CN109021250A - A kind of preparation of waterborne polyurethane modified montmorillonite nano-composite emulsion - Google Patents
A kind of preparation of waterborne polyurethane modified montmorillonite nano-composite emulsion Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses a kind of preparations of waterborne polyurethane modified montmorillonite nano-composite emulsion, belong to organic-inorganic hybrid nanocomposite lotion field.The present invention uses hydrochloric acid to carry out montmorillonite first, and acidolysis is modified, and the addition of hydrochloric acid makes sulfonate modified dose of organic amine to be easier to enter between lamella, is subsequently added into anion-modified dose of organic amine sulfonate, further effectively to open cheating engaging layer spacing；There are reactive amino in anion-modified dose, are reacted using amino with isocyanates, can further enhance the interaction with aqueous polyurethane matrix, prepare the sulfonate modified montmorillonite nano-composite emulsion of aqueous polyurethane/organic amine.The nano-composite emulsion of the method for the present invention preparation has preferable dispersion stabilization, while the introducing of inorganic nanoparticles significantly improves the heat of aqueous polyurethane coating, mechanical property, and montmorillonite layer structure enhances barrier property again.The dispersion can be widely applied to the fields such as excellent barrier property, food resistant to high temperature, medical packaging.
Description
Technical field
The present invention relates to a kind of preparations of waterborne polyurethane modified montmorillonite nano-composite emulsion, belong to organic and inorganic and receive
Rice multiple emulsion field.
Background technique
Compared with solvent type PU, it is organic molten to reduce synthesis process kind in the synthesis process using water as solvent by aqueous PU
The volatilization and danger of agent；Nontoxic when use, pollution-free, do not burn, is inexpensive, the performance with common solvent type PU, is that one kind is answered
It is extensive " green material " with prospect.With the progress of industrial technology, people increasingly increase the performance requirement of material, to material
It is modified to improve its performance or increase specific function and become the trend of industrial development and research.In recent years, inorganic nano is used
Particle such as nano Si 02, nanometer Ti02, montmorillonite etc. is to the polyurethane-modified extensive concern for causing industry and academia.
Montmorillonite is a kind of clay of cationic, and basic structural unit is to be clipped in two layers of silicon by a piece of alumina octahedral
The layer structure formed between oxygen tetrahedron by sharing oxygen atom.Exactly this special structure makes montmorillonite surface in negative electricity
Property and be able to carry out it is stronger cation exchange etc..But the hydrophilic and oleophobic property strong due to montmorillonite layer surface, it is unfavorable
Disperse in organic phase in it and soaked by organic phase, when preparing polymer Nano composite material of montmorillonite, it usually needs
Montmorillonite is carried out organically-modified.Purpose is that drop low-surface-energy, makes to become lipophilic from hydrophily between cheating engaging layer, simultaneously
Increase its interlamellar spacing, is conducive to macromolecular chain or monomer enters interlayer, to prepare the nanocomposite of removing form.
In the modifying process of montmorillonite, most common organic modifiers be cation modifier, anion-modified dose,
Polymer monomer and coupling agent etc..It is living with anionic surface for using the montmorillonite of organic cation modifier modification
Property agent be modifying agent report it is very few.But the correlated performance of organic modification montmonrillonite mainly with organic modification montmonrillonite interlamellar spacing
Size, the length of organic intercalation agent carbochain are related with property, thus anionic organo montmorillonite be also in modified montmorillonoid not
The seed type that can lack.In an aqueous medium, anion has the montmorillonite of negative electrical charge by ion exchange and ion pair interlayer
It is adsorbed, while nonpolarity stronger particle Van der Waals force can occur for the C-H bond of surfactant between cheating engaging layer
And adsorb, negative charge density increases due to having adsorbed anion between cheating engaging layer at this time, and the repulsion of such interlayer also accordingly increases
Add, to expand interlamellar spacing.
It is reported at present to have anion-modified dose of Organic Montmorillonitewith Sodium Laurylsulfonate of Chen Haiqun et al., it is modified
Between montmorillonite and aqueous polyurethane matrix afterwards simply by intermolecular hydrogen bonding effect achieve the effect that it is compatible, disperse it is compatible
Property and mechanical property etc. need to be improved.
Summary of the invention
To solve the above-mentioned problems, the present invention provides the preparation sides of waterborne polyurethane modified montmorillonite nano-composite emulsion
Method, anion-modified dose of organic amine sulfonate of use, there are reactive amino, pass through covalent bond between aqueous polyurethane
Effect, compared with the dodecyl sodium sulfate without reactive amino in strand is as modifying agent, method of the invention has
The advantages that good dispersion, high intensity, low moisture absorption.
The first purpose of the invention is to provide a kind of preparation sides of waterborne polyurethane modified montmorillonite nano-composite emulsion
Method, comprising: utilize the sulfonate modified montmorillonite of anionic modifying agent organic amine, base polyurethane prepolymer for use as is added in modified montmorillonoid
Middle composite emulsifying, obtains nano-composite emulsion.
In one embodiment, the anionic modifying agent (organic amine sulfonate) be it is following any one or it is more
Kind: amino-containing ether chain compound, 2- [(2- aminoethyl) amino] ethanesulfonic acid sodium, diphenylamine sulfonic acid sodium salt, ethylenediamine sodium sulfonate.
In one embodiment, using organic amine compound modified montmorillonoid, including by anionic modifying agent with
Acid montmorillonite is mixed according to weight ratio 1:(1-5), water as solvent, is dispersed spare.
In one embodiment, the content of montmorillonite is aqueous polyurethane dosage in the nano-composite emulsion
0.01wt%-40wt%.
In one embodiment, the weight ratio of the base polyurethane prepolymer for use as and modified montmorillonoid is 100 by dry weight:
(0.1-20)。
In one embodiment, the solid of the nano-composite emulsion contains for 5%-20%.
In one embodiment, the raw material of the nano-composite emulsion includes: the oligomer polyol of 50-80wt%,
The diisocyanate cpd of 15-30wt%, multi-hydroxy carboxy acid's compound of 2-5wt%, 0.05-10wt% organic amine sulfonic acid
Salt, 0.05-10wt% montmorillonite.
In one embodiment, which comprises
1) base polyurethane prepolymer for use as is obtained；
2) acid montmorillonite is obtained:
3) anionic modifier modification montmorillonite；By anionic modifying agent and acid montmorillonite ratio 1:(1-5) it is added
In container, water as solvent stirs 3-8h, mixing speed 100-500rmp at 20-60 DEG C, by the modified montmorillonoid being prepared from
Heart washing, is dispersed in water spare；
4) modified montmorillonoid and base polyurethane prepolymer for use as, which are mixed, disperses, and it is multiple to obtain waterborne polyurethane modified montmorillonite-based nano
Close lotion.
In one embodiment, 1) described includes: that it is polynary that oligomer is added dropwise according to the ratio in diisocyanate cpd
Then pure and mild catalyst is gradually heated to 55-65 DEG C in 45-55 DEG C of reaction 1-2h after being added dropwise, hydrophilic monomer is added,
Reaction 6-8h is carried out at a temperature of this, isocyanates (NCO) content of performed polymer is generated with the measurement of toluene-di-n-butylamine method, when connecing
When nearly NCO theoretical value, the base polyurethane prepolymer for use as of NCO sealing end is made.
In one embodiment, the diisocyanate cpd described in 1) selects 2,4- toluene di-isocyanate(TDI), 2,
6- toluene di-isocyanate(TDI), isophorone diisocyanate, diphenyl methane 4,4 '-diisocyanate, methylcyclohexyl two are different
One of cyanate, 2,2,4- trimethyl hexamethylene diisocyanate.
In one embodiment, the oligomer polyol described in 1) selects polyethylene glycol, polypropylene glycol, polytetrahydrofuran
Glycol, polycaprolactone polyol, polycarbonate glycol, polyoxyethylene-poly-oxypropylene polyoxyethylene glycol, polyadipate second two
Alcohol esterdiol, polybutylene glyool adipate, polyethylene terephthalate glycol, polybutylene terephthalate (PBT) two
Alcohol, α, alpha, omega-dihydroxy polydimethyl siloxane, dihydroxy polydiphenylsiloxane, dihydroxy trifluompropyl methyl polysiloxane
Middle one or more, molecular weight ranges 400-10000.
In one embodiment, the hydrophilic monomer used in 1) selects dihydromethyl propionic acid, dimethylolpropionic acid, methyl two
One of ethanol amine.
In one embodiment, 2) described includes: montmorillonite and water weight ratio (0.005-1): 1 is added in container and fills
Divide swelling, salt acid for adjusting pH is then added, pH is adjusted to 1-5,3-8h, mixing speed 100- are stirred at 40-100 DEG C
2000rp/min, will be spare after obtained acid montmorillonite centrifuge washing.
In one embodiment, the montmorillonite is to receive base montmorillonite, potassium base montmorillonite, calcium-base montmorillonite or lithium base
Montmorillonite.
In one embodiment, the montmorillonite specific surface area 30-1000m2/g, aperture 3-30nm, cation exchange
Capacity 30-300meq/100g.
In one embodiment, the sulfonate modified modified montmorillonoid of organic amine and the mass ratio of deionized water are in 3)
1g:5-100ml.
In one embodiment, 4) described includes: that modified montmorillonoid is added in base polyurethane prepolymer for use as addition reaction vessel
Dispersion liquid, stirs 3-8h at 40-100 DEG C, and mixing speed 100-2000rmp/min prepares aqueous polyurethane/modified montmorillonoid
Nano-composite emulsion.
In one embodiment, the nano-composite emulsion drying and forming-film that the method also includes preparing.
In one embodiment, the solid of the nano-composite emulsion contains for 5%-20%；The drying of the multiple emulsion
Condition is 60-150 DEG C.
A second object of the present invention is to provide the waterborne polyurethane modified montmorillonites being prepared according to the method described above to receive
Rice multiple emulsion.
Third object of the present invention is to provide the films that the nano-composite emulsion is prepared.
Fourth object of the present invention is to provide application of the nano-composite emulsion in terms of preparing packaging material, including
The packaging material of field of food and medicine.
The principle of the invention lies in: since unmodified montmorillonite is extremely difficult to good dispersion in the polymer matrix
Property；The present invention first uses hydrochloric acid to carry out acidolysis to montmorillonite and is modified, the active force between the addition reduction montmorillonite layer of hydrochloric acid,
Make sulfonate modified dose of organic amine to be easier to enter between lamella, is subsequently added into anion-modified dose of organic amine sulfonate, passes through
The organic-philic effect of the positive electric attraction and alkyl chain of montmorillonite interlayer cation, successfully makes anion-modified dose of organic amine sulfonic acid
Salt enters between cheating engaging layer, to further effectively open cheating engaging layer spacing；Anion-modified dose of organic amine sulfonate molecules
There are reactive amino in structure, are reacted using amino with isocyanates, can further enhance and aqueous polyurethane matrix
Interaction.The sulfonate modified montmorillonite dispersions of the organic amine of formation and polyurethane are acted on, aqueous polyurethane/organic is prepared
The sulfonate modified montmorillonite nano-composite emulsion of amine.
Beneficial effects of the present invention:
The present invention uses anionic modifying agent organic amine sulfonate, enters organic amine sulfonate between cheating engaging layer, has
Effect opens cheating engaging layer spacing, improves the compatibility of montmorillonite and organic matter；Amino in organic amine sulfonate structures simultaneously
It is reacted with isocyanates, further promotes the interaction of montmorillonite and aqueous polyurethane matrix, preparation stability is more preferable, intensity
It is higher, the resistance to hygroscopicity more preferably sulfonate modified Nano composite material of montmorillonite of aqueous polyurethane/organic amine.Meanwhile it inorganic receiving
The introducing of rice grain significantly improves the heat of aqueous polyurethane coating, mechanical property, and montmorillonite layer structure makes barrier property again
It can enhancing.Nano-composite emulsion of the invention can be widely applied to the neck such as excellent barrier property, food resistant to high temperature, medical packaging
Domain.
Detailed description of the invention
The tensile property of the film of Fig. 1 embodiment 1, embodiment 2 and comparative example 1；
The water absorption rate of the film of Fig. 2 embodiment 1, embodiment 2 and comparative example 1；
The aqueous polyurethane of Fig. 3 embodiment 2 and comparative example 1/ester/modified montmorillonite nano multiple emulsion digital photo；
Wherein A is the sulfonate modified montmorillonite nano-composite emulsion of aqueous polyurethane/organic amine, and B is aqueous polyurethane/dodecyl sulphur
Sour sodium ester/modified montmorillonite nano multiple emulsion.
Specific embodiment
In order to preferably explain the present invention, the present invention is further explained in detail combined with specific embodiments below.
Embodiment 1: the preparation of aqueous polyurethane emulsion and film
24.08g isophorone two is added in the 250mL four-neck flask equipped with blender, thermometer and reflux condensing tube
Isocyanates (IPDI) and four drop dibutyl tin dilaurate (DBTDL) catalyst, are leaked while stirring with dropping liquid at room temperature
70.92g polycarbonate glycol (PCD2000) is added dropwise in bucket, and rate of addition controls in 1.5h, anti-at 50 ± 5 DEG C after being added dropwise
1-2h is answered, temperature is controlled at 40-50 DEG C；60 ± 5 DEG C are then heated to, is added 5g dihydromethyl propionic acid (DMPA), 3-5h is reacted；
The extent of reaction is measured by toluene-di-n-butylamine back titration method, until measurement NCO group content reaches theoretical value；Obtain poly- ammonia
Ester performed polymer.
Deionized water is added dropwise into the system of base polyurethane prepolymer for use as to be emulsified；Film, drying obtain aqueous polyurethane
Film.
Embodiment 2: the preparation of aqueous polyurethane/ester/modified montmorillonite nano multiple emulsion and film
Aqueous polyurethane/ester/modified montmorillonite nano multiple emulsion prepares as follows:
(1) montmorillonite is modified using anionic modifying agent 2- [(2- aminoethyl) amino] ethanesulfonic acid sodium:
Montmorillonite 1.0g is weighed, 100ml distilled water is added to be made into 1% montmorillonite dispersions, is sufficiently stirred to obtain uniform
Dispersion liquid is 2.00 with the pH that dilute hydrochloric acid adjusts solution, after temperature reaches 40 DEG C, by n (2- [(2- aminoethyl) amino] second sulphur
Sour sodium): anionic modifying agent organic amine sulfonate is added in the proportion of m (MMT)=0.6, and sufficiently reaction is uniformly suspended
Liquid.By centrifugation, the solvent in above-mentioned products therefrom is removed, sediment is obtained, is repeatedly washed with deionized water, ethyl alcohol.It will
Obtained product is dry, is ground up, sieved, and can be prepared by modified montmorillonoid.
(2) aqueous polyurethane and modified montmorillonoid are mixed with nano-composite emulsion:
The modified montmorillonoid for taking certain mass is swollen 1h with 20mL deionized water at normal temperature, and ultrasonic wave disperses 30min,
Keep its fully dispersed in water；Modified montmorillonoid after dispersion is added drop-wise in the base polyurethane prepolymer for use as after triethylamine neutralizes, room
Under temperature under 1200rmp revolving speed high-speed stirred 30min, defoam 30min after be made aqueous polyurethane/ester/modified montmorillonite nano it is compound
Lotion.
The preparation of aqueous polyurethane/ester/modified montmorillonite nano composite membrane:
By obtained aqueous polyurethane/ester/modified montmorillonite nano multiple emulsion, in a mold, done at 60 DEG C of vacuum drying oven
It is dry for 24 hours, obtain the sulfonate modified montmorillonite-based nano composite membrane of aqueous polyurethane/organic amine.
Comparative example 1: the preparation of aqueous polyurethane/Organic Montmorillonitewith Sodium Laurylsulfonate nano-composite emulsion and film
(1) montmorillonite is modified using common anionic modifying agent dodecyl sodium sulfate:
Montmorillonite 1.0g is weighed, 100ml distilled water is added to be made into 1% montmorillonite dispersions, is sufficiently stirred to obtain uniform
Dispersion liquid is 2.00 with the pH that dilute hydrochloric acid adjusts solution, after temperature reaches 40 DEG C, by n (dodecyl sodium sulfate): m (MMT)
Anionic modifying agent is added in=0.6 proportion, and sufficiently reaction obtains uniform suspension.By centrifugation, above-mentioned gained is produced
Solvent in object removes, and obtains sediment, is repeatedly washed with deionized water, ethyl alcohol.By the drying of obtained product, it is ground up, sieved,
It can be prepared by modified montmorillonoid.
(2) aqueous polyurethane and modified montmorillonoid are mixed with nano-composite emulsion:
The modified montmorillonoid for taking certain mass is swollen 1h with 20mL deionized water at normal temperature, and ultrasonic wave disperses 30min,
Keep its fully dispersed in water；Modified montmorillonoid after dispersion is added drop-wise in the base polyurethane prepolymer for use as after triethylamine neutralizes, room
Under temperature under 1200rmp revolving speed high-speed stirred 30min, defoam that aqueous polyurethane/dodecyl sodium sulfate is made after 30min is modified
Montmorillonite nano-composite emulsion.
The preparation of aqueous polyurethane/Organic Montmorillonitewith Sodium Laurylsulfonate nano composite membrane:
By obtained aqueous polyurethane/Organic Montmorillonitewith Sodium Laurylsulfonate nano-composite emulsion, in a mold, Yu Zhen
Drying for 24 hours, obtains aqueous polyurethane/Organic Montmorillonitewith Sodium Laurylsulfonate nano composite membrane at 60 DEG C of empty baking oven.
Tensile property and water absorption rate test are carried out to the film that embodiment 1, embodiment 2 and comparative example 1 obtain, as a result such as
Shown in Fig. 1 and Fig. 2.
As can be seen from Figure 1 the sulfonate modified montmorillonite-based nano composite membrane of aqueous polyurethane/organic amine is shown than pure
The slightly lower elongation at break of aqueous polyurethane, but the sulfonate modified montmorillonite-based nano composite membrane of aqueous polyurethane/organic amine is shown
Much higher beginning modulus and stress out, while aqueous polyurethane/Organic Montmorillonitewith Sodium Laurylsulfonate nano composite membrane mould
It is higher that amount and intensity compare water-based polyurethane film, but montmorillonite-based nano more sulfonate modified than aqueous polyurethane/organic amine is compound
Film is low.
As can be seen from Figure 2 modified compared to water-based polyurethane film and aqueous polyurethane/dodecyl sodium sulfate to cover
De- soil nano composite membrane, the sulfonate modified montmorillonite-based nano composite membrane of aqueous polyurethane/organic amine show lower water absorption rate.
Wherein, the sample of extension test carries out cutting process with dumbbell mold (ASTM D638 V-type), uses the U.S.
5960 type microcomputer controlled electronic universal tester of Instron company carries out polymer nanocomposites according to GB 1040-92
Tension test；Sample (m1) is placed in distilled water after water absorption rate (WA) test will be dry, is impregnated at room temperature, after certain time takes out
Surface deionized water is sucked with blotting paper and is weighed (m2), and water absorption rate (WA) is calculated by formula (1):
In addition, also measured were emulsion intercalation method.Fig. 3 shows the sulfonate modified montmorillonite of aqueous polyurethane/organic amine
Nano-composite emulsion and aqueous polyurethane/Organic Montmorillonitewith Sodium Laurylsulfonate nano-composite emulsion place sedimentation after a week
Situation, as can be seen from the figure the sulfonate modified montmorillonite nano-composite emulsion of aqueous polyurethane/organic amine is compared to common yin
Ion shows good stability.
Although the present invention has been described by way of example and in terms of the preferred embodiments, it is not intended to limit the invention, any to be familiar with this skill
The people of art can do various change and modification, therefore protection model of the invention without departing from the spirit and scope of the present invention
Enclosing subject to the definition of the claims.
Claims (10)
1. a kind of nano-composite emulsion, which is characterized in that the preparation method of the nano-composite emulsion includes: to utilize anionic
Modified montmorillonoid is added composite emulsifying in base polyurethane prepolymer for use as, obtains nanometer by the sulfonate modified montmorillonite of modifying agent organic amine
Multiple emulsion.
2. nano-composite emulsion according to claim 1, which is characterized in that the anionic modifying agent (organic amine
Compound) be it is following any one or it is a variety of: amino-containing ether chain compound, 2- [(2- aminoethyl) amino] ethanesulfonic acid sodium,
Diphenylamine sulfonic acid sodium salt, ethylenediamine sodium sulfonate.
3. nano-composite emulsion according to claim 1, which is characterized in that taken off using modified cover of organic amine compound
Soil, including anionic modifying agent is mixed with acid montmorillonite according to weight ratio 1:(1-5), water as solvent, disperse spare.
4. nano-composite emulsion according to claim 1, which is characterized in that montmorillonite in the nano-composite emulsion
Content is the 0.01wt%-40wt% of aqueous polyurethane dosage.
5. nano-composite emulsion according to claim 1, which is characterized in that the solid of the nano-composite emulsion contains for 5%-
20%.
6. nano-composite emulsion according to claim 1, which is characterized in that the preparation method packet of the nano-composite emulsion
It includes:
1) base polyurethane prepolymer for use as is obtained；
2) acid montmorillonite is obtained；
3) anionic modifier modification montmorillonite: by anionic modifying agent and acid montmorillonite ratio 1:(1-5) container is added
In, water as solvent stirs 3-8h, mixing speed 100-500rmp at 20-60 DEG C, and the modified montmorillonoid being prepared centrifugation is washed
It washs, is dispersed in water spare；
4) modified montmorillonoid and base polyurethane prepolymer for use as, which are mixed, disperses, and obtains waterborne polyurethane modified montmorillonite-based nano Composite Milk
Liquid.
7. nano-composite emulsion according to claim 6, which is characterized in that 2) described includes: montmorillonite and water weight ratio
(0.005-1): 1 is added in container and is sufficiently swollen, and salt acid for adjusting pH is then added, and pH is adjusted to 1-5, stirs at 40-100 DEG C
3-8h, mixing speed 100-2000rp/min are mixed, it will be spare after obtained acid montmorillonite centrifuge washing.
8. nano-composite emulsion according to claim 6, which is characterized in that 4) described includes: base polyurethane prepolymer for use as addition
In reaction vessel, modified montmorillonoid dispersion liquid is added, 3-8h, mixing speed 100-2000rmp/min are stirred at 40-100 DEG C,
Prepare aqueous polyurethane/ester/modified montmorillonite nano multiple emulsion.
9. the film being prepared using nano-composite emulsion described in claim 1.
10. application of the nano-composite emulsion described in claim 1 in terms of preparing packaging material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110577653A (en) * | 2019-09-10 | 2019-12-17 | 陕西科技大学 | Emulsion nano composite emulsion based on electrostatic self-assembly and preparation method thereof |
| CN115028797A (en) * | 2022-06-24 | 2022-09-09 | 盛鼎高新材料有限公司 | Organic silicon modified polyurethane elastomer and preparation method thereof |
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