CN114213659B - 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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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 89
- 239000010703 silicon Substances 0.000 title claims abstract description 89
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229920000412 polyarylene Polymers 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 52
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 19
- 239000011593 sulfur Substances 0.000 claims abstract description 19
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 24
- -1 diaryl silane Chemical compound 0.000 claims description 23
- 150000002989 phenols Chemical class 0.000 claims description 21
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 235000010290 biphenyl Nutrition 0.000 claims description 15
- 239000004305 biphenyl Substances 0.000 claims description 15
- 125000001624 naphthyl group Chemical group 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 229910000077 silane Inorganic materials 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000000010 aprotic solvent Substances 0.000 claims description 11
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 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
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 229930185605 Bisphenol Natural products 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-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
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-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
- 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 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 150000003457 sulfones Chemical class 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 6
- 230000014759 maintenance of location Effects 0.000 abstract description 35
- 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
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 238000002844 melting Methods 0.000 description 25
- 230000008018 melting Effects 0.000 description 25
- 238000010438 heat treatment Methods 0.000 description 20
- 239000004734 Polyphenylene sulfide Substances 0.000 description 18
- 229920000069 polyphenylene sulfide Polymers 0.000 description 18
- 230000009477 glass transition Effects 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 238000000465 moulding Methods 0.000 description 11
- 241000612182 Rexea solandri Species 0.000 description 10
- 238000001746 injection moulding Methods 0.000 description 10
- 238000000520 microinjection Methods 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 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
- 239000000203 mixture Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 239000012153 distilled water Substances 0.000 description 3
- OIZQEPBFZDVGKV-UHFFFAOYSA-N (4,4-dichlorocyclohexa-1,5-dien-1-yl)-phenylmethanone Chemical compound C1=CC(Cl)(Cl)CC=C1C(=O)C1=CC=CC=C1 OIZQEPBFZDVGKV-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical class C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- RANCECPPZPIPNO-UHFFFAOYSA-N 2,5-dichlorophenol Chemical compound OC1=CC(Cl)=CC=C1Cl RANCECPPZPIPNO-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
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000003756 stirring Methods 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
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 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
- 239000011248 coating agent Substances 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
- 230000009977 dual effect Effects 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
- 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
- 239000000463 material Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 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
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
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- 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 a heat-resistant silicon-containing polyarylene sulfide and a preparation method thereof, belonging to the fields 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 dihalogenated aromatic compound and a silicon-containing dihalogenated monomer as main raw materials and adopting the existing method for preparing the polyarylene sulfide; wherein the silicon-containing dihalogen monomer is selected from the group consisting of: dihalosilanes or dihalosilanes. The invention combines the characteristics of silicon-based heat-resistant toughness and rigidity and strength of polyarylene sulfide, and prepares a series of linear, double-chain and surface heat-resistant silicon-containing polyarylene sulfide obtained by bulk polymerization, compared with the prior polyarylene sulfide, 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 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 ultra-high temperature environment.
Description
Technical Field
The invention provides a heat-resistant silicon-containing polyarylene sulfide and a preparation method thereof, belonging to the fields of polymer chemistry and physics.
Background
The silicon compound, especially the silicon resin, has excellent heat resistance, cold resistance, weather resistance, electrical insulation, hydrophobicity, anti-sticking and demolding properties, and the like, and has the dual characteristics of organic resin and inorganic resin. However, pure silicone resins generally belong to thermosetting resins, have low mechanical strength and poor secondary processing and molding properties. 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 sulfide, such as polyphenylene sulfide (PPS), polyphenylene sulfide ketone (PPSK), and polyphenylene sulfide sulfone (PPSF), has the characteristics of high temperature resistance, chemical corrosion resistance, excellent electrical properties, radiation resistance, flame resistance, high mechanical strength, and stable dimensions, and can be widely used as coating, plastic, structural material, binder, fiber, and film in the fields of automobiles, aerospace, petrochemical industry, light industrial machinery, electronics, food, and engineering technology. Main preparation of para-polyarylene sulfide in industrial production at presentThe method comprises the following steps: (1) Sodium sulfide (Na) 2 S,xH 2 O, 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, etc., sodium sulfide paradichlorobenzene (DCB) in an inert gas (e.g., N 2 ) Then, preparing Polyphenylene Sulfide (PPS) by pressurizing or normal pressure reaction in a polar solvent (NMP); (2) a method for preparing sulfur and aromatic compounds by reaction. As reported in US patent 3878176, CN 95111471.9, etc., polyphenylene sulfide (PPS) or high molecular weight polyarylene sulfide is synthesized by pressurizing sulfur and sodium carbonate as raw materials in a polar solvent; (3) Sodium hydrosulfide and polyhalogenation methods, such as those reported in EP 278276, JP Sho-61 0477330, JP Hei-2 30236, etc.
However, it has poor toughness and low impact strength, and it is necessary to modify the structure to improve the toughness and impact strength and further improve the heat resistance.
Disclosure of Invention
Aiming at the defects, the invention combines the characteristics of silicon-based heat-resistant toughness, rigidity and strength of polyarylene sulfide, and prepares a series of linear, double-chain and surface heat-resistant silicon-containing polyarylene sulfide obtained by bulk polymerization, compared with the prior polyarylene sulfide, 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 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 ultra-high 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 dihalogenated aromatic compound and a silicon-containing dihalogenated monomer as main raw materials and adopting the existing method for preparing the polyarylene sulfide; wherein the silicon-containing dihalogen monomer is selected from the group consisting of: dihalosilanes or dihalosilanes.
Further, the dihalosilane is: bis (4-haloaryl) diarylsilanes) (e.g) Or (3, 5-dihaloaromatic radicals)Radical) triarylsilanes (e.g. +.>) The aryl is phenyl, biphenyl, naphthyl or the like.
Further, the dihalosiloxane is prepared by the following method: the dihalosiloxane is prepared by reacting halogenated aryl silane with phenolic compounds in aprotic solvent at room temperature to 160 ℃; the ratio (mol) of haloarylsilane to phenolic compound is determined by the number of moles of reactive halogen to the number of moles of phenolic groups of the phenolic compound, the number of moles of reactive halogen in the haloarylsilane: phenolic compound molar number of phenolic groups = 1-1.05: 1.
further, the haloaryl silane is selected from: dihalodiarylsilanesTrihalomonoaryl silanesOr tetrahalosilanes->Wherein R is 1 Selected from: phenyl, biphenyl, naphthyl, and the like; r is R 2 Selected from: phenyl, biphenyl, naphthyl, and the like; r is R 1 And R is 2 The same or different.
Further, the phenolic compound is selected from: monohaloaromatic phenolic compounds, dihaloaromatic monophenols or dihaloaromatic bisphenols.
Still further, the monohalogenated aromatic phenolic compound is selected from the group consisting of: para-halophenolMethahalophenol->Halogenated naphthol-> Etc., Y= -S-, -S->or-O-, X is halogen.
Still further, the dihalo-aromatic monophenol compound is selected from:
etc.
Still further, the dihaloaromatic bisphenol compound is selected from the group consisting of:
etc.
Still further, the silicon-containing dihalogen monomer is selected from the group consisting of: bis (4-haloaryl) diaryl silane, (3, 5-dihaloaryl) triarylsilane, 4-dihaloaryl-diaryl siloxane, bis (2, 5-dihaloaryl) -diaryl siloxane, or tetrakis (2, 5-dichloro-diaryl) siloxane; the alkyl is phenyl, biphenyl or naphthyl.
Further, sulfur-containing monomers: (dihaloaromatic compound+silicon-containing dihalo monomer) molar ratio = 0.90-1.10, preferably 0.95-1.05; dihaloaromatic compounds: silicon-containing dihalogen monomer molar ratio = 60-99: 40 to 1 (mol).
Further, the sulfur-containing monomer is selected from: sodium hydrosulfide, sodium sulfide or hydrogen sulfide.
Further, the dihaloaromatic compound is selected from:
1, 4-dihalobenzenes2, 4-dihalophenyl->3, 5-dihalobenzene,
4,4' -dihalobiphenyl4,4' -dihalodiphenylsulfones
4,4' -dihalobenzophenone
4,4' -dihalodiphenyl ether or
And the like, X is halogen.
Further, when the silicon-containing dihalogen monomer is dihalosilane, the heat-resistant silicon-containing polyarylene sulfide is prepared by the following steps: firstly, dehydrating sulfur-containing monomers until the water content is less than or equal to 1.0 weight percent, and then adding dihalosilane and dihaloaromatic compounds to carry out polymerization reaction for 3-12 hours at 180-300 ℃ under normal pressure or 1-20 MPa pressure; then polymerizing for 1-8 hours under the protection of inert gas at the pressure of 1-20 MPa and the temperature of 200-320 ℃ to obtain a high polymer; finally, performing post-treatment according to the method for preparing the polyarylene sulfide.
Further, when the silicon-containing dihalogen monomer is dihalosiloxane, the method for preparing the heat-resistant silicon-containing polyarylene sulfide comprises the following steps:
1) Reacting halogenated aryl silane with a phenolic compound in an aprotic solvent at a temperature of between room temperature and 160 ℃ to form dihalosiloxane;
2) Dehydrating the sulfur-containing monomer until the water content is less than or equal to 1.0wt%; if water is abundant, the dihalosiloxane monomer can be hydrolyzed;
3) The dehydrated sulfur-containing monomer obtained in the step 2), the dihalosiloxane obtained in the step 1) and the dihalogenated aromatic compound are polymerized for 1 to 6 hours at 180 to 300 ℃ under normal pressure or 1 to 20MPa pressure to obtain a uniform polymer with low polymerization degree;
4) The polymer with low polymerization degree obtained in the step 3) is polymerized for 1 to 8 hours under the protection of inert gas under the pressure of 1 to 20MPa and the temperature of 200 to 320 ℃ to obtain a high polymer;
5) And (3) carrying out post-treatment on the high polymer obtained in the step (4) by referring to a post-treatment method for preparing the polyarylene sulfide, and obtaining the corresponding linear, double-chain and surface heat-resistant silicon-containing series polyarylene sulfide according to the silicon-containing dihalogen monomers participating in polymerization.
Further, in the 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 step 2), the sulfur-containing monomer dehydration reaction is: under normal pressure, the sulfur-containing monomer is dehydrated in aprotic solvent under the protection of inert gas at room temperature to 200 ℃.
Further, in step 2), in the dehydration reaction of the sulfur monomer, the aprotic polar solvent includes: any 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, dimethylsulfoxide or sulfolane.
Further, in step 5), the post-treatment method comprises the following steps: washing the polymer obtained in the step 4) with deionized water 10-20 times of the polymer at 60-100 ℃ for at least 3 times, and drying the polymer 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 adopting the method.
Further, the structural formula of the heat-resistant silicon-containing polyarylene sulfide is one of the following structural formulas:
wherein R is 1 And R is 2 Selected 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 1 1 ≤40,60≤m 2 ≤99,n≥100;
Y=Z=-S-、or-O-.
The third technical problem to be solved by the invention is to provide a method for simultaneously improving heat resistance and toughness of polyarylene sulfide, which comprises the following steps: introducing a silicon-containing dihalogen monomer in the preparation process of the polyarylene sulfide; wherein the silicon-containing dihalogen monomer is dihalosilane or dihalosiloxane.
The fourth technical problem to be solved by the invention is to provide a preparation method of dihalosiloxane, which comprises the following steps: the dihalosiloxane is prepared by reacting halogenated aryl silane with phenolic compounds in aprotic solvent at room temperature to 160 ℃; mole number of reactive halogen in haloarylsilane: phenolic compound molar number of phenolic groups = 1-1.05: 1.
further, the haloaryl silane is selected from: dihalodiarylsilanesTrihalomonoaryl silanesOr tetrahalosilanes->Wherein R is 1 Selected from: phenyl, biphenyl, naphthyl, and the like; r is R 2 Selected from: phenyl, biphenyl, naphthyl, and the like; r is R 1 And R is 2 May be the same or different.
Further, the phenolic compound is selected from: monohaloaromatic phenolic compounds, dihaloaromatic monophenols or dihaloaromatic bisphenols.
Still further, the monohalogenated aromatic phenolic compound is selected from the group consisting of: para-halophenolMethahalophenol->Halogenated naphthol-> Etc., Y= -S-, -S->or-O-, X is halogen.
Still further, the dihalo-aromatic monophenol compound is selected from:
etc.
Still further, the dihaloaromatic bisphenol compound is selected from the group consisting of:
etc.
The fifth technical problem to be solved by the present invention is to provide a dihalosiloxane, which is prepared by the above method.
Further, the dihalosiloxane is selected from: 4, 4-dihalodiaryl-diaryl-siloxane, bis (2, 5-dihalodiaryl) -diaryl-siloxane or tetrakis (2, 5-dichloro-diaryl) -siloxane; the alkyl is phenyl, biphenyl or naphthyl.
The invention has the beneficial effects that:
according to the invention, the characteristics of silicon-based heat-resistant toughness and rigidity and strength of the polyarylene sulfide are combined to prepare a series of heat-resistant silicon-containing polyarylene sulfide obtained by bulk polymerization, compared with the prior polyarylene sulfide, 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 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 ultra-high temperature environment; in addition, the elongation at break of the obtained modified polyarylene sulfide is improved from 3-5% to 25%, and is improved 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: the silicon-containing monomer and the phenolic compound react in an aprotic solvent at room temperature to 160 ℃ to form a silicon-containing dihalogen substance, wherein the reaction is normal pressure, and the specific reaction can be referred to as one of the following reaction formulas:
wherein X, Y is the same halogen atom or different halogen atoms;
and a second step of: dehydrating sodium sulfide, and dehydrating sulfide in an aprotic solvent under the protection of nitrogen at normal pressure and room temperature to 200 ℃;
and a third step of: the dehydrated sulfur, dihalosiloxane and dihalo aromatic compound are polymerized under normal pressure or 1-20 MPa pressure at 180-300 ℃ to form uniform polymer with low polymerization degree;
fourth step: polymerizing the uniform polymer with low polymerization degree under the protection of nitrogen for 1-8 hours under the pressure of 1-20 MPa and the temperature of 200-320 ℃, and obtaining corresponding linear, double-chain and surface silicon-based heat-resistant serial polyarylene sulfide according to the silicon-based monomers participating in polymerization;
the reaction formulas of the second to fourth steps are as follows:
Z=-S-、/>or-O-;
/>
/>
fifth step: and in the post-treatment and purification process, the obtained square reactant is washed 6 times by 10-20 times of deionized water with the weight of 60-100 ℃, and is dried in a drying oven with the temperature of 80-120 ℃ for 12-48 hours, so that the final linear, double-chain and surface silicon-based heat-resistant series polyarylene sulfide is obtained.
The above-described aspects of the present invention will be described in further detail below by way of specific embodiments of the present invention. It should not be understood that the scope of the above subject matter of the present invention is limited to the following examples only. Various substitutions and alterations are also possible, without departing from the spirit of the invention, and are intended to be within the scope of the invention.
Example 1 preparation of a Linear backbone silicon-containing anaerobic silicon-based polyarylene sulfide.
Into a 1L reactor was charged 250ml NMP,21gNaOH,40.5g sodium hydrosulfide (70% by weight), heated to 200℃under nitrogen, distilled water 79ml, and charged 12.36g of bis (4-bromophenyl) diphenylsilane69.83g of paradichlorobenzene is reacted 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, drying at 110 ℃ for 24 hours to obtain 58g of white product with the yield: 93%.
The product was thermally analyzed at a heating rate of 10 ℃/min in a nitrogen atmosphere, and the melting point was measured by DSC and the thermal decomposition temperature by TG. The product is subjected to injection molding at 290-310 ℃ by a Hake micro injection molding machine to form mechanical sample bars, and the tensile strength, the elongation at break and the impact strength of the product are tested.
The test results are: the glass transition temperature was 88 ℃, melting point tm=286 ℃. The quality retention rate at 550 ℃ is 70%, and the quality retention rate at 600 ℃ is 58% higher than that of pure PPS (63% and 49%). The tensile strength is 75MPa, the elongation at break is 15%, and the impact strength is 50J/M.
EXAMPLE 2 Linear side chain silicon-containing anaerobic silicon-based polyarylene sulfide and preparation
250ml NMP,21gNaOH,40.5 was charged into a 1L reactorg sodium hydrosulfide (70 wt%) was heated to 200℃under nitrogen protection, 79ml of distilled water was added with 18.55g (3, 5-dibromophenyl) triphenylsilane67.99g of p-dichlorobenzene is reacted for 3 hours at 220 ℃ to form a uniform low molecular polymer; heating to 265 ℃ for reaction for 3 hours, cooling to 110 ℃, slowly adding deionized water, filtering, washing, drying at 110 ℃ for 24 hours to obtain 63g of white product with the yield: 94%.
The product was thermally analyzed at a heating rate of 10 ℃/min in a nitrogen atmosphere, and the melting point was measured by DSC and the thermal decomposition temperature by TG. The product is subjected to injection molding at 290-310 ℃ by a Hake micro injection molding machine to form mechanical sample bars, and the tensile strength, the elongation at break and the impact strength of the product are tested.
The test results are: the glass transition temperature was 85 ℃, melting point tm=289 ℃. The quality retention rate at 550 ℃ is 60%, the quality retention rate at 600 ℃ is 57%, and the quality retention rate is higher than that of pure PPS (63% and 49%). The tensile strength is 76MPa, the elongation at break is 25%, and the impact strength is 60J/M.
EXAMPLE 3 preparation of Linear backbone silicon-containing based polyarylene sulfide
(1) 25.32g of dichlorodiphenylsilane was added to a three-necked flask containing 200ml of N, N-dimethylacetamide, followed by 25.72g of 4-chlorophenol, 10ml of triethylamine, and the mixture was stirred and heated to 120℃under nitrogen protection for 8 hours. Cooled to room temperature, washed 4 times with deionized water, washed 2 times with absolute ethanol, and dried under vacuum at 80 ℃ for 8 hours. 42.55g of a white fine powder product is obtained, the yield is 97%, and the structure is 4, 4-dichloro diphenyl-diphenyl siloxane, and the structure is a silicon-based monomer polymerized by silicon-containing silicon-based polyarylene sulfide with a linear main chain.
(2) Adding 250ml NMP,20.5gNaOH,40.5g 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-dichloro diphenyl-diphenyl siloxane obtained in (1), and 69.83g of p-dichlorobenzene, 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 61.5g of white product with the yield: 95%.
The product was thermally analyzed at a heating rate of 10 ℃/min in a nitrogen atmosphere, and the melting point was measured by DSC and the thermal decomposition temperature by TG. The product is subjected to injection molding at 290-310 ℃ by a Hake micro injection molding machine to form mechanical sample bars, and the tensile strength, the elongation at break and the impact strength of the product are tested.
The test results are: the glass transition temperature was 85 ℃, melting point tm=285 ℃. The quality retention rate at 550 ℃ is 71%, and the quality retention rate at 600 ℃ is 62% higher than that of pure PPS (63% and 49%). The tensile strength is 70MPa, the elongation at break is 12%, and the impact strength is 55J/M.
EXAMPLE 4 Linear double-stranded silicon-containing based polyarylene sulfide and preparation
(1) 25.32g of dichlorodiphenyl silane was added to a three-necked flask containing 200ml of N, N-dimethylacetamide, 32.6g of 2, 5-dichlorophenol was then added, 10ml of triethylamine was added, and the mixture was stirred and heated to 130℃under nitrogen protection to react for 8 hours. Cooled to room temperature, washed 4 times with deionized water, washed 2 times with absolute ethanol, and dried under vacuum at 80 ℃ for 8 hours. 49.36g of a white fine powder product is obtained, the yield is 97%, and the structure is bis (2, 5-dichlorobenzene) -diphenylsiloxane (506.20), and the structure is a silicon-based monomer polymerized by the next linear double-chain silicon-containing silicon-based polyarylene sulfide.
(2) Adding 250ml NMP,20.5gNaOH,40.5g 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 reacting 69.83g of p-dichlorobenzene 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 white product with the yield: 94%.
The product was thermally analyzed at a heating rate of 10 ℃/min in a nitrogen atmosphere, and the melting point was measured by DSC and the thermal decomposition temperature by TG. The product is subjected to injection molding at 290-310 ℃ by a Hake micro injection molding machine to form mechanical sample bars, and the tensile strength, the elongation at break and the impact strength of the product are tested.
The test results are: the glass transition temperature was 85 ℃, melting point tm=295 ℃. The quality retention rate at 550 ℃ is 69%, the quality retention rate at 600 ℃ is 57%, and the quality retention rate is higher than that of pure PPS (63% and 49%). The tensile strength is 72MPa, the elongation at break is 15%, and the impact strength is 58J/M.
Example 5 preparation of a planar silicon-containing based polyarylene sulfide.
(1) 25.32g of dichlorodiphenyl silane was introduced into a three-necked flask containing 200ml of N, N-dimethylacetamide, 17.91g of 2, 5-chlorohydroquinone was then added, 10ml of triethylamine was added, and the temperature was raised to 120℃under nitrogen protection with stirring to react for 8 hours. Cooled to room temperature, washed 4 times with deionized water, washed 2 times with absolute ethanol, and dried under vacuum at 80 ℃ for 8 hours. 35.01g of white fine powder product is obtained, the yield is 96%, and the structure isThe structure is a silicon-based monomer polymerized by the next step of silicon-containing silicon-based polyarylene sulfide.
(2) Into a 1L reactor, 250ml NMP,20.5gNaOH,40.5g sodium hydrosulfide (70 wt%) was charged, heated to 200℃under nitrogen protection, 89ml of distilled water was obtained, and the silicon-based monomer obtained in (1) was charged8.98g of paradichlorobenzene 69.83g, 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, drying at 110 ℃ for 24 hours to obtain 59.5g of white product with the yield: 93%. />
The product was thermally analyzed at a heating rate of 10 ℃/min in a nitrogen atmosphere, and the melting point was measured by DSC and the thermal decomposition temperature by TG. The product is subjected to injection molding at 290-310 ℃ by a Hake micro injection molding machine to form mechanical sample bars, and the tensile strength, the elongation at break and the impact strength of the product are tested.
The test results are: the glass transition temperature was 105 ℃, melting point tm=285 ℃. The quality retention rate at 550 ℃ is 72%, and the quality retention rate at 600 ℃ is 60% and is higher than that of pure PPS (63% and 49%). The tensile strength is 75MPa, the elongation at break is 11%, and the impact strength is 65J/M.
EXAMPLE 6 preparation of Linear backbone silicon-containing based polyarylene sulfide
(1) 16.99g of silicon tetrachloride were introduced into a three-necked flask containing 200ml of N, N-dimethylacetamide, 65.2g of 2, 5-dichlorophenol were then added, 10ml of triethylamine was added, and the mixture was stirred and heated to 120℃under nitrogen protection for 8 hours. Cooled to room temperature, washed 4 times with deionized water, washed 2 times with absolute ethanol, and dried under vacuum at 80 ℃ for 8 hours. 65.55g of a white fine powder product is obtained, the yield is 96%, and the structure is tetra (2, 5-dichloro diphenyl) yl-siloxane, and the structure is a silicon-based monomer polymerized by the next step of surface silicon-containing silicon-based polyarylene sulfide.
(2) 250ml NMP,20.5gNaOH,40.5g sodium hydrosulfide (70 wt%) is added into a 1L reactor, the mixture is heated to 200 ℃ under the protection of nitrogen, 89ml of water is fractionated, 4.22g of tetra (2, 5-dichloro diphenyl) yl-siloxane obtained in the step (1) and 69.83g of paradichlorobenzene are added, and the mixture reacts 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 57.5g of white product with the yield: 96%.
The product was thermally analyzed at a heating rate of 10 ℃/min in a nitrogen atmosphere, and the melting point was measured by DSC and the thermal decomposition temperature by TG. The product is subjected to injection molding at 290-310 ℃ by a Hake micro injection molding machine to form mechanical sample bars, and the tensile strength, the elongation at break and the impact strength of the product are tested.
The test results are: the glass transition temperature was 85 ℃, melting point tm=283 ℃. The quality retention rate at 550 ℃ is 71%, and the quality retention rate at 600 ℃ is 59% higher than that of pure PPS (63% and 49%). The tensile strength is 77MPa, the elongation at break is 18 percent, and the impact strength is 65J/M.
Example 7
As in example 1. P-dichlorobenzene 69.83g: 67.99g of p-dichlorobenzene instead4, 4-dichlorobenzophenone 3.14 g->
60g of white product is obtained, yield: 94%.
The product was thermally analyzed at a heating rate of 10 ℃/min in a nitrogen atmosphere, and the melting point was measured by DSC and the thermal decomposition temperature by TG. The product is subjected to injection molding at 290-320 ℃ by a Hake micro injection molding machine to form mechanical sample bars, and the tensile strength, the elongation at break and the impact strength of the product are tested.
The test results are: the glass transition temperature was 92 ℃, melting point tm=291℃. The quality retention rate at 550 ℃ is 70%, and the quality retention rate at 600 ℃ is 59% higher than that of pure PPS (63% and 49%). The tensile strength is 80MPa, the elongation at break is 12%, and the impact strength is 55J/M.
Example 8
Same as in example 3. P-dichlorobenzene 69.83g: 67.99g of p-dichlorobenzene instead4, 4-dichlorodiphenyl sulfone 3.59 g->
59g of white product was obtained in yield: 92%.
The product was thermally analyzed at a heating rate of 10 ℃/min in a nitrogen atmosphere, and the melting point was measured by DSC and the thermal decomposition temperature by TG. The product is subjected to injection molding at 290-320 ℃ by a Hake micro injection molding machine to form mechanical sample bars, and the tensile strength, the elongation at break and the impact strength of the product are tested.
The test results are: the glass transition temperature was 95 ℃, melting point tm=287 ℃. The quality retention rate at 550 ℃ is 69%, and the quality retention rate at 600 ℃ is 59% higher than that of pure PPS (63% and 49%). The tensile strength is 77MPa, the elongation at break is 16%, and the impact strength is 62J/M.
Example 9
Same as in example 4. P-dichlorobenzene 69.83g: 67.99g of p-dichlorobenzene instead4.11g of 4, 4-dibromodiphenyl ether->
59.5g of white product was obtained in yield: 93%.
The product was thermally analyzed at a heating rate of 10 ℃/min in a nitrogen atmosphere, and the melting point was measured by DSC and the thermal decomposition temperature by TG. The product is subjected to injection molding at 290-330 ℃ by a Hake micro injection molding machine to form mechanical sample bars, and the tensile strength, the elongation at break and the impact strength of the product are tested.
The test results are: the glass transition temperature was 98 ℃, melting point tm=293℃. The quality retention rate at 550 ℃ is 72%, and the quality retention rate at 600 ℃ is 60% and is higher than that of pure PPS (63% and 49%). The tensile strength is 75MPa, the elongation at break is 18%, and the impact strength is 62J/M.
Example 10
Same as in example 5. P-dichlorobenzene 69.83g: 67.99g of p-dichlorobenzene instead4, 4-dibromobiphenyl 3.91 g->
60.2g of white product is obtained, yield: 93%.
The product was thermally analyzed at a heating rate of 10 ℃/min in a nitrogen atmosphere, and the melting point was measured by DSC and the thermal decomposition temperature by TG. The product is subjected to injection molding at 290-310 ℃ by a Hake micro injection molding machine to form mechanical sample bars, and the tensile strength, the elongation at break and the impact strength of the product are tested.
The test results are: the glass transition temperature is 110 ℃, melting point tm=296 ℃. The quality retention rate at 550 ℃ is 71%, and the quality retention rate at 600 ℃ is 60% and higher than that of pure PPS (63% and 49%). The tensile strength is 77MPa, the elongation at break is 10 percent, and the impact strength is 62J/M.
Comparative example 1 (polymerization of only non-silicon-based monomer)
Adding 250ml NMP,20gNaOH,125.8g sodium hydrosulfide into a 1L reactor, stirring under the protection of nitrogen, heating to 200 ℃, fractionating 79ml of water, adding 73.5g of paradichlorobenzene, and reacting at 220 ℃ for 3 hours, wherein the first-stage reaction is completed; heating to 260 ℃ for reaction for 3 hours, cooling to 150 ℃, slowly adding deionized water, filtering, washing, drying at 110 ℃ for 24 hours to obtain 50g of white product with the yield: 93%.
The test results are: the glass transition temperature is 89 ℃, and the melting point tm=282 ℃; the mass retention rate at 550 ℃ is 63% and the mass retention rate at 600 ℃ is 49%. The tensile strength is 68MPa, the elongation at break is 4.6 percent, and the impact strength is 27J/M.
Comparative example 2 (polymerization of only non-silicon-based monomer)
As in comparative example 1. 73.5g of paradichlorobenzene, 71.66g of paradichlorobenzene instead4, 4-dichlorobenzophenone 3.14 g->
51g of white product was obtained in yield: 92%.
The test results are: glass transition temperature 90 ℃, melting point tm=283 ℃. The mass retention rate at 550 ℃ is 62%, and the mass retention rate at 600 ℃ is 50%. The tensile strength is 68MPa, the elongation at break is 4.6 percent, and the impact strength is 27J/M.
Comparative example 3 (polymerization of only non-silicon-based monomer)
As in comparative example 1. 73.5g of paradichlorobenzene, 71.66g of paradichlorobenzene instead4, 4-dichlorodiphenyl sulfone 3.59 g->
52g of white product were obtained, yield: 93%.
The test results are: glass transition temperature 93 ℃, melting point tm=281 ℃. The mass retention rate at 550 ℃ is 62% and the mass retention rate at 600 ℃ is 47%. The tensile strength is 65MPa, the elongation at break is 4.9%, and the impact strength is 25J/M.
Comparative example 4 (polymerization of only non-silicon based monomer)
As in comparative example 1. 73.5g of paradichlorobenzene, 71.66g of paradichlorobenzene instead4.11g of 4, 4-dibromodiphenyl ether->
52g of white product were obtained, yield: 93%.
The test results are: glass transition temperature 90 ℃, melting point tm=281 ℃. The mass retention rate at 550 ℃ is 61% and the mass retention rate at 600 ℃ is 46%. The tensile strength is 66MPa, the elongation at break is 3.9 percent, and the impact strength is 26J/M.
Comparative example 5 (polymerization of only non-silicon based monomer)
As in comparative example 1. 73.5g of paradichlorobenzene, 71.66g of paradichlorobenzene instead4, 4-dibromobiphenyl 3.91 g->
51g of white product was obtained in yield: 94%.
The test results are: glass transition temperature 92 ℃, melting point tm=283 ℃. The mass retention rate at 550 ℃ is 63% and the mass retention rate at 600 ℃ is 48%. The tensile strength is 70MPa, the elongation at break is 4.4 percent, and the impact strength is 30J/M.
Claims (14)
1. A method for preparing heat-resistant silicon-containing polyarylene sulfide, which is characterized by comprising the following steps: taking a sulfur-containing monomer, a dihalogenated aromatic compound and a silicon-containing dihalogen monomer as main raw materials, firstly dehydrating the sulfur-containing monomer until the water content is less than or equal to 1.0 weight percent, and then adding the silicon-containing dihalogen monomer and the dihalogenated aromatic compound to carry out polymerization reaction for 1-12 hours at 180-300 ℃ under normal pressure or 1-20 MPa pressure; then polymerizing for 1-8 hours under the protection of inert gas at the pressure of 1-20 MPa and the temperature of 200-320 ℃ to prepare the heat-resistant silicon-containing polyarylene sulfide;
wherein the silicon-containing dihalogen monomer is selected from the group consisting of: dihalosilanes or dihalosilanes; the dihalosilane or dihalosiloxane is selected from: bis (4-haloaryl) diaryl silane, (3, 5-dihaloaryl) triarylsilane, 4-dihaloaryl-diaryl siloxane, bis (2, 5-dihaloaryl) -diaryl siloxane, or tetrakis (2, 5-dichloro-diaryl) siloxane; the aryl is phenyl, biphenyl or naphthyl.
2. The method for preparing the heat-resistant silicon-containing polyarylene sulfide according to claim 1, wherein the dihalosiloxane is prepared by the following method: the dihalosiloxane is prepared by reacting halogenated aryl silane with phenolic compounds in aprotic solvent at room temperature to 160 ℃; mole number of reactive halogen in haloarylsilane: phenolic compound molar number of phenolic groups = 1-1.05: 1, a step of;
the haloaryl silane is selected from: dihalodiarylsilanesTrihalomonoaryl silanes->Or tetrahalosilanes->Wherein R is 1 Selected from: phenyl, biphenyl or naphthyl; r is R 2 Selected from: phenyl, biphenyl or naphthyl; r is R 1 And R is 2 The same or different;
the phenolic compound is selected from: monohaloaromatic phenolic compounds, dihaloaromatic monophenols or dihaloaromatic bisphenols.
3. The method for preparing heat-resistant silicon-containing polyarylene sulfide according to claim 2, wherein,
the monohalogenated aromatic phenol compound is selected from the group consisting of:
Y=-S-、or-O-, X is halogen;
the dihalo-aromatic monophenol compound is selected from:
the dihalogen aromatic bisphenol compound is selected from the group consisting of:
4. the method for producing a heat-resistant silicon-containing polyarylene sulfide according to any one of claims 1 to 3, wherein the molar ratio of the raw materials is: sulfur-containing monomer: (dihaloaromatic compound+silicon-containing dihalo monomer) =0.90 to 1.10; dihaloaromatic compounds: silicon-containing dihalo monomer = 60-99: 40 to 1.
5. A method of preparing a heat resistant silicon containing polyarylene sulfide according to any of claims 1 to 3, wherein the sulfur containing monomer is selected from the group consisting of: sodium hydrosulfide, sodium sulfide or hydrogen sulfide;
the dihaloaromatic compound is selected from: 1, 4-dihalobenzene, 2, 4-dihalobenzene, 3, 5-dihalobenzene, 4' -dihalobenzene sulfone, 4' -dihalobenzophenone or 4,4' -dihalobenzophenone.
6. The method for producing a heat-resistant silicon-containing polyarylene sulfide according to any one of claims 1 to 3, wherein when the silicon-containing dihalosilane is a dihalosilane, the method for producing a heat-resistant silicon-containing polyarylene sulfide is: firstly, dehydrating sulfur-containing monomers until the water content is less than or equal to 1.0 weight percent, and then adding dihalosilane and dihaloaromatic compounds to carry out polymerization reaction for 3-12 hours at 180-300 ℃ under normal pressure or 1-20 MPa pressure; then polymerizing for 1-8 hours under the protection of inert gas at the pressure of 1-20 MPa and the temperature of 200-320 ℃ to obtain a high polymer; finally, performing post-treatment according to the method for preparing the polyarylene sulfide.
7. The method for producing a heat-resistant silicon-containing polyarylene sulfide according to any one of claims 1 to 3, wherein when the silicon-containing dihalogen monomer is a dihalosiloxane, the method for producing a heat-resistant silicon-containing polyarylene sulfide comprises the steps of:
1) Reacting halogenated aryl silane with a phenolic compound in an aprotic solvent at a temperature of between room temperature and 160 ℃ to form dihalosiloxane;
2) Dehydrating the sulfur-containing monomer until the water content is less than or equal to 1.0wt%;
3) The dehydrated sulfur-containing monomer obtained in the step 2), the dihalosiloxane obtained in the step 1) and the dihalogenated aromatic compound are polymerized for 1 to 6 hours at 180 to 300 ℃ under normal pressure or 1 to 20MPa pressure to obtain a uniform polymer with low polymerization degree;
4) The polymer with low polymerization degree obtained in the step 3) is polymerized for 1 to 8 hours under the protection of inert gas under the pressure of 1 to 20MPa and the temperature of 200 to 320 ℃ to obtain a high polymer;
5) And (3) carrying out post-treatment on the high polymer obtained in the step (4) by referring to a method for preparing the polyarylene sulfide post-treatment.
8. The method for producing a heat-resistant silicon-containing polyarylene sulfide according to claim 7, wherein 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.
9. The method for preparing heat-resistant silicon-containing polyarylene sulfide according to claim 7, wherein in step 2), the dehydration reaction of the sulfur-containing monomer is: under normal pressure, the sulfur-containing monomer is dehydrated in an aprotic solvent under the protection of inert gas at the temperature of between room temperature and 200 ℃; the aprotic polar solvent comprises: any 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, dimethylsulfoxide, or sulfolane.
10. The method for preparing heat-resistant silicon-containing polyarylene sulfide according to claim 7, wherein in step 5), the post-treatment method is: washing the polymer obtained in the step 4) with deionized water 10-20 times of the polymer at 60-100 ℃ for at least 3 times, and drying the polymer in a drying oven at 80-120 ℃ for 12-48 hours.
11. A heat resistant silicon-containing polyarylene sulfide, characterized in that it is produced by the method according to any one of claims 1 to 10.
12. The heat resistant, silicon-containing polyarylene sulfide according to claim 11, wherein the heat resistant, silicon-containing polyarylene sulfide has a structural formula of one of the following structural formulas:
wherein R is 1 And R is 2 Selected 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 1 1 ≤40,60≤m 2 ≤99,n≥100;
13. A method for simultaneously improving heat resistance and toughness of polyarylene sulfide, which is characterized by comprising the following steps: introducing a silicon-containing dihalogen monomer in the preparation process of the polyarylene sulfide; wherein the silicon-containing dihalogen monomer is dihalosilane or dihalosiloxane; the dihalosilane or dihalosiloxane is selected from: bis (4-haloaryl) diaryl silane, (3, 5-dihaloaryl) triarylsilane, 4-dihaloaryl-diaryl siloxane, bis (2, 5-dihaloaryl) -diaryl siloxane, or tetrakis (2, 5-dichloro-diaryl) siloxane; the aryl is phenyl, biphenyl or naphthyl.
14. The method for simultaneously improving the heat resistance and the toughness of a polyarylene sulfide according to claim 13,
the dihalosiloxane is prepared by the following method: the dihalosiloxane is prepared by reacting halogenated aryl silane with phenolic compounds in aprotic solvent at room temperature to 160 ℃; mole number of reactive halogen in haloarylsilane: phenolic compound molar number of phenolic groups = 1-1.05: 1, a step of;
the haloaryl silane is selected from: dihalodiarylsilanesTrihalomonoaryl silanes->Or tetrahalosilanes->Wherein R is 1 Selected from: phenyl, biphenyl or naphthyl; r is R 2 Selected from: phenyl, biphenyl or naphthyl; r is R 1 And R is 2 The same or different;
the phenolic compound is selected from: monohaloaromatic phenolic compounds, dihaloaromatic monophenols or dihaloaromatic bisphenols.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1317016A (en) * | 1962-03-07 | 1963-02-01 | Monsanto Chemicals | Improvements to silicon-containing substances |
JPH05105774A (en) * | 1991-10-04 | 1993-04-27 | Nitto Boseki Co Ltd | Surface-treated sheet-like article and carbon-reinforced polyphenylene sulfide resin molded product |
CN1143652A (en) * | 1995-08-21 | 1997-02-26 | 四川联合大学 | Method for preparing polyarylene sulfide with high molecular and high toughness |
CN1461763A (en) * | 2002-05-31 | 2003-12-17 | 四川大学 | Polyaryl thioether sulfone and its preparation method |
JP2008075003A (en) * | 2006-09-22 | 2008-04-03 | Dainippon Ink & Chem Inc | Polyarylene sulfide resin composition and pipe for fluid |
KR20200136316A (en) * | 2019-05-27 | 2020-12-07 | 주식회사 엘지화학 | Method for preparing polyarylene sulfide |
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WO2018226425A1 (en) * | 2017-06-06 | 2018-12-13 | Dow Silicones Corporation | Method of making halosiloxane |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1317016A (en) * | 1962-03-07 | 1963-02-01 | Monsanto Chemicals | Improvements to silicon-containing substances |
JPH05105774A (en) * | 1991-10-04 | 1993-04-27 | Nitto Boseki Co Ltd | Surface-treated sheet-like article and carbon-reinforced polyphenylene sulfide resin molded product |
CN1143652A (en) * | 1995-08-21 | 1997-02-26 | 四川联合大学 | Method for preparing polyarylene sulfide with high molecular and high toughness |
CN1461763A (en) * | 2002-05-31 | 2003-12-17 | 四川大学 | Polyaryl thioether sulfone and its preparation method |
JP2008075003A (en) * | 2006-09-22 | 2008-04-03 | Dainippon Ink & Chem Inc | Polyarylene sulfide resin composition and pipe for fluid |
KR20200136316A (en) * | 2019-05-27 | 2020-12-07 | 주식회사 엘지화학 | Method for preparing polyarylene sulfide |
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