CN112759886B - TPE (thermoplastic elastomer) alloy for bonding and encapsulating polyphenyl ether as well as preparation method and application thereof - Google Patents
TPE (thermoplastic elastomer) alloy for bonding and encapsulating polyphenyl ether as well as preparation method and application thereof Download PDFInfo
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- CN112759886B CN112759886B CN202011602689.7A CN202011602689A CN112759886B CN 112759886 B CN112759886 B CN 112759886B CN 202011602689 A CN202011602689 A CN 202011602689A CN 112759886 B CN112759886 B CN 112759886B
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- C08L53/00—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
- 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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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
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Abstract
The invention discloses a TPE alloy for bonding and encapsulating polyphenyl ether and a preparation method and application thereof, wherein a certain proportion of non-polar thermoplastic elastomer, polar thermoplastic elastomer and engineering plastic are compounded, and then components such as plasticizer, compatilizer and the like are added to prepare the TPE alloy together, so that the compatibility between two phases is improved, the bonding force between the two phases is improved, and the heat resistance of the TPE alloy material can also be improved; the TPE alloy prepared by the invention can be widely applied to a polyphenyl ether bonding and encapsulating process.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a TPE alloy for bonding and encapsulating polyphenyl ether, and a preparation method and application thereof.
Background
Polyphenylene Ether (PPE) has excellent mechanical properties, heat resistance, flame retardancy and the like, and is widely applied to the automobile industry, the electronic and electrical industry, the mechanical industry, the chemical industry and the like.
In order to endow a material product with comfortable touch, improve the holding property, improve the product aesthetic degree and the product added value and improve the anti-falling property of a plastic product, a rubber coating injection bonding process is generally adopted to bond polyphenyl ether, the rubber coating utilizes the compatibility of soft rubber and hard plastic rubber during softening and melting, the better the compatibility of the two materials is, the easier the bonding is, a bonding layer is formed on the contact surface of the hard plastic rubber and the soft rubber, the rubber coating bonding property of the soft rubber and the hard plastic rubber is greatly improved, a thermoplastic elastomer (TPE for short) material is a novel high polymer material between rubber and resin, not only can replace part of rubber, but also can modify the plastic, and the application is more and more realized in the fields of automobile industry, electronic appliances, electric wires and cables and the like. Chinese patent CN102181169A discloses a TPE alloy material for PBT adhesive encapsulation, which is prepared from components such as thermoplastic elastomer, engineering plastic, plasticizer and the like, but the TPE alloy material for the PBT adhesive encapsulation has the defects of poor PPE encapsulation effect, poor cohesiveness, insufficient heat resistance and the like when being used for the PPE adhesive encapsulation, still belongs to the difficulty in the industry, and has no related application patent in China.
Disclosure of Invention
The invention aims to solve the technical problems of poor cohesiveness and insufficient heat resistance of the traditional TPE alloy to PPE adhesive encapsulation, and provides a TPE alloy for polyphenylene ether adhesive encapsulation, which can improve the compatibility of the TPE alloy and PPE and improve the cohesiveness and heat resistance of the TPE alloy to PPE adhesive encapsulation.
It is a further object of the present invention to provide a process for preparing a TPE alloy for polyphenylene ether adhesive encapsulation.
It is another object of the present invention to provide a use of a TPE alloy for polyphenylene ether adhesive encapsulation.
The above purpose of the invention is realized by the following technical scheme:
the TPE alloy for the bonding encapsulation of the polyphenyl ether comprises the following components in parts by mass:
the non-polar thermoplastic elastomer is one or more polymers of styrene, butadiene and isoprene; the polar thermoplastic elastomer is one or more of polyurethane, polyester elastomer, nylon-based elastomer, EVA and surlyn resin; the engineering plastic is one or more of polyphenyl ether, polyphenylene sulfide, polyamide, polycarbonate and polyester.
The invention takes polar thermoplastic elastomer and nonpolar thermoplastic elastomer as base materials, and adds engineering plastics, wherein the polar thermoplastic elastomer is easy to form hydrogen bonds with ether groups in PPE molecular structure, thus improving the compatibility between TPE alloy and PPE, further improving the adhesive force between TPE alloy and PPE two phases, and introducing the engineering plastics, and utilizing the synergistic effect of molecular winding between the polar thermoplastic elastomer and the engineering plastics, the heat resistance of the material is greatly improved.
Preferably, the composition comprises the following components in parts by mass:
preferably, the non-polar thermoplastic elastomer is one or more of styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-propylene-styrene block copolymer and styrene-ethylene-propylene-styrene block copolymer.
Preferably, the polar thermoplastic elastomer is one or more of polyurethane, polyester elastomer and EVA.
Preferably, the engineering plastic is one or more of polyphenyl ether, polyamide and polycarbonate.
The plasticizer of the invention includes but is not limited to one or more of paraffin oil, naphthenic oil, lipid plasticizer, petroleum resin and the like.
The compatilizer provided by the invention comprises one or more of maleic anhydride grafted styrene copolymer, maleic anhydride grafted olefin copolymer, maleic anhydride grafted polyolefin, glycidyl methacrylate grafted styrene copolymer, glycidyl methacrylate grafted olefin copolymer and glycidyl methacrylate grafted polyolefin.
The filler of the invention comprises one or more of calcium carbonate, talcum powder, wollastonite, mica, kaolin and silicon dioxide.
The auxiliary agent comprises but is not limited to one or more of an antioxidant, a light stabilizer, a lubricant and an anti-hydrolysis agent.
The invention protects the preparation method of the TPE alloy, which comprises the following steps:
uniformly mixing the non-polar thermoplastic elastomer, the polar thermoplastic elastomer and the plasticizer, then adding the engineering plastic, the compatilizer, the filler and the auxiliary agent, uniformly mixing, extruding, granulating and drying to obtain the TPE alloy.
The invention also protects the application of the TPE alloy in the bonding encapsulation of the polyphenyl ether.
A polyphenylene ether adhesive encapsulated article comprises the TPE alloy.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the non-polar thermoplastic elastomer, the polar thermoplastic elastomer and the engineering plastic are compounded according to a certain proportion, then the plasticizer, the compatilizer and other components are added to prepare the TPE alloy together, and the compatibility between the TPE alloy and the PPE is improved by introducing the specific polar engineering plastic, the polar thermoplastic elastomer and the engineering plastic, so that the bonding force with the PPE is improved, and in addition, the heat resistance of the TPE alloy material is improved; the TPE alloy prepared by the invention can be widely applied to a polyphenyl ether bonding and encapsulating process.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
The raw materials used in the respective examples and comparative examples:
non-polar thermoplastic elastomer: SEBS (SEBS 1652, kraton);
polar thermoplastic elastomer TPU: TPU 1180A, basf;
polar thermoplastic elastomer TPEE: hytral 4056, dupont;
polar thermoplastic elastomer EVA: escorene Ultra FL 02020, exxon Mobil;
engineering plastics: polyphenylene ether PPE (NORYL Resin WCA871A, saber base);
engineering plastics: polyamide PA (ULTRAMID 8202C, basff)
Engineering plastics: polycarbonate PC (LUPOY PC 1300-03, LG)
Plasticizer: 90# white oil (PW-90, japan Bright);
a compatilizer: maleic anhydride grafted POE (Fusabond N493, dupont);
filling: heavy calcium carbonate;
antioxidant: irganox 1010, irgafos 168, pasteur;
light stabilizer: cyasorb UV-3808pps, cyastemin.
Example 1
A TPE alloy for polyphenylene ether adhesive encapsulation comprises the following components in parts by mass in Table 1.
The preparation method of the TPE alloy for bonding and encapsulating the polyphenyl ether comprises the following steps:
putting the thermoplastic elastomer into a low-speed mixer, adding the plasticizer while stirring, sucking dry and uniformly mixing all the plasticizer; putting the thermoplastic elastomer containing the plasticizer and all other materials into a high-speed mixer to be uniformly mixed; and (3) feeding the uniformly mixed materials into a double-screw extruder in a weightless manner, extruding at 230 ℃, granulating and drying to obtain the TPE alloy, wherein the length-diameter ratio of the double-screw extruder is 60/1, and the retention time of the materials in the screw is 90s.
Examples 2 to 11 and comparative examples 1 to 3
The components and their parts by mass of examples 2 to 11 and comparative examples 1 to 3 are shown in tables 1 and 2 below, and the preparation method thereof is the same as example 1.
TABLE 1 Components and parts by mass of the examples
TABLE 2 Components in respective proportions and parts by mass thereof
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Non-polar thermoplastic elastomer SEBS | 70 | 40 | 60 |
| Polar thermoplastic elastomer TPU | 30 | ||
| Engineering Plastic Polyphenylene Ether (PPE) | 10 | ||
| Plasticizer No. 90 white oil | 20 | 20 | 20 |
| Compatilizer maleic anhydride grafted POE | 10 | 10 | 10 |
| Heavy calcium carbonate as filler | 30 | 30 | 30 |
| Irganox 1010 | 0.1 | 0.1 | 0.1 |
| Irgafos 168 | 0.1 | 0.1 | 0.1 |
| Light stabilizer Cyasorb UV-3808pps | 0.1 | 0.1 | 0.1 |
Performance testing
1. Test method
(1) Encapsulation peel strength (VDI 2019): firstly, polyphenylene ether (PPE) is manufactured into a rectangular plate with the thickness of 2.0mm and the thickness of 150 x 40mm through an injection molding or die pressing process, then the rectangular plate is placed into an encapsulation mold, and TPE alloy is adhered to the surface of a PPE plate through the injection molding or die pressing process; stripping the TPE soft rubber from the rubber coating test plate by adopting a universal testing machine and a special clamp; measuring and recording the force during the peeling process; the larger the value is, the better the encapsulation effect is, and when the value reaches 2.0, the application requirement is met.
(2) Heat resistance effect test method (ISO 188): making TPE alloy into 100 × 100mm square plates with thickness of 2.0mm by injection molding or die pressing process, and cutting into I-shaped dumbbell-shaped sample strips with at least 10 pieces for use by a custom cutter, wherein 5 pieces are tested for tensile strength delta 0 And elongation at break ε 0 5 of the test pieces were placed in a forced air drying oven at 110 ℃ for 1000 hours, and then the tensile strength delta was measured t And elongation at break ε t The tensile strength retention ratio delta was calculated 0 /δ t X 100% and elongation at break holding ratio ε 0 /ε t X 100%. The larger the retention rate of tensile strength and the retention rate of elongation at break is, the better the heat resistance is, and when the retention rates of tensile strength and elongation at break are both more than 50%, the application requirements can be met.
2. Test results
TABLE 3 results of Performance test of each example and comparative example
As can be seen from the results of table 3, comparative example 1 and comparative example 3, to which the polar thermoplastic elastomer was not added, had a lower encapsulation peel strength and a poor encapsulation effect, while comparative example 2, to which the polar thermoplastic elastomer was added and to which the engineering plastic was not added, had an encapsulation peel strength increased to 2.0, but the retention of tensile strength and elongation at break after aging was very low and the heat resistance was poor; from example 6, it can be seen that the addition of 10 parts of polar thermoplastic elastomer and 10 parts of engineering plastic increases the peel strength of the encapsulation to 3.3N/mm, and the heat resistance is excellent; example 7 shows that the addition of 30 parts of polar thermoplastic elastomer and 10 parts of engineering plastic can increase the peel strength of the encapsulation to 4.8N/mm, and the performance retention rate after aging is more than 50%, which reaches a good level; in examples 1 to 5, 30 parts of polar thermoplastic elastomer and 10 parts of engineering plastic were added, and both the encapsulation property and the heat resistance reached excellent levels.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (7)
1. The application of TPE alloy in bonding and encapsulating polyphenyl ether is characterized in that the TPE alloy comprises the following components in parts by mass:
the non-polar thermoplastic elastomer is one or more of styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-propylene-styrene block copolymer and styrene-ethylene-propylene-styrene block copolymer; the polar thermoplastic elastomer is one or more of polyurethane, polyester elastomer, nylon-based elastomer, EVA and surlyn resin; the engineering plastic is polyphenyl ether.
2. The application of the composition as claimed in claim 1, which comprises the following components in parts by mass:
3. the use according to claim 1, wherein the polar thermoplastic elastomer is one or more of polyurethane, polyester elastomer, EVA.
4. The use according to claim 1, wherein the plasticizer is one or more of paraffin oil, naphthenic oil, lipid plasticizer and petroleum resin.
5. The use of claim 1, wherein the compatibilizer is one or more of maleic anhydride grafted styrene copolymer, maleic anhydride grafted polyolefin, glycidyl methacrylate grafted styrene copolymer, and glycidyl methacrylate grafted polyolefin.
6. The use as claimed in any one of claims 1 to 5, wherein the TPE alloy is prepared by a process comprising the steps of:
uniformly mixing the non-polar thermoplastic elastomer, the polar thermoplastic elastomer and the plasticizer, then adding the engineering plastic, the compatilizer, the filler and the auxiliary agent, uniformly mixing, extruding, granulating and drying to obtain the TPE alloy.
7. A polyphenylene ether adhesive encapsulated article comprising a TPE alloy according to any of claims 1 to 5.
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| US7671130B2 (en) * | 2004-12-16 | 2010-03-02 | Exxonmobil Chemical Patents Inc. | Thermoplastic elastomers having improved adhesive properties |
| CN102558739B (en) * | 2011-04-21 | 2015-04-22 | 深圳市塑源实业有限公司 | Preparation method of TPE (thermoplastic elastomer) alloy material for PCTG bonding and encapsulating |
| CN103554819A (en) * | 2013-10-28 | 2014-02-05 | 深圳市科聚新材料有限公司 | Thermoplastic elastomer (TPE) alloy for nylon adhesive encapsulation and preparation method thereof |
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