CN114213659A - Heat-resistant silicon-containing polyarylene sulfide and preparation method thereof - Google Patents
Heat-resistant silicon-containing polyarylene sulfide and preparation method thereof Download PDFInfo
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- CN114213659A CN114213659A CN202111610300.8A CN202111610300A CN114213659A CN 114213659 A CN114213659 A CN 114213659A CN 202111610300 A CN202111610300 A CN 202111610300A CN 114213659 A CN114213659 A CN 114213659A
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- polyarylene sulfide
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- 229920000412 polyarylene Polymers 0.000 title claims abstract description 71
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 67
- 239000010703 silicon Substances 0.000 title claims abstract description 67
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 51
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011593 sulfur Substances 0.000 claims abstract description 19
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 5
- -1 halogenated aryl silane Chemical compound 0.000 claims description 41
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 24
- 150000002989 phenols Chemical class 0.000 claims description 20
- 235000010290 biphenyl Nutrition 0.000 claims description 19
- 239000004305 biphenyl Substances 0.000 claims description 19
- 125000001624 naphthyl group Chemical group 0.000 claims description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 19
- 229910000077 silane Inorganic materials 0.000 claims description 18
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000000010 aprotic solvent Substances 0.000 claims description 12
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 150000001491 aromatic compounds Chemical class 0.000 claims description 9
- 229930185605 Bisphenol Natural products 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- 238000011282 treatment Methods 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 5
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 5
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 5
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 150000003463 sulfur Chemical class 0.000 claims description 3
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 2
- GWCFTYITFDWLAY-UHFFFAOYSA-N 1-ethylazepan-2-one Chemical compound CCN1CCCCCC1=O GWCFTYITFDWLAY-UHFFFAOYSA-N 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- WPPOGHDFAVQKLN-UHFFFAOYSA-N N-Octyl-2-pyrrolidone Chemical compound CCCCCCCCN1CCCC1=O WPPOGHDFAVQKLN-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000014759 maintenance of location Effects 0.000 abstract description 33
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 13
- 238000012662 bulk polymerization Methods 0.000 abstract description 3
- 230000004580 weight loss Effects 0.000 abstract description 3
- 150000003568 thioethers Chemical class 0.000 abstract 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- 238000002844 melting Methods 0.000 description 25
- 230000008018 melting Effects 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000004734 Polyphenylene sulfide Substances 0.000 description 18
- 229920000069 polyphenylene sulfide Polymers 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- 230000009477 glass transition Effects 0.000 description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 238000001746 injection moulding Methods 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 229920001296 polysiloxane Polymers 0.000 description 10
- 150000004763 sulfides Chemical class 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001816 cooling Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 125000005843 halogen group Chemical group 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 3
- RANCECPPZPIPNO-UHFFFAOYSA-N 2,5-dichlorophenol Chemical compound OC1=CC(Cl)=CC=C1Cl RANCECPPZPIPNO-UHFFFAOYSA-N 0.000 description 2
- OKISUZLXOYGIFP-UHFFFAOYSA-N 4,4'-dichlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=C(Cl)C=C1 OKISUZLXOYGIFP-UHFFFAOYSA-N 0.000 description 2
- FTDZECHQBVIHKZ-UHFFFAOYSA-N 5,5-dibromo-2-phenylcyclohexa-1,3-diene Chemical group C1=CC(Br)(Br)CC=C1C1=CC=CC=C1 FTDZECHQBVIHKZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UYGFDYMFXPXXLL-UHFFFAOYSA-N (3,5-dibromophenyl)-triphenylsilane Chemical compound BrC1=CC(Br)=CC([Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 UYGFDYMFXPXXLL-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UTEBJTKMYMQRIF-UHFFFAOYSA-N bis(4-bromophenyl)-diphenylsilane Chemical compound C1=CC(Br)=CC=C1[Si](C=1C=CC(Br)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 UTEBJTKMYMQRIF-UHFFFAOYSA-N 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/025—Preparatory processes
- C08G75/0259—Preparatory processes metal hydrogensulfides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/0209—Polyarylenethioethers derived from monomers containing one aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/0227—Polyarylenethioethers derived from monomers containing two or more aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/0236—Polyarylenethioethers containing atoms other than carbon or sulfur in a linkage between arylene groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention provides heat-resistant silicon-containing polyarylene sulfide and a preparation method thereof, belonging to the field of polymer chemistry and physics. The invention provides a preparation method of heat-resistant silicon-containing polyarylene sulfide, which comprises the following steps: the heat-resistant silicon-containing polyarylene sulfide is prepared by taking a sulfur-containing monomer, a double-halogen aromatic compound and a silicon-containing double-halogen monomer as main raw materials and adopting the existing method for preparing polyarylene sulfide; wherein the silicon-containing bis-halogen monomer is selected from: a bis-halosilane or a bis-halosiloxane. The invention combines the characteristics of silicon-based heat-resistant toughness and polyarylene sulfide rigidity and strength to prepare a series of linear, double-chain and surface heat-resistant silicon-containing polyarylene sulfides obtained by bulk polymerization, compared with the existing polyarylene sulfides, the obtained modified polyarylene sulfide has higher thermal decomposition temperature, particularly the weight loss at 550-650 ℃ is far lower than that of pure polyarylene sulfide, the retention rate can reach 60-80%, and the polyarylene sulfide can be used in an ultrahigh temperature environment.
Description
Technical Field
The invention provides heat-resistant silicon-containing polyarylene sulfide and a preparation method thereof, belonging to the field of polymer chemistry and physics.
Background
The silicon compound, particularly the silicon resin, has excellent heat resistance, cold resistance, weather resistance, electrical insulation, hydrophobicity, anti-sticking and demolding property and the like, and has double characteristics of organic resin and inorganic resin. However, pure silicone resins generally belong to thermosetting resins, have low mechanical strength and poor secondary processing moldability. Therefore, the novel high-performance polymer is formed with other thermoplastic polymers according to the characteristics, and the performance of the novel high-performance polymer can be greatly improved.
Polyarylene sulfides, such as polyphenylene sulfide (PPS), polyphenylene sulfide ketone (PPSK), polyphenylene sulfide sulfone (PPSF), are used as coatings, plastics, structural materials, adhesives, fibers and films, and can be widely applied to the fields of automobiles, aerospace, petrochemical industry, light industrial machinery, electronics, food and engineering technology due to the characteristics of high temperature resistance, chemical corrosion resistance, excellent electrical property, radiation resistance, flame resistance, high mechanical strength, stable size and the like. The main preparation method of the polyarylene sulfide in the current industrial production comprises the following steps: (1) sodium sulfide (Na)2S，xH2O, x ═ 9, 7, 5, 2,5, 2, 7, 2, 8, 2, 9). As reported in U.S. Pat. No. 3,354,129, U.S. Pat. No. 4,808,698, Chinese patent CN 200510022437.6, CN 95111495.6 and the like, sodium sulfide paradichlorobenzene (DCB) is used in an inert gas (e.g., N)2) Preparing Polyphenylene Sulfide (PPS) by pressure or normal pressure reaction in a polar solvent (NMP); (2) a preparation method of sulfur and aromatic compound. As reported in US 3878176, CN 95111471.9, etc., polyphenylene sulfide (PPS) or high molecular weight polyarylene sulfide (high molecular weight polyarylene sulfide) is synthesized under pressure in a polar solvent using sulfur and sodium carbonate as raw materials; (3) the reaction of sodium hydrosulfide with polyhalogenates is reported in EP 278276, JP-S-610477330, JP-H-230236 and the like.
However, they are inferior in toughness and low in impact strength, and it is necessary to modify their structure to improve their toughness and impact strength and further to improve their heat resistance.
Disclosure of Invention
Aiming at the defects, the invention combines the characteristics of silicon-based heat-resistant toughness and the rigidity and strength of the polyarylene sulfide to prepare a series of linear, double-chain and surface heat-resistant silicon-containing polyarylene sulfides obtained by bulk polymerization, compared with the existing polyarylene sulfides, the obtained modified polyarylene sulfide has higher thermal decomposition temperature, particularly the weight loss of the modified polyarylene sulfide is far lower than that of the pure polyarylene sulfide at 550-650 ℃, the retention rate of the modified polyarylene sulfide can reach 60-80%, and the modified polyarylene sulfide can be used in an ultrahigh temperature environment.
The technical scheme of the invention is as follows:
the first technical problem to be solved by the invention is to provide a preparation method of heat-resistant silicon-containing polyarylene sulfide, which comprises the following steps: the heat-resistant silicon-containing polyarylene sulfide is prepared by taking a sulfur-containing monomer, a double-halogen aromatic compound and a silicon-containing double-halogen monomer as main raw materials and adopting the existing method for preparing polyarylene sulfide; wherein the silicon-containing bis-halogen monomer is selected from: a bis-halosilane or a bis-halosiloxane.
Further, the bis-halosilane is: bis (4-haloaryl) diarylsilanes) (e.g.
) Or (3, 5-dihaloaryl) triarylsilanes (e.g. phenyl-substituted) triarylsilanes
) And the aryl is phenyl, biphenyl, naphthyl or the like.
Further, the double halogenated siloxane is prepared by the following method: halogenated aryl silane and phenolic compound react in an aprotic solvent at room temperature to 160 ℃ to prepare the double halogenated siloxane; the ratio (mol) of the haloarylsilane to the phenolic compound is determined from the number of moles of the reaction halogen to the number of moles of the phenolic group of the phenolic compound, the number of moles of the reaction halogen in the haloarylsilane: the molar number of the phenolic groups of the phenolic compound is 1-1.05: 1.
further, the haloaryl silane is selected from the group consisting of: dihalodiarylsilane
Trihalo-aryl silanes
Or tetrahalosilanes
Wherein R is1Selected from: phenyl, biphenyl, or naphthyl, etc.; r2Is selected from: phenyl, biphenyl, or naphthyl, etc.; r1And R2The same or different.
Further, the phenolic compound is selected from: a monohalogenated aromatic phenol compound, a bishaloaromatic monophenol compound or a bishaloaromatic bisphenol compound.
Still further, the monohalogenated aromatic phenolic compound is selected from: para-halophenol
M-halophenol
Halogenated naphthols
Etc., Y is-S-),
or-O-, X is halogen.
Still further, the bis-halogenated aromatic monophenols are selected from:
Still further, the bis-halogenated aromatic bisphenol compound is selected from:
Still further, the silicon-containing dihalogen monomer is selected from: bis (4-haloaryl) diarylsilane, (3, 5-dihaloaryl) triarylsilane, 4-dihalodiaryl-diarylsiloxane, bis (2, 5-dihaloaryl) -diarylsiloxane, or tetrakis (2, 5-dichlorodiaryl) -siloxane; the alkyl group is phenyl, biphenyl, or naphthyl.
Further, the sulfur-containing monomer: (the molar ratio of the dihaloaromatic compound to the silicon-containing dihalomonomer) is 0.90 to 1.10, preferably 0.95 to 1.05; bis-halogenated aromatic compound: the molar ratio of the silicon-containing double halogenated monomer is 60-99: 40 to 1 (mol).
Further, the sulfur-containing monomer is selected from the group consisting of: sodium hydrosulfide, sodium sulfide or hydrogen sulfide.
Further, the bis-halogenated aromatic compound is selected from:
1, 4-dihalobenzenes
2, 4-dihalobenzenes
3, 5-dihalobenzene,
4, 4' -dihalobiphenyl
4, 4' -dihalodiphenylsulfone
Further, when the silicon-containing dihalogen monomer is a dihalosilane, the heat-resistant silicon-containing polyarylene sulfide is prepared by the following steps: firstly, dehydrating a sulfur-containing monomer until the water content is less than or equal to 1.0 wt%, and then adding the bis-halosilane and the bis-halogenated aromatic compound to perform polymerization reaction for 3-12 hours at 180-300 ℃ under normal pressure or 1-20 MPa; then polymerizing for 1-8 hours under the conditions of 1-20 MPa pressure and 200-320 ℃ under the protection of inert gas to obtain a high polymer; and finally, carrying out post-treatment according to a post-treatment method for preparing the polyarylene sulfide.
Further, when the silicon-containing dihalogen monomer is a bishalosiloxane, the method for preparing the heat-resistant silicon-containing polyarylene sulfide includes the steps of:
1) halogenated aryl silane and phenolic compound react in an aprotic solvent at room temperature to 160 ℃ to form double halogenated siloxane;
2) dehydrating the sulfur-containing monomer until the water content is less than or equal to 1.0 wt%; if the moisture content is high, the double-halogen siloxane monomer can be hydrolyzed;
3) carrying out polymerization reaction on the dehydrated sulfur-containing monomer obtained in the step 2), the bishalosiloxane obtained in the step 1) and a bishaloaromatic compound for 1-6 hours at the temperature of 180-300 ℃ under normal pressure or the pressure of 1-20 MPa to obtain a uniform polymer with low polymerization degree;
4) polymerizing the low-polymerization-degree polymer obtained in the step 3) for 1-8 hours under the conditions of 1-20 MPa pressure and 200-320 ℃ under the protection of inert gas to obtain a high polymer;
5) and (3) carrying out post-treatment on the high polymer obtained in the step 4) according to a method for preparing the polyarylene sulfide post-treatment, and obtaining the corresponding linear, double-chain and surface heat-resistant silicon-containing polyarylene sulfide according to the silicon-containing double-halogen monomer participating in polymerization.
Further, in step 1), the solvent is tetrahydrofuran, dichloroethane, dimethyl sulfoxide, dichloromethane, chloroform, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, 6-cyclohexylpyrrolidone, N-ethylpyrrolidone, N-octylpyrrolidone, hexamethylphosphoric triamide, or the like.
Further, in the step 2), the dehydration reaction of the sulfur-containing monomer is as follows: under normal pressure, the sulfur-containing monomer is dehydrated in an aprotic solvent at the room temperature of 200 ℃ under the protection of inert gas.
Further, in the step 2), in the dehydration reaction of sulfur monomer, the aprotic polar solvent includes: any one of N-methyl-2-pyrrolidone (NMP), N-cyclohexylpyrrolidone (NCHP), 1, 3-dimethyl-2-imidazolidinone (DMI), Hexamethylphosphoramide (HMPA), N-dimethylacetamide, N-dimethylamide, N-ethylcaprolactam, N-vinylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone (MI) lactam, tetramethylurea, dimethyl sulfoxide, or sulfolane.
Further, in step 5), the post-processing method comprises: washing the high polymer obtained in the step 4) for at least 3 times at 60-100 ℃ by using 10-20 times of deionized water, and drying in a drying oven at 80-120 ℃ for 12-48 hours.
The second technical problem to be solved by the invention is to provide a heat-resistant silicon-containing polyarylene sulfide, which is prepared by the method.
Further, the structural formula of the heat-resistant silicon-containing polyarylene sulfide is one of the following structural formulas:
in the formula, R1And R2Selected from: phenyl, biphenyl, or naphthyl; in the formula I, a is more than or equal to 1 and less than or equal to 40, b is more than or equal to 60 and less than or equal to 99, and n is more than or equal to 100; in the formula II, m is more than or equal to 11≤40，60≤m2≤99，n≥100；
Y＝Z＝-S-、
or-O-.
The third technical problem to be solved by the present invention is to provide a method for simultaneously improving the heat resistance and toughness of polyarylene sulfide, which comprises: introducing a silicon-containing double-halogen monomer in the preparation process of the polyarylene sulfide; wherein the silicon-containing double-halogen monomer is double-halogen silane or double-halogen siloxane.
The fourth technical problem to be solved by the present invention is to provide a preparation method of a bis-halo siloxane, wherein the preparation method comprises: halogenated aryl silane and phenolic compound react in an aprotic solvent at room temperature to 160 ℃ to prepare the double halogenated siloxane; moles of halogen reacted in the haloaryl silane: the molar number of the phenolic groups of the phenolic compound is 1-1.05: 1.
further, the haloaryl silane is selected from the group consisting of: dihalodiarylsilane
Trihalo-aryl silanes
Or tetrahalosilanes
Wherein R is1Selected from: phenyl, biphenyl, or naphthyl, etc.; r2Selected from: phenyl, biphenyl, or naphthyl, etc.; r1And R2May be the same or different.
Further, the phenolic compound is selected from: a monohalogenated aromatic phenol compound, a bishaloaromatic monophenol compound or a bishaloaromatic bisphenol compound.
Still further, the monohalogenated aromatic phenolic compound is selected from: para-halophenol
M-halophenol
Halogenated naphthols
Etc., Y is-S-),
or-O-, X is halogen.
Still further, the bis-halogenated aromatic monophenols are selected from:
Still further, the bis-halogenated aromatic bisphenol compound is selected from:
The fifth technical problem to be solved by the present invention is to provide a dihalosiloxane which is produced by the above method.
Further, the bis-halosiloxane is selected from the group consisting of: 4, 4-dihalodiaryl-diarylsiloxane, bis (2, 5-dihaloaryl) -diarylsiloxane, or tetrakis (2, 5-dichlorodiaryl) siloxane; the alkyl group is phenyl, biphenyl, or naphthyl.
The invention has the beneficial effects that:
the invention combines the characteristics of silicon-based heat-resistant toughness and polyarylene sulfide rigidity and strength to prepare a series of heat-resistant silicon-containing polyarylene sulfides obtained by bulk polymerization, compared with the existing polyarylene sulfides, the obtained modified polyarylene sulfides have higher thermal decomposition temperature, particularly the weight loss of the modified polyarylene sulfides is far lower than that of the pure polyarylene sulfides at 550-650 ℃, the retention rate of the modified polyarylene sulfides can reach 60-80%, and the modified polyarylene sulfides can be used in an ultrahigh temperature environment; in addition, the elongation at break of the obtained modified polyarylene sulfide is increased to 25% from 3-5%, and is increased by more than 5 times.
Detailed Description
The invention provides a preparation method of heat-resistant silicon-containing polyarylene sulfide, which comprises the following steps:
the first step is as follows: the silicon-containing monomer and the phenolic compound react in an aprotic solvent at room temperature to 160 ℃ to form a silicon-based double-halogen substance, the reaction is normal pressure, and the specific reaction can refer to one of the following reaction formulas:
wherein X, Y are the same halogen atom, or different halogen atoms;
the second step is that: dehydrating sodium sulfide, and dehydrating sulfide in an aprotic solvent at normal pressure and room temperature to 200 ℃ under the protection of nitrogen;
the third step: polymerizing dehydrated sulfur, bis-halogenated siloxane and bis-halogenated aromatic compound at normal pressure or 1-20 MPa and 180-300 ℃ to form a uniform polymer with low polymerization degree;
the fourth step: polymerizing the uniform low-polymerization-degree polymer under the protection of nitrogen for 1-8 hours under the conditions of 1-20 MPa pressure and 200-320 ℃, and obtaining corresponding linear, double-chain and surface silicon-based heat-resistant polyarylene sulfide according to the silicon-based monomers participating in polymerization;
the reaction formulae of the second to fourth steps are as follows:
the fifth step: and (3) performing post-treatment and purification, washing the obtained compound with 10-20 times of deionized water with the weight of 60-100 ℃ for 6 times, and drying in a drying oven with the temperature of 80-120 ℃ for 12-48 hours to obtain the final linear, double-chain and surface silicon-based heat-resistant polyarylene sulfide.
The above-mentioned contents of the present invention will be further described in detail by the following specific embodiments of examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. Various substitutions and alterations according to the general knowledge and conventional practice in the art are intended to be included within the scope of the present invention without departing from the technical spirit of the present invention as described above.
Example 1 preparation and preparation of a linear backbone silicon-and oxygen-free silicon-containing polyarylene sulfide.
A1L reactor was charged with 250ml of NMP, 21g of NaOH, 40.5g of sodium hydrosulfide (70 wt%), heated to 200 ℃ under nitrogen, and 79ml of water was fractionated, 12.36g of bis (4-bromophenyl) diphenylsilane was added
69.83g of p-dichlorobenzene and reacting for 3 hours at 220 ℃ to form a uniform low-molecular polymer; heating to 260 ℃ for reaction for 3 hours, cooling to 120 ℃, slowly adding deionized water, filtering, washing, and drying at 110 ℃ for 24 hours to obtain 58g of white product, wherein the yield is as follows:93％。
the product was analyzed thermally, the temperature was raised at 10 ℃/min per minute in a nitrogen atmosphere, the melting point was measured by DSC and the thermal decomposition temperature was measured by TG. And (3) performing injection molding on the product at 290-310 ℃ by using a Haake miniature injection molding machine to obtain a mechanical sample strip, and testing the tensile strength, the elongation at break and the impact strength of the mechanical sample strip.
The test results are: the glass transition temperature is 88 ℃ and the melting point Tm is 286 ℃. The mass retention rate at 550 ℃ is 70 percent, and the mass retention rate at 600 ℃ is 58 percent, which is higher than that of pure PPS (63 percent and 49 percent). The tensile strength is 75MPa, the elongation at break is 15 percent, and the impact strength is 50J/M.
Example 2 preparation of Linear side chain silicon-and-oxygen-free silicon-containing polyarylene sulfide
A1L reactor was charged with 250ml of NMP, 21g of NaOH, 40.5g of sodium hydrosulfide (70 wt%), heated to 200 ℃ under nitrogen, and 79ml of water was fractionated, 18.55g of (3, 5-dibromophenyl) triphenylsilane was added
67.99g of p-dichlorobenzene, and reacting at 220 ℃ for 3 hours to form a uniform low-molecular polymer; heating to 265 ℃ for reaction for 3 hours, cooling to 110 ℃, slowly adding deionized water, filtering, washing, and drying at 110 ℃ for 24 hours to obtain 63g of white product, wherein the yield is as follows: 94 percent.
The product was analyzed thermally, the temperature was raised at 10 ℃/min per minute in a nitrogen atmosphere, the melting point was measured by DSC and the thermal decomposition temperature was measured by TG. The product is injected and molded into a mechanical sample strip by a Haake mini-type injection molding machine at the temperature of 290 ℃ and 310 ℃, and the tensile strength, the elongation at break and the impact strength of the mechanical sample strip are tested.
The test results are: the glass transition temperature is 85 ℃ and the melting point Tm is 289 ℃. The mass retention rate at 550 ℃ is 60 percent, and the mass retention rate at 600 ℃ is 57 percent, which is higher than that of pure PPS (63 percent and 49 percent). The tensile strength is 76MPa, the elongation at break is 25 percent, and the impact strength is 60J/M.
EXAMPLE 3 Linear backbone Silicone-based polyarylene sulfide and preparation thereof
(1) 25.32g of dichlorodiphenylsilane is added into a three-necked bottle filled with 200ml of N, N-dimethylacetamide, then 25.72g of 4-chlorophenol and 10ml of triethylamine are added, and the mixture is stirred and heated to 120 ℃ under the protection of nitrogen to react for 8 hours. Cooled to room temperature, washed with deionized water 4 times, washed with absolute ethanol 2 times, and dried under vacuum at 80 ℃ for 8 hours. 42.55g of a white fine powder product was obtained in 97% yield from 4, 4-dichlorodiphenyl-diphenylsiloxane, a silicon-based monomer for the next linear backbone silicone-based polyarylene sulfide polymerization.
(2) Adding 250ml of NMP, 20.5g of NaOH and 40.5g of sodium hydrosulfide (70 wt%) into a 1L reactor, heating to 200 ℃ under the protection of nitrogen, fractionating to obtain 89ml of water, adding 10.95g of 4, 4-dichlorodiphenyl-diphenylsiloxane obtained in the step (1) and 69.83g of p-dichlorobenzene, and reacting for 3 hours at 225 ℃ to form a uniform low-molecular polymer; heating to 263 ℃ for reaction for 3 hours, cooling to 100 ℃, slowly adding deionized water, filtering, washing, and drying at 110 ℃ for 24 hours to obtain 61.5g of a white product, wherein the yield is as follows: 95 percent.
The product was analyzed thermally, the temperature was raised at 10 ℃/min per minute in a nitrogen atmosphere, the melting point was measured by DSC and the thermal decomposition temperature was measured by TG. The product is injected and molded into a mechanical sample strip by a Haake mini-type injection molding machine at the temperature of 290 ℃ and 310 ℃, and the tensile strength, the elongation at break and the impact strength of the mechanical sample strip are tested.
The test results are: the glass transition temperature was 85 ℃ and the melting point Tm was 285 ℃. The mass retention at 550 ℃ is 71%, and the mass retention at 600 ℃ is 62%, which is higher than that of pure PPS (63%, 49%). The tensile strength is 70MPa, the breaking elongation is 12 percent, and the impact strength is 55J/M.
Example 4 preparation of Linear double-stranded Silicone-containing silicon-based polyarylene sulfide
(1) 25.32g of dichlorodiphenylsilane is added into a three-necked bottle containing 200ml of N, N-dimethylacetamide, 32.6g of 2, 5-dichlorophenol and 10ml of triethylamine are added, and the mixture is stirred under the protection of nitrogen and heated to 130 ℃ for reaction for 8 hours. Cooled to room temperature, washed with deionized water 4 times, washed with absolute ethanol 2 times, and dried under vacuum at 80 ℃ for 8 hours. 49.36g of a white fine powder product was obtained in 97% yield from bis (2, 5-dichlorobenzene) -diphenylsiloxane (506.20) which was the next step in the linear two-chain silicone-containing silicone-based polyarylene sulfide polymerization of silicon-based monomers.
(2) Adding 250ml of NMP, 20.5g of NaOH and 40.5g of sodium hydrosulfide (70 wt%) into a 1L reactor, heating to 200 ℃ under the protection of nitrogen, fractionating to obtain 89ml of water, adding 12.66g of bis (2, 5-dichlorobenzene) -diphenylsiloxane obtained in the step (1) and 69.83g of p-dichlorobenzene, and reacting at 225 ℃ for 3.5 hours to form a uniform low-molecular polymer; heating to 265 ℃ for reaction for 2.5 hours, cooling to 100 ℃, slowly adding deionized water, filtering, washing, and drying at 110 ℃ for 24 hours to obtain 62.5g of a white product, wherein the yield is as follows: 94 percent.
The product was analyzed thermally, the temperature was raised at 10 ℃/min per minute in a nitrogen atmosphere, the melting point was measured by DSC and the thermal decomposition temperature was measured by TG. The product is injected and molded into a mechanical sample strip by a Haake mini-type injection molding machine at the temperature of 290 ℃ and 310 ℃, and the tensile strength, the elongation at break and the impact strength of the mechanical sample strip are tested.
The test results are: the glass transition temperature was 85 ℃ and the melting point Tm was 295 ℃. The mass retention rate at 550 ℃ is 69%, and the mass retention rate at 600 ℃ is 57%, which is higher than that of pure PPS (63%, 49%). The tensile strength of the material is 72MPa, the elongation at break is 15 percent, and the impact strength is 58J/M.
Example 5 preparation of a facial silicone-containing polyarylene sulfide.
(1) 25.32g of dichlorodiphenylsilane is added into a three-necked bottle filled with 200ml of N, N-dimethylacetamide, then 17.91g of 2, 5-chlorohydroquinone is added, 10ml of triethylamine is added, and the mixture is stirred under the protection of nitrogen and heated to 120 ℃ to react for 8 hours. Cooled to room temperature, washed with deionized water 4 times, washed with absolute ethanol 2 times, and dried under vacuum at 80 ℃ for 8 hours. Obtaining the white fine powder product 35.01g with the yield of 96 percent and the structure
The structure is a silicon-based monomer polymerized by next-step silicone-containing silicon-based polyarylene sulfide.
(2) 250ml of NMP, 20.5g of NaOH, 40.5g of sodium hydrosulfide (70 wt%), heated to 200 ℃ under the protection of nitrogen gas, are placed in a 1L reactor, 89ml of water is fractionated, and the silicon-based monomer obtained in (1) is added
8.98g of p-dichlorobenzene69.83g, react for 3 hours at 225 ℃ to form a uniform low molecular polymer; heating to 263 ℃ for reaction for 3 hours, cooling to 100 ℃, slowly adding deionized water, filtering, washing, and drying at 110 ℃ for 24 hours to obtain 59.5g of a white product, wherein the yield is as follows: 93 percent.
The product was analyzed thermally, the temperature was raised at 10 ℃/min per minute in a nitrogen atmosphere, the melting point was measured by DSC and the thermal decomposition temperature was measured by TG. The product is injected and molded into a mechanical sample strip by a Haake mini-type injection molding machine at the temperature of 290 ℃ and 310 ℃, and the tensile strength, the elongation at break and the impact strength of the mechanical sample strip are tested.
The test results are: the glass transition temperature was 105 ℃ and the melting point Tm was 285 ℃. The mass retention rate at 550 ℃ is 72 percent, and the mass retention rate at 600 ℃ is 60 percent, which is higher than that of pure PPS (63 percent and 49 percent). The tensile strength is 75MPa, the elongation at break is 11 percent, and the impact strength is 65J/M.
EXAMPLE 6 Linear backbone Silicone-based polyarylene sulfide and preparation thereof
(1) 16.99g of silicon tetrachloride is added into a three-necked bottle containing 200ml of N, N-dimethylacetamide, 65.2g of 2, 5-dichlorophenol and 10ml of triethylamine are added, and the mixture is stirred and heated to 120 ℃ under the protection of nitrogen to react for 8 hours. Cooled to room temperature, washed with deionized water 4 times, washed with absolute ethanol 2 times, and dried under vacuum at 80 ℃ for 8 hours. 65.55g of a fine white powder product was obtained in 96% yield in the form of tetrakis (2, 5-dichlorodiphenyl) siloxane, which is the next step in the polymerization of a silicone-based silicone-containing polyarylene sulfide.
(2) Adding 250ml of NMP, 20.5g of NaOH and 40.5g of sodium hydrosulfide (70 wt%) into a 1L reactor, heating to 200 ℃ under the protection of nitrogen, fractionating to obtain 89ml of water, adding 4.22g of tetra (2, 5-dichlorodiphenyl) siloxane obtained in the step (1) and 69.83g of p-dichlorobenzene, and reacting at 225 ℃ for 3 hours to form a uniform low-molecular polymer; heating to 263 ℃ for reaction for 3 hours, cooling to 100 ℃, slowly adding deionized water, filtering, washing, and drying at 110 ℃ for 24 hours to obtain 57.5g of white product, yield: 96 percent.
The product was analyzed thermally, the temperature was raised at 10 ℃/min per minute in a nitrogen atmosphere, the melting point was measured by DSC and the thermal decomposition temperature was measured by TG. The product is injected and molded into a mechanical sample strip by a Haake mini-type injection molding machine at the temperature of 290 ℃ and 310 ℃, and the tensile strength, the elongation at break and the impact strength of the mechanical sample strip are tested.
The test results are: the glass transition temperature was 85 ℃ and the melting point Tm was 283 ℃. The mass retention at 550 ℃ is 71%, and the mass retention at 600 ℃ is 59%, which is higher than that of pure PPS (63%, 49%). The tensile strength is 77MPa, the breaking elongation is 18 percent, and the impact strength is 65J/M.
Example 7
The same as in example 1. P-dichlorobenzene (69.83 g): changed to 67.99g of p-dichlorobenzene
3.14g of 4, 4-dichlorobenzophenone
60g of white product is obtained, yield: 94 percent.
The product was analyzed thermally, the temperature was raised at 10 ℃/min per minute in a nitrogen atmosphere, the melting point was measured by DSC and the thermal decomposition temperature was measured by TG. The product is injected and molded into a mechanical sample strip by a Haake mini-type injection molding machine at 290-320 ℃, and the tensile strength, the elongation at break and the impact strength of the mechanical sample strip are tested.
The test results are: the glass transition temperature was 92 ℃ and the melting point Tm was 291 ℃. The mass retention at 550 ℃ is 70%, and the mass retention at 600 ℃ is 59%, which is higher than that of pure PPS (63%, 49%). The tensile strength is 80MPa, the breaking elongation is 12 percent, and the impact strength is 55J/M.
Example 8
The same as in example 3. P-dichlorobenzene (69.83 g): changed to 67.99g of p-dichlorobenzene
3.59g of 4, 4-dichlorodiphenyl sulfone
59g of white product is obtained, yield: 92 percent.
The product was analyzed thermally, the temperature was raised at 10 ℃/min per minute in a nitrogen atmosphere, the melting point was measured by DSC and the thermal decomposition temperature was measured by TG. The product is injected and molded into a mechanical sample strip by a Haake mini-type injection molding machine at 290-320 ℃, and the tensile strength, the elongation at break and the impact strength of the mechanical sample strip are tested.
The test results are: the glass transition temperature is 95 ℃ and the melting point Tm is 287 ℃. The mass retention at 550 ℃ is 69%, the mass retention at 600 ℃ is 59%, and is higher than that of pure PPS (63%, 49%). The tensile strength is 77MPa, the breaking elongation is 16 percent, and the impact strength is 62J/M.
Example 9
The same as in example 4. P-dichlorobenzene (69.83 g): changed to 67.99g of p-dichlorobenzene
4.11g of 4, 4-dibromodiphenyl ether
59.5g of white product is obtained, yield: 93 percent.
The product was analyzed thermally, the temperature was raised at 10 ℃/min per minute in a nitrogen atmosphere, the melting point was measured by DSC and the thermal decomposition temperature was measured by TG. The product is injected and molded into a mechanical sample strip by a Haake mini-type injection molding machine at 290 ℃ and 330 ℃, and the tensile strength, the elongation at break and the impact strength of the mechanical sample strip are tested.
The test results are: the glass transition temperature is 98 ℃ and the melting point Tm is 293 ℃. The mass retention rate at 550 ℃ is 72 percent, and the mass retention rate at 600 ℃ is 60 percent, which is higher than that of pure PPS (63 percent and 49 percent). The tensile strength is 75MPa, the elongation at break is 18 percent, and the impact strength is 62J/M.
Example 10
The same as in example 5. P-dichlorobenzene (69.83 g): changed to 67.99g of p-dichlorobenzene
3.91g of 4, 4-dibromobiphenyl
60.2g of white product is obtained, yield: 93 percent.
The product was analyzed thermally, the temperature was raised at 10 ℃/min per minute in a nitrogen atmosphere, the melting point was measured by DSC and the thermal decomposition temperature was measured by TG. The product is injected and molded into a mechanical sample strip by a Haake mini-type injection molding machine at the temperature of 290 ℃ and 310 ℃, and the tensile strength, the elongation at break and the impact strength of the mechanical sample strip are tested.
The test results are: the glass transition temperature is 110 ℃ and the melting point Tm is 296 ℃. The mass retention rate at 550 ℃ is 71 percent, and the mass retention rate at 600 ℃ is 60 percent, which is higher than that of pure PPS (63 percent and 49 percent). The tensile strength is 77MPa, the breaking elongation is 10 percent, and the impact strength is 62J/M.
Comparative example 1 (No silicon based monomer alone is polymerized)
Adding 250ml of NMP, 20g of NaOH and 125.8g of sodium hydrosulfide into a 1L reactor, stirring under the protection of nitrogen, heating to 200 ℃, fractionating to obtain 79ml of water, adding 73.5g of p-dichlorobenzene, reacting for 3 hours at 220 ℃, and finishing the first-stage reaction; heating to 260 ℃ for reaction for 3 hours, cooling to 150 ℃, slowly adding deionized water, filtering, washing, and drying at 110 ℃ for 24 hours to obtain 50g of white product, wherein the yield is as follows: 93 percent.
The test results are: the glass transition temperature is 89 ℃, and the melting point Tm is 282 ℃; the mass retention rate at 550 ℃ is 63 percent, and the mass retention rate at 600 ℃ is 49 percent. The tensile strength is 68MPa, the breaking elongation is 4.6 percent, and the impact strength is 27J/M.
Comparative example 2 (No silicon based monomer alone participating in polymerization)
As in comparative example 1. 73.5g of p-dichlorobenzene was replaced with 71.66g of p-dichlorobenzene
3.14g of 4, 4-dichlorobenzophenone
51g of white product is obtained, yield: 92 percent.
The test results are: the glass transition temperature is 90 ℃ and the melting point Tm is 283 ℃. The mass retention rate at 550 ℃ is 62 percent, and the mass retention rate at 600 ℃ is 50 percent. The tensile strength is 68MPa, the breaking elongation is 4.6 percent, and the impact strength is 27J/M.
Comparative example 3 (No silicon based monomer alone participating in polymerization)
As in comparative example 1. 73.5g of p-dichlorobenzene was replaced with 71.66g of p-dichlorobenzene
3.59g of 4, 4-dichlorodiphenyl sulfone
52g of white product is obtained, yield: 93 percent.
The test results are: the glass transition temperature is 93 ℃ and the melting point Tm is 281 ℃. The mass retention rate at 550 ℃ is 62 percent, and the mass retention rate at 600 ℃ is 47 percent. The tensile strength is 65MPa, the breaking elongation is 4.9 percent, and the impact strength is 25J/M.
Comparative example 4 (No silicon based monomer alone participating in polymerization)
As in comparative example 1. 73.5g of p-dichlorobenzene was replaced with 71.66g of p-dichlorobenzene
4.11g of 4, 4-dibromodiphenyl ether
52g of white product is obtained, yield: 93 percent.
The test results are: the glass transition temperature is 90 ℃ and the melting point Tm is 281 ℃. The mass retention rate at 550 ℃ is 61 percent, and the mass retention rate at 600 ℃ is 46 percent. The tensile strength is 66MPa, the elongation at break is 3.9 percent, and the impact strength is 26J/M.
Comparative example 5 (No silicon based monomer alone participating in polymerization)
As in comparative example 1. 73.5g of p-dichlorobenzene was replaced with 71.66g of p-dichlorobenzene
3.91g of 4, 4-dibromobiphenyl
51g of white product is obtained, yield: 94 percent.
The test results are: the glass transition temperature is 92 ℃ and the melting point Tm is 283 ℃. The mass retention rate at 550 ℃ is 63 percent, and the mass retention rate at 600 ℃ is 48 percent. The tensile strength is 70MPa, the elongation at break is 4.4 percent, and the impact strength is 30J/M.
Claims (10)
1. A preparation method of heat-resistant silicon-containing polyarylene sulfide is characterized by comprising the following steps: the heat-resistant silicon-containing polyarylene sulfide is prepared by taking a sulfur-containing monomer, a double-halogen aromatic compound and a silicon-containing double-halogen monomer as main raw materials and adopting the existing method for preparing polyarylene sulfide; wherein the silicon-containing bis-halogen monomer is selected from: a bis-halosilane or a bis-halosiloxane.
2. The method of claim 1, wherein the bis-halosilane is: bis (4-haloaryl) diarylsilane) or (3, 5-dihaloaryl) triarylsilane, the aryl group being phenyl, biphenyl, or naphthyl;
further, the double halogenated siloxane is prepared by the following method: halogenated aryl silane and phenolic compound react in an aprotic solvent at room temperature to 160 ℃ to prepare the double halogenated siloxane; moles of halogen reacted in the haloaryl silane: the molar number of the phenolic groups of the phenolic compound is 1-1.05: 1;
further, the haloaryl silane is selected from the group consisting of: dihalodiarylsilane
Trihalo-aryl silanes
Or tetrahalosilanes
Wherein R is1Selected from: phenyl, biphenyl, or naphthyl; r2Selected from: phenyl, biphenyl, or naphthyl; r1And R2The same or different;
further, the phenolic compound is selected from: a monohalogenated aromatic phenol compound, a bishaloaromatic monophenol compound or a bishaloaromatic bisphenol compound.
3. The method for producing a heat-resistant silicon-containing polyarylene sulfide according to claim 2,
the monohalogenated aromatic phenolic compound is selected from:
Y＝-S-、
or-O-, X is halogen;
further, the bis-halogenated aromatic monophenols are selected from:
further, the bis-halogenated aromatic bisphenol compound is selected from:
further, the silicon-containing bis-halogen monomer is selected from: bis (4-haloaryl) diarylsilane, (3, 5-dihaloaryl) triarylsilane, 4-dihalodiaryl-diarylsiloxane, bis (2, 5-dihaloaryl) -diarylsiloxane, or tetrakis (2, 5-dichlorodiaryl) -siloxane; the alkyl group is phenyl, biphenyl, or naphthyl.
4. The method for preparing the heat-resistant silicon-containing polyarylene sulfide as claimed in any one of claims 1 to 3, wherein the molar ratio of the raw materials is: sulfur-containing monomers: (bis-halogenated aromatic compound + silicon-containing bis-halogenated monomer) 0.90 to 1.10; bis-halogenated aromatic compound: 60-99% of silicon-containing double-halogenated monomer: 40-1;
further, the sulfur-containing monomer is selected from the group consisting of: sodium hydrosulfide, sodium sulfide or hydrogen sulfide;
further, the bis-halogenated aromatic compound is selected from: 1, 4-dihalobenzene, 2, 4-dihalobenzene, 3, 5-dihalobenzene, 4 '-dihalobiphenyl, 4' -dihalodiphenylsulfone, 4 '-dihalobenzophenone or 4, 4' -dihalodiphenylether.
5. The method according to any one of claims 1 to 4, wherein when the silicon-containing dihalogen monomer is a dihalosilane, the method for producing the heat-resistant silicon-containing polyarylene sulfide is: firstly, dehydrating a sulfur-containing monomer until the water content is less than or equal to 1.0 wt%, and then adding the bis-halosilane and the bis-halogenated aromatic compound to perform polymerization reaction for 3-12 hours at 180-300 ℃ under normal pressure or 1-20 MPa; then polymerizing for 1-8 hours under the conditions of 1-20 MPa pressure and 200-320 ℃ under the protection of inert gas to obtain a high polymer; and finally, carrying out post-treatment according to a post-treatment method for preparing the polyarylene sulfide.
6. The method according to any one of claims 1 to 4, wherein when the silicon-containing bis-halogen monomer is a bis-halosiloxane, the method comprises the steps of:
1) halogenated aryl silane and phenolic compound react in an aprotic solvent at room temperature to 160 ℃ to form double halogenated siloxane;
2) dehydrating the sulfur-containing monomer until the water content is less than or equal to 1.0 wt%;
3) carrying out polymerization reaction on the dehydrated sulfur-containing monomer obtained in the step 2), the bishalosiloxane obtained in the step 1) and a bishaloaromatic compound for 1-6 hours at the temperature of 180-300 ℃ under normal pressure or the pressure of 1-20 MPa to obtain a uniform polymer with low polymerization degree;
4) polymerizing the low-polymerization-degree polymer obtained in the step 3) for 1-8 hours under the conditions of 1-20 MPa pressure and 200-320 ℃ under the protection of inert gas to obtain a high polymer;
5) post-treating the high polymer obtained in the step 4) according to a method for preparing polyarylene sulfide post-treatment;
further, in step 1), the aprotic solvent is tetrahydrofuran, dichloroethane, dimethyl sulfoxide, dichloromethane, chloroform, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, 6-cyclohexylpyrrolidone, N-ethylpyrrolidone, N-octylpyrrolidone, or hexamethylphosphoric triamide;
further, in the step 2), the dehydration reaction of the sulfur-containing monomer is as follows: under normal pressure, carrying out dehydration reaction on a sulfur-containing monomer in an aprotic solvent at the room temperature of 200 ℃ under the protection of inert gas;
further, in the step 2), in the dehydration reaction of sulfur monomer, the aprotic polar solvent includes: any one of N-methyl-2-pyrrolidone, N-cyclohexylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, hexamethylphosphoramide, N-dimethylacetamide, N-dimethylamide, N-ethylcaprolactam, N-vinylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone lactam, tetramethylurea, dimethyl sulfoxide, or sulfolane;
further, in step 5), the post-processing method comprises: washing the high polymer obtained in the step 4) for at least 3 times at 60-100 ℃ by using 10-20 times of deionized water, and drying in a drying oven at 80-120 ℃ for 12-48 hours.
7. A heat-resistant silicon-containing polyarylene sulfide, which is prepared by the method of any one of claims 1 to 6;
further, the structural formula of the heat-resistant silicon-containing polyarylene sulfide is one of the following structural formulas:
in the formula, R1And R2Selected from: phenyl, biphenyl, or naphthyl; in the formula I, a is more than or equal to 1 and less than or equal to 40, b is more than or equal to 60 and less than or equal to 99, and n is more than or equal to 100; in the formula II, m is more than or equal to 11≤40，60≤m2≤99，n≥100；
Y＝Z＝-S-、
or-O-.
8. A method for simultaneously improving the heat resistance and the toughness of polyarylene sulfide is characterized by comprising the following steps: introducing a silicon-containing double-halogen monomer in the preparation process of the polyarylene sulfide; wherein the silicon-containing double-halogen monomer is double-halogen silane or double-halogen siloxane;
further, the bis-halosilane is: bis (4-haloaryl) diarylsilane) or (3, 5-dihaloaryl) triarylsilane, the aryl group being phenyl, biphenyl, or naphthyl;
further, the double halogenated siloxane is prepared by the following method: halogenated aryl silane and phenolic compound react in an aprotic solvent at room temperature to 160 ℃ to prepare the double halogenated siloxane; moles of halogen reacted in the haloaryl silane: the molar number of the phenolic groups of the phenolic compound is 1-1.05: 1;
further, the haloaryl silane is selected from the group consisting of: dihalodiarylsilane
Trihalo-aryl silanes
Or tetrahalosilanes
Wherein R is1Selected from: phenyl, biphenyl, or naphthyl; r2Selected from: phenyl, biphenyl, or naphthyl; r1And R2The same or different;
further, the phenolic compound is selected from: a monohalogenated aromatic phenol compound, a bishaloaromatic monophenol compound or a bishaloaromatic bisphenol compound.
9. A preparation method of double halogenated siloxane is characterized by comprising the following steps: halogenated aryl silane and phenolic compound react in an aprotic solvent at room temperature to 160 ℃ to prepare the double halogenated siloxane; moles of halogen reacted in the haloaryl silane: the molar number of the phenolic groups of the phenolic compound is 1-1.05: 1;
further, the haloaryl silane is selected from the group consisting of: dihalodiarylsilane
Trihalo-aryl silanes
Or tetrahalosilanes
Wherein R is1Selected from: phenyl, biphenyl, or naphthyl; r2Selected from: phenyl, biphenyl, or naphthyl; r1And R2May be the same or different;
further, the phenolic compound is selected from: a monohalogenated aromatic phenol compound, a bishaloaromatic monophenol compound or a bishaloaromatic bisphenol compound.
10. A bis-halosiloxane prepared by the method of claim 9;
further, the bis-halosiloxane is selected from the group consisting of: 4, 4-dihalodiaryl-diarylsiloxane, bis (2, 5-dihaloaryl) -diarylsiloxane, or tetrakis (2, 5-dichlorodiaryl) siloxane; the alkyl group is phenyl, biphenyl, or naphthyl.
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