | ??51 |
| Elongation at break (%) | ??183 | ??284 | ??327 | ??301 | ??217 |
| Socle girder notched Izod impact strength (J/m) | ??614 | ??NB | ??NB | ??NB | ??829 |
Annotate: each performance records with the following method in the table: tensile strength, elongation at break: ASTM-D638; Notched Izod impact strength: ASTM-D256.
Wherein: NB represents under the testing standard of being given (5.5J), and the batten of being tested is not thrust.
Claims (6)
1. the preparation method of a high-ductility nylon in-situ alloy, it is characterized in that, this high-ductility nylon in-situ alloy is obtained by the polymerization in the presence of polytetrahydrofuran of cyclic lactames monomer, its preparation method is the utilization screw extrusion press, cyclic lactames monomer, polytetrahydrofuran, anionic initiator and promotor one reacted extrude, comprise the steps:
A mixes raw material by following proportioning (weight part):
(A) cyclic lactames monomer 75-95 weight part,
(B) polytetrahydrofuran 5-25 weight part,
(C) anionic initiator 0.01-5 weight part,
(D) promotor 0.01-5 weight part,
(E) can comprise oxidation inhibitor, stablizer, toughner, tinting material 0-10 weight part;
B extrudes said mixture through screw extrusion press.
2. the preparation method of high-ductility nylon in-situ alloy as claimed in claim 1 is characterized in that, described screw extrusion press comprises single screw extrusion machine, twin screw extruder or multiple screw extruder; The length-to-diameter ratio of forcing machine is in the 15-100 scope, and rotating speed is 10-600 rev/min, and controllable temperature adopts a plurality of charging openings between 30-500 ℃, and additional side is to drawing-in device, liquid quantitative feeding device, vacuum pumping hardware.
3. the preparation method of high-ductility nylon in-situ alloy as claimed in claim 1 is characterized in that, described cyclic lactames monomer comprises one or more of butyrolactam, hexanolactam, spicy inner formyl amine, caprinolactam and laurolactam.
4. the preparation method of high-ductility nylon in-situ alloy as claimed in claim 1 is characterized in that, described polytetrahydrofuran is a molecular weight greater than 1000 polytetrahydrofuran.
5. the preparation method of high-ductility nylon in-situ alloy as claimed in claim 1 is characterized in that, described anionic initiator is the compound with lactan anion structure.
6. the preparation method of high-ductility nylon in-situ alloy as claimed in claim 1, it is characterized in that, described promotor is the compound that contains two above groups in acid anhydrides, acyl chlorides, the isocyanic ester, as tolylene diisocyanate, '-diphenylmethane diisocyanate, p-phthaloyl chloride, m-phthaloyl chloride or pyromellitic dianhydride etc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810207969A CN101760012A (en) | 2008-12-26 | 2008-12-26 | Method for preparing high-ductility nylon in-situ alloy |
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| Application Number | Priority Date | Filing Date | Title |
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| CN200810207969A CN101760012A (en) | 2008-12-26 | 2008-12-26 | Method for preparing high-ductility nylon in-situ alloy |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391501A (en) * | 2011-08-08 | 2012-03-28 | 株洲时代新材料科技股份有限公司 | High-strength super-toughness casting nylon piling machine cushion and preparation method thereof |
| CN105399947A (en) * | 2015-12-16 | 2016-03-16 | 江苏科技大学 | Reactive extrusion preparation method of polyamide 6-polyether polyurethane copolymer |
| CN109851778A (en) * | 2018-12-29 | 2019-06-07 | 恒天纤维集团有限公司 | A kind of method that anionic ring-opening polymerization prepares polybutyrolactam |
| CN110591346A (en) * | 2019-09-17 | 2019-12-20 | 湖北洋田塑料制品有限公司 | High-temperature-resistant oil-modified nylon 6 composite material and preparation method thereof |
-
2008
- 2008-12-26 CN CN200810207969A patent/CN101760012A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391501A (en) * | 2011-08-08 | 2012-03-28 | 株洲时代新材料科技股份有限公司 | High-strength super-toughness casting nylon piling machine cushion and preparation method thereof |
| CN102391501B (en) * | 2011-08-08 | 2014-03-26 | 株洲时代新材料科技股份有限公司 | High-strength super-toughness casting nylon piling machine cushion and preparation method thereof |
| CN105399947A (en) * | 2015-12-16 | 2016-03-16 | 江苏科技大学 | Reactive extrusion preparation method of polyamide 6-polyether polyurethane copolymer |
| CN109851778A (en) * | 2018-12-29 | 2019-06-07 | 恒天纤维集团有限公司 | A kind of method that anionic ring-opening polymerization prepares polybutyrolactam |
| CN109851778B (en) * | 2018-12-29 | 2022-01-04 | 恒天纤维集团有限公司 | Method for preparing polybutyrolactam by anion ring-opening polymerization |
| CN110591346A (en) * | 2019-09-17 | 2019-12-20 | 湖北洋田塑料制品有限公司 | High-temperature-resistant oil-modified nylon 6 composite material and preparation method thereof |
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Open date: 20100630 |