CN107722235A - A kind of low VOC polyurethane resins - Google Patents
A kind of low VOC polyurethane resins Download PDFInfo
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- CN107722235A CN107722235A CN201710902448.6A CN201710902448A CN107722235A CN 107722235 A CN107722235 A CN 107722235A CN 201710902448 A CN201710902448 A CN 201710902448A CN 107722235 A CN107722235 A CN 107722235A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The present invention proposes a kind of low VOC polyurethane resins, including component A and B component；The component A contains the composition of following mass parts：5 90 parts of polyester and/or poly- hydroxy acrylate, 2 80 parts can reaction monomers, 0 0.2 parts of polymerization inhibitors；The B component includes isocyanates, 0 2.0 parts of the organic peroxide of 5 60 parts of parts by weight.Polyurethane composition objects system proposed by the present invention, by low viscosity can reaction monomers and poly- Hydroxylated acrylic resin or polyester and diisocyanate form, can reaction monomers on the one hand reduce the viscosity of polyurethane system, the polymer of crosslinking on the other hand can also be formed with polyurethanes molecule chain reaction in the presence of initiator and accelerator；And poly- Hydroxylated acrylic resin or polyester are cross-linked into polyurethane resin with diisocyanate.The macromolecule polyalcohol that two kinds of reactions are formed turns into the fluoropolymer resin of solidification.
Description
Technical field
The invention belongs to the field of high-molecular organic material, and in particular to a kind of composition containing isocyanates.
Background technology
Polyurethane is conventional industrial protection and decorative coating, has good ageing resistace and decay resistance.
But the VOC of the coating (VOC) content is higher, generally 70%~20%, therefore its feature of environmental protection is poor.
The usual practice for solving this problem is to prepare aqueous polyurethane coating, but waterborne polyurethane resin has anti-corrosion, adhesive force
With the fatal defects such as loss of properties on aging, it is difficult to reach the performance indications of conventional solvent type polyurethane, therefore limit its application.
Polyurethane is the polymer of HMW, and the polyurethane products of its 80-90% mass fraction are extremely sticky, it is impossible to apply
Work；Hybrid pigment etc. can be carried out with organic solvent dispersion to 40%-70% to operate, but VOC is also significantly increased therewith.Obtain both
Ensure the low VOC products of the good adhesive property of urethane composition again with low-viscosity polyurethane, be that this area does not solve also
The problem of.
The content of the invention
For the weak point of this area, of the invention first purpose is to propose a kind of low VOC polyurethane resins.
Second object of the present invention goes out the application of the low VOC polyurethane.
Third object of the present invention is to propose a kind of coating containing the low VOC polyurethane resins.
The concrete technical scheme for realizing above-mentioned purpose of the present invention is：
A kind of low VOC polyurethane resins, including component A and B component；The component A contains the composition of following mass parts：5-
90 parts of polymer, 2-80 parts can reaction monomers, 0-0.2 part polymerization inhibitors；The B component includes the isocyanide of parts by weight 5-60 parts
Acid esters, the organic peroxide of 0-2.0 parts；The polymer is polyester and/or poly- hydroxy acrylate.
For this now with the current composition, polymerization inhibitor can not had to；If there is the polymerization inhibitor in composition, A B C mixing
It can be placed after preparing 1 year.
Preferably, the polyester is the PEPA that molecular weight is 1000-3000, and the poly- hydroxy acrylate is point
Son amount 1000-5000 poly- hydroxyl acrylic resin, the polyester and poly- hydroxy acrylate have 70- independently of each other
200mgKOH/g hydroxyl value.
Wherein, it is described can reaction monomers be selected from butyl acrylate, 2-ethyl hexyl acrylate, lauryl acrylate, 2,3 dihydroxy first
Base propyl acrylate, methacrylate, Tetrahydrofurfuryl Methacrylate, acrylate, methyl-prop
Olefin(e) acid cyclohexyl, isobornyl methacrylate, isodecyl acrylate, triethylene glycol divinyl ether, Isosorbide-5-Nitrae-cyclohexane dimethanol
The poly- second two of divinyl ether, 4- hydroxy butyl vinyl ethers, glycerol carbonate propenyl ether, dodecyl vinyl, methoxyl group
Alcohol monomethacrylates, methoxy poly (ethylene glycol) mono acrylic ester, methoxyl group tripropylene glycol mono acrylic ester, methoxy propyl oxygen
Base neopentyl glycol mono acrylic ester, methoxy ethoxy trimethylolpropane diacrylate, glycols dimethacrylate
Ester, glycols diacrylate, propandiols dimethylacrylate, propandiols diacrylate, DPG class two
It is acrylate, tripropylene glycol class diacrylate, Isosorbide-5-Nitrae butanediol category diacrylate, 1,6 hexylene glycol class diacrylates, new
Diacrylate, trimethylolpropane trimethacrylate, methacrylic acid phosphate monoester, metering system acid phosphoric acid are double
Ester, acrylated phosphate, Bing olefin(e) acid Er Evil cyclopentadienyls ester, aliphatic monoacrylate, trifunctional methacrylate, trifunctional
Acrylate, tertiary amine acrylate, styrene, to benzene divinyl, 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester, 2- hydroxyls
Propyl propionate, butyl 2-hydroxypropanoate, 3- hydroxy methyl propionates, 3- hydroxypropionates, ethyl 3-hydroxybutanoate, hydroxyacetic acid
Butyl ester, hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxy propyl methacrylate, hy-droxybutyl
In one or more.
A kind of optional technical scheme of the present invention is that the polymer is polyester and poly- hydroxy acrylate, the low VOC
Polyurethane resin also includes component C accelerator, and the accelerator is naphthenate, ethylhexanoate salt, dimethylaniline, diethylbenzene
Amine, dimethyl-p-toluidine, triethylenediamine, dimethylacetoacetamide, p-methyl benzenesulfonic acid, dodecyl sodium sulfate,
One or more in quaternary ammonium salt, thio alcohol, two (2- ethoxys) para-totuidine.
A preferred technical solution of the present invention is that the polymer of the component A is 20-70 parts, and the polymer is poly-
Ester or the combination for polyester and poly- hydroxy acrylate in mass ratio 1: 1.6-3, it is described can reaction monomers be first kind monomer and
The combination of second class monomer, the first kind monomer are selected from 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester, 2 hydroxy propanoic acid third
Ester, butyl 2-hydroxypropanoate, 3- hydroxy methyl propionates, 3- hydroxypropionates, ethyl 3-hydroxybutanoate, Butyl Glycolate,
Hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxy propyl methacrylate, methacrylate,
One kind in hy-droxybutyl, trimethylolpropane trimethacrylate；(this first kind monomer is the monomer for having hydroxyl)
The second class monomer is selected from butyl acrylate, 2-ethyl hexyl acrylate, lauryl acrylate, 2,3 bishydroxymethyls third
Olefin(e) acid propyl ester, Tetrahydrofurfuryl Methacrylate, acrylate, cyclohexyl methacrylate, methacrylic acid
Isobornyl thiocyanoacetate, isodecyl acrylate, triethylene glycol divinyl ether, Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether, 4- hydroxyl butyl second
Alkene ether, glycerol carbonate propenyl ether, dodecyl vinyl, methoxy poly (ethylene glycol) monomethacrylates, methoxy
Base polyethylene glycol monoacrylate, methoxyl group tripropylene glycol mono acrylic ester, methoxy propoxy neopentyl glycol mono acrylic ester,
Glycols dimethylacrylate, glycols diacrylate, propandiols dimethylacrylate, propandiols dipropyl
Olefin(e) acid ester, DPG class diacrylate, tripropylene glycol class diacrylate, Isosorbide-5-Nitrae butanediol category diacrylate, 1,6 oneself
Glycols diacrylate, neopentylglycol diacrylate, methacrylic acid phosphate monoester, methacrylic acid phosphate diester, third
Olefin(e) acid phosphate, Bing olefin(e) acid Er Evil cyclopentadienyls ester, aliphatic monoacrylate, trifunctional methacrylate, trifunctional propylene
Acid esters, tertiary amine acrylate, styrene, to two kinds in benzene divinyl, the weight ratio of the two is 1: 0.8-1.5.(this second class
Monomer has double bond, and crosslink density is higher, and resistance to acids and bases is good).
Another optimal technical scheme of the present invention is that the component A contains the polymer of 50-80 parts, the polymer
For the combination of poly- hydroxy acrylate or polyester and poly- hydroxy acrylate in mass ratio 1: 1-10, it is described can reaction monomers be
Butyl 2-hydroxypropanoate, 3- hydroxy methyl propionates, ethyl 3-hydroxybutanoate, gamma butyrolactone, ethyl 3-hydroxybutanoate, 3- hydroxyls third
Acetoacetic ester, Butyl Glycolate, 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester, 2 hydroxy propanoic acid propyl ester, 3- hydracrylic acid second
More than two kinds of combination in ester, Butyl Glycolate, every kind of monomer are 1-10 parts independently of each other.
The monomer for not having double bond only plays diluting effect, avoids the use of volatile solvent.The present invention preferably uses boiling point
It is different it is a variety of can reaction monomers be used cooperatively, with the drying property of regulation composition.
Wherein, the isocyanates is hexamethylene diisocyanate (HDI), HDI biurets, HDI trimer, different Fo Er
Ketone diisocyanate (IPDI), IPDI addition products, IPDI tripolymers, dicyclohexyl methyl hydride diisocyanate (HMDI) and its addition
Thing, toluene di-isocyanate(TDI) (TDI), TDI addition products, TDI tripolymers, methyl diphenylene diisocyanate (MDI), MDI additions
One or more in thing, XDI (XDI), XDI addition products.
The polymerization inhibitor is hydroquinones, p-tert-Butylcatechol, benzaldehyde, aromatic amine, p methoxy phenol
In one kind；
It is different that the organic peroxide is selected from benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, hydrogen peroxide
One or more in propyl benzene, di-isopropyl peroxydicarbonate, t-amyl peroxy compound, di-tert-butyl peroxide；
The accelerator is naphthenate, ethylhexanoate salt, dimethylaniline, diethylaniline, dimethyl-p-toluidine, three
Ethylene diamine, dimethylacetoacetamide, p-methyl benzenesulfonic acid, dodecyl sodium sulfate, quaternary ammonium salt, thio alcohol, two (2- hydroxyls
Ethyl) para-totuidine one or more.
It is highly preferred that the isocyanates is one kind in HDI trimer or TDI tripolymers, HDI biurets, isocyanic acid
Ester and can reaction monomers mass ratio be 0.6-2: 1.
Because commercially available HDI biurets contain solvent mostly, therefore it is not so good as HDI trimer or TDI tripolymers just with HDI biurets
Profit.
Further optimization formula of the invention is that the component A contains the composition of following mass parts：The polyester of 60-80 parts
With poly- hydroxy acrylate, 20-40 parts can reaction monomers, 0-0.2 part polymerization inhibitors；The B component is the isocyanic acid of 20-60 parts
Ester.
In above-mentioned optimization formula, polyester and poly- hydroxy acrylate in mass ratio 1: 1-10 combine, preferably 1: 1.5-5
Combination, more preferably 1: 1.6-3 combination.
Application of the low VOC polyurethane resins of the present invention as coating and embedding agent.
A kind of coating, containing described low VOC polyurethane resins, the coating is by the first component, the low VOC polyurethane
B component 5-60 parts of resin, component C 0-2.0 parts composition,
First component contains 60 parts of the component A of low VOC polyurethane resins, pigment 3-60 parts, filler 4-60 parts, silicic acid
Salt 0-8.5 parts, levelling agent 0.2-1 parts, defoamer 0.1-0.5 parts, wetting agent 0.2-0.5 parts, organobentonite 0.1-2 parts.
Composition in above-mentioned coating is one in commercially available conventional products, such as the optional titanium dioxide of pigment, iron oxide
Kind or it is a variety of, filler from blanc fixe, white carbon, the one or more in nano silicon, silicate be talcum powder,
One or more in clay, magnesium silicate, montmorillonite.Levelling agent, defoamer, wetting agent are purchased in market.
The beneficial effects of the present invention are：
Polyurethane composition objects system proposed by the present invention, by low viscosity can reaction monomers and poly- Hydroxylated acrylic resin or
Polyester and diisocyanate composition, can reaction monomers on the one hand reduce the viscosity of polyurethane system, on the other hand can also be
The polymer of crosslinking is formed in the presence of initiator and accelerator with polyurethanes molecule chain reaction；And poly- hydroxy acrylic acid
Resin or polyester are cross-linked into polyurethane resin with diisocyanate.The macromolecule polyalcohol that two kinds of reactions are formed turns into the poly- of solidification
Polymer resin.
The standby coating of the polyurethane due to can reaction monomers take part in the reaction of resin matrix and turn into polyurethane resin
Final constituent, therefore VOC is extremely low.Because the system has typical polyurethanes design feature, therefore have
The characteristics of good mechanical performances such as adhesive force, shock resistance, pliability, stretch-proof, while its corrosion resistance and resistance to ag(e)ing also pole
To be excellent.
Embodiment
Following examples further illustrate present disclosure, but should not be construed as limiting the invention.
With reference to embodiment, the embodiment of the present invention is described in further detail.Following examples are
For illustrating the present invention, rather than for limiting the scope of the present invention.
Embodiment 1
Using the raw material of poly- hydroxyl acrylic resin of mass fraction 85%, (purchased in market, its viscosity is 6000- to the present embodiment
10000 centipoises, 23 DEG C).
Component A：Poly- 70 parts of hydroxyl acrylic resin (hydroxyl value 70), 2 parts of hydroxypropyl acrylate, 15 parts of 2-ethyl hexyl acrylate,
13 parts of butyl acrylate.
After each composition mixing of component A, viscosity is 4 glasss of 35s (23 DEG C) of painting.
B component：20 parts of HDI trimer N3390,1.4 parts of methyl ethyl ketone peroxide.
0.3 part of component C cobalt iso-octoate (4% solution).
The preparation method of the present embodiment polyurethane：Poly- hydroxyl acrylic resin, hydroxypropyl acrylate, 2-ethyl hexyl acrylate
It is well mixed with butyl acrylate and becomes component A；N3390 and methyl ethyl ketone peroxide are mixed into B component.Component C is accelerator
Cobalt iso-octoate.Three separately packs.
There is polyurethane prepared by the present embodiment VOC to be less than 10%, anti-aging detection establishing criteria《GB/T14522-
2008 Industry Machineries coating artificial weathering test method fluorescent ultraviolet lamp》QUV experiments are measured up to 1500 hours
(UVA-340).Viscosity is 4 glasss of 50s of painting.Adhesive force is tested according to ASTMD 4541-2009《Using Portable adhesion-force tester
Determine the test method of coating pull-out strength》, it is 5Mpa to measure adhesive force.
VOC detection methods are：The flat ware of metal dries 30min in 105 ± 2 DEG C of baking ovens, is then placed in drier to making
With.After ABC mixing, the flat ware of metal is laid in, 24h is placed under the conditions of 23 ± 2 DEG C of temperature, humidity 50 ± 5%, then 105
60min is dried in ± 2 DEG C of baking ovens, it is parallel to do two parts of experiments.Weigh m before heating1(canister m0With reactant quality sum) and
Quality m after heating2, non-volatile content ω (NV) formula
ω (NV)=(m2-m0)/((m1-m0)
1- ω produce VOC values.The VOC values of the present embodiment polyurethane are 9.6%.
Embodiment 2
Component A：70 parts of polyester resin (hydroxyl value 175), 2 parts of hydroxypropyl acrylate, 13 parts of isodecyl acrylate (IDA), third
15 parts of olefin(e) acid butyl ester.
B component：55 parts of HDI trimer N3390,1.4 parts of cyclohexanone peroxide.
Component C：0.15 part of cobalt iso-octoate (4% solution).
The preparation method of the present embodiment polymer coating：Polyester resin, hydroxypropyl acrylate, isodecyl acrylate and third
Olefin(e) acid butyl ester is well mixed to become component A；N3390 and methyl ethyl ketone peroxide are mixed into B component.Component C is that accelerator is different pungent
Sour cobalt.
Polyurethane VOC values prepared by the present embodiment are 4%, have the characteristics of VOC is less than 10%, anti-aging to press《GB/
T14522-2008 Industry Machineries coating artificial weathering test method fluorescent ultraviolet lamp》QUV experiments are measured up to 1000
Hour (UVA-340).Viscosity is 4 glass 60 of painting.Adhesive force is tested according to ASTM D 4541-2009《Surveyed using Portable adhesion-force
Try the test method of instrument measure coating pull-out strength》, it is 11.8Mpa to measure adhesive force.
Embodiment 3
Component A：20 parts of polyester resin (hydroxyl value 175), poly- 50 parts of hydroxyl acrylic resin (hydroxyl value 70), acrylic acid hydroxypropyl
2 parts of ester, 13 parts of isodecyl acrylate (IDA), 15 parts of butyl acrylate.
B component：30 parts of HDI trimer N3390.1.4 parts of cyclohexanone peroxide.
Component C：0.15 part of cobalt iso-octoate (4% solution).
Polyurethane VOC values 6.2% prepared by the present embodiment.It is anti-aging to press《GB/T14522-2008 Industry Machineries
With coating artificial weathering test method fluorescent ultraviolet lamp》QUV experiments are measured up to 1500 hours (UVA-340).Viscosity is painting 4
Cup 40s.Adhesive force is tested according to ASTM D 4541-2009《Using Portable adhesion-force tester measure coating pull-out strength
Test method》, it is 9Mpa to measure adhesive force.
Embodiment 4
Component A：Poly- 74 parts of hydroxyl acrylic resin (hydroxyl value 70), 1 part of hydroxy-ethyl acrylate, lauryl acrylate 20
Part, 5 parts of trimethylolpropane trimethacrylate.
B component：23 parts of HDI biurets N75,2 parts of benzoyl peroxide.
Component C：0.5 part of cobalt iso-octoate (4% solution).
The preparation method of the present embodiment polymer coating：Poly- hydroxyl acrylic resin, hydroxypropyl acrylate, methyl-prop
E pioic acid methyl ester and trimethylolpropane trimethacrylate, which are well mixed, becomes component A；N75 and methyl ethyl ketone peroxide are mixed into B
Component.Component C is accelerator cobalt iso-octoate.Three separately packs.
It is 9.2% that polyurethane prepared by the present embodiment, which has VOC, anti-aging to press《GB/T14522-2008 mechanical industries
Product coating artificial weathering test method fluorescent ultraviolet lamp》Measure QUV experiments more than 1500 hours (UVA-340).It is attached
Put forth effort test according to ASTM D 4541-2009《Using the experiment side of Portable adhesion-force tester measure coating pull-out strength
Method》, it is 6.9Mpa to measure adhesive force.
Embodiment 5
Component A：Poly- hydroxyl acrylic resin (purchased in market, hydroxyl value 70, molecular weight 4500.85% effective content) 73 parts, carbon
1 part of acid propylene ester, 12 parts of butyl 2-hydroxypropanoate, 9 parts of 3- hydroxy methyl propionates, 2 parts of ethyl 3-hydroxybutanoate, hydroxyacetic acid fourth
3 parts of ester.
B component：23 parts of HDI biurets N75 (being free of solvent).
Polyurethane VOC values prepared by the present embodiment are 8.9%, anti-aging to press《GB/T14522-2008 mechanical industries are produced
Product coating artificial weathering test method fluorescent ultraviolet lamp》Measure QUV experiments more than 1500 hours (UVA-340).Viscosity
To apply 4 glasss of 40s.Adhesive force is tested according to ASTM D 4541-2009《Pulled open using Portable adhesion-force tester measure coating
The test method of intensity》, it is 8.5Mpa to measure adhesive force.
Embodiment 6
Component A：Poly- 45 parts of hydroxyl acrylic resin (hydroxyl value 70), 27 parts of polyester resin (hydroxyl value 175), gamma butyrolactone 4
Part, 9 parts of butyl 2-hydroxypropanoate, 5 parts of ethyl 3-hydroxybutanoate, 7 parts of 3- hydroxypropionates, 3 parts of Butyl Glycolate.
B component：27 parts of HDI trimer N3390.
In this formula, polyester and poly- hydroxy acrylate in mass ratio 1: 1.67 combine, and combination property is good, wherein：This
Polyurethane VOC values 5.3% prepared by embodiment, it is anti-aging to press《GB/T14522-2008 Industry Machinery coating is artificial
Weathering test method fluorescent ultraviolet lamp》QUV experiments are measured up to 1600 hours (UVA-340).Viscosity is 4 glasss of 40s of painting.Attachment
Power is tested according to ASTM D 4541-2009《Using the test method of Portable adhesion-force tester measure coating pull-out strength》,
It is 10.2Mpa to measure adhesive force.
Embodiment 7
Component A：Poly- 54 parts of hydroxyl acrylic resin (hydroxyl value 70), 18 parts of polyester resin (hydroxyl value 175), gamma butyrolactone 4
Part, 9 parts of butyl 2-hydroxypropanoate, 5 parts of ethyl 3-hydroxybutanoate, 7 parts of 3- hydroxypropionates, 3 parts of Butyl Glycolate.
B component：27 parts of HDI trimer N3390.
In this formula, the combination of polyester and poly- hydroxy acrylate in mass ratio 1: 3, the polyurethane VOC values of preparation
5.3%, it is anti-aging to press《GB/T14522-2008 Industry Machineries coating artificial weathering test method fluorescent ultraviolet
Lamp》QUV experiments are measured up to 1500 hours (UVA-340).Viscosity is 4 glasss of 40s of painting.Adhesive force is tested according to ASTM D 4541-
2009《Using the test method of Portable adhesion-force tester measure coating pull-out strength》, it is 10.0Mpa to measure adhesive force.
Embodiment 8
60 parts of component A in embodiment 1,25 parts of titanium dioxide, blanc fixe 5,8.5 parts of talcum powder, 0.5 part of levelling agent,
0.2 part of defoamer, 0.3 part of wetting agent, the A groups after 0.5 part of scattered grinding of all components mixing of organobentonite as coating
Point；The B component of coating is HDI trimer N3390；Methyl ethyl ketone peroxide；Component C is accelerator (normal-temperature reaction) cobalt iso-octoate.
The preparation method of polyurethane coating：The components of ABC tri- by weight 100: 15: 0.05 mixing, stir, then
Spraying is brushed.The VOC of the coating is 5.5%, has good salt spray resistance and adhesive force.
Similarly, coating made of embodiment 1,2,3,4,5,6,7 is respectively labeled as coating 1, coating 2, coating 3, coating
4th, coating 5, coating 6, coating 7.The VOC of each coating is respectively less than 5%, other performance indications such as following table：
Although the present invention is described in detail with most preferred embodiment above, those skilled in the art are not it is to be understood that inclined
On the premise of from inventive concept and spirit, any improvement and modification made to the present invention, still fall within claimed
Within the scope of.
Claims (11)
1. a kind of low VOC polyurethane resins, including component A and B component；Characterized in that, the component A contains following mass parts
Composition：The polymer of 5-90 parts, 2-80 parts can reaction monomers, 0-0.2 part polymerization inhibitors；The B component includes parts by weight 5-
60 parts of isocyanates, the organic peroxide of 0-2.0 parts；The polymer is polyester and/or poly- hydroxy acrylate.
2. low VOC polyurethane resins according to claim 1, it is characterised in that the polyester is that molecular weight is 1000-
3000 PEPA, the poly- hydroxy acrylate is molecular weight 1000-5000 poly- hydroxyl acrylic resin, described
Polyester and poly- hydroxy acrylate have 70-200mgKOH/g hydroxyl value independently of each other.
3. low VOC polyurethane resins according to claim 1, it is characterised in that it is described can reaction monomers be selected from acrylic acid
Butyl ester, 2-ethyl hexyl acrylate, lauryl acrylate, 2,3 bishydroxymethyl propyl acrylates, methacrylate, methyl-prop
Olefin(e) acid tetrahydrofuran methyl esters, acrylate, cyclohexyl methacrylate, isobornyl methacrylate, acrylic acid
Isodecyl ester, triethylene glycol divinyl ether, Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether, 4- hydroxy butyl vinyl ethers, glycerine carbonic acid
Ester propenyl ether, dodecyl vinyl, methoxy poly (ethylene glycol) monomethacrylates, methoxy poly (ethylene glycol) list propylene
Acid esters, methoxyl group tripropylene glycol mono acrylic ester, methoxy propoxy neopentyl glycol mono acrylic ester, the hydroxyl of methoxy ethoxy three
Diacrylate, glycols dimethylacrylate, glycols diacrylate, propandiols dimethyl propylene
Olefin(e) acid ester, propandiols diacrylate, DPG class diacrylate, tripropylene glycol class diacrylate, Isosorbide-5-Nitrae butanediol
Class diacrylate, 1,6 hexylene glycol class diacrylates, neopentylglycol diacrylate, trimethylolpropane trimethacrylate,
Methacrylic acid phosphate monoester, methacrylic acid phosphate diester, acrylated phosphate, Bing olefin(e) acid Er Evil cyclopentadienyls ester, aliphatic list third
Olefin(e) acid ester, trifunctional methacrylate, trifunctional group acrylate, tertiary amine acrylate, styrene, to benzene divinyl,
2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester, 2 hydroxy propanoic acid propyl ester, butyl 2-hydroxypropanoate, 3- hydroxy methyl propionates, 3-
Hydroxypropionate, ethyl 3-hydroxybutanoate, Butyl Glycolate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, methacrylic acid
One or more in hydroxyl ethyl ester, hydroxy propyl methacrylate, hy-droxybutyl.
4. low VOC polyurethane resins according to claim 1, it is characterised in that the polymer is polyester and poly- hydroxyl
Acrylate, the low VOC polyurethane resins also include component C accelerator, the accelerator be naphthenate, ethylhexanoate salt,
Dimethylaniline, diethylaniline, dimethyl-p-toluidine, triethylenediamine, dimethylacetoacetamide, to toluene sulphur
One or more in acid, dodecyl sodium sulfate, quaternary ammonium salt, thio alcohol, two (2- ethoxys) para-totuidine.
5. the low VOC polyurethane resins according to claim any one of 1-4, it is characterised in that the polymer is 20-70
Part, it is polyester, or the combination for polyester and poly- hydroxy acrylate in mass ratio 1: 1.6-3,
It is described can reaction monomers be first kind monomer and the second class monomer combination, the first kind monomer is selected from 2 hydroxy propanoic acid
Methyl esters, 2 hydroxy propanoic acid ethyl ester, 2 hydroxy propanoic acid propyl ester, butyl 2-hydroxypropanoate, 3- hydroxy methyl propionates, 3- hydracrylic acid second
Ester, ethyl 3-hydroxybutanoate, Butyl Glycolate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, first
One kind in base hydroxypropyl acrylate, methacrylate, hy-droxybutyl, trimethylolpropane trimethacrylate；
The second class monomer is selected from butyl acrylate, 2-ethyl hexyl acrylate, lauryl acrylate, 2,3 bishydroxymethyl acrylic acid
The different ice of propyl ester, Tetrahydrofurfuryl Methacrylate, acrylate, cyclohexyl methacrylate, methacrylic acid
Piece ester, isodecyl acrylate, triethylene glycol divinyl ether, Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether, 4- hydroxyl butyl vinyls
Ether, glycerol carbonate propenyl ether, dodecyl vinyl, methoxy poly (ethylene glycol) monomethacrylates, methoxyl group gather
Diethylene glycol monoacrylate, methoxyl group tripropylene glycol mono acrylic ester, methoxy propoxy neopentyl glycol mono acrylic ester, second two
Alcohols dimethylacrylate, glycols diacrylate, propandiols dimethylacrylate, propandiols diacrylate
Ester, DPG class diacrylate, tripropylene glycol class diacrylate, Isosorbide-5-Nitrae butanediol category diacrylate, 1,6 hexylene glycols
Class diacrylate, neopentylglycol diacrylate, methacrylic acid phosphate monoester, methacrylic acid phosphate diester, acrylic acid
Phosphate, Bing olefin(e) acid Er Evil cyclopentadienyls ester, aliphatic monoacrylate, trifunctional methacrylate, trifunctional group acrylate,
Tertiary amine acrylate, styrene, to two kinds in benzene divinyl, the weight ratio of the two is 1: 0.8-1.5.
6. the low VOC polyurethane resins according to claim any one of 1-4, it is characterised in that the component A contains 50-
80 parts of polymer, the polymer are poly- hydroxy acrylate or are polyester and poly- hydroxy acrylate in mass ratio 1: 1-
10 combination, it is described can reaction monomers be butyl 2-hydroxypropanoate, 3- hydroxy methyl propionates, ethyl 3-hydroxybutanoate, in γ fourths
Ester, ethyl 3-hydroxybutanoate, 3- hydroxypropionates, Butyl Glycolate, 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester,
More than two kinds of combination in 2 hydroxy propanoic acid propyl ester, 3- hydroxypropionates, Butyl Glycolate, every kind of monomer is independently of each other
For 1-10 parts.
7. the low VOC polyurethane resins according to claim any one of 1-4, it is characterised in that the isocyanates is six
Methylene diisocyanate (HDI), HDI biurets, HDI trimer, IPDI (IPDI), IPDI additions
Thing, IPDI tripolymers, dicyclohexyl methyl hydride diisocyanate (HMDI) and its addition product, toluene di-isocyanate(TDI) (TDI), TDI
Addition product, TDI tripolymers, methyl diphenylene diisocyanate (MDI), MDI addition products, XDI
(XDI), the one or more in XDI addition products；
The polymerization inhibitor is in hydroquinones, p-tert-Butylcatechol, benzaldehyde, aromatic amine, p methoxy phenol
It is a kind of；
The organic peroxide is selected from benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, hydrogen peroxide isopropyl
One or more in benzene, di-isopropyl peroxydicarbonate, t-amyl peroxy compound, di-tert-butyl peroxide.
8. the low VOC polyurethane resins according to claim any one of 1-4, it is characterised in that the isocyanates is HDI
One kind in tripolymer, TDI tripolymers, HDI biurets, isocyanates and can reaction monomers mass ratio be 0.6-2: 1.
9. the low VOC polyurethane resins according to claim any one of 1-4, it is characterised in that the component A contains following
The composition of mass parts：The polyester of 60-80 parts and poly- hydroxy acrylate, 20-40 parts can reaction monomers, 0-0.2 part polymerization inhibitors；
The B component is the isocyanates of 20-60 parts.
10. application of the low VOC polyurethane resins as coating and embedding agent described in claim any one of 1-9.
11. a kind of coating, contain the low VOC polyurethane resins described in claim any one of 1-10, it is characterised in that the painting
Material is made up of the first component, B component 5-60 parts of the low VOC polyurethane resins, component C 0-2.0 parts,
First component contains 60 parts of the component A of the low VOC polyurethane resins, pigment 3-60 parts, filler 4-60 parts, silicic acid
Salt 0-8.5 parts, levelling agent 0.2-1 parts, defoamer 0.1-0.5 parts, wetting agent 0.2-0.5 parts, organobentonite 0.1-2 parts.
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| CN110358416A (en) * | 2019-07-09 | 2019-10-22 | 湖南松井新材料股份有限公司 | Dedicated low VOC water-repellent paint of mobile phone and its preparation method and application |
| CN111518250A (en) * | 2020-04-30 | 2020-08-11 | 西安天元化工有限责任公司 | Thermosetting polyurethane resin and application thereof |
| CN111849232A (en) * | 2020-07-31 | 2020-10-30 | 西安天元化工有限责任公司 | Polyurethane resin capable of being cured by low-temperature free radical polymerization and application thereof |
| CN114763447A (en) * | 2021-10-22 | 2022-07-19 | 安徽柏枝新材料有限公司 | Acrylic polyurethane coating and preparation method thereof |
| WO2023123652A1 (en) * | 2021-12-30 | 2023-07-06 | 清远高新华园科技协同创新研究院有限公司 | Polyurethane reaction promoter, preparation method therefor, and use thereof |
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| CN104640894A (en) * | 2012-09-11 | 2015-05-20 | Sika技术股份公司 | Two-component polyurethane composition |
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| CN110358416A (en) * | 2019-07-09 | 2019-10-22 | 湖南松井新材料股份有限公司 | Dedicated low VOC water-repellent paint of mobile phone and its preparation method and application |
| CN111518250A (en) * | 2020-04-30 | 2020-08-11 | 西安天元化工有限责任公司 | Thermosetting polyurethane resin and application thereof |
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| CN114763447A (en) * | 2021-10-22 | 2022-07-19 | 安徽柏枝新材料有限公司 | Acrylic polyurethane coating and preparation method thereof |
| WO2023123652A1 (en) * | 2021-12-30 | 2023-07-06 | 清远高新华园科技协同创新研究院有限公司 | Polyurethane reaction promoter, preparation method therefor, and use thereof |
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| CN107722235B (en) | 2020-04-24 |
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