CN104559179A - Preparation method for anti-oxidation polyphenylene sulfide resin - Google Patents
Preparation method for anti-oxidation polyphenylene sulfide resin Download PDFInfo
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- CN104559179A CN104559179A CN201510035644.9A CN201510035644A CN104559179A CN 104559179 A CN104559179 A CN 104559179A CN 201510035644 A CN201510035644 A CN 201510035644A CN 104559179 A CN104559179 A CN 104559179A
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- polyphenylene sulfide
- antioxidant
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- butyl
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- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 128
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 128
- 239000011347 resin Substances 0.000 title claims abstract description 23
- 229920005989 resin Polymers 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000003064 anti-oxidating effect Effects 0.000 title abstract 3
- 239000006185 dispersion Substances 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000001704 evaporation Methods 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims abstract description 4
- 230000008018 melting Effects 0.000 claims abstract description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 63
- 239000003963 antioxidant agent Substances 0.000 claims description 57
- 235000006708 antioxidants Nutrition 0.000 claims description 57
- 230000003647 oxidation Effects 0.000 claims description 48
- 238000007254 oxidation reaction Methods 0.000 claims description 48
- 239000003112 inhibitor Substances 0.000 claims description 35
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- -1 arene compound Chemical class 0.000 claims description 20
- 239000005864 Sulphur Substances 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 8
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- XAQKFOUWWAKVCH-UHFFFAOYSA-N OP(O)OP(O)O.C(C)(C)(C1=CC=CC=C1)C1=C(C=CC(=C1)C(C)(C)C1=CC=CC=C1)C(O)C(CO)(CO)CO Chemical class OP(O)OP(O)O.C(C)(C)(C1=CC=CC=C1)C1=C(C=CC(=C1)C(C)(C)C1=CC=CC=C1)C(O)C(CO)(CO)CO XAQKFOUWWAKVCH-UHFFFAOYSA-N 0.000 claims description 5
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000003857 carboxamides Chemical class 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002530 phenolic antioxidant Substances 0.000 claims description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 claims description 3
- CTZIWUMXEISMIY-UHFFFAOYSA-N C(C)(C)(C)C=1C=C(CCCOP(OCC)(O)=O)C=C(C1O)C(C)(C)C Chemical compound C(C)(C)(C)C=1C=C(CCCOP(OCC)(O)=O)C=C(C1O)C(C)(C)C CTZIWUMXEISMIY-UHFFFAOYSA-N 0.000 claims description 3
- PLAFTLBFNIMFNQ-UHFFFAOYSA-N OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)CN)C(C)(C)C)C(O)C(CO)(CO)CO Chemical class OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)CN)C(C)(C)C)C(O)C(CO)(CO)CO PLAFTLBFNIMFNQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 claims description 2
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 claims description 2
- UDFARPRXWMDFQU-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(3,5-ditert-butyl-4-hydroxyphenyl)methylsulfanylmethyl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CSCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 UDFARPRXWMDFQU-UHFFFAOYSA-N 0.000 claims description 2
- JFQPDNZSMCACBL-UHFFFAOYSA-N C(C)(C)(CC)C1=C(O)C=C(C=C1O)C(C)(C)CC Chemical compound C(C)(C)(CC)C1=C(O)C=C(C=C1O)C(C)(C)CC JFQPDNZSMCACBL-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N Caprolactam Natural products O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000003205 fragrance Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 2
- 150000003672 ureas Chemical class 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims 2
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 claims 1
- GWGQGJDKNKYSRM-UHFFFAOYSA-N S(C1=C(C=CC2=CC=CC=C12)C=O)C1=C(C=CC2=CC=CC=C12)C=O Chemical compound S(C1=C(C=CC2=CC=CC=C12)C=O)C1=C(C=CC2=CC=CC=C12)C=O GWGQGJDKNKYSRM-UHFFFAOYSA-N 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 abstract description 10
- 238000003756 stirring Methods 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 5
- 239000007800 oxidant agent Substances 0.000 abstract 9
- 239000002270 dispersing agent Substances 0.000 abstract 3
- 230000006698 induction Effects 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 10
- 239000002105 nanoparticle Substances 0.000 description 9
- 238000007669 thermal treatment Methods 0.000 description 9
- 238000007605 air drying Methods 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 230000003245 working effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 2
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000008301 phosphite esters Chemical class 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- PJKVFARRVXDXAD-UHFFFAOYSA-N 2-naphthaldehyde Chemical compound C1=CC=CC2=CC(C=O)=CC=C21 PJKVFARRVXDXAD-UHFFFAOYSA-N 0.000 description 1
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical compound C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/375—Thiols containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention discloses a preparation method for anti-oxidation polyphenylene sulfide resin, which comprises the following steps: 1, blending, namley, dispersing polyphenylene sulfide resin to form nano/micro polyphenylene sulfide particles by a high-temperature solution method, adding an oxidant into a dispersing agent, conducting heating-stirring dispersion or ultrasonic-stirring dispersion to form an oxidant solution or turbid liquid, dispersing the nano/micro polyphenylene sulfide particles into the oxidant solution or turbid liquid, and evaporating or filtering the dispersing agent in the oxidant solution or turbid liquid so as to realize oxidant coating on the surfaces of the nano/micro polyphenylene sulfide particles to form nano/micro polyphenylene sulfide particles of which the surface are coated with the oxidant; 2, drying, namely, fully drying the nano/micro polyphenylene sulfide particles obtained in step 1, and removing the dispersing agent absorbed or embedded in the nano/micro polyphenylene sulfide particles of which the surface are coated with oxidant; and 3, preparing the anti-oxidation polyphenylene sulfide resin by melting. The method realizes uniform dispersion of the oxidant and uniform mixing of polyphenylene sulfide and the oxidant.
Description
Technical field
The present invention relates to the field of chemical synthesis, specifically a kind of preparation method of antioxidant polyphenylene sulfide resin.
Background technology
Polyphenylene sulfide (PPS) full name is polyphenylene thioether, it is a kind of High performance plastic resin, there is excellent thermotolerance, chemical resistance, flame retardant resistance, radiation hardness and excellent electrical property and dimensional stability, its intensity and hardness are all very high, available multiple forming method is processed, and can precise forming.PPS resin melt temperature 280 DEG C, decomposition temperature is greater than 480 DEG C, and life-time service temperature can reach 200 DEG C; Chemical resistance can compare favourably with the tetrafluoroethylene of the title having " kings of plastics ", and except acid with strong oxidizing property, PPS is dissolved in any solvent hardly below 200 DEG C; Its limiting oxygen index(LOI) is 44 ~ 53, and combustionproperty reaches the V-0/5V level of UL94, is the highest level of combustion safety; Specific inductivity 3.9 ~ 5.1, arc resistance is 34s; Molding shrinkage is 0.15% ~ 0.3%, minimumly reaches 0.01%.
PPS relies on the performance of its excellence to make it be widely used in the high-tech sectors such as petrochemical complex, automobile, machinery industry, electric, aerospace and military project.China's industry development, environmental protection pressure is huge, and PPS is used for high temperature filtration desulfurization as environment-friendly materials to be favored just day by day.
When PPS uses as high-temperature-resistant filtering material, in high-temperature flue gas, temperature is generally between 160 ~ 180 DEG C, instantaneously reaches more than 200 DEG C, and requires to reach more than 3 years work-ing life.Although PPS has excellent thermostability, due to very easily oxidized under the environment that evil is omited like this containing sulphur atom in molecular structure, easily cause macromolecular fracture to degrade, had a strong impact on the work-ing life of PPS high temperature filter bag.
Therefore, in order to extend the work-ing life of PPS product, improve PPS antioxidant property, in prior art, application number is 201310698508.9 disclose the antiseized spunlace non-woven filter material of a kind of antioxidant polyphenylene sulfide and production method thereof, and the method adds the antioxidant property that a certain amount of anti-oxidant master batch containing thio-2 acid di-esters oxidation inhibitor improves polyphenylene sulfide in polyphenylene sulfide melting process; But the oxidation inhibitor volatility that the method is selected is comparatively large, and poor with polymeric matrix consistency, in melt-processed process, p-poly-phenyl thioether antioxidant property improves less; It is dispersed that the method that the method directly adds anti-oxidant master batch in melting process is also difficult to realize oxidation inhibitor.
Found by By consulting literatures, improving the oxidation inhibitor also not adopting phosphorous acid esters in polyphenylene sulfide antioxidant property, and general phosphite ester kind antioxidant hydrolytic resistance is poor.Therefore, how to significantly improve PPS antioxidant property, realize the dispersed of oxidation inhibitor, realize the Homogeneous phase mixing of PPS and oxidation inhibitor, and the phosphite ester kind antioxidant filtering out the antioxidant property being applicable to raising polyphenylene sulfide has realistic meaning.
Summary of the invention
For the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is, a kind of preparation method of antioxidant polyphenylene sulfide resin is provided, comprises the following steps: the first step, blended: to adopt o to be dispersed into by polyphenylene sulfide and receive micro-polyphenylene sulfide particle; Oxidation inhibitor is joined in dispersion agent, through heated and stirred dispersion or ultrasonic agitation dispersion, form antioxidant solution or suspension liquid; Micro-polyphenylene sulfide Granular composite will be received in antioxidant solution or suspension liquid, by evaporating the dispersion agent in antioxidant solution or suspension liquid or filtering, realize oxidation inhibitor and receiving the coated of micro-polyphenylene sulfide particle surface, form micro-polyphenylene sulfide particle of receiving that Surface coating has oxidation inhibitor; Second step, dry: the micro-polyphenylene sulfide particle of the receiving the first step obtained carries out abundant drying, remove the dispersion agent receiving absorption or embedding in micro-polyphenylene sulfide particle that Surface coating has oxidation inhibitor; 3rd step, antioxidant polyphenylene sulfide resin is prepared in melting.The method achieve the dispersed of oxidation inhibitor, achieve the Homogeneous phase mixing of polyphenylene sulfide and oxidation inhibitor.
The technical scheme that the present invention solve the technical problem is, provide a kind of preparation method of antioxidant polyphenylene sulfide resin, it is characterized in that, the method comprises the following steps:
The first step, blended: to adopt o to be dispersed into by polyphenylene sulfide and receive micro-polyphenylene sulfide particle; Oxidation inhibitor is joined in dispersion agent, through heated and stirred dispersion or ultrasonic agitation dispersion, form antioxidant solution or suspension liquid; Micro-polyphenylene sulfide Granular composite will be received in antioxidant solution or suspension liquid, by evaporating the dispersion agent in antioxidant solution or suspension liquid or filtering, realize oxidation inhibitor and receiving the coated of micro-polyphenylene sulfide particle surface, form micro-polyphenylene sulfide particle of receiving that Surface coating has oxidation inhibitor;
The Heating temperature of described heated and stirred dispersion is room temperature to 300 DEG C, and churning time is 5 minutes to 48 hours; The churning time of described ultrasonic agitation dispersion is 5 minutes to 24 hours;
Second step, dry: the micro-polyphenylene sulfide particle of the receiving the first step obtained carries out abundant drying, remove the dispersion agent receiving absorption or embedding in micro-polyphenylene sulfide particle that Surface coating has oxidation inhibitor, normal pressure or vacuum-drying 2-48h, drying temperature is room temperature ~ 260 DEG C;
3rd step, anti-oxidant PPS is prepared in melting: what obtained by second step driedly receives micro-polyphenylene sulfide particle, melt extrudes, ordinary method granulation, namely obtain antioxidant polyphenylene sulfide resin in conventional twin screw or single screw extruder.
The solvent that o in the described the first step uses comprises at least one in organic amide, double ring arene compound or condensed-nuclei aromatics compound, and the temperature range of o is 220-300 DEG C.
Described organic amide comprises at least one in N-alkyl caprolactam, N-alkyl pyrrolidone, N-cycloalkanylpyrrole alkane ketone, N, N-dialkylimidazolium alkane ketone, tetraalkyl ureas or six alkylphosphonic acid carboxylic acid triamides; Described double ring arene compound comprise in biphenyl, halogenated biphenyl one or both; Described condensed-nuclei aromatics compound comprise naphthalene halide, anthracene, halo anthracene, phenanthrene or halo luxuriant and rich with fragrance at least one.
Dispersion agent in the described the first step is at least one in water, lower boiling organic amine, low-boiling point alcohol, hydrochloric ether, lower boiling alkane or low boiling point arene.
Oxidation inhibitor in the described the first step is at least one in phenolic antioxidant, sulphur ester antioxidant or phosphoric acid ester oxidation inhibitor.
Described phenolic antioxidant is 4, 4'-dihydroxybiphenyl, 4, 4'-methylene-bis (2, 6-DI-tert-butylphenol compounds), 4, 4'-butylidene two (the 6-tertiary butyl-3-methylphenol), 4, 4'-fourth fork two (3 methy 6 tert butyl phenol), 4, 4'-dihydroxy-phenyl-cyclohexane, 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 1, 1, 3-tri-(2-methyl-4-hydroxyl-5-trimethylphenylmethane base) butane, 2, 5-di-tert-butyl hydroquinone, 2, 5-bis-tert-pentyl Resorcinol or 4, at least one in 4'-butylidene two (the 6-tertiary butyl-3-methylphenol), described sulphur ester antioxidant is 4,4'-thiobis (the 6-tertiary butyl-3-methylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), 1, at least one in 1'-thiobis (beta naphthal) or two (3,5-di-tert-butyl-4-hydroxyl benzyl) thioether, described phosphoric acid ester oxidation inhibitor is two (2,4-dicumylphenyl) pentaerythritol diphosphites, 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid, two (3,5-di-t-butyl-4-cyanobenzyls phosphonic acids mono ethyl ester) calcium, the different monooctyl ester of tricresyl phosphite, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, two (2,4-di-tert-butyl-phenyl) at least one in pentaerythritol diphosphites or two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites.
Drying temperature in described second step is 110 DEG C ~ 150 DEG C.
According to the antioxidant polyphenylene sulfide resin that the preparation method of described antioxidant polyphenylene sulfide resin obtains, it is characterized in that comprising polyphenylene sulfide and oxidation inhibitor, the mass percent of described oxidation inhibitor accounts for 0.1 ~ 3% of total amount.
The present invention's beneficial effect is compared with the conventional method: preparation technology is simple, with pure PPS resin-phase ratio, oxidation induction temperature improves 5-10 DEG C, under the environment of 200 DEG C, rate of oxidation reduces, resistance of oxidation improves, thermo-oxidative stability improves, and extends the work-ing life of PPS product under severe rugged environment.Polyphenylene sulfide is insoluble to any solvent at normal temperatures, and how oxidation inhibitor evenly spreads in PPS becomes blended difficult point, and therefore the present invention adopts o to be dispersed into by polyphenylene sulfide to receive micro-polyphenylene sulfide particle; Oxidation inhibitor is joined in dispersion agent, through heated and stirred dispersion or ultrasonic agitation dispersion, form antioxidant solution or suspension liquid; Micro-polyphenylene sulfide Granular composite will be received in antioxidant solution or suspension liquid, by evaporating the dispersion agent in antioxidant solution or suspension liquid or filtering, realize oxidation inhibitor and receiving the coated of micro-polyphenylene sulfide particle surface, form micro-polyphenylene sulfide particle of receiving that Surface coating has oxidation inhibitor.
Embodiment
Provide specific embodiments of the invention below.Specific embodiment, only for further describing the present invention, does not limit the protection domain of the application's claim.
Embodiment 1
Polyphenylene sulfide slice is in N-Methyl pyrrolidone, the nano-particle of diameter 500 nanometer-2 microns is prepared at 245 DEG C, take and receive micro-polyphenylene sulfide particle (Mw=52000) and two (2,4-dicumylphenyl) pentaerythritol diphosphites, its quality proportioning is 99:1, uses ethanol to do dispersion agent, 2 hours are uniformly mixed at 230 DEG C, at 110 DEG C, vacuum-drying 24h, melt extrudes on the twin screw extruder, is a granulated into antioxidant polyphenylene sulfide.The oxidation induction temperature of gained antioxidant polyphenylene sulfide is 481.9 DEG C, and XPS shows under 200 DEG C of air atmospheres after thermal treatment 1h, and PPS element sulphur is not oxidized.
Embodiment 2
Polyphenylene sulfide slice is in 1-chloronaphthalene, the nano-particle of diameter 300 nanometer-2 microns is prepared at 205 DEG C, take and receive micro-polyphenylene sulfide particle (Mw=52000) and 4,4'-methylene-bis (2,6 di t butyl phenol), its quality proportioning is 99:1, use ethanol to do dispersion agent, mix 2 hours under stirring at normal temperature, vacuum-drying 24h at 110 DEG C, melt extrude on the twin screw extruder, be a granulated into antioxidant polyphenylene sulfide.The oxidation induction temperature of gained antioxidant polyphenylene sulfide is 483.0 DEG C, and XPS shows under 200 DEG C of air atmospheres after thermal treatment 1h, and PPS element sulphur is not oxidized.
Embodiment 3
Polyphenylene sulfide slice is in N-Methyl pyrrolidone, the nano-particle of diameter 500 nanometer-2 microns is prepared at 245 DEG C, take and receive micro-polyphenylene sulfide particle (Mw=52000) and 2,5 di tert butyl hydroquinone, its quality proportioning is 98:2, ethanol is used to do dispersion agent, stir 2 hours at 150 DEG C, then normal pressure forced air drying 24 hours at 80 DEG C, vacuum-drying 24h at 110 DEG C, melt extrude on the twin screw extruder, be a granulated into antioxidant polyphenylene sulfide.The oxidation induction temperature of gained antioxidant polyphenylene sulfide is 482.6 DEG C, and XPS shows under 200 DEG C of air atmospheres after thermal treatment 1h, and PPS element sulphur is not oxidized.
Embodiment 4
Polyphenylene sulfide slice is in N-Methyl pyrrolidone, the nano-particle of diameter 500 nanometer-2 microns is prepared at 245 DEG C, take and receive micro-polyphenylene sulfide particle (Mw=52000) and 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid, its quality proportioning is 98:2, ethamine is used to do dispersion agent, stir 3 hours at 100 DEG C, then normal pressure forced air drying 24 hours at 80 DEG C, vacuum-drying 24h at 110 DEG C, melt extrude on the twin screw extruder, be a granulated into antioxidant polyphenylene sulfide.The oxidation induction temperature of the antioxidant polyphenylene sulfide of gained is 484.2 DEG C, and XPS shows under 200 DEG C of air atmospheres after thermal treatment 1h, and PPS element sulphur is not oxidized.
Embodiment 5
Polyphenylene sulfide slice is at N, in N-methylimidazole alkane ketone, the nano-particle of diameter 500 nanometer-2 microns is prepared at 245 DEG C, take and receive micro-polyphenylene sulfide particle (Mw=52000) and two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, its quality proportioning is 98:2, benzene is used to do dispersion agent, stir 2.5 hours at 200 DEG C, normal pressure forced air drying 24 hours at 80 DEG C again, at 110 DEG C, vacuum-drying 24h, melt extrudes on the twin screw extruder, is a granulated into antioxidant polyphenylene sulfide.The oxidation induction temperature of the antioxidant polyphenylene sulfide of gained is 483.5 DEG C, and XPS shows under 200 DEG C of air atmospheres after thermal treatment 1h, and PPS element sulphur is not oxidized.
Embodiment 6
Polyphenylene sulfide slice is in N-methyl caprolactam, the nano-particle of diameter 500 nanometer-2 microns is prepared at 245 DEG C, take receive micro-polyphenylene sulfide particle (Mw=52000) and), 2, 2'-thiobis (4-methyl-6-tert-butylphenol), 4, 4'-fourth fork two (3 methy 6 tert butyl phenol), its quality proportioning is 98:1.5:0.5, use water as dispersion agent, magnetic force ultrasonic agitation mixes 2 hours, normal pressure forced air drying 24h at 120 DEG C again, vacuum-drying 24h at 120 DEG C, melt extrude on the twin screw extruder, be a granulated into antioxidant polyphenylene sulfide.The oxidation induction temperature of the antioxidant polyphenylene sulfide of gained is 487.4 DEG C, and XPS shows under 240 DEG C of air atmospheres after thermal treatment 1h, and PPS element sulphur is not oxidized.
Embodiment 7
Polyphenylene sulfide slice is in 1-chrloroanthracene, the nano-particle of diameter 300 nanometer-2 microns is prepared at 215 DEG C, take and receive micro-polyphenylene sulfide particle (Mw=52000), two (2,4-dicumylphenyl) pentaerythritol diphosphites and 4,4'-fourth fork two (3 methy 6 tert butyl phenol), its quality proportioning is 98:1.5:0.5, use ethanol as dispersion agent, magnetic force ultrasonic agitation mixes 4 hours, normal pressure forced air drying 24h at 120 DEG C again, at 120 DEG C, vacuum-drying 24h, melt extrudes on the twin screw extruder, is a granulated into antioxidant polyphenylene sulfide.The oxidation induction temperature of the antioxidant polyphenylene sulfide of gained is 488.1 DEG C, and XPS shows under 240 DEG C of air atmospheres after thermal treatment 1h, and PPS element sulphur is not oxidized.
Comparative example 1
Polyphenylene sulfide slice is in 1-chloronaphthalene, prepare the nano-particle of diameter 300 nanometer-2 microns at 205 DEG C, take and receive micro-polyphenylene sulfide particle (Mw=52000), do not add any oxidation inhibitor vacuum-drying 24h at 110 DEG C, melt extrude on the twin screw extruder, granulation.The oxidation induction temperature of the pure polyphenylene sulfide of gained is 471.3 DEG C, and XPS shows under 200 DEG C of air atmospheres after thermal treatment 1h, and the oxidized ratio of PPS element sulphur is 2.6%.
Comparative example 2
Polyphenylene sulfide slice is in N-Methyl pyrrolidone, the nano-particle of diameter 500 nanometer-2 microns is prepared at 245 DEG C, take and receive micro-polyphenylene sulfide particle (Mw=52000) and two (2,4-dicumylphenyl) pentaerythritol diphosphites, its quality proportioning is 99:1, does not use dispersion agent, adopt the method for mechanically mixing, at 110 DEG C, vacuum-drying 24h, melt extrudes on the twin screw extruder, is a granulated into antioxidant polyphenylene sulfide.The oxidation induction temperature of the antioxidant polyphenylene sulfide of gained is 476.7 DEG C, and XPS shows under 200 DEG C of air atmospheres after thermal treatment 1h, and the oxidized ratio of PPS element sulphur is 1.2%.
Oxidation induction temperature is the one tolerance means measuring polymkeric substance thermo-oxidative stability, concrete grammar reference standard GB/T 19466.6-2009, the model of U.S. TA company is used to record for SDT Q600 thermogravimetric analyzer, test condition is oxygen atmosphere, atmosphere flow velocity is 50ml/min, temperature rise rate 10 DEG C/min.
Sample is exposed 1h under the air ambient of 200 DEG C, uses the model of ThermoFisher company of the U.S. for the oxidized situation of K-Aepan x-ray photoelectron spectroscopy test sample.
Claims (8)
1. a preparation method for antioxidant polyphenylene sulfide resin, is characterized in that, the method comprises the following steps:
The first step, blended: to adopt o to be dispersed into by polyphenylene sulfide and receive micro-polyphenylene sulfide particle; Oxidation inhibitor is joined in dispersion agent, through heated and stirred dispersion or ultrasonic agitation dispersion, form antioxidant solution or suspension liquid; Micro-polyphenylene sulfide Granular composite will be received in antioxidant solution or suspension liquid, by evaporating the dispersion agent in antioxidant solution or suspension liquid or filtering, realize oxidation inhibitor and receiving the coated of micro-polyphenylene sulfide particle surface, form micro-polyphenylene sulfide particle of receiving that Surface coating has oxidation inhibitor;
The Heating temperature of described heated and stirred dispersion is room temperature to 300 DEG C, and churning time is 5 minutes to 48 hours; The churning time of described ultrasonic agitation dispersion is 5 minutes to 24 hours;
Second step, dry: the micro-polyphenylene sulfide particle of the receiving the first step obtained carries out abundant drying, remove the dispersion agent receiving absorption or embedding in micro-polyphenylene sulfide particle that Surface coating has oxidation inhibitor, normal pressure or vacuum-drying 2-48h, drying temperature is room temperature ~ 260 DEG C;
3rd step, anti-oxidant PPS is prepared in melting: what obtained by second step driedly receives micro-polyphenylene sulfide particle, melt extrudes, ordinary method granulation, namely obtain antioxidant polyphenylene sulfide resin in conventional twin screw or single screw extruder.
2. the preparation method of antioxidant polyphenylene sulfide resin according to claim 1, it is characterized in that solvent that the o in the described the first step uses comprises at least one in organic amide, double ring arene compound or condensed-nuclei aromatics compound, the temperature range of o is 220-300 DEG C.
3. the preparation method of antioxidant polyphenylene sulfide resin according to claim 2, it is characterized in that described organic amide comprises at least one in N-alkyl caprolactam, N-alkyl pyrrolidone, N-cycloalkanylpyrrole alkane ketone, N, N-dialkylimidazolium alkane ketone, tetraalkyl ureas or six alkylphosphonic acid carboxylic acid triamides; Described double ring arene compound comprise in biphenyl, halogenated biphenyl one or both; Described condensed-nuclei aromatics compound comprise naphthalene halide, anthracene, halo anthracene, phenanthrene or halo luxuriant and rich with fragrance at least one.
4. the preparation method of antioxidant polyphenylene sulfide resin according to claim 1, the dispersion agent that it is characterized in that in the described the first step is at least one in water, lower boiling organic amine, low-boiling point alcohol, hydrochloric ether, lower boiling alkane or low boiling point arene.
5. the preparation method of antioxidant polyphenylene sulfide resin according to claim 1, the oxidation inhibitor that it is characterized in that in the described the first step is at least one in phenolic antioxidant, sulphur ester antioxidant or phosphoric acid ester oxidation inhibitor.
6. the preparation method of antioxidant polyphenylene sulfide resin according to claim 5, it is characterized in that described phenolic antioxidant is 4, 4'-dihydroxybiphenyl, 4, 4'-methylene-bis (2, 6-DI-tert-butylphenol compounds), 4, 4'-butylidene two (the 6-tertiary butyl-3-methylphenol), 4, 4'-fourth fork two (3 methy 6 tert butyl phenol), 4, 4'-dihydroxy-phenyl-cyclohexane, 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 1, 1, 3-tri-(2-methyl-4-hydroxyl-5-trimethylphenylmethane base) butane, 2, 5-di-tert-butyl hydroquinone, 2, 5-bis-tert-pentyl Resorcinol or 4, at least one in 4'-butylidene two (the 6-tertiary butyl-3-methylphenol), described sulphur ester antioxidant is 4,4'-thiobis (the 6-tertiary butyl-3-methylphenol), 2, at least one in 2'-thiobis (4-methyl-6-tert-butylphenol), 1,1'-thiobis (beta naphthal) or two (3,5-di-tert-butyl-4-hydroxyl benzyl) thioether, described phosphoric acid ester oxidation inhibitor is two (2,4-dicumylphenyl) pentaerythritol diphosphites, 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid, two (3,5-di-t-butyl-4-cyanobenzyls phosphonic acids mono ethyl ester) calcium, the different monooctyl ester of tricresyl phosphite, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, two (2,4-di-tert-butyl-phenyl) at least one in pentaerythritol diphosphites or two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites.
7. the preparation method of antioxidant polyphenylene sulfide resin according to claim 1, is characterized in that the drying temperature in described second step is 110 DEG C ~ 150 DEG C.
8. according to the antioxidant polyphenylene sulfide resin that the preparation method of antioxidant polyphenylene sulfide resin according to claim 1 obtains, it is characterized in that comprising polyphenylene sulfide and oxidation inhibitor, the mass percent of described oxidation inhibitor accounts for 0.1 ~ 3% of total amount.
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| CN112159539A (en) * | 2020-09-11 | 2021-01-01 | 湖南华曙高科技有限责任公司 | Novel polyphenylene sulfide powder for selective laser sintering, preparation method thereof and polyphenylene sulfide mixed powder |
| CN112552642A (en) * | 2019-09-26 | 2021-03-26 | 合肥杰事杰新材料股份有限公司 | Polyether-ether-ketone composition with excellent ageing resistance and preparation method thereof |
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| CN112159539B (en) * | 2020-09-11 | 2022-06-07 | 湖南华曙高科技股份有限公司 | Novel polyphenylene sulfide powder for selective laser sintering, preparation method thereof and polyphenylene sulfide mixed powder |
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