CN109486379A - Acrylic acid modified alkyd resin secondary breakup system and preparation method thereof - Google Patents
Acrylic acid modified alkyd resin secondary breakup system and preparation method thereof Download PDFInfo
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- CN109486379A CN109486379A CN201811048124.1A CN201811048124A CN109486379A CN 109486379 A CN109486379 A CN 109486379A CN 201811048124 A CN201811048124 A CN 201811048124A CN 109486379 A CN109486379 A CN 109486379A
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- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
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Abstract
The present invention relates to a kind of preparation methods of low VOC acrylic acid modified alkyd resin secondary breakup body.The composition and mass percentage of the dispersion are as follows: alkyd resin 20~40%, acrylic resin 8~20%, organic solvent 2~9%, deionized water 46~58%.Dispersion VOC content of the invention lower than 10%(solid content be 45%) and dispersibility preferably, solid content is larger, viscosity, moderate in grain size, and preferable with paint film richness prepared by this dispersion, and gloss is higher, and cost is relatively low.Average grain diameter is small, and average grain diameter is 60~160 nm, and particle diameter distribution is narrow, and polydispersity coefficient PDI is 0.05~0.15, has good homogeneity, is conducive to the comprehensive performance for improving film.Viscosity is smaller, is conducive to mixing subsequent construction of the coating in the process with curing agent.Dispersion has preferable mobility, stability height, stands storage 60 days or more under room temperature without variations such as any layering, sedimentation, precipitations, particle size and distribution, viscosity are without significant change.
Description
Technical field
The present invention relates to a kind of acrylic acid modified alkyd resin secondary breakup systems and preparation method thereof.
Background technique
Alkyd resin is that dosage is maximum in coating synthetic resin, and most widely used a kind of conventional resins can be used in
Make amino-stoving varnish and double-component polyurethane coating etc..With the quickening of " oil changes water " process in recent years, environmentally protective is aqueous
Coating just gradually replaces solvent based coating, it has also become the mainstream of paint development, and the exploitation of various high performance water-base resins is
Obtain the basis of high-quality water paint.
Aqueous alkide resin includes water soluble alkyd resin and emulsion-type alkyd resin.Water soluble alkyd resin is that have one
Determine acid value, the stablizing solution formed in the presence of a certain amount of organic cosolvent, acid value is higher and solid content is lower.Tradition
Emulsion-type alkyd resin be by means of the effect of emulsifier by resin emulsion dispersion in water, particle diameter it is larger and store
Stability is not good enough, and since the presence of emulsifier will affect final paint film property；Secondary breakup body is that monomer first aggregates into
Prepolymer, then disperse in water, a kind of dispersion that phase transition obtains, the aqueous alkide resin that this method obtains occur for continuous phase
Dispersion has the characteristics that partial size is small and solid content is high, and avoids using emulsifier, is conducive to mentioning for final paint film property
It is high.
Chinese patent CN102796228A discloses a kind of preparation method of waterborne alkyd dispersion, using with-
S03The binary acid and diol reaction of M group prepare intermediate polyester, and later and vegetable fatty acids, polyalcohol, polyacid are anti-
Alkyd resin should be prepared, finally plus water dispersion, has obtained aqueous dispersion.Chinese patent CN102796228A uses trimellitic acid
Acid anhydride, polyalcohol, unsaturated fatty acid reaction are prepared for aqueous alkide resin, and when use neutralizes again, is diluted with water to obtain alkyd tree
Rouge dispersion, VOC content is 24~27% in resin.In order to reduce the VOC content of alkyd resin, Chinese patent
CN104530322A is modified alkyd resin with acrylic resin, although VOC content can effectively be down to 17% in resin,
Be also need further to be added when water-reducible certain proportion alcohol ethers solvent could enough water go to disperse, final VOC content
About 27%.
Summary of the invention
One of the objects of the present invention is to provide two fractions of acrylic acid modified alkyd resin that a kind of VOC content is lower than 10%
Granular media.
The second object of the present invention is to provide the preparation method of the dispersion.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
A kind of acrylic acid modified alkyd resin secondary breakup system, it is characterised in that the composition and quality hundred of the dispersion
Divide content are as follows: alkyd resin 20~40%, acrylic resin 8~20%, organic solvent 2~9%, deionized water surplus；Admittedly containing
Amount are as follows: 38~45%.
Above-mentioned organic solvent is made of solvent I and solvent II；The solvent I are as follows: dimethylbenzene, toluene, 200# solvent
The one or more of oil, 100# solvent naphtha；The solvent II are as follows: 200# solvent naphtha, 100# solvent naphtha, methyl iso-butyl ketone (MIBK),
Cyclohexanone, acetophenone, methyl acetate, ethyl acetate, n-butyl acetate, amyl acetate, ethylene glycol ethyl ether, ethylene glycol monobutyl ether,
Ethylene glycol ether acetate, 2-Butoxyethyl acetate, propylene glycol monomethyl ether, propylene-glycol ethyl ether, propylene glycol monobutyl ether, dipropylene glycol
At least one in methyl ether, dipropylene glycol ethyl ether, dipropylene, propylene glycol methyl ether acetate and propylene-glycol ethyl ether acetate
Kind.
A method of preparing above-mentioned acrylic acid modified alkyd resin secondary breakup body, it is characterised in that the tool of this method
Steps are as follows for body:
A. oleophylic section PoSynthesis: fatty acid, polyalcohol, polyacid, catalyst, solvent I are uniformly mixed, are to slowly warm up to
190~230 DEG C, when reaction is to acid value < 10mmg KOH/g, 120~170 DEG C are cooled to, 2~15 parts of solvents II and 0.2 are added
~0.8 part of initiator keeps the temperature 0.5~1h, obtains oleophylic section Po；The fatty acid, polyalcohol, polyacid, catalyst and molten
The composition and mass percentage of agent I are as follows:
B. hydrophilic section PwSynthesis: in step a acquired solution, continue 0.6~3 part of initiator of dropwise addition and 20~50 parts contain parent
The acrylc hybrids of aqueous monomer drip off in 0.5~2h, continue 1~2h of heat preservation；70~90 DEG C are cooled to, organic amine is added
Neutralizer stirs 10~30min；Make the degree of neutralization 80~120% of solution；
C. in step b resulting polymers solution, by required solid content calculation amount uniformly, be added dropwise deionized water at a slow speed, 1
It is added dropwise in~3h, is down to room temperature to get acrylic acid modified alkyd resin secondary breakup body is arrived.
Above-mentioned fatty acid are as follows: linolenic acid, behenic acid, tall oil acid, vegetable seed oleic acid, dehydrated castor oleic acid, castor oil
The one or more of acid, cocinic acid.
Above-mentioned polyalcohol are as follows: ethylene glycol, 1,2-PD, 1,3-PD, neopentyl glycol, glycerine, trihydroxy methyl
The one or more of propane, trimethylolethane, pentaerythrite.
Above-mentioned polyacid are as follows: phthalic anhydride, maleic anhydride, terephthalic acid (TPA), M-phthalic acid, oneself two
The one or more of acid, decanedioic acid, trimellitic anhydride.
Above-mentioned catalyst are as follows: dibutyl tin dilaurate, di-nbutyltin oxide, Mono-n-butyltin, butyl isopropyl
Alcohol titanium, titanium tetraethoxide, the one or more of four normal propyl alcohol titaniums, four n-butyl titaniums.
The composition and mass percentage of acrylc hybrids described in above-mentioned steps b containing hydrophilic monomer are as follows:
Above-mentioned alkyl-acrylates or alicyclic esters monomer are as follows: the C of acrylic or methacrylic acid1~C18Alkane
Base ester, cyclohexyl acrylate, acrylic acid -4- t-butyl cyclohexyl methacrylate, isobornyl acrylate, acrylic acid tetrahydrofuran ester, methyl
Cyclohexyl acrylate, methacrylic acid -4- t-butyl cyclohexyl methacrylate, isobornyl methacrylate or methacrylic acid tetrahydrofuran
Ester.
Above-mentioned hydroxy acryl acid esters monomer are as follows: hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl,
Hydroxyethyl methacrylate, hydroxy propyl methacrylate or methacrylate.
The above-mentioned acrylic monomer containing hydrophilic radical are as follows: at least one of acrylic acid, methacrylic acid；
Above-mentioned vinyl monomer are as follows: styrene, vinyltoluene, vinyl naphthalene, acrylonitrile or methacrylonitrile.
Organic amine described in above-mentioned steps b are as follows: N, N- dimethylethanolamine, triethylamine, ammonium hydroxide, N-ethylmorpholine, AMP95
(2-amino-2-methyl-1-propanol), triethanolamine, at least one of diethanol amine.
Initiator described in upper step b are as follows: azodiisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, peroxidating
Lauroyl, the peroxidating trimethylacetic acid tert-butyl ester, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate, peroxidating two
Lauroyl, di t-amyl peroxide, di-t-butyl peroxide, peroxidized t-butyl perbenzoate, tert-butyl peroxy acetate, peroxidating
At least one of diisopropylbenzene (DIPB), isopropyl benzene hydroperoxide, cumyl t-butyl peroxide.
In the present invention, PoWith PwUsed monomer weight ratio is 80:20~50:50.Hydrophilic section PwIt is fewer, resin swelling
Degree reduces, and number of particles is reduced after phase reversal, and partial size increases, but hydrophilic section PwVery few, the package of particle is less able, leads
The dispersion stabilization of particle is caused to be deteriorated, therefore PoWith PwThe used preferred 75:25~60:40 of monomer weight ratio.
In the present invention, the dosage of the deionized water is 110~150 parts by weight, makes the solid content of dispersion
40~45%.
Present invention has an advantage that in a small amount of combination solvent, using the secondary breakup of acrylic acid modified alkyd resin
Technology no longer needs to that cosolvent additionally is added, and directly plus water dispersion obtains VOC content lower than 10% (solid content 45%) and disperses
Property it is preferable, solid content is larger, viscosity, moderate in grain size, and preferable with paint film richness prepared by this dispersion, and gloss is higher,
Cost is relatively low.Average grain diameter is small, and average grain diameter is 60~160nm, and particle diameter distribution is narrow, and polydispersity coefficient PDI is 0.05~0.15,
With good homogeneity, be conducive to the comprehensive performance for improving film.Viscosity is smaller, be conducive to during coating with solidification
The mixing subsequent construction of agent.Dispersion has preferable mobility, and stability is high, stands storage 60 days or more nothings under room temperature
The variations such as any layering, sedimentation, precipitation, particle size and distribution, viscosity are without significant change.
Specific embodiment
Below with reference to embodiment, the invention will be further described, but protection scope of the present invention is not limited only to this.
Embodiment one: a kind of preparation method of low VOC acrylic acid modified alkyd resin secondary breakup body is specific as follows:
Weigh soybean oleic acid 30.4g, hexylene glycol 20.8g, ricinoleic acid 18.5g, trimethylolpropane 10.5g, phthalic anhydride
52.2g, pentaerythrite 17.9g, dimethylbenzene 8.6g and Dibutyltin oxide 0.1g are added to configured with blender, condenser and water
In 1 liter of reactor of separator, N is led in reaction flask2Material in reaction flask is heated to 170 DEG C from room temperature, keeps the temperature 20- by protection
30min is continuously heating to 185 DEG C, keeps the temperature 40-50min, is warming up to 200 DEG C, esterification continues at such a temperature, disappears
Water removal, until when acid value is less than 5 milligrams of KOH/g.
145 DEG C are cooled to, by 100#Solvent naphtha 9.4g, ethylene glycol monomethyl ether 18g and di-t-butyl peroxide (DTBP) 0.8g
It is added in reaction vessel, keeps the temperature 30min；By methyl methacrylate (MMA) 20.6g, n-butyl acrylate (BA) 8.1g, methyl
The mixing of hydroxy-ethyl acrylate (HEMA) 11.5g, styrene (St) 5g, acrylic acid (AA) 4.8g and di-t-butyl peroxide 1.5g
Object at the uniform velocity instills in reaction vessel, and control drips off in 1.5h, continues to keep the temperature 1h；90 DEG C are cooled to, N, N- dimethyl second is added
Hydramine (DMEA) 5.94g stirs 15min；Deionized water 220g is slowly at the uniform velocity added to reaction vessel, control is dripped in 1.5h
It is complete；50 DEG C are cooled to hereinafter, a kind of low VOC acrylic acid modified alkyd resin secondary breakup body can be obtained.
The specific preparation method of embodiment two~seven is as shown in embodiment one.Design parameter and performance indicator are shown in Table 1.
Table 1: the relevant parameter and performance indicator of dispersion prepared by embodiment one~seven
Embodiment eight
Compared with Example 1, this example is intended to show the acrylic acid modified alkyd resin two of different types of polyacid monomer
Grade dispersion and preparation method thereof, specific as follows:
Weigh soybean oleic acid 30.4g, hexylene glycol 20.8g, ricinoleic acid 18.5g, trimethylolpropane 10.5g, cis-butenedioic anhydride
34.6g, pentaerythrite 17.9g, dimethylbenzene 8.6g and Dibutyltin oxide 0.1g are added to configured with blender, condenser and water
In 1 liter of reactor of separator, N is led in reaction flask2Material in reaction flask is heated to 170 DEG C from room temperature, keeps the temperature 20- by protection
30min is continuously heating to 185 DEG C, keeps the temperature 40-50min, is warming up to 200 DEG C, esterification continues at such a temperature, disappears
Water removal, until when acid value is less than 5 milligrams of KOH/g.
145 DEG C are cooled to, by 100#Solvent naphtha 9.4g, ethylene glycol monomethyl ether 18g and di-t-butyl peroxide 0.8g are added anti-
It answers in container, keeps the temperature 30min；By methyl methacrylate 20.6g, n-butyl acrylate 8.1g, hydroxyethyl methacrylate
11.5g, styrene 5g, acrylic acid 4.8g and di-t-butyl peroxide 1.5g mixture at the uniform velocity instill in reaction vessel, control
It is dripped off in 1.5h, continues to keep the temperature 1h；90 DEG C are cooled to, N, N- dimethylethanolamine 5.94g is added, stirs 15min；To go from
Reaction vessel is slowly at the uniform velocity added in sub- water 220g, and control drips off in 1.5h；50 DEG C are cooled to hereinafter, can be obtained a kind of low
VOC acrylic acid modified alkyd resin secondary breakup body.
Embodiment nine
Compared with Example 1, this example is intended to show the acrylic acid modified alkyd resin two of different types of monomeric polyol
Grade dispersion and preparation method thereof, specific as follows:
Weigh soybean oleic acid 30.4g, hexylene glycol 20.8g, ricinoleic acid 18.5g, glycerine 7.2g, phthalic anhydride 52.2g,
27.4g neopentyl glycol, dimethylbenzene 8.6g and Dibutyltin oxide 0.1g are added to configured with blender, condenser and separator
1 liter of reactor in, in reaction flask lead to N2Material in reaction flask is heated to 170 DEG C from room temperature, keeps the temperature 20-30min by protection,
185 DEG C are continuously heating to, 40-50min is kept the temperature, is warming up to 200 DEG C, esterification continues at such a temperature, eliminates water, directly
Until when acid value is less than 5 milligrams of KOH/g.
145 DEG C are cooled to, by 100#Solvent naphtha 9.4g, ethylene glycol monomethyl ether 18g and di-t-butyl peroxide 0.8g are added anti-
It answers in container, keeps the temperature 30min；By methyl methacrylate 20.6g, n-butyl acrylate 8.1g, hydroxyethyl methacrylate
11.5g, styrene 5g, acrylic acid 4.8g and di-t-butyl peroxide 1.5g mixture at the uniform velocity instill in reaction vessel, control
It is dripped off in 1.5h, continues to keep the temperature 1h；90 DEG C are cooled to, N, N- dimethylethanolamine 5.94g is added, stirs 15min；To go from
Reaction vessel is slowly at the uniform velocity added in sub- water 220g, and control drips off in 1.5h；50 DEG C are cooled to hereinafter, can be obtained a kind of low
VOC acrylic acid modified alkyd resin secondary breakup body.
Embodiment ten
Compared with Example 1, this example is intended to show two fraction of acrylic acid modified alkyd resin of different types of fatty acid
Granular media and preparation method thereof, specific as follows:
Weigh linolenic acid 27.6g, hexylene glycol 20.8g, ricinoleic acid 18.5g, trimethylolpropane 10.5g, phthalic anhydride
52.2g, pentaerythrite 17.9g, dimethylbenzene 8.6g and Dibutyltin oxide 0.1g are added to configured with blender, condenser and water
In 1 liter of reactor of separator, N is led in reaction flask2Material in reaction flask is heated to 170 DEG C from room temperature, keeps the temperature 20- by protection
30min is continuously heating to 185 DEG C, keeps the temperature 40-50min, is warming up to 200 DEG C, esterification continues at such a temperature, disappears
Water removal, until when acid value is less than 5 milligrams of KOH/g.
145 DEG C are cooled to, by 100#Solvent naphtha 9.4g, ethylene glycol monomethyl ether 18g and di-t-butyl peroxide 0.8g are added anti-
It answers in container, keeps the temperature 30min；By methyl methacrylate 20.6g, n-butyl acrylate 8.1g, hydroxyethyl methacrylate
11.5g, styrene 5g, acrylic acid 4.8g and di-t-butyl peroxide 1.5g mixture at the uniform velocity instill in reaction vessel, control
It is dripped off in 1.5h, continues to keep the temperature 1h；90 DEG C are cooled to, N, N- dimethylethanolamine 5.94g is added, stirs 15min；To go from
Reaction vessel is slowly at the uniform velocity added in sub- water 220g, and control drips off in 1.5h；50 DEG C are cooled to hereinafter, can be obtained a kind of low
VOC acrylic acid modified alkyd resin secondary breakup body.
Embodiment 11
Compared with Example 1, this example is intended to show the acrylic acid modified of different types of hydroxy acryl acid esters monomer
Alkyd resin secondary breakup body and preparation method thereof, specific as follows:
Weigh soybean oleic acid 30.4g, hexylene glycol 20.8g, ricinoleic acid 18.5g, trimethylolpropane 10.5g, cis-butenedioic anhydride
34.6g, pentaerythrite 17.9g, dimethylbenzene 8.6g and Dibutyltin oxide 0.1g are added to configured with blender, condenser and water
In 1 liter of reactor of separator, N is led in reaction flask2Material in reaction flask is heated to 170 DEG C from room temperature, keeps the temperature 20- by protection
30min is continuously heating to 185 DEG C, keeps the temperature 40-50min, is warming up to 200 DEG C, esterification continues at such a temperature, disappears
Water removal, until when acid value is less than 5 milligrams of KOH/g.
145 DEG C are cooled to, by 100#Solvent naphtha 9.4g, ethylene glycol monomethyl ether 18g and di-t-butyl peroxide 0.8g are added anti-
It answers in container, keeps the temperature 30min；By methyl methacrylate 20.6g, n-butyl acrylate 8.1g, hydroxy-ethyl acrylate 10.2g,
The mixture of styrene 5g, acrylic acid 4.8g and di-t-butyl peroxide 1.5g at the uniform velocity instill in reaction vessel, control in 1.5h
It inside drips off, continues to keep the temperature 1h；90 2 DEG C are cooled to, N, N- dimethylethanolamine 5.94g is added, stirs 15min；By deionized water
Reaction vessel is slowly at the uniform velocity added in 220g, and control drips off in 1.5h；50 DEG C are cooled to hereinafter, a kind of low VOC third can be obtained
Olefin(e) acid modified alkyd resin secondary breakup body.
Embodiment 12
Compared with Example 1, this example is intended to show the acrylic acid modified alkyd resin of different types of vinyl monomer
Secondary breakup body and preparation method thereof, specific as follows:
Weigh soybean oleic acid 30.4g, hexylene glycol 20.8g, ricinoleic acid 18.5g, trimethylolpropane 10.5g, phthalic anhydride
52.2g, pentaerythrite 17.9g, dimethylbenzene 8.6g and Dibutyltin oxide 0.1g are added to configured with blender, condenser and water
In 1 liter of reactor of separator, N is led in reaction flask2Material in reaction flask is heated to 170 DEG C from room temperature, keeps the temperature 20- by protection
30min is continuously heating to 185 DEG C, keeps the temperature 40-50min, is warming up to 200 DEG C, esterification continues at such a temperature, disappears
Water removal, until when acid value is less than 5 milligrams of KOH/g.
145 DEG C are cooled to, by 100#Solvent naphtha 9.4g, ethylene glycol monomethyl ether 18g and di-t-butyl peroxide 0.8g are added anti-
It answers in container, keeps the temperature 30min；By methyl methacrylate 20.6g, n-butyl acrylate 8.1g, hydroxyethyl methacrylate
11.5g, acrylonitrile 5g, acrylic acid 4.8g and di-t-butyl peroxide 1.5g mixture at the uniform velocity instill in reaction vessel, control
It is dripped off in 1.5h, continues to keep the temperature 1h；90 DEG C are cooled to, N, N- dimethylethanolamine 5.94g is added, stirs 15min；To go from
Reaction vessel is slowly at the uniform velocity added in sub- water 220g, and control drips off in 1.5h；50 DEG C are cooled to hereinafter, can be obtained a kind of low
VOC acrylic acid modified alkyd resin secondary breakup body.
Embodiment 13
Compared with Example 1, this example is intended to show the acrylic modified alkyd tree of different acrylic ester monomer combinations
Rouge secondary breakup body and preparation method thereof, specific as follows:
Weigh soybean oleic acid 30.4g, hexylene glycol 20.8g, ricinoleic acid 18.5g, trimethylolpropane 10.5g, phthalic anhydride
52.2g, pentaerythrite 17.9g, dimethylbenzene 8.6g and Dibutyltin oxide 0.1g are added to configured with blender, condenser and water
In 1 liter of reactor of separator, N is led in reaction flask2Material in reaction flask is heated to 170 DEG C from room temperature, keeps the temperature 20- by protection
30min is continuously heating to 185 DEG C, keeps the temperature 40-50min, is warming up to 200 DEG C, esterification continues at such a temperature, disappears
Water removal, until when acid value is less than 5 milligrams of KOH/g.
145 DEG C are cooled to, by 100#Solvent naphtha 9.4g, ethylene glycol monomethyl ether 18g and di-t-butyl peroxide 0.8g are added anti-
It answers in container, keeps the temperature 30min；By isobornyl methacrylate 20.5g, n-butyl acrylate 8.2g, hydroxyethyl methacrylate second
Ester 11.48g, styrene 5g, acrylic acid 4.8g and di-t-butyl peroxide 1.5g mixture at the uniform velocity instill in reaction vessel, control
System drips off in 1.5h, continues to keep the temperature 1h；90 DEG C are cooled to, N, N- dimethylethanolamine 5.94g is added, stirs 15min；It will go
Reaction vessel is slowly at the uniform velocity added in ionized water 220g, and control drips off in 1.5h；50 DEG C are cooled to hereinafter, can be obtained a kind of low
VOC acrylic acid modified alkyd resin secondary breakup body.
Embodiment 14
Compared with Example 1, this example is intended to show the acrylic acid modified alkyd resin two of different types of acrylic monomers
Grade dispersion and preparation method thereof, specific as follows:
Weigh soybean oleic acid 30.4g, hexylene glycol 20.8g, ricinoleic acid 18.5g, trimethylolpropane 10.5g, cis-butenedioic anhydride
34.6g, pentaerythrite 17.9g, dimethylbenzene 8.6g and Dibutyltin oxide 0.1g are added to configured with blender, condenser and water
In 1 liter of reactor of separator, N is led in reaction flask2Material in reaction flask is heated to 170 DEG C from room temperature, keeps the temperature 20- by protection
30min is continuously heating to 185 DEG C, keeps the temperature 40-50min, is warming up to 200 DEG C, esterification continues at such a temperature, disappears
Water removal, until when acid value is less than 5 milligrams of KOH/g.
145 DEG C are cooled to, by 100#Solvent naphtha 9.4g, ethylene glycol monomethyl ether 18g and di-t-butyl peroxide 0.8g are added anti-
It answers in container, keeps the temperature 30min；By methyl methacrylate 17.8g, n-butyl acrylate 10g, hydroxyethyl methacrylate
11.5g, styrene 5g, first class acrylic acid 5.7g and di-t-butyl peroxide 1.5g mixture at the uniform velocity instill in reaction vessel,
Control drips off in 1.5h, continues to keep the temperature 1h；90 DEG C are cooled to, N, N- dimethylethanolamine 5.94g is added, stirs 15min；It will
Reaction vessel is slowly at the uniform velocity added in deionized water 220g, and control drips off in 1.5h；50 DEG C are cooled to hereinafter, one kind can be obtained
Low VOC acrylic acid modified alkyd resin secondary breakup body.
Table 2: the performance indicator of dispersion prepared by embodiment eight~14
The above description is only a preferred embodiment of the present invention, is not intended to restrict the invention, it is clear that those skilled in the art
Various changes and modifications can be made to the invention by member, but must not be detached from the spirit and scope of the present invention.
The raw material provided in all embodiments is all identical, and the range of choice of each raw material provided in claims
It is more.More embodiments and performance parameter for using different material please be provided.
Claims (14)
1. a kind of acrylic acid modified alkyd resin secondary breakup system, it is characterised in that the composition and quality percentage of the dispersion
Content are as follows: 20~40 % of alkyd resin, 8~20 % of acrylic resin, 2~9 % of organic solvent, deionized water surplus；Solid content
Are as follows: 38~45%.
2. acrylic acid modified alkyd resin secondary breakup body according to claim 1, it is characterised in that described is organic molten
Agent is made of solvent I and solvent II；The solvent I are as follows: dimethylbenzene, toluene, 200# solvent naphtha, 100# solvent naphtha one kind or
It is several；The solvent II are as follows: 200# solvent naphtha, 100# solvent naphtha, methyl iso-butyl ketone (MIBK), cyclohexanone, acetophenone, tumer
Ester, ethyl acetate, n-butyl acetate, amyl acetate, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, ethylene glycol ether acetate, second two
Alcohol monobutyl ether acetate, propylene glycol monomethyl ether, propylene-glycol ethyl ether, propylene glycol monobutyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, two
At least one of propandiol butyl ether, propylene glycol methyl ether acetate and propylene-glycol ethyl ether acetate.
3. a kind of method for preparing acrylic acid modified alkyd resin secondary breakup body according to claim 1 or 2, feature
Being this method, specific step is as follows:
A. oleophylic section PoSynthesis: fatty acid, polyalcohol, polyacid, catalyst, solvent I are uniformly mixed, it is to slowly warm up to 190~
230 DEG C, when reaction is to acid value < 10mmg KOH/g, be cooled to 120~170 DEG C, be added 2~15 parts of solvents II and 0.2~
0.8 part of initiator keeps the temperature 0.5~1 h, obtains oleophylic section Po；The fatty acid, polyalcohol, polyacid, catalysts and solvents
I composition and mass percentage are as follows:
Fatty acid: 15~35 parts；
Polyalcohol: 20~35 parts；
Polyacid: 10~35 parts；
I: 2~8 parts of solvent；
Catalyst: 0.05~0.16 part；
B. hydrophilic section PwSynthesis: in step a acquired solution, continue 0.6~3 part of initiator of dropwise addition and 20~50 parts contain hydrophilic list
The acrylc hybrids of body drip off in 0.5~2 h, continue 1~2 h of heat preservation；70~90 DEG C are cooled to, is added in organic amine
10~30 min are stirred with agent；Make 80~120 % of degree of neutralization of solution；
C. in step b resulting polymers solution, by required solid content calculation amount uniformly, be added dropwise deionized water at a slow speed, 1~3
It is added dropwise in h, is down to room temperature to get acrylic acid modified alkyd resin secondary breakup body is arrived.
4. according to the method described in claim 3, it is characterized in that the fatty acid are as follows: linolenic acid, behenic acid, tall oil
The one or more of acid, vegetable seed oleic acid, dehydrated castor oleic acid, ricinoleic acid, cocinic acid.
5. according to the method described in claim 3, it is characterized in that the polyalcohol are as follows: ethylene glycol, 1,2-PD, 1,3-
The one or more of propylene glycol, neopentyl glycol, glycerine, trimethylolpropane, trimethylolethane, pentaerythrite.
6. according to the method described in claim 3, it is characterized in that the polyacid are as follows: phthalic anhydride, maleic two
The one or more of acid anhydrides, terephthalic acid (TPA), M-phthalic acid, adipic acid, decanedioic acid, trimellitic anhydride.
7. according to the method described in claim 3, it is characterized in that the catalyst are as follows: dibutyl tin dilaurate, two are just
Butyl tin oxide, Mono-n-butyltin, butyl isopropyl titanate, titanium tetraethoxide, one kind or several of four normal propyl alcohol titaniums, four n-butyl titaniums
Kind.
8. according to the method described in claim 3, it is characterized in that containing the acrylc hybrids of hydrophilic monomer described in step b
Composition and mass percentage are as follows:
Acrylic acid alkyl or alicyclic esters monomer: 10~35 parts；
Hydroxy acryl acid esters monomer: 2~18 parts；
Acrylic monomer containing hydrophilic radical: 2~5 parts；
Vinyl monomer: 0~20 part.
9. according to the method described in claim 8, it is characterized in that the alkyl-acrylates or alicyclic esters monomer
Are as follows: the C of acrylic or methacrylic acid1~C18Arrcostab, cyclohexyl acrylate, acrylic acid -4- t-butyl cyclohexyl methacrylate, propylene
Sour isobornyl thiocyanoacetate, acrylic acid tetrahydrofuran ester, cyclohexyl methacrylate, methacrylic acid -4- t-butyl cyclohexyl methacrylate, methyl-prop
Olefin(e) acid isobornyl thiocyanoacetate or tetrahydrofurfuryl methacrylate.
10. according to the method described in claim 8, it is characterized in that the hydroxy acryl acid esters monomer are as follows: acrylic acid
Hydroxyl ethyl ester, hydroxypropyl acrylate, hy-droxybutyl, hydroxyethyl methacrylate, hydroxy propyl methacrylate or metering system
Sour hydroxy butyl ester.
11. according to the method described in claim 8, it is characterized in that the acrylic monomer containing hydrophilic radical are as follows: third
At least one of olefin(e) acid, methacrylic acid.
12. according to the method described in claim 8, it is characterized in that the vinyl monomer are as follows: styrene, vinyl first
Benzene, vinyl naphthalene, acrylonitrile or methacrylonitrile.
13. according to the method described in claim 3, it is characterized in that organic amine described in step b are as follows: N, N- dimethyl ethanol
Amine, triethylamine, ammonium hydroxide, N-ethylmorpholine, AMP95(2- amino-2-methyl -1- propyl alcohol), triethanolamine, in diethanol amine extremely
Few one kind.
14. according to the method described in claim 3, it is characterized in that initiator described in step b are as follows: azodiisobutyronitrile, idol
The different heptonitrile of nitrogen two, dibenzoyl peroxide, dilauroyl peroxide, the peroxidating trimethylacetic acid tert-butyl ester, dicetyl peroxydicarbonate diisopropyl
Ester, di-cyclohexylperoxy di-carbonate, dilauroyl peroxide, di t-amyl peroxide, di-t-butyl peroxide, benzoyl peroxide
T-butyl formate, tert-butyl peroxy acetate, cumyl peroxide, isopropyl benzene hydroperoxide, in cumyl t-butyl peroxide
At least one.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111777749A (en) * | 2020-07-06 | 2020-10-16 | 华伦纳路新材料有限公司 | Acrylic acid modified waterborne baking varnish alkyd resin and preparation method thereof |
| CN114456305A (en) * | 2022-02-15 | 2022-05-10 | 江苏富琪森新材料有限公司 | Highlight type acrylic latex and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497221A (en) * | 2014-12-04 | 2015-04-08 | 北京金汇利应用化工制品有限公司 | Waterborne acrylic modified alkyd resin and preparation method of aqueous dispersion of alkyd resin |
| CN107163192A (en) * | 2017-06-28 | 2017-09-15 | 上海大学 | Cation-type water-thinned Hydroxylated acrylic resin secondary breakup body and preparation method thereof |
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2018
- 2018-09-10 CN CN201811048124.1A patent/CN109486379A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497221A (en) * | 2014-12-04 | 2015-04-08 | 北京金汇利应用化工制品有限公司 | Waterborne acrylic modified alkyd resin and preparation method of aqueous dispersion of alkyd resin |
| CN107163192A (en) * | 2017-06-28 | 2017-09-15 | 上海大学 | Cation-type water-thinned Hydroxylated acrylic resin secondary breakup body and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111777749A (en) * | 2020-07-06 | 2020-10-16 | 华伦纳路新材料有限公司 | Acrylic acid modified waterborne baking varnish alkyd resin and preparation method thereof |
| CN114456305A (en) * | 2022-02-15 | 2022-05-10 | 江苏富琪森新材料有限公司 | Highlight type acrylic latex and preparation method and application thereof |
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