CN109897130A - A kind of preparation method of water-soluble acrylic hard resin - Google Patents
A kind of preparation method of water-soluble acrylic hard resin Download PDFInfo
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- CN109897130A CN109897130A CN201910220296.0A CN201910220296A CN109897130A CN 109897130 A CN109897130 A CN 109897130A CN 201910220296 A CN201910220296 A CN 201910220296A CN 109897130 A CN109897130 A CN 109897130A
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Abstract
The invention discloses a kind of preparation methods of water-soluble acrylic hard resin, and soft monomer, hard monomer, other required ingredients are imported in the reactor of energy continuous work, polymerization reaction occurs in the effect of initiator and the system of solvent and obtains required product.Resulting product purity is high of the present invention, narrowly distributing, viscosity is low, and molecular weight is higher than market similar product；In actual use, rate of drying is fast, glossiness is high, wear-resisting, and resin coating film weatherability, adhesive force are better than similar product, has outstanding compatibility, metastatic, and printing is splendid, is highly suitable to be applied for the industries such as high-grade coating, gloss oil, ink.
Description
Technical field:
The present invention relates to the preparation field of acrylic solid resin, a kind of particularly water-soluble acrylic hard resin
Preparation method.
Background technique:
High volatile matter in existing oleoresin product is very big on environment, health influence, and national environmental protection monitoring is got over
Come tighter, the environmental consciousness of the common people is also increasingly stronger, keeps water-based ink, gloss oil and water paint market increasing, and market is used
It is more be acrylic emulsion lotion, but lotion is easy residual emulsifying agents and the complete monomer of unreacted, and another various additives are more,
VOC content is also higher.Properties of product are unstable, and weatherability is general, are easy to after-tack, poor water resistance, are used in low-end market mostly.City
Product emulsion quality is irregular on field, and many consumers is caused to hold the suspicious attitude the use of water paint.Market needs height
The water-base resin of quality, too resin (50000~100000) molecular weight of high molecular weight increase a bit, can all make ink, coating
In viscosity increase very much, unstable quality.Hard resin of other molecular weight 5000~10000 or so, molecular weight are less than normal
Keep weatherability, adhesive force, the solvent resistance aspect of product slightly inadequate.If can produce a kind of molecular weight 10000~
20000, the lower aqueous solid resin of viscosity can preferably solve the above problems, quality is more excellent, and the scope of application is wider
It is general.
Summary of the invention:
It is an object of the present invention to solve the deficiency of the existing technology and provide a kind of water-soluble acrylic hard resins
Preparation method.
The technical solution adopted by the present invention are as follows:
A kind of preparation method of water-soluble acrylic hard resin, which is characterized in that specific step is as follows:
1) soft monomer needed, hard monomer, other function monomer, other components, initiator, flow promortor conduct are got out
Raw material；
2) soft monomer, hard monomer, other function monomer, other components and initiator are introduced directly into tubular reactor and are mixed
It closes, while introducing flow promortor and obtaining mixed material, the mixed material is kept to keep certain flow rate in tubular reactor, guarantee
Mixed material stops 1~120 minute in tubular reactor, and it is anti-that the pressure of tubular reactor is maintained at 0.2~3.5Mpa, tubular type
Mixed material temperature in device is answered to be maintained at 150~350 DEG C, material to be mixed is flowed out out of tubular reactor to be obtained containing residual monomer
Mobility semi-finished product；
3) devolatilization processing is carried out to the mobility semi-finished product containing residual monomer that step 2) obtains, removes and recycles remaining
The impurity such as initiator, flow promortor and unreacted monomer, obtain recovered material and required product after cooling.
Soft monomer is at least one of Isooctyl acrylate monomer, ethyl acrylate, butyl acrylate, decyl acrylate, is used
Amount accounts for the 0~20% of ingredient total weight, preferably 1~15%.
Hard monomer be styrene, methyl styrene, methyl methacrylate, acrylonitrile, in vinyl acetate at least
One kind, dosage account for the 0~70% of ingredient total weight, preferably 2~65%.
Other function monomer is methyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate, first
At least one of base lauryl acid esters, hydroxyethyl methacrylate, acrylic acid, maleic anhydride, fumaric acid, dosage, which accounts for, matches
Expect 0~50%, preferably the 5~40% of total weight.
Initiator is this formyl of peroxidating, azodiisobutyronitrile, lauroyl peroxide, di-tert-butyl peroxide, peroxide
Change at least one of t-butyl perbenzoate, cumyl peroxide, tert-butyl hydroperoxide, dosage accounts for ingredient total weight
0.2~5%.
Other components are 3- isooctyl mercaptopropionate, n- dodecyl mereaptan, mercaptoethanol, isopropanol, sodium hydrogensulfite sulfydryl
At least one of propionic acid, a- methyl styrene dimer body, carbon tetrachloride, dosage accounts for the 0~15% of ingredient total weight.
Flow promortor are as follows: propylene glycol, dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol (DEG), fourth
At least one of dintrile, ethylene carbonate, dosage account for the 0~22% of ingredient total weight, preferably 1~18%.
Raw material further includes recovered material, and dosage accounts for the 0~20% of ingredient total weight, preferably 1~15%.
Preferably, mixed material stops 2~80 minutes in tubular reactor, and mixed material temperature is protected in tubular reactor
It holds at 180~350 DEG C.
For products therefrom weight average molecular weight between 12500~13500, resin aqueous solution viscosity is 3100cps.
Compared with prior art, the beneficial effects of the present invention are:
The present invention solves deficiency in the prior art, while resulting product purity is high, and narrowly distributing, viscosity is low, molecule
It measures higher than market similar product；In actual use, rate of drying is fast, glossiness is high, wear-resisting, resin coating film weatherability, attached
Put forth effort to be better than similar product, have outstanding compatibility, metastatic, printing is splendid, be highly suitable to be applied for high-grade coating,
The industries such as gloss oil, ink.
Specific embodiment:
A kind of preparation method of water-soluble acrylic hard resin, the specific steps are as follows:
1) soft monomer needed, hard monomer, other function monomer, other components, initiator, flow promortor conduct are got out
Raw material；
2) soft monomer, hard monomer, other function monomer, other components and initiator are introduced directly into tubular reactor and are mixed
It closes, while introducing flow promortor and obtaining mixed material, the mixed material is kept to keep certain flow rate in tubular reactor, guarantee
Mixed material stops 1~120 minute in tubular reactor, and it is anti-that the pressure of tubular reactor is maintained at 0.2~3.5Mpa, tubular type
Mixed material temperature in device is answered to be maintained at 150~350 DEG C, material to be mixed is flowed out out of tubular reactor to be obtained containing residual monomer
Mobility semi-finished product；
3) devolatilization processing is carried out to the mobility semi-finished product containing residual monomer that step 2) obtains, removes and recycles remaining
The substances such as initiator, flow promortor and unreacted monomer, obtain recovered material and required product after cooling；
Soft monomer is at least one of Isooctyl acrylate monomer, ethyl acrylate, butyl acrylate, decyl acrylate, is used
Amount accounts for the 0~20% of ingredient total weight；Hard monomer is styrene, methyl styrene, methyl methacrylate, acrylonitrile, acetic acid
At least one in vinyl acetate, dosage account for the 0~70% of ingredient total weight；
Other function monomer is methyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate, first
At least one of base lauryl acid esters, hydroxyethyl methacrylate, acrylic acid, maleic anhydride, fumaric acid, dosage, which accounts for, matches
Expect the 0~50% of total weight；
Initiator is peroxidating two formyls, azodiisobutyronitrile, lauroyl peroxide, di-tert-butyl peroxide, mistakes
At least one of t-butyl perbenzoate, cumyl peroxide, tert-butyl hydroperoxide are aoxidized, dosage accounts for ingredient total weight
0.2~5%；
Other components are 3- isooctyl mercaptopropionate, n- dodecyl mereaptan, mercaptoethanol, isopropanol, sodium hydrogensulfite sulfydryl
At least one of propionic acid, a- methyl styrene dimer body, carbon tetrachloride, dosage accounts for the 0~15% of ingredient total weight；
Flow promortor are as follows: propylene glycol, dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol (DEG), fourth
At least one of dintrile, ethylene carbonate, dosage account for the 0~22% of ingredient total weight；
Raw material further includes recovered material, and dosage accounts for the 0~20% of ingredient total weight.
Embodiment one: by 1.1kg (2.36%) soft monomer, 29kg (62.11%) hard monomer, 13kg (27.84%) function
Monomer, the initiator of 0.3kg (0.64%), the other components of 3.29kg (7.05%), 2kg (4.28%) flow promortor mixing after
Reactor reaction is introduced, temperature is maintained at 240 DEG C, pressure 0.5mpa, then carries out devolatilization processing, true to the material obtained after reaction
Sky -0.05mpa, the material cooling after devolatilization obtain product (reference table 1)；
Embodiment two: by 0.4kg (2.35%) soft monomer, 11kg (64.71%) hard monomer, 5.5kg (32.35%) other
Function monomer, the initiator of 0.1kg (0.59%), 1.5kg (8.82%) flow promortor mixing after introduce reactor reaction, temperature
Degree is maintained at 230 DEG C, pressure 0.3mpa, then carries out devolatilization processing, vacuum -0.07mpa to the material obtained after reaction, after devolatilization
Material cooling obtain product (reference table 1)；
Embodiment three: by 2.5kg (2.63%) soft monomer, 60kg (63.09%) hard monomer, 30kg (31.55%) other
Draw after function monomer, the initiator of 0.6kg (0.63%), the flow promortor of 3kg (3.15%), the mixing of 2kg (2.1%) reclaimed materials
Enter reactor reaction, temperature is maintained at 230 DEG C, pressure 0.4mpa, then carries out devolatilization processing, true to the material obtained after reaction
Sky -0.06mpa, the material cooling after devolatilization obtain product (reference table 1)；
Example IV: by 1kg (3.55%) soft monomer, 18kg (63.97%) hard monomer, 9kg (31.98%) other function
Monomer, the initiator of 0.14kg (0.5%), 4.5kg (15.99%) flow promortor mixing after introduce reactor reaction, temperature
It is maintained at 220 DEG C, pressure 0.5mpa, then devolatilization processing, vacuum -0.06mpa are carried out to the material obtained after reaction, after devolatilization
Material cooling obtains product (reference table 1).
Table 1
| Project | Embodiment one | Embodiment two | Embodiment three | Example IV |
| Appearance | Transparent (micro- Huang) | Transparent (micro- Huang) | It is transparent (white) | It is transparent (white) |
| Acid value | 218 | 219 | 218 | 218 |
| Solid content | 98.5% | 98.2% | 98.2% | 98% |
| TG | 105 | 105 | 105 | 105 |
| Mn | 13500 | 13600 | 13700 | 13600 |
Compared with market similar product molecular weight, viscosity:
Table 2
| Producer | Molecular weight Mn | Viscosity | TG | Acid value |
| Foreign brand name A | 8600 | 3200cps | 85 | 215 |
| Foreign brand name B | 8500 | 3000cps | 100 | 212 |
| This patent product | 13500 | 3100cps | 105 | 218 |
Performance comparison of the different product in water paint:
Table 3
Viscosity is seen from comparison in same level, this patent molecular weight product is higher than in similar product, adhesive force and
Good weatherability is in similar product.Therefore it is all according to the configuration described in the scope of the patent application of the present invention, the equivalent change done of feature and principle
Change or modify, is included in the scope of the patent application of the present invention.
Claims (10)
1. a kind of preparation method of water-soluble acrylic hard resin, which is characterized in that specific step is as follows:
1) soft monomer needed, hard monomer, other function monomer, other components, initiator, flow promortor are got out as former
Material；
2) soft monomer, hard monomer, other function monomer, other components and initiator are introduced directly into tubular reactor and are mixed,
Introducing flow promortor obtains mixed material simultaneously, and the mixed material is kept to keep certain flow rate in tubular reactor, guarantees mixed
It closes material to stop in tubular reactor 1~120 minute, the pressure of tubular reactor is maintained at 0.2~3.5Mpa, pipe reaction
Mixed material temperature is maintained at 150~350 DEG C in device, and material to be mixed is flowed out out of tubular reactor to be obtained containing residual monomer
Mobility semi-finished product；
3) devolatilization processing is carried out to the mobility semi-finished product containing residual monomer that step 2) obtains, removes and recycles remaining initiation
The impurity such as agent, flow promortor and unreacted monomer, obtain recovered material and required product after cooling.
2. a kind of preparation method of water-soluble acrylic hard resin according to claim 1, it is characterised in that:
The soft monomer is at least one of Isooctyl acrylate monomer, ethyl acrylate, butyl acrylate, decyl acrylate, is used
Amount accounts for the 0~20% of ingredient total weight.
3. a kind of preparation method of water-soluble acrylic hard resin according to claim 1, it is characterised in that:
The hard monomer be styrene, methyl styrene, methyl methacrylate, acrylonitrile, in vinyl acetate at least
One kind, dosage account for the 0~70% of ingredient total weight.
4. a kind of preparation method of water-soluble acrylic hard resin according to claim 1, it is characterised in that:
The other function monomer is methyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate, first
At least one of base lauryl acid esters, hydroxyethyl methacrylate, acrylic acid, maleic anhydride, fumaric acid, dosage, which accounts for, matches
Expect the 0~50% of total weight.
5. a kind of preparation method of water-soluble acrylic hard resin according to claim 1, it is characterised in that:
The initiator is this formyl of peroxidating, azodiisobutyronitrile, lauroyl peroxide, di-tert-butyl peroxide, peroxide
Change at least one of t-butyl perbenzoate, cumyl peroxide, tert-butyl hydroperoxide, dosage accounts for ingredient total weight
0.2~5%.
6. a kind of preparation method of water-soluble acrylic hard resin according to claim 1, it is characterised in that:
The other components are 3- isooctyl mercaptopropionate, n- dodecyl mereaptan, mercaptoethanol, isopropanol, sodium hydrogensulfite sulfydryl
At least one of propionic acid, a- methyl styrene dimer body, carbon tetrachloride, dosage accounts for the 0~15% of ingredient total weight.
7. a kind of preparation method of water-soluble acrylic hard resin according to claim 1, it is characterised in that:
The flow promortor are as follows: propylene glycol, dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol (DEG), fourth
At least one of dintrile, ethylene carbonate, dosage account for the 0~22% of ingredient total weight.
8. a kind of preparation method of water-soluble acrylic hard resin according to claim 1, it is characterised in that:
The raw material further includes recovered material, and dosage accounts for the 0~20% of ingredient total weight.
9. a kind of preparation method of water-soluble acrylic hard resin according to claim 1, it is characterised in that:
The mixed material stops 2~80 minutes in tubular reactor, and mixed material temperature is maintained at 180 in tubular reactor
~350 DEG C.
10. a kind of preparation method of water-soluble acrylic hard resin according to claim 1, it is characterised in that:
For the products therefrom weight average molecular weight between 12500~13500, resin aqueous solution viscosity is 3100cps.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111690293A (en) * | 2020-05-27 | 2020-09-22 | 鹤山市科鼎功能材料有限公司 | Resin for washable glass temporary protection ink and preparation method thereof |
| CN112094533A (en) * | 2020-09-27 | 2020-12-18 | 湖北淡雅香生物科技股份有限公司 | Slow-drying-treated flexo-printing environment-friendly tipping paper water-based ink and preparation method thereof |
| CN113105576A (en) * | 2021-04-14 | 2021-07-13 | 英德市捷成化工有限公司 | Resin modified acrylic emulsion with core-shell structure and preparation method and application thereof |
| CN114133484A (en) * | 2021-12-09 | 2022-03-04 | 江西联合化工有限公司 | Method for preparing acrylic resin by adopting tubular reactor |
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| CN104311726A (en) * | 2014-10-30 | 2015-01-28 | 中国科学院化学研究所 | Method for preparing solid acrylic resin |
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| CN1144810A (en) * | 1995-07-03 | 1997-03-12 | Basf公司 | Continuous preparation of polymers and apparatus therefor |
| CN101575397A (en) * | 2009-06-02 | 2009-11-11 | 中山大学 | Method for preparing water-soluble solid styrene/acrylic resin and application thereof |
| CN104031202A (en) * | 2014-06-17 | 2014-09-10 | 中国科学院化学研究所 | Polyacrylic acid printing ink resin and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111690293A (en) * | 2020-05-27 | 2020-09-22 | 鹤山市科鼎功能材料有限公司 | Resin for washable glass temporary protection ink and preparation method thereof |
| CN112094533A (en) * | 2020-09-27 | 2020-12-18 | 湖北淡雅香生物科技股份有限公司 | Slow-drying-treated flexo-printing environment-friendly tipping paper water-based ink and preparation method thereof |
| CN113105576A (en) * | 2021-04-14 | 2021-07-13 | 英德市捷成化工有限公司 | Resin modified acrylic emulsion with core-shell structure and preparation method and application thereof |
| CN114133484A (en) * | 2021-12-09 | 2022-03-04 | 江西联合化工有限公司 | Method for preparing acrylic resin by adopting tubular reactor |
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Application publication date: 20190618 |