CN105348521A - Segmented copolymer containing transparent polyamide and polyether and synthetic method of segmented copolymer - Google Patents
Segmented copolymer containing transparent polyamide and polyether and synthetic method of segmented copolymer Download PDFInfo
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Abstract
The invention discloses a segmented copolymer containing transparent polyamide and polyether and a synthetic method of the segmented copolymer. The synthetic method includes the preparation steps that aromatic diacid monomers, aliphatic diacid monomers, alicyclic diamine monomers, polyether and necessary auxiliaries are sequentially added into a high-pressure reactor according to a certain proportion, the temperature is increased to 200-220 DEG C stage by stage under the protection of protective gas after gas replacement, the temperature and pressure are kept constant for 0.5-3 h, then the temperature continues to be increased to 250-300 DEG C through heating, the pressure is controlled to be within 1.5-3 MPa, a pressure-maintaining constant-temperature reaction is performed for 1-5 h, then the gas is slowly released till normal pressure is reached within 1-3 h, then vacuumizing is performed for 0.5-3 h, and after the reaction is finished, pressuring and discharging are performed. The light transmittance of the prepared copolymer is 85-95%, and the copolymer is resistant to boiling water and ethyl alcohol and has other excellent properties.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of high transparency polyamide material with and preparation method thereof.
Background technology
Polymeric amide (PA) is the general name of resin containing recurring amide radical group (-CONH-) on molecular chain, is commonly called as nylon, be the kind that kind is maximum, output maximum and purposes is the widest in five large general engineering plastic in the world.Transparent nylon is one indispensable in nylon family, and it is a kind of nylon of amorphous or crystallite, and compared with other transparent plasticss, its transparency is better than polycarbonate (PC), close to polymethylmethacrylate (PMMA).In addition, it also has the performances such as good thermostability, impact property, electrical insulating property, dimensional stability, ageing resistance and linear expansivity are little, finished product shrinking percentage is low, nontoxic, odorless, is widely used in the fields such as automobile, electric, mechanical, optics, physical culture.
Transparent nylon is succeeded in developing early than Dynamit Nobel AG (DynamitNobel) by Germany in 1966 and realizes industrialization, the country such as Japan, the U.S., Switzerland, France has also carried out research and production in succession subsequently, and the transparent nylon of existing multiple kind is researched and developed successfully and achieves industrialization at present.The domestic research about transparent nylon is less, start late, and industrialization is blank especially, complete dependence on import, and therefore exploitation has the transparent polyamide material of autonomous property right, fills the domestic gaps, has great importance to the fast development of domestic relevant industries.
The transparent nylon of prior art synthesis is mainly divided into three kinds: Semi-aromatic transparent polyamide, aromatic series transparent polyamide and aliphatics transparent polyamide, and research mainly concentrates on aliphatics transparent nylon:
Patent DE4310970 is with acyclic straight diacid and 4, and 4 '-diamino cyclohexyl-methane (PACM) is raw material, obtained transparent polyamide, and the second-order transition temperature of its PACM12 prepared is 140 DEG C, and fusing point is 248 DEG C, and recrystallization point is 180 DEG C; The second-order transition temperature of PACM10 is 149 DEG C, and fusing point is 269 DEG C, and recrystallization point is 180 DEG C.
Patent US20120142810A1 obtains transparent polyamide with alicyclic diamine, acyclic straight diamines, alicyclic diacids or acyclic straight diacid, then it is obtained injection grade transparent polyamide with hypocrystalline fatty polyamide mixing copolymerization.The transmittance of obtained transparent polyamide can reach 91%, and mist degree is less than 5%.
Patent CN103589151A obtains transparent polyamide with straight chain diamine, alicyclic diamine and di-carboxylic acid, then when add must auxiliary agent with semicrystalline polyamides blending extrusion in twin screw extruder, obtain copolymerization transparent polyamide, the transmittance of this kind of transparent polyamide is more than 90%.
Patent CN103483581A is with the diamine containing unsymmetrical structure or contain the diamine of phenyl ring and the diprotic acid synthesis amorphous polyamide salt containing ring texture, it is polymerized obtained transparent polyamide with the auxiliary agent of polymeric amide 46 salt, polyamide 66 salt, polyamide 610 salt, polyamide 1010 salt and necessity, the transmittance of this kind of transparent polyamide is about 85% again.
In above-described patent, be utilize the existence of alicyclic ring to destroy the regularity of macromolecular chain, cause the non-crystallizable or crystallite of polymeric amide and make it transparent.The transparency that these copolymerization transparent polyamides synthesized by aliphatics and alicyclic diamines and aliphatic diacid have had and low mist degree, but after alcohol immersion, mist degree can increase, and water-intake rate is also higher.Transparent polyamide such as containing PACM has crystallite characteristic, can improve some performances of transparent amorphous polyamides, as: solvent resistance or stress cracking.But it absorbs the water of 3.5wt% at 23 DEG C under saturation conditions; Transparent polyamide containing MACM absorbs the water of 3wt% at 23 DEG C under saturation conditions, illustrates that this transparent polyamide makes it not carry out steam sterilizing.Reduce the water-intake rate of this type of transparent polyamide, the performance improving its not resistance to alcoholic solvent, to its use range of expansion, extends its work-ing life and has great importance.
Because of the introducing of phenyl ring or alicyclic ring, the toughness of transparent polyamide can decline relatively, and patent US480796, US5280087 etc. introduce PTMG segment on transparent polyamide chain, and its toughness is improved, but its transparency is not enough; Patent CN1696177A, CN1708538A etc. also introduce the glycols polyether units such as PTMG on transparent polyamide chain, but in the present invention other polyethers for relate to wherein; Patent US20120142810A, CN1303589151A etc. by transparent polyamide with containing semicrystalline polyamides copolymerization or the good transparent nylon of blended preparation toughness, but toughness improve and not obvious.
In order to reduce the water-intake rate of this type of transparent polyamide, improve the performance of its not resistance to alcoholic solvent, improve its toughness again, the present invention introduces aromatic acid and polyether segment on transparent polyamide chain simultaneously simultaneously, and synthesis contains the transparent copolymer of transparent polyamide and polyether block.The introducing of aromatic ring, decreases the hydrogen bond that in amorphous phase, amide group and water molecules are formed, hinders water molecules and penetrate between polyamide molecule, thus reduce its water-intake rate, also improves the performance of its not resistance to alcoholic solvent simultaneously; The introducing of polyether block, its toughness is improved.
Summary of the invention
The present invention aims to provide that a kind of transparency is high, the transparent copolymer of excellent combination property and synthetic method thereof.
Contain a synthetic method for transparent polyamide and polyether block copolymer, it is characterized in that, comprise the following steps:
Aromatic dicarboxylic acid mono, binary aliphatic acid mono, cycloalphatic diamine monomer, polyethers and required auxiliary agent are joined in autoclave by a certain percentage successively, under the protection of shielding gas, 200 ~ 220 DEG C are warming up to stage by stage after substitution gas, constant temperature and pressure reaction 0.5 ~ 3 hour, then continue to be heated to 250 ~ 300 DEG C, control pressure is at 1.5 ~ 3MPa, pressurize isothermal reaction is after 1 ~ 5 hour, slow venting, exitted in 1 ~ 3 hour to normal pressure, then vacuumize reaction 0.5 ~ 3 hour, reaction terminate, suppress, discharging; Wherein in temperature-rise period stage by stage, open 80 ~ 100 DEG C time and stir, stir speed (S.S.) is 50 ~ 70r/min, starts slow venting when pressure is at 1.5 ~ 2.5MPa.
Aromatic dicarboxylic acid mono of the present invention is one or more in m-phthalic acid, terephthalic acid and naphthalene diacid, preferred m-phthalic acid and terephthalic acid.
Binary aliphatic acid mono of the present invention is one or more in pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid, tetradecane diacid, pentadecane diacid, Thapsic acid, pentadecane dicarboxylic acid, octadecane diacid, nonadecen diacid, octadecane dicarboxylic acid, nonadecane dicarboxylic acid, preferred hexanodioic acid, sebacic acid and dodecanedioic acid.
The mol ratio of aromatic dicarboxylic acid mono of the present invention and binary aliphatic acid mono is 1: 9 ~ 9: 1.
Cycloalphatic diamine of the present invention is 4, 4 '-diamino cyclohexyl-methane (PACM), 4, 4 '-diamino cyclohexyl propane (PACP), 3, 3 '-dimethyl-4, 4 '-diamino cyclohexyl propane (MACM), 3, 3 '-diethyl-4, 4 '-diamino cyclohexyl propane (EACM), 3, 3 ', 5, 5 '-tetramethyl--4, one or more in your ketone diamines (IPD) of 4 '-diamino cyclohexyl propane (TMACM) and different fluorine, the amount of cycloalphatic diamine monomer and polyethers molar weight summation are 1.0 ~ 1.1 times of diprotic acid molar weight.
Polyethers of the present invention is one or more in polyoxyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene ether diol (PTMG), polytrimethylene ether glycol (PO3G), polyethyleneoxide diamine, polypropyleneoxide diamine, polyoxypropylene triamine, poly-tetramethylene ether diamine, content is at 5 ~ 50wt% of total copolymer weight, preferably 10 ~ 25wt%.
Auxiliary agent of the present invention comprises end-capping reagent, oxidation inhibitor, catalyzer, whitening agent, thermo-stabilizer, softening agent, releasing agent and fire retardant, wherein end-capping reagent is phenylformic acid, acetic acid, propionic acid or Tetra hydro Phthalic anhydride, preferred phenylformic acid, preferred phenylformic acid, addition is 0.01 ~ 1wt% of diprotic acid and diamine monomer total mass, preferably 0.02 ~ 0.5wt%; Oxidation inhibitor is one or more mixing in stannous octoate, dibutyl tin laurate and tin protochloride, preferred tin protochloride, and addition is 0.01 ~ 1wt% of diacid and diamine monomer total mass, preferably 0.02 ~ 0.5wt%; Catalyzer is sodium phosphate, phosphoric acid, calcium phosphate, sodium phosphite, phosphorous acid magnesium, Arizona bacilli, one or more in zinc phosphite, inferior sodium phosphate, ortho phosphorous acid magnesium, Lime Hypophosphate and ortho phosphorous acid zinc, preferred inferior sodium phosphate, addition is 0.01 ~ 0.5wt% of diacid and diamine monomer total mass, preferably 0.02 ~ 0.2wt%; The content of other each auxiliary agents is 0.01 ~ 0.5%, preferably equal 0.01 ~ 0.1wt%.
Shielding gas of the present invention is the one in nitrogen, argon gas, helium and carbonic acid gas, preferred nitrogen and carbonic acid gas.
A kind of containing transparent polyamide and polyether block copolymer, it is characterized in that, synthesized by aromatic dicarboxylic acid mono, binary aliphatic acid mono, cycloalphatic diamine monomer, polyethers and auxiliary agent; Wherein said aromatic dicarboxylic acid mono and the mol ratio of binary aliphatic acid mono are 1: 9 ~ 9: 1; Content of polyether is 5 ~ 50wt% of total copolymer weight; The amount of cycloalphatic diamine monomer and polyethers molar weight summation are 1.0 ~ 1.1 times of diprotic acid molar weight.
The transmittance of multipolymer of the present invention is 85 ~ 95%, soaks transmittance reduced rate after month in ethanol and be less than 5% under room temperature, and soak 24 hours transmittance reduced rates in boiling water and be less than 10%, saturated water absorption is less than 2.2%.
The present invention compared with prior art, has following beneficial effect:
(1) the present invention utilizes molecular design theory to introduce benzene ring structure and soft segment on transparent polyamide molecular chain, reduces the water-intake rate of transparent polyamide, improves the performance of its not resistance to alcoholic solvent, improve its toughness simultaneously.
(2) the present invention adopts " single stage method " to prepare the multipolymer of transparent polyamide and polyethers, namely adds raw material directly in reactor.This method synthesis technique is simple, decreases due to salification process, effectively shortens polymerization cycle, improve working efficiency, the use to ethanol in salification process can be reduced simultaneously, reduce cost, decrease and use alcohol solvent and the dangerous fire etc. that brings is unfavorable for the production safety factor of production.
Embodiment
Further illustrate the present invention below by embodiment, following examples are the concrete embodiment of the present invention, but embodiments of the present invention are by the restriction of following embodiment.
Embodiment 1
By m-phthalic acid, sebacic acid, 4,4 '-diamino cyclohexyl-methane (PACM), polyethyleneoxide diamine and required auxiliary agent join in autoclave by a certain percentage successively, and wherein polyethyleneoxide diamine content is the 10wt% of gross weight.With nitrogen replacement gas 6 times, then inflated with nitrogen to pressure is 0.2MPa, sealed reactor.Heat temperature raising, controls temperature rise rate, makes temperature rise to 210 DEG C stage by stage, constant temperature and pressure 1 hour, and wherein open 90 DEG C time and stir, stir speed (S.S.) is 60r/min, starts slow venting when pressure is at 1.8MPa; Then continue to be heated to 275 DEG C, control pressure is at 2.2MPa, and pressurize isothermal reaction 2 hours, slowly exits afterwards, exits to normal pressure in 2 hours, then vacuumizes 1 hour, and reaction terminates, suppresses, discharging, can obtain transparent copolymer.
Embodiment 2
By terephthalic acid, dodecanedioic acid, 4,4 '-diamino cyclohexyl-methane (PACM), polypropyleneoxide diamine and required auxiliary agent join in autoclave by a certain percentage successively, and wherein polypropyleneoxide diamine content is the 15wt% of gross weight.With nitrogen replacement gas 6 times, then inflated with nitrogen to pressure is 0.2MPa, sealed reactor.Heat temperature raising, controls temperature rise rate, makes temperature rise to 210 DEG C stage by stage, constant temperature and pressure 1 hour, and wherein open 90 DEG C time and stir, stir speed (S.S.) is 60r/min, starts slow venting when pressure is at 1.8MPa; Then continue to be heated to 275 DEG C, control pressure at 2.2MPa, pressurize isothermal reaction 2 hours, slowly exit afterwards, exitted in 2 hours to normal pressure, then vacuumize 1 hour, reaction terminates, suppresses, discharging, can obtain high transparency polymeric amide PACMT/PACM12.
Embodiment 3
By m-phthalic acid, sebacic acid, 3,3 '-dimethyl-4,4 '-diamino cyclohexyl-methane (MACM), polyoxypropylene triamine and required auxiliary agent join in autoclave by a certain percentage successively, and wherein polyoxypropylene triamine content is the 20wt% of gross weight.With nitrogen replacement gas 6 times, then inflated with nitrogen to pressure is 0.2MPa, sealed reactor.Heat temperature raising, controls temperature rise rate, makes temperature rise to 220 DEG C stage by stage, constant temperature and pressure 1 hour, and wherein open 90 DEG C time and stir, stir speed (S.S.) is 60r/min, starts slow venting when pressure is at 1.8MPa; Then continue to be heated to 275 DEG C, control pressure at 2.2MPa, pressurize isothermal reaction 2 hours, slowly exit afterwards, exitted in 2 hours to normal pressure, then vacuumize 1 hour, reaction terminates, suppresses, discharging, can obtain high transparency polymeric amide MACMI/MACM10.
Embodiment 4
By terephthalic acid, dodecanedioic acid, 3,3 '-dimethyl-4,4 '-diamino cyclohexyl-methane (MACM), poly-tetramethylene ether diamine.And required auxiliary agent joins in autoclave by a certain percentage successively, wherein poly-tetramethylene ether diamine content is the 15wt% of gross weight.With nitrogen replacement gas 6 times, then inflated with nitrogen to pressure is 0.2MPa, sealed reactor.Heat temperature raising, controls temperature rise rate, makes temperature rise to 220 DEG C stage by stage, constant temperature and pressure 1 hour, and wherein open 90 DEG C time and stir, stir speed (S.S.) is 60r/min, starts slow venting when pressure is at 1.8MPa; Then continue to be heated to 275 DEG C, control pressure at 2.2MPa, pressurize isothermal reaction 2 hours, slowly exit afterwards, exitted in 2 hours to normal pressure, then vacuumize 1 hour, reaction terminates, suppresses, discharging, can obtain high transparency polymeric amide MACMT/MACM12.
Embodiment 5
By m-phthalic acid, sebacic acid, 4,4 '-diamino cyclohexyl propane (PACP), polyoxyethylene glycol and required auxiliary agent join in autoclave by a certain percentage successively, and wherein polyethyleneglycol content is the 20wt% of gross weight.With nitrogen replacement gas 6 times, then inflated with nitrogen to pressure is 0.2MPa, sealed reactor.Heat temperature raising, controls temperature rise rate, makes temperature rise to 210 DEG C stage by stage, constant temperature and pressure 1 hour, and wherein open 90 DEG C time and stir, stir speed (S.S.) is 60r/min, starts slow venting when pressure is at 1.8MPa; Then continue to be heated to 275 DEG C, control pressure at 2.2MPa, pressurize isothermal reaction 2 hours, slowly exit afterwards, exitted in 2 hours to normal pressure, then vacuumize 1 hour, reaction terminates, suppresses, discharging, can obtain high transparency polymeric amide PACPI/PACP10.
Embodiment 6
By terephthalic acid, dodecanedioic acid, 4,4 '-diamino cyclohexyl propane (PACP), polypropylene glycol and required auxiliary agent join in autoclave by a certain percentage successively, and wherein polypropylene glycol content is the 25wt% of gross weight.With nitrogen replacement gas 6 times, then inflated with nitrogen to pressure is 0.2MPa, sealed reactor.Heat temperature raising, controls temperature rise rate, makes temperature rise to 210 DEG C stage by stage, constant temperature and pressure 1 hour, and wherein open 90 DEG C time and stir, stir speed (S.S.) is 60r/min, starts slow venting when pressure is at 1.8MPa; Then continue to be heated to 275 DEG C, control pressure at 2.2MPa, pressurize isothermal reaction 2 hours, slowly exit afterwards, exitted in 2 hours to normal pressure, then vacuumize 1 hour, reaction terminates, suppresses, discharging, can obtain high transparency polymeric amide PACPT/PACP12.
The high transparency polymeric amide performance test obtained to embodiment 1 ~ 6, the results are shown in Table 2.
Table 1 embodiment 1 ~ 6 formula table
The properties of high transparency polymeric amide prepared by table 2 embodiment 1 ~ 6
Note: transmittance 1: record without boiling water or Ethanol Treatment; Transmittance 2: soak in ethanol after 1 month and record; Transmittance 3:: soak in boiling water after 24 hours and record.
Claims (10)
1. contain a synthetic method for transparent polyamide and polyether block copolymer, it is characterized in that, comprise the following steps:
Aromatic dicarboxylic acid mono, binary aliphatic acid mono, cycloalphatic diamine monomer, polyethers and auxiliary agent are joined in autoclave successively, under the protection of shielding gas, 200 ~ 220 DEG C are warming up to stage by stage after substitution gas, constant temperature and pressure reaction 0.5 ~ 3 hour, then continue to be heated to 250 ~ 300 DEG C, control pressure is at 1.5 ~ 3MPa, pressurize isothermal reaction is after 1 ~ 5 hour, slow venting, exitted in 1 ~ 3 hour to normal pressure, then reaction is vacuumized 0.5 ~ 3 hour, after reaction terminates, to suppress, discharging; Wherein in temperature-rise period stage by stage, open 80 ~ 100 DEG C time and stir, stir speed (S.S.) is 50 ~ 70r/min, starts slow venting when pressure is at 1.5 ~ 2.5MPa.
2. a kind of synthetic method containing transparent polyamide and polyether block copolymer according to claim 1, is characterized in that, described aromatic dicarboxylic acid mono is one or more in m-phthalic acid, terephthalic acid and naphthalene diacid; Described binary aliphatic acid mono is one or more in pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid, tetradecane diacid, pentadecane diacid, Thapsic acid, pentadecane dicarboxylic acid, octadecane diacid, nonadecen diacid, octadecane dicarboxylic acid, nonadecane dicarboxylic acid; Described aromatic dicarboxylic acid mono and the mol ratio of binary aliphatic acid mono are 1: 9 ~ 9: 1.
3. a kind of synthetic method containing transparent polyamide and polyether block copolymer according to claim 1, it is characterized in that, described cycloalphatic diamine monomer is 4, 4 '-diamino cyclohexyl-methane (PACM), 4, 4 '-diamino cyclohexyl propane (PACP), 3, 3 '-dimethyl-4, 4 '-diamino cyclohexyl propane (MACM), 3, 3 '-diethyl-4, 4 '-diamino cyclohexyl propane (EACM), 3, 3 ', 5, 5 '-tetramethyl--4, one or more in your ketone diamines (IPD) of 4 '-diamino cyclohexyl propane (TMACM) and different fluorine, the amount of cycloalphatic diamine monomer and polyethers molar weight summation are 1.0 ~ 1.1 times of diprotic acid molar weight, described polyethers is one or more in polyoxyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene ether diol (PTMG), polytrimethylene ether glycol (PO3G), polyethyleneoxide diamine, polypropyleneoxide diamine, polyoxypropylene triamine, poly-tetramethylene ether diamine, and content is 5 ~ 50wt% of total copolymer weight.
4. a kind of synthetic method containing transparent polyamide and polyether block copolymer according to claim 1, it is characterized in that, described auxiliary agent comprises end-capping reagent, described end-capping reagent is phenylformic acid, acetic acid, propionic acid or Tetra hydro Phthalic anhydride, and addition is 0.01 ~ 1wt% of diprotic acid and diamine monomer total mass.
5. a kind of synthetic method containing transparent polyamide and polyether block copolymer according to claim 1, it is characterized in that, described auxiliary agent comprises oxidation inhibitor, oxidation inhibitor is one or more mixing in stannous octoate, dibutyl tin laurate and tin protochloride, and addition is 0.01 ~ 1wt% of diprotic acid and diamine monomer total mass.
6. a kind of synthetic method containing transparent polyamide and polyether block copolymer according to claim 1, it is characterized in that, described auxiliary agent comprises catalyzer, catalyzer is sodium phosphate, phosphoric acid, calcium phosphate, sodium phosphite, phosphorous acid magnesium, Arizona bacilli, one or more in zinc phosphite, inferior sodium phosphate, ortho phosphorous acid magnesium, Lime Hypophosphate and ortho phosphorous acid zinc, addition is 0.01 ~ 0.5wt% of diprotic acid and diamine monomer total mass.
7. a kind of synthetic method containing transparent polyamide and polyether block copolymer according to claim 1, it is characterized in that, described shielding gas is the one in nitrogen, argon gas, helium and carbonic acid gas.
8., containing transparent polyamide and a polyether block copolymer, it is characterized in that, synthesized by aromatic dicarboxylic acid mono, binary aliphatic acid mono, cycloalphatic diamine monomer, polyethers and auxiliary agent; Wherein said aromatic dicarboxylic acid mono and the mol ratio of binary aliphatic acid mono are 1: 9 ~ 9: 1; Content of polyether is 5 ~ 50wt% of total copolymer weight; The amount of cycloalphatic diamine monomer and polyethers molar weight summation are 1.0 ~ 1.1 times of diprotic acid molar weight.
9. one according to claim 8 contains transparent polyamide and polyether block copolymer, it is characterized in that, the transmittance of described transparent copolymer is 85 ~ 95%.
10. one according to claim 8 contains transparent polyamide and polyether block copolymer, it is characterized in that, soak transmittance reduced rate after month under described transparent copolymer room temperature in ethanol and be less than 5%, soak 24 hours transmittance reduced rates in boiling water and be less than 10%, saturated water absorption is less than 2.2%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106700064A (en) * | 2016-12-28 | 2017-05-24 | 浙江新和成特种材料有限公司 | Semi-aromatic polyamide production method and semi-aromatic polyamide |
| CN107955163A (en) * | 2016-10-17 | 2018-04-24 | 上海杰事杰新材料(集团)股份有限公司 | Ultra-toughness polyamide and preparation method thereof |
| CN109206613A (en) * | 2018-07-20 | 2019-01-15 | 沧州旭阳科技有限公司 | The purposes of the preparation method of polyamide elastomer, elastomer prepared therefrom and the elastomer |
| CN116606433A (en) * | 2023-04-28 | 2023-08-18 | 湘潭大学 | Preparation method and application of heat-resistant transparent polyether amide |
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| JPS59193923A (en) * | 1983-04-19 | 1984-11-02 | Ube Ind Ltd | Production of block polyester amide |
| CN101466772A (en) * | 2006-06-14 | 2009-06-24 | 阿肯马法国公司 | Copolymers having amide units and ether units with improved optical properties |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS59193923A (en) * | 1983-04-19 | 1984-11-02 | Ube Ind Ltd | Production of block polyester amide |
| CN101466772A (en) * | 2006-06-14 | 2009-06-24 | 阿肯马法国公司 | Copolymers having amide units and ether units with improved optical properties |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107955163A (en) * | 2016-10-17 | 2018-04-24 | 上海杰事杰新材料(集团)股份有限公司 | Ultra-toughness polyamide and preparation method thereof |
| CN106700064A (en) * | 2016-12-28 | 2017-05-24 | 浙江新和成特种材料有限公司 | Semi-aromatic polyamide production method and semi-aromatic polyamide |
| CN109206613A (en) * | 2018-07-20 | 2019-01-15 | 沧州旭阳科技有限公司 | The purposes of the preparation method of polyamide elastomer, elastomer prepared therefrom and the elastomer |
| CN116606433A (en) * | 2023-04-28 | 2023-08-18 | 湘潭大学 | Preparation method and application of heat-resistant transparent polyether amide |
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