CN101759852A - Preparation method of semi-aromatic polyamide - Google Patents
Preparation method of semi-aromatic polyamide Download PDFInfo
- Publication number
- CN101759852A CN101759852A CN200810220464A CN200810220464A CN101759852A CN 101759852 A CN101759852 A CN 101759852A CN 200810220464 A CN200810220464 A CN 200810220464A CN 200810220464 A CN200810220464 A CN 200810220464A CN 101759852 A CN101759852 A CN 101759852A
- Authority
- CN
- China
- Prior art keywords
- acid
- diamine
- reaction
- aliphatic diamine
- semi
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a preparation method of semi-aromatic polyamide. In the method, aromatic dicarboxylic acid and a recovery aliphatic diamine concentrated solution containing 4-14 carbon atoms are used for preparing the semi-aromatic polyamide, thereby reducing the waste of raw material diamine in production, reducing the production cost and simultaneously lightening the influence of environmental pollution. The semi-aromatic polyamide has higher crystallinity, inherent viscosity and heat-resistance temperature, good hue, low active terminal group content, good processing stability and no corrosion to moulds. Through a prepolymerization reaction, a prepolymer with the inherent viscosity [eta] within the range of 0.06-0.3dl/g measured in 96 percent sulfuric acid at 25 DEG C can be obtained. After a tackification reaction, the inherent viscosity [eta] of the semi-aromatic polyamide is 0.8-2.5dl/g, the melting point of the semi-aromatic polyamide is 270-330 DEG C, the content of terminal carboxyl groups is 15-80mol/t, and the content of terminal amino groups is 15-80mol/t.
Description
Technical field
What the present invention relates to is the technology of preparing of semiaromatic polyamide composition.
Background technology
Fatty polyamide, as PA6, PA66, have excellent physical strength, thermotolerance, chemical proofing, wearability and self lubricity, and frictional coefficient is low, its Application Areas comprises electronic apparatus, trolley part, furniture, building materials and fiber, has become one of most important engineering plastics.
Semiaromatic polyamide composition is diamines or dicarboxylic acid and the aliphatic dicarboxylic acid or the diamines of band aromatic nucleus, through the prepared polyamide resin of polycondensation, is a kind of in the aromatic polyamide.Owing in the polymeric amide molecular backbone chain, imported aromatic nucleus, thereby thermotolerance and mechanical property have been improved, reduced water-intake rate, and more suitable P/C ratio is arranged, be the high resin of thermotolerance between general engineering plastic nylon and thermostability engineering plastic PEEK, be mainly used in automobile and electric and electronic industry.Develop rapidly along with high-tech, its application has new breakthrough and progress, and the market requirement is in rising trend.The semiaromatic polyamide composition product mainly contains polymeric amide MXD6,6T/66,6T/6I, 6T/6I/66,6T/M-5T and 9T at present.
Patent JP57200420, JP58111829, EP1074585A1, CN1624021A disclose the preparation method of polymeric amide MXD6.In the method that is proposed, in batch reactor aromatic diamine is added drop-wise in the fused aliphatic dicarboxylic acid, the water that the system temperature that raises is simultaneously removed the condensation generation carries out polyreaction.CN1451677A has described the solid-phase tack producing method of a kind of polymeric amide MXD6, preserves polymeric amide under given conditions, even initial polymeric amide is from preparing the back to spending 20 days solid-phase tack producing or the longer time, the polymeric amide MXD6 Huang degree that makes is very low.
Because the fusing point of polyamide 6 T has exceeded its decomposition temperature, must add the 3rd monomer to reduce fusing point.Polyamide 6 T multipolymer is that the diamine components polycondensation of 6-hexanediamine composition obtains by the dicarboxylic acid component who mainly is made up of terephthalic acid and m-phthalic acid or hexanodioic acid with mainly by 1.The amide group concentration of polyamide 6 T multipolymer is higher, can cause chemical proofing, water absorption resistance, the melt-processed less stable of polymkeric substance.Add the 3rd a large amount of monomers and reduced crystallinity of polymer, also can cause thermotolerance, chemical proofing, water absorption resistance and the dimensional stability of polymkeric substance to descend.
Patent US5516882, US5981692 and US962628 have described with terephthalic acid, m-phthalic acid, 1,6-hexanodioic acid, 1,6-hexanediamine and 2-methyl isophthalic acid, 5-pentamethylene diamine are main raw material, the method for coming synthesizing polyamides 6T multipolymer by the high-temperature fusion polymerization more than 300 ℃.Patent US6140459 has described with terephthalic acid, 1, and 6-hexanediamine and another kind of aliphatic long-chain di-carboxylic acid are raw material, come synthesizing polyamides 6T multipolymer by melt polymerization.Yet when adopting the melt polymerization process semiaromatic polyamide composition, the secondary polymerization reaction temperature can surpass the fusing point of polymkeric substance, and overstand at high temperature, the DeR of various side reactions and polymkeric substance is violent, the phenomenon that causes polymkeric substance tone variation, physical strength reduction and formability to degenerate easily.
Patent US5663284 discloses a kind of method for preparing polyamide 6 T/66 polymkeric substance, earlier carry out first-stage polymerization having under the condition that water exists, temperature of reaction is lower than melting point polymer, keep pressure by make up water in autoclave when discharging, prepolymer obtains the high viscosity polymkeric substance by exhaust twin screw extruder fusion tackify.But in order to obtain satisfying the prepolymer of fusion tackify requirement, the prepolymerization temperature is near the fusing point of polymkeric substance, to improve the limiting viscosity of prepolymer.
In the prior art, patent US6133406 has proposed a kind of polymerization technique of semiaromatic polyamide composition: earlier under the condition that has water to exist, prepolymer at the synthetic low limiting viscosity of lower temperature, through the prepolymer of the higher limiting viscosity of solid-phase tack producing prepared in reaction, melt extrude the polymkeric substance that tackify obtains high limiting viscosity through twin screw more then.This route relates to prepolymerization reaction, solid-phase tack producing, fusion tackify polystep reaction, requires complicated production stage and equipment.
Among the patent US6156869, after obtaining prepolymer, can obtain polymeric amide 9T resin by long solid-phase tack producing, this technical requirements prepolymer has higher limiting viscosity.Polymeric amide 9T has higher degree of crystallinity, dimensional stability and lower water-intake rate.
In the prior art, obtain the semiaromatic polyamide composition prepolymer of higher limiting viscosity, can realize by the water that improves the prepolymerization temperature or discharge in the prepolymerization reaction system.Raising prepolymerization temperature can cause the generation of side reaction, also can improve reaction pressure, to the also corresponding raising of the requirement of equipment.The water of discharging in the reaction can vapor away unreacted diamine, and the result causes the monomeric unit ratio of prepolymer greatly different with the initial monomers ratio that joins reactor, can not guarantee the molar ratio balance of monomer di-carboxylic acid and diamine.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, a kind of new preparation method of semi-aromatic polyamide is provided.When carrying out the semiaromatic polyamide composition suitability for industrialized production, in the process of draining and blowing, have unreacted aliphatic diamine and oligopolymer and be brought into recovery system.Preparation method of the present invention is that the waste water that will contain aliphatic diamine concentrates recovery, is used to prepare semiaromatic polyamide composition as raw material.
To achieve these goals, the present invention adopts following technical scheme:
A kind of preparation method of semi-aromatic polyamide comprises that be that raw material prepares with aromatic binary carboxylic acid with the aliphatic diamine that contains 4 to 14 carbon atoms, and described aliphatic diamine is for reclaiming the aliphatic diamine concentrated solution.
In above-mentioned preparation method, the mass concentration of described recovery aliphatic diamine concentrated solution is preferably 1%～90%.
In above-mentioned preparation method, described aromatic binary carboxylic acid is preferably terephthalic acid, m-phthalic acid, 2-methyl terephthalic acid, 2,5-dichloroterephthalicacid acid, 2,6-is dioctyl phthalate, 1 how, 4-is dioctyl phthalate, 4 how, 4 '-biphenyl dicarboxylic acid or 2,2 '-biphenyl dicarboxylic acid.
In above-mentioned preparation method, the described aliphatic diamine that contains 4 to 14 carbon atoms is straight chain aliphatic diamine, side chain aliphatic diamine or cycloalphatic diamine.Described straight chain aliphatic diamine is preferably 1,4-butanediamine, 1,6-hexanediamine, 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 1,1,11-11 carbon diamines or 1,12-12 carbon diamines.Described side chain aliphatic diamine is preferably the 2-methyl isophthalic acid, 5-pentamethylene diamine, 3-methyl isophthalic acid, 5-pentamethylene diamine, 2,4-dimethyl-1,6-hexanediamine, 2,2,4-trimethylammonium-1,6-hexanediamine, 2,4,4-trimethylammonium-1,6-hexanediamine, 2-methyl isophthalic acid, 8-octamethylenediamine or 5-methyl isophthalic acid, 9-nonamethylene diamine.Described cycloalphatic diamine is preferably cyclohexane diamine, methylcyclohexane diamines or 4,4 '-diamino-dicyclohexyl methane.
In above-mentioned preparation method, described raw material carries out prepolymerization earlier, and the prepolymer that obtains prepares the semiaromatic polyamide composition of high limiting viscosity by solid-phase tack producing or fusion tackify.The synthetic of described prepolymer is raw material, deionized water, end-capping reagent, catalyzer to be joined carry out the prepolymerization reaction in the autoclave, the amount of catalyzer is 0.01～2% of a raw material weight, the amount of end-capping reagent is 0.2～10% of a feed molar number, amount of deionized water is 10～50% of a raw material, temperature of reaction is 200～280 ℃, reaction times is 1～6 hour, and reaction system pressure 1～5Mpa reaction down obtains.The reaction later stage keep-ups pressure stable by the water in the discharge system.
In above-mentioned preparation method, described catalyzer is phosphoric acid, phosphorous acid, Hypophosporous Acid, 50 or its salt or its ester; Described end-capping reagent is monocarboxylic acid or monoamine.When the amount of end-capping reagent is too high, can cause the molecular weight of polymkeric substance less than normal; The amount of end-capping reagent is crossed when hanging down, and can cause the molecular weight active end group content bigger than normal or polymkeric substance of polymkeric substance bigger than normal.
In above-mentioned preparation method, described solid-phase tack producing temperature of reaction is 220～280 ℃, and the reaction times is 3～20 hours; The reaction of fusion tackify is to carry out on the extrusion equipment of band venting port, and temperature of reaction is 290～350 ℃, and the fusion tackify reaction times is 1～8 minute.The tackify of prepolymer can be realized by solid-phase tack producing or fusion tackify.The advantage of solid-phase tack producing is that temperature of reaction is low, and DeR is few, and the polymeric amide tone, dimensional stability, the thermotolerance that obtain are better; The advantage of fusion tackify is that the reaction times is shorter.Wherein, solid-phase tack producing method preferably.
In above-mentioned preparation method, as required, can add oxidation inhibitor, lubricant, nucleator, fire retardant, tinting material, softening agent, static inhibitor; Also can strengthen by adding glass fibre, carbon fiber, mineral filler; Can also prepare polymer alloy with other polymer blending simultaneously.
Compared with prior art, the present invention has following beneficial effect:
In the prior art, oligomer residue is not fully utilized, and environment is caused very big pollution.The present invention is directed to the deficiencies in the prior art and defective, the method that is prepared semiaromatic polyamide composition by aromatic binary carboxylic acid and the recovery aliphatic diamine concentrated solution that contains 4 to 14 carbon atoms is provided.Advantage of the present invention is the waste that has reduced the raw material diamines in suitability for industrialized production, has reduced production cost, has alleviated the influence of environmental pollution simultaneously.
The semiaromatic polyamide composition of the present invention's preparation has higher degree of crystallinity, limiting viscosity and heat resisting temperature, and form and aspect are good, and active end group content is low, and good processing stability is not corroded mould.By the prepolymerization reaction, the limiting viscosity [η] that can obtain measuring in 25 ℃ 96% sulfuric acid is the prepolymer in 0.06～0.3dl/g scope.After the tackify reaction, the limiting viscosity of semiaromatic polyamide composition [η] is 0.8～2.5dl/g, and the fusing point of semiaromatic polyamide composition is 270～330 ℃; Content of carboxyl end group is 15～80mol/t; Terminal amino group content is 15～80mol/t.
Embodiment
Present invention is described for mode that will be by embodiment, but do not limit the invention.All characteristics are all measured by the following method in embodiment and reference examples.
1. limiting viscosity [η]
In 25 ℃ the vitriol oil, measure concentration and be 0.05,0.1,0.3 and the logarithm reduced viscosity η of the polymeric amide of 1g/dl
Inh
η
inh＝[ln(t
1/t
0)]/C
Wherein, η
InhExpression logarithm reduced viscosity (dl/g), t
0The flushing time (sec) of expression solvent, t
1The flushing time (sec) of expression sample solution, C represents the concentration (g/dl) of sample solution.
With η
InhData to be extrapolated to concentration be 0, with the limiting viscosity [η] that obtains sample.
2. hold amido content
With full-automatic current potential titration apparatus titration sample end amido content.Get the 0.5g polymkeric substance, add phenol 45ml and anhydrous methanol 3ml, reflux after the observation sample dissolves fully, is chilled to room temperature, with the hydrochloric acid standard solution titration end amido content of having demarcated.
3. content of carboxyl end group
With full-automatic current potential titration apparatus titration sample content of carboxyl end group.Get the 0.5g polymkeric substance, add ortho-cresol 50ml, the dissolving that refluxes is put cold back and is added 400 μ L formaldehyde solutions rapidly, with the KOH-ethanolic soln titration content of carboxyl end group of having demarcated.
4. fusing point Tm
Adopt the fusing point of Perkin Elmer DSC-6 analyser specimen, nitrogen atmosphere, flow velocity are 40mL/min.Earlier be warming up to 340 ℃ during test, keep 2min, be cooled to 50 ℃ with 10 ℃/min then, be warming up to 340 ℃ with 10 ℃/min again, endotherm peak temperature at this moment is made as fusing point Tm at 340 ℃ with 10 ℃/min.
5. degree of crystallinity
Measure crystallinity of polymer with X-ray diffraction method.The fused polymkeric substance is prepared amorphous sample with the liquid nitrogen quenching, and the X-ray diffraction peak area of amorphous sample and polymer samples is respectively S
1And S
2, calculate degree of crystallinity by following formula.
X
c＝(S
2-S
1)/S
2×100
Wherein, X
cExpression degree of crystallinity (%), S
1The X-ray diffraction peak area of expression amorphous sample, S
2The X-ray diffraction peak area of expression polymer samples.
6. tensile strength and elongation at break
With the semiaromatic polyamide composition injection moulding of preparation is the dumb-bell shape batten, according to its tensile strength of standard testing and the elongation at break of ASTM.
Embodiment 1
In the 20L autoclave pressure of being furnished with magnetic force coupling stirring, prolong, gas phase mouth, charging opening, pressure venting, add 3323g (20mol) terephthalic acid, 17230g (20mol) decamethylene diamine concentrated solution (concentration 20wt%), 73.27g (0.6mol) phenylformic acid, 6.77g (counting 0.1wt%) sodium hypophosphite, begin behind the nitrogen purging to heat up based on raw-material gross weight.Be warmed up to 220 ℃ under agitation 2 hours, reaction mixture was stirred 1 hour at 220 ℃, under agitation make the temperature of reactant be elevated to 230 ℃ then.Be reflected under the constant voltage of 230 ℃ constant temperature and 2.5MPa and proceed 2 hours, keep-up pressure constantly by removing formed water, discharging after reaction is finished is the prepolymer of 0.150dl/g thereby obtain limiting viscosity [η].Prepolymer was in 80 ℃ of following vacuum-dryings 24 hours, solid-phase tack producing 10 hours under 260 ℃ of nitrogen atmospheres then, obtain the PA10T resin, fusing point is 321 ℃, limiting viscosity [η] is 1.43dl/g, and end amido content is 37mol/t, and content of carboxyl end group is 41mol/t, tensile strength 88MPa, elongation at break 6%.The results are shown in the table 1.
Embodiment 2
Repeat embodiment 1, different is that decamethylene diamine concentrated solution concentration changes 50wt% into, Change Weight To 6892g.The results are shown in the table 1.
Embodiment 3
Repeat embodiment 1, different is that decamethylene diamine concentrated solution concentration changes 80wt% into, Change Weight To 4307.5g.The results are shown in the table 1.
Embodiment 4
Repeat embodiment 2, different is that raw material changes 2824g (17mol) terephthalic acid, 498g (3mol) m-phthalic acid and 6892g (20mol) (concentration 50wt%) decamethylene diamine concentrated solution into.The results are shown in the table 1.
Embodiment 5
Repeat embodiment 2, different is that the tackify mode changes the fusion tackify into, 330 ℃ of tackify temperature, 5 minutes tackify time.The results are shown in the table 1.
Comparative Examples 1
Repeat embodiment 2, different is to change into adding 3323g (20mol) terephthalic acid, 3446g (20mol) decamethylene diamine, 2.2L deionized water.The results are shown in the table 1.
Comparative Examples 2
Repeat embodiment 4, different is that raw material changes 2824g (17mol) terephthalic acid, 498g (3mol) m-phthalic acid and 3446g (20mol) decamethylene diamine, 2.2L deionized water into.The results are shown in the table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative Examples 1 | Comparative Examples 2 | |
| Terephthalic acid (mol%) | ??100 | ??100 | ??100 | ??85 | ??100 | ??100 | ??85 |
| M-phthalic acid (mol%) | ??15 | ??15 | |||||
| 1 (mol%) | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 |
| Prepolymer limiting viscosity [η] (dl/g) | ??0.150 | ??0.151 | ??0.158 | ??0.152 | ??0.160 | ??0.160 | ??0.160 |
| The tackify mode | Solid-phase tack producing | Solid-phase tack producing | Solid-phase tack producing | Solid-phase tack producing | The fusion tackify | Solid-phase tack producing | Solid-phase tack producing |
| Polymeric amide limiting viscosity [η] (dl/g) | ??1.43 | ??1.40 | ??1.45 | ??1.37 | ??1.40 | ??1.41 | ??1.40 |
| End amido content (mol/t) | ??37 | ??55 | ??54 | ??66 | ??42 | ??31 | ??29 |
| Content of carboxyl end group (mol/t) | ??41 | ??68 | ??63 | ??68 | ??45 | ??88 | ??93 |
| Fusing point (℃) | ??321 | ??321 | ??321 | ??294 | ??321 | ??319 | ??291 |
| Degree of crystallinity (%) | ??28 | ??26 | ??27 | ??15 | ??26 | ??24 | ??11 |
| Tensile strength (MPa) | ??88 | ??88 | ??87 | ??73 | ??88 | ??89 | ??75 |
| Elongation at break (%) | ??6 | ??6 | ??6 | ??10 | ??6 | ??9 | ??15 |
Claims (10)
1. a preparation method of semi-aromatic polyamide comprises that be that raw material prepares with aromatic binary carboxylic acid with the aliphatic diamine that contains 4 to 14 carbon atoms, and it is characterized in that: described aliphatic diamine is for reclaiming the aliphatic diamine concentrated solution.
2. method according to claim 1 is characterized in that: the mass concentration of described recovery aliphatic diamine concentrated solution is 1%～90%.
3. method according to claim 1 is characterized in that: described raw material is carried out prepolymerization earlier, and the prepolymer that obtains prepares the semiaromatic polyamide composition of high limiting viscosity by solid-phase tack producing or fusion tackify.
4. method according to claim 3 is characterized in that: the synthetic of prepolymer is raw material, deionized water, end-capping reagent and catalyzer to be joined carry out the prepolymerization reaction in the autoclave; The amount of catalyzer is 0.01～2% of a raw material weight, the amount of end-capping reagent is 0.2～10% of a feed molar number, and amount of deionized water is 10～50% of a raw material, and temperature of reaction is 200～280 ℃, reaction times is 1～6 hour, and reaction system pressure 1～5Mpa is reaction down.
5. method according to claim 4 is characterized in that: described catalyzer is phosphoric acid, phosphorous acid, Hypophosporous Acid, 50 or its salt or its ester; Described end-capping reagent is monocarboxylic acid or monoamine.
6. method according to claim 3 is characterized in that: described solid-phase tack producing temperature of reaction is 220～280 ℃, and the reaction times is 3～20 hours; The reaction of fusion tackify is to carry out on the extrusion equipment of band venting port, and temperature of reaction is 290～350 ℃, and the fusion tackify reaction times is 1～8 minute.
7. method according to claim 1, it is characterized in that: described aromatic binary carboxylic acid is terephthalic acid, m-phthalic acid, 2-methyl terephthalic acid, 2,5-dichloroterephthalicacid acid, 2,6-is dioctyl phthalate, 1 how, 4-is dioctyl phthalate, 4 how, 4 '-biphenyl dicarboxylic acid or 2,2 '-biphenyl dicarboxylic acid.
8. method according to claim 1 is characterized in that: the described aliphatic diamine that contains 4 to 14 carbon atoms is straight chain aliphatic diamine, side chain aliphatic diamine or cycloalphatic diamine.
9. method according to claim 8 is characterized in that: described straight chain aliphatic diamine is 1,4-butanediamine, 1,6-hexanediamine, 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 1,1,11-11 carbon diamines or 1,12-12 carbon diamines; Described side chain aliphatic diamine is the 2-methyl isophthalic acid, 5-pentamethylene diamine, 3-methyl isophthalic acid, 5-pentamethylene diamine, 2,4-dimethyl-1,6-hexanediamine, 2,2,4-trimethylammonium-1,6-hexanediamine, 2,4,4-trimethylammonium-1,6-hexanediamine, 2-methyl isophthalic acid, 8-octamethylenediamine or 5-methyl isophthalic acid, 9-nonamethylene diamine; Described cycloalphatic diamine is cyclohexane diamine, methylcyclohexane diamines or 4,4 '-diamino-dicyclohexyl methane.
10. method according to claim 1 is characterized in that: add one or more be mixed in oxidation inhibitor, lubricant, nucleator, fire retardant, tinting material, softening agent, static inhibitor, glass fibre, carbon fiber, mineral filler, other polymkeric substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102204648A CN101759852B (en) | 2008-12-26 | 2008-12-26 | Preparation method of semi-aromatic polyamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102204648A CN101759852B (en) | 2008-12-26 | 2008-12-26 | Preparation method of semi-aromatic polyamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101759852A true CN101759852A (en) | 2010-06-30 |
| CN101759852B CN101759852B (en) | 2012-05-30 |
Family
ID=42491246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102204648A Expired - Fee Related CN101759852B (en) | 2008-12-26 | 2008-12-26 | Preparation method of semi-aromatic polyamide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101759852B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102796368A (en) * | 2012-07-25 | 2012-11-28 | 四川大学 | Preparation method of semi-aromatic polyamide alloy |
| CN104211953A (en) * | 2014-08-05 | 2014-12-17 | 金发科技股份有限公司 | Polyamide resin and polyamide composition containing same |
| WO2014201859A1 (en) * | 2013-06-21 | 2014-12-24 | 金发科技股份有限公司 | High-fluidity pa10t polyamide resin, and polyamide composition consisting of same |
| CN103451760B (en) * | 2012-06-01 | 2016-12-14 | 上海杰事杰新材料(集团)股份有限公司 | A kind of preparation method of Half-aromatic polyamide with flame resistance fiber and products thereof |
| CN106633040A (en) * | 2016-12-12 | 2017-05-10 | 中山大学 | Polyamide as well as synthesis method and application thereof |
| CN108424641A (en) * | 2018-04-08 | 2018-08-21 | 中国科学院理化技术研究所 | A kind of semiaromatic polyamide composition and preparation method thereof of random copolymerization toughening |
| US11505649B2 (en) | 2017-09-28 | 2022-11-22 | Dupont Polymers, Inc. | Polymerization process |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL8001763A (en) * | 1980-03-26 | 1981-10-16 | Stamicarbon | PREPARATION OF POLYTETRAMETHYLENE ADIPAMIDE. |
| KR100344888B1 (en) * | 1994-08-17 | 2002-11-23 | 도레이 가부시끼가이샤 | Copolymerized polyamide and a production process/thereof |
| SG71170A1 (en) * | 1997-11-18 | 2000-03-21 | Mitsui Chemicals Inc | Process for preparing aromatic polyamides |
| DE60216854T2 (en) * | 2001-06-05 | 2007-09-06 | KURARAY CO., LTD, Kurashiki | polyamide composition |
| DE102005051400A1 (en) * | 2005-10-25 | 2007-04-26 | Basf Ag | Polyamides of meta-xylylenediamine and adipic acid having an amino end group content of less than 15 mmol / kg |
-
2008
- 2008-12-26 CN CN2008102204648A patent/CN101759852B/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103451760B (en) * | 2012-06-01 | 2016-12-14 | 上海杰事杰新材料(集团)股份有限公司 | A kind of preparation method of Half-aromatic polyamide with flame resistance fiber and products thereof |
| CN102796368A (en) * | 2012-07-25 | 2012-11-28 | 四川大学 | Preparation method of semi-aromatic polyamide alloy |
| CN102796368B (en) * | 2012-07-25 | 2014-10-15 | 四川大学 | Preparation method of semi-aromatic polyamide alloy |
| WO2014201859A1 (en) * | 2013-06-21 | 2014-12-24 | 金发科技股份有限公司 | High-fluidity pa10t polyamide resin, and polyamide composition consisting of same |
| CN104211953A (en) * | 2014-08-05 | 2014-12-17 | 金发科技股份有限公司 | Polyamide resin and polyamide composition containing same |
| CN106633040A (en) * | 2016-12-12 | 2017-05-10 | 中山大学 | Polyamide as well as synthesis method and application thereof |
| CN106633040B (en) * | 2016-12-12 | 2019-02-19 | 中山大学 | A kind of polyamide and its synthetic method and application |
| US11505649B2 (en) | 2017-09-28 | 2022-11-22 | Dupont Polymers, Inc. | Polymerization process |
| CN108424641A (en) * | 2018-04-08 | 2018-08-21 | 中国科学院理化技术研究所 | A kind of semiaromatic polyamide composition and preparation method thereof of random copolymerization toughening |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101759852B (en) | 2012-05-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101759853B (en) | Method for preparing semi-aromatic polyamide | |
| CN101492534B (en) | Process for preparing semi-aromatic polyamides | |
| CN101456949B (en) | Semi-aromatic polyamide and preparation method thereof | |
| CN101463130B (en) | Semi-aromatic polyamide and low wastewater discharge preparation thereof | |
| CN101759852B (en) | Preparation method of semi-aromatic polyamide | |
| CN101759851B (en) | Semi-aromatic polyamide and preparation method thereof | |
| CN102575100B (en) | Flame-retardant polyamide resin composition | |
| CN102803386B (en) | Polyamide resin composition and molded product | |
| CN103154087B (en) | Molded polyamide resin article | |
| CN104387581A (en) | Method for preparing semi-aromatic copolymerized polyamide resin and resin | |
| CN103642036A (en) | Polyamide resin and polyamide composition composed of same | |
| TW201130886A (en) | Copolymerized polyamide | |
| CN110218311B (en) | Flame-retardant semi-aromatic polyamide and preparation method thereof | |
| CN101503512A (en) | Semi-aromatic polyamide and preparation thereof | |
| CN113444241B (en) | Polyamide and preparation method thereof | |
| CN114716668A (en) | Semi-aromatic polyamide resin and preparation method and application thereof | |
| CN102660019B (en) | High temperature-resistant nylon/ polybutylece terephthalate (PBT)/polyethylene terephthalate (PET) copolymer, and preparation method and application thereof | |
| CN102660020B (en) | High-temperature resistant nylon/PEN/PBT/PET copolymer and preparation method thereof | |
| CN102786683B (en) | Semi-aromatic polyamide, its preparation method, its composition and its application | |
| CN102260374A (en) | Polyamide resin containing biomass group | |
| JP5321434B2 (en) | Polyamide resin composition for SMT connectors | |
| CN114685981A (en) | Application of dendritic polyamide-amine polymer as additive for improving heat resistance, hydrolysis resistance and alcoholysis resistance of polyamide composition | |
| CN103642037A (en) | Polyamide resin and polyamide composition composed of same | |
| KR102208253B1 (en) | Polyamide Resin Composition for injection molding of thin product and molded product thererof | |
| JP2013095777A (en) | Polyamide resin composition for printed board surface mounting component and printed board surface mounting component obtained by molding the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120530 Termination date: 20201226 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |