CN107474236A - A kind of reactive emulsifier, its preparation method and application - Google Patents
A kind of reactive emulsifier, its preparation method and application Download PDFInfo
- Publication number
- CN107474236A CN107474236A CN201710548582.0A CN201710548582A CN107474236A CN 107474236 A CN107474236 A CN 107474236A CN 201710548582 A CN201710548582 A CN 201710548582A CN 107474236 A CN107474236 A CN 107474236A
- Authority
- CN
- China
- Prior art keywords
- emulsifying agent
- reaction
- emulsion
- compound
- reactive emulsifier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 C*(NON)O*(C)OC(C)(C)* Chemical compound C*(NON)O*(C)OC(C)(C)* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
- C08G65/2624—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention discloses a kind of reactive emulsifier, its preparation method and application for emulsion polymerization, and it includes the compound as shown in formula (I) and/or formula (II)：
Description
Technical field
The invention belongs to surfactant field, and in particular to a kind of emulsion polymerization high response emulsifying agent and its preparation
Method.
Background technology
Emulsion polymerization is to prepare the conventional means of HMW, aqueous polymer dispersions, and resulting polymers emulsion is extensive
Applied to industrial circles such as building inside and outside wall coating, adhesive, paper sizing agent.Emulsifying agent refers to make emulsion stable
Surfactant, it is widely used in the industries such as food, commodity, chemical industry.In emulsion polymerization process, the main function of emulsifying agent
It is the place that nucleation, reaction and growth are provided for polymer particle, stable non-homogeneous polymerization process, and ensure product emulsion
Dispersion stabilization in storage, transportation.But during polymer emulsion film forming, because emulsifier molecules physics is inhaled
Polymer particle surface is invested, with the migration in the volatilization and wet film of moisture, emulsifier molecules can be from polymer particle surface
Desorption, enrichment region is internally formed either with water translocation to film and the interface of base material or air in polymer coating film, right
The performances such as the water-fast and attachment of film adversely affect.
Reactive emulsifier refers to have on emulsifier molecules and can gathered with the unsaturated double-bond of monomer reaction in emulsion
During conjunction, emulsifying agent absorption provides colloid-stabilised effect on polymer particle surface, at the same the double bond on emulsifier molecules with
Monomer is copolymerized, and emulsifier molecules chemistry is anchored in into particle surface.In follow-up film forming procedure, emulsifier molecules are just not
Physics desorption can occur with moisture evaporation and gather, the water resistance of film also can be lifted effectively.Patent document CN
This is disclosed in 200580021149.7, CN 01822897.6, CN 201280051789.2, CN 201380003074.4
A kind of emulsifying agent structure.The hydrophobic side absorption of such emulsifier molecules is on polymer particle surface, and water-wet side stretches to aqueous phase
So as to provide electric charge or steric stabilization, the content of unsaturated double-bond determines that it is effective with monomer reaction in emulsifying agent
Property, the compound containing reactive double bond is more in emulsifying agent, and the emulsifying agent that dissociates in later stage emulsion film forming is fewer, polymer emulsion
Film forming water resistance it is better.
Existing reactive emulsifier, in order that unsaturated double-bond is in the hydrophobic side of emulsifier molecules, generally use is not
Saturated alkyl fatty alcohol reacts with the glycidyl ether compound with unsaturated double-bond, or uses allyl halide and benzene
Vinylation phenol reactant, hydrophobic alkyl chain is combined with unsaturated double-bond.Such method is required to use base catalyst
And higher reaction temperature, cause inevitable double bond to be lost；Consider further that follow-up possible alkoxide, sulphation or
Phosphorylation etc. is reacted, and effective double bond content of reactive emulsifier can be reduced further, causes the reduction of product reactivity.With
The raising and the increase of market usage amount that market is water-fast to product, weather resistance requires, the film forming water resistance of polymer emulsion
Higher requirement is it is also proposed, and water resistance decline problem caused by one of its key technical problem emulsifying agent is also urgently to be resolved hurrily,
Continual exploitation, which goes out performance, more to be had, the New-type emulsifier suitable for commercial Application.
The content of the invention
It is an object of the invention to solve the above problems, there is provided and a kind of high response emulsifying agent, its double bond retention rate is high, and
Process conditions are gentle, simple to operate, are adapted to industrialized production.
First aspect present invention, there is provided a kind of high response emulsifying agent, it includes structure shown in formula (I) and/or formula (II)
Compound：
Wherein, R1For the combination of the alkyl of 4~30 carbon atoms, alkyl phenyl, alkoxy or above-mentioned group；It is preferred that 8
The alkyl of~16 carbon atoms, such as the octyl group of straight chain or branched structure, 2- ethylhexyls, nonyl, Zhong Renji, decyl, 11
Alkyl, dodecyl, tridecyl, myristyl, cetyl etc..
R2、R3It is independently selected from hydrogen atom or methyl, preferably hydrogen atom.
Wherein, AO is optionally from the alkoxy of 2~4 carbon numbers；(AO)m(AO)nCarried out for multiple oxyalkylene units
The group that addition polymerization is formed, such as any one in oxirane, expoxy propane or epoxy butane or several mixing
The unit that thing addition is formed, the AO in each unit may be the same or different addition polymerization mode and do not limit, can be it is random altogether
Poly- or block copolymerization.；M, n is independently selected from 1~30 integer, preferably 3~20 integer, more selects 5
~10 integer；Wherein, the molar ratio of ethyoxyl is 70~100%, preferably 90~100% in AO, is mainly based upon water
The consideration of dissolubility and emulsifying agent cloud point.
X is for hydrogen atom or selected from-SO3M、-COOM、-PO3M2、-PO3MH or-CO-R4- COOM represents hydrophilic
Property anionic group, wherein M represents hydrogen atom, alkali metal atom, alkaline earth metal atom, ammonium residue or alkanolamine residue, R4Table
Show the residue of binary acid or acid anhydrides.
It will be appreciated by those skilled in the art that when X is alkali metal salt, alkali salt, ammonium salt, or the salt of alkanolamine residue
When, i.e., it is-SO including it3H、-COOH、-PO3H2Or-CO-R4The anion that one or more levels ionization of-COOH group is formed
The group formed with cations such as alkali metal ion, alkaline-earth metal ions, ammonium ion, alkanolamine ions.According to it is above-mentioned from
The charge number of son, both including 1 molecular formula-SO3H、-COOH、-PO3H2Or-CO-R4The salt that-COOH is formed with 1 cation,
Also the salt that the above-mentioned group of polymolecular and 1 cation are formed, and the above-mentioned group of 1 molecule and the formation of multiple cations are included
Salt.
Second aspect of the present invention, there is provided a kind of preparation method of high response emulsifying agent, comprise the following steps：
(1) fat primary amine carries out ring-opening reaction with the glycidyl ether compound with unsaturated double-bond, obtains containing formula
(A) and compound shown in formula (B) intermediate；
Wherein, R1For the combination of the alkyl of 4~30 carbon atoms, alkyl phenyl, alkoxy or above-mentioned group, preferably 8
The alkyl of~16 carbon atoms, such as the octyl group of straight chain or branched structure, 2- ethylhexyls, nonyl, Zhong Renji, decyl, 11
Alkyl, dodecyl, tridecyl, myristyl, cetyl etc..
R2、R3It is independently selected from hydrogen atom or methyl, preferably hydrogen atom.
(2) gained intermediate carries out alkoxylate with epoxyalkane in step (1), obtains including formula (I) and formula (II) institute
Show the emulsifying agent of compound.
In the step (1), fat primary amine reacts with the glycidyl ether compound with unsaturated double-bond, is primary first
Amine groups obtain compound (A) with epoxide group reaction generation secondary amine group and hydroxyl, then secondary amine group and glycidol ether
Compound reaction generation tertiary amine group and hydroxyl obtain compound (B).By adjusting fat primary amine and glycidyl ether compound
Ratio, thus it is possible to vary the content of compound (A) and compound (B) in intermediate obtained by step (1), and then change step (2)
Compound (I) and the content of (II) in emulsifying agent.
Fat primary amine and glycidol ether mol ratio are 1/0.7~1/2.3, preferably 1/1.0~1/ in the step (1)
2.1, more preferably 1/1.05~1/2.0.Reaction equation shown in step (1) is only to illustrate reaction mechanism, does not represent real reaction product
Ratio.
Preferably, reaction temperature is 0~150 DEG C in step (1), and reaction pressure is the MPa of normal pressure~2.0, and the reaction time is
1~10 hour；Fat primary amine can be used to be added to the charging sequence in glycidyl ether compound, vice versa.For ease of
Control course of reaction and suppress the reaction of hydroxyl and glycidyl ether compound, further preferably, reaction temperature is 30~90 DEG C,
Reaction pressure is normal pressure~1.0MPa, and the reaction time is 4~8 hours, and fat primary amine is added to using glycidyl ether compound
In charging sequence.
As example, with unsaturated double described in primary amine of the fat primary amine preferably with 8~16 carbon atom alkyls
The preferred allyl glycidyl ether of glycidyl ether compound (AGE) of key.
Epoxyalkane in the step (2) is any one or a few in the oxyalkylene containing 2~4 carbon atoms
It is any or several in mixture, such as oxirane, expoxy propane or epoxy butane；The product formula (I) of formation and (II)
AO in compound is the alkoxy of 2~4 carbon numbers, (AO)m(AO)nAddition is carried out for multiple oxyalkylene units to gather
Close and formed, the AO in each unit may be the same or different, and addition polymerization mode does not limit, and can be random copolymerization, can also
It is block copolymerization.The molar content ratio of ethyoxyl is 70~100%, preferably 90~100% in AO, is mainly based upon water-soluble
The consideration of property and emulsifying agent cloud point；Wherein, m, n are identical or different, optionally from 1~30 integer, preferably 3~20 integer,
More preferably 5~10 integer.
In step (2), the active group of compound (A) reaction is respectively secondary amine group and hydroxyl, the difference of reactivity
It is likely to result in extent of alkoxylation and the difference of oxyalkyl units number.The active group of alkoxylation is in formula (B)
Symmetrical hydroxyl, extent of alkoxylation and oxyalkyl units number are believed that essentially identical.Its reaction mechanism is as follows：
Wherein, → represent that the active group of alkoxylation can be carried out.
Wherein, AO is-CH (R6)CH2O-, R6For hydrogen, methyl or ethyl.
Preferably, in step (2), the temperature of alkoxylation is 0~150 DEG C, and reaction pressure is normal pressure~2.0MPa,
Reaction time is 1~10 hour；Catalyst does not limit clearly, can be the general catalysis for epoxyalkane ring-opening reaction
Agent, such as potassium hydroxide, sodium hydroxide, sodium methoxide, sodium hydrogen, aluminium chloride, barium chloride, boron trifluoride or quaternary ammonium salt etc..Reaction
Condition can the molecular weight of product and oxyalkylene raw material as requested, be adjusted with reference to existing literature.
The present invention optionally further can carry out the reaction such as sulphation or phosphorylation to gained emulsifying agent in step (2) and obtain
Derivative anionic reactive emulsifying agent, preparation method refer to the progress of prior art literature conventional method.Obtain formula (I) and/
The emulsifying agent of formula (II) compound structure.
Reactive emulsifier of the present invention, the X in formula (I) and (II) is for hydrogen atom or with-SO3M、-COOM、-
PO3M2、-PO3MH or-CO-R4The hydrophilic anions group that-COOM is represented.X selection depends on the emulsification finally needed
Agent type, non-ionic reaction emulsifying agent selection hydrogen atom, anionic reactive emulsifying agent then can be optionally to institute in step (2)
Obtain non-ionic reaction emulsifying agent and carry out the reactions such as sulphation, phosphorylation or esterification acquisition.Wherein, M represents hydrogen atom, alkali gold
Belong to atom, alkaline earth metal atom, ammonium residue or alkanolamine residue, the selection depending on reaction reagent used and neutralization reagent.Alkali
Metallic atom such as lithium, sodium or potassium, alkaline earth metal atom such as magnesium or calcium, or ammonium or alkanolamine residue；Ammonium residue includes ammonia
The ammonium or alkylamine of water, such as monomethyl amine or the ammonium of dipropylamine etc.；Alkanolamine residue includes MEA residue, diethanol
Amine residue and triethanolamine residue etc..R4Represent the residue of binary acid or acid anhydrides, for example, the residue of phthalic acid, to benzene two
The residue of formic acid, the residue of maleic anhydride, the residue etc. of phthalic anhydride.As example, non-ionic reaction emulsifying agent, X
For hydrogen atom；Anionic reactive emulsifying agent, X preferably-SO3M。
As example, to reactive emulsifier introducing-SO of the present invention3During M groups, the sulfur acidizing reagent that can select
There is SO3, oleum, sulfuric acid, aqueous sulfuric acid, sulfamic acid, chlorosulfonic acid etc., reaction temperature is 0~150 DEG C, reaction pressure
For normal pressure~2.0MPa, the reaction time is 1~10 hour, can add retarder thinner or catalyst, such as ammonia as needed
Base sulfonic acid technique needs to add urea as catalyst.In the case that M is hydrogen atom in the reaction product, neutralization reagent can select
Select sodium hydroxide, potassium hydroxide, ammoniacal liquor, MEA, diethanol amine, triethanolamine or alkylamine (such as AMP-95) etc..
For sulphation anionic reactive emulsifying agent, M is preferably amine residue, i.e.-SO3NH4。
To the anionic reactive emulsifying agent introducing-PO3M2With-PO3During MH groups, the phosphorylation agent that can select
There are phosphorus pentoxide, polyphosphoric acid, orthophosphoric acid, phosphorous oxychloride etc., reaction temperature is room temperature~150 DEG C, and reaction pressure is normal pressure,
Reaction time is 1~10 hour.In the case that M in reaction product is hydrogen atom, neutralization reagent can select hydroxide
Sodium, potassium hydroxide, ammoniacal liquor, MEA, diethanol amine, triethanolamine or alkylamine (such as AMP-95) etc..For phosphoric acid
Change anionic reactive type emulsifying agent, M is preferably Na or K atoms.
The present invention also provides a kind of intermediate, including compound (A) and/or compound (B)：
Present invention also offers a kind of intermediate for including compound (A) and compound (B) to prepare high response emulsification
Application in agent.
Present invention also offers the compound of structure shown in formula (I) and/or formula (II) as emulsifying agent, in emulsion polymerization
Application；And/or application of the preparation method of reactive emulsifier in emulsion polymerization.
Reactive emulsifier of the present invention is mainly used in aqueous emulsion polymerization, and wherein non-ionic reaction emulsifying agent can be with
Conventional anion emulsifying agent is used cooperatively, and anionic reactive emulsifying agent can be used alone or match somebody with somebody with non-ionic reaction emulsifying agent
Close and use.Reactive emulsifier of the present invention can be used in acrylic acid ester emulsion, phenylethylene ethylene/propenoic acid ester emulsion, acetic acid
Vinyl acetate emulsion, SBR (phenylethylene/butadiene) emulsion, ABS (acrylonitrile/butadiene/styrene) emulsion, BR (butadiene) breasts
The emulsion polymerization systems such as liquid, IR (isobutene) emulsion, NBR (acrylonitrile/butadiene) emulsion.Applicable polymerized monomer is included but not
It is limited to：Acrylic acid, methyl acrylate, butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, acrylonitrile, acryloyl
Amine, hydroxy-ethyl acrylate, styrene, divinylbenzene, vinyl acetate, vinyl chloride, dichloroethylene, butadiene, isoprene, chlorine
Butadiene, ethene, maleic anhydride, itaconic acid etc..Its usage amount is monomer adds quality in emulsion 0.2%~20%, preferably
For 0.5%~5.0%.
Compared with prior art, the present invention has the advantages that：
(1) there are double hydrophilic segments to construct in reactive emulsifier molecular structure of the invention, fully ensures that emulsifying agent
Emulsion-stabilizing function, and double bond content is high, reactivity is high, enables emulsifying agent more efficiently and polymerized monomer is reacted, so as to
Make resulting polymers emulsion that there is more excellent stability and film forming water resistance；
(2) unsaturated double-bond is in hydrophobic side in reactive emulsifier molecule of the invention, is more beneficial for itself and monomer
Copolymerization, so as to which emulsifier molecules are anchored in into particle surface, in polymer emulsion film forming procedure, be not susceptible to physics desorption and
Gather, be greatly improved the water resistance of film；
(3) reactive emulsifier provided by the present invention can select to be prepared into non-ionic reaction breast according to the actual requirements
Agent or anionic reactive emulsifying agent, so as to adapt to the use of different condition and occasion, and it can be used alone or anti-with other
Answering property emulsifying agent is used cooperatively, and adaptability is good, is widely used；
(4) reactive emulsifier of the invention uses fat primary amine and unsaturated glycidyl ether as raw material, in reaction not
Needing highly basic, reaction condition is gentle, substantially increases double bond retention rate as catalyst；And it is simple to operate, can be according to actual production
Product demand adjusts material rate, and condition is easily-controllable, environment-friendly, and no three industrial wastes produce, and is adapted to industrialized production.
Embodiment
General formula compound of the present invention and its preparation method and application is done further below in conjunction with specific embodiment
Detailed description.The following example is merely illustrative the ground description and interpretation present invention, and is not necessarily to be construed as protecting the present invention
The limitation of scope.In the range of all technologies realized based on the above of the present invention are encompassed by it is contemplated that protecting.
Unless otherwise indicated, the raw material and reagent used in following examples is commercial goods, or can be by
It is prepared by perception method.Unless otherwise specified, otherwise " % " in terms of mass fraction.
Intermediate prepares and performance test
Embodiment 1：
Using cocounut oil primary amine (C12/14 primary amine,C) reacted with allyl glycidyl ether, reaction pressure is
The molar ratio example of normal pressure, cocounut oil primary amine and allyl glycidyl ether is 1/1.05, and the mole of cocounut oil primary amine can basisThe amine value index (272~285mgKOH/g) or actual measurement amine value of C products calculate.
Weigh 200g moisture content it is up to standard (<1000ppm)C cocounut oil primary amine (surveys total amine value 275mgKOH/g)
Into reactor, under nitrogen protection, stirring is warming up to 30 DEG C.Allyl glycidyl ether is slowly added dropwise into reactor to be total to
117.56g, it is added dropwise in 1 hour, continues stirring 7 hours, cool, be sampled as 1-1# samples.
Embodiment 2：
The molar ratio example of the method for reference implementation example 1, cocounut oil primary amine and allyl glycidyl ether is 1/1.05.Claim
Taking cocounut oil primary amine, stirred under nitrogen atmosphere is warming up to 90 DEG C into reactor.It is sweet that allyl glycidyl is slowly added dropwise into reactor
Oily ether, it is added dropwise in 1 hour, continues stirring 3 hours, cool, be sampled as 1-2# samples.
According to the ingredient proportion of cocounut oil primary amine and allyl glycidyl ether in embodiment 1 and embodiment 2, gained 1-1# samples
Product and 1-2# samples mainly by following formula (A-1) structure compound group into,
Wherein R1The alkyl of predominantly 8~16 carbon atoms, this is due to that the fat primary amine raw material comes from natural coconut oil
Fat.
Embodiment 3：
The molar ratio example of the method for reference implementation example 1, cocounut oil primary amine and allyl glycidyl ether is 1/2.0.Claim
Taking cocounut oil primary amine, stirred under nitrogen atmosphere is warming up to 30 DEG C into reactor.It is sweet that allyl glycidyl is slowly added dropwise into reactor
Oily ether, it is added dropwise in 2 hours, continues stirring 6 hours, cool, be sampled as 1-3# samples.
According to the ingredient proportion of cocounut oil primary amine and allyl glycidyl ether in embodiment 3, gained 1-3# samples mainly by
Formula (B-1) structural compounds form,
Wherein R1The alkyl of predominantly 8~16 carbon atoms.
Embodiment 4：
As control sample, using C12/14 natural fatty alcohols (CAS No.80206-82-2) and allyl glycidol
Ether reacts, and the molar ratio example of C12/14 natural fatty alcohols and allyl glycidyl ether is 1/1.05, wherein C12/14 alcohol
Mole can according to actual measurement hydroxyl value calculate.
200g C12/14 alcohol (actual measurement hydroxyl value 288mgKOH/g) is weighed into reactor, adds 0.6g potassium hydroxide, heating
To 100 DEG C, dehydration 1 hour to moisture content it is up to standard (<1000ppm), continue to be warming up to 140 DEG C under nitrogen protection, slowly to reaction
The common 123.12g of allyl glycidyl ether is added dropwise in kettle, is added dropwise in 1 hour, continues stirring 3 hours, cools, is sampled as 1-
4# samples.
According to the ingredient proportion of fatty alcohol and allyl glycidyl ether in embodiment 4, gained 1-4# samples are mainly under
Formula (C-1) compound group into,
Wherein R5The alkyl of predominantly 8~16 carbon atoms, this is due to that the fatty raw polyol comes from natural coconut grease.
Use the reaction of H-NMR determination samples 1-1#, 1-2#, 1-3# and comparative sample 1-4# allyl glycidyl ether
The double bond retention rate of rate and product, as a result as shown in table 1.
The reactivity of the allyl glycidyl ether of table 1 and the double bond retention rate of product
From upper table result, fatty alcohol is significantly lower than using the temperature of fat primary amine and allyl glycidyl ether reaction
Make the condition of the reaction of raw material, products obtained therefrom relative to comparative sample 1-4# there is higher reaction conversion ratio and double bond to retain
Rate.
Nonionic emulsifier prepares and performance test
Embodiment 5：
Alkoxide reaction is carried out to the gained sample 1-1# of embodiment 1, the temperature of alkoxylation is 140 DEG C, reaction pressure
Power is 0.4MPa, and the reaction time is about 4 hours, adds the potassium hydroxide for accounting for 1-1# sample qualities 0.3% as catalyst.1-
The molar ratio example of 1# samples and oxirane is 1/15.
Take 200g 1-1# samples to be placed in reactor, add 0.6g potassium hydroxide and stir, be warming up to 85 DEG C and start to be dehydrated
1 hour, after moisture content is up to standard, 140 DEG C are continuously heating under nitrogen protection, oxirane is slowly added into reactor
408.24g, cure constant to pressure and ensure that total reaction time is 4 hours, obtain 2-1# samples.
According to the ingredient proportion of 1-1# samples and oxirane in embodiment 5, gained 2-1# samples are mainly by formula
Compound group into,
Wherein R1The alkyl of predominantly 8~16 carbon atoms；M and n is integer, and it adds and equal to 15.
Embodiment 6：
The method of reference implementation example 5, alkoxide reaction, 1-1# samples and epoxy are carried out to the gained sample 1-1# of embodiment 1
The molar ratio example of ethane is 1/20.
Take 200g 1-1# to be placed in reactor, add 0.6g potassium hydroxide and stir, be warming up to 85 DEG C and start to be dehydrated
1 hour, after moisture content is up to standard, 140 DEG C are continuously heating under nitrogen protection, oxirane is slowly added into reactor
544.33g, guarantee total reaction time followed by aging is 4 hours, obtains 2-2# samples.According to 1-1# samples and ring in embodiment 6
The ingredient proportion of oxidative ethane, gained 2-2# samples mainly by formula compound group into：
Wherein R1The alkyl of predominantly 8~16 carbon atoms；M and n is integer, and it adds and equal to 20.
Embodiment 7：
The method of reference implementation example 5, alkoxide reaction, 1-2# samples and epoxy are carried out to the gained sample 1-2# of embodiment 2
The molar ratio example of ethane is 1/15.
Take 250g 1-2# to be placed in reactor, add 0.6g potassium hydroxide and stir.85 DEG C are warming up to start to be dehydrated
1 hour, after moisture content is up to standard, 0.4MPa is forced under nitrogen protection, is warming up to 140 DEG C, epoxy is slowly added into reactor
Ethane 510.31g, guarantee total reaction time followed by aging is 4 hours or so, obtains 2-3# samples.
According to the ingredient proportion of 1-2# samples and oxirane in embodiment 7, gained 2-3# samples are mainly tied by formula (I-1)
Structure compound group into.
Embodiment 8：
The method of reference implementation example 5, alkoxide reaction, 1-3# samples and epoxy are carried out to the gained sample 1-3# of embodiment 3
The molar ratio example of ethane is 1/15.
Take 250g 1-3# to be placed in reactor, add 0.6g potassium hydroxide and stir.85 DEG C are warming up to start to be dehydrated
1 hour, after moisture content is up to standard, pressurize under nitrogen protection, be warming up to 140 DEG C, oxirane is slowly added into reactor
382.26g, guarantee total reaction time followed by aging is 4 hours, obtains 2-4# samples.
According to the ingredient proportion of 1-3# samples and oxirane in embodiment 8, gained 2-4# samples are mainly by formula
Compound group into：
Wherein R1The alkyl of predominantly 8~16 carbon atoms；The integer that m is about 7~8.
Embodiment 9：
The method of reference implementation example 5, alkoxide reaction, 1-4# samples and epoxy are carried out to the gained sample 1-4# of embodiment 4
The molar ratio example of ethane is 1/15.
Take 250g 1-4# to be placed in reactor, be warming up to 85 DEG C and start dehydration 1 hour, after moisture content is up to standard, protected in nitrogen
Under be warming up to 140 DEG C, oxirane 525.24g is slowly added into reactor, guarantee total reaction time followed by aging is 4 small
When, obtain 2-5# samples.
According to the ingredient proportion of 1-4# samples and oxirane in embodiment 9, gained 2-5# samples are mainly by formula
Compound group into：
Wherein R5The alkyl of predominantly 8~16 carbon atoms；M is about 15.
Using the double bond retention rate of H-NMR measure products, comparative sample 2-1#, 2-2#, 2-3#, 2-4# and comparative sample 2-
5# double bond retention rate, as a result as shown in table 2.As can be seen from the table, emulsifying agent double bond retention rate obtained by the inventive method is bright
It is aobvious to be higher than comparative sample 2-5#.
The double bond retention rate of the alkoxylation products of table 2
Anion emulsifier prepares and performance test experiment
Embodiment 10：
Sulfating reaction is carried out to the gained sample 2-2# of embodiment 6, the hydroxyl of emulsifying agent end is converted into sulfate, made
It turns into anion emulsifier.
150g 2-2# samples and 1.6g urea is added in reaction bulb, 100 DEG C is heated under nitrogen protection, then divides 3
Secondary addition 12.3g sulfamic acids, continue stirring 4 hours.Cooling, filter after adding ethanol stirring, had after filtrate revolving
The anionic reactive emulsifying agent 3-1# products of ammonium residue.
Gained 3-1# samples are mainly made up of following structural compounds：
Wherein R1The alkyl of predominantly 8~16 carbon atoms；M and n is integer, and it adds and equal to 20.
Embodiment 11：
The method of reference implementation example 10, sulfating reaction is carried out to the gained sample 2-3# of embodiment 7, by emulsifying agent end
Hydroxyl is converted into sulfate, becomes anion emulsifier.
100g 2-3# samples and 1.1g urea is added in reaction bulb, 80 DEG C is heated under nitrogen protection, then divides 3 times
10.1g sulfamic acids are added, continue stirring 4 hours.Cooling, filtered after adding ethanol, there must be amine residue after filtrate revolving
Anionic reactive emulsifying agent 3-2# products.
Gained 3-2# samples are mainly made up of following structural compounds：
Wherein R1The alkyl of predominantly 8~16 carbon atoms；M and n is integer, and it adds and equal to 15.
Embodiment 12：
The method of reference implementation example 10, sulfating reaction is carried out to the gained sample 2-4# of embodiment 8, by emulsifying agent end
Hydroxyl is converted into sulfate, becomes anion emulsifier.
200g 2-4# samples and 2.2g urea is added in reaction bulb, 80 DEG C is heated under nitrogen protection, then divides 3 times
20.5g sulfamic acids are added, continue stirring 4 hours.Cooling, filter, can be obtained after filtrate revolving residual with amine after adding ethanol
The anionic reactive emulsifying agent 3-3# products of base.
Gained 3-3# samples are mainly made up of following structural compounds：
Wherein R1The alkyl of predominantly 8~16 carbon atoms；The integer that m is about 7~8.
Embodiment 13：
Sulfating reaction is carried out to the gained sample 2-3# of embodiment 7, the hydroxyl of emulsifying agent end is converted into sulfate, made
It turns into anion emulsifier.
150g 2-3# samples are added in reaction bulb, nitrogen protection is lower carry out ice-water bath make reaction temperature maintain 0~
5 DEG C, 36.3g chlorosulfonic acids are then added dropwise into system, continue stirring 4 hours.Added after end in sodium hydrate aqueous solution progress
With can obtain the anionic reactive emulsifying agent 3-4# products of sodium sulphate end group.
Gained 3-4# samples are mainly made up of following structural compounds：
Wherein R1The alkyl of predominantly 8~16 carbon atoms；M and n is integer, and it adds and equal to 15.
Embodiment 14：
The method of reference implementation example 10, sulfating reaction is carried out to the gained sample 2-5# of embodiment 9, by emulsifying agent end
Hydroxyl is converted into sulfate, becomes anion emulsifier.
200g 2-5# samples and 2.2g urea is added in reaction bulb, 80 DEG C is heated under nitrogen protection, then divides 3 times
20.5g sulfamic acids are added, continue stirring 4 hours.Cooling, filter, can be obtained after filtrate revolving residual with amine after adding ethanol
The anionic reactive emulsifying agent 3-5# products of base.
Gained 3-5# samples are mainly made up of following structural compounds：
Wherein R5The alkyl of predominantly 8~16 carbon atoms；M is about 15.
Embodiment 15：
Phosphorylation reaction is carried out to the gained sample 2-3# of embodiment 7, the hydroxyl of emulsifying agent end is converted into phosphate, made
It turns into anion emulsifier.
200g 2-3# samples are added in reaction bulb, 40 DEG C is warming up under nitrogen protection, then adds by several times into system
Enter 23.6g phosphorus pentoxides, be warming up to 80 DEG C and continue stirring 4 hours.Sodium hydrate aqueous solution is added after end to be neutralized, can
The anionic reactive emulsifying agent 3-6# products of sodium phosphate end group are obtained, are the mixture of phosphate monoester and phosphate diester.
Use H-NMR determination samples 3-1#, 3-2#, 3-3# and comparative sample 3-5# double bond retention rate and sulfonation degree, knot
Fruit is as shown in table 3.From result, emulsifying agent sample of the invention has higher double bond retention rate relative to sample 3-5#.
The double bond retention rate and sulfonation degree of the sulphation of table 3 and Phosphorylated products
<Emulsion polymerization example>
Fully to examine or check application of the high response emulsifying agent of the present invention in emulsion polymerization and polymer emulsion product
Advantage, carry out stable emulsion polymerisation using reactive emulsifier involved in the present invention, and with conventional non-reacted emulsifying agent
It is compared.Water-white property, the water absorption rate of main examination emulsion polymerization process stability, slag yield and emulsion film forming.
Conventional non-reacted emulsifying agent is from lauryl sodium sulfate (K-12) and the C12/14 natural fatty alcohols of 9 EO numbers
The emulsifier combination of ether (AEO-9).Because non-ionic reaction emulsifying agent is difficult to be used alone to stable emulsion polymerization, in embodiment
It is middle to substitute C12/14 natural fats alcohol ether (AEO-9) using non-ionic reaction emulsifying agent, with lauryl sodium sulfate (K-12)
It is applied in combination.
Embodiment 16：
Using Styrene-Acrylate Emulsion Polymerization system, emulsion solid content 47.75%, emulsion polymer is calculated according to Fox equations
Glass transition temperature is 3.9 DEG C, and the total usage amount of emulsifying agent accounts for the 1.34% of monomer mass.
1.67g lauryl sodium sulfate, 1.67g AEO-9 are weighed, is dissolved in 122.03g deionized waters and is made
Emulsifier aqueous solution.Weigh 181.67g butyl acrylates, 155.72g methyl methacrylates, 5.19g metering systems simultaneously
Acid, 3.11g hydroxy-ethyl acrylates and 25.95g styrene, it is well mixed, it is water-soluble is added slowly with stirring foregoing emulsifying agent
In liquid, the pre-emulsion of monomer is made.
Weigh 1.04g ammonium persulfates and be dissolved in 10.38g deionized waters, initiator solution is made.
Add in the reaction vessel for possessing reflux condensing tube, thermometer, mechanical agitation and peristaltic pump, syringe pump feed arrangement
Enter stirring and dissolving under 254.45g deionized waters, 0.83g lauryl sodium sulfate, 0.83g AEO-9,150rpm rotating speeds.Then to
The initiator solution formed containing 1.04g ammonium persulfates and 10.38g deionized waters is added in system, 80 DEG C is warming up to and protects
Temperature 15 minutes.The pre-emulsion of monomer is added dropwise into system using peristaltic pump, drips off within 6 hours；Syringe pump is used simultaneously to system
Middle dropwise addition initiator solution, drip off within 6 hours.After the pre-emulsion and initiator solution of monomer are added dropwise, continue insulation 1
Hour, it is cooled to 40 DEG C.First adding the TBHP aqueous solution in backward system, (0.39g TBHPs dissolve
In 10.38g deionized waters) and the sodium formaldehyde sulphoxylate aqueous solution (0.26g sodium formaldehyde sulphoxylates are dissolved in 10.38g
In deionized water), 30 minutes followed by aging.Room temperature is cooled to, ph value of emulsion is adjusted to 9~10 using ammoniacal liquor, uses 100 mesh
Filter-cloth filtering discharges, and obtains samples of latex 4-0#.
Embodiment 17：
Using Styrene-Acrylate Emulsion Polymerization system, emulsion solid content 47.75%, emulsion polymer is calculated according to Fox equations
Glass transition temperature is 3.9 DEG C, and the total usage amount of emulsifying agent accounts for the 1.34% of monomer mass.
1.67g lauryl sodium sulfate is weighed, non-ionic reaction emulsifying agent 2-2# made from 1.67g embodiments 6, by it
It is dissolved in 122.03g deionized waters and emulsifier aqueous solution is made.Weigh 181.67g butyl acrylates, 155.72g methyl simultaneously
Methyl acrylate, 5.19g methacrylic acids, 3.11g hydroxy-ethyl acrylates and 25.95g styrene, it is well mixed, under agitation
It is slowly added into foregoing emulsifier aqueous solution, the pre-emulsion of monomer is made.
Weigh 1.04g ammonium persulfates and be dissolved in 10.38g deionized waters, initiator solution is made.
Add in the reaction vessel for possessing reflux condensing tube, thermometer, mechanical agitation and peristaltic pump, syringe pump feed arrangement
Enter 254.45g deionized waters, 0.83g lauryl sodium sulfate, 0.83g non-ionic reaction emulsifying agent 2-2#, 150rpm rotating speeds
Lower stirring and dissolving.Then it is water-soluble that the initiator containing 1.04g ammonium persulfates and 10.38g deionized waters composition is added into system
Liquid, it is warming up to 80 DEG C and is incubated 15 minutes.The pre-emulsion of monomer is added dropwise into system using peristaltic pump, drips off within 6 hours；Together
When using syringe pump initiator solution is added dropwise into system, drip off within 6 hours.Pre-emulsion and the initiator solution drop of monomer
After adding, continue insulation 1 hour, be cooled to 40 DEG C.First the TBHP aqueous solution (0.39g is added in backward system
TBHP is dissolved in 10.38g deionized waters) and (the 0.26g formaldehyde conjunction time of the sodium formaldehyde sulphoxylate aqueous solution
Niter cake is dissolved in 10.38g deionized waters), 30 minutes followed by aging.Room temperature is cooled to, using ammoniacal liquor by ph value of emulsion
Regulation is discharged using 100 mesh filter-cloth filterings to 9~10, obtains samples of latex 4-1#.
Embodiment 18：
Using Styrene-Acrylate Emulsion Polymerization system, emulsion solid content 47.75%, emulsion polymer is calculated according to Fox equations
Glass transition temperature is 3.9 DEG C, and the total usage amount of emulsifying agent accounts for the 1.34% of monomer mass.
Anionic reactive emulsifying agent 3-1# made from 3.34g embodiments 10 is weighed, is dissolved in 122.03g deionizations
Emulsifier aqueous solution is made in water.Weigh 181.67g butyl acrylates, 155.72g methyl methacrylates, 5.19g first simultaneously
Base acrylic acid, 3.11g hydroxy-ethyl acrylates and 25.95g styrene, it is well mixed, is added slowly with stirring foregoing emulsification
In the agent aqueous solution, the pre-emulsion of monomer is made.
Weigh 1.04g ammonium persulfates and be dissolved in 10.38g deionized waters, initiator solution is made.
Add in the reaction vessel for possessing reflux condensing tube, thermometer, mechanical agitation and peristaltic pump, syringe pump feed arrangement
Enter stirring and dissolving under 254.45g deionized waters, 1.66g anionic reactive emulsifying agent 3-1#, 150rpm rotating speeds.Then to body
The initiator solution formed containing 1.04g ammonium persulfates and 10.38g deionized waters is added in system, 80 DEG C is warming up to and is incubated
15 minutes.The pre-emulsion of monomer is added dropwise into system using peristaltic pump, drips off within 6 hours；Simultaneously using syringe pump into system
Initiator solution is added dropwise, drips off within 6 hours.After the pre-emulsion and initiator solution of monomer are added dropwise, it is small to continue insulation 1
When, it is cooled to 40 DEG C.First adding the TBHP aqueous solution in backward system, (0.39g TBHPs are dissolved in
In 10.38g deionized waters) and the sodium formaldehyde sulphoxylate aqueous solution (0.26g sodium formaldehyde sulphoxylates are dissolved in 10.38g and gone
In ionized water), 30 minutes followed by aging.Room temperature is cooled to, ph value of emulsion is adjusted to 9~10 using ammoniacal liquor, filtered using 100 mesh
Cloth filtering and discharging, obtain samples of latex 4-2#.
Embodiment 19：
Using Styrene-Acrylate Emulsion Polymerization system, emulsion solid content 47.75%, emulsion polymer is calculated according to Fox equations
Glass transition temperature is 3.9 DEG C, and the total usage amount of emulsifying agent accounts for the 1.34% of monomer mass.
Anionic reactive emulsifying agent 3-2# made from 3.34g embodiments 11 is weighed, is dissolved in 122.03g deionizations
Emulsifier aqueous solution is made in water.Weigh 181.67g butyl acrylates, 155.72g methyl methacrylates, 5.19g first simultaneously
Base acrylic acid, 3.11g hydroxy-ethyl acrylates and 25.95g styrene, it is well mixed, is added slowly with stirring foregoing emulsification
In the agent aqueous solution, the pre-emulsion of monomer is made.
Weigh 1.04g ammonium persulfates and be dissolved in 10.38g deionized waters, initiator solution is made.
Add in the reaction vessel for possessing reflux condensing tube, thermometer, mechanical agitation and peristaltic pump, syringe pump feed arrangement
Enter stirring and dissolving under 254.45g deionized waters, 1.66g anionic reactive emulsifying agent 3-2#, 150rpm rotating speeds.Then to body
The initiator solution formed containing 1.04g ammonium persulfates and 10.38g deionized waters is added in system, 80 DEG C is warming up to and is incubated
15 minutes.The pre-emulsion of monomer is added dropwise into system using peristaltic pump, drips off within 6 hours；Simultaneously using syringe pump into system
Initiator solution is added dropwise, drips off within 6 hours.After the pre-emulsion and initiator solution of monomer are added dropwise, it is small to continue insulation 1
When, it is cooled to 40 DEG C.First adding the TBHP aqueous solution in backward system, (0.39g TBHPs are dissolved in
In 10.38g deionized waters) and the sodium formaldehyde sulphoxylate aqueous solution (0.26g sodium formaldehyde sulphoxylates are dissolved in 10.38g and gone
In ionized water), 30 minutes followed by aging.Room temperature is cooled to, ph value of emulsion is adjusted to 9~10 using ammoniacal liquor, filtered using 100 mesh
Cloth filtering and discharging, obtain samples of latex 4-3#.
Embodiment 20：
Using Styrene-Acrylate Emulsion Polymerization system, emulsion solid content 47.75%, emulsion polymer is calculated according to Fox equations
Glass transition temperature is 3.9 DEG C, and the total usage amount of emulsifying agent accounts for the 1.34% of monomer mass.
Anionic reactive emulsifying agent 3-3# made from 3.34g embodiments 12 is weighed, is dissolved in 122.03g deionizations
Emulsifier aqueous solution is made in water.Weigh 181.67g butyl acrylates, 155.72g methyl methacrylates, 5.19g first simultaneously
Base acrylic acid, 3.11g hydroxy-ethyl acrylates and 25.95g styrene, it is well mixed, is added slowly with stirring foregoing emulsification
In the agent aqueous solution, the pre-emulsion of monomer is made.
Weigh 1.04g ammonium persulfates and be dissolved in 10.38g deionized waters, initiator solution is made.
Add in the reaction vessel for possessing reflux condensing tube, thermometer, mechanical agitation and peristaltic pump, syringe pump feed arrangement
Enter stirring and dissolving under 254.45g deionized waters, 1.66g anionic reactive emulsifying agent 3-3#, 150rpm rotating speeds.Then to body
The initiator solution formed containing 1.04g ammonium persulfates and 10.38g deionized waters is added in system, 80 DEG C is warming up to and is incubated
15 minutes.The pre-emulsion of monomer is added dropwise into system using peristaltic pump, drips off within 6 hours；Simultaneously using syringe pump into system
Initiator solution is added dropwise, drips off within 6 hours.After the pre-emulsion and initiator solution of monomer are added dropwise, it is small to continue insulation 1
When, it is cooled to 40 DEG C.First adding the TBHP aqueous solution in backward system, (0.39g TBHPs are dissolved in
In 10.38g deionized waters) and the sodium formaldehyde sulphoxylate aqueous solution (0.26g sodium formaldehyde sulphoxylates are dissolved in 10.38g and gone
In ionized water), 30 minutes followed by aging.Room temperature is cooled to, ph value of emulsion is adjusted to 9~10 using ammoniacal liquor, filtered using 100 mesh
Cloth filtering and discharging, obtain samples of latex 4-4#.
Embodiment 21：
Using Styrene-Acrylate Emulsion Polymerization system, emulsion solid content 47.75%, emulsion polymer is calculated according to Fox equations
Glass transition temperature is 3.9 DEG C, and the total usage amount of emulsifying agent accounts for the 1.34% of monomer mass.
Weigh made from anionic reactive emulsifying agent 3-1#, 1.67g embodiment 6 made from 1.67g embodiments 10 it is non-from
Sub- reactive emulsifier 2-2#, is dissolved in 122.03g deionized waters and emulsifier aqueous solution is made.Weigh simultaneously
181.67g butyl acrylates, 155.72g methyl methacrylates, 5.19g methacrylic acids, 3.11g hydroxy-ethyl acrylates and
25.95g styrene, it is well mixed, is added slowly with stirring in foregoing emulsifier aqueous solution, the pre-emulsification of monomer is made
Liquid.
Weigh 1.04g ammonium persulfates and be dissolved in 10.38g deionized waters, initiator solution is made.
Add in the reaction vessel for possessing reflux condensing tube, thermometer, mechanical agitation and peristaltic pump, syringe pump feed arrangement
Enter 254.45g deionized waters, 0.83g anionic reactive emulsifying agent 3-1#, 0.83g non-ionic reaction emulsifying agent 2-2#,
Stirring and dissolving under 150rpm rotating speeds.Then add what is formed containing 1.04g ammonium persulfates and 10.38g deionized waters into system
Initiator solution, it is warming up to 80 DEG C and is incubated 15 minutes.The pre-emulsion of monomer is added dropwise into system using peristaltic pump, 6 is small
When drip off；Initiator solution is added dropwise into system using syringe pump simultaneously, drips off within 6 hours.The pre-emulsion of monomer and initiation
After the agent aqueous solution is added dropwise, continues insulation 1 hour, be cooled to 40 DEG C.First TBHP water is added in backward system
Solution (0.39g TBHPs are dissolved in 10.38g deionized waters) and the sodium formaldehyde sulphoxylate aqueous solution (0.26g
Sodium formaldehyde sulphoxylate is dissolved in 10.38g deionized waters), 30 minutes followed by aging.Room temperature is cooled to, will using ammoniacal liquor
Ph value of emulsion is adjusted to 9~10, is discharged using 100 mesh filter-cloth filterings, is obtained samples of latex 4-5#.
Embodiment 22：
Using Styrene-Acrylate Emulsion Polymerization system, emulsion solid content 47.75%, emulsion polymer is calculated according to Fox equations
Glass transition temperature is 3.9 DEG C, and the total usage amount of emulsifying agent accounts for the 1.34% of monomer mass.
Anionic reactive emulsifying agent 3-4# made from 3.34g embodiments 13 is weighed, is dissolved in 122.03g deionizations
Emulsifier aqueous solution is made in water.Weigh 181.67g butyl acrylates, 155.72g methyl methacrylates, 5.19g first simultaneously
Base acrylic acid, 3.11g hydroxy-ethyl acrylates and 25.95g styrene, it is well mixed, is added slowly with stirring foregoing emulsification
In the agent aqueous solution, the pre-emulsion of monomer is made.
Weigh 1.04g ammonium persulfates and be dissolved in 10.38g deionized waters, initiator solution is made.
Add in the reaction vessel for possessing reflux condensing tube, thermometer, mechanical agitation and peristaltic pump, syringe pump feed arrangement
Enter stirring and dissolving under 254.45g deionized waters, 1.66g anionic reactive emulsifying agent 3-4#, 150rpm rotating speeds.Then to body
The initiator solution formed containing 1.04g ammonium persulfates and 10.38g deionized waters is added in system, 80 DEG C is warming up to and is incubated
15 minutes.The pre-emulsion of monomer is added dropwise into system using peristaltic pump, drips off within 6 hours；Simultaneously using syringe pump into system
Initiator solution is added dropwise, drips off within 6 hours.After the pre-emulsion and initiator solution of monomer are added dropwise, it is small to continue insulation 1
When, it is cooled to 40 DEG C.First adding the TBHP aqueous solution in backward system, (0.39g TBHPs are dissolved in
In 10.38g deionized waters) and the sodium formaldehyde sulphoxylate aqueous solution (0.26g sodium formaldehyde sulphoxylates are dissolved in 10.38g and gone
In ionized water), 30 minutes followed by aging.Room temperature is cooled to, ph value of emulsion is adjusted to 9~10 using ammoniacal liquor, filtered using 100 mesh
Cloth filtering and discharging, obtain samples of latex 4-6#.
Apply example 23：Emulsion polymerization performance test is tested
For the emulsion polymerization process in embodiment 16~22 and polymer emulsion sample 4-0#~4-6#, respectively to anti-
Slag yield, emulsion appearance, the water-white property of emulsion film forming and the water absorption rate answered are tested, and method of testing is as follows.
Emulsion polymerization slag yield is tested：
After emulsion polymerization terminates, emulsion is filtered using 100 mesh nylon filtering cloths, will be solidifying on filter cloth, bottle wall and agitating paddle
Glue thing is collected, rinsed, and wet gel thing is dried 2 hours at 105 DEG C and weighed, and with the quality of desiccant gel thing divided by is gathered
Close the gross mass of monomer, you can calculate the slag yield of polymerisation.
Emulsion appearance is tested：
Polymer emulsion is diluted to 0.1 mass % with deionized water, and diluting emulsion is added to 25 milliliters of glass examinations
Guan Zhong, the outward appearance of parallel comparative polymer product emulsion.With the difference of emulsion particle diameter, diluting emulsion shows milky (grain
Footpath is larger) to the change of micro- blue (particle diameter is smaller).
The water-white property test of polymer emulsion film forming：
Emulsion is applied on a glass using wet film maker, wet-film thickness is 200 microns, is then dried at room temperature for 24
Hour.Glass plate is immersed in 40 DEG C of deionized waters, applied respectively in 4 hours, 12 hours and 24 hours sight glass plate surfaces
Whether film there is blushing.
Polymer emulsion film forming water absorption rate test：
15g emulsions are weighed in glass culture dish, at 80 DEG C dry 10 hours it is fully transparent to film, film center
The part of 2 centimetres of about 2 cm x is removed, it is m1 to weigh quality, is then soaked 24 hours in deionized water, and table is blotted in taking-up
Face, it is m2 to weigh quality, and emulsion film forming water absorption rate can be calculated as (m2-m1)/m1 × 100%.
Comparative sample 4-0#~4-6# emulsion applications the performance test results are as shown in table 4.
The application performance of the polymer emulsion of table 4
From result, using the emulsifying agent and the polymer emulsion 4-1# of conventional emulsifier use in conjunction of the present invention, with
And using emulsifying agent polymer emulsion 4-2#~4-6# of the present invention relative to the polymer emulsion using conventional emulsifier
4-0#, tool more excellent emulsion-stabilizing and film forming water resistance.
It should be appreciated that specific embodiment described above is only used for explaining the present invention, it is not intended to limit the present invention.By
Among the obvious changes or variations that the spirit of the present invention is extended out is still in protection scope of the present invention.
Claims (10)
1. a kind of reactive emulsifier, it is characterised in that include the compound of structure shown in formula (I) and/or formula (II)：
Wherein, R1For the combination of the alkyl of 4~30 carbon atoms, alkyl phenyl, alkoxy or above-mentioned group；R2、R3It is only respectively
Vertical is selected from hydrogen atom or methyl；(AO)m(AO)nThe group of addition polymerization formation is carried out for multiple oxyalkylene units, often
Individual AO is optionally from the alkoxy of 2~4 carbon atoms；M, n is independently selected from 1~30 integer；X is hydrogen atom or choosing
From-SO3M、-COOM、-PO3M2、-PO3MH or-CO-R4The hydrophilic anions group that-COOM is represented, wherein M expressions hydrogen atom,
Alkali metal atom, alkaline earth metal atom, ammonium residue or alkanolamine residue, R4Represent the residue of binary acid or acid anhydrides.
2. reactive emulsifier as claimed in claim 1, it is characterised in that R1For the alkyl of 8~16 carbon atoms；R2、R3Point
Not independent is selected from hydrogen atom or methyl；X is selected from hydrogen atom or-SO3M, M have definition described above；M, n is independently
Be selected from 5~10 integer.
3. reactive emulsifier as claimed in claim 1 or 2, it is characterised in that the molar content ratio of ethyoxyl in the AO
Example is 70~100%, preferably 90~100%.
4. the preparation method of the reactive emulsifier as described in claim 1-3 is any, it is characterised in that comprise the following steps：
A) fat primary amines carry out ring-opening reaction with the glycidyl ether compound with unsaturated double-bond, obtain including formula (A)
And/or the intermediate of (B)；
B) the above-mentioned intermediates of carry out alkoxylate with epoxyalkane, obtain reactive emulsifier；
Wherein R1、R2、R3With definition described above.
5. preparation method as claimed in claim 4, it is characterised in that fat primary amine and glycidol ether in the step a)
The reaction molar ratio of compound is 1/0.7~1/2.3, preferably 1/1.0~1/2.1, more preferably 1/1.05~1/2.0.
6. preparation method as claimed in claim 4, it is characterised in that further comprise carrying out sulphur to emulsifying agent obtained by step b)
Anionic reactive emulsifying agent derived from acidifying or phosphorylation reaction acquisition.
7. a kind of intermediate, it is characterised in that compound (A) and/or compound (B) including such as following formula：
8. application of the intermediate as claimed in claim 7 in reactive emulsifier is prepared.
9. application of the emulsifying agent as described in claim 1-3 is any in emulsion polymerization.
10. application of the preparation method of the reactive emulsifier as described in claim 4-6 is any in emulsion polymerization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710548582.0A CN107474236B (en) | 2017-07-07 | 2017-07-07 | Reactive emulsifier, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710548582.0A CN107474236B (en) | 2017-07-07 | 2017-07-07 | Reactive emulsifier, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107474236A true CN107474236A (en) | 2017-12-15 |
| CN107474236B CN107474236B (en) | 2021-03-16 |
Family
ID=60594918
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710548582.0A Active CN107474236B (en) | 2017-07-07 | 2017-07-07 | Reactive emulsifier, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107474236B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109796587A (en) * | 2018-12-25 | 2019-05-24 | 联泓(江苏)新材料研究院有限公司 | A kind of reactive emulsifier and its preparation method and application of stability and the excellent substitution containing alkenyl of film forming water resistance |
| CN109810249A (en) * | 2018-12-25 | 2019-05-28 | 联泓(江苏)新材料研究院有限公司 | A kind of stability and the hydrogenation type emulsifier of excellent water resistance and its preparation method and application |
| CN114249900A (en) * | 2020-09-24 | 2022-03-29 | 万华化学集团股份有限公司 | Preparation method of epoxy emulsifier, epoxy resin aqueous dispersion and preparation method |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007116946A1 (en) * | 2006-03-31 | 2007-10-18 | Nippon Shokubai Co., Ltd. | Polyalkylene glycol copolymer, polyalkylene glycol monomer, and production method thereof |
| CN102504238A (en) * | 2011-10-10 | 2012-06-20 | 江苏博特新材料有限公司 | Unsaturated polyether monomer, comb-like branched copolymer cement dispersant prepared by the same, and preparation method thereof |
| CN102604469A (en) * | 2012-02-13 | 2012-07-25 | 中国船舶重工集团公司第七二五研究所 | Latent self-repair microcapsule and preparation method thereof |
| CN103906768A (en) * | 2011-10-07 | 2014-07-02 | 第一工业制药株式会社 | Emulsion polymerization method using reactive emulsifying agent, aqueous polymer dispersion obtained by same, and polymer film |
| CN104781348A (en) * | 2012-11-06 | 2015-07-15 | 湛新奥地利有限公司 | Aqueous dispersions of a multifunctional primary amine, process for its preparation, and use thereof |
| CN104870512A (en) * | 2012-12-21 | 2015-08-26 | 赫克塞尔合成有限公司 | Fast cure epoxy resin systems |
| CN106883379A (en) * | 2017-02-27 | 2017-06-23 | 江苏中路工程技术研究院有限公司 | A kind of aqueous epoxy resin curing agent, its preparation method and the water-base epoxy pitch containing the curing agent, its preparation method and application |
-
2017
- 2017-07-07 CN CN201710548582.0A patent/CN107474236B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007116946A1 (en) * | 2006-03-31 | 2007-10-18 | Nippon Shokubai Co., Ltd. | Polyalkylene glycol copolymer, polyalkylene glycol monomer, and production method thereof |
| CN103906768A (en) * | 2011-10-07 | 2014-07-02 | 第一工业制药株式会社 | Emulsion polymerization method using reactive emulsifying agent, aqueous polymer dispersion obtained by same, and polymer film |
| CN102504238A (en) * | 2011-10-10 | 2012-06-20 | 江苏博特新材料有限公司 | Unsaturated polyether monomer, comb-like branched copolymer cement dispersant prepared by the same, and preparation method thereof |
| CN102604469A (en) * | 2012-02-13 | 2012-07-25 | 中国船舶重工集团公司第七二五研究所 | Latent self-repair microcapsule and preparation method thereof |
| CN104781348A (en) * | 2012-11-06 | 2015-07-15 | 湛新奥地利有限公司 | Aqueous dispersions of a multifunctional primary amine, process for its preparation, and use thereof |
| CN104870512A (en) * | 2012-12-21 | 2015-08-26 | 赫克塞尔合成有限公司 | Fast cure epoxy resin systems |
| CN106883379A (en) * | 2017-02-27 | 2017-06-23 | 江苏中路工程技术研究院有限公司 | A kind of aqueous epoxy resin curing agent, its preparation method and the water-base epoxy pitch containing the curing agent, its preparation method and application |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109796587A (en) * | 2018-12-25 | 2019-05-24 | 联泓(江苏)新材料研究院有限公司 | A kind of reactive emulsifier and its preparation method and application of stability and the excellent substitution containing alkenyl of film forming water resistance |
| CN109810249A (en) * | 2018-12-25 | 2019-05-28 | 联泓(江苏)新材料研究院有限公司 | A kind of stability and the hydrogenation type emulsifier of excellent water resistance and its preparation method and application |
| CN109796587B (en) * | 2018-12-25 | 2021-08-13 | 联泓(江苏)新材料研究院有限公司 | Alkenyl-substituted reactive emulsifier with excellent stability, film-forming water resistance and preparation method and application thereof |
| CN109810249B (en) * | 2018-12-25 | 2022-05-10 | 联泓(江苏)新材料研究院有限公司 | Hydrogenation reaction type emulsifier with excellent stability and water resistance, and preparation method and application thereof |
| CN114249900A (en) * | 2020-09-24 | 2022-03-29 | 万华化学集团股份有限公司 | Preparation method of epoxy emulsifier, epoxy resin aqueous dispersion and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107474236B (en) | 2021-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109796587B (en) | Alkenyl-substituted reactive emulsifier with excellent stability, film-forming water resistance and preparation method and application thereof | |
| CN107474236A (en) | A kind of reactive emulsifier, its preparation method and application | |
| KR101481989B1 (en) | Surfactant composition for emulsion polymerization | |
| US5346973A (en) | Pourable liquid surfactant concentrate | |
| US4299975A (en) | Sulfosuccinate emulsifiers | |
| JPH0575001B2 (en) | ||
| CN103890014A (en) | Emulsifying agent for emulsion polymerization | |
| EP1318157B1 (en) | Surfactant for emulsion polymerization | |
| JPS58147412A (en) | Novel water-soluble copolymer and its preparation | |
| CN109810249B (en) | Hydrogenation reaction type emulsifier with excellent stability and water resistance, and preparation method and application thereof | |
| US4525525A (en) | Use of bis-semiesters of sulfosuccinic acid with polyether diols based on ethylene oxide/propylene oxide or their salts as surface-active agents | |
| US8142681B2 (en) | Aqueous surfactant compositions with a low pour point | |
| JP3756391B2 (en) | Surfactant composition for emulsion polymerization | |
| JP2003261605A (en) | Reactive surface active agent | |
| Gan et al. | W/O MICROEMULSION OF POLYKERIZABLE COMPONENTS | |
| US8519071B2 (en) | Low-viscosity aqueous compositions | |
| JP6662937B2 (en) | Extended surfactants for emulsion polymerization | |
| CN107459607B (en) | Double tracer polycarboxylate water-reducers of a kind of phosphorus spectrum, fluorescence and preparation method thereof | |
| CN115612032A (en) | Synthesis method of acrylic thickener | |
| US20110245414A1 (en) | Copolymerizable (Meth)Acrylic Acid Esters | |
| JP4889651B2 (en) | Use for emulsion polymerization of fatty alcohol polyglycol ether sulfate | |
| JP4271363B2 (en) | Preparation of alkenyl polyether | |
| CN111019119B (en) | Reactive emulsifier and preparation method and application thereof | |
| CN110283265A (en) | Styrene-vinyl versatate acrylate class copolymer emulsion and preparation method | |
| JPH0199639A (en) | Emulsifier for aqueous resin dispersion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |