Inorganic/lignin type polymer composite nanoparticles, preparation method therefor and application thereof

Abstract

The preparation method includes: adding an activating agent into a basic alkaline lignin solution first, then adding a carboxylating agent and reacting to obtain a carboxylated alkaline lignin; dissolving a phosphorylating agent into water, adding epichlorohydrin, and reacting to obtain a hydroxyl phosphate type compound; mixing the carboxylated alkaline lignin and the hydroxyl phosphate type compound and reacting to obtain a lignin type polymer; adding an inorganic nanoparticle suspension into the lignin type polymer and adding an acid for codeposition to obtain the product after aging and drying.

Claims

1. A method of preparing inorganic/lignin polymer composite nanoparticles, comprising: (1) dissolving an alkaline lignin solid into water to formulate a suspension at a concentration of 30%-50% by weight, adjusting the pH to 9-12 with an alkalinity regulator, heating to 60 C. -90 C., adding an activating agent, and reacting for 0.5-2 hours; dissolving a carboxylating agent in a formulation into water to formulate a solution at a concentration of 10%-30% by weight, adding to the above alkaline lignin suspension, and reacting for 1-3 hours at 60 C. -90 C. to obtain carboxylated alkaline lignin; (2) dissolving a phosphorylating agent in the formulation into water to formulate a solution at a concentration of 10%-35% by weight, adding epichlorohydrin, heating to 30 C. -90 C., and reacting for 0.5-3 hours to obtain a hydroxyl phosphate compound; (3) mixing the carboxylated alkaline lignin in (1) with the hydroxyl phosphate compound in (2), adjusting the pH to 10-13 with an alkalinity regulator, heating to 75 C. -95 C., reacting for 0.5-2 hours, and cooling to room temperature to obtain a liquid lignin polymer; (4) adding inorganic nanoparticles into water to formulate a suspension at a concentration of 10%-40% by weight, adding a pretreatment agent, stirring well before adding the liquid lignin polymer in (3), heating to 50 C.-80 C., reacting for 0.5-2 hours, then adding an acidity regulator to regulate the pH to 3-5 before ageing at 50 C. -80 C. for 0.5-4 hours, and then spray-drying to produce the inorganic/lignin polymer composite nanoparticles; the amount of each reactant is as follows in parts by weight: TABLE-US-00004 alkaline lignin 100 inorganic nanoparticles 5-80 activating agent 2-10 carboxylating agent 5-20 phosphorylating agent 5-20 epichlorohydrin 5-15 pretreatment agent 5-10 the activating agent is one or two agents selected from the group consisting of dioxane, sodium periodate, ethanol, isopropanol and acetone; the inorganic nanoparticles are one selected from the group consisting of nano silica, nano alumina, nano zinc oxide, nano titanium dioxide and nano calcium carbonate; the carboxylating agent is one or two agents selected from the group consisting of monochloroacetic acid, monobromoacetic acid, monoiodoacetic acid, sodium monochloroacetate and dichloroacetic acid; the phosphorylating agent is one or two agents selected from the group consisting of sodium dihydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, and diammonium hydrogen phosphate; and the pretreatment agent is one selected from the group consisting of ethanol, acetone, glycerol, isopropanol and cyclohexane.

2. The method of preparing the inorganic/lignin polymer composite nanoparticles according to claim 1, wherein: the alkaline lignin is one or two substances selected from the group consisting of wheat straw alkaline lignin, bamboo pulp alkaline lignin, reed alkaline lignin, wood pulp alkaline lignin, cotton pulp alkaline lignin and bagasse alkaline lignin.

3. The method of preparing the inorganic/lignin polymer composite nanoparticles according to claim 1, wherein: the alkalinity regulator is NaOH aqueous solution at a concentration of 30% by mass.

4. The method of preparing the inorganic/lignin polymer composite nanoparticles according to claim 1, wherein: the acidity regulator is sulfuric acid, phosphoric acid or hydrochloric acid.

5. The acidity regulator according to claim 4, wherein: the sulfuric acid, the phosphoric acid or the hydrochloric acid has a mass concentration of 10%-30%.

6. An inorganic/lignin polymer composite nanoparticles prepared by the method according to claim 1.

7. Application of the inorganic/lignin polymer composite nanoparticles according to claim 6, wherein: blending the inorganic/lignin polymer composite nanoparticles with plastics or rubbers in an amount of 10%-40% by dry-basis weight of the plastics or the rubbers, to produce a polymer composite material.

8. An inorganic/lignin polymer composite nanoparticle is prepared by the method according to claim 2.

9. An inorganic/lignin polymer composite nanoparticle is prepared by the method according to claim 3.

10. An inorganic/lignin polymer composite nanoparticle is prepared by the method according to claim 4.

11. An inorganic/lignin polymer composite nanoparticle is prepared by the method according to claim 5.

12. Application of the inorganic/lignin polymer composite nanoparticles according to claim 8, wherein: blending the inorganic/lignin polymer composite nanoparticles with plastics or rubbers in an amount of 10%-40% by dry-basis weight of the plastics or the rubbers, to produce a polymer composite material.

13. Application of the inorganic/lignin polymer composite nanoparticles according to claim 9, wherein: blending the inorganic/lignin polymer composite nanoparticles with plastics or rubbers in an amount of 10%-40% by dry-basis weight of the plastics or the rubbers, to produce a polymer composite material.

14. Application of the inorganic/lignin polymer composite nanoparticles according to claim 10, wherein: blending the inorganic/lignin polymer composite nanoparticles with plastics or rubbers in an amount of 10%-40% by dry-basis weight of the plastics or the rubbers, to produce a polymer composite material.

15. Application of the inorganic/lignin polymer composite nanoparticles according to claim 11, wherein: blending the inorganic/lignin polymer composite nanoparticles with plastics or rubbers in an amount of 10%-40% by dry-basis weight of the plastics or the rubbers, to produce a polymer composite material.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows the infrared spectrum of the lignin type polymer prepared in Example 5 and the raw material wood pulp alkaline lignin.

(2) FIG. 2 shows a TEM image of nano silica.

(3) FIG. 3 shows a TEM image of the silica/lignin type polymer composite nanoparticles prepared in Example 1.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(4) The present invention will be described below in detail with reference to drawings and examples; however, the scope of protection claimed by the present invention is not limited to the scope indicated by the examples.

EXAMPLE 1

(5) Dissolving 100 g bagasse alkaline lignin solid into water to formulate a suspension at a concentration of 30% by weight, regulating the pH to 9 with NaOH at a mass concentration of 30%, heating to 60 C., adding 2 g dioxane, and reacting for 0.5 hour; dissolving 5 g monochloroacetic acid into water to formulate a solution at a concentration of 10% by weight and adding to the above alkaline lignin suspension, and reacting for 1 hour at 60 C. to produce a carboxylated alkaline lignin.

(6) Dissolving 5 g sodium dihydrogen phosphate into water to formulate a solution at a concentration of 10% by weight, adding 5 g epichlorohydrin, heating to 30 C., and reacting for 0.5 hour to produce a hydroxyl phosphate type compound.

(7) Mixing the obtained carboxylated alkaline lignin and the hydroxyl phosphate type compound, regulating the pH to 10 with NaOH at a mass concentration of 30%, heating to 75 C., reacting for 0.5 hour, and cooling to room temperature to produce a liquid lignin type polymer.

(8) Adding 5 g nano silica into water to formulate a suspension at a concentration of 40% by weight, adding 5 g ethanol, stirring well before adding the above liquid lignin type polymer, heating to 50 C., reacting for 0.5 hour, then adding sulfuric acid at a mass concentration of 25% to regulate the pH to 3 and ageing at 50 C. for 1 hour, and then spray-drying to produce the inorganic/lignin type polymer composite nanoparticles.

EXAMPLE 2

(9) Dissolving 100 g wheat straw alkaline lignin solid into water to formulate a suspension at a concentration of 50% by weight, regulating the pH to 12 with NaOH at a mass concentration of 30%, heating to 90 C., adding 10 g ethanol, and reacting for 2 hours; dissolving 15 g monochloroacetic acid and 5 g monobromo acetanilide into water to formulate a solution at a concentration of 30% by weight and adding to the above alkaline lignin suspension, and reacting for 3 hours at 90 C. to produce a carboxylated alkaline lignin.

(10) Dissolving 20 g dipotassium hydrogen phosphate into water to formulate a solution at a concentration of 35% by weight, adding 15 g epichlorohydrin, heating to 90 C., and reacting for 3 hours to produce a hydroxyl phosphate type compound.

(11) Mixing the obtained carboxylated alkaline lignin and the hydroxyl phosphate type compound, regulating the pH to 13 with NaOH at a mass concentration of 30%, heating to 95 C., reacting for 2 hours, and cooling to room temperature; and stirring well to produce a liquid lignin type polymer.

(12) Adding 80 g zinc oxide into water to formulate a suspension at a concentration of 40% by weight, adding 10 g glycerol, stirring well before adding the above liquid lignin type polymer, heating to 80 C., reacting for 2 hours, then adding phosphoric acid at a mass concentration of 30% to regulate the pH to 55 and ageing at 80 C. for 4 hours, and then spray-drying to produce the inorganic/lignin type polymer composite nanoparticles.

EXAMPLE 3

(13) Dissolving 50 g reed alkaline lignin and 50 g bamboo pulp alkaline lignin solid into water to formulate a suspension at a concentration of 40% by weight, regulating the pH to 11 with NaOH at a mass concentration of 30%, heating to 70 C., adding 4 g acetone, and reacting for 1.5 hours; dissolving 5 g monoiodoacetic acid and 10 g dichloroacetic acid into water to formulate a solution at a concentration of 30% by weight and adding to the above alkaline lignin suspension, and reacting for 1.5 hours at 80 C. to produce a carboxylated alkaline lignin.

(14) Dissolving 10 g sodium dihydrogen phosphate and 5 g diammonium hydrogen phosphate into water to formulate a solution at a concentration of 20% by weight, adding 10 g epichlorohydrin, heating to 30 C., and reacting for 2 hours to produce a hydroxyl phosphate type compound.

(15) Mixing the obtained carboxylated alkaline lignin and the hydroxyl phosphate type compound, regulating the pH to 11 with NaOH at a mass concentration of 30%, heating to 90 C., reacting for 1 hour, and cooling to room temperature to produce a liquid lignin type polymer.

(16) Adding 20 g nano titanium dioxide into water to formulate a suspension at a concentration of 20% by weight, adding 8 g ethanol, stirring well before adding the above liquid lignin type polymer, heating to 60 C., reacting for 1.5 hours, then adding phosphoric acid at a mass concentration of 15% to regulate the pH to 4.5 and ageing at 80 C. for 2 hours, and then spray-drying to produce the inorganic/lignin type polymer composite nanoparticles.

EXAMPLE 4

(17) Dissolving 70 g cotton pulp alkaline lignin and 30 g wood pulp alkaline lignin solid into water to formulate a suspension at a concentration of 50% by weight, regulating the pH to 9 with NaOH at a mass concentration of 30%, heating to 60 C., adding 5 g isopropanol and 5 g ethanol, and reacting for 0.5 hour; dissolving 10 g monochloroacetic acid into water to formulate a solution at a concentration of 15% by weight and adding to the above alkaline lignin suspension, and reacting for 3 hours at 60 C. to produce a carboxylated alkaline lignin.

(18) Dissolving 10 g potassium dihydrogen phosphate and 10 g disodium hydrogen phosphate into water to formulate a solution at a concentration of 35% by weight, adding 15 g epichlorohydrin, heating to 80 C., and reacting for 1 hour to produce a hydroxyl phosphate type compound.

(19) Mixing the obtained carboxylated alkaline lignin and the hydroxyl phosphate type compound, heating to 80 C., reacting for 1 hour, and cooling to room temperature to produce a liquid lignin type polymer.

(20) Adding 15 g nano alumina into water to formulate a suspension at a concentration of 25% by weight, adding 6 g isopropanol, stirring well before adding the above liquid lignin type polymer, heating to 80 C., reacting for 1 hour, then adding hydrochloric acid at a mass concentration of 20% to regulate the pH to 4 and ageing at 60 C. in a water bath for 3 hours, and then spray-drying to produce the inorganic/lignin type polymer composite nanoparticles.

EXAMPLE 5

(21) Dissolving 100 g wood pulp alkaline lignin solid into water to formulate a suspension at a concentration of 35% by weight, regulating the pH to 12 with NaOH at a mass concentration of 30%, heating to 75 C., added 1 g sodium periodate and 4 g ethanol, and reacting for 1 hour; dissolving 10 g monoiodoacetic acid agent and 10 g sodium monochloroacetate into water to formulate a solution at a concentration of 20% by weight and adding to the above alkaline lignin suspension, and reacting for 1 hour at 90 C. to produce a carboxylated alkaline lignin.

(22) Dissolving 10 g potassium dihydrogen phosphate into water to formulate a solution at a concentration of 30% by weight, adding 10 g epichlorohydrin, heating to 50 C., and reacting for 2 hours to produce a hydroxyl phosphate type compound.

(23) Mixing the obtained carboxylated alkaline lignin and the hydroxyl phosphate type compound, regulating the pH to 12 with NaOH at a mass concentration of 30%, heating to 80 C., reacting for 1.5 hours, and cooling to room temperature; adding 4 g polyethylene glycol and 2 g hexadecyl trimethoxy ammonium bromide, and stirring well to produce a liquid lignin type polymer.

(24) Adding 35 g nano calcium carbonate into water to formulate a suspension at a concentration of 10% by weight, adding 5 g acetone, stirring well before adding the above liquid lignin type polymer, heating to 75 C., reacting for 0.5 hour, then adding hydrochloric acid at a mass concentration of 20% to regulate the pH to 5 and ageing at 70 C. for 4 hours, and then spray-drying to produce the inorganic/lignin type polymer composite nanoparticles.

EXAMPLE 6

(25) Dissolving 60 g bamboo pulp alkaline lignin and 40 g reed alkaline lignin solid into water to formulate a suspension at a concentration of 45% by weight, regulating the pH to 10 with NaOH at a mass concentration of 30%, heating to 85 C., adding 4 g dioxane, and reacting for 2 hours; dissolving 5 g monochloroacetic acid and 12 g sodium monochloroacetate into water to formulate a solution at a concentration of 20% by weight and adding to the above alkaline lignin suspension, and reacting for 1 hour at 85 C. to produce a carboxylated alkaline lignin.

(26) Dissolving 8 g sodium dihydrogen phosphate and 7 g dipotassium hydrogen phosphate into water to formulate a solution at a concentration of 20% by weight, adding 12 g epichlorohydrin, heating to 60 C., and reacting for 2.5 hours to produce a hydroxyl phosphate type compound.

(27) Mixing the obtained carboxylated alkaline lignin and the hydroxyl phosphate type compound, regulating the pH to 10 with NaOH at a mass concentration of 30%, heating to 75 C., reacting for 2 hours, and cooling to room temperature; adding 4 g nonylphenol polyoxyethylene ether, and stirring well to produce a liquid lignin type polymer.

(28) Adding 5 g nano silica into water to formulate a suspension at a concentration of 15% by weight, adding 5 g cyclohexane, stirring well before adding the above liquid lignin type polymer, heating to 55 C., reacting for 1 hour, then adding sulfuric acid at a mass concentration of 10% to regulate the pH to 3 and ageing at 50 C. for 1.5 hours, and then spray-drying to produce the inorganic/lignin type polymer composite nanoparticles.

DESCRIPTION OF EFFECTS OF EXAMPLES

(29) FIG. 1 shows an infrared spectrum of the lignin type polymer prepared in Example 5 (referred to as Example 5) and the raw material wood pulp alkaline lignin. It can be known from this figure that, compared to the wood pulp alkaline lignin, Example 5 has weaker absorption than the alkaline lignin at 2940 cm.sup.1 (CH stretching vibration of a methyl, a methylene and a methine) and 1120 cm.sup.1 (CO on a lilac unit), indicating that the modification reaction removes a methoxyl off part of the aromatic ring; Example 5 has weaker absorption than the alkaline lignin at 1610 cm.sup.1 and 1520 cm.sup.1 (skeletal vibration of an aromatic ring), 1460 cm.sup.1 (deformation of a methyl CH) and 1230 cm.sup.1 (CO stretching of a guaiacyl), indicating that the modification reaction changes the molecular structure of the alkaline lignin to a larger extent; compared to the wood pulp alkaline lignin, Example 5 has stronger absorption at 1710 cm.sup.1, which is a characteristic peak of a carboxyl group, and has stronger absorption at 556 cm.sup.1, which is a characteristic peak of a phosphate group, both indicating the introduction of more active functional groups, i.e. carboxyl groups and phosphate groups, into the molecule of Example 5.

(30) FIG. 2 shows a TEM image of nano silica. FIG. 3 shows a TEM image of the silica/lignin type polymer composite nanoparticles prepared in Example 1. It can be seen obviously by comparing FIG. 2 and FIG. 3 that, nano silica is easy to agglomerate and has poor dispersibility, while the prepared silica/lignin type polymer composite nanoparticles have good dispersibility and significantly reduced glomeration among particles, and also have a uniform particle size of about 35 nm With the process used in other examples similar to Example 1, it is found through tests that the TEM images of the products obtained in other examples are basically consistent with those of the products of Example 1, and will therefore not be repeated.

(31) TABLE-US-00002 TABLE 1 Blending mass ratio Tensile (Assistant:high- Tensile elongation Density density strength at break (g .Math. Name polyethylene) (Mpa) (%) cm.sup.3) High-density 21.98 230.22 0.85 polyethylene Calcium 10:100 24.85 65.85 1.01 carbonate/high-density polyethylene composite material Nano silica/high-density 10:100 25.34 83.15 0.99 polyethylene composite material Products of Example 10:100 30.33 92.16 0.92 1/high-density polyethylene composite material Products of Example 30:100 29.78 91.23 0.90 3/high-density polyethylene composite material Products of Example 40:100 29.96 91.36 0.88 4/high-density polyethylene composite material * The symbol in the table means blank.

(32) Table 1 shows the results of blending modification of the inorganic/lignin type polymer composite nanoparticles obtained in Examples 1, 3 and 4 of the present invention and the high-density polyethylene.

(33) The experimental operation method is as follows: Mixing an assistant (calcium carbonate, nano silica or the products of the examples) with high-density polyethylene pellets according to a certain mass ratio, then physically blending them at 150 C. with a mill for 20 minutes, and then molding the cake to produce the assistant/high-density polyethylene composite material.The tensile strength, tensile elongation at break and other mechanical properties of the composite material are determined with an MTS universal tester, and density as well.

(34) The calcium carbonate used in the experiments is the modified calcium carbonate used in the industrial blow molding. It can be seen from Table 1 that, although the tensile elongation at break of each composite material is lower than that of the high-density polyethylene, the tensile elongation at break of the composite materials obtained from Examples 1, 3 and 4 is far greater than that of the composite materials obtained from calcium carbonate or nano silica, which indicates that the composite materials obtained from Examples 1, 3 and 4 have good toughness and have exceeded the calcium carbonate strengthened polyethylene materials currently commonly used in industry.

(35) The tensile strength of the composite materials obtained from Examples 1, 3 and 4 is 30.33 Mpa, 29.78 Mpa and 29.96 Mpa, respectively, greater than 24.85 Mpa of the calcium carbonate strengthened polyethylene material, 25.34 Mpa of the nano silica strengthened polyethylene material, and 21.98 Mpa of the high-density polyethylene, which indicates that composite materials obtained from Examples 1, 3 and 4, compared with the original plastics and calcium carbonate or nano silica strengthened plastics, have tensile strength that is not reduced but significantly increased. The data of density indicate that, the composite materials obtained from Examples 1, 3 and 4 are between the original high-density polyethylene and the calcium carbonate or nano silica strengthened polyethylene material in density; compared with the inorganic calcium carbonate or nano silica strengthened polyethylene material, the inorganic/lignin type polymer composite nanoparticles obtained in the present invention have advantage in density; therefore, under the same volume, the composite materials obtained from Examples 1, 3 and 4 have less mass, which characteristic will be advantageous to broadening their application field and reducing cost.

(36) TABLE-US-00003 TABLE 2 Blending Peeling mass ratio Tensile strength Elongation (strengthening strength (kN .Math. at break Name agent:rubber) (Mpa) m.sup.1) (%) Acrylonitrile-butadiene 3.09 11.87 856.13 rubber Nano silica/ 10:100 23.87 55.75 564.78 acrylonitrile-butadiene rubber composite material Products of Example 10:100 28.54 61.46 682.33 2/acrylonitrile- butadiene rubber composite material Products of Example 40:100 27.93 60.57 677.84 6/acrylonitrile- butadiene rubber composite material * The symbol in the table means blank.

(37) Table 2 shows the results of blending modification of the inorganic/lignin type polymer composite nanoparticles obtained from Examples 2 and 6 of the present invention and the acrylonitrile-butadiene rubber. The experimental operation method is as follows: At normal temperature, adding 100 parts of acrylonitrile-butadiene rubber to a two-roller mill, adding in turn 1.5 parts of sulfur, 5 parts of zinc oxide, and 1 part of stearic acid to blend, adding a strengthening agent (nano silica or products of the examples) according to a certain mass ratio (10-40 parts) to blend, and then adding 1 part of an accelerant DM (dibenzothiazole disulfide) to blend for 15 min. Vulcanizing the blending product at 145 C. for 30 min to produce a strengthening agent/acrylonitrile-butadiene rubber composite material. Finally, the tensile strength, peeling strength, elongation at break and other mechanical property data of the composite material are determined with an MTS universal tester. It can be seen from Table 2 that, the tensile strength of the rubber material strengthened with the products obtained from Examples 2 and 6 is obviously greater than that of the nano silica strengthened rubber material currently commonly used in industry. On one hand, the lignin molecules, with many active functional groups on the surface thereof, can provide an intermolecular hydrogen bond, an electrostatic force, the - stacking interaction, the cation- interaction and other various intermolecular forces, and have active chemical reaction activity and good compatibility with the rubber molecules having polarity; with the synergy between the alkaline lignin and the inorganic nanoparticles, the particles are uniformly dispersed and have high surface activity, making the acting force between the inorganic/lignin type polymer composite nanoparticles and the rubber molecules increased, cohesion of gross rubber increased, and the chain segment not easy to slide while being stretched. On the other hand, the three-dimensional spatial network structure of the lignin is advantageous to increasing its crosslinking density with rubber molecules, thus increasing the tensile strength of the rubber composite materials. Besides, it can be seen from this table that, the rubber filled with the products from Examples 2 and 6 is superior in peeling strength to the rubber filled with nano silica. The rubbers strengthened with the products from Examples 2 and 6 and with nano silica have less elongation at break than the pre-compounded acrylonitrile-butadiene rubber, because addition of a filler may increase crosslinking density of the rubber in the vulcanizing process, thus reducing elongation at break of the rubber. However, the rubbers filled with the products from Examples 2 and 6 are both superior to the rubber filled with nano silica, which indicates that the composite materials obtained from Examples 2 and 6 have good toughness, and the rubber is not easy to be destroyed in the deformation process and has exceeded the rubber material strengthened with nano silica that is currently commonly used in industry.