CN109517580B - Preparation method of bamboo liquid-collagen polypeptide composite adhesive - Google Patents
Preparation method of bamboo liquid-collagen polypeptide composite adhesive Download PDFInfo
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- CN109517580B CN109517580B CN201811335106.1A CN201811335106A CN109517580B CN 109517580 B CN109517580 B CN 109517580B CN 201811335106 A CN201811335106 A CN 201811335106A CN 109517580 B CN109517580 B CN 109517580B
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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
- C09J197/00—Adhesives based on lignin-containing materials
- C09J197/02—Lignocellulosic material, e.g. wood, straw or bagasse
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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
- C09J189/00—Adhesives based on proteins; Adhesives based on derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
Abstract
The invention discloses a preparation method of a bamboo liquid-collagen polypeptide composite adhesive, which comprises the following steps: 1) putting bamboo powder into alkali liquor in a reaction kettle, and carrying out primary alkali thermal degradation reaction to obtain bamboo liquor; 2) adding leather scraps into the bamboo liquid in the reaction kettle, and performing secondary alkali thermal degradation reaction on the leather scraps to obtain bamboo liquid-collagen mixed degradation liquid; 3) mechanically press-filtering the bamboo liquid-collagen mixed degradation liquid, and collecting filtrate; 4) and adjusting the pH value of the filtrate, adding a cross-linking agent and a plasticizer, and stirring for reaction to obtain the bamboo liquid-collagen polypeptide composite adhesive. The preparation method of the bamboo liquid-collagen polypeptide composite adhesive utilizes biomass resources and is low in production cost.
Description
Technical Field
The invention belongs to the technical field of wood adhesives, and particularly relates to a preparation method of a bamboo liquid-collagen polypeptide composite adhesive.
Background
The wood adhesive is large in usage amount in China, the market prospect is good, and particularly the market demand for environment-friendly laminated plates is continuously increased. In the prior art, aldehyde adhesives still occupy the dominant position of wood adhesives, urea-formaldehyde resins, phenol-formaldehyde resins and melamine formaldehyde resins are commonly used, and although the raw materials of the wood adhesives are low in price, the content of volatile formaldehyde in the wood adhesives is high, so that potential harm is brought to the health of people, and environmental pollution is caused. In addition, raw materials for producing the aldehyde adhesive are all from non-renewable resources such as petroleum, and with the gradual exhaustion of fossil resources and the enhancement of environmental awareness of people, the strength for researching and developing the wood adhesive with low formaldehyde or no formaldehyde is continuously strengthened. The development of formaldehyde-free green and environment-friendly wood adhesives by using biomass as a basic raw material becomes a major hot point direction for the development of the existing wood adhesives, namely, the formaldehyde-free biomass adhesives are one of novel materials in the industry. For example, CN108359407A discloses a modified vegetable protein adhesive, which is prepared from the following components in parts by weight: 25-35 parts of plant protein meal, 0.5-1.5 parts of dopamine modified polypropylene fiber, 2-6 parts of glycerol triglycidyl ether and 65-75 parts of water. CN106753221A discloses a modified vegetable protein adhesive, the active ingredients of which include vegetable protein meal, PEI (polyethyleneimine), and TA (tannic acid). The starting points of the two invention applications are that agricultural products such as soybean, cottonseed, peanut or sunflower are used as raw materials, the agricultural products are processed into vegetable protein meal (powder), and dopamine modified polypropylene fiber or TA/PEI is used for enhancing the mechanical property of the adhesive. However, the protein molecules contained in these agricultural products have weak binding force and low mechanical properties, and consumption of agricultural products is not practical in areas with agricultural difficulties and food scarcity, and the reinforcing agent also increases production cost.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a bamboo liquid-collagen polypeptide composite adhesive which utilizes biomass resources and has low production cost.
The technical solution of the invention is as follows: a preparation method of a bamboo liquid-collagen polypeptide composite adhesive comprises the following steps:
1) putting bamboo powder into alkali liquor in a reaction kettle, and carrying out primary alkali thermal degradation reaction to obtain bamboo liquor;
2) adding leather scraps into the bamboo liquid in the reaction kettle, and performing secondary alkali thermal degradation reaction on the leather scraps to obtain bamboo liquid-collagen mixed degradation liquid;
3) mechanically press-filtering the bamboo liquid-collagen mixed degradation liquid, and collecting filtrate;
4) and adjusting the pH value of the filtrate, adding a cross-linking agent and a plasticizer, and stirring for reaction to obtain the bamboo liquid-collagen polypeptide composite adhesive.
Compared with the prior art, the invention has the following prominent substantive characteristics and remarkable progress:
the invention discloses a preparation method of an alkaline bamboo liquid-collagen polypeptide composite adhesive, which utilizes the Manrads reaction formed by bamboo fibers and protein polypeptide in the hot pressing process to supplement a cross-linking agent to obtain a macromolecular reticular adhesive and improve the adhesive force. The adhesive has the technical effects of no formaldehyde, no volatile solvent and good water resistance, can form good adhesive strength for wood adhesion, and improves the physical and chemical functions of the adhesive.
Preferably, the bamboo powder in step 1) is prepared by washing bamboo with hydrogen peroxide, then air-drying and grinding. More preferably, the bamboo and hydrogen peroxide are washed for 20-40 min at the weight ratio of 1: 0.8-1.2. Specifically, the processing mode of the bamboo powder is as follows: 1) washing the bamboo with hydrogen peroxide with the pH of 3-4 and the mass fraction of 1-3%; 2) and (3) washing, drying until the water content is 20-25 wt%, and then grinding until the granularity is 30-50 meshes to obtain the bamboo powder. The invention utilizes natural bamboo as raw material to process into bamboo powder, which not only can reduce the production cost of the adhesive, but also can bring good environmental benefit and economic benefit.
Further preferably, the age of the bamboo is less than 2 years. The bamboo objects with the age of less than 2 years are similar in structural components and degradation conditions, so that the bamboo objects are easy to degrade and high in degradation efficiency.
Further preferably, the bamboo object is a bamboo trunk, a bamboo branch, a bamboo leaf or a bamboo shell. The bamboo trunk, the bamboo branches, the bamboo leaves or the bamboo shells are easy to collect, a large amount of bamboo matters are produced after harvesting every year and are applied to a bamboo industry chain, so that the transformation and the upgrade of the bamboo industry are facilitated, and the development and the application of the bamboo material resources are improved.
Preferably, the leather scraps of the step 2) are used after the chrome tanned leather blue wet leather discarded by a tannery is shaved, trimmed, dried and crushed. Specifically, the processing mode of the leather scraps is as follows: 1) uniformly shaving, trimming and drying scraps of chrome tanned leather blue wet leather discarded by a tannery; 2) drying until the water content is 20-25 wt%, and crushing until the length is 2-4 mm. The adhesive is prepared from natural waste chrome tanned leather wet blue leather, so that the production cost of the adhesive can be reduced, and good environmental benefit and economic benefit can be brought.
Preferably, the weight ratio of the bamboo powder to the leather scraps is 1: 1.5-2.5.
Preferably, the raw materials for the primary degradation reaction in the step 1) comprise the following components in parts by weight: 100 parts of bamboo powder, 5-10 parts of NaOH and 200-250 parts of water. The bamboo powder is prepared by washing bamboo with hydrogen peroxide, air drying, and grinding; the bamboo material is selected from dried bamboo, bamboo branch, bamboo leaf or bamboo shell. The raw materials adopt NaOH to carry out primary alkali thermal degradation on the bamboo powder, excessive alkali liquor still exists in the bamboo liquid after the primary alkali thermal degradation reaction is finished, the alkali thermal degradation reaction of leather scraps can be finished in the step 2), and thus, the method does not need to add additional alkali liquor, is simple to operate and has low cost. Of course, KOH can also be used to prepare lye, which likewise can be degraded.
Preferably, the temperature of the primary degradation reaction in the step 1) is 140-150 ℃, the pressure is 0.35-0.5 MPa, and the reaction time is 60-90 min.
Preferably, the temperature of the secondary degradation reaction in the step 2) is 110-120 ℃, the pressure is 0.15-0.2 MPa, and the reaction time is 60-120 min.
Preferably, the filtrate in the step 3) is yellow brown transparent liquid, the viscosity is 100-150 mPa & s, and the solid content is 30-35%.
Preferably, the reaction temperature in the step 4) is 50-80 ℃, and the reaction time is 40-80 min.
Preferably, the step 4) crosslinking agent is epichlorohydrin. The macromolecular reticular adhesive can be obtained by adding the cross-linking agent, the adhesive force is greatly improved, the viscosity reaches 200-250mPas, and the standard requirement of the existing wood adhesive is met.
Preferably, the plasticizer in step 4) is one or a mixture of any two of glycerol, diethylene glycol and tributyl citrate.
Preferably, the pH of the liquid is adjusted to 3.5-5.5 by using 10wt% sulfuric acid in the step 4).
Preferably, in the step 4), the cross-linking agent accounts for 1.0-2.0% of the weight of the filtrate, and the plasticizer accounts for 2.0-4.0% of the weight of the filtrate.
Preferably, the equipment used for pressure filtration in the step 3) is a plate-and-frame filter press. The plate and frame filter press model was BMS4/420-UB, and the pressure was 6 kg.
The invention has the following remarkable advantages and beneficial effects:
1) the bamboo contains a large amount of plant cellulose (namely bamboo fiber), and the water resistance, the adhesive force, the strength and the mechanical property of the adhesive can be improved by utilizing bamboo liquid obtained by degrading bamboo powder made of the bamboo under the alkaline condition; the leather contains a large amount of animal protein, leather scraps are degraded to obtain collagen polypeptide, bamboo powder and the leather scraps are sequentially degraded and liquefied together to obtain bamboo liquid-collagen mixed degradation liquid, the bamboo fibers and the collagen polypeptide undergo a Raman reaction in the hot-pressing degradation process, so that the viscosity of a product is improved, and the synthesized composite adhesive can completely become a substitute of an aldehyde adhesive;
2) the bamboo powder degradation needs more violent conditions, the leather scrap degradation conditions are milder, the bamboo objects are degraded for the first time under the conditions of high temperature, high pressure and multiple alkali, then the leather scraps are put into the bamboo liquid degraded by the bamboo objects, and the leather scraps are degraded for the second time under the conditions of low temperature, low pressure and less alkali, so that the energy and the materials needed by the reaction can be saved by degrading the bamboo liquid and the leather scraps in sequence according to the degradation conditions of the bamboo objects and the alkali amount, and the yield and the efficiency of the degradation reaction are high;
3) only NaOH, a cross-linking agent and a plasticizer need to be purchased before preparation, the raw materials are small in variety and dosage and low in price, and the main reaction raw materials utilize natural waste biomass resources, including natural or waste bamboo and waste chrome tanning, leather and wet blue leather of a tannery, so that the production cost is reduced, the regeneration and resource utilization of the waste biomass is realized, the waste discharge is reduced, the environmental pollution is reduced, and the requirements of the current times on green, environmental protection and sustainable development are met;
4) the preparation method has simple reaction conditions and convenient and easy operation, most impurities can be removed only by mechanical filter pressing after degradation, then macromolecular reticular adhesive can be obtained by adding a cross-linking agent, and the viscosity of the adhesive is further improved;
5) the adhesive can form good adhesive strength for wood adhesion, the viscosity meets the standard requirements of the existing wood adhesive, and the adhesive has good water resistance, adhesive force, strength and mechanical properties, and can greatly improve the physical and chemical functions of the adhesive; and the preparation and application of the adhesive realize the effects of no formaldehyde and no volatile solvent.
Detailed Description
The invention will be further described in the following with reference to specific embodiments for the purpose of enhancing the understanding of the invention, but the invention is not limited in any way.
The invention relates to a plurality of raw materials, wherein the bamboo powder is prepared by washing bamboo with hydrogen peroxide, then airing and grinding; the leather scraps are used after the chrome tanned leather wet blue leather discarded by a tannery is shaved evenly, trimmed, dried and crushed; NaOH, epichlorohydrin, glycerol, diethylene glycol and tributyl citrate are all purchased from the market.
The invention relates to various instruments, namely a high-pressure reaction kettle and a plate-and-frame filter press, which are purchased from the market.
In the invention, a plurality of parameters such as particle size, temperature, pressure, time, mass fraction and viscosity are presented, and units (such as mesh, DEG C, MPa, min,%, and mPas) are uniformly marked after being limited at the upper limit, such as 30-50 mesh, 140-150 ℃, 0.35-0.5 MPa, 60-90 min, 30-35%, and 100-150 mPas. Of course, the unit can be marked after the upper limit value and the lower limit value, such as 30 meshes to 50 meshes, 140 ℃ to 150 ℃, 0.35mPa to 0.5MPa, 60min to 90min, 30 percent to 35 percent, 100 mPa.s to 150 mPa.s. The two parameter ranges can be expressed in any way, in the embodiment, values are taken from the upper limit value, the lower limit value and the middle value of the parameter, and the numerical values are all in units.
Example 1
1) Preparing bamboo liquid: washing 100 parts by weight of dried bamboo, bamboo branches, bamboo leaves and bamboo shoot shells with the age of less than 2 years with hydrogen peroxide 100 parts by weight with the mass fraction of 1% and the pH of 3 for 30min, then airing, and crushing to 30 meshes to obtain bamboo powder; weighing the following components in parts by weight: 100 parts of bamboo powder, 5 parts of NaOH and 200 parts of water are put into a high-pressure reaction kettle, and subjected to primary degradation reaction for 90min at the temperature of 140 ℃ and the pressure of 0.35MPa, and then cooled to obtain bamboo liquid;
2) preparing mixed degradation liquid: uniformly shaving, trimming and drying chrome tanned leather wet blue leather discarded by a tannery, and crushing to obtain leather scraps with the length of 2 mm; adding 150 parts of leather scraps into a high-pressure reaction kettle containing bamboo liquid, performing secondary degradation reaction for 120min at the temperature of 110 ℃ and under the pressure of 0.15MPa, and cooling to obtain bamboo liquid-collagen mixed degradation liquid;
3) purifying bamboo liquid-collagen liquid: taking out the mixed liquid of the bamboo liquid and the leather scraps, and performing pressure filtration by using a plate-and-frame filter press with the pressure of 6kg and the filter press cloth of BMQ3/320-250(500 meshes) to obtain a filtrate; the filtrate is yellow brown transparent liquid, the viscosity is 100 mPa.s, and the solid content is 33%;
4) preparing bamboo liquid-collagen polypeptide composite glue: pouring the filtrate into a reaction kettle, adjusting the pH of the liquid to 3.5 by using 10wt% of sulfuric acid, heating to 50 ℃, adding epichlorohydrin accounting for 1.0% of the weight of the liquid and glycerol accounting for 2.0%, stirring and reacting for 80min to obtain the bamboo liquid-collagen polypeptide composite hot-pressing adhesive with the viscosity of 200mPa & s and the solid content of 35%.
Example 2
1) Preparing bamboo liquid: washing 100 parts by weight of waste bamboo trunk, bamboo branches, bamboo leaves and bamboo shoot shells with the age of less than 2 years with hydrogen peroxide solution of 80 parts by weight and the pH value of 4 and the mass fraction of 3 percent for 30min, then airing, and crushing to 50 meshes to obtain bamboo powder; weighing the following components in parts by weight: 100 parts of bamboo powder, 10 parts of NaOH and 250 parts of water are put into a high-pressure reaction kettle, and subjected to a primary degradation reaction for 90min at 150 ℃ and 0.5MPa, and then cooled to obtain bamboo liquid;
2) preparing mixed degradation liquid: uniformly shaving, trimming and drying chrome tanned leather wet blue leather discarded by a tannery, and crushing to obtain leather scraps with the length of 4 mm; adding 250 parts of leather scraps into a high-pressure reaction kettle containing bamboo liquid, performing secondary degradation reaction for 60min at the temperature of 120 ℃ and under the pressure of 0.2MPa, and cooling to obtain bamboo liquid-collagen mixed degradation liquid;
3) purifying bamboo liquid-collagen liquid: taking out the mixed liquid of the bamboo liquid and the leather scraps, and performing pressure filtration by using a plate-and-frame filter press with the pressure of 6kg and the filter press cloth of BMQ3/320-250(500 meshes) to obtain a filtrate; the filtrate is yellow brown transparent liquid, the viscosity is 150 mPa.s, and the solid content is 35 percent;
4) preparing bamboo liquid-collagen polypeptide composite glue: pouring the filtrate into a reaction kettle, adjusting the pH of the liquid to 4 by using 10wt% of sulfuric acid, heating to 80 ℃, adding epichlorohydrin accounting for 2.0% of the weight of the liquid and diethylene glycol accounting for 4.0%, stirring and reacting for 80min to obtain the bamboo liquid-collagen polypeptide composite hot-pressing adhesive with the viscosity of 200mPa & s and the solid content of 40%.
Example 3
1) Preparing bamboo liquid: washing 100 parts by weight of dried bamboo, bamboo branches, bamboo leaves and bamboo shoot shells with the age of less than 2 years with hydrogen peroxide 120 parts by weight with the mass fraction of 2% and the pH value of 3 for 30min, then airing, and crushing to 40 meshes to obtain bamboo powder; weighing the following components in parts by weight: putting 100 parts of bamboo powder, 8 parts of NaOH and 220 parts of water into a high-pressure reaction kettle, carrying out primary degradation reaction for 75min at the temperature of 140 ℃ and under the pressure of 0.4MPa, and cooling to obtain bamboo liquid;
2) preparing mixed degradation liquid: uniformly shaving, trimming and drying chrome tanned leather wet blue leather discarded by a tannery, and crushing to a length of 3mm to obtain leather scraps; adding 200 parts of leather scraps into a high-pressure reaction kettle containing bamboo liquid, performing secondary degradation reaction for 90min at the temperature of 115 ℃ and under the pressure of 0.18MPa, and cooling to obtain bamboo liquid-collagen mixed degradation liquid;
3) purifying bamboo liquid-collagen liquid: taking out the mixed liquid of the bamboo liquid and the leather scraps, and performing pressure filtration by using a plate-and-frame filter press with the pressure of 6kg and the filter press cloth of BMQ3/320-250(500 meshes) to obtain a filtrate; the filtrate is yellow brown transparent liquid, the viscosity is 120 mPa.s, and the solid content is 34%;
4) preparing bamboo liquid-collagen polypeptide composite glue: pouring the filtrate into a reaction kettle, adjusting the pH of the liquid to 4.5 by using 10wt% of sulfuric acid, heating to 60 ℃, adding epichlorohydrin accounting for 1.5% of the weight of the liquid and tributyl citrate accounting for 3.0%, stirring and reacting for 60min to obtain the bamboo liquid-collagen polypeptide composite hot-pressed adhesive with the viscosity of 200mPa & s and the solid content of 35%.
Example 4
1) Preparing bamboo liquid: washing 100 parts by weight of dried bamboo, bamboo branches, bamboo leaves and bamboo shoot shells with the age of less than 1 year with hydrogen peroxide 100 parts by weight and with the pH value of 3 and the mass fraction of 3% for 30min, then airing, and crushing to 35 meshes to obtain bamboo powder; weighing the following components in parts by weight: 100 parts of bamboo powder, 6 parts of NaOH and 220 parts of water are put into a high-pressure reaction kettle, and subjected to primary degradation reaction for 90min at the temperature of 140 ℃ and the pressure of 0.45MPa, and then cooled to obtain bamboo liquid;
2) preparing mixed degradation liquid: uniformly shaving, trimming and drying chrome tanned leather wet blue leather discarded by a tannery, and crushing to obtain leather scraps with the length of 2 mm; adding 150 parts of leather scraps into a high-pressure reaction kettle containing bamboo liquid, performing secondary degradation reaction for 100min at the temperature of 115 ℃ and under the pressure of 0.18MPa, and cooling to obtain bamboo liquid-collagen mixed degradation liquid;
3) purifying bamboo liquid-collagen liquid: taking out the mixed liquid of the bamboo liquid and the leather scraps, and performing pressure filtration by using a plate-and-frame filter press with the pressure of 6kg and the filter press cloth of BMQ3/320-250(500 meshes) to obtain a filtrate; the filtrate is yellow brown transparent liquid, the viscosity is 100 mPa.s, and the solid content is 33%;
4) preparing bamboo liquid-collagen polypeptide composite glue: pouring the filtrate into a reaction kettle, adjusting the pH of the liquid to 3.5 by using 10wt% of sulfuric acid, heating to 60 ℃, adding epichlorohydrin accounting for 1.0% of the weight of the liquid and glycerol accounting for 2.0%, stirring and reacting for 60min to obtain the bamboo liquid-collagen polypeptide composite hot-pressing adhesive with the viscosity of 200mPa & s and the solid content of 35%.
Example 5
1) Preparing bamboo liquid: washing 100 parts by weight of waste bamboo trunk, bamboo branches, bamboo leaves and bamboo shoot shells with the age of less than 1 year with hydrogen peroxide solution of 80 parts by weight and with the pH value of 4 and the mass fraction of 2.5 percent for 30min, then airing, and crushing to 45 meshes to obtain bamboo powder; weighing the following components in parts by weight: 100 parts of bamboo powder, 8 parts of NaOH and 250 parts of water are put into a high-pressure reaction kettle, and subjected to primary degradation reaction for 70min at the temperature of 150 ℃ and under the pressure of 0.4MPa, and the temperature is reduced to obtain bamboo liquid;
2) preparing mixed degradation liquid: uniformly shaving, trimming and drying chrome tanned leather wet blue leather discarded by a tannery, and crushing to obtain leather scraps with the length of 4 mm; adding 250 parts of leather scraps into a high-pressure reaction kettle containing bamboo liquid, performing secondary degradation reaction for 90min at the temperature of 115 ℃ and under the pressure of 0.2MPa, and cooling to obtain bamboo liquid-collagen mixed degradation liquid;
3) purifying bamboo liquid-collagen liquid: taking out the mixed liquid of the bamboo liquid and the leather scraps, and performing pressure filtration by using a plate-and-frame filter press with the pressure of 6kg and the filter press cloth of BMQ3/320-250(500 meshes) to obtain a filtrate; the filtrate is yellow brown transparent liquid, the viscosity is 150 mPa.s, and the solid content is 35 percent;
4) preparing bamboo liquid-collagen polypeptide composite glue: pouring the filtrate into a reaction kettle, adjusting the pH of the liquid to 4 by using 10wt% of sulfuric acid, heating to 70 ℃, adding epichlorohydrin accounting for 2.0% of the weight of the liquid and diethylene glycol accounting for 4.0%, stirring and reacting for 70min to obtain the bamboo liquid-collagen polypeptide composite hot-pressing adhesive with the viscosity of 200mPa & s and the solid content of 40%.
Example 6
1) Preparing bamboo liquid: washing 100 parts by weight of dried bamboo, bamboo branches, bamboo leaves and bamboo shoot shells with the age of less than 1 year with hydrogen peroxide 120 parts by weight with the mass fraction of 2.8% and the pH of 3 for 30min, then airing, and crushing to 40 meshes to obtain bamboo powder; weighing the following components in parts by weight: 100 parts of bamboo powder, 8 parts of KOH and 240 parts of water are put into a high-pressure reaction kettle, and subjected to primary degradation reaction for 65min at the temperature of 140 ℃ and the pressure of 0.45MPa, and then cooled to obtain bamboo liquid;
2) preparing mixed degradation liquid: uniformly shaving, trimming and drying chrome tanned leather wet blue leather discarded by a tannery, and crushing to a length of 3mm to obtain leather scraps; adding 200 parts of leather scraps into a high-pressure reaction kettle containing bamboo liquid, performing secondary degradation reaction for 80min at the temperature of 110 ℃ and under the pressure of 0.2MPa, and cooling to obtain bamboo liquid-collagen mixed degradation liquid;
3) purifying bamboo liquid-collagen liquid: taking out the mixed liquid of the bamboo liquid and the leather scraps, and performing pressure filtration by using a plate-and-frame filter press with the pressure of 6kg and the filter press cloth of BMQ3/320-250(500 meshes) to obtain a filtrate; the filtrate is yellow brown transparent liquid, the viscosity is 120 mPa.s, and the solid content is 34%;
4) preparing bamboo liquid-collagen polypeptide composite glue: pouring the filtrate into a reaction kettle, adjusting the pH of the liquid to 4.5 by using 10wt% of sulfuric acid, heating to 80 ℃, adding epichlorohydrin with the weight of 1.5% of the liquid and tributyl citrate with the weight of 3.0%, stirring and reacting for 50min to obtain the bamboo liquid-collagen polypeptide composite hot-pressing adhesive with the viscosity of 200mPa & s and the solid content of 35%.
Example 7
1) Preparing bamboo liquid: washing 100 parts by weight of dried bamboo, bamboo branches, bamboo leaves and bamboo shoot shells with hydrogen peroxide 100 parts by weight for 30min at a pH of 3 and a mass fraction of 2.8%, then drying in the air, and crushing to 40 meshes to obtain bamboo powder; weighing the following components in parts by weight: putting 100 parts of bamboo powder, 8 parts of NaOH and 240 parts of water into a high-pressure reaction kettle, carrying out primary degradation reaction for 65min at the temperature of 140 ℃ and under the pressure of 0.45MPa, and cooling to obtain bamboo liquid;
2) preparing mixed degradation liquid: uniformly shaving, trimming and drying chrome tanned leather wet blue leather discarded by a tannery, and crushing to a length of 3mm to obtain leather scraps; adding 200 parts of leather scraps into a high-pressure reaction kettle containing bamboo liquid, performing secondary degradation reaction for 80min at the temperature of 110 ℃ and under the pressure of 0.2MPa, and cooling to obtain bamboo liquid-collagen mixed degradation liquid;
3) purifying bamboo liquid-collagen liquid: taking out the mixed liquid of the bamboo liquid and the leather scraps, and performing filter pressing to obtain a filtrate; the filtrate is yellow brown transparent liquid, the viscosity is 140mPa & s, and the solid content is 34%;
4) preparing bamboo liquid-collagen polypeptide composite glue: pouring the filtrate into a reaction kettle, adjusting the pH of the liquid to 3.5 by using 10wt% of sulfuric acid, heating to 80 ℃, adding epichlorohydrin accounting for 1.5% of the weight of the liquid, glycerol accounting for 1.0% of the weight of the liquid and diethylene glycol accounting for 1.0% of the weight of the liquid, stirring and reacting for 50min to obtain the bamboo liquid-collagen polypeptide composite hot-pressing adhesive with the viscosity of 235mPa & s and the solid content of 35%.
Example 8
1) Preparing bamboo liquid: washing 100 parts by weight of dried bamboo, bamboo branches, bamboo leaves and bamboo shoot shells with the age of less than 2 years with hydrogen peroxide solution of 90 parts by weight and with the pH value of 3 and the mass fraction of 2.8% for 30min, then airing, and crushing to 40 meshes to obtain bamboo powder; weighing the following components in parts by weight: putting 100 parts of bamboo powder, 8 parts of NaOH and 240 parts of water into a high-pressure reaction kettle, carrying out primary degradation reaction for 65min at the temperature of 140 ℃ and under the pressure of 0.45MPa, and cooling to obtain bamboo liquid;
2) preparing mixed degradation liquid: uniformly shaving, trimming and drying chrome tanned leather wet blue leather discarded by a tannery, and crushing to a length of 3mm to obtain leather scraps; adding 200 parts of leather scraps into a high-pressure reaction kettle containing bamboo liquid, performing secondary degradation reaction for 80min at the temperature of 110 ℃ and under the pressure of 0.2MPa, and cooling to obtain bamboo liquid-collagen mixed degradation liquid;
3) purifying bamboo liquid-collagen liquid: taking out the mixed liquid of the bamboo liquid and the leather scraps, and performing pressure filtration by using a plate-and-frame filter press with the pressure of 6kg and the filter press cloth of BMQ3/320-250(500 meshes) to obtain a filtrate; the filtrate is yellow brown transparent liquid, the viscosity is 130mPa & s, and the solid content is 34%;
4) preparing bamboo liquid-collagen polypeptide composite glue: pouring the filtrate into a reaction kettle, adjusting the pH of the liquid to 4.5 by using 10wt% of sulfuric acid, heating to 80 ℃, adding epichlorohydrin accounting for 2.0% of the weight of the liquid, glycerol accounting for 1.0% of the weight of the liquid and tributyl citrate accounting for 1.0% of the weight of the liquid, stirring and reacting for 50min to obtain the bamboo liquid-collagen polypeptide composite hot-pressing adhesive with the viscosity of 250mPa & s and the solid content of 35%.
Example 9
1) Preparing bamboo liquid: washing 100 parts by weight of dried bamboo, bamboo branches, bamboo leaves and bamboo shoot shells with the age of less than 1 year with hydrogen peroxide 110 parts by weight with the mass fraction of 2.8% and the pH of 3 for 30min, then airing, and crushing to 40 meshes to obtain bamboo powder; weighing the following components in parts by weight: putting 100 parts of bamboo powder, 8 parts of NaOH and 240 parts of water into a high-pressure reaction kettle, carrying out primary degradation reaction for 65min at the temperature of 140 ℃ and under the pressure of 0.45MPa, and cooling to obtain bamboo liquid;
2) preparing mixed degradation liquid: uniformly shaving, trimming and drying chrome tanned leather wet blue leather discarded by a tannery, and crushing to a length of 3mm to obtain leather scraps; adding 200 parts of leather scraps into a high-pressure reaction kettle containing bamboo liquid, performing secondary degradation reaction for 80min at the temperature of 110 ℃ and under the pressure of 0.2MPa, and cooling to obtain bamboo liquid-collagen mixed degradation liquid;
3) purifying bamboo liquid-collagen liquid: taking out the mixed liquid of the bamboo liquid and the leather scraps, and performing pressure filtration by using a plate-and-frame filter press with the pressure of 6kg and the filter press cloth of BMQ3/320-250(500 meshes) to obtain a filtrate; the filtrate is yellow brown transparent liquid, the viscosity is 145mPa & s, and the solid content is 34%;
4) preparing bamboo liquid-collagen polypeptide composite glue: pouring the filtrate into a reaction kettle, adjusting the pH of the liquid to 4 by using 10wt% of sulfuric acid, heating to 80 ℃, adding 2 wt% of epichlorohydrin, 1.0% of tributyl citrate and 1.0% of diethylene glycol, stirring and reacting for 50min to obtain the bamboo liquid-collagen polypeptide composite hot-pressing adhesive with the viscosity of 240mPa & s and the solid content of 35%.
Example 10
1) Preparing bamboo liquid: washing 100 parts by weight of dried bamboo, bamboo branches, bamboo leaves and bamboo shoot shells with the age of less than 2 years with hydrogen peroxide 100 parts by weight with the mass fraction of 1% and the pH of 3 for 30min, then airing, and crushing to 30 meshes to obtain bamboo powder; weighing the following components in parts by weight: 100 parts of bamboo powder, 10 parts of NaOH and 250 parts of water are put into a high-pressure reaction kettle, and subjected to primary degradation reaction for 80min at 145 ℃ and 0.45MPa, and then cooled to obtain bamboo liquid;
2) preparing mixed degradation liquid: uniformly shaving, trimming and drying chrome tanned leather wet blue leather discarded by a tannery, and crushing to obtain leather scraps with the length of 2 mm; adding 200 parts of leather scraps into a high-pressure reaction kettle containing bamboo liquid, performing secondary degradation reaction for 120min at the temperature of 120 ℃ and under the pressure of 0.15MPa, and cooling to obtain bamboo liquid-collagen mixed degradation liquid;
3) purifying bamboo liquid-collagen liquid: taking out the mixed liquid of the bamboo liquid and the leather scraps, adjusting the pH of the liquid to 3.5 by using 10wt% sulfuric acid, and performing pressure filtration by using a plate and frame filter press with the pressure of 6kg and the filter press cloth of BMQ3/320-250(500 meshes) to obtain a filtrate; the filtrate is yellow brown transparent liquid, the viscosity is 150 mPa.s, and the solid content is 33%;
4) preparing bamboo liquid-collagen polypeptide composite glue: pouring the filtrate into a reaction kettle, heating to 50 ℃, adding epoxy chloropropane accounting for 2.0 percent of the weight of the filtrate and glycerol accounting for 4.0 percent of the weight of the filtrate, stirring and reacting for 80min to obtain the bamboo liquid-collagen polypeptide composite hot-pressing adhesive with the viscosity of 250mPa & s and the solid content of 35 percent.
Examples of the applications
The adhesive is used for preparing poplar three-ply boards with the board thickness of 2mm and the double-sided glue application of 200g/m2The pressing force is 1.2MPa, the temperature is 120 ℃, and the hot pressing time is 90 min. The performance test of the adhesive is carried out according to GB/T14074-. The basic analytical indices of the adhesive are shown in Table 1:
table 1: basic analytical index of adhesive
| Appearance of the product | viscosity/mPas | pH (Dilute 10 times) | Solid content/%) | Ash content | Dry glue 24h water absorption/percent |
| Yellowish brown viscous liquid | 200～250 | 8.0～9.0 | 35～40 | 5.1～5.7 | 60～80 |
As can be seen from Table 1, the ash content is only 5.1 to 5.7%, indicating that the amount of the additive is small. The water absorption of the dry glue for 24 hours is 60-80%, which indicates moderate hydrophilicity, and the dry glue swells in a hydrophilic mode after being bonded. The viscosity, the pH value and the solid content all reach the standard requirements of the existing wood adhesive, so that the bamboo liquid-collagen polypeptide composite adhesive prepared by the invention can completely replace aldehyde adhesives.
Claims (7)
1. A preparation method of a bamboo liquid-collagen polypeptide composite adhesive is characterized by comprising the following steps:
1) putting bamboo powder into alkali liquor in a reaction kettle, and carrying out primary alkali thermal degradation reaction to obtain bamboo liquor; the raw materials for the primary degradation reaction comprise the following components in parts by weight: 100 parts of bamboo powder, 5-10 parts of NaOH and 200-250 parts of water, wherein the temperature of the primary degradation reaction is 140-150 ℃, the pressure is 0.35-0.5 MPa, and the reaction time is 60-90 min;
2) leather scraps are added into the bamboo liquid in the reaction kettle, the weight ratio of the bamboo powder to the leather scraps is 1: 1.5-2.5, and secondary leather scrap alkaline thermal degradation reaction is carried out to obtain bamboo liquid-collagen mixed degradation liquid;
3) mechanically press-filtering the bamboo liquid-collagen mixed degradation liquid, and collecting filtrate;
4) and adjusting the pH value of the filtrate, adding a cross-linking agent and a plasticizer, and stirring for reaction to obtain the bamboo liquid-collagen polypeptide composite adhesive.
2. The preparation method of the bamboo liquid-collagen polypeptide composite adhesive as claimed in claim 1, wherein the bamboo powder is prepared by washing bamboo with hydrogen peroxide, then air-drying and grinding.
3. The preparation method of the bamboo liquid-collagen polypeptide composite adhesive as claimed in claim 1, wherein the leather scraps are used after chrome tanned leather wet blue leather discarded by a tannery is shaved, trimmed, dried and crushed.
4. The preparation method of the bamboo liquid-collagen polypeptide composite adhesive according to claim 1, wherein the temperature of the secondary degradation reaction in the step 2) is 110-120 ℃, the pressure is 0.15-0.2 MPa, and the reaction time is 60-120 min.
5. The preparation method of the bamboo liquid-collagen polypeptide composite adhesive according to claim 1, wherein the reaction temperature in the step 4) is 50-80 ℃, and the reaction time is 40-80 min.
6. The preparation method of the bamboo liquid-collagen polypeptide composite adhesive as claimed in claim 1, wherein in the step 4), the cross-linking agent is epichlorohydrin, and the plasticizer is one or a mixture of any two of glycerol, diethylene glycol and tributyl citrate.
7. The preparation method of the bamboo liquid-collagen polypeptide composite adhesive as claimed in claim 1, wherein in the step 4), 10wt% of sulfuric acid is used to adjust the pH of the liquid to 3.5-5.5, the cross-linking agent accounts for 1.0-2.0% of the weight of the filtrate, and the plasticizer accounts for 2.0-4.0% of the weight of the filtrate.
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