CN102070778B - Method for preparing high-concentration polyoxy alkyl allyl ether sulfonate - Google Patents
Method for preparing high-concentration polyoxy alkyl allyl ether sulfonate Download PDFInfo
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- CN102070778B CN102070778B CN2010105983542A CN201010598354A CN102070778B CN 102070778 B CN102070778 B CN 102070778B CN 2010105983542 A CN2010105983542 A CN 2010105983542A CN 201010598354 A CN201010598354 A CN 201010598354A CN 102070778 B CN102070778 B CN 102070778B
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- ether sulfonate
- alkene ether
- polyoxy
- alkane alkene
- carbonatoms
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- -1 polyoxy Polymers 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title abstract description 16
- 239000000047 product Substances 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims abstract description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 71
- 239000011734 sodium Substances 0.000 claims description 37
- 150000001336 alkenes Chemical class 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 30
- 229910052708 sodium Inorganic materials 0.000 claims description 27
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 26
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 11
- 239000004064 cosurfactant Substances 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000011591 potassium Chemical group 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 150000001924 cycloalkanes Chemical class 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000012661 block copolymerization Methods 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims 1
- 229920001519 homopolymer Polymers 0.000 claims 1
- 229920005604 random copolymer Polymers 0.000 claims 1
- 239000013543 active substance Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 239000004094 surface-active agent Substances 0.000 abstract description 6
- 150000002191 fatty alcohols Chemical class 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 19
- 230000007062 hydrolysis Effects 0.000 description 18
- 238000006460 hydrolysis reaction Methods 0.000 description 18
- 230000035484 reaction time Effects 0.000 description 18
- 229910052938 sodium sulfate Inorganic materials 0.000 description 15
- 235000011152 sodium sulphate Nutrition 0.000 description 15
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 13
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 12
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 7
- 229920001451 polypropylene glycol Polymers 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 6
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 6
- TYWMIZZBOVGFOV-UHFFFAOYSA-N tetracosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCO TYWMIZZBOVGFOV-UHFFFAOYSA-N 0.000 description 6
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000006277 sulfonation reaction Methods 0.000 description 4
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 3
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 3
- KJWMCPYEODZESQ-UHFFFAOYSA-N 4-Dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=C(O)C=C1 KJWMCPYEODZESQ-UHFFFAOYSA-N 0.000 description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical class CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical class CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical class CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 150000000211 1-dodecanols Chemical class 0.000 description 1
- 208000006558 Dental Calculus Diseases 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- PCAXGMRPPOMODZ-UHFFFAOYSA-N disulfurous acid, diammonium salt Chemical class [NH4+].[NH4+].[O-]S(=O)S([O-])(=O)=O PCAXGMRPPOMODZ-UHFFFAOYSA-N 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical class CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- LIXVMPBOGDCSRM-UHFFFAOYSA-N nonylbenzene Chemical class CCCCCCCCCC1=CC=CC=C1 LIXVMPBOGDCSRM-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical class CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical class [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical class CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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Abstract
The invention relates to a method for preparing high-concentration polyoxy alkyl allyl ether sulfonate, which belongs to the technical field of organic compound synthesis. In the method provided by the invention, the polyoxy alkyl allyl ether sulfonate of fatty alcohol or alkylphenol is used as raw materials to be directly sulfonated in a microemulsion system through sulphite for obtaining the polyoxy alkyl allyl ether sulfonate. Compared with the traditional water-phase system, the method provided by the invention has the advantages that through building a reaction system into microemulsion, the material concentration in the reaction system and the yield of polyoxy alkyl allyl ether sulfonate surface active agents are greatly improved, the generation of hydrolysates of polyoxy alkyl allyl ether is reduced, the product yield of the preparation method is high, byproducts are few, the cost is low, the process is simple, and the polyoxy alkyl allyl ether sulfonate products with high active substance contents can be obtained.
Description
Technical field
The present invention relates to a kind of preparation method of high density polyoxy alkane alkene ether sulfonate, belong to the organic cpds synthesis technical field.
Background technology
Polyoxy alkane alkene ether sulfonate tensio-active agent belongs to anion-nonionic type tensio-active agent, has good salt tolerance, dispersing property and compatibility; This kind of what is more important tensio-active agent still has fabulous stability under the extreme environment of strong acid and strong base, HTHP, can be widely used in the application scenario that oil, papermaking, weaving, industry and extraordinary cleaning etc. have special requirement.
The preparation method of polyoxy alkane alkene ether sulfonate tensio-active agent is a lot; Be broadly divided into the third sultone method, sulfoalkyl method, alkene additive process and sulphite sulfonation method etc.; But these preparing methods exist like problems such as raw materials cost are high, productive rate is low, seriously polluted mostly, are restricting suitability for industrialized production.Though and have problems such as raw material facile hydrolysis, sulphonation rate be low by the technology that the alcohol ether sulfuric acid directly transforms the synthol ether sulfonate through the sulphite sulfonation; Low in raw material cost is easy to get, flow process short, pollute advantages such as little, simple to operate but have, and has still caused research interest.(Speciality Petrochemicals such as Zhao Fulin; 1996 (5): under 196 ℃, be solvent 22 ~ 24) with water; Transformed through sulphite by fatty alcohol polyoxyethylene ether sulfate and to have synthesized aliphatic alcohol polyoxyethylene sulfonate, productive rate is merely 62%, and fatty alcohol polyoxyethylene ether sulfate concentration is the highest in the reactant can only be 14.0%; Otherwise material viscous can't solve chemical industry problems such as mass-and heat-transfer difficulty.CN 101255127A discloses a kind of method of utilizing fatty alcohol polyoxyethylene ether sulfate synthetic fatty alcohol polyethenoxy ether sulphonate title product at aqueous phase; Though declare to obtain than higher productive rates of above-mentioned bibliographical information such as Zhao Fulin; But can not solve material viscous under the high density equally; Chemical industry problems such as mass-and heat-transfer difficulty so can only react being lower than under 26% the lower concentration state, can't obtain high reactivity produce article.Therefore; Caused research interest though directly transform the sulphite sulfonation method technology of synthol ether sulfonate by the alcohol ether sulfuric acid; But fail to solve material viscous under the high density at present, chemical industry problems such as mass-and heat-transfer difficulty make that the industrial applications unclear prospect of this operational path is bright.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of high density polyoxy alkane alkene ether sulfonate.The core of new preparation process is to make and is reflected at micro emulsion and carries out in mutually; Improve in the reaction system material concentration greatly and therefore improved title product polyoxy alkane alkene ether sulfonate surfactant concentrations and productive rate, reduced the generation of hydrolysising by-product polyoxy alkane alkene ether.Use the polyoxy alkane alkene ether sulfonate surfactant product that this method can obtain high reactivity thing content easily.
In addition, the present invention utilizes reaction raw materials and reaction product to be characteristics of surfactant, and need not to add tensio-active agent can form microemulsion system through adding oil, water and cosurfactant, realizes the micro emulsion phase reaction.
Technical scheme of the present invention: a kind of preparation method of high density polyoxy alkane alkene ether sulfonate is characterized in that: form microemulsion with polyoxy alkane alkene ether sulphate raw material and a certain proportion of cosurfactant, organic solvent and water, with mol ratio
n(polyoxy alkane alkene ether sulphate):
nThe sulphonating agent of (sulphonating agent)=1:1 ~ 8 is being pressed reaction 2 ~ 10 h under the heat condition, and take out the cooling back, the inorganic salt that filtering precipitate is come out, and promptly obtaining active matter content can be up to 60% high density polyoxy alkane alkene ether sulfonate product.
Described polyoxy alkane alkene ether sulphate raw material has following general structure:
R in the formula
1Be carbonatoms C
8~ C
24Straight chain, side chain or cyclic alkane base, or carbonatoms is C
14~ C
24Alkyl phenyl; In the formula-(OR
2)-unit does
,
,
,
,
,
Or
Group, n=0 ~ 50 ,-(OR
2)
n-be above-mentioned-(OR
2)-unitary homopolymerization, block copolymerization or random copolymerization structure; M is sodium, potassium or NH
4 +
Described sulphonating agent is sodium, potassium or NH
4 +Sulphite, hydrosulphite or pyrosulfite in one or more mixtures.
Said cosurfactant is carbonatoms C
3~ C
12Straight chain, side chain or cycloalkyl alcohol, or carbonatoms is C
3~ C
6Polyvalent alcohol; Said organic solvent is carbonatoms C
6~ C
24Straight chain, side chain or cyclic alkane, or carbonatoms is C
6~ C
24Aromatic hydrocarbon.
Said a certain proportion of cosurfactant, organic solvent and water, its certain proportion are meant that mass ratio does
m(raw material):
m(cosurfactant):
m(organic solvent):
m(water)=1:0.05 ~ 0.2:0.2 ~ 1.3:0.3 ~ 1.3.
Said pressure heat condition is 150 ~ 220 ℃.
Said microemulsion is meant that the water dilution with arbitrary proportion can both obtain isotropy, thermodynamically stable clear solution.
Described polyoxy alkane alkene ether sulfonate product has following general structure:
R in the formula
1Be carbonatoms C
8~ C
24Straight chain, side chain or cyclic alkane base, or carbonatoms is C
14~ C
24Alkyl phenyl; In the formula-(OR
2)-unit does
,
,
,
,
,
Or
Group, n=0 ~ 50 ,-(OR
2)
n-be above-mentioned-(OR
2)-unitary homopolymerization, block copolymerization or random copolymerization; M is sodium, potassium or NH
4 +
The sulphite sulfonation method technology that directly transforms the synthol ether sulfonate with existing alcohol ether sulfuric acid is compared, and the present invention has following beneficial effect:
1, the present invention utilizes reaction raw materials polyoxy alkane alkene ether sulphate and reaction product polyoxy alkane alkene ether sulfonate to be characteristics of surfactant; Need not to add tensio-active agent and promptly can make the composition microemulsion system through in reaction system, adding oil, water and cosurfactant; Realize the micro emulsion phase reaction, with low cost.
2, utilize microemulsion system high density, low viscous characteristic, solved the chemical industry problems such as mass-and heat-transfer in the high density reaction, have practicality.
3, in microemulsion system, react, and at aqueous phase reacting phase ratio, can obtain high density polyoxy alkane alkene ether sulfonate product.
4, the ordered arrangement of tensio-active agent in micro emulsion helps suppressing hydrolytic side reactions, thereby improves reaction yield.
5, after reaction completion and the cooling, excess inorganic salts can precipitate from microemulsion system automatically, is easy to separate, and subsequent disposal is simple, and technical process is short.
Description of drawings
Fig. 1 is the infared spectrum of reactor product among the embodiment 1.
Fig. 2 is the infared spectrum of reactor product in the Comparative Examples 1.
Embodiment
Embodiment 1: in 1 L potheater, add 210 g lauryl alcohol T 46155 (3) sodium sulfate, 252 g Na
2SO
3, 60 g dodecyls, 60 g water; 15 g amylalcohols, temperature of reaction are 190-195 ℃, and the reaction times is 6 h; Take out the cooling back, and the inorganic salt that filtering precipitate is come out obtain lauryl alcohol T 46155 (3) sodium sulfonate product; Recording percent hydrolysis is 12%, sulphonation rate 87%, and lauryl alcohol T 46155 (3) ether sulfonic acid na concn is 53% in the gained reactor product.Its infared spectrum shows that middle mutually raw material lauryl alcohol T 46155 (3) sodium sulfate of micro emulsion all transforms shown in accompanying drawing 1.
Comparative Examples 1 (water react): in 1 L potheater, add 210 g lauryl alcohol T 46155 (3) sodium sulfate, 252 g Na
2SO
3, 135 g water, temperature of reaction is 190-195 ℃, and the reaction times is 6 h, and at this moment, because the material viscosity problem, material is burned by high temperature, can't obtain title product.Therefore, experiment can only be carried out in the dilute solution system: in 1 L potheater, add 105 g lauryl alcohol T 46155 (3) ether sodium sulfates, 126 g Na
2SO
3, 500 g water, temperature of reaction is 190-195 ℃; Reaction times is 6 h, and the inorganic salt that filtering precipitate is come out are taken out in the cooling back; Obtain lauryl alcohol T 46155 (3) sodium sulfonate product; Recording the raw material percent hydrolysis is 9%, and sulphonation rate is 62%, and lauryl alcohol T 46155 (3) ether sulfonic acid na concn is merely 8% in the gained reactor product.Its infared spectrum shows behind the water react and still contains unconverted lauryl alcohol T 46155 (3) ether sodium sulfate raw material in the product shown in accompanying drawing 2.
Embodiment 2: in 1 L potheater, add 210 g n-Octanol Soxylat A 25-7 (50) sodium sulfate, 86 g Na
2SO
3, 46 g hexanaphthenes, 160 g water; 11 g propyl alcohol, temperature of reaction are 160-165 ℃, and the reaction times is 3 h; Take out the cooling back, and the inorganic salt that filtering precipitate is come out obtain n-Octanol Soxylat A 25-7 (50) sodium sulfonate product; Recording sulphonation rate is 85%, and percent hydrolysis is 9%, and the concentration of n-Octanol Soxylat A 25-7 (50) sodium sulfonate is 41% in the gained reactor product.
Embodiment 3: in 1 L potheater, add 210 g isooctyl alcohol Soxylat A 25-7 (5) ammonium sulfate, 160 g (NH
4)
2SO
3, the 100 g tetradecanes, 22 g water; 30 g hexanols, temperature of reaction are 170-175 ℃, and the reaction times is 6 h; Take out the cooling back, and the inorganic salt that filtering precipitate is come out obtain isooctyl alcohol Soxylat A 25-7 (5) ammonium sulphonate product; Recording sulphonation rate is 86%, and percent hydrolysis is 11%, and the concentration of isooctyl alcohol Soxylat A 25-7 (5) ammonium sulphonate is 50% in the gained reactor product.
Embodiment 4: in the 1L potheater, add 210g lauryl alcohol T 46155 (6) sodium sulfate, 200 g Na
2SO
3, 120 g heptane, 60 g water, 15 g amylalcohols; Temperature of reaction is 160-165 ℃, and the reaction times is 6 h, after the reaction cooled, crosses the elimination deposition; Most of solvent is removed in underpressure distillation, adds 1000 in the mixture g Virahol is static to spend the night, and removes the inorganic salt that are precipitated out, solvent evaporated; Obtain the solid sulfoacid product salt, and measure the total content of Anionic Active in the solid with acidic mixed indicator two-phase titration (GB/T20199-2006), the percent hydrolysis that calculates raw material is 5%; The gained solid is dissolved in the acidic aqueous solution, heats this solution to 4 h that seethe with excitement, measure the content of sulfosalt surfactant again with acidic mixed indicator two-phase titration, the gained sulphonation rate is 85%; The concentration of lauryl alcohol T 46155 (6) sodium sulfonate is 44% in the gained reactor product.
Embodiment 5: in 1 L potheater, add 210 g lauryl alcohol polyoxypropylene (3) ether sodium sulfates, 63 g Na
2SO
3, 90 g hexanes, 90 g water; 20 g butanols, temperature of reaction are 150-155 ℃, and the reaction times is 4 h; Take out the cooling back, and the inorganic salt that filtering precipitate is come out obtain lauryl alcohol polyoxypropylene (3) ether sulfonic acid sodium product; Recording sulphonation rate is 78%, and percent hydrolysis is 8%, and the concentration of lauryl alcohol polyoxypropylene (3) ether sulfonic acid sodium is 40% in the gained reactor product.
Embodiment 6: in 1 L potheater, add 210 g sodium lauryl sulphate, 180 g Na
2SO
3, 80 g toluene, 65g water, 25 g glycerine reaction temperature are 190-195 ℃, and the reaction times is 5 h, obtains the sodium laurylsulfonate product, and recording sulphonation rate is 81%, and percent hydrolysis is 10%, the concentration of sodium laurylsulfonate is 45% in the gained reactor product.
Embodiment 7: in 1 L potheater, add 210 g iso-octyl cyclohexyl alcohol polyoxy butylene ether (2) sodium sulfate, 210 g Na
2SO
3, 42 g octyl group benzene, 180 g water; 15 g Ucar 35, temperature of reaction are 200-205 ℃, and the reaction times is 6 h; Obtain iso-octyl cyclohexyl alcohol polyoxy butylene ether (2) sodium sulfonate product; Recording sulphonation rate is 85%, and percent hydrolysis is 12%, and the concentration of iso-octyl cyclohexyl alcohol polyoxy butylene ether (2) sodium sulfonate is 40% in the gained reactor product.
Embodiment 8: in 1 L potheater, add 210 g isomerous tridecanol polyoxy butylene ether (2) Soxylat A 25-7 (6) polyoxypropylene (6) sodium sulfate, wherein polyoxy butylene-T 46155-polyoxypropylene is the random copolymerization structure, 120 g Na
2SO
3, 60 g NaHSO
3, 180 g mixing n-Hexadecanes, 42 g water; 12 g sorbyl alcohols, temperature of reaction are 205-210 ℃, and the reaction times is 9 h; Take out the cooling back, and the inorganic salt that filtering precipitate is come out obtain isomerous tridecanol polyoxy butylene ether (2) T 46155 (6) polyoxypropylene (6) sodium sulfonate product; Recording sulphonation rate is 87%, and percent hydrolysis is 13%, and the concentration of isomerous tridecanol polyoxy butylene ether (2) T 46155 (6) polyoxypropylene (6) sodium sulfonate is 41% in the gained reactor product.
Embodiment 9: at 1 M
3Add 290 kg tetradecyl alcohol T 46155 (6) sodium sulfate, 84 kg NaHSO in the potheater
3, 60 kg side chain eicosanes, 60 kg water; 15 kg hexanols, temperature of reaction are 205-210 ℃, and the reaction times is 6 h; Obtain tetradecyl alcohol T 46155 (6) sodium sulfonate product; Recording sulphonation rate is 85%, and percent hydrolysis is 10%, and the concentration of tetradecyl alcohol T 46155 (6) sodium sulfonate is 58% in the gained reactor product.
Embodiment 10: in 1 L potheater, add 210 g octyl phenol polyethenoxy ether (15) vitriolate of tartar, 200 g KHSO
3, 50 g tetracosanes, 60 g water; 42 g octanols, temperature of reaction are 170-175 ℃, and the reaction times is 8 h; Take out the cooling back, and the inorganic salt that filtering precipitate is come out obtain octyl phenol polyethenoxy ether (15) potassium sulfonate product; Recording sulphonation rate is 80%, and percent hydrolysis is 13%, and octyl phenol polyethenoxy ether (15) potassium sulfonate concentration is 46% in the gained reactor product.
Embodiment 11: in 1 L potheater, add 210 g stearyl alcohol polyethenoxy ether (48) ammonium sulfate, 120 g ammonium pyrosulfites, 90 g side chain n-Hexadecanes, 60 g water; 12 g nonyl alcohols, temperature of reaction are 150-155 ℃, and the reaction times is 6 h; Take out the cooling back, and the inorganic salt that filtering precipitate is come out obtain stearyl alcohol polyethenoxy ether (48) ammonium sulphonate product; Recording sulphonation rate is 75%, and percent hydrolysis is 8%, and the concentration of stearyl alcohol polyethenoxy ether (48) ammonium sulphonate is 42% in the gained reactor product.
Embodiment 12: in 1 L potheater, add 210 g isomery stearyl alcohol polyethenoxy ether (6) Soxylat A 25-7 (25) sodium sulfate, wherein, polyoxypropylene-T 46155 is the block copolymerization structure, 100 g Na
2SO
3, 42 g octyl group benzene, 63 g water; 25 g pentanediols, temperature of reaction are 180-185 ℃, and the reaction times is 3 h; Take out the cooling back, and the inorganic salt that filtering precipitate is come out obtain isomery stearyl alcohol polyethenoxy ether (6) Soxylat A 25-7 (25) sodium sulfonate product; Recording sulphonation rate is 79%, and percent hydrolysis is 9%, and the concentration of isomery stearyl alcohol polyethenoxy ether (6) Soxylat A 25-7 (25) sodium sulfonate is 48% in the gained reactor product.
Embodiment 13: at 1 M
3Add 210 kg 4-dodecylphenol polyethenoxy ether (8) polyoxy butylene ether (8) Soxylat A 25-7 (12) sodium sulfate in the potheater, wherein polyoxypropylene-polyoxy butylene-T 46155 is the block copolymerization structure, 140 kg Sodium Pyrosulfites; 60 kg 200# solvent oils, 80 kg water, 15 kg isooctyl alcohol; Temperature of reaction is 180-185 ℃; Reaction times is 4 h, and the inorganic salt that filtering precipitate is come out are taken out in the cooling back; Obtain 4-dodecylphenol polyethenoxy ether (8) polyoxy butylene ether (8) Soxylat A 25-7 (12) sodium sulfonate product; Recording sulphonation rate is 78%, and percent hydrolysis is 9%, and the concentration of 4-dodecylphenol polyethenoxy ether (8) polyoxy butylene ether (8) Soxylat A 25-7 (12) sodium sulfonate is 47% in the gained reactor product.
Embodiment 14: in 1 L potheater, add two polyoxyethylene octylphenol ether (15) sodium sulfate of 210 g, 150 g NaHSO
3, 65 g dodecylbenzenes, 85 g water; 20 g enanthol, temperature of reaction are 215-220 ℃, and the reaction times is 10 h; Take out the cooling back, and the inorganic salt that filtering precipitate is come out obtain polyoxyethylene octylphenol ether (15) sulfonic acid acid sodium product; Recording sulphonation rate is 87%, and percent hydrolysis is 13%, and the concentration of polyoxyethylene octylphenol ether in the gained reactor product (15) sulfonic acid acid sodium is 48%.
Embodiment 15: in 1 L potheater, add 210 g tetracosanol polyoxy butylene ether (10) ammonium sulfate, 135 g NH
4HSO
3, 90 g dodecyls, 80 g water; 18 g hexalin, temperature of reaction are 190-195 ℃, and the reaction times is 4 h; Take out the cooling back, and the inorganic salt that filtering precipitate is come out obtain tetracosanol polyoxy butylene ether (10) ammonium sulphonate product; Recording sulphonation rate is 85%, and percent hydrolysis is 10%, and the concentration of tetracosanol polyoxy butylene ether (10) ammonium sulphonate is 45% in the gained reactor product.
Embodiment 16: in 1 L potheater, add two nonyl phenol poly-oxypropylene ether (8) sodium sulfate of 210 g, 120 g NaHSO
3, the two nonyl benzenes of 46 g, 65 g water; 14 g lauryl alcohols, temperature of reaction are 165-170 ℃, and the reaction times is 7 h; Take out the cooling back, and the inorganic salt that filtering precipitate is come out obtain two nonyl phenol poly-oxypropylene ether (8) sodium sulfonate products; Recording sulphonation rate is 85%, and percent hydrolysis is 11%, and the concentration of two nonyl phenol poly-oxypropylene ether (8) sodium sulfonates is 54% in the gained reactor product.
Claims (7)
1. the preparation method of a high density polyoxy alkane alkene ether sulfonate is characterized in that: form microemulsion with polyoxy alkane alkene ether sulphate raw material and a certain proportion of cosurfactant, organic solvent and water, with mol ratio
n(polyoxy alkane alkene ether sulphate):
nThe sulphonating agent of (sulphonating agent)=1:1 ~ 8 is being pressed heat condition reaction 2 ~ 10 h down, the taking-up of cooling back, and the inorganic salt that filtering precipitate is come out promptly obtain active matter content up to 60% polyoxy alkane alkene ether sulfonate product; Said a certain proportion of cosurfactant, organic solvent and water, its certain proportion are meant that mass ratio does
m(polyoxy alkane alkene ether sulphate raw material):
m(cosurfactant):
m(organic solvent):
m(water)=1:0.05 ~ 0.2:0.2 ~ 1.3:0.3 ~ 1.3.
2. the preparation method of high density polyoxy alkane alkene ether sulfonate according to claim 1 is characterized in that described polyoxy alkane alkene ether sulphate raw material has following general structure:
R in the formula
1Be carbonatoms C
8~ C
24Straight chain, side chain or cyclic alkane base, or carbonatoms is C
14~ C
24Alkyl phenyl; In the formula-(OR
2)-unit does
,
,
,
,
,
Or
Group, n=0 ~ 50 ,-(OR
2)
n-be above-mentioned-(OR
2)-unitary homopolymerization, block copolymerization or random copolymerization structure; M is sodium, potassium or NH
4 +
3. the preparation method of high density polyoxy alkane alkene ether sulfonate according to claim 1 is characterized in that described sulphonating agent is sodium, potassium or NH
4 +Sulphite, hydrosulphite or pyrosulfite in one or more mixtures.
4. the preparation method of high density polyoxy alkane alkene ether sulfonate according to claim 1 is characterized in that said cosurfactant is carbonatoms C
3~ C
12Straight chain, side chain or cycloalkanol, or carbonatoms is C
3~ C
6Polyvalent alcohol; Said organic solvent is carbonatoms C
6~ C
24Straight chain, side chain or cyclic alkane, or carbonatoms is C
6~ C
24Aromatic hydrocarbon.
5. the preparation method of high density polyoxy alkane alkene ether sulfonate according to claim 1 is characterized in that said pressure heat condition is 150 ~ 220 ℃.
6. the preparation method of high density polyoxy alkane alkene ether sulfonate according to claim 1 is characterized in that said microemulsion is meant that the water dilution with arbitrary proportion can both obtain isotropy, thermodynamically stable clear solution.
7. the preparation method of high density polyoxy alkane alkene ether sulfonate according to claim 1 is characterized in that described polyoxy alkane alkene ether sulfonate product has following general structure:
R in the formula
1Be carbonatoms C
8~ C
24Straight chain, side chain or cyclic alkane base, or carbonatoms is C
14~ C
24Alkyl phenyl; In the formula-(OR
2)-unit does
,
,
,
,
,
Or
Group, n=0 ~ 50 ,-(OR
2)
n-be above-mentioned-(OR
2)-unitary homopolymer, segmented copolymer or random copolymers; M is sodium, potassium or NH
4 +
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|---|---|---|---|---|
| CN101255127A (en) * | 2008-04-01 | 2008-09-03 | 江南大学 | Synthesis of aliphatic alcohol polyoxyethylene sulfonate and complex formulation used for tertiary oil recovery displacement agent |
| CN101343245A (en) * | 2008-08-22 | 2009-01-14 | 江南大学 | Method for preparing fatty acid methyl ester sulphonic salt with low-disodium salt content by using earlier sulfonation and later esterification technique |
| JP4271319B2 (en) * | 1999-11-30 | 2009-06-03 | 花王株式会社 | Method for producing polyoxyethylene alkyl ether sulfate |
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| JP4271319B2 (en) * | 1999-11-30 | 2009-06-03 | 花王株式会社 | Method for producing polyoxyethylene alkyl ether sulfate |
| CN101255127A (en) * | 2008-04-01 | 2008-09-03 | 江南大学 | Synthesis of aliphatic alcohol polyoxyethylene sulfonate and complex formulation used for tertiary oil recovery displacement agent |
| CN101343245A (en) * | 2008-08-22 | 2009-01-14 | 江南大学 | Method for preparing fatty acid methyl ester sulphonic salt with low-disodium salt content by using earlier sulfonation and later esterification technique |
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