CN105985522B - Highly branched polysiloxanes and hybrid materials and methods of forming the same - Google Patents
Highly branched polysiloxanes and hybrid materials and methods of forming the same Download PDFInfo
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- CN105985522B CN105985522B CN201510083438.5A CN201510083438A CN105985522B CN 105985522 B CN105985522 B CN 105985522B CN 201510083438 A CN201510083438 A CN 201510083438A CN 105985522 B CN105985522 B CN 105985522B
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- -1 polysiloxanes Polymers 0.000 title claims abstract description 68
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title claims description 34
- 238000000034 method Methods 0.000 title claims description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910000077 silane Inorganic materials 0.000 claims abstract description 87
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 56
- 239000000377 silicon dioxide Substances 0.000 claims description 25
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- 125000003368 amide group Chemical group 0.000 claims description 9
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 238000006701 autoxidation reaction Methods 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 125000001931 aliphatic group Chemical group 0.000 abstract 3
- 125000003277 amino group Chemical group 0.000 abstract 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 98
- 239000010408 film Substances 0.000 description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- 238000003756 stirring Methods 0.000 description 37
- 239000007788 liquid Substances 0.000 description 34
- 239000007864 aqueous solution Substances 0.000 description 22
- MSGKKIDCUSRVQE-UHFFFAOYSA-N C[Si](=O)C.CN(C=O)C Chemical compound C[Si](=O)C.CN(C=O)C MSGKKIDCUSRVQE-UHFFFAOYSA-N 0.000 description 20
- 230000003301 hydrolyzing effect Effects 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 12
- HZBAVWLZSLOCFR-UHFFFAOYSA-N oxosilane Chemical compound [SiH2]=O HZBAVWLZSLOCFR-UHFFFAOYSA-N 0.000 description 11
- 238000010992 reflux Methods 0.000 description 11
- 210000003097 mucus Anatomy 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- CRUILBNAQILVHZ-UHFFFAOYSA-N 1,2,3-trimethoxybenzene Chemical compound COC1=CC=CC(OC)=C1OC CRUILBNAQILVHZ-UHFFFAOYSA-N 0.000 description 8
- 101100373011 Drosophila melanogaster wapl gene Proteins 0.000 description 8
- 210000004483 pasc Anatomy 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 238000001879 gelation Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229940030010 trimethoxybenzene Drugs 0.000 description 4
- 241000790917 Dioxys <bee> Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910003978 SiClx Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 229920005573 silicon-containing polymer Polymers 0.000 description 2
- 238000013517 stratification Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Abstract
The highly branched polysiloxane of the present invention comprises: 1 part by weight of oligomer of first silane and 0.05 to 20 parts by weight of second silane, wherein the first silane is Si (R)1)2(OR2)2Each R of1Each independently being an acrylic group, an epoxy group, a vinyl group, an amino group, an aromatic group, or an aliphatic group, and each R2Each is an aliphatic group; wherein the second silane is Si (R)3)(OR4)3，R3Is an acrylic group, an epoxy group, a vinyl group, an amino group, an aromatic group, or an aliphatic group, and each R is4Each is an aliphatic radical.
Description
[technical field]
The present invention relates to hybrid material, relate more particularly to the composition and forming method of its high branch's polysiloxanes.
[background technique]
The products such as 3C electronics, display or illumination develop both facing to light and short direction.Thickness of glass as substrate
It is gradually reduced from a few micrometers toward 0.1 microns, and frangible glass needs transparent protective layer.Transparent protective layer needs heat-resisting
Property, to reach the process requirement (at least 300~350 DEG C) of existing plating ITO.Usually as the high molecular material of protective layer, in addition to this
Body has outside coloring problem, can also xanthochromia crossing high temperature.At present can high temperature resistant transparent selection is silicone (silicone) system again
The polysiloxanes (polysiloxane) of system, therefore developing new silicone materials or its manufacturing method thereof is trend of the times.
[summary of the invention]
One embodiment of the invention provide high branch's polysiloxanes, be by the oligomer of the first silane of 1 parts by weight, with
Second crosslinked with silicane of 0.05 to 20 parts by weight forms, wherein the first silane is Si (R1)2(OR2)2, every R1Respectively acrylic acid
Base, epoxy group, vinyl, amido, aromatic radical or fat-based, and every R2Respectively fat-based；Wherein the second silane is Si
(R3)(OR4)3, R3For acrylic, epoxy group, vinyl, amido or fat-based, and every R4Respectively fat-based.
The hybrid material that one embodiment of the invention provides, is by above-mentioned high branch's polysiloxanes and 0.01 to 70 weight
There is the inorganic oxide of hydroxyl to react on the surface of amount part.
One embodiment of the invention provides the forming method of high branch's polysiloxanes, comprising: takes the first silane of 1 parts by weight
Oligomer forms high branch's polysiloxanes with the second crosslinked with silicane of 0.05 to 20 parts by weight, wherein the first silane is Si (R1)2
(OR2)2, every R1Respectively acrylic, epoxy group, vinyl, amido, aromatic radical or fat-based, and every R2Respectively
Fat-based；Wherein the second silane is Si (R3)(OR4)3, R3For acrylic, epoxy group, vinyl, amido, aromatic radical or rouge
Fat base, and every R4Respectively fat-based.
The forming method for the hybrid material that one embodiment of the invention provides, comprising: above-mentioned high branch's polysiloxanes is taken, with
And 0.01 to 70 parts by weight surface have hydroxyl inorganic oxide react.
[Detailed description of the invention]
Fig. 1 is the schematic diagram of the forming method of high branch's polysiloxanes and hybrid material in one embodiment of the invention.
[description of symbols]
1 first silane；
3 oligomers；
5 second silane；
7 high branch's polysiloxanes；
9 surfaces have the inorganic oxide of hydroxyl；
11 hybrid materials.
[specific embodiment]
As shown in Figure 1, the first silane 1 of 1 parts by weight hydrolytic polymerization in acidic aqueous solution is taken to form oligomer 3.At this
It invents in an embodiment, the structure of the first silane 1 is Si (R1)2(OR2)2, every R1Respectively acrylic, epoxy group, second
Alkenyl, amido, aromatic radical or fat-based, and every R2Respectively fat-based.It is acid water-soluble in an embodiment of the present invention
Liquid further includes alcohols such as methanol, ethyl alcohol, isopropanol, to adjust hydrolysis rate.The viscosity of above-mentioned oligomer can be between 10cps
To between 500cps.If the viscosity of oligomer is excessively high, the product being subsequently formed easily is atomized.If the viscosity of oligomer is too low,
Gelation problems are not can avoid when subsequent cross-linking step then.
Then the second silane 5 of 0.05 to 20 parts by weight or 0.1 to 10 parts by weight is taken to mix with the solution of above-mentioned oligomer,
It is cross-linked to form high branch's polysiloxanes 7.Second silane 5 is Si (R3)(OR4)3, R3For acrylic, epoxy group, vinyl, amine
Base, aromatic radical or fat-based, and every R4Respectively fat-based.If the dosage of the second silane 5 is excessively high, cross-linking products are easily solidifying
Gelatinization and subsequent applications can not be carried out.If the dosage of the second silane 5 is too low, Ze Gao branch polysiloxanes is in coating film forming after-hardening
Not exclusively.
In the present invention, fat-based can be straight chain or branching, saturated or unsaturated, such as can be selected from 1-18
A carbon atom, alkyl, naphthenic base, alkenyl and the alkynyl of especially 1-10 carbon atom.Fat-based useful in this application
Example includes methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, neopentyl, uncle
Amyl, hexyl such as n-hexyl, heptyl such as n-heptyl, octyl such as n-octyl, iso-octyl and 2,2,4- tri-methyl-amyls, nonyl
Base such as n-nonyl, decyl such as positive decyl, dodecyl, octadecyl, naphthenic base such as cyclopenta, cyclohexyl, suberyl
And methylcyclohexyl, vinyl, acrylic, allyl, methacrylic, acetenyl, propinyl, methylacetylenyl.Aromatic radical
Including aryl, aralkyl or alkaryl with 6-20 carbon atom.The example of aryl useful in this application includes phenyl,
Xenyl, naphthalene, o-, m- and p- tolyl, xylyl, benzyl, ethylphenyl.
In an embodiment of the present invention, it can further take the surface of 0.01 to 70 parts by weight that there is the inorganic oxide of hydroxyl
Object 9 is reacted with above-mentioned high branch's polysiloxanes 7, forms hybrid material 11.The hydroxyl and inorganic oxide of high branch's polysiloxanes 7
Hydroxyls dehydrate formation-the O-Si-O- on 9 surfaces is bonded.If the dosage of inorganic oxide is excessively high, easily (aggregation) is agglomerated
And reduce the light transmittance of hybrid material.In an embodiment of the present invention, inorganic oxide 9 can be silica, titanium oxide, oxidation
Aluminium or combinations of the above.In an embodiment of the present invention, the partial size of inorganic oxide 9 is between 0.1nm between 1000nm.
If the partial size of inorganic oxide is excessive, product transparency is influenced.
Above-mentioned hybrid material 11 can be coated on substrate such as glass or ceramics, and protective coating can be formed after heat hardening.
In an embodiment of the present invention, the light transmittance of protective coating is between 90% to 99.9%, and heat resistance can be of about 450
℃.Above-mentioned high transparency and the clear coat of high heat resistance can effectively protect substrate.
In order to which above and other purpose, feature and advantage of the invention can be clearer and more comprehensible, several embodiments are cited below particularly
The appended diagram of cooperation, is described in detail below:
Embodiment
Embodiment 1 (the second silane/the first silane=5:1)
By 10g dimethylformamide dimethyl oxosilane, 72.0g isopropanol, 6.0g0.01MHCl aqueous solution and 26.3g deionized water
It pours into 1L round-bottomed bottle and mixes, stirring at 35 DEG C makes its hydrolytic polymerization form oligomer, 50~200cps of viscosity for 1.5 hours.
Then 50g methyl trimethoxy oxosilane is added in above-mentioned oligomer, stirs 1.5 hours at 35 DEG C to be cross-linked to form the poly- silicon of high branch
Oxygen alkane.Through water removal and isopropanol is concentrated under reduced pressure, transparent mucus is obtained.
It is heated to 170 DEG C of hardening after above-mentioned hyalomucoid is formed a film with blade coating, is formed with a thickness of 0.1~200 μm
Film (baking oven film forming).The heat resistance of above-mentioned film is up to 210 DEG C, and transparency is 92% (colorimeter).
Embodiment 2 (the second silane/the first silane=3:1)
By 15g dimethylformamide dimethyl oxosilane, 72.0g isopropanol, 6.0g0.01MHCl aqueous solution and 26.6g deionized water
It pours into 1L round-bottomed bottle and mixes, stirring at 35 DEG C makes its hydrolytic polymerization form oligomer, 50~200cps of viscosity for 1.5 hours.
Then 45g methyl trimethoxy oxosilane is added in above-mentioned oligomer, stirs 1.5 hours at 35 DEG C to be cross-linked to form the poly- silicon of high branch
Oxygen alkane.Through water removal and isopropanol is concentrated under reduced pressure, transparent mucus is obtained.
It is heated to 170 DEG C of hardening after above-mentioned transparent mucus is formed a film with blade coating, is formed with a thickness of 0.1~200 μm
Film (baking oven film forming).The heat resistance of above-mentioned film is 210 DEG C, and transparency is 92% (colorimeter).
Embodiment 3 (the second silane/the first silane=1:1)
By 30g dimethylformamide dimethyl oxosilane, 72.0g isopropanol, 6.0g0.01MHCl aqueous solution and 27.8g deionized water
It pours into 1L round-bottomed bottle and mixes, stirring at 35 DEG C makes its hydrolytic polymerization form oligomer, 50~200cps of viscosity for 1.5 hours.
Then 30g methyl trimethoxy oxosilane is added in above-mentioned oligomer, stirs 1.5 hours at 35 DEG C to be cross-linked to form the poly- silicon of high branch
Oxygen alkane.Through water removal and isopropanol is concentrated under reduced pressure, transparent mucus is obtained.
It is heated to 210 DEG C of hardening after above-mentioned transparency liquid is formed a film with blade coating, is formed with a thickness of 0.1~200 μm
Film (baking oven film forming).The heat resistance of above-mentioned film is 210 DEG C, and transparency is 92% (colorimeter).
Embodiment 4 (the second silane/the first silane=1:3)
By 45g dimethylformamide dimethyl oxosilane, 72.0g isopropanol, 6.0g0.01MHCl aqueous solution and 28.8g deionized water
It pours into 1L round-bottomed bottle and mixes, stirring at 35 DEG C makes its hydrolytic polymerization form oligomer, 50~200cps of viscosity for 1.5 hours.
Then 15g methyl trimethoxy oxosilane is added in above-mentioned oligomer, stirs 1.5 hours at 35 DEG C to be cross-linked to form the poly- silicon of high branch
Oxygen alkane.Through water removal and isopropanol is concentrated under reduced pressure, hyalomucoid is obtained.
It is heated to 210 DEG C of hardening after above-mentioned transparent mucus is formed a film with blade coating, is formed with a thickness of 0.1~200 μm
Film (baking oven film forming).The heat resistance of above-mentioned film is 300 DEG C, and transparency is 92% (colorimeter).
Embodiment 5 (the second silane/the first silane=1:10)
By 54.5g dimethylformamide dimethyl oxosilane, 72.0g isopropanol, 6.0g0.01MHCl aqueous solution and 30.1g deionization
Water is poured into 1L round-bottomed bottle and is mixed, and stirring at 35 DEG C makes its hydrolytic polymerization formation oligomer for 1.5 hours, and viscosity 50~
200cps.Then 5.45g methyl trimethoxy oxosilane is added in above-mentioned oligomer, stirs 1.5 hours at 35 DEG C to be cross-linked to form
High branch's polysiloxanes.Through water removal and isopropanol is concentrated under reduced pressure, transparent mucus is obtained.
It is heated to 210 DEG C of hardening after above-mentioned transparent mucus is formed a film with blade coating, is formed with a thickness of 0.1~200 μm
Film (baking oven film forming).The heat resistance of above-mentioned film is 400 DEG C, and transparency is 92% (colorimeter).
Comparative example 1 (the second silane/the first silane=12:1)
By 4.62g dimethylformamide dimethyl oxosilane, 72.0g isopropanol, 6.0g0.01MHCl aqueous solution and 25.4g deionization
Water is poured into 1L round-bottomed bottle and is mixed, and stirring at 35 DEG C makes its hydrolytic polymerization formation oligomer for 1.5 hours, and viscosity 50~
200cps.Then 55.4g methyl trimethoxy oxosilane is added in above-mentioned oligomer, stirs 1.5 hours at 35 DEG C to be cross-linked to form
High branch's polysiloxanes.Through water removal and isopropanol is concentrated under reduced pressure, hyalomucoid is obtained.Above-mentioned product is gelation in a short time
(gel) it is not available.
Comparative example 2 (the second silane/the first silane=1:20)
By 57.1g dimethylformamide dimethyl oxosilane, 72.0g isopropanol, 6.0g0.01MHCl aqueous solution and 29.7g deionization
Water is poured into 1L round-bottomed bottle and is mixed, and stirring at 35 DEG C makes its hydrolytic polymerization form oligomer for 1.5 hours.Then by 2.86g methyl
Front three oxosilane is added in above-mentioned oligomer, stirs 1.5 hours at 35 DEG C to be cross-linked to form high branch's polysiloxanes.It is dense through depressurizing
Contracting water removal and isopropanol, obtain transparent mucus.
It is heated to 400 DEG C of hardening after above-mentioned transparent mucus is formed a film with blade coating, is formed with a thickness of 0.1~200 μm
Film.The hardening of above-mentioned film is incomplete.
Comparative example 3 (the second silane reacts with the first silane one, the second silane/the first silane=3:1)
By 15.0g dimethylformamide dimethyl oxosilane, 45.0g methyl trimethoxy oxosilane, 72.0g isopropanol, 6.0g0.01M HCl
Aqueous solution is poured into 1L round-bottomed bottle with 26.6g deionized water and is mixed, gelation after being stirred 1.5 hours at 35 DEG C and be not available.
Comparative example 4 (the second silane reacts with the first silane one, the second silane/the first silane=1:1)
By 30.0g dimethylformamide dimethyl oxosilane, 30.0g methyl trimethoxy oxosilane, 72.0g isopropanol, 6.0g0.01M HCl
Aqueous solution is poured into 1L round-bottomed bottle with 27.8g deionized water and is mixed, gelation after being stirred 1.5 hours at 35 DEG C and be not available.
Comparative example 5 (the second silane reacts with the first silane one, the second silane/the first silane=1:3)
By 45.0g dimethylformamide dimethyl oxosilane, 15.0g methyl trimethoxy oxosilane, 72.0g isopropanol, 6.0g0.01M HCl
Aqueous solution is poured into 1L round-bottomed bottle with 16.06g deionized water and is mixed, and forms transparency liquid shapes after 35 DEG C of stirrings 1.5 are small.It will
Above-mentioned transparency liquid is heated to 210 DEG C of hardening after forming a film with blade coating, form the film with a thickness of 0.1~200 μm.It is above-mentioned thin
Film has crack phenomenon.
Comparative example 6 (first by the second polymerizable silane at oligomer again with the first silane reaction, the second silane/the first silane=
1:1)
By 30g methyl trimethoxy oxosilane, 72.0g isopropanol, 6.0g0.01M HCL aqueous solution, fall with 27.8g deionized water
Enter and mixed in 1L round-bottomed bottle, stirring at 35 DEG C makes its hydrolytic polymerization form oligomer for 1.5 hours, and viscosity is not surveyed.Then by 30g
Dimethylformamide dimethyl oxosilane is added in above-mentioned oligomer, stirs 1.5 hours at 35 DEG C to be cross-linked to form high branch's polysiloxanes.Through
Water removal and isopropanol is concentrated under reduced pressure, obtains transparent mucus.Above-mentioned product in a short time i.e. gelation (gel) and be not available.
Table 1
By the comparison of table 1 it is found that the first silane is first taken to form oligomer, then there is it with the process sequence of the second crosslinked with silicane
Necessity and the ratio of the first silane and the second silane also need suitably.If taking the first silane and the second silane simultaneous reactions,
Or the second silane reaction is first taken to add the first silane, product is not that gelation is exactly that film-forming quality is poor.
Embodiment 6 (the second silane/the first silane=3:1, high branch's polysiloxanes: silica=70:30)
By 15.0g dimethylformamide dimethyl oxosilane, 72.0g isopropanol, 6.0g 0.01M HCL aqueous solution, with 16.06g go from
Sub- water is poured into 1L round-bottomed bottle and is mixed, and stirring at 35 DEG C makes its hydrolytic polymerization formation oligomer for 1.5 hours, and viscosity 50~
200cps.Then by the isopropanol dispersion liquid of 45.0g 3- (trimethoxy silane base) propyl acrylate and 68.69g silica
(purchased from the IPA-ST of Nissan Chemical, 10~15nm of partial size) is added in above-mentioned oligomer, stirs 1.5 hours at 35 DEG C
To form high branch's polysiloxanes and aoxidize the hybrid material of pasc reaction.Through water removal and isopropanol is concentrated under reduced pressure, it is transparent to obtain micro- Huang
Liquid (59.30g), silica content 30.43wt%, and the content of high branch's polysiloxanes is 69.57wt%.It will be above-mentioned micro-
Yellow transparency liquid be heated to after being formed a film with blade coating 170 DEG C hardening, formed with a thickness of 0.1~200 μm film (baking oven at
Film).The heat resistance of above-mentioned film is 210 DEG C, and transparency is 92% (colorimeter).
Embodiment 7 (the second silane/the first silane=10:1, high branch's polysiloxanes: silica=72:28)
By 6.0g dimethylformamide dimethyl oxosilane, 79.2g isopropanol, 6.6g 0.01M HCL aqueous solution, with 14.42g go from
Sub- water is poured into 1L round-bottomed bottle and is mixed, and stirring at 35 DEG C makes its hydrolytic polymerization formation oligomer for 1.5 hours, and viscosity 50~
200cps.Then by the isopropanol dispersion liquid of 60.0g 3- (trimethoxy silane base) propyl acrylate and 76.58g silica
(purchased from the IPA-ST of Nissan Chemical, 10~15nm of partial size) is added in above-mentioned oligomer, stirs 1.5 hours at 35 DEG C
To form high branch's polysiloxanes and aoxidize the hybrid material of pasc reaction.Through water removal and isopropanol is concentrated under reduced pressure, it is transparent to obtain micro- Huang
Liquid (80.20g), silica content 28.65wt%, and the content of high branch's polysiloxanes is 71.35wt%.It will be above-mentioned micro-
Yellow transparency liquid be heated to after being formed a film with blade coating 170 DEG C hardening, formed with a thickness of 0.1~200 μm film (baking oven at
Film).The heat resistance of above-mentioned film is 210 DEG C, and transparency is 92% (colorimeter).
Embodiment 8 (the second silane/the first silane=10:1, high branch's polysiloxanes: silica=62:38)
By 6.0g dimethylformamide dimethyl oxosilane, 79.2g isopropanol, 6.6g 0.01M HCL aqueous solution, with 14.42g go from
Sub- water is poured into 1L round-bottomed bottle and is mixed, and stirring at 35 DEG C makes its hydrolytic polymerization formation oligomer for 1.5 hours, and viscosity 50~
200cps.Then the isopropanol of 60.0g 3- (trimethoxy silane base) propyl acrylate and 119.13g silica is dispersed
Liquid (purchased from the IPA-ST of Nissan Chemical, 10~15nm of partial size) is added in above-mentioned oligomer, stirs 10 minutes at 35 DEG C
To form high branch's polysiloxanes and aoxidize the hybrid material of pasc reaction.Through water removal and isopropanol is concentrated under reduced pressure, it is transparent to obtain micro- Huang
Liquid (92.70g), silica content 38.55wt%, and the content of high branch's polysiloxanes is 61.45wt%.It will be above-mentioned micro-
Yellow transparency liquid be heated to after being formed a film with blade coating 170 DEG C hardening, formed with a thickness of 0.1~200 μm film (baking oven at
Film).The heat resistance of above-mentioned film is 210 DEG C, and transparency is 92% (colorimeter).
Embodiment 9 (the second silane/the first silane=1:1, high branch's polysiloxanes: silica=90:10)
By 50.0g dimethylformamide dimethyl oxosilane, 60g isopropanol, 5.6g 0.01MHCl aqueous solution and 9.4g deionized water
It pours into 1L round-bottomed bottle and mixes, stirring at 35 DEG C makes its hydrolytic polymerization form oligomer, 50~200cps of viscosity for 2 hours.It connects
50.0g trimethoxymethylsila,e is added, 35 DEG C stir 1.5 hours to form high branch's silicone materials.20.0g
Above-mentioned high branch is added in the isopropanol dispersion liquid (purchased from the IPA-ST of Nissan Chemical, 10~15nm of partial size) of silica
It in silicone materials, is stirred 10 minutes at 35 DEG C, to form high branch's polysiloxanes and aoxidize the hybrid material of pasc reaction.Through
Water removal and isopropanol is concentrated under reduced pressure, obtains transparency liquid (65.2g), silica content 10wt%, and high branch's polysiloxanes
Content is 90wt%.It is heated to 210 DEG C of hardening after above-mentioned transparency liquid is formed a film with blade coating, is formed with a thickness of 0.1~200
μm film (baking oven film forming).The heat resistance of above-mentioned film is 210 DEG C, and transparency is 92% (colorimeter).
Embodiment 10 (the second silane/the first silane=1:10, high branch's polysiloxanes: silica=93:7)
By 30.0g dimethylformamide dimethyl oxosilane, 10g isopropanol, 2g 0.01M HCL aqueous solution, fall with 5.1g deionized water
Enter and mixed in 1L round-bottomed bottle, stirring at 35 DEG C makes its hydrolytic polymerization form oligomer, 50~200cps of viscosity for 1.5 hours.It connects
The trimethoxymethylsila,e of 3.0g is added, 1.5 hours are stirred at 35 DEG C to form high branch's silicone materials.6.0g
Above-mentioned high branch is added in the isopropanol dispersion liquid (purchased from the IPA-ST of Nissan Chemical, 10~15nm of partial size) of silica
In silicone materials, 10 minutes are stirred at 35 DEG C to form high branch's polysiloxanes and aoxidize the hybrid material of pasc reaction.Through
Water removal and isopropanol is concentrated under reduced pressure, obtains transparency liquid (22.1g), silica content 7wt%, and high branch's polysiloxanes contains
Amount is 93wt%.It is heated to 210 DEG C of hardening after above-mentioned transparency liquid is formed a film with blade coating, is formed with a thickness of 0.1~200 μm
Film (baking oven film forming).The heat resistance of above-mentioned film is 400 DEG C, and transparency is 92% (colorimeter).
Embodiment 11 (the second silane/the first silane=2:1)
20.0g dimethylformamide dimethyl oxosilane, 72g isopropanol, 6g 0.01MHCl aqueous solution and 20.8g deionized water are fallen
Entering and is mixed in 1L round-bottomed bottle, stirring is heated to reflux at 90 DEG C makes its hydrolytic polymerization form oligomer for 1.5 hours, and viscosity is 50~
200cps.Then 40.0g trimethoxy-benzene base silane is added, continuation is heated to reflux stirring 1.5 hours at 90 DEG C, to form height
Branch's silicone materials.Water core isopropanol is removed through being concentrated under reduced pressure, obtains transparency liquid (44.3g).By above-mentioned transparency liquid
It is heated to 210 DEG C of hardening after forming a film with blade coating, forms the film (baking oven film forming) with a thickness of 0.1~200 μm.Above-mentioned film
Heat resistance be 400 DEG C, and transparency be 92% (colorimeter).
Embodiment 12 (the second silane/the first silane=2:1, high branch's polysiloxanes: silica=90:10)
20.0g dimethylformamide dimethyl oxosilane, 72g isopropanol, 6g 0.01MHCl aqueous solution and 20.8g deionized water are fallen
Entering and is mixed in 1L round-bottomed bottle, stirring is heated to reflux at 90 DEG C makes its hydrolytic polymerization form oligomer for 1.5 hours, and viscosity is 50~
200cps.Then 40.0g trimethoxy-benzene base silane is added, continuation is heated to reflux stirring 1.5 hours at 90 DEG C, to form height
Branch's silicone materials.Then by the isopropanol dispersion liquid (IPA- purchased from Nissan Chemical of 17.0g silica
ST, 10~15nm of partial size) it is added in above-mentioned oligomer, continuation is heated to reflux stirring at 90 DEG C 30 minutes to form the poly- silicon of high branch
The hybrid material of oxygen alkane and oxidation pasc reaction.Water core isopropanol is removed through being concentrated under reduced pressure, obtains transparency liquid 49.1g, dioxy
SiClx content is 10.39wt%, and the content of high branch's polysiloxanes is 89.61wt%.By above-mentioned transparency liquid to scrape cutter painting
It is heated to 210 DEG C of hardening after cloth film forming, forms the film (baking oven film forming) with a thickness of 0.1~200 μm.The heat resistance of above-mentioned film
It is 400 DEG C, and transparency is 92% (colorimeter).
Embodiment 13 (the second silane/the first silane=2:1, high branch's polysiloxanes: silica=80:20)
By 20.0g dimethylformamide dimethyl oxosilane, 72g isopropanol, 6g 0.01MHCl aqueous solution, fall with 20.8g deionized water
Entering and is mixed in 1L round-bottomed bottle, stirring is heated to reflux at 90 DEG C makes its hydrolytic polymerization form oligomer for 1.5 hours, and viscosity is 50~
200cps.Then 40.0g trimethoxy-benzene base silane is added, continuation is heated to reflux stirring 1.5 hours at 90 DEG C, to form height
Branch's silicone materials.Then by the isopropanol dispersion liquid (IPA- purchased from Nissan Chemical of 38.3g silica
ST, 10~15nm of partial size) it is added in above-mentioned oligomer, continuation is heated to reflux stirring at 90 DEG C 30 minutes to form the poly- silicon of high branch
The hybrid material of oxygen alkane and oxidation pasc reaction.Water and isopropanol are removed through being concentrated under reduced pressure, obtains transparency liquid 56.4g, dioxy
SiClx content is 20.37wt%, and the content of high branch's polysiloxanes is 79.63wt%.By above-mentioned transparency liquid to scrape cutter painting
It is heated to 210 DEG C of hardening after cloth film forming, forms the film (baking oven film forming) with a thickness of 0.1~200 μm.The heat resistance of above-mentioned film
It is 400 DEG C, and transparency is 92% (colorimeter).
Embodiment 14 (the second silane/the first silane=2:1, high branch's polysiloxanes: silica=70:30)
20.0g dimethylformamide dimethyl oxosilane, 72g isopropanol, 6g 0.01MHCl aqueous solution and 20.8g deionized water are fallen
Entering and is mixed in 1L round-bottomed bottle, stirring is heated to reflux at 90 DEG C makes its hydrolytic polymerization form oligomer for 1.5 hours, and viscosity is 50~
200cps.Then 40.0g trimethoxy-benzene base silane is added, continuation is heated to reflux stirring 1.5 hours at 90 DEG C, to form height
Branch's silicone materials.Then by the isopropanol dispersion liquid (IPA- purchased from Nissan Chemical of 65.9g silica
ST, 10~15nm of partial size) it is added in above-mentioned oligomer, continuation is heated to reflux stirring at 90 DEG C 30 minutes to form the poly- silicon of high branch
The hybrid material of oxygen alkane and oxidation pasc reaction.Water core isopropanol is removed through being concentrated under reduced pressure, obtains transparency liquid 63.0g, dioxy
SiClx content is 31.38wt%, and the content of high branch's polysiloxanes is 68.62wt%.By above-mentioned transparency liquid to scrape cutter painting
It is heated to 210 DEG C of hardening after cloth film forming, forms the film (baking oven film forming) with a thickness of 0.1~200 μm.The heat resistance of above-mentioned film
It is 400 DEG C, and transparency is 92% (colorimeter).
Table 2
As shown in Table 2, the substituent group on the second silane has multiple choices.
Comparative example 7
By the commercially available dimethyl silicone polymer of 30.0g (purchased from the DMS-S35 of Gelest, viscosity 5000cps), 30.0g
Trimethoxymethylsila,e, 72.0g isopropanol, 6.0g 0.01M HCL aqueous solution and 16.06g deionized water pour into 1L round bottom
It is mixed in bottle, trimethoxymethylsila,e and DMS-S35 can not be mixed mutually, become fog-like liquid, stratification.
Comparative example 8
By the commercially available dimethyl silicone polymer of 10.0g (purchased from the DMS-S35 of Gelest, viscosity 5000cps), 10.0g
The isopropanol dispersion liquid (purchased from the IPA-ST of Nissan Chemical, 10~15nm of partial size) of silica pours into 1L round-bottomed bottle
Mixing, the isopropanol dispersion liquid and DMS-S35 of silica can not be mixed mutually, become fog-like liquid, stratification.
By comparative example 7 and 8 it is found that if by the oligomer that the first silane hydrolyzate is polymerized be replaced into macromolecule (viscosity compared with
It is high), then it can not form transparent film.
Although the present invention is disclosed as above with multiple embodiments, however, it is not to limit the invention, any this technology neck
Technical staff in domain, without departing from the spirit and scope of the present invention, when can arbitrarily change and retouch, therefore the present invention
Protection scope should be subject to scope defined by appended claims.
Claims (12)
1. a kind of high branch's polysiloxanes, be by:
The oligomer of first silane of 1 parts by weight is formed with the second crosslinked with silicane of 0.1 to 10 parts by weight,
Wherein first silane is Si (R1)2(OR2)2, every R1Respectively epoxy group, amido, aromatic radical or fat-based, and it is every
One R2Respectively fat-based；
Wherein second silane is Si (R3)(OR4)3, R3For epoxy group, amido, aromatic radical or fat-based, and every R4Respectively
Fat-based.
2. high branch's polysiloxanes as described in claim 1, wherein R1Or R3For acrylic or vinyl.
3. high branch's polysiloxanes as described in claim 1, wherein the viscosity of the oligomer of first silane be 10cps extremely
500cps。
4. a kind of hybrid material, by including that substance reaction below forms:
High branch's polysiloxanes described in claim 1, and
The surface of 0.01 to 70 parts by weight has the inorganic oxide of hydroxyl.
5. hybrid material as claimed in claim 4, wherein there is the inorganic oxide of hydroxyl to be selected from silica, oxidation on surface
Titanium, aluminium oxide or combinations of the above.
6. hybrid material as claimed in claim 4, wherein surface have the partial size of the inorganic oxide of hydroxyl be 0.1nm extremely
1000nm。
7. a kind of forming method of high branch's polysiloxanes, comprising:
The oligomer for taking the first silane of 1 parts by weight forms the poly- silicon oxygen of high branch with the second crosslinked with silicane of 0.1 to 10 parts by weight
Alkane,
Wherein first silane is Si (R1)2(OR2)2, every R1Respectively epoxy group, amido, aromatic radical or fat-based, and it is every
One R2Respectively fat-based；
Wherein second silane is Si (R3)(OR4)3, R3For epoxy group, amido, aromatic radical or fat-based, and every R4Respectively
Fat-based.
8. the forming method of high branch's polysiloxanes as claimed in claim 7, wherein R1Or R3For acrylic or vinyl.
9. the forming method of high branch's polysiloxanes as claimed in claim 7, the wherein viscosity of the oligomer of first silane
For 10cps to 500cps.
10. a kind of forming method of hybrid material, comprising:
High branch's polysiloxanes described in claim 1 is taken, and
There is the inorganic oxide of hydroxyl to react on the surface of 0.01 to 70 parts by weight.
11. the forming method of hybrid material as claimed in claim 10, wherein there is the inorganic oxide of hydroxyl to select on surface
Autoxidation silicon, titanium oxide, aluminium oxide or combinations of the above.
12. the forming method of hybrid material as claimed in claim 10, wherein surface has the inorganic oxide of hydroxyl
Partial size is 0.1nm to 1000nm.
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| US14/582,342 US20160185911A1 (en) | 2014-12-24 | 2014-12-24 | Polysiloxane and hybrid material and method for manufacturing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1209429C (en) * | 1999-07-07 | 2005-07-06 | 卡伯特微电子公司 | CMP composition containing silane modified abrasive particles |
| CN102086267A (en) * | 2010-12-20 | 2011-06-08 | 青岛科技大学 | Amino-containing organic silicon resin fire retardant and preparation method thereof |
| CN103980712A (en) * | 2013-11-18 | 2014-08-13 | 长兴化学工业股份有限公司 | Organic-inorganic composite resin, coating composition containing the same and application thereof |
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2015
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1209429C (en) * | 1999-07-07 | 2005-07-06 | 卡伯特微电子公司 | CMP composition containing silane modified abrasive particles |
| CN102086267A (en) * | 2010-12-20 | 2011-06-08 | 青岛科技大学 | Amino-containing organic silicon resin fire retardant and preparation method thereof |
| CN103980712A (en) * | 2013-11-18 | 2014-08-13 | 长兴化学工业股份有限公司 | Organic-inorganic composite resin, coating composition containing the same and application thereof |
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