CN111592768A - Nylon encapsulating TPE material of vulcanized SEBS base material and preparation method thereof - Google Patents
Nylon encapsulating TPE material of vulcanized SEBS base material and preparation method thereof Download PDFInfo
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- CN111592768A CN111592768A CN202010442201.2A CN202010442201A CN111592768A CN 111592768 A CN111592768 A CN 111592768A CN 202010442201 A CN202010442201 A CN 202010442201A CN 111592768 A CN111592768 A CN 111592768A
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- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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Abstract
The invention relates to a nylon encapsulated TPE material of a vulcanized SEBS (styrene-ethylene-butadiene-styrene) base material, which comprises the following components in percentage by mass: 20-30% of vulcanized styrene butadiene styrene copolymer, 15-35% of plastic processing oil, 5-20% of compatilizer, 5-25% of calcium carbonate, 5-15% of monomer tackifying resin and 0.5-3% of anti-aging auxiliary agent; the vulcanized styrene-butadiene-styrene copolymer is prepared by extruding and granulating the styrene-butadiene-styrene copolymer and a vulcanizing agent through a double-screw extruder; the vulcanization rate of the vulcanized styrene butadiene styrene copolymer is 0.05-2%, the Shore hardness is less than or equal to 80A, and the melt index of 2.16kg at 190 ℃ is more than or equal to 5g/10 min. According to the invention, the compatilizer, the monomer tackifying resin and the anti-aging auxiliary agent can improve the rubber coating adhesion effect of the TPE material on the nylon injection molding, and the vulcanized SEBS and the maleic anhydride grafted polypropylene compatilizer are added to increase the adhesion performance of the TPE material and the nylon material.
Description
Technical Field
The invention relates to the technical field of TPE (thermoplastic elastomer) elastomer materials, in particular to a nylon-encapsulated TPE material with a vulcanized SEBS (styrene-ethylene-butadiene-styrene) base material and a preparation method thereof.
Background
The nylon, also called polyimide PA, has good comprehensive properties including mechanical properties, heat resistance and abrasion resistance, is a good material for replacing metals such as steel, iron, copper and the like with plastics, and is one of important engineering plastics. Because nylon has a relatively hard surface texture, in some applications such as: handles, etc. of children's toys, various electric tools, and kitchen utensils cause uncomfortable hand feeling. The thermoplastic elastomer (TPE) material is an elastomer material with adjustable hardness, and the thermoplastic elastomer is coated or secondarily injection-bonded on the surface of the nylon part, so that the shock absorption and the skid resistance are realized, and the hand feeling comfort degree of holding or holding nylon tools and toys is improved.
At present, the TPE encapsulation nylon on the market has lower bonding strength, the encapsulation nylon has poor effect, and the encapsulation or secondary injection molding injection adhesive material has the problem of weak bonding force.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a nylon encapsulated TPE material of a vulcanized SEBS base material and a preparation method thereof; the material can be used for adhering and encapsulating the surface of a nylon product with high strength, can also be subjected to secondary injection molding and injection molding, and can realize green recycling of the material.
In order to achieve the purpose, the technical scheme provided by the invention is as follows: the nylon encapsulated TPE material of the vulcanized SEBS base material comprises the following components in percentage by mass: 20-30% of vulcanized styrene butadiene styrene copolymer, 15-35% of plastic processing oil, 5-20% of compatilizer, 5-25% of calcium carbonate, 5-15% of monomer tackifying resin and 0.5-3% of anti-aging auxiliary agent; the vulcanized styrene-butadiene-styrene copolymer is prepared by extruding and granulating the styrene-butadiene-styrene copolymer and a vulcanizing agent through a double-screw extruder; the vulcanization rate of the vulcanized styrene butadiene styrene copolymer is 0.05-2%, the Shore hardness is less than or equal to 80A, and the melt index of the vulcanized styrene butadiene styrene copolymer at 190 ℃ and 2.16kg is more than or equal to 5g/10 min.
In the technical scheme, the plastic processing oil is at least one of 150N naphthenic oil, 300 naphthenic oil, 500 naphthenic oil, KN4010 naphthenic oil, KN4006 naphthenic oil, white oil and paraffin oil.
In the technical scheme, the compatilizer is at least one of maleic anhydride grafted polypropylene (PP-MAH), maleic anhydride grafted styrene butadiene styrene copolymer (SEBS-MAH), maleic anhydride grafted nylon (PA-MAH) and maleic anhydride grafted ethylene-octene copolymer (POE-MAH).
In the technical scheme, the calcium carbonate is at least one of light calcium carbonate, heavy calcium carbonate and superfine calcium carbonate, and the mesh number of the calcium carbonate is 1000-3000 meshes.
In the technical scheme, the monomer tackifying resin is at least one of rosin resin, coumarone resin, petroleum resin, EVA hot melt adhesive and nylon hot melt adhesive.
In the technical scheme, the anti-aging auxiliary agent is at least one of an antioxidant 1010, an antioxidant 1076, an antioxidant 168, an antioxidant 626, an ultraviolet absorbent UV-531, an ultraviolet absorbent UV-9 and an ultraviolet absorbent UV-326.
In the technical scheme, the vulcanized styrene-butadiene-styrene copolymer is prepared by uniformly mixing 98-99.5% of styrene-butadiene-styrene copolymer and 0.5-2% of vulcanizing agent, and extruding and granulating the mixture by a double-screw extruder.
In the above technical scheme, the vulcanizing agent is at least one of dicumyl peroxide (DCP), Benzoyl Peroxide (BPO) and sulfur peroxide (S).
In order to achieve the above object, the present invention further provides a method for preparing the above TPE material, comprising the steps of:
firstly, preparing a vulcanized styrene butadiene styrene copolymer, placing a styrene butadiene styrene copolymer SEBS in a stirring cylinder, placing at least one raw material of dicumyl peroxide (DCP), Benzoyl Peroxide (BPO) and sulfur peroxide (S) in the stirring cylinder, uniformly mixing the raw material with the styrene butadiene styrene copolymer SEBS, conveying the mixture into a feeding cylinder of a double-screw extruder, and extruding and granulating the mixture by the double-screw extruder to obtain vulcanized styrene butadiene styrene copolymer particles;
secondly, placing the prepared vulcanized styrene butadiene styrene copolymer particles, plastic processing oil, a compatilizer, calcium carbonate, tackifying resin and an anti-aging auxiliary agent in a stirring cylinder, uniformly mixing, conveying to a feeding cylinder of a double-screw extruder, and extruding and granulating by the double-screw extruder to obtain a nylon encapsulated TPE material; wherein, the temperature of each area of the double-screw extruder is respectively as follows: the first area is 100-150 ℃, the second area is 130-160 ℃, the third area is 160-180 ℃, the fourth area is 160-180 ℃, the fifth area is 160-180 ℃, the sixth area is 170-180 ℃, the seventh area is 160-170 ℃, and the head is 150-160 ℃.
The invention has the beneficial effects that the compatilizer, the monomer tackifying resin and the anti-aging auxiliary agent can improve the rubber coating adhesion effect of the TPE material on a nylon injection molding, the vulcanized SEBS and the maleic anhydride grafted polypropylene compatilizer are added, the polarity of the TPE material is greatly increased, and the adhesion performance of the TPE material and the nylon material is improved.
Detailed Description
Specific embodiments of the present invention are described.
The first embodiment is that a nylon encapsulated TPE material of a vulcanized SEBS base material comprises the following components in percentage by mass: 20% of vulcanized styrene butadiene styrene copolymer (vulcanized SEBS), 35% of plastic processing oil, 20% of compatilizer, 13% of calcium carbonate, 10% of monomer tackifying resin and 2% of anti-aging auxiliary agent; the vulcanized styrene-butadiene-styrene copolymer is prepared by extruding and granulating the styrene-butadiene-styrene copolymer and a vulcanizing agent through a double-screw extruder; the vulcanization rate of the vulcanized styrene butadiene styrene copolymer is 0.05-2%, the Shore hardness is less than or equal to 80A, and the melt index of 2.16kg at 190 ℃ is more than or equal to 5g/10 min.
The plastic processing oil is at least one of 150N naphthenic oil, 300 naphthenic oil, 500 naphthenic oil, KN4010 naphthenic oil, KN4006 naphthenic oil, white oil and paraffin oil.
The compatilizer is maleic anhydride grafted polypropylene PP-MAH.
The calcium carbonate is at least one of light calcium carbonate, heavy calcium carbonate and superfine calcium carbonate, and the mesh number of the calcium carbonate is 1000-3000 meshes.
The monomer tackifying resin is at least one of rosin resin, coumarone resin, petroleum resin, EVA hot melt adhesive and nylon hot melt adhesive.
The anti-aging auxiliary agent is at least one of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 626, ultraviolet absorbent UV-531, ultraviolet absorbent UV-9 and ultraviolet absorbent UV-326.
The vulcanized styrene-butadiene-styrene copolymer is prepared by uniformly mixing 98-99.5% of styrene-butadiene-styrene copolymer and 0.5-2% of vulcanizing agent, and extruding and granulating the mixture by a double-screw extruder.
The vulcanizing agent is at least one of dicumyl peroxide (DCP), Benzoyl Peroxide (BPO) and sulfur peroxide (S).
Example two, a nylon encapsulated TPE material of a vulcanized SEBS substrate, which is composed of the following components by mass percent: 25% of vulcanized styrene butadiene styrene copolymer (vulcanized SEBS), 35% of plastic processing oil, 15% of compatilizer, 10% of calcium carbonate, 13% of monomer tackifying resin and 2% of anti-aging auxiliary agent; the vulcanized styrene-butadiene-styrene copolymer is prepared by extruding and granulating the styrene-butadiene-styrene copolymer and a vulcanizing agent through a double-screw extruder; the vulcanization rate of the vulcanized styrene butadiene styrene copolymer is 0.05-2%, the Shore hardness is less than or equal to 80A, and the melt index of 2.16kg at 190 ℃ is more than or equal to 5g/10 min.
The plastic processing oil is at least one of 150N naphthenic oil, 300 naphthenic oil, 500 naphthenic oil, KN4010 naphthenic oil, KN4006 naphthenic oil, white oil and paraffin oil.
The compatilizer is maleic anhydride grafted polypropylene PP-MAH.
The calcium carbonate is at least one of light calcium carbonate, heavy calcium carbonate and superfine calcium carbonate, and the mesh number of the calcium carbonate is 1000-3000 meshes.
The monomer tackifying resin is at least one of rosin resin, coumarone resin, petroleum resin, EVA hot melt adhesive and nylon hot melt adhesive.
The anti-aging auxiliary agent is at least one of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 626, ultraviolet absorbent UV-531, ultraviolet absorbent UV-9 and ultraviolet absorbent UV-326.
The vulcanized styrene-butadiene-styrene copolymer is prepared by uniformly mixing 98-99.5% of styrene-butadiene-styrene copolymer and 0.5-2% of vulcanizing agent, and extruding and granulating the mixture by a double-screw extruder.
The vulcanizing agent is at least one of dicumyl peroxide (DCP), Benzoyl Peroxide (BPO) and sulfur peroxide (S).
Example three, a nylon encapsulated TPE material of a vulcanized SEBS substrate, which is composed of the following components by mass percent: 28% of vulcanized styrene butadiene styrene copolymer (vulcanized SEBS), 35% of plastic processing oil, 15% of compatilizer, 10% of calcium carbonate, 10% of monomer tackifying resin and 2% of anti-aging auxiliary agent; the vulcanized styrene-butadiene-styrene copolymer is prepared by extruding and granulating the styrene-butadiene-styrene copolymer and a vulcanizing agent through a double-screw extruder; the vulcanization rate of the vulcanized styrene butadiene styrene copolymer is 0.05-2%, the Shore hardness is less than or equal to 80A, and the melt index of 2.16kg at 190 ℃ is more than or equal to 5g/10 min.
The plastic processing oil is at least one of 150N naphthenic oil, 300 naphthenic oil, 500 naphthenic oil, KN4010 naphthenic oil, KN4006 naphthenic oil, white oil and paraffin oil.
The compatilizer is maleic anhydride grafted polypropylene PP-MAH.
The calcium carbonate is at least one of light calcium carbonate, heavy calcium carbonate and superfine calcium carbonate, and the mesh number of the calcium carbonate is 1000-3000 meshes.
The monomer tackifying resin is at least one of rosin resin, coumarone resin, petroleum resin, EVA hot melt adhesive and nylon hot melt adhesive.
The anti-aging auxiliary agent is at least one of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 626, ultraviolet absorbent UV-531, ultraviolet absorbent UV-9 and ultraviolet absorbent UV-326.
The vulcanized styrene-butadiene-styrene copolymer is prepared by uniformly mixing 98-99.5% of styrene-butadiene-styrene copolymer and 0.5-2% of vulcanizing agent, and extruding and granulating the mixture by a double-screw extruder.
The vulcanizing agent is at least one of dicumyl peroxide (DCP), Benzoyl Peroxide (BPO) and sulfur peroxide (S).
Example four, a nylon encapsulated TPE material of a vulcanized SEBS substrate, which is composed of the following components by mass percent: 30% of vulcanized styrene butadiene styrene copolymer (vulcanized SEBS), 35% of plastic processing oil, 13% of compatilizer, 10% of calcium carbonate, 10% of monomer tackifying resin and 2% of anti-aging auxiliary agent; the vulcanized styrene-butadiene-styrene copolymer is prepared by extruding and granulating the styrene-butadiene-styrene copolymer and a vulcanizing agent through a double-screw extruder; the vulcanization rate of the vulcanized styrene butadiene styrene copolymer is 0.05-2%, the Shore hardness is less than or equal to 80A, and the melt index of 2.16kg at 190 ℃ is more than or equal to 5g/10 min.
The plastic processing oil is at least one of 150N naphthenic oil, 300 naphthenic oil, 500 naphthenic oil, KN4010 naphthenic oil, KN4006 naphthenic oil, white oil and paraffin oil.
The compatilizer is maleic anhydride grafted polypropylene PP-MAH.
The calcium carbonate is at least one of light calcium carbonate, heavy calcium carbonate and superfine calcium carbonate, and the mesh number of the calcium carbonate is 1000-3000 meshes.
The monomer tackifying resin is at least one of rosin resin, coumarone resin, petroleum resin, EVA hot melt adhesive and nylon hot melt adhesive.
The anti-aging auxiliary agent is at least one of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 626, ultraviolet absorbent UV-531, ultraviolet absorbent UV-9 and ultraviolet absorbent UV-326.
The vulcanized styrene-butadiene-styrene copolymer is prepared by uniformly mixing 98-99.5% of styrene-butadiene-styrene copolymer and 0.5-2% of vulcanizing agent, and extruding and granulating the mixture by a double-screw extruder.
The vulcanizing agent is at least one of dicumyl peroxide (DCP), Benzoyl Peroxide (BPO) and sulfur peroxide (S).
Example five, a nylon encapsulated TPE material of a vulcanized SEBS substrate, which is composed of the following components by mass percent: 30% of vulcanized styrene butadiene styrene copolymer (vulcanized SEBS), 25% of plastic processing oil, 20% of compatilizer, 25% of calcium carbonate, 0% of monomer tackifying resin and 0% of anti-aging auxiliary agent; the vulcanized styrene-butadiene-styrene copolymer is prepared by extruding and granulating the styrene-butadiene-styrene copolymer and a vulcanizing agent through a double-screw extruder; the vulcanization rate of the vulcanized styrene butadiene styrene copolymer is 0.05-2%, the Shore hardness is less than or equal to 80A, and the melt index of 2.16kg at 190 ℃ is more than or equal to 5g/10 min.
The plastic processing oil is at least one of 150N naphthenic oil, 300 naphthenic oil, 500 naphthenic oil, KN4010 naphthenic oil, KN4006 naphthenic oil, white oil and paraffin oil.
The compatilizer is maleic anhydride grafted polypropylene PP-MAH.
The calcium carbonate is at least one of light calcium carbonate, heavy calcium carbonate and superfine calcium carbonate, and the mesh number of the calcium carbonate is 1000-3000 meshes.
The monomer tackifying resin is at least one of rosin resin, coumarone resin, petroleum resin, EVA hot melt adhesive and nylon hot melt adhesive.
The anti-aging auxiliary agent is at least one of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 626, ultraviolet absorbent UV-531, ultraviolet absorbent UV-9 and ultraviolet absorbent UV-326.
The vulcanized styrene-butadiene-styrene copolymer is prepared by uniformly mixing 98-99.5% of styrene-butadiene-styrene copolymer and 0.5-2% of vulcanizing agent, and extruding and granulating the mixture by a double-screw extruder.
The vulcanizing agent is at least one of dicumyl peroxide (DCP), Benzoyl Peroxide (BPO) and sulfur peroxide (S).
The preparation method of the nylon encapsulated TPE material of the vulcanized SEBS substrate comprises the following steps:
firstly, preparing a vulcanized styrene butadiene styrene copolymer, placing a styrene butadiene styrene copolymer SEBS in a stirring cylinder, placing at least one raw material of dicumyl peroxide (DCP), Benzoyl Peroxide (BPO) and sulfur peroxide (S) in the stirring cylinder, uniformly mixing the raw material with the styrene butadiene styrene copolymer SEBS, conveying the mixture into a feeding cylinder of a double-screw extruder, and extruding and granulating the mixture by the double-screw extruder to obtain vulcanized styrene butadiene styrene copolymer particles;
secondly, placing the prepared vulcanized styrene butadiene styrene copolymer particles, plastic processing oil, a compatilizer, calcium carbonate, tackifying resin and an anti-aging auxiliary agent in a stirring cylinder, uniformly mixing, conveying to a feeding cylinder of a double-screw extruder, and extruding and granulating by the double-screw extruder to obtain a nylon encapsulated TPE material; wherein, the temperature of each area of the double-screw extruder is respectively as follows: the first area is 100-150 ℃, the second area is 130-160 ℃, the third area is 160-180 ℃, the fourth area is 160-180 ℃, the fifth area is 160-180 ℃, the sixth area is 170-180 ℃, the seventh area is 160-170 ℃, and the head is 150-160 ℃.
Samples were prepared according to the above-described preparation method for the formulations of examples 1-5, and the hardness, tensile strength, and adhesion of the TPE materials were compared, and the results are shown in the following Table. Hardness test standard: refer to the astm d-2240 standard; the adhesive force is tested by adopting a stripping experiment, and the stripping success rate (%) after encapsulation is as follows: each example produced 100 test samples for the encapsulation peel test, testing whether the TPE material could be peeled from the nylon material with a peel force of 200N, and dividing the number of successfully peeled samples by 100 to give the post encapsulation peel success ratio (%). Among them, as can be seen from table one, the tensile strength of example three is the best; in the fifth embodiment, no monomer tackifying resin and no aging-resistant auxiliary agent are added, and the peeling success rate and the retention rate after encapsulation are the worst.
The common TPE material is difficult to bond with nylon because the polarity difference between the common TPE material and the nylon material is too large and the crystallinity of the nylon is higher; according to the invention, the compatilizer, the monomer tackifying resin and the anti-aging auxiliary agent are used, so that the rubber coating adhesion effect of the TPE material on a nylon injection molding piece can be improved, the polarity of the TPE material is greatly increased by adding the vulcanized SEBS and the maleic anhydride grafted polypropylene compatilizer, and the adhesion performance of the TPE material and the nylon material is improved.
The technical scope of the present invention is not limited to the above embodiments, and any modifications, equivalent variations and modifications made to the above embodiments according to the technical spirit of the present invention still fall within the technical scope of the present invention.
Claims (9)
1. The nylon encapsulated TPE material of the vulcanized SEBS base material is characterized by comprising the following components in percentage by mass: 20-30% of vulcanized styrene butadiene styrene copolymer, 15-35% of plastic processing oil, 5-20% of compatilizer, 5-25% of calcium carbonate, 5-15% of monomer tackifying resin and 0.5-3% of anti-aging auxiliary agent; the vulcanized styrene-butadiene-styrene copolymer is prepared by extruding and granulating the styrene-butadiene-styrene copolymer and a vulcanizing agent through a double-screw extruder; the vulcanization rate of the vulcanized styrene butadiene styrene copolymer is 0.05-2%, the Shore hardness is less than or equal to 80A, and the melt index of the vulcanized styrene butadiene styrene copolymer at 190 ℃ and 2.16kg is more than or equal to 5g/10 min.
2. The material of claim 1, wherein the plastic processing oil is at least one of 150N naphthenic oil, 300 naphthenic oil, 500 naphthenic oil, KN4010 naphthenic oil, KN4006 naphthenic oil, white oil, and paraffin oil.
3. The material of claim 2, wherein the compatibilizer is at least one of a maleic anhydride grafted polypropylene (PP-MAH), a maleic anhydride grafted styrene butadiene styrene copolymer (SEBS-MAH), a maleic anhydride grafted nylon (PA-MAH), and a maleic anhydride grafted ethylene octene copolymer (POE-MAH).
4. The vulcanized SEBS-based nylon-encapsulated TPE material as claimed in claim 3, wherein the calcium carbonate is at least one of light calcium carbonate, heavy calcium carbonate and ultrafine calcium carbonate, and the mesh number of the calcium carbonate is 1000-3000 meshes.
5. The material of claim 4, wherein the monomeric tackifying resin is at least one of rosin resin, coumarone resin, petroleum resin, EVA hot melt adhesive, and nylon hot melt adhesive.
6. The nylon encapsulated TPE material of the vulcanized SEBS substrate as claimed in claim 5, wherein the anti-aging auxiliary agent is at least one of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 626, ultraviolet absorbent UV-531, ultraviolet absorbent UV-9 and ultraviolet absorbent UV-326.
7. The nylon encapsulated TPE material of the vulcanized SEBS base material as claimed in claim 6, wherein the vulcanized styrene butadiene styrene copolymer is prepared by uniformly mixing 98% -99.5% of styrene butadiene styrene copolymer and 0.5% -2% of vulcanizing agent and performing extrusion granulation by a twin-screw extruder.
8. The vulcanized SEBS-based nylon encapsulated TPE material of claim 7, wherein the vulcanizing agent is at least one of dicumyl peroxide (DCP), Benzoyl Peroxide (BPO) and sulfur peroxide (S).
9. A method of making the TPE material of claims 1-8, comprising the steps of:
firstly, preparing a vulcanized styrene butadiene styrene copolymer, placing the styrene butadiene styrene copolymer SEBS in a stirring cylinder, placing at least one vulcanizing agent of dicumyl peroxide (DCP), Benzoyl Peroxide (BPO) and sulfur peroxide (S) in the stirring cylinder, uniformly mixing the vulcanizing agent with the styrene butadiene styrene copolymer SEBS, conveying the mixture into a feeding cylinder of a double-screw extruder, and extruding and granulating by the double-screw extruder to obtain vulcanized styrene butadiene styrene copolymer particles;
secondly, placing the prepared vulcanized styrene butadiene styrene copolymer particles, plastic processing oil, a compatilizer, calcium carbonate, tackifying resin and an anti-aging auxiliary agent in a stirring cylinder, uniformly mixing, conveying to a feeding cylinder of a double-screw extruder, and extruding and granulating by the double-screw extruder to obtain a nylon encapsulated TPE material; wherein, the temperature of each area of the double-screw extruder is respectively as follows: the first area is 100-150 ℃, the second area is 130-160 ℃, the third area is 160-180 ℃, the fourth area is 160-180 ℃, the fifth area is 160-180 ℃, the sixth area is 170-180 ℃, the seventh area is 160-170 ℃, and the head is 150-160 ℃.
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Application publication date: 20200828 |