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Title:
PHENOLIC RESIN COMPOSITIONS AS BINDERS IN REFRACTORY ARTICLES
Document Type and Number:
WIPO Patent Application WO/2023/192765
Kind Code:
A4
Abstract:
A liquid phenolic resin composition for use as a binder for a refractory article, the phenolic resin composition comprising a phenol formaldehyde resin, wherein the phenolic resin composition has a reduced vaporization percentage of phenolic compounds. The phenolic resin composition is used in refractory compositions comprising at least 50 wt.% of one or more refractory aggregate(s), based on a total weight of the refractory composition. There is also disclosed a refractory article, such as a brick, formed into a shape comprising said refractory composition and heating until the phenolic resin composition is at least 20% cured and having a green strength after curing at 170 °C for 5 hours sufficient for handling the solid without falling apart. The bricks can be used to make inner liners of ladles which can transport and pour molten metals.

Inventors:
PENDALWAR SHEKHAR L (US)
WRIGHT JAMES T (US)
ARTHUR LISA M (US)
RIEDLINGER DARREN A (US)
CELIKBAG YUSUF (US)
VENTZ TOMASZ (US)
Application Number:
PCT/US2023/064270
Publication Date:
January 25, 2024
Filing Date:
March 14, 2023
Export Citation:
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Assignee:
ARCLIN USA LLC (US)
HARBISONWALKER INT HOLDINGS INC (US)
International Classes:
B22D41/05; B22D41/12; C04B38/00
Attorney, Agent or Firm:
DAHLEN, Garth M. (US)
Download PDF:
Claims:
AMENDED CLAIMS received by the International Bureau on 12 Dec 2023 (12.12.2023)

1. A liquid phenolic resin composition for use as a binder for a refractory article, the phenolic resin composition comprising a phenol formaldehyde resin, wherein the phenolic resin composition has a vaporization percentage of phenol of less than 4.1% as measured by the following steps:

(a) curing 5 grams of liquid resin at 170 °C for 5 hours to form a solid;

(b) cooling the solid to room temperature and then weighing 1 gram of the solid;

(c) heating the 1 gram of solid in a tube furnace from room temperature to 1000 °C at 15 °C/minute, and then being held at 1000 °C under an inert atmosphere for 10 minutes to form a vaporized composition;

(d) collecting the vaporized composition that vaporizes off from the solid in step (c);

(e) quantifying the amount of phenol that vaporized from the solid in step (c); and

(f) determining the amount of the vaporized phenol as a percentage of the 1 gram of cooled solid in step (b).

2. The phenolic resin composition according to claim 1, wherein the phenolic resin composition meets one or more of the following properties: a) viscosity is 50-10,000 cPs, as measured with a Brookfield RVF viscometer using a No. 1 spindle at 20 rpm, at 25°C; b) pH is 7 to less than 11 ; c) nonvolatile content is 65-85 wt.%; and d) free formaldehyde of less than about 0.3 wt. %.

3. The phenolic resin composition according to claim 1, wherein the vaporization percentage of the phenol is less than Reference Sample R-l as measured during a step of heating the phenolic resin composition to at least 1000 °C.

4. The phenolic resin composition according to claim 1 , wherein the number average molecular weight (Mn) of the phenol formaldehyde resin is less than 3000 g/mol as measured by gel permeation chromatography (GPC), or the weight average molecular weight (Mw) of the phenol formaldehyde resin is less than 5000 g/mol, as measured by GPC, or the phenol formaldehyde resin has a polydispersity (Mw/Mn) is less than 10.

5. A liquid phenolic resin composition for use as a binder for a refractory article, the phenolic resin composition comprising a phenol formaldehyde resin formed from one or more phenolic

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AMENDED SHEET (ARTICLE 19) compound(s) (P) and one or more formaldehyde compound(s) (F), wherein the phenol formaldehyde resin is optionally formed in the presence of a reaction catalyst, said phenolic resin composition has the following feature (I) and/or (II), wherein feature (I) the phenol formaldehyde resin has a molar ratio (MR) of F to P of greater than

1.2, and feature (II) the phenolic resin composition further comprises one or more vapor suppressant(s), wherein the phenolic resin composition has a vaporization percentage of (P) as measured by the following steps:

(a) curing 5 grams of liquid resin at 170 °C for 5 hours to form a solid;

(b) cooling the solid to room temperature and then weighing 1 gram of the solid;

(c) heating the 1 gram of solid in a tube furnace from room temperature to 1000 °C at 15 °C/minute, and then being held at 1000 °C under an inert atmosphere for 10 minutes to form a vaporized composition;

(d) collecting the vaporized composition that vaporizes off from the solid in step (c);

(e) quantifying the amount of (P) that vaporized from the solid in step (c); and

(f) determining the amount of the vaporized (P) as a percentage of the 1 gram of cooled solid in step (b); wherein the vaporization percentage of the one or more phenolic compounds which is less than a reference phenolic resin composition lacking both features (I) and (II).

6. The phenolic resin composition according to claim 5, wherein the vaporization percentage of the (P) is less than 4.1%.

7. The phenolic resin composition according to claim 5, wherein the phenolic resin composition meets one or more of the following properties: a) viscosity is 50-10,000 cPs, as measured with a Brookfield RVF viscometer using a No. 1 spindle at 20 rpm, at 25°C; b) pH is 7 to less than 11 ; c) nonvolatile content is 65-85 wt.%; and d) free formaldehyde of less than about 0.3 wt. %.

8. A liquid phenolic resin composition for use as a binder for a refractory article, the phenolic resin composition comprising a phenol formaldehyde resin formed from one or more phenolic

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AMENDED SHEET (ARTICLE 19) compound(s) (P) and one or more formaldehyde compound(s) (F), wherein the phenol formaldehyde resin is optionally formed in the presence of a reaction catalyst, said phenolic resin composition has the following feature (I) and/or (II), wherein feature (I) the phenol formaldehyde resin has a molar ratio (MR) of F to P of greater than

I.2, and feature (II) the phenolic resin composition further comprises one or more vapor suppressant(s), and wherein a vaporization percentage of the (P) is less than Reference Sample R-l.

9. The phenolic resin composition according to claim 1, wherein the phenolic resin composition further comprises one or more vapor suppressant(s) selected from magnesium-containing compound; manganese-containing compound; iron-containing compound; cobalt-containing compound; nickel-containing compound; copper-containing compound; tin-containing compound; phosphorus-containing compound; silicon-containing compound; aluminum- containing compound; zinc-containing compound; molybdenum-containing compound; boron- containing compound; zirconium-containing compound; vanadium-containing compound; chromium-containing compound, calcium-containing compound, tungsten-containing compound, titanium-containing compound, niobium-containing compound, cerium-containing compound and mixtures thereof, or wherein the one or more vapor suppressant(s) is one or more plant-based component(s).

10. The phenolic resin composition according to claim 1, wherein the phenolic resin composition further comprises one or more vapor suppressant(s) present in an amount of 0.01 to 20 parts by weight per 100 parts by weight of the phenolic resin composition.

I I. The phenolic resin composition according to claim 5, wherein the phenolic resin composition further comprises one or more vapor suppressant(s) selected from magnesium-containing compound; manganese-containing compound; iron-containing compound; cobalt-containing compound; nickel-containing compound; copper-containing compound; tin-containing compound; phosphorus-containing compound; silicon-containing compound; aluminum- containing compound; zinc-containing compound; molybdenum-containing compound; boron- containing compound; zirconium-containing compound; vanadium-containing compound; chromium-containing compound, calcium-containing compound, tungsten-containing compound, titanium-containing compound, niobium-containing compound, cerium-containing compound and mixtures thereof, or wherein the one or more vapor suppressant(s) is one or more plant-based component(s).

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AMENDED SHEET (ARTICLE 19)

12. The phenolic resin composition according to claim 11, wherein the phenolic resin composition further comprises one or more vapor suppressant(s) present in an amount of 0.01 to 20 parts by weight per 100 parts by weight of the phenolic resin composition.

13. The phenolic resin composition according claim 1, further comprising one or more adhesion promotor(s).

14. The phenolic resin composition according claim 13, wherein the one or more adhesion promotor(s) is one or more silane coupling agent(s).

15. The phenolic resin composition according claim 5, wherein the phenolic resin composition has the feature (I) the phenol formaldehyde resin has a molar ratio (MR) of F to P of greater than 1.2 and further comprises one or more adhesion promotor(s).

16. The phenolic resin composition according claim 15, wherein the one or more adhesion promotor(s) is one or more silane coupling agent(s).

17. A refractory composition comprising the phenolic resin composition according to claim 1 and at least 50 wt.% of one or more refractory aggregate(s), based on a total weight of the refractory composition.

18. A refractory composition comprising the phenolic resin composition according to claim 5 and at least 50 wt.% of one or more refractory aggregate(s), based on a total weight of the refractory composition.

19. A refractory article formed into a shape comprising said refractory composition according to claim 17 and heating until the phenolic resin composition is at least 20% cured and having a green strength after curing at 170 °C for 5 hours sufficient for handling a solid without falling apart.

20. A refractory article formed into a shape comprising said refractory composition according to claim 18 and heating until the phenolic resin composition is at least 20% cured and having a green strength after curing at 170 °C for 5 hours sufficient for handling a solid without falling apart.

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AMENDED SHEET (ARTICLE 19)

21. The refractory article according to claim 19, wherein the article is a brick.

22. The refractory article according to claim 20, wherein the article is a brick.

23. A ladle for transporting and pouring molten metals, wherein said ladle is formed with an inner liner formed by stacking at least two bricks according to claim 21 along the bottom and sides of a ladle shaped metal outer liner, and then heating the stacked bricks to a temperature sufficient to carbonize the resin thereby forming the inner liner of the ladle.

24. A ladle for transporting and pouring molten metals, wherein said ladle is formed with an inner liner formed by stacking at least two bricks according to claim 22 along the bottom and sides of a ladle shaped metal outer liner, and then heating the stacked bricks to a temperature sufficient to carbonize the resin thereby forming the inner liner of the ladle.

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AMENDED SHEET (ARTICLE 19)