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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- Prior art keywords
- methyl
- modified polyacrylate
- acrylate
- monomer
- silicone modified
- Prior art date
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Links
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 21
- 229920001296 polysiloxane Polymers 0.000 title claims description 16
- 239000000178 monomer Substances 0.000 claims abstract description 39
- -1 vinyl siloxane Chemical class 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001412 amines Chemical class 0.000 claims abstract description 5
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 5
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 8
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000012429 reaction media Substances 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract 2
- 238000006386 neutralization reaction Methods 0.000 abstract 1
- 239000003973 paint Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 229920002554 vinyl polymer Polymers 0.000 abstract 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N trimethyl-ethylene Natural products CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 229920006222 acrylic ester polymer Polymers 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 2
- 239000005050 vinyl trichlorosilane Substances 0.000 description 2
- DAXZJJHDDZHZPA-UHFFFAOYSA-N 1-butoxybutane;1,3,5-triazine-2,4,6-triamine Chemical compound CCCCOCCCC.NC1=NC(N)=NC(N)=N1 DAXZJJHDDZHZPA-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
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 |
Applications Claiming Priority (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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1887926A true CN1887926A (en) | 2007-01-03 |
| CN100410286C CN100410286C (en) | 2008-08-13 |
Family
ID=37577210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100611049A Expired - Fee Related CN100410286C (en) | 2006-06-07 | 2006-06-07 | Silicone modified polyacrylate and its prepn and application |
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| Country | Link |
|---|---|
| CN (1) | CN100410286C (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102220726A (en) * | 2011-06-10 | 2011-10-19 | 珠海市乐通化工股份有限公司 | Waterborne varnish replacing covered film |
| CN101724326B (en) * | 2009-12-14 | 2012-07-04 | 杭州师范大学 | Waterborne organic silicon-acrylic acid self-stratifying coating |
| CN101638299B (en) * | 2008-08-01 | 2012-07-18 | 绵阳惠利电子材料有限公司 | Laminated glass edge protective coating |
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