CN115785672A - Polyphenylene sulfone composite material and preparation method and application thereof - Google Patents
Polyphenylene sulfone composite material and preparation method and application thereof Download PDFInfo
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- CN115785672A CN115785672A CN202211563756.8A CN202211563756A CN115785672A CN 115785672 A CN115785672 A CN 115785672A CN 202211563756 A CN202211563756 A CN 202211563756A CN 115785672 A CN115785672 A CN 115785672A
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- polyphenylsulfone
- composite material
- fibers
- amide group
- resin
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- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 229920012287 polyphenylene sulfone Polymers 0.000 title description 30
- 238000002360 preparation method Methods 0.000 title description 7
- 229920000491 Polyphenylsulfone Polymers 0.000 claims abstract description 57
- 125000003368 amide group Chemical group 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000000835 fiber Substances 0.000 claims abstract description 21
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 10
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000002250 absorbent Substances 0.000 claims abstract description 4
- 230000002745 absorbent Effects 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims description 29
- 229930185605 Bisphenol Natural products 0.000 claims description 25
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 25
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 10
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 10
- 239000004917 carbon fiber Substances 0.000 claims description 10
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims description 9
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 claims description 7
- 229920006231 aramid fiber Polymers 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- -1 3, 5-di-tert-butyl-4-hydroxyphenyl Chemical group 0.000 claims description 4
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 229920002748 Basalt fiber Polymers 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 239000004760 aramid Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 150000008430 aromatic amides Chemical group 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 150000001408 amides Chemical class 0.000 abstract 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000010998 test method Methods 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 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 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 210000003097 mucus Anatomy 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a polyphenylsulfone composite material which comprises the following components in parts by weight: 60-80 parts of polyphenylsulfone resin; 20-40 parts of fibers; 0.1 to 0.2 portion of acid absorbent; 0 to 0.3 part of antioxidant. The invention adopts the polyphenylsulfone polymer containing specific aromatic amide group, and the unshared electron pair and carbonyl on the amino nitrogen in the amide group
Description
Technical Field
The invention relates to the technical field of high polymer materials, and particularly relates to a polyphenylsulfone composite material and a preparation method and application thereof.
Background
Polyphenylene sulfone is a thermoplastic special engineering plastic, and is widely applied to the fields of electronics, electrical appliances, machinery, automobiles, medical appliances and the like for a long time due to excellent comprehensive properties of heat resistance, hot water resistance, creep resistance, dimensional stability, chemical resistance, no toxicity, flame retardance and the like. The use of plastics instead of metals has the advantages of cost reduction, high flexibility of product design and light weight, and with the trend of consumer demand, "steel is replaced by plastics", in many practical applications, impact resistance is a key property, and hardness, processability and heat resistance of materials need to be considered. However, the conventional polyphenylsulfone has the problem of easy stress cracking, and because the processing temperature of the polyphenylsulfone is generally high, the polyphenylsulfone resin is partially hydrolyzed and the mechanical property is deteriorated due to the defects of the structure of the polyphenylsulfone resin during the processing. Therefore, modification of polyphenylsulfone to improve strength is a hot research focus for polyphenylsulfone materials.
Disclosure of Invention
The invention aims to provide a polyphenylsulfone composite material which has high strength, high hardness and high heat resistance.
The invention is realized by the following technical scheme:
the polyphenylsulfone composite material is characterized by comprising the following components in parts by weight:
60-80 parts of polyphenylsulfone resin;
20-40 parts of fibers;
0.1 to 0.2 portion of acid absorbent;
0 to 0.3 portion of antioxidant;
wherein the polyphenylsulfone resin is derived from the following monomers in mole percent:
10-35mol% of 4,4' -biphenol;
15-40mol% of amide group-containing bisphenol monomer;
45-55mol% of 4,4' -dichlorodiphenyl sulfone;
the amide group-containing bisphenol monomer is as follows:
，
wherein R is 1 And R 2 Are respectively as
、
、
Any one of a heterocyclic aromatic group or polycyclic aromatic group; n is said 1 Is a positive integer greater than or equal to 1; the R is 3 Is composed of
、
、
、
、
、
、
、
Oxygen atom, sulfur atom or a linear or branched aliphatic divalent group of more than 6 carbon atoms, wherein n 2 Is a positive integer from 1 to 6; the heterocyclic aromatic group is an aromatic group in which atoms constituting a ring contain at least one hetero atom in addition to carbon atoms; the polycyclic aromatic group means an aromatic group in which two or more benzene rings are connected in a fused ring form.
Preferably, the polyphenylsulfone resin is derived from monomers comprising, in mole percent:
10-30mol% of 4,4' -biphenol;
20-35mol% of amide group-containing bisphenol monomer;
48-52mol% of 4,4' -dichlorodiphenyl sulfone.
Preferably, the amide group-containing bisphenol monomer is selected from
、
、
、
、
Or
Any one of them.
More preferably, the amide group-containing bisphenol monomer is selected from
、
Or
Any one of them.
Further preferably, the amide group-containing bisphenol monomer is selected from
Or
Any one of them.
Preferably, the proportion of cyclic oligomer in the polyphenylsulfone resin is less than 1.3wt%; preferably 1.0wt% to 1.1wt%.
Preferably, the polyphenylsulfone resin has a weight average molecular weight of 68000 to 80000 daltons.
The preparation method of the polyphenylsulfone resin comprises the following steps:
s1: salt forming reaction: adding a solvent into a reaction kettle, stirring and heating to 60-80 ℃, adding 4,4 '-biphenol, 4' -dichlorodiphenol and an amide group-containing bisphenol monomer, then adding a salt forming agent, a high-efficiency catalyst and a water separating agent, continuously stirring and heating to 170-200 ℃, and salifying for 1-3 hours; wherein the solvent is at least one of N-methyl pyrrolidone, N '-dimethylformamide, N' -dimethylacetamide, diphenyl sulfone, dimethyl sulfoxide and sulfolane; the high-efficiency catalyst is at least one of tributyl phosphine, triphenyl phosphine and tri-tert-butyl phosphine, and the molar weight of the catalyst is 0.01-0.1% of that of 4, 4-dichlorodiphenyl sulfone; the salt forming agent is at least one of potassium hydroxide, potassium carbonate, sodium hydroxide or sodium carbonate; the molar weight of the salt forming agent is 1.05 to 1.3 times that of the 4, 4-dichlorodiphenyl sulfone;
s2: polymerization reaction: evaporating water separating agent, heating to 220-240 deg.C, stirring at 40-80r/min, maintaining the temperature for 3-6h, increasing stirring speed to 80-90r/min to set viscosity to obtain polyphenylsulfone resin mucus, cooling, pulverizing, filtering, washing, and drying to obtain product; wherein the water separating agent is at least one of toluene, xylene, mesitylene, o-trimethylbenzene, m-trimethylbenzene, ethylbenzene and meta-ethylbenzene.
The fiber is selected from any one or more of glass fiber, carbon fiber, aramid fiber, basalt fiber, propionitrile fiber, boron fiber or whisker; preferably, the fiber is selected from any one or more of carbon fiber, aramid fiber or calcium sulfate whisker; more preferably, the fibers are carbon fibers.
The acid acceptor of the invention can be selected from any one or more of aluminum oxide, calcium oxide or magnesium oxide.
The antioxidant can be any one or more of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene or 2, 8-di-tert-butyl-4-methylphenol.
The invention also provides a preparation method of the polyphenylsulfone composite material, which comprises the following steps: adding the components into a double-screw extruder according to the proportion, carrying out melt mixing, extruding and granulating to obtain the polyphenylsulfone composite material. Preferably, the rotation speed of the screw is 420 to 485 rpm, and the processing temperature is 300 to 380 ℃.
The invention also provides application of the polyphenylsulfone composite material in the fields of electronics, automobiles and aviation. The alloy can be used for replacing metal and applied to parts such as automobile bumpers, airplane engine fairings and the like.
Compared with the prior art, the invention has the following beneficial effects:
the invention selects the polyphenylsulfone polymer containing specific aromatic amide group, the unshared electron pair on the amino nitrogen in the amide group and the carbonyl
Electrons form a conjugated system, so that the electron cloud density on nitrogen is reduced, the proton accepting capability is weakened, at the moment, the C-N bond has a certain degree of double bond property, and a firm hydrogen bond exists in an amide group, so that the molecule has good mechanical property; meanwhile, the amide group can be combined with the fiber in situ, the defect that the polyphenylsulfone resin is easy to stress crack is effectively overcome, the problem that the mechanical property of the material is deteriorated due to poor compatibility of the traditional polyphenylsulfone resin and the fiber in the prior art is solved, the polyphenylsulfone composite material which simultaneously has high strength, high hardness and high heat resistance is prepared, and the polyphenylsulfone composite material can replace metal to be applied to the fields of electronic appliances, automobiles and aviation and can meet the use requirement of the material under the development trend of replacing steel with plastic.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the concept of the invention. All falling within the scope of the present invention.
The sources of experimental raw materials used by the invention are as follows:
4,4' -biphenol: is sold on the market;
4,4' -dichlorodiphenyl sulfone: is sold on the market;
amide group-containing bisphenol monomer a:
commercially available;
amide group-containing bisphenol monomer B:
commercially available;
containing acyl radicalsAmine group bisphenol monomer C:
commercially available;
amide group-containing bisphenol monomer D:
commercially available;
amide group-containing bisphenol monomer E:
commercially available;
fiber 1: carbon fiber, commercially available;
fiber 2: aramid fiber, commercially available;
fiber 3: calcium sulfate whiskers, commercially available;
acid-absorbing agent: alumina, commercially available;
antioxidant: pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], commercially available.
Table 1/table 2 method of preparation of polyphenylsulfone resin: s1: salt forming reaction: adding a solvent into a reaction kettle, stirring and heating to 60-80 ℃, adding 4,4 '-biphenol, 4' -dichlorodiphenol and an amide group-containing bisphenol monomer, then adding a salt forming agent (potassium carbonate), a high-efficiency catalyst (tributylphosphine) and a water-dividing agent (toluene), continuously stirring and heating to 170-200 ℃ to form salt for 1-3h; s2: polymerization reaction: distilling off water-separating agent, heating to 220-240 deg.C, stirring at 40-80r/min, maintaining the temperature for 3-6h, increasing stirring speed to 80-90r/min to set viscosity to obtain polyphenylsulfone resin mucus, cooling, pulverizing, filtering, washing, and drying to obtain the product.
Method for testing weight average molecular weight: reference GB/T36214.4-2018;
the content test method of the cyclic oligomer comprises the following steps: refer to GB/T27843-2011.
Table 1: 1-6 repeating unit mol content of polyphenylene sulfone resin
| Polyphenylene sulfone resin-1 | Polyphenylene sulfone resin-2 | Polyphenylene sulfone resin-3 | Polyphenylene sulfone resin-4 | Polyphenylene sulfone resin-5 | Polyphenylene sulfone resin-6 | |
| 4,4' -biphenol, mol% | 35 | 30 | 25 | 20 | 15 | 10 |
| Amide group-containing bisphenol monomer A, mol% | 20 | 22 | 25 | 30 | 33 | 35 |
| 4,4' -dichlorodiphenyl sulfone, mol% | 45 | 48 | 50 | 50 | 52 | 55 |
| Weight average molecular weight, kDa | 72 | 74 | 76 | 75 | 74 | 73 |
| The ratio of cyclic oligomers, based on | 1.27 | 1.15 | 1.23 | 1.24 | 1.12 | 1.26 |
Table 2: polyphenylene sulfone resin 7-13 repeating unit molar content
| Polyphenylene sulfone resin-7 | Polyphenylene sulfone resin-8 | Polyphenylsulfone resin-9 | Polyphenylsulfone resin-10 | Polyphenylene sulfone resin-11 | Polyphenylsulfone resin-12 | Polyphenylene sulfone resin-13 | |
| 4,4' -Biphenyldiol, mol% | 20 | 20 | 20 | 20 | 50 | 30 | 15 |
| Amide group-containing bisphenol monomer A, mol% | 10 | 45 | |||||
| Bisphenol monomer B containing amido group, mol% | 30 | ||||||
| Amide group-containing bisphenol monomer C, mol% | 30 | ||||||
| Amide group-containing bisphenol monomer D, mol% | 30 | ||||||
| Amide group-containing bisphenol monomer E, mol% | 30 | ||||||
| 4,4' -dichlorodiphenyl sulfone, mol% | 50 | 50 | 50 | 50 | 50 | 60 | 40 |
| Weight average molecular weight, kDa | 75 | 75 | 76 | 74 | 74 | 63 | 62 |
| The ratio of cyclic oligomers% | 1.01 | 1.09 | 1.03 | 1.14 | 1.89 | 1.45 | 1.35 |
Preparation of polyphenylsulfone composites of examples and comparative examples:
adding the components into a double-screw extruder according to the mixture ratio of the components in the table 3/table 4, carrying out melt mixing at the screw rotating speed of 420-485 rpm and the processing temperature of 300-380 ℃, and carrying out extrusion granulation to obtain the polyphenylsulfone composite material.
Relevant performance test methods or standards:
(1) Heat distortion temperature: the test method is referred to ISO 75-1/-2.
(2) Tensile strength: the test method is according to ISO527.
(3) Impact strength of the simply supported beam notch: the test method is according to ISO 180/1A.
(4) Rockwell hardness: the test method is according to ASTM D785.
Table 3: examples 1-6 polyphenylene sulfone composites the respective component ratios (in parts by weight) and the associated performance test results
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| Polyphenylene sulfone resin-1 | 75 | |||||
| Polyphenylene sulfone resin-2 | 75 | |||||
| Polyphenylene sulfone resin-3 | 75 | |||||
| Polyphenylene sulfone resin-4 | 75 | |||||
| Polyphenylene sulfone resin-5 | 75 | |||||
| Polyphenylene sulfone resin-6 | 75 | |||||
| Carbon fiber | 25 | 25 | 25 | 25 | 25 | 25 |
| Aramid fiber | ||||||
| Acid-absorbing agent | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Antioxidant agent | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Heat distortion temperature/. Degree.C | 210 | 212 | 213 | 214 | 211 | 210 |
| Tensile strength/MPa | 117 | 118 | 119 | 117 | 117 | 115 |
| Impact strength/kJ/m 2 of simply supported beam gap | 85 | 86 | 88 | 88 | 89 | 84 |
| Rockwell hardness/HRC | 180 | 182 | 183 | 182 | 181 | 183 |
Table 4: examples 7-13 polyphenylene sulfone composites the proportions (in parts by weight) of the various constituents and the results of the associated Performance tests
| Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | Example 12 | Example 13 | Example 14 | |
| Polyphenylene sulfone resin-7 | 75 | 75 | 75 | 60 | ||||
| Polyphenylene sulfone resin-8 | 75 | |||||||
| Polyphenylsulfone resin-9 | 75 | 80 | ||||||
| Polyphenylene sulfone resin-10 | 75 | |||||||
| Carbon fiber | 25 | 25 | 25 | 25 | 40 | 20 | ||
| Aramid fiber | 25 | |||||||
| Calcium sulfate whisker | 25 | |||||||
| Acid-absorbing agent | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.1 | 0.2 |
| Antioxidant agent | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | / |
| Heat distortion temperature/. Degree.C | 216 | 214 | 216 | 212 | 206 | 208 | 218 | 212 |
| Tensile strength/MPa | 124 | 122 | 125 | 117 | 110 | 115 | 128 | 115 |
| Impact strength/kJ/m of simply supported beam gap 2 | 92 | 89 | 90 | 87 | 85 | 88 | 94 | 86 |
| Rockwell hardness/HRC | 185 | 183 | 185 | 181 | 175 | 180 | 190 | 179 |
Table 5: comparative examples 1-4 polyphenylene sulfone composite Material Each component proportion (by weight) and related Performance test results
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Polyphenylene sulfone resin-7 | 100 | |||
| Polyphenylene sulfone resin-11 | 75 | |||
| Polyphenylene sulfone resin-12 | 75 | |||
| Polyphenylsulfone resin-13 | 75 | |||
| Carbon fiber | 25 | 25 | 25 | |
| Acid-absorbing agent | 0.2 | 0.2 | 0.2 | 0.2 |
| Antioxidant agent | 0.1 | 0.1 | 0.1 | 0.1 |
| Heat distortion temperature/. Degree.C | 198 | 206 | 208 | 206 |
| Tensile strength/MPa | 94 | 102 | 105 | 108 |
| Impact strength/kJ/m of simply supported beam gap 2 | 72 | 78 | 81 | 83 |
| Rockwell hardness/HRC | 130 | 145 | 152 | 158 |
The results show that the polyphenylsulfone composite material prepared by selecting the polyphenylsulfone polymer containing the specific aromatic amide group and adding a certain amount of fibers, acid absorbent, antioxidant and other auxiliary agents has the tensile strength of more than or equal to 110Mpa and the impact strength of more than or equal to 84kJ/m 2 The Rockwell hardness is more than or equal to 175HRC, the thermal deformation temperature is more than or equal to 206 ℃, and the high strength, the high hardness and the high heat resistance can be simultaneously considered.
Claims (9)
1. The polyphenylsulfone composite material is characterized by comprising the following components in parts by weight:
60-80 parts of polyphenylsulfone resin;
20-40 parts of fibers;
0.1 to 0.2 portion of acid absorbent;
0 to 0.3 part of antioxidant;
wherein the polyphenylsulfone resin is derived from the following monomers in mole percent:
10-35mol% of 4,4' -biphenol;
15-40mol% of amide group-containing bisphenol monomer;
45-55mol% of 4,4' -dichlorodiphenyl sulfone;
the amide group-containing bisphenol monomer is as follows:
，
wherein R is 1 And R 2 Are respectively as
、
、
Any one of a heterocyclic aromatic group or polycyclic aromatic group; n is 1 Is a positive integer greater than or equal to 1; the R is 3 Is composed of
、
、
、
、
、
、
、
Oxygen atom, sulfur atom or a linear or branched aliphatic divalent group of more than 6 carbon atoms, wherein n 2 Is a positive integer of 1 to 6; the heterocyclic aromatic group is an aromatic group in which atoms constituting a ring contain at least one hetero atom in addition to carbon atoms; the polycyclic aromatic group means an aromatic group in which two or more benzene rings are connected in a fused ring form.
2. The polyphenylsulfone composite material of claim 1, wherein the polyphenylsulfone resin is derived from monomers comprising, in mole percent:
10-30mol% of 4,4' -biphenol;
20-35mol% of amide group-containing bisphenol monomer;
48-52mol% of 4,4' -dichlorodiphenyl sulfone.
3. The polyphenylsulfone composite material of claim 1, wherein the amide group-containing bisphenol monomer is selected from the group consisting of
、
、
、
、
Or
Any one of the above; preferably, the amide group-containing bisphenol monomer is selected from
、
Or
Any one of the above; more preferably, the amide group-containing bisphenol monomer is selected from
Or
Any one of them.
4. The polyphenylsulfone composite material of claim 1, wherein the polyphenylsulfone resin has a cyclic oligomer content of less than 1.3wt%, based on the total weight of the polyphenylsulfone resin; preferably 1.0wt% to 1.1wt%.
5. The polyphenylsulfone composite material of claim 1, wherein the polyphenylsulfone resin has a weight average molecular weight of 68000 to 80000 daltons.
6. The polyphenylsulfone composite material according to claim 1, wherein the fibers are selected from any one or more of glass fibers, carbon fibers, aramid fibers, basalt fibers, propionitrile fibers, boron fibers or calcium sulfate whiskers; preferably, the fiber is selected from any one or more of carbon fiber, aramid fiber or calcium sulfate whisker; more preferably, the fibers are carbon fibers.
7. The polyphenylsulfone composite material according to claim 1, wherein the acid acceptor is selected from one or more of alumina, calcium oxide and magnesium oxide; the antioxidant is selected from any one or more of pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene or 2, 8-di-tert-butyl-4-methylphenol.
8. The method for preparing polyphenylsulfone composite material according to any one of claims 1-7, comprising the steps of: adding the components into a double-screw extruder according to the proportion, carrying out melt mixing, extruding and granulating to obtain the polyphenylsulfone composite material.
9. Use of the polyphenylsulfone composite material of any of claims 1-7 in the fields of electronics, automotive and aerospace.
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