CN105884976A - Water-borne wood paint resin used outdoors and preparation method thereof - Google Patents
Water-borne wood paint resin used outdoors and preparation method thereof Download PDFInfo
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- CN105884976A CN105884976A CN201410823025.1A CN201410823025A CN105884976A CN 105884976 A CN105884976 A CN 105884976A CN 201410823025 A CN201410823025 A CN 201410823025A CN 105884976 A CN105884976 A CN 105884976A
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Abstract
The invention discloses a water-borne wood paint resin used outdoors and a preparation method thereof. The water-borne wood paint resin is prepared from, 20-45% of (methyl)acrylate monomers, 1-30% of fluorinated acrylate monomers, 0.2-10% of functional monomers, 0.1-10% of emulgator, 0.1-5% of initiator and 40-70% of water. The core-shell emulsion polymerization is adopted for the resin, and the resin has good adhesive force, film-forming property, hardness and the like on woodware, can be widely applied to furniture and other outdoor woodware products, and meanwhile has excellent effects of aging resistance, water resistance, pollution resistance and corrosion resistance by containing fluorine elements.
Description
Technical field
The invention belongs to waterborne acrylic paint field, particularly to outdoor aqueous wooden ware coating resins and preparation method thereof.
Background technology
Along with the increase day by day of outdoor woodenware articles for use now, owing to outdoor wooden articles needs long-term by outdoor rain drop erosion, sunlight directly shines, in order to prolong
Long wooden articles service life out of doors, surface anticorrosion, anti ageing property are had higher requirement by many outdoor wooden articles.China is specially
Profit CN200710120215 describes a kind of woodenware resin, adds nanometer A12O3 slurry, effectively raise woodenware during resin polymerization
The hardness of resin and wearability.In order to improve the anticorrosion of woodenware resin, ageing resistace further, described in Chinese patent CN200710090102
A kind of preparation method of woodcare paint, it uses aqueous acrylic modified ester-polyurethane resin emulsion, add nano inorganic antimicrobial agent and nano combined bear from
Sub-additive, this multifunctional water woodenware pigment, there is the effect of antibacterial and mouldproof, can be used for outdoor woodenware product.
But, aging resistance that woodenware material to realize, anticorrosive property, need face coat effectively by the external world (rainwater, dirt, ultraviolet etc.)
Keep apart.Owing to fluorine atom has the characteristic that radius is little, electronegativity is big, polarizability is little, therefore, molecular structure is the most stable, has preferably
Thermally-stabilised and chemical stability.Simultaneously as fluorine atom to check the constraint effect of its electron outside nucleus and bonding electrons cloud relatively strong, C-F key can pole
The property changed is low, thus fluoropolymer has extremely low surface energy and special surface property (resistance to water, oil resistivity and stain resistance), various liquid pair
The surface of fluoropolymer treated has very difficult moistening, the characteristic adhered to and assemble.
Therefore, the present invention intends introducing fluorochemical in woodwork coating resin, and fluorine element is transportable in surface, forms effective surface protection, has
Effect improves the waterproof antifouling property on woodenware surface, isolates outside contamination, is beneficial to the maintenance of outdoor wooden articles, and with common woodenware resin-phase ratio, its
The performance of ultraviolet-resistant aging is also greatly enhanced.Meanwhile, use core shell self crosslinking system to prepare woodenware resin, both can ensure the room of woodenware surface resin
The increase of the hardness of temperature film forming, the most beneficially coating surface.So, fluorine-containing core shell self crosslinking resin be one of outdoor woodenware developer resin important
Direction and trend.
Summary of the invention
The invention provides a kind of outdoor aqueous wooden ware coating resins, its product has that adhesive force is good, good film-forming property, hardness high, and has excellence
Aging resistance, the feature such as waterproof anti-soil.
The outdoor aqueous wooden ware coating resins that the present invention provides, the content of its component and each component is:
(methyl) acrylic ester monomer (20%-45%)
Fluorinated acrylate monomer (1%-30%)
Functional monomer (0.2%-10%)
Emulsifying agent (0.1%-10%)
Initiator (0.1%-5%)
Water (40%-70%)
Above mark is weight fraction.
(methyl) acrylic ester monomer used in outdoor aqueous wooden ware coating resins of the present invention is (methyl) acrylic acid methyl ester., (methyl) third
Olefin(e) acid ethyl ester, (methyl) butyl acrylate, (methyl) glycidyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid,
The esters of acrylic acids such as (methyl) 2-(Acryloyloxy)ethanol, (methyl) Hydroxypropyl acrylate, (methyl) octadecyl acrylate (ten diester, hexadecyl ester)
One or more of monomer.
Fluorinated acrylate monomer structural formula used in outdoor aqueous wooden ware coating resins of the present invention is shown in claim 3.
Functional monomer used in outdoor aqueous wooden ware coating resins of the present invention includes styrene, acrylonitrile, divinylbenzene, diacetone acrylamide acyl
Amine, N hydroxymethyl acrylamide, triethylamine, adipic dihydrazide one or more.
Nuclear monomer used in outdoor aqueous wooden ware coating resins of the present invention is (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl)
Butyl acrylate, (methyl) glycidyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid one or more；Shell list
Body is (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) glycidyl acrylate, (methyl)
Isobornyl acrylate, (methyl) acrylic acid, (methyl) 2-(Acryloyloxy)ethanol, (methyl) Hydroxypropyl acrylate, (methyl) octadecyl acrylate
(ten diester, hexadecyl ester), styrene, acrylonitrile, divinylbenzene, N-[2-(2-methyl-4-oxopentyl), N hydroxymethyl acrylamide, triethylamine, oneself
Dihydrazi, fluorinated acrylate monomer one or more.
Emulsifying agent used in outdoor aqueous wooden ware coating resins of the present invention includes alkylsulfonate, alkylbenzenesulfonate, polyoxyethylene alkylphenol base ether
One or more.
The present invention provides the preparation method of external aqueous wood paint resin as follows:
Nuclear monomer is put in emulsifying agent, deionized water mixed liquor, emulsifying, prepare pre-emulsion.Pre-emulsion and initiator are placed in flask, 40 DEG C-85 DEG C,
It is stirred at reflux reaction 0.5-2h；Residue pre-emulsion and part initiator are added dropwise to reaction system, 1-5h；Insulation reaction 1-4h；Continue dropping afterwards
Shell monomer and residue initiator, 1-5h；Insulation reaction 1-4h；Cooling, filtration, obtain final emulsion.
Nuclear monomer (acrylic ester monomer) is put in emulsifying agent, deionized water mixed liquor, emulsifying, prepare pre-emulsion.By part pre-emulsion with
Part initiator is placed in flask, 40 DEG C-85 DEG C, is stirred at reflux reaction 0.5-2h；Residue pre-emulsion and part initiator are added dropwise to reaction system,
1-5h；Insulation reaction 1-4h；(acrylic ester monomer accounts for 50%-90%, and function monomer accounts for 2%-10%, fluorine-containing list to continue dropping shell monomer afterwards
Body accounts for 10%-50%) and residue initiator, 1-5h；Insulation reaction 1-4h；Cooling, filtration, obtain final emulsion.
The invention have one characteristic that employing core shell self crosslinking prepares emulsion for wood, nucleocapsid structure can be logical while having excellent room temperature film-forming
Cross self-crosslinking and keep the hardness that paint film is good；Another characteristic of the present invention is to add fluorinated acrylate monomer in shell monomer, owing to fluorine element is peculiar
Low-surface-energy, can make woodenware coating surface have excellence water repellent even soil repellency energy, outside contamination can be effectively isolated in woodenware surface, simultaneously
The uvioresistant performance that fluorine element has had, the ageing resistace of paint film is also greatly improved.
Detailed description of the invention
1. by methyl methacrylate 30g, butyl methacrylate 5.4g, isobornyl methacrylate 2.3g, OP-10 1.5g, dodecyl sodium sulfonate
Sodium 1.5g, deionized water 130g, be stirred together for pre-emulsification；To be emulsified completely after, pre-emulsion 40g is added round-bottomed flask, 80 DEG C are reacted to
Without backflow, in 1 hour, drip residue pre-emulsion；It is incubated 2 hours；Methyl methacrylate 18.2g, acrylic acid 3g, butyl acrylate
27.1g, ethyl acrylate 2g, acrylic acid-2-(perfluoro hexyl) ethyl ester 28.7g, Hydroxypropyl acrylate 2.3g are blended and were added dropwise in 2 hours
In reactant liquor；It is incubated 2 hours；Cooling, adds in ammonia and pH to 7；Filter, obtain product.
2. OP-10 1.2g, dodecylbenzene sodium sulfonate 2.7g, deionized water 148g being put in round-bottomed flask, stirring is warmed up to 75 DEG C；Nuclear monomer first
Base acrylic acid methyl ester. 27g, ethyl acrylate 3.1g, butyl methacrylate 1.8g, methacrylic acid-2-(perfluoro capryl) propyl ester 2.5g are altogether
Gradually it is added dropwise in reaction in being mixed in 2 hours；It is incubated 1 hour；Shell monomer methyl methacrylate 7.1g, isobornyl methacrylate 2.3g,
Methacrylic acid-2-(perfluoro capryl) propyl ester 38.7g, methacrylic acid 1.5g, N-[2-(2-methyl-4-oxopentyl) 2g are blended in 2.5 hours dropping
Enter in reactant liquor；It is incubated 2 hours；Cooling, adds in ammonia and pH to 7；Add adipic dihydrazide 1g；Filter, obtain product.
3. by acrylonitrile 2.0g, methyl methacrylate 29g, butyl methacrylate 3.1g, OP-10 1.0g, sodium lauryl sulphate 1.0g, go from
Sub-water 70g, is stirred together for pre-emulsification；To be emulsified completely after, pre-emulsion 40g is added round-bottomed flask, 80 DEG C are reacted to without backflow, 1 hour
Inside drip residue pre-emulsion；It is incubated 1 hour；By divinylbenzene 1.5g, methyl methacrylate 13.9g, acrylic acid 3g, acrylic acid
Butyl ester 18.1g, ethyl acrylate 2g, acrylic acid-2-(perfluoro hexyl) ethyl ester 35.2g, 2-(Acryloyloxy)ethanol 1.8g, OP-10 1.2g, ten
Sodium dialkyl sulfate 1.2g, it is stirred together for pre-emulsification and was added dropwise in reactant liquor in 2 hours；It is incubated 2 hours；Add in ammonia and pH
To 7: cooling, filter, obtain product.
Claims (7)
1. an outdoor aqueous wooden ware coating resins, its component include (methyl) acrylic ester monomer, fluorinated acrylate monomer, functional monomer,
Emulsifying agent, initiator and water, it is characterised in that resin uses in nucleocapsid structure and polymer fluorine-containing groups, the percentage by weight of each component
Content is:
(methyl) acrylic ester monomer (20%-45%)
Fluorinated acrylate monomer (1%-30%)
Functional monomer (0.2%-10%)
Emulsifying agent (0.1%-10%)
Initiator (0.1%-5%)
Water (40%-70%)
Above mark is weight fraction.
A kind of outdoor aqueous wooden ware coating resins the most according to claim 1, it is characterised in that described (methyl) acrylic ester monomer is (first
Base) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) glycidyl acrylate, (methyl) third
Olefin(e) acid isobornyl thiocyanoacetate, (methyl) acrylic acid, (methyl) 2-(Acryloyloxy)ethanol, (methyl) Hydroxypropyl acrylate, (methyl) acrylic acid 18
One or more of the acrylic ester monomers such as ester (ten diester, hexadecyl ester).
A kind of outdoor aqueous wooden ware coating resins the most according to claim 1, it is characterised in that described fluorinated acrylate monomer structural formula is:
A:H, CH3RF:CnF2n+1(n=4～12)
B:-(CH2)n-(n=1～5),
Or-(CH2)n-M (n=1～5)
Wherein M:-S-,-SO2-、(T:CnH2n+1, n=1～4).
A kind of outdoor aqueous wooden ware coating resins the most according to claim 1, it is characterised in that described functional monomer includes styrene, propylene
Nitrile, divinylbenzene, N-[2-(2-methyl-4-oxopentyl), N hydroxymethyl acrylamide, triethylamine, adipic dihydrazide one or more.
A kind of outdoor aqueous wooden ware coating resins the most according to claim 1, it is characterised in that nuclear monomer is (methyl) acrylic acid methyl ester., (methyl)
Ethyl acrylate, (methyl) butyl acrylate, (methyl) glycidyl acrylate, (methyl) isobornyl acrylate, (methyl) third
One or more of olefin(e) acid；Shell monomer is (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl)
Glycidyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid, (methyl) 2-(Acryloyloxy)ethanol, (methyl) propylene
Acid hydroxypropyl acrylate, (methyl) octadecyl acrylate (ten diester, hexadecyl ester), styrene, acrylonitrile, divinylbenzene, diacetone acrylamide acyl
Amine, N hydroxymethyl acrylamide, triethylamine, adipic dihydrazide, fluorinated acrylate monomer one or more.
A kind of outdoor aqueous wooden ware coating resins the most according to claim 1, it is characterised in that described emulsifying agent includes alkylsulfonate, alkylbenzene
Sulfonate, polyoxyethylene alkylphenol base ether one or more.
A kind of outdoor aqueous wooden ware coating resins the most according to claim 1, it is characterised in that the method for preparation is as follows:
Nuclear monomer (acrylic ester monomer) is put in emulsifying agent, deionized water mixed liquor, emulsifying, prepare pre-emulsion, by pre-for part breast
Liquid and part initiator are placed in flask, 40 DEG C-85 DEG C, are stirred at reflux reaction 0.5-2h；Residue pre-emulsion and part initiator are added dropwise to instead
Answer system, 1-5h；Insulation reaction 1-4h；The shell monomer of continuation dropping afterwards (acrylic ester monomer accounts for 50%-90%, and function monomer accounts for 2%-10%,
Fluorochemical monomer accounts for 10%-50%) and residue initiator, 1-5h；Insulation reaction 1-4h；Cooling, filtration, obtain final emulsion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201410823025.1A CN105884976A (en) | 2014-12-26 | 2014-12-26 | Water-borne wood paint resin used outdoors and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410823025.1A CN105884976A (en) | 2014-12-26 | 2014-12-26 | Water-borne wood paint resin used outdoors and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589216A (en) * | 2016-12-03 | 2017-04-26 | 范进 | Fluorine-containing polyacrylic acid latex and preparation method thereof |
| CN106699985A (en) * | 2016-11-15 | 2017-05-24 | 湖北工业大学 | Super-long super slow release type polycarboxylic acid slump-retaining agent master batch |
| CN108409911A (en) * | 2018-01-19 | 2018-08-17 | 大连理工大学 | A kind of preparation method of super-hydrophobicity automatically cleaning fluoresent coating |
| WO2018237118A1 (en) * | 2017-06-21 | 2018-12-27 | Swimc Llc | Aqueous dispersion of polymeric particles having core-shell structure, the preparation thereof and the coating formed therefrom |
| CN112079964A (en) * | 2020-09-29 | 2020-12-15 | 湖南隆森化工有限公司 | Core-shell fluorine-containing waterproof agent and preparation method thereof |
| CN112608414A (en) * | 2020-07-28 | 2021-04-06 | 杭州传化精细化工有限公司 | Fluorine-containing copolymer emulsion and preparation method and application thereof |
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| CN103980418A (en) * | 2014-05-23 | 2014-08-13 | 深圳天鼎精细化工制造有限公司 | Cationic waterborne organic fluorine acrylate polymer as well as preparation method and application of cationic waterborne organic fluorine acrylate polymer |
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| CN101845114A (en) * | 2010-05-28 | 2010-09-29 | 北京化工大学 | Preparation method of fluorinated acrylate microemulsion |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106699985A (en) * | 2016-11-15 | 2017-05-24 | 湖北工业大学 | Super-long super slow release type polycarboxylic acid slump-retaining agent master batch |
| CN106589216A (en) * | 2016-12-03 | 2017-04-26 | 范进 | Fluorine-containing polyacrylic acid latex and preparation method thereof |
| WO2018237118A1 (en) * | 2017-06-21 | 2018-12-27 | Swimc Llc | Aqueous dispersion of polymeric particles having core-shell structure, the preparation thereof and the coating formed therefrom |
| US11739233B2 (en) | 2017-06-21 | 2023-08-29 | Guangdong Huarun Paints Co., Ltd. | Aqueous dispersion of polymeric particles having core-shell structure, the preparation thereof and the coating formed therefrom |
| CN108409911A (en) * | 2018-01-19 | 2018-08-17 | 大连理工大学 | A kind of preparation method of super-hydrophobicity automatically cleaning fluoresent coating |
| CN108409911B (en) * | 2018-01-19 | 2020-07-14 | 大连理工大学 | Preparation method of super-hydrophobic self-cleaning fluorescent coating |
| CN112608414A (en) * | 2020-07-28 | 2021-04-06 | 杭州传化精细化工有限公司 | Fluorine-containing copolymer emulsion and preparation method and application thereof |
| CN112608414B (en) * | 2020-07-28 | 2022-09-06 | 杭州传化精细化工有限公司 | Fluorine-containing copolymer emulsion and preparation method and application thereof |
| CN112079964A (en) * | 2020-09-29 | 2020-12-15 | 湖南隆森化工有限公司 | Core-shell fluorine-containing waterproof agent and preparation method thereof |
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Application publication date: 20160824 |