CN109593183A - High-crystallinity polyether ketone ketone and preparation method thereof - Google Patents
High-crystallinity polyether ketone ketone and preparation method thereof Download PDFInfo
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- CN109593183A CN109593183A CN201811376022.2A CN201811376022A CN109593183A CN 109593183 A CN109593183 A CN 109593183A CN 201811376022 A CN201811376022 A CN 201811376022A CN 109593183 A CN109593183 A CN 109593183A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/127—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from carbon dioxide, carbonyl halide, carboxylic acids or their derivatives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
- C08G2261/344—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing heteroatoms
- C08G2261/3442—Polyetherketones
Abstract
The invention belongs to macromolecule synthesising technology field, it is specifically related to a kind of high-crystallinity polyether ketone ketone and preparation method thereof.The present invention on main polymer chain by introducing a kind of molecular structure E that can be nucleated, make it that can quickly form the nuclei of crystallization in molding process, further promote the raising of crystallization rate, promote the raising of crystallinity simultaneously, prepared polyether ketone ketone material can effectively reduce cost in molding process.Polyether ketone ketone prepared by the present invention is with the flexible chain in cold crystallization process than the random copolymerization polyether ketone ketone fastly at least 1/3 with identical T/I ratio and without containing E structure, crystallization enthalpy is than with identical T/I ratio and without containing the random copolymerization polyether ketone ketone greatly at least 5J/g of E structure, maximum crystallization temperature is at least 5 DEG C higher than the random copolymerization polyether ketone ketone with identical T/I ratio and without containing E structure.
Description
Technical field
The invention belongs to macromolecule synthesising technology field, it is specifically related to a kind of high-crystallinity polyether ketone ketone and its preparation side
Method.
Background technique
Polyether ketone ketone (PEKK) resin is a kind of special engineering plastics with excellent properties, belongs to the one of poly(aryl ether ketone)
Kind, the chemical structure of the mutual proper alignment of phenyl ring ehter bond ketone group, imparts the stable chemical bond of numberator height in molecular structure
Characteristic makes it have excellent mechanical performance, radiation resistance, high temperature resistant, chemical corrosion resistance and good electrical insulating property
And flame retardant property, machine-shaping can be carried out by processing methods such as extrusion, injection molding, moldings, in aerospace, electronics electricity
There is high application demand in terms of gas, automobile and petroleum.
Since the presence there are two carbonyl makes it with biggish rigidity inside polyether ketone ketone molecular structure unit, compare
For its similar polyphosphazene polymer ether ether ketone, polyether ketone ketone has higher glass transition temperature, but simultaneously because it has
There is biggish rigidity to make its crystallization rate and crystallinity lower than similar polyphosphazene polymer ether ether ketone, especially for reduce its
Melting temperature introduces after m-phthaloyl chloride base, and crystallization rate is slower.Usually, polyether ketone ketone is as engineering plastics
In use, needing its crystallinity with sufficient degree to obtain its optimal mechanical performance and weatherability.Although by prolonging
Apply enough annealing times after its long time and injection molding in injection molding it may be implemented and is fully crystallized, but this
For sample, production efficiency is just reduced very much.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of high-crystallinity polyether ketone ketone.The polyether ketone ketone
Crystallization enthalpy and maximum crystallization temperature in cold crystallization process is higher than random copolymerization polyether ketone ketone, and flexible chain compares random copolymerization
Polyether ketone ketone is short, makes it that can effectively reduce cost in molding process；Invention also provides preparation methods.
High-crystallinity polyether ketone ketone of the present invention, polyether ketone ketone main polymer chain include with flowering structure:
Wherein: A is representedStructure
B is representedStructure
D is representedStructure
E is representedStructure；
In E, G group is representedStructure；In G, R group be-CH3 orOne of.
Wherein:
(a), (b), (c) and (d) structure proportional presence in the polymer backbone, and (c) with (d) structure in polyether ketone ketone
Amount in main polymer chain is no more than 0.5% and is not less than 0.05%, amount of (a) structure in polyether ketone ketone main polymer chain
Regulated and controled between 59.95~89.5%, (b) amount of the structure in polyether ketone ketone main polymer chain between 10~40% into
Row regulation.
Polyether ketone ketone of the present invention has the flexible chain (t in cold crystallization process1/2) than having identical T/I
Than and without containing E structure random copolymerization polyether ketone ketone fastly at least 1/3.
Polyether ketone ketone of the present invention is with the crystallization enthalpy (dH) in cold crystallization process than with identical T/I ratio and not
Random copolymerization polyether ketone ketone greatly at least 5J/g containing E structure.
Polyether ketone ketone of the present invention is with the maximum crystallization temperature (Tcc) in cold crystallization than having identical T/I ratio
And at least 5 DEG C of random copolymerization polyether ketone ketone height without containing E structure.
Wherein: T/I is the mass ratio or molar ratio of paraphthaloyl chloride and m-phthaloyl chloride.
The preparation method of high-crystallinity polyether ketone ketone of the present invention, specifically includes the following steps:
(1) paraphthaloyl chloride measured, m-phthaloyl chloride, diphenyl ether, 1,3- hexichol oxygen are added into reaction flask
Base, seven methyl of 5-, eight silsesquioxane benzene (HDOI) and a certain amount of polar non-solute, control temperature are not higher than -10 DEG C；
(2) lewis base measured is put into reaction flask, controls temperature in reaction flask and is no more than -10 DEG C；
(3) aluminum trichloride (anhydrous) is slowly added to reaction flask, temperature in reaction flask is kept to be no more than -10 DEG C；
(4) slowly temperature in reaction flask is warmed to room temperature, continues stirring until stirring is motionless, it is ripe then to stop stirring
Change 4~8 hours, substance is jelly in reaction flask at this time；
(5) gum polymers in reaction flask are taken out, ice water is added and smashes it through filter with pulverizer, obtain white powder
Obtained white powder PEKK is flowed back with dilute hydrochloric acid and is washed twice by last shape PEKK, and then pure water filters afterwards three times, sets
In vacuum drying oven, 100 DEG C baking for 24 hours to get arrive high-crystallinity polyether ketone ketone.
Wherein:
The integral molar quantity of paraphthaloyl chloride described in step (1) and m-phthaloyl chloride and diphenyl ether and 1,3- hexichol
Oxygroup, the molar ratio of the integral molar quantity of seven methyl of 5-, eight silsesquioxane benzene (HDOI) is in 0.99~1.01 range, more ratio of greater inequality
It is 0.995~1.005.
Polar non-solute described in step (1) be methylene chloride, 1,2- dichloroethanes, o-dichlorohenzene, nitrobenzene,
Any one or a few in tetrachloroethanes, carbon disulfide or nitromethane.
Lewis base described in step (2) is N, N '-dimethyl formamide, dimethyl acetamide, diphenyl sulphone (DPS), triphenyl
Phosphine oxide, nitropropane, sulfolane, dimethyl sulfoxide, dimethyl sulfone, N, N- dimethyl pyrrolidone, anhydrous lithium chloride or anhydrous
Any one in sodium chloride, lewis base dosage are 0.5~4 times of diphenyl ether mole in step (1).
Aluminum trichloride (anhydrous) mole dosage described in step (3) is paraphthaloyl chloride and m-phthaloyl chloride total moles
2 times of amount add 0.1~1.5 times of diphenyl ether mole plus 1 times of lewis base mole.
The present invention is to make it in processing and forming by introducing a kind of molecular structure E that can be nucleated on main polymer chain
The nuclei of crystallization can be quickly formed in the process, further promote the raising of crystallization rate, while promoting the raising of crystallinity, it is made
Standby polyether ketone ketone material can effectively reduce cost in molding process.
Compared with the prior art, the present invention has the following beneficial effects:
(1) crystallization enthalpy ratio of the polyether ketone ketone of the present invention in cold crystallization process has identical T/I ratio and does not contain E
The random copolymerization polyether ketone ketone greatly at least 5J/g of structure；Maximum crystallization temperature is than with identical T/I ratio and without containing the nothing of E structure
At least 5 DEG C of copolyether ketone ketone height of rule；Flexible chain is than with identical T/I ratio and without containing the random copolymerization polyethers of E structure
Ketone ketone fastly at least 1/3.
(2) polyether ketone ketone prepared by the present invention, due to processing rank in injection molding with faster crystallization rate
Section, significantly reduces, the process-cycle of the product made shortens, and effectively reduces the processing cost of product cooling time.
Detailed description of the invention
Fig. 1 is the DSC curve of embodiment 2.
Fig. 2 is the DSC curve of comparative example 2.
Specific embodiment
The invention will be further described with reference to embodiments.
Comparative example 1
The preparation (T/I=60/40) of random copolymerization polyether ketone ketone
In four mouthfuls of reaction flasks of the 500mL with mechanical stirring, thermometer, condenser pipe and device for absorbing tail gas, it is added
17.021g (0.100mol) diphenyl ether, 8.121g m-phthaloyl chloride (0.040mol), 12.181g paraphthaloyl chloride
(0.060mol) is then added 150g dichloromethane solution, then places it in -15 DEG C of alcohol bath, open and stir and lead to
Enter nitrogen, when temperature is down to -10 DEG C or less in reaction flask, 11.69g N is added, then N '-dimethyl formamide adds in batches
Enter aluminum trichloride (anhydrous) 60.00g (0.45mol), keeps temperature in reaction flask to be no more than -10 DEG C in adition process, to tri-chlorination
After aluminium is added, continues after stirring 30min, room temperature environment will be moved in four-hole bottle, and continue to stir, until reaction flask
Interior viscosity rises to until can not stirring, and continues static curing 8h at room temperature.It is spawn in four-hole bottle at this time, it will
After it takes out, it is added in ice water and smashes it through filter with pulverizer.Obtain white powder PEKK.The white powder that will be obtained
PEKK is flowed back with dilute hydrochloric acid and is washed twice, and then pure water filters afterwards three times.It is placed in vacuum drying oven, is toasted at 100 DEG C
For 24 hours to get having arrived PEKK-1.
Embodiment 1
The preparation (T/I=60/40) of modified random copolymerization polyether ketone ketone
In four mouthfuls of reaction flasks of the 500mL with mechanical stirring, thermometer, condenser pipe and device for absorbing tail gas, it is added
17.004g (0.0999mol) diphenyl ether, 8.121g m-phthaloyl chloride (0.040mol), 12.181g paraphthaloyl chloride
(0.060mol), 0.078g HDOI (0.0001mol) are then added 150g dichloromethane solution, then place it in -15 DEG C
It in alcohol bath, opens and stirs and be passed through nitrogen, when temperature is down to -10 DEG C or less in reaction flask, 11.69g N, N '-two is added
Then methylformamide is added portionwise aluminum trichloride (anhydrous) 60.00g (0.45mol), temperature in reaction flask is kept in adition process
No more than -10 DEG C, after being added to alchlor, continues after stirring 30min, will move to room temperature environment in four-hole bottle, and after
It is continuous to be stirred, until viscosity in reaction flask rises to and can not stir, continue static curing 8h at room temperature.Four mouthfuls at this time
It is spawn in bottle, after being drawn off, is added in ice water and smashes it through filter with pulverizer.Obtain white powder
PEKK.Obtained white powder PEKK is flowed back with dilute hydrochloric acid and is washed twice, then pure water filters afterwards three times.It is placed in true
In empty baking oven, in 100 DEG C of bakings for 24 hours to get having arrived PEKK-3.
Comparative example 2
The preparation (T/I=75/25) of random copolymerization polyether ketone ketone
In four mouthfuls of reaction flasks of the 500mL with mechanical stirring, thermometer, condenser pipe and device for absorbing tail gas, it is added
17.021g (0.100mol) diphenyl ether, 5.076g m-phthaloyl chloride (0.025mol), 15.227g paraphthaloyl chloride
(0.075mol) is then added 150g dichloromethane solution, then places it in -15 DEG C of alcohol bath, open and stir and lead to
Enter nitrogen, when temperature is down to -10 DEG C or less in reaction flask, 11.69g N is added, then N '-dimethyl formamide adds in batches
Enter aluminum trichloride (anhydrous) 60.00g (0.45mol), keeps temperature in reaction flask to be no more than -10 DEG C in adition process, to tri-chlorination
After aluminium is added, continues after stirring 30min, room temperature environment will be moved in four-hole bottle, and continue to stir, until reaction flask
Interior viscosity rises to until can not stirring, and continues static curing 8h at room temperature.It is spawn in four-hole bottle at this time, it will
After it takes out, it is added in ice water and smashes it through filter with pulverizer.Obtain white powder PEKK.The white powder that will be obtained
PEKK is flowed back with dilute hydrochloric acid and is washed twice, and then pure water filters afterwards three times.It is placed in vacuum drying oven, is toasted at 100 DEG C
For 24 hours to get having arrived PEKK-2.
Embodiment 2
The preparation (T/I=75/25) of modified random copolymerization polyether ketone ketone
In four mouthfuls of reaction flasks of the 500mL with mechanical stirring, thermometer, condenser pipe and device for absorbing tail gas, it is added
17.004g (0.0999mol) diphenyl ether, 5.076g m-phthaloyl chloride (0.025mol), 15.227g paraphthaloyl chloride
(0.075mol), 0.078g HDOI (0.0001mol) are then added 150g dichloromethane solution, then place it in -15 DEG C
Alcohol bath in, open stir simultaneously be passed through nitrogen, when temperature is down to -10 DEG C or less in reaction flask, addition 11.69g N, N ' -
Then dimethylformamide is added portionwise aluminum trichloride (anhydrous) 60.00g (0.45mol), temperature in reaction flask is kept in adition process
Degree is no more than -10 DEG C, after being added to alchlor, continues after stirring 30min, room temperature environment will be moved in four-hole bottle, and
Continue to stir, until viscosity in reaction flask rises to and can not stir, continues static curing 8h at room temperature.At this time four
It is spawn in mouth bottle, after being drawn off, is added in ice water and smashes it through filter with pulverizer.Obtain white powder
PEKK.Obtained white powder PEKK is flowed back with dilute hydrochloric acid and is washed twice, then pure water filters afterwards three times.It is placed in true
In empty baking oven, in 100 DEG C of bakings for 24 hours to get having arrived PEKK-4.
The structure of HDOI described in embodiment 1 and embodiment 2 are as follows:
The obtained polyether ketone ketone polymer of embodiment 1-2 and comparative example 1-2 is passed through following steps to carry out after purification
Test:
By polyether ketone ketone crude product 6g, it is added in stirred tank, the mixing for adding 120g aqueous formic acid and acetylacetone,2,4-pentanedione is molten
Liquid, wherein the mass ratio of aqueous formic acid and acetylacetone,2,4-pentanedione is 3.8:1, and aqueous formic acid concentration 95% is warming up to 105 DEG C, stirs
Reflux washing 8h is mixed, most solutions are removed through filtering, then use 75% aqueous formic acid agitator treating 4h of 60g concentration, mistake
After filter, polymer washs 4h with 120g water room temperature in third stirred tank, centrifugation, in a vacuum drying oven after 100 DEG C of dry 5h
The polyether ketone ketone purified.
Inherent viscosity uses dark type viscometer, with dense H2SO4Make solvent, be configured to the solution of 0.5g/L, in steady temperature T
Four-point method is used at=25 ± 0.1 DEG C, measures the inherent viscosity of polymer.The glass transition temperature and fusing point of polymer use
Differential scan calorimeter (DSC) is tested, under nitrogen atmosphere, heating rate be 10 DEG C/min, 40~380 DEG C of temperature elevating range.
Using the melting temperature and melting enthalpy of TADSC2000 test polyether ketone ketone, under nitrogen atmosphere, 10 DEG C of heating rate/
Min, is then cooled to 50 DEG C, 10 DEG C/min of rate of temperature fall, then with identical temperature rate by 50~400 DEG C of temperature elevating range
Recycling one time, takes the crystallization temperature (Tcc) and crystallization enthalpy of second of rate of temperature fall by 50~400 DEG C of test scope.With following public affairs
Formula calculates:
Wherein Δ H is the melting enthalpy of PEKK, Δ H100%Reach melting enthalpy when 100% crystallization, value 130J/ for PEKK
g。t1/2It is the time (taking second of temperature lowering curve) used that relative crystallinity reaches 50%, referred to as half-crystallization time.
The performance parameter of 2 polyether ketone ketone of table
| Test item | Unit | Comparative example 1 | Comparative example 2 | Embodiment 1 | Embodiment 2 |
| Glass transition temperature | ℃ | 157.6 | 168.6 | 153.1 | 162.6 |
| Melting temperature (Tm) | ℃ | 316.4 | 347.6 | 314.5 | 354.5 |
| Crystallization temperature (Tcc) | ℃ | 233.3 | 257.13 | 245.5 | 288.52 |
| Crystallization enthalpy | J/g | 22.6 | 35.34 | 28.7 | 43.17 |
| t1/2 | min | 4.68 | 4.06 | 2.54 | 2.12 |
Claims (10)
1. a kind of high-crystallinity polyether ketone ketone, it is characterised in that: polyether ketone ketone main polymer chain includes with flowering structure:
Wherein: A is representedStructure
B is representedStructure
D is representedStructure
E is representedStructure；
In E, G group is representedStructure；In G, R group be-CH3 orIn
One kind.
2. high-crystallinity polyether ketone ketone according to claim 1, it is characterised in that: (a), (b), (c) and (d) structure are poly-
Proportional presence in ether ketone ketone polymer main chain, and (c) be no more than with amount of (d) structure in polyether ketone ketone main polymer chain
0.5% and be not less than 0.05%, amount of (a) structure in polyether ketone ketone main polymer chain between 59.95~89.5% into
Row regulation, (b) amount of the structure in polyether ketone ketone main polymer chain is regulated and controled between 10~40%.
3. high-crystallinity polyether ketone ketone according to claim 1, it is characterised in that: polyether ketone ketone has in cold crystallization process
In flexible chain than the random copolymerization polyether ketone ketone fastly at least 1/3 with identical T/I ratio and without containing E structure.
4. high-crystallinity polyether ketone ketone according to claim 1, it is characterised in that: polyether ketone ketone has in cold crystallization process
In crystallization enthalpy than with identical T/I ratio and do not contain E structure random copolymerization polyether ketone ketone greatly at least 5J/g.
5. high-crystallinity polyether ketone ketone according to claim 1, it is characterised in that: polyether ketone ketone has in cold crystallization
Maximum crystallization temperature is at least 5 DEG C higher than the random copolymerization polyether ketone ketone with identical T/I ratio and without containing E structure.
6. a kind of preparation method of high-crystallinity polyether ketone ketone described in claim 1, it is characterised in that: specifically include following step
It is rapid:
(1) paraphthaloyl chloride measured, m-phthaloyl chloride, diphenyl ether, bis- phenoxy group of 1,3-, 5- are added into reaction flask
Seven methyl, eight silsesquioxane benzene and a certain amount of polar non-solute, control temperature are not higher than -10 DEG C；
(2) lewis base measured is put into reaction flask, controls temperature in reaction flask and is no more than -10 DEG C；
(3) aluminum trichloride (anhydrous) is added to reaction flask, temperature in reaction flask is kept to be no more than -10 DEG C；
(4) temperature in reaction flask is warmed to room temperature, continues stirring until stirring is motionless, it is small then to stop stirring curing 4~8
When, substance is jelly in reaction flask at this time；
(5) gum polymers in reaction flask are taken out, ice water is added and smashes it through filter with pulverizer, obtain white powder
Obtained white powder PEKK is flowed back with dilute hydrochloric acid and is washed twice by PEKK, and then pure water filters afterwards three times, is placed in true
In empty baking oven, 100 DEG C baking for 24 hours to get arrive high-crystallinity polyether ketone ketone.
7. the preparation method of high-crystallinity polyether ketone ketone according to claim 6, it is characterised in that: described in step (1)
Paraphthaloyl chloride and m-phthaloyl chloride integral molar quantity and bis- phenoxy group of diphenyl ether and 1,3-, seven methyl of 5-, eight silicon sesquialter
The molar ratio of the integral molar quantity of oxygen alkane benzene is in 0.99~1.01 range.
8. the preparation method of high-crystallinity polyether ketone ketone according to claim 6, it is characterised in that: described in step (1)
Polar non-solute be methylene chloride, 1,2- dichloroethanes, o-dichlorohenzene, nitrobenzene, tetrachloroethanes, carbon disulfide or nitre
Any one or a few in methylmethane.
9. the preparation method of high-crystallinity polyether ketone ketone according to claim 6, it is characterised in that: described in step (2)
Lewis base be N, N '-dimethyl formamide, dimethyl acetamide, diphenyl sulphone (DPS), triphenylphosphine oxide, nitropropane, sulfolane,
Dimethyl sulfoxide, dimethyl sulfone, N, any one in N- dimethyl pyrrolidone, anhydrous lithium chloride or anhydrous sodium chloride, road
This easy base amount is 0.5~4 times of diphenyl ether mole in step (1).
10. the preparation method of high-crystallinity polyether ketone ketone according to claim 6, it is characterised in that: described in step (3)
Aluminum trichloride (anhydrous) mole dosage be that 2 times of paraphthaloyl chloride and m-phthaloyl chloride integral molar quantity rub plus lewis base
1 times of that amount adds 0.1~1.5 times of diphenyl ether mole.
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