CN109971156A - A kind of acrylic ester modified water-soluble polyurethane lotion and preparation method thereof - Google Patents
A kind of acrylic ester modified water-soluble polyurethane lotion and preparation method thereof Download PDFInfo
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- CN109971156A CN109971156A CN201910218122.0A CN201910218122A CN109971156A CN 109971156 A CN109971156 A CN 109971156A CN 201910218122 A CN201910218122 A CN 201910218122A CN 109971156 A CN109971156 A CN 109971156A
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- 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
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- 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
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- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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Abstract
The invention discloses a kind of acrylic ester modified water-soluble polyurethane lotion and preparation method thereof, which includes: to synthesize to obtain terminal hydroxy group type polyacrylate by free radical random copolymerization using the chain-transferring agent of acrylate monomer and hydroxyl as raw material；Chain extender and the first crosslinking agent are added in diisocyanate, polymer diatomic alcohol and hydrophilic monomer, obtains isocyanate terminated fundamental mode Waterborne Polyurethane Prepolymer；By terminal hydroxy group type polyacrylate and isocyanate terminated fundamental mode Waterborne Polyurethane Prepolymer block, the block modified aqueous polyurethane emulsion of polyacrylate is made by pre-polymer process；Using the block modified aqueous polyurethane emulsion of polyacrylate as seed, Interpenetrating Polymer Network Type acrylate swelling-block modified aqueous polyurethane multiple emulsion is obtained by Soap free cationic emulision legal system with acrylate monomer, the second crosslinking agent.Multiple emulsion of the invention has the characteristics that solid content is high, stability of emulsion is excellent, glue film water-tolerant.
Description
Technical field
The present invention relates to acrylic ester modified water-soluble polyurethane technical fields, and in particular to a kind of acrylic ester modified water-soluble
Polyaminoester emulsion and preparation method thereof.
Background technique
Under the overall background for limiting volatile organic compound emission in the world, as environmentally friendly production
Product --- the aqueous polyurethane without organic solvent has obtained faster development in the industry.Water-base polyurethane material comprehensive performance
It is excellent, there is fabulous film forming, wearability, solvent resistance, adhesive property and good cryogenic property, on numerous substrates
Different application requirements can be adapted to excellent adhesive force and by structural adjustment, be therefore widely used in adhesive, apply
Material, rubber, printing ink, in leather finishing agent.
Compared with solvent borne polyurethane, the addition of hydrophilic radical will lead to dry water-borne polyurethane bond in aqueous polyurethane
Film shows poor water resistance, film forming and flexibility etc., and aqueous polyurethane emulsion solid content is low, application cost phase
To higher, it is made to receive certain limitation in practical application.
Acrylic polymer has excellent resistance to ag(e)ing, water resistance, compatibility and low in cost, is widely used
In industrial circle, but have the shortcomings that hot sticky and cold short.If both aqueous polyurethane and polyacrylate is compound, can make
Product has the excellent adhesion of aqueous polyurethane, the resistance to ag(e)ing of flexibility and polyacrylate, water resistance, and energy simultaneously
Production cost can be greatly reduced, widen practical ranges.
The acrylic ester modified water-soluble polyurethane of domestic report mainly uses seed emulsion polymerization to prepare at present.Publication number
A kind of waterborne polyurethane-acrylate emulsion prepared by seed emulsion polymerization method is disclosed for the patent specification of CN102093516A
Method, acrylic ester modified water-soluble polyurethane lotion has been obtained by external ions type emulsifier, has been prepared in this way
Compatibility in obtained product containing the emulsifier for being largely difficult to remove and between aqueous polyurethane and acrylate is poor, though
Its right apparent stability of emulsion increased, but can cause biggish negative effect to the properties of lotion.
The patent specification of Publication No. CN104788623A discloses a kind of intercrossed network type water-borne polyurethane-acrylate
The preparation method of ester composite emulsion has obtained acrylate using the method for the swelling of disposable pre-emulsification and semi-continuous emulsion polymerizing
Modified aqueous polyurethane emulsion, but there are the speed that acrylate swelling enters aqueous polyurethane inside particles for this method
Slowly, the problem of polymerization technique complexity, and acrylate dosage is still without biggish promotion.
In addition, also there is part document to prepare acrylic ester modified water-soluble polyurethane lotion using copolymerization method.Publication No.
The patent specification of CN106634548A discloses a kind of polyurethane/acrylate hybridisation emulsion and preparation method thereof, pass through to
Unsaturated double-bond is introduced in aqueous polyurethane, is then further introduced into acrylate monomer and is copolymerized to obtain acrylic ester modified water-soluble
Polyaminoester emulsion, this method also need additional emulsifier to maintain emulsion-stabilizing and there are acrylate dosages lower, lotion
The obvious problem of reduced performance.
In view of disadvantages described above, it is quite necessary to provide a kind of by segment copolymerization method/Soap free cationic emulision method/interpenetrating
Polymer network method overcomes problem above to prepare the method for high dosage acrylic ester modified water-soluble polyurethane lotion.
Summary of the invention
For shortcoming existing for this field, the present invention provides a kind of acrylic ester modified water-soluble polyurethane lotions
Preparation method prepares high dosage acrylic acid by segment copolymerization method/Soap free cationic emulision method/interpenetrating polymer networks method
The method of ester modified aqueous polyurethane emulsion, solves between aqueous polyurethane and high dosage acrylate that compatibility is poor to ask
Topic overcomes the introducing of high dosage acrylate in the prior art to need the defect of additional emulsifier, substantially increases modified water-soluble
The dosage of acrylate in polyaminoester emulsion, and introduce crosslinking interpenetrating between polyacrylate and aqueous polyurethane and polymerize
Object network structure further improves the comprehensive performance of product.
A kind of preparation method of acrylic ester modified water-soluble polyurethane lotion, comprising: with acrylate monomer and hydroxyl
Chain-transferring agent be raw material, synthesize to obtain terminal hydroxy group type polyacrylate by free radical random copolymerization；In diisocyanate, gather
It closes and chain extender and the first crosslinking agent is added in object dihydric alcohol and hydrophilic monomer, it is pre- to obtain isocyanate terminated fundamental mode aqueous polyurethane
Aggressiveness；By terminal hydroxy group type polyacrylate and isocyanate terminated fundamental mode Waterborne Polyurethane Prepolymer block, dispersed by performed polymer
Legal system obtains the block modified aqueous polyurethane emulsion of polyacrylate；It is kind with the block modified aqueous polyurethane emulsion of polyacrylate
Son obtains Interpenetrating Polymer Network Type acrylic acid by Soap free cationic emulision legal system with acrylate monomer, the second crosslinking agent
Ester swelling-block modified aqueous polyurethane multiple emulsion.
The specific steps of the preparation method of the acrylic ester modified water-soluble polyurethane lotion include:
(1) acrylate monomer, the chain-transferring agent of hydroxyl and solvent are mixed, oil-soluble initiator is added, 65~
Terminal hydroxy group type polyacrylate is obtained after reacting 5~15h at 75 DEG C；
(2) by after vacuum dehydration polymer diatomic alcohol and hydrophilic monomer mix, the stirring and dissolving 0.5 at 60~65 DEG C
Diisocyanate and organic tin catalyst are added after~1h, is warming up to 70~75 DEG C of 3~4h of insulation reaction, chain extension is then added
Agent and the first crosslinking agent the reaction was continued 1~2h, obtain isocyanate terminated fundamental mode Waterborne Polyurethane Prepolymer；
(3) terminal hydroxy group type polyacrylate is added in isocyanate terminated fundamental mode Waterborne Polyurethane Prepolymer, supplemented with
Machine tin catalyst reacts 3~4h under 70~75 DEG C and nitrogen protection, reaction temperature is then reduced to 35~40 DEG C, is added
Enter and react 10~15min with the neutralizer of the hydrophilic monomer equimolar amounts, be then cooled to -5~5 DEG C, deionization is added
Water emulsification pretreatment obtains the block modified aqueous polyurethane emulsion of polyacrylate；
(4) by the acrylate monomer, the second crosslinking agent and 10%~30% water soluble starter be added to it is poly-
In arylate blocks modified aqueous polyurethane emulsion, 0.5~1h of stirring swelling, is passed through nitrogen, is warming up at 40~45 DEG C
40%~80% water soluble starter is added after 65~70 DEG C, 0.5~1h of insulation reaction then raises temperature to 75~80 DEG C of reactions
1~2h adds remaining water soluble starter, then heats to 85~90 DEG C of 2~3h of reaction, obtains interpenetrating polymer networks
Type acrylate swelling-block modified aqueous polyurethane multiple emulsion.
In step (1), the acrylate monomer is selected from methyl acrylate, ethyl acrylate, the positive ester of acrylic acid, propylene
Misery ester, 2-Propenoic acid, 2-methyl-, octyl ester, butyl methacrylate, methyl methacrylate, ethyl methacrylate, styrene and third
One of alkene nitrile is a variety of.
Preferably, the chain-transferring agent of the hydroxyl is mercaptoethanol or mercaprol.
Preferably, the dosage of the chain-transferring agent of the hydroxyl be step (1) acrylate monomer quality 4%~
6%.
The terminal hydroxy group type polyacrylate number-average molecular weight is 1500~2500gmol-1。
The oil-soluble initiator is azodiisobutyronitrile, azobisisoheptonitrile, cumyl peroxide or peroxidating
Dibenzoyl.
Preferably, the dosage of the oil-soluble initiator be step (1) acrylate monomer quality 0.8%~
1.2%.
In step (2), the diisocyanate be isophorone diisocyanate, hexamethylene diisocyanate or 4,
4 '-dicyclohexyl methyl hydride diisocyanates, Toluene-2,4-diisocyanate, 4- diisocyanate or 4,4 '-methyl diphenylene diisocyanates.
The additional amount of the diisocyanate is according in the block modified aqueous polyurethane emulsion of polyacrylate
Isocyanate group and the molar ratio of hydroxyl are calculated.
The polymer diatomic alcohol is polyethylene glycol, polypropylene glycol or polycaprolactone glycol, number-average molecular weight 1000
~3000gmol-1。
The additional amount of the polymer diatomic alcohol with the additional amount of step (3) middle-end oh type polyacrylate increase
And it correspondingly reduces.
The organic tin catalyst is dibutyl tin dilaurate or stannous octoate.
The hydrophilic monomer is dihydromethyl propionic acid or dimethylolpropionic acid.
The hydrophilic monomer quality account for step (2), the reactant gross mass of (3) 3%~5%.
The chain extender is 1,4- butanediol, dipropylene glycol, ethylene glycol, propylene glycol or neopentyl glycol.
The chain extender quality account for step (2), the reactant gross mass of (3) 3%~5%.
First crosslinking agent is trimethylolpropane or glycerol or pentaerythrite.
First crosslinking agent quality account for step (2), the reactant gross mass of (3) 0.5%~2%.
In step (3), the additional amount of the terminal hydroxy group type polyacrylate is total no more than step (2), the reactant of (3)
The 50% of quality.
The neutralizer is triethylamine or triethanolamine.
Hydroxyl in the block modified aqueous polyurethane emulsion of the polyacrylate comes from polymer diatomic alcohol, hydrophily
Monomer, chain extender, the first crosslinking agent and terminal hydroxy group type polyacrylate.
Isocyanate group and the molar ratio of hydroxyl are 1.1 in the block modified aqueous polyurethane emulsion of the polyacrylate
~1.5:1.
Solid content in the block modified aqueous polyurethane emulsion of the polyacrylate is 35%~45%.
In step (4), the water soluble starter is potassium peroxydisulfate or ammonium persulfate.
The water soluble starter accounts for the 0.6%~1% of the acrylate monomer quality of step (4).
In step (4), the dosage of the acrylate monomer is not more than the block modified aqueous polyurethane of polyacrylate
The 240% of solid masses in lotion.
Second crosslinking agent is glycidyl methacrylate.
Second dosage of crosslinking agent is not more than the 7.5% of the acrylate monomer quality of step (4).
Interpenetrating Polymer Network Type acrylate swelling-block modified aqueous polyurethane multiple emulsion solid content
It is 35%~45%.
Compared with prior art, the present invention major advantage includes:
(1) present invention is using terminal hydroxy group type polyacrylate and aqueous polyurethane block copolymerization, to utilize similar compatibility
A large amount of acrylate are successfully introduced into aqueous polyurethane by principle.Compared with the aqueous polyurethane of unfilled block polyacrylate,
Polyacrylate of the block on aqueous polyurethane provides physical compatibility for acrylate Fast-swelling, so as to avoid cream
The use of agent improves the dosage of acrylate in modified aqueous polyurethane emulsion.The dosage of acrylate is up to polypropylene
2.4 times of solid masses in the block modified aqueous polyurethane emulsion of acid esters.
(2) present invention uses glycidyl methacrylate for the second crosslinking agent, so that polyacrylate gathers with aqueous
The structure that the interpenetrating that is cross-linked with each other is formd between urethane further improves the comprehensive performance of product.
(3) products of the present invention has the characteristics that solid content is high, stability of emulsion is excellent, glue film water-tolerant, and
Simple process, production cost are low, environmentally protective, it can be achieved that heavy industrialization.The poly- ammonia of acrylic ester modified water-soluble of the invention
Ester lotion can be used for water-based ink binder, leather finishing agent and all kinds of surface coverings.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of the terminal hydroxy group type polyacrylate of embodiment 1；
Fig. 2 is the terminal hydroxy group type polyacrylate and the block modified Waterborne Polyurethane Prepolymer of polyacrylate of embodiment 1
Nuclear magnetic resonance (1H-NMR) spectrogram；
Fig. 3 a, the acrylate that 3b, 3c are comparative example swelling-block modified aqueous polyurethane multiple emulsion transmission electron microscope
Photo；
Fig. 3 d, the Interpenetrating Polymer Network Type acrylate that 3e, 3f are embodiment 1 swelling-block modified aqueous polyurethane
The transmission electron microscope photo of multiple emulsion.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip
Part, or according to the normal condition proposed by manufacturer.
Embodiment 1
Step 1: 25g methyl methacrylate, 25g acrylate N-butyl, 2.5g mercaptoethanol being added in the reactor
And 0.5g azodiisobutyronitrile initiator, 70 DEG C of reaction 10.0h are warming up to, obtain terminal hydroxy group type polyacrylate after cooling.
Step 2: the polypropylene glycol and 3.0g dihydroxymethyl third that 50g relative molecular mass is 2000 being added in the reactor
33.75g isophorone diisocyanate and 0.1g dibutyl tin dilaurate is added after being warming up to 60 DEG C of stirring and dissolving 0.5h in acid
Catalyst is warming up to 75 DEG C of reaction 3.0h, and 5.0g butanediol, 1.0g trimethylolpropane reaction 1.0h is then added, and chain extension is anti-
Should after the completion of be added 10g terminal hydroxy group type polyacrylate and 0.1g dibutyltin dilaurate catalyst, after insulation reaction 3.0h
Obtain the block modified Waterborne Polyurethane Prepolymer of polyacrylate.
Step 3: 2.26g triethylamine and 195g deionized water being added after being cooled to 40 DEG C, in 0 DEG C, 1800r min-1Condition
Lower high speed shearing emulsification obtains the block modified aqueous polyurethane emulsion of polyacrylate that solid content is 35%.
Step 4: 0.074g potassium peroxydisulfate being dissolved in 5g deionized water and obtains initiator solution, weighs 28.57g poly- third
The block modified aqueous polyurethane emulsion of olefin(e) acid ester, 12g methyl methacrylate, 0.3g glycidyl methacrylate and 18g
Reactor is added in deionized water, and stirring 0.5h is swollen monomer sufficiently at 45 DEG C, and 20% initiator solution is first added, is warming up to
65 DEG C of insulation reaction 1.0h, then 60% initiator solution is slowly added dropwise into system, 75 DEG C of insulation reaction 2.0h are warming up to, most
After 20% initiator solution is added, be warming up to 85 DEG C of insulation reaction 3.0h, obtain solid content be 35% interpenetrating polymer net
Network type acrylate swelling-block modified aqueous polyurethane multiple emulsion.
As shown in Figure 1, in the infrared spectrogram of terminal hydroxy group type polyacrylate, 3442cm-1There is apparent hydroxyl in place
Stretching vibration absworption peak, 2500~2590cm-1Place illustrates that mercaptoethanol is bonded by chain transfer reaction without S-H characteristic absorption peak
To polyacrylate molecular.
As shown in Fig. 2, in terminal hydroxy group type polyacrylate1In H-NMR figure, terminal hydroxy group type polyacrylate end two
Proton (~S-CH on methylene2-CH2- OH) formant homolysis be divided into double peak, chemical shift appear in 3.72/3.71 and
2.70/2.69.Occur in the nuclear magnetic spectrogram of the block modified aqueous polyurethane of polyacrylate 2.70 and 3.64 two it is new
Proton resonance peak, analysis belong to the proton on former two methylene in terminal hydroxy group type polyacrylate end, are clearly prepared
Polyacrylate block modified aqueous polyurethane.
As shown in Fig. 3 d~3f, Interpenetrating Polymer Network Type acrylate that the present embodiment obtains swelling-block modified water
Property polyurethane multiple emulsion latex particle inside exist and dye deeper region, and it is more equal to dye deeper area distribution
It is even, and belong to the aqueous polyurethane strand with higher cloud density due to dyeing deeper region, it was demonstrated that interpenetrating
Polymer network type acrylate swelling-block modified aqueous polyurethane latex particle is interpenetrating polymer networks structure.
Multiple emulsion average grain diameter 75nm obtained by the present embodiment, the water absorption rate that compound cutan impregnates 48h at 25 DEG C are
4.06%, tensile strength 17.60MPa, elongation at break 787%.
Comparative example
Compared with Example 1, difference, which is only that in step 4, is added without the second crosslinking agent glycidyl methacrylate,
Other steps and condition are all the same, obtain acrylate swelling-block modified aqueous polyurethane multiple emulsion.
As shown in Fig. 3 a~3c, acrylate that this comparative example obtains swelling-block modified aqueous polyurethane multiple emulsion
Latex particle dyes deeper only particle extexine, it was demonstrated that the acrylate swelling-that comparative example obtains is block modified aqueous poly-
Urethane multiple emulsion latex particle does not have interpenetrating polymer networks structure.
Embodiment 2
Step 1: 25g methyl methacrylate, 25g acrylate N-butyl, 2.0g mercaptoethanol being added in the reactor
And 0.6g azodiisobutyronitrile initiator, 65 DEG C of reaction 15.0h are warming up to, obtain terminal hydroxy group type polyacrylate after cooling.
Step 2: the polypropylene glycol and 4.0g dihydroxymethyl third that 40g relative molecular mass is 2000 being added in the reactor
32.06g isophorone diisocyanate and 0.1g dibutyl tin dilaurate is added after being warming up to 63 DEG C of stirring and dissolving 0.5h in acid
Catalyst is warming up to 73 DEG C of reaction 3.5h, and 4.0g butanediol, 1.0g trimethylolpropane reaction 1.5h is then added, and chain extension is anti-
Should after the completion of be added 20g terminal hydroxy group type polyacrylate and 0.1g dibutyltin dilaurate catalyst, after insulation reaction 3.5h
Obtain the block modified Waterborne Polyurethane Prepolymer of polyacrylate.
Step 3: 3.02g triethylamine and 156g deionized water being added after being cooled to 38 DEG C, in -5 DEG C, 2000r min-1Condition
Lower high speed shearing emulsification obtains the block modified aqueous polyurethane emulsion of polyacrylate that solid content is 40%.
Step 4: 0.202g potassium peroxydisulfate being dissolved in 5g deionized water and obtains initiator solution, weighs 25g polypropylene
The block modified aqueous polyurethane emulsion of acid esters, 18g methyl methacrylate, 6g n-butyl acrylate, the contracting of 1.2g methacrylic acid
Reactor is added in water glyceride and 29g deionized water, and 1.0h is stirred at 40 DEG C is swollen monomer sufficiently, is first added 10% and causes
Agent aqueous solution is warming up to 70 DEG C of insulation reaction 0.5h, then 80% initiator solution is slowly added dropwise into system, is warming up to 80
DEG C, insulation reaction 1.0h is eventually adding 10% initiator solution, is warming up to 90 DEG C, insulation reaction 2.0h, and obtaining solid content is
42% Interpenetrating Polymer Network Type acrylate swelling-block modified aqueous polyurethane multiple emulsion.
Multiple emulsion average grain diameter 80nm obtained by the present embodiment, the water absorption rate that compound cutan impregnates 48h at 25 DEG C are
3.64%, tensile strength 18.85MPa, elongation at break 521%.
Embodiment 3
Step 1: 25g methyl methacrylate, 25g acrylate N-butyl, 3.0g mercaptoethanol being added in the reactor
And 0.4g azodiisobutyronitrile initiator, 75 DEG C of reaction 5.0h are warming up to, obtain terminal hydroxy group type polyacrylate after cooling.
Step 2: the polypropylene glycol and 5.0g dihydroxymethyl third that 20g relative molecular mass is 2000 being added in the reactor
29.72g isophorone diisocyanate and 0.1g dibutyl tin dilaurate is added after being warming up to 65 DEG C of stirring and dissolving 0.5h in acid
Catalyst is warming up to 70 DEG C of reaction 4.0h, and 5.0g butanediol, 1.0g trimethylolpropane reaction 2.0h is then added, and chain extension is anti-
Should after the completion of be added 40g terminal hydroxy group type polyacrylate and 0.1g dibutyltin dilaurate catalyst, after insulation reaction 4.0h
Obtain the block modified Waterborne Polyurethane Prepolymer of polyacrylate.
Step 3: 3.77g triethylamine and 125g deionized water being added after being cooled to 35 DEG C, in 5 DEG C, 2500r min-1Condition
Lower high speed shearing emulsification obtains the block modified aqueous polyurethane emulsion of polyacrylate that solid content is 45%.
Step 4: 0.258g potassium peroxydisulfate being dissolved in 5g deionized water and obtains initiator solution, weighs 22.22g poly- third
The block modified aqueous polyurethane emulsion of olefin(e) acid ester, 6g methyl methacrylate, 18g n-butyl acrylate, 1.8g methacrylic acid
Reactor is added in ethylene oxidic ester and 27g deionized water, and 1.0h is stirred at 40 DEG C is swollen monomer sufficiently, is first added 15% and draws
Agent aqueous solution is sent out, 65 DEG C of insulation reaction 1.0h is warming up to, then 70% initiator solution is slowly added dropwise into system, is warming up to 75
DEG C, insulation reaction 2.0h is eventually adding 15% initiator solution, is warming up to 85 DEG C, insulation reaction 3.0h, and obtaining solid content is
45% Interpenetrating Polymer Network Type acrylate swelling-block modified aqueous polyurethane multiple emulsion.
Multiple emulsion average grain diameter 88nm obtained by the present embodiment, the water absorption rate that compound cutan impregnates 48h at 25 DEG C are
3.95%, tensile strength 12.35MPa, elongation at break 932%.
Embodiment 4
Step 1: 25g methyl methacrylate, 25g acrylate N-butyl, 2.5g mercaptoethanol being added in the reactor
And 0.6g azodiisobutyronitrile initiator, 70 DEG C of reaction 10.0h are warming up to, obtain terminal hydroxy group type polyacrylate after cooling.
Step 2: the polypropylene glycol and 4.0g dihydroxymethyl third that 40g relative molecular mass is 2000 being added in the reactor
32.06g isophorone diisocyanate and 0.1g dibutyl tin dilaurate is added after being warming up to 60 DEG C of stirring and dissolving 0.5h in acid
Catalyst is warming up to 75 DEG C of reaction 3.0h, and 4.0g butanediol, 1.0g trimethylolpropane reaction 1.0h is then added, and chain extension is anti-
Should after the completion of be added 20g terminal hydroxy group type polyacrylate and 0.1g dibutyltin dilaurate catalyst, after insulation reaction 3.0h
Obtain the block modified Waterborne Polyurethane Prepolymer of polyacrylate.
Step 3: 3.02g triethylamine and 156g deionized water being added after being cooled to 40 DEG C, in 0 DEG C, 1500r min-1Condition
Lower high speed shearing emulsification obtains the block modified aqueous polyurethane emulsion of polyacrylate that solid content is 40%.
Step 4: 0.101g potassium peroxydisulfate being dissolved in 5g deionized water and obtains initiator solution, weighs 25g polypropylene
The block modified aqueous polyurethane emulsion of acid esters, 6g methyl methacrylate, 6g n-butyl acrylate, 0.6g Glycidyl methacrylate
Reactor is added in glyceride and 14g deionized water, and 0.5h is stirred at 45 DEG C is swollen monomer sufficiently, and 20% initiator is first added
Aqueous solution is warming up to 70 DEG C of insulation reaction 0.5h, then 60% initiator solution is slowly added dropwise into system, is warming up to 80 DEG C,
Insulation reaction 1.0h is eventually adding 20% initiator solution, is warming up to 90 DEG C, insulation reaction 2.0h, and obtaining solid content is
40% Interpenetrating Polymer Network Type acrylate swelling-block modified aqueous polyurethane multiple emulsion.
Multiple emulsion average grain diameter 73nm obtained by the present embodiment, the water absorption rate that compound cutan impregnates 48h at 25 DEG C are
4.13%, tensile strength 19.24MPa, elongation at break 681%.
In addition, it should also be understood that, those skilled in the art can be to this hair after having read foregoing description content of the invention
Bright to make various changes or modifications, these equivalent forms also fall within the scope of the appended claims of the present application.
Claims (10)
1. a kind of preparation method of acrylic ester modified water-soluble polyurethane lotion, comprising: with acrylate monomer and hydroxyl
Chain-transferring agent is raw material, synthesizes to obtain terminal hydroxy group type polyacrylate by free radical random copolymerization；In diisocyanate, polymerization
Chain extender and the first crosslinking agent are added in object dihydric alcohol and hydrophilic monomer, obtains isocyanate terminated fundamental mode aqueous polyurethane pre-polymerization
Body；By terminal hydroxy group type polyacrylate and isocyanate terminated fundamental mode Waterborne Polyurethane Prepolymer block, pass through pre-polymer process
The block modified aqueous polyurethane emulsion of polyacrylate is made；It is kind with the block modified aqueous polyurethane emulsion of polyacrylate
Son obtains Interpenetrating Polymer Network Type acrylic acid by Soap free cationic emulision legal system with acrylate monomer, the second crosslinking agent
Ester swelling-block modified aqueous polyurethane multiple emulsion.
2. the preparation method of acrylic ester modified water-soluble polyurethane lotion according to claim 1, which is characterized in that specific
Step includes:
(1) acrylate monomer, the chain-transferring agent of hydroxyl and solvent are mixed, oil-soluble initiator is added, at 65~75 DEG C
Terminal hydroxy group type polyacrylate is obtained after 5~15h of lower reaction；
(2) by after vacuum dehydration polymer diatomic alcohol and hydrophilic monomer mix, 0.5~1h of stirring and dissolving at 60~65 DEG C
Diisocyanate and organic tin catalyst are added afterwards, is warming up to 70~75 DEG C of 3~4h of insulation reaction, be then added chain extender and
First crosslinking agent the reaction was continued 1~2h, obtains isocyanate terminated fundamental mode Waterborne Polyurethane Prepolymer；
(3) terminal hydroxy group type polyacrylate is added in isocyanate terminated fundamental mode Waterborne Polyurethane Prepolymer, adds organotin
Class catalyst reacts 3~4h under 70~75 DEG C and nitrogen protection, and reaction temperature is then reduced to 35~40 DEG C, be added with
The neutralizer of the hydrophilic monomer equimolar amounts reacts 10~15min, is then cooled to -5~5 DEG C, and deionized water is added and cuts
It cuts emulsification and obtains the block modified aqueous polyurethane emulsion of polyacrylate；
(4) acrylate monomer, the second crosslinking agent and 10%~30% water soluble starter are added to polypropylene
In the block modified aqueous polyurethane emulsion of acid esters, 0.5~1h of stirring swelling, is passed through nitrogen at 40~45 DEG C, it is warming up to 65~
After 70 DEG C be added 40%~80% water soluble starter, 0.5~1h of insulation reaction, then raise temperature to 75~80 DEG C reaction 1~
2h adds remaining water soluble starter, then heats to 85~90 DEG C of 2~3h of reaction, obtains Interpenetrating Polymer Network Type
Acrylate swelling-block modified aqueous polyurethane multiple emulsion.
3. the preparation method of acrylic ester modified water-soluble polyurethane lotion according to claim 2, which is characterized in that step
(1) in, the acrylate monomer is selected from methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate, methyl
One in 2-ethyl hexyl acrylate, butyl methacrylate, methyl methacrylate, ethyl methacrylate, styrene and acrylonitrile
Kind is a variety of；
The chain-transferring agent of the hydroxyl is mercaptoethanol or mercaprol；
The oil-soluble initiator is azodiisobutyronitrile, azobisisoheptonitrile, cumyl peroxide or diphenyl peroxide
Formyl.
4. the preparation method of acrylic ester modified water-soluble polyurethane lotion according to claim 2 or 3, which is characterized in that
In step (1), the dosage of the chain-transferring agent of the hydroxyl is the 4%~6% of the acrylate monomer quality of step (1)；
The dosage of the oil-soluble initiator is the 0.8%~1.2% of the acrylate monomer quality of step (1).
5. the preparation method of acrylic ester modified water-soluble polyurethane lotion according to claim 2, which is characterized in that step
(2) in, the hydrophilic monomer is dihydromethyl propionic acid or dimethylolpropionic acid；
The chain extender is 1,4- butanediol, dipropylene glycol, ethylene glycol, propylene glycol or neopentyl glycol；
First crosslinking agent is trimethylolpropane or glycerol or pentaerythrite.
6. the preparation method of acrylic ester modified water-soluble polyurethane lotion according to claim 2 or 5, which is characterized in that
In step (2), the hydrophilic monomer quality account for step (2), the reactant gross mass of (3) 3%~5%；
The chain extender quality account for step (2), the reactant gross mass of (3) 3%~5%；
First crosslinking agent quality account for step (2), the reactant gross mass of (3) 0.5%~2%.
7. the preparation method of acrylic ester modified water-soluble polyurethane lotion according to claim 2, which is characterized in that step
(3) in, the additional amount of the terminal hydroxy group type polyacrylate is not more than the 50% of the reactant gross mass of step (2), (3).
8. the preparation method of acrylic ester modified water-soluble polyurethane lotion according to claim 2, which is characterized in that step
(4) in, the water soluble starter is potassium peroxydisulfate or ammonium persulfate；
Second crosslinking agent is glycidyl methacrylate.
9. the preparation method of acrylic ester modified water-soluble polyurethane lotion according to claim 2 or 8, which is characterized in that
In step (4), the water soluble starter is the 0.6%~1% of the acrylate monomer quality of step (4)；
The dosage of the acrylate monomer is no more than solid masses in the block modified aqueous polyurethane emulsion of polyacrylate
240%；
Second dosage of crosslinking agent is not more than the 7.5% of the acrylate monomer quality of step (4).
10. a kind of preparation of acrylic ester modified water-soluble polyurethane lotion described in any claim according to claim 1~9
Interpenetrating Polymer Network Type acrylate swelling-block modified aqueous polyurethane multiple emulsion that method is prepared.
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| CN115505158A (en) * | 2022-10-26 | 2022-12-23 | 南宝树脂（佛山）有限公司 | Water-based treating agent suitable for high-elasticity EVA material and preparation method thereof |
| CN115505158B (en) * | 2022-10-26 | 2023-05-19 | 南宝树脂（佛山）有限公司 | Water-based treating agent suitable for high-elasticity EVA material and preparation method thereof |
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