CN1887926A - Silicone modified polyacrylate and its prepn and application - Google Patents
Silicone modified polyacrylate and its prepn and application Download PDFInfo
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- CN1887926A CN1887926A CN 200610061104 CN200610061104A CN1887926A CN 1887926 A CN1887926 A CN 1887926A CN 200610061104 CN200610061104 CN 200610061104 CN 200610061104 A CN200610061104 A CN 200610061104A CN 1887926 A CN1887926 A CN 1887926A
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- modified polyacrylate
- acrylate
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Abstract
The present invention relates to water soluble organosilicon modified polyacrylate and its preparation process. The organosilicon modified polyacrylate has number average molecular weight of 33,000-70,000, and is prepared through the first free radical polymerization with monomers, including (methyl) acrylate 15-85 wt%, hydroxyl group containing acrylate 6-18 wt%, (methyl) acrylic acid 5-17 wt%, styrene 0-25 wt%, acrylonitrile 0-15 wt%, Veova 0-30 wt% and vinyl siloxane 1-20 wt%, under the action of initiator inside alcohol or alcohol ether medium, and the subsequent neutralization with ammonia or organic amine to produce salt. The polymer of the present invention has high storage stability, high water resistance, high chemical resistance, excellent heat resistance and electric insulating performance, and may be used widely as filming material for various paint products.
Description
Technical field
The present invention relates to silicone modified polyacrylate, relate in particular to a kind of water-soluble organic silicon modified polyacrylate and its production and application.
Background technology
Because good film forming properties, the acrylic ester polymer water miscible liquid has been widely used in the filmogen of coating, generally uses in building coating.But its pollution resistance is bad, and is water-fast and weather resisteant is all relatively poor, can not satisfy application and application requiring as base materials such as metal, glass, carbon fibers.Thus, the product of modification occurred acrylic polymers is carried out, normally introduced organosilicon and carry out modification, silicone compounds commonly used utilizes the Si-O bond energy bigger than C-C key bond energy, to light, thermally-stabilised, is difficult for the characteristic of degraded.What adopt in early days is to add silicone resin in acrylic polymers, yet this two base polymers consistency is not good enough, makes the storage and the construction existing problems of this class coating.What in recent years, research was maximum is that acrylic polymers is carried out chemical modification.In U.S. Pat 5214095, disclose a kind of ethylenically unsaturated monomer and a kind of hydrolyzable silane is introduced in the emulsion polymerization systems simultaneously in the presence of a kind of water-containing solvent, thereby the dispersion stabilization of the water miscible liquid that obtains is poor.Even will add in this water miscible liquid as the dispersion agent or the emulsifying agent of stablizer, when adding coating formation promotor or mineral dye in this water miscible liquid, the cohesion of water miscible liquid might take place still.At this moment,
Even form that promotor or mineral dye can mix with water miscible liquid and when not occurring condensing in coating, the gloss difference of the coating that obtains by this emulsion.In addition, must use a large amount of stablizers, thereby the poor water resistance of the coating that obtains by this emulsion.Chinese patent CN94194922.2 discloses a kind of silicone-modified acrylate polymer emulsion, wherein uses to contain sulfonic ethylenically unsaturated monomer, still has stability problem, and its water tolerance is also satisfactory inadequately on the other hand.Chinese patent CN01105010.1 discloses a kind of organosilicon-modified acrylate emulsion, and it is at the polysiloxane of polymerization reaction late stage introducing hydroxyl, however the poor water resistance of this emulsion.
Summary of the invention
An object of the present invention is to overcome the deficiencies in the prior art, a kind of water miscible organic-silicon-modified acrylic ester polymer is provided.
Another object of the present invention provides a kind of water miscible organic-silicon-modified acrylic ester polymer of water-tolerant.
Another object of the present invention provides the preparation method of water miscible organic-silicon-modified acrylic ester polymer.
A further object of the invention provides a kind of application method of the aqueous solution in coating of organic-silicon-modified acrylic ester polymer.
For achieving the above object, technical scheme provided by the invention is:
A kind of silicone modified polyacrylate, the number-average molecular weight of this polymkeric substance is 33,000-70,000, radical polymerization can take place under the initiator effect by the vinylsiloxane of vinyl cyanide, 0-30% tertiary ethylene carbonate and the 1-20% of the vinylbenzene of (methyl) vinylformic acid of the hydroxy acryl acid ester of (methyl) acrylate of monomer: 15-85%, 6-18%, 5-17%, 0-25%, 0-15% in it in alcohols or pure ethers medium, with making with salify in ammonia or the organic amine, wherein each monomeric per-cent is mass percent again.
As the present invention's technical scheme on the other hand:
A kind of preparation method of silicone modified polyacrylate comprises:
I. monomer pre-mixing
(methyl) acrylate, the hydroxy acryl acid ester of 6-18%, (methyl) vinylformic acid of 5-17%, the vinylbenzene of 0-25%, the vinyl cyanide of 0-15%, the 0-30% tertiary ethylene carbonate of 15-85% are mixed, and add initiator and mix, obtain the monomer premixture;
Ii. polyreaction
To handle and the reactor that adds reaction medium under agitation is warmed up to 80-100 ℃ through rare gas element, the monomer premixture of Dropwise 5 0% in 1-2 hour, control reaction temperature 100-130 ℃, interrupt dripping monomer premixture isothermal reaction 1-3 hour, therebetween vinylsiloxane is joined in the monomer premixture, continue to drip monomer mixture, the control rate of addition carries out reaction constant temperature, dropwise the continuation isothermal reaction, termination reaction when assaying reaction thing viscosity is 80-90s;
Iii. in and salify
The product of polyreaction is cooled to 40-45 ℃, add in ammonia or the organic amine and salify.
Owing to adopt chemical method the Si-O key to be incorporated in the side chain of polymkeric substance, heat-resisting, the chemical resistant properties of the polymkeric substance after the modification are improved, and owing in polymkeric substance, contain unreacted hydroxyl, make polymkeric substance to cooperate, can make the coating of base materials such as suitable metal, vitreous carbon fiber with amino polymer, isocyanate polymer.
Embodiment
(methyl) of the present invention acrylate can be selected (methyl) vinylformic acid C for use
1-C
8The mixture of any one in the alkyl ester or its any several arbitrary proportions.
Preferred Hydroxyethyl acrylate of hydroxy acrylate of the present invention or Propylene glycol monoacrylate.
Vinylsiloxane preferred formula of the present invention is CH
2=CHSi (OR
1)
3Siloxanes, R wherein
1It is alkyl.Especially preferred R
1Be C
1-C
4The vinylsiloxane of alkyl.Vinylsiloxane used in the present invention can be made by the vinyl trichloro silane catalyzed alcoholysis.
The present invention is described by the following examples.
1. vinylsiloxane preparation
By stoichiometry, organosilicon raw material vinyl trichloro silane 100g is dropped into reactor, with ethanol 69g dissolving Pt (PPh
3)
4Be put into behind the 1g in the header tank, 13 ± 1 ℃ of control temperature of reaction kettle drip high-order tank liquor, and the dropping time was controlled at 4.5 hours, and the isothermal reaction time was at 6.5 hours.According to the HCl amount control reaction end that reaction is emitted, the vacuum filtration unreacted monomer, recording transformation efficiency is that state is 72%.HCl adopts intensification nitrogen method to remove.
2. polymkeric substance is synthetic
(1) prescription
Polymkeric substance one prescription:
| Monomer mass percentage ratio (%) in the monomer premixture | Initiator accounts for monomer premixture mass percent (%) | The trimethyl-ethylene siloxanes accounts for monomer premixture mass percent (%) | |||||
| Vinylformic acid | Butyl acrylate | Propylene glycol monoacrylate | Methyl methacrylate | Vinylbenzene | Hydrogen phosphide cumene | Azo two isobutyls are fine | The trimethyl-ethylene siloxanes |
| 6 | 45 | 7 | 21 | 21 | 2 | 1.5 | 5 |
Polymkeric substance two prescriptions:
| Monomer mass percentage ratio (%) in the monomer premixture | Initiator accounts for monomer premixture mass percent (%) | The trimethyl-ethylene siloxanes accounts for monomer premixture mass percent (%) | |||||
| Vinylformic acid | Butyl methacrylate | Hydroxyethyl acrylate | Methyl methacrylate | Vinyl cyanide | Hydrogen phosphide cumene | Azo two isobutyls are fine | The trimethyl-ethylene siloxanes |
| 9 | 38 | 12 | 31 | 10 | 1.5 | 1.5 | 8 |
Polymkeric substance three prescriptions:
| Monomer mass percentage ratio (%) in the monomer premixture | Initiator accounts for monomer premixture mass percent (%) | The trimethyl-ethylene siloxanes accounts for monomer premixture mass percent (%) | |||||
| Vinylformic acid | Butyl acrylate | Propylene glycol monoacrylate | Methyl methacrylate | Tertiary ethylene carbonate | Hydrogen phosphide cumene | Diisopropyl azodicarboxylate | The trimethyl-ethylene siloxanes |
| 11 | 40 | 7 | 21 | 21 | 2 | 1.5 | 11 |
(2) processing step and operational condition
After monomer removes stopper, at first press the technical recipe regulation and monomer is added in the configuration still, after mixing through filter.Then hydrogen phosphide cumene and Diisopropyl azodicarboxylate are also dropped in the configuration still and monomer mixes, put into header tank.
With rare gas element clearance response still, treat excluding air after, press monomer weight percentage ratio 50% and add reaction medium propylene glycol butyl ether, continue to feed rare gas element, material in reactor under agitation is warming up to 80 ℃.Stop heating, drip monomer and initiator mixture, appoint the interior monomeric heat of polymerization of reactor that material temperature is risen to 105 ℃ of temperature of reaction automatically.In 1-1.5 hour, drip monomer and initiator mixture amount and reach 50% o'clock of its total amount, interrupt dripping isothermal reaction 1 hour.
Meanwhile, the trimethyl-ethylene siloxanes is joined in the header tank of dress monomer and initiator mixture, and stir.After 1 hour, continue to drip the mixture of monomer, initiator trimethyl-ethylene siloxanes, and the control rate of addition, make the temperature of reaction of material keep constant.Last material added at 2 hours, and isothermal reaction is 3 hours again, assaying reaction viscosity reach 85s (be coated with-4 glasss, 25 ℃, polymkeric substance: dehydrated alcohol=1: 2), termination reaction.
With interlayer cooling water temperature to 40 ℃, by metering, add 28% ammoniacal liquor, the limit edged stirs, and is that 7.5-8.5 gets final product with PH instrumentation pH value.
Obtain the polymkeric substance of three prescriptions respectively, its performance sees the following form:
| Index name | The polymkeric substance of filling a prescription | Two polymkeric substance of filling a prescription | The prescription terpolymer | Remarks |
| Outward appearance | Faint yellow viscous fluid | Faint yellow viscous fluid | Faint yellow viscous fluid | Range estimation |
| Number-average molecular weight (Mn) | 48580 | 51360 | 49870 | Membrane osmotic pressure method |
| Softening temperature | 83 | 107 | 96 | Ring and ball method |
| Solid content (%) | 64.5 | 66.7 | 65.3 | Press GB1725-79 (88) |
| Viscosity (is coated with-4,25 ℃, s) | 87 | 97 | 89 | Press GB1723-79 (polymkeric substance: water=1: 0.5) |
| PH value | 7.5 | 7.5 | 7.5 | The PH test paper |
3. the Application Example---water-soluble silicon third resin glass baking varnish
Fill a prescription two polymkeric substance, 15g butyl ether melamine resin solidifying agent, 1g BYK-028 defoamer, 30g Virahol, 154 pure water of 100g are mixed and stir evenly.Filter with 400 mesh filter screens, obtain the water-soluble silicon third resin glass baking varnish.It refers to see the following form:
| Test event | Outward appearance | Solid content (%) | Viscosity (is coated with-4,25 ℃, s) | PH value |
| Test result | Faint yellow viscous fluid | 25.3 | 23 | 7.3 |
Be sprayed on glass pane surface with this varnish, be put in behind the surface drying in the baking oven, in 160 ℃ of bakings 40 minutes, film thickness was the 10-15 micron.Surveying its performance sees the following form:
| Test event | Film thickness (micron) | Hardness (H) | Anti-acetone wiping (inferior) | Water tolerance (hour) |
| Test result | 10-15 | 4 | 100 | 72 |
Above embodiment describes in detail the present invention, but to should not be construed be any limitation of the invention to embodiment.Any modification of being done in the claim scope all is subjected to protection of the present invention.
Claims (10)
1. silicone modified polyacrylate, the number-average molecular weight of this polymkeric substance is 33,000-70,000, radical polymerization can take place under the initiator effect by the vinylsiloxane of vinyl cyanide, 0-30% tertiary ethylene carbonate and the 1-20% of the vinylbenzene of (methyl) vinylformic acid of the hydroxy acryl acid ester of (methyl) acrylate of monomer: 15-85%, 6-18%, 5-17%, 0-25%, 0-15% in it in alcohols or pure ethers medium, with making with salify in ammonia or the organic amine, wherein each monomeric per-cent is mass percent again.
2. silicone modified polyacrylate according to claim 1 is characterized in that described (methyl) acrylate is (methyl) vinylformic acid C
1-C
8The mixture of any one in the alkyl ester or its arbitrary proportion.
3. silicone modified polyacrylate according to claim 2 is characterized in that described (methyl) acrylate is (methyl) butyl acrylate or (methyl) isobutyl acrylate.
4. silicone modified polyacrylate according to claim 1 is characterized in that described hydroxy acrylate is Hydroxyethyl acrylate or Propylene glycol monoacrylate.
5. silicone modified polyacrylate according to claim 1 is characterized in that described vinylsiloxane general formula is CH
2=CHSi (OR
1)
3, R wherein
1Be C
1-C
4Alkyl.
6. the preparation method of a silicone modified polyacrylate comprises:
(1) monomer pre-mixing
(methyl) acrylate, the hydroxy acryl acid ester of 6-18%, (methyl) vinylformic acid of 5-17%, the vinylbenzene of 0-25%, the vinyl cyanide of 0-15%, the 0-30% tertiary ethylene carbonate of 15-85% are mixed, and add initiator and mix, obtain the monomer premixture;
(2) polyreaction
To handle and the reactor that adds reaction medium under agitation is warmed up to 80-100 ℃ through rare gas element, the monomer premixture of Dropwise 5 0% in 1-2.0 hour, control reaction temperature 100-130 ℃, interrupt dripping monomer premixture isothermal reaction 1-3 hour, therebetween vinylsiloxane is joined in the monomer premixture, continue to drip monomer mixture, the control rate of addition carries out reaction constant temperature, dropwise the continuation isothermal reaction, termination reaction when assaying reaction thing viscosity is 80-90s;
(3) in and salify
The product of polyreaction is cooled to 40-45 ℃, add in ammonia or the organic amine and salify.
7. the preparation method of silicone modified polyacrylate according to claim 6, it is characterized in that wherein initiator is a kind of or two kinds of mixing in hydrogen phosphide cumene and the Diisopropyl azodicarboxylate, consumption is respectively the 1-3% and the 0.5-2% of monomer premixture total mass.
8. the preparation method of silicone modified polyacrylate according to claim 6 is characterized in that reaction medium wherein is alcohol or pure ethers organic solvent.
9. the preparation method of silicone modified polyacrylate according to claim 6 is characterized in that with ammoniacal liquor in the product of polyreaction and salify, and regulates pH value to 7.5-8.5.
10. each the application of the aqueous solution in coating of polymkeric substance of claim 1-5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100611049A CN100410286C (en) | 2006-06-07 | 2006-06-07 | Silicone modified polyacrylate and its prepn and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100611049A CN100410286C (en) | 2006-06-07 | 2006-06-07 | Silicone modified polyacrylate and its prepn and application |
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| Publication Number | Publication Date |
|---|---|
| CN1887926A true CN1887926A (en) | 2007-01-03 |
| CN100410286C CN100410286C (en) | 2008-08-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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