CN104193782B - Double bond containing phosphate compound and its preparation method and application - Google Patents
Double bond containing phosphate compound and its preparation method and application Download PDFInfo
- Publication number
- CN104193782B CN104193782B CN201410404437.1A CN201410404437A CN104193782B CN 104193782 B CN104193782 B CN 104193782B CN 201410404437 A CN201410404437 A CN 201410404437A CN 104193782 B CN104193782 B CN 104193782B
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- Prior art keywords
- double bond
- bond containing
- phosphate compound
- monomer
- present
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- -1 phosphate compound Chemical class 0.000 title claims abstract description 76
- 239000010452 phosphate Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 32
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 41
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000011780 sodium chloride Substances 0.000 claims description 14
- 150000002118 epoxides Chemical class 0.000 claims description 8
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 7
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 230000000875 corresponding Effects 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- AIIITCMZOKMJIM-UHFFFAOYSA-N 2-(prop-2-enoylamino)propane-2-sulfonic acid Chemical compound OS(=O)(=O)C(C)(C)NC(=O)C=C AIIITCMZOKMJIM-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
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- 238000010189 synthetic method Methods 0.000 abstract description 3
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- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-O hydron;prop-2-enamide Chemical compound [H+].NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-O 0.000 abstract description 2
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
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- 125000000217 alkyl group Chemical group 0.000 description 18
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 125000001118 alkylidene group Chemical group 0.000 description 12
- DLYUQMMRRRQYAE-UHFFFAOYSA-N Phosphorus pentoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 10
- 239000000839 emulsion Substances 0.000 description 10
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- 229910052757 nitrogen Inorganic materials 0.000 description 7
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K [O-]P([O-])([O-])=O Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 5
- 238000007792 addition Methods 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
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- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
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- 229920000137 polyphosphoric acid Polymers 0.000 description 4
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- 238000003756 stirring Methods 0.000 description 4
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 229920001748 Polybutylene Polymers 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
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- 150000001875 compounds Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- ULUAUXLGCMPNKK-UHFFFAOYSA-L 2-sulfobutanedioate Chemical compound OS(=O)(=O)C(C([O-])=O)CC([O-])=O ULUAUXLGCMPNKK-UHFFFAOYSA-L 0.000 description 2
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- GQZXNSPRSGFJLY-UHFFFAOYSA-N Hypophosphorous acid Chemical compound OP=O GQZXNSPRSGFJLY-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M NaHCO3 Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L Sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
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- 150000001340 alkali metals Chemical class 0.000 description 2
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- 125000005233 alkylalcohol group Chemical group 0.000 description 2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium(0) Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000003301 hydrolyzing Effects 0.000 description 2
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
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- DYEQHQNRKZJUCT-UHFFFAOYSA-N 1,2-dimethylidenecyclohexane Chemical group C=C1CCCCC1=C DYEQHQNRKZJUCT-UHFFFAOYSA-N 0.000 description 1
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N 2-methyl-2-propenoic acid methyl ester Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 125000001421 myristyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000001400 nonyl 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])C([H])([H])[H] 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
- 230000003647 oxidation Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000000737 periodic Effects 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- ZTHYODDOHIVTJV-UHFFFAOYSA-N propyl 3,4,5-trihydroxybenzoate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- WQDUMFSSJAZKTM-UHFFFAOYSA-N sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000004079 stearyl 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])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])[H] 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention relates to a kind of double bond containing reactive monomer and synthetic method thereof and application, particularly relate to a kind of double bond containing phosphate compound, its preparation method and above-claimed cpd as monomer's application in the polymer.Double bond containing monomer of the present invention, selects more suitably raw material, and the product color making synthesis is shallower.Structure involved by double bond containing monomer of the present invention, advantageously improves the dispersion of water soluble acrylic acid esters polymer, anti-coagulation, and reactive structure more can provide good paint film resistance to water；Can also be with hydrophilic monomer acrylic acid, acryloyl ammonium, acrylamido isopropyl sulfonic acid, the polymerization under peroxidation such as Sodium styrene sulfonate makes dispersion liquid, processes for synthetic water and oilfield additive etc..
Description
Technical field
The present invention relates to a kind of double bond containing reactive monomer and synthetic method thereof and application, particularly relate to one
Double bond containing phosphate compound, its preparation method and above-claimed cpd are as monomer in the polymer
Application.
Background technology
In recent years, reactive emulsifier, the reactive monomer containing hydrophilic functional groups is in heterogeneous polymerization, especially exist
Emulsion polymerization is widely used.According to the literature, polymerizability emulsifying agent and the reaction of polymerization can be participated in containing double bond
Property containing hydrophilic functional groups monomer, in the presence of containing peroxide, can be copolymerized with monomer, thus drop
Low conventional surfactants consumption in emulsion is polymerized, decreases conventional surfactants and occurs when film forming
Migrate, improve the water resistance of paint film；The most described monomer participates in copolymerization, it is also possible to change the property of copolymer
Energy.
Organophosphorus ester early has document report as dispersant, in studying in early days, and organic containing acrylate group
Phosphate ester occupies critical role.
WO01/74826A1 discloses the copolymerizable acrylate kind phosphate ester of a kind of following structure:
WO2003/072632A1 discloses the phosphate ester that a kind of following structures alone and phosphatase reaction obtain and divides
Powder: TO-(CO-A-O)n-(B-O)mH, wherein, T can be alkenyl；When n is 0, this monomer is
Polyether structure containing alkenyl, i.e. obtains a kind of alkenyl polyether phosphate ester structure.
In alkenyl polyether phosphate ester structure compound, the polyether phosphate containing pi-allyl becomes a research
Focus.
CN101679567A discloses [CH2=CH-CH2-R2-O-]xP(O)(OM)3-x, wherein R2For bivalence
Linking group, such as polyalkylene oxide group, this patent disclosed that and a kind of derives the phosphoric acid to allyl polyether
Ester.This patent also discloses the application in coating of this monomer, can give the scrub resistance that coating improves.
CN103772626A also discloses that a kind of allyl polyethenoxy ether phosphate ester, as a kind of copolymerization list
Body is used for preparing comb polymer molecule flotation agent.
But the color and luster of allyl polyether phosphate ester product is relatively deep at present, and the application in a lot of fields can be limited
System, accordingly, it would be desirable to the reactive phosphorus acid ester product of a kind of more preferable color and luster.
Summary of the invention
The invention provides a kind of double bond containing phosphate compound and synthetic method thereof and as monomer
Apply in the polymer.
First aspect of the present invention is to provide a kind of double bond containing phosphate compound, and it has a following structure (I):
Wherein:
R1Selected from the alkenyl that end group is non-conjugated carbon-carbon double bond；
R2Selected from (A-O)nH or (A-O)n—；Wherein, A is in alkylidene, cycloalkylidene, arlydene
One or more, n is the numerical value of >=0；
R3Selected from (C-O)m, wherein, one or more in alkylidene, cycloalkylidene, arlydene of C,
M is the numerical value of >=0；
M1And M2Can be identical or different, and it is independently selected from H, cation；
X is the numerical value of 1-2；Y, z can be identical or different, and separately selected from the numerical value of 0-2；Y+z+x=3.
In the content that the present invention is above-mentioned, described R1Can be selected from straight-chain aliphatic thiazolinyl, branched aliphatic olefin
Base, wherein, end group is non-conjugated carbon-carbon double bond.
In a kind of preferred embodiment of the content that the present invention is above-mentioned, described R1Preferably there is following structure:
CH2=CR4-, wherein, R4Alkyl, alkyl is replaced selected from H, alkyl, aromatic radical, cycloalkyl, aromatic radical
Substituted aromatic base, alkyl-substituted cycloalkyl.
R of the present invention4In:
It is highly preferred that described alkyl is preferably the alkyl of the alkyl of C1-C10, more preferably C1-C8, more
Be preferably C1-C6 alkyl, as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, the tert-butyl group,
Amyl group, hexyl, octyl group, decyl etc..
It is highly preferred that described aromatic radical is preferably the fragrance of the aromatic radical of C6-C18, more preferably C6-C15
The aromatic radical of base, more preferably C6-C12, such as phenyl, naphthyl, anthryl.
It is highly preferred that described cycloalkyl is preferably the cycloalkanes of the cycloalkyl of C3-C18, more preferably C4-C15
Base, the more preferably cycloalkyl of C5-C12, the cycloalkyl of C6-C10, such as cyclopropyl, cyclobutyl, ring penta
Base, cyclohexyl etc..
It is highly preferred that described aromatic radical replaces alkyl is preferably (C6-C12) aromatic radical replacement (C1-C6)
Alkyl, such as benzyl, 2-phenylethyl, 1-phenylethyl.
It is highly preferred that described alky-substituted aromatic base is preferably (C1-C6) alkyl replaces (C6-C12) virtue
Perfume base, such as aminomethyl phenyl, ethylphenyl, propyl group phenyl, isopropyl phenyl, 3,5-dimethylphenyl, trimethylbenzene
Base, diethyl phenyl, methyl-ethyl-phenyl.
It is highly preferred that described alkyl-substituted cycloalkyl is preferably (C1-C6) alkyl replaces (C3-C10) ring
Alkyl, as methylcyclopropyl groups, methylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, dimethylcyclopentyl,
Dimethylcyclohexyl etc..
Most preferably, R1It is preferably selected from CH2=CH-, CH2=C (CH3)-。
In foregoing of the present invention, R2Can be to be preferably selected from (A-O)nH, or (A-O)nT,
Wherein T is for being selected from:
-P (=O) (OM1)t(OM2)2-t, t is 0,1 or 2；
-P (=O) (OM1) (Pm), Pm is selected from:
In foregoing of the present invention, described A and C can be identical or different, it is possible to is independently selected from straight
Chain alkylidene, sub-branched alkyl, contain or not contain the cycloalkylidene of substituent group, contain or not contain substituent group
Arylene.
Wherein, described sub-branched alkyl is preferably selected from alkyl substituted alkylene, aromatic radical substituted alkylene, ring
Alkyl substituted alkylene.Wherein: described alkyl substituted alkylene is preferably (C2-C6) alkyl and replaces (C2-C6)
Alkylidene, more preferably (C2-C4) alkyl replace (C2-C4) alkylidene；Described aromatic radical replaces alkylene
Base is preferably (C6-C12) aromatic radical and replaces (C2-C6) alkylidene, more preferably (C6-C10) fragrance
Base replaces (C2-C4) alkylidene；Described cycloalkyl substituted alkylidene is preferably (C3-C10) cycloalkyl and takes
Generation (C2-C6) alkylidene, more preferably (C3-C6) cycloalkyl substituted (C2-C4) alkylidene.
Wherein, it is highly preferred that A and C be separately preferably-CH (D)-CH (E)-, wherein, D, E
Separately it is preferably selected from the aromatic radical of the alkyl of H, C1-C6, C6-C12；More preferably selected from H,
The alkyl of C1-C4, the aromatic radical of C6-C10；It is highly preferred that D, E be separately preferably selected from H,
Phenyl, benzyl, methyl, ethyl, propyl group, isopropyl, butyl, amyl group, hexyl.
It is highly preferred that described A and C is separately preferably selected from the alkylidene of C1-C6, more preferably choosing
From the alkylidene of C2-C4, such as-CH2-CH2-、-CH2-CH(CH3)-、-CH2-CH2-CH2-、
-CH2-CH(CH3)-CH2-、-CH(CH3)-CH2-CH2-、-CH2-CH(C6H5)-、
-CH2-CH(C6H11)-、-CH2-CH(CH2-C6H5)-、-CH2-CH(CH2-C3H5)-、
-CH2-CH(CH2-C6H11)-、-CH2-CH(C3H5)-。
It is highly preferred that described A and C is separately preferably selected from-CH2-CH(C6H5)-、-CH2-CH2-、
-CH2-CH(CH3)-CH2-、-CH2-CH(CH3)-、-CH2-CH2-CH2-CH2-、
-CH(CH3)-CH2-CH2-、-CH(CH3)-C(CH3)-、-CH(C2H5)-CH2-。
It should be noted that, described (A-O)n, and (C-O)mCan be separately selected from the homopolymerization of a kind of monomer
Thing, the copolymer of various of monomer, when selected from the copolymer of various of monomer, A and C is separately selected from upper
State at least two in A and C of definition.
It is highly preferred that described (A-O)n, and (C-O)mCan separately be selected from polyoxyethylene ether,
Polyethenoxy ether, polybutylene ether, polyoxyethylene poly-oxygen propylene aether, polyoxyethylene polybutylene ether, polyoxy third
Alkene polyoxyethylene ether, polybutylene polyoxyethylene ether, polyphenylene oxides ethylene polyoxyethylene ether etc..
In foregoing of the present invention, n and m can be identical or different.
Wherein, n is preferably 0-20, more preferably 0-18, more preferably 0-14, more preferably 0-10, more
It is preferably 0-8, more preferably 0-6, more preferably 0-4, more preferably 0-3, more preferably 0-2, more excellent
Elect 0-1 as, most preferably n=0.
Wherein, m is preferably selected from 0-20, more preferably 0-16, more preferably 0-10, more preferably 0-5,
More preferably m ＞ 0；More preferably m selected from 0.1-20, more preferably 0.1-16, more preferably 0.1-10,
More preferably 0.1-5；More preferably m selected from 0.2-20, more preferably 0.2-16, more preferably 0.2-10,
More preferably 0.2-5；More preferably m selected from 0.5-20, more preferably 0.5-16, more preferably 0.5-10,
More preferably 0.5-5.
It should be noted that, above-mentioned m, the n of the present invention, x, y, z can be with integer, it is also possible to be non-integer,
When any one or more in m, n, x, y, z are for non-integer, it is meant that it is a kind of mixture,
M, n, x, y, z are average.
In the content that the present invention is above-mentioned, described M1And M2, if it does, be separately preferably selected from H,
Metal, NH4+, wherein, described metal is more preferably alkali metal, such as potassium, sodium, lithium.
It is highly preferred that described M1And M2, if it does, be separately preferably selected from H, potassium, sodium, and
NH4+。
In one preferred embodiment of the present invention, described double bond containing compound at least includes that containing of following structure is double
One or more in the phosphate compound of key:
Second aspect of the present invention is to provide a kind of method preparing above-mentioned double bond containing phosphate compound, step
Including:
Step 1, it is provided that phosphoric acid,
Step 2, containing double bond shown in one or more and/or the structure formula (II) in glycerin ether shown in structural formula (II-1)
Alcohol ether in one or more, with phosphatase reaction, obtain the double bond containing phosphate ester shown in structure formula (III)
Compound；
Wherein, R1、R2、R3, x there is implication identical defined in first aspect of the present invention.
Wherein, the preparation method of double bond containing alcohol ether shown in structure formula (II) preferably comprises following steps:
Step 1.1, it is provided that one or more in glycerin ether shown in structural formula (II-1)；
Step 1.2, in the presence of described glycerin ether and catalyst, adds one or more epoxides and carries out
Reaction, obtains double bond containing alcohol ether shown in structure formula (II).
In method described in second aspect of the present invention, it is former that described epoxide refers to one or more oxygen
The ring-like ether that son and two adjacent carbon atoms are constituted, the most oxygen-containing three-membered ring ether compound；Its open loop gathers
R is generated after conjunction3Group.
Wherein, described epoxide is preferably following structure:
Wherein, wherein, D, E have implication identical defined in first aspect of the present invention.
Preferably, described epoxide is selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide
In any one or a few.
In the method described in second aspect of the present invention, catalyst described in step 1.2 can be epoxide
Conventional ring-opening polymerization catalyst, such as base catalyst or acid catalyst, but need not when addition styrene oxide
Acid catalyst and use base catalysis.Wherein:
Described base catalyst can be selected from hydroxide, alkoxide, organic amine, and preferably alkali metal hydroxide
Thing, alkali metal alcoholates or organic amine, such as triethylamine, sodium alkoxide, potassium alcoholate, sodium hydroxide, potassium hydroxide, hydrogen
Alcohol in Barium monoxide, calcium hydroxide, described sodium alkoxide (or potassium alcoholate) can be methanol, ethanol etc..
Described acid catalyst can be non-oxidizable aqueous Bronsted acid or Louis (Lewis) acid, described Louis
This acid is such as BF3Deng.
Described catalyst amount is unrestricted, but preferably accounts for the 0.001%-1% of reactant gross weight, more excellent
Elect 0.005%-0.5% as, more preferably 0.01%-0.3%.
In method described in second aspect of the present invention, react described in step 1.2 and carry out under inert gas shielding
Reaction.It will be appreciated to those of skill in the art that described noble gas refers to be not involved in the gas of described reaction
Body, such as nitrogen, helium, argon etc..
In method described in second aspect of the present invention, described in step 1.2, the temperature of reaction is preferably 80-170 DEG C
In arbitrary temp or temperature range, wherein, the determination method of temperature may is that with GC and/or HPLC
Epoxide content in final raw material < less than 0.2%, and the charging reaction time is with no more than 5 is measured etc. method
Hour for reaction temperature range.
In method described in second aspect of the present invention, at the temperature disclosed above, described in step 1.2 one or more
Epoxide can be to add or add in certain sequence or the most in-order after arbitrarily mixing
Add.
Wherein, described phosphoric acid being to add with the form of phosphoric acid, or can add other thing that can generate phosphoric acid
Plant in reaction system, generate phosphoric acid.As described phosphoric acid can be derived from polyphosphoric acids, phosphoric anhydride, five oxidations two
Any one or a few in phosphorus, phosphoric acid.
Wherein, in the step 2 of second aspect of the present invention, reaction temperature preferably control 50-85 DEG C it
Between arbitrary temp or temperature range, the more preferably arbitrary temp between 70 DEG C-80 DEG C or temperature range.
Wherein, in the step 2 of second aspect of the present invention, the response time is preferably 1-10h, more preferably
2-9h, more preferably 5-8h.
Wherein, in the step 2 of second aspect of the present invention, can carry out under anaerobic atmosphere, and be preferably
Carry out under atmosphere of inert gases.It will be appreciated to those of skill in the art that described noble gas to refer to not to join
With the gas of described reaction, such as nitrogen, helium, argon etc..
Wherein, in the step 2 of second aspect of the present invention, phosphoric acid is preferred with described double bond containing alcohol ether mol ratio
It is 1: 0.3-3, more preferably 1: 0.5-2.5, more preferably 1: 0.8-2.2.
Wherein, in the step 2 of second aspect of the present invention, it is also possible to be included in the water after phosphorylation reaction terminates
Solving step, described hydrolysing step is preferably: under the conditions of 70-80 DEG C, hydrolysis insulation 45min-90min,
More preferably 60-80min.
Wherein, in described hydrolysing step, can additionally add water, amount of water preferably accounts for the 30% of total phosphoric acid amount
Or it is lower.
Wherein, in a kind of preferred embodiment of second aspect of the present invention, also include shown in structure formula (III)
Double bond containing phosphate compound mix with the solution containing alkali, be neutralized and obtain the step of corresponding salt.
In the preferred embodiment shown, the described solution containing alkali can be ammonia, sodium hydrate aqueous solution, hydrogen-oxygen
Change aqueous solutions of potassium.
Wherein, in described N-process, temperature is preferably ambient temperature between the reaction temperature in step 2
Arbitrary temp or temperature range, more preferably 10-60 DEG C, more preferably 20-60 DEG C, more preferably 30-60 DEG C,
Such as 40 DEG C, 50 DEG C.
Third aspect of the present invention is to provide double bond containing phosphate compound shown in a kind of said structure (I) and exists
Application in polyreaction, including:
Step 1, joins in reaction system by described double bond containing phosphate compound,
Step 2, initiator and described in deposit double bond containing phosphate compound under, double bond containing polymerization monomer
Carry out polyaddition reaction；Wherein, the consumption of described double bond containing phosphate compound can account for total monomer weight
0.5-30% (percentage by weight).
In application described in third aspect of the present invention, described double bond containing polymerization monomer is preferably vinyl list
Body, and preferably at least have a vinyl to be positioned at the vinyl monomer of end.
The citing of described double bond containing polymerization monomer includes: alkyl acrylate, alkyl methacrylate, third
Acrylamide, Methacrylamide, N-substituent methyl acrylamide, N-substituted acrylamide, acrylic acid, methyl
Acrylic acid, vinylacetate, styrene, itaconic acid, alkyl itaconates, above-mentioned acid salt in any one
Plant or several.
Wherein, described Arrcostab is preferably the Arrcostab of C1-C25, as methyl ester, ethyl ester, propyl ester, isopropyl ester,
Butyl ester, own ester, different monooctyl ester, lauryl alcohol ester, tetradecyl alchohol ester, hexadecanol ester, octadecyl.
Wherein, described N-replace can monosubstituted or two replacements, its substituent group is preferably selected from (C1-C18)
Any one or a few in alkyl, (C6-C18) aromatic radical, (C3-C18) cycloalkyl, such as methyl, second
Base, propyl group, isopropyl, butyl, isobutyl group, the tert-butyl group, phenyl, benzyl, cyclopropyl, cyclohexyl, ring
Any one or a few in amyl group, cyclohexyl.Described substituent group can also contain carboxyl, nitro, sulfonic group,
Any one or a few group in halogen atom, hydroxyl, ester group, carbonyl, aldehyde radical.
It is highly preferred that the citing of described double bond containing polymerization monomer includes: acrylic acid methyl ester., ethyl acrylate,
Butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, butyl methacrylate, methacrylic acid ten
Eight alcohol esters, styrene, vinylacetate, acrylic acid, methacrylic acid, itaconic acid, itaconic acid esters, third
Olefin(e) acid ethyl acetoacetate, Methacrylamide, acrylamide, acrylamido isopropyl sulfonic acid, styrene
Any one or a few in sodium sulfonate.
In application described in third aspect of the present invention, described addition polymerization can use emulsion polymerization, solution to gather
Close, suspension polymerisation, more preferably emulsion are polymerized, the method most preferably using aqueous emulsion polymerization.
Emulsifying agent used by described aqueous emulsion polymerization is such as: alkyl ethoxylated 2-Sulfosuccinic acid esters, alkyl ethoxylated sulfur
Any one or a few in esters of gallic acid, alkyl ethoxylated phosphoric acid ester and their salt.Wherein, described salt
Can be any one or a few in slaine, ammonium salt；More preferably periodic table of elements IA, Group IIA metal
Any one or a few in salt, ammonium salt；More preferably one or more in potassium salt, sodium salt, ammonium salt.
Wherein, described alkyl ethoxylated 2-Sulfosuccinic acid esters emulsifying agent and salt thereof can be selected from C6-C20 alkane
Base alcohol polyethers (degree of polymerization is preferably 3-15) sulfosuccinate, more preferably C8-C18 fatty alcohol polyoxy
Vinyl Ether sulfosuccinate, more preferably C10-C16 fatty alcohol-polyoxyethylene ether sulfosuccinate, with
And any one in their salt, such as: polyoxyethylene lauryl ether sulfosuccinate and disodium salt thereof,
Any one or a few in di-ammonium salts.
Wherein, described alkyl ethoxylated sulfuric acid ester emulsifying agent and salt thereof and can be selected from C6-C20 alkylol
Polyethers (degree of polymerization is preferably 3-15) sulfuric ester, more preferably C8-C18 fatty alcohol-polyoxyethylene ether sulphuric acid
In ester, more preferably C10-C16 polyoxyethylene alkyl ether sulfate and their salt any one or
Several, such as: Dodecyl Polyoxyethylene Ether sulfuric ester, tridecanol polyoxyethylene ether sulfuric ester, oleic alcohol polyoxyethylene
Ether sulfuric ester, isooctanol polyethoxylate sulfuric ester, nonyl polyoxyethylenated alcohol sulfuric ester and their magnesium
Any one or a few in salt, potassium salt, sodium salt, ammonium salt.
Wherein, described alkyl ethoxylated phosphoric acid esters wedding agents and salt thereof can be selected from selected from C6-C20 alkyl
Alcohol polyethers (degree of polymerization is preferably 3-15, more preferably 4-12) phosphate ester, more preferably C8-C18 fat
Polyoxyethylenated alcohol phosphate ester, more preferably C10-C16 aliphatic alcohol polyoxyvinethene phosphate, such as: 12
Any one or a few in polyoxyethylenated alcohol phosphate and their sodium salt, ammonium salt.
In the application described in third aspect of the present invention, described initiator can use peroxide, persulfide,
Any one or a few in azo-compound, more preferably any one in persulfide, peroxide or
Several.
It is highly preferred that described initiator is selected from: Ammonium persulfate., sodium peroxydisulfate, potassium peroxydisulfate, in hydrogen peroxide
Any one or a few.
The method of emulsion polymerization has been reported that in a lot of data, and then available pre-emulsification mix monomer method arrives reaction temperature
Spending direct dripping method, then pre-emulsification mix monomer method arrives reaction temperature, drips after using bottom seed addition polymerization again
Addition, it is possible to use monomer dripping method, it is possible to use the methods such as hud polymerization method.
Double bond containing monomer of the present invention, selects more suitably raw material, makes the product color of synthesis
Shallower.Structure involved by double bond containing monomer of the present invention, advantageously improves water-and acrylate
The dispersion of base polymer, anti-coagulation, reactive structure more can provide good paint film resistance to water；Can also be with
Hydrophilic monomer acrylic acid, acryloyl ammonium, acrylamido isopropyl sulfonic acid, Sodium styrene sulfonate etc. is at peroxide
Under compound effect, dispersion liquid is made in polymerization, processes and oilfield additive etc. for synthetic water.
Accompanying drawing explanation
Fig. 1 is double bond containing compound infrared spectrum in an embodiment of the present invention；
Fig. 2 is double bond containing phosphate compound infrared spectrum in an embodiment of the present invention；
Fig. 3 is double bond containing phosphate compound infrared spectrum in another kind embodiment of the present invention；
Fig. 4 is double bond containing phosphate ester ammonium salt compound infrared spectrum in an embodiment of the present invention.
Detailed description of the invention
Below by specific embodiment, present invention is made a more detailed description, so that being better understood from this
Invention it should be appreciated that, following embodiment does not limit the scope of the invention.
Embodiment 1
By allylin (1mol), add Feldalat NM (in terms of the 0.1wt% of total amount), add autoclave,
It is again heated to 120 DEG C, in nitrogen environment, slowly adds oxirane 44g (1mol), react.
Lower the temperature after having reacted, obtain the alcohol ether MEPG-M1 of band double bond.
Embodiment 2
By allylin (1mol), hydro-oxidation potassium (in terms of the 0.1wt% of total amount), add high pressure
Still, is again heated to 120 DEG C, first deviates from water, to moisture qualified after, in a nitrogen environment, slowly add epoxy
Propane 116g (2mol) lowers the temperature after having reacted, and obtains the alcohol ether MEPG-M2 of band double bond, its ultrared spectrum
Figure is shown in Fig. 1, wherein, and 1078cm-1Go out for C-O-C absworption peak, 1373cm-1Place is the methylene being connected with oxygen
Absworption peak.
Embodiment 3
The alcohol ether MPEG-M1 (1mol) of band double bond is added in 1000ml reaction bulb, under nitrogen bubble,
Under the conditions of 50 DEG C, slowly add 45g115% polyphosphoric acid, add 16g phosphoric anhydride the most at this temperature,
It is incubated 2 hours after adding, then is warmed up to be incubated 8 hours at 78-82 DEG C, be subsequently adding 18g water, then be incubated
1 hour, then lowering the temperature, filter and obtain double bond containing alcohol ether phosphate WP-1, its infrared spectrum is shown in Fig. 2,
978cm-1Place is P-O, P=O absworption peak.
Use similar method, replace MEPG-M1 to be raw material reaction with the alcohol ether MEPG-M2 of band double bond,
Respectively obtaining corresponding phosphate ester WP-2, its infrared spectrum is shown in Fig. 3.
WP-1, WP-2 are added in the aqueous solution containing ammonium hydroxide slowly at 40-60 DEG C, are neutralized to pH value
=6.5-7.5, solid content is 24-26%, obtain corresponding ammonium salt be WPA-1 (its infrared spectrum is shown in Fig. 4,
3223cm-1Place is for N-H absworption peak), WPA-2.
Embodiment 4
Allylin 1 mole, is added in 1000ml reaction bulb, under nitrogen bubble, then at 50 DEG C
Slowly add 55g115% polyphosphoric acid, add 15g phosphoric anhydride the most at this temperature, after adding, be incubated 2
Hour it is warmed up to 78-82 DEG C again and is incubated 8 hours, be subsequently adding 18g water, then be incubated 1 hour, then drop
Temperature, filters and obtains corresponding phosphate ester WP-3.
Same as in Example 3, the ammonium salt aqueous solution obtaining 24-26% after neutralization is WPA-3.
Comparative example
Allyl polyethenoxy ether (EO=5) 1 mole: 278 grams
Hypophosphorous acid 50%:0.73 gram
Polyphosphoric acids 115%:60.25 gram
Phosphorus pentoxide: 34.3 grams
Aqueous hydrogen peroxide solution: 1.83 grams
In 1000ml reaction bulb, add allyl polyethenoxy ether and hypophosphorous acid, under nitrogen bubble, then
Slowly add 60.25g115% phosphoric acid at 45 DEG C, mix 1 hour, the most again at a temperature of 55 DEG C, slowly
Xu adds 15g phosphoric anhydride, is incubated 2 hours at 60 DEG C after adding, then is warmed up to 80 DEG C of insulations 8 hours, so
The aqueous hydrogen peroxide solution of rear addition 1g30%, then it is incubated 4 hours, then lower the temperature, filter and obtain accordingly
Phosphate ester BJ-5.Neutralizing into ammonium salt is BJA-5.
Table 1 gives phosphate compound and the comparative example phosphoric acid that the above embodiment of the present invention gained contains double bond
The color and luster of ester compounds compares.
Table 1, product color compares
Can draw from the color and luster analysis of above table 1, the double bond containing phosphate ester of the present invention and salt thereof compare pi-allyl
Epoxide polyether phosphate and salt thereof have the most preferably color and luster.
By the emulsion aggregation test of the product acrylic ester monomer that embodiment 3-4 obtains, condition such as table 2.
Table 2
Wherein: AA is acrylic acid, AM is acrylamide, and ST is styrene, and BA is butyl acrylate, and A-171 is second
Thiazolinyl trimethoxy silane, PS-725A is alkyl alcohol ethoxylates ammonium phosphate salt
Step is as follows:
Step 1, in the 1000ml flask with stirring, adds pre-emulsified deionized water, is subsequently adding
Emulsifying agent WPA-1, PS-725A, after stirring and dissolving, add butyl acrylate, styrene, propylene slowly
Adding after acid, acrylamide water dissolution, finally will add after sodium bicarbonate water dissolution, pre-emulsion stirs
After 0.5-1 hour standby.
Step 2, then at another with four mouthfuls of 1000ml of stirring, condenser, Dropping funnel and thermometer
In flask, add bottom water, emulsifying agent, be warmed up to 80 DEG C.Prepare the aqueous solution of Ammonium persulfate. simultaneously.
Step 3, when still temperature to 80 DEG C, adds the i.e. pre-emulsion 20g of bottom seed, at the beginning of being simultaneously introduced
Beginning initiator ammonium persulfate, starts reaction, and bottom emulsion has obvious blue light to occur, after reacting half an hour, with
Time dropping pre-emulsion and dropping initiator solution, within 180 minutes, drip off, add A-171, then at 80-84 DEG C
It is incubated 1.5 hours.Cooling, with in ammonia and after, filter.
Replace WPA-1 with WPA-2, WPA-4, repeat above-mentioned test.Result shows, filtering residue equal ＜ 0.1g.
Table 3, emulsion property test result in the embodiment of the present invention
| Test event | WPA-1 | WPA-2 | WPA-3 |
| During discharging, 300 mesh filter and always go out the quantity of slag (g) | <0.1 | <0.1 | <0.1 |
| 5000rmp/min, 15min, 300 mesh filters | Without slag | Without slag | Without slag |
| Emulsion viscosity, mPa s (3#, 60rmp) | 680 | 594 | 606 |
| Water-whitening resistance (24 hours) | > 96 hours | > 96 hours | > 96 hours |
Water-whitening resistance is tested: is coated with dry film about 22-25 μm by bar on a glass, is dried 25 DEG C of temperature
24 hours, write No. 4 fonts at the glass plate back side, plate put in pure water, observe font to do not see for
Time only, the time is the longest, and water-whitening resistance can be the best, from table 1 it follows that breast in the embodiment of the present invention
Liquid is respectively provided with good water-whitening resistance.
Testing result from table 3 is it can be seen that double bond containing alcohol ether phosphate provided by the present invention is prepared as
Emulsion, there is good stability, stir after 15 minutes under the speed of 5000r/min, do not go out
Now precipitate.
Being described in detail the specific embodiment of the present invention above, but it is intended only as example, the present invention is also
It is not restricted to particular embodiments described above.To those skilled in the art, any the present invention is carried out
Equivalent modifications and substitute the most all among scope of the invention.Therefore, without departing from the spirit of the present invention and model
Enclose lower made impartial conversion and amendment, all should contain within the scope of the invention.
Claims (5)
1. a double bond containing phosphate compound, it is characterised in that it has a following structure (I):
Wherein:
R1Selected from the alkenyl that end group is non-conjugated carbon-carbon double bond, described R1Selected from following structure: CH2=CH-,
CH2=C (CH3)-；
R2Selected from (A-O)n—H；
R3Selected from (C-O)m—；
Wherein, A and C separately selected from following any one :-CH2-CH2-、-CH2-CH(CH3)-CH2-、
-CH2-CH(CH3)-、-CH2-CH2-CH2-CH2-、-CH(CH3)-CH2-CH2-、
-CH(CH3)-C(CH3)-、-CH(C2H5)-CH2-；N be 0-20, m be 0-20；
M1And M2Identical or different, and it is independently selected from H, cation；
X is the numerical value of 1-2；Y, z are identical or different, and separately selected from the numerical value of 0-2；Y+z+x=3.
2. prepare the method for double bond containing phosphate compound described in claim 1 for one kind, it is characterised in that step
Including:
Step 1, it is provided that phosphoric acid,
Step 2, double bond containing alcohol ether shown in glycerin ether shown in structural formula (II-1) or structure formula (II), anti-with phosphoric acid
Should, obtain the double bond containing phosphate compound shown in structure formula (III)；
Wherein, R1、R2、R3, x there is the implication identical with defined in claim 1.
Method the most according to claim 2, it is characterised in that double bond containing alcohol ether shown in structure formula (II)
Preparation method comprise the steps:
Step 1.1, it is provided that glycerin ether shown in structural formula (II-1)；
Step 1.2, in the presence of described glycerin ether and catalyst, adds epoxide and reacts, obtain
Double bond containing alcohol ether shown in structure formula (II).
Method the most according to claim 2, it is characterised in that also include containing shown in structure formula (III)
The phosphate compound of double bond mixes with the solution containing alkali, is neutralized the step obtaining corresponding salt.
5. double bond containing phosphate compound application in the polymerization shown in a structure (I), it is characterised in that
Wherein, R1、R2、R3, x, y, z there is the implication identical with defined in claim 1；
Including:
Step 1, joins in reaction system by described double bond containing phosphate compound,
Step 2, initiator and described in deposit double bond containing phosphate compound under, double bond containing polymerization monomer
Carrying out polyaddition reaction, wherein, the consumption of described double bond containing phosphate compound accounts for total monomer weight
0.5-30%.
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| CN201410404437.1A CN104193782B (en) | 2014-08-15 | Double bond containing phosphate compound and its preparation method and application |
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| CN201410404437.1A CN104193782B (en) | 2014-08-15 | Double bond containing phosphate compound and its preparation method and application |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0244841A2 (en) * | 1986-05-07 | 1987-11-11 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Surface active compounds having a polymerizable moiety |
| CN101679567A (en) * | 2007-05-07 | 2010-03-24 | 罗地亚管理公司 | Polymer and use thereof |
| CN103554470A (en) * | 2013-10-09 | 2014-02-05 | 上海优创化学品有限公司 | Alcohol ether containing double bond and phosphate ester thereof, and production method for alcohol ether and phosphate ester thereof |
| CN103772626A (en) * | 2014-01-23 | 2014-05-07 | 焦作超达环保科技有限公司 | Preparation method of comb type high-molecular flotation agent |
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0244841A2 (en) * | 1986-05-07 | 1987-11-11 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Surface active compounds having a polymerizable moiety |
| CN101679567A (en) * | 2007-05-07 | 2010-03-24 | 罗地亚管理公司 | Polymer and use thereof |
| CN103554470A (en) * | 2013-10-09 | 2014-02-05 | 上海优创化学品有限公司 | Alcohol ether containing double bond and phosphate ester thereof, and production method for alcohol ether and phosphate ester thereof |
| CN103772626A (en) * | 2014-01-23 | 2014-05-07 | 焦作超达环保科技有限公司 | Preparation method of comb type high-molecular flotation agent |
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