CN101503512A - Semi-aromatic polyamide and preparation thereof - Google Patents
Semi-aromatic polyamide and preparation thereof Download PDFInfo
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- CN101503512A CN101503512A CNA2009100375425A CN200910037542A CN101503512A CN 101503512 A CN101503512 A CN 101503512A CN A2009100375425 A CNA2009100375425 A CN A2009100375425A CN 200910037542 A CN200910037542 A CN 200910037542A CN 101503512 A CN101503512 A CN 101503512A
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Abstract
The invention discloses semi-aromatic polyamide and a preparation method thereof. In the invention, aromatic polybasic carboxylic acid and aliphatic polybasic amine containing 4 to 14 carbon atoms are employed as raw materials to prepare the semi-aromatic polyamide, and the obtained semi-aromatic polyamide has a novel structure. In the method, semi-aromatic polyamide salt with high purity is synthesized to prepare the semi-aromatic polyamide, which avoids loss of the polybasic amine, can control mol ratio of the polybasic carboxylic acid to the polybasic amine accurately, and obtain the polyamide with high intrinsic viscosity. And monomers are purified through a salification process, which improves melting point, crystallinity and mechanical property of the semi-aromatic polyamide. A prepolymerization reaction produces a prepolymer with the intrinsic viscosity eta of 0.06-0.3dl/g determined in 96% sulfuric acid at 25 DEG C. A tackification reaction allows that the intrinsic 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 terminal carboxyl group content is 15-80mol/t, and the terminal amino group content is 15-80mol/t.
Description
Technical field
The present invention relates to 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 by the dicarboxylic acid component who mainly is made up of terephthalic acid and m-phthalic acid or hexanodioic acid and is mainly obtained by the diamine components polycondensation of 1,6-hexanediamine composition.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 ℃.It is raw material that patent US6140459 has described with terephthalic acid, 1,6-hexanediamine and another kind of aliphatic long-chain di-carboxylic acid, comes 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.
Not having with the aromatic series polycarboxylic acid in the prior art is the report that raw material prepares semiaromatic polyamide composition with the aliphatic polyamine that contains 4 to 14 carbon atoms.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, a kind of preparation method of semi-aromatic polyamide that can prepare novel texture is provided.
Another object of the present invention provides the semiaromatic polyamide composition that utilizes the novel texture that above-mentioned preparation method prepares.
To achieve these goals, the present invention adopts following technical scheme:
Preparation method of semi-aromatic polyamide of the present invention, adopting aromatic series polycarboxylic acid and the aliphatic polyamine that contains 4 to 14 carbon atoms is that raw material prepares.Be specially: in organic solvent, carry out neutralization reaction with the aromatic series polycarboxylic acid with the aliphatic polyamine that contains 4 to 14 carbon atoms earlier and obtain semiaromatic polyamide composition salt, after the centrifugation, will obtain purified semiaromatic polyamide composition salt after the throw out washing that obtain.Because selected organic solvent can dissolve aromatic series polycarboxylic acid and aliphatic polyamine, but can not dissolve semiaromatic polyamide composition salt, can separate, purify the semiaromatic polyamide composition salt that generates at an easy rate.Under the condition that has water to exist, be that raw material carries out prepolymerization then with semiaromatic polyamide composition salt, again with prepolymer further by solid-phase tack producing or fusion tackify prepared in reaction semiaromatic polyamide composition resin.
In above-mentioned preparation method, described aromatic series polycarboxylic acid is preferably trimellitic acid, trimesic acid or Pyromellitic Acid.
In above-mentioned preparation method, the described aliphatic polyamine that contains 4 to 14 carbon atoms 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, diethylenetriamine, triethylene tetramine, tetraene five amine or polyethylene polyamine.
In above-mentioned preparation method, described organic solvent is preferably N-Methyl pyrrolidone or dimethyl formamide.
In above-mentioned preparation method, the temperature of reaction of described solid-phase tack producing is 220～280 ℃, and the reaction times is 3～20 hours, carries out under nitrogen atmosphere or under the vacuum condition.Described fusion tackify is to carry out on the extrusion equipment of band venting port, and the temperature of reaction of fusion tackify is 290～350 ℃, and the fusion tackify reaction times is 1～8 minute.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, the synthetic preferred version of prepolymer is: raw material salt, deionized water, end-capping reagent and catalyzer are carried out the prepolymerization reaction; The amount of catalyzer is 0.01～2% of a raw material salt weight, and the amount of end-capping reagent is 0.2～10% of a raw material salt mole number, and amount of deionized water is 10～50% of a raw material salt; Prepolymerized temperature of reaction is 200～280 ℃, and the reaction times is 1～6 hour, reaction system pressure 1～5MPa.Catalyzer is phosphoric acid, phosphorous acid, Hypophosporous Acid, 50 or its salt or its ester.End-capping reagent is monocarboxylic acid or monoamine, wherein preferred monocarboxylic acid, because with respect to monoamine, monocarboxylic acid toxicity is little, and is not volatile, is convenient to handle.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.If the amount of deionized water that adds is very few, material will solidify in the polymeric process so, and reaction can't be carried out, and product can't be discharged in reactor; If the water yield that adds is excessive, the speed of polyreaction can reduce, the prepolymer limiting viscosity that obtains also can reduce, can't carry out the tackify reaction smoothly, and in order to improve the limiting viscosity of speed of response and prepolymer, in polymerization process, to discharge a large amount of water, will inevitably cause the serious loss of polyamine, destroy monomeric molar ratio.
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.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:
The present invention prepares semiaromatic polyamide composition by first synthesis of high purity semiaromatic polyamide composition salt, has avoided the loss of polyamine, can control the mol ratio of polycarboxylic acid and polyamine exactly, obtains the polymeric amide of high limiting viscosity.And by salification process monomer is purified, improved fusing point, degree of crystallinity and the mechanical property of semiaromatic polyamide composition.By the prepolymerization reaction, the limiting viscosity [η] that can obtain measuring in 25 ℃ 96% sulfuric acid is the prepolymer of 0.06～0.3dl/g.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 Comparative 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
2x100
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 5250g (25mol) trimellitic acid and 2579.25g (25mol) diethylenetriamine, 91.6g (0.75mol) phenylformic acid, 7.83g (counting 0.1wt%) sodium hypophosphite, 2.2L deionized water, heat up behind the nitrogen purging 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 2MPa and proceed 2 hours, keep-up pressure constantly by removing formed water, discharging after reaction is finished is the prepolymer of 0.163dl/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 trimellitic acid polyamines resin, fusing point is 350 ℃, limiting viscosity [η] is 1.45dl/g, and end amido content is 32mol/t, and content of carboxyl end group is 39mol/t, tensile strength 83MPa, elongation at break 10%.The results are shown in the table 1.
Embodiment 2
Repeat embodiment 1, different is to change trimellitic acid into trimesic acid, the results are shown in the table 1.
Embodiment 3
Repeat embodiment 1, different is that raw material changes 6350g (25mol) Pyromellitic Acid and 3655.75g (25mol) triethylene tetramine into.The results are shown in the table 1.
Comparative Examples 1
Repeat embodiment 1, different is that raw material changes 4200g (20mol) trimellitic acid and 3486.3g (30mol) hexanediamine into.The results are shown in the table 1.
Comparative Examples 2
Repeat Comparative Examples 1, it is different that different is is to change trimellitic acid into trimesic acid, the results are shown in the table 1.
Comparative Examples 3
Repeat embodiment 1, different is that raw material changes 5080g (20mol) Pyromellitic Acid and 4648.4g (40mol) hexanediamine into.The results are shown in the table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | |
| Trimellitic acid (mol%) | 100 | 200 | ||||
| Trimesic acid (mol%) | 100 | 200 | ||||
| Pyromellitic Acid (mol%) | 100 | 100 | ||||
| Diethylenetriamine (mol%) | 100 | 100 | ||||
| Triethylene tetramine (mol%) | 100 | |||||
| Hexanediamine (mol%) | 300 | 300 | 200 | |||
| Prepolymer limiting viscosity [η] (dl/g) | 0.163 | 0.165 | 0.170 | 0.160 | 0.142 | 0.156 |
| The tackify mode | Solid-phase tack producing | Solid-phase tack producing | Solid-phase tack producing | Solid-phase tack producing | Solid-phase tack producing | Solid-phase tack producing |
| Polymeric amide limiting viscosity [η] (dl/g) | 1.45 | 1.46 | 1.43 | 1.42 | 1.39 | 1.43 |
| End amido content (mol/t) | 32 | 42 | 37 | 29 | 31 | 33 |
| Content of carboxyl end group (mol/t) | 39 | 45 | 41 | 93 | 88 | 56 |
| Degree of crystallinity (%) | 13 | 26 | 28 | 11 | 24 | 25 |
| Tensile strength (MPa) | 83 | 98 | 100 | 82 | 98 | 100 |
| Elongation at break (%) | 10 | 6 | 5 | 10 | 5 | 5 |
Claims (10)
1. preparation method of semi-aromatic polyamide is characterized in that: the aliphatic polyamine that adopts the aromatic series polycarboxylic acid and contain 4 to 14 carbon atoms is that raw material prepares.
2. preparation method according to claim 1, it is characterized in that: in organic solvent, carry out neutralization reaction with the aromatic series polycarboxylic acid with the aliphatic polyamine that contains 4 to 14 carbon atoms earlier and obtain semiaromatic polyamide composition salt, under the condition that has water to exist, be that raw material carries out prepolymerization then with semiaromatic polyamide composition salt, again with prepolymer further by solid-phase tack producing or fusion tackify prepared in reaction semiaromatic polyamide composition resin.
3. preparation method according to claim 1 is characterized in that: described aromatic series polycarboxylic acid is trimellitic acid, trimesic acid or Pyromellitic Acid.
4. preparation method according to claim 1 is characterized in that: the described aliphatic polyamine that contains 4 to 14 carbon atoms 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, diethylenetriamine, triethylene tetramine, tetraene five amine or polyethylene polyamine.
5. preparation method according to claim 2 is characterized in that: described organic solvent is N-Methyl pyrrolidone or dimethyl formamide.
6. preparation method according to claim 2 is characterized in that: the temperature of reaction of described solid-phase tack producing is 220～280 ℃, and the reaction times is 3～20 hours, carries out under nitrogen atmosphere or under the vacuum condition;
Described fusion tackify is to carry out on the extrusion equipment of band venting port, and the temperature of reaction of fusion tackify is 290～350 ℃, and the fusion tackify reaction times is 1～8 minute.
7. preparation method according to claim 2 is characterized in that: the synthetic of prepolymer is that raw material salt, deionized water, end-capping reagent and catalyzer are carried out the prepolymerization reaction; The amount of catalyzer is 0.01～2% of a raw material salt weight, and the amount of end-capping reagent is 0.2～10% of a raw material salt mole number, and amount of deionized water is 10～50% of a raw material salt; Prepolymerized temperature of reaction is 200～280 ℃, and the reaction times is 1～6 hour, reaction system pressure 1～5MPa.
8. preparation method according to claim 7 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.
9. preparation method according to claim 1 is characterized in that: add oxidation inhibitor, lubricant, nucleator, fire retardant, tinting material, softening agent, static inhibitor, glass fibre, carbon fiber, mineral filler or other polymkeric substance in raw material.
10. the semiaromatic polyamide composition that utilizes the described preparation method of claim 1 to obtain.
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| CN102380336A (en) * | 2011-09-07 | 2012-03-21 | 金发科技股份有限公司 | Reactor for producing material easy to produce powder, and preparation method of the material |
| CN102719093A (en) * | 2012-01-09 | 2012-10-10 | 金发科技股份有限公司 | Halogen-free fire-retardant polyamide composition and its preparation method and use |
| CN102964590A (en) * | 2012-11-30 | 2013-03-13 | 金发科技股份有限公司 | Polyamide and preparation method and application thereof |
| CN112480396A (en) * | 2020-10-31 | 2021-03-12 | 山东广垠新材料有限公司 | Process and apparatus for producing semi-aromatic polyamide |
| CN112646173A (en) * | 2020-12-04 | 2021-04-13 | 中仑塑业（福建）有限公司 | Semi-aromatic polyamide resin and preparation method thereof |
| US11505649B2 (en) | 2017-09-28 | 2022-11-22 | Dupont Polymers, Inc. | Polymerization process |
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2009
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102380336A (en) * | 2011-09-07 | 2012-03-21 | 金发科技股份有限公司 | Reactor for producing material easy to produce powder, and preparation method of the material |
| CN102719093A (en) * | 2012-01-09 | 2012-10-10 | 金发科技股份有限公司 | Halogen-free fire-retardant polyamide composition and its preparation method and use |
| CN102719093B (en) * | 2012-01-09 | 2015-01-07 | 金发科技股份有限公司 | Halogen-free fire-retardant polyamide composition and its preparation method and use |
| CN102964590A (en) * | 2012-11-30 | 2013-03-13 | 金发科技股份有限公司 | Polyamide and preparation method and application thereof |
| CN102964590B (en) * | 2012-11-30 | 2014-06-25 | 金发科技股份有限公司 | Polyamide and preparation method and application thereof |
| US11505649B2 (en) | 2017-09-28 | 2022-11-22 | Dupont Polymers, Inc. | Polymerization process |
| CN112480396A (en) * | 2020-10-31 | 2021-03-12 | 山东广垠新材料有限公司 | Process and apparatus for producing semi-aromatic polyamide |
| CN112646173A (en) * | 2020-12-04 | 2021-04-13 | 中仑塑业（福建）有限公司 | Semi-aromatic polyamide resin and preparation method thereof |
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