CN108752670A - A kind of rubber plastic blend expanded material and preparation method thereof - Google Patents
A kind of rubber plastic blend expanded material and preparation method thereof Download PDFInfo
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- CN108752670A CN108752670A CN201810547503.9A CN201810547503A CN108752670A CN 108752670 A CN108752670 A CN 108752670A CN 201810547503 A CN201810547503 A CN 201810547503A CN 108752670 A CN108752670 A CN 108752670A
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Abstract
The invention belongs to technical field of polymer materials, and in particular to a kind of rubber plastic blend expanded material and preparation method thereof.Include the component of following parts by weight：25-35 parts of rubber plastic blend material, 5-8 parts of foaming agent, 0.05-0.3 parts of vulcanizing agent, 1.5-1.8 parts of accelerating agent, 25-35 parts of filler, 5-8 parts of carbon black, 0.5-1 parts of paraffin, 15-20 parts of chlorinated paraffin, 0.1-0.2 parts of stearic acid, 1-2 parts of epoxidized soybean oil, 0.3-0.5 parts of zinc oxide, 0.5-1 parts of polyethylene glycol, 0.1-0.5 parts of anti-aging agent.The present invention is selected by the proportion optimizing of component, in gained rubber plastic blend expanded material, chloride ion content < 400ppm, after wrapping up copper pipe, it can be in temperature 60 C, in the environment of humidity 95% ± 3%, 240 hours are lasted, the copper pipe color of the color of copper pipe close to no package rubber plastic blend expanded material.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of rubber plastic blend expanded material and its preparation side
Method.
Background technology
Rubber expanded material has the excellent properties such as light, material province, sound insulation, damping, specific strength height, with the matrix not foamed
Material is compared, and various aspects of performance all improves a lot, and if impact strength is than unexpanded preceding 6-7 times of improve, toughness can be improved 4
Times, fatigue life can extend 5 times, and can be by modified be made with different particularity such as being blended, filling, enhance to it
The rubber expanded material of energy meets the needs of various different purposes.
Nitrile rubber is by butadiene and acrylonitrile through a kind of synthetic rubber made from emulsion polymerization, abbreviation NBR.Butyronitrile
Rubber mainly uses emulsion polymerization at low temperature to produce, and chemical property is stablized, and processing performance is good；Oil resistivity is fabulous, wearability compared with
Height, heat resistance are preferable；Also there is good water resistance, air-tightness and excellent adhesive property.But the polarity of nitrile rubber is non-
Chang Qiang, it is generally not so good with the compatibility of other polymer, to improve processability and performance, nitrile rubber also often with naturally
The non-polar rubbers such as rubber, butadiene-styrene rubber, butadiene rubber are used in combination.
Currently, the expanded material of nitrile rubber is substantially the expanded material of NBR/PVC rubber plastic blends, NBR/PVC rubber and plastics
Expanded material is typically employed in the packaging of electric appliance, sole, movement handle, pipeline heat insulation performance etc..NBR/PVC rubber plastic blends
There is expanded material flexibility, flexible foam insulating product to have light, soft, heat-resisting, fire-retardant, corrosion-resistant, at low cost, efficient
The features such as, foreground is had a vast market, is the much-talked-about topic studied at present.
For example, Chinese patent literature CN107200879A, discloses a kind of nitrile rubber microcellular foam material, formula is such as
Under：Formula includes 100 parts of nitrile rubber blend composition, 0-4 parts of Ca/Zn stabilizers, 0-200 parts of filler, 0-50 parts of plasticizer, vulcanization
0.6-5 parts of agent；0.5-6 parts of vulcanization accelerator, 2-5 parts of antioxidant 4010.Wherein, nitrile rubber blend composition includes nitrile rubber
50-100 parts, 0-50 parts of polyvinyl chloride；Filler is one or more in carbon black, white carbon, calcium carbonate, kaolin, staple fiber；
Plasticizer is one or more in aromatic naphtha, paraffin oil, dioctyl phthalate, and vulcanizing agent is that sulphur or peroxidating two are different
One kind in propyl benzene, it is one or more in vulcanization accelerator DM, TMTD, TAIC, CBS, HVA-2, it is also wrapped in the formula
Activator is included, described activator 3-15 parts, the activator is zinc oxide, and stearic acid is used in combination.The rubber that the patent document provides
Expanded material is compared with traditional foaming product, and the uniform foam cell of expanded material obtained by the present invention is controllable, and mechanical property is preferable,
Stable quality, and asepsis environment-protecting can be used in high-grade product, can be used as car engine vibration-absorptive material, sealing material, foaming ground cushion
Etc. various fields.
But the nitrile rubber microcellular foam material provided in above patent document, use when, have chlorion analysis
Go out, when as heat preservation cold insulation technical field, be often wrapped in outside copper pipe and carry out heat preservation cold insulation, use a period of time
After cause copper pipe to be corroded blackening, influence the service life of pipeline.
Invention content
Therefore, the technical problem to be solved in the present invention is to overcome chlorion in rubber plastic blend expanded material in the prior art
Be precipitated and free sulphur existing for defect, to provide a kind of rubber plastic blend expanded material and preparation method thereof.
In order to solve the above technical problems, the application adopts the following technical scheme that：
A kind of rubber plastic blend expanded material, includes the component of following parts by weight：
25-35 parts of rubber plastic blend material, 5-8 parts of foaming agent, 0.05-0.3 parts of vulcanizing agent, 1.5-1.8 parts of accelerating agent, filler
25-35 parts, 5-8 parts of carbon black, 0.5-1 parts of paraffin, 15-20 parts of chlorinated paraffin, 0.1-0.2 parts of stearic acid, 1-2 parts of epoxidized soybean oil,
0.3-0.5 parts of zinc oxide, 0.5-1 parts of polyethylene glycol, 0.1-0.5 parts of anti-aging agent.
Preferably, include the component of following parts by weight：
28-32 parts of rubber plastic blend material, 6-7 parts of foaming agent, 0.15-0.25 parts of vulcanizing agent, 1.6 parts of accelerating agent, filler 28-32
Part, 6-7 parts of carbon black, 0.6-0.8 parts of paraffin, 16-18 parts of chlorinated paraffin, 0.12-0.18 parts of stearic acid, epoxidized soybean oil 1.2-1.6
Part, 0.35-0.45 parts of zinc oxide, 0.6-0.8 parts of polyethylene glycol, 0.2-0.4 parts of anti-aging agent.
Further, the rubber plastic blend material is the mixture of nitrile rubber and polyvinyl chloride,
Wherein, the mass ratio of nitrile rubber and polyvinyl chloride is 2-5:1.
Further, the vulcanizing agent is sulfurless vulcanizing agent,
Preferably, the sulfurless vulcanizing agent is N, penylene bismaleimide or 4 between N'-, 4 '-dithio morpholines.
Further, the foaming agent is AC foaming agents；
And/or the filler is talcum powder, at least one of aluminium hydroxide；
And/or the accelerating agent is dimethyl dithiocarbamate class or thuriam acceserator.
Further, the anti-aging agent is 2-mercaptobenzimidazole, at least one in N, N'- bis- (betanaphthyl) p-phenylenediamine
Kind.
A kind of preparation method of above-mentioned rubber plastic blend expanded material, includes the following steps：
It is kneaded：By rubber plastic blend material, foaming agent, filler, carbon black, stearic acid, polyethylene glycol, paraffin, anti-aging agent, chlorination stone
Wax and epoxidized soybean oil are mixed by formula ratio, after high-temperature mixing, are processed into film；
Freshening：After above-mentioned film is stored 18-30 hours, accelerating agent, zinc oxide and vulcanizing agent is added, carries out secondary multiple
Refining, is processed into adhesive tape；
Foaming：After above-mentioned adhesive tape extrusion molding, step up cure foaming processing is carried out.
Further, the mixing step is：
Rubber plastic blend material is mixed with chlorinated paraffin and epoxidized soybean oil by formula ratio, rubber plastic blend material is pre-processed,
Pretreated condition is to handle 4-5min at 90-100 DEG C；
Then it is mixed with foaming agent, filler, carbon black, stearic acid, polyethylene glycol, paraffin, anti-aging agent, after high-temperature mixing,
It is processed into film.
Further, the step up cure foaming treatment conditions are：It is carried out at sulfur foam molding by eight sections
Reason, the temperature of eight section are followed successively by 125-130 DEG C, 132-137 DEG C, 138-143 DEG C, 145-150 DEG C, 151-156 DEG C,
157-162 DEG C, 163-165 DEG C, 165-165 DEG C.Preferably, the time of step up cure foaming is 20-30min.
Further, the condition of the mixing is：155-165 DEG C of temperature, time 12-15 minute；
And/or the condition of the freshening is：45-50 DEG C of temperature, time 3-5 minute.
Technical solution of the present invention has the following advantages that：
1. rubber plastic blend expanded material provided by the invention, includes the component of following parts by weight：Rubber plastic blend material 25-35
Part, 5-8 parts of foaming agent, 0.05-0.3 parts of vulcanizing agent, 1.5-1.8 parts of accelerating agent, 25-35 parts of filler, 5-8 parts of carbon black, paraffin
0.5-1 parts, 15-20 parts of chlorinated paraffin, 0.1-0.2 parts of stearic acid, 1-2 parts of epoxidized soybean oil, 0.3-0.5 parts of zinc oxide, poly- second two
0.5-1 parts of alcohol, 0.1-0.5 parts of anti-aging agent.Inventive formulation is easy without using chlorine vinegar, haloflex, chliorinated polyvinyl chloride etc.
The raw material of chlorion are precipitated, reduce chloride ion content in product；Chlorinated paraffin and epoxidized soybean oil are used in combination, can be to greatest extent
Inhibition chlorion precipitation, filler and carbon black being capable of enhanced article hardness and anti-flammabilitys；Polyethylene glycol and paraffin play sizing material
Lubricating action；Stearic acid and zinc oxide are sulfur foam activating agents, promote the formation of foaming.The present invention is matched by the optimization of component
Than selecting, in gained rubber plastic blend expanded material, chloride ion content < 400ppm can be in temperature 60 C, humidity after wrapping up copper pipe
In 95% ± 3% environment, 240 hours are lasted, the copper pipe color of the color of copper pipe close to no rubber-plastic foamed product of package.
2. rubber plastic blend expanded material provided by the invention, the rubber plastic blend material is the mixed of nitrile rubber and polyvinyl chloride
Close material, wherein the mass ratio of nitrile rubber and polyvinyl chloride is 2-5:1.The present invention by the ratio optimization to rubber plastic blend material,
The oil resistivity of rubber plastic blend expanded material can be obviously improved.
3. rubber plastic blend expanded material provided by the invention, vulcanizing agent are sulfurless vulcanizing agent, it is preferred that the nonsulfur vulcanization
Agent is N, penylene bismaleimide or 4 between N'-, 4 '-dithio morpholines.Pass through the selection of vulcanizing agent so that institute of the present invention
It obtains in rubber plastic blend expanded material without free sulphur.
4. rubber plastic blend expanded material provided by the invention, the anti-aging agent is 2-mercaptobenzimidazole, bis- (β-of N, N'-
At least one of naphthalene) p-phenylenediamine.The selection of anti-aging agent can further control the content of free chloro ion, meanwhile,
It can also inhibit the corrosion of copper pipe when use.
5. the preparation method of rubber plastic blend expanded material provided by the invention, including be kneaded：By rubber plastic blend material, foaming
Agent, filler, carbon black, stearic acid, polyethylene glycol, paraffin, anti-aging agent, chlorinated paraffin and epoxidized soybean oil are mixed by formula ratio, through height
After temperature is kneaded, it is processed into film；Freshening：After above-mentioned film is stored 18-30 hours, accelerating agent, zinc oxide and vulcanizing agent is added,
Secondary freshening is carried out, adhesive tape is processed into；Foaming：After above-mentioned adhesive tape extrusion molding, step up cure foaming processing is carried out.This
Invention can make product full cure foam by adjusting technique and foaming method.
6. the preparation method of rubber plastic blend expanded material provided by the invention, the mixing step are：
Rubber plastic blend material is mixed with chlorinated paraffin and epoxidized soybean oil by formula ratio, rubber plastic blend material is pre-processed,
Pretreated condition is to handle 4-5min at 90-100 DEG C；Then with foaming agent, filler, carbon black, stearic acid, polyethylene glycol,
Paraffin, anti-aging agent mixing, after high-temperature mixing, are processed into film.By first by rubber plastic blend material and chlorinated paraffin and epoxy beans
Oil mixing pretreatment, can further decrease the chloride ion content of gained rubber plastic blend foamed products.
7. the preparation method of rubber plastic blend expanded material provided by the invention, the step up cure foaming processing passes through
Eight sections carry out sulfur foam forming processes, and the temperature of eight section is followed successively by 125-130 DEG C, 132-137 DEG C, 138-143
DEG C, 145-150 DEG C, 151-156 DEG C, 157-162 DEG C, 163-165 DEG C, 165-165 DEG C.The present invention passes through to the excellent of foaming condition
Change selection, can also further decrease the chloride ion content of gained rubber plastic blend foamed products.
Specific implementation mode
In order to better understand the present invention, with reference to embodiment, the present invention is described in further detail.But this
The protection domain of invention is not limited to the range that embodiment is stated.Experimental method described in following embodiment and comparative examples,
Unless otherwise specified, it is conventional method；The reagent and material commercially obtain unless otherwise specified.
1 part in the embodiment of the present invention and comparative example corresponds to 1kg.
Embodiment 1
The present embodiment provides a kind of rubber plastic blend expanded materials, including following component：Rubber plastic blend material (nitrile rubber
22.5kg, polyvinyl chloride 2.5kg) 25 parts, 8 parts of AC foaming agents, 0.05 part of sulphur, accelerating agent (dimethyl dithiocarbamic acid
Sodium) 1.8 parts, 25 parts of filler (talcum powder), 8 parts of carbon black, 0.5 part of paraffin, 20 parts of chlorinated paraffin, 0.1 part of stearic acid, epoxidized soybean oil
2 parts, 0.3 part of zinc oxide, 1 part of polyethylene glycol, 124 0.1 parts of anti-aging agent.
Preparation method is：By rubber plastic blend material, foaming agent, filler, carbon black, stearic acid, polyethylene glycol, paraffin, prevent always
Agent, chlorinated paraffin and epoxidized soybean oil mix according to the above ratio, are plasticized and are mixed by mixer high temperature, and temperature is 165 DEG C, at plasticizing
Reason 12 minutes, is subsequently processed into the film for being about 1 centimetre for thickness.
After above-mentioned film is stored 18 hours, accelerating agent, zinc oxide and vulcanizing agent is added, in the secondary freshening of open mill, freshening
Condition is 50 DEG C, and 5 minutes time, it is about 12 centimetres to be subsequently processed into width, and thickness is about 1 centimetre of adhesive tape.
After above-mentioned adhesive tape is by vulcameter detection normally, single screw extrusion machine is fed, baking oven vulcanization is sent into after extrusion molding
Foaming.
The baking oven sulfur foam is, sulfur foam molding is carried out by 8 section baking ovens, foamed time 20min, described
Baking oven (preceding 7th area) temperature is trapezoidal incremental, and eight zone temperatures of the baking oven are 125-130 DEG C, 132-137 DEG C, 138-143
℃、145-150℃、151-156℃、157-162℃、163-165℃、165-165℃。
Embodiment 2
The present embodiment provides a kind of rubber plastic blend expanded materials, including following component：Rubber plastic blend material (nitrile rubber
12.5kg, polyvinyl chloride 12.5kg) 35 parts, 5 parts of AC foaming agents, 0.3 part of sulphur, 1.5 parts of accelerating agent (thuriam acceserator),
35 parts of filler (aluminium hydroxide), 5 parts of carbon black, 1 part of paraffin, 15 parts of chlorinated paraffin, 0.2 part of stearic acid, 1 part of epoxidized soybean oil, oxidation
0.5 part of zinc, 0.5 part of polyethylene glycol, 124 0.5 parts of anti-aging agent.
Preparation method is：By rubber plastic blend material, foaming agent, filler, carbon black, stearic acid, polyethylene glycol, paraffin, prevent always
Agent, chlorinated paraffin and epoxidized soybean oil mix according to the above ratio, are plasticized and are mixed by mixer high temperature, and temperature is 155 DEG C, at plasticizing
Reason 15 minutes, is subsequently processed into the film for being about 1 centimetre for thickness.
After above-mentioned film is stored 30 hours, accelerating agent, zinc oxide and vulcanizing agent is added, in the secondary freshening of open mill, freshening
Condition is 45 DEG C, and 5 minutes time, it is about 12 centimetres to be processed into width, and thickness is about 1 centimetre of adhesive tape.
After above-mentioned adhesive tape is by vulcameter detection normally, single screw extrusion machine is fed, baking oven vulcanization is sent into after extrusion molding
Foaming.
The baking oven sulfur foam is, sulfur foam molding is carried out by 8 section baking ovens, foamed time 30min, described
Baking oven (preceding 7th area) temperature is trapezoidal incremental, and eight zone temperatures of the baking oven are 125-130 DEG C, 132-137 DEG C, 138-143
℃、145-150℃、151-156℃、157-162℃、163-165℃、165-165℃。
Embodiment 3
The present embodiment provides a kind of rubber plastic blend expanded materials, including following component：Rubber plastic blend material (nitrile rubber
23kg, polyvinyl chloride 2kg) 30 parts, 7 parts of AC foaming agents, 0.2 part of sulphur, accelerating agent (dimethyl dithiocarbamic acid ammonium) 1.6
Part, 30 parts of filler (talcum powder), 6 parts of carbon black, 0.8 part of paraffin, 17 parts of chlorinated paraffin, 0.15 part of stearic acid, epoxidized soybean oil 1.5
Part, 0.4 part of zinc oxide, 0.6 part of polyethylene glycol, 124 0.3 parts of anti-aging agent.
Preparation method is：By rubber plastic blend material, foaming agent, filler, carbon black, stearic acid, polyethylene glycol, paraffin, prevent always
Agent, chlorinated paraffin and epoxidized soybean oil mix according to the above ratio, are plasticized and are mixed by mixer high temperature, and temperature is 160 DEG C, at plasticizing
Reason 14 minutes, is subsequently processed into the film for being about 1 centimetre for thickness.
After above-mentioned film is stored 24 hours, accelerating agent, zinc oxide and vulcanizing agent is added, in the secondary freshening of open mill, freshening
Condition is 45 DEG C, and 4 minutes time, it is about 12 centimetres to be processed into width, and thickness is about 1 centimetre of adhesive tape.
After above-mentioned adhesive tape is by vulcameter detection normally, single screw extrusion machine is fed, baking oven vulcanization is sent into after extrusion molding
Foaming.
The baking oven sulfur foam is, sulfur foam molding is carried out by 8 section baking ovens, foamed time 25min, described
Baking oven (preceding 7th area) temperature is trapezoidal incremental, and eight zone temperatures of the baking oven are 125-130 DEG C, 132-137 DEG C, 138-143
℃、145-150℃、151-156℃、157-162℃、163-165℃、165-165℃。
Embodiment 4
The present embodiment provides a kind of rubber plastic blend expanded materials, including following component：Rubber plastic blend material (nitrile rubber
17kg, polyvinyl chloride 8kg) 30 parts, 7 parts of AC foaming agents, 0.2 part of sulphur, accelerating agent (dimethyl dithiocarbamic acid ammonium) 1.6
Part, 30 parts of filler (talcum powder), 6 parts of carbon black, 0.8 part of paraffin, 17 parts of chlorinated paraffin, 0.15 part of stearic acid, epoxidized soybean oil 1.5
Part, 0.4 part of zinc oxide, 0.6 part of polyethylene glycol, 124 0.3 parts of anti-aging agent.
Preparation method is：By rubber plastic blend material, foaming agent, filler, carbon black, stearic acid, polyethylene glycol, paraffin, prevent always
Agent, chlorinated paraffin and epoxidized soybean oil mix according to the above ratio, are plasticized and are mixed by mixer high temperature, and temperature is 160 DEG C, at plasticizing
Reason 13 minutes, is subsequently processed into the film for being about 1 centimetre for thickness.
After above-mentioned film is stored 24 hours, accelerating agent, zinc oxide and vulcanizing agent is added, in the secondary freshening of open mill, freshening
Condition is 45 DEG C, and 3 minutes time, it is about 12 centimetres to be processed into width, and thickness is about 1 centimetre of adhesive tape.
After above-mentioned adhesive tape is by vulcameter detection normally, single screw extrusion machine is fed, baking oven vulcanization is sent into after extrusion molding
Foaming.
The baking oven sulfur foam is, sulfur foam molding is carried out by 8 section baking ovens, foamed time 25min, described
Baking oven (preceding 7th area) temperature is trapezoidal incremental, and eight zone temperatures of the baking oven are 125-130 DEG C, 132-137 DEG C, 138-143
℃、145-150℃、151-156℃、157-162℃、163-165℃、165-165℃。
Embodiment 5
The present embodiment provides a kind of rubber plastic blend expanded materials, including following component：Rubber plastic blend material (nitrile rubber
20.8kg, polyvinyl chloride 4.2kg) 30 parts, 7 parts of AC foaming agents, 0.2 part of sulphur, accelerating agent (dimethyl dithiocarbamic acid
Ammonium) 1.6 parts, 30 parts of filler (talcum powder), 6 parts of carbon black, 0.8 part of paraffin, 17 parts of chlorinated paraffin, 0.15 part of stearic acid, epoxy beans
1.5 parts of oil, 0.4 part of zinc oxide, 0.6 part of polyethylene glycol, 124 0.3 parts of anti-aging agent.
Preparation method is：By rubber plastic blend material, foaming agent, filler, carbon black, stearic acid, polyethylene glycol, paraffin, prevent always
Agent, chlorinated paraffin and epoxidized soybean oil mix according to the above ratio, are plasticized and are mixed by mixer high temperature, and temperature is 160 DEG C, at plasticizing
Reason 12 minutes, is subsequently processed into the film for being about 1 centimetre for thickness.
After above-mentioned film is stored 24 hours, accelerating agent, zinc oxide and vulcanizing agent is added, in the secondary freshening of open mill, freshening
Condition is 45 DEG C, and 4 minutes time, it is about 12 centimetres to be processed into width, and thickness is about 1 centimetre of adhesive tape.
After above-mentioned adhesive tape is by vulcameter detection normally, single screw extrusion machine is fed, baking oven vulcanization is sent into after extrusion molding
Foaming.
The baking oven sulfur foam is, sulfur foam molding is carried out by 8 section baking ovens, foamed time 25min, described
Baking oven (preceding 7th area) temperature is trapezoidal incremental, and eight zone temperatures of the baking oven are 125-130 DEG C, 132-137 DEG C, 138-143
℃、145-150℃、151-156℃、157-162℃、163-165℃、165-165℃。
Embodiment 6
The present embodiment provides a kind of rubber plastic blend expanded materials, including following component：Rubber plastic blend material (nitrile rubber
20kg, polyvinyl chloride 5kg) 30 parts, 6 parts of AC foaming agents, 0.15 part of penylene bismaleimide between N, N'-, accelerating agent (dimethyl
Ammonium dithiocarbamate) 1.6 parts, 28 parts of filler (talcum powder), 6 parts of carbon black, 0.6 part of paraffin, 16 parts of chlorinated paraffin, stearic acid
0.12 part, 1.2 parts of epoxidized soybean oil, 0.35 part of zinc oxide, 0.6 part of polyethylene glycol, 124 0.2 parts of anti-aging agent.
Preparation method is：By rubber plastic blend material, foaming agent, filler, carbon black, stearic acid, polyethylene glycol, paraffin, prevent always
Agent, chlorinated paraffin and epoxidized soybean oil mix according to the above ratio, are plasticized and are mixed by mixer high temperature, and temperature is 160 DEG C, at plasticizing
Reason 14 minutes, is subsequently processed into the film for being about 1 centimetre for thickness.
After above-mentioned film is stored 24 hours, accelerating agent, zinc oxide and vulcanizing agent is added, in the secondary freshening of open mill, freshening
Condition is 50 DEG C, and 4 minutes time, it is about 12 centimetres to be processed into width, and thickness is about 1 centimetre of adhesive tape.
After above-mentioned adhesive tape is by vulcameter detection normally, single screw extrusion machine is fed, baking oven vulcanization is sent into after extrusion molding
Foaming.
The baking oven sulfur foam is, sulfur foam molding is carried out by 8 section baking ovens, foamed time 25min, described
Baking oven (preceding 7th area) temperature is trapezoidal incremental, and eight zone temperatures of the baking oven are 125-130 DEG C, 132-137 DEG C, 138-143
℃、145-150℃、151-156℃、157-162℃、163-165℃、165-165℃。
Embodiment 7
The present embodiment provides a kind of rubber plastic blend expanded materials, including following component：Rubber plastic blend material (nitrile rubber
18.75kg, polyvinyl chloride 6.25kg) 30 parts, 7 parts of AC foaming agents, 4,4 ' -0.25 part of dithio morpholines, accelerating agent (dimethyl
Ammonium dithiocarbamate) 1.6 parts, 32 parts of filler (talcum powder), 7 parts of carbon black, 0.8 part of paraffin, 18 parts of chlorinated paraffin, stearic acid
0.18 part, 1.6 parts of epoxidized soybean oil, 0.45 part of zinc oxide, 0.8 part of polyethylene glycol, 124 0.4 parts of anti-aging agent.
Preparation method is：By rubber plastic blend material, foaming agent, filler, carbon black, stearic acid, polyethylene glycol, paraffin, prevent always
Agent, chlorinated paraffin and epoxidized soybean oil mix according to the above ratio, are plasticized and are mixed by mixer high temperature, and temperature is 160 DEG C, at plasticizing
Reason 15 minutes, is subsequently processed into the film for being about 1 centimetre for thickness.
After above-mentioned film is stored 24 hours, accelerating agent, zinc oxide and vulcanizing agent is added, in the secondary freshening of open mill, freshening
Condition is 45 DEG C, and 4 minutes time, it is about 12 centimetres to be processed into width, and thickness is about 1 centimetre of adhesive tape.
After above-mentioned adhesive tape is by vulcameter detection normally, single screw extrusion machine is fed, baking oven vulcanization is sent into after extrusion molding
Foaming.
The baking oven sulfur foam is, sulfur foam molding is carried out by 8 section baking ovens, foamed time 25min, described
Baking oven (preceding 7th area) temperature is trapezoidal incremental, and eight zone temperatures of the baking oven are 125-130 DEG C, 132-137 DEG C, 138-143
℃、145-150℃、151-156℃、157-162℃、163-165℃、165-165℃。
Embodiment 8
The present embodiment provides a kind of rubber plastic blend expanded materials, including following component：Rubber plastic blend material (nitrile rubber
20kg, polyvinyl chloride 5kg) 30 parts, 6 parts of AC foaming agents, 0.15 part of penylene bismaleimide between N, N'-, accelerating agent (dimethyl
Ammonium dithiocarbamate) 1.6 parts, 28 parts of filler (talcum powder), 6 parts of carbon black, 0.6 part of paraffin, 16 parts of chlorinated paraffin, stearic acid
0.12 part, 1.2 parts of epoxidized soybean oil, 0.35 part of zinc oxide, 0.6 part of polyethylene glycol, 0.2 part of 2-mercaptobenzimidazole.
Preparation method is：By rubber plastic blend material, foaming agent, filler, carbon black, stearic acid, polyethylene glycol, paraffin, prevent always
Agent, chlorinated paraffin and epoxidized soybean oil mix according to the above ratio, are plasticized and are mixed by mixer high temperature, and temperature is 160 DEG C, at plasticizing
Reason 15 minutes, is subsequently processed into the film for being about 1 centimetre for thickness.
After above-mentioned film is stored 24 hours, accelerating agent, zinc oxide and vulcanizing agent is added, in the secondary freshening of open mill, freshening
Condition is 50 DEG C, and 4 minutes time, it is about 12 centimetres to be processed into width, and thickness is about 1 centimetre of adhesive tape.
After above-mentioned adhesive tape is by vulcameter detection normally, single screw extrusion machine is fed, baking oven vulcanization is sent into after extrusion molding
Foaming.
The baking oven sulfur foam is, sulfur foam molding is carried out by 8 section baking ovens, foamed time 25min, described
Baking oven (preceding 7th area) temperature is trapezoidal incremental, and eight zone temperatures of the baking oven are 125-130 DEG C, 132-137 DEG C, 138-143
℃、145-150℃、151-156℃、157-162℃、163-165℃、165-165℃。
Embodiment 9
The present embodiment provides a kind of rubber plastic blend expanded materials, including following component：Rubber plastic blend material (nitrile rubber
18.75kg, polyvinyl chloride 6.25kg) 30 parts, 7 parts of AC foaming agents, 4,4 ' -0.25 part of dithio morpholines, accelerating agent (dimethyl
Ammonium dithiocarbamate) 1.6 parts, 32 parts of filler (talcum powder), 7 parts of carbon black, 0.8 part of paraffin, 18 parts of chlorinated paraffin, stearic acid
0.18 part, 1.6 parts of epoxidized soybean oil, 0.45 part of zinc oxide, 0.8 part of polyethylene glycol, 0.4 part of N, N'- bis- (betanaphthyl) p-phenylenediamine.
Preparation method is：By rubber plastic blend material, foaming agent, filler, carbon black, stearic acid, polyethylene glycol, paraffin, prevent always
Agent, chlorinated paraffin and epoxidized soybean oil mix according to the above ratio, are plasticized and are mixed by mixer high temperature, and temperature is 160 DEG C, at plasticizing
Reason 15 minutes, is subsequently processed into the film for being about 1 centimetre for thickness.
After above-mentioned film is stored 24 hours, accelerating agent, zinc oxide and vulcanizing agent is added, in the secondary freshening of open mill, freshening
Condition is 50 DEG C, and 4 minutes time, it is about 12 centimetres to be processed into width, and thickness is about 1 centimetre of adhesive tape.
After above-mentioned adhesive tape is by vulcameter detection normally, single screw extrusion machine is fed, baking oven vulcanization is sent into after extrusion molding
Foaming.
The baking oven sulfur foam is, sulfur foam molding is carried out by 8 section baking ovens, foamed time 25min, described
Baking oven (preceding 7th area) temperature is trapezoidal incremental, and eight zone temperatures of the baking oven are 125-130 DEG C, 132-137 DEG C, 138-143
℃、145-150℃、151-156℃、157-162℃、163-165℃、165-165℃。
Embodiment 10
The present embodiment provides a kind of rubber plastic blend expanded materials, including following component：Rubber plastic blend material (nitrile rubber
20kg, polyvinyl chloride 5kg) 30 parts, 6 parts of AC foaming agents, 0.15 part of penylene bismaleimide between N, N'-, accelerating agent (dimethyl
Ammonium dithiocarbamate) 1.6 parts, 28 parts of filler (talcum powder), 6 parts of carbon black, 0.6 part of paraffin, 16 parts of chlorinated paraffin, stearic acid
0.12 part, 1.2 parts of epoxidized soybean oil, 0.35 part of zinc oxide, 0.6 part of polyethylene glycol, 0.2 part of 2-mercaptobenzimidazole.
Preparation method is：Rubber plastic blend material is mixed with chlorinated paraffin and epoxidized soybean oil by formula ratio, by rubber plastic blend
Material is pre-processed, and pretreated condition is to handle 4min at 100 DEG C；
Then it is mixed with foaming agent, filler, carbon black, stearic acid, polyethylene glycol, paraffin, anti-aging agent, pass through mixer height
Temperature plasticizing mixing, temperature is 160 DEG C, and plastics processing 15 minutes is subsequently processed into the film for being about 1 centimetre for thickness.
After above-mentioned film is stored 24 hours, accelerating agent, zinc oxide and vulcanizing agent is added, in the secondary freshening of open mill, freshening
Condition is 50 DEG C, and 4 minutes time, it is about 12 centimetres to be processed into width, and thickness is about 1 centimetre of adhesive tape.
After above-mentioned adhesive tape is by vulcameter detection normally, single screw extrusion machine is fed, baking oven vulcanization is sent into after extrusion molding
Foaming.
The baking oven sulfur foam is, sulfur foam molding is carried out by 8 section baking ovens, foamed time 25min, described
Baking oven (preceding 7th area) temperature is trapezoidal incremental, and eight zone temperatures of the baking oven are 125-130 DEG C, 132-137 DEG C, 138-143
℃、145-150℃、151-156℃、157-162℃、163-165℃、165-165℃。
Embodiment 11
The present embodiment provides a kind of rubber plastic blend expanded materials, including following component：Rubber plastic blend material (nitrile rubber
18.75kg, polyvinyl chloride 6.25kg) 30 parts, 7 parts of AC foaming agents, 4,4 ' -0.25 part of dithio morpholines, accelerating agent (dimethyl
Ammonium dithiocarbamate) 1.6 parts, 32 parts of filler (talcum powder), 7 parts of carbon black, 0.8 part of paraffin, 18 parts of chlorinated paraffin, stearic acid
0.18 part, 1.6 parts of epoxidized soybean oil, 0.45 part of zinc oxide, 0.8 part of polyethylene glycol, 0.4 part of N, N'- bis- (betanaphthyl) p-phenylenediamine.
Preparation method is：Rubber plastic blend material is mixed with chlorinated paraffin and epoxidized soybean oil by formula ratio, by rubber plastic blend
Material is pre-processed, and pretreated condition is to handle 5min at 90 DEG C；
Then it is mixed with foaming agent, filler, carbon black, stearic acid, polyethylene glycol, paraffin, anti-aging agent, passes through mixer high temperature
Plasticizing mixing, temperature are 160 DEG C, and plastics processing 15 minutes is subsequently processed into the film for being about 1 centimetre for thickness.
After above-mentioned film is stored 24 hours, accelerating agent, zinc oxide and vulcanizing agent is added, in the secondary freshening of open mill, freshening
Condition is 50 DEG C, and 4 minutes time, it is about 12 centimetres to be processed into width, and thickness is about 1 centimetre of adhesive tape.
After above-mentioned adhesive tape is by vulcameter detection normally, single screw extrusion machine is fed, baking oven vulcanization is sent into after extrusion molding
Foaming.
The baking oven sulfur foam is, sulfur foam molding is carried out by 8 section baking ovens, foamed time 25min, described
Baking oven (preceding 7th area) temperature is trapezoidal incremental, and eight zone temperatures of the baking oven are 125-130 DEG C, 132-137 DEG C, 138-143
℃、145-150℃、151-156℃、157-162℃、163-165℃、165-165℃。
Comparative example 1
The present embodiment provides a kind of rubber plastic blend expanded materials, including following component：Rubber plastic blend material (nitrile rubber
23kg, polyvinyl chloride 2kg) 30 parts, 7 parts of AC foaming agents, 0.2 part of sulphur, accelerating agent (dimethyl dithiocarbamic acid ammonium) 1.6
Part, 30 parts of filler (talcum powder), 6 parts of carbon black, 0.8 part of paraffin, 17 parts of chlorinated paraffin, 0.15 part of stearic acid, 0.4 part of zinc oxide,
0.6 part of polyethylene glycol, 124 0.3 parts of anti-aging agent.
Preparation method is：By rubber plastic blend material, foaming agent, filler, carbon black, stearic acid, polyethylene glycol, paraffin, prevent always
It agent, chlorinated paraffin and mixes according to the above ratio, is plasticized and is mixed by mixer high temperature, temperature is 160 DEG C, and plastics processing 14 divides
Clock is subsequently processed into the film for being about 1 centimetre for thickness.
After above-mentioned film is stored 24 hours, accelerating agent, zinc oxide and vulcanizing agent is added, in the secondary freshening of open mill, freshening
Condition is 50 DEG C, and 4 minutes time, it is about 12 centimetres to be processed into width, and thickness is about 1 centimetre of adhesive tape.
After above-mentioned adhesive tape is by vulcameter detection normally, single screw extrusion machine is fed, baking oven vulcanization is sent into after extrusion molding
Foaming.
The baking oven sulfur foam is, sulfur foam molding is carried out by 8 section baking ovens, foamed time 25min, described
Baking oven (preceding 7th area) temperature is trapezoidal incremental, and eight zone temperatures of the baking oven are 125-130 DEG C, 132-137 DEG C, 138-143
℃、145-150℃、151-156℃、157-162℃、163-165℃、165-165℃。
Comparative example 2
The present embodiment provides a kind of rubber plastic blend expanded materials, including following component：Rubber plastic blend material (nitrile rubber
23kg, polyvinyl chloride 2kg) 30 parts, 7 parts of AC foaming agents, 0.2 part of sulphur, accelerating agent (dimethyl dithiocarbamic acid ammonium) 1.6
Part, 30 parts of filler (talcum powder), 6 parts of carbon black, 0.8 part of paraffin, 0.15 part of stearic acid, 1.5 parts of epoxidized soybean oil, 0.4 part of zinc oxide,
0.6 part of polyethylene glycol, 124 0.3 parts of anti-aging agent.
Preparation method is：By rubber plastic blend material, foaming agent, filler, carbon black, stearic acid, polyethylene glycol, paraffin, prevent always
Agent and epoxidized soybean oil mix according to the above ratio, are plasticized and are mixed by mixer high temperature, and temperature is 160 DEG C, plastics processing 14 minutes,
It is subsequently processed into the film for being about 1 centimetre for thickness.
After above-mentioned film is stored 24 hours, accelerating agent, zinc oxide and vulcanizing agent is added, in the secondary freshening of open mill, freshening
Condition is 45 DEG C, and 4 minutes time, it is about 12 centimetres to be processed into width, and thickness is about 1 centimetre of adhesive tape.
After above-mentioned adhesive tape is by vulcameter detection normally, single screw extrusion machine is fed, baking oven vulcanization is sent into after extrusion molding
Foaming.
The baking oven sulfur foam is, sulfur foam molding is carried out by 8 section baking ovens, foamed time 25min, described
Baking oven (preceding 7th area) temperature is trapezoidal incremental, and eight zone temperatures of the baking oven are 125-130 DEG C, 132-137 DEG C, 138-143
℃、145-150℃、151-156℃、157-162℃、163-165℃、165-165℃。
Performance test
1 chloride ion content is tested
The test method of chloride ion content：
1 gram or so of weight is sampled, sample is put into 100 milliliters of closed container；
40 milliliters of pure water are added into container, cover sealing cover, concussion about 30 seconds, make sample be stained with moisture manually, and
24 hours are stood under conditions of 90 DEG C；
It is shaken 30 seconds manually again when taking out closed container, after solution cooling, takes out liquid, analyzed using ion chromatograph
Chloride ion content in soak；
The ion concentration of soak is converted to the chloride ion content of foaming product.
The product of embodiment 3, embodiment 7-11 and comparative example 1-2 is tested, concrete outcome is shown in Table 1.
The content of chlorion in 1 sample of table
From the data in upper table it is found that being used cooperatively for epoxidized soybean oil and chlorinated paraffin, can significantly reduce chlorine in sample
Ion concentration, pre-treatment step can further decrease chloride ion content in sample, and the selection of anti-aging agent also has certain reduction
The effect of chloride ion content.
After above-mentioned sample is wrapped up copper pipe, 240 hours can be lasted in temperature 60 C, the environment of humidity 95% ± 3%,
The color of copper pipe is close to no copper pipe color for wrapping up rubber plastic blend foaming product, and the copper pipe color that comparative example packet is crossed becomes
It is black.
The test of 2 free sulphurs
The test method of free sulphur is：
Standard uses ASTM C471M-13《The detection of gypsum superfine product sulfur content》.
Principle：Rubber and plastic is shredded into small granular, use toluene as organic extractant, extract the sulphur in rubber and plastic, recycled
Liquid chromatograph tests out sulfur content.
The product of 4-7 of the embodiment of the present invention and embodiment 10 are tested, test result is shown in Table 2.
The content of free sulphur in 2 sample of table
| Sample | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 10 |
| Sulfur content, mg/kg | 128 | 135 | 8 | 6 | It is not detected |
From the data in upper table it is found that the selection of vulcanizing agent can significantly reduce the free sulfur content in sample, to preparing
The adjustment of method can further decrease the free sulfur content in sample.
3 oil resistivitys are tested
Oil resistivity test method is：Oil resistivity measurement is carried out by the method for GB/T1690, wherein immersion liquid is ASTM3#
Oil, 80 degree of soaking temperature, 100 hours test periods.
Oil resistivity test, specific test result are carried out to the sample of 3-6 of the embodiment of the present invention and embodiment 8, embodiment 10
It is shown in Table 3.
The oil resistance of 3 sample of table is tested
| Sample | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 8 | Embodiment 10 |
| Oil resistivity | 20 | 16 | 15 | 14 | 13 | 12 |
It, can be notable from the data in table it is found that the adjustment that nitrile rubber in rubber plastic blend material and polyvinyl chloride match
The oil resistance of sample is improved, the adjustment of vulcanizing agent, anti-aging agent and technique has certain influence to sulfur content of dissociating in sample, but
Unobvious.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And thus amplify out it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of rubber plastic blend expanded material, which is characterized in that include the component of following parts by weight：
25-35 parts of rubber plastic blend material, 5-8 parts of foaming agent, 0.05-0.3 parts of vulcanizing agent, 1.5-1.8 parts of accelerating agent, filler 25-35
Part, 5-8 parts of carbon black, 0.5-1 parts of paraffin, 15-20 parts of chlorinated paraffin, 0.1-0.2 parts of stearic acid, 1-2 parts of epoxidized soybean oil, zinc oxide
0.3-0.5 parts, 0.5-1 parts of polyethylene glycol, 0.1-0.5 parts of anti-aging agent.
2. rubber plastic blend expanded material according to claim 1, which is characterized in that include the component of following parts by weight：
28-32 parts of rubber plastic blend material, 6-7 parts of foaming agent, 0.15-0.25 parts of vulcanizing agent, 1.6 parts of accelerating agent, 28-32 parts of filler,
6-7 parts of carbon black, 0.6-0.8 parts of paraffin, 16-18 parts of chlorinated paraffin, 0.12-0.18 parts of stearic acid, 1.2-1.6 parts of epoxidized soybean oil,
0.35-0.45 parts of zinc oxide, 0.6-0.8 parts of polyethylene glycol, 0.2-0.4 parts of anti-aging agent.
3. rubber plastic blend expanded material according to claim 1 or 2, which is characterized in that the rubber plastic blend material is butyronitrile
The mixture of rubber and polyvinyl chloride,
Wherein, the mass ratio of nitrile rubber and polyvinyl chloride is 2-5:1.
4. rubber plastic blend expanded material according to claim 3, which is characterized in that the vulcanizing agent is sulfurless vulcanizing agent,
Preferably, the sulfurless vulcanizing agent is N, penylene bismaleimide or 4 between N'-, 4 '-dithio morpholines.
5. rubber plastic blend expanded material according to claim 3, which is characterized in that
The foaming agent is AC foaming agents；
And/or the filler is talcum powder, at least one of aluminium hydroxide；
And/or the accelerating agent is dimethyl dithiocarbamate class or thuriam acceserator.
6. rubber plastic blend expanded material according to claim 4 or 5, which is characterized in that the anti-aging agent is 2- sulfydryl benzene
And imidazoles, at least one of N, N'- bis- (betanaphthyl) p-phenylenediamine.
7. the preparation method of the rubber plastic blend expanded material described in a kind of any one of claim 1-6, which is characterized in that including
Following steps：
It is kneaded：By rubber plastic blend material, foaming agent, filler, carbon black, stearic acid, polyethylene glycol, paraffin, anti-aging agent, chlorinated paraffin and
Epoxidized soybean oil is mixed by formula ratio, after high-temperature mixing, is processed into film；
Freshening：After above-mentioned film is stored 18-30 hours, accelerating agent, zinc oxide and vulcanizing agent is added, carries out secondary freshening, adds
Work is at adhesive tape；
Foaming：After above-mentioned adhesive tape extrusion molding, step up cure foaming processing is carried out.
8. the preparation method of rubber plastic blend expanded material according to claim 7, which is characterized in that the mixing step
For：
Rubber plastic blend material is mixed with chlorinated paraffin and epoxidized soybean oil by formula ratio, rubber plastic blend material is pre-processed, it is pre- to locate
The condition of reason is to handle 4-5min at 90-100 DEG C；
Then it is mixed with foaming agent, filler, carbon black, stearic acid, polyethylene glycol, paraffin, anti-aging agent, after high-temperature mixing, processing
At film.
9. the preparation method of rubber plastic blend expanded material according to claim 7 or 8, which is characterized in that the segmentation sulphur
Changing foaming treatment conditions is：Sulfur foam forming processes are carried out by eight sections, the temperature of eight section is followed successively by
125-130 DEG C, 132-137 DEG C, 138-143 DEG C, 145-150 DEG C, 151-156 DEG C, 157-162 DEG C, 163-165 DEG C, 165-165
℃。
10. the preparation method of rubber plastic blend expanded material according to claim 7 or 8, which is characterized in that the mixing
Condition is：155-165 DEG C of temperature, time 12-15 minute；
And/or the condition of the freshening is：45-50 DEG C of temperature, time 3-5 minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810547503.9A CN108752670A (en) | 2018-05-31 | 2018-05-31 | A kind of rubber plastic blend expanded material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810547503.9A CN108752670A (en) | 2018-05-31 | 2018-05-31 | A kind of rubber plastic blend expanded material and preparation method thereof |
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| CN111087710A (en) * | 2020-01-19 | 2020-05-01 | 赢胜节能集团有限公司 | Compression molding heat-insulation mute rubber-plastic sound-absorbing board and preparation method thereof |
| CN111117015A (en) * | 2020-01-06 | 2020-05-08 | 神州节能科技集团有限公司 | Rubber and plastic product with low TVOC release amount and preparation method thereof |
| CN111574759A (en) * | 2020-06-09 | 2020-08-25 | 神州节能科技集团有限公司 | Green environment-friendly rubber and plastic product and preparation method thereof |
| CN111763362A (en) * | 2020-07-28 | 2020-10-13 | 惠州优比贝柠科技股份有限公司 | Fireproof rubber foamed sheet and preparation method thereof |
| CN111793255A (en) * | 2020-07-28 | 2020-10-20 | 惠州优比贝柠科技股份有限公司 | Environment-friendly composite mineral wool foam insulation board and preparation method thereof |
| CN112608536A (en) * | 2020-11-29 | 2021-04-06 | 无锡市东北塘永丰橡塑厂 | Preparation method of tough and wear-resistant rubber and plastic product |
| CN113150417A (en) * | 2021-03-15 | 2021-07-23 | 北京环冷科技有限公司 | Flexible low-temperature cryogenic heat-insulating material and preparation method thereof |
| CN113621185A (en) * | 2021-08-30 | 2021-11-09 | 华美节能科技集团有限公司 | Halogen-free rubber-plastic heat-insulating material and preparation method thereof |
| CN114058092A (en) * | 2020-07-31 | 2022-02-18 | 中国石油化工股份有限公司 | Composition for polymer material, polymer material and preparation method thereof |
| CN114058093A (en) * | 2020-07-31 | 2022-02-18 | 中国石油化工股份有限公司 | Foaming material composition, foaming material and preparation method thereof |
| CN116003930A (en) * | 2021-10-21 | 2023-04-25 | 新疆天业（集团）有限公司 | Blending PVC micro-infiltrating irrigation pipe |
| EP4235170A1 (en) * | 2022-02-25 | 2023-08-30 | Sumitomo Rubber Industries, Ltd. | Method of quantification of free sulfur |
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| CN111117015A (en) * | 2020-01-06 | 2020-05-08 | 神州节能科技集团有限公司 | Rubber and plastic product with low TVOC release amount and preparation method thereof |
| CN111087710A (en) * | 2020-01-19 | 2020-05-01 | 赢胜节能集团有限公司 | Compression molding heat-insulation mute rubber-plastic sound-absorbing board and preparation method thereof |
| CN111574759A (en) * | 2020-06-09 | 2020-08-25 | 神州节能科技集团有限公司 | Green environment-friendly rubber and plastic product and preparation method thereof |
| CN111763362A (en) * | 2020-07-28 | 2020-10-13 | 惠州优比贝柠科技股份有限公司 | Fireproof rubber foamed sheet and preparation method thereof |
| CN111793255A (en) * | 2020-07-28 | 2020-10-20 | 惠州优比贝柠科技股份有限公司 | Environment-friendly composite mineral wool foam insulation board and preparation method thereof |
| CN114058093A (en) * | 2020-07-31 | 2022-02-18 | 中国石油化工股份有限公司 | Foaming material composition, foaming material and preparation method thereof |
| CN114058092A (en) * | 2020-07-31 | 2022-02-18 | 中国石油化工股份有限公司 | Composition for polymer material, polymer material and preparation method thereof |
| CN112608536A (en) * | 2020-11-29 | 2021-04-06 | 无锡市东北塘永丰橡塑厂 | Preparation method of tough and wear-resistant rubber and plastic product |
| CN113150417A (en) * | 2021-03-15 | 2021-07-23 | 北京环冷科技有限公司 | Flexible low-temperature cryogenic heat-insulating material and preparation method thereof |
| CN113621185A (en) * | 2021-08-30 | 2021-11-09 | 华美节能科技集团有限公司 | Halogen-free rubber-plastic heat-insulating material and preparation method thereof |
| CN116003930A (en) * | 2021-10-21 | 2023-04-25 | 新疆天业（集团）有限公司 | Blending PVC micro-infiltrating irrigation pipe |
| CN116003930B (en) * | 2021-10-21 | 2024-02-20 | 新疆天业（集团）有限公司 | Blending PVC micro-infiltrating irrigation pipe |
| EP4235170A1 (en) * | 2022-02-25 | 2023-08-30 | Sumitomo Rubber Industries, Ltd. | Method of quantification of free sulfur |
| CN116852621A (en) * | 2023-04-27 | 2023-10-10 | 苏州恒瑞达家用地垫有限公司 | Preparation method and device of environment-friendly rubber-plastic foaming product without formamide |
| CN116852621B (en) * | 2023-04-27 | 2024-10-29 | 苏州恒瑞达家用地垫有限公司 | Preparation method and device of environment-friendly rubber-plastic foaming product without formamide |
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