CN111040112B - Polyurethane resin prepared from coffee grounds and application thereof - Google Patents
Polyurethane resin prepared from coffee grounds and application thereof Download PDFInfo
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- CN111040112B CN111040112B CN201911298310.5A CN201911298310A CN111040112B CN 111040112 B CN111040112 B CN 111040112B CN 201911298310 A CN201911298310 A CN 201911298310A CN 111040112 B CN111040112 B CN 111040112B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a polyurethane resin prepared from coffee grounds, which is prepared from the following components: polyester diol, a chain extender, coffee grounds, diisocyanate, an antioxidant, a dispersant, a solvent and a blocking agent. The invention creatively takes coffee grounds as the starting raw material to chemically modify polyurethane, and the prepared polyurethane resin has excellent peel strength, thermal aging property and hydrolysis resistance.
Description
Technical Field
The invention relates to a polyurethane resin and a preparation method thereof.
Background
The polyurethane synthetic leather is a composite material consisting of a polyurethane coating and a base material, the polyurethane coating is generally divided into a surface layer and a bonding layer, and polyurethane resin in the bonding layer is used for bonding the surface layer and the base material together. The adhesive force of the bonding layer and the base material plays a crucial role in the quality and style of the whole synthetic leather.
Along with the improvement of living standard of people, the quality requirement of leather products is higher and higher, for example, the adhesive force of a bonding layer, the adhesive force after glue brushing and the thermal aging performance in the field of shoe leather put forward high requirements. In the field of shoe leather, particularly sports shoes, the requirement on the peel strength of an adhesive is high, the ordinary adhesive is difficult to achieve ultrahigh peel strength, and meanwhile, gluing operation is carried out in the shoe making process, so that the peel strength is further reduced due to glue corrosion, and the phenomenon of degumming sometimes occurs in the use process; in addition, the physical properties of the shoe leather are reduced due to aging of the adhesive in the using process of the shoe leather, so that the service life of the shoe leather is influenced, and huge losses are brought to consumers and related suppliers. In addition, because the glue used by the current adhesive and glue brushing for shoes is solvent type glue, the leather smell problem caused by the solvent type glue also influences the consumption desire of consumers to a great extent.
The coffee grounds contain more abundant caffeic acid, grease, protein, mineral substances, vitamins and the like, and are typical bio-based materials. At present, the coffee grounds are mainly used as fertilizers and fuels abroad, the practical value is low, and the coffee grounds are mostly discarded as wastes at home, so that the waste and the environmental pollution are caused. In recent years, methods for recycling the waste water have been explored, but a phenomenon of discarding the waste water in large quantities still exists, and it is a very meaningful task to effectively utilize the waste water and generate high added value.
Disclosure of Invention
The invention aims to provide polyurethane resin with high peel strength, good thermal aging property, good solvent resistance and excellent comprehensive physical properties, and synthesis and application thereof, so as to overcome the defects of the prior art.
The polyurethane resin prepared from the coffee grounds is prepared from the following raw materials: polyester diol, a chain extender, coffee grounds, diisocyanate, an antioxidant, a dispersant, a solvent and a blocking agent.
The polyester diol is selected from one or more of poly-1, 4-butanediol adipate diol with the number average molecular weight of 1000-3500, poly-1, 6-hexanediol adipate diol, poly-neopentyl glycol adipate diol, poly-ethylene adipate diol, poly-methyl propylene adipate diol, poly-epsilon-caprolactone diol and polycarbonate diol, and is preferably poly-1, 4-butanediol adipate with the number average molecular weight of 2000.
The chain extender is one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol and methyl propylene glycol, and 1, 4-butanediol is preferred.
The diisocyanate is toluene diisocyanate or 4,4 '-diphenylmethane diisocyanate, preferably 4, 4' -diphenylmethane diisocyanate.
The antioxidant is hindered phenol antioxidant or phosphite antioxidant, preferably hindered phenol antioxidant BHT.
The dispersant is polyether modified polysiloxane, preferably BYK-3760, YCK-1040 and YCK-1250.
The end-capping agent is methanol and/or a coupling agent, and the coupling agent is a silane coupling agent, preferably KH550, KH560 and KH 570.
The coffee grounds are provided by Starbucks, USA, and have average particle size of 1 micrometer and unit water content of less than 500 ppm.
The solvent is at least one of dimethylformamide, toluene, butanone and ethyl acetate, and dimethylformamide and butanone are preferred.
The polyurethane resin prepared from the coffee grounds is prepared from the following components in percentage by mass as starting raw materials:
20.0 to 25.0 percent of polyester dihydric alcohol
Chain extender 1.0-3.0%
Diisocyanate 5.0-10.0%
0.02 to 0.05 percent of antioxidant
0.2 to 10.0 percent of coffee grounds
0.02 to 0.05 percent of dispersant
0.05 to 0.25 percent of end capping agent
The balance of solvent
Preferably, the polyurethane resin prepared from coffee grounds is prepared from the following components in percentage by mass as starting raw materials:
20.0 to 25.0 percent of polyester dihydric alcohol
Chain extender 1.0-3.0%
Diisocyanate 5.0-10.0%
0.02 to 0.05 percent of antioxidant
0.2 to 2.0 percent of coffee grounds
0.02 to 0.05 percent of dispersant
0.05 to 0.25 percent of end capping agent
The balance of solvent
The synthesis method of the polyurethane resin prepared by using the coffee grounds comprises the following steps:
(1) uniformly mixing an antioxidant, polyester diol, a chain extender, coffee grounds and dimethylformamide at 50-60 ℃ under normal pressure;
(2) adding diisocyanate in 2-4 batches, heating to 70-80 ℃, and reacting for 4-6 hours in a heat preservation manner;
(3) adding dimethylformamide;
(4) mixing an end-capping reagent and butanone, adding the mixture, terminating the reaction, and preserving heat at a certain temperature for 1-2 hours;
(5) adding dispersant and coffee grounds to obtain the product with the solid content of 30-35% and the final viscosity of 80-140PaS/25 ℃.
The adding amount of the dimethylformamide in the step (1) is 55-65% of the total mass of the solvent, and the adding amount of the dimethylformamide in the step (3) is 15-20% of the total mass of the solvent.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention creatively takes coffee grounds as the starting raw material to chemically modify polyurethane, and the prepared polyurethane resin has excellent peel strength, thermal aging property and hydrolysis resistance. Compared with the common polyester adhesive, the resin has better hydrolysis resistance; compared with polyether type adhesive, the adhesive has higher peel strength and better thermal aging property; compared with special polyester adhesives, the cost is lower; compared with the copolymerization type adhesive, the cost is lower, and the comprehensive physical property is more excellent.
(2) At present, the yield of the domestic coffee grounds is more and more, but the recycling mode is limited, and the problem of environmental pollution is increasingly serious. The invention provides a brand new method for recycling the coffee grounds, and plays a positive role in environmental protection.
(3) The adhesive prepared by the invention is applied to synthetic leather, and the coffee grounds have the effect of adsorbing pungent smell, and meanwhile, the synthetic leather has light coffee smell and is pleasant.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be noted that these examples are only for illustrating the present invention, and are not intended to limit the scope of the present invention. Modifications and adaptations of the present invention may occur to those skilled in the art and are within the scope of the present invention. The starting materials used in the following examples are all commercially available.
Comparative example 1
Comparative example 1 was prepared wherein the polyester diol used was 1, 4-butanediol adipate diol having a number average molecular weight of 2000, the chain extender was 1, 4-butanediol, and the end-capping reagent was methanol.
The raw materials and the quality used in comparative example 1 are as follows:
| name of raw materials | Mass (gram) | Percent (%) |
| Antioxidant BHT | 2.00 | 0.05% |
| Poly (1, 4-butylene adipate) glycol (number average molecular weight 2000) | 900 | 22.47% |
| 1, 4-butanediol | 50 | 1.25% |
| 4, 4' -diphenylmethane diisocyanate | 250 | 6.24% |
| Dimethyl formamide | 2240 | 55.92% |
| Butanone | 560 | 13.97% |
| Methanol | 4 | 0.1% |
| Total mass | 4006 | 100% |
The preparation steps are as follows:
1) uniformly mixing antioxidant BHT, poly adipic acid 1, 4-butanediol glycol, 1, 4-butanediol and dimethylformamide (70 percent of the total amount) at 50-60 ℃;
2) adding 4, 4-diphenylmethane diisocyanate in batches, heating to 70-80 ℃, and reacting for 4-6 hours;
3) supplementing 4, 4-diphenylmethane diisocyanate;
4) adding dimethylformamide (30% of the total amount), and adjusting the viscosity;
5) butanone and methanol are mixed and added, the mixture is stirred for 1 to 2 hours at the temperature of between 70 and 80 ℃, and the end capping reaction is stopped, the final viscosity is controlled to be between 80 and 140PaS/25 ℃, and a sample A is obtained.
Example 1
The polyester diol used in this example is poly 1, 4-butylene glycol adipate with a number average molecular weight of 2000, the chain extender is 1, 4-butylene glycol, the end-capping reagent is methanol, and the coffee grounds are ground and dried, and the addition amount is 1% of the solid content of the polyurethane resin.
The raw materials and the quality used in the present example are as follows:
| name of raw materials | Mass (gram) | Percent (%) |
| Antioxidant BHT | 2.00 | 0.05% |
| Dispersant BYK-3760 | 0.50 | 0.01% |
| Poly (1, 4-butylene adipate) glycol (number average molecular weight 2000) | 900 | 22.40% |
| Coffee grounds | 12 | 0.3% |
| 1, 4-butanediol | 50 | 1.24% |
| 4, 4' -diphenylmethane diisocyanate | 250 | 6.22% |
| Dimethyl formamide | 2240 | 55.74% |
| Butanone | 560 | 13.94% |
| Methanol | 4 | 0.1% |
| Total mass | 4018.5 | 100% |
The preparation steps are as follows:
1) uniformly mixing antioxidant BHT, dispersant, polyester dihydric alcohol, coffee grounds, 1, 4-butanediol and dimethylformamide (70 percent of the total amount) at 50-60 ℃;
2) adding 4, 4-diphenylmethane diisocyanate in batches, heating to 70-80 ℃, and reacting for 4-6 hours;
3) supplementing 4, 4-diphenylmethane diisocyanate;
4) adding dimethylformamide (30% of the total amount), and adjusting the viscosity;
5) butanone and methanol were mixed and added, and the reaction was terminated by capping with stirring at 40-50 ℃ for 1-2 hours, with the final viscosity controlled at 80-140PaS/25 ℃ to give sample B1.
Example 2
The polyester diol used in this example is poly 1, 4-butylene glycol adipate with a number average molecular weight of 2000, the chain extender is 1, 4-butylene glycol, the end-capping reagent is methanol, and the coffee grounds are ground and dried, and the addition amount is 2% of the solid content of the polyurethane resin.
The raw materials and the quality used in the present example are as follows:
| name of raw materials | Mass (gram) | Percent (%) |
| Antioxidant BHT | 2.00 | 0.05% |
| Dispersant YCK-1040 | 1.00 | 0.02% |
| Poly (1, 4-butylene adipate) glycol (number average molecular weight 2000) | 900 | 22.31% |
| Coffee grounds | 24 | 0.6% |
| 1, 4-butanediol | 50 | 1.24% |
| 4, 4' -diphenylmethane diisocyanate | 250 | 6.2% |
| Dimethyl formamide | 2240 | 55.58% |
| Butanone | 560 | 13.9% |
| Methanol | 4 | 0.1% |
| Total mass | 4031 | 100% |
The preparation steps are as follows:
1) uniformly mixing antioxidant BHT, dispersant, polyester dihydric alcohol, coffee grounds, 1, 4-butanediol and dimethylformamide (70 percent of the total amount) at 50-60 ℃;
2) adding 4, 4-diphenylmethane diisocyanate in batches, heating to 70-80 ℃, and reacting for 4-6 hours;
3) supplementing 4, 4-diphenylmethane diisocyanate;
4) adding dimethylformamide (30% of the total amount), and adjusting the viscosity;
5) butanone and methanol were mixed and added, and the reaction was terminated by capping with stirring at 40-50 ℃ for 1-2 hours, with the final viscosity controlled at 80-140PaS/25 ℃ to give sample B2.
Example 3
The polyester diol used in this example is poly 1, 4-butylene glycol adipate with a number average molecular weight of 2000, the chain extender is 1, 4-butylene glycol, the end-capping reagent is methanol, and the coffee grounds are ground and dried, and the addition amount is 3% of the solid content of the polyurethane resin.
The raw materials and the quality used in the present example are as follows:
| name of raw materials | Mass (gram) | Percent (%) |
| Antioxidant BHT | 2.00 | 0.05% |
| Dispersant YCK-1250 | 1.50 | 0.03% |
| Poly (1, 4-butylene adipate) glycol (number average molecular weight 2000) | 900 | 22.26% |
| Coffee grounds | 36 | 0.89% |
| 1, 4-butanediol | 50 | 1.23% |
| 4, 4' -diphenylmethane diisocyanate | 250 | 6.18% |
| Dimethyl formamide | 2240 | 55.42% |
| Butanone | 560 | 13.84% |
| Methanol | 4 | 0.1% |
| Total mass | 4043.5 | 100% |
The preparation steps are as follows:
1) uniformly mixing antioxidant BHT, dispersant, polyester dihydric alcohol, coffee grounds, 1, 4-butanediol and dimethylformamide (70 percent of the total amount) at 50-60 ℃;
2) adding 4, 4-diphenylmethane diisocyanate in batches, heating to 70-80 ℃, and reacting for 4-6 hours;
3) supplementing 4, 4-diphenylmethane diisocyanate;
4) adding dimethylformamide (30% of the total amount), and adjusting the viscosity;
5) butanone and methanol were mixed and added, and the reaction was terminated by capping with stirring at 40-50 ℃ for 1-2 hours, with the final viscosity controlled at 80-140PaS/25 ℃ to give sample B3.
Example 4
The polyester diol used in this example is poly 1, 4-butylene glycol adipate with a number average molecular weight of 2000, the chain extender is 1, 4-butylene glycol, the end-capping reagent is methanol, and the coffee grounds are ground and dried, and the addition amount is 4% of the solid content of the polyurethane resin.
The raw materials and the quality used in the present example are as follows:
| name of raw materials | Mass (gram) | Percent (%) |
| Antioxidant BHT | 2.00 | 0.05% |
| Dispersant BYK-3760 | 2.00 | 0.05 |
| Poly (1, 4-butylene adipate) glycol (number average molecular weight 2000) | 900 | 22.19% |
| Coffee grounds | 48 | 1.18% |
| 1, 4-butanediol | 50 | 1.22% |
| 4, 4' -diphenylmethane diisocyanate | 250 | 6.16% |
| Dimethyl formamide | 2240 | 55.24% |
| Butanone | 560 | 13.81% |
| Methanol | 4 | 0.1% |
| Total mass | 4056 | 100% |
The preparation steps are as follows:
1) uniformly mixing antioxidant BHT, dispersant, polyester dihydric alcohol, coffee grounds, 1, 4-butanediol and dimethylformamide (70 percent of the total amount) at 50-60 ℃;
2) adding 4, 4-diphenylmethane diisocyanate in batches, heating to 70-80 ℃, and reacting for 4-6 hours;
3) supplementing 4, 4-diphenylmethane diisocyanate;
4) adding dimethylformamide (30% of the total amount), and adjusting the viscosity;
5) butanone and methanol were mixed and added, and the reaction was terminated by capping with stirring at 40-50 ℃ for 1-2 hours, with the final viscosity controlled at 80-140PaS/25 ℃ to give sample B4.
Example 5
The polyester diol used in this example is poly 1, 4-butylene glycol adipate with a number average molecular weight of 2000, the chain extender is 1, 4-butylene glycol, the end-capping agent is gamma-aminopropyl triethoxysilane (KH 550), and the coffee grounds are ground and dried, and the addition amount is 1% of the solid content of the polyurethane resin.
The raw materials and the quality used in the present example are as follows:
| name of raw materials | Mass (gram) | Percent (%) |
| Antioxidant BHT | 2.00 | 0.05% |
| Dispersant YCK-1040 | 0.05 | 0.01% |
| Poly (1, 4-butylene adipate) glycol (number average molecular weight 2000) | 900 | 22.39% |
| Coffee grounds | 12 | 0.3% |
| 1, 4-butanediol | 50 | 1.24% |
| 4, 4' -diphenylmethane diisocyanate | 250 | 6.22% |
| Dimethyl formamide | 2240 | 55.71% |
| Butanone | 560 | 13.93% |
| Gamma-aminopropyltriethoxysilane (KH 550) | 6 | 0.15% |
| Total mass | 4020.5 | 100% |
The preparation steps are as follows:
1) uniformly mixing antioxidant BHT, dispersant, polyester dihydric alcohol, coffee grounds, 1, 4-butanediol and dimethylformamide (70 percent of the total amount) at 50-60 ℃;
2) adding 4, 4-diphenylmethane diisocyanate in batches, heating to 70-80 ℃, and reacting for 4-6 hours at a high temperature;
3) supplementing 4, 4-diphenylmethane diisocyanate;
4) adding dimethylformamide (30% of the total amount), and adjusting the viscosity;
5) butanone and KH550 were mixed and dosed, and the reaction was terminated by stirring at 40-50 ℃ for 1-2 hours with the final viscosity controlled at 80-140PaS/25 ℃ to give sample B5.
Example 6
The polyester diol used in this example is poly 1, 4-butanediol adipate with a number average molecular weight of 2000, the chain extender is 1, 4-butanediol, the end-capping agent is gamma- (2, 3-glycidoxy) propyl trimethoxy silane (KH 560), and the coffee grounds are ground and dried, and the addition amount is 2% of the solid content of the polyurethane resin.
The raw materials and the quality used in the present example are as follows:
| name of raw materials | Mass (gram) | Percent (%) |
| Antioxidant BHT | 2.00 | 0.05% |
| Dispersant BYK-3760 | 1.00 | 0.02% |
| Poly (1, 4-butylene adipate) glycol (number average molecular weight 2000) | 900 | 22.31% |
| Coffee grounds | 24 | 0.6% |
| 1, 4-butanediol | 50 | 1.24% |
| 4, 4' -diphenylmethane diisocyanate | 250 | 6.2% |
| Dimethyl formamide | 2240 | 55.55% |
| Butanone | 560 | 13.88% |
| KH560 | 6 | 0.15% |
| Total mass | 4033 | 100% |
The preparation steps are as follows:
1) uniformly mixing antioxidant BHT, dispersant, polyester dihydric alcohol, coffee grounds, 1, 4-butanediol and dimethylformamide (70 percent of the total amount) at 50-60 ℃;
2) adding 4, 4-diphenylmethane diisocyanate in batches, heating to 70-80 ℃, and reacting for 4-6 hours;
3) supplementing 4, 4-diphenylmethane diisocyanate;
4) adding dimethylformamide (30% of the total amount), and adjusting the viscosity;
5) butanone and KH560 are mixed and added, and the mixture is stirred at 60-70 ℃ for 1-2 hours to terminate the reaction, and the final viscosity is controlled at 80-140PaS/25 ℃, thus obtaining sample B6.
Example 7
The polyester diol used in this example is poly 1, 4-butylene glycol adipate with a number average molecular weight of 2000, the chain extender is 1, 4-butylene glycol, the end-capping agent is gamma-methacryloxypropyl trimethoxysilane (KH 570), and the coffee grounds are ground and dried, and the addition amount is 3% of the solid content of the polyurethane resin.
The raw materials and the quality used in the present example are as follows:
| name of raw materials | Mass (gram) | Percent (%) |
| Antioxidant BHT | 2.00 | 0.05% |
| Dispersant YCK-1250 | 1.50 | 0.03% |
| Poly (1, 4-butylene adipate) glycol (number average molecular weight 2000) | 900 | 22.25% |
| Coffee grounds | 36 | 0.89% |
| 1, 4-butanediol | 50 | 1.24% |
| 4, 4' -diphenylmethane diisocyanate | 250 | 6.18% |
| Dimethyl formamide | 2240 | 55.38% |
| Butanone | 560 | 13.83% |
| KH570 | 6 | 0.15% |
| Total mass | 4045.5 | 100% |
The preparation steps are as follows:
1) uniformly mixing antioxidant BHT, dispersant, polyester glycol, coffee grounds (50% of the total amount), 1, 4-butanediol and dimethylformamide (70% of the total amount) at 50-60 ℃;
2) adding 4, 4-diphenylmethane diisocyanate in batches, heating to 70-80 ℃, and reacting for 4-6 hours;
3) supplementing 4, 4-diphenylmethane diisocyanate;
4) adding dimethylformamide (30% of the total amount), and adjusting the viscosity;
5) mixing butanone and KH570, adding, stirring at 60-70 deg.C for 1-2 hr, and terminating reaction;
6) the remaining coffee powder (50% of the total) was added and stirred at 60-70 ℃ for 1-2 hours, with the final viscosity controlled at 80-140PaS/25 ℃ to give sample B7.
Example 8
The polyester diol used in this example is poly 1, 4-butylene glycol adipate with a number average molecular weight of 2000, the chain extender is 1, 4-butylene glycol, the end-capping agent is gamma-aminopropyl triethoxysilane (KH 550), and the coffee grounds are ground and dried, and the addition amount is 4% of the solid content of the polyurethane resin.
The raw materials and the quality used in the present example are as follows:
| name of raw materials | Mass (gram) | Percent (%) |
| Antioxidant BHT | 2.00 | 0.05% |
| Dispersant BYK-3760 | 2.00 | 0.05% |
| Poly (1, 4-butylene adipate) glycol (number average molecular weight 2000) | 900 | 22.19% |
| Coffee grounds | 48 | 1.18% |
| 1, 4-butanediol | 50 | 1.23% |
| 4, 4' -diphenylmethane diisocyanate | 250 | 6.15% |
| Dimethyl formamide | 2240 | 55.21% |
| Butanone | 560 | 13.80% |
| KH550 | 6 | 0.15% |
| Total mass | 4058 | 100% |
The preparation steps are as follows:
1) uniformly mixing antioxidant BHT, dispersant, polyester glycol, coffee grounds (50% of the total amount), 1, 4-butanediol and dimethylformamide (70% of the total amount) at 50-60 ℃;
2) adding 4, 4-diphenylmethane diisocyanate in batches, heating to 70-80 ℃, and reacting for 4-6 hours;
3) supplementing 4, 4-diphenylmethane diisocyanate;
4) adding dimethylformamide (30% of the total amount), and adjusting the viscosity;
5) mixing butanone and KH550, adding, stirring at 60-70 deg.C for 1-2 hr, and terminating reaction;
6) the remaining coffee powder (50% of the total) was added and stirred at 60-70 ℃ for 1-2 hours, with the final viscosity controlled at 80-140PaS/25 ℃ to give sample B8.
Examples of applications of the examples illustrate:
the resin application comprises film making and leather making, wherein the raw materials used in the leather making comprise the synthesized resin, the Huafeng group surface layer resin, a solvent, a color chip and a functional auxiliary agent, wherein:
the synthetic resin had 1 control A, 8 example B1-B8;
the Huafeng group polyurethane surface resin JF-HSY-SK 62;
solvents include dimethylformamide and butanone;
the color chip is black, such as pigment SP-1698 (black) from Bayster;
the functional assistant is organic silicon, such as BYK-L9565 of Bick chemical company;
surface layer slurry preparation, the mass percentage of the raw materials is as follows:
| JF-HSY-SK62 | 43.0-54.0% |
| solvent(s) | 43.0-54.0% |
| SP-1698 | 2.0-4.0% |
| BYK-9565 | 0.02%-0.04% |
Preparing slurry at the bottom layer, wherein the raw materials comprise the following components in percentage by mass:
| resin composition | 60.0-80.0% |
| Solvent(s) | 20.0-40.0% |
The film preparation and leather making application of the polyurethane resin comprises the following steps:
the film making method comprises the following steps: coating the sample resin on mirror release paper according to the coating thickness of 0.15mm, baking for 10-15min at 130 ℃, and taking out the sample resin from the release paper to obtain the resin adhesive film.
The tanning method comprises the following steps: step one, putting 100 parts of surface layer resin JF-HSY-SK62 (Shanghai Huafeng material science and technology Co., Ltd.), 70 parts of dimethylformamide, 30 parts of butanone, 0.05 part of flatting agent BYK-L9565 and 6 parts of black sheet SP-1698 into a sampling cup in sequence, stirring and mixing uniformly by a dispersion machine, coating the mixed solution on DE-7 release paper according to the coating thickness of 0.15mm, baking for 3-5min at 130 ℃, and preparing 9 surface layers by the same method; and step two, putting the comparative sample, 100 parts of dimethylformamide and 15 parts of butanone into a sample cup in sequence, stirring and mixing uniformly by a dispersion machine, coating prepared bottom layer slurry on release paper coated with a surface layer, directly pasting a shoe leather microfiber substrate (Shanghai Huafeng microfiber science and technology Co., Ltd.) with the thickness of 0.8mm and the specification of H2, rolling the substrate by a rolling rod back and forth for 3-5 times, baking the substrate in an oven at 135 ℃ for 5-8 minutes, and then releasing the substrate from the release paper to obtain the leather sample.
The basic mechanical property test method comprises the following steps: the resin synthesized in the examples was knife-coated on a mirror release paper to a coating thickness of not 0.2mm, and placed in an oven to be dried. The film was cut into a size of 2.5cm by 3.5cm, and the modulus, elongation and breaking strength of the resin were measured by a universal tester (high-speed railway technologies, Ltd., Al-7000-MT), and data were recorded.
The peel strength test method comprises the following steps: and (3) sequentially cutting a plurality of sample pieces on the prepared leather sample by using a sample cutting mold (30 × 120 mm), wherein the number of the warp sample pieces and the weft sample pieces is half respectively, and the names and the warp and weft directions of the leather samples are marked on the back surfaces of the sample pieces. Brushing glue on the surface of the leather sample, pasting, rolling, and then drying in an oven. The specimens were each mounted on a universal tester (high-speed rail technologies, inc., Al-7000-MT) for testing, and peel strength data were recorded.
The heat aging performance test method comprises the following steps: and placing the prepared leather sample into a 120 ℃ oven, placing the leather sample for one week, taking out the leather sample, and testing and recording data according to a peel strength testing method.
The hydrolysis resistance test method comprises the following steps: and (3) placing the prepared leather sample into a NaOH solution with the concentration of less than 10%, standing for 24 hours, taking out, cleaning and drying, and testing and recording data according to a peel strength testing method.
Solvent resistance test method: the prepared leather sample is dropped with 10 drops of butanone on the back surface, and after 1 minute, the leather sample is observed to be kept.
Physical property tests of examples 1 to 8 and comparative example 1 are shown in the following table:
| comparative example 1 | Example 1 | Example 2 | Example 3 | Example 4 | |
| Basic mechanical properties | 2.5/560/22 | 2.6/563/24 | 2.7/556/27 | 2.8/549/29 | 2.7/550/34 |
| Peel Strength/(kg/3 cm) | 5.4 | 7.0 | 7.4 | 8.0 | 8.2 |
| Heat aging property/(kg/3 cm) | 3.2 | 4.7 | 5.3 | 6.0 | 6.8 |
| Hydrolytic Property/(kg/3 cm) | 2.7 | 4.2 | 5.3 | 6.2 | 7.0 |
| Solvent resistance | Good wine | Good wine | Good wine | Superior food | Superior food |
| Example 5 | Example 6 | Example 7 | Example 8 | ||
| Basic mechanical properties | 2.7/570/26 | 2.8/590/29 | 2.8/580/31 | 2.8/580/36 | |
| Peel Strength/(kg/3 cm) | 7.7 | 8.0 | 8.5 | 8.6 | |
| Heat aging property/(kg/3 cm) | 5.8 | 6.4 | 6.8 | 7.3 | |
| Hydrolytic Property/(kg/3 cm) | 5.4 | 6.4 | 6.7 | 7.2 | |
| Solvent resistance | Good wine | Superior food | Superior food | Superior food |
As can be seen from the table above, the polyurethane resin prepared by the invention has the characteristics of high peel strength, good thermal aging performance, good hydrolysis resistance and the like, and has unique coffee smell.
Claims (4)
1. The polyurethane adhesive prepared from the coffee grounds is characterized by being prepared from the following components in percentage by mass as starting raw materials:
20.0 to 25.0 percent of polyester dihydric alcohol
Chain extender 1.0-3.0%
Diisocyanate 5.0-10.0%
0.02 to 0.05 percent of antioxidant
0.2 to 10.0 percent of coffee grounds
0.02 to 0.05 percent of dispersant
0.05 to 0.25 percent of end capping agent
The balance of solvent;
the polyester diol is selected from one or more of poly (1, 4-butylene adipate) diol, poly (1, 6-hexanediol adipate) diol, poly (neopentyl glycol adipate) diol, poly (ethylene adipate) diol, poly (methyl propylene adipate) diol, poly (epsilon-caprolactone) diol and polycarbonate diol with the number average molecular weight of 1000-3500;
the chain extender is one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol and methyl propylene glycol;
the diisocyanate is 4, 4' -diphenylmethane diisocyanate;
the antioxidant is hindered phenol antioxidant or phosphite antioxidant; the dispersant is polyether modified polysiloxane; the end-capping reagent is methanol and/or silane coupling agent; the solvent is at least one of dimethylformamide, toluene, butanone and ethyl acetate;
the coffee grounds are provided by Starbucks, USA, and have average particle size of 1 micrometer and unit water content of less than 500 ppm.
2. The polyurethane adhesive prepared from coffee grounds according to claim 1, wherein the polyurethane adhesive is prepared from the following components in percentage by mass:
0.2 to 2.0 percent of coffee grounds.
3. The method for preparing a polyurethane adhesive prepared from coffee grounds according to any one of claims 1 to 2, comprising the steps of:
(1) uniformly mixing an antioxidant, polyester diol, a chain extender, coffee grounds and dimethylformamide at 50-60 ℃ under normal pressure;
(2) adding diisocyanate in 2-4 batches, heating to 70-80 ℃, and reacting for 4-6 hours in a heat preservation manner;
(3) adding dimethylformamide;
(4) mixing an end-capping reagent and butanone, adding the mixture, terminating the reaction, and preserving heat at a certain temperature for 1-2 hours;
(5) adding dispersant and coffee grounds to obtain the product with the solid content of 30-35% and the final viscosity of 80-140PaS/25 ℃.
4. The method for preparing polyurethane adhesive from coffee grounds according to claim 3, wherein the amount of dimethylformamide added in the step (1) is 55-65% of the total mass of the solvent, and the amount of dimethylformamide added in the step (3) is 15-20% of the total mass of the solvent.
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| CN111909347A (en) * | 2020-06-28 | 2020-11-10 | 合肥科天水性科技有限责任公司 | Antibacterial and antiviral anionic waterborne polyurethane resin and preparation method thereof |
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| CN113861926A (en) * | 2021-11-23 | 2021-12-31 | 上海灵啊实业有限公司 | Bi-component polyurethane adhesive and coffee grounds composition and preparation method thereof |
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