CN105418823B - High water resistance is alkaline-resisting to the preparation of high scrubbing resistance acrylate and vinyl acetate emulsion and related coating - Google Patents
High water resistance is alkaline-resisting to the preparation of high scrubbing resistance acrylate and vinyl acetate emulsion and related coating Download PDFInfo
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- CN105418823B CN105418823B CN201610033694.8A CN201610033694A CN105418823B CN 105418823 B CN105418823 B CN 105418823B CN 201610033694 A CN201610033694 A CN 201610033694A CN 105418823 B CN105418823 B CN 105418823B
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- acrylate
- vinyl acetate
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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
- C08F218/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
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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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D131/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
- C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09D131/04—Homopolymers or copolymers of vinyl acetate
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
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Abstract
It is alkaline-resisting to the preparation of high scrubbable acrylate and vinyl acetate emulsion and related coating that the present invention discloses a kind of high water resistance, including：The composition of first part's nucleocapsid is as follows：Vinylacetate 200 300, butyl acrylate 50 70, acrylic acid 01,05 parts by weight of methacrylic acid ethylidene-urea ethoxylated ester (MEEU), trimethylolpropane trimethacrylate (TMPTMA) 05；The composition of second part nucleocapsid is as follows：Methacrylic acid 50 120, butyl acrylate 20 60, methacrylic acid ethylidene-urea ethoxylated ester (MEEU) 05, trimethylolpropane trimethacrylate (TMPTMA) 05.
Description
Technical field
The invention belongs to building coating field, lotion compound directions, and in particular to a kind of alkaline-resisting and high scrubbing resistance of high water resistance
The preparation of acrylate and vinyl acetate emulsion and related coating.
Background technology
It is main former with vinylacetate in numerous inner-outer wall product emulsions for taking emulsion polymerization as main synthesis technology
No matter the acrylate and vinyl acetate emulsion of material synthesis suffers from very important status in industrial circle or in scientific research field.China is in 20 generation
It records and has begun to the development work of acrylate and vinyl acetate emulsion the fifties, the seventies, acrylate and vinyl acetate emulsion industry had the development advanced by leaps and bounds.And biography
The phenylpropyl alcohol or pure-acrylic emulsion of system are compared, and acrylate and vinyl acetate emulsion is by its excellent application property, smaller smell, unique rheological characteristic
Can, the advantages that cheap, caking property is strong, film forming stability is good, it is deep to be favored by vast coating manufacturer and consumer.Widely
For the fields such as timber processing, fabric bonding, furniture construction, paper plate bonding, building coating.
But acrylate and vinyl acetate emulsion also has its own unsurmountable defect.Its primary raw material vinylacetate water solubility is higher, inhales
Water rate is higher compared to other acrylics, and acrylate and vinyl acetate emulsion water resistance is less desirable.In addition, vinylacetate is in water
Property, hydrolysis is especially easy under alkaline condition, cause molecule chain break, have significant shadow for the overall performance of paint film
It rings, is especially embodied in above water-alkali resistance and scrubbable performance.On the other hand, Protection glue of the acrylate and vinyl acetate emulsion due to macromolecule
The addition of body, such as polyvinyl alcohol or hydroxylated cellulose so that grain size is significantly larger than phenylpropyl alcohol or pure-acrylic emulsion, emulsion particle
Specific surface area very little, smaller for the bearing capacity of powder, the later stage performance of paint film receives strong influence.Therefore how to protect
On the basis of holding acrylate and vinyl acetate emulsion advantage, it is always what acrylate and vinyl acetate emulsion was studied to further increase its water-alkali resistance and scrubbable performance
Important directions.The specific surface area very little of particle, smaller for the bearing capacity of powder, the later stage performance of paint film receives greatly
It influences.
Invention content
In view of the above-mentioned problems, the present invention provides a kind of system of water-alkali resistance and high scrubbing resistance acrylate and vinyl acetate emulsion and related coating
It is standby.
In order to achieve the above objectives, the alkaline-resisting and high scrubbable acrylate and vinyl acetate emulsion of high water resistance of the present invention, including：
The composition of first part's nucleocapsid is as follows：Vinylacetate 200-300, butyl acrylate 50-70, acrylic acid 0-
1, methacrylic acid ethylidene-urea ethoxylated ester (MEEU) 0-5 parts by weight, trimethylolpropane trimethacrylate (TMPTMA) 0-
5；
The composition of second part nucleocapsid is as follows：Methacrylic acid 50-120, butyl acrylate 20-60, metering system
Sour ethylidene-urea ethoxylated ester (MEEU) 0-5, trimethylolpropane trimethacrylate (TMPTMA) 0-5.
Further, the ratio of first part's nucleocapsid and second part nucleocapsid is between 50/50 to 95/5.
Further, further include the raw material of following parts by weight：
It is hydroxylated cellulose Plus300 1-5, lauryl sodium sulfate 2-6, nonionic emulsifier Abex 25155-20, anti-
Answer type emulsifier SVS 0-1, ammonium persulfate 0.5-2 and deionized water 400-500.
Best component：Hydroxylated cellulose Plus300 1.5, lauryl sodium sulfate 4, nonionic emulsifier Abex
2515 5.5, reactive emulsifier SVS 0.5, ammonium persulfate 0.5 and deionized water 450.
Further, include the component of following parts by weight：Hydroxylated cellulose Plus300 1.5, lauryl sodium sulfate 4,
Nonionic emulsifier Abex 2,515 5.5, reactive emulsifier SVS 0.5, ammonium persulfate 0.5 and deionized water 450.
Further, it also comprises the following components：Surfactant also has initiator, thermal initiator, Redox Initiator
Agent also has pH buffer, antifoaming agent, fungicide.
Further, the surfactant is by anion surfactant, polymerisable surfactant, non-ionic surface
Activating agent forms.
In order to achieve the above objectives, the preparation of the alkaline-resisting coating related to the scrubbable acrylate and vinyl acetate emulsion of height of high water resistance of the present invention,
It is characterized in that, is prepared using the component described in the alkaline-resisting and high scrubbable acrylate and vinyl acetate emulsion of above-mentioned high water resistance.
Advantageous effect
The present invention has following advantageous effect with the prior art：
It is water-fast resistance to can to evade conventional emulsions in performance for the acrylate and vinyl acetate emulsion that the present invention is synthesized by cleverly structure design
The defect of alkali.The introducing of multiple functions monomer is so that the performance of lotion obtains great raising.To the water-alkali resistance of paint film
Property and scrubbable performance are greatly improved.
The third product of vinegar of synthesis is free of APEO, and low formaldehyde, no benzene homologues and other disposals of pollutants, and particle diameter distribution is very
Narrow, product stability is fine.In crucial performance, and comparing for domestic and international main rival has excellent water-fast
Alkaline resistance properties is especially embodied in scrub performance.And other performances such as color development, covering, levelling etc., then it is consistent to maintain vinegar third
Advantage.Final excellent product performance and environmentally protective.
Specific implementation mode
The present invention will be further described below.
The present invention synthesizes acrylate and vinyl acetate emulsion using emulsion polymerization technique, and specific function group hydrophobization is added in building-up process
Modified hydroxylated cellulose HEC successfully draws functionalization hydrophobic grouping while as protecting colloid protection emulsion polymerization
Enter to emulsion particle surface.To on final paint film product obtained, the color development of guarantee vinegar third itself and rheological property it is same
When, substantially increase the water-alkali resistance of vinegar third and scrubbable performance.
Acrylate and vinyl acetate emulsion is prepared using the preparation process of nucleocapsid.It is successfully introduced into hard monomer in shell, such as styrene and first
Base methyl acrylate etc. has good water-fast resistance to allow the advantage of acrylate and vinyl acetate emulsion combination phenylpropyl alcohol and pure-acrylic emulsion
Alkalinity, especially so that scrubbable performance is greatly improved.
Functional monomer and multi-functional cross-linking system are added in emulsion polymerization process, can be formed in film forming procedure solely
Special network blackboard, on the one hand improves the compactness of paint film, on the other hand also improves mutual between color stuffing
Effect, to greatly improve the overall performance of product.
The alkaline-resisting and high scrubbable acrylate and vinyl acetate emulsion of high water resistance of the present invention：
1. using special hydrophobically modified hydroxylated cellulose Plus300, additive amount 1%, so as to by hydrophobic grouping at
Work(is introduced into the surface of emulsion particle, improves the water-alkali resistance of paint film and scrubbable performance
2. using nucleocapsid, shell proportion is 30%, successfully that styrene and methyl methacrylate etc. is hard single
Body introduces shell, and the Tg of nucleocapsid separately designs as 0 and 30oC, so that VAC- MMA system is successfully combined phenylpropyl alcohol and pure third advantage, carries
High whole performance.
3. introducing functional monomer methacrylic acid ethylidene-urea ethoxylated ester and trifunctional cross-linking monomer trihydroxy methyl
Propane triacrylate greatly improves the compactness of paint film and the compatibility with color stuffing.
The action principle of main innovation point：
1 hydroxyethyl cellulose：
Vinylacetate since its own is water-soluble preferably, and easily exists as most important a kind of raw material in acrylate and vinyl acetate emulsion
Decomposed in aqueous phase system, thus polymerization process other than common small-molecular emulsifier, it is also necessary to the protection of macromolecular is added
Colloid.Hydroxylated cellulose is frequently utilized for acrylate and vinyl acetate emulsion polymerization as a kind of environmentally protective, biodegradable macromolecular.In addition to
While ensureing that emulsion polymerization is smoothed out, the excellent freeze thaw stability of emulsion particle, mechanical stability, freeze thawing can also be provided
Stability and dilution stability.Common HEC structural formulas, the structural formula of standard are as follows：
Hydroxyethyl cellulose oxidative dehydrogenation under the action of initiator generates macromolecular radical, vinylacetate and propylene
Acid monomers can carry out chain propagation reaction with macromolecular radical, and monomer is caused to be grafted on hydroxylated cellulose.Monomer is due to certainly
Body property is different, and the rate of grafting is also not quite similar.The generation of grafting improves paint film while increasing lotion molecular weight
Water-alkali resistance performance.Monomer is grafted the mechanism of hydroxylated cellulose, and main Grafting mechanism is as follows：
Hydrophobic modification cellulose Plus300 is superior to other hydroxyethyl celluloses in properties, especially shows
In terms of water-alkali resistance and scrubbing resistance, water-alkali resistance is not blistering after a test not to whiten, and has excellent performance.And it is scrubbable
Performance is also very outstanding.Further illustrate hydrophobising groups introducing can significantly more efficient blocking moisture and other substances for
The decomposition of strand protects paint film not destroyed further.
2 nucleocapsids
The structure of lotion can largely determine the performance of final paint film.Due to the structure and performance of vinylacetate
Differ larger with other acrylic monomers, therefore its reactivity ratio gap is also bigger, it is especially highly difficult with the copolymerization of MMA and St,
Rate of polymerization is slower.The reactivity ratio of vinylacetate and common acrylic monomers is as in the table below.With conventional method be difficult by
MMA and St are introduced among acrylate and vinyl acetate emulsion, and the polymerization of nucleocapsid can then well solve this problem.
Table：Vinylacetate is compared with the reactivity ratio of other acrylic monomers
The copolymerization that stratum nucleare is acrylate and vinyl acetate emulsion VA/BA is designed in the present invention, shell is the lotion MMA/BA of pure third or phenylpropyl alcohol
Or St/BA.
The design of 1 nucleocapsid can greatly improve the entirety of paint film, can be very good the properties of balance vinegar third.Make
Vinegar third is obtained while keeping intrinsic advantage, the advantage of pure third and phenylpropyl alcohol is combined well, improves the whole resistance of paint film.
2 70/30 nucleocapsid ratio can be very good to reach excellent water-alkali resistance and scrubbable performance.And in MMA
Between ST, it is contemplated that the discharge of VOC benzene homologues, therefore selected MMA as shell monomers.
3 wet adhesions promote monomer and cross-linking monomer
Other than the monomer of main reaction, a small amount of function monomer can adjust the performance of entire lotion.It is selected in the present invention
With two kinds of function monomers：Wet adhesion captax EEU and trifunctional cross-linking monomer TMPTMA.The change of MEEU and TMPTMA
The chemical structural formula for learning both structural formulas is as follows：
MEEU also has structure of the five-membered ring containing N, and the Polarity comparision of monomer is strong, can largely improve wet adhesion effect
Fruit, while increasing the interaction between color stuffing.And TMPTMA is the crosslinking agent of trifunctional, it can be effectively so that breast
Inside liquid particles molecule segment crosslinking get up, increase the compactness extent of emulsion film, to improve paint film water-alkali resistance and
Scrubbable performance.
1 function monomer and cross-linking monomer have polymerization process important influence, further can also influence final paint
Film properties.
Polarity is too strong in the case that 2 wet adhesions promote monomer MEEU additions excessive to generate negative shadow to polymerization process
It rings, instead bad for the dispersion of color stuffing, 2% additive amount is best；
The gel of lotion can be had an impact after the introducing of 3 TMPTMA trifunctionals.Addition is excessive, and crosslinking is excessive,
Excessive gel particle is inevitably produced in polymerization process.Another aspect crosslink density it is excessive so that emulsion film forming
In the process, sub-chain motion is obstructed, and generates the effect of microphase-separated, affects final performance.Therefore best additive amount is 2%.
Embodiment
Coating prepares the progress of according to the form below formula.In coating preparation Special dispersing cylinder, deionized water is added and opens stirring,
Pigment wetting agent (EW107) is sequentially added, pigment dispersing agent (SN5040) and multifunctional assistant AMP-95, stirring and dissolving finish
Afterwards, rotating speed is carried to 1500-1800 revs/min, then sequentially adds powder, disperseed 40 minutes under this speed；It then will dispersion
It is ground again after good slurry, fineness is allowed to reach 40 μm or less.Lotion is added in dispersion cylinder under stirring at low speed again, while will meter
Lotion, antifoaming agent, thickener, the AMP-95 inputs of amount are mixed evenly, and filter up to ordor removing coating.
Table coating assessment formula
The application performance of coating is as follows：
Color development test is tested using color difference meter after dispersed paste.
To the present invention it should be understood that embodiment described above, to the purpose of the present invention, technical solution and beneficial to effect
Fruit has carried out further details of explanation, these are only the embodiment of the present invention, is not intended to limit the present invention, it is every
Within the spiritual principles of the present invention, made any modification, equivalent substitution, improvement and etc. should be included in the protection of the present invention
Within the scope of, the scope of protection of the present invention shall be subject to the scope of protection defined by the claims.
Claims (6)
1. a kind of alkaline-resisting and high scrubbable acrylate and vinyl acetate emulsion of high water resistance, which is characterized in that including：
The composition of first part's nucleocapsid is as follows：Vinylacetate 200-300, butyl acrylate 50-70, acrylic acid 0-1, first
Base acrylic acid ethylidene-urea ethoxylated ester (MEEU) 5, trimethylolpropane trimethacrylate (TMPTMA) 5；Wherein, the composition of core
For vinylacetate, acrylic acid, methacrylic acid ethylidene-urea ethoxylated ester (MEEU), trimethylolpropane trimethacrylate
(TMPTMA)；The group of shell becomes：Butyl acrylate, acrylic acid, methacrylic acid ethylidene-urea ethoxylated ester (MEEU), three hydroxyl first
Base propane triacrylate (TMPTMA)；
The composition of second part nucleocapsid is as follows：Methyl methacrylate 50-120, butyl acrylate 20-60, metering system
Sour ethylidene-urea ethoxylated ester (MEEU) 5, trimethylolpropane trimethacrylate (TMPTMA) 5；Wherein, the group of core becomes methyl
Methyl acrylate, butyl acrylate, methacrylic acid ethylidene-urea ethoxylated ester (MEEU), trimethylolpropane trimethacrylate
(TMPTMA)；The group of shell becomes methyl methacrylate, butyl acrylate, methacrylic acid ethylidene-urea ethoxylated ester
(MEEU), trimethylolpropane trimethacrylate (TMPTMA)；
Further include the raw material of following parts by weight in addition to first part's nucleocapsid, second part nucleocapsid：
Hydroxylated cellulose Plus300 1-5, lauryl sodium sulfate 2-6,2515 5-20 of nonionic emulsifier Abex, response type
Emulsifier SVS 0-1, ammonium persulfate 0.5-2 and deionized water 400-500；Control first part's nucleocapsid and second
The Tg of pyrene shell structure center is that the Tg of 0, shell is 30 DEG C.
2. the alkaline-resisting and high scrubbable acrylate and vinyl acetate emulsion of high water resistance according to claim 1, which is characterized in that first part's core
The ratio of shell structure and second part nucleocapsid is between 50/50 to 95/5.
3. the alkaline-resisting and high scrubbable acrylate and vinyl acetate emulsion of high water resistance according to claim 1, which is characterized in that including weighing as follows
Measure the component of part：It is hydroxylated cellulose Plus300 1.5, lauryl sodium sulfate 4, nonionic emulsifier Abex 2,515 5.5, anti-
Answer type emulsifier SVS 0.5, ammonium persulfate 0.5 and deionized water 450.
4. the alkaline-resisting and high scrubbable acrylate and vinyl acetate emulsion of high water resistance according to claim 1, which is characterized in that further include as follows
Component：Surfactant, thermal initiator, redox initiator, pH buffer, antifoaming agent and fungicide.
5. the alkaline-resisting and high scrubbable acrylate and vinyl acetate emulsion of high water resistance according to claim 4, which is characterized in that live on the surface
Property agent is made of anion surfactant, polymerisable surfactant, nonionic surfactant.
6. a kind of preparation of the alkaline-resisting coating related to the scrubbable acrylate and vinyl acetate emulsion of height of high water resistance, which is characterized in that wanted using right
The component described in the alkaline-resisting and high scrubbable acrylate and vinyl acetate emulsion of 1 to 5 any high water resistance is asked to be prepared.
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| CN201610033694.8A CN105418823B (en) | 2016-01-19 | 2016-01-19 | High water resistance is alkaline-resisting to the preparation of high scrubbing resistance acrylate and vinyl acetate emulsion and related coating |
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| CN201610033694.8A CN105418823B (en) | 2016-01-19 | 2016-01-19 | High water resistance is alkaline-resisting to the preparation of high scrubbing resistance acrylate and vinyl acetate emulsion and related coating |
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Denomination of invention: Preparation of vinegar acrylic lotion and related coatings with high water and alkali resistance and high scrub resistance Effective date of registration: 20230506 Granted publication date: 20180831 Pledgee: Agricultural Bank of China Limited Nanxiong Sub branch Pledgor: GUANGDONG HENGGUANG NEW MATERIAL TECHNOLOGY CO.,LTD. Registration number: Y2023980039881 |
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