CN104262628B - Main chain organo silicone polyether sulphone resin containing line style and cage modle and preparation method thereof - Google Patents
Main chain organo silicone polyether sulphone resin containing line style and cage modle and preparation method thereof Download PDFInfo
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- CN104262628B CN104262628B CN201410515004.3A CN201410515004A CN104262628B CN 104262628 B CN104262628 B CN 104262628B CN 201410515004 A CN201410515004 A CN 201410515004A CN 104262628 B CN104262628 B CN 104262628B
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- main chain
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- 239000011347 resin Substances 0.000 title claims abstract description 23
- 229920005989 resin Polymers 0.000 title claims abstract description 23
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 125000001174 sulfone group Chemical group 0.000 title claims abstract description 9
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 8
- 125000000962 organic group Chemical group 0.000 title claims abstract description 8
- 229920000570 polyether Polymers 0.000 title claims abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- -1 methoxyl group Chemical group 0.000 claims abstract description 15
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 13
- 150000003457 sulfones Chemical class 0.000 claims abstract description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 7
- 239000000376 reactant Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical class CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 5
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims abstract description 3
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000005375 organosiloxane group Chemical group 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims 2
- GZSRSEKMHAYHNS-UHFFFAOYSA-N C1(=CC=CC=C1)S(=O)(=O)C1=CC=CC=C1.[F] Chemical compound C1(=CC=CC=C1)S(=O)(=O)C1=CC=CC=C1.[F] GZSRSEKMHAYHNS-UHFFFAOYSA-N 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 239000004695 Polyether sulfone Substances 0.000 abstract description 41
- 229920006393 polyether sulfone Polymers 0.000 abstract description 41
- 229920000642 polymer Polymers 0.000 abstract description 37
- 238000009835 boiling Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 abstract description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 abstract description 2
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 abstract 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 abstract 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 abstract 1
- NVYQDQZEMGUESH-UHFFFAOYSA-N dimethylsilyloxy(dimethyl)silane Chemical class C[SiH](C)O[SiH](C)C NVYQDQZEMGUESH-UHFFFAOYSA-N 0.000 abstract 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 abstract 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 15
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 230000002209 hydrophobic effect Effects 0.000 description 11
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910002808 Si–O–Si Inorganic materials 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 5
- 239000005770 Eugenol Substances 0.000 description 5
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 229960002217 eugenol Drugs 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 229910018557 Si O Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004377 microelectronic Methods 0.000 description 3
- 230000003252 repetitive effect Effects 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 235000021050 feed intake Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011806 microball Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
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- 229910052805 deuterium Inorganic materials 0.000 description 1
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- 238000005213 imbibition Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000005267 main chain polymer Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000090 poly(aryl ether) Polymers 0.000 description 1
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- Silicon Polymers (AREA)
Abstract
A kind of main chain organo silicone polyether sulphone resin containing line style and cage modle and preparation method thereof, belongs to technical field of polymer chemistry.It is with 3,13 2 (2 methoxyl group 4 propylphenol) octaphenyl cage-type silsesquioxane (2OH DDSQ) and 1,1,3,3 tetramethyl disiloxanes 1,3 two (3 methoxyl group 4 propylphenol) (2OH PDMS) and difluorodiphenyl sulfone are reactant, with N, N dimethylacetylamide, N, the high boiling solvents such as N dimethylformamide, N-methyl pyrrolidones, sulfolane are solvent, with one or both in sodium carbonate, potassium carbonate, cesium carbonate as salt forming agent, with toluene as water entrainer.Synthetic route of the present invention is simple, and raw material is easy to get, and product is easy to processing, and the polyether sulfone random vinyl chloride made has the heat resistance of excellence, and hydrophobicity, solvent resistance and low-dielectric energy, be a kind of novel high polymer material with fine prospects for commercial application.
Description
Technical field
The invention belongs to technical field of polymer chemistry, be specifically related to a kind of main chain containing line style and the organosilicon of cage modle
Oxygen alkane polyethersulfone resin and preparation method thereof.
Background technology
Polyethersulfone resin is as a kind of special engineering plastics, with its good mechanical property and excellent heat-resisting quantity
Can, it is used in the fields such as space flight, military affairs, microelectronic component widely.But due to the distinctive molecule of polyether sulfone
Structure and element composition so that its dielectric constant higher (κ>3.3), hydrophobic performance are the most excellent (CA<80o),
Limit it in microelectronics and the application in hydrophobic material field.Carry out novel polyether sulfone Molecular Design with modified
The main direction of studying of research polyether sulfone materials the most in recent years, as carried out graft modification, end to polyether sulfone
Base introduce introduce on functional groups or main chain have three-dimensional structure to nonplanar structure, in order to change Jie of polyether sulfone
Electricity, hydrophobic performance, extend its application in terms of functional material.
Cage-type silsesquioxane (POSS) is a kind of novel nano-material, itself have excellent heat resistance,
Non-oxidizability and low-dielectric energy.POSS is the hollow-core construction with the inorganic silica of cube polyhedron as framework, outward
Portion is by the cincture of organofunctional group institute, good with the compatibility of organic polymer, and has the strongest designing
Property.As that reported in the past is incorporated into the POSS of single functionality in polymer with the method for grafting or end-blocking, can
To improve hydrophobic, dielectric and hot property (B.S.Kim, P.T.Mather, the Macromolecules of material
2002,35,8,378 8384), but product graft rate and the extent of reaction are the most not exclusively, and material exists certain defect.
Recently, people have been the hyperbranched polymer-modified research (J.Am. of POSS monomer of substantial amounts of eight degrees of functionality
Chem.Soc.2001,123,11420-11430), have an advantage in that and POSS can be incorporated into polymerization owner
Chain, thus change molecular composition and the structure of main polymer chain, but its polymerization process easily causes reaction system
Crosslinking.
Dihydroxy octaphenyl cage-type silsesquioxane (2OH-DDSQ) is in unsaturated cage-type silsesquioxane
A kind of (Chinese patent, publication number: 103204872A, publication date: 20130717), it is by Si-O-Si
The organosilicon structures with class Double-layer clamp template framework of key composition ,-OH the group the highest by reactivity is symmetrical
The two ends of distribution double plate, can form, by hydrolytic condensation or nucleophilic displacement process, the line that structure composition is clear and definite
Property polymer.Along with the introducing of this big rigid radical of 2OH-DDSQ, polymer segment motion is limited
System, the nano hollow structure of 2OH-DDSQ reduces again the packing density of polymer simultaneously, working in coordination with of the two
Effect makes the dielectric of polymer substantially reduce.The surface of silicone components can be low, easily at polymer surfaces simultaneously
Enrichment, can improve the hydrophobic performance of polymer.
Linear polydimethylsiloxane-be one there is surface can be low, heat endurance is high, and Chain Flexibility is high
Organic-inorganic hybrid material.The introducing of linear polyorganosiloxane component, can improve polymeric material in many aspects
The performance of material, such as, can reduce water imbibition and the dielectric constant of material, improves the gas permeability of material and anti-oxidant energy
Power, improves processing characteristics.These copolymers introducing linear polyorganosiloxane are particularly suitable for microelectronics
Device and hydrophobic coating field.But cage-type silsesquioxane and Linear volatile silicone are collectively incorporated into polyether sulfone tree
Fat, and its dielectric, hydrophobic and heat endurance are carried out comprehensive study, pertinent literature and patent also rarely have report
Road.
Summary of the invention
The technical problem to be solved in the present invention is, contains 3 with main chain, 13-bis-(2-methoxyl group-4-propylphenol)
Octaphenyl cage-type silsesquioxane (2OH-DDSQ) (Chinese patent, publication number: 103204872A, open
Day: 20130717) and 1,1,3,3-tetramethyl disiloxane-1,3-two (3-methoxyl group-4-propylphenol)
(2OH-PDMS) (US20100249276A1) linear bis-phenol series oligomer is raw material, with difluorodiphenyl
Sulfone monomer copolycondensation, prepares main chain and contains line style and the polyethersulfone resin of cage modle times organosiloxane, is total to for random
Polymers.
Based on polyethersulfone resin, 3,13-bis-(2-methoxyl group-4-propylphenol) octaphenyl cage-type silsesquioxane and
1,1,3,3-tetramethyl disiloxane-1, the excellent properties of 3-bis-(3-methoxyl group-4-propylphenol) series oligomer,
The present invention synthesizes angle from MOLECULE DESIGN, cage-type silsesquioxane, linear organosiloxane is collectively incorporated into
In polyethersulfone resin, synthesize a kind of novel structure, formed controlled, main chain containing line style and the organic silica of cage modle
The polyethersulfone resin of alkane.This material has the excellent of cage-type silsesquioxane, linear organic silica and polyethersulfone resin concurrently
Point, is a kind of novel high polymer material with excellent functionality.
The preparation method of the main chain 2OH-PDMS linear bis-phenol oligomer containing Si-O-Si is as follows:
1,1,3,3-tetramethyl dihydro siloxane oligomers and eugenol is added in the container of nitrogen protection,
The amount of the material of 1,1,3,3-tetramethyl dihydro siloxane oligomers and eugenol ratio for 1:2.1～2.5, is made with toluene
For system solvent (mass fraction of toluene is the 20%～30% of solution, i.e. toluene/(toluene+eugenol+1,1,3,3-
Tetramethyl dihydro siloxane oligomers), the Karst catalyst of dropping catalytic amount, it is warmed up to 60～90 DEG C instead
Answer 12～24h, stop heating and be cooled to room temperature.The rotation of whole liquid system is evaporated off toluene, and decompression is distilled off not
The low boiling component of reaction, obtaining water white transparency after cooling has the product of certain viscosity, i.e. main chain containing Si-O-Si
2OH-PDMS series bis-phenol oligomer.And by FTIR, NMR, mass spectrum to its structure with form into
Row characterizes.
The main chain 2OH-PDMS series bis-phenol oligomer synthetic reaction formula containing Si-O-Si is as follows:
Wherein p is the degree of polymerization of linear siloxane, is the integer of 0～1000；
The present invention, with 2OH-PDMS, 2OH-DDSQ and difluorodiphenyl sulfone as raw material, has synthesized a kind of main chain
In containing line style and the polyethersulfone resin of cage modle organosiloxane, the structural formula of its elementary cell is as follows:
Wherein 0 m 1, represents the ratio shared by each group in elementary cell, and p is linear organosiloxane
The degree of polymerization, be the integer of 0～1000.
Concrete preparation method: with 3,13-bis-(2-methoxyl group-4-propylphenol) octaphenyl cage-type silsesquioxane
(2OH-DDSQ) with 1,1,3,3-tetramethyl disiloxane-1,3-two (3-methoxyl group-4-propylphenol)
(2OH-PDMS) and difluorodiphenyl sulfone be reactant, with N, N dimethylacetylamide, N, N dimethyl formyl
The high boiling solvents such as amine, N-methyl pyrrolidones, sulfolane are solvent, with sodium carbonate, potassium carbonate, cesium carbonate
In one or both be salt forming agent, with the low polar high-boiling solvent such as toluene, dimethylbenzene as water entrainer；
Corresponding operating flow process: add reactant, solvent, salt forming agent and water entrainer liter in the container of nitrogen protection
Warm to 130 DEG C～150 DEG C, band water salt-forming reaction 2～4h；It is warming up to 160～170 DEG C, 180～190 the most respectively
DEG C and 190～210 DEG C of each reaction 2h～4h；Last discharging, in deionized water, is respectively washed with water and ethanol after pulverizing
Wash 3～5 times, obtain main chain containing linear organosiloxane and the polyethersulfone resin of cage-type silsesquioxane；Wherein,
3,13-bis-(2-methoxyl group-4-propylphenol) octaphenyl cage-type silsesquioxane, 1,1,3,3-tetramethyl two silica
Alkane-1, the mol ratio of 3-bis-(3-methoxyl group-4-propylphenol) siloxanes and difluorodiphenyl sulfone is m:1-m:1,
0 m 1, potassium carbonate is 1.5～1.00: 1 with the mol ratio of difluorodiphenyl sulfone, and the quality of solvent is reactive material
4～5 times of amount, the volume of water entrainer is the 30%～50% of solvent volume.Dividing of product is determined by GPC
Son amount, by differential scanning calorimetric, thermal weight loss, water contact angle tests, infrared and surface-element analysis test etc.
The performance of product is characterized by method.
The synthetic reaction formula of the polyethersulfone resin of the present invention be presented herein below:
Wherein, 0 < m < 1, n represents the degree of polymerization, is the integer of 1～1000；
The present invention uses main chain to contain the biphenol monomer of Linear volatile silicone, the biphenol monomer synthesis of cage-type silsesquioxane
Main chain contains line style and the polyethersulfone resin of cage modle siloxane structure.Along with Si-O-Si repetitive in main chain
With the introducing of methoxyl group side base, the Tg of polymer is reduced to embodiment 1 to implementing by conventional polyether sulfone 230 DEG C
64 DEG C of example 5～135 DEG C, it is very beneficial for machine-shaping.The heat endurance of polymer is the most notable simultaneously
Change.And polymer solvent resistance is excellent, being practically insoluble in any common solvents under normal temperature, Static Water connects
Feeler can reach the 113o of embodiment six, and hydrophobic performance is excellent, and dielectric constant test shows that its numerical value is minimum
It is a kind of well dielectric materials for embodiment 20 respective value 2.36.
Synthetic route of the present invention is simple, and raw material is easy to get, and product is easy to processing, and make polyether sulfone randomly altogether
Poly resin has the heat resistance of excellence, and hydrophobicity, solvent resistance and low-dielectric energy, be that one has fine work
The novel high polymer material of industry application prospect.
Accompanying drawing explanation
Fig. 1. the infrared spectrum of 2OH-PDMS-6 in embodiment 1；
Fig. 2. 2OH-PDMS-6 in embodiment 11H nuclear magnetic spectrogram；
Fig. 3. polymer poly ether sulfone 1～51H nuclear magnetic spectrogram；
Fig. 4. polyether sulfone 4 in embodiment 129Si nuclear magnetic spectrogram；
Fig. 5. the water contact angle test value of the polyether sulfone 1～6 of embodiment 1 preparation；
Fig. 6. the infrared spectrum of polymer in embodiment 4；
Fig. 7. the glass transition temperature curve of polymer in embodiment 4；
Fig. 8. the thermogravimetric curve of polymer in embodiment 4
Fig. 9. the X-ray diffraction curve of polymer in embodiment 4
Figure 10. the dielectric constant test result of polymer in embodiment 4
Detailed description of the invention
Embodiment 1
The first step: add octamethylcy-clotetrasiloxane (2.966g, 0.01mol) in the container of nitrogen protection,
1,1,3,3-tetramethyl two hydrogen siloxane (1.3432g, 0.01mol), acidity of catalyst phenylethylene micro ball (0.215g,
Weight/mass percentage composition ω %=0.05%) and solvent dry toluene (18ml), 80 DEG C of constant temperature 24 hours, it is filtered to remove
Catalyst, with the most neutral with system in flaky calcium carbonate, reducing pressure after rotation steaming, it is anti-that unreacted low boiling is distilled off
Answer thing and product, obtain the main chain linear polydimethylsiloxane-containing 6 Si-O repetitives
(2H-PDMS-6), product quality 3.94g.
Second step: add 2H-PDMS-6 (3.94g, 0.0095mol), eugenol in the container of nitrogen protection
(3.28g, 0.01995mol), Karst catalyst 5 using toluene (29ml) as solvent, 80 DEG C of constant temperature
8～10h, it is then cooled to room temperature, after rotation is evaporated off solvent toluene, decompression distillation, obtaining water white transparency has one
Determine the product of viscosity, the i.e. main chain bis-phenol oligomer (2OH-PDMS-6) containing Si-O-Si, productivity: 89.3%.
The infrared spectrum of 2OH-PDMS-6 is measured with NicoletImpact410 Fourier transformation infrared spectrometer,
Sweep limits 4000～400cm-1, resolution ratio 4cm-1, KBr compressing tablet, result is shown in Fig. 1.Can be seen by Fig. 1
Go out, 2127cm-1The Si--H bond peak at place and 1625cm-1Neighbouring C=C double bond peak has disappeared, and 1100
cm-1Place Si-O-S key, 2900cm-1Neighbouring CH3、3400cm-1Neighbouring OH peak is all in oligomer INFRARED SPECTRUM
Figure occurs.
The nuclear-magnetism of 2OH-PDMS-6 is measured with Bruker Advance 510 type NMR (300MHz)
Resonance hydrogen spectrum, with deuterated DMSO as solvent, with TMS (tetramethylsilane) as internal standard, test result is shown in
Fig. 2.Occur in that the characteristic peak of linear polydimethylsiloxane-and each characteristic peak of eugenol in fig. 2, and
Disappear at Si-H absworption peak 4.75ppm, by characteristic peak area ratio, 2OH-PDMS-6 (its of provable synthesis
Structural formula is identical with the structural formula of the 2OH-PDMS described in summary of the invention, n=6) it is consistent with expected structure.
2OH-PDMS-6,2OH-DDSQ, difluorodiphenyl sulfone and potassium carbonate are joined nitrogen protection by the 3rd step
Container in, with N-methyl pyrrolidones as solvent, toluene is water entrainer.Being warming up to 140 DEG C, band water becomes salt
Reaction 4h.Order is warming up to 160 DEG C, 180 DEG C and 200 DEG C each reaction 2h.Stirring discharging in deionized water,
Pulverize, respectively wash 5 times with water and ethanol, obtain the main chain polyether sulfone containing linear dimethyl siloxane different content,
Both main chain contained cage modle and linear silsesquioxane polyether sulfone 1～6.The when productivity that feeds intake is shown in Table 1.
Table 1: main chain contains line style and the when productivity that feeds intake of cage modle polyether sulfone 1～6
Measure in main chain containing linear and cage type with Bruker Advance 510 type NMR (300MHz)
The proton nmr spectra of silsesquioxane polyether sulfone 1～5, with TMS (tetramethylsilane) as internal standard, with deuterium
It is that solvent test result is shown in Fig. 3 for DMSO.As seen from Figure 3, have containing line style and cage modle in main chain
In the spectrogram of the polyether sulfone 1～5 of machine silsesquioxane, along with the increase of the content of cage-type silsesquioxane, its h
The characteristic peak area at place gradually rises, and the characteristic peak area at linear siloxane a is gradually reduced, its each
Peak has and belongs to accurately.
Polyether sulfone 4 obtained by the present embodiment29Si nuclear magnetic spectrogram is shown in Fig. 4 (wherein m=0.3).From polymer
Nuclear magnetic spectrogram in can be seen that characteristic peak a, the b peak position representing linear siloxane is correct, and peak intensity is bright
Aobvious.The characteristic peak c, d that represent cage-type silsesquioxane also appear in position accurately.In this proof polymer both
Cage modle organic sesqui siloxane is contained again containing line style polymethyl siloxane.
The hydrophobic performance of the polyether sulfone series polymer obtained by the present embodiment is by the Static water contact angles of Fig. 5
Numerical value, has it can be seen that this material water contact angle is all higher than 90o with cage-type silsesquioxane changes of contents figure
Good hydrophobic performance.
Embodiment 2
Changing rate of charge to be polymerized, building-up process is same as in Example 1, and preparing main chain has with cage modle containing line style
The polyether sulfone 7～12 of organic siloxane different content.The when productivity that feeds intake is shown in Table 2.
Table 2: change the polymerization of the polyether sulfone after rate of charge and feed intake and product
Embodiment 3
Changing rate of charge to be polymerized, building-up process is same as in Example 1, prepares polyether sulfone 13～18.Feed intake
When productivity is shown in Table 3.
Table 3: the when productivity that feeds intake of polyether sulfone 13～18
In embodiment 2 with embodiment 3, by changing K2CO3The mol ratio of consumption and difluorodiphenyl sulfone
Testing, result shows that productivity is higher when the two ratio is between 1.1～1.2:1.
Embodiment 4:
Addition octamethylcy-clotetrasiloxane (2.966g, 0.01mol) in the container of nitrogen protection, 1,1,3,3-
Tetramethyl two hydrogen siloxane (0.6716g, 0.005mol), acidity of catalyst phenylethylene micro ball (0.215g, 0.05%)
With dry toluene (15ml), 80 DEG C of constant temperature 24 hours, Filtration of catalyst, with in flaky calcium carbonate and body
System is to neutral, and after rotation is steamed, decompression is distilled off unreacted low boiling reactant and product, obtains main chain containing 4
The linear polydimethylsiloxane-(2H-PDMS-4) of Si-O repetitive.Productivity: 95%.
2OH-PDMS-4,2OH-DDSQ, difluorodiphenyl sulfone and potassium carbonate is added in the container of nitrogen protection,
With N-methyl pyrrolidones as solvent, with toluene as water entrainer.It is warming up to 140 DEG C, band water salt-forming reaction 3h.
Order is warming up to 160 DEG C, 180 DEG C and 200 DEG C each reaction 2h.Discharging, in deionized water, is pulverized, is used water
Respectively wash with ethanol 5 times, prepare the main chain polyether sulfone 19-23 containing line style with cage-type silsesquioxane.
Table 4: the when productivity that feeds intake of polyether sulfone 19～23
Measure the infrared spectrum of polymer with NicoletImpact410 Fourier transformation infrared spectrometer, see Fig. 6.
From fig. 6 it can be seen that at 1094cm-1The infrared absorption peak at place is Si-O key, 1259cm-1And 848cm-1
Place's Si-C key, each infrared signature absworption peak shows that two kinds of structural silicone oxygen alkane have successfully been incorporated into polymerization
In the middle of thing.
With METTLER TOLEDO DSC 821eDifferential scanning thermometric analysis instrument measures polyether sulfone 19～23
Glass transition temperature, nitrogen atmosphere, test scope 0～300 DEG C, 10 DEG C/min of heating rate, result is shown in figure
7.As seen from Figure 7, the glass transition temperature (T of polymerg) along with the increasing of cage-type silsesquioxane content
Add and increase.
Pyris 1TGA (Perkin Elmer) thermal analyzer is utilized to measure polyether sulfone 19～23 thermal weight loss temperature, empty
Gas condition, temperature range 100～800 DEG C, heating rate is 10 DEG C/min.Before testing by sample at 100 DEG C
The driest lower 24h, to remove solvent and the moisture of residual in sample.Result is shown in Fig. 8, it is seen that polymer
Thermal weight loss temperature (the T of 5%d) all there is more than 356 DEG C good heat-resistant stability.
The X-ray diffractogram of polymer is shown in Fig. 9.The most each polymer has two diffraction maximums,
And along with the height increasing peak of cage-type silsesquioxane content increases, and half-peak breadth narrows.This illustrates polymerization
The regular performance of the crystal property of thing, chain gradually strengthens.Prove that cage-type silsesquioxane is tied with cage modle in the polymer
Structure exists, and has been incorporated in polymer.
Figure 10 is the dielectric constant change curve with frequency of polymer, therefrom it will be seen that polymer
Jie put constant all below 3.1, the amount mark at cage modle material is 5% to be to have minimum 2.3, be one very
Good dielectric materials.
The dissolubility of test polymer under the conditions of normal temperature (20 DEG C), heating (80 DEG C) respectively.Result shows,
The main chain polymer containing line style and cage modle organic sesqui siloxane has the solvent resistant performance of excellence, is specifically shown in Table
5。
Table 5: the dissolubility of polyether sulfone 19～23
Note: ++: normal temperature is solvable+heat solvable-: heat insoluble.
By the performance statistics of table 6 polymer it can be seen that the molecular weight of polymer is higher and concentration is compared in distribution.
Table 6: the performance of polyether sulfone 19～23
The controlled 2OH-PDMS-n monomer of chain length of present invention synthesis and 2OH-DDSQ and difluorodiphenyl
Sulfone carries out copolymerization, is successfully prepared main chain and contains line style and the polyethersulfone resin of cage modle organic sesqui siloxane, and
Characterizing it, result is consistent with expection.Result of study shows, main chain contains line style and the organic sesquialter of cage modle
Glass transition temperature (the T of the polyaryl ether sulphone resin of siloxanesg) with cage-type silsesquioxane content increase and
Raise.This is the introducing of the rigid structure due to cage-type silsesquioxane, reduces what the motion of strand caused.
The good thermal stability of polymer, and along with its heat endurance of increase of cage-type silsesquioxane content has carried
High.Water contact angle test result shows, owing to the introducing of organic sesqui siloxane significantly enhances polymer
Hydrophobic performance.The dielectric constant minimum of polymer can reach less than 2.4 simultaneously, is a kind of good low Jie
Electric material.
Claims (5)
1. main chain contains line style and an organo silicone polyether sulphone resin for cage modle, the structural formula of its basic structural unit
As follows:
Wherein 0 m 1, p are the degree of polymerization of linear organosiloxane, are the integer of 0～1000.
2. a kind of main chain described in claim 1 is containing line style and the preparation side of the organo silicone polyether sulphone resin of cage modle
Method, it is characterised in that: in the container of nitrogen protection, add reactant, solvent, salt forming agent and water entrainer
It is warming up to 130 DEG C～150 DEG C, band water salt-forming reaction 2～4h；Be warming up to the most respectively 160～170 DEG C,
180～190 DEG C and 190～210 DEG C each reaction 2h～4h；Last discharging, in deionized water, is used after pulverizing
Water and ethanol respectively wash 3～5 times, obtain poly-containing linear organosiloxane and cage-type silsesquioxane of main chain
Ether sulfone resin；Wherein, reactant is 3,13-bis-(2-methoxyl group-4-propylphenol) octaphenyl cage model sesquialter
Siloxanes, 1,1,3,3-tetramethyl disiloxane-1,3-two (3-methoxyl group-4-propylphenol) siloxanes and two
Fluorine diphenyl sulphone (DPS), its mol ratio is m:1-m:1,0 m 1；Salt forming agent and difluorodiphenyl sulfone mole
Ratio is 1.5～1.00: 1；The quality of solvent is 4～5 times of reactant quality, and the volume of water entrainer is solvent
The 30%～50% of volume.
A kind of main chain the most as claimed in claim 2 is containing line style and the preparation of the organo silicone polyether sulphone resin of cage modle
Method, it is characterised in that: solvent is N, N dimethylacetylamide, N, N dimethylformamide, N-methyl
Pyrrolidones or sulfolane.
A kind of main chain the most as claimed in claim 2 is containing line style and the preparation of the organo silicone polyether sulphone resin of cage modle
Method, it is characterised in that: salt forming agent is one or both in sodium carbonate, potassium carbonate, cesium carbonate.
A kind of main chain the most as claimed in claim 2 is containing line style and the preparation of the organo silicone polyether sulphone resin of cage modle
Method, it is characterised in that: water entrainer is toluene or dimethylbenzene.
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| CN103204872A (en) * | 2013-04-14 | 2013-07-17 | 吉林大学 | Dyhydroxyl cage-type silsesquioxane monomer and preparation method thereof |
| CN103613764A (en) * | 2013-12-06 | 2014-03-05 | 吉林大学 | Polyarylether sulphone resin with main chain containing cage-type silsesquioxane double-deck structure and preparation method thereof |
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| CN103204872A (en) * | 2013-04-14 | 2013-07-17 | 吉林大学 | Dyhydroxyl cage-type silsesquioxane monomer and preparation method thereof |
| CN103613764A (en) * | 2013-12-06 | 2014-03-05 | 吉林大学 | Polyarylether sulphone resin with main chain containing cage-type silsesquioxane double-deck structure and preparation method thereof |
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