CN109705346A - Polyphenylene sulfide and the preparation method and application thereof without lithium chloride and additive - Google Patents
Polyphenylene sulfide and the preparation method and application thereof without lithium chloride and additive Download PDFInfo
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- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 57
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 title abstract description 40
- 239000000654 additive Substances 0.000 title abstract description 10
- 230000000996 additive effect Effects 0.000 title abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000005864 Sulphur Substances 0.000 claims abstract description 22
- 239000007790 solid phase Substances 0.000 claims abstract description 22
- 150000004816 dichlorobenzenes Chemical class 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000000725 suspension Substances 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000010792 warming Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 37
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 20
- DHAZIUXMHRHVMP-UHFFFAOYSA-N butyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OCCCC DHAZIUXMHRHVMP-UHFFFAOYSA-N 0.000 claims description 19
- 238000010189 synthetic method Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000006073 displacement reaction Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002808 molecular sieve Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 7
- 238000005352 clarification Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 230000007613 environmental effect Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000002242 deionisation method Methods 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000007796 conventional method Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000007423 decrease Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920006351 engineering plastic Polymers 0.000 description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- MERJTCXDDLWWSK-UHFFFAOYSA-N 1-methylpyrrole pyrrolidin-2-one Chemical compound CN1C=CC=C1.N1C(CCC1)=O MERJTCXDDLWWSK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000011825 aerospace material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning 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
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The present invention relates to a kind of polyphenylene sulfide and the preparation method and application thereof without lithium chloride and additive.S101: under atmosphere of inert gases, sulphur powder and catalyst being added in reaction kettle, solvent is added later, heats and stirs evenly, until forming unit for uniform suspension；S102: dichloro-benzenes being added into suspension, is warming up to 120~150 DEG C with the rate of 1~5 DEG C/min and constant temperature stirs 1~3h；S103: the product that S102 is obtained is cooled to room temperature, and is separated by solid-liquid separation later and is taken solid phase；S104: solid phase is adopted to drying after being washed with deionized, obtains polyphenylene sulfide.Preparation method provided by the invention, not only effectively prevent the use of lithium chloride and additive in conventional method, and the polyphenylene sulfide being prepared is had excellent performance, chlorinity is extremely low, mobility and thermal stability are good, synthesis cost also further decreases, so as to effectively improve the economic benefit and social benefit in production process.
Description
Technical field
The present invention relates to macromolecule resins to synthesize field, and in particular to a kind of polyphenylene sulfide without lithium chloride and additive
And the preparation method and application thereof.
Background technique
Polyphenylene sulfide (PPS) is used as a kind of performance special engineering plastics outstanding, has the title of " plastics gold ", is to be so far
The only highest special engineering plastics of cost performance are both one of six big general engineering plastics and one of eight big aerospace materials.Although
Polyphenyl thioether material only has short 40 years or so time using the time, but have developed rapidly, it has also become the first product of special engineering plastics
Board.Polyphenylene sulfide has excellent physicochemical properties, and has good compatibility, being widely used in other materials
The high-tech sectors such as work, automobile, electronic apparatus, military affairs, environmental protection and aerospace.
The industrial production of PPS mainly uses sodium sulfide method at present, with N-Methyl pyrrolidone (NMP) for solvent, in chlorination
High temperature polycondensation generation is carried out with paracide (P-DCB) under the participation of lithium auxiliary agent, Main By product is sodium chloride.Due to
Auxiliary agent lithium chloride is expensive, directly influences production cost to the effect that it is recycled.Meanwhile the separation of byproduct sodium chloride
There is important meaning for prevention and treatment environmental pollution with resource utilization.In addition, in the washing and way of distillation recycling of completing PPS product
After NMP, the sodium chloride and LiCl promoter of by-product are primarily present in resin cleaning solution and NMP bottoms.
For above-mentioned status, people have carried out many explorations, as using being filtered for multiple times with washing methods removal by-product salt
Method, but the method recovery process is cumbersome, and energy consumption is higher；Or lithium salts is separated using the precipitation method, but the lithium salts of precipitation method recycling needs
Other chemical substances are consumed, and is reacted again with hydrochloric acid after sediment separating and dehydrating and lithium chloride is made, reaction route is long, Bu Nengbao
Demonstrate,prove the high-recovery of lithium chloride.
Based on this, the synthetic method for providing a kind of novel polyphenylene sulfide without lithium chloride and additive is particularly important.
Summary of the invention
For the defects in the prior art, the present invention is intended to provide a kind of polyphenylene sulfide without lithium chloride and additive and
Preparation method and application.Preparation method provided by the invention not only effectively prevents lithium chloride and additive in conventional method
Use, and the polyphenylene sulfide being prepared is had excellent performance, chlorinity is extremely low, mobility and thermal stability are good, synthesis
Cost also further decreases, so as to effectively improve the economic benefit and social benefit in production process.
For this purpose, the invention provides the following technical scheme:
In a first aspect, the present invention provides a kind of synthetic method of polyphenylene sulfide, comprising the following steps: S101: inertia
Under atmosphere, sulphur powder and catalyst are added in reaction kettle, solvent is added later, heats and stirs evenly, until anti-
It answers and forms uniform suspension in kettle；S102: being added dichloro-benzenes into the suspension that S101 is obtained, with the rate of 1~5 DEG C/min
It is warming up to 120~150 DEG C and constant temperature stirs 1~3h；S103: the product that S102 is obtained is cooled to room temperature, and is separated by solid-liquid separation later
And take solid phase；S104: solid phase is adopted to drying after being washed with deionized, obtains polyphenylene sulfide.
Preferably, in S101: catalyst includes tetradecanoic acid butyl ester, La (NO3)3And carrier；And tetradecanoic acid butyl ester, La
(NO3)3(0.5~2.5) is followed successively by with the molar ratio of carrier: (0.01~0.05): 10.
Preferably, carrier selects MCM-41 mesopore molecular sieve and/or carbon carrier, and more preferably MCM-41 mesopore molecular sieve.
Preferably, the preparation method of catalyst, comprising the following steps: S201: by tetradecanoic acid butyl ester, La (NO3)3And load
Body is mixed and stirred for clarification, is dried later；S202: the product that S201 is obtained is heated up and is protected under nitrogen atmosphere
Temperature processing, carries out cooling and isothermal holding later, finally obtains catalyst.
Preferably, in S202: the product that S201 is obtained is placed in the nitrogen stream that gas flow rate is 20~100mL/min,
2~5h of constant temperature after being heated to 220 DEG C~280 DEG C with the heating rate of 1~3 DEG C/min, later with the cooling speed of 2~6 DEG C/min
Rate is cooled to 50 DEG C~80 DEG C.
Preferably, in S101: atmosphere of inert gases selects argon gas, and preferably passes first into gas in argon gas displacement reaction system
Body, and keep 60~90mL/min of gas flow.
Preferably, in S104: the deionization washing of the quality such as addition in solid phase, and preferably wash 2~3 times.
Preferably, the molar ratio of sulphur powder, catalyst, solvent and dichloro-benzenes is followed successively by 1:(0.005~0.05): (3~
8): (1.05~1.30)；It is highly preferred that solvent selects N-Methyl pyrrolidone.
Second aspect, the polyphenylene sulfide being prepared using the method for the present invention.
The third aspect, polyphenylene sulfide provided by the invention chemical industry, automobile, electronic apparatus, military affairs, environmental protection and
Application in aerospace field.
Above-mentioned technical proposal provided by the invention has the advantage that
(1) applicant has found by numerous studies: preparation method provided by the invention not only effectively prevents conventional method
The use of middle lithium chloride and additive, and the polyphenylene sulfide being prepared is had excellent performance, chlorinity is extremely low, mobility and
Thermal stability is good, and synthesis cost also further decreases, so as to effectively improve the economic benefit in production process and society's effect
Benefit.
(2) it is different from the preparation method of traditional polyphenylene sulfide, i.e., with paracide and sulphur in the presence of LiCl promoter
Change sodium and carry out high temperature polycondensation generation, auxiliary agent lithium chloride is expensive and target product in chlorinity it is higher, and then significant shadow
Ring properties of product.And the present invention selects load tetradecanoic acid butyl ester and La (NO using sulphur powder and dichloro-benzenes as raw material3)3Point
Sub- sieve catalyst is reacted in the effect of polar solvent N-Methyl pyrrolidone, to effectively drop in PPS resin generating process
Low chlorine element, and the use of lithium chloride is avoided, finally obtain ultralow chloride polyphenylene sulfide resin.
(3) target product polyphenylene sulfide high income of the present invention, high-quality, molecular structure is by phenyl ring and divalent sulfur in benzene
The linear sulfur-containing aromatic polymers of the inline composition of contraposition interaction of ring have excellent thermal stability, anti-flammability and corrosion-resistant
Property, the economic benefit and social benefit in production process can be effectively improved；In addition, the aromatic rings of rigidity and thioether flexible
In conjunction with, make polyphenylene sulfide macromolecular with just based on again have very high mobility.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Specific embodiment
The embodiment of technical solution of the present invention will be described in detail below.Following embodiment is only used for clearer
Illustrate technical solution of the present invention, therefore be only used as example, and not intended to limit the protection scope of the present invention.
Experimental method in following embodiments is unless otherwise specified conventional method.Examination as used in the following examples
Material is tested, is to be commercially available from conventional reagent shop unless otherwise specified.Quantitative test in following embodiment, is all provided with
Three repeated experiments are set, data are the average value or mean+SD of three repeated experiments.
The present invention provides a kind of synthetic method of polyphenylene sulfide, comprising the following steps:
S101: in the case where inert gas argon atmospher is enclosed, sulphur powder and catalyst are added in reaction kettle, N- first is added later
Base pyrrolidones is heated and is stirred evenly, until forming uniform suspension in reaction kettle.Wherein, catalyst includes the tetradecane
Acid butyl ester, La (NO3)3With MCM-41 mesopore molecular sieve；And tetradecanoic acid butyl ester, La (NO3)3With MCM-41 mesopore molecular sieve
Molar ratio is followed successively by (0.5~2.5): (0.01~0.05): 10；Sulphur powder, catalyst, N-Methyl pyrrolidone and dichloro-benzenes
Molar ratio be followed successively by 1:(0.005~0.05): (3~8): (1.05~1.30).
S102: being added dichloro-benzenes into the suspension that S101 is obtained, and is warming up to 120~150 with the rate of 1~5 DEG C/min
DEG C and constant temperature stir 1~3h.
S103: the product that S102 is obtained is cooled to room temperature, and is separated by solid-liquid separation later and is taken solid phase.
S104: solid phase is adopted to drying after being washed with deionized, obtains polyphenylene sulfide.
In further embodiment of the invention, the preparation method of catalyst, comprising the following steps: S201: by 14
Alkanoic acid butyl ester, La (NO3)3It is mixed and stirred for carrier to clarification, is dried later；S202: the product that S201 is obtained is placed in
Gas flow rate is in the nitrogen stream of 20~100mL/min, after being heated to 220 DEG C~280 DEG C with the heating rate of 1~3 DEG C/min
2~5h of constant temperature is cooled to 50 DEG C~80 DEG C later with the rate of temperature fall of 2~6 DEG C/min, finally obtains catalyst.
In further embodiment of the invention, in S101: passing first into gas in argon gas displacement reaction system, and protect
Hold 60~90mL/min of gas flow.
It is illustrated With reference to embodiment:
Embodiment one
The present embodiment provides a kind of synthetic methods of polyphenylene sulfide, comprising the following steps:
S101: gas in argon gas displacement reaction system is passed first into, and keeps gas flow 90mL/min, by sulphur powder
It is added in reaction kettle with catalyst, N-Methyl pyrrolidone is added later, heats and stirs evenly, until being formed in reaction kettle equal
Even suspension.Wherein, the molar ratio of sulphur powder, catalyst, N-Methyl pyrrolidone and dichloro-benzenes is followed successively by 1:0.05:3:
1.30。
Catalyst includes that molar ratio is followed successively by the tetradecanoic acid butyl ester of 2.5:0.05:10, La (NO3)3With mesoporous point of MCM-41
Son sieve；Preparation method includes the following steps: S201: by tetradecanoic acid butyl ester, La (NO3)3It is mixed and stirred for carrier to clear
Clearly, it is dried later；S202: the product that S201 is obtained be placed in gas flow rate be 100mL/min nitrogen stream in, with 1 DEG C/
Constant temperature 5h after the heating rate of min is heated to 220 DEG C, is cooled to 50 DEG C later with the rate of temperature fall of 2 DEG C/min, finally obtains and urge
Agent.
S102: being added dichloro-benzenes into the suspension that S101 is obtained, and is warming up to 150 DEG C and constant temperature with the rate of 5 DEG C/min
Stir 3h.
S103: the product that S102 is obtained is cooled to room temperature, and is separated by solid-liquid separation later and is taken solid phase.
S104: solid phase is adopted to drying after being washed with deionized, obtains polyphenylene sulfide.
Embodiment two
The present embodiment provides a kind of synthetic methods of polyphenylene sulfide, comprising the following steps:
S101: gas in argon gas displacement reaction system is passed first into, and keeps gas flow 60mL/min, by sulphur powder
It is added in reaction kettle with catalyst, N-Methyl pyrrolidone is added later, heats and stirs evenly, until being formed in reaction kettle equal
Even suspension.Wherein, the molar ratio of sulphur powder, catalyst, N-Methyl pyrrolidone and dichloro-benzenes is followed successively by 1:0.005:
8:1.02.
Catalyst includes that molar ratio is followed successively by the tetradecanoic acid butyl ester of 0.5:0.01:10, La (NO3)3With mesoporous point of MCM-41
Son sieve；Preparation method includes the following steps: S201: by tetradecanoic acid butyl ester, La (NO3)3It is mixed and stirred for carrier to clear
Clearly, it is dried later；S202: the product that S201 is obtained be placed in gas flow rate be 20mL/min nitrogen stream in, with 3 DEG C/
Constant temperature 2h after the heating rate of min is heated to 280 DEG C, is cooled to 80 DEG C later with the rate of temperature fall of 6 DEG C/min, finally obtains and urge
Agent.
S102: being added dichloro-benzenes into the suspension that S101 is obtained, and is warming up to 120 DEG C and constant temperature with the rate of 1 DEG C/min
Stir 1h.
S103: the product that S102 is obtained is cooled to room temperature, and is separated by solid-liquid separation later and is taken solid phase.
S104: solid phase is adopted to drying after being washed with deionized, obtains polyphenylene sulfide.
Embodiment three
The present embodiment provides a kind of synthetic methods of polyphenylene sulfide, comprising the following steps:
S101: gas in argon gas displacement reaction system is passed first into, and keeps gas flow 80mL/min, by sulphur powder
It is added in reaction kettle with catalyst, N-Methyl pyrrolidone is added later, heats and stirs evenly, until being formed in reaction kettle equal
Even suspension.Wherein, the molar ratio of sulphur powder, catalyst, N-Methyl pyrrolidone and dichloro-benzenes is followed successively by 1:0.01:5:
1.1。
Catalyst includes that molar ratio is followed successively by the tetradecanoic acid butyl ester of 1.5:0.03:10, La (NO3)3With mesoporous point of MCM-41
Son sieve；Preparation method includes the following steps: S201: by tetradecanoic acid butyl ester, La (NO3)3It is mixed and stirred for carrier to clear
Clearly, it is dried later；S202: the product that S201 is obtained be placed in gas flow rate be 60mL/min nitrogen stream in, with 2 DEG C/
Constant temperature 3h after the heating rate of min is heated to 260 DEG C, is cooled to 60 DEG C later with the rate of temperature fall of 3 DEG C/min, finally obtains and urge
Agent.
S102: being added dichloro-benzenes into the suspension that S101 is obtained, and is warming up to 130 DEG C and constant temperature with the rate of 3 DEG C/min
Stir 2h.
S103: the product that S102 is obtained is cooled to room temperature, and is separated by solid-liquid separation later and is taken solid phase.
S104: solid phase is adopted to drying after being washed with deionized, obtains polyphenylene sulfide.
In addition, following comparative example is arranged in order to further highlight the advantage of technical solution of the present invention.It should be noted that
Following comparative examples are arranged on the basis of embodiment three.
Comparative example one
This comparative example provides a kind of synthetic method of polyphenylene sulfide, comprising the following steps:
S101: gas in argon gas displacement reaction system is passed first into, and keeps gas flow 80mL/min, by sulphur powder
It is added in reaction kettle with catalyst, N-Methyl pyrrolidone is added later, heats and stirs evenly, until being formed in reaction kettle equal
Even suspension.Wherein, the molar ratio of sulphur powder, catalyst, N-Methyl pyrrolidone and dichloro-benzenes is followed successively by 1:0.01:5:
1.1。
Catalyst includes the tetradecanoic acid butyl ester and MCM-41 mesopore molecular sieve that molar ratio is followed successively by 1.5:10；Its preparation side
Method is the following steps are included: S201: tetradecanoic acid butyl ester and carrier being mixed and stirred for clarification, are dried later；S202: will
The product that S201 is obtained is placed in the nitrogen stream that gas flow rate is 60mL/min, is heated to 260 DEG C with the heating rate of 2 DEG C/min
Constant temperature 3h afterwards is cooled to 60 DEG C later with the rate of temperature fall of 3 DEG C/min, finally obtains catalyst.
S102: being added dichloro-benzenes into the suspension that S101 is obtained, and is warming up to 130 DEG C and constant temperature with the rate of 3 DEG C/min
Stir 2h.
S103: the product that S102 is obtained is cooled to room temperature, and is separated by solid-liquid separation later and is taken solid phase.
S104: solid phase is adopted to drying after being washed with deionized, obtains polyphenylene sulfide.
Comparative example two
This comparative example provides a kind of synthetic method of polyphenylene sulfide, comprising the following steps:
S101: gas in argon gas displacement reaction system is passed first into, and keeps gas flow 80mL/min, by sulphur powder
It is added in reaction kettle with catalyst, N-Methyl pyrrolidone is added later, heats and stirs evenly, until being formed in reaction kettle equal
Even suspension.Wherein, the molar ratio of sulphur powder, catalyst, N-Methyl pyrrolidone and dichloro-benzenes is followed successively by 1:0.01:5:
1.1。
Catalyst includes mesoporous point of tetradecanoic acid butyl ester, aluminium oxide and MCM-41 that molar ratio is followed successively by 1.5:0.03:10
Son sieve；Preparation method includes the following steps: S201: tetradecanoic acid butyl ester, aluminium oxide and carrier are mixed and stirred for clarification,
It is dried later；S202: the product that S201 is obtained is placed in the nitrogen stream that gas flow rate is 60mL/min, with 2 DEG C/min
Heating rate be heated to 260 DEG C after constant temperature 3h, be cooled to 60 DEG C later with the rate of temperature fall of 3 DEG C/min, finally obtain catalysis
Agent.
S102: being added dichloro-benzenes into the suspension that S101 is obtained, and is warming up to 130 DEG C and constant temperature with the rate of 3 DEG C/min
Stir 2h.
S103: the product that S102 is obtained is cooled to room temperature, and is separated by solid-liquid separation later and is taken solid phase.
S104: solid phase is adopted to drying after being washed with deionized, obtains polyphenylene sulfide.
Comparative example three
This comparative example provides a kind of synthetic method of polyphenylene sulfide, comprising the following steps:
S101: gas in argon gas displacement reaction system is passed first into, and keeps gas flow 80mL/min, by sulphur powder
It is added in reaction kettle, N-Methyl pyrrolidone is added later, heats and stirs evenly, until forming uniform suspend in reaction kettle
Liquid.Wherein, the molar ratio of sulphur powder, N-Methyl pyrrolidone and dichloro-benzenes is followed successively by 1:5:1.1.
S102: being added dichloro-benzenes into the suspension that S101 is obtained, and is warming up to 130 DEG C and constant temperature with the rate of 3 DEG C/min
Stir 2h.
S103: the product that S102 is obtained is cooled to room temperature, and is separated by solid-liquid separation later and is taken solid phase.
S104: solid phase is adopted to drying after being washed with deionized, obtains polyphenylene sulfide.
In addition, measuring each embodiment and comparative example in order to preferably highlight the advantage of technical solution of the present invention and being prepared
Polyphenylene sulfide performance, such as chlorinity, fusing point, melt flow rate (MFR), Mw molecular weight and product yield, table specific as follows
It is shown.
The polyphenylene sulfide performance data list that each embodiment of table 1 is prepared
The polyphenylene sulfide performance data list that each comparative example of table 2 is prepared
Each embodiment and comparative example polyphenylene sulfide Mw molecular weight of table 3 and yield list
| Mw molecular weight | Product yield/% | |
| Embodiment one | 50855 | 95.8 |
| Embodiment two | 53139 | 94.9 |
| Embodiment three | 52952 | 95.5 |
| Comparative example one | 45217 | 91.3 |
| Comparative example two | 36509 | 90.5 |
| Comparative example three | 20016 | 89.1 |
Certainly, the case where being enumerated in addition to embodiment one to embodiment three, in the ratios of other raw material components, preparation process
Other conditions and parameter etc. are also possible.
Preparation method provided by the invention not only effectively prevents the use of lithium chloride and additive in conventional method, and
And the polyphenylene sulfide being prepared is had excellent performance, chlorinity is extremely low, mobility and thermal stability are good, synthesis cost is also into one
Step reduces, so as to effectively improve the economic benefit and social benefit in production process.In addition, being different from traditional polyphenylene sulfide
Preparation method, i.e., high temperature polycondensation generation, auxiliary agent are carried out with paracide and vulcanized sodium in the presence of LiCl promoter
Lithium chloride is expensive and target product in chlorinity it is higher, and then significantly affect properties of product.And the present invention is with sulphur powder
It is raw material with dichloro-benzenes, selects load tetradecanoic acid butyl ester and La (NO3)3Molecular sieve catalyst, in polar solvent N- methyl pyrrole
Pyrrolidone effect is reacted, so that chlorine element be effectively reduced in PPS resin generating process, and avoids the use of lithium chloride,
Finally obtain ultralow chloride polyphenylene sulfide resin.
In the description of this specification, it is to be understood that reference term " one embodiment ", " is shown " some embodiments "
The description of example ", " specific example " or " some examples " etc. mean specific features described in conjunction with this embodiment or example, structure,
Material or feature are included at least one embodiment or example of the invention.In the present specification, above-mentioned term is shown
The statement of meaning property is necessarily directed to identical embodiment or example.Moreover, specific features, structure, material or the spy of description
Point may be combined in any suitable manner in any one or more of the embodiments or examples.In addition, without conflicting with each other,
Those skilled in the art can be by different embodiments or examples described in this specification and different embodiments or examples
Feature is combined.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (10)
1. a kind of synthetic method of polyphenylene sulfide, which comprises the following steps:
S101: under atmosphere of inert gases, sulphur powder and catalyst is added in reaction kettle, solvent is added later, heats and stirs
It mixes uniformly, until forming uniform suspension in reaction kettle；
Dichloro-benzenes is added in the suspension that S102: Xiang Suoshu S101 is obtained, is warming up to 120~150 with the rate of 1~5 DEG C/min
DEG C and constant temperature stir 1~3h；
S103: the obtained product of the S102 is cooled to room temperature, is separated by solid-liquid separation later and takes solid phase；
S104: the solid phase is adopted to drying after being washed with deionized, obtains polyphenylene sulfide.
2. the synthetic method of polyphenylene sulfide according to claim 1, it is characterised in that:
In the S101:
The catalyst includes tetradecanoic acid butyl ester, La (NO3)3And carrier；And the tetradecanoic acid butyl ester, La (NO3)3And carrier
Molar ratio be followed successively by (0.5~2.5): (0.01~0.05): 10.
3. the synthetic method of polyphenylene sulfide according to claim 2, it is characterised in that:
The carrier selects MCM-41 mesopore molecular sieve and/or carbon carrier, and preferably MCM-41 mesopore molecular sieve.
4. the synthetic method of polyphenylene sulfide according to claim 2, it is characterised in that:
The preparation method of the catalyst, comprising the following steps:
S201: by tetradecanoic acid butyl ester, La (NO3)3It is mixed and stirred for carrier to clarification, is dried later；
S202: the product that the S201 is obtained carries out heating and isothermal holding under nitrogen atmosphere, is cooled down later and is protected
Temperature processing, finally obtains the catalyst.
5. the synthetic method of polyphenylene sulfide according to claim 2, it is characterised in that:
In the S202:
The obtained product of the S201 is placed in the nitrogen stream that gas flow rate is 20~100mL/min, with 1~3 DEG C/min's
2~5h of constant temperature after heating rate is heated to 220 DEG C~280 DEG C, later with the rate of temperature fall of 2~6 DEG C/min be cooled to 50 DEG C~
80℃。
6. the synthetic method of polyphenylene sulfide according to claim 1, it is characterised in that:
In the S101:
The atmosphere of inert gases selects argon gas, and preferably passes first into gas in argon gas displacement reaction system, and keep gas
60~90mL/min of flow.
7. the synthetic method of polyphenylene sulfide according to claim 1, it is characterised in that:
In the S104:
The deionization washing of the quality such as addition in the solid phase, and preferably wash 2~3 times.
8. the synthetic method of described in any item polyphenylene sulfides according to claim 1~7, it is characterised in that:
The sulphur powder, the catalyst, the solvent and the dichloro-benzenes molar ratio be followed successively by 1:(0.005~
0.05): (3~8): (1.05~1.30)；
Preferably, the solvent selects N-Methyl pyrrolidone.
9. the polyphenylene sulfide that any one of claim 1~8 the method is prepared.
10. polyphenylene sulfide as claimed in claim 9 navigates in chemical industry, automobile, electronic apparatus, military affairs, environmental protection and aviation
Application in its field.
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