CN103554470A - Alcohol ether containing double bond and phosphate ester thereof, and production method for alcohol ether and phosphate ester thereof - Google Patents
Alcohol ether containing double bond and phosphate ester thereof, and production method for alcohol ether and phosphate ester thereof Download PDFInfo
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- CN103554470A CN103554470A CN201310468589.3A CN201310468589A CN103554470A CN 103554470 A CN103554470 A CN 103554470A CN 201310468589 A CN201310468589 A CN 201310468589A CN 103554470 A CN103554470 A CN 103554470A
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Abstract
The invention relates to a reactive emulsifier and a preparation method and application of the emulsifier, especially to an emulsifier with a bifunctional group and a hydrophilic structure, wherein the emulsifier can improve dispersion and anticoagulation performance of an emulsion, and a reactive structure can better provide good water resistance of a film. The invention provides an alcohol ether having a structure (I) as described in the specification and a phosphate ester thereof and preparation methods and application of the alcohol ether and the phosphate ester thereof.
Description
Technical field
The present invention relates to a kind of reactive emulsifier, and the preparation method and application of described emulsifying agent, relate in particular to a kind of emulsifying agent of the hydrophilic-structure containing bifunctional, the dispersion, the anti-freezing that are conducive to improve emulsion are poly-, and reactive structure more can provide good paint film water tolerance.
Background technology
Use emulsion polymerization technology is produced the existing history for many years of high molecular polymer, and letex polymerization has speed of response is fast, heat of polymerization easily spreads, can prepare high viscosity polymkeric substance, reduces the advantages such as environmental pollution.The synthetic of water-based emulsion need to be realized with emulsifying agent, the effect of emulsifying agent is: when it is dispersed in dispersate surperficial, form film or electrostatic double layer, can make disperse phase with electric charge, so just can stop the small droplets of disperse phase to condense mutually, make the emulsion of formation more stable.Letex polymerization is under the effect of emulsifying agent and by means of mechanical stirring, makes monomer in water, be dispersed into milk sap, by initiator, is caused and the polyreaction of carrying out.
But defect is also deposited in letex polymerization, common emulsifying agent is normally attached to polymer beads sub-surface with physical adsorption way, reaches thermodynamic(al)equilibrium with its environment, thereby realizes stabilization of polymer particle.When environment exists certain stress, this thermodynamic(al)equilibrium can be destroyed, and desorb will occur emulsifying agent molecule, and result causes that between polymer particle, generation is sticky also, makes the loss of stability of polymer latex; In latex film forming process, common emulsifying agent is to residue among polymer solids with small molecules, and it can move to film surface and set up the thermodynamic(al)equilibrium of mating with environmental facies, and this just causes the water tolerance decline of polymeric film.
Problem for above-mentioned existence, domestic and international many researchists have proposed some solutions, wherein adopt more and relatively effective means be exactly in polymerization process, emulsifying agent molecule is combined on particle surface, adopts reactive emulsifier in the mode of covalent linkage.Reactive emulsifier, in polymerization process, can the mode with covalent linkage be combined in emulsifying agent molecule on particle surface, and namely emulsifying agent molecule is to be no longer combined by physical adsorption with covalent bonds with macromolecular chain.Under this condition, no longer may there is desorb in emulsifying agent molecule, thereby make to be subject to electrostatic repulsion and larger steric restriction effect in polymer particle coalescing process, and the stability of latex is improved.In addition, the film forming of polymer latex will no longer be subject to the impact of emulsifying agent migration, because be in fact almost impossible with the emulsifying agent molecule generation migration of covalent bonds, the water resistance of polymeric film also will be improved; Reactive emulsifier and polymer chain with chemical bonds after, last polymer latex will no longer have (or seldom measuring) emulsifying agent and exist with free state, this polymkeric substance for agglomeration separation cleaning from latex is also very important, and the recycle of waste water is simultaneously more prone to; Therefore, there are a lot of companies to release reactive emulsifying agent can solve some bad problems of paint film abroad.
In recent years, reactive emulsifier is in heterophase polymerization, and the especially application in letex polymerization, has caused domestic and international colleague's very big interest.According to the literature, reactive emulsifier can roughly be divided into 3 classes by its performance and the effect in letex polymerization, containing two bond energys participate in the polymerizability emulsifying agent of polymerizations, containing azo or the isostructural surface living initiator agent of peroxide with shift the surface active transfer agent of group containing chain.This special construction of reactive emulsifier has determined the characteristic of himself, be that reactive emulsifier itself both can play common emulsifying agent in letex polymerization, can participate in polymerization process again, and before and after reaction and in process, its emulsifying property does not reduce.Current reactive emulsifying agent report is a lot, as US20020123588A1 has reported with acrylic or methacrylic acid Soxylat A 25-7 or polyethenoxy ether phosphate ester structure: R
1-C (O)-R
2-X, US4814514 has reported the product R that reacts again polyethers with alkyl alcohol polyethers with glycidyl ether
1o-(AO)
x-CH
2cH (O-(AO)
y-H)-CH
2-O-CH
2c (R)=CH
2, EP1318157A1 has reported CH
2=C (CH
3)-CH
2cH
2-(AO)
a(EO)
b-SO
3m, EP0472837A1 has reported CH
3-CH=CH-ph-O (AO)
n-H; CN101284846B discloses a kind of reactive phosphorus acid esters emulsifying agent CH
2=C (CH
3)-C (O)-O-CH
2-CH (CH
2-OH)-O-PO (OH)
2.
Summary of the invention
The present invention on the basis of existing technology, provides a kind of reactive emulsifier that contains bifunctional hydrophilic-structure.
First aspect of the present invention is to provide a kind of double bond containing alcohol ether, and described alcohol ether has following structure (I):
In double bond containing alcohol ether described in first aspect of the present invention, x1 and x2 can be identical or different, and y1 and y2 also can be identical or different, and z1 and z2 also can be identical or different; N1 and n2 also can be identical or different.
Wherein, n1, n2, x1, x2, y1, y2, z1, z2 can be zero simultaneously, or at least one is not 0, and to be preferably at least one be not 0.
More preferably: x1, x2, y1, y2, z1, z2 be the numerical value between 0-100 respectively independently, and be 0 during difference; And be preferably x(x=x1+x2), y(y=y1+y2), z(z=z1+z2) in be 0 when at least x, y are different, more preferably x and y are not all 0.
More preferably: n1 and n2 be the numerical value between 0-10 respectively independently, and be 0 during difference, i.e. n(n=n1+n2) be not 0.
In a kind of preferred embodiment in the present invention aspect first:
X is 0-200, is preferably 0-160, is preferably 0-100, is preferably 0-80, is preferably 0-50; More preferably 1-200, more preferably 1-160, more preferably 1-100, more preferably 1-80, more preferably 1-50; More preferably 2-200, more preferably 2-160, more preferably 2-100, more preferably 2-80, more preferably 2-50;
Y is 0-200, is preferably 0-160, is preferably 0-100, is preferably 0-80, is preferably 0-50; More preferably 1-200, more preferably 1-160, more preferably 1-100, more preferably 1-80, more preferably 1-50; More preferably 2-200, more preferably 2-160, more preferably 2-100, more preferably 2-80, more preferably 2-50;
Z is 0-200, is preferably 0-160, is preferably 0-100, is preferably 0-80, is preferably 0-50; More preferably 1-200, more preferably 1-160, more preferably 1-100, more preferably 1-80, more preferably 1-50; More preferably 2-200, more preferably 2-160, more preferably 2-100, more preferably 2-80, more preferably 2-50;
N is 0-20, is preferably 0-16, is preferably 0-10, is preferably 0-8, is preferably 0-4.
Wherein, x=x1+x2, y=y1+y2, z=z1+z2, n=n1+n2.
Should be understood that, said n, n1, n2, x, x1, x2, y, y1, y2, z, z1, z2 can be integer or decimal, when being in the situation of decimal, described in first aspect of the present invention, double bond containing alcohol ether refers to mixture, and now n, n1, n2, x, x1, x2, y, y1, y2, z, z1, z2 refer to the multiple mean polymerisation degree containing monomeric unit in two key alcohol ethers.As two kinds of double bond containing alcohol ethers in the situation of n=0 and n=1 mixed according to 1: 1, n averages 0.5, therefore, n, n1, n2, x, x1, x2, y, y1, y2, z, z1, z2 can be the decimal between 0-1, as 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8 etc., also can be greater than 1 decimal.
In double bond containing alcohol ether described in first aspect of the present invention, n1 and n2 can be identical or different, and are preferably independently 0-10 respectively, are preferably 0-9, more preferably 0-8, more preferably 0-7, more preferably 0-6, more preferably 0-5,0-4 more preferably.
One skilled in the art will appreciate that in structural formula (I), SO, EO, PO can be in molecular chain random distribution, be alternately distributed or block distributed, the present invention is preferably block distributed; And SO, EO, PO and the order of EO block on molecular chain can be adjusted, in the present invention, be preferably according to the order of SO, EO, PO and EO block from one end of group A and B to M
1or M
2one end distributes successively.
In double bond containing alcohol ether described in first aspect of the present invention, M
1, M
2can be identical or different, and respectively independently selected from H or metal, described metal is preferably potassium, sodium, M
1, M
2h more preferably.
In double bond containing alcohol ether described in first aspect of the present invention, A is double bond containing alkyl, and is preferably double bond containing C
3-C
5alkyl, described pair of key can be one or more, but in the situation of a plurality of pairs of keys, two keys are non-conterminous; Described pair of key can be positioned at or not be positioned at the end of alkyl, and is preferably the end that is positioned at alkyl.
A for example as: allyl group, alkene butyl etc., more preferably allyl group.
In double bond containing alcohol ether described in first aspect of the present invention, B is C
1-C
5alkyl; Can be the alkyl of straight chain or branching, as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-etc., and be preferably methyl, ethyl, n-propyl, more preferably methyl or ethyl, more preferably ethyl.
In double bond containing alcohol ether described in first aspect of the present invention, EO is-CH
2-CH
2-O-.
In double bond containing alcohol ether described in first aspect of the present invention, PO is-CH (D)-CH (G)-O-and, D and G are H, C respectively independently
1-C
5alkyl, but be H when different; Wherein, D and G are preferably respectively H, methyl, ethyl independently, but are H when different, most preferably, PO for example as-CH (CH
3)-CH (CH
3)-O-,-CH (C
2h
5)-CH
2-O-,-CH
2-CH (C
2h
5)-O-,-CH
2-CH (CH
3)-O-,-CH (CH
3)-CH
2-O-; And be preferably-CH (CH
3)-CH
2-O-,-CH (C
2h
5)-CH
2-O-.
In double bond containing alcohol ether described in first aspect of the present invention, SO is-CH (ph)-CH
2-O-and/or-CH
2-CH (ph)-O-, ph is phenyl; And be preferably-CH (ph)-CH
2-O-.
Second aspect of the present invention is to provide a kind of production method of above-mentioned double bond containing alcohol ether, described method steps comprises: the described compound of structural formula (I-1) (also becoming below compound (I-1)) of take is raw material, under catalyst action, according to predetermined order of addition(of ingredients), add epoxy compounds, react, obtain described double bond containing alcohol ether; Wherein, described epoxy compounds is selected from Styryl oxide, oxyethane, epoxy compounds
in any one or a few mixture.
In method described in second aspect of the present invention, A is double bond containing alkyl, and is preferably double bond containing C
3-C
5alkyl, described pair of key can be one or more, but in the situation of a plurality of pairs of keys, two keys are non-conterminous; Described pair of key can be positioned at or not be positioned at the end of alkyl, and is preferably the end that is positioned at alkyl.
A for example as: allyl group, alkene butyl etc., more preferably allyl group.
In method described in second aspect of the present invention, B is H, C
1-C
5alkyl; Can be the alkyl of straight chain or branching, as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-etc., and be preferably methyl, ethyl, n-propyl, more preferably methyl or ethyl, more preferably ethyl.
More preferably, compound (I-1) for example as:
In method described in second aspect of the present invention, D and G are preferably respectively H, methyl, ethyl independently, but are H when different, most preferably, and epoxy compounds
for example as
deng; And be preferably
or
In method described in second aspect of the present invention, described catalyzer can be alkaline catalysts or acid catalyst, wherein:
1) described alkaline catalysts can be to be selected from oxyhydroxide, alkoxide, organic amine, and is preferably alkali metal hydroxide, alkali metal alcoholates or organic amine, as triethylamine, sodium alkoxide, potassium alcoholate, sodium hydroxide, potassium hydroxide, hydrated barta, calcium hydroxide etc.Alcohol in described sodium alkoxide (or potassium alcoholate) can be methyl alcohol, ethanol, propyl alcohol etc.
2) described acid catalyst can be non-oxidizable moisture protonic acid or Louis (Lewis) acid, and described protonic acid can be sulfonic acid, organic carboxyl acid etc., as acetic acid, trifluoromethanesulfonic acid, fluoro sulfonic acid etc.; Described Lewis acid is as BF
3deng.
Described catalyst levels is unrestricted, but is preferably the 0.001%-2% that accounts for reactant gross weight, more preferably 0.1-1%.
In method described in second aspect of the present invention, described reaction can be carried out in the atmosphere that contains oxygen or oxygen-free gas, and is preferably under protection of inert gas and reacts.
Those skilled in the art can understand, and described rare gas element refers to the gas that does not participate in described reaction, as nitrogen, argon gas etc.
In method described in second aspect of the present invention, temperature of reaction is preferably 80-160 ℃, is preferably in 90-120 as 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ etc.
In method described in second aspect of the present invention, Styryl oxide, oxyethane and epoxy compounds
can feed in raw material, or different rings oxygen compound is reinforced respectively simultaneously; Order of addition(of ingredients) can be adjusted according to the molecular structure of required synthetic double bond containing alcohol ether.
In a kind of preferred embodiment aspect second of the present invention, be preferably and add successively in order Styryl oxide, first oxyethane epoxy compounds
with second batch oxyethane.That is:
Step 1, under catalyst I exists, compound (I-1) carries out ring-opening reaction with Styryl oxide and generates intermediate MEPG-M1;
Step 2, under described catalyst I I exists, intermediate MEPG-M1 and first oxyethane carry out ring-opening reaction and generate intermediate MEPG-M11;
Step 3, under described catalyst I II exists, intermediate MEPG-M11 and epoxy compounds
carry out ring-opening reaction, generate intermediate MEPG-M12;
Step 4, under described catalyst I V exists, intermediate MEPG-M12 and second batch oxyethane carry out ring-opening reaction, generate described double bond containing alcohol ether.
Wherein, described catalyst I-IV can be identical or different, and respectively independently selected from any one above-mentioned catalyzer in second aspect of the present invention.
Described in second aspect of the present invention in preferred embodiment, compound (I-1) is preferably 1 with Styryl oxide mol ratio: 0-20, more preferably 1: 1-20, be preferably 1: 1-18, more preferably 1: 1-16, more preferably 1: 1-14, more preferably 1: 1-12, more preferably 1: 1-10, more preferably 1: 1-8, as 1: 6 or 1: 4; More preferably 1: 2-20, is preferably 1: 2-18, more preferably 1: 2-16, more preferably 1: 2-14, more preferably 1: 2-12, more preferably 1: 2-10, more preferably 1: 2-8.
Described in second aspect of the present invention in preferred embodiment, compound (I-1) and first oxyethane mol ratio are preferably 1: 0-200, be preferably 1: 0-160, be preferably 1: 0-100, be preferably 1: 0-80, be preferably 1: 0-50, more preferably 1: 1-200, more preferably 1: 1-160, more preferably 1: 1-100, as 1: 80,1: 60,1: 50 or 1: 40, more preferably 1: 2-200, more preferably 1: 2-160, more preferably 1: 2-100, as 2: 80,2: 60,2: 50 or 2: 40.
Described in second aspect of the present invention in preferred embodiment, compound (I-1) and propylene oxide mol ratio are preferably 1: 0-200, be preferably 1: 0-160, be preferably 1: 0-100, be preferably 1: 0-80, be preferably 1: 0-50, more preferably 1: 1-200, more preferably 1: 1-160, more preferably 1: 1-100, as 1: 80,1: 60,1: 50 or 1: 40, more preferably 1: 2-200, more preferably 1: 2-160, more preferably 1: 2-100, as 2: 80,2: 60,2: 50 or 2: 40.
Described in second aspect of the present invention in preferred embodiment, compound (I-1) and second batch oxyethane mol ratio are preferably 1: 0-200, be preferably 1: 0-160, be preferably 1: 0-100, be preferably 1: 0-80, be preferably 1: 0-50, more preferably 1: 1-200, more preferably 1: 1-160, more preferably 1: 1-100, as 1: 80,1: 60,1: 50 or 1: 40, more preferably 1: 2-200, more preferably 1: 2-160, more preferably 1: 2-100, as 2: 80,2: 60,2: 50 or 2: 40.
Should be understood that, when Styryl oxide, first oxyethane, propylene oxide, second batch oxyethane consumption are 0, mean and can omit described in second aspect of the present invention any one or more in the step 1-4 in embodiment, but the present invention is preferably, at least comprise in step 1-4, step 1-4 can not omit simultaneously.
Third aspect of the present invention is to provide a kind of double bond containing alcohol ether phosphate, and described alcohol ether phosphate has following structure (II) or (III):
In double bond containing alcohol ether phosphate described in third aspect of the present invention, n1, n2, n3, n4, x1, x2, x3, x4, y1, y2, y3, y4, z1, z2, z3, z4 can be 0 simultaneously, but are 0 while being preferably difference.And to be preferably in n1, n2, n3, n4 at least one be not 0(n(n=n1+n2+n3+n4) be not 0).
Preferably: n1, n2, n3, n4 can be identical or different, and be independently preferably respectively 0-10, be preferably 0-9, more preferably 0-8, more preferably 0-7, more preferably 0-6, more preferably 0-5,0-4 more preferably.
In double bond containing alcohol ether phosphate described in third aspect of the present invention, x1, x2, x3, x4 can be identical or different; Y1, y2, y3, y4 can be identical or different; Z1, z2, z3, z4 can be identical or different.
Preferably: x1, x2, x3, x4, y1, y2, y3, y4, z1, z2, z3, z4 are the integer of 0-100 respectively independently; When more preferably different, be 0; X(x=x1+x2+x3+x4 at least more preferably), y(y=y1+y2+y3+y4) be 0 when different, more preferably x, y are not all 0.
In double bond containing alcohol ether phosphate described in third aspect of the present invention, q is 0-1.
In a kind of preferred embodiment of third aspect of the present invention:
X is 0-400, is preferably 0-320, is preferably 0-200, is preferably 0-160, is preferably 0-100, be preferably 0-80, be preferably 0-50, more preferably 1-400, is preferably 1-320, is preferably 1-200, be preferably 1-160, be preferably 1-100, be preferably 1-80, be preferably 1-50; More preferably 2-400, is preferably 2-320, is preferably 2-200, is preferably 2-160, is preferably 2-100, is preferably 2-80, is preferably 2-50; More preferably 4-400, is preferably 4-320, is preferably 4-200, is preferably 4-160, is preferably 4-100, is preferably 4-80, is preferably 4-50;
Y is 0-400, is preferably 0-320, is preferably 0-200, is preferably 0-160, is preferably 0-100, be preferably 0-80, be preferably 0-50, more preferably 1-400, is preferably 1-320, is preferably 1-200, be preferably 1-160, be preferably 1-100, be preferably 1-80, be preferably 1-50; More preferably 2-400, is preferably 2-320, is preferably 2-200, is preferably 2-160, is preferably 2-100, is preferably 2-80, is preferably 2-50; More preferably 4-400, is preferably 4-320, is preferably 4-200, is preferably 4-160, is preferably 4-100, is preferably 4-80, is preferably 4-50;
Z is 0-400, is preferably 0-320, is preferably 0-200, is preferably 0-160, is preferably 0-100, be preferably 0-80, be preferably 0-50, more preferably 1-400, is preferably 1-320, is preferably 1-200, be preferably 1-160, be preferably 1-100, be preferably 1-80, be preferably 1-50; More preferably 2-400, is preferably 2-320, is preferably 2-200, is preferably 2-160, is preferably 2-100, is preferably 2-80, is preferably 2-50; More preferably 4-400, is preferably 4-320, is preferably 4-200, is preferably 4-160, is preferably 4-100, is preferably 4-80, is preferably 4-50;
N is preferably 1-40, more preferably 1-36, more preferably 1-32, more preferably 1-24, more preferably 1-20, more preferably 1-18,1-16 more preferably, more preferably 1-12,1-10 more preferably, more preferably 1-9, more preferably 1-8,1-6 more preferably, more preferably 1-5, more preferably 1-4; More preferably 2-20, more preferably 2-18,2-16 more preferably, more preferably 2-12,2-10 more preferably, more preferably 2-9, more preferably 2-8,2-6 more preferably, 2-5 more preferably, 2-4 more preferably, as 3; More preferably 4-20, more preferably 4-18,4-16 more preferably, more preferably 4-12,4-10 more preferably, more preferably 4-9, more preferably 4-8, more preferably 4-6, more preferably 4-5;
Wherein, n=n1+n2+n3+n4, x=x1+x2+x3+x4, y=y1+y2+y3+y4, z=z1+z2+z3+z4.
Should be understood that, said n, x, y, z, q can be integer or decimal, in the situation that n, x, y, z or q are decimal, described in third aspect of the present invention, double bond containing alcohol ether phosphate refers to mixture, and now n, x, y, z, q refer to the average content of relevant group in the multiple mean polymerisation degree containing monomeric unit in two key alcohol ether phosphates or each molecule.As two kinds of double bond containing alcohol ethers in the situation of n=0 and n=1 mixed according to 1: 1, n averages 0.5, and therefore, n, x, y, z, q can be the decimal between 0-1, as 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8 etc., n, x, y, z also can be greater than 1 decimal.
Similarly, one skilled in the art will appreciate that SO, EO, PO can be in molecular chain random distribution, be alternately distributed or block distributed, the present invention is preferably block distributed; And SO, EO, PO and the order of EO block on molecular chain can be adjusted, in the present invention, be preferably according to the order of SO, EO, PO and EO and distribute successively to phosphate-based one end from one end of group A and B.
In double bond containing alcohol ether phosphate described in third aspect of the present invention, M
3, M
4, M
5, M
6can be identical or different, and respectively independently selected from H, metal, described metal is preferably any one or a few the mixing being selected from potassium, sodium, calcium, barium, magnesium, iron, copper, aluminium; And be preferably any one or a few the mixing in ammonium, potassium, sodium; M
3, M
4, M
5, M
6most preferably be H.
In double bond containing alcohol ether phosphate described in third aspect of the present invention, A is double bond containing alkyl, and is preferably double bond containing C
3-C
5alkyl, described pair of key can be one or more, but in the situation of a plurality of pairs of keys, two keys are non-conterminous; Described pair of key can be positioned at or not be positioned at the end of alkyl, and is preferably and is positioned at alkyl end.
A for example as: allyl group, alkene butyl etc., more preferably allyl group.
In double bond containing alcohol ether phosphate described in third aspect of the present invention, B is C
1-C
5alkyl; Can be the alkyl of straight chain or branching, as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-etc., and be preferably methyl, ethyl, n-propyl, more preferably methyl or ethyl, more preferably ethyl.
In double bond containing alcohol ether phosphate described in third aspect of the present invention, EO is-CH
2-CH
2-O-.
In double bond containing alcohol ether phosphate described in third aspect of the present invention, PO is-CH (D)-CH (G)-O-and, D and G are H, C respectively independently
1-C
5alkyl, but be H when different; Wherein, D and G are preferably respectively H, methyl, ethyl independently, but are H when different, most preferably, PO for example as :-CH (CH
3)-CH
2-O-,-CH
2-CH (CH
3)-O-,-CH (CH
3)-CH (CH
3)-O-,-CH (C
2h
5)-CH
2-O-,-CH
2-CH (C
2h
5)-O-; And be preferably-CH (CH
3)-CH
2-O-,-CH (C
2h
5)-CH
2-O-.
In double bond containing alcohol ether phosphate described in third aspect of the present invention, SO is-CH (ph)-CH
2-O-and/or-CH
2-CH (ph)-O-, wherein, ph is phenyl; And be preferably-CH (ph)-CH
2-O-.
In double bond containing alcohol ether phosphate described in third aspect of the present invention, Y can be for H or-O-PO (OM
3) (OM
4); And be preferably-O-PO (OM
3) (OM
4) or-O-PO (OH)
2.
In a preferred embodiment of the present invention, structural formula (III) is preferably structural formula (III-1) and/or (III-2):
The 4th aspect of the present invention is to provide a kind of above-mentioned method containing two key alcohol ether phosphates of producing, and step comprises:
Step 1, provides the double bond containing alcohol ether described in first aspect of the present invention;
Step 2, described double bond containing alcohol ether and phosphatase reaction, obtain described double bond containing alcohol ether phosphate.
Wherein, in step 1, described double bond containing alcohol ether can be produced or be prepared by the method described in second aspect of the present invention.
Wherein, phosphoric acid described in step 2 can be can in reaction system, generate the material of phosphoric acid arbitrarily from phosphoric acid, phosphoric acid solution, polyphosphoric acid, phosphoric anhydride etc.
Wherein, in step 2, temperature of reaction is preferably arbitrary temp or the temperature range being controlled between 60-90 ℃, as 70 ℃, and 75 ℃, 80 ℃, 85 ℃ etc.
Wherein, in step 2, the reaction times is preferably 1-24h, 2-20h more preferably, and more preferably 4-15h, is preferably 5-12h, more preferably 6-10h.
Wherein, in step 2, reaction can be to carry out under air atmosphere or anaerobic atmosphere, and is preferably under atmosphere of inert gases and carries out.
Those skilled in the art can understand, and described rare gas element refers to the gas that does not participate in described reaction, as nitrogen, argon gas etc.
Wherein, in step 2, phosphoric acid and described double bond containing alcohol ether mol ratio are preferably 1: 0.1-3, more preferably 1: 0.5-2.5, more preferably 1: 0.8-2.In a kind of preferred embodiment aspect the 4th of the present invention, wherein, n, x, y, z are 0, and now, phosphoric acid and described double bond containing alcohol ether mol ratio are preferably 1: 0.1-3, more preferably 1: 0.5-2.5, more preferably 1: 0.75-2.
In a kind of preferred embodiment aspect the 4th of the present invention, wherein, in step 2, by the reaction product of phosphoric acid and described double bond containing alcohol ether with containing alkali aqueous solution, mix, neutralize, obtain corresponding salt.In described preferred embodiment, described can be ammoniacal liquor, aqueous sodium hydroxide solution, potassium hydroxide aqueous solution containing alkali aqueous solution.
In described N-process, temperature is preferably envrionment temperature to arbitrary temp or temperature range between the temperature of reaction in step 2, and more preferably 10-60 ℃, more preferably 20-60 ℃, 30-60 ℃ more preferably, as 40 ℃, 50 ℃.
The 5th aspect of the present invention is to provide a kind of reactive emulsifier, and described reactive emulsifier comprises:
1) double bond containing alcohol ether or its salt described in first aspect of the present invention; And/or
2) the double bond containing alcohol ether phosphate described in third aspect of the present invention or any one or a few the mixture in its salt.
In a kind of preferred embodiment of the 5th aspect of the present invention, described reactive emulsifier can comprise third aspect of the present invention structural formula (II) or (III) a kind of or its mixture in described double bond containing alcohol ether phosphate.
Embodiment
Below by specific embodiment, content of the present invention is made a more detailed description, so that better understand the present invention, but should be understood that, following embodiment does not limit the scope of the invention.
Embodiment 1
In 1000ml flask, add TriMethylolPropane(TMP) mono allyl ether 174g(1mol); sodium methylate 1g; first with under micro-nitrogen gas stream protection; add and be warmed up to 90 ℃, first methanol removal, then slowly drips Styryl oxide 2.1-2.3mol; temperature control is incubated certain hour at 90-120 ℃ after being added dropwise to complete; sampling analysis, with GC or HPLC, analyzing without epoxy styrene is terminal, obtains intermediate (MEPG-M1)
By intermediate MEPG-M1(1mol), add sodium methylate (in total amount 0.1%), add autoclave, reheat to 120 ℃, vacuumize, methanol removal, passing into nitrogen has put after air again, slowly add oxyethane to the amount 440g(10mol of regulation), reacted rear cooling, obtain the alcohol ether MEPG-M11 with two keys.
Infrared and nuclear magnetic spectrogram analytical results shows: in the present embodiment products therefrom structure: n=2.1-2.3, x=10.
Embodiment 2
In 1000ml flask, add TriMethylolPropane(TMP) mono allyl ether 174g(1mol); boron trifluoride ethyl ether complex 2g; first with under micro-nitrogen gas stream protection; add and be warmed up to 90 ℃, slowly drip Styryl oxide 2.1-2.3mol, temperature control is at 90-120 ℃; be added dropwise to complete rear insulation certain hour; sampling analysis, with GC or HPLC, analyzing without epoxy styrene is terminal, obtains intermediate (MEPG-M1).
By intermediate MEPG-M1(1mol), add sodium methylate (in total amount 0.1%), add autoclave, reheat to 120 ℃, vacuumize, then pass into nitrogen and put after air, slowly add propylene oxide to the amount 580g(10mol of regulation), react rear cooling, obtained the alcohol ether MEPG-M12 with two keys.
Infrared and nuclear magnetic spectrogram analytical results shows: in the present embodiment products therefrom structure: n=2.1-2.3, y=10.
Embodiment 3
By intermediate MEPG-M1(1mol), add sodium methylate (in total amount 0.1%), add autoclave, reheat to 120 ℃, vacuumize, first methanol removal, and then pass into nitrogen and put after air, slowly add oxyethane to the amount 176g(4mol of regulation), then switch to propylene oxide to specified amount 232g(4mol) reacted rear cooling, obtain the alcohol ether MEPG-M13 with two keys.
Infrared and nuclear magnetic spectrogram analytical results shows: in the present embodiment products therefrom structure: n=2.1-2.3, x=4, y=4.
Embodiment 4
By intermediate MEPG-M1(1mol), hydro-oxidation potassium (in total amount 0.1%), add autoclave, reheat to 120 ℃, vacuumize, first deviate from water, after qualified to moisture, and then pass into nitrogen and put after air, slowly add oxyethane to the amount 352g(8mol of regulation), then switch to propylene oxide to specified amount 580(10mol) reacted rear cooling, obtain the alcohol ether MEPG-M14 with two keys.
Infrared and nuclear magnetic spectrogram analytical results shows: in the present embodiment products therefrom structure: n=2.1-2.3, x=8, y=10.
Embodiment 5
By intermediate MEPG-M1(1mol), add sodium methylate (in total amount 0.1%), add autoclave, reheat to 120 ℃, vacuumize, first deviate from methyl alcohol, and then pass into nitrogen and put after air, slowly add oxyethane to the amount 88g(2mol of regulation), then switch to propylene oxide to specified amount 232(4mol) switch to again oxyethane to specified amount 176(4mol) reacted rear cooling, obtain the alcohol ether MEPG-M15 with two keys.
Infrared and nuclear magnetic spectrogram analytical results shows: in the present embodiment products therefrom structure: n=2.1-2.3, x=2, y=4, z=4.
Embodiment 6
By Glycerin monoene propyl ester (1mol), add sodium methylate (in total amount 0.1%), add autoclave, reheat to 120 ℃, vacuumize, first deviate from methyl alcohol, and then pass into nitrogen and put after air, slowly add oxyethane to the amount 88g(2mol of regulation), obtain the alcohol ether MEPG-M16 with two keys.
Embodiment 7
By Glycerin monoene propyl ester (1mol), add sodium methylate (in total amount 0.1%), add autoclave, reheat to 120 ℃, vacuumize, first deviate from methyl alcohol, and then pass into nitrogen and put after air, slowly add propylene oxide to the amount 116g(2mol of regulation), obtain the alcohol ether MEPG-M17 with two keys.
Embodiment 8
By Glycerin monoene propyl ester (1mol), add sodium methylate (in total amount 0.1%), add autoclave, reheat to 120 ℃, vacuumize, first deviate from methyl alcohol, and then pass into nitrogen and put after air, slowly add oxyethane to the amount 116g(2mol of regulation), and then add propylene oxide to the amount 88g(2mol of regulation), obtain the alcohol ether MEPG-M18 with two keys.
Embodiment 9
By the alcohol ether MEPG-M11(1mol of the two keys of band) be added in 1000ml reaction flask, under 50 ℃ of conditions, slowly add 45g115% phosphoric acid, and then at this temperature, add 16g phosphoric anhydride, after adding, at 70-90 ℃, be incubated 8 hours, then add 18g water, be incubated again 1 hour, then cooling, filter and double bond containing alcohol ether phosphate FP-1.
Adopt similar method, alcohol ether MEPG-M16, MEPG-M17, MEPG-M18, replacement MEPG-M11 reaction with the two keys of band, obtain respectively corresponding phosphoric acid ester FP-2, FP-3, FP-4.
FP-1, FP-2, FP-3, FP-4, in the 40-60 ℃ of aqueous solution being slowly added to containing ammonium hydroxide, are neutralized to pH value=6.5-7.5, and solid content is 24-26%, and obtaining corresponding ammonium salt is FP-1-1, FP-2-1, FP-3-1, FP-4-1.
Embodiment 10
TriMethylolPropane(TMP) monoene propyl ester 1mol, be added in 1000ml reaction flask, at 50 ℃, slowly add 55g115% phosphoric acid again, and then at this temperature, add 15g phosphoric anhydride, after adding, 70-90 ℃ of insulation 8 hours, then add 18g water, then be incubated 1 hour, then cooling, filter and corresponding phosphoric acid ester FP-5.
FP-5 to pH value=6.5-7.5, obtains the finished product FP-5-1 of 40-45% weight content with ammonia neutralization.
The emulsifier production that embodiment 1-10 is obtained carries out the letex polymerization of vinyl monomer, and step is as follows:
Step 1, in the 1000ml flask with stirring, add pre-emulsified deionized water, then add emulsifying agent FP-1-1, PS-625A, after stirring and dissolving, slowly add butyl acrylate, vinylbenzene, vinylformic acid, acrylamide with adding after water dissolution, finally by sodium bicarbonate with adding after water dissolution, pre-emulsion stirs after 0.5-1 hour standby.
Step 2, then at another in the flask with the four-hole 1000ml of stirring, condenser, dropping funnel and thermometer, adds water at the bottom of still, emulsifying agent, is warmed up to 80 ℃.Prepare the aqueous solution of ammonium persulphate simultaneously.
Step 3, when still temperature to 80 ℃, by seed at the bottom of still, be that pre-emulsion 20g adds, add initial initiator ammonium persulphate simultaneously, start reaction, at the bottom of still, emulsion has obvious blue light to occur, react after half an hour, drip pre-emulsion simultaneously and drip initiator solution, within 180 minutes, drip off, add A-171, then 80-84 ℃ of insulation 1.5 hours.Cooling, after ammonia neutralization, filters.
Polymerizing condition is as follows:
Wherein: AA is vinylformic acid, AM is acrylamide, and ST is vinylbenzene, and BA is butyl acrylate, and A-171 is vinyltrimethoxy silane, and PS-625A is alkyl alcohol Soxylat A 25-7 ammonium phosphate salt
FP-2-1, FP-3-1, FP-4-1, FP-5-1 replace FP-1-1, repeat above-mentioned test.
Result shows, the equal < 0.1g of filter residue.
Table 1, emulsion property test result in the embodiment of the present invention
Water-whitening resistance test: be coated with the about 22-25 μ of dry film m with line rod on sheet glass, 25 ℃ of temperature, be dried 24 hours, at the sheet glass back side, write No. 4 font, plate is put into pure water, observe font till the time not seeing, the time is longer, and water-whitening resistance can be better, as can be seen from Table 1, in the embodiment of the present invention, emulsion all has good water-whitening resistance.
Detected result from table 1 can find out, the emulsion that double bond containing alcohol ether phosphate provided by the present invention is prepared into, has satisfactory stability performance, stirs after 15 minutes under the speed of 5000r/min, occurs precipitation.
Above specific embodiments of the invention be have been described in detail, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and alternative also all among category of the present invention.Therefore, equalization conversion and the modification done without departing from the spirit and scope of the invention, all should contain within the scope of the invention.
Claims (11)
1. a double bond containing alcohol ether, is characterized in that, described alcohol ether has following structure (I):
Wherein:
A is double bond containing alkyl; B is C
1-C
5alkyl; M
1, M
2respectively independently selected from H or metal;
EO is-CH
2-CH
2-O-,
PO is-CH (D)-CH (G)-O-and, D and G are H, C respectively independently
1-C
5alkyl, but be H when different;
SO is-CH (ph)-CH
2-O-and/or-CH
2-CH (ph)-O-, ph is phenyl,
X1, y1, x2, y2, z1, z2 are the numerical value between 0-100 respectively independently, and n1, n2 are the numerical value between 0-10.
2. double bond containing alcohol ether according to claim 1, is characterized in that, A is C
3-C
5alkyl.
3. double bond containing alcohol ether according to claim 2, is characterized in that, A is allyl group.
4. double bond containing alcohol ether according to claim 1, is characterized in that, B is selected from methyl, ethyl, n-propyl.
5. double bond containing alcohol ether according to claim 1, is characterized in that, D and G be respectively independently selected from H, methyl, ethyl, but is H when different.
6. a production method for double bond containing alcohol ether as claimed in claim 1, is characterized in that, step comprises:
The described compound of structural formula (I-1) of take is raw material, under catalyst action, according to predetermined order of addition(of ingredients), adds epoxy compounds to react, and obtains double bond containing alcohol ether described in claim 1; Wherein, described epoxy compounds is selected from: Styryl oxide, oxyethane, epoxy compounds
in any one or a few;
Wherein, A, B, D, G are all identical with implication described in claim 1.
7. a double bond containing alcohol ether phosphate, is characterized in that, described alcohol ether phosphate has following structure (II) or (III):
Wherein:
A is double bond containing alkyl; B is C
1-C
5alkyl; Y be H or-O-PO (OM
3) (OM
4); M
3, M
4, M
5, M
6respectively independently selected from H, metal;
EO is-CH
2-CH
2-O-;
PO is-CH (D)-CH (G)-O-and, D and G are H, C respectively independently
1-C
5alkyl, but be H when different;
SO is-CH (ph)-CH
2-O-and/or-CH
2-CH (ph)-O-, ph is phenyl;
X1, y1, z1, x2, y2, z2, x3, y3, z3, x4, y4, z4 are 0-100 respectively independently;
N1, n2, n3, n4 are 0-10;
Q is 0-1.
8. double bond containing alcohol ether phosphate according to claim 7, is characterized in that, described Y is-O-PO (OM
3) (OM
4), or q is 1.
9. a method of producing double bond containing alcohol ether phosphate as claimed in claim 7, is characterized in that, step comprises:
Step 1, provides double bond containing alcohol ether as claimed in claim 1;
Step 2, described double bond containing alcohol ether and phosphatase reaction, obtain double bond containing alcohol ether phosphate claimed in claim 7.
10. method according to claim 9, is characterized in that, reaction described in step 2, and temperature remains on arbitrary temp or the temperature range between 60-90 ℃.
11. 1 kinds of reactive emulsifiers, is characterized in that, comprise double bond containing alcohol ether claimed in claim 1 or its salt, and/or comprise any one or a few the mixture in double bond containing alcohol ether phosphate claimed in claim 7 or its salt.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193782A (en) * | 2014-08-15 | 2014-12-10 | 上海优创化学品有限公司 | Double bond-containing organic phosphate compound as well as preparation method and application thereof |
| CN104193782B (en) * | 2014-08-15 | 2017-01-04 | 上海优创化学品有限公司 | Double bond containing phosphate compound and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4156667A (en) * | 1977-02-28 | 1979-05-29 | Scm Corporation | Aqueous polyester coatings |
| EP0244841A2 (en) * | 1986-05-07 | 1987-11-11 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Surface active compounds having a polymerizable moiety |
| US20020123588A1 (en) * | 2000-03-31 | 2002-09-05 | Herve Adam | Polymerizable compounds and use thereof |
-
2013
- 2013-10-09 CN CN201310468589.3A patent/CN103554470B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4156667A (en) * | 1977-02-28 | 1979-05-29 | Scm Corporation | Aqueous polyester coatings |
| EP0244841A2 (en) * | 1986-05-07 | 1987-11-11 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Surface active compounds having a polymerizable moiety |
| US20020123588A1 (en) * | 2000-03-31 | 2002-09-05 | Herve Adam | Polymerizable compounds and use thereof |
Non-Patent Citations (1)
| Title |
|---|
| ZHONGYU，ET AL: "A facile synthesis of branched poly(ethylene glycol) and its heterobifunctional derivatives", 《POLYMER CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193782A (en) * | 2014-08-15 | 2014-12-10 | 上海优创化学品有限公司 | Double bond-containing organic phosphate compound as well as preparation method and application thereof |
| CN104193782B (en) * | 2014-08-15 | 2017-01-04 | 上海优创化学品有限公司 | Double bond containing phosphate compound and its preparation method and application |
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