CN108484845A - A kind of preparation method of sea shell micropowder modified water-soluble hydroxy polyacrylate resin - Google Patents
A kind of preparation method of sea shell micropowder modified water-soluble hydroxy polyacrylate resin Download PDFInfo
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- CN108484845A CN108484845A CN201810117479.5A CN201810117479A CN108484845A CN 108484845 A CN108484845 A CN 108484845A CN 201810117479 A CN201810117479 A CN 201810117479A CN 108484845 A CN108484845 A CN 108484845A
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- sea shell
- shell micropowder
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
Abstract
The present invention discloses a kind of preparation method of sea shell micropowder modified water-soluble hydroxy polyacrylate resin,570 ethanol solution mixed at high speed of sea shell micropowder and KH,It is sieved after dry to obtain modified sea shell micropowder,Butyl glycol ether is added in Scattered Kettle,Add modified sea shell micropowder,High-speed stirred obtains modified sea shell micropowder slurry,After butyl glycol ether is added in a kettle,Modified sea shell micropowder slurry is added,It is warming up to 130 DEG C,It is continuously added to acrylic acid,Acrylate,The mixed solution of hydroxy acrylate and initiator,Heat preservation 2 hours,Cool to 40 DEG C,N is added,N dimethylethanolamines,Stirring 30 minutes,Deionized water is added,Resin solid content is adjusted to 30% 42%,Continue stirring 30 minutes,Filter blowing,The sea shell micropowder modified water-soluble hydroxy polyacrylate resin prepared using the method for the present invention,It is directly blended relative to by sea shell micropowder and water polyacrylic acid,Stability and performance of the sea shell micropowder in resin can be improved.
Description
Technical field
The invention belongs to polymer-modified preparation field, more particularly to a kind of sea shell micropowder modified water-soluble hydroxyl polyacrylic acid
The preparation method of ester resin.
Background technology
Shell is the calcium that protection body soft is formed by by a kind of molluscan secretion of special gland cell
Compound.The calcium carbonate and a small amount of chitin element and protein etc. that the main component of shell is 95%.It is prepared and is polymerize using oyster shell whiting
When object/shell composite material, in order to improve the comprehensive performance of composite material frequently with the method for carrying out surface modification to oyster shell whiting.
If Chinese patent application publication number CN106883642A uses high-temperature calcination that can improve the stability of oyster shell whiting, it is applied to heat preservation
Coating material, but high-temperature calcination does not help the binding force for improving oyster shell whiting and organic coating resin；Aliphatic acid and its salt
It is also used for the modification of oyster shell whiting, but the substance and oyster shell whiting surface binding force be not strong, well firm boundary layer cannot be formed；
The surface that can also be used for oyster shell whiting using silane coupling agent or titante coupling agent is modified, and can be improved oyster shell whiting and be polymerize
The interface compatibility of object is used for the preparation of shell powder composite material；Using aldehyde material（Such as Chinese patent application publication number
CN102604433A）It is reacted with oyster shell whiting and oyster shell whiting surface-active also can be improved, latter two method is changed by the surface of oyster shell whiting
Though property can improve the interface compatibility of oyster shell whiting and organic material, the two is connected in a manner of chemical bond, oyster shell whiting
Still there is an interface with organic resin, water and organic solvent etc. can be permeated by the interface micro chink of the two, be made
Water-fast, the solvent resistance of oyster shell whiting modified organic material are affected.
Invention content
In view of the deficiencies of the prior art, mesh of the invention is to provide a kind of by chemical bond raising oyster shell whiting and resin
A kind of preparation method of sea shell micropowder modified water-soluble polyacrylate resin of intermolecular forces.
To achieve the goals above, the technical solution adopted by the present invention is：
A kind of preparation method of sea shell micropowder modified water-soluble hydroxy polyacrylate resin, includes the following steps：
1, by Silane coupling reagent KH-570（Methacryloxypropyl trimethoxy silane）It is formulated as the second that weight ratio is 50%
Alcoholic solution, sea shell micropowder and KH-570 ethanol solutions press 50:1 ratio mixes 10 minutes in high-speed mixer, makes KH-570
It is uniformly distributed on sea shell micropowder surface, after sea shell micropowder drying drying after mixing, crosses 200 mesh screens and obtain modified shellfish
Shell micro mist；
2, it is added butyl glycol ether in Scattered Kettle, is added step 1 treated modified sea shell micropowder, high-speed stirred 20 minutes,
Modified sea shell micropowder is scatter to obtain the modification shell that modified sea shell micropowder content is 20% in organic solvent butyl glycol ether
Micro mist slurry head；
3, the composition of raw materials of sea shell micropowder modified water-soluble hydroxy polyacrylate resin is：6-10 parts of acrylic acid, 30-60 parts of propylene
Acid esters, 5-20 parts of hydroxy acrylates, 0.5-5 parts of initiators, 2-20 parts of modified sea shell micropowders, are parts by weight above；
4, total amount and second two added in above-mentioned raw materials formula equivalent but the modified sea shell micropowder slurry of deduction are added in a kettle
Then remaining butyl glycol ether after alcohol butyl ether amount presses list of ingredients and modified sea shell micropowder slurry is added in reaction kettle, is warming up to
130 DEG C, it is continuously added to the mixed solution of acrylic acid, acrylate, hydroxy acrylate and initiator, feed time is 4 hours,
2 hours are kept the temperature after adding, cools to 40 DEG C, the N with added acrylic acid equimolar amounts, N- dimethylethanolamines, stirring 30 is added
Minute, deionized water is added, resin solid content is adjusted to 30%-42%, continues stirring 30 minutes, filters blowing.
The acrylate is methyl acrylate, ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, metering system
It is one or more in sour methyl esters, butyl methacrylate.
The hydroxy acrylate is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and methyl-prop
It is one or more in olefin(e) acid hydroxypropyl acrylate.
The initiator is benzoyl peroxide, two different heptan of the benzoyl peroxide tert-butyl ester, azodiisobutyronitrile and azo
One kind in nitrile.
Beneficial effects of the present invention：
The present invention improves a kind of sea shell micropowder modified water-soluble polypropylene of oyster shell whiting and resin intermolecular forces by chemical bond
The preparation method of acid ester resin is first modified oyster shell whiting using KH-570, introduces double bond group on oyster shell whiting surface, so
Add thermal-initiated polymerization after being mixed afterwards with acrylate monomer, is finally keyed oyster shell whiting and acrylate by chemistry
Come, binding force between oyster shell whiting and acrylic resin is improved, to improve the water-fast, resistance to of oyster shell whiting/acrylic resin compound material
The performances such as solvent.
Specific implementation mode
In order to achieve the above object with effect, technical scheme of the present invention is further understood, following spy enumerates preferable implementation
Example, is described in detail below：
Embodiment 1
0.05 part of KH-570 is dissolved in 0.05 part of ethyl alcohol to be uniformly mixed, by 5 parts of sea shell micropowders and KH-570 ethanol solutions in high speed
It is mixed 10 minutes in mixing machine, KH-570 is made to be uniformly distributed on sea shell micropowder surface.By sea shell micropowder drying after mixing
After drying, crosses 200 mesh screens and obtain modified sea shell micropowder.
20 parts of butyl glycol ethers are added in Scattered Kettle, treated modified sea shell micropowder, high-speed stirred 20 is added
Minute, sea shell micropowder is scatter in organic solvent to obtain modified sea shell micropowder slurry.
62 parts of butyl glycol ethers are added in a kettle, reaction kettle is added in the modification sea shell micropowder slurry of above-mentioned preparation
In, 130 DEG C are warming up to, by 10 parts of acrylic acid, 20 parts of butyl acrylates, 30 parts of methyl methacrylates, 15 parts of methacrylic acids
Hydroxyl ethyl ester, 2 parts of azodiisobutyronitriles are weighed and are uniformly mixed, and are added continuously in reaction kettle, feed time is 4 hours, after adding
Heat preservation 2 hours cools to 40 DEG C, and 12.4 parts of N are added, and N- dimethylethanolamines stir 30 minutes, and 41 parts of deionized waters are added,
Continue stirring 30 minutes, filters blowing, obtain sea shell micropowder modified water-soluble hydroxy polyacrylate resin.
Embodiment 2
0.06 part of KH-570 is dissolved in 0.06 part of ethyl alcohol to be uniformly mixed, 6 parts of sea shell micropowders and KH-570 ethanol solutions are pressed in height
It is mixed 10 minutes in fast mixing machine, KH-570 is made to be uniformly distributed on sea shell micropowder surface.Sea shell micropowder after mixing is dried
After dry, cross 200 mesh screens and obtain modified sea shell micropowder.24 parts of butyl glycol ethers are added in Scattered Kettle, above-mentioned place is added
Sea shell micropowder scatter to obtain modified sea shell micropowder slurry by the sea shell micropowder after reason, high-speed stirred 20 minutes in organic solvent
Material.
39 parts of butyl glycol ethers are added in a kettle, reaction kettle is added in the modification sea shell micropowder slurry of above-mentioned preparation
In, it is warming up to 130 DEG C.By 6 parts of acrylic acid, 15 parts of ethyl acrylates, 15 parts of methyl methacrylates, 20 parts of hydroxyethyl methacrylates
Propyl ester, 1 part of benzoyl peroxide are weighed and are uniformly mixed, and are added continuously in reaction kettle, feed time is 4 hours, is protected after adding
Temperature 2 hours cools to 40 DEG C, and 7.4 parts of N are added, and N- dimethylethanolamines stir 30 minutes, and 31.5 parts of deionized waters are added, after
Continuous stirring 30 minutes, filters blowing, obtains sea shell micropowder modified water-soluble hydroxy polyacrylate resin.
Embodiment 3
0.02 part of KH-570 is dissolved in 0.02 part of ethyl alcohol to be uniformly mixed, 2 parts of sea shell micropowders and KH-570 ethanol solutions are pressed in height
It is mixed 10 minutes in fast mixing machine, KH-570 is made to be uniformly distributed on sea shell micropowder surface.Sea shell micropowder after mixing is dried
After dry, cross 200 mesh screens and obtain modified sea shell micropowder.8 parts of butyl glycol ethers are added in Scattered Kettle, above-mentioned processing is added
Sea shell micropowder scatter to obtain modified sea shell micropowder slurry by sea shell micropowder afterwards, high-speed stirred 20 minutes in organic solvent.
32.5 parts of butyl glycol ethers are added in a kettle, reaction kettle is added in the modification sea shell micropowder slurry of above-mentioned preparation
In, 130 DEG C are warming up to, by 8 parts of acrylic acid, 20 parts of butyl methacrylates, 10 parts of hydroxyethyl methacrylates, 0.5 part of azo
Two different heptonitriles, which weigh, to be uniformly mixed, and is added continuously in reaction kettle, and feed time is 4 hours, and 2 hours are kept the temperature after adding, and is cooled down
To 40 DEG C, 9.9 parts of N are added, N- dimethylethanolamines stir 30 minutes, and 20.2 parts of deionized waters are added, and continue 30 points of stirring
Clock filters blowing, obtains sea shell micropowder modified water-soluble hydroxy polyacrylate resin.
Embodiment 4
0.1 part of KH-570 is dissolved in 0.1 part of ethyl alcohol to be uniformly mixed, 10 parts of sea shell micropowders and KH-570 ethanol solutions are pressed in high speed
It is mixed 10 minutes in mixing machine, KH-570 is made to be uniformly distributed on sea shell micropowder surface.By sea shell micropowder drying after mixing
After drying, crosses 200 mesh screens and obtain modified sea shell micropowder.40 parts of butyl glycol ethers are added in Scattered Kettle, above-mentioned processing is added
Sea shell micropowder scatter to obtain modified sea shell micropowder slurry by sea shell micropowder afterwards, high-speed stirred 20 minutes in organic solvent.
49 parts of butyl glycol ethers are added in a kettle, reaction kettle is added in the modification sea shell micropowder slurry of above-mentioned preparation
In, it is warming up to 130 DEG C.By 10 parts of acrylic acid, 10 parts of methyl acrylates, 15 parts of Isooctyl acrylate monomers, 25 parts of methyl methacrylates
Ester, 15 parts of hydroxy-ethyl acrylates, 4 parts of benzoyl peroxides are weighed and are uniformly mixed, and are added continuously in reaction kettle, feed time is
4 hours, 2 hours are kept the temperature after adding, cools to 40 DEG C, 12.4 parts of N are added, N- dimethylethanolamines stir 30 minutes, are added
44.5 parts of deionized waters continue stirring 30 minutes, filter blowing, obtain sea shell micropowder modified water-soluble hydroxy polyacrylate tree
Fat.
Embodiment 5
0.2 part of KH-570 is dissolved in 0.2 part of ethyl alcohol to be uniformly mixed, 20 parts of sea shell micropowders and KH-570 ethanol solutions are pressed in high speed
It is mixed 10 minutes in mixing machine, KH-570 is made to be uniformly distributed on sea shell micropowder surface.By sea shell micropowder drying after mixing
After drying, crosses 200 mesh screens and obtain modified sea shell micropowder.80 parts of butyl glycol ethers are added in Scattered Kettle, above-mentioned processing is added
Sea shell micropowder scatter to obtain modified sea shell micropowder slurry by sea shell micropowder afterwards, high-speed stirred 20 minutes in organic solvent.
35 parts of butyl glycol ethers are added in a kettle, reaction kettle is added in the modification sea shell micropowder slurry of above-mentioned preparation
In, it is warming up to 130 DEG C.By 10 parts of acrylic acid, 25 parts of butyl acrylates, 35 parts of methyl methacrylates, 15 parts of acrylic acid hydroxypropyls
Ester, 5 parts of benzoyl peroxide tert-butyl esters are weighed and are uniformly mixed, and are added continuously in reaction kettle, feed time is 4 hours, is added
2 hours are kept the temperature afterwards, cools to 40 DEG C, 12.4 parts of N are added, N- dimethylethanolamines stir 30 minutes, and 57.5 parts of deionizations are added
Water continues stirring 30 minutes, filters blowing, obtains sea shell micropowder modified water-soluble hydroxy polyacrylate resin.
1 comparative sample of embodiment
0.05 part of KH-570 is dissolved in 0.05 part of ethyl alcohol to be uniformly mixed, 5 parts of sea shell micropowders and KH-570 ethanol solutions are pressed in height
It is mixed 10 minutes in fast mixing machine, KH-570 is made to be uniformly distributed on sea shell micropowder surface.Sea shell micropowder after mixing is dried
After dry, cross 200 mesh screens and obtain modified sea shell micropowder.20 parts of butyl glycol ethers are added in Scattered Kettle, above-mentioned place is added
It is micro- to be scatter to obtain modified shell by the modification sea shell micropowder after reason, high-speed stirred 20 minutes in organic solvent for sea shell micropowder
Slurry material.
In a kettle be added 62 parts of butyl glycol ethers, be warming up to 130 DEG C, by 10 parts of acrylic acid, 20 parts of butyl acrylates,
30 parts of methyl methacrylates, 15 parts of hydroxyethyl methacrylates, 2 parts of azodiisobutyronitriles are weighed and are uniformly mixed, and are continuously added to
Into reaction kettle, feed time is 4 hours, and 2 hours are kept the temperature after adding, and after reaction, cools to 40 DEG C, 12.4 parts of N are added,
N- dimethylethanolamines stir 30 minutes, and 41 parts of deionized waters are added, and continue stirring 30 minutes, the modification of above-mentioned preparation is added
Sea shell micropowder slurry continues stirring 30 minutes, filters blowing, obtains sea shell micropowder and water-based hydroxyl polyacrylate resin physics
Contrast sample is blended.
Resin prepared by embodiment 1 and 1 comparative sample of embodiment is pressed into surface compositions and is configured to coating：
100 parts of resin
Amino resins（Cyanogen spy 325）10 parts
0.5 part of wetting agent
0.2 part of antifoaming agent
50 parts of ethyl alcohol
30 parts of water
It by prepared coating even application on tinplate, is toasted 20 minutes at 160 DEG C, taking-up is stood overnight, test
24 hours water resistances and 4 hours resistance to 50% alcohol performances, test comparison result such as table one：
Table one
| Resin variety | Water resistance（24 hours） | Resistance to ethyl alcohol（50%, 4 hours） |
| Embodiment 1 | It is unchanged | It is unchanged |
| 1 comparative sample of embodiment | White spotted finiss | Whiten, blister |
The present invention is modified oyster shell whiting using KH-570, and in the processing procedure, the methoxy silane key in KH-570 exists
Hydrolyzed under the action of ethyl alcohol and moisture in air, generate with reactivity silicone hydroxyl and with the activity on oyster shell whiting surface
Base reaction by chemical bond by KH-570 so that be connected to oyster shell whiting surface, and the KH-570 strand other ends just make with double bond
Oyster shell whiting carries the double bond group with reactivity by modified on surface.
During resin polymerization, in the sea shell micropowder that acrylic acid, acrylate, hydroxy acrylate and KH-570 are modified
Double bond group initiator and heating under the action of pass through radical addition polymerization reaction generate chemistry key connection macromolecular
Structure is also anchored at sea shell micropowder in a manner of chemical bond on organic macromolecule chain.Finally by oyster shell whiting and acrylate tree
Fat is connected by chemical bond, binding force between oyster shell whiting and acrylic resin is improved, to improve oyster shell whiting/acrylic resin
The performances such as the water-fast of composite material, solvent resistant.
Claims (4)
1. a kind of preparation method of sea shell micropowder modified water-soluble hydroxy polyacrylate resin, it is characterised in that：Preparation method
Include the following steps：
（1）, silane coupling agent methacryloxypropyl trimethoxy silane KH-570 is formulated as to the second that weight ratio is 50%
Alcoholic solution, sea shell micropowder and the KH-570 ethanol solutions press 50:1 ratio mixes 10 minutes in high-speed mixer, makes institute
It states KH-570 to be uniformly distributed on the sea shell micropowder surface, after sea shell micropowder drying drying after mixing, crosses 200 mesh sieve
Net obtains modified sea shell micropowder；
（2）, in Scattered Kettle be added butyl glycol ether after, be added step（1）Treated the modified sea shell micropowder, high-speed stirring
It mixes 20 minutes, scattering to obtain modified sea shell micropowder content in organic solvent butyl glycol ether by the modified sea shell micropowder is
20% modification sea shell micropowder slurry；
（3）, sea shell micropowder modified water-soluble hydroxy polyacrylate resin composition of raw materials be：6-10 parts of acrylic acid, 30-60 parts third
Olefin(e) acid ester, 5-20 parts of hydroxy acrylates, 0.5-5 parts of initiators, the 2-20 parts of modified sea shell micropowders, are parts by weight above
Number；
（4）, total amount and above-mentioned raw materials formula equivalent is added in a kettle but deducts second added in modified sea shell micropowder slurry
Then remaining butyl glycol ether after glycol butyl ether amount presses list of ingredients and the modified sea shell micropowder slurry is added in reaction kettle,
130 DEG C are warming up to, the mixed solution of acrylic acid, acrylate, hydroxy acrylate and initiator is continuously added to, feed time is
4 hours, 2 hours are kept the temperature after adding, cools to 40 DEG C, is added the N with added acrylic acid equimolar amounts, N- dimethylethanolamines,
Stirring 30 minutes is added deionized water, resin solid content is adjusted to 30%-42%, continues stirring 30 minutes, filters blowing.
2. a kind of preparation method of sea shell micropowder modified water-soluble hydroxy polyacrylate resin as described in claim 1, special
Sign is：The acrylate is methyl acrylate, ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, methacrylic acid
It is one or more in methyl esters, butyl methacrylate.
3. a kind of preparation method of sea shell micropowder modified water-soluble hydroxy polyacrylate resin as described in claim 1, special
Sign is：The hydroxy acrylate is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and metering system
It is one or more in sour hydroxypropyl acrylate.
4. a kind of preparation method of sea shell micropowder modified water-soluble hydroxy polyacrylate resin as described in claim 1, special
Sign is：The initiator is benzoyl peroxide, the benzoyl peroxide tert-butyl ester, azodiisobutyronitrile and azobisisoheptonitrile
In one kind.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810117479.5A CN108484845A (en) | 2018-02-06 | 2018-02-06 | A kind of preparation method of sea shell micropowder modified water-soluble hydroxy polyacrylate resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810117479.5A CN108484845A (en) | 2018-02-06 | 2018-02-06 | A kind of preparation method of sea shell micropowder modified water-soluble hydroxy polyacrylate resin |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101082182A (en) * | 2007-06-29 | 2007-12-05 | 东华大学 | Preparation of shell micro-powder reinforced super-high molecular weight polyethylene fibre composite non woven cloth |
| CN102604433A (en) * | 2012-02-14 | 2012-07-25 | 浙江大学 | Preparation method of aldehyde modified shell micro powder |
| CN103571235A (en) * | 2013-10-28 | 2014-02-12 | 浙江大学舟山海洋研究中心 | Preparation method of prismatic biological calcium carbonate |
| CN104294603A (en) * | 2014-08-01 | 2015-01-21 | 国家海洋局第三海洋研究所 | Preparation method for shell-based environment-friendly weaving coating adhesive |
| CN104558447A (en) * | 2014-12-12 | 2015-04-29 | 杭州吉华高分子材料股份有限公司 | Inorganic nano composite anti-doodling resin and preparation method thereof |
-
2018
- 2018-02-06 CN CN201810117479.5A patent/CN108484845A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101082182A (en) * | 2007-06-29 | 2007-12-05 | 东华大学 | Preparation of shell micro-powder reinforced super-high molecular weight polyethylene fibre composite non woven cloth |
| CN102604433A (en) * | 2012-02-14 | 2012-07-25 | 浙江大学 | Preparation method of aldehyde modified shell micro powder |
| CN103571235A (en) * | 2013-10-28 | 2014-02-12 | 浙江大学舟山海洋研究中心 | Preparation method of prismatic biological calcium carbonate |
| CN104294603A (en) * | 2014-08-01 | 2015-01-21 | 国家海洋局第三海洋研究所 | Preparation method for shell-based environment-friendly weaving coating adhesive |
| CN104558447A (en) * | 2014-12-12 | 2015-04-29 | 杭州吉华高分子材料股份有限公司 | Inorganic nano composite anti-doodling resin and preparation method thereof |
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Application publication date: 20180904 |