CN113388172A - Rubber sheet capable of stopping slipping on ice and preparation method thereof - Google Patents
Rubber sheet capable of stopping slipping on ice and preparation method thereof Download PDFInfo
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
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Abstract
The invention discloses an ice top-stop sliding rubber sheet and a preparation method thereof. The preparation method comprises the following steps: firstly, plasticating rubber to a wrapping roller, adding white carbon black, a plasticizing agent, zinc oxide, stearic acid, an anti-aging agent and an anti-scorching agent, mixing, adding an accelerator and sulfur, and performing triangular wrapping to obtain a mixed material; plasticating the mixed material to a wrapping roller, adding modified glass fiber, mixing, and carrying out calendering orientation to obtain a single-layer glass fiber orientation sheet material; and finally, superposing single-layer glass fiber oriented sheets, vulcanizing, cooling and slicing along the direction vertical to the length of the glass fiber to obtain the ice top stop sliding rubber sheet. The invention utilizes multiple calendering orientations to directionally arrange the glass fibers, and then slices the glass fibers in the direction vertical to the orientation, so that the prepared anti-slip rubber sheet has excellent anti-slip performance on ice, and the preparation method has the advantages of simple operation, convenient processing, low energy consumption, environmental protection and no pollution.
Description
Technical Field
The invention relates to the technical field of sole slip prevention, in particular to an ice top slip stopping rubber sheet and a preparation method thereof.
Background
With the continuous pursuit of shoe material quality and multi-functionalization, the shoe manufacturing industry is also developing towards high performance and multi-functionalization. The non-slip property is one of the most important properties of the sole material, which directly affects the safety of the shoe when worn. The anti-skid performance of the rubber can be represented by the dynamic friction coefficient and the static friction coefficient of the sole and a wet road surface, and the larger the friction coefficient is, the better the anti-skid performance is. In winter in northern China, the weather is cold, the road surface is easy to freeze, and the ice surface is provided with a quasi-liquid layer even at a very low temperature, and the quasi-liquid layer serves as a lubricating layer, so that the friction coefficient of the interface of ice and a sole is very low. Therefore, the common rubber sole material has poor anti-skid effect on ice surface, and is easy to slip down, thereby causing trauma and fracture, and causing serious or even life danger.
The rubber sole has excellent wear resistance, waterproofness and wearing comfort, and is the sole material with the largest consumption at present. However, the anti-skid performance of the rubber sole is not satisfactory, and the improvement of the anti-skid performance of the rubber material has become one of the research contents.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an ice top-stop sliding rubber sheet and a preparation method thereof. The invention utilizes multiple calendering orientations to directionally arrange the glass fibers, and then slices the glass fibers in the direction vertical to the orientation, so that the prepared anti-slip rubber sheet has excellent anti-slip performance on ice, and the preparation method has the advantages of simple operation, convenient processing, low energy consumption, environmental protection and no pollution.
The technical scheme of the invention is as follows:
an anti-icing anti-skidding rubber sheet comprises the following raw materials in parts by weight: 45-55 parts of rubber, 15-30 parts of white carbon black, 4-5 parts of plasticizer, 2-4 parts of zinc oxide, 1-2 parts of stearic acid, 0.3-1.2 parts of anti-aging agent, 0.5-1.5 parts of accelerator, 2-5 parts of sulfur, 0.1-0.3 part of anti-scorching agent and 20-55 parts of modified glass fiber.
The rubber is one or more of nitrile rubber, styrene butadiene rubber and natural rubber; the particle size of the white carbon black is 200-1000 meshes; the plasticizer is one or more of dibutyl phthalate, dioctyl adipate and dioctyl azelate.
The anti-aging agent is one or more of RD, 4010NA and MB; the accelerator is one or more of dibenzothiazyl disulfide, tetrabenzylthiuram disulfide and zinc dibutyl dithiocarbamate; the scorch retarder is one or more of N-cyclohexylthiophthalimide, phthalic anhydride and nitrosodiphenylamine; the particle size of the zinc oxide is 0.1-10 mu m.
The preparation method of the modified glass fiber comprises the following steps: and mixing the ethanol solution with a silane coupling agent, soaking the glass fiber in the mixed solution of the ethanol and the silane coupling agent for 15-30 min, and drying to obtain the modified glass fiber.
The glass fiber is chopped glass fiber, the diameter of a monofilament is 5-30 mu m, the length of the monofilament is 0.7-5 cm, and the chopped glass fiber is purchased from China megalithic corporation.
The mass concentration of the ethanol is 95%, and the pH value is 3-5; the silane coupling agent is one or more of Si-69, KH550 and KH 570; the mass ratio of the ethanol to the silane coupling agent is 8-12: 1; the drying temperature is 80-120 ℃, and the drying time is 1-3 h.
A preparation method of an anti-icing anti-skidding rubber sheet comprises the following steps:
(1) plasticating 45-55 parts of rubber to a wrapping roller, adding 15-30 parts of white carbon black, 4-5 parts of plasticizer, 2-4 parts of zinc oxide, 1-2 parts of stearic acid, 0.3-1.2 parts of anti-aging agent and 0.1-0.3 part of anti-scorching agent, mixing, adding 0.5-1.5 parts of accelerator and 2-5 parts of sulfur, and performing triangular wrapping to obtain a mixed material;
(2) plasticating the mixed material prepared in the step (1) to a wrapping roller, adding 20-55 parts of modified glass fiber for mixing, and performing calendering orientation between two rollers to obtain a single-layer glass fiber oriented sheet material;
(3) and (3) overlapping the single-layer glass fiber oriented sheets prepared in the step (2), vulcanizing, cooling, and slicing along the direction vertical to the length of the glass fiber to obtain the ice top sliding rubber sheet.
Further, in the steps (1) and (2), the plastication is carried out in a two-roll open mill; in the step (1), the mixing time is 10-15 min; the triangular packaging frequency is 10-20.
Further, in the step (2), the roller spacing of the double rollers is 1-4 mm; the rolling times are 10-15 times.
Further, in the step (3), the single-layer glass fiber oriented sheet materials are sequentially stacked on the vulcanization mold according to the same orientation direction; the vulcanization temperature is 150-170 ℃, and the time is 15-35 min; the cooling is natural cooling in air; the thickness of the anti-skidding rubber sheet on the ice is 2-4 mm.
The beneficial technical effects of the invention are as follows:
(1) the anti-slip rubber sheet on ice prepared by the invention can be used for soles, the obtained soles have good anti-slip performance on ice, and the maximum static friction coefficient and the maximum dynamic friction coefficient on ice can respectively reach 0.65 and 0.37.
(2) The preparation method disclosed by the invention is simple to operate, the orientation degree of the glass fiber can be ensured to be higher by repeatedly rolling through the double-roller open mill, and the obtained anti-skidding rubber sheet on ice is excellent in anti-skidding effect.
(3) The invention adopts a plurality of single-layer sheets to be directly bonded by hot pressing without adding sulfur, and sulfur and adhesive are not additionally used for bonding, thereby saving the working procedure and the cost.
(4) According to the invention, through pretreatment of the glass fiber, the bonding force between the glass fiber and the rubber matrix is enhanced, the glass fiber is not easy to fall off in the using process, and the service life is prolonged.
Drawings
FIG. 1 is an SEM photograph of an ice top sliding rubber sheet prepared in example 3 of the present invention.
FIG. 2 is an SEM photograph of an ice top slip rubber sheet prepared in comparative example 1 of the present invention to which unmodified glass fibers were added.
Fig. 3 is an SEM image of a single-calendering oriented ice top slip rubber sheet prepared according to comparative example 2 of the present invention.
Detailed Description
So that the manner in which the features and advantages of the invention, as well as the objects and functions attained by the method can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to the embodiments thereof which are illustrated in the appended drawings.
Example 1
The rubber anti-slip sheet on the ice comprises the following raw materials in parts by weight:
45 parts of nitrile butadiene rubber, 20 parts of white carbon black (with the particle size of 200 meshes, purchased from Shanghai Yingyun New Material Co., Ltd.), 4 parts of dioctyl adipate plasticizer, 2 parts of zinc oxide (with the particle size of 0.1 mu m, purchased from Shanghai Yingyun New Material Co., Ltd.), 1 part of stearic acid (purchased from Yongzihao rubber chemical Co., Ltd.), 0.8 part of antioxidant MB (purchased from Shanghai Junpu chemical Co., Ltd.), 1.2 parts of accelerator dibenzothiazyl disulfide, 2 parts of sulfur (purchased from Xinghua chemical Co., Ltd., Anqing), 0.1 part of scorch retarder N-cyclohexylthiophthalimide and 20 parts of modified glass fiber.
The preparation method of the modified glass fiber comprises the following steps: 80g of ethanol solution with the pH value of 3 and the mass concentration of 95 percent is mixed with 10g of silane coupling agent Si-69 (the mass ratio of the ethanol solution to the silane coupling agent is 8:1), 100g of glass fiber (the glass fiber is chopped glass fiber, the diameter of a monofilament is 6 +/-1 mu m, the length of the monofilament is 0.8 +/-0.1 cm, and the glass fiber is purchased from China giant Stone Co., Ltd.) is soaked in the mixed solution of ethanol and the silane coupling agent for 15min and dried for 1h at the temperature of 80 ℃ to obtain the modified glass fiber.
The preparation method of the rubber sheet capable of stopping sliding on ice comprises the following steps:
(1) plasticating 45 parts of nitrile rubber to a wrapping roller in a double-roller open mill, adding 20 parts of white carbon black, 4 parts of plasticizer, 2 parts of zinc oxide, 1 part of stearic acid, 0.8 part of anti-aging agent and 0.1 part of anti-scorching agent, mixing for 10min, adding 1.2 parts of accelerator and 2 parts of sulfur, and performing triangular wrapping for 15 times to obtain a mixed material;
(2) plasticating the mixed material prepared in the step (1) to a wrapping roller, adding 20 parts of modified glass fiber, mixing, setting the roller distance of two rollers to be 1mm, and performing calendering orientation for 10 times between the two rollers to obtain a single-layer glass fiber oriented sheet material;
(3) and (3) sequentially stacking 15 single-layer glass fiber oriented sheets prepared in the step (2) on a vulcanization mold according to the same orientation direction, vulcanizing at 150 ℃ for 15min, naturally cooling in air, and slicing along the direction vertical to the length of the glass fiber to obtain the ice top-stop-slip rubber sheet, wherein the thickness of the ice top-stop-slip rubber sheet is 2 mm.
Example 2
The rubber anti-slip sheet on the ice comprises the following raw materials in parts by weight:
50 parts of natural rubber, 20 parts of white carbon black (with the particle size of 500 meshes, purchased from Shanghai Yingyun New Material Co., Ltd.), 5 parts of dioctyl phthalate plasticizer, 3 parts of zinc oxide (with the particle size of 1 mu m, purchased from Shanghai Yingyun New Material Co., Ltd.), 1 part of stearic acid (purchased from Yongshize Hao rubber chemical Co., Ltd.), 0.3 part of antioxidant 4010NA (purchased from Shanghai Junpu chemical Co., Ltd.), 0.5 part of accelerator tetrabenzylthiuram disulfide, 3 parts of sulfur (purchased from Xinghu chemical Co., Ltd., Chongqing), 0.2 part of antiscorching nitrosodiphenylamine and 25 parts of modified glass fiber.
The preparation method of the modified glass fiber comprises the following steps: 90g of ethanol solution with the pH value of 4 and the mass concentration of 95 percent is mixed with 10g of silane coupling agent KH550 (the mass ratio of the ethanol solution to the silane coupling agent is 9:1), 100g of glass fiber (the glass fiber is chopped glass fiber, the diameter of a monofilament is 15 +/-2 mu m, the length of the monofilament is 2 +/-0.3 cm, and the glass fiber is purchased from China megastone GmbH) is soaked in the mixed solution of ethanol and the silane coupling agent for 25min and dried for 2h at the temperature of 100 ℃ to obtain the modified glass fiber.
The preparation method of the rubber sheet capable of stopping sliding on ice comprises the following steps:
(1) plasticating 50 parts of natural rubber to a wrapping roller in a double-roller open mill, adding 20 parts of white carbon black, 5 parts of plasticizer, 3 parts of zinc oxide, 1 part of stearic acid, 0.3 part of anti-aging agent and 0.2 part of anti-scorching agent, mixing for 12min, adding 0.5 part of accelerator and 3 parts of sulfur, and performing triangular wrapping for 10 times to obtain a mixed material;
(2) plasticating the mixed material prepared in the step (1) to a wrapping roller, adding 25 parts of modified glass fiber, mixing, setting the roller distance of two rollers to be 2mm, and performing calendering orientation for 13 times between the two rollers to obtain a single-layer glass fiber oriented sheet material;
(3) and (3) sequentially stacking 15 single-layer glass fiber oriented sheets prepared in the step (2) on a vulcanization mold according to the same orientation direction, vulcanizing at 160 ℃ for 25min, naturally cooling in air, and slicing along the direction vertical to the length of the glass fiber to obtain the ice top-stop-slip rubber sheet, wherein the thickness of the ice top-stop-slip rubber sheet is 3 mm.
Example 3
The rubber anti-slip sheet on the ice comprises the following raw materials in parts by weight:
50 parts of nitrile butadiene rubber, 30 parts of white carbon black (with the particle size of 800 meshes, purchased from Shanghai Ying-Yuan New Material Co., Ltd.), 4 parts of dibutyl phthalate plasticizer, 4 parts of zinc oxide (with the particle size of 5 mu m, purchased from Shanghai Ying-Yuan New Material Co., Ltd.), 1.5 parts of stearic acid (purchased from Yongshize Hao rubber chemical Co., Ltd.), 1.2 parts of antioxidant RD (purchased from Shanghai Junpu chemical Co., Ltd.), 1 part of accelerator zinc dibutyl dithiocarbamate, 4 parts of sulfur (purchased from Chonghua chemical Co., Ltd., Anqing), 0.3 part of antiscorching agent phthalic anhydride and 40 parts of modified glass fiber.
The preparation method of the modified glass fiber comprises the following steps: 100g of ethanol solution with pH of 4.5 and mass concentration of 95 percent is mixed with 10g (the mass ratio of the ethanol solution to the silane coupling agent is 10:1) of silane coupling agent Si-69, 100g of glass fiber (the glass fiber is chopped glass fiber, the diameter of a monofilament is 20 +/-3 mu m, the length of the glass fiber is 3.5 +/-0.4 cm, and the glass fiber is purchased from China megalithic corporation.) is soaked in the mixed solution of ethanol and the silane coupling agent for 30min and dried at 110 ℃ for 2.5h, and the modified glass fiber is obtained.
The preparation method of the rubber sheet capable of stopping sliding on ice comprises the following steps:
(1) plasticating 50 parts of nitrile rubber to a wrapping roller in a double-roller open mill, adding 30 parts of white carbon black, 4 parts of plasticizer, 4 parts of zinc oxide, 1.5 parts of stearic acid, 1.2 parts of anti-aging agent and 0.3 part of anti-scorching agent, mixing for 15min, adding 1 part of accelerator and 4 parts of sulfur, and performing triangular wrapping for 20 times to obtain a mixed material;
(2) plasticating the mixed material prepared in the step (1) to a wrapping roller, adding 40 parts of modified glass fiber, mixing, setting the roller distance of two rollers to be 3mm, and carrying out calendering orientation for 12 times between the two rollers to obtain a single-layer glass fiber oriented sheet material;
(3) and (3) sequentially stacking 15 single-layer glass fiber oriented sheets prepared in the step (2) on a vulcanization mold according to the same orientation direction, vulcanizing at 165 ℃ for 30min, naturally cooling in air, and slicing along the direction vertical to the length of the glass fiber to obtain the ice top-stop-slip rubber sheet, wherein the thickness of the ice top-stop-slip rubber sheet is 3.5 mm.
Example 4
55 parts of styrene butadiene rubber, 15 parts of white carbon black (with the particle size of 1000 meshes, purchased from Shanghai Yingyun New Material Co., Ltd.), 4 parts of dioctyl azelate plasticizer, 2.5 parts of zinc oxide (with the particle size of 10 mu m, purchased from Shanghai Yingyun New Material Co., Ltd.), 2 parts of stearic acid (purchased from Yongshize Hao rubber chemical Co., Ltd.), 1.2 parts of antioxidant MB (purchased from Shanghai Junpu chemical Co., Ltd.), 1.5 parts of accelerator dibenzothiazyl disulfide, 5 parts of sulfur (purchased from Xinghua chemical Co., Ltd., Anqing), 0.3 part of antiscorching agent N-cyclohexylthiophthalimide and 55 parts of modified glass fiber.
The preparation method of the modified glass fiber comprises the following steps: 120g of ethanol solution with pH value of 5 and mass concentration of 95 percent is mixed with 10g (the mass ratio of the ethanol solution to the silane coupling agent is 12:1) of the silane coupling agent KH570, 100g of glass fiber (the glass fiber is chopped glass fiber, the diameter of a monofilament is 27 +/-3 mu m, the length of the monofilament is 4.5 +/-0.5 cm, and the glass fiber is purchased from China megastone GmbH.) is soaked in the mixed solution of the ethanol and the silane coupling agent for 30min and dried for 3h at 120 ℃ to obtain the modified glass fiber.
The preparation method of the rubber sheet capable of stopping sliding on ice comprises the following steps:
(1) plasticating 55 parts of styrene butadiene rubber to a wrapping roller in a double-roller open mill, adding 15 parts of white carbon black, 4 parts of plasticizer, 2.5 parts of zinc oxide, 2 parts of stearic acid, 1.2 parts of anti-aging agent and 0.3 part of anti-scorching agent, mixing for 15min, adding 1.5 parts of accelerator and 4.5 parts of sulfur, and performing triangular wrapping for 20 times to obtain a mixed material;
(2) plasticating the mixed material prepared in the step (1) to a wrapping roller, adding 55 parts of modified glass fiber, mixing, setting the roller distance of two rollers to be 4mm, and performing calendering orientation for 15 times between the two rollers to obtain a single-layer glass fiber oriented sheet material;
(3) and (3) sequentially stacking 15 single-layer glass fiber oriented sheets prepared in the step (2) on a vulcanization mold according to the same orientation direction, vulcanizing at 170 ℃ for 35min, naturally cooling in air, and slicing along the direction vertical to the length of the glass fiber to obtain the ice top-stop-slip rubber sheet, wherein the thickness of the ice top-stop-slip rubber sheet is 4 mm.
Comparative example 1
An ice rubber slip stopper added with unmodified glass fiber comprises the following raw materials in parts by weight:
50 parts of nitrile butadiene rubber, 30 parts of white carbon black (with the particle size of 800 meshes, purchased from Shanghai Ying-Yuan New Material Co., Ltd.), 4 parts of dibutyl phthalate plasticizer, 4 parts of zinc oxide (with the particle size of 5 mu m, purchased from Shanghai Ying-Yuan New Material Co., Ltd.), 1.5 parts of stearic acid (purchased from Heizhiha rubber chemical Co., Ltd.), 1.2 parts of antioxidant RD (purchased from Shanghai Junpu chemical Co., Ltd.), 1 part of accelerator zinc dibutyl dithiocarbamate, 4 parts of sulfur (purchased from Xinghua chemical Co., Ltd., Anqing), 0.3 part of antiscorching agent phthalic anhydride, 40 parts of glass fiber (the glass fiber is chopped glass fiber, the monofilament diameter is 20 +/-3 mu m, the length is 3.5 +/-0.4 cm, purchased from China Julian Co., Ltd.)
An ice top-stop sliding rubber sheet added with unmodified glass fibers is prepared by the following steps:
(1) plasticating 50 parts of nitrile rubber to a wrapping roller in a double-roller open mill, adding 30 parts of white carbon black, 4 parts of plasticizer, 4 parts of zinc oxide, 1.5 parts of stearic acid, 1.2 parts of anti-aging agent and 0.3 part of anti-scorching agent, mixing for 15min, adding 1 part of accelerator and 4 parts of sulfur, and performing triangular wrapping for 20 times to obtain a mixed material;
(2) plasticating the mixed material prepared in the step (1) to a wrapping roller, adding 40 parts of glass fiber, mixing, setting the roller distance of two rollers to be 3mm, and carrying out calendering orientation for 12 times between the two rollers to obtain a single-layer glass fiber oriented sheet material;
(3) and (3) sequentially stacking 15 single-layer glass fiber oriented sheets prepared in the step (2) on a vulcanization mold according to the same orientation direction, vulcanizing at 165 ℃ for 30min, naturally cooling in air, and slicing along the direction vertical to the length of the glass fiber to obtain the ice top-stop-slip rubber sheet, wherein the thickness of the ice top-stop-slip rubber sheet is 3.5 mm.
Comparative example 2
The ice rubber slip stopper prepared by single calendering orientation comprises the following raw materials in parts by weight:
50 parts of nitrile butadiene rubber, 30 parts of white carbon black (with the particle size of 800 meshes, purchased from Shanghai Ying-Yuan New Material Co., Ltd.), 4 parts of dibutyl phthalate plasticizer, 4 parts of zinc oxide (with the particle size of 5 mu m, purchased from Shanghai Ying-Yuan New Material Co., Ltd.), 1.5 parts of stearic acid (purchased from Yongshize Hao rubber chemical Co., Ltd.), 1.2 parts of antioxidant RD (purchased from Shanghai Junpu chemical Co., Ltd.), 1 part of accelerator zinc dibutyl dithiocarbamate, 4 parts of sulfur (purchased from Chonghua chemical Co., Ltd., Anqing), 0.3 part of antiscorching agent phthalic anhydride and 40 parts of modified glass fiber.
The preparation method of the modified glass fiber comprises the following steps: 100g of ethanol solution with pH value of 4.5 and mass concentration of 95 percent is mixed with 10g (the mass ratio of the ethanol solution to the silane coupling agent is 10:1) of silane coupling agent Si-69, 100g of glass fiber (the glass fiber is chopped glass fiber, the diameter of a monofilament is 20 +/-3 mu m, the length is 3.5 +/-0.4 cm, and the glass fiber is purchased from China megalithic Co., Ltd.) is soaked in the mixed solution of ethanol and the silane coupling agent for 30min and dried at 110 ℃ for 2.5h, and the modified glass fiber is obtained.
A single-orientation prepared anti-icing anti-skidding rubber sheet is prepared by the following steps:
(1) plasticating 50 parts of nitrile rubber to a wrapping roller in a double-roller open mill, adding 30 parts of white carbon black, 4 parts of plasticizer, 4 parts of zinc oxide, 1.5 parts of stearic acid, 1.2 parts of anti-aging agent and 0.3 part of anti-scorching agent, mixing for 15min, adding 1 part of accelerator and 4 parts of sulfur, and performing triangular wrapping for 20 times to obtain a mixed material;
(2) plasticating the mixed material prepared in the step (1) to a wrapping roller, adding 40 parts of modified glass fiber, mixing, setting the roller distance of a double roller to be 3mm, and performing single-time calendering to obtain a single-layer glass fiber oriented sheet material;
(3) and (3) sequentially stacking 15 single-layer glass fiber oriented sheets prepared in the step (2) on a vulcanization mold according to the same orientation direction, vulcanizing at 165 ℃ for 30min, naturally cooling in air, and slicing along the direction vertical to the length of the glass fiber to obtain the ice top-stop-slip rubber sheet, wherein the thickness of the ice top-stop-slip rubber sheet is 3.5 mm.
Comparative example 3
An ice rubber sliding stopper prepared by using a single piece of oriented sheet stock comprises the following raw materials in parts by weight:
50 parts of nitrile butadiene rubber, 30 parts of white carbon black (with the particle size of 800 meshes, purchased from Shanghai Ying-Yuan New Material Co., Ltd.), 4 parts of dibutyl phthalate plasticizer, 4 parts of zinc oxide (with the particle size of 5 mu m, purchased from Shanghai Ying-Yuan New Material Co., Ltd.), 1.5 parts of stearic acid (purchased from Yongshize Hao rubber chemical Co., Ltd.), 1.2 parts of antioxidant RD (purchased from Shanghai Junpu chemical Co., Ltd.), 1 part of accelerator zinc dibutyl dithiocarbamate, 4 parts of sulfur (purchased from Chonghua chemical Co., Ltd., Anqing), 0.3 part of antiscorching agent phthalic anhydride and 40 parts of modified glass fiber.
The preparation method of the modified glass fiber comprises the following steps: 100g of ethanol solution with pH of 4.5 and mass concentration of 95 percent is mixed with 10g (the mass ratio of the ethanol solution to the silane coupling agent is 10:1) of silane coupling agent Si-69, 100g of glass fiber (the glass fiber is chopped glass fiber, the diameter of a monofilament is 20 +/-3 mu m, the length of the glass fiber is 3.5 +/-0.4 cm, and the glass fiber is purchased from China megalithic corporation.) is soaked in the mixed solution of ethanol and the silane coupling agent for 30min and dried at 110 ℃ for 2.5h, and the modified glass fiber is obtained.
The preparation method of the rubber sheet capable of stopping sliding on ice comprises the following steps:
(1) plasticating 50 parts of nitrile rubber to a wrapping roller in a double-roller open mill, adding 30 parts of white carbon black, 4 parts of plasticizer, 4 parts of zinc oxide, 1.5 parts of stearic acid, 1.2 parts of anti-aging agent and 0.3 part of anti-scorching agent, mixing for 15min, adding 1 part of accelerator and 4 parts of sulfur, and performing triangular wrapping for 20 times to obtain a mixed material;
(2) plasticating the mixed material prepared in the step (1) to a wrapping roller, adding 40 parts of modified glass fiber, mixing, setting the roller distance of two rollers to be 3mm, and carrying out calendering orientation for 12 times between the two rollers to obtain a single-layer glass fiber oriented sheet material;
(3) and (3) vulcanizing the single-layer glass fiber oriented sheet stock prepared in the step (2) on a vulcanization mold at 165 ℃ for 30min, naturally cooling in air, and slicing along the direction vertical to the length of the glass fiber to obtain the ice top-dead-slip rubber sheet prepared from the single oriented sheet stock, wherein the thickness of the ice top-dead-slip rubber sheet is 3.5 mm.
Comparative example 4
The rubber sheet without the glass fiber comprises the following raw materials in parts by weight:
50 parts of nitrile butadiene rubber, 30 parts of white carbon black (with the particle size of 800 meshes, purchased from Shanghai Ying-Yuan New Material Co., Ltd.), 4 parts of dibutyl phthalate plasticizer, 4 parts of zinc oxide (with the particle size of 5 mu m, purchased from Shanghai Ying-Yuan New Material Co., Ltd.), 1.5 parts of stearic acid (purchased from Yongshize Hao rubber chemical Co., Ltd.), 1.2 parts of antioxidant RD (purchased from Shanghai Junpu chemical Co., Ltd.), 1 part of accelerator zinc dibutyl dithiocarbamate, 4 parts of sulfur (purchased from Kongxing chemical Co., Ltd., Anqing), and 0.3 part of antiscorching phthalic anhydride.
The preparation method of the ice top-stop sliding rubber sheet without adding modified glass fiber comprises the following steps:
(1) plasticating 50 parts of nitrile rubber to a wrapping roller in a double-roller open mill, adding 30 parts of white carbon black, 4 parts of plasticizer, 4 parts of zinc oxide, 1.5 parts of stearic acid, 1.2 parts of anti-aging agent and 0.3 part of anti-scorching agent, mixing for 15min, adding 1 part of accelerator and 4 parts of sulfur, and performing triangular wrapping for 20 times to obtain a mixed material
(2) Plasticating the mixed material prepared in the step (1) to a wrapping roller, setting the roller distance of two rollers to be 3mm, and rolling for 12 times between the two rollers to obtain single-layer oriented sheet materials;
(3) and (3) sequentially stacking 15 single-layer oriented sheets prepared in the step (2) on a vulcanization mold, vulcanizing at 165 ℃ for 30min, naturally cooling in air, and slicing along the direction vertical to the sheets to obtain the rubber sheets, wherein the thickness of the rubber sheets is 3.5 mm.
Test example 1
The rubber sheets prepared in example 3 and comparative examples 1 to 2 were observed by a scanning electron microscope, and the results are shown in FIGS. 1 to 3, respectively. It can be seen that in fig. 2, the glass fiber which is not modified by the silane coupling agent has poor binding ability with the rubber matrix, and a gap is formed between the glass fiber and the rubber; the modified glass fiber in the figure 1 is well combined with rubber, and the rubber matrix is better coated on the surface of the glass fiber; in the uncalendered orientation shown in FIG. 3, the glass fibers in the rubber sheet were prepared without orientation.
Test example 2
The mechanical properties of the anti-slip rubber sheets obtained in examples 1-4 and comparative examples 1-4 were tested by using a universal testing machine, and the specific test methods were performed according to GB/T528-2009 and GB/T529-2008 (tensile rate 500mm/min), and the test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the rubber sheets obtained in examples 1-4 have good mechanical properties, in which 100% strain stress and tear strength can reach 8.4MPa and 61.1mm N, respectively-1(ii) a The mechanical property of the comparative example 1 added with the unmodified glass fiber is obviously reduced compared with that of the comparative example 2 without calendering orientation. It can be seen from aging experiments that surface modification and calendering orientation of the silane coupling agent can improve the aging resistance of the material. Wherein, the 100% strain stress of comparative example 1 is reduced by 0.7MPa, and the tear strength is reduced by 6.9mm N-1Comparative example 2 shows a decrease of 0.6MPa and 9.3mm N, respectively-1While example 3 decreased by 0.5MPa and 9.6mm N, respectively-1Compared with the comparative ratio, the mechanical property of the embodiment 3 of the invention is obviously improved.
Test example 3
The abrasion resistance of the anti-slip rubber sheets prepared in the examples 1-4 and the comparative examples 1-4 was tested by an Akron abrasion machine, the specific test method was performed according to GB/T1689-.
TABLE 2
| Akron abrasion loss/cm3 | |
| Example 1 | 0.48 |
| Example 2 | 0.42 |
| Example 3 | 0.37 |
| Example 4 | 0.32 |
| Comparative example 1 | 0.52 |
| Comparative example 2 | 0.51 |
| Comparative example 3 | 0.55 |
| Comparative example 4 | 0.68 |
As can be seen from Table 2, after the modification by the silane coupling agent, the binding capacity of the glass fiber and the rubber matrix is increased, and the wear resistance is obviously increased.
Test example 4
The ice top slip rubber sheets obtained in examples 1-4 above and the rubber sheets of comparative examples 1-2 were placed on an ice surface and tested for coefficient of friction according to GB 10006-1988, the results of which are shown in Table 2.
TABLE 3
Referring to the above table 3, the friction coefficients on the ice surface of the ice top slip rubber sheets prepared in examples 1 to 4 were all improved relative to those of comparative examples 1 to 4, indicating that the prepared rubber sheets had good ice top slip effects. After 20 times of friction experiments on the ice surface, the friction coefficient of the comparative example 1 with the unmodified glass fiber is obviously reduced, which indicates that the unmodified glass fiber is poorly combined with the rubber matrix; comparative example 3 is not sliced by a slicer, and compared with the example with a plurality of slices, the friction coefficient is obviously reduced, which shows that the surface exposure of the glass fiber can improve the anti-slip performance of the material on the ice surface; the friction coefficient of the sample added with the modified glass fiber is basically unchanged, which shows that the material has better durability.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The anti-skid rubber sheet on ice is characterized by comprising the following raw materials in parts by weight: 45-55 parts of rubber, 15-30 parts of white carbon black, 4-5 parts of plasticizer, 2-4 parts of zinc oxide, 1-2 parts of stearic acid, 0.3-1.2 parts of anti-aging agent, 0.5-1.5 parts of accelerator, 2-5 parts of sulfur, 0.1-0.3 part of anti-scorching agent and 20-55 parts of modified glass fiber.
2. The anti-icing anti-skidding rubber sheet as claimed in claim 1, wherein the rubber is one or more of nitrile rubber, styrene butadiene rubber and natural rubber; the particle size of the white carbon black is 200-1000 meshes; the plasticizer is one or more of dibutyl phthalate, dioctyl adipate and dioctyl azelate.
3. The anti-icing anti-skidding rubber sheet according to claim 1, wherein the anti-aging agent is one or more of RD, 4010NA and MB; the accelerator is one or more of dibenzothiazyl disulfide, tetrabenzylthiuram disulfide and zinc dibutyl dithiocarbamate; the scorch retarder is one or more of N-cyclohexylthiophthalimide, phthalic anhydride and nitrosodiphenylamine; the particle size of the zinc oxide is 0.1-10 mu m.
4. The anti-icing non-slippery rubber sheet according to claim 1, wherein the modified glass fiber is prepared by the following steps: and mixing the ethanol solution with a silane coupling agent, soaking the glass fiber in the mixed solution of the ethanol and the silane coupling agent for 15-30 min, and drying to obtain the modified glass fiber.
5. The anti-icing anti-skidding rubber sheet as claimed in claim 4, wherein the glass fiber is chopped glass fiber, the diameter of a single filament is 5-30 μm, the length of the single filament is 0.7-5 cm, and the single filament is purchased from China megastone GmbH.
6. The anti-icing non-slip rubber sheet according to claim 4, wherein the mass concentration of the ethanol is 95%, and the pH value is 3-5; the silane coupling agent is one or more of Si-69, KH550 and KH 570; the mass ratio of the ethanol to the silane coupling agent is 8-12: 1; the drying temperature is 80-120 ℃, and the drying time is 1-3 h.
7. A method for preparing the rubber sheet for stopping slipping on ice as claimed in claim 1, wherein the method comprises the steps of:
(1) plasticating 45-55 parts of rubber to a wrapping roller, adding 15-30 parts of white carbon black, 4-5 parts of plasticizer, 2-4 parts of zinc oxide, 1-2 parts of stearic acid, 0.3-1.2 parts of anti-aging agent and 0.1-0.3 part of anti-scorching agent, mixing, adding 0.5-1.5 parts of accelerator and 2-5 parts of sulfur, and performing triangular wrapping to obtain a mixed material;
(2) plasticating the mixed material prepared in the step (1) to a wrapping roller, adding 20-55 parts of modified glass fiber for mixing, and performing calendering orientation between two rollers to obtain a single-layer glass fiber oriented sheet material;
(3) and (3) overlapping the single-layer glass fiber oriented sheets prepared in the step (2), vulcanizing, cooling, and slicing along the direction vertical to the length of the glass fiber to obtain the ice top sliding rubber sheet.
8. The method according to claim 7, wherein in steps (1), (2), the mastication is carried out in a two-roll mill; in the step (1), the mixing time is 10-15 min; the triangular packaging frequency is 10-20.
9. The preparation method according to claim 7, wherein in the step (2), the roller spacing of the twin rollers is 1-4 mm; the rolling times are 10-15 times.
10. The method according to claim 7, wherein in the step (3), the single glass fiber oriented sheets are stacked in the same orientation direction on the vulcanization mold; the vulcanization temperature is 150-170 ℃, and the time is 15-35 min; the cooling is natural cooling in air; the thickness of the anti-skidding rubber sheet on the ice is 2-4 mm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117143403A (en) * | 2023-10-31 | 2023-12-01 | 河北华密新材科技股份有限公司 | Impact-resistant and shock-absorbing rubber part and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110258886A1 (en) * | 2010-04-26 | 2011-10-27 | Ku Do Moon | Slip-Resistant Rubber Composition, Outsole Using the Rubber Composition and Method of Manufacturing the Outsole |
| CN102964645A (en) * | 2012-11-29 | 2013-03-13 | 泰亚鞋业股份有限公司 | Ice surface anti-slip rubber sports shoe soles and manufacturing method thereof |
| CN109942919A (en) * | 2019-04-02 | 2019-06-28 | 晋江市鑫铭鞋材科技有限公司 | A kind of ice face Anti-skidding rubber sole formula and its manufacture craft |
| CN110317375A (en) * | 2019-07-24 | 2019-10-11 | 温州市宜和鞋材有限公司 | A kind of ice face oil-proof anti-skid footwear material and preparation method thereof |
| CN112239574A (en) * | 2019-07-16 | 2021-01-19 | 林扬发 | Rubber for stopping ice sliding and preparation method thereof |
| CN112574478A (en) * | 2020-11-24 | 2021-03-30 | 福建省莆田市联盛鞋业有限公司 | Composition of ice top-dead-slip sheet, preparation method and ice top-dead-slip sole material |
-
2021
- 2021-07-02 CN CN202110751745.1A patent/CN113388172B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110258886A1 (en) * | 2010-04-26 | 2011-10-27 | Ku Do Moon | Slip-Resistant Rubber Composition, Outsole Using the Rubber Composition and Method of Manufacturing the Outsole |
| CN102964645A (en) * | 2012-11-29 | 2013-03-13 | 泰亚鞋业股份有限公司 | Ice surface anti-slip rubber sports shoe soles and manufacturing method thereof |
| CN109942919A (en) * | 2019-04-02 | 2019-06-28 | 晋江市鑫铭鞋材科技有限公司 | A kind of ice face Anti-skidding rubber sole formula and its manufacture craft |
| CN112239574A (en) * | 2019-07-16 | 2021-01-19 | 林扬发 | Rubber for stopping ice sliding and preparation method thereof |
| CN110317375A (en) * | 2019-07-24 | 2019-10-11 | 温州市宜和鞋材有限公司 | A kind of ice face oil-proof anti-skid footwear material and preparation method thereof |
| CN112574478A (en) * | 2020-11-24 | 2021-03-30 | 福建省莆田市联盛鞋业有限公司 | Composition of ice top-dead-slip sheet, preparation method and ice top-dead-slip sole material |
Non-Patent Citations (1)
| Title |
|---|
| 卞军 等主编: "《聚合物共混改性基础》", 31 January 2018, 西安交通大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117143403A (en) * | 2023-10-31 | 2023-12-01 | 河北华密新材科技股份有限公司 | Impact-resistant and shock-absorbing rubber part and preparation method thereof |
| CN117143403B (en) * | 2023-10-31 | 2024-02-02 | 河北华密新材科技股份有限公司 | Impact-resistant and shock-absorbing rubber part and preparation method thereof |
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