CN103894231A - Reversed micelle nanometer aluminum oxide catalytic system and method for synthesizing modified epoxy plasticizer - Google Patents
Reversed micelle nanometer aluminum oxide catalytic system and method for synthesizing modified epoxy plasticizer Download PDFInfo
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- CN103894231A CN103894231A CN201410075521.3A CN201410075521A CN103894231A CN 103894231 A CN103894231 A CN 103894231A CN 201410075521 A CN201410075521 A CN 201410075521A CN 103894231 A CN103894231 A CN 103894231A
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- 239000004014 plasticizer Substances 0.000 title claims abstract description 64
- 239000004593 Epoxy Substances 0.000 title claims abstract description 51
- 239000000693 micelle Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000003197 catalytic effect Effects 0.000 title abstract description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 title abstract 5
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 229910001388 sodium aluminate Inorganic materials 0.000 claims abstract description 14
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 88
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 75
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 58
- 239000003054 catalyst Substances 0.000 claims description 44
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 30
- 239000000344 soap Substances 0.000 claims description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- 150000004668 long chain fatty acids Chemical class 0.000 claims description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 24
- 150000002191 fatty alcohols Chemical class 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 239000012046 mixed solvent Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 13
- 239000000460 chlorine Substances 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 12
- 235000019253 formic acid Nutrition 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 239000004519 grease Substances 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 7
- 238000006722 reduction reaction Methods 0.000 claims description 7
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 239000011630 iodine Substances 0.000 claims description 6
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 125000001033 ether group Chemical group 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 239000004033 plastic Substances 0.000 abstract description 12
- 229920003023 plastic Polymers 0.000 abstract description 12
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 9
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 9
- 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 abstract description 5
- 239000003063 flame retardant Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- NEHDRDVHPTWWFG-UHFFFAOYSA-N Dioctyl hexanedioate Chemical compound CCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCC NEHDRDVHPTWWFG-UHFFFAOYSA-N 0.000 abstract 2
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 abstract 2
- QKUNKVYPGIOQNP-UHFFFAOYSA-N 4,8,11,14,17,21-hexachlorotetracosane Chemical compound CCCC(Cl)CCCC(Cl)CCC(Cl)CCC(Cl)CCC(Cl)CCCC(Cl)CCC QKUNKVYPGIOQNP-UHFFFAOYSA-N 0.000 abstract 1
- 150000002118 epoxides Chemical class 0.000 abstract 1
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- 238000007710 freezing Methods 0.000 description 15
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- 230000010355 oscillation Effects 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000004809 thin layer chromatography Methods 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 235000012424 soybean oil Nutrition 0.000 description 10
- 239000003549 soybean oil Substances 0.000 description 10
- 239000003921 oil Substances 0.000 description 9
- 235000019198 oils Nutrition 0.000 description 9
- 150000002924 oxiranes Chemical class 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000007664 blowing Methods 0.000 description 6
- 238000004737 colorimetric analysis Methods 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000013517 stratification Methods 0.000 description 5
- 235000019197 fats Nutrition 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical class C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- IMYZYCNQZDBZBQ-SJORKVTESA-N (9S,10R)-epoxyoctadecanoic acid Chemical compound CCCCCCCC[C@H]1O[C@H]1CCCCCCCC(O)=O IMYZYCNQZDBZBQ-SJORKVTESA-N 0.000 description 2
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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
- 239000004480 active ingredient Substances 0.000 description 2
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- GXCLVBGFBYZDAG-UHFFFAOYSA-N N-[2-(1H-indol-3-yl)ethyl]-N-methylprop-2-en-1-amine Chemical compound CN(CCC1=CNC2=C1C=CC=C2)CC=C GXCLVBGFBYZDAG-UHFFFAOYSA-N 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000009874 alkali refining Methods 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
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- 238000005286 illumination Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical class [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical class [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a reversed micelle nanometer aluminum oxide catalytic system. The micelle nanometer aluminum oxide catalytic system is prepared by the method comprising the following steps: dissolving azobenzene into an organic solvent; adding sodium aluminate aqueous solution until reaching saturation; introducing carbon dioxide; then carrying out complete ultrasonic reaction under temperature of 50 to 60 DEG C to obtain the reversed micelle nanometer aluminum oxide catalytic system. The invention also discloses a method for synthesizing a modified epoxy plasticizer with the reversed micelle nanometer aluminum oxide catalytic system. Compared with the prior art, the novel plasticizer has the advantages of being high in epoxide number, and outstanding in compatibility with PVC (Polyvinyl Chloride) plastic; the flash point is high, thus the mobility is small, and overflowing is unlikely to occur; the color is relatively light, so that the novel plasticizer can be widely applied to the plastic industry; because of high electrical resistivity, the novel plasticizer is high in flame retardant performance and can be applied to the flame-retardant plastic industry to replace a chlorcosane plasticizer well; in addition, the performance is improved; the novel plasticizer is high in resistance to low temperature due to low solidifying point, and can also replace DOS (Di N Octyl Sebacate) and DOA (Di N Octyl Adipate) plasticizers well.
Description
Technical field
The invention belongs to field of fine chemical, specifically relate to a kind of method of reverse micelle nano aluminium oxide catalyst system and catalyzing and synthesis modification epoxy plasticizer.
Background technology
Plasticizer is the industrial macromolecular material auxiliary agent being widely used, and adds this material in plastic processing, can make its pliability strengthen, and easily processing, is widely used in industrial use.Plasticiser has aliphatic dibasic acid ester, Phthalates (comprising phthalate, terephthalate class), the many esters of gallic acid of benzene, benzoates, polyol ester class, chlorinated hydrocarbons, epoxies, citric acid ester type, polyesters etc. multiple from classification of chemical structure.
Chlorinated paraffin wax is the most frequently used flame-retardant plasticizer, but due to its color and taste not good, a lot of fields all cannot be used.Dioctyl adipate is because its cold resistance better and is extensively approved by masses, and still because its compatibility is poor, and the meeting of placement produces fuel-displaced phenomenon for a long time, therefore can only use as extender plasticizer.Epoxy plasticizer is the class plasticizer being made through epoxidation by vegetable oil or unrighted acid, mainly contain epoxidised soybean oil, epoxidised linseed oil and unrighted acid epoxidised ester, as epoxyoleic acid butyl ester, epoxyoleic acid monooctyl ester, epoxyoleic acid ester in the last of the ten Heavenly stems etc.Epoxy plasticizer is a kind of novel environment-friendly plasticizer of rising in recent years, and is more and more subject to everybody welcome, because epoxy grease has good heat resistance, stability, compatibility, can play stabilizing agent and plasticizer double action.
The synthetic of traditional handicraft epoxy plasticizer added hydrogen peroxide and formic acid wherein take vegetable fat as raw material, under sulphuric acid catalysis effect, reacts and gets, and this reaction is comparatively slow and accessory substance is more.Also have for traditional handicraft and carry out improved bibliographical information at present, the patent documentation that for example publication number is CN102703225A discloses a kind of production method of Plasticizer Epoxidized Soybean Oil, load weighted soybean oil, formic acid are added to reactor, then dripping hydrogen peroxide, to carry out epoxidation synthetic, after question response, wash, finally by crossing distillation dehydration, finally make, the weight fraction of raw material system consists of: 95～100 parts of soybean oils, weight concentration are that 50～78 parts, 27～50% hydrogen peroxide, weight concentration are 8～13 parts, 85% formic acid.The method production technology is safe and reliable, still, prepares plasticizer properties of product single, and structure and purposes are also comparatively single.For making up the single defect of existing plasticizer performance, some producer starts employing and makes up mutually deficiency separately by composite mode.The patent documentation that for example publication number is CN103483741A discloses a kind of PVC ester plasticizer, is grouped into by the one-tenth of following weight portion: diethylene glycol dibenzoate 10～30; Polyvinyl chloride 10～20; Active carbon 5～10; Glycerine 3～5; Soda ash 5～8; Octyl group oxirane 1～5; Epoxidized soybean oil 1～3.The advantage of this PVC ester plasticizer is: plasticizing efficiency is high, cold-resistant, heat-resisting, anti-pollution, resistance to extraction, and animal migration is good, and electrical insulating property is good, stable to photo-thermal.
But while adopting above-mentioned preparation method to prepare plasticizer, cost is higher on the one hand, technique is comparatively complicated; On the other hand, due to the complexity of raw material, the plasticizer unstable properties preparing, application is seriously limited.
Summary of the invention
The invention provides a kind of reverse micelle nano aluminium oxide catalyst system and catalyzing, utilize this catalyst system and catalyzing can the good modified epoxy plasticizer of processability, and preparation technology be simple.
The present invention also provides a kind of method that adopts self-control reverse micelle nano aluminium oxide catalyst system and catalyzing catalyzing and synthetizing modified epoxy plasticizer, both realized the recycling of vegetable oil residue material, can improve again the performance of plasticizer, expand the application of plasticizer, in original technical foundation, improve simultaneously, improve yield, reduced the generation of byproduct.
A kind of reverse micelle nano aluminium oxide catalyst system and catalyzing, utilize following method to prepare: azobenzene is dissolved in organic solvent, add sodium aluminate aqueous solution to saturated, pass into carbon dioxide, be under 50～60 ℃ of conditions in temperature, ultrasonic reaction is complete, prepares reverse micelle nano aluminium oxide catalyst system and catalyzing.
Prepare in reverse micelle nano aluminium oxide catalyst system and catalyzing process, described organic solvent can select antithesis pyridine to have better deliquescent neat solvent or mixed solvent, for example can adopt alcohols solvent, ketones solvent etc., also can adopt the mixed solvent of alcohols solvent and alkane solvents, as preferably, described organic solvent is the mixed solvent of normal heptane and n-butanol, wherein the volume ratio of normal heptane and n-butanol is 5～30:1, as further preferred, described normal heptane and the volume ratio of n-butanol are 10:1, experimental results show that, while adopting the mixed solvent of this ratio, the reverse micelle nano aluminium oxide catalyst system and catalyzing stability preparing is higher, and catalytic activity is high.
In the present invention, azobenzene compound, as a kind of photoswitch surfactant, under the effect of light, is controlled its surface-active variation.Its effect is mainly to provide microreactor for micella forms.Described azobenzene concentration in organic solvent can determine according to actual needs, and as preferably, described azobenzene concentration in organic solvent is 1 × 10
-6～6 × 10
-3mol/L.Add after organic solvent, for realizing the quick dissolving of azobenzene, and form constitutionally stable micellar structure, as preferably, can select ultrasonic processing 30～60min, more preferably ultrasonic processing 30min.
The concentration of described sodium aluminate aqueous solution can be adjusted according to actual needs, and as preferably, the mass percent concentration of described sodium aluminate aqueous solution is 5～10%.While adding sodium aluminate aqueous solution, add to when saturated and just muddy and finish, the amount that this muddy terminal adds when turnover changes according to solution light transmittance is terminal point determining, and dripping quantity changes according to the concentration of each configuration micellar solution.Drip sodium aluminate aqueous solution generally at room temperature.
Be added dropwise to complete after sodium aluminate aqueous solution, form for accelerating micella, and stable micellar structure, as preferably, can suitably continue sonic oscillation, the sonic oscillation time can be determined according to actual needs, be generally 30min～1h.
Passing into the time that carbon dioxide carries out ultrasonic reaction need to determine according to actual conditions, and general ultrasonic reaction 1～4 hour, gets final product to obtain required catalyst system and catalyzing-reverse micelle nano aluminium oxide catalyst system and catalyzing.This catalyst system and catalyzing can change by external conditions such as illumination the catalytic performance of system, is a kind of novel catalyst.
The present invention also provides a kind of method of utilizing above-mentioned reverse micelle nano aluminium oxide catalyst system and catalyzing synthesis modification epoxy plasticizer, comprising:
(1) in raw oil material soap stock, add acid, hierarchy of control pH value is 1～3, utilizes extractant to extract aliphatic acid wherein, removes extractant, and concentrate constant temperature in-25～15 ℃ of refrigerators is placed, and filters and obtains LCFA;
(2) LCFA step (1) being obtained is dissolved in non-proton organic solvent, under the effect of lithium aluminium hydride catalytic reduction, carries out reduction reaction, obtains corresponding long-chain fatty alcohol;
(3) long-chain fatty alcohol step (2) being obtained mixes with terephthalic acid (TPA), add the reverse micelle nano aluminium oxide catalyst system and catalyzing that utilizes said method to prepare, under ultrasound condition, 50～70 ℃ react completely, and obtain the system liquid that contains phthalic acid two long-chain fat esters;
(4) obtain adding hydrogen peroxide, formic acid to carry out epoxy reaction in system liquid to step (3), epoxy reaction completes and obtains epoxy finished fluid;
(5) in the epoxy finished fluid obtaining to step (4), pass into chlorine, UV-irradiation carries out chlorination reaction simultaneously, and the complete post processing of chlorination reaction obtains modified epoxy plasticizer.
In step (1), byproduct when grease soap stock is alkali refining animal and plant fat, can select the multiple soap stock material that contains hard soap, for example, can adopt rapeseed oil soapstock, soybean oil soap stock, peanut oil soap stock, wheat malt oil soap stock or animal oil soap stock etc.Wherein grease soap stock active ingredient fatty acid sodium salt general formula is: RCOONa.Wherein the content of hard soap is not strict with, and all can be used for raw material of the present invention and uses.As preferably, described raw oil material soap stock is soybean oil grease soap stock, and iodine number is 110～130%, is mainly the mixing-in fat acid sodium-salt of the unsaturated hydrocarbons such as 12 carbon, 14 carbon, 18 carbon, 20 carbon, wherein take linoleic fatty acids sodium salt as main.
In step (1), as preferably, described acid is the concentrated sulfuric acid, and the addition of the concentrated sulfuric acid is 16～32% of grease soap stock weight.Add after the concentrated sulfuric acid, for guaranteeing the abundant acidifying of hard soap, as preferably, can adopt and continue to stir 3～6 hours.
In step (1), described extractant can be selected the good solvent of long-chain fat solubility in acid, for example can adopt alcohols solvent, as preferably, described extractant is one or more in ethanol, methyl alcohol or normal propyl alcohol, isopropyl alcohol etc., as further preferred, described extractant is ethanol.The use amount of extractant is substantially to extract LCFA completely and to be as the criterion.
In step (1), remove after extractant, concentrate constant temperature in-25～15 ℃ of refrigerators is placed, and high-solidification point LCFA is separated out from concentrate, filters and obtains low-freezing LCFA.Constant temperature is placed and can be determined according to actual needs, is generally 10～24 hours, and as preferably, described constant temperature time of repose is 12 hours.After constant temperature has left standstill, can obtain the LCFA that freezing point is lower.
In step (2), described non-proton organic solvent can be selected ether, oxolane etc., and as preferably, described non-proton organic solvent is ether.The volume ratio of LCFA and non-proton organic solvent is generally 1:2～3.The addition of lithium aluminium hydride is 0.01～0.1% of LCFA weight, and reaction is generally carried out under room temperature or low temperature, and for example reaction temperature is generally 0～30 ℃, and the reaction time is generally 6～10 hours.
In step (3), described long-chain fatty alcohol and the mol ratio of terephthalic acid (TPA) are 2～4:1, while selecting the feeding intake of this ratio, can guarantee that terephthalic acid (TPA) reacts completely substantially, can avoid again long-chain fatty alcohol wastage of material.
In step (3), the addition of reverse micelle nano aluminium oxide catalyst system and catalyzing can be determined according to actual needs, as preferably, the addition of described reverse micelle nano aluminium oxide catalyst system and catalyzing is according to 0.01～0.1 times of calculating that wherein molal weight of Al is terephthalic acid (TPA).This step reaction time is generally 2～5 hours, can adopt the method for thin-layer chromatography to judge reaction end.
In step (4), epoxy reaction can adopt under ultrasound condition and carry out, and reaction temperature is generally 50～70 ℃, further selects to carry out 2～3 hours under 60～65 ℃ of constant temperature.Add the iodine number of the system liquid that the amount of hydrogen peroxide need to obtain according to step (3) to determine, calculate according to following formula: iodine number × 0.36 × system liquid weight/100 simultaneously.The addition of formic acid calculates according to quality × 0.12 of hydrogen peroxide.After having reacted, need to leave standstill, layering, organic layer can obtain epoxy product after washing and drying.
In step (5), chlorination reaction generally can be carried out at normal temperatures and pressures, after having reacted, utilizes nitrogen that residual chlorine air-blowing in liquid is gone out, and products obtained therefrom is our needed new plasticizer, can adopt equally thin-layer chromatography to judge reaction end.
Raw material of the present invention and reagent, all can adopt commercially available prod, also can prepare voluntarily, or adopt reaction pin material of other techniques etc.
New plasticizer of the present invention has following character:
Epoxide number is greater than 6.00%; Flash-point is greater than 200 ℃; Color is less than or equal to (Pt-Co colorimetric method) No. 50; Resistivity is greater than 2 × 10
12Ω cm; Freezing point is less than or equal to-50 ℃.With 9,12-18 (carbon) dienoic acid sodium salt raw material, for example, the structure of the modified epoxy plasticizer preparing is shown below:
Compared with prior art, new plasticizer of the present invention has the following advantages:
(1) epoxide number of the modified epoxy plasticizer that the present invention prepares is higher, have good compatibility, and in molecule, benzene ring structure is comparatively stable with PVC plastics, also contributes to the improvement with the compatibility of PVC plastics.Can substitute Plasticizer Epoxidized Soybean Oil, and performance more.
(2) flash-point of the modified epoxy plasticizer that the present invention prepares is higher, makes its animal migration less, is difficult for overflowing.
(3) color of the modified epoxy plasticizer that the present invention prepares is more shallow, can be used for plastic industry more widely.
(5) resistivity of the modified epoxy plasticizer that the present invention prepares is larger, has good anti-flammability, can be used for, in flame retardant plastics industry, can well substituting chlorinated paraffin wax plasticizer, and performance more.
(6) freezing point of the modified epoxy plasticizer that the present invention prepares is lower, has good resistance to low temperature.Can well substitute DOS, DOA plasticizer.
The specific embodiment
For further illustrating technical scheme of the present invention, be below the preferred embodiment of the present invention, it should be pointed out that the those skilled in the art for the art, the present invention can also have various modifications and variations.Under the premise without departing from the principles of the invention, any modification of doing, be equal to replacement, improvement etc., within protection scope of the present invention all should be included in.
In following embodiment, the raw oil material soap stock adopting all derives from the byproduct of Zhejiang Province Jia'aoEnvironmental Science and Technology Co., Ltd, be mainly soybean oil grease soap stock, iodine number 115%, addition is 200g, and soap stock active ingredient fatty acid sodium salt general formula is: RCOONa, and R is take 12 carbon, 14 carbon, 18 carbon, 20 carbon unsaturated alkyls as main, main component is 9,12-18 (carbon) dienoic acid sodium salt).Also can adopt as required other grease soap stocks is raw material, all can adopt method of the present invention to prepare new plasticizer, can not form limitation of the invention further.
Embodiment 1
Azobenzene is dissolved in 100ml normal heptane/n-butanol mixed solvent, and the volume ratio of mixed solvent normal heptane/n-butanol is 10:1, is configured to concentration 1 × 10
-6the solution of mol/L, afterwards sonic oscillation 30min.
Under room temperature condition, dropwise add the sodium aluminate aqueous solution that the mass percent concentration that prepared is 5% with dropper, add to and finish (about 9g) when saturated and just muddy, add and finish the rear sonic oscillation 30min that continues, form to accelerate micella, and stable micellar structure, when passing into carbon dioxide wherein afterwards, continue ultrasonic reaction 1 hour, 50 ℃ of reaction temperatures, get final product to obtain required catalyst system and catalyzing-reverse micelle nano aluminium oxide catalyst system and catalyzing.
To dripping the concentrated sulfuric acid (concentrated sulfuric acid addition be soap stock weight 16%) in raw oil material soap stock, control within the scope of the about 2-3 of pH of solution, stir after 3h, extract wherein aliphatic acid as extractant with ethanol, ethanol consumption is about 500mL, get alcohol layer and remove wherein and to put it in 15 ℃ of refrigerators constant temperature after ethanol 12 hours, filter and obtain the LCFA that required freezing point is lower.Be dissolved in (volume ratio of LCFA and ether is 1:2) in ether, under lithium aluminium hydride (weight of lithium aluminium hydride reduction be LCFA weight 0.1%) catalytic reduction effect, react, 0 ℃ of reaction temperature, in 6 hours reaction time, can obtain long-chain fatty alcohol.To adding a certain amount of self-control catalyst system and catalyzing (catalyst system and catalyzing amount according to 0.01 times of calculating that wherein the molal weight of Al is terephthalic acid (TPA)) in long-chain fatty alcohol (0.5mol) and raw material terephthalic acid (TPA) (0.25mol) (molar ratio of long-chain fatty alcohol and terephthalic acid (TPA) is 6:3), and put it in ultrasonic reactor 50 ℃ of reactions 2 hours, complete through thin-layer chromatography detection reaction.By this reaction system, under 60 ℃ of thermostatic ultrasonic conditions, add hydrogen peroxide, the 5g formic acid of 50g, and continue thermostatic ultrasonic 2 hours.Stratification, washing, obtains epoxy product after dehydration.
Under normal temperature and pressure, stir to passing into chlorine in gained epoxy finished product, and with UV-irradiation approximately 3 hours, then with nitrogen, residual chlorine air-blowing in liquid is gone out, products obtained therefrom is our needed new plasticizer, adopts equally thin-layer chromatography to judge reaction end.
Products measure result is as follows:
Epoxide number: 6.07%
Flash-point: 205 ℃
Color: No. 50 (Pt-Co colorimetric method)
Resistivity: 2.04 × 10
12Ω cm
Freezing point :-50 ℃.
Embodiment 2
Azobenzene is dissolved in 100mL normal heptane/n-butanol mixed solvent, and the mol ratio of mixed solvent normal heptane/n-butanol is 10:1, and being configured to mass percent concentration is 3 × 10
-5the solution of mol/L, afterwards sonic oscillation 30min.Under room temperature condition, dropwise add the concentration that prepared at 7% sodium aluminate aqueous solution with dropper, add to and finish (about 6g) when saturated and just muddy, add and finish the rear sonic oscillation 45min that continues, form to accelerate micella, and stable micellar structure, when passing into carbon dioxide wherein afterwards, continue ultrasonic reaction 2 hours, 55 ℃ of reaction temperatures, get final product to obtain required catalyst system and catalyzing-reverse micelle nano aluminium oxide catalyst system and catalyzing.
To dripping the concentrated sulfuric acid (concentrated sulfuric acid addition be soap stock weight 16%) in raw oil material soap stock, control within the scope of the about 1-2 of pH of solution, stir after 3h, extract wherein aliphatic acid as extractant with ethanol, ethanol consumption is about 500mL, get alcohol layer and remove wherein and to put it in 5 ℃ of refrigerators constant temperature after ethanol 12 hours, filter and obtain the LCFA that required freezing point is lower.Be dissolved in (volume ratio of LCFA and ether is 1:2) in ether, reaction (weight of lithium aluminium hydride reduction be LCFA weight 0.1%) under the effect of lithium aluminium hydride catalytic reduction, 0 ℃ of reaction temperature, in 6 hours reaction time, can obtain long-chain fatty alcohol.To adding a certain amount of self-control catalyst system and catalyzing (catalyst system and catalyzing amount according to 0.01 times of calculating that wherein the molal weight of Al is terephthalic acid (TPA)) in long-chain fatty alcohol (0.5mol) and raw material terephthalic acid (TPA) (0.25mol) (molar ratio of long-chain fatty alcohol and terephthalic acid (TPA) is 6:3), and put it in ultrasonic reactor 50 ℃ of reactions 2 hours, complete through thin-layer chromatography detection reaction.By this reaction system, under 60 ℃ of thermostatic ultrasonic conditions, add hydrogen peroxide, the 15g formic acid of 50g, and continue thermostatic ultrasonic 2 hours.Stratification, washing, obtains epoxy product after dehydration.
Under normal temperature and pressure, stir to passing into chlorine in gained epoxy finished product, and with UV-irradiation approximately 3 hours, then with nitrogen, residual chlorine air-blowing in liquid is gone out, products obtained therefrom is our needed new plasticizer, adopts equally thin-layer chromatography to judge reaction end.
Products measure result is as follows:
Epoxide number: 6.14%
Flash-point: 217 ℃
Color: No. 50 (Pt-Co colorimetric method)
Resistivity: 3.25 × 10
12Ω cm
Freezing point :-50 ℃.
Embodiment 3
Azobenzene is dissolved in 100ml normal heptane/n-butanol mixed solvent, and the mol ratio of mixed solvent normal heptane/n-butanol is 10:1, and being configured to mass percent concentration is 6 × 10
-3the solution of mol/L, afterwards sonic oscillation 30min.Under room temperature condition, dropwise add the concentration that prepared at 10% sodium aluminate aqueous solution with dropper, add to and finish (about 6g) when saturated and just muddy, add and finish the rear sonic oscillation 60min that continues, form to accelerate micella, and stable micellar structure, when passing into carbon dioxide wherein afterwards, continue ultrasonic reaction 3 hours, 60 ℃ of reaction temperatures, get final product to obtain required catalyst system and catalyzing-reverse micelle nano aluminium oxide catalyst system and catalyzing.
To dripping the concentrated sulfuric acid (concentrated sulfuric acid addition be soap stock weight 16%) in raw oil material soap stock, control within the scope of the about 2-3 of pH of solution, stir after 3h, extract wherein aliphatic acid as extractant with ethanol, ethanol consumption is about 500mL, get alcohol layer and remove wherein and after ethanol, put it in-5 ℃ of refrigerators constant temperature 12 hours, filter and obtain the LCFA that required freezing point is lower.Be dissolved in (volume ratio of LCFA and ether is 1:2) in ether, reaction (weight of lithium aluminium hydride reduction be LCFA weight 0.1%) under the effect of lithium aluminium hydride catalytic reduction, 0 ℃ of reaction temperature, in 6 hours reaction time, can obtain long-chain fatty alcohol.To adding a certain amount of self-control catalyst system and catalyzing (catalyst system and catalyzing amount according to 0.01 times of calculating that wherein the molal weight of Al is terephthalic acid (TPA)) in long-chain fatty alcohol (0.5mol) and raw material terephthalic acid (TPA) (0.25mol) (molar ratio of long-chain fatty alcohol and terephthalic acid (TPA) is 6:3), and put it in ultrasonic reactor 50 ℃ of reactions 2 hours, complete through thin-layer chromatography detection reaction.By this reaction system, under 60 ℃ of thermostatic ultrasonic conditions, add hydrogen peroxide, the 15g formic acid of 50g, and continue thermostatic ultrasonic 2 hours.Stratification, washing, obtains epoxy product after dehydration.
Under normal temperature and pressure, stir to passing into chlorine in gained epoxy finished product, and with UV-irradiation approximately 3 hours, then with nitrogen, residual chlorine air-blowing in liquid is gone out, products obtained therefrom is our needed new plasticizer, adopts equally thin-layer chromatography to judge reaction end.
Products measure result is as follows:
Epoxide number: 6.32%
Flash-point: 230 ℃
Color: No. 50 (Pt-Co colorimetric method)
Resistivity: 5.23 × 10
12Ω cm
Freezing point :-63 ℃.
Embodiment 4
Azobenzene is dissolved in 100ml normal heptane/n-butanol mixed solvent, and the mol ratio of mixed solvent normal heptane/n-butanol is 10:1, and being configured to mass percent concentration is 6 × 10
-3the solution of mol/L, afterwards sonic oscillation 30min.Under room temperature condition, dropwise add the concentration that prepared at 10% sodium aluminate aqueous solution with dropper, add to and finish (about 8g) when saturated and just muddy, add and finish the rear sonic oscillation 60min that continues, form to accelerate micella, and stable micellar structure, when passing into carbon dioxide wherein afterwards, continue ultrasonic reaction 3 hours, 60 ℃ of reaction temperatures, get final product to obtain required catalyst system and catalyzing-reverse micelle nano aluminium oxide catalyst system and catalyzing.
To dripping the concentrated sulfuric acid (concentrated sulfuric acid addition be soap stock weight 20%) in raw oil material soap stock, control within the scope of the about 2-3 of pH of solution, stir after 4h, extract wherein aliphatic acid as extractant with ethanol, ethanol consumption is about 500mL, get alcohol layer and remove wherein and after ethanol, put it in-15 ℃ of refrigerators constant temperature 12 hours, filter and obtain the LCFA that required freezing point is lower.Be dissolved in (volume ratio of LCFA and ether is 1:2) in ether, reaction (weight of lithium aluminium hydride reduction be LCFA weight 0.05%) under the effect of lithium aluminium hydride catalytic reduction, 10 ℃ of reaction temperatures, in 7 hours reaction time, can obtain long-chain fatty alcohol.To adding a certain amount of self-control catalyst system and catalyzing (catalyst system and catalyzing amount according to 0.05 times of calculating that wherein the molal weight of Al is terephthalic acid (TPA)) in long-chain fatty alcohol (0.32mol) and raw material terephthalic acid (TPA) (0.12mol) (molar ratio of long-chain fatty alcohol and terephthalic acid (TPA) is 8:3), and put it in ultrasonic reactor 60 ℃ of reactions 3 hours, complete through thin-layer chromatography detection reaction.By this reaction system, under 60 ℃ of thermostatic ultrasonic conditions, add hydrogen peroxide, the 15g formic acid of 50g, and continue thermostatic ultrasonic 2 hours.Stratification, washing, obtains epoxy product after dehydration.
Under normal temperature and pressure, stir to passing into chlorine in gained epoxy finished product, and with UV-irradiation approximately 3 hours, then with nitrogen, residual chlorine air-blowing in liquid is gone out, products obtained therefrom is our needed new plasticizer, adopts equally thin-layer chromatography to judge reaction end.
Products measure result is as follows:
Epoxide number: 6.55%
Flash-point: 243 ℃
Color: No. 50 (Pt-Co colorimetric method)
Resistivity: 7.06 × 10
12Ω cm
Freezing point :-75 ℃
Embodiment 5
Azobenzene is dissolved in 150ml normal heptane/n-butanol mixed solvent, and the mol ratio of mixed solvent normal heptane/n-butanol is 10:1, and being configured to mass percent concentration is 6 × 10
-3the solution of mol/L, afterwards sonic oscillation 30min.Under room temperature condition, dropwise add the concentration that prepared at 10% sodium aluminate aqueous solution with dropper, add to and finish (about 10g) when saturated and just muddy, add and finish the rear sonic oscillation 60min that continues, form to accelerate micella, and stable micellar structure, when passing into carbon dioxide wherein afterwards, continue ultrasonic reaction 3 hours, 60 ℃ of reaction temperatures, get final product to obtain required catalyst system and catalyzing-reverse micelle nano aluminium oxide catalyst system and catalyzing.
To dripping the concentrated sulfuric acid (concentrated sulfuric acid addition be soap stock weight 32%) in raw oil material soap stock, control within the scope of the about 1-2 of pH of solution, stir after 6h, extract wherein aliphatic acid as extractant with ethanol, ethanol consumption is about 600mL, get alcohol layer and remove wherein and after ethanol, put it in-25 ℃ of refrigerators constant temperature 12 hours, filter and obtain the LCFA that required freezing point is lower.Be dissolved in (volume ratio of LCFA and ether is 1:2) in ether, reaction (weight of lithium aluminium hydride reduction be LCFA weight 0.1%) under the effect of lithium aluminium hydride catalytic reduction, 20 ℃ of reaction temperatures, in 10 hours reaction time, can obtain long-chain fatty alcohol.To adding a certain amount of self-control catalyst system and catalyzing (catalyst system and catalyzing amount according to 0.10 times of calculating that wherein the molal weight of Al is terephthalic acid (TPA)) in long-chain fatty alcohol (0.60mol) and raw material terephthalic acid (TPA) (0.15mol) (molar ratio of long-chain fatty alcohol and terephthalic acid (TPA) is 12:3), and put it in ultrasonic reactor 70 ℃ of reactions 5 hours, complete through thin-layer chromatography detection reaction.By this reaction system, under 60 ℃ of thermostatic ultrasonic conditions, add hydrogen peroxide, the 15g formic acid of 50g, and continue thermostatic ultrasonic 2 hours.Stratification, washing, obtains epoxy product after dehydration.
Under normal temperature and pressure, stir to passing into chlorine in gained epoxy finished product, and with UV-irradiation approximately 3 hours, then with nitrogen, residual chlorine air-blowing in liquid is gone out, products obtained therefrom is our needed new plasticizer, adopts equally thin-layer chromatography to judge reaction end.
Products measure result is as follows:
Epoxide number: 6.75%
Flash-point: 258 ℃
Color: No. 50 (Pt-Co colorimetric method)
Resistivity: 6.45 × 10
12Ω cm
Freezing point :-75 ℃.
From above-described embodiment, utilize the epoxide number of the modified epoxy plasticizer that the inventive method prepares higher, all, more than 6%, there is good compatibility with PVC plastics, and benzene ring structure is comparatively stable in molecule, also contribute to the improvement with the compatibility of PVC plastics.Can substitute Plasticizer Epoxidized Soybean Oil, and performance more.Utilize the flash-point of the modified epoxy plasticizer that the inventive method prepares higher, all, more than 200 ℃, make its animal migration less, be difficult for overflowing.The color of the modified epoxy plasticizer being prepared by the inventive method is more shallow, can be used for plastic industry more widely.The resistivity of the modified epoxy plasticizer being prepared by the inventive method is larger, all 2 × 10
12more than Ω cm, there is good anti-flammability, can be used for, in flame retardant plastics industry, can well substituting chlorinated paraffin wax plasticizer, and performance more.The freezing point of the modified epoxy plasticizer that the present invention prepares is lower, all, below-50 ℃, has good resistance to low temperature.Can well substitute DOS, DOA plasticizer.
Claims (10)
1. a reverse micelle nano aluminium oxide catalyst system and catalyzing, it is characterized in that, utilize following method to prepare: azobenzene is dissolved in organic solvent, add sodium aluminate aqueous solution to saturated, pass into carbon dioxide, be that under 50～60 ℃ of conditions, ultrasonic reaction is complete in temperature, prepare reverse micelle nano aluminium oxide catalyst system and catalyzing.
2. reverse micelle nano aluminium oxide catalyst system and catalyzing according to claim 1, is characterized in that, described organic solvent is the mixed solvent of normal heptane and n-butanol, and wherein the volume ratio of normal heptane and n-butanol is 5～30:1.
3. reverse micelle nano aluminium oxide catalyst system and catalyzing according to claim 1, is characterized in that, described azobenzene concentration in organic solvent is 1 × 10
-6～6 × 10
-3mol/L.
4. reverse micelle nano aluminium oxide catalyst system and catalyzing according to claim 1, is characterized in that, the mass percent concentration of described sodium aluminate aqueous solution is 5～10%.
5. a method for synthesis modification epoxy plasticizer, comprising:
(1) in raw oil material soap stock, add acid, hierarchy of control pH value is 1～3, utilizes extractant to extract aliphatic acid wherein, removes extractant, and concentrate constant temperature in-25～15 ℃ of refrigerators is placed, and filters and obtains LCFA;
(2) LCFA step (1) being obtained is dissolved in non-proton organic solvent, under the effect of lithium aluminium hydride catalytic reduction, carries out reduction reaction, obtains corresponding long-chain fatty alcohol;
(3) long-chain fatty alcohol step (2) being obtained mixes with terephthalic acid (TPA), add the reverse micelle nano aluminium oxide catalyst system and catalyzing described in the arbitrary claim of claim 1-4, under ultrasound condition, 50～70 ℃ react completely, and obtain the system liquid that contains phthalic acid two long-chain fat esters;
(4) in the system liquid obtaining to step (3), add hydrogen peroxide, formic acid to carry out epoxy reaction, epoxy reaction completes and obtains epoxy finished fluid;
(5) in the epoxy finished fluid obtaining to step (4), pass into chlorine, UV-irradiation carries out chlorination reaction simultaneously, and the complete post processing of chlorination reaction obtains modified epoxy plasticizer.
6. the method for synthesis modification epoxy plasticizer according to claim 5, is characterized in that, in step (1), described acid is the concentrated sulfuric acid, and the addition of the concentrated sulfuric acid is 16～32% of grease soap stock weight; Described extractant is ethanol.
7. the method for synthesis modification epoxy plasticizer according to claim 5, is characterized in that, in step (2), described non-proton organic solvent is ether; The addition of described lithium aluminium hydride is 0.01～0.1% of LCFA weight.
8. the method for synthesis modification epoxy plasticizer according to claim 5, is characterized in that, in step (3), described long-chain fatty alcohol and the mol ratio of terephthalic acid (TPA) are 2～4:1.
9. the method for synthesis modification epoxy plasticizer according to claim 5, is characterized in that, in step (3), the addition of described reverse micelle nano aluminium oxide catalyst system and catalyzing is according to 0.01～0.1 times of calculating that wherein molal weight of Al is terephthalic acid (TPA).
10. the method for synthesis modification epoxy plasticizer according to claim 5, it is characterized in that, in step (4), the iodine number of the system liquid that the addition of hydrogen peroxide need to obtain according to step (3) is determined, calculates: iodine number × 0.36 × system liquid weight/100 according to following formula simultaneously; The addition of formic acid calculates according to quality × 0.12 of hydrogen peroxide.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105837631A (en) * | 2016-04-01 | 2016-08-10 | 浙江嘉澳环保科技股份有限公司 | Phosphorus-containing modified epoxy plasticizer preparation method and plasticizer prepared through method |
| CN111217769A (en) * | 2020-02-29 | 2020-06-02 | 华南理工大学 | Method for synthesizing epoxy compound by catalyzing olefin epoxidation through nano aluminum oxide |
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| CN101372539B (en) * | 2008-07-31 | 2011-07-06 | 浙江嘉澳环保科技股份有限公司 | Method for producing environment-friendly type plasticiser using waste oil and oil foot |
| CN102936074A (en) * | 2012-12-03 | 2013-02-20 | 浙江嘉澳环保科技股份有限公司 | Pretreatment method of epoxy type plasticizer production wastewater |
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| US2771472A (en) * | 1956-11-20 | Epoxyoctadecyl adipates | ||
| CN101372539B (en) * | 2008-07-31 | 2011-07-06 | 浙江嘉澳环保科技股份有限公司 | Method for producing environment-friendly type plasticiser using waste oil and oil foot |
| CN101993783A (en) * | 2010-09-30 | 2011-03-30 | 浙江嘉澳环保科技股份有限公司 | Method for preparing modified aliphatic ester plasticizer |
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| CN105837631A (en) * | 2016-04-01 | 2016-08-10 | 浙江嘉澳环保科技股份有限公司 | Phosphorus-containing modified epoxy plasticizer preparation method and plasticizer prepared through method |
| CN111217769A (en) * | 2020-02-29 | 2020-06-02 | 华南理工大学 | Method for synthesizing epoxy compound by catalyzing olefin epoxidation through nano aluminum oxide |
| CN111217769B (en) * | 2020-02-29 | 2023-04-21 | 华南理工大学 | A kind of method utilizing nano-alumina to catalyze olefin epoxidation to synthesize epoxy compound |
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