CN105985522A - 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
- Publication number
- CN105985522A CN105985522A CN201510083438.5A CN201510083438A CN105985522A CN 105985522 A CN105985522 A CN 105985522A CN 201510083438 A CN201510083438 A CN 201510083438A CN 105985522 A CN105985522 A CN 105985522A
- Authority
- CN
- China
- Prior art keywords
- silane
- polysiloxanes
- high branch
- fat
- oligomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 polysiloxanes Polymers 0.000 title claims abstract description 70
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 64
- 239000000463 material Substances 0.000 title claims description 36
- 238000000034 method Methods 0.000 title claims description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 91
- 229910000077 silane Inorganic materials 0.000 claims abstract description 86
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 56
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 25
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 10
- 125000003368 amide group Chemical group 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 150000003254 radicals Chemical class 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 125000003700 epoxy group Chemical group 0.000 abstract 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 98
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 47
- 238000003756 stirring Methods 0.000 description 37
- 239000007788 liquid Substances 0.000 description 34
- 239000010409 thin film Substances 0.000 description 33
- 239000010408 film Substances 0.000 description 31
- 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
- 239000011248 coating agent Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 230000003301 hydrolyzing effect Effects 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 12
- 210000003097 mucus Anatomy 0.000 description 11
- HZBAVWLZSLOCFR-UHFFFAOYSA-N oxosilane Chemical compound [SiH2]=O HZBAVWLZSLOCFR-UHFFFAOYSA-N 0.000 description 11
- 238000010992 reflux Methods 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 10
- 238000006384 oligomerization reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000243 solution 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
- 238000001879 gelation Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 4
- 229940030010 trimethoxybenzene Drugs 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910003978 SiClx Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 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
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 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 2
- 239000010410 layer Substances 0.000 description 2
- 229920000435 poly(dimethylsiloxane) 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
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 125000000304 alkynyl 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
- 230000015572 biosynthetic process Effects 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
- 238000010586 diagram Methods 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 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
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005286 illumination Methods 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
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[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
- 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
- 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 1
- 125000001624 naphthyl group Chemical group 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
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 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
- 229920000642 polymer Polymers 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000012239 silicon dioxide Nutrition 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
- 125000005023 xylyl group Chemical group 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
- Silicon Compounds (AREA)
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 composition and the formation side of its high branch polysiloxanes
Method.
[background technology]
The products such as 3C electronics, display or illumination develop both facing to compact direction.As base
The thickness of glass of plate gradually reduces toward 0.1 microns from a few micrometers, and frangible glass needs transparency protected
Layer.Protective clear layer needs thermostability, to reach the process requirement (at least 300~350 DEG C) of existing plating ITO.
Usually used as the macromolecular material of protective layer, in addition to itself has coloring problem, also can xanthochromia crossing high temperature.
Energy the most transparent high temperature resistant selection at present is i.e. the polysiloxanes of silicone (silicone) system
(polysiloxane), therefore develop new silicone materials or its manufacturing method thereof is trend of the times.
[summary of the invention]
The high branch polysiloxanes that one embodiment of the invention provides, is by the widow of the first silane of 1 weight portion
Polymers, forms with the second crosslinked with silicane of 0.05 to 20 weight portion, and wherein the first silane is Si (R1)2(OR2)2,
Each R1Respectively acrylic, epoxy radicals, vinyl, amido, aromatic radical or fat-based, and often
One R2It is respectively fat-based;Wherein the second silane is Si (R3)(OR4)3, R3For acrylic, epoxy radicals,
Vinyl, amido or fat-based, and each R4It is respectively fat-based.
The hybrid material that one embodiment of the invention provides, is by above-mentioned high branch polysiloxanes, and
The surface of 0.01 to 70 weight portion has the inorganic oxide reaction of hydroxyl and forms.
One embodiment of the invention provides the forming method of high branch polysiloxanes, including: take 1 weight portion
The oligomer of the first silane, forms high branch polysiloxanes with the second crosslinked with silicane of 0.05 to 20 weight portion,
Wherein the first silane is Si (R1)2(OR2)2, each R1Be respectively acrylic, epoxy radicals, vinyl,
Amido, aromatic radical or fat-based, and each R2It is respectively fat-based;Wherein the second silane is
Si(R3)(OR4)3, R3For acrylic, epoxy radicals, vinyl, amido, aromatic radical or fat-based,
And each R4It is respectively fat-based.
The forming method of the hybrid material that one embodiment of the invention provides, including: take above-mentioned high branch and gather
Siloxanes, and the surface of 0.01 to 70 weight portion have hydroxyl inorganic oxide reaction form.
[accompanying drawing explanation]
Fig. 1 is in one embodiment of the invention, showing of the forming method of high branch polysiloxanes and hybrid material
It is intended to.
[description of reference numerals]
1 first silane;
3 oligomers;
5 second silane;
7 high branch polysiloxanes;
9 surfaces have the inorganic oxide of hydroxyl;
11 hybrid materials.
[detailed description of the invention]
As it is shown in figure 1, the first silane 1 hydrolytic polymerization in acidic aqueous solution taking 1 weight portion forms oligomerization
Thing 3.In an embodiment of the present invention, the structure of the first silane 1 is Si (R1)2(OR2)2, each R1Respectively
From for acrylic, epoxy radicals, vinyl, amido, aromatic radical or fat-based, and each R2Each
For fat-based.In an embodiment of the present invention, acidic aqueous solution comprises alcohols such as methanol, second further
Alcohol, isopropanol, to adjust hydrolysis rate.The viscosity of above-mentioned oligomer can be between 10cps to 500cps.
If the viscosity of oligomer is too high, then the product being subsequently formed easily is atomized.If the viscosity of oligomer is too low,
Gelation problems then cannot be avoided during follow-up cross-linking step.
Then the second silane 5 of 0.05 to 20 weight portion or 0.1 to 10 weight portion and the molten of above-mentioned oligomer are taken
Liquid mixes, and is cross-linked to form high branch polysiloxanes 7.Second silane 5 is Si (R3)(OR4)3, R3For acrylic acid
Base, epoxy radicals, vinyl, amido, aromatic radical or fat-based, and each R4It is respectively fat-based.
If the consumption of the second silane 5 is too high, then the easy gelation of cross-linking products and cannot be carried out subsequent applications.If the
The consumption of disilane 5 is too low, and Ze Gao branch polysiloxanes is incomplete in coating film forming after-hardening.
In the present invention, fat-based can be straight chain or branched, saturated or undersaturated, such as may be used
With selected from have the alkyl of 1-18 carbon atom, particularly 1-10 carbon atom, cycloalkyl, thiazolinyl and
Alkynyl.The example of the most useful fat-based includes methyl, ethyl, n-pro-pyl, isopropyl,
Normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, neopentyl, tertiary pentyl, hexyl is the most just
Hexyl, heptyl such as n-heptyl, octyl group such as n-octyl, iso-octyl and 2,2,4-tri-methyl-amyls, nonyl
Base such as n-nonyl, the such as positive decyl of decyl, dodecyl, octadecyl, cycloalkyl such as ring penta
Base, cyclohexyl, suberyl and methylcyclohexyl, vinyl, acrylic, pi-allyl, methacrylic,
Acetenyl, propinyl, methylacetylenyl.Aromatic radical includes having the aryl of 6-20 carbon atom, virtue
Alkyl or alkaryl.The example of the most useful aryl includes phenyl, xenyl, naphthyl,
O-, m-and p-tolyl, xylyl, benzyl, ethylphenyl.
In an embodiment of the present invention, the surface that can take 0.01 to 70 weight portion further has hydroxyl
Inorganic oxide 9 reacts with above-mentioned high branch polysiloxanes 7, forms hybrid material 11.The poly-silica of high branch
The hydroxyl of alkane 7 forms-O-Si-O-bond with the hydroxyls dehydrate on inorganic oxide 9 surface.If inorganic oxide
Consumption too high, the most easily cohesion (aggregation) and reduce the transmittance of hybrid material.In the present invention one
In embodiment, inorganic oxide 9 can be silicon oxide, titanium oxide, aluminium oxide or combinations of the above.
In an embodiment of the present invention, the particle diameter of inorganic oxide 9 is between 0.1nm to 1000nm.If
The particle diameter of inorganic oxide is excessive, then affect product transparency.
Above-mentioned hybrid material 11 can be coated on base material such as glass or pottery, can form guarantor after heat hardening
Protect coating.In an embodiment of the present invention, the transmittance of protective coating between 90% to 99.9%,
And thermostability is up to about 450 DEG C.The clear coat that above-mentioned high transparency is heat-resisting with height can effectively protect base material.
In order to above and other purpose, feature and the advantage of the present invention can be become apparent, hereafter special
Coordinate appended diagram for number embodiment, be 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 is poured in 1L round-bottomed bottle and is mixed, and within 1.5 hours, makes its hydrolytic polymerization form oligomerization 35 DEG C of stirrings
Thing, its viscosity 50~200cps.Then 50g methyl trimethoxy oxosilane is added in above-mentioned oligomer, 35
DEG C stirring 1.5 hours to be cross-linked to form high branch polysiloxanes.Through concentrating under reduced pressure except water and isopropanol, obtain
Bright mucus.
By above-mentioned hyalomucoid with scraper for coating film forming post-heating to 170 DEG C of hardening, forming thickness is
The thin film (baking oven film forming) of 0.1~200 μm.The thermostability of above-mentioned thin film reaches 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 is poured in 1L round-bottomed bottle and is mixed, and within 1.5 hours, makes its hydrolytic polymerization form oligomerization 35 DEG C of stirrings
Thing, its viscosity 50~200cps.Then 45g methyl trimethoxy oxosilane is added in above-mentioned oligomer, 35
DEG C stirring 1.5 hours to be cross-linked to form high branch polysiloxanes.Through concentrating under reduced pressure except water and isopropanol, obtain
Bright mucus.
By above-mentioned transparent mucus with scraper for coating film forming post-heating to 170 DEG C of hardening, forming thickness is
The thin film (baking oven film forming) of 0.1~200 μm.The thermostability of above-mentioned thin 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 is poured in 1L round-bottomed bottle and is mixed, and within 1.5 hours, makes its hydrolytic polymerization form oligomerization 35 DEG C of stirrings
Thing, its viscosity 50~200cps.Then 30g methyl trimethoxy oxosilane is added in above-mentioned oligomer, 35
DEG C stirring 1.5 hours to be cross-linked to form high branch polysiloxanes.Through concentrating under reduced pressure except water and isopropanol, obtain
Bright mucus.
By above-mentioned transparency liquid with scraper for coating film forming post-heating to 210 DEG C of hardening, forming thickness is
The thin film (baking oven film forming) of 0.1~200 μm.The thermostability of above-mentioned thin 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 is poured in 1L round-bottomed bottle and is mixed, and within 1.5 hours, makes its hydrolytic polymerization form oligomerization 35 DEG C of stirrings
Thing, its viscosity 50~200cps.Then 15g methyl trimethoxy oxosilane is added in above-mentioned oligomer, 35
DEG C stirring 1.5 hours to be cross-linked to form high branch polysiloxanes.Through concentrating under reduced pressure except water and isopropanol, obtain
Bright mucus.
By above-mentioned transparent mucus with scraper for coating film forming post-heating to 210 DEG C of hardening, forming thickness is
The thin film (baking oven film forming) of 0.1~200 μm.The thermostability of above-mentioned thin 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
Deionized water is poured in 1L round-bottomed bottle and is mixed, and within 1.5 hours, makes its hydrolytic polymerization form oligomerization 35 DEG C of stirrings
Thing, its viscosity 50~200cps.Then 5.45g methyl trimethoxy oxosilane is added in above-mentioned oligomer,
35 DEG C are stirred 1.5 hours to be cross-linked to form high branch polysiloxanes.Through concentrating under reduced pressure except water and isopropanol,
Transparent mucus.
By above-mentioned transparent mucus with scraper for coating film forming post-heating to 210 DEG C of hardening, forming thickness is
The thin film (baking oven film forming) of 0.1~200 μm.The thermostability of above-mentioned thin 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
Deionized water is poured in 1L round-bottomed bottle and is mixed, and within 1.5 hours, makes its hydrolytic polymerization form oligomerization 35 DEG C of stirrings
Thing, its viscosity 50~200cps.Then 55.4g methyl trimethoxy oxosilane is added in above-mentioned oligomer,
35 DEG C are stirred 1.5 hours to be cross-linked to form high branch polysiloxanes.Through concentrating under reduced pressure except water and isopropanol,
Hyalomucoid.Above-mentioned product at short notice be gelation (gel) and cannot use.
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
Deionized water is poured in 1L round-bottomed bottle and is mixed, and within 1.5 hours, makes its hydrolytic polymerization form oligomerization 35 DEG C of stirrings
Thing.Then 2.86g methyl trimethoxy oxosilane is added in above-mentioned oligomer, 35 DEG C of stirrings 1.5 hours with
It is cross-linked to form high branch polysiloxanes.Through concentrating under reduced pressure except water and isopropanol, obtain transparent mucus.
By above-mentioned transparent mucus with scraper for coating film forming post-heating to 400 DEG C of hardening, forming thickness is
The thin film of 0.1~200 μm.The hardening of above-mentioned thin film is incomplete.
Comparative example 3 (the second silane and the first silane one react, 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/water solution is poured in 1L round-bottomed bottle with 26.6g deionized water and is mixed, 35 DEG C of stirrings
Gelation after 1.5 hours and cannot use.
Comparative example 4 (the second silane and the first silane one react, the second silane/the first silane=1:1)
By 30.0g dimethylformamide dimethyl oxosilane, 30.0g methyl trimethoxy oxosilane, 72.0g isopropanol, 6.0g
0.01M HCl/water solution is poured in 1L round-bottomed bottle with 27.8g deionized water and is mixed, and stirs 1.5 at 35 DEG C
Gelation after hour and cannot use.
Comparative example 5 (the second silane and the first silane one react, the second silane/the first silane=1:3)
By 45.0g dimethylformamide dimethyl oxosilane, 15.0g methyl trimethoxy oxosilane, 72.0g isopropanol, 6.0g
0.01M HCl/water solution is poured in 1L round-bottomed bottle with 16.06g deionized water and is mixed, and stirs 1.5 at 35 DEG C
Transparency liquid shape is formed after little.By above-mentioned transparency liquid with scraper for coating film forming post-heating to 210 DEG C of hardening,
Form the thin film that thickness is 0.1~200 μm.Above-mentioned thin film has crack performance.
Comparative example 6 (first the second polymerizable silane is become oligomer again with the first silane reaction, the second silane/the
One silane=1:1)
By 30g methyl trimethoxy oxosilane, 72.0g isopropanol, 6.0g0.01M HCl/water solution and 27.8g
Deionized water is poured in 1L round-bottomed bottle and is mixed, and within 1.5 hours, makes its hydrolytic polymerization form oligomerization 35 DEG C of stirrings
Thing, its viscosity is not surveyed.Then 30g dimethylformamide dimethyl oxosilane is added in above-mentioned oligomer, at 35 DEG C
Stir 1.5 hours to be cross-linked to form high branch polysiloxanes.Through concentrating under reduced pressure except water and isopropanol, obtain transparent
Mucus.Above-mentioned product at short notice be gelation (gel) and cannot use.
Table 1
From the comparison of table 1, first take the first silane and form oligomer, then with the system of the second crosslinked with silicane
Cheng Shunxu has its necessity, and the ratio of the first silane and the second silane also needs suitably.If taking first
Silane and the second silane simultaneous reactions, or first taking the second silane reaction adds the first silane, its product
Be not gelation be exactly that film-forming quality is poor.
Embodiment 6 (the second silane/the first silane=3:1, high branch polysiloxanes: silicon oxide=70:30)
By 15.0g dimethylformamide dimethyl oxosilane, 72.0g isopropanol, 6.0g 0.01M HCl/water solution and
16.06g deionized water is poured in 1L round-bottomed bottle and is mixed, and within 1.5 hours, makes its hydrolytic polymerization be formed 35 DEG C of stirrings
Oligomer, its viscosity 50~200cps.Then by 45.0g 3-(trimethoxy silane base) propyl acrylate
With the isopropanol dispersion liquid of 68.69g silicon oxide (purchased from the IPA-ST of Nissan Chemical, particle diameter
10~15nm) add in above-mentioned oligomer, 35 DEG C of stirrings 1.5 hours with formed high branch polysiloxanes with
The hybrid material of silicon oxide reaction.Through concentrating under reduced pressure except water and isopropanol, obtain micro-yellow transparency liquid
(59.30g), silica content is 30.43wt%, and the content of high branch polysiloxanes is 69.57wt%.
By above-mentioned micro-yellow transparency liquid with scraper for coating film forming post-heating to 170 DEG C of hardening, forming thickness is
The thin film (baking oven film forming) of 0.1~200 μm.The thermostability of above-mentioned thin film is 210 DEG C, and transparency is
92% (colorimeter).
Embodiment 7 (the second silane/the first silane=10:1, high branch polysiloxanes: silicon oxide=72:28)
By 6.0g dimethylformamide dimethyl oxosilane, 79.2g isopropanol, 6.6g 0.01M HCl/water solution and
14.42g deionized water is poured in 1L round-bottomed bottle and is mixed, and within 1.5 hours, makes its hydrolytic polymerization be formed 35 DEG C of stirrings
Oligomer, its viscosity 50~200cps.Then by 60.0g 3-(trimethoxy silane base) propyl acrylate
With the isopropanol dispersion liquid of 76.58g silicon oxide (purchased from the IPA-ST of Nissan Chemical, particle diameter
10~15nm) add in above-mentioned oligomer, 35 DEG C of stirrings 1.5 hours with formed high branch polysiloxanes with
The hybrid material of silicon oxide reaction.Through concentrating under reduced pressure except water and isopropanol, obtain micro-yellow transparency liquid
(80.20g), silica content is 28.65wt%, and the content of high branch polysiloxanes is 71.35wt%.
By above-mentioned micro-yellow transparency liquid with scraper for coating film forming post-heating to 170 DEG C of hardening, forming thickness is
The thin film (baking oven film forming) of 0.1~200 μm.The thermostability of above-mentioned thin film is 210 DEG C, and transparency is
92% (colorimeter).
Embodiment 8 (the second silane/the first silane=10:1, high branch polysiloxanes: silicon oxide=62:38)
By 6.0g dimethylformamide dimethyl oxosilane, 79.2g isopropanol, 6.6g 0.01M HCl/water solution and
14.42g deionized water is poured in 1L round-bottomed bottle and is mixed, and within 1.5 hours, makes its hydrolytic polymerization be formed 35 DEG C of stirrings
Oligomer, its viscosity 50~200cps.Then by 60.0g 3-(trimethoxy silane base) propyl acrylate
With the isopropanol dispersion liquid of 119.13g silicon oxide (purchased from the IPA-ST of Nissan Chemical, particle diameter
10~15nm) add in above-mentioned oligomer, stir 10 minutes to form high branch polysiloxanes and oxygen at 35 DEG C
The hybrid material of SiClx reaction.Through concentrating under reduced pressure except water and isopropanol, obtain micro-yellow transparency liquid (92.70g),
Silica content is 38.55wt%, and the content of high branch polysiloxanes is 61.45wt%.By above-mentioned micro-Huang
Transparency liquid, with scraper for coating film forming post-heating to 170 DEG C of hardening, forms the thin film that thickness is 0.1~200 μm
(baking oven film forming).The thermostability of above-mentioned thin film is 210 DEG C, and transparency is 92% (colorimeter).
Embodiment 9 (the second silane/the first silane=1:1, high branch polysiloxanes: silicon oxide=90:10)
By 50.0g dimethylformamide dimethyl oxosilane, 60g isopropanol, 5.6g 0.01MHCl aqueous solution and 9.4g
Deionized water is poured in 1L round-bottomed bottle and is mixed, and within 2 hours, makes its hydrolytic polymerization form oligomer 35 DEG C of stirrings,
Its viscosity 50~200cps.Then 50.0g trimethoxymethylsila,e is added, stir 1.5 hours at 35 DEG C
To form high branch silicone materials.The isopropanol dispersion liquid of 20.0g silicon oxide is (purchased from Nissan
The IPA-ST of Chemical, particle diameter 10~15nm) add in above-mentioned high branch silicone materials, at 35 DEG C
Stir 10 minutes, to form the hybrid material that high branch polysiloxanes reacts with silicon oxide.Through concentrating under reduced pressure
Except water and isopropanol, obtaining transparency liquid (65.2g), silica content is 10wt%, and the poly-silica of high branch
The content of alkane is 90wt%.By above-mentioned transparency liquid with scraper for coating film forming post-heating to 210 DEG C of hardening,
Form the thin film (baking oven film forming) that thickness is 0.1~200 μm.The thermostability of above-mentioned thin film is 210 DEG C, and thoroughly
Lightness is 92% (colorimeter).
Embodiment 10 (the second silane/the first silane=1:10, high branch polysiloxanes: silicon oxide=93:7)
By 30.0g dimethylformamide dimethyl oxosilane, 10g isopropanol, 2g 0.01M HCl/water solution and 5.1g
Deionized water is poured in 1L round-bottomed bottle and is mixed, and within 1.5 hours, makes its hydrolytic polymerization form oligomerization 35 DEG C of stirrings
Thing, its viscosity 50~200cps.Then the trimethoxymethylsila,e of 3.0g is added, 35 DEG C of stirrings
1.5 hours to form high branch silicone materials.The isopropanol dispersion liquid of 6.0g silicon oxide is (purchased from Nissan
The IPA-ST of Chemical, particle diameter 10~15nm) add in above-mentioned high branch silicone materials, at 35 DEG C
Stir 10 minutes to form the hybrid material that high branch polysiloxanes reacts with silicon oxide.Remove through concentrating under reduced pressure
Water and isopropanol, obtain transparency liquid (22.1g), and silica content is 7wt%, and high branch polysiloxanes
Content is 93wt%.By above-mentioned transparency liquid with scraper for coating film forming post-heating to 210 DEG C of hardening, formed
Thickness is the thin film (baking oven film forming) of 0.1~200 μm.The thermostability of above-mentioned thin film is 400 DEG C, and transparency
It 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 are gone with 20.8g
Ionized water is poured in 1L round-bottomed bottle and is mixed, and is heated to reflux stirring 1.5 hours at 90 DEG C and makes its hydrolytic polymerization shape
Becoming oligomer, its viscosity is 50~200cps.Then 40.0g trimethoxy-benzene base silane is added, continue
It is heated to reflux stirring 1.5 hours at 90 DEG C, to form high branch silicone materials.Remove through concentrating under reduced pressure
Water core isopropanol, obtains transparency liquid (44.3g).By above-mentioned transparency liquid with scraper for coating film forming post-heating
To 210 DEG C of hardening, form the thin film (baking oven film forming) that thickness is 0.1~200 μm.The thermostability of above-mentioned thin film
It is 400 DEG C, and transparency is 92% (colorimeter).
Embodiment 12 (the second silane/the first silane=2:1, high branch polysiloxanes: silicon oxide=90:10)
20.0g dimethylformamide dimethyl oxosilane, 72g isopropanol, 6g 0.01MHCl aqueous solution are gone with 20.8g
Ionized water is poured in 1L round-bottomed bottle and is mixed, and is heated to reflux stirring 1.5 hours at 90 DEG C and makes its hydrolytic polymerization shape
Becoming oligomer, its viscosity is 50~200cps.Then 40.0g trimethoxy-benzene base silane is added, continue
It is heated to reflux stirring 1.5 hours at 90 DEG C, to form high branch silicone materials.Then by 17.0g bis-
The isopropanol dispersion liquid (purchased from the IPA-ST of Nissan Chemical, particle diameter 10~15nm) of silicon oxide adds
In above-mentioned oligomer, continue to be heated to reflux stirring 30 minutes to form high branch polysiloxanes and oxygen at 90 DEG C
The hybrid material of SiClx reaction.Remove water core isopropanol through concentrating under reduced pressure, obtain transparency liquid 49.1g, its
Dioxide-containing silica is 10.39wt%, and the content of high branch polysiloxanes is 89.61wt%.By above-mentioned
Prescribed liquid, with scraper for coating film forming post-heating to 210 DEG C of hardening, forms the thin film that thickness is 0.1~200 μm
(baking oven film forming).The thermostability of above-mentioned thin film is 400 DEG C, and transparency is 92% (colorimeter).
Embodiment 13 (the second silane/the first silane=2:1, high branch polysiloxanes: silicon oxide=80:20)
By 20.0g dimethylformamide dimethyl oxosilane, 72g isopropanol, 6g 0.01MHCl aqueous solution and 20.8g
Deionized water is poured in 1L round-bottomed bottle and is mixed, and is heated to reflux stirring 1.5 hours at 90 DEG C and makes its hydrolytic polymerization
Forming oligomer, its viscosity is 50~200cps.Then 40.0g trimethoxy-benzene base silane is added, continue
Continue and be heated to reflux stirring 1.5 hours at 90 DEG C, to form high branch silicone materials.Then by 38.3g
The isopropanol dispersion liquid (purchased from the IPA-ST of Nissan Chemical, particle diameter 10~15nm) of silicon dioxide adds
Enter in above-mentioned oligomer, continue 90 DEG C be heated to reflux stirring 30 minutes with formed high branch polysiloxanes with
The hybrid material of silicon oxide reaction.Remove water and isopropanol through concentrating under reduced pressure, obtain transparency liquid 56.4g,
Its dioxide-containing silica is 20.37wt%, and the content of high branch polysiloxanes is 79.63wt%.By above-mentioned
Transparency liquid, with scraper for coating film forming post-heating to 210 DEG C of hardening, forms the thin film that thickness is 0.1~200 μm
(baking oven film forming).The thermostability of above-mentioned thin film is 400 DEG C, and transparency is 92% (colorimeter).
Embodiment 14 (the second silane/the first silane=2:1, high branch polysiloxanes: silicon oxide=70:30)
20.0g dimethylformamide dimethyl oxosilane, 72g isopropanol, 6g 0.01MHCl aqueous solution are gone with 20.8g
Ionized water is poured in 1L round-bottomed bottle and is mixed, and is heated to reflux stirring 1.5 hours at 90 DEG C and makes its hydrolytic polymerization shape
Becoming oligomer, its viscosity is 50~200cps.Then 40.0g trimethoxy-benzene base silane is added, continue
It is heated to reflux stirring 1.5 hours at 90 DEG C, to form high branch silicone materials.Then by 65.9g bis-
The isopropanol dispersion liquid (purchased from the IPA-ST of Nissan Chemical, particle diameter 10~15nm) of silicon oxide adds
In above-mentioned oligomer, continue to be heated to reflux stirring 30 minutes to form high branch polysiloxanes and oxygen at 90 DEG C
The hybrid material of SiClx reaction.Remove water core isopropanol through concentrating under reduced pressure, obtain transparency liquid 63.0g, its
Dioxide-containing silica is 31.38wt%, and the content of high branch polysiloxanes is 68.62wt%.By above-mentioned
Prescribed liquid, with scraper for coating film forming post-heating to 210 DEG C of hardening, forms the thin film that thickness is 0.1~200 μm
(baking oven film forming).The thermostability of above-mentioned thin film 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 polydimethylsiloxane commercially available for 30.0g, (purchased from the DMS-S35 of Gelest, viscosity is
5000cps), 30.0g trimethoxymethylsila,e, 72.0g isopropanol, 6.0g 0.01M HCl/water solution,
Pouring in 1L round-bottomed bottle with 16.06g deionized water and mix, trimethoxymethylsila,e and DMS-S35 cannot
Mixing, becomes fog-like liquid, stratification mutually.
Comparative example 8
By polydimethylsiloxane commercially available for 10.0g, (purchased from the DMS-S35 of Gelest, viscosity is
5000cps), the isopropanol dispersion liquid of 10.0g silicon oxide is (purchased from the IPA-ST of Nissan Chemical, particle diameter
10~15nm) pouring in 1L round-bottomed bottle and mix, the isopropanol dispersion liquid of silicon oxide and DMS-S35 cannot be mutual
Mix mutually, become fog-like liquid, stratification.
From comparative example 7 and 8, if the oligomer that the first silane hydrolyzate is polymerized is replaced into macromolecule
(viscosity is higher), then cannot form transparent thin film.
Although the present invention discloses as above with multiple embodiments, so it is not limited to the present invention, any
Those skilled in the art, without departing from the spirit and scope of the present invention, arbitrary when making
Changing and retouching, therefore protection scope of the present invention should be defined in the range of standard with claims.
Claims (10)
1. a Zhong Gao branch polysiloxanes, be by:
The oligomer of the first silane of 1 weight portion, forms with the second crosslinked with silicane of 0.05 to 20 weight portion,
Wherein this first silane is Si (R1)2(OR2)2, each R1It is respectively acrylic, epoxy radicals, second
Thiazolinyl, amido, aromatic radical or fat-based, and each R2It is respectively fat-based;
Wherein this second silane is Si (R3)(OR4)3, R3For acrylic, epoxy radicals, vinyl, amido,
Aromatic radical or fat-based, and each R4It is respectively fat-based.
High branch the most as claimed in claim 1 polysiloxanes, wherein the oligomer of this first silane is viscous
Degree is 10cps to 500cps.
3. a hybrid material, it is by including that following substance reaction forms:
High branch polysiloxanes described in claim 1, and
The surface of 0.01 to 70 weight portion has the inorganic oxide of hydroxyl.
4. hybrid material as claimed in claim 3, wherein surface has this inorganic oxide bag of hydroxyl
Include silicon oxide, titanium oxide, aluminium oxide or combinations of the above.
5. hybrid material as claimed in claim 3, wherein surface has this inorganic oxide of hydroxyl
Particle diameter is 0.1nm to 1000nm.
6. the forming method of a Zhong Gao branch polysiloxanes, including:
Take the oligomer of the first silane of 1 weight portion, form with the second crosslinked with silicane of 0.05 to 20 weight portion
High branch polysiloxanes,
Wherein this first silane is Si (R1)2(OR2)2, each R1It is respectively acrylic, epoxy radicals, second
Thiazolinyl, amido, aromatic radical or fat-based, and each R2It is respectively fat-based;
Wherein this second silane is Si (R3)(OR4)3, R3For acrylic, epoxy radicals, vinyl, amido,
Aromatic radical or fat-based, and each R4It is respectively fat-based.
The forming method of high branch the most as claimed in claim 6 polysiloxanes, wherein this first silane
The viscosity of oligomer is 10cps to 500cps.
8. a forming method for hybrid material, including:
Take the high branch polysiloxanes described in claim 1, and
The surface of 0.01 to 70 weight portion has the inorganic oxide reaction of hydroxyl and forms.
9. the forming method of hybrid material as claimed in claim 8, wherein surface has this nothing of hydroxyl
Machine oxide includes silicon oxide, titanium oxide, aluminium oxide or combinations of the above.
10. the forming method of hybrid material as claimed in claim 8, wherein surface has being somebody's turn to do of hydroxyl
The particle diameter of inorganic oxide is 0.1nm to 1000nm.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/582,342 | 2014-12-24 | ||
US14/582,342 US20160185911A1 (en) | 2014-12-24 | 2014-12-24 | Polysiloxane and hybrid material and method for manufacturing the same |
TW103145161 | 2014-12-24 | ||
TW103145161A TWI512012B (en) | 2014-12-24 | 2014-12-24 | Hyperbranched polysiloxane and hybrid material and method for manufacturing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105985522A true CN105985522A (en) | 2016-10-05 |
CN105985522B CN105985522B (en) | 2019-06-28 |
Family
ID=57042463
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510083438.5A Active CN105985522B (en) | 2014-12-24 | 2015-02-16 | Highly branched polysiloxanes and hybrid materials and methods of forming the same |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105985522B (en) |
Citations (3)
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 |
-
2015
- 2015-02-16 CN CN201510083438.5A patent/CN105985522B/en active Active
Patent Citations (3)
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 |
Also Published As
Publication number | Publication date |
---|---|
CN105985522B (en) | 2019-06-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR100276803B1 (en) | Silicone Emulsion Coating Composition And Method Of Making The Same | |
CN1093900C (en) | Ovenable food tray and its mfg. method | |
CN110041473B (en) | Silicon-modified water-based acrylic emulsion and preparation method and application thereof | |
CN1286885C (en) | Organofunctional silicone copolymers and the saponification products thereof | |
US20110034615A1 (en) | Process for producing sugar-plum-shaped particle | |
CN104231918B (en) | The quick-dry type oiliness infiltration nano combined protective agent of film-forming type and preparation method and application | |
CN104812854B (en) | Superhydrophilic antireflection coating composition comprising silicone compounds utilizes its Superhydrophilic antireflection film and preparation method thereof | |
CN106118456A (en) | A kind of ceramic tile antilubricant and its preparation method and application | |
CN107892748A (en) | A kind of preparation method of room-temperature moisture cured silicones | |
CN105348998A (en) | Organosilicon modified waterborne photo-curing epoxy-acrylic coating and preparation method thereof | |
CN103382236B (en) | Silicon-acralyte latex of a kind of high silicone content and preparation method thereof | |
JP2008504209A5 (en) | ||
JP5730012B2 (en) | Solvent-free coating solution for film formation, coating solution and method for producing film | |
CN101517003A (en) | Oxide fine particle-containing organic-inorganic hybrid polymer composition and method for producing the same | |
JPH026556A (en) | Baking device coating | |
CN106554500A (en) | A kind of hydrophobically modified epoxy resin and preparation method thereof | |
CN101490176A (en) | Oxide particle-containing resin composition and method for producing the same | |
CN105985522A (en) | Highly branched polysiloxanes and hybrid materials and methods of forming the same | |
CN105348899A (en) | Coupling agent | |
NO771940L (en) | DIFFICULT STATEMENTS OF SILICO-ORGANIC COMPOUNDS | |
CN108587444A (en) | A kind of environmental protection coating material and preparation method thereof | |
CN102585234B (en) | Macromolecular coupling agent, preparation method and application thereof | |
JP2000334373A (en) | Inorganic coated article | |
CN104311863A (en) | Methyl silicone resin thin film and preparation method thereof | |
JPH10158594A (en) | Silicone-transfer film and transfer constituent |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |