LIGNIN DEGRADATION PRODUCT-BISPHENOL A-POLYURETHANE POLYCONDENSATE ADDITIVE AND PREPARATION METHOD THEREOF

Abstract

The invention discloses a lignin degradation product-bisphenol A-polyurethane polycondensate additive, and a preparation method thereof. Lignin is used as a raw material, and is degraded by an alkali activator, a metal catalyst and nitrobenzene to obtain the lignin degradation product; then, the obtained lignin degradation product is uniformly mixed with bisphenol A, and polyurethane is added; finally, the additive is obtained after heating reaction and drying. The preparation process of the invention is simple, and the obtained lignin degradation product has a small and stable molecular weight and has abundant phenolic hydroxyl and alcoholic hydroxyl sites, which can improve the dispersibility of the product, with strong cohesiveness and good waterproofness. It solves the problem of industrial application that lignin replaces part of phenols in the prior art, which leads to the decline of product performance, improves the total substitution rate of chemicals derived from biomass to bisphenol A derived from fossil resources, and significantly reducing the discharge of phenolic compounds. The additive is an environment-friendly polymeric material with excellent development potential.

Claims

1. A preparation method of a lignin degradation product-bisphenol A-polyurethane polycondensate additive, comprising the following steps: (1) The lignin, alkali activator, metal catalyst and water were stirred evenly, nitrobenzene was added and reacted for 2-6 h at 200-300° C. Then, the reaction liquid was cooled to 40-60° C., and the lignin degradation products were obtained after removing the solid residues. (2) Bisphenol A is added to the lignin degradation product obtained in step (1) and stirred evenly. Then, polyurethane is added, at the temperature of 70-100° C. for a reaction for 2.0-5.0 h, cooling down and discharging after the reaction obtaining brown liquid, and thus to obtain the lignin degradation product-bisphenol A-polyurethane polycondensate additive after drying.

2. The preparation method of the lignin degradation product-bisphenol A-polyurethane polycondensate additive according to claim 1, wherein raw materials include, by mass, 15.0%-30% of lignin, 5.0%-10.5% of alkali activator, 1.0%-3.0% of metal catalyst, 6.5%-12.0% of nitrobenzene, 2.0%-10.0% of bisphenol A, 5.0/0-15.00% of polyurethane, and 43.0%-70.0% of water, 100% in total.

3. The preparation method of the lignin degradation product-bisphenol A-polyurethane polycondensate additive according to claim 1, wherein the lignin comprises any one or more of organosolv lignin, enzymatic hydrolyzed lignin, milled-wood lignin, sulphate lignin, sulfonate lignin, alkali lignin and natural lignin.

4. The preparation method of the lignin degradation product-bisphenol A-polyurethane polycondensate additive according to claim 3, wherein raw materials include, by mass, 15.0%-30% of lignin, 5.0%-10.5% of alkali activator, 1.0%/9-3.0% of metal catalyst, 6.5%-12.0% of nitrobenzene, 2.0%-10.0% of bisphenol A, 5.0%-15.0% of polyurethane, and 43.0%-70.0% of water, 100% in total.

5. The preparation method of the lignin degradation product-bisphenol A-polyurethane polycondensate additive according to claim 1, wherein the alkali activator comprises any one or more of KOH, NaOH, Mg(OH).sub.2, LiOH and Ca(OH).sub.2.

6. The preparation method of the lignin degradation product-bisphenol A-polyurethane polycondensate additive according to claim 5, wherein raw materials include, by mass, 15.0%-30% of lignin, 5.0%-10.5% of alkali activator, 1.0%-3.0% of metal catalyst, 6.5%-12.0% of nitrobenzene, 2.0%-10.0% of bisphenol A, 5.0%-15.0% of polyurethane, and 43.0%-70.0% of water, 100% in total.

7. The preparation method of the lignin degradation product-bisphenol A-polyurethane polycondensate additive according to claim 1, wherein the metal catalyst comprises any one or more of NiCl.sub.2, CoCl.sub.2, MoCl.sub.2, LaMnO.sub.3 and LaCoO.sub.3.

8. The preparation method of the lignin degradation product-bisphenol A-polyurethane polycondensate additive according to claim 7, wherein raw materials include, by mass, 15.0%-30% of lignin, 5.0%-10.5% of alkali activator, 1.0%-3.0% of metal catalyst, 6.5%-12.0% of nitrobenzene, 2.0%-10.0% of bisphenol A, 5.0%-15.0% of polyurethane, and 43.0%-70.0% of water, 100% in total.

9. A lignin degradation product-bisphenol A-polyurethane polycondensate additive prepared by the method according to claim 1, wherein an insoluble matter content of the additive is less than or equal to 0.5%, and a relative molecular mass Mn is 8000-50000.

10. A lignin degradation product-bisphenol A-polyurethane polycondensate additive prepared by the method according to claim 9, wherein raw materials include, by mass, 15.0%-30% of lignin, 5.0%-10.5% of alkali activator, 1.0%-3.0% of metal catalyst, 6.5%-12.0% of nitrobenzene, 2.0%-10.0% of bisphenol A, 5.0%-15.0% of polyurethane, and 43.0%-70.0% of water, 100% in total.

11. A lignin degradation product-bisphenol A-polyurethane polycondensate additive prepared by the method according to claim 9, wherein the lignin comprises any one or more of organosolv lignin, enzymatic hydrolyzed lignin, milled-wood lignin, sulphate lignin, sulfonate lignin, alkali lignin and natural lignin.

12. A lignin degradation product-bisphenol A-polyurethane polycondensate additive prepared by the method according to claim 9, wherein the alkali activator comprises any one or more of KOH, NaOH, Mg(OH).sub.2, LiOH and Ca(OH).sub.2.

13. A lignin degradation product-bisphenol A-polyurethane polycondensates additive prepared by the method according to claim 9, wherein the metal catalyst comprises anyone or more of NiCl.sub.2, CoCl.sub.2, MoCl.sub.2, LaMnO.sub.3 and LaCoO.sub.3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0022] In order to make the content of the invention easier to understand, the technical solution of the invention will be further explained below with reference to specific embodiments, but the invention is not limited to this.

Embodiment 1

[0023] 251.0 kg of Eucommia lignin, 107.6 kg of potassium hydroxide, 35.9 kg of NiCl.sub.2 and 850.2 kg of water were evenly mixed by stirring, and 143.4 kg of nitrobenzene was added for a reaction for 3.4 hours at 250° C.; after a reaction solution was cooled to 48° C., lignin degradation product was obtained after removing solid residues; and 89.6 kg of bisphenol A was added to the lignin degradation product, the mixture was stirred evenly, then 179.3 kg of polyurethane was added, the temperature was increased to 95° C. for a reaction for 2.0 hours. After the reaction completed, the temperature was lowered and the material was removed to obtain brown liquid, and the brown liquid was dried to obtain a ceramic additive with a relative molecular mass M.sub.n of 12500.

Embodiment 2

[0024] 251.0 kg of bamboo lignin, 107.6 kg of magnesium hydroxide, 23.9 kg of CoCl.sub.2 and 537.8 kg of water were evenly mixed by stirring, and 83.7 kg of nitrobenzene was added for a reaction for 2.5 hours at 300′C; after a reaction solution was cooled to 45′C, a lignin degradation product was obtained after removing solid residues; and 71.7 kg of bisphenol A was added to the lignin degradation product, the mixture was stirred evenly, then 143.4 kg of polyurethane was added, the temperature was increased to 95′C for a reaction for 3.0 hours. After the reaction completed, the temperature was lowered and the material was removed to obtain brown liquid, and the brown liquid was dried to obtain a dye dispersant with a relative molecular mass M.sub.n of 28500.

Embodiment 3

[0025] 143.4 kg of palm lignin and 100 kg of corncob lignin, 108.2 kg of sodium hydroxide, 13.5 kg of LaCoO.sub.3 and 689.5 kg of water were evenly mixed by stirring, and 108.2 kg of nitrobenzene was added for a reaction for 4.5 hours at 266° C.; after a reaction solution was cooled to 50° C., a lignin degradation product was obtained after removing solid residues; and 67.6 kg of bisphenol A was added to the lignin degradation product, the mixture was stirred evenly, then 121.9 kg of polyurethane was added, the temperature was increased to 100° C. for a reaction for 2.8 hours. After the reaction completed, the temperature was lowered and the material was removed to obtain brown liquid, and the brown liquid was dried to obtain a binder with a relative molecular mass M.sub.n of 41200.

Embodiment 4

[0026] 390.7 kg of Chinese ash lignin, 125.0 kg of magnesium hydroxide, 31.3 kg of LaMnO.sub.3 and 687.6 kg of water were evenly mixed by stirring, and 140.7 kg of nitrobenzene was added for a reaction for 5.0 hours at 220′C; after a reaction solution was cooled to 50° C., lignin degradation product was obtained after removing solid residues; and 62.5 kg of bisphenol A was added to the lignin degradation product, the mixture was stirred evenly, then 125.0 kg of polyurethane was added, the temperature was increased to 88′C for a reaction for 3.0 hours, After the reaction completed, the temperature was lowered and the material was removed to obtain brown liquid, and the brown liquid was dried to obtain a ceramic additive with a relative molecular mass M.sub.n of 15200.

Embodiment 5

[0027] 302.5 kg of Eucommia lignin, 37.8 kg of magnesium hydroxide and 67.4 kg of sodium hydroxide, 39.5 kg of NiCl.sub.2 and 631.2 kg of water were evenly mixed by stirring, and 92.1 kg of nitrobenzene was added for a reaction for 5.5 hours at 185′C; after a reaction solution was cooled to 50′C, 1 lignin degradation product was obtained after removing solid residues; and 52.6 kg of bisphenol A was added to the lignin degradation product, the mixture was stirred evenly, then 92.1 kg of formaldehyde was added, the temperature was increased to 80° C. for a reaction for 2.5 hours. After the reaction completed, the temperature was lowered and the material was removed to obtain brown liquid, and the brown liquid was dried to obtain a coal water slurry additive with a relative molecular mass M.sub.n of 28620.

Embodiment 6

[0028] 221.0 kg of corncob lignin, 49.1 kg of sodium hydroxide, 16.4 kg of LaMnO.sub.3 and 368.3 kg of water were evenly mixed by stirring, and 65.5 kg of nitrobenzene was added for a reaction for 4.0 hours at 260° C.; after a reaction solution was cooled to 55° C., a lignin degradation product was obtained after removing solid residues; and 32.7 kg of bisphenol A was added to the lignin degradation product, the mixture was stirred evenly, then 65.5 kg of polyurethane was added, the temperature was increased to 95′C for a reaction for 2.0 hours. After the reaction completed, the temperature was lowered and the material was removed to obtain brown liquid, and the brown liquid was dried to obtain a concrete water reducing agent with a relative molecular mass M.sub.n of 13800.

Embodiment 7

[0029] 238.5 kg of bamboo lignin, 95.4 kg of potassium hydroxide, 35.8 kg of MoCl.sub.2 and 620.1 kg of water were evenly mixed by stirring, and 83.5 kg of nitrobenzene was added for a reaction for 3.0 hours at 285′C; after a reaction solution was cooled to 60° C., lignin degradation product was obtained after removing solid residues; and 47.7 kg of bisphenol A was added to the lignin degradation product, the mixture was stirred evenly, then 71.6 kg of polyurethane was added, the temperature was increased to 88′C for a reaction for 2.4 hours. After the reaction completed, the temperature was lowered and the material was removed to obtain brown liquid, and the brown liquid was dried to obtain a dye dispersant with a relative molecular mass M.sub.n of 28800.

Embodiment 8

[0030] 201.8 kg of corncob lignin, 57.7 kg of sodium hydroxide, 7.2 kg of MoCl.sub.2 and 324.1 kg of water were evenly mixed by stirring, and 50.4 kg of nitrobenzene was added for a reaction for 5.2 hours at 255° C.; after a reaction solution was cooled to 55′C, a lignin degradation product was obtained after removing solid residues; and 28.8 kg of bisphenol A was added to the lignin degradation product, the mixture was stirred evenly, then 50.4 kg of polyurethane was added, the temperature was increased to 90° C. for a reaction for 3.0 hours. After the reaction completed, the temperature was lowered and the material was removed to obtain brown liquid, and the brown liquid was dried to obtain a concrete water reducing agent with a relative molecular mass M.sub.n of 8790.

Embodiment 9

[0031] 78.4 kg of Eucommia lignin, 133.6 kg of bamboo lignin, 74.2 kg of sodium hydroxide, 21.2 kg of CoCl.sub.2 and 519.4 kg of water were evenly mixed by stirring, and 106.0 kg of nitrobenzene was added for a reaction for 5.0 hours at 280° C.; after a reaction solution was cooled to 50° C., lignin degradation product was obtained after removing solid residues; and 31.8 kg of bisphenol A was added to the lignin degradation product, the mixture was stirred evenly, then 95.4 kg of polyurethane was added, the temperature was increased to 95′C for a reaction for 2.5 hours. After the reaction completed, the temperature was lowered and the material was removed to obtain brown liquid, and the brown liquid was dried to obtain a binder with a relative molecular mass M.sub.n of 48520.

Embodiment 10

[0032] 246.7 kg of Eucommia lignin, 67.3 kg of sodium hydroxide, 11.2 kg of NiCl.sub.2 and 504.6 kg of water were evenly mixed by stirring, and 112.1 kg of nitrobenzene was added for a reaction for 4.0 hours at 280° C.; after a reaction solution was cooled to 521, lignin degradation product was obtained after removing solid residues; and 56.1 kg of bisphenol A was added to the lignin degradation product, the mixture was stirred evenly, then 123.4 kg of polyurethane was added, the temperature was increased to 98′C for a reaction for 3.5 hours. After the reaction completed, the temperature was lowered and the material was removed to obtain brown liquid, and the brown liquid was dried to obtain a coal water slurry additive with a relative molecular mass M.sub.n of 32500.

[0033] Performance Test:

[0034] 1. Binder

[0035] By referring to GB/T14732-2017, the performance of the products obtained in the embodiments and similar products was tested. The test results are shown in Table 1.

TABLE-US-00001 TABLE 1 Properties of binder Free Impact bisphenol Bending tough- Dosage A content strength ness Products (wt %) (wt %) (MPa) (kl/m.sup.2) Embodiment 1 0.3 1.42 252 33 Embodiment 2 0.3 1.55 243 27 Embodiment 3 0.3 0.95 319 44 Embodiment 4 0.3 1.23 275 31 Embodiment 5 0.3 1.24 295 35 Embodiment 6 0.3 1.33 288 36 Embodiment 7 0.3 1.15 267 38 Embodiment 8 0.3 1.18 300 38 Embodiment 9 0.3 0.97 322 48 Embodiment 10 0.3 1.23 281 40

[0036] As can be seen from Table 1, compared with other products, the products obtained in Embodiments 3 and 9 have fewer free bisphenol A compounds, higher bending strength and stronger impact toughness, thus being suitable for serving as binders.

[0037] 2. Ceramic Additive

[0038] The composition (wt %) of ceramic slurry is shown in Table 2. The products obtained in the embodiments and other similar products were added to ceramic slurry for comparison in terms of fluidity, viscosity and green strength. The results are shown in Table 3. The green flexural strength test was conducted by referring to GBT3810.4□2006 Part 4: Determination of rupture modulus and breaking strength.

TABLE-US-00002 TABLE 2 Composition of ceramic slurry (wt %) Calcium- Black enriched Porcelain Pyrophyllite Clay talc rice clay Diopside 21 25 10 14 18 12

TABLE-US-00003 TABLE 3 Comparison of products in fluidity, viscosity and green strength Green Dosage Specific Outflow Viscosity strength Products (wt %) weight time (s) (MPa .Math. s) (MPa) Sodium 0.3 1.7020 37 176 1.52 tripoly- phosphate Sodium 0.3 1.7015 43 190 1.48 silicate Water glass 0.3 1.7054 40 186 1.48 Embodiment 1 0.3 1.7098 36 186 2.33 Embodiment 2 0.3 1.7001 38 190 2.05 Embodiment 3 0.3 1.7044 44 205 1.88 Embodiment 4 0.3 1.7057 33 175 2.30 Embodiment 5 0.3 1.7069 39 178 2.05 Embodiment 6 0.3 1.7077 40 178 2.12 Embodiment 7 0.3 1.7023 42 200 1.88 Embodiment 8 0.3 1.7034 45 209 2.04 Embodiment 9 0.3 1.7002 41 198 2.08 Embodiment 10 0.3 1.7095 38 191 2.13

[0039] As can be seen from Table 3, compared with other products, the products obtained in Embodiments 1 and 4 have shorter outflow time and higher strength, thus being suitable for serving as ceramic additives.

[0040] 3. Dye Dispersant

[0041] The thermal stability of the products obtained in the embodiments to vat dyes was tested and rated according to HG/T 3507□2008 “Sodium lignin sulphonate dispersing agent” and HG/t 3399□2001 “Determination of dye diffusion performance”. The test results are shown in Table 4.

TABLE-US-00004 TABLE 4 Comparison of products in thermal stability Thermal stability (tested with olive T dye) Products 80° C. 100° C. 130° C. 150° C. Embodiment 1 Grade 5 Grade 4 Grade 3 Grade 3 Embodiment 2 Grade 5 Grade 5 Grade 5 Grade 5 Embodiment 3 Grade 5 Grade 5 Grade 4 Grade 3 Embodiment 4 Grade 5 Grade 5 Grade 4 Grade 4 Embodiment 5 Grade 5 Grade 5 Grade 4 Grade 3 Embodiment 6 Grade 5 Grade 4 Grade 4 Grade 4 Embodiment 7 Grade 5 Grade 5 Grade 5 Grade 5 Embodiment 8 Grade 5 Grade 5 Grade 4 Grade 3 Embodiment 9 Grade 5 Grade 4 Grade 4 Grade 3 Embodiment 10 Grade 4 Grade 4 Grade 3 Grade 3

[0042] As can be seen from Table 4, compared with other products, the products obtained in Embodiments 2 and 7 have better thermal stability, thus being suitable for serving as dye dispersants.

[0043] 4. Coal Water Slurry Dispersant

[0044] The products obtained in the embodiments and similar products were tested for the dispersibility and stability of coal water slurry. Heishan coal was selected as the research object. After crushing, grinding, screening and grading, a certain amount of water and dispersant products (dosage of 0.3 wt %) were added and stirred evenly to obtain coal water slurry with different concentrations. The test results are shown in Table 5.

TABLE-US-00005 TABLE 5 Comparison of products of the invention in dispersibility and stability Slurry concentration Viscosity 7-day Products (%) (MPa .Math. s) Fluidity stability Embodiment 1 64.8 1450 B Grade 1 Embodiment 2 63.9 1380 A Grade 2 Embodiment 3 64.7 1440 A Grade 1 Embodiment 4 65.5 1580 B Grade 2 Embodiment 5 68.8 1860 A Grade 1 Embodiment 6 63.5 1350 B Grade 1 Embodiment 7 64.8 1500 A Grade 1 Embodiment 8 66.7 1680 B Grade 2 Embodiment 9 67.0 1700 B Grade 2 Embodiment 10 68.5 1840 A Grade 1

[0045] As can be seen from Table 5, compared with other products, the products obtained in Embodiments 5 and 10 have higher slurry concentration and higher viscosity, thus being suitable for serving as coal water slurry dispersants.

[0046] 5. Concrete Water Reducing Agent

[0047] By referring to GB/T2794□1995, the performance of the products obtained in the embodiments and similar products was tested. The test results are shown in Table 6.

TABLE-US-00006 TABLE 6 Comparison of products in strength and fluidity 7-day 28-day com- com- pressive pressive Cement strength strength Dosage paste ratio ratio Rusting of Products (wt %) fluidity (%) (%) steel bars Industrial 0.3 180 125 117 Passivation sodium sulfonate Embodiment 1 0.3 178 130 124 Passivation Embodiment 2 0.3 175 135 130 Passivation Embodiment 3 0.3 180 132 126 Passivation Embodiment 4 0.3 177 124 120 Passivation Embodiment 5 0.3 181 126 121 Passivation Embodiment 6 0.3 173 137 134 Passivation Embodiment 7 0.3 179 127 122 Passivation Embodiment 8 0.3 172 135 133 Passivation Embodiment 9 0.3 176 127 122 Passivation Embodiment 0.3 183 125 120 Passivation 10

[0048] As can seen from Table 6, compared with other products, the products obtained in Embodiments 6 and 8 have lower cement paste fluidity, higher compressive strength ratios and smaller changes after being left to stand, thus being suitable for serving as concrete water reducing agents.

[0049] The above embodiments are only preferred ones of the invention, and all equivalent changes and modifications made according to the scope of the patent application of the invention should be within the scope of the invention.