阅读说明：本技术 一种新型透气防水橡胶复合材料及其制备方法 (Novel breathable waterproof rubber composite material and preparation method thereof ) 是由 翟俊学 杜正甬 聂嘉谦 蔡伟强 毕晓杰 于 2021-09-02 设计创作，主要内容包括：本发明公开了一种新型透气防水橡胶复合材料及其制备方法,属于功能高分子复合材料领域。所述制备方法包括以橡胶配合硫化剂、促进剂、防老剂、补强剂作为基体材料,在其中加入含有化学发泡剂和水溶性物质的高流动性聚合物,通过高温混炼制备成连续相结构的混炼胶,硫化和溶析成孔后得到一种新型的连续通道结构的透气防水橡胶复合材料。本发明的有益效果在于本发明提供的新型透气防水橡胶复合材料,具有良好的防水透气性能和力学性能,可用于制作防水透气橡胶、弹性体制品。(The invention discloses a novel breathable waterproof rubber composite material and a preparation method thereof, and belongs to the field of functional polymer composite materials. The preparation method comprises the steps of taking rubber matched with a vulcanizing agent, an accelerator, an anti-aging agent and a reinforcing agent as base materials, adding a high-fluidity polymer containing a chemical foaming agent and a water-soluble substance into the base materials, preparing a rubber compound with a continuous phase structure through high-temperature mixing, and vulcanizing and dissolving out to form holes to obtain the novel breathable waterproof rubber composite material with the continuous channel structure. The novel breathable waterproof rubber composite material has good waterproof and breathable performance and mechanical performance, and can be used for manufacturing waterproof breathable rubber and elastomer products.)

1. The novel breathable waterproof composite material is characterized by being prepared from the following raw materials: 80-120 parts of rubber, 0.5-10 parts of vulcanizing agent, 0.01-5 parts of accelerator, 0.5-5 parts of anti-aging agent, 10-80 parts of reinforcing agent, 80-120 parts of high-fluidity polymer, 1-20 parts of chemical foaming agent and 5-50 parts of water-soluble substance.

2. The novel breathable waterproof composite of claim 1, wherein said rubber is one of a non-polar rubber or a polar rubber;

the vulcanizing agent is one or a mixture of sulfur, polysulfide, peroxide, metal oxide or phenolic resin;

the accelerator is one or a mixture of thiuram, thiazole, sulfenamide, dithiocarbamate or guanidine;

the anti-aging agent is one or a mixture of more of diphenylamine, p-phenylenediamine, phenol, organic sulfide or phosphite ester;

the reinforcing agent is one or a mixture of more of carbon black, white carbon black, argil, kaolin, calcium carbonate or short fibers;

the high-fluidity polymer is one of polyolefin homopolymer or polyolefin copolymer;

the chemical foaming agent is one or a mixture of more of N, N' -dinitrosopentamethylenetetramine, azodicarbonamide, azodiisobutyronitrile, benzenesulfonyl hydrazide, p-diphenylsulfonyl hydrazide, sodium bicarbonate, ammonium bicarbonate or sodium citrate;

the water-soluble substance is one of water-soluble organic substance or water-soluble inorganic substance.

3. The novel breathable waterproof composite material according to claim 1, characterized in that the preparation method of the novel breathable waterproof composite material comprises the following steps:

step 1: blending rubber, a vulcanizing agent, an accelerator, an anti-aging agent and a reinforcing agent to obtain a rubber matrix material;

step 2: adding a chemical foaming agent and a water-soluble substance into the high-fluidity polymer and uniformly mixing to obtain a pore-forming polymer composite material;

and step 3: mixing the base material obtained in the step 1 with the pore-forming polymer composite material obtained in the step 2, and mixing to prepare a rubber compound with a continuous phase structure to obtain a rubber/high-fluidity polymer alloy material;

and 4, step 4: and vulcanizing and forming holes in the rubber/high-fluidity polymer composite material to obtain the novel breathable waterproof rubber composite material with a continuous channel structure.

4. The novel breathable waterproof composite material as claimed in claim 3, wherein in the step 3, the mixing comprises the steps of open mixing or banburying at 60-80 ℃ and screw extrusion at 160-200 ℃; the continuous phase structure is a microstructure of continuous uniform phase existing in the mixed composite material of the rubber and the high-fluidity polymer.

5. The novel breathable waterproof composite material according to claim 3, characterized in that the vulcanization temperature is 140-200 ℃, the vulcanization pressure is 10-50 MPa, and the vulcanization time is 0.02-10 h.

6. The preparation method of the novel breathable waterproof composite material is characterized by comprising the following steps of:

step 1: blending rubber, a vulcanizing agent, an accelerator, an anti-aging agent and a reinforcing agent to obtain a rubber matrix material;

step 2: adding a chemical foaming agent and a water-soluble substance into the high-fluidity polymer and uniformly mixing to obtain a pore-forming polymer composite material;

and step 3: mixing the base material obtained in the step 1 with the pore-forming polymer composite material obtained in the step 2, and mixing to prepare a rubber compound with a continuous phase structure to obtain a rubber/high-fluidity polymer alloy material;

and 4, step 4: and vulcanizing and forming holes in the rubber/high-fluidity polymer composite material to obtain the novel breathable waterproof rubber composite material with a continuous channel structure.

7. The production method according to claim 6,

the rubber is one of nonpolar rubber or polar rubber, and the filler content of the rubber is 80-120 parts;

the vulcanizing agent is one or a mixture of more of sulfur, polysulfide, peroxide, metal oxide or phenolic resin, and the addition amount of the vulcanizing agent is 0.5-10 parts;

the accelerator is one or a mixture of several of thiuram, thiazole, sulfenamide, dithiocarbamate or guanidine, and the addition amount of the accelerator is 0.01-5 parts;

the anti-aging agent is one or a mixture of more of diphenylamine, p-phenylenediamine, phenol, organic sulfide or phosphite ester, and the addition amount of the anti-aging agent is 0.5-5 parts;

the reinforcing agent is one or a mixture of more of carbon black, white carbon black, argil, kaolin, calcium carbonate or short fibers, and the addition amount of the reinforcing agent is 10-80 parts;

the high-fluidity polymer is one of polyolefin homopolymer or polyolefin copolymer, and the weight is 80-120 parts;

the chemical foaming agent is one or a mixture of more of N, N' -dinitrosopentamethylenetetramine, azodicarbonamide, azodiisobutyronitrile, benzenesulfonyl hydrazide, p-diphenylsulfonyl hydrazide, sodium bicarbonate, ammonium bicarbonate or sodium citrate, and the addition amount of the chemical foaming agent is 1-20 parts;

the water-soluble substance is water-soluble organic substance or water-soluble inorganic substance, and the amount of the water-soluble blood substance is 5-50 parts.

8. The novel breathable waterproof composite material as claimed in claim 6, wherein in the step 3, the mixing comprises the steps of open mixing or banburying at 60-80 ℃ and screw extrusion at 160-200 ℃; the continuous phase structure is a microstructure of continuous uniform phase existing in the mixed composite material of the rubber and the high-fluidity polymer.

9. The novel breathable waterproof composite material according to claim 6, characterized in that the vulcanization temperature is 140-200 ℃, the vulcanization pressure is 10-50 MPa, and the vulcanization time is 0.02-10 h.

Technical Field

The invention relates to the technical field of functional polymer composite materials, in particular to a novel breathable waterproof rubber composite material and a preparation method thereof.

Background

The common rubber product has air tightness, so that moisture can not be discharged in the wearing occasion of a human body, even bacteria can be bred, and the use comfort is seriously influenced. Through the selection of raw materials for rubber formula and the design of a moisture permeation passage, certain moisture permeation and surface waterproof properties can be endowed to the rubber product. In the prior documents related to the breathable rubber and products thereof, most of the breathable rubber can only realize the functions of ventilation and water resistance by arranging mechanical holes and bonding gaps; the other part is additionally provided with a waterproof breathable film, which is not body type breathable waterproof rubber. In order to solve the contradiction between the air permeability and the mechanical property of the body type breathable waterproof rubber, the invention adopts a method of blending rubber and high-fluidity polymer to enable the latter to form a microcosmic continuous phase, and forms continuous through holes which can transmit water vapor but not liquid water by virtue of pore-forming materials in the high-fluidity polymer, thereby preparing the novel breathable waterproof rubber composite material with good air permeability and waterproof property.

Disclosure of Invention

Aiming at the problems and defects in the prior art, the invention aims to provide a novel breathable waterproof rubber composite material and a preparation method thereof to solve the problems in the prior art.

In order to achieve the purpose, the invention provides a novel breathable waterproof composite material, which is prepared from the following raw materials: 80-120 parts of rubber, 0.5-10 parts of vulcanizing agent, 0.01-5 parts of accelerator, 0.5-5 parts of anti-aging agent, 10-80 parts of reinforcing agent, 80-120 parts of high-fluidity polymer, 1-20 parts of chemical foaming agent and 5-50 parts of water-soluble substance.

Preferably, the rubber is one of a non-polar rubber or a polar rubber;

the vulcanizing agent is one or a mixture of sulfur, polysulfide, peroxide, metal oxide or phenolic resin;

the accelerator is one or a mixture of thiuram, thiazole, sulfenamide, dithiocarbamate or guanidine;

the anti-aging agent is one or a mixture of more of diphenylamine, p-phenylenediamine, phenol, organic sulfide or phosphite ester;

the reinforcing agent is one or a mixture of more of carbon black, white carbon black, argil, kaolin, calcium carbonate or short fibers;

the high-fluidity polymer is one of polyolefin homopolymer or polyolefin copolymer;

the chemical foaming agent is one or a mixture of more of N, N' -dinitrosopentamethylenetetramine, azodicarbonamide, azodiisobutyronitrile, benzenesulfonyl hydrazide, p-diphenylsulfonyl hydrazide, sodium bicarbonate, ammonium bicarbonate or sodium citrate;

the water-soluble substance is one of water-soluble organic substance or water-soluble inorganic substance.

Preferably, the preparation method of the novel breathable waterproof composite material comprises the following steps:

step 1: blending rubber, a vulcanizing agent, an accelerator, an anti-aging agent and a reinforcing agent to obtain a rubber matrix material;

step 2: adding a chemical foaming agent and a water-soluble substance into the high-fluidity polymer and uniformly mixing to obtain a pore-forming polymer composite material;

and step 3: mixing the base material obtained in the step 1 with the pore-forming polymer composite material obtained in the step 2, and mixing to prepare a rubber compound with a continuous phase structure to obtain a rubber/high-fluidity polymer alloy material;

and 4, step 4: and vulcanizing and forming holes in the rubber/high-fluidity polymer composite material to obtain the novel breathable waterproof rubber composite material with a continuous channel structure.

Preferably, in the step 3, the mixing comprises the steps of open mixing or banburying at 60-80 ℃ and screw extrusion at 160-200 ℃; the continuous phase structure is a microstructure of continuous uniform phase existing in the mixed composite material of the rubber and the high-fluidity polymer.

Preferably, the vulcanization temperature is 140-200 ℃, the vulcanization pressure is 10-50 MPa, and the vulcanization time is 0.02-10 h.

Secondly, the invention provides a preparation method of the novel breathable waterproof composite material, which comprises the following steps:

step 1: blending rubber, a vulcanizing agent, an accelerator, an anti-aging agent and a reinforcing agent to obtain a rubber matrix material;

step 2: adding a chemical foaming agent and a water-soluble substance into the high-fluidity polymer and uniformly mixing to obtain a pore-forming polymer composite material;

and step 3: mixing the base material obtained in the step 1 with the pore-forming polymer composite material obtained in the step 2, and mixing to prepare a rubber compound with a continuous phase structure to obtain a rubber/high-fluidity polymer alloy material;

and 4, step 4: and vulcanizing and forming holes in the rubber/high-fluidity polymer composite material to obtain the novel breathable waterproof rubber composite material with a continuous channel structure.

Preferably, the first and second electrodes are formed of a metal,

the rubber is one of nonpolar rubber or polar rubber, and the filler content of the rubber is 80-120 parts;

the vulcanizing agent is one or a mixture of more of sulfur, polysulfide, peroxide, metal oxide or phenolic resin, and the addition amount of the vulcanizing agent is 0.5-10 parts;

the accelerator is one or a mixture of several of thiuram, thiazole, sulfenamide, dithiocarbamate or guanidine, and the addition amount of the accelerator is 0.01-5 parts;

the anti-aging agent is one or a mixture of more of diphenylamine, p-phenylenediamine, phenol, organic sulfide or phosphite ester, and the addition amount of the anti-aging agent is 0.5-5 parts;

the reinforcing agent is one or a mixture of more of carbon black, white carbon black, argil, kaolin, calcium carbonate or short fibers, and the addition amount of the reinforcing agent is 10-80 parts;

the high-fluidity polymer is one of polyolefin homopolymer or polyolefin copolymer, and the weight is 80-120 parts;

the chemical foaming agent is one or a mixture of more of N, N' -dinitrosopentamethylenetetramine, azodicarbonamide, azodiisobutyronitrile, benzenesulfonyl hydrazide, p-diphenylsulfonyl hydrazide, sodium bicarbonate, ammonium bicarbonate or sodium citrate, and the addition amount of the chemical foaming agent is 1-20 parts;

the water-soluble substance is water-soluble organic substance or water-soluble inorganic substance, and the amount of the water-soluble blood substance is 5-50 parts.

Preferably, in the step 3, the mixing comprises the steps of open mixing or banburying at 60-80 ℃ and screw extrusion at 160-200 ℃; the continuous phase structure is a microstructure of continuous uniform phase existing in the mixed composite material of the rubber and the high-fluidity polymer.

9. The novel breathable waterproof composite material according to claim 6, characterized in that the vulcanization temperature is 140-200 ℃, the vulcanization pressure is 10-50 MPa, and the vulcanization time is 0.02-10 h.

The invention has the beneficial effects that:

1. the rubber composite material prepared by the invention has excellent air permeability;

2. the rubber composite material prepared by the invention has good waterproof performance;

3. the rubber composite material prepared by the invention adopts a regulation and control method of a micro continuous phase structure of a high polymer blending material, and the prepared rubber composite material has good comprehensive properties such as air permeability, water resistance, mechanical property and the like;

4. the rubber composite material prepared by the invention can be applied to the breathable and waterproof fields of waterproof cloth, rubber boots, protective clothing, diving suits and the like.

Detailed Description

In order to clearly illustrate the technical features of the present solution, the present solution is explained below by way of specific embodiments. However, the embodiment of the present invention is not limited thereto, and conventional conditions are referred to for parameters not particularly mentioned.

Example 1

The embodiment provides a novel breathable waterproof natural rubber/high styrene rubber composite material and a preparation method thereof, and the preparation method comprises the following steps:

(1) blending 80 parts of natural rubber, 5 parts of sulfur, 0.5 part of polysulfide, 0.01 part of thiuram, 1.0 part of thiazole, 5 parts of zinc oxide, 2 parts of stearic acid, 0.5 part of diphenylamine, 5 parts of phenol, 10 parts of carbon black and 80 parts of argil to obtain a natural rubber base material;

(2) adding 1 part of N, N' -dinitrosopentamethylenetetramine, 20 parts of sodium bicarbonate, 1 part of zinc oxide and 1 part of stearic acid into 80 parts of polyolefin copolymer high styrene rubber, and uniformly mixing to obtain pore-forming high styrene rubber;

(3) mixing a natural rubber base material and pore-forming high styrene rubber according to the weight ratio of 80: mixing the raw materials in a mass ratio of 20, and extruding the mixture by a screw at a temperature of 200 ℃ to prepare the natural rubber alloy material containing the microcosmic continuous high styrene phase structure.

(4) And vulcanizing and shaping the natural rubber/high styrene alloy material for 0.02h at 140 ℃ and 50MPa, and decomposing a chemical foaming agent into holes to obtain the novel breathable waterproof natural rubber/high styrene rubber composite material with a continuous channel structure.

Example 2

The embodiment provides a novel breathable waterproof styrene-butadiene rubber/ethylene-octene copolymer composite material and a preparation method thereof, and the preparation method comprises the following steps:

(1) blending 120 parts of styrene-butadiene rubber, 1 part of sulfur, 10 parts of cross-linked phenolic resin, 0.02 part of dithiocarbamate, 1 part of sulfenamide, 5 parts of guanidine, 3 parts of zinc oxide, 1 part of stearic acid, 1.0 part of p-phenylenediamine, 5 parts of organic sulfide anti-aging agent, 30 parts of white carbon black and 80 parts of calcium carbonate to obtain a styrene-butadiene rubber matrix material;

(2) adding 2 parts of azodicarbonamide, 10 parts of ammonium bicarbonate, 10 parts of sodium chloride and 10 parts of cane sugar into 120 parts of polyolefin copolymer ethylene-octene copolymer (POE) and uniformly mixing to obtain POE capable of forming holes;

(3) mixing a styrene butadiene rubber base material and POE (polyolefin elastomer) capable of forming holes according to the proportion of 85: 15, and preparing the styrene butadiene rubber alloy material containing the microcosmic continuous POE phase structure by open milling at 80 ℃ and extruding by a screw at 160 ℃.

(4) And vulcanizing and shaping the styrene butadiene rubber/POE alloy material for 0.25h at 160 ℃ and 10MPa, decomposing a chemical foaming agent into holes, soaking in water, and removing sodium chloride and cane sugar to obtain the novel breathable waterproof styrene butadiene rubber/ethylene-octene copolymer composite material with a continuous channel structure.

Example 3

The embodiment provides a novel breathable waterproof chloroprene rubber/phenolic resin composite material and a preparation method thereof, and the preparation method comprises the following steps:

(1) 100 parts of chloroprene rubber, 5 parts of zinc oxide, 4 parts of magnesium oxide, 1 part of thiazole, 1 part of dithiocarbamate, 1 part of stearic acid, 1 part of phosphite ester, 10 parts of kaolin and 10 parts of nylon short fiber are blended to obtain a chloroprene rubber matrix material;

(2) adding 3 parts of azobisisobutyronitrile, 5 parts of benzenesulfonyl hydrazide, 10 parts of sodium citrate and 10 parts of polyoxyethylene into 100 parts of reinforced phenolic resin, and uniformly mixing to obtain pore-forming phenolic resin;

(3) mixing chloroprene rubber base material and pore-forming phenolic resin according to the ratio of 88: mixing the materials according to the mass ratio of 12, banburying at 80 ℃ and extruding by a screw rod at 160 ℃ to prepare the chloroprene rubber alloy material containing the microcosmic continuous phenolic resin phase structure.

(4) And vulcanizing and shaping the chloroprene rubber/phenolic resin alloy material for 0.5h at 160 ℃ and 20MPa, decomposing a chemical foaming agent into pores, soaking in water, and removing polyoxyethylene to obtain the novel breathable waterproof chloroprene rubber composite material with a continuous channel structure.

Example 4

The embodiment provides a novel breathable waterproof silicone rubber/thermoplastic polyurethane composite material and a preparation method thereof, and the preparation method comprises the following steps:

(1) 100 parts of silicon rubber, 0.4 part of dicumyl peroxide, 2 parts of diphenyl silanediol, 5 parts of iron oxide red and 40 parts of white carbon black are blended to obtain a silicon rubber base material;

(2) adding 3 parts of p-diphenyl sulfonyl hydrazide and 10 parts of sodium citrate into 100 parts of thermoplastic polyurethane elastomer (TPU), and uniformly mixing to obtain a pore-forming TPU material;

(3) mixing a silicon rubber base material and a pore-forming TPU material according to the ratio of 90: mixing the materials according to the mass ratio of 10, banburying at 160 ℃ and extruding by a screw rod at 200 ℃ to prepare the silicone rubber alloy material containing the microcosmic continuous TPU phase structure.

(4) And curing the silicon rubber/TPU alloy material for 0.2h at 200 ℃ and 15MPa, decomposing a chemical foaming agent into pores, and then performing cold pressing and shaping to obtain the novel breathable waterproof silicon rubber/thermoplastic polyurethane composite material with the continuous channel structure.

Comparative example 1:

comparative example 1 differs from example 1 only in that: the natural rubber/high styrene alloy material does not contain pore-forming materials of N, N' -dinitrosopentamethylenetetramine and sodium bicarbonate.

Comparative example 2:

comparative example 2 differs from example 2 only in that: the styrene butadiene rubber/POE alloy material does not contain pore-forming materials such as azodicarbonamide, ammonium bicarbonate, sodium chloride and cane sugar.

Comparative example 3:

comparative example 3 differs from example 3 only in that: the chloroprene rubber/phenolic resin alloy material does not contain pore-forming materials of azodiisobutyronitrile, benzenesulfonyl hydrazide, sodium citrate and polyoxyethylene.

Comparative example 4:

comparative example 4 differs from example 4 only in that: the silicon rubber/TPU alloy material does not contain pore-forming material pairs, p-diphenylsulfonyl hydrazide and sodium citrate.

Experimental methods

(1) Mixing by an open mill: opening the open mill, and controlling the temperature of the surface of the roller to be 60-200 ℃; adding high-fluidity polymer and pore-forming material, and wrapping the roller; adding the mixed rubber base material in proportion, and cutting the mixture three times respectively by using a left cutter and a right cutter; thin passing for 6 times with small roll spacing; and (5) increasing the roller distance according to the thickness of the die and the product, and then discharging and cooling for later use.

(2) Mixing by an internal mixer: opening an internal mixer, controlling the temperature of an internal mixing chamber to be 60-200 ℃ and controlling the rotating speed to be 20-120 r/min; adding the mixed high-fluidity polymer and pore-forming material mixture, pressing down the upper top plug, and mixing for 1 min; and opening the upper top bolt, adding the mixed rubber base material in proportion, pressing the upper top bolt, mixing until the torque is stable, discharging the rubber, and standing for 24 hours for later use.

(3) Screw extrusion: opening the extruder, controlling the temperature of the charging barrel at 60-200 ℃ and the rotating speed at 20-120 r/min; adding the mixed rubber/high-fluidity polymer composite material, mixing until the torque is stable, discharging the rubber, and standing for 24 hours for later use.

(4) And (3) sheet discharging of an open mill: and (3) adding the uniformly mixed rubber compound to an open mill, adjusting the roller spacing according to the thickness of the die and the product, and discharging and cooling for later use.

(5) And (3) vulcanization and pore forming: after standing for 2h, testing a vulcanization characteristic curve and positive process vulcanization time by using a vulcanization instrument; vulcanizing a sample by using a flat vulcanizing machine, and selecting vulcanization pressure; setting the vulcanization temperature and the vulcanization time according to the result of the vulcanization instrument; standing the vulcanized sample for 12 hours for later use.

(6) Dissolving out to form a hole: and (3) placing the vulcanized sample containing the water-soluble material into a container filled with water for soaking, changing water once every 2h, taking out after pore forming is stable, and drying for later use.

(7) And (3) performance testing: measuring the wetting property of the sample by using a contact angle measuring instrument, wherein the volume of distilled water drops is 5 mu L, and each sample selects 5 different positions to measure and take an average value; according to GB/T12704-2009, adding 34ml of distilled water into a moisture permeable cup with an inner diameter of 60mm and a depth of 22mm, enabling the distance between the water surface and a sample to be about 10mm, then fully sealing, measuring the mass (accurate to 0.001 g) after balancing for 1h, 2h and the like, and calculating the moisture permeability according to the mass reduction value, the sample area and the test time; the tensile property is tested by an electronic tensile machine according to GB/T528-2009, the sample is a dumbbell-shaped test sample with the thickness of about 2mm and the width of 4mm, and the tensile rate is 500 mm/min.

TABLE 1 Properties of examples 1, 2, 3, 4 and comparative examples 1, 2, 3, 4

Sample (I)	Example 1	Comparative example 1	Example 2	Comparative example 2
					Water contact angle/° c	116.5	114.3	113.7	112.2
Water vapor permeability/(g/m)2d）	0.097	0	0.116	0
					Tensile strength/MPa	12.7	14.5	11.7	12.8
Tear Strength/(N/mm)	37.3	45.1	36.2	43.8
					Sample (I)	Example 3	Comparative example 3	Example 4	Comparative example 4
Water contact angle/° c	115.0	114.1	122.7	122.0
					Water vapor permeability/(g/m)2d）	0.106	0	0.122	0
Tensile strength/MPa	11.1	13.1	11.0	13.1
					Tear Strength/(N/mm)	34.1	39.4	33.5	37.7