阅读说明：本技术 一种彩钢夹芯板用高强度抗菌芯材及其制备方法 (High-strength antibacterial core material for color steel sandwich panel and preparation method thereof ) 是由 万贤虎 万子涵 于 2020-12-14 设计创作，主要内容包括：本发明公开了一种彩钢夹芯板用高强度抗菌芯材及其制备方法,其中制备方法包括：将碱木质素溶液采用超滤法按分子量进行分级分离,收集得到截留液A和透过液B；用纳米银、有机硅季铵盐对截留液A中的高分子量碱木质素组分进行改性,得到碱木质素基添加剂A；以环氧氯丙烷作为交联剂,将聚乙二醇接枝到透过液B中的低分子量碱木质素组分上,得到碱木质素基添加剂B；将碱木质素基添加剂A、碱木质素基添加剂B按一定比例加入聚氨酯发泡保温材料的原料中,进行发泡、熟化、固化,即得。本发明制备的彩钢夹芯板用芯材具有高强度、高抗菌性能,能够满足医疗、制药等特殊行业的使用需求。(The invention discloses a high-strength antibacterial core material for a color steel sandwich panel and a preparation method thereof, wherein the preparation method comprises the following steps: carrying out fractionation on the alkali lignin solution according to molecular weight by adopting an ultrafiltration method, and collecting to obtain trapped fluid A and permeate B; modifying the high molecular weight alkali lignin component in the trapped fluid A by using nano silver and organic silicon quaternary ammonium salt to obtain an alkali lignin-based additive A; grafting polyethylene glycol onto a low-molecular-weight alkali lignin component in the permeate liquid B by using epoxy chloropropane as a crosslinking agent to obtain an alkali lignin-based additive B; adding the alkali lignin-based additive A and the alkali lignin-based additive B into the raw materials of the polyurethane foaming thermal insulation material according to a certain proportion, and carrying out foaming, curing and curing to obtain the polyurethane foaming thermal insulation material. The core material for the color steel sandwich panel prepared by the invention has high strength and high antibacterial performance, and can meet the use requirements of special industries such as medical treatment, pharmacy and the like.)

1. A preparation method of a high-strength antibacterial core material for a color steel sandwich panel is characterized by comprising the following steps:

s1, carrying out ultrafiltration on the alkali lignin solution with the mass fraction of 20-30% by using an ultrafiltration membrane with the molecular weight cutoff of 5000-7000Da, and collecting to obtain a cutoff liquid A and a permeate liquid B;

s2, adding nano silver into the trapped fluid A, performing ultrasonic dispersion uniformly, performing oscillation adsorption for 12-24h at 40-60 ℃, adding organic silicon quaternary ammonium salt, performing oscillation reaction for 6-12h at 70-80 ℃, adjusting the pH of the obtained reaction liquid to 2-3 after the reaction is finished, and performing freeze drying on the obtained precipitate to obtain an alkali lignin-based additive A;

s3, mixing polyethylene glycol, epichlorohydrin, tetra-n-butylammonium chloride and sodium hydroxide according to a mass ratio of 1: (1-2): (0.01-0.02): (2-3), uniformly mixing, stirring and reacting at 40-60 ℃ for 1-3h, and after the reaction is finished, mixing the obtained reaction liquid with the permeation liquid B according to the volume ratio of (1-3): 1, uniformly mixing, stirring and reacting at 70-80 ℃ for 2-4h, cooling the obtained reaction liquid to room temperature after the reaction is finished, adjusting the pH value to be neutral, and then freeze-drying to obtain an alkali lignin-based additive B;

s4, according to parts by mass, firstly, uniformly mixing 20-30 parts of polyether polyol, 20-30 parts of polyester polyol, 4-6 parts of cyclopentane, 5-8 parts of alkali lignin-based additive A, 2-3 parts of alkali lignin-based additive B, 3-5 parts of organic silicon foam stabilizer and 0.3-0.5 part of water, then adding 65-85 parts of polymethylene polyphenyl polyisocyanate and 2-3 parts of cross-linking agent, uniformly mixing to obtain a mixture, injecting the mixture into a mold, and carrying out foaming, foam curing and curing to obtain the polyurethane foam.

2. The preparation method of the high-strength antibacterial core material for the color steel sandwich panel according to claim 1, wherein the preparation method of the alkali lignin solution comprises the following steps: adding wheat straw alkali lignin into alkaline solution with pH of 9.5-10, and stirring at 60-80 deg.C until it is sufficiently dissolved; preferably, the alkaline solution is NaOH aqueous solution and Na₂CO₃Aqueous solution, KOH aqueous solution, K₂CO₃At least one of aqueous solutions.

3. The preparation method of the high-strength antibacterial core material for the color steel sandwich panel according to claim 1 or 2, wherein in the step S2, the ratio of the nano silver, the organosilicon quaternary ammonium salt and the trapped fluid a is (0.3-0.5) g: (30-40) mL: 100 mL.

4. The method for preparing a high-strength antibacterial core material for a color steel sandwich panel according to any one of claims 1 to 3, wherein in the step S2, the organosilicon quaternary ammonium salt is organosilicon quaternary ammonium salt DC 5700.

5. The method for preparing a high-strength antibacterial core material for a color steel sandwich panel according to any one of claims 1 to 4, wherein the hydroxyl value of the polyether polyol is 400-520mgKOH/g, and the viscosity at 25 ℃ is 4000-7500 mPa.S; the hydroxyl value of the polyester polyol is 300-350mgKOH/g, and the viscosity at 25 ℃ is 1500-3500 mPa.S; the content of isocyanic acid radical of polymethylene polyphenyl polyisocyanate is 30-40%.

6. The method for preparing a high-strength antibacterial core material for a color steel sandwich panel according to any one of claims 1 to 5, wherein the cross-linking agent is trimethylolpropane.

7. The preparation method of the high-strength antibacterial core material for the color steel sandwich panel according to any one of claims 1 to 6, wherein in the step S4, the mixture is injected into a mold, foamed at 50-55 ℃, cured at normal temperature for 1-2 hours in a foaming manner, and cured at 80-90 ℃ for 2-4 hours to obtain the color steel sandwich panel.

8. A high-strength antibacterial core material for a color steel sandwich panel, which is obtained by the preparation method of any one of claims 1 to 7.

Technical Field

The invention relates to the technical field of heat insulation materials, in particular to a high-strength antibacterial core material for a color steel sandwich board and a preparation method thereof.

Background

The color steel sandwich board is a common building material, consists of a panel made of upper and lower layers of metal or nonmetal materials and an inner core positioned in the middle of the panel, and has the advantages of light weight, simple and convenient installation, good heat preservation effect and the like, and the performances of heat preservation, heat insulation, sound absorption and the like of the color steel sandwich board are mainly determined by the material of the core layer. The core material of the color steel sandwich board mainly comprises phenolic aldehyde, polystyrene, hard polyurethane, polyester, rock wool and the like, wherein the hard polyurethane is one of the core materials with the best heat preservation and insulation effects, and is widely applied. In recent years, with the popularization and application of color steel sandwich panels in the industries of medical treatment, pharmacy and the like, in order to meet the requirements of sterilization and disinfection in special occasions, how to improve the antibacterial performance of the core material for the color steel sandwich panel becomes a new challenge. Meanwhile, the physical properties of the core material are often weakened by adding a large amount of the antibacterial agent, and the expected antibacterial effect cannot be achieved if the addition amount is too low, so how to balance the physical properties and the antibacterial properties of the core material becomes a problem of current key attention.

Disclosure of Invention

Based on the technical problems in the background art, the invention provides a high-strength antibacterial core material for a color steel sandwich board and a preparation method thereof.

The invention provides a preparation method of a high-strength antibacterial core material for a color steel sandwich panel, which comprises the following steps:

s1, carrying out ultrafiltration on the alkali lignin solution with the mass fraction of 20-30% by using an ultrafiltration membrane with the molecular weight cutoff of 5000-7000Da, and collecting to obtain a cutoff liquid A and a permeate liquid B;

s2, adding nano silver into the trapped fluid A, performing ultrasonic dispersion uniformly, performing oscillation adsorption for 12-24h at 40-60 ℃, adding organic silicon quaternary ammonium salt, performing oscillation reaction for 6-12h at 70-80 ℃, adjusting the pH of the obtained reaction liquid to 2-3 after the reaction is finished, and performing freeze drying on the obtained precipitate to obtain an alkali lignin-based additive A;

s3, mixing polyethylene glycol, epichlorohydrin, tetra-n-butylammonium chloride and sodium hydroxide according to a mass ratio of 1: (1-2): (0.01-0.02): (2-3), uniformly mixing, stirring and reacting at 40-60 ℃ for 1-3h, and after the reaction is finished, mixing the obtained reaction liquid with the permeation liquid B according to the volume ratio of (1-3): 1, uniformly mixing, stirring and reacting at 70-80 ℃ for 2-4h, cooling the obtained reaction liquid to room temperature after the reaction is finished, adjusting the pH value to be neutral, and then freeze-drying to obtain an alkali lignin-based additive B;

s4, according to parts by mass, firstly, uniformly mixing 20-30 parts of polyether polyol, 20-30 parts of polyester polyol, 4-6 parts of cyclopentane, 5-8 parts of alkali lignin-based additive A, 2-3 parts of alkali lignin-based additive B, 3-5 parts of organic silicon foam stabilizer and 0.3-0.5 part of water, then adding 65-85 parts of polymethylene polyphenyl polyisocyanate and 2-3 parts of cross-linking agent, uniformly mixing to obtain a mixture, injecting the mixture into a mold, and carrying out foaming, foam curing and curing to obtain the polyurethane foam.

Preferably, the preparation method of the alkali lignin solution comprises the following steps: adding wheat straw alkali lignin into alkaline solution with pH of 9.5-10, and stirring at 60-80 deg.C until it is sufficiently dissolved; preferably, the alkaline solution is NaOH aqueous solution and Na₂CO₃Aqueous solution, KOH aqueous solution, K₂CO₃At least one of aqueous solutions.

Preferably, in the step S2, the ratio of the nano silver, the organosilicon quaternary ammonium salt and the retention solution a is (0.3-0.5) g: (30-40) mL: 100 mL.

Preferably, in step S2, the quaternary ammonium silicone salt is quaternary ammonium silicone salt DC 5700.

Preferably, the polyether polyol has a hydroxyl value of 400-520mgKOH/g and a viscosity of 4000-7500 mPa.S at 25 ℃; the hydroxyl value of the polyester polyol is 300-350mgKOH/g, and the viscosity at 25 ℃ is 1500-3500 mPa.S; the content of isocyanic acid radical of polymethylene polyphenyl polyisocyanate is 30-40%.

Preferably, the crosslinking agent is trimethylolpropane.

Preferably, in the step S4, the mixture is injected into a mold, foamed at 50-55 ℃, cured at normal temperature for 1-2 hours, and cured at 80-90 ℃ for 2-4 hours, so as to obtain the foam.

A high-strength antibacterial core material for a color steel sandwich panel is prepared by the preparation method.

The invention has the following beneficial effects:

the method comprises the steps of firstly, carrying out fractional separation on a wheat straw alkali lignin solution according to the molecular weight by adopting an ultrafiltration membrane with the molecular weight cutoff of 5000-7000Da, and collecting a cutoff liquid A and a permeate liquid B, wherein the cutoff liquid A is a high molecular weight alkali lignin component, and the permeate liquid B is a low molecular weight alkali lignin component; on one hand, the high molecular weight alkali lignin component in the trapped fluid A is used for adsorbing the nano silver, the high molecular weight alkali lignin is used for fixing the nano silver in a net structure to form a compound due to the fact that the three-dimensional net structure is complex and the pores are large, the surface of the formed compound is modified by using the organic silicon quaternary ammonium salt, the organic silicon quaternary ammonium salt is grafted on the surface of the compound, and therefore the alkali lignin-based additive A is obtained, and the antibacterial performance of the material can be effectively improved through the synergistic effect of the lignin, the organic silicon quaternary ammonium salt and the nano silver; on the other hand, epichlorohydrin is used as a cross-linking agent, polyethylene glycol is grafted to a low-molecular-weight alkali lignin component in the permeate liquid B to obtain an alkali lignin-based additive B, and on the basis of low molecular-weight alkali lignin component and high surface activity, the surface activity of the low-molecular-weight alkali lignin component is further improved through a hydrophilic polymer in a grafting reaction, so that the low-molecular-weight alkali lignin component can be uniformly distributed on a foam interface, an excellent foam stabilizing effect is achieved, the foam quality is improved, and the strength of polyurethane foam is further improved through cross-linking of active groups. According to the invention, the alkali lignin-based additive A and the alkali lignin-based additive B are added into the raw materials of the polyurethane foam heat-insulating material according to a certain proportion, and the high-strength antibacterial core material for the color steel sandwich board is prepared by foaming, curing and curing, so that the high-strength antibacterial core material has high strength and good antibacterial performance, and can meet the use requirements of special industries such as medical treatment and pharmacy.

Detailed Description

The technical solution of the present invention will be described in detail below with reference to specific examples.

Example 1

A preparation method of a high-strength antibacterial core material for a color steel sandwich panel comprises the following steps:

s1, adding wheat straw alkali lignin into a NaOH aqueous solution with the pH value of 9.5, stirring at 60 ℃ until the wheat straw alkali lignin is fully dissolved to obtain an alkali lignin solution with the mass fraction of 20%, performing ultrafiltration on the obtained alkali lignin solution by using an ultrafiltration membrane with the molecular weight cutoff of 5000Da, and collecting to obtain a cutoff liquid A and a permeate liquid B;

s2, adding nano silver into the trapped fluid A, performing ultrasonic dispersion uniformly, performing oscillation adsorption at 40 ℃ for 24 hours, adding organosilicon quaternary ammonium salt DC5700, performing oscillation reaction at 70 ℃ for 12 hours, adjusting the pH of the obtained reaction liquid to 2 after the reaction is finished, and performing freeze drying on the obtained precipitate to obtain the alkali lignin-based additive A, wherein the ratio of the nano silver to the organosilicon quaternary ammonium salt to the trapped fluid A is 0.3 g: 30mL of: 100 mL;

s3, mixing polyethylene glycol, epichlorohydrin, tetra-n-butylammonium chloride and sodium hydroxide according to a mass ratio of 1: 1: 0.01: 2, uniformly mixing, stirring at 40 ℃ for reaction for 3 hours, and after the reaction is finished, mixing the obtained reaction liquid with a permeation liquid B according to a volume ratio of 1: 1, uniformly mixing, stirring at 70 ℃ for reaction for 4 hours, cooling the obtained reaction liquid to room temperature after the reaction is finished, adjusting the pH value to be neutral, and then freeze-drying to obtain an alkali lignin-based additive B;

s4, according to parts by mass, firstly, uniformly mixing 20 parts of polyether polyol, 20 parts of polyester polyol, 4 parts of cyclopentane, 5 parts of alkali lignin-based additive A, 2 parts of alkali lignin-based additive B, 3 parts of organic silicon foam stabilizer and 0.3 part of water, then adding 65 parts of polymethylene polyphenyl polyisocyanate and 2 parts of trimethylolpropane, uniformly mixing to obtain a mixture, injecting the mixture into a mold, foaming at 50 ℃, then curing for 1 hour at normal temperature, and curing for 4 hours at 80 ℃ to obtain the polyurethane foam.

The polyether polyol has the model number of Puranol RF 4190, the hydroxyl value of 475-; the polyester polyol is PS-3152 in Qingdao Ruinou chemical industry, the hydroxyl value is 330mgKOH/g, and the viscosity is 1700-2700 mPa.S at 25 ℃; the polymethylene polyphenyl polyisocyanate is of the type of the Dow PAPI-135C, and the content of isocyanic acid radical is 30-32.1%.

Example 2

A preparation method of a high-strength antibacterial core material for a color steel sandwich panel comprises the following steps:

s1, adding wheat straw alkali lignin into a NaOH aqueous solution with the pH value of 10, stirring at 75 ℃ until the wheat straw alkali lignin is fully dissolved to obtain an alkali lignin solution with the mass fraction of 25%, performing ultrafiltration on the obtained alkali lignin solution by using an ultrafiltration membrane with the molecular weight cutoff of 6000Da, and collecting to obtain a trapped fluid A and a permeate B;

s2, adding nano silver into the trapped fluid A, performing ultrasonic dispersion uniformly, performing oscillation adsorption for 18h at 50 ℃, adding organosilicon quaternary ammonium salt DC5700, performing oscillation reaction for 10h at 75 ℃, adjusting the pH of the obtained reaction liquid to 2.5 after the reaction is finished, and performing freeze drying on the obtained precipitate to obtain the alkali lignin-based additive A, wherein the ratio of the nano silver to the organosilicon quaternary ammonium salt to the trapped fluid A is 0.35 g: 35mL of: 100 mL;

s3, mixing polyethylene glycol, epichlorohydrin, tetra-n-butylammonium chloride and sodium hydroxide according to a mass ratio of 1: 1.5: 0.015: 2.5, uniformly mixing, stirring at 45 ℃ for reaction for 2h, and after the reaction is finished, mixing the obtained reaction liquid with the permeation liquid B according to the volume ratio of 2: 1, uniformly mixing, stirring at 75 ℃ for reaction for 3 hours, cooling the obtained reaction liquid to room temperature after the reaction is finished, adjusting the pH value to be neutral, and then freeze-drying to obtain an alkali lignin-based additive B;

s4, according to parts by mass, firstly, uniformly mixing 24 parts of polyether polyol, 28 parts of polyester polyol, 5 parts of cyclopentane, 6 parts of alkali lignin-based additive A, 2.5 parts of alkali lignin-based additive B, 4 parts of organic silicon foam stabilizer and 0.4 part of water, then adding 80 parts of polymethylene polyphenyl polyisocyanate and 2.5 parts of trimethylolpropane, uniformly mixing to obtain a mixture, injecting the mixture into a mold, foaming at 53 ℃, curing for 1.5h at normal temperature, and curing for 3h at 85 ℃ to obtain the polyurethane foam.

The polyether polyol has the model number of Puranol RF 4190, the hydroxyl value of 475-; the polyester polyol is PS-3152 in Qingdao Ruinou chemical industry, the hydroxyl value is 330mgKOH/g, and the viscosity is 1700-2700 mPa.S at 25 ℃; the polymethylene polyphenyl polyisocyanate is of the type of the Dow PAPI-135C, and the content of isocyanic acid radical is 30-32.1%.

Example 3

A preparation method of a high-strength antibacterial core material for a color steel sandwich panel comprises the following steps:

s1, adding wheat straw alkali lignin into a NaOH aqueous solution with the pH value of 10, stirring at 80 ℃ until the wheat straw alkali lignin is fully dissolved to obtain an alkali lignin solution with the mass fraction of 30%, performing ultrafiltration on the obtained alkali lignin solution by using an ultrafiltration membrane with the molecular weight cutoff of 7000Da, and collecting to obtain a trapped fluid A and a permeate B;

s2, adding nano silver into the trapped fluid A, performing ultrasonic dispersion uniformly, performing oscillation adsorption for 12 hours at 60 ℃, adding organosilicon quaternary ammonium salt DC5700, performing oscillation reaction for 6 hours at 80 ℃, adjusting the pH of the obtained reaction liquid to 3 after the reaction is finished, and performing freeze drying on the obtained precipitate to obtain the alkali lignin-based additive A, wherein the ratio of the nano silver, the organosilicon quaternary ammonium salt and the trapped fluid A is 0.5 g: 40mL of: 100 mL;

s3, mixing polyethylene glycol, epichlorohydrin, tetra-n-butylammonium chloride and sodium hydroxide according to a mass ratio of 1: 2: 0.02: 3, uniformly mixing, stirring at 60 ℃ for reaction for 1h, and after the reaction is finished, mixing the obtained reaction solution with the permeation solution B according to a volume ratio of 3: 1, uniformly mixing, stirring at 80 ℃ for reaction for 2 hours, cooling the obtained reaction liquid to room temperature after the reaction is finished, adjusting the pH value to be neutral, and then freeze-drying to obtain an alkali lignin-based additive B;

s4, according to parts by mass, firstly, uniformly mixing 30 parts of polyether polyol, 30 parts of polyester polyol, 6 parts of cyclopentane, 8 parts of alkali lignin-based additive A, 3 parts of alkali lignin-based additive B, 5 parts of organic silicon foam stabilizer and 0.5 part of water, then adding 85 parts of polymethylene polyphenyl polyisocyanate and 3 parts of trimethylolpropane, uniformly mixing to obtain a mixture, injecting the mixture into a mold, foaming at 55 ℃, then curing for 2 hours at normal temperature, and curing for 2 hours at 90 ℃ to obtain the polyurethane foam.

The polyether polyol has the model number of Puranol RF 4190, the hydroxyl value of 475-; the polyester polyol is PS-3152 in Qingdao Ruinou chemical industry, the hydroxyl value is 330mgKOH/g, and the viscosity is 1700-2700 mPa.S at 25 ℃; the polymethylene polyphenyl polyisocyanate is of the type of the Dow PAPI-135C, and the content of isocyanic acid radical is 30-32.1%.

Comparative example 1

According to the mass parts, 24 parts of polyether polyol, 28 parts of polyester polyol, 5 parts of cyclopentane, 4 parts of an organic silicon foam stabilizer and 0.4 part of water are uniformly mixed, then 80 parts of polymethylene polyphenyl polyisocyanate and 2.5 parts of trimethylolpropane are added and uniformly mixed to obtain a mixture, the mixture is injected into a mold and foamed at 53 ℃, then the foam is cured for 1.5 hours at normal temperature, and then the mixture is cured for 3 hours at 85 ℃ to obtain the polyurethane foam stabilizer.

The polyether polyol has the model number of Puranol RF 4190, the hydroxyl value of 475-; the polyester polyol is PS-3152 in Qingdao Ruinou chemical industry, the hydroxyl value is 330mgKOH/g, and the viscosity is 1700-2700 mPa.S at 25 ℃; the polymethylene polyphenyl polyisocyanate is of the type of the Dow PAPI-135C, and the content of isocyanic acid radical is 30-32.1%.

The core materials prepared in examples 1-3 and comparative example 1 are subjected to performance tests, wherein the compressive strength is referred to GB/T8813, the thermal conductivity is referred to GB/T3399, and the density is referred to GB/T6343; antibacterial performance was referred to QB/T2591. The test results are shown in tables 1 and 2.

TABLE 1 physical Properties of core Material

	Example 1	Example 2	Example 3	Comparative example 1
					Compressive Strength (kPa)	158	174	163	137
Coefficient of thermal conductivity (W/mK)	0.0237	0.0241	0.0248	0.0259
					Density (g/cm)3)	39.4	39.7	40.3	41.0

TABLE 2 antibacterial Properties of core materials

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.