Process to break down cellulose polymers and produce cellular solid or solid reaction products

• US 4,226,982 A
• Filed: 02/21/1979
• Issued: 10/07/1980
• Est. Priority Date: 09/11/1970
• Status: Expired due to Term

• Current Assignee: David H. Blount
• Original Assignee: David H. Blount
• Inventors: Blount, David H.
• Primary Examiner(s): Griffin, Ronald W.
• Application Number:
  US06/013,139
• Time in Patent Office: 594 Days
• Field of Search: 536/101, 260/17.2 R, 260/17.4 R, 260/17.4 CL, 260/9, 260/17.3, 521/84, 521/125, 521/130, 521/175
• US Class Current: 536/101
• CPC Class Codes: C08B 1/08 Alkali cellulose
• CPC Class Codes: C08B 15/00 Preparation of other cellulose derivatives or modified cellulose , e.g. complexes
• CPC Class Codes: C08G 18/6484 Polysaccharides and derivatives thereof
• CPC Class Codes: C08H 8/00 Macromolecular compounds derived from lignocellulosic materials pretreatment thereof B27N

Abstract

Small particles of cellulose-containing plants are mixed with an alkali metal hydroxide, such as lye flakes, in the ratio of about 2 parts by weight of the plant to 1 to 3 parts by weight of the alkali metal hydroxide, then heated to 150° C. to 220° C. for 5 to 60 minutes while agitating until the plant particles soften or melt, thereby producing broken-down cellulose polymers in the form of dark brown particles or powder.

Claims

1. The process for the production of water-soluble broken-down alkali metal cellulose polymer by the following steps:

(a) mixing 2 parts by weight of a cellulose-containing plant with 1 to 3 parts by weight of an alkali metal hydroxide;

(b) heating the mixture at 150°

C. to 220°

C. while agitating for 5 to 60 minutes, thereby

(c) producing a water-soluble broken-down alkali metal cellulose polymer.

2. The process of claim 1 wherein the alkali metal hydroxide is selected from the group consisting of sodium hydroxide, potassium hydroxide or mixtures thereof.

3. The process of claim 1 wherein an additional step is taken following step (c) of claim 1 wherein 20% to 200% by weight of water is added, based on the weight of the alkali metal cellulose polymer, to the broken-down alkali metal cellulose polymer, thereby producing an aqueous solution of broken-down alkali metal cellulose polymer.

4. The product produced by the process of claim 1.

5. The process of claim 1 wherein water is added to the alkali metal cellulose polymer, then filtered to remove any insoluble alkali metal cellulose polymer, thereby recovering the alkali metal cellulose not soluble in water.

6. The product produced by the process of claim 5.

7. The process of claim 1 wherein water is added to the alkali metal cellulose polymer, then filtered to remove the insoluble alkali metal cellulose;

the alkali metal cellulose polymer is precipitated from the water by the addition of a mineral acid or an organic acid until the pH is 5 to 7, then filtered, thereby recovering the broken-down cellulose polymer.

8. The product produced by the process of claim 7.

15. The process of claim 11 wherein additional steps are taken wherein 2 parts by weight of the broken-down alkali metal cellulose as produced in step (c) of claim 1, and 1 to 4 parts by weight of an organic polyisocyanate are mixed, then agitated for 10 to 60 minutes at a temperature between 20°

C. to 70°

C., thereby producing a polyisocyanate-broken-down cellulose prepolymer, then 10% to 100% by weight of a curing agent, based on weight of the prepolymer, and selected from the group consisting of water, water containing 1% to 10% by weight of an amine catalyst, water containing 10% to 60% by weight of a polyhydroxy compound, water containing 10% to 60% by weight of silica sol, water containing up to 5% by weight of an emulsifying agent, water containing 10% to 50% by weight of sodium silicate, and mixtures thereof, is added to the prepolymer while agitating at 20°

C. to 80°

C. for 5 to 20 minutes, thereby producing a cellular solid or solid polyisocyanate-broken-down cellulose product.

16. The process of claim 15 wherein the organic polyisocyanate is selected from the group consisting of tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate and mixtures thereof, and the phosgenation product of an anilineformaldehyde condensation.

17. The product produced by the process of claim 16.

18. The process of claim 1 wherein additional steps are taken wherein 1 to 3 parts by weight of the broken-down alkali metal cellulose, 1 to 3 parts by weight of a polyol, and 1 to 3 parts by weight of an organic polyisocyanate are mixed and the resultant mixture is allowed to react, thereby producing a polyurethane-broken-down cellulose cellular solid product.

19. The product produced by the process of claim 18.

20. The process of claim 18 wherein the organic polyisocyanate is selected from the group consisting of tolylene-2,4-diisocyanate;

tolylene-2,6-diisocyanate and mixtures thereof and the phosgenation product of aniline-formaldehyde condensation product.

21. The process of claim 1 wherein 1 to 4 parts by weight of the broken-down alkali metal cellulose and 3 parts by weight of an isocyanate-terminated polyurethane prepolymer are mixed and the resultant mixture is allowed to react, thereby producing a polyurethane-broken-down cellulose cellular solid or solid product.

22. The process of claim 21 wherein the isocyanate-terminated polyurethane prepolymer is selected from the group consisting of an isocyanate-terminated polyester, isocyanate-terminated polyether, isocyanate-terminated polybutadiene, isocyanate-terminated polysulfide and mixtures thereof.

23. The product produced by the process of claim 21.

24. The process of claim 1 wherein additional steps are taken wherein 1 part by weight of the broken-down alkali metal cellulose polymer, as produced in step (c) of claim 1, is added to water to produce an aqueous solution containing 20% to 60% solids, then mixed with 1 to 10 parts by weight of an organic polyisocyanate or polyisothiocyanate, and the resultant mixture is allowed to react, thereby producing a polyisosyanate-broken-down cellulose cellular solid or solid product.

25. The process of claim 24 wherein the polyisocyanate is selected from tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate and mixtures thereof, and polyphenyl-polymethylene-isocyanates.

26. The product produced by the process of claim 24.

27. The process of claim 1 wherein additional steps are taken wherein 10 parts by weight of an aqueous solution containing 20% to 60% by weight of the broken-down alkali metal cellulose polymer, as produced in step (c) of claim 1, are mixed with 10 to 100 parts by weight of an isocyanate-terminated polyurethane prepolymer and 0.001 to 0.01 part by weight of an amine catalyst and the resultant mixture is allowed to react, thereby producing a polyurethane-broken-down cellulose cellular solid or solid product.

28. The process of claim 27 wherein the isocyanate-terminated polyurethane prepolymer is selected from the group consisting of an isocyanate-terminated polyester, isocyanate-terminated polyether, isocyanate-terminated polybutadiene, isocyanate-terminated polysulfide and mixtures thereof.

29. The product produced by the process of claim 27.

30. The process of claim 1 wherein additional steps are taken wherein 1 to 3 parts by weight of the broken-down alkali metal cellulose polymer, as produced in step (c) of claim 1, 1 to 3 parts by weight of an oxidated silicon compound, selected from the group consisting of silica, alkali metal silicates, alkaline earth metal silicates, natural silicates containing free silicic groups and mixtures thereof, 1 to 3 parts by weight of a polyol and 3 parts by weight of an organic polyisocyanate or polyisothiocyanate are mixed, allowing the resultant mixture to react, thereby producing a polyurethane-silicate-broken-down cellulose cellular solid or solid product.

31. The process of claim 30 wherein the polyisocyanate is selected from the groups consisting of tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate and mixtures thereof, polyphenyl-polymethylene-isocyanate and mixtures thereof.

32. The product produced by the process of claim 30.

9. The process for the production of broken-down cellulose foam by mixing 2 parts by weight of a cellulose-containing plant with 1 to 3 parts by weight of an alkali metal hydroxide selected from the group consisting of sodium hydroxide, potassium hydroxide or mixtures thereof, then heating the mixture at 150°

C. to 200°

C. while agitating for 5 to 60 minutes, thereby producing a water-soluble broken-down alkali metal cellulose polymer;

then 1 to 5 parts by weight of an aldehyde selected from the group consisting of formaldehyde, acetaldehyde, propionic aldehyde, furfural, crotonaldehyde, acrolein, benzaldehyde, butyl aldehyde, pentanals, hexanals, heptanals, octanals and mixtures thereof, are mixed with 2 parts by weight of the broken-down alkali metal cellulose polymer, then agitated at ambient temperature for 10 to 120 minutes, thereby producing an aldehyde-broken-down alkali metal cellulose copolymer, then an acid compound, selected from the group consisting of mineral acid, organic acid, hydrogen-containing salt, and mixtures thereof, is added until the pH is 6 to 7, thereby producing an aldehyde-broken-down cellulose copolymer, a cellular solid product, without the addition of a volatile blowing agent.

10. The product produced by the process of claim 9.

11. The process for the production of aminoplast-broken-down cellulose foam by mixing 2 parts by weight of a cellulose-containing plant with 1 to 3 parts by weight of an alkali metal hydroxide selected from the group consisting of sodium hydroxide, potassium hydroxide or mixtures thereof, then heating the mixture at 150°

C. to 220°

C. while agitating for 5 to 60 minutes, thereby producing a water-soluble broken-down alkali metal cellulose polymer;

then 0.5 to 5 mols of an aldehyde per mol of the amino compound and selected from the group consisting of aqueous solution of formaldehyde, acetaldehyde, propionic aldehyde, furfural, crotonaldehyde, acrolein, butyl aldehyde, pentanals, hexanals, heptanals, octanals, paraformaldehyde and mixtures thereof, 1 to 5 parts by weight of an amino compound, selected from the group consisting of urea, thiourea, alkyl ureas, alkyl thiourea, melamine, polyamines, aniline and mixtures thereof, and 2 parts by weight of the broken-down alkali metal cellulose, are mixed, then agitated at a temperature between ambient temperature and 100°

C. for 10 minutes to 12 hours, thereby producing an aminoplast-broken-down cellulose resin;

then an acid compound, selected from the group consisting of a mineral acid, an organic acid and inorganic hydrogen-containing salt, is added until the pH is 5 to 7 while agitating until said resin begins to expand, thereby producing a cellular solid aminoplast-cellulose product, without the addition of a volatile blowing agent.

12. The product produced by the process of claim 11.

13. The process for the production of phenoplast-broken-down cellulose foam by mixing 2 parts by weight of a cellulose-containing plant with 1 to 3 parts by weight of an alkali metal hydroxide selected from the group consisting of sodium hydroxide, potassium hydroxide or mixtures thereof, then heating the mixture at 150°

C. to 220°

C. while agitating for 5 to 60 minutes, thereby producing a water-soluble broken-down alkali metal cellulose polymer, then 1 to 5 parts by weight of a phenol compound, selected from the group consisting of phenol, cresol, creosote, cresylic acid, resorcinol, Bisphenol A, cashew nut shell liquid, 2,6-dimethylphenol, p-tert-butyl-phenol and mixtures thereof, 1 to 5 mols of an aldehyde, selected from the group consisting of aqueous solution of formaldehyde, acetaldehyde, propionic aldehyde, furfural, crotonaldehyde, acrolein, butyl aldehyde, paraformaldehyde, pentanals, hexanals and mixtures thereof, and 2 parts by weight of the broken-down alkali metal cellulose are mixed, then agitated at a temperature from ambient to 100°

C. for 10 minutes to 12 hours, thereby producing a phenoplast-broken-down alkali metal cellulose resin, then an acid compound, selected from the group consisting of a mineral acid, an organic acid and an inorganic hydrogen-containing salt, or mixtures thereof, is added to said resin while agitating until the pH is 5 to 7, and the mixture begins to expand, thereby producing a cellular solid phenoplast-broken-down cellulose product;

1 to 5 mols of the aldehyde are added for each mol of phenol and no volatile blowing agents are added.

14. The product produced by the process of claim 13.

33. The process for the production of a foamed broken-down cellulose polymers which has lost a CO₂ radical per each basic polymer unit by mixing 2 parts by weight of a cellulose-containing plant with 1 to 3 parts by weight of an alkali metal hydroxide selected from the group consisting of sodium hydroxide, potassium hydroxide or mixtures thereof, then heating the mixture at 150°

C. to 220°

C. while agitating for 5 to 60 minutes, thereby producing a water-soluble broken-down alkali metal cellulose polymer, then an acid compound, selected from the group consisting of mineral acids, organic acids, inorganic hydrogen-containing salts and mixtures thereof, is added to the broken-down alkali metal cellulose until the pH is 5 to 7 and the mixture expands, thereby producing a cellular solid broken-down cellulose product, without the addition of a volatile blowing agent.

34. The product produced by the process of claim 33.

35. The process for the production of foamed broken-down lignin-cellulose polymer which has lost a CO₂ radical per each basic cellulose polymer unit by mixing 2 parts by weight of a plant containing lignin and cellulose with 1 to 3 parts by weight of an alkali metal hydroxide selected from the group consisting of sodium hydroxide, potassium hydroxide or mixtures thereof, then heating the mixture at 150°

C. to 220°

C. while agitating for 5 to 60 minutes, thereby producing a water-soluble broken-down alkali metal lignin-cellulose polymer which has lost a CO₂ radical per each basic cellulose polymer unit, then an acid compound, consisting of mineral acids, organic acids, inorganic hydrogen-containing salts and mixtures thereof, is added to the broken-down alkali metal lignin-cellulose polymer until the pH is 5 to 7 and the mixture expands, thereby producing broken-down lignin-cellulose foam, without the addition of a volatile blowing agent.