CN113388172B - 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 PDF

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CN113388172B
CN113388172B CN202110751745.1A CN202110751745A CN113388172B CN 113388172 B CN113388172 B CN 113388172B CN 202110751745 A CN202110751745 A CN 202110751745A CN 113388172 B CN113388172 B CN 113388172B
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glass fiber
rubber
ice
rubber sheet
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CN113388172A (en
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倪忠斌
汪文杰
顾浩煜
施冬健
陈明清
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Jiangnan University
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Jiangnan University
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • 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
    • A43B13/04—Plastics, rubber or vulcanised fibre
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    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
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    • C08K3/20—Oxides; Hydroxides
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    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
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    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Abstract

The invention discloses an ice anti-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

Rubber sheet capable of stopping sliding on ice and preparation method thereof
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 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 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 scorch retarder 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 scorch retarder, 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), 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 image of a non-modified glass fiber-added anti-skid rubber sheet on ice prepared by comparative example 1 of the present invention.
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 manner in which the above recited features and advantages are attained and 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 antiskid sheet on 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: the modified glass fiber was obtained by mixing 80g of an ethanol solution having a pH of 3 and a mass concentration of 95% with 10g (mass ratio of the ethanol solution to the silane coupling agent: 8:1) of a silane coupling agent Si-69, immersing 100g of a glass fiber (glass fiber is a chopped glass fiber, monofilament diameter is 6 ± 1 μm, length is 0.8 ± 0.1cm, purchased from gigantism corp., ltd., china) in the mixed solution of ethanol and the silane coupling agent for 15min, and drying at 80 ℃ for 1 h.
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 antiskid sheet on 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: mixing 90g of ethanol solution with the pH value of 4 and the mass concentration of 95% with 10g (the mass ratio of the ethanol solution to the silane coupling agent is 9:1) of the silane coupling agent KH550, soaking 100g of glass fiber (the glass fiber is chopped glass fiber, the monofilament diameter is 15 +/-2 mu m, the length is 2 +/-0.3 cm, and the glass fiber is purchased from China megalithic corporation) in the mixed solution of the ethanol and the silane coupling agent for 25min, and drying 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 scorch retarder, 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 anti-ice anti-slip rubber sheet, wherein the thickness of the anti-ice anti-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 Yingyun New materials Co., Ltd.), 4 parts of dibutyl phthalate plasticizer, 4 parts of zinc oxide (with the particle size of 5 mu m, purchased from Shanghai Yingyun New materials Co., Ltd.), 1.5 parts of stearic acid (purchased from Heizhihao 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 Cushing chemical Co., Ltd.), 0.3 part of scorch retarder phthalic anhydride and 40 parts of modified glass fiber.
The preparation method of the modified glass fiber comprises the following steps: 100g of an ethanol solution with pH of 4.5 and a mass concentration of 95% was mixed with 10g (the mass ratio of the ethanol solution to the silane coupling agent was 10:1) of the silane coupling agent Si-69, 100g of a glass fiber (a glass fiber was a chopped glass fiber, a monofilament diameter was 20. + -. 3 μm, a length was 3.5. + -. 0.4cm, and purchased from Kyoho, Inc., China) was immersed in the mixed solution of ethanol and the silane coupling agent for 30min, and dried at 110 ℃ for 2.5h, to obtain a 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 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 scorch retarder, 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 for mixing, setting the roller distance of two rollers to be 3mm, and calendering and orienting 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 Yingyun New materials Co., Ltd.), 4 parts of dibutyl phthalate plasticizer, 4 parts of zinc oxide (with the particle size of 5 mu m, purchased from Shanghai Yingyun New materials Co., Ltd.), 1.5 parts of stearic acid (purchased from Heizhihao 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, 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 Juguo 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 vulcanizing 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 anti-ice anti-slip rubber sheet, wherein the thickness of the anti-ice anti-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 Yingyun New materials Co., Ltd.), 4 parts of dibutyl phthalate plasticizer, 4 parts of zinc oxide (with the particle size of 5 mu m, purchased from Shanghai Yingyun New materials Co., Ltd.), 1.5 parts of stearic acid (purchased from Heizhihao 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 Cushing chemical Co., Ltd.), 0.3 part of scorch retarder 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 megalite GmbH.) is soaked in the mixed solution of the ethanol and the silane coupling agent for 30min and dried for 2.5h at 110 ℃ to obtain the modified glass fiber.
A single-orientation preparation method of an ice anti-stop sliding rubber sheet 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 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 antiskid sheet 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 an ethanol solution with pH of 4.5 and a mass concentration of 95% was mixed with 10g (the mass ratio of the ethanol solution to the silane coupling agent was 10:1) of the silane coupling agent Si-69, 100g of a glass fiber (a glass fiber was a chopped glass fiber, a monofilament diameter was 20. + -. 3 μm, a length was 3.5. + -. 0.4cm, and purchased from Kyoho, Inc., China) was immersed in the mixed solution of ethanol and the silane coupling agent for 30min, and dried at 110 ℃ for 2.5h, to obtain a 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 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 material prepared in the step (2) on a vulcanizing 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 anti-ice anti-slippery rubber sheet prepared from the single-layer oriented sheet material, wherein the thickness of the anti-ice anti-slippery 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 rubber, 30 parts of white carbon black (with the particle size of 800 meshes, purchased from Shanghai Yingyun New materials Co., Ltd.), 4 parts of dibutyl phthalate plasticizer, 4 parts of zinc oxide (with the particle size of 5 mu m, purchased from Shanghai Yingyun New materials Co., Ltd.), 1.5 parts of stearic acid (purchased from Heizhihao 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 Cushing chemical Co., Ltd.), and 0.3 part of scorch retarder phthalic anhydride.
The preparation method of the ice anti-stop sliding rubber sheet without the addition of the 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; in FIG. 1, the modified glass fiber is well combined with rubber, and the rubber matrix is well coated on the surface of the glass fiber; in the uncalendered orientation shown in FIG. 3, the glass fibers in the resulting rubber sheet were not oriented.
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
Figure BDA0003144911490000091
Figure BDA0003144911490000101
As can be seen from Table 1, the rubber sheets obtained in examples 1 to 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 the aging resistance of the material can be improved by the surface modification and the calendering orientation of the silane coupling agent. Of these, 100% strain of comparative example 1The stress is reduced by 0.7MPa, the tearing strength is reduced by 6.9mm N -1 Comparative example 2 shows a decrease of 0.6MPa and 9.3mm N, respectively -1 While example 3 decreased by 0.5MPa and 9.6mm N, respectively -1 Compared 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/cm 3
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 anti-skid rubber sheets on ice prepared in examples 1-4 and the rubber sheets in comparative examples 1-2 were placed on an ice surface and subjected to a friction coefficient test according to GB 10006-1988, the test results of which are shown in Table 2.
TABLE 3
Figure BDA0003144911490000111
Referring to table 3 above, the friction coefficients on the ice surface of the anti-icing 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 anti-icing effect. After 20 times of friction experiments on the ice surface, the friction coefficient of the comparative example 1 added 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 (5)

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 scorch retarder and 20-55 parts of modified glass fiber;
the rubber is one or more of nitrile rubber, styrene butadiene rubber and natural rubber;
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 glass fiber is purchased from China megalithic corporation;
the preparation method of the modified glass fiber comprises the following steps: mixing an 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 modified glass fiber;
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;
the preparation method of the rubber sheet capable of stopping slipping on ice 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 scorch retarder, 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) superposing the single-layer glass fiber oriented sheets prepared in the step (2), and slicing the sheets in a direction perpendicular to the length direction of the glass fibers after vulcanization and cooling to obtain the ice anti-stop sliding rubber sheet;
in the step (2), the rolling times are 10-15;
in the step (3), the single-layer glass fiber oriented sheet materials are sequentially stacked on a vulcanization mold according to the same orientation direction in the stacking process; the vulcanization temperature is 150-170 ℃, and the time is 15-35 min; the cooling is natural cooling in air; the thickness of the ice top sliding rubber sheet is 2-4 mm; the number of the overlapped sheets is 15.
2. The anti-icing non-slip rubber sheet according to claim 1, wherein the white carbon black has a particle size of 200 to 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 anti-slip rubber sheet according to claim 1, wherein in steps (1), (2), the mastication is performed in a two-roll mill; in the step (1), the mixing time is 10-15 min; the triangular packaging times are 10-20.
5. The anti-icing anti-skidding rubber sheet according to claim 1, wherein in the step (2), the roller spacing of the two rollers is 1-4 mm; the rolling times are 10-15 times.
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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
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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

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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

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