TWI512012B - Hyperbranched polysiloxane and hybrid material and method for manufacturing the same - Google Patents

Description

High-branched polyoxane and mixed material and method of forming same

This invention relates to hybrid materials, and more particularly to the composition and formation of high branched polyoxyalkylenes.

3C electronics, displays, or lighting products are moving in a light, short, and short direction. The thickness of the glass as the substrate is gradually reduced from several micrometers to about 0.1 micrometer, and the fragile glass requires a transparent protective layer. The transparent protective layer requires heat resistance to meet the current ITO-plated process requirements (at least 300-350 ° C). The polymer material, which is often used as a protective layer, has yellowing in addition to the coloring problem itself. The current high temperature and transparent choice is the polysiloxane of the silicone system, so the development of new polyoxyalkylene materials or their processes is a trend.

According to one embodiment of the present invention, a high-branched polyoxyalkylene is obtained by crosslinking 1 part by weight of an oligomer of a first decane with 0.05 to 20 parts by weight of a second decane, wherein the first decane-based Si ( R ¹ ) ₂ (OR ² ) ₂ , each R ^{1 is} each an acryl group, an epoxy group, a vinyl group, an amine group, an aryl group, or a fat group, and each R ² is an aliphatic group; wherein the second decane Si(R ³ )(OR ⁴ ) ₃ , R ³ is an acryl group, an epoxy group, a vinyl group, an amine group, or an aliphatic group, and each R ⁴ is an aliphatic group.

A mixed material according to an embodiment of the present invention is obtained by reacting the above-mentioned high-branched polyoxane and 0.01 to 70 parts by weight of an inorganic oxide having a hydroxyl group on its surface.

A method for forming a high-branched polyoxane according to an embodiment of the present invention comprises: taking 1 part by weight of an oligomer of a first decane, and crosslinking with 0.05 to 20 parts by weight of a second decane to form a high-branched polyfluorene Oxane, wherein the first decane is Si(R ¹ ) ₂ (OR ² ) ₂ , and each R ^{1 is} each an acryl, epoxy, vinyl, amine, aryl, or aliphatic group, and each R ² each being a fatty group; wherein the second decane is Si(R ³ )(OR ⁴ ) ₃ , R ³ is an acryl group, an epoxy group, a vinyl group, an amine group, an aryl group, or a fat group, and each R ⁴ Each is a fat base.

A method for forming a mixed material according to an embodiment of the present invention comprises: reacting the above-mentioned high-branched polyoxyalkylene oxide, and 0.01 to 70 parts by weight of an inorganic oxide having a hydroxyl group on the surface thereof.

1‧‧‧ first decane

3‧‧‧ oligomer

5‧‧‧Secondane

7‧‧‧High-branched polyoxyalkylene

9‧‧‧Inorganic oxides with hydroxyl groups on the surface

11‧‧‧Mixed materials

Fig. 1 is a schematic view showing a method of forming a highly branched polyoxyalkylene and a mixed material in an embodiment of the present invention.

As shown in Fig. 1, 1 part by weight of the first decane 1 was hydrolyzed and polymerized in an acidic aqueous solution to form an oligomer 3. In an embodiment of the invention, the first decane 1 has a structure of Si(R ¹ ) ₂ (OR ² ) ₂ , and each of R ¹ is an acryl group, an epoxy group, a vinyl group, an amine group, an aryl group, Or a fatty group, and each R ^{2 is} each a fatty group. In an embodiment of the invention, the acidic aqueous solution further comprises an alcohol such as methanol, ethanol, isopropanol to adjust the rate of hydrolysis. The viscosity of the above oligomers may be between 10 cps and 500 cps. If the viscosity of the oligomer is too high, the subsequently formed product is easily atomized. If the viscosity of the oligomer is too low, the gelation problem cannot be avoided in the subsequent crosslinking step.

Next, 0.05 to 20 parts by weight or 0.1 to 10 parts by weight of the second decane 5 is mixed with the solution of the above oligomer, and crosslinked to form a highly branched polyoxane 7. The second decane 5 is Si(R ³ )(OR ⁴ ) ₃ , R ³ is an acryl group, an epoxy group, a vinyl group, an amine group, an aryl group, or an aliphatic group, and each R ⁴ is an aliphatic group. If the amount of the second decane 5 is too high, the crosslinked product is easily gelled and cannot be used for subsequent applications. If the amount of the second decane 5 is too low, the highly branched polyoxyalkylene is incompletely hardened after being coated into a film.

In one embodiment of the present invention, 0.01 to 70 parts by weight of the inorganic oxide 9 having a hydroxyl group on the surface may be further reacted with the above-mentioned high-branched polyoxosiloxane 7 to form a mixed material 11. The hydroxyl group of the highly branched polyoxyalkylene 7 is dehydrated with the hydroxyl group on the surface of the inorganic oxide 9 to form an -O-Si-O-bond. If the amount of the inorganic oxide is too high, aggregation is liable to lower the transmittance of the mixed material. In an embodiment of the invention, the inorganic oxide 9 may be cerium oxide, titanium oxide, aluminum oxide, or a combination thereof. In an embodiment of the invention, the inorganic oxide 9 has a particle size between 0.1 nm and 1000 nm. If the particle size of the inorganic oxide is too large, the transparency of the product is affected.

The above-mentioned mixed material 11 can be applied to a substrate such as glass or ceramic, and after heat hardening, a protective coating can be formed. In an embodiment of the invention, the protective coating has a transmittance of between 90% and 99.9% and a heat resistance of up to about 450 °C. The above transparent transparent coating with high heat resistance can effectively protect the substrate.

The above and other objects, features, and advantages of the present invention are obtained. It can be more obvious and easy to understand. The following specific examples are combined with the attached drawings to explain in detail as follows:

Example

Example 1 (second decane/first decane = 5:1)

10 g of dimethyldimethoxydecane, 72.0 g of isopropyl alcohol, 6.0 g of 0.01 M aqueous HCl, and 26.3 g of deionized water were poured into a 1 L round bottom flask, and stirred at 35 ° C for 1.5 hours. The hydrolytic polymerization forms an oligomer with a viscosity of 50 to 200 cps. Next, 50 g of methyltrimethoxy decane was added to the above oligomer, and stirred at 35 ° C for 1.5 hours to crosslink to form a highly branched polyoxyalkylene. The water was separated from the isopropanol by concentration under reduced pressure to obtain a clear mucus.

The transparent mucus was applied as a film by a doctor blade, and then heated to 170 ° C to be cured to form a film having a thickness of 0.1 to 200 μm (oven film formation). The above film had heat resistance of 210 ° C and a transparency of 92% (colorimeter).

Example 2 (second decane/first decane = 3:1)

15 g of dimethyldimethoxydecane, 72.0 g of isopropyl alcohol, 6.0 g of 0.01 M aqueous HCl, and 26.6 g of deionized water were poured into a 1 L round bottom flask, and stirred at 35 ° C for 1.5 hours. The hydrolytic polymerization forms an oligomer with a viscosity of 50 to 200 cps. Next, 45 g of methyltrimethoxy decane was added to the above oligomer, and stirred at 35 ° C for 1.5 hours to crosslink to form a highly branched polyoxyalkylene. The water was separated from the isopropanol by concentration under reduced pressure to obtain a clear mucus.

The transparent mucus was applied as a film by a doctor blade, and then heated to 170 ° C to be cured to form a film having a thickness of 0.1 to 200 μm (oven film formation). The above film had a heat resistance of 210 ° C and a transparency of 92% (colorimeter).

Example 3 (second decane / first decane = 1:1)

30 g of dimethyldimethoxydecane, 72.0 g of isopropyl alcohol, 6.0 g of 0.01 M aqueous HCl, and 27.8 g of deionized water were poured into a 1 L round bottom flask, and stirred at 35 ° C for 1.5 hours. The hydrolytic polymerization forms an oligomer with a viscosity of 50 to 200 cps. Next, 30 g of methyltrimethoxy decane was added to the above oligomer, and stirred at 35 ° C for 1.5 hours to crosslink to form a highly branched polyoxyalkylene. The water was separated from the isopropanol by concentration under reduced pressure to obtain a clear mucus.

The transparent liquid was applied as a film by a doctor blade, and then heated to 210 ° C to be cured to form a film having a thickness of 0.1 to 200 μm (oven film formation). The above film had a heat resistance of 210 ° C and a transparency of 92% (colorimeter).

Example 4 (second decane / first decane = 1:3)

45 g of dimethyldimethoxydecane, 72.0 g of isopropyl alcohol, 6.0 g of 0.01 M aqueous HCl, and 28.8 g of deionized water were poured into a 1 L round bottom flask, and stirred at 35 ° C for 1.5 hours. The hydrolytic polymerization forms an oligomer with a viscosity of 50 to 200 cps. Next, 15 g of methyltrimethoxy decane was added to the above oligomer, and stirred at 35 ° C for 1.5 hours to crosslink to form a highly branched polyoxyalkylene. The water was separated from the isopropanol by concentration under reduced pressure to obtain a clear mucus.

The transparent mucus was applied as a film by a doctor blade, and then heated to 210 ° C to be cured to form a film having a thickness of 0.1 to 200 μm (oven film formation). The above film had a heat resistance of 300 ° C and a transparency of 92% (colorimeter).

Example 5 (second decane / first decane = 1:10)

54.5 g of dimethyldimethoxydecane, 72.0 g of isopropyl alcohol, 6.0 g of 0.01 M aqueous HCl, and 30.1 g of deionized water were poured into a 1 L round bottom flask, and stirred at 35 ° C for 1.5 hours. The hydrolysis polymerizes to form an oligomer having a viscosity of 50 to 200 cps. Next, 5.45 g of methyltrimethoxy decane was added to the above oligomer at 35 The mixture was stirred at ° C for 1.5 hours to crosslink to form a highly branched polyoxyalkylene. The water was separated from the isopropanol by concentration under reduced pressure to obtain a clear mucus.

The transparent mucus was applied as a film by a doctor blade, and then heated to 210 ° C to be cured to form a film having a thickness of 0.1 to 200 μm (oven film formation). The above film had a heat resistance of 400 ° C and a transparency of 92% (colorimeter).

Comparative Example 1 (second decane/first decane = 12:1)

4.62 g of dimethyldimethoxydecane, 72.0 g of isopropyl alcohol, 6.0 g of 0.01 M aqueous HCl, and 25.4 g of deionized water were poured into a 1 L round bottom flask, and stirred at 35 ° C for 1.5 hours. The hydrolysis polymerizes to form an oligomer having a viscosity of 50 to 200 cps. Next, 55.4 g of methyltrimethoxy decane was added to the above oligomer, and stirred at 35 ° C for 1.5 hours to crosslink to form a highly branched polyoxyalkylene. The water was separated from the isopropanol by concentration under reduced pressure to obtain a clear mucus. The above product is gelled in a short time and cannot be used.

Comparative Example 2 (second decane / first decane = 1:20)

57.1 g of dimethyldimethoxydecane, 72.0 g of isopropyl alcohol, 6.0 g of 0.01 M aqueous HCl, and 29.7 g of deionized water were poured into a 1 L round bottom flask, and stirred at 35 ° C for 1.5 hours. It undergoes hydrolysis polymerization to form an oligomer. Next, 2.86 g of methyltrimethoxy decane was added to the above oligomer, and stirred at 35 ° C for 1.5 hours to crosslink to form a highly branched polyoxyalkylene. The water was separated from the isopropanol by concentration under reduced pressure to obtain a clear mucus.

The transparent mucus was applied as a film by a doctor blade, and then heated to 400 ° C to be cured to form a film having a thickness of 0.1 to 200 μm. The hardening of the above film is incomplete.

Comparative Example 3 (second decane reacted with first decane, second decane / first decane = 3:1)

15.0 g of dimethyldimethoxydecane, 45.0 g of methyltrimethoxydecane, 72.0 g of isopropanol, 6.0 g of 0.01 M aqueous HCl, and 26.6 g of deionized water were poured into a 1 L round bottom bottle. The mixture was stirred at 35 ° C for 1.5 hours and then gelled and could not be used.

Comparative Example 4 (second decane reacted with first decane, second decane / first decane = 1:1)

30.0 g of dimethyldimethoxydecane, 30.0 g of methyltrimethoxydecane, 72.0 g of isopropanol, 6.0 g of 0.01 M aqueous HCl, and 27.8 g of deionized water were poured into a 1 L round bottom bottle. The mixture was stirred at 35 ° C for 1.5 hours and then gelled and could not be used.

Comparative Example 5 (second decane was reacted with first decane, second decane / first decane = 1:3)

45.0 g of dimethyldimethoxydecane, 15.0 g of methyltrimethoxydecane, 72.0 g of isopropanol, 6.0 g of 0.01 M aqueous HCl, and 16.06 g of deionized water were poured into a 1 L round bottom bottle. The mixture was stirred and stirred at 35 ° C for 1.5 hours to form a transparent liquid. The transparent liquid was applied as a film by a doctor blade, and then heated to 210 ° C to be cured to form a film having a thickness of 0.1 to 200 μm. The above film has a cracking phenomenon.

Comparative Example 6 (polymerization of the second decane to an oligomer followed by reaction with the first decane, second decane / first decane = 1:1)

30 g of methyltrimethoxy decane, 72.0 g of isopropyl alcohol, 6.0 g of 0.01 M aqueous HCl, and 27.8 g of deionized water were poured into a 1 L round bottom flask, and stirred at 35 ° C for 1.5 hours to cause hydrolysis polymerization. An oligomer was formed and its viscosity was not measured. Next, 30 g of dimethyldimethoxydecane was added to the above oligomer, and stirred at 35 ° C for 1.5 hours to crosslink to form a highly branched polyoxyalkylene. The water was separated from the isopropanol by concentration under reduced pressure to obtain a clear mucus. The above product is gelled in a short time and cannot be used.

Table 1

As can be seen from the comparison of the first table, it is necessary to first take the first decane to form an oligomer and then cross-link the second decane, and the ratio of the first decane to the second decane is also appropriate. If the first decane is reacted with the second decane at the same time, or the second decane is first reacted and then the first decane is added, the product is not gelatinized or the film forming property is poor.

Example 6 (second decane/first decane = 3:1, high branched polyoxane: yttrium oxide = 70:30)

15.0 g of dimethyldimethoxydecane, 72.0 g of isopropyl alcohol, 6.0 g of 0.01 M aqueous HCl, and 16.06 g of deionized water were poured into a 1 L round bottom flask, and stirred at 35 ° C for 1.5 hours. The hydrolysis polymerizes to form an oligomer having a viscosity of 50 to 200 cps. Next, 45.0 g of 3-(trimethoxydecyl)propyl acrylate and 68.69 g of an isopropyl alcohol dispersion of cerium oxide (IPA-ST available from Nissan Chemical, particle size 10-15 nm) were added to the above oligomerization. Stir at 35 ° C for 1.5 hours to form a high A mixed material in which a branched polyoxane is reacted with cerium oxide. Concentration and concentration of water and isopropanol under reduced pressure gave a yellowish transparent liquid (59.30 g), a cerium oxide content of 30.43 wt%, and a high-branched polyoxane content of 69.57 wt%. The yellowish transparent liquid was applied as a film by a doctor blade, and then heated to 170 ° C to be cured to form a film having a thickness of 0.1 to 200 μm (oven film formation). The above film had a heat resistance of 210 ° C and a transparency of 92% (colorimeter).

Example 7 (second decane/first decane = 10:1, high branched polyoxane: yttrium oxide = 72:28)

6.0 g of dimethyl dimethoxy decane, 79.2 g of isopropyl alcohol, 6.6 g of 0.01 M HCl aqueous solution, and 14.42 g of deionized water were poured into a 1 L round bottom flask, and stirred at 35 ° C for 1.5 hours. The hydrolysis polymerizes to form an oligomer having a viscosity of 50 to 200 cps. Next, 60.0 g of 3-(trimethoxydecyl)propyl acrylate was added to 76.58 g of an isopropyl alcohol dispersion of cerium oxide (IPA-ST available from Nissan Chemical, particle size 10-15 nm) to the above oligomerization. The mixture was stirred at 35 ° C for 1.5 hours to form a mixed material in which a highly branched polyoxyalkylene was reacted with cerium oxide. Concentration and concentration of water and isopropanol under reduced pressure gave a yellowish transparent liquid (80.20 g), a yttrium oxide content of 28.65 wt%, and a high branched polyoxane content of 71.35 wt%. The yellowish transparent liquid was applied as a film by a doctor blade, and then heated to 170 ° C to be cured to form a film having a thickness of 0.1 to 200 μm (oven film formation). The above film had a heat resistance of 210 ° C and a transparency of 92% (colorimeter).

Example 8 (second decane/first decane = 10:1, high-branched polyoxane: yttrium oxide = 62:38)

6.0 g of dimethyl dimethoxy decane, 79.2 g of isopropyl alcohol, 6.6 g of 0.01 M HCl aqueous solution, and 14.42 g of deionized water were poured into a 1 L round bottom bottle and mixed at 35 The mixture was stirred for 1.5 hours at ° C to hydrolyze and polymerize to form an oligomer having a viscosity of 50 to 200 cps. Next, 60.0 g of 3-(trimethoxydecyl)propyl acrylate was added to the above oligomerization with 119.13 g of an isopropyl alcohol dispersion of cerium oxide (IPA-ST available from Nissan Chemical, particle size 10-15 nm). The mixture was stirred at 35 ° C for 10 minutes to form a mixed material in which a highly branched polyoxyalkylene was reacted with cerium oxide. Concentration and concentration of water and isopropanol under reduced pressure gave a yellowish transparent liquid (92.70 g), a yttrium oxide content of 38.55 wt%, and a high branched polyoxane content of 61.45 wt%. The yellowish transparent liquid was applied as a film by a doctor blade, and then heated to 170 ° C to be cured to form a film having a thickness of 0.1 to 200 μm (oven film formation). The above film had a heat resistance of 210 ° C and a transparency of 92% (colorimeter).

Example 9 (second decane/first decane = 1:1, high-branched polyoxane: yttrium oxide = 90:10)

50.0 g of dimethyldimethoxydecane, 60 g of isopropyl alcohol, 5.6 g of 0.01 M aqueous HCl, and 9.4 g of deionized water were poured into a 1 L round bottom flask, and stirred at 35 ° C for 2 hours. The hydrolytic polymerization forms an oligomer with a viscosity of 50 to 200 cps. Next, 50.0 g of trimethoxymethyl decane was added and stirred at 35 ° C for 1.5 hours to form a highly branched polyoxyalkylene material. 20.0 g of an isopropyl alcohol dispersion of cerium oxide (IPA-ST from Nissan Chemical, particle size 10-15 nm) was added to the above-mentioned high-branched polyoxyalkylene material, and stirred at 35 ° C for 10 minutes to form a high branching polymerization. A mixed material of a reaction of a siloxane with cerium oxide. Concentration of water and isopropanol under reduced pressure gave a clear liquid (65.2 g), a yttrium oxide content of 10 wt%, and a high-branched polyoxane content of 90 wt%. The transparent liquid was applied as a film by a doctor blade, and then heated to 210 ° C to be cured to form a film having a thickness of 0.1 to 200 μm (oven film formation). The above film had a heat resistance of 210 ° C and a transparency of 92% (colorimeter).

Example 10 (second decane/first decane = 1:10, high-branched polyfluorene Oxyalkane: yttrium oxide = 93:7)

30.0 g of dimethyldimethoxydecane, 10 g of isopropanol, 2 g of 0.01 M aqueous HCl, and 5.1 g of deionized water were poured into a 1 L round bottom flask, and stirred at 35 ° C for 1.5 hours to hydrolyze. Polymerization forms oligomers with a viscosity of 50 to 200 cps. Next, 3.0 g of trimethoxymethyl decane was added and stirred at 35 ° C for 1.5 hours to form a highly branched polyoxyalkylene material. 6.0 g of iridium oxide dispersion of cerium oxide (IPA-ST from Nissan Chemical, particle size 10-15 nm) was added to the above-mentioned high-branched polyoxyalkylene material, and stirred at 35 ° C for 10 minutes to form a high-branched polyfluorene. A mixed material of oxane and cerium oxide. Concentration of water and isopropanol under reduced pressure gave a clear liquid (22.1 g), a yttrium oxide content of 7 wt%, and a high-branched polyoxane content of 93 wt%. The transparent liquid was applied as a film by a doctor blade, and then heated to 210 ° C to be cured to form a film having a thickness of 0.1 to 200 μm (oven film formation). The above film had a heat resistance of 400 ° C and a transparency of 92% (colorimeter).

As can be seen from the second table, the substituents on the second decane have various options.

Comparative Example 7

30.0 g of commercially available polydimethyloxane (DMS-S35 from Gelest, viscosity 5,000 cps), 30.0 g of trimethoxymethylnonane, 72.0 g of isopropanol, 6.0 g of 0.01 M HCl The aqueous solution was mixed with 16.06 g of deionized water and poured into a 1 L round bottom bottle. The trimethoxymethyl decane and DMS-S35 could not be mixed with each other to form a misty liquid, which was allowed to stand for stratification.

Comparative Example 8

10.0 g of commercially available polydimethyloxane (DMS-S35 from Gelest, viscosity: 5000 cps), 10.0 g of iridium oxide dispersion of cerium oxide (IPA-ST available from Nissan Chemical, particle size) 10~15nm) was poured into a 1L round bottom bottle, and the iridium oxide dispersion of cerium oxide and DMS-S35 could not be mixed with each other to form a misty liquid, and the layer was allowed to stand.

As is apparent from Comparative Examples 7 and 8, when the oligomer obtained by hydrolyzing and polymerizing the first decane was replaced with a polymer (having a high viscosity), a transparent film could not be formed.

While the invention has been described above in terms of several embodiments, it is not intended to limit the invention, and any one of ordinary skill in the art can be modified and modified without departing from the spirit and scope of the invention. Therefore, the scope of the invention is defined by the scope of the appended claims.

1‧‧‧ first decane

3‧‧‧ oligomer

5‧‧‧Secondane

7‧‧‧High-branched polyoxyalkylene

9‧‧‧Inorganic oxides with hydroxyl groups on the surface

11‧‧‧Mixed materials

Claims (8)

A highly branched polyoxyalkylene obtained by crosslinking 1 part by weight of a first decane oligomer with 0.1 to 10 parts by weight of a second decane, wherein the first decane is Si(R ¹ ) ₂ (OR ² ) ₂ , each R ^{1 is} each an acryl group, an epoxy group, a vinyl group, an amine group, an aryl group, or a fat group, and each R ² is an aliphatic group; wherein the second decane is Si ( R ³ )(OR ⁴ ) ₃ , R ³ is an acryl group, an epoxy group, a vinyl group, an amine group, an aryl group, or a fat group, and each R ⁴ is an aliphatic group, wherein the oligomerization of the first decane The viscosity of the substance is between 10 cps and 500 cps. A mixed material comprising: a high-branched polyoxyalkylene as described in claim 1 and 0.01 to 70 parts by weight of an inorganic oxide having a hydroxyl group on its surface. The mixed material of claim 2, wherein the inorganic oxide having a hydroxyl group on the surface comprises cerium oxide, titanium oxide, aluminum oxide, or a combination thereof. The mixed material according to claim 2, wherein the inorganic oxide having a hydroxyl group on the surface has a particle diameter of from 0.1 nm to 1000 nm. A method for forming a high-branched polyoxane, comprising: taking 1 part by weight of an oligomer of a first decane, and crosslinking with 0.1 to 10 parts by weight of a second decane to form a high-branched polyoxane, wherein the a monodecane-based Si(R ¹ ) ₂ (OR ² ) ₂ , each R ¹ being an acryl group, an epoxy group, a vinyl group, an amine group, an aryl group, or a fat group, and each R ² is a fat group Wherein the second decane is Si(R ³ )(OR ⁴ ) ₃ , R ³ is an acryl group, an epoxy group, a vinyl group, an amine group, an aryl group, or an aliphatic group, and each R ⁴ is a fat group Wherein the oligomer of the first decane has a viscosity of between 10 cps and 500 cps. A method for forming a mixed material, comprising: reacting a high-branched polyoxyalkylene as described in claim 1 and 0.01 to 70 parts by weight of an inorganic oxide having a hydroxyl group on its surface. The method for forming a mixed material according to claim 6, wherein the inorganic oxide having a hydroxyl group on the surface comprises cerium oxide, titanium oxide, aluminum oxide, or a combination thereof. The method for forming a mixed material according to claim 6, wherein the inorganic oxide having a hydroxyl group on the surface has a particle diameter of from 0.1 nm to 1000 nm.