CN108623811A - One kind containing POSS structure ultralow dielectric poly aryl ether ketone polymers and preparation method thereof - Google Patents
One kind containing POSS structure ultralow dielectric poly aryl ether ketone polymers and preparation method thereof Download PDFInfo
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- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
- C08G65/4043—(I) or (II) containing oxygen other than as phenol or carbonyl group
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Abstract
One kind belonging to high molecular material and its preparing technical field containing POSS structure ultralow dielectric poly aryl ether ketone polymers and preparation method thereof.Preparation method of the present invention containing POSS structure ultralow dielectric poly aryl ether ketone polymers, synthesizes in two steps：The first step synthesizes the poly aryl ether ketone polymer of different carboxyl structure contents；Second step, under DCC/DMAP catalytic conditions, the poly(aryl ether ketone) of different carboxyl structure contents and mono amino POSS occur it is amide condensed react, prepare the poly aryl ether ketone polymer of different POSS structural contents.Polymer remains the excellent mechanical property and processing performance of poly(aryl ether ketone) containing carboxyl structure, the introducing of POSS structures, while the dielectric constant that polymer is greatly lowered, further promote and improve the mechanical property and hot property of polymer, so that the poly aryl ether ketone polymer of structure containing POSS is had both ultralow dielectric and excellent comprehensive performance, has a good application prospect.
Description
Technical field
The invention belongs to high molecular material and its preparing technical fields, and in particular to one kind containing the ultralow dielectric of POSS structures
Constant poly aryl ether ketone polymer and preparation method thereof.
Background technology
With the fast development of electronic information technology, the high performance of electronic component and compact in size, it is desirable that dielectric
Interlayer dielectic has lower dielectric constant, therefore the material for developing low-k is particularly important.
The dielectric constant of polytetrafluoroethylene (PTFE) between 1.8~2.2, and with dielectric loss it is small, not by frequency, temperature and
The advantages that humidity influences, is well used in electronic information field.But polytetrafluoroethylene material there are bad mechanical property,
The big disadvantage of coefficient of thermal expansion, limits its scope of application.Polyimides has excellent hot property, chemical stability, mechanics
Performance and dielectric properties, have obtained comparing and have been widely applied in microelectronics technology.The dielectric constant of polyimides usually exists
Between 3.0~3.4, higher dielectric constant constrains its extensive use in integrated circuit fields.Reduce Jie of polyimides
The method of electric constant, which mainly has, to be introduced fluorine-containing destructing and large volume side group structure and prepares with microcellular structure polyimides.Though
Right dielectric constant is substantially reduced, but R＆D costs is brought to increase or the problem of mechanical properties decrease to a certain extent.In electronics
Industrial circle develops the high molecular material with low-k and excellent combination property, is still current research and development focus.
Poly(aryl ether ketone) is the high-performance aromatic high polymer that main chain contains rigid benzene ring structure and carbonyl structure, is had excellent
High temperature resistant, radiation hardness, mechanical property and the advantages that processing performance, because its excellent comprehensive performance has been widely used in electricity
The high-grade, precision and advanced technical field such as sub- electric appliance, automobile, medical treatment, nuclear industry and aerospace.Similarly, draw in poly(aryl ether ketone) segment
Enter fluorine-containing destructing and large volume side group structure, the dielectric constant of poly(aryl ether ketone) material can be reduced, expand it in electronic field
Application.Polysilsesquioxane (POSS) is a kind of organic-inorganic hybrid material with nano-scale cage structure, is drawn
Enter into polymer architecture, can not only play the role of nanometer enhancing, improve the mechanical property of polymer, unique cage type
Hollow-core construction can significantly reduce the dielectric constant of polymer.The present invention passes through nucleophilic displacement of fluorine road from MOLECULE DESIGN angle
Line, the poly aryl ether ketone polymer of different carboxyl structure contents of the design synthesis with excellent mechanical performance, utilizes carboxyl functional group
Can be reactive again, dicyclohexylcarbodiimide/4-dimethylaminopyridine (DCC/DMAP) catalyst system and catalyzing is selected, by mono amino
POSS compounds are introduced by chemical grafting method in poly(aryl ether ketone) structure, to prepare with ultralow dielectric
Poly aryl ether ketone polymer, Polymeric dielectric constant is minimum up to 1.36.DCC/DMAP catalysis prepares the polyarylether of structure containing POSS
The advantages of ketone polymer has reaction condition mild, and product is easily purified.POSS structures are incorporated in polyarylether in a manner of covalent bond
In ketone structure, its scattering problem in the polymer of effective solution.Finally, poly(aryl ether ketone) containing carboxyl structure is based on to polymerize
Object under DCC/DMAP catalytic conditions, introduces POSS structures by rear chemical grafting method, it is excellent can to retain original polymer
Mechanical property, and POSS structures can make the mechanical property of polymer and hot property further be promoted and be improved.To
Synthesize a kind of poly(aryl ether ketone) dielectric material with ultralow dielectric and excellent combination property.
Invention content
The purpose of the present invention is to provide one kind containing POSS structure ultralow dielectric poly aryl ether ketone polymers and its system
Preparation Method.The poly aryl ether ketone polymer of structure containing POSS of the present invention, structural formula are as follows.
In structure above, m=0.1~1, n are the integer of 50-70.
Preparation method of the present invention containing POSS structure ultralow dielectric poly aryl ether ketone polymers, in two steps
Synthesis：The first step synthesizes the poly aryl ether ketone polymer of different carboxyl structure contents；Second step, under DCC/DMAP catalytic conditions,
The poly(aryl ether ketone) of different carboxyl structure contents and mono amino POSS occur it is amide condensed react, prepare different POSS structural contents
Poly aryl ether ketone polymer.It is as follows：
(1) preparation of different carboxyl structure content poly aryl ether ketone polymers
Using double fluorine monomers of commercialization, biphenol monomer as reaction monomers, biphenol monomer be biphenol monomer containing carboxyl structure with
The mixing of other biphenol monomers；Wherein, the molar ratio of the total dosage of double fluorine monomers and the total dosage of biphenol monomer is 1~1.03：1, it is double
The mole dosage percentage of the biphenol monomer containing carboxyl structure is 10~100% in phenol monomer；Using sulfolane as solvent, make reactant
The solid content of system is 20~30%；Using toluene as dehydrating agent, potassium carbonate is salt forming agent, salt forming agent be biphenol monomer total mole number with
The half number summation of monomer molar containing carboxy bisphenol 1.05~1.10 times (when without using other biphenol monomers, salt forming agent
Dosage be 1.58~1.65 times of the number of monomer molar containing carboxy bisphenol)；Reaction monomers, potassium carbonate, sulfolane and toluene are added
Enter into reaction vessel, 120~130 DEG C are warming up under the conditions of nitrogen protection, keeps the reflux of toluene azeotrope with water, reaction 2~3
The water hour generated to reaction is taken out of completely, then is warming up to 190~220 DEG C the reaction was continued 8~16 hours；After reaction,
Polymeric reaction product is discharged in 5~10% hydrochloric acid of mass fraction, obtains pale solid；After pulverizer crushes, respectively
With ethyl alcohol and water washing is distilled 6~8 times, to remove excessive monomeric compound, solvent and inorganic salts；It is finally true at 70~90 DEG C
It is 10~12 hours dry under empty condition, obtain the poly aryl ether ketone polymer of different carboxyl structure contents；
The double fluorine monomers addressed in above-mentioned preparation process are 4,4 '-difluoro benzophenones, and biphenol monomer containing carboxyl structure is
3,5- dihydroxy-benzoic acids, other biphenol monomers are hexafluoro bisphenol-a, 3,3 ', 5,5 '-tetramethyl -4,4 '-'-biphenyl diphenols or bis-phenol
A。
The poly aryl ether ketone polymer of difference carboxyl structure content of the present invention to prepare reaction equation as follows：
In above-mentioned polymerisation formula, m=0.1~1；The integer that n is 50~70；
(2) preparation of the poly aryl ether ketone polymer of difference POSS structural contents
Using tetrahydrofuran as solvent, the poly aryl ether ketone polymer of different carboxyl structure contents is configured to mass volume ratio
(mg/mL) a concentration of 5~10% polymer solution dissolves under the conditions of nitrogen protection and magnetic agitation in ice-water bath；It waits for anti-
Answer system be 0 DEG C when, the tetrahydrofuran solution of DMAP is added drop-wise in above-mentioned polymer solution with the speed of 3~5 drops/minute,
Recession is added dropwise and removes ice-water bath；After temperature of reaction system is restored to room temperature, it is added and carboxyl molal quantity into reaction system
Then the tetrahydrofuran solution of DCC is added drop-wise to reaction by identical mono amino POSS compounds with the speed of 3~5 drops/minute again
In system；Spherical condensation tube is installed on reaction unit, is reacted 20~24 hours under room temperature；After reaction, product exists
It discharges in distilled water, flocculent polymer is precipitated；It is washed 6~10 times, is removed residual in polymer repeatedly with distilled water and ethyl alcohol respectively
Solvent, DCC and the DMAP stayed, it is finally 10~12 hours dry under 70~90 DEG C of vacuum conditions, it obtains containing different POSS structures
The poly aryl ether ketone polymer of content.In this step operation, the poly aryl ether ketone polymer carboxyl functional group of different carboxyl structure contents
Molar ratio with DCC, DMAP is 1.0：1.0~1.2：0.10~0.12.
The poly aryl ether ketone polymer of difference POSS structural contents of the present invention to prepare reaction equation as follows：
In above-mentioned polymerisation formula, m=0.1~1；The integer that n is 50~70.
The poly aryl ether ketone polymer of different POSS structural contents prepared by the present invention, is by traditional poly(aryl ether ketone) system
On the basis of Preparation Method synthesizes poly aryl ether ketone polymer containing carboxyl structure, then under DCC/DMAP catalytic conditions, chemical graft
POSS structures.Remain poly(aryl ether ketone) containing carboxyl structure excellent mechanical property and processing performance.On the other hand, POSS structures
Introduce, while the dielectric constant that polymer is greatly lowered, further promoted and improved polymer mechanical property and
Hot property.The poly aryl ether ketone polymer of structure containing POSS has both ultralow dielectric and excellent comprehensive performance, has good answer
Use foreground.
Description of the drawings
Fig. 1：Carboxyl structure molar content prepared by the embodiment of the present invention 1 to embodiment 4 is 10%, 20%, 30% and
(curve a, b, c, d are respectively carboxyl structure molar content to the infrared spectrum spectrogram of 100% poly aryl ether ketone polymer in figure
10%, the infrared spectrum spectrogram of 20%, 30%, 100% poly(aryl ether ketone))；
As shown in Figure 1, it can be seen that 1651cm-1The vibration absorption peak of C=O keys, 1600cm between phenyl ring in main chain-1With
1510cm-1Locate the skeleton stretching vibration absworption peak that absorption peak is phenyl ring, 1248cm-1For the vibration absorption peak of Ar-O-Ar,
1162cm-1And 1115cm-1It is the vibration absorption peak of C-F keys, 1248cm-1For O-H deformation vibrations peak.Pass through polymeric infrared light
The ownership of each absorption peak is composed, can prove to successfully synthesize poly aryl ether ketone polymer containing carboxyl structure.
Fig. 2：Carboxyl structure molar content prepared by the embodiment of the present invention 1 to embodiment 4 is 10%, 20%, 30% and
The thermogravimetric curve of 100% poly aryl ether ketone polymer；(figure a, b, c, d be respectively carboxyl molar content 10%, 20%, 30%,
100% poly(aryl ether ketone))；
From thermogravimetric curve as can be seen that the polyarylether that carboxyl structure molar content is 10%, 20%, 30% and 100%
The temperature of ketone polymer thermal weight loss 5% is respectively 540 DEG C, 515 DEG C, 480 DEG C and 400 DEG C.With carboxyl knot in polymer architecture
The increase of structure content, 5% thermal weight loss temperature continuously decreases, but still shows more excellent thermal stability.
Fig. 3：POSS structure molar contents prepared by the embodiment of the present invention 7 to embodiment 10 are 10%, 20%, 30% and
100% poly aryl ether ketone polymer infrared spectrum spectrogram (in figure a, b, c, d be respectively POSS structures molar content 10%,
20%, the infrared spectrum spectrogram of 30%, 100% poly(aryl ether ketone))；
It is can be found that by comparison diagram 1 and Fig. 3：1728cm in the infared spectrum of the poly(aryl ether ketone) of structure containing POSS-1Locate carboxyl
Characteristic absorption peak disappear substantially, while in 1548cm-1Place has the absorption peak of N-H amido bonds to occur.POSS groups pass through amide
The mode of condensation reaction is grafted in poly aryl ether ketone polymer structure, it was demonstrated that the poly(aryl ether ketone) for being successfully prepared the structure containing POSS is poly-
Close object.
Fig. 4：POSS structure molar contents prepared by the embodiment of the present invention 7 to embodiment 10 are 10%, 20%, 30% and
100% poly aryl ether ketone polymer photoelectron spectroscopy figure (in figure a, b, c, d be respectively POSS structures molar content 10%,
20%, 30%, 100% poly(aryl ether ketone) photoelectron spectroscopy figure)；
As shown in figure 4, further being proved it can be found that containing N and Si elements in polymer from polymer photoelectron power spectrum
The successful preparation of the poly aryl ether ketone polymer of the structure containing POSS.
Fig. 5：Carboxyl structure molar content prepared by the embodiment of the present invention 1 to embodiment 4 is 10%, 20%, 30% and
100% poly aryl ether ketone polymer and POSS structure molar contents prepared by embodiment 7 to embodiment 10 be 10%, 20%,
The thermogravimetric curve of 30% and 100% poly aryl ether ketone polymer；Fig. 5 (A) to Fig. 5 (D) is respectively carboxyl structure and POSS knots
The thermogravimetric curve of the identical molar content polymer of structure.Wherein, a is polymer containing carboxyl structure, and b is topology convergence containing POSS
Object；
From fig. 5, it can be seen that the poly aryl ether ketone polymer that POSS structure molar contents are 10%, 20%, 30% and 100%
The temperature of thermal weight loss 5% is respectively 550 DEG C, 555 DEG C, 490 DEG C and 440 DEG C, shows excellent thermal stability.Pass through comparison
The thermogravimetric curve of carboxyl structure identical molar content polymer with POSS structures, it can be seen that after POSS structures introduce, polymerization
The thermal stability of object is improved.
Fig. 6：Carboxyl structure molar content prepared by the embodiment of the present invention 1 to embodiment 4 is 10%, 20%, 30% and
100% poly aryl ether ketone polymer and POSS structure molar contents prepared by embodiment 7 to embodiment 10 be 10%, 20%,
The dielectric constant of 30% and 100% poly aryl ether ketone polymer；Fig. 6 (A) to Fig. 6 (D) is respectively carboxyl structure and POSS structures
The dielectric constant of identical molar content polymer.Wherein, a is polymer containing carboxyl structure, and b is structural polymer containing POSS；
It may be evident from figure 6 that the dielectric constant of the structural polymer containing POSS of identical molar content is significantly lower than
Polymer containing carboxyl structure, the introducing of POSS structures significantly reduce the dielectric constant of polymer.In DCC/DMAP catalytic conditions
Under, POSS structures are grafted in the form of covalent bond in poly aryl ether ketone polymer structure, and the content of POSS structures can regulate and control；
The dielectric constant of polymer is continuously decreased with the increase of POSS structural contents, and POSS structure molar contents are 100% polymer
Dielectric constant down to 1.36, there are excellent dielectric properties.
Table 1：The poly aryl ether ketone polymer of different carboxyl structure molar contents prepared by the embodiment of the present invention 1 to embodiment 4
Mechanical performance data；
Table 2：The poly aryl ether ketone polymer of different POSS structures molar contents prepared by the embodiment of the present invention 7 to embodiment 10
Mechanical performance data；
Data of mechanical shows that the poly aryl ether ketone polymer of different carboxyl structure molar contents is tied from different POSS
The poly aryl ether ketone polymer of structure molar content all has more excellent mechanical property.Pass through the mechanical property ratio of table 1 and table 2
Compared with, it is apparent that, the introducing of POSS structures makes the mechanical property of polymer be further enhanced.
Table 1：The mechanical performance data of the poly aryl ether ketone polymer of different carboxyl structure molar contents
| Polymer stretch modulus (MPa) elongation at break (%) |
| 10% polymer 642 9 of carboxyl structure molar content |
| 20% polymer 645 9 of carboxyl structure molar content |
| 30% polymer 652 10 of carboxyl structure molar content |
| 100% polymer 673 11 of carboxyl structure molar content |
Table 2：The mechanical performance data of the poly aryl ether ketone polymer of different POSS structures molar contents
Specific implementation mode
Embodiment 1：
4,4'- difluorodiphenyls are sequentially added into the 100mL three-necked flasks equipped with nitrogen branch pipe, mechanical agitation and water knockout drum
Ketone 4.41g (0.02mol), 3,5- dihydroxy-benzoic acids 0.31g (0.002mol), hexafluoro bisphenol-a 6.05g (0.018mol),
Potassium carbonate 3.05g (0.022mol), sulfolane 20mL (solid content 30%), water entrainer toluene 10mL.Under the conditions of nitrogen protection,
Reaction system is heated to 130 DEG C, when water knockout drum liquid level upper layer occurs muddy, keeps reaction 3 hours, it is ensured that by reaction system
Water all take out of.Toluene is released later, reaction system is heated to 220 DEG C, sustained response 5 hours.After reaction, it will produce
Object, which pours into 10% hydrochloric acid solution of preprepared mass fraction, to be cured, and by product after tissue pulverizer crushes, is used respectively
Distilled water and ethyl alcohol wash 6 times, to remove reaction dissolvent, unreacted monomer compound and inorganic salts, finally by polymer 80
It is 12 hours dry in DEG C vacuum drying oven, it obtains the poly(aryl ether ketone) of structure containing hexafluoro bisphenol-a that carboxyl structure molar content is 10% and gathers
Close object, yield 98%.
Embodiment 2：
Such as embodiment 1,4,4'- difluoro benzophenones 4.41g (0.02mol), 3 are sequentially added in 100mL three-necked flasks,
5- dihydroxy-benzoic acids 0.62g (0.004mol), hexafluoro bisphenol-a 5.38g (0.016mol), potassium carbonate 3.33g (0.024mol),
Sulfolane 20mL, water entrainer toluene 10mL.Reaction condition, polymer are refined and drying process is same as Example 1, obtain carboxyl
The poly aryl ether ketone polymer of structure containing hexafluoro bisphenol-a that structure molar content is 20%, yield 97%.
Embodiment 3：
Such as embodiment 1,4,4'- difluoro benzophenones 4.41g (0.02mol), 3 are sequentially added in 100mL three-necked flasks,
5- dihydroxy-benzoic acids 0.93g (0.006mol), hexafluoro bisphenol-a 4.71g (0.014mol), potassium carbonate 3.49g (0.025mol),
Sulfolane 20mL, water entrainer toluene 10mL.Reaction condition, polymer are refined and drying process is same as Example 1, obtain carboxyl
The poly aryl ether ketone polymer of structure containing hexafluoro bisphenol-a that structure molar content is 30%, yield 97%.
Embodiment 4：
Such as embodiment 1,4,4'- difluoro benzophenones 4.41g (0.02mol), 3 are sequentially added in 100mL three-necked flasks,
5- dihydroxy-benzoic acids 3.10g (0.02mol), potassium carbonate 4.55g (0.033mol), sulfolane 20mL, water entrainer toluene 10mL.
Reaction condition, polymer are refined and drying process is same as Example 1, obtain the poly- virtue that carboxyl structure molar content is 100%
Ether ketone polymer, yield 98%.
Embodiment 5：
Such as Examples 1 to 33, hexafluoro bisphenol-a is replaced with into 3,3 ', 5,5 '-tetramethyl -4,4 '-'-biphenyl diphenols respectively obtain
The poly aryl ether ketone polymer of structure containing tetramethyl biphenyl that carboxyl structure molar content is 10%, 20% and 30%, yield 96~
98%.
Embodiment 6：
Such as Examples 1 to 33, hexafluoro bisphenol-a is replaced with into bisphenol-A, respectively obtain carboxyl structure molar content be 10%,
20% and 30% poly aryl ether ketone polymer containing structure of bisphenol A, yield 96~98%.
Embodiment 7：
The poly aryl ether ketone polymer that the accurate carboxyl structure molar content for weighing the preparation of 2g embodiments 1 is 10%, is added to
In 50mL three-necked flasks containing 15mL tetrahydrofuran solvents, under the conditions of nitrogen protection and magnetic agitation, dissolved in ice-water bath.It waits for
When system temperature is 0 DEG C, the 0.0029gDMAP that 4mL tetrahydrofurans dissolve is added drop-wise to reaction system with the speed of 4 drops/minute
In.After being all added dropwise, ice-water bath is removed, after temperature of reaction system is returned to room temperature, is added into system and rubs with carboxyl
The identical mono amino POSS compounds 0.2000g (0.002mol) of your number.Then 0.0480g 4mL tetrahydrofurans dissolved
DCC is added drop-wise to the speed of 4 drops/minute in reaction system.Spherical condensation tube is installed on reaction unit, is reacted under room temperature
24 hours.After reaction, product discharges in distilled water, and flocculent polymer is precipitated.It is washed repeatedly with distilled water and ethyl alcohol respectively
It washs 8 times, removes remaining solvent, DCC and DMAP in polymer.It is finally dried 12 hours in 80 DEG C of vacuum drying ovens, obtains POSS
The poly aryl ether ketone polymer of structure containing hexafluoro bisphenol-a that structure molar content is 10%, yield 98%.
Embodiment 8：
Such as embodiment 7, the poly aryl ether ketone polymer that carboxyl structure molar content prepared by embodiment 1 is 10% is replaced with
The poly aryl ether ketone polymer that carboxyl structure molar content prepared by embodiment 2 is 20%.Adjust DCC, DMAP and mono amino POSS
The quality of compound is respectively 0.0960g, 0.0058g and 0.4000g.Operating procedure, reaction condition, polymer are refined and dry
Process is same as Example 7, obtains the poly aryl ether ketone polymer of structure containing hexafluoro bisphenol-a that POSS structure molar contents are 20%,
Yield 97%.
Embodiment 9：
Such as embodiment 7, the poly aryl ether ketone polymer that carboxyl structure molar content prepared by embodiment 1 is 10% is replaced with
The poly aryl ether ketone polymer that carboxyl structure molar content prepared by embodiment 3 is 30%.Adjust DCC, DMAP and mono amino POSS
The quality of compound is respectively 0.1440g, 0.0087g and 0.6000g.Operating procedure, reaction condition, polymer are refined and dry
Process is same as Example 7, obtains the poly aryl ether ketone polymer of structure containing hexafluoro bisphenol-a that POSS structure molar contents are 30%,
Yield 96%.
Embodiment 10：
Such as embodiment 7, the poly aryl ether ketone polymer that carboxyl structure molar content prepared by embodiment 1 is 10% is replaced with
The poly aryl ether ketone polymer that carboxyl structure molar content prepared by embodiment 4 is 100%.Adjust DCC, DMAP and mono amino POSS
The quality of compound is respectively 0.4800g, 0.0290g and 2.0000g.Operating procedure, reaction condition, polymer are refined and dry
Process is same as Example 7, obtains the poly aryl ether ketone polymer that POSS structure molar contents are 100%, yield 97%.
Embodiment 11：
Such as embodiment 7~9, the carboxyl structure molar content that respectively prepared by selection example 5 is 10%, 20% and 30%
The poly aryl ether ketone polymer of structure containing tetramethyl biphenyl is reactant, finally obtain POSS structure molar contents be respectively 10%,
20% and 30% poly aryl ether ketone polymer of structure containing tetramethyl biphenyl, yield 96~98%.
Embodiment 12：
Such as embodiment 7~9, the carboxyl structure molar content that respectively prepared by selection example 6 is 10%, 20% and 30%
Poly aryl ether ketone polymer containing structure of bisphenol A is reactant, and it is respectively 10%, 20% and to finally obtain POSS structure molar contents
30% poly aryl ether ketone polymer containing structure of bisphenol A, yield 96~98%.
Claims (3)
1. one kind containing POSS structure ultralow dielectric poly aryl ether ketone polymers, structural formula is as follows：
X：
In above-mentioned polymerisation formula, m=0.1~1；The integer that n is 50~70.
2. a kind of preparation method containing POSS structure ultralow dielectric poly aryl ether ketone polymers described in claim 1,
Steps are as follows：
(1) preparation of different carboxyl structure content poly aryl ether ketone polymers
Using double fluorine monomers, biphenol monomer as reaction monomers, biphenol monomer is biphenol monomer containing carboxyl structure and other biphenol monomers
Mixing；Wherein, the molar ratio of the total dosage of double fluorine monomers and the total dosage of biphenol monomer is 1~1.03: 1, contains carboxylic in biphenol monomer
The mole dosage percentage of based structures biphenol monomer is 10~100%；Using sulfolane as solvent, the solid content of reaction system is set to be
20~30%；Using toluene as dehydrating agent, potassium carbonate is salt forming agent, and salt forming agent is that biphenol monomer total mole number contains carboxylic with half
(when without using other biphenol monomers, the dosage of salt forming agent is containing carboxylic to 1.05~1.10 times of base biphenol monomer molal quantity summation
1.58~1.65 times of base biphenol monomer molal quantity)；Reaction monomers, potassium carbonate, sulfolane and toluene are added to reaction vessel
In, it is warming up to 120~130 DEG C under the conditions of nitrogen protection, keeps the reflux of toluene azeotrope with water, reaction extremely reaction life in 2~3 hours
At water taken out of completely, then be warming up to 190~220 DEG C the reaction was continued 8~16 hours；After reaction, polymerisation is produced
Object discharges in 5~10% hydrochloric acid of mass fraction, obtains pale solid；After pulverizer crushes, ethyl alcohol and distillation are used respectively
Water washing 6~8 times, to remove excessive monomeric compound, solvent and inorganic salts；It is finally dry under 70~90 DEG C of vacuum conditions
10~12 hours, obtain the poly aryl ether ketone polymer of different carboxyl structure contents；
(2) preparation of the poly aryl ether ketone polymer of difference POSS structural contents
Using tetrahydrofuran as solvent, it is a concentration of that the poly aryl ether ketone polymer of different carboxyl structure contents is configured to mass volume ratio
5~10% polymer solution dissolves under the conditions of nitrogen protection and magnetic agitation in ice-water bath；Wait for that reaction system is 0 DEG C
When, the tetrahydrofuran solution of DMAP is added drop-wise in above-mentioned polymer solution with the speed of 3~5 drops/minute, recession is added dropwise
Remove ice-water bath；After temperature of reaction system is restored to room temperature, mono amino identical with carboxyl molal quantity is added into reaction system
Then the tetrahydrofuran solution of DCC is added drop-wise to the speed of 3~5 drops/minute in reaction system by POSS compounds again；Anti-
It answers and spherical condensation tube is installed on device, react 20~24 hours under room temperature；After reaction, product goes out in distilled water
Flocculent polymer is precipitated in material；Washed repeatedly 6~10 times with distilled water and ethyl alcohol respectively, remove polymer in remaining solvent,
DCC and DMAP, it is finally 10~12 hours dry under 70~90 DEG C of vacuum conditions, obtain the poly- virtue containing different POSS structural contents
Ether ketone polymer；Wherein, the molar ratio of the poly aryl ether ketone polymer carboxyl functional group and DCC, DMAP of different carboxyl structure contents
It is 1.0: 1.0~1.2: 0.10~0.12.
3. a kind of preparation method containing POSS structure ultralow dielectric poly aryl ether ketone polymers as claimed in claim 2,
It is characterized in that：Double fluorine monomers are 4,4 '-difluoro benzophenones, and biphenol monomer containing carboxyl structure is 3,5- dihydroxy-benzoic acids,
Other biphenol monomers are hexafluoro bisphenol-a, 3,3 ', 5,5 '-tetramethyl -4,4 '-'-biphenyl diphenols or bisphenol-A.
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| CN116285863A (en) * | 2023-02-17 | 2023-06-23 | 深圳市聚芯源新材料技术有限公司 | Composite engineering plastic with low dielectric constant and preparation method thereof |
| CN116285863B (en) * | 2023-02-17 | 2024-01-23 | 深圳市聚芯源新材料技术有限公司 | Composite engineering plastic with low dielectric constant and preparation method thereof |
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