CN1253962A - Poly (ester-amide-ether) segmented copolymer and its preparation method and application - Google Patents
Poly (ester-amide-ether) segmented copolymer and its preparation method and application Download PDFInfo
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- CN1253962A CN1253962A CN 98124811 CN98124811A CN1253962A CN 1253962 A CN1253962 A CN 1253962A CN 98124811 CN98124811 CN 98124811 CN 98124811 A CN98124811 A CN 98124811A CN 1253962 A CN1253962 A CN 1253962A
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Abstract
The present invention relates to a poly (ester-amide-ether) segmented copolymer, its hard chain segment is polyester-polyamide segment and its soft chain segment is polytetramethylene ether (PTMG). The preparation method of said above-mentioned segmented copolymer is characterized by that after the ester exchange reaction is implemented and the polyester oligomer is prepared, the polyester oligomer and melt-depolymerized polyamide and polyether are melt-copolycondensated so as to obtain the invented product. Said method is simple in operation, suitable for industrial production, and the obtained product can be used as reinforcing and toughening modifier for nylon.
Description
The present invention relates to a kind of poly-(ester-amide-ether) segmented copolymer and method for making and the application in polyamide alloy.
Polyester elastomer is a kind of excellent property, and broad-spectrum thermoplastic elastomer can obtain the different elastomer material of a series of performances by changing the hard section of polyester with polyester soft segment.As far back as the initial stage eighties, people such as E Sorta have just synthesized poly-(ester-amide-ether) segmented copolymer (Polymer, Vol.21,728-732, July 1980), this author adopts the dimethyl ester that has following structure, includes polymeric amide, carry out transesterify, prepare with the polyethers melt co-polycondensation again.
The nineties, Stoyko Fakirov (Makromo1.Chem vol.193,2391-2404,1992) etc. the people in autoclave, synthesizes performed polymer with hexanolactam and hexanodioic acid earlier again, obtains polyester-polyamide-polyethers with polyether reactant again, the aforesaid method operating equipment requires high, complex process.
The objective of the invention is to overcome the shortcoming of complex process in the prior art, propose directly with nylon polymer synthetic a kind of novel poly-(ester-amide-ether) segmented copolymer and method for making thereof.
It is hard for poly-(ester-amide-ether) segmented copolymer that the present invention succeeds in developing, soft chain segment has following structure:
Hard segment wherein:
Soft chain segment:
R1=dibasic alcohol divalent radical in the formula, described dibasic alcohol is ethylene glycol or butyleneglycol, R2=low molecular polyether divalent radical, m=5～11 wherein, n=14～28, x=0～3, y=1～3.
Be polyamic acid, the acid amides section is 0～50% in the molecular fraction of the hard section of multipolymer.
Polyester elastomer is hard, the soft chain segment weight ratio is 25: 75～70: 30.
Above-mentioned polymkeric substance is when dibasic alcohol employing butyleneglycol, and polyethers adopts polytetramethylene ether (PTMG), and nylon adopts PA6, and during m=5, resulting polymers has following structure:
Hard segment wherein:
Soft chain segment:
Above-mentioned hard, soft chain segment weight ratio is 25: 75～70: 30.
The preparation method of poly-(ester-amide-ether) segmented copolymer among the present invention:
Raw material is a dimethyl terephthalate (DMT), dibasic alcohol, polyethers and transesterification catalyst and polycondensation catalyst, wherein transesterification catalyst be magnesium, manganese, calcium, etc. acetate or ethanolamines, polycondensation catalyst is the salt and the derivative thereof of organic titanate class or titanium.Synthesize and carry out step by step in the following order:
(1) in reaction vessel, adds dimethyl terephthalate (DMT) (DMT) 100 parts of (weight part) and dibasic alcohol 90～140
Part, 0.01～0.095 part of catalyzer slowly is heated to 140 ℃ under nitrogen protection, treat that DMT begins
After the fusing, begin to stir, temperature is increased to 220 ℃ gradually from 180 ℃, react 1.5～3 hours, must
To molten mass, when the quantity of methyl alcohol that steams be the Theoretical Calculation amount 80～90% the time, transesterify is finished.
(2) in above-mentioned molten mass, drop into 0-40 part nylon polymerization body, under nitrogen protection, be warming up to 245 ℃, treat the Buddhist nun
The whole fusions of dragon polymer add 0.2～1 part in 45-200 part polyethers and oxidation inhibitor, polycondensation catalyst 0.02～0.2
Part, and be warming up to 250 ℃.
(3) be decompressed to 0.1～0.5Pa aftercondensated 2～3 hours through twice, can obtain the many blocks of polyester-polyamide-polyethers
Multipolymer.
Above-mentioned polymkeric substance dissolves through chloroform, carries out purifying twice with the methyl alcohol reprecipitation again, and recording intrinsic viscosity is 1.05～1.21.
A kind of poly-(ester-amide-ether) segmented copolymer of the present invention can be used as the flexibilizer additive of nylon and nylon, ABS alloy, makes alloy toughness, tension, bending strength all increase.
The structure of above-mentioned polymkeric substance by
1H-NMR proves that its chemical shift of proton provides: hard segment in table 1:
Soft chain segment:
Chemical shift of proton in table 1. (PBT-PA6)-PTMG segmented copolymer structure
Poly-(ester-amide-ether) segmented copolymer synthetic operation of the present invention preparation is easy, and, soft chain segment hard by changing be the polymeric amide input ratio when, can obtain different acid amides section content, the product of different hard, soft section ratios.
Embodiment 1.
In 2.5 liters of reactors; drop into 434g DMT; 363g ethylene glycol and transesterification catalyst 0.2g; slowly heating under protection of nitrogen gas; stir after being warming up to DMT fusing (about 140 ℃) since 70 ℃; temperature is warming up to 180 ℃, begins to have methyl alcohol to steam, and is warming up to 220 ℃ gradually; reacted about 1.5 hours; when the methyl alcohol amount of steaming reaches 120g, add 24.6g nylon 6, under nitrogen protection; be warming up to 245 ℃; after treating the whole fusions of nylon, adding 563g molecular weight is 2000 PTMG, 10g oxidation inhibitor and 0.2g polycondensation catalyst; continue to be heated to 250 ℃; begin decompression, be decompressed to 0.1～0.5Pa aftercondensated 2～3 hours through twice, obtain hard; the soft chain segment ratio is 40: 60; the PET-PA6-PTMG (2000) that contains 10% (molar percentage) nylon 6 in the hard section, intrinsic viscosity [η]=1.21.Embodiment 2.
In 2.5 liters of reactors; drop into 455g DMT; 348g ethylene glycol and transesterification catalyst 0.2g; slowly heating under protection of nitrogen gas; stir after being warming up to DMT fusing (about 140 ℃) since 70 ℃; temperature is warming up to 180 ℃, begins to have methyl alcohol to steam, and is warming up to 220 ℃ gradually; reacted about 1.5 hours; when the methyl alcohol amount of steaming reaches 125g, add 51.3g nylon 6, under nitrogen protection; be warming up to 245 ℃; after treating the whole fusions of nylon, adding 530g molecular weight is 1000 PTMG, 10g oxidation inhibitor and 0.2g polycondensation catalyst; continue to be heated to 250 ℃; begin decompression, be decompressed to 0.1～0.5Pa aftercondensated 2～3 hours through twice, obtain hard; the soft chain segment ratio is 40: 60; the PET-PA6-PTMG (1000) that contains 20% (molar percentage) nylon 6 in the hard section, intrinsic viscosity [η]=1.15.Embodiment 3.
In 2.5 liters of reactors; drop into 537g DMT; 637g 1; 4-butyleneglycol and transesterification catalyst 0.2g; slowly heat under protection of nitrogen gas, be warming up to since 70 ℃ and stir after DMT melts (about 140 ℃), temperature is warming up to 180 ℃; begin to have methyl alcohol to steam; be warming up to 220 ℃ gradually, reacted about 1.5 hours, when the methyl alcohol amount of steaming reaches 150g; add 68.3g nylon 6; under nitrogen protection, be warming up to 245 ℃, treat the whole fusions of nylon after; adding 353g molecular weight is 1000 PTMG; 10g oxidation inhibitor and 0.2g polycondensation catalyst continue to be heated to 250 ℃, begin decompression; be decompressed to 0.1～0.5Pa aftercondensated 2～3 hours through twice; obtain hard; the soft chain segment ratio is 60: 40, contains the PBT-PA6-PTMG (1000) of 20% (molar percentage) nylon 6 in the hard section, intrinsic viscosity [η]=1.08.Embodiment 4.
In 2.5 liters of reactors; drop into 520g DMT; 654g 1; 4-butyleneglycol and transesterification catalyst 0.2g; slowly heat under protection of nitrogen gas, be warming up to since 70 ℃ and stir after DMT melts (about 140 ℃), temperature is warming up to 180 ℃; begin to have methyl alcohol to steam; be warming up to 220 ℃ gradually, reacted about 1.5 hours, when the methyl alcohol amount of steaming reaches 145g; add 87.7g nylon; under nitrogen protection, be warming up to 245 ℃, treat the whole fusions of nylon after; adding 353g molecular weight is 1000 PTMG; 10g oxidation inhibitor and 0.2g polycondensation catalyst continue to be heated to 250 ℃, begin decompression; be decompressed to 0.1～0.5Pa aftercondensated 2～3 hours through twice; obtain hard; the soft chain segment ratio is 60: 40, contains the PBT-PA6-PTMG (1000) of 25% (molar percentage) nylon 6 in the hard section, intrinsic viscosity [η]=1.05.Embodiment 5.
Adopt and make a good job of dry 85 parts of good nylon 6 in advance, the polymerisate that obtains among 15 parts of embodiment 3, the styrol copolymer of 2 parts of maleic anhydride grafts and 2 parts of oxidation inhibitor, in screw extrusion press blend extrude, granulation, be injection molded into batten after the gained blend pellet drying, its tensile break strength is 86.5Mpa, yield strength is 63.6Mpa, flexural strength is 82.7Mpa, and shock strength is 107.3J/m at 20 ℃, is 78.3J/m in the time of-20 ℃.Embodiment 6.
Adopt and make a good job of dry 70 parts of good nylon 6 in advance, (Jiization institute produces 15 parts of ABS, rubber segments content is 40%), the polymerisate that obtains among 15 parts of embodiment 4, the styrol copolymer of 2 parts of maleic anhydride grafts and 2 parts of oxidation inhibitor, in screw extrusion press blend extrude, granulation, be injection molded into batten after the gained blend pellet drying, its tensile break strength is 61.3Mpa, yield strength is 52.2Mpa, flexural strength is 68.2Mpa, and shock strength is 124.4J/m at 20 ℃, is 105.6J/m in the time of-20 ℃.
Claims (7)
1. one kind is gathered (ester-amide-ether) segmented copolymer, it is characterized in that described segmented copolymer has following structural formula:
In the formula
Be hard segment,
Be soft chain segment, R1 is the dibasic alcohol divalent radical, R2 polytetramethylene ether n=14～28, x=0～3, y=1～3.
2. poly-(ester-amide-ether) segmented copolymer according to claim 1 is characterized in that described dibasic alcohol is ethylene glycol or butyleneglycol.
3. poly-its intrinsic viscosity of (ester-amide-ether) segmented copolymer [η] according to claim 2 is 1.05～1.21.
4. poly-(ester-amide-ether) segmented copolymer according to claim 1 is characterized in that hard in the segmented copolymer, soft chain segment weight ratio is 25: 75～70: 30.
5. the method for making of poly-(ester-amide-ether) segmented copolymer according to claim 1 is characterized in that carrying out in the following order:
(1) with 100 parts of dimethyl terephthalate (DMT), 90～140 parts of oxalic acids, 0.01～0.095 part of catalyzer exists
180 ℃～220 ℃ were reacted 1.5～3 hours, and obtained molten mass.
(2) in above-mentioned molten mass, add 0-40 part nylon polymerization body, 40-200 part polyethers, 0.2-1 part oxidation inhibitor,
0.02～0.2 part of polycondensation catalyst is warming up to 250 ℃.
(3), carried out polycondensation 2～3 hours through being decompressed to 0.1～0.5Pa.
6. the method for making of poly-(ester-amide-ether) segmented copolymer according to claim 5 is characterized in that described polyethers is a polytetramethylene ether.
7. the purposes of poly-(ester-amide-ether) segmented copolymer according to claim 1 is characterized in that can be used as the toughner in nylon or the nylon-ABS alloy material.
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| CN98124811A CN1100811C (en) | 1998-11-13 | 1998-11-13 | Poly (ester-amide-ether) segmented copolymer and its preparation method and application |
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| CN98124811A CN1100811C (en) | 1998-11-13 | 1998-11-13 | Poly (ester-amide-ether) segmented copolymer and its preparation method and application |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100335526C (en) * | 2001-12-10 | 2007-09-05 | 纳幕尔杜邦公司 | Polytrimethylene ether ester and is use |
| CN101460546B (en) * | 2006-12-08 | 2012-06-27 | 阿肯马法国公司 | Polyamide, polyester and polyether block copolymer |
| CN103321038A (en) * | 2013-06-07 | 2013-09-25 | 张家港市德宝化工有限公司 | Decontamination finishing agent used for polyester fiber, and preparation method thereof |
| CN103321049A (en) * | 2013-06-07 | 2013-09-25 | 张家港市德宝化工有限公司 | Washing-resistant agent used for polyester fiber, and preparation method thereof |
| CN103321050A (en) * | 2013-06-07 | 2013-09-25 | 张家港市德宝化工有限公司 | In-bath crease-resisting agent used in polyester fiber, and preparation method thereof |
| CN103334320A (en) * | 2013-06-07 | 2013-10-02 | 张家港市德宝化工有限公司 | High-temperature leveling agent for polyester fibers and preparation method thereof |
| CN103451944A (en) * | 2013-08-22 | 2013-12-18 | 张家港市德宝化工有限公司 | Durable cationic antistatic agent for polyester fabrics and preparation method thereof |
| CN105330854A (en) * | 2015-12-07 | 2016-02-17 | 中北大学 | Polyether block semi-aromatic polyamide copolymer and synthetic method thereof |
| CN115926155A (en) * | 2022-11-11 | 2023-04-07 | 万华化学集团股份有限公司 | Double-melting-point thermoplastic elastomer and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3839245A (en) * | 1972-03-30 | 1974-10-01 | Emery Industries Inc | Poly(ether-ester-amide) antistatic compositions derived from dimr acids |
| FR2418250A1 (en) * | 1978-02-24 | 1979-09-21 | Ato Chimie | ENVELOPE IN THERMOPLASTIC POLYMER MATERIAL FOR GOLF BALLS AND GOLF BALLS CONTAINING SUCH A WRAP |
| DE3917017A1 (en) * | 1989-05-24 | 1990-11-29 | Inventa Ag | THERMOPLASTICALLY PROCESSABLE ELASTOMEROUS BLOCKCOPOLYETHERESTERETHERAMIDES, PROCESS FOR THEIR PREPARATION AND THEIR USE |
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1998
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100335526C (en) * | 2001-12-10 | 2007-09-05 | 纳幕尔杜邦公司 | Polytrimethylene ether ester and is use |
| CN101460546B (en) * | 2006-12-08 | 2012-06-27 | 阿肯马法国公司 | Polyamide, polyester and polyether block copolymer |
| CN103321049B (en) * | 2013-06-07 | 2015-08-05 | 张家港市德宝化工有限公司 | For the resistance to lotion and preparation method thereof of polyester fiber |
| CN103321049A (en) * | 2013-06-07 | 2013-09-25 | 张家港市德宝化工有限公司 | Washing-resistant agent used for polyester fiber, and preparation method thereof |
| CN103321050A (en) * | 2013-06-07 | 2013-09-25 | 张家港市德宝化工有限公司 | In-bath crease-resisting agent used in polyester fiber, and preparation method thereof |
| CN103334320A (en) * | 2013-06-07 | 2013-10-02 | 张家港市德宝化工有限公司 | High-temperature leveling agent for polyester fibers and preparation method thereof |
| CN103321050B (en) * | 2013-06-07 | 2015-04-22 | 张家港市德宝化工有限公司 | In-bath crease-resisting agent used in polyester fiber, and preparation method thereof |
| CN103321038A (en) * | 2013-06-07 | 2013-09-25 | 张家港市德宝化工有限公司 | Decontamination finishing agent used for polyester fiber, and preparation method thereof |
| CN103321038B (en) * | 2013-06-07 | 2015-08-05 | 张家港市德宝化工有限公司 | For the soil release finishing agent and preparation method thereof of polyester fiber |
| CN103451944A (en) * | 2013-08-22 | 2013-12-18 | 张家港市德宝化工有限公司 | Durable cationic antistatic agent for polyester fabrics and preparation method thereof |
| CN103451944B (en) * | 2013-08-22 | 2015-07-01 | 张家港市德宝化工有限公司 | Durable cationic antistatic agent for polyester fabrics and preparation method thereof |
| CN105330854A (en) * | 2015-12-07 | 2016-02-17 | 中北大学 | Polyether block semi-aromatic polyamide copolymer and synthetic method thereof |
| CN105330854B (en) * | 2015-12-07 | 2017-06-06 | 中北大学 | Polyether block semiaromatic polyamide composition copolymer and its synthetic method |
| CN115926155A (en) * | 2022-11-11 | 2023-04-07 | 万华化学集团股份有限公司 | Double-melting-point thermoplastic elastomer and preparation method thereof |
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| CN1100811C (en) | 2003-02-05 |
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