CN109096475A - The preparation method of gutter oil alkyd performed polymer and its preparation method of modified aqueous acrylic acid resin dispersion - Google Patents
The preparation method of gutter oil alkyd performed polymer and its preparation method of modified aqueous acrylic acid resin dispersion Download PDFInfo
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
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Abstract
The invention discloses a kind of preparation method of gutter oil alkyd performed polymer and its preparation methods of modified aqueous acrylic acid resin dispersion, using gutter oil as primary raw material, instead of vegetable oil and vegetable fatty acids, and combine methyl propanediol, Glycerin, a kind of low cost is made in M-phthalic acid etc., high acid value, the alkyd resin of high hydroxyl value is as performed polymer bottom material, acrylic resin is modified with it, and simultaneously high speed shear phase inversion is oil in water dispersion to neutralized rear plus deionized water, it obtains a kind of cheap, lower VOC and lower smell (relative to classic water-soluble acrylic resin), simple process, the water soluble acrylic acid dispersion of excellent combination property.Resulting water-based acrylic resin dispersion is suitable for the production of aqueous amino baking varnish.
Description
Technical field
The invention belongs to acrylic resin paint technical field more particularly to a kind of preparation sides of gutter oil alkyd performed polymer
The preparation method of method and its modified aqueous acrylic acid resin dispersion.
Background technique
Acrylic resin paint is the synthetic resin coating using acrylic resin as main film forming substance, because it is with excellent
The performances such as different adhesive force, water resistance, guarantor's light colour retention, are widely used in the fields such as automobile, hardware, engineering machinery, bridge.
Fast development with modern industry and the dynamics to environmental improvement increasingly increase, people to coating used also gradually
More stringent requirements are proposed.Cost performance is high, and VOC content is low, and all kinds of coating of economical environment-protective are in the market by favor.Traditional
Acrylic resin paint will adapt to the demand in market, certainly will reduce cost of material under the premise of not influencing product quality, mention
High performance-price ratio；Smell and VOC content are reduced by channels such as Water-borne modifications, reduces the pollution to environment.Acrylic resin is improved to apply
The quality and performance of material, are critically depend on the performance of its film forming matter.
Presently disclosed Chinese patent CN104231245A, using hogwash fat, rosin, polyalcohol, polyacid, through alcoholysis,
One kind is made from dry alkyd resin in esterification, and the antirust paint antiseptic property as made from the alkyd resin is excellent, finishing coat light obtained
Damp high, clarity is good.But using C9 aromatic, turpentine oil, coking xylene as diluted solvent, VOC content is high, smell weight, environment
It is seriously polluted.
Presently disclosed Chinese patent CN103709384A, using purified gutter oil, polyalcohol, polyacid, through alcohol
One kind is made from dry alkyd resin in solution, esterification, which can be used for producing dual-component polyurethane woodwork coating, cost of material
It is low, but using dimethylbenzene as reflux solvent, using 200# solvent naphtha as diluted solvent, VOC content is high, and environmental pollution is serious.
The method that tradition prepares water-based acrylic resin is using acrylic monomers mixture, vinyl monomer with carboxyl
For raw material, the polymer with carboxyl is prepared by polymerization, is then neutralized with alkali appropriate (such as amine), to reach water dispersion or water
Dissolubility.Water-based acrylic resin color made from this method is low, and paint film is plentiful, excellent water resistance, but by acrylic monomers valence
The influence that lattice rise steadily, resin raw material obtained is high, causes finished product paint cost performance low, market acceptance is very low.
Presently disclosed Chinese patent CN103725145B, using vegetable fatty acids, polyalcohol, polyacid after being esterified
Alkyd resin is made, then carries out copolyreaction with the mixture of acrylic acid and it's ester monomer, obtains a kind of water alcohol acid after neutralized
Resin-propylene acid resin hybrid.The resin storage stability, hydrolytic resistance are good, aqueous amino baking varnish hardness obtained is high,
Adhesive force is good, corrosion resistance is strong, but production cost is still higher.
Summary of the invention
The technical problems to be solved by the present invention are: using gutter oil as primary raw material, instead of vegetable oil and vegetable oil
The alkyd resin of a kind of low cost, high acid value, high hydroxyl value is made as performed polymer bottom material, with it to acrylic resin in fatty acid
It is modified, and neutralized rear progress Water-borne modification, obtains cheap, the lower VOC of one kind and lower smell (relative to tradition
Water soluble acrylic resin), simple process, excellent combination property water soluble acrylic acid dispersion.Resulting water soluble acrylic acid tree
Rouge dispersion is suitable for the production of aqueous amino baking varnish.The technical problems to be solved by the invention are given by the following technical programs
To realize:
A kind of preparation method of gutter oil alkyd performed polymer mixed liquor, is made of the component of following parts by weight:
Gutter oil refers to raw existing all kinds of poor oils, such as the frying oil of the edible oil, Reusability recycled.Long-term food
With cancer may be caused, to the very harmful of human body.With the improvement of people's living standards, China's catering industry generates every year
The amount of gutter oil obviously increase.How gutter oil is reasonably utilized, so that it is turned waste into wealth, just receive the pass of various circles of society
Note.
The main component of gutter oil is fatty acid triglyceride, can replace soya-bean oil, tung oil, linseed oil in paint field
Equal vegetable oil carry out esterification dehydration with polyacid, after esterification, vacuumize de- after carrying out alcoholysis using lithium hydroxide
Dimethylbenzene during dereaction is to be made a kind of alkyd resin.In the present invention, using the alkyd resin as a kind of performed polymer,
It is spare.
The preparation method operates as follows:
Firstly, by after above-mentioned gutter oil, methyl propanediol, Glycerin, lithium hydroxide investment reaction kettle, to reaction kettle
In be passed through inert gas, and be warming up to 75-85 DEG C, preferably 80 DEG C, start to stir and be continuously heating to 220-235 DEG C, it is warm herein
2 hours are at least kept the temperature under degree to end-point of alcoholysis (end-point of alcoholysis: 1 part of alcoholysate be dissolved in 5 part of 95% ethyl alcohol transparent limpid).
Then, cool down, when temperature is down to 200 DEG C or less, stop stirring, and stop being passed through inert gas.Metering investment
Mono-n-butyltin, M-phthalic acid, cis-butenedioic anhydride, antioxidant and dimethylbenzene open stirring, and are passed through inert gas.It is warming up to diformazan
Benzene reflux (enters reaction kettle without air after flowing back normally in the refuxing esterification water smoking into the refuxing esterification water smoking
Afterwards), stop being passed through inert gas.During refuxing esterification is dehydrated, temperature of charge must not exceed 250 DEG C.Heat preservation is opened after 2-2.5 hours
Begin sampling its acid value of survey and viscosity, and soaking time preferably 2 hours, acid value was advisable with 10-15mgKOH/g, and viscosity is with 300-500s
(at room temperature with apply -4 glasss measure viscosity number) is advisable.After the two qualification, 180 DEG C are cooled to, is decompressed to vacuum with decompressor
About 0.02-0.08MPa is spent, goes out dimethylbenzene with pumping, find time about 25-30min, preferably 30min, until extracting out in condenser
The transparent drop-wise of object removes decompressor, be cooled to 140 DEG C hereinafter, be made a kind of high-solid lower-viscosity, high acid value, high hydroxyl value ground
Ditch oleyl alcohol acid performed polymer mixed liquor.
Since the composition of gutter oil is more complicated, the iodine number between batch is very unstable.To realize alkyd performed polymer to third
The modification of olefin(e) acid resin, it is necessary to improve the degree of unsaturation of gutter oil, be carried out with providing enough double bonds and acrylic monomer
Copolymerization.The present invention is spelled into suitable cis-butenedioic anhydride as polyacid, is built using its pair to improve the double key number of alkyd performed polymer
Amount.
The present invention uses trimethylolpropane as polyalcohol, using M-phthalic acid as polyacid, can significantly improve
The hydrolytic resistance of the acrylic resin modified dispersion of gutter oil alkyd performed polymer improves storage characteristics.
The application of methyl propanediol can reduce to a certain degree the viscous of gutter oil alkyd performed polymer mixed liquor obtained
Degree, and then the acrylic resin modified dispersion of gutter oil alkyd performed polymer is being prepared with gutter oil alkyd performed polymer mixed liquor obtained
The use of butyl glycol ether solvent can be reduced when body.
The acrylic resin modified dispersion of gutter oil alkyd performed polymer is prepared with above-mentioned gutter oil alkyd performed polymer mixed liquor
Method it is as follows:
It is made of the component of following parts by weight:
Specifically, the preparation method operates as follows:
(1) to premix kettle in measure intensively ditch oleyl alcohol acid performed polymer mixed liquor, acrylic acid, butyl acrylate, styrene,
Methyl methacrylate and 0.91-1.7 parts of BPO, are stirred until homogeneous mixing, and premix is made；Preferably BPO parts by weight dosage is
0.91 part.
(2) semicontinuous dropwise addition technique is used, reflux condensing tube, agitating device, temperature control system and dropping funel are being had
Reactor in, be added butyl glycol ether solvent.After being warming up to 120-130 DEG C, by premix quality made from step (1)
10%-20% is added in reactor, is stirred until homogeneous dispersion, then keeps the temperature 0.5 h-1h, the preferred 0.5h of soaking time.Again uniformly
Remaining premix is added dropwise, is added dropwise in 3-4h, adds 10%~20% initiator (relative to having added after keeping the temperature 1-1.5h
Initiator), preferably 10%, while polymerization temperature is properly increased 4-5 DEG C, continue to keep the temperature 2-3h, then sampling analysis, until monomer
Stop reaction when conversion ratio reaches 98% or more and be cooled to 60-70 DEG C, in 15-20 minutes or so dropwise addition N, N dimethyl ethanol amine
Neutralize 80% carboxylic group；Gutter oil alkyd performed polymer modified aqueous acrylic acid resin oil-based system is made.
(3) continue heat preservation at 70 DEG C, to gutter oil made from step (2) under the high-speed stirred revolving speed of 700-1000rpm
First part's deionized water is added dropwise in alkyd performed polymer modified aqueous acrylic acid resin oil-based system, makes gutter oil alkyd pre-polymerization structural reform
Property water-based acrylic resin oil-based system be transformed into oil-in-water system, time for adding is controlled at 60-80 minutes or so, is set at this time
Rouge solid content is 70% or so；Then second part deionized water is added dropwise, time for adding was controlled at 15-30 minutes, at this time resin
Gutter oil alkyd performed polymer modified aqueous acrylic acid the first dispersion of resin is made 50% or so in solid content.
(4) gutter oil alkyd performed polymer modified water-soluble third made from step (3) finally is added in Part III deionized water
In the first dispersion of olefin(e) acid resin, adding manner is added rapidly in dispersion in preferably 15 minutes, and dispersion is allowed to cool down, and is used
200 mesh sock filtrations packaging, is finally made gutter oil alkyd performed polymer modified aqueous acrylic acid the second dispersion of resin, i.e. trench
Oleyl alcohol acid performed polymer modified aqueous acrylic acid resin dispersion, final dispersion hydroxyl are 1.5% or so.
The dosage of first part's deionized water and adding manner and mixing speed in step (3), it is possible to prevente effectively from occurring
Scoriform.And make to form uniform, stable dispersion oil-in-water system.
Because in alkyd performed polymer, containing largely reserved hydroxyl, the application of acrylate monomers can be avoided or reduced, from
And reduce the cost of raw material of resin dispersion.
Traditional water-borne dispersions are in synthesis, because viscosity is higher, need to have reacted in bottom material using a large amount of solvent
Need to take out partial solvent after, complex process can reduce solvent usage using the alkyd performed polymer of above-mentioned high-solid lower-viscosity, save
Remove solvent removal step.Not only simplify technique, greatly reduce VOC content (in finishing coat, this case preparation gutter oil alkyd performed polymer
The dosage of modified aqueous acrylic acid resin dispersion is 50-70%, under the dosage, VOC amount≤100g/L) and, the water being configured to
The smell of property acrylic-amino hot curing varnish is obviously improved.
The invention has the following advantages:
1. the cost of material of alkyd resin performed polymer has not only been greatly reduced using gutter oil as raw material in the present invention, and
And waste utilization is truly realized, reduce pollution of dining table, also reduces the consumption of the vegetable oil resources such as soya-bean oil.
2. the composition due to gutter oil is more complicated, the iodine number between batch is very unstable.To realize alkyd performed polymer pair
The modification of acrylic resin, it is necessary to improve the degree of unsaturation of gutter oil, with provide enough double bonds and acrylic monomer into
Row copolymerization.The present invention is spelled into suitable cis-butenedioic anhydride as polyacid, is built using its pair to improve the double bond of alkyd performed polymer
Quantity.
3. use trimethylolpropane as polyalcohol in the step, it, can be significant using M-phthalic acid as polyacid
Improve the hydrolytic resistance of resin.
4. because reserving hydroxyl containing a large amount of in alkyd performed polymer, it is possible to reduce the dosage of acrylate monomers, to drop
The cost of raw material of low resin dispersion.
5. traditional water-borne dispersions are in synthesis, because viscosity is higher, need in bottom material using a large amount of solvent, reaction
Needing to take out partial solvent after the completion, complex process can reduce solvent usage using the alkyd performed polymer of above-mentioned high-solid lower-viscosity,
Save solvent removal step.Technique is not only simplified, VOC content is greatly reduced, the water soluble acrylic acid amino baking varnish being configured to
Smell is obviously improved.
6. being modified with trench oleyl alcohol acid performed polymer to conventional acrylic resin, and Water-borne modification is carried out, resulting water
Property acrylic acid dispersion taken into account that alkyd resin is cheap, easy for construction and acrylic resin protects the good advantage of light colour retention,
And truly greatly reduce the VOC content and smell of coating.The aqueous amino baking varnish made from the dispersion, it is former
Expect at low cost, the full light of paint film appearance has preferable hardness and flexibility.Water thinning can directly be added when construction, be a
The very high economical environment-protective coating of cost performance.
Specific embodiment
The present invention is described in further detail below with reference to embodiment:
Embodiment 1:
The composition of raw materials of gutter oil alkyd performed polymer mixed liquor is prepared as shown in table 1-1:
Table 1-1:
Preparing gutter oil alkyd performed polymer mixed liquor using above-mentioned raw materials formula, specific step is as follows:
Firstly, put into reaction kettle gutter oil, methyl propanediol, Glycerin, lithium hydroxide, then to reaction kettle
In be passed through inert gas, and be warming up to 80 DEG C and start to stir and be continuously heating to 220-225 DEG C, keep the temperature 2 hours at this temperature
To end-point of alcoholysis.
Then, cool down, when temperature is down to 200 DEG C, stop stirring, and stop being passed through inert gas, metering investment is as follows
Raw material Mono-n-butyltin, M-phthalic acid, cis-butenedioic anhydride, antioxidant and the dimethylbenzene of parts by weight, start stirring, and be passed through indifferent gas
Body then heats to refluxing xylene, and into the refuxing esterification water smoking, refluxing xylene is normal in the refuxing esterification water smoking
Afterwards, i.e., after entering reaction kettle without air, stopping is passed through inert gas, and refuxing esterification water smoking temperature of charge is 245-250 DEG C,
Heat preservation starts sampling and surveys its acid value and viscosity after 2 hours, when acid value is 10-15mgKOH/g, and measured at room temperature with -4 glasss of painting viscous
When degree is 300-500s, 180 DEG C are cooled to, is decompressed to vacuum degree 0.02MPa with decompressor, goes out dimethylbenzene with pumping, extracted out
Time is 25min, until the transparent drop-wise of extract in condenser, removes decompressor and cools down, be made and be cooled to 140 DEG C,
A kind of high-solid lower-viscosity, high acid value, high hydroxyl value gutter oil alkyd performed polymer mixed liquor, it is spare.
Gutter oil alkyd performed polymer modified aqueous acrylic acid tree is prepared with obtained gutter oil alkyd performed polymer mixed liquor
The composition of raw materials of rouge dispersion is as shown in table 1-2:
Table 1-2:
The specific step of gutter oil alkyd performed polymer modified aqueous acrylic acid resin dispersion is prepared using above-mentioned raw materials formula
It is rapid as follows: (1) to premix measured in kettle intensively ditch oleyl alcohol acid performed polymer mixed liquor, acrylic acid, butyl acrylate, styrene,
Methyl methacrylate and 9.1kgBPO are stirred until homogeneous mixing.
(2) semicontinuous dropwise addition technique is used, reflux condensing tube, agitating device, temperature control system and dropping funel are being had
Reactor in, be added butyl glycol ether solvent.After being warming up to 120 DEG C, 10% of premix quality made from step (1) is added
Enter in reactor, is stirred until homogeneous dispersion, then keeps the temperature 0.5h.Remaining premix is dropped evenly again, is added dropwise in 3h, is protected
It is added 10% initiator (relative to initiator has been added) after temperature 1, while polymerization temperature is improved 4~5 DEG C, continue heat preservation 2, then
N, N dimethyl was added dropwise at 15 minutes until stopping reaction when monomer conversion reaches 98% or more is cooled to 70 DEG C in sampling analysis
Carboxylic group in ethanol amine with 80%；Gutter oil alkyd performed polymer modified aqueous acrylic acid resin oil-based system is made.
(3) continue heat preservation at 70 DEG C, to gutter oil alkyd made from step (2) under the high-speed stirred revolving speed of 1000rpm
First part's deionized water is added dropwise in performed polymer modified aqueous acrylic acid resin oil-based system, makes gutter oil alkyd performed polymer modified water
Property acrylic resin oil-based system be transformed into oil-in-water system, time for adding is controlled at 60 minutes or so, and resin contains admittedly at this time
Amount is 70% or so；Then second part deionized water is added dropwise, time for adding was controlled at 15 minutes, and resin solid content exists at this time
50% or so, gutter oil alkyd performed polymer modified aqueous acrylic acid the first dispersion of resin is made.
(4) gutter oil alkyd performed polymer modified water-soluble third made from step (3) finally is added in Part III deionized water
In the first dispersion of olefin(e) acid resin, adding manner is added rapidly in dispersion in preferably 15 minutes, and dispersion is allowed to cool down, and is used
200 mesh sock filtrations packaging, is finally made gutter oil alkyd performed polymer modified aqueous acrylic acid the second dispersion of resin, i.e. trench
Oleyl alcohol acid performed polymer modified aqueous acrylic acid resin dispersion, final dispersion solid content are 40% or so { (40 ± 2) % }, hydroxyl
Base is 1.5% or so.
Embodiment 2
The composition of raw materials of gutter oil alkyd performed polymer mixed liquor is prepared as shown in table 2-1:
Table 2-1:
| Material name | Inventory, Kg | Specification |
| Gutter oil | 460 | —— |
| Methyl propanediol | 160 | Industrial goods |
| Glycerin | 400 | Industrial goods |
| Lithium hydroxide | 0.6 | Chemicals |
| M-phthalic acid | 520 | Industrial goods |
| Mono-n-butyltin | 2 | Chemicals |
| Cis-butenedioic anhydride | 80 | Industrial goods |
| Antioxidant | 3 | Chemicals |
| Dimethylbenzene | 80 | Industrial goods |
Preparing gutter oil alkyd performed polymer mixed liquor using above-mentioned raw materials formula, specific step is as follows:
Firstly, put into reaction kettle gutter oil, methyl propanediol, Glycerin, lithium hydroxide, then to reaction kettle
In be passed through inert gas, and be warming up to 80 DEG C and start to stir and be continuously heating to 230-235 DEG C, keep the temperature 2 hours at this temperature
To end-point of alcoholysis.
Then, cool down, when temperature is down to 180 DEG C, stop stirring, and stop being passed through inert gas, metering investment is as follows
Raw material Mono-n-butyltin, M-phthalic acid, cis-butenedioic anhydride, antioxidant and the dimethylbenzene of parts by weight, start stirring, and be passed through indifferent gas
Body then heats to refluxing xylene, and into the refuxing esterification water smoking, refluxing xylene is normal in the refuxing esterification water smoking
Afterwards, i.e., after entering reaction kettle without air, stopping is passed through inert gas, and refuxing esterification water smoking temperature of charge is 235-240 DEG C,
Heat preservation starts sampling and surveys its acid value and viscosity after 2 hours, when acid value is 10-15mgKOH/g, and measured at room temperature with -4 glasss of painting viscous
When degree is 300-500s, 180 DEG C are cooled to, is decompressed to vacuum degree 0.08MPa with decompressor, goes out dimethylbenzene with pumping, extracted out
Time is 25min, until the transparent drop-wise of extract in condenser, removes decompressor and cools down, be made and be cooled to 140 DEG C,
A kind of high-solid lower-viscosity, high acid value, high hydroxyl value gutter oil alkyd performed polymer mixed liquor, it is spare.
Gutter oil alkyd performed polymer modified aqueous acrylic acid tree is prepared with obtained gutter oil alkyd performed polymer mixed liquor
The composition of raw materials of rouge dispersion is as shown in table 2-2:
Table 2-2:
| Material name | Inventory, Kg | Specification |
| Gutter oil alkyd performed polymer mixed liquor | 250 | Self-control |
| BPO | 15 | Industrial goods |
| Acrylic acid | 200 | Industrial goods |
| Butyl acrylate | 200 | Industrial goods |
| Styrene | 100 | Industrial goods |
| Methyl methacrylate | 100 | Industrial goods |
| Neutralizer | 50 | Industrial goods |
| Butyl glycol ether | 150 | Industrial goods |
| First part's deionized water | 200 | Self-control |
| Second part deionized water | 400 | Self-control |
| Part III deionized water | 400 | Self-control |
The specific step of gutter oil alkyd performed polymer modified aqueous acrylic acid resin dispersion is prepared using above-mentioned raw materials formula
It is rapid as follows: (1) to premix measured in kettle intensively ditch oleyl alcohol acid performed polymer mixed liquor, acrylic acid, butyl acrylate, styrene,
The BPO of methyl methacrylate and 12.5kg is stirred until homogeneous mixing.
(2) semicontinuous dropwise addition technique is used, reflux condensing tube, agitating device, temperature control system and dropping funel are being had
Reactor in, be added butyl glycol ether solvent.After being warming up to 120 DEG C, 20% of premix quality made from step (1) is added
Enter in reactor, is stirred until homogeneous dispersion, then keeps the temperature 0.5h.Remaining premix is dropped evenly again, is added dropwise in 4h, is protected
20% initiator (relative to initiator has been added) is added after temperature 1, while polymerization temperature is properly increased 4~5 DEG C, continues to keep the temperature
3h, then sampling analysis was added dropwise until stopping reaction when monomer conversion reaches 98% or more is cooled to 70 DEG C at 15 minutes or so
N, in N dimethyl ethanol amine and 80% carboxylic group；Gutter oil alkyd performed polymer modified aqueous acrylic acid resinon phase is made
System.
(3) continue to keep the temperature at 70 DEG C, it is pre- to gutter oil alkyd made from step (2) under the high-speed stirred revolving speed of 800rpm
First part's deionized water is added dropwise in aggressiveness modified aqueous acrylic acid resin oil-based system, makes gutter oil alkyd performed polymer modified water-soluble
Acrylic resin oil-based system is transformed into oil-in-water system, and time for adding is controlled at 60 minutes or so, at this time resin solid content
70% or so；Then second part deionized water is added dropwise, time for adding was controlled at 15 minutes, and resin solid content is 50% at this time
Gutter oil alkyd performed polymer modified aqueous acrylic acid the first dispersion of resin is made in left and right.
(4) gutter oil alkyd performed polymer modified water-soluble third made from step (3) finally is added in Part III deionized water
In the first dispersion of olefin(e) acid resin, adding manner is added rapidly in dispersion in preferably 15 minutes, and dispersion is allowed to cool down, and is used
200 mesh sock filtrations packaging, is finally made gutter oil alkyd performed polymer modified aqueous acrylic acid the second dispersion of resin, i.e. trench
Oleyl alcohol acid performed polymer modified aqueous acrylic acid resin dispersion, final dispersion solid content are 40% { (40 ± 2) % }, and hydroxyl is
1.5% or so.
Embodiment 3
The composition of raw materials of gutter oil alkyd performed polymer mixed liquor is prepared as shown in table 3-1:
Table 3-1:
Preparing gutter oil alkyd performed polymer mixed liquor using above-mentioned raw materials formula, specific step is as follows:
Firstly, put into reaction kettle gutter oil, methyl propanediol, Glycerin, lithium hydroxide, then to reaction kettle
In be passed through inert gas, and be warming up to 80 DEG C and start to stir and be continuously heating to 230-235 DEG C, keep the temperature 2 hours at this temperature
To end-point of alcoholysis.
Then, cool down, when temperature is down to 200 DEG C, stop stirring, and stop being passed through inert gas, metering investment is as follows
Raw material Mono-n-butyltin, M-phthalic acid, cis-butenedioic anhydride, antioxidant and the dimethylbenzene of parts by weight, start stirring, and be passed through indifferent gas
Body then heats to refluxing xylene, and into the refuxing esterification water smoking, refluxing xylene is normal in the refuxing esterification water smoking
Afterwards, i.e., after entering reaction kettle without air, stopping is passed through inert gas, and refuxing esterification water smoking temperature of charge is 240-250 DEG C,
Heat preservation starts sampling and surveys its acid value and viscosity after 2 hours, when acid value is 10-15mgKOH/g, and measured at room temperature with -4 glasss of painting viscous
When degree is 300-500s, 180 DEG C are cooled to, is decompressed to vacuum degree 0.06MPa with decompressor, goes out dimethylbenzene with pumping, extracted out
Time is 25min, until the transparent drop-wise of extract in condenser, removes decompressor and cools down, be made and be cooled to 140 DEG C,
A kind of high-solid lower-viscosity, high acid value, high hydroxyl value gutter oil alkyd performed polymer mixed liquor, it is spare.
Gutter oil alkyd performed polymer modified aqueous acrylic acid tree is prepared with obtained gutter oil alkyd performed polymer mixed liquor
The composition of raw materials of rouge dispersion is as shown in table 3-2:
Table 3-2:
The specific step of gutter oil alkyd performed polymer modified aqueous acrylic acid resin dispersion is prepared using above-mentioned raw materials formula
It is rapid as follows: (1) to premix measured in kettle intensively ditch oleyl alcohol acid performed polymer mixed liquor, acrylic acid, butyl acrylate, styrene,
The BPO of methyl methacrylate and 15.65kg is stirred until homogeneous mixing.
(2) semicontinuous dropwise addition technique is used, reflux condensing tube, agitating device, temperature control system and dropping funel are being had
Reactor in, be added butyl glycol ether solvent.After being warming up to 120 DEG C, 15% of premix quality made from step (1) is added
Enter in reactor, is stirred until homogeneous dispersion, then keeps the temperature 0.5h.Remaining premix is dropped evenly again, is added dropwise in 3.5h,
15% initiator (relative to initiator has been added) is added after heat preservation 1, while polymerization temperature is properly increased 4~5 DEG C, continues to keep the temperature
2.5h, then sampling analysis dripped until stopping reaction when monomer conversion reaches 98% or more is cooled to 70 DEG C at 15 minutes or so
Add N, in N dimethylethanolamine and 80% carboxylic group；Gutter oil alkyd performed polymer modified aqueous acrylic acid resinon is made
Phase system.
(3) continue to keep the temperature at 70 DEG C, it is pre- to gutter oil alkyd made from step (2) under the high-speed stirred revolving speed of 700rpm
First part's deionized water is added dropwise in aggressiveness modified aqueous acrylic acid resin oil-based system, makes gutter oil alkyd performed polymer modified water-soluble
Acrylic resin oil-based system is transformed into oil-in-water system, and time for adding is controlled at 60 minutes or so, at this time resin solid content
70% or so；Then second part deionized water is added dropwise, time for adding was controlled at 15 minutes, and resin solid content is 50% at this time
Gutter oil alkyd performed polymer modified aqueous acrylic acid the first dispersion of resin is made in left and right.
(4) gutter oil alkyd performed polymer modified water-soluble third made from step (3) finally is added in Part III deionized water
In the first dispersion of olefin(e) acid resin, adding manner is added rapidly in dispersion in preferably 15 minutes, and dispersion is allowed to cool down, and is used
200 mesh sock filtrations packaging, is finally made gutter oil alkyd performed polymer modified aqueous acrylic acid the second dispersion of resin, i.e. trench
Oleyl alcohol acid performed polymer modified aqueous acrylic acid resin dispersion, final dispersion solid content are 40% { (40 ± 2) % }, and hydroxyl is
1.5% or so.
The gutter oil alkyd performed polymer modified aqueous acrylic acid resin prepared using embodiment 1, embodiment 2 and embodiment 3
Formulated white water-borne acrylic-amino hot curing varnish, wherein gutter oil alkyd performed polymer modified aqueous acrylic acid resin
The mass content of dispersion is 60-70%, is crosslinked by I type baking-type in HG/T4758-2014 " water-based acrylic resin coating "
The standard of curable coating carries out performance detection, and testing result is shown in Table 4, as can be seen from Table 4 embodiment 1, embodiment 2, reality
I type baking-type in HG/T4758-2014 " water-based acrylic resin coating " can be met by applying example 3 indices of sample being made
The technical requirements of crosslinking curing type coating.
Table 4:
Remarks:
1, the VOC content of traditional solvent-borne acrylic resin paint is about 500-600g/L, traditional water-soluble acrylic acid tree
The VOC content of grease coating material is about 250-300g/L, by gutter oil alkyd performed polymer modified aqueous acrylic acid resin dispersion of the present invention
Coating VOC made from body contains amount≤100g/L.2, VOC test method: according to GB/T23986-2009, " paint and varnish volatilizees
The measurement gas chromatography of property organic compound (VOC) content " in method 3 tested.
Claims (3)
1. a kind of preparation method of gutter oil alkyd performed polymer mixed liquor, it is characterised in that: described method includes following steps:
Firstly, putting into the raw material of following parts by weight into reaction kettle: 20-23 parts of gutter oil, 5-8 parts of methyl propanediol, trihydroxy
20-25 parts of propane, 0.01-0.03 parts of lithium hydroxide, inert gas is then passed through into reaction kettle, and be warming up to 75-85 DEG C and open
Begin to stir and be continuously heating to 220-235 DEG C, at least keeps the temperature 2 hours to end-point of alcoholysis at this temperature；
Then, cool down, when temperature is down to 200 DEG C or less, stop stirring, and stop being passed through inert gas, metering investment is as follows
3-4 parts of 20-26 parts of 0.1-0.15 parts of raw material Mono-n-butyltin, M-phthalic acid, cis-butenedioic anhydride, the antioxidant 0.05- of parts by weight
0.15 part and dimethylbenzene 3-4 parts, stirring is started, and be passed through inert gas, then heat to refluxing xylene, into refuxing esterification
In the water smoking, after refluxing xylene is normal in the refuxing esterification water smoking, i.e., after entering reaction kettle without air, stopping is passed through inertia
Gas, refuxing esterification water smoking temperature of charge must not exceed 250 DEG C, heat preservation start after 2-2.5 hour sampling survey its acid value with
Viscosity is cooled to 180-160 when acid value is 10-15mgKOH/g, and when to measure viscosity be 300-500s with -4 glasss of painting at room temperature
DEG C, it is decompressed to vacuum degree 0.02-0.08MPa with decompressor, goes out dimethylbenzene with pumping, is found time as 25-30min, until
The transparent drop-wise of extract in condenser removes decompressor and cools down, gutter oil alkyd performed polymer mixed liquor is made.
2. the preparation method of gutter oil alkyd performed polymer mixed liquor according to claim 1, which is characterized in that the only son
The parts by weight of base tin oxide are 0.1 part.
3. the preparation method of gutter oil alkyd performed polymer modified aqueous acrylic acid resin dispersion, it is characterised in that: the method
Include the following steps:
(1) the gutter oil alkyd performed polymer as claimed in claim 1 or 2 of 15-25 parts of parts by weight of investment is measured into premix kettle
Mixed liquor, the acrylic acid of 15-20 parts by weight, the butyl acrylate of 15-20 parts by weight, the styrene of 10-15 parts by weight, 5-10 weight
The methyl methacrylate and 0.91-1.7 parts of BPO for measuring part, are stirred until homogeneous mixing, and premix is made；
(2) firstly, using semicontinuous dropwise addition technique, reflux condensing tube, agitating device, temperature control system and dropping funel are being had
Reactor in, it is 10-15 parts of butyl glycol ether solvent that parts by weight, which are added,；
Then, after being warming up to 120-130 DEG C, the 10%-20% of premix quality made from step (1) is added in reactor,
It is stirred until homogeneous dispersion, then keeps the temperature 0.5h-1h, then drops evenly remaining premix, time for adding is 3-4 hours, is added dropwise
After keep the temperature 1-1.5h after add the BPO for having added the 10%-20% of BPO mass, while improving 4-5 DEG C of polymerization temperature, and after
Continue insurance temperature 2-3h, then sampling analysis, until stop reacting and being cooled to 60-70 DEG C when monomer conversion reaches 98% or more,
15-20 minutes or so dropwise addition N, the carboxylic group of 80-85%, it is pre- to be made gutter oil alkyd in N dimethyl ethanol amine and in material
Aggressiveness modified aqueous acrylic acid resin oil-based system；
(3) continue heat preservation at 70 DEG C, to gutter oil alkyd made from step (2) under the high-speed stirred revolving speed of 700-1000rpm
15-20 parts of deionized waters are added dropwise in performed polymer modified aqueous acrylic acid resin oil-based system, keep gutter oil alkyd pre-polymerization modifies
Water-based acrylic resin oil-based system is transformed into oil-in-water system, and time for adding is controlled at 60-80 minutes or so；Then again to body
30-40 parts of deionized waters are added dropwise in system, time for adding was controlled at 15-30 minutes, and gutter oil alkyd performed polymer modified water-soluble is made
The first dispersion of acrylic resin；
(4) weight is added into gutter oil alkyd performed polymer modified aqueous acrylic acid the first dispersion of resin made from step (3)
The deionized water that part is 30-40 parts is measured, adjustment dispersion contains admittedly and dispersion is allowed to cool down, then is packed with 200 mesh sock filtrations, most
Obtained gutter oil alkyd performed polymer modified aqueous acrylic acid the second dispersion of resin, i.e. gutter oil alkyd performed polymer modified water-soluble eventually
Acrylic dispersion.
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| CN100999570A (en) * | 2007-01-12 | 2007-07-18 | 福建豪迪涂料科技股份有限公司 | Process of producing alkyd resin using waste oil |
| CN103709384A (en) * | 2013-12-02 | 2014-04-09 | 安庆菱湖涂料有限公司 | Method for synthesis of paint alkyd resin from purified waste oil |
| CN103725145A (en) * | 2013-12-13 | 2014-04-16 | 武汉工程大学 | Aqueous alkide resin-acrylic acid resin hybrid coating and preparation method thereof |
| CN105175693A (en) * | 2015-07-23 | 2015-12-23 | 三棵树涂料股份有限公司 | High-solid and low-viscosity short oil alkyd resin and preparation method therefor |
| US20160075891A1 (en) * | 2014-09-16 | 2016-03-17 | Eastman Chemical Company | Polymeric compositions with improved noise suppression |
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|---|---|---|---|---|
| CN100999570A (en) * | 2007-01-12 | 2007-07-18 | 福建豪迪涂料科技股份有限公司 | Process of producing alkyd resin using waste oil |
| CN103709384A (en) * | 2013-12-02 | 2014-04-09 | 安庆菱湖涂料有限公司 | Method for synthesis of paint alkyd resin from purified waste oil |
| CN103725145A (en) * | 2013-12-13 | 2014-04-16 | 武汉工程大学 | Aqueous alkide resin-acrylic acid resin hybrid coating and preparation method thereof |
| US20160075891A1 (en) * | 2014-09-16 | 2016-03-17 | Eastman Chemical Company | Polymeric compositions with improved noise suppression |
| CN105175693A (en) * | 2015-07-23 | 2015-12-23 | 三棵树涂料股份有限公司 | High-solid and low-viscosity short oil alkyd resin and preparation method therefor |
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