CN106866869A - A kind of preparation method of core shell structure hydroxyl acrylic emulsion - Google Patents
A kind of preparation method of core shell structure hydroxyl acrylic emulsion Download PDFInfo
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- CN106866869A CN106866869A CN201710102922.7A CN201710102922A CN106866869A CN 106866869 A CN106866869 A CN 106866869A CN 201710102922 A CN201710102922 A CN 201710102922A CN 106866869 A CN106866869 A CN 106866869A
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- 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
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- 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
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- 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
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- 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
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- C09D133/12—Homopolymers or copolymers of methyl methacrylate
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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Abstract
The invention discloses a kind of preparation method of core shell structure hydroxyl acrylic emulsion, effectively by acrylic monomers pre-emulsification technology, seeded emulsion polymerization technology, core shell emulsion polymerization technology, self-crossing emulsion polymerization technique, emulsion polymerization technology is combined, using the monomer pre-emulsification of seeded emulsion polymerization part, the monomer of core emulsion polymerization part is directly added dropwise the pre-emulsified technique of monomer with shell emulsion polymerization part, and in core, different initiator rate of addition is selected in shell emulsion polymerization process respectively, and core, anion emulsifier and nonionic emulsifier compounding of the shell from different performance, effectively control emulsion particle diameter and distribution；In the case of not produced in building-up process or only producing very small amount gum deposit, the emulsifying agent for making emulsion be added in synthesizing accounts for less than the 6% of acrylic monomers total amount（Account for less than the 3% of synthesized emulsion total amount）.
Description
Technical field
The present invention relates to a kind of preparation method of core shell structure hydroxyl acrylic emulsion.
Background technology
Coating Water-borne modification is one of important directions of paint development.And the Water-borne modification of woodwork coating, on the one hand want increased force
Degree improves the gap of the performance, diminution and oiliness woodcare paint of water-borne wood coating；On the other hand it is water-borne wood coating to be reduced
Cost, only in this way can just make water-borne wood coating be easy to be received by consumers in general.
Water paint includes one-component and double-component water paint.The paint film property of wherein single-component water-based coating includes resistance to
The aspect such as aqueous, chemical-resistant and hardness is bad, larger with oil paint gap, and the popularization for seriously limiting water paint should
With.The mechanical performance of double-component water paint, water resistance and chemical-resistant are suitable with solvent wood coatings, can good gram
The shortcoming of single-component water-based coating is taken.In January, 2015, China issued the method on imposing the consumption tax to solvent based coating
Order so that double-component water paint will turn into the first-selection of high-grade water paint.
At present, due to acrylic emulsion, price is relatively low and rate of drying is very fast compared with other water paint resins,
Acrylic emulsion still has a wide range of applications in aqueous wooden ware and plastic coating particularly aqueous wooden ware priming paint field.But it is general
Logical acrylic emulsion is difficult to meet water-borne wood coating to such as hardness, water resistance, alcohol resistance, the aspect such as stain resistant will
Ask, it is therefore desirable to common acrylic emulsion additional crosslink agent is modified to improve its performance.
The hydroxyl acrylic emulsion for traditionally synthesizing is modified using additional crosslink agent to acrylic emulsion, there is drying
Slow and bad with curing agent compatibility the characteristics of, the main paint film that is presented with of film outward appearance difference is transparent poor, and gloss is low, its master
It is hydroxy polyacrylate emulsion to the emulsion dispersion ability of curing agent and bad with the compatibility of curing agent to want reason.
The content of the invention
The present invention seeks to：A kind of preparation method of core shell structure hydroxyl acrylic emulsion is provided, using chemical modification
Method, being introduced when hydroxyl acrylic emulsion synthesizes can occur the monomer of self-crosslinking under certain condition, while crosslinking official
Can group the outer layer of emulsion particle is distributed in by special process, in film forming procedure or film forming can produce certain journey after for a period of time
The crosslinking of degree, so that film has the performance of part thermosetting resin, then can be largely overcoming the existing skill of the above
The deficiency of art.
The technical scheme is that：A kind of preparation method of core shell structure hydroxyl acrylic emulsion, specifically includes following
Step：
Step 1)：The emulsifying agent of acrylic monomers gross mass 1~5% will be accounted for, acrylic monomers gross mass 0.5~3% is accounted for
PH and account for the deionized water of acrylic monomers gross mass 30~90% under 500~2000 revs/min of stirring conditions
Mixing 30 minutes；Then input accounts for the acrylic monomers of acrylic monomers gross mass 1-30%, high at 2000~30000 revs/min
The fast emulsified 15-30min of emulsification condition, obtains the pre-emulsion of seed emulsion monomer；
Step 2)：To step 1) in obtained seed emulsion monomer pre-emulsion in letting nitrogen in and deoxidizing, be then warmed up to
80℃；Under 50~200 revs/min of stirring conditions, the initiator that addition accounts for acrylic monomers gross mass 0.2~1% triggers polymerization
Reaction, polymerisation heat release is incubated 30 minutes after terminating, and obtains seed emulsion；
Step 3)：Under 50~300 revs/min of stirring conditions, to step 2) in instill in obtained seed emulsion and account for third
The acrylic monomers of acrylic monomer gross mass 30~45%, while instilling the initiation for accounting for acrylic monomers gross mass 0.02~1%
Agent, time for adding 1~3 hour；After dripping, insulation reaction 30~90 minutes；Add again and account for acrylic monomers gross mass 0.01
~1% initiator, insulation reaction 1~3 hour, obtains core partial emulsion；
Step 4)：Take and account for the emulsifying agent of acrylic monomers gross mass 1~4% and account for acrylic monomers gross mass 5~30%
Deionized water is added in emulsifier, is mixed 3~20 minutes under 500~2000 revs/min of stirring conditions；Acrylic monomers will be accounted for total
The acrylic monomers of quality 20~60%, the self-crosslinking function monomer for accounting for acrylic monomers gross mass 1~6% and account for acrylic acid list
The alkyl acrylic of body gross mass 0.5~4% mixes 3~20 minutes under 50~300 revs/min of stirring conditions；Input accounts for propylene
The acrylic monomers of acid monomers gross mass 30-45%, under 2000~30000 revs/min of high speed emulsification conditions, emulsifies 10~60 points
Clock, obtains the pre-emulsion of shell emulsion monomer；
Step 5)：Under 50~300 revs/min of stirring conditions, by step 4) in obtained shell emulsion monomer pre-emulsification
Liquid at the uniform velocity instills step 3) in obtained core partial emulsion, while instillation accounts for acrylic monomers gross mass 0.02~1%
Initiator, time for adding 1~3 hour；After dripping, insulation reaction 30~90 minutes；Add again and account for acrylic monomers gross mass
0.01~0.5% initiator；After dripping, 0.5~2 hour is incubated；Then 70 degree are cooled to, after adding post-treatment agent to carry out
Elimination reaction, continues to be incubated 1~2 hour；Cooling, 7~10,10~40 points of time for adding are adjusted to pH value regulator by pH value
Clock；Finally above-mentioned product is filtered, core shell structure hydroxyl acrylic emulsion is obtained.
Used as preferred technical scheme, the acrylic monomers is obtained by the material mixing of following mass percent：10%
~20% atomic number of alkyl carbon is 1~15 alkyl methacrylate, third that 10%~20% atomic number of alkyl carbon is 1~15
Olefin(e) acid Arrcostab and 10%~20% acrylic acid aromatic compound；
Wherein described alkyl methacrylate is methyl methacrylate, EMA, methacrylic acid fourth
One kind in ester, pentylmethacrylate, hexyl methacrylate, n octyl methacrylate, EHMA or
It is various；
The alkyl acrylate is methyl acrylate, ethyl acrylate, butyl acrylate, amyl acrylate, acrylic acid
One or more in own ester, 2-EHA；
The acrylic acid aromatic compound is in styrene, methyl styrene, 3- t-butyl styrenes, 2- chlorostyrenes
One or more.
As preferred technical scheme, the step 1) described in pH be sodium acid carbonate.
As preferred technical scheme, step 4) described in self-crosslinking function monomer for atomic number of alkyl carbon be 1~15
Acrylate functional monomer；Wherein acrylate functional monomer be hydroxyethyl methacrylate, hydroxy propyl methacrylate,
N hydroxymethyl acrylamide, GMA, DAAM, methylene diacrylamine, amination acyl
One or more in imines, acrylamide glycolic acid esters；
The alkyl acrylic is one or more in acrylic acid, methacrylic acid or methylene-succinic acid.
As preferred technical scheme, step 5) in pH value is adjusted to 7~10 with pH value regulator after, instill auxiliary from
Crosslinking agent, time for adding is 20~60 minutes, continues to stir 10~30 minutes after dripping off；Filtering, that is, obtain core shell structure hydroxyl
Acrylic emulsion；Wherein auxiliary self-crosslinking agent is hydrazine class compound that atomic number of alkyl carbon is 1~15；The hydrazine chemical combination
Thing is one or more in the hydrazine of adipic acid two, carbon acid dihydrazide, careless acid dihydrazide, succinic acid hydrazide ii.
As preferred technical scheme, step 5) described in post-treatment agent be by 0.01~0.1% TBHP
Constituted with 0.01~0.1% 2 hydration sodium bisulphite formaldehyde；
The pH value regulator is triethylamine, isopropylamine, n-propylamine, n-butylamine, dimethylamine, dimethyl amine, diethyl
The mixture of one or more in methylamine, dimethylethanolamine, front three ethylethanolamine, aminomethylpropanol, ammoniacal liquor.
Used as preferred technical scheme, the emulsifying agent is 0.01~0.1% anion emulsifier and 0.01~0.1%
The blended emulsifier that nonionic emulsifier is compounded；
Wherein step 1) in anion emulsifier used be selected from lauryl sodium sulfate, ammonium lauryl sulfate, dodecane
One or more in base sodium sulfonate and neopelex；Step 1) in nonionic emulsifier used it is poly- selected from alkyl phenol
One or more in compound, the AEO of oxygen vinethene；
Wherein step 4) in anion emulsifier used be selected from alkyl diphenyl ether disodium sulfonate salt, alkyl polyoxyethylene acyl sulphur
Sour sodium, tributyl phenol sodium sulfonate of ethoxylated, allyl polyethenoxy ether derivative ammonium sulfate and allyl polyethenoxy ether
One or more in ammonium sulfate；Step 4) in nonionic emulsifier used be selected from alkyl polyoxyethylene ether phosphate, tributyl
One kind in phenol polyethenoxy ether, alkyl polyoxyethylene ether, allyl polyethenoxy ether, acrylic acid polyoxyethylene polyoxypropylene ether
Or it is several.
Used as preferred technical scheme, the initiator is persulfuric acid salt initiator.
The present invention by acrylic monomers pre-emulsification technology, seed and core shell emulsion polymerization technology, self-crossing emulsion polymerization skill
Art and emulsion polymerization technology are combined, and by using seed emulsion monomer pre-emulsification, core partial monosomy is directly added dropwise and shell parts
Monomer pre-emulsification, the Particular craft that core, shell parts are compounded from different anions emulsifying agent and nonionic emulsifier respectively,
Effectively control emulsion particle diameter and emulsion stability.Requirement of the emulsifying agent that core, shell parts are used to aspect of performance is different, core part
The hydrophily and low critical micelle concentration of emulsifying agent are emphasized so that the latex particle number for being formed is enough and sufficiently small；Shell parts
The emulsifiability of emulsifying agent is emphasized, the pre-emulsion for obtaining will be stablized, while providing hydroxy functional monomer, there is provided further crosslinking
Solidification.The core shell structure hydroxyl acrylic emulsion of preparation is made by process above, it is special with obvious core shell structure and self-crosslinking
Property, weight average molecular weight is 13~150,000, and molecular weight distribution degree is 2~2.5；Latex particle size is distributed in 40nm~120nm, average grain
Footpath is 60~100nm；Core partial vitrification temperature is 50~100 DEG C, and shell parts glass transition temperature is 0~30 DEG C.
It is of the invention effective by acrylic monomers pre-emulsification technology, seeded emulsion polymerization technology, core shell emulsion polymerization skill
Art, self-crossing emulsion polymerization technique, emulsion polymerization technology are combined, using the monomer pre-emulsification of seeded emulsion polymerization part, core
The monomer of emulsion polymerization part is directly added dropwise the pre-emulsified technique of monomer with shell emulsion polymerization part, and gathers in core, shell emulsion
Select different initiator rate of addition during conjunction respectively, and core, shell are from the anion emulsifier of different performance and non-
Ionic emulsifying agent is compounded, and effectively controls emulsion particle diameter and distribution；Do not produced in building-up process or only produce very small amount gum deposit
In the case of, the emulsifying agent for making emulsion be added in synthesizing accounts for less than the 6% of acrylic monomers total amount and (accounts for synthesized emulsion total amount
Less than 3%).
It is an advantage of the invention that：
1. the core shell structure hydroxyl acrylic emulsion that prepared by the present invention has soft shell stone structure, can add less when in use
Or coalescents are not added with, it is very environmentally friendly；And its emulsion particle average grain diameter is 60~100nm, with nano effect, for Waterborne wood
Device priming paint grinability is good, and the permeability, wetability to base material are good, and adhesive force is strong, and film is fine and close, the transparency is good, and gloss is higher, puts down
Slip is good；
2. the present invention is cheap, and expensive organosiloxane monomer is replaced using relatively common self-cross linking monomer
And fluoro-acrylate monomer, emulsion property is improved using advanced polymerization technique, make obtained acrylic emulsion cheap, can
It is widely used in aqueous woodware paint, plastic paint metallic paint；
3. the emulsion of present invention synthesis is non-thermoplastic, its solvent resistance, water-fast, solvent resistance, heat resistance, resistant etc.
Physical and chemical performance all improves a lot, while improve the freeze-thaw stability and storage stability of emulsion；
4. emulsifier of the invention is small, only accounts for less than the 6% of monomer total amount, accounts for less than the 3% of emulsion.
Specific embodiment
It is specific purposes, the function that can further appreciate that feature of the invention, technological means and reached, will ties below
The invention will be further described and explanation to close specific embodiment.
Embodiment 1:
It is as shown in table 1 from each component composition and content in this implementation：
The each component composition of 1 embodiment of table 1 and content table：
Wherein, the compound abbreviation OP-10 of APES；Two hydration sodium bisulphite formaldehydes are also two water beetles
Aldehyde closes sodium bisulphite or rongalite；Aminomethylpropanol abbreviation AMP-95.
A kind of preparation method of core shell structure hydroxyl acrylic emulsion, including the following steps for carrying out in order：
The pre-emulsification of step one, seed emulsion monomer
By 1.00g anion emulsifiers dodecyl sodium sulfate and 0.50gOP-10,0.60gpH value buffer solution sodium acid carbonate
In 32.45g deionized waters addition emulsifier, mix 10 minutes under 1000 revs/min of stirring conditions；Acrylic monomers is taken, i.e.,
4.80g methyl methacrylates, 0.4g Isooctyl acrylate monomers, the butyl acrylate of 0.40g are well mixed, high at 7500 revs/min
In at the uniform velocity instilling emulsifier under fast emulsification condition, time for adding 30 minutes；Continue emulsification 30 minutes at a high speed after dripping off, obtain seed
The pre-emulsion of emulsion monomer；
Step 2, preparation seed emulsion
By in the pre-emulsion of seed emulsion monomer obtained by step one input reactor, in 150 revs/min of mixing speed
Under, it is warmed up to 80 DEG C；To nitrogen is led in reactor, except oxygen, after temperature reaches 80 DEG C, by the over cure that 0.60g concentration is 10%
Sour aqueous solutions of potassium is disposably added in system；After blue light occurs in emulsion and exothermic peak terminates, continue to be incubated 30 minutes, obtain
To seed emulsion；
Step 3, prepare core partial emulsion
Take methyl methacrylate, the styrene of 6.10g, the butyl acrylate of 1.57g of acrylic monomers, i.e. 6.76g
After well mixed, under 150 revs/min of stirring conditions, at the uniform velocity in seed emulsion obtained by instillation step 2；1.50g is instilled simultaneously
Concentration is 10% persulfate aqueous solution；Control was dripped off in 3 hours；After dripping, insulation reaction 60 minutes；It is disposable to mend
The persulfate aqueous solution that concentration containing 0.15g is 10% is added, insulation reaction 3 hours obtains core partial emulsion；
The pre-emulsification of step 4, shell emulsion monomer
Alkyl polyoxyethylene acyl sodium sulfonate solution, the alkoxy that 0.50g concentration is 50% that 1.00g concentration is 50% is taken to gather
Oxygen ethene ethereal solution and 14.35g deionized waters are added in emulsifier, are mixed 10 minutes under 1000 revs/min of stirring conditions；Take third
The methyl methacrylate of acrylic monomer, i.e. 3.84g, the styrene of 2.40g, the butyl acrylate of 9.23g and self-crosslinking function
The mixing of monomer 7g hydroxyethyl methacrylates, 1.20gN- NMAs and other functions monomer 0.80g methacrylic acids
Uniformly, in instilling emulsifier under 7500 revs/min of high speed emulsification conditions, time for adding 30 minutes；Continue to emulsify at a high speed after dripping off
30 minutes, obtain the pre-emulsion of shell emulsion monomer；
Step 5, prepare core shell structure hydroxyl acrylic emulsion
Under 150 revs/min of stirring conditions, the pre-emulsion of step 4 gained shell parts emulsion monomer is at the uniform velocity instilled into step
In three gained core partial emulsions, while instilling the persulfate aqueous solution that 3.00g concentration is 10%, drip off within 5 hours；Drip
Afterwards, insulation reaction 1 hour；The persulfate aqueous solution that 0.15g concentration is 10% is added again；Insulation reaction 1 hour；Cool to 70
DEG C, the TBHP aqueous solution that 0.50g concentration is 10% is added dropwise to, time for adding 20 minutes is incubated 30 points after dripping off
Clock, then be added dropwise to rongalite that 0.50g concentration is 10% (two hydration sodium bisulphite formaldehydes) aqueous solution and carry out rear elimination reaction,
Continue insulation reaction 2 hours；When acrylic monomers conversion ratio reaches more than 98%, cooling is added dropwise to three second of 2.60g10%
Amine aqueous solution adjusts the pH value of product；Room temperature filtering and discharging is cooled to, that is, obtains core shell structure hydroxyl acrylic emulsion.
Embodiment 2:
It is as shown in table 2 from each component composition and content in this implementation：
The each component composition of 2 embodiment of table 2 and content table：
A kind of preparation method of core shell structure hydroxyl acrylic emulsion, including the following steps for carrying out in order：
The pre-emulsification of step one, seed emulsion monomer
By 1.20g anion emulsifiers dodecyl sodium sulfate and 0.40g AEOs (AEO-7),
0.40gpH value buffer solution sodium acid carbonates and 27.11g deionized waters are added in emulsifier, are mixed under 1200 revs/min of stirring conditions
5 minutes；Take acrylic monomers, i.e. 1.38g methyl methacrylates, 1.50g styrene, 0.19g butyl acrylate mixing it is equal
It is even, at the uniform velocity instilling emulsifier under 10000 revs/min of high speed emulsification conditions, time for adding 20 minutes；Continue breast at a high speed after dripping off
Change 20 minutes, obtain the pre-emulsion of seed emulsion monomer；
Step 2, preparation seed emulsion
By in the pre-emulsion of seed emulsion monomer obtained by step step one input reactor, in 200 revs/min of stirring
Under speed, 70 DEG C are warmed up to；It is 10% by 0.40g concentration after temperature reaches 70 DEG C except oxygen to nitrogen is led in reactor
Persulfate aqueous solution is disposably added in system；After blue light occurs in emulsion and exothermic peak terminates, continue to be incubated 20 points
Clock, obtains seed emulsion；
Step 3, prepare core partial emulsion
Take methyl methacrylate, the styrene of 9.15g, the butyl acrylate of 1.18g of acrylic monomers, i.e. 8.39g
After well mixed, under 100 revs/min of stirring conditions, at the uniform velocity in seed emulsion obtained by instillation step 2；1.00g is instilled simultaneously
Concentration is 10% persulfate aqueous solution；Control was dripped off in 3 hours；After dripping, insulation reaction 60 minutes；It is disposable to mend
The persulfate aqueous solution that 0.10g concentration is 10% is added, insulation reaction 3 hours obtains core partial emulsion；
The pre-emulsification of step 4, shell emulsion monomer
It is 50% alkoxy polyoxy to take the alkyl polyoxyethylene acyl sodium sulfonate solution, 0.40g concentration that 1.20g concentration is 50%
Ethene ethereal solution and 18.64g deionized waters are added in emulsifier, are mixed 5 minutes under 1200 revs/min of stirring conditions；Take acrylic acid
The methyl methacrylate of monomer, i.e. 3.99g, the styrene of 4.35g, the butyl acrylate of 7.07g and self-crosslinking function monomer
1.20g DAAMs and other functions monomer 1.20g methacrylic acids are well mixed, and bar is emulsified at a high speed at 10000 revs/min
Under part in instillation emulsifier, time for adding 20 minutes；Continue emulsification 20 minutes at a high speed after dripping off, obtain the pre-emulsion of shell emulsion monomer；
Step 5, prepare core shell structure hydroxyl acrylic emulsion
Under 200 revs/min of stirring conditions, the pre-emulsion of step 4 gained shell parts emulsion monomer is at the uniform velocity instilled into step
In three gained core partial emulsions, while instilling the persulfate aqueous solution that 2.00g concentration is 10%, drip off within 4 hours；Drip
Afterwards, insulation reaction 1 hour；The persulfate aqueous solution that 0.10g concentration is 10% is added again；Insulation reaction 1 hour；Cool to 70
DEG C, the TBHP aqueous solution that 0.30g concentration is 10% is added dropwise to, time for adding 20 minutes is incubated 30 minutes after dripping off
The aqueous solution for being added dropwise to the rongalite (two hydration sodium bisulphite formaldehydes) that 0.30g concentration is 10% afterwards carries out rear elimination reaction,
Continue insulation reaction 2 hours；When acrylic monomers conversion ratio reaches more than 98%, cooling, it is 10% to be added dropwise to 3.26g concentration
Ammonia aqueous solution adjust product pH value；It is added dropwise to the auxiliary self-crosslinking function monomer adipic acid two that 4.00g concentration is 10%
The aqueous solution of hydrazine；250 revs/min are stirred 30 minutes after dripping off, and filtering and discharging obtains core shell structure hydroxyl acrylic emulsion.
Embodiment 3
It is as shown in table 3 from each component composition and content in this implementation：
The each component composition of 3 embodiment of table 3 and content table：
A kind of preparation method of core shell structure hydroxyl acrylic emulsion, including the following steps for carrying out in order：
The pre-emulsification of step one, seed emulsion monomer
By 0.80g anion emulsifiers ammonium lauryl sulfate and 0.80g nonionic emulsifier APESs
(TX-100), in 0.60gpH buffer solutions sodium acid carbonate and 30.59g deionized waters addition emulsifier, in 800 revs/min of stirring conditions
Lower mixing 15 minutes；Take acrylic monomers, i.e. 7.50g methyl methacrylates, the butyl acrylate of 0.50g is well mixed,
In at the uniform velocity instilling emulsifier under 6000 revs/min of high speed emulsification conditions, time for adding 20 minutes；Continue 40 points of emulsification at a high speed after dripping off
Clock, obtains the pre-emulsion of seed emulsion monomer；
Step 2, preparation seed emulsion
By in the pre-emulsion of seed emulsion monomer obtained by step one input reactor, in 300 revs/min of mixing speed
Under, it is warmed up to 85 DEG C；To nitrogen is led in reactor, except oxygen, after temperature reaches 85 DEG C, by the over cure that 0.33g concentration is 10%
Sour aqueous ammonium is disposably added in system；After blue light occurs in emulsion and exothermic peak terminates, continue to be incubated 30 minutes, obtain
To seed emulsion；
Step 3, prepare core partial emulsion
Take the methyl methacrylate of acrylic monomers, i.e. 13.12g, 0.88g butyl acrylate it is well mixed after,
Under 150 revs/min of stirring conditions, at the uniform velocity in seed emulsion obtained by instillation step 2；The mistake that 2.50g concentration is 10% is instilled simultaneously
Ammonium sulfate solution；Control was dripped off in 3 hours；After dripping, insulation reaction 60 minutes；Disposably add into 0.17g concentration
It is 10% ammonium persulfate aqueous solution, insulation reaction 3 hours obtains core partial emulsion；
The pre-emulsification of step 4, shell emulsion monomer
Alkyl polyoxyethylene acyl sodium sulfonate solution, 0.80g g concentration that 0.80g concentration is 50% are taken for 50% alkoxy is poly-
Oxygen ethene ethereal solution and 7.61g deionized waters are added in emulsifier, are mixed 15 minutes under 800 revs/min of stirring conditions；Take propylene
The methyl methacrylate of acid monomers, i.e. 5.50g, the butyl acrylate of 10.50g and self-crosslinking function monomer 1.20g methylene
Diacrylamine and other functions monomer 0.80g methacrylic acids are well mixed, are instilled under 6000 revs/min of high speed emulsification conditions
In emulsifier, time for adding 20 minutes；Continue emulsification 40 minutes at a high speed after dripping off, obtain the pre-emulsion of shell emulsion monomer；
Step 5, prepare core shell structure hydroxyl acrylic emulsion
Under 200 revs/min of stirring conditions, the pre-emulsion of step 4 gained shell parts emulsion monomer is at the uniform velocity instilled into step
In three gained core partial emulsions, while instilling the ammonium persulfate aqueous solution that 2.50g concentration is 10%, drip off within 5 hours；Drip
Afterwards, insulation reaction 1 hour；The ammonium persulfate aqueous solution that 0.17g g concentration is 10% is added again；Insulation reaction 1 hour；Cool to
70 DEG C, the TBHP aqueous solution that 0.30g concentration is 10% is added dropwise to, time for adding 20 minutes is incubated 30 after dripping off
Removing is anti-after the aqueous solution of rongalite that 0.30g concentration is 10% (two hydration sodium bisulphite formaldehydes) is added dropwise to after minute carrying out
Should, continue insulation reaction 2 hours；When acrylic monomers conversion ratio reaches more than 98%, it is 10% to be added dropwise to 7.40g concentration
AMP-95 (aminomethylpropanol) aqueous solution adjusts the pH value of product；It is added dropwise to the auxiliary self-crosslinking function monomer of 4.00g10%
The aqueous solution of succinic acid hydrazide ii；250 revs/min are stirred 30 minutes after dripping off, and filtering and discharging obtains core shell structure hydroxy
Yogurt liquid.
In order to further illustrate the preparation method of core shell structure hydroxyl acrylic emulsion of the present invention, the present invention is to reality
The performance for applying the acrylic emulsion of the preparation of example 1,2 and 3 is detected that detection method is as follows：
Emulsion solid content is with reference to GB1725-79 standards；
PH value uses the glass-calomel electrode pH meter demarcated with cushioning liquid to determine；
Viscosity rotary viscosity design determining, unit CPS；
Mechanical stability:Before measure, emulsion sample is first then charged into special agitating device with 100 mesh filter-cloth filterings
In, stirred 10 minutes with starching 6096 ms/min of end line speed, then again with 100 mesh filter-cloth filterings, if without gel, illustrating breast
Liquid good mechanical stability, judges to pass through；If gel, the gel piece that will be leached is weighed after 105 DEG C of dryings, dry state jello
It is more, illustrate that emulsion mechanical stability is poorer；
Freeze-thaw stability：10 grams of emulsion samples are placed in 15 milliliters of plastic bottle.2 are placed in subzero 20 DEG C of refrigerator
Hour, take out and melt 6 hours in room temperature, it is a circulation, by three circulations for freeze-thaw stability is qualified, judge to pass through；
Calcium ion stability：5% calcium chloride solution is prepared, according to 1：4 ratio mixes with emulsion, static 48 hours,
If occurred without gel, and without lamination, then Calcium ion stability would be qualified, judges to pass through；
Bin stability：Placed 7 days in 50 DEG C of constant temperature oven, taking-up is placed into room temperature observation, if gone out without gel
It is existing, and without lamination, then bin stability is qualified, judges to pass through；
Dilution stability：By emulsion：Water=1：10 ratios are well mixed, and place 48 hours, not stratified, be not demulsified, and dilute
Qualified stability, judges to pass through；
MFT is tested using MFT instrument；
Emulsion particle particle diameter and distribution, are surveyed with Malvern AutoSizer LocFc963 laser diffraction particle sizes distribution instrument
It is fixed；
Glass transition temperature, is determined, with the different glass of core shell with the differential scanning calorimeter DSC of German Nai Chi companies
Glass transition temperature characterizes the core shell structure of emulsion；
Degree of cross linking test after emulsion film forming：With 400 microns of blade applicator knifing, place 7 days at room temperature, take 2 grams or so
The film for preparing, with acetone soak 2 hours, after taking-up 105 DEG C of dryings to constant weight, weigh, this numerical value and acetone soak
The percentage of preceding film weight amount is the degree of cross linking after emulsion film forming, and emulsion oneself is characterized with the degree of cross linking after emulsion film forming
Crosslinking degree；
The relative molecular mass and molecular weight distribution of emulsion, first emulsion coagulation, are washed out resulting polymers, then with four
Hydrogen furans dissolves, and is determined with gel permeation chrommatograph GPC.
Acrylic microemulsion test result prepared by the various embodiments described above is as shown in table 4.
Acrylic microemulsion the performance test results prepared by 4 embodiment of form 1,2 and 3：
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe
The personage for knowing this technology all can carry out modifications and changes under without prejudice to spirit and scope of the invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete with institute under technological thought without departing from disclosed spirit such as
Into all equivalent modifications or change, should be covered by claim of the invention.
Claims (8)
1. a kind of preparation method of core shell structure hydroxyl acrylic emulsion, it is characterised in that specifically include following steps：
Step 1）：The emulsifying agent that acrylic monomers gross mass 1~5% will be accounted for is, the pH value for accounting for acrylic monomers gross mass 0.5~3%
Buffer mixes 30 points with the deionized water for accounting for acrylic monomers gross mass 30~90% under 500~2000 revs/min of stirring conditions
Clock；Then input accounts for the acrylic monomers of acrylic monomers gross mass 1-30%, in 2000~30000 revs/min of high speed emulsification conditions
Emulsified 15-30min, obtains the pre-emulsion of seed emulsion monomer；
Step 2）：To step 1）In obtained seed emulsion monomer pre-emulsion in letting nitrogen in and deoxidizing, be then warmed up to 80 DEG C；
Under 50~200 revs/min of stirring conditions, addition accounts for the initiator initiated polymerization of acrylic monomers gross mass 0.2~1%, gathers
Close after exothermic heat of reaction terminates and be incubated 30 minutes, obtain seed emulsion；
Step 3）：Under 50~300 revs/min of stirring conditions, to step 2）In instill in obtained seed emulsion and account for acrylic acid
The acrylic monomers of monomer gross mass 30~45%, while instilling the initiator for accounting for acrylic monomers gross mass 0.02~1%, is added dropwise
1~3 hour time；After dripping, insulation reaction 30~90 minutes；Add again and account for drawing for acrylic monomers gross mass 0.01~1%
Hair agent, insulation reaction 1~3 hour obtains core partial emulsion；
Step 4）：Take and account for the emulsifying agent of acrylic monomers gross mass 1~4% and account for the deionization of acrylic monomers gross mass 5~30%
Water is added in emulsifier, is mixed 3~20 minutes under 500~2000 revs/min of stirring conditions；Acrylic monomers gross mass 20 will be accounted for
~60% acrylic monomers, the self-crosslinking function monomer for accounting for acrylic monomers gross mass 1~6% and account for acrylic monomers gross mass
0.5~4% alkyl acrylic mixes 3~20 minutes under 50~300 revs/min of stirring conditions；Input accounts for the total matter of acrylic monomers
The acrylic monomers of 30-45% is measured, under 2000~30000 revs/min of high speed emulsification conditions, is emulsified 10~60 minutes, obtain shell
The pre-emulsion of emulsion monomer；
Step 5）：Under 50~300 revs/min of stirring conditions, by step 4）In obtained shell emulsion monomer pre-emulsion it is even
Speed instills step 3）In in obtained core partial emulsion, while instilling the initiation for accounting for acrylic monomers gross mass 0.02~1%
Agent, time for adding 1~3 hour；After dripping, insulation reaction 30~90 minutes；Add again and account for acrylic monomers gross mass 0.01
~0.5% initiator；After dripping, 0.5~2 hour is incubated；Then 70 degree are cooled to, are removed after adding post-treatment agent to carry out
Reaction, continues to be incubated 1~2 hour；Cooling, 7~10, time for adding 10~40 minutes are adjusted to pH value regulator by pH value；
Finally above-mentioned product is filtered, core shell structure hydroxyl acrylic emulsion is obtained.
2. the preparation method of core shell structure hydroxyl acrylic emulsion according to claim 1, it is characterised in that the propylene
Acid monomers are obtained by the material mixing of following mass percent：10%~20% atomic number of alkyl carbon is 1~15 methacrylic acid
Arrcostab, the alkyl acrylate that 10%~20% atomic number of alkyl carbon is 1~15 and 10%~20% acrylic acid aromatic compound；
Wherein described alkyl methacrylate is methyl methacrylate, EMA, butyl methacrylate, first
One or more in base amyl acrylate, hexyl methacrylate, n octyl methacrylate, EHMA；
The alkyl acrylate be methyl acrylate, ethyl acrylate, butyl acrylate, amyl acrylate, Hexyl 2-propenoate,
One or more in 2-EHA；
The acrylic acid aromatic compound is in styrene, methyl styrene, 3- t-butyl styrenes, 2- chlorostyrenes
Plant or various.
3. the preparation method of core shell structure hydroxyl acrylic emulsion according to claim 1, it is characterised in that the step
1）Described in pH be sodium acid carbonate.
4. the preparation method of core shell structure hydroxyl acrylic emulsion according to claim 1, it is characterised in that step 4）In
The self-crosslinking function monomer is acrylate functional monomer that atomic number of alkyl carbon is 1~15；Wherein acrylate function
Property monomer be hydroxyethyl methacrylate, hydroxy propyl methacrylate, N hydroxymethyl acrylamide, methyl propenoic acid glycidyl
One kind or many in ester, DAAM, methylene diacrylamine, aminimide, acrylamide glycolic acid esters
Kind；
The alkyl acrylic is one or more in acrylic acid, methacrylic acid or methylene-succinic acid.
5. the preparation method of core shell structure hydroxyl acrylic emulsion according to claim 1, it is characterised in that step 5）In
After pH value is adjusted into 7~10 with pH value regulator, auxiliary self-crosslinking agent is instilled, time for adding is 20~60 minutes, after dripping off
Continue to stir 10~30 minutes；Filtering, that is, obtain core shell structure hydroxyl acrylic emulsion；Wherein auxiliary self-crosslinking agent is alkane
Base carbon number is 1~15 hydrazine class compound；The hydrazine class compound is the hydrazine of adipic acid two, carbon acid dihydrazide, the acyl of oxalic acid two
One or more in hydrazine, succinic acid hydrazide ii.
6. the preparation method of core shell structure hydroxyl acrylic emulsion according to claim 1, it is characterised in that step 5）In
The post-treatment agent is by 0.01~0.1% TBHP and 0.01~0.1% 2 hydration sodium bisulphite formaldehyde structure
Into;
The pH value regulator be triethylamine, isopropylamine, n-propylamine, n-butylamine, dimethylamine, dimethyl amine, diethyl methyl amine,
The mixture of one or more in dimethylethanolamine, front three ethylethanolamine, aminomethylpropanol, ammoniacal liquor.
7. the preparation method of core shell structure hydroxyl acrylic emulsion according to claim 1, it is characterised in that the emulsification
Agent is the blended emulsifier that 0.01~0.1% anion emulsifier and 0.01~0.1% nonionic emulsifier are compounded；
Wherein step 1）In anion emulsifier used be selected from lauryl sodium sulfate, ammonium lauryl sulfate, dodecyl sulphur
One or more in sour sodium and neopelex；Step 1）In nonionic emulsifier used be selected from alkyl phenol polyoxy second
One or more in compound, the AEO of alkene ether；
Wherein step 4）In anion emulsifier used be selected from alkyl diphenyl ether disodium sulfonate salt, alkyl polyoxyethylene acyl sulfonic acid
Sodium, tributyl phenol sodium sulfonate of ethoxylated, allyl polyethenoxy ether derivative ammonium sulfate and allyl polyethenoxy ether sulphur
One or more in sour ammonium；Step 4）In nonionic emulsifier used be selected from alkyl polyoxyethylene ether phosphate, tributyl phenol
One kind in APEO, alkyl polyoxyethylene ether, allyl polyethenoxy ether, acrylic acid polyoxyethylene polyoxypropylene ether or
It is several.
8. the preparation method of core shell structure hydroxyl acrylic emulsion according to claim 1, it is characterised in that the initiation
Agent is persulfuric acid salt initiator.
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