CN110066479B - Preparation method of corrosion-resistant high-strength non-slip mat - Google Patents
Preparation method of corrosion-resistant high-strength non-slip mat Download PDFInfo
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Abstract
The invention relates to a preparation method of a corrosion-resistant high-strength non-slip mat, and belongs to the technical field of plastic materials. The invention uses 4-methyl benzoic acid and thionyl chloride to prepare methoxybenzoyl chloride based benzene bis-adipoyl chloride, then uses methoxybenzoyl chloride based benzene bis-adipoyl chloride and thionyl chloride to react with chitosan, uses hydroxylation reaction to graft on chitosan molecules, leads the chitosan to modify and introduce amide and sulfone compounds into the molecules, uses phenyl and other organic groups to strengthen the cross-linking density and the spatial structure among the molecules, effectively improves the mechanical property of the anti-skid pad, mixes rice hulls and the modified chitosan, uses high temperature and high pressure and cellulose enzyme hydrolysis to decompose the rice hulls to obtain cellulose, peels off plant fibers, meanwhile, the surfaces of the cellulose and the plant fiber have hydroxyl, carboxyl and other epoxy groups at high temperature and high pressure, so that the dispersion effect of chitosan molecules in the non-slip mat is improved, and the non-slip mat has a wide application prospect.
Description
Technical Field
The invention relates to a preparation method of a corrosion-resistant high-strength non-slip mat, and belongs to the technical field of plastic materials.
Background
The non-slip mat divide into the multiple, mainly has car non-slip mat, bathroom non-slip mat, hotel's non-slip mat, callus on the sole, the doormat, the stair non-slip mat, yoga non-slip mat, carpet non-slip mat, toolbox non-slip mat etc.. The non-slip mat can be divided into: rubber non-slip mat, PVC non-slip mat, PU non-slip mat, AB glue non-slip mat, silica gel non-slip mat, magic glue non-slip mat and so on.
The non-slip mat can be divided into different categories according to different classification standards, such as: according to the function division: the non-slip mat mainly comprises a mobile phone non-slip mat, an automobile non-slip mat, a bathroom non-slip mat, a stair non-slip mat, a yoga non-slip mat, a carpet non-slip mat, a tool box non-slip mat, a cup non-slip mat and the like; the material is divided into: the non-slip mat can be divided into: rubber slipmat, PVC slipmat, PU slipmat, AB glue slipmat, silica gel slipmat, magic glue slipmat, etc. The anti-slip mat for the mobile phone, the anti-slip mat for the automobile and the magic glue are new product terms in recent years, and although the names of the anti-slip mat are different, the anti-slip mat for the mobile phone, the automobile and the cigarette case are all pads used for preventing the mobile phone, the perfume, the coin, the cigarette case and the like from sliding. The anti-skid rubber is usually made of PVC soft rubber, AB rubber, PU, common silica gel and high polymer materials, and the bottom of the anti-skid rubber is flat, so that the anti-skid rubber can play a role in skid resistance due to high polymer adsorption capacity.
With the increasing improvement of living standard of people, people continuously pursue high-grade on floor decoration materials such as toilets, kitchens, balconies and the like, and a great amount of glass tiles and floor tiles which are as bright as mirrors are selected to achieve the purposes of fashion and high grade. However, once the floor materials are wet or seeped, slip and other accidents are easy to happen during activities, especially under the action of soap foam, shampoo and the like, the slip and other accidents happen easily on the floor of a shower room and the floor of a bath pool. In order to meet the requirements of skid resistance, sanitation and comfort in the bathing and bathing processes, various skid-resistant base plates, particularly bathing base plates, are produced at the same time, products such as synthetic rubber base plates, PVC foamed base plates, EVA foamed base plates and the like are produced in succession, and the use of the products plays a certain role in preventing slipping. For the current slipmat, ubiquitous tear strength is low, perishable scheduling problem, and life is low, can't satisfy long-term operation requirement.
Researchers are constantly improving the performance of non-slip mats and the production method of non-slip mats. At present, polyester fiber warp-knitted cloth is mostly used as base cloth, PVC is soaked on the base cloth for molding, and the non-slip mat with the thickness of 1.5-10 mm is manufactured. The invention discloses a method for producing PVC (polyvinyl chloride resin) foaming non-slip mat, which takes fiber mesh as base cloth, PVC as main material, plasticizer, calcium carbonate and synthetic glue as auxiliary materials, wherein the plasticizer is vegetable oil or DINCH, the formula of the plasticizer is vegetable oil or DINCH 20-50%, PVC 25-45%, calcium carbonate 15-25%, fiber mesh 5-10%, synthetic glue 1-5%, other auxiliary agents and natural perfume 1-5% according to weight ratio, and the PVC foaming non-slip mat is produced according to the following process: mixing vegetable oil/PVC- > stirring- > measuring viscosity- > adjusting viscosity- > stirring and scraping or extruding gluing- > net hanging- > heating and foaming- > molding and rolling. The PVC anti-skid pad is prepared by taking polyester fiber warp-knitted cloth (the cloth surface of which is divided into screen cloth and plain cloth) as base cloth, wherein the screen cloth anti-skid pad has a mesh hole shape, and the plain cloth has a diameter knitting pattern shape. The flat cloth can be used for producing similar products with similar thickness and similar gram weight, but the radial-knitted flat cloth has only soft and hard hand feeling no matter how to be adjusted, and cannot have stiff and smooth characteristics.
Therefore, the invention provides the non-slip mat with good corrosion resistance and high tearing strength, which has positive significance in the technical field of plastic materials.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the defects that the prior non-slip mat is easy to corrode and has poor mechanical strength and is easy to tear, the preparation method of the corrosion-resistant high-strength non-slip mat is provided.
In order to solve the technical problems, the invention adopts the technical scheme that:
the preparation method of the corrosion-resistant high-strength non-slip mat comprises the following steps:
putting the enzymolysis product, polyvinyl chloride resin and styrene-butadiene resin into a blender, mixing and stirring for 50-70 min under the conditions that the temperature is 125-135 ℃ and the mixing rotating speed is 160-180 r/min to obtain a prefabricated product, weighing the prefabricated product, zinc stearate, azodicarbonamide, zinc oxide and barium carbonate, putting the prefabricated product, zinc stearate, azodicarbonamide, zinc oxide and barium carbonate into a reaction kettle, raising the temperature in the kettle to 140-150 ℃, mixing and stirring for 25-35 min under the condition that the rotating speed is 300-320 r/min, discharging and cooling to obtain the corrosion-resistant high-strength non-slip mat;
the preparation method of the enzymolysis product comprises the following steps:
(1) putting the modified reaction liquid and acetone with the temperature of-15 to-10 ℃ into a beaker, uniformly mixing, performing suction filtration to obtain filter residue, washing the filter residue 3-5 times by using ammonia water with the mass fraction of 5-7% to obtain a reaction product, weighing the reaction product, rice hulls and an acetic acid solution with the mass fraction of 16-18%, and putting the reaction product, the rice hulls and the acetic acid solution into a reaction kettle;
(2) filling nitrogen into a reaction kettle until the pressure in the kettle is increased to 2.0-2.2 MPa, increasing the temperature in the kettle to 230-240 ℃, carrying out constant-temperature and constant-pressure reaction for 50-60 min, dropwise adding a sodium carbonate solution with the mass fraction of 15-17% after the reaction to adjust the pH value to be neutral to obtain a hydrolysate, adding cellulase into the reaction kettle, increasing the temperature in the kettle to 30-34 ℃, stirring for 45-55 min at the rotating speed of 600-620 r/min by using a stirrer to obtain an enzymolysis product, placing the enzymolysis product into a vacuum drying box, and concentrating and drying for 3-4 h under the conditions of the vacuum degree of 90-110 Pa and the temperature of 60-70 ℃;
the preparation method of the modified reaction solution comprises the following steps:
(1) weighing 4-methylbenzoic acid, adding thionyl chloride and N, N-dimethylformamide into a three-neck flask, placing the three-neck flask into a water bath kettle with a water bath temperature of 60-64 ℃, and mixing and stirring for 4-6 hours by using a stirrer at a rotating speed of 400-440 r/min to obtain a reaction solution;
(2) putting the reaction liquid and thionyl chloride into a four-neck flask with a condensation reflux pipe, placing the beaker into a water bath kettle with a water bath temperature of 90-100 ℃, placing magnetic rotating beads into the four-neck flask, performing condensation reflux for 5-6 hours under the condition that the magnetic rotating speed is 500-520 r/min to prepare a reaction product, placing the reaction product into a vacuum drying oven, and drying under the conditions that the vacuum degree is 80-120 Pa and the temperature is 65-67 ℃ to prepare a dried product;
(3) putting chitosan and 13-15% by mass of a methane sulfonic acid solution into a beaker, mixing and stirring for 120-140 min at the rotating speed of 600-620 r/min by using a stirrer to prepare a mixed solution, uniformly mixing a dried product and chloroform to prepare a mixed emulsion, putting the mixed solution into a conical flask, putting the conical flask into an ice water bath, dropwise adding the mixed emulsion with the mass of 20-24% of the mixed solution into the conical flask at the dropwise adding speed of 20-24 mL/min, and mixing and stirring for 3-5 h at the rotating speed of 600-620 r/min by using the stirrer after the dropwise adding is finished to prepare a modified reaction solution.
The enzymatic hydrolysis product comprises, by weight, 8-10 parts of an enzymatic hydrolysis product, 13-15 parts of polyvinyl chloride resin and 5-7 parts of styrene-butadiene resin.
The weight portion of the prefabricated product is 7-9 portions, the weight portion of zinc stearate is 0.4-0.6 portion, the weight portion of azodicarbonamide is 0.3-0.5 portion, the weight portion of zinc oxide is 0.3-0.5 portion, and the weight portion of barium carbonate is 0.8-1.0 portion.
In the preparation method of the enzymolysis product, the mass ratio of the modified reaction solution to acetone with the temperature of-15 to-10 ℃ is 1: 10.
according to the preparation method of the enzymolysis product, the reaction product is 7-9 parts by weight, the rice husk is 3.8-4.0 parts by weight, and the acetic acid solution with the mass fraction of 16-18% is 10-12 parts by weight.
In the preparation method of the enzymolysis product, the mass of cellulase added into the reaction kettle is 3-5% of that of the hydrolysis product.
The preparation method of the modified reaction solution comprises the following steps of 13-15 parts by weight of 4-methylbenzoic acid, 23-25 parts by weight of thionyl chloride and 0.3-0.5 part by weight of N, N-dimethylformamide.
In the preparation method of the modified reaction solution, the mass ratio of the reaction solution to thionyl chloride is 3: 5.
in the preparation method of the modified reaction solution, the mass ratio of chitosan to a methane sulfonic acid solution with the mass fraction of 13-15% is 1: 20, the mass ratio of the dried product to chloroform is 1: 15.
the beneficial technical effects of the invention are as follows:
(1) the invention firstly mixes and reacts 4-methyl benzoic acid, thionyl chloride and N, N-dimethyl formamide, thionyl chloride is added after reaction for condensation reflux stirring, the mixture is dried in vacuum after stirring to prepare a dried product, then chitosan is dissolved in methane sulfonic acid solution, the dried product is dissolved in chloroform, the mixture is mixed and stirred to prepare modified reaction liquid, the modified reaction liquid is mixed with frozen acetone, filtration is carried out after mixing to obtain filter residue, then the filter residue is mixed with rice husk, the mixture is put into a reaction kettle for high-temperature and high-pressure reaction after mixing, then enzymatic hydrolysis is prepared by adding cellulase, finally the enzymatic hydrolysis product is mixed with resin at high temperature, zinc stearate, zinc oxide and other auxiliary agents are added after mixing, the mixture is discharged at high temperature to obtain the corrosion-resistant high-strength anti-skid pad, the invention utilizes 4-methyl benzoic acid and thionyl chloride to prepare methoxybenzoyl chloride-benzene-adipyl chloride, reacting methoxybenzoyl chloride-phenyl-adipyl chloride and thionyl chloride with chitosan, grafting the chitosan molecules on the chitosan molecules by hydroxylation reaction to modify the chitosan, introducing amide and sulfone compounds into molecular chains of the chitosan, and reinforcing the cross-linking density and the spatial structure among the molecules by using phenyl and other organic groups added later, so that the mechanical property of the non-slip mat is effectively improved, and meanwhile, the chitosan molecules are coated, so that the amide and polysulfone coat the molecules in the non-slip mat, and the non-slip mat is difficult to corrode by using the stable chemical property of the non-slip mat;
(2) the rice hulls and the modified chitosan are mixed, the rice hulls are decomposed by high temperature and high pressure and cellulase enzymolysis to obtain cellulose, plant fibers in the cellulose are separated, the cellulose and the plant fibers are modified at the high temperature and high pressure, hydroxyl groups, carboxyl groups and other epoxy groups are generated on the surfaces of the cellulose and the plant fibers, adsorption of modified chitosan molecules is enhanced, the cross-linking density among the molecules is further enhanced, the chitosan is coated by the cellulose and the plant fibers, the distance among the chitosan molecules is increased, the dispersion effect of the chitosan molecules in the anti-slip pad is improved, and the anti-slip pad has a wide application prospect.
Detailed Description
Weighing 13-15 parts of 4-methylbenzoic acid, 23-25 parts of thionyl chloride and 0.3-0.5 part of N, N-dimethylformamide in parts by weight, putting the three-neck flask into a three-neck flask, putting the three-neck flask into a water bath kettle with a water bath temperature of 60-64 ℃, and mixing and stirring the three-neck flask for 4-6 hours by using a stirrer at a rotating speed of 400-440 r/min to prepare a reaction solution; mixing the reaction solution and thionyl chloride according to the mass ratio of 3: 5, putting the flask into a four-neck flask with a condensation reflux pipe, placing the flask into a water bath kettle with a water bath temperature of 90-100 ℃, placing magnetic rotating beads into the four-neck flask, performing condensation reflux for 5-6 hours under the condition that the magnetic rotating speed is 500-520 r/min to prepare a reaction product, placing the reaction product into a vacuum drying oven, and drying under the conditions that the vacuum degree is 80-120 Pa and the temperature is 65-67 ℃ to prepare a dried product; mixing chitosan and a methane sulfonic acid solution with the mass fraction of 13-15% according to the mass ratio of 1: 20, putting the mixture into a beaker, mixing and stirring the mixture for 120-140 min at the rotating speed of 600-620 r/min by using a stirrer to prepare a mixed solution, and mixing the dried product and chloroform according to the mass ratio of 1: 15, uniformly mixing to obtain a mixed emulsion, placing the mixed solution into a conical flask, placing the conical flask into an ice-water bath, dropwise adding the mixed emulsion with the mass of 20-24% of the mixed solution into the conical flask at the dropwise adding speed of 20-24 mL/min, and after dropwise adding, mixing and stirring for 3-5 hours by using a stirrer at the rotating speed of 600-620 r/min to obtain a modified reaction solution; mixing the modified reaction solution with acetone at the temperature of-15 to-10 ℃ in a mass ratio of 1: 10, putting the mixture into a beaker, uniformly mixing, performing suction filtration to obtain filter residue, washing the filter residue for 3-5 times by using ammonia water with the mass fraction of 5-7% to obtain a reaction product, and putting 7-9 parts of the reaction product, 3.8-4.0 parts of rice husk and 10-12 parts of acetic acid solution with the mass fraction of 16-18% into a reaction kettle; filling nitrogen into the reaction kettle until the pressure in the kettle is increased to 2.0-2.2 MPa, increasing the temperature in the kettle to 230-240 ℃, reacting at constant temperature and constant pressure for 50-60 min, dropwise adding 15-17% by mass of sodium carbonate solution after reaction to adjust the pH value to be neutral to obtain a hydrolysate, adding cellulase accounting for 3-5% by mass of the hydrolysate into the reaction kettle, increasing the temperature in the kettle to 30-34 ℃, stirring with a stirrer at the rotating speed of 600-620 r/min for 45-55 min to obtain an enzymolysis product, placing the enzymolysis product into a vacuum drying oven, and concentrating and drying for 3-4 h under the conditions of the vacuum degree of 90-110 Pa and the temperature of 60-70 ℃; putting 8-10 parts by weight of the enzymolysis product, 13-15 parts by weight of polyvinyl chloride resin and 5-7 parts by weight of styrene-butadiene resin into a blender, mixing and stirring for 50-70 min under the conditions that the temperature is 125-135 ℃ and the mixing rotating speed is 160-180 r/min to obtain a prefabricated product, weighing 7-9 parts by weight of the prefabricated product, 0.4-0.6 part by weight of zinc stearate, 0.3-0.5 part by weight of azodicarbonamide, 0.3-0.5 part by weight of zinc oxide and 0.8-1.0 part by weight of barium carbonate into a reaction kettle, raising the temperature in the kettle to 140-150 ℃, mixing and stirring for 25-35 min under the condition that the rotating speed is 300-320 r/min, discharging and cooling to obtain the corrosion-resistant high-strength non-slip mat.
Preparation of modified reaction solution: weighing 13 parts of 4-methylbenzoic acid, 23 parts of thionyl chloride and 0.3 part of N, N-dimethylformamide according to parts by weight, putting the three-neck flask into a three-neck flask, placing the three-neck flask into a water bath kettle with a water bath temperature of 60 ℃, and mixing and stirring the three-neck flask for 4 hours by using a stirrer at a rotating speed of 400r/min to prepare a reaction solution;
mixing the reaction solution and thionyl chloride according to the mass ratio of 3: 5, putting the flask into a four-neck flask with a condensation reflux pipe, putting the flask into a water bath kettle with a water bath temperature of 90 ℃, putting magnetic rotating beads into the four-neck flask, performing condensation reflux for 5 hours under the condition that the magnetic rotating speed is 500r/min to prepare a reaction product, putting the reaction product into a vacuum drying box, and drying under the conditions that the vacuum degree is 80Pa and the temperature is 65 ℃ to prepare a dried product;
mixing chitosan and a methane sulfonic acid solution with the mass fraction of 13% according to the mass ratio of 1: 20, putting the mixture into a beaker, mixing and stirring the mixture for 120min at the rotating speed of 600r/min by using a stirrer to prepare a mixed solution, and mixing the dried product and chloroform according to the mass ratio of 1: 15, uniformly mixing to obtain mixed emulsion, placing the mixed solution into a conical flask, placing the conical flask into an ice-water bath, dropwise adding the mixed emulsion with the mass of 20% of the mixed solution into the conical flask at the dropwise adding speed of 20mL/min, and mixing and stirring for 3 hours at the rotating speed of 600r/min by using a stirrer after the dropwise adding is finished to obtain modified reaction liquid;
preparation of an enzymolysis product:
mixing the modified reaction solution with acetone at the temperature of-15 ℃ according to the mass ratio of 1: 10, putting the mixture into a beaker, uniformly mixing, performing suction filtration to obtain filter residue, washing the filter residue for 3 times by using ammonia water with the mass fraction of 5% to obtain a reaction product, and weighing 7 parts of the reaction product, 3.8 parts of rice hull and 10 parts of acetic acid solution with the mass fraction of 16% into a reaction kettle according to the parts by weight;
introducing nitrogen into the reaction kettle until the pressure in the reaction kettle is increased to 2.0MPa, increasing the temperature in the reaction kettle to 230 ℃, carrying out constant-temperature and constant-pressure reaction for 50min, dropwise adding a sodium carbonate solution with the mass fraction of 15% after the reaction to adjust the pH value to be neutral to obtain a hydrolysate, adding cellulase with the mass fraction of 3% of the hydrolysate into the reaction kettle, increasing the temperature in the reaction kettle to 30 ℃, stirring the mixture for 45min at the rotating speed of 600r/min by using a stirrer to obtain an enzymolysis product, placing the enzymolysis product into a vacuum drying box, and concentrating and drying the enzymolysis product for 3h under the conditions of the vacuum degree of 90Pa and the temperature of 60 ℃;
preparing the corrosion-resistant high-strength non-slip mat:
putting 8 parts of the enzymolysis product, 13 parts of polyvinyl chloride resin and 5 parts of styrene-butadiene resin into a blender, mixing and stirring for 50min at the temperature of 125 ℃ and the mixing speed of 160r/min to obtain a prefabricated product, weighing 7 parts of the prefabricated product, 0.4 part of zinc stearate, 0.3 part of azodicarbonamide, 0.3 part of zinc oxide and 0.8 part of barium carbonate into a reaction kettle, raising the temperature in the kettle to 140 ℃, mixing and stirring for 25min at the speed of 300r/min, discharging and cooling to obtain the corrosion-resistant high-strength non-slip mat.
Preparation of modified reaction solution: weighing 14 parts of 4-methylbenzoic acid, 24 parts of thionyl chloride and 0.4 part of N, N-dimethylformamide in parts by weight, putting the three-neck flask into a water bath kettle with a water bath temperature of 62 ℃, and mixing and stirring the three-neck flask for 5 hours by using a stirrer at a rotating speed of 420r/min to prepare a reaction solution;
mixing the reaction solution and thionyl chloride according to the mass ratio of 3: 5, putting the flask into a four-neck flask with a condensation reflux pipe, putting the flask into a water bath kettle with a water bath temperature of 95 ℃, putting magnetic rotating beads into the four-neck flask, performing condensation reflux for 5.5 hours under the condition that the magnetic rotating speed is 510r/min to prepare a reaction product, putting the reaction product into a vacuum drying oven, and drying under the conditions that the vacuum degree is 100Pa and the temperature is 66 ℃ to prepare a dried product;
mixing chitosan and a methane sulfonic acid solution with the mass fraction of 14% according to the mass ratio of 1: 20, putting the mixture into a beaker, mixing and stirring the mixture for 130min at the rotating speed of 610r/min by using a stirrer to prepare a mixed solution, and mixing the dried product and chloroform according to the mass ratio of 1: 15, uniformly mixing to obtain mixed emulsion, placing the mixed solution into a conical flask, placing the conical flask into an ice-water bath, dropwise adding the mixed emulsion with the mass of 22% of the mixed solution into the conical flask at the dropwise adding speed of 22mL/min, and mixing and stirring for 4 hours at the rotating speed of 610r/min by using a stirrer after the dropwise adding is finished to obtain modified reaction liquid;
preparation of an enzymolysis product:
mixing the modified reaction solution with acetone at the temperature of-12 ℃ in a mass ratio of 1: 10, putting the mixture into a beaker, uniformly mixing, performing suction filtration to obtain filter residue, washing the filter residue for 4 times by using ammonia water with the mass fraction of 6% to obtain a reaction product, and putting 8 parts of the reaction product, 3.9 parts of rice hull and 11 parts of acetic acid solution with the mass fraction of 17% into a reaction kettle in parts by weight;
introducing nitrogen into the reaction kettle until the pressure in the reaction kettle is increased to 2.1MPa, increasing the temperature in the reaction kettle to 235 ℃, carrying out constant-temperature and constant-pressure reaction for 55min, dropwise adding a 16 mass percent sodium carbonate solution after the reaction to adjust the pH value to be neutral to obtain a hydrolysate, adding cellulase with the mass of 4 percent of the hydrolysate into the reaction kettle, increasing the temperature in the reaction kettle to 32 ℃, stirring the mixture for 50min at the rotating speed of 610r/min by using a stirrer to obtain an enzymolysis product, placing the enzymolysis product into a vacuum drying box, and concentrating and drying the enzymolysis product for 3.5h under the conditions of the vacuum degree of 100Pa and the temperature of 65 ℃;
preparing the corrosion-resistant high-strength non-slip mat:
putting 9 parts of the enzymolysis product, 14 parts of polyvinyl chloride resin and 6 parts of styrene-butadiene resin into a blender, mixing and stirring for 62min at the temperature of 130 ℃ and the mixing speed of 170r/min to obtain a prefabricated product, weighing 8 parts of the prefabricated product, 0.5 part of zinc stearate, 0.4 part of azodicarbonamide, 0.4 part of zinc oxide and 0.9 part of barium carbonate into a reaction kettle, raising the temperature in the kettle to 145 ℃, mixing and stirring for 30min at the speed of 310r/min, discharging and cooling to obtain the corrosion-resistant high-strength non-slip mat.
Preparation of modified reaction solution: weighing 15 parts of 4-methylbenzoic acid, 25 parts of thionyl chloride and 0.5 part of N, N-dimethylformamide in parts by weight, putting the three-neck flask into a water bath kettle with a water bath temperature of 64 ℃, and mixing and stirring the mixture for 6 hours by using a stirrer at a rotating speed of 440r/min to prepare a reaction solution;
mixing the reaction solution and thionyl chloride according to the mass ratio of 3: 5, putting the flask into a four-neck flask with a condensation reflux pipe, putting the flask into a water bath kettle with a water bath temperature of 100 ℃, putting magnetic rotating beads into the four-neck flask, performing condensation reflux for 6 hours under the condition that the magnetic rotating speed is 520r/min to prepare a reaction product, putting the reaction product into a vacuum drying box, and drying under the conditions that the vacuum degree is 120Pa and the temperature is 67 ℃ to prepare a dried product;
mixing chitosan and a methane sulfonic acid solution with the mass fraction of 15% according to the mass ratio of 1: 20, putting the mixture into a beaker, mixing and stirring the mixture for 140min at the rotating speed of 620r/min by using a stirrer to prepare a mixed solution, and mixing the dried product and chloroform according to the mass ratio of 1: 15, uniformly mixing to obtain mixed emulsion, placing the mixed solution into a conical flask, placing the conical flask into an ice-water bath, dropwise adding the mixed emulsion with the mass of 24% of the mixed solution into the conical flask at the dropwise adding speed of 24mL/min, and mixing and stirring for 5 hours at the rotating speed of 620r/min by using a stirrer after the dropwise adding is finished to obtain modified reaction liquid;
preparation of an enzymolysis product:
mixing the modified reaction solution with acetone at the temperature of-10 ℃ in a mass ratio of 1: 10, putting the mixture into a beaker, uniformly mixing, performing suction filtration to obtain filter residue, washing the filter residue for 5 times by using 7% ammonia water by mass fraction to obtain a reaction product, and putting 9 parts of the reaction product, 4.0 parts of rice hull and 12 parts of 18% acetic acid solution by mass fraction into a reaction kettle according to parts by weight;
introducing nitrogen into the reaction kettle until the pressure in the reaction kettle is increased to 2.2MPa, increasing the temperature in the reaction kettle to 240 ℃, carrying out constant-temperature and constant-pressure reaction for 60min, dropwise adding a sodium carbonate solution with the mass fraction of 17% after the reaction to adjust the pH value to be neutral to obtain a hydrolysate, adding cellulase with the mass fraction of 5% into the reaction kettle, increasing the temperature in the reaction kettle to 34 ℃, stirring the cellulase with a stirrer at the rotating speed of 620r/min for 55min to obtain an enzymolysis product, placing the enzymolysis product into a vacuum drying box, and concentrating and drying for 4h under the conditions of the vacuum degree of 110Pa and the temperature of 70 ℃;
preparing the corrosion-resistant high-strength non-slip mat:
putting 10 parts of the enzymolysis product, 15 parts of polyvinyl chloride resin and 7 parts of styrene-butadiene resin into a blender, mixing and stirring for 70min at the temperature of 135 ℃ and the mixing speed of 180r/min to obtain a prefabricated product, weighing 9 parts of the prefabricated product, 0.6 part of zinc stearate, 0.5 part of azodicarbonamide, 0.5 part of zinc oxide and 1.0 part of barium carbonate into a reaction kettle, raising the temperature in the kettle to 150 ℃, mixing and stirring for 35min at the speed of 320r/min, discharging and cooling to obtain the corrosion-resistant high-strength non-slip mat.
Comparative example 1: the preparation was substantially the same as in example 2 except that the modification reaction solution was absent.
Comparative example 2: essentially the same procedure as in example 2 was followed except that the enzymatic product was absent.
Comparative example 3: shenzhen a corrosion-resistant high-strength non-slip mat.
The breaking strength and the tearing strength are tested according to the HG/T3086-2011 standard.
And (3) acid corrosion resistance testing: the non-slip mats of examples 1 to 3 and comparative example were placed in a 20% hydrochloric acid solution for 48 hours to observe surface changes.
And (3) testing alkali corrosion resistance: the non-slip mats of examples 1 to 3 and comparative example were placed in a 1mol/L sodium hydroxide solution for 48 hours, and the surface change was observed.
TABLE 1 measurement results of slipmat properties
| Test items | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Breaking Strength (N/5 cm) | 2345 | 2348 | 2350 | 1890 | 1935 | 2024 |
| Tear Strength (kN/m) | 51.8 | 52.3 | 52.7 | 33.8 | 35.6 | 38.9 |
| Acid corrosion resistance | Surface non-cracking | Surface non-cracking | Surface non-cracking | Surface cracking | Surface cracking | Surface cracking |
| Alkali corrosion resistance | Surface non-cracking | Surface non-cracking | Surface non-cracking | Surface cracking | Surface cracking | Surface cracking |
According to the detection data, the corrosion-resistant high-strength non-slip mat prepared by the invention has the advantages of high mechanical strength, high tearing strength, difficulty in tearing, no crack on the surface after being soaked in acidic and alkaline solutions, good corrosion resistance and wide application prospect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, but rather as the subject matter of the invention is to be construed in all aspects and as broadly as possible, and all changes, equivalents and modifications that fall within the true spirit and scope of the invention are therefore intended to be embraced therein.
Claims (9)
1. A preparation method of a corrosion-resistant high-strength non-slip mat is characterized by comprising the following specific preparation steps:
putting the enzymolysis product, polyvinyl chloride resin and styrene-butadiene resin into a blender, mixing and stirring for 50-70 min under the conditions that the temperature is 125-135 ℃ and the mixing rotating speed is 160-180 r/min to obtain a prefabricated product, weighing the prefabricated product, zinc stearate, azodicarbonamide, zinc oxide and barium carbonate, putting the prefabricated product, zinc stearate, azodicarbonamide, zinc oxide and barium carbonate into a reaction kettle, raising the temperature in the kettle to 140-150 ℃, mixing and stirring for 25-35 min under the condition that the rotating speed is 300-320 r/min, discharging and cooling to obtain the corrosion-resistant high-strength non-slip mat;
the specific preparation steps of the enzymolysis product are as follows:
(1) putting the modified reaction liquid and acetone with the temperature of-15 to-10 ℃ into a beaker, uniformly mixing, performing suction filtration to obtain filter residue, washing the filter residue 3-5 times by using ammonia water with the mass fraction of 5-7% to obtain a reaction product, weighing the reaction product, rice hulls and an acetic acid solution with the mass fraction of 16-18%, and putting the reaction product, the rice hulls and the acetic acid solution into a reaction kettle;
(2) filling nitrogen into a reaction kettle until the pressure in the kettle is increased to 2.0-2.2 MPa, increasing the temperature in the kettle to 230-240 ℃, carrying out constant-temperature and constant-pressure reaction for 50-60 min, dropwise adding a sodium carbonate solution with the mass fraction of 15-17% after the reaction to adjust the pH value to be neutral to obtain a hydrolysate, adding cellulase into the reaction kettle, increasing the temperature in the kettle to 30-34 ℃, stirring for 45-55 min at the rotating speed of 600-620 r/min by using a stirrer to obtain an enzymolysis product, placing the enzymolysis product into a vacuum drying box, and concentrating and drying for 3-4 h under the conditions of the vacuum degree of 90-110 Pa and the temperature of 60-70 ℃;
the specific preparation steps of the modified reaction solution are as follows:
(1) weighing 4-methylbenzoic acid, thionyl chloride and N, N-dimethylformamide, putting the 4-methylbenzoic acid, thionyl chloride and N, N-dimethylformamide into a three-neck flask, putting the three-neck flask into a water bath kettle with a water bath temperature of 60-64 ℃, and mixing and stirring for 4-6 hours by using a stirrer at a rotating speed of 400-440 r/min to prepare a reaction solution;
(2) putting the reaction liquid and thionyl chloride into a four-neck flask with a condensation reflux pipe, placing the beaker into a water bath kettle with a water bath temperature of 90-100 ℃, placing magnetic rotating beads into the four-neck flask, performing condensation reflux for 5-6 hours under the condition that the magnetic rotating speed is 500-520 r/min to prepare a reaction product, placing the reaction product into a vacuum drying oven, and drying under the conditions that the vacuum degree is 80-120 Pa and the temperature is 65-67 ℃ to prepare a dried product;
(3) putting chitosan and 13-15% by mass of a methane sulfonic acid solution into a beaker, mixing and stirring for 120-140 min at the rotating speed of 600-620 r/min by using a stirrer to prepare a mixed solution, uniformly mixing a dried product and chloroform to prepare a mixed emulsion, putting the mixed solution into a conical flask, putting the conical flask into an ice water bath, dropwise adding the mixed emulsion with the mass of 20-24% of the mixed solution into the conical flask at the dropwise adding speed of 20-24 mL/min, and mixing and stirring for 3-5 h at the rotating speed of 600-620 r/min by using the stirrer after the dropwise adding is finished to prepare a modified reaction solution.
2. The preparation method of the corrosion-resistant high-strength non-slip mat according to claim 1, characterized in that: preferably, the enzymolysis product is 8-10 parts by weight, the polyvinyl chloride resin is 13-15 parts by weight, and the styrene-butadiene resin is 5-7 parts by weight.
3. The preparation method of the corrosion-resistant high-strength non-slip mat according to claim 1, characterized in that: preferably, the weight parts of the prefabricated product are 7-9 parts, 0.4-0.6 part of zinc stearate, 0.3-0.5 part of azodicarbonamide, 0.3-0.5 part of zinc oxide and 0.8-1.0 part of barium carbonate.
4. The preparation method of the corrosion-resistant high-strength non-slip mat according to claim 1, characterized in that: the mass ratio of the modified reaction solution in the specific preparation step (1) of the enzymolysis product to acetone at the temperature of-15 to-10 ℃ is 1: 10.
5. the preparation method of the corrosion-resistant high-strength non-slip mat according to claim 1, characterized in that: in the specific preparation step (1) of the enzymatic hydrolysate, the preferable weight portions of the reaction product are 7-9 parts, the rice hull is 3.8-4.0 parts, and the mass fraction of the acetic acid solution is 16-18% is 10-12 parts.
6. The preparation method of the corrosion-resistant high-strength non-slip mat according to claim 1, characterized in that: and (3) specifically preparing the enzymolysis product, wherein the mass of the cellulase added into the reaction kettle in the step (2) is 3-5% of that of the hydrolysis product.
7. The preparation method of the corrosion-resistant high-strength non-slip mat according to claim 1, characterized in that: the specific preparation step (1) of the modified reaction solution preferably comprises 13-15 parts by weight of 4-methylbenzoic acid, 23-25 parts by weight of thionyl chloride and 0.3-0.5 part by weight of N, N-dimethylformamide.
8. The preparation method of the corrosion-resistant high-strength non-slip mat according to claim 1, characterized in that: the mass ratio of the reaction solution to thionyl chloride in the specific preparation step (2) of the modified reaction solution is 3: 5.
9. the preparation method of the corrosion-resistant high-strength non-slip mat according to claim 1, characterized in that: specifically preparing the modified reaction solution, wherein the mass ratio of the chitosan to the methane sulfonic acid solution with the mass fraction of 13-15% in the step (3) is 1: 20, the mass ratio of the dried product to chloroform is 1: 15.
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| JPH10286864A (en) * | 1997-04-16 | 1998-10-27 | Misawa Homes Co Ltd | Manufacture of woody member |
| CN104804226A (en) * | 2015-04-29 | 2015-07-29 | 青岛海蓝海洋复合功能材料科技有限公司 | High-tenacity automotive plastic |
| KR101605510B1 (en) * | 2015-07-08 | 2016-03-22 | 주식회사 티지에프 | Polyvinyl-Chloride Pipe Having Improved Corrosion Resistance And Durability |
| CN106432985A (en) * | 2016-11-24 | 2017-02-22 | 安徽意力电缆有限公司 | PVC (polyvinyl chloride) cable material formulation |
| CN108976660A (en) * | 2018-06-28 | 2018-12-11 | 安徽博泰塑业科技有限公司 | A kind of corrosion-resistant pvc pipe and its processing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10286864A (en) * | 1997-04-16 | 1998-10-27 | Misawa Homes Co Ltd | Manufacture of woody member |
| CN104804226A (en) * | 2015-04-29 | 2015-07-29 | 青岛海蓝海洋复合功能材料科技有限公司 | High-tenacity automotive plastic |
| KR101605510B1 (en) * | 2015-07-08 | 2016-03-22 | 주식회사 티지에프 | Polyvinyl-Chloride Pipe Having Improved Corrosion Resistance And Durability |
| CN106432985A (en) * | 2016-11-24 | 2017-02-22 | 安徽意力电缆有限公司 | PVC (polyvinyl chloride) cable material formulation |
| CN108976660A (en) * | 2018-06-28 | 2018-12-11 | 安徽博泰塑业科技有限公司 | A kind of corrosion-resistant pvc pipe and its processing method |
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