CN114672091B - Method for simultaneously improving multiple properties of ethylene-vinyl acetate copolymer - Google Patents

Method for simultaneously improving multiple properties of ethylene-vinyl acetate copolymer Download PDF

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CN114672091B
CN114672091B CN202210163760.9A CN202210163760A CN114672091B CN 114672091 B CN114672091 B CN 114672091B CN 202210163760 A CN202210163760 A CN 202210163760A CN 114672091 B CN114672091 B CN 114672091B
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vinyl acetate
acetate copolymer
ethylene
parts
preparation
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CN114672091A (en
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申利国
徐思奕
林红军
刘汉洲
李建喜
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Zhejiang Normal University CJNU
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34928—Salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a method for simultaneously improving various properties of an ethylene-vinyl acetate copolymer, and provides a preparation method of a modified ethylene-vinyl acetate copolymer, which comprises the following steps: providing a feedstock comprising: ethylene vinyl acetate copolymer, silane modified nano silicon dioxide, ferric hydroxide and intumescent flame retardant; and uniformly mixing the raw materials, and then extruding and granulating to obtain the modified ethylene-vinyl acetate copolymer. The preparation method has the improvement effect on the mechanical property, the expansion flame retardant property and the hydrophobic property of the ethylene-vinyl acetate copolymer. The modified ethylene-vinyl acetate copolymer provided by the invention can be used for preparing high-performance cable materials, has the advantages of simple equipment, low cost and the like, and is easy for large-scale industrial application.

Description

Method for simultaneously improving multiple properties of ethylene-vinyl acetate copolymer
Technical Field
The invention relates to the technical field of polymer modification, in particular to a method for simultaneously improving multiple properties of an ethylene-vinyl acetate copolymer.
Background
EVA resin is ethylene-vinyl acetate copolymer, and the content of Vinyl Acetate (VA) is generally 5% -40%. Compared with polyethylene, EVA has the advantages that the vinyl acetate monomer is introduced into the molecular chain, so that the high crystallinity is reduced, the flexibility, the impact resistance, the filler compatibility and the heat sealing performance are improved, and the EVA is widely applied to the fields of foaming shoe materials, functional greenhouse films, packaging films, hot melt adhesives, wires, cables, toys and the like. However, the flammability of EVA compared to other plastic materials limits its application. Therefore, there is a great deal of attention to improving the flame retardancy of EVA.
EVA can promote the fire resistance through the mode of adding the intumescent flame retardant, but this can make its mechanical properties decline seriously, and the phosphorus flame retardant that contains in the intumescent flame retardant is liable to absorb water simultaneously, can destroy the flame retardant effect, therefore, improves the mechanical properties and the hydrophobicity of fire-retardant EVA vital.
It would be desirable to develop a method for improving the flame retardancy, hydrophobicity and mechanical properties of EVA at the same time.
Disclosure of Invention
The invention aims to provide a method for simultaneously improving various properties of an ethylene-vinyl acetate copolymer, and the EVA is modified by the preparation method, so that the mechanical property, the intumescent flame retardant property and the hydrophobic property can be simultaneously improved.
To this end, in a first aspect, the present invention provides a process for the preparation of a modified ethylene vinyl acetate copolymer comprising providing a feedstock: the raw materials comprise: ethylene vinyl acetate copolymer, silane modified nano silicon dioxide, ferric hydroxide and intumescent flame retardant; uniformly mixing the raw materials to obtain a mixed material; and sequentially carrying out melt blending and extrusion granulation on the mixed materials to obtain the modified ethylene-vinyl acetate copolymer.
Further, the raw materials comprise, by weight, 80 parts of ethylene-vinyl acetate copolymer, 3-6 parts of silane modified nano silicon dioxide, 0.5-2 parts of ferric hydroxide and 10-16 parts of intumescent flame retardant.
Further, the raw materials for preparing the intumescent flame retardant comprise: ammonium polyphosphate, melamine, pentaerythritol.
In some embodiments, the mass ratio of ammonium polyphosphate, melamine, and pentaerythritol is 3 to 2:1:1, a step of; for example 3:1:1.
in some embodiments, the method of preparing the intumescent flame retardant comprises: per 100 parts by weight of ammonium polyphosphate: melamine: pentaerythritol ratio is 3:1:1 weight part of silane coupling agent is added on the basis of the mass ratio of 1, and the intumescent flame retardant is prepared by uniformly mixing.
Further, the mixing is performed by a high-speed mixer; the mixing conditions include: the rotating speed is 800-1000rpm, and the time is 5-10min; for example at 900rpm for 5 minutes.
Further, melt blending is performed by a kneader or a twin-screw extruder.
Further, the extrusion granulation was performed by a twin screw extruder.
Further, the temperature of the melt blending is 110-130 ℃ and the time is 10-15min; for example, melt blending at 120℃for 10min.
In a second aspect of the invention, there is provided a modified ethylene vinyl acetate copolymer prepared according to the method of the first aspect of the invention.
In a third aspect of the invention, there is provided the use of the modified ethylene vinyl acetate copolymer in the preparation of a cable material.
At present, no related study on the use of silane modified nano silicon dioxide to simultaneously improve the mechanical property and the hydrophobic property of EVA exists in the prior art, and the preparation method of the EVA cable material with high flame retardance, high hydrophobicity and high mechanical property by using the silane modified nano silicon dioxide has important application value and academic significance.
Compared with the prior art, the technical scheme of the invention has the following steps:
(1) The invention provides a preparation method of a modified ethylene-vinyl acetate copolymer, which can improve the mechanical property, the intumescent flame retardant property and the hydrophobic property of the ethylene-vinyl acetate copolymer. The performance of the modified ethylene-vinyl acetate copolymer prepared by the invention is detectedThe tensile strength can reach more than 20.3Mpa, and the elongation at break can reach more than 685%; the water absorption performance test is carried out on the material, the water contact angle is 99 degrees, and the water absorption rate is below 0.1 percent; the flame retardant performance of the glass fiber was tested, and the heat release rate was 537.2kW/m 2 The total heat release amount was 148.6MJ/m 2 The following is given.
(2) The modified ethylene-vinyl acetate copolymer provided by the invention can be used for preparing high-performance cable materials, has the advantages of simple equipment, low cost and the like, and is easy for large-scale industrial application.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. In the drawings:
fig. 1: the tensile strength and elongation at break detection result of the modified EVA material prepared by the preparation method provided by the invention;
fig. 2: the water absorption detection result of the modified EVA material prepared by the preparation method provided by the invention;
fig. 3: the water contact angle detection result of the modified EVA material prepared by the preparation method provided by the invention;
fig. 4: the heat release rate detection result of the modified EVA material prepared by the preparation method provided by the invention;
fig. 5: the total heat release amount of the modified EVA material prepared by the preparation method provided by the invention is detected.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
Example 1
The embodiment provides a modified EVA material, and the preparation method thereof is as follows:
(1) Per 100 parts by weight of ammonium polyphosphate: melamine: pentaerythritol ratio is 3:1:1 weight part of silane coupling agent kh550 is added on the basis of the mass ratio of 1, and uniformly mixed by a high-speed mixer at 500rpm for 5min to prepare an Intumescent Flame Retardant (IFR);
(2) According to parts by weight, 14 parts of IFR, 1 part of FeOOH, 5 parts of silane modified nano silicon dioxide R106 and 80 parts of EVA2803 are put into a high-speed mixer to be evenly mixed, and the rotation speed is 900rpm for 5min, so as to obtain a mixed material;
(3) And (3) putting the mixed material obtained in the step (2) into a double-screw extruder, carrying out melt blending at 120 ℃ for 10min, and granulating to obtain a modified EVA material which can be used as a flame-retardant EVA cable material.
Example 2
The embodiment provides a modified EVA material, and the preparation method thereof is as follows:
(1) Per 100 parts by weight of ammonium polyphosphate: melamine: pentaerythritol ratio is 3:1:1 weight part of silane coupling agent kh550 is added on the basis of the mass ratio of 1, and uniformly mixed by a high-speed mixer at 500rpm for 5min to prepare an Intumescent Flame Retardant (IFR);
(2) According to parts by weight, putting 16 parts of IFR, 1 part of FeOOH, 4 parts of silane modified nano silicon dioxide R106 and 80 parts of EVA2803 into a high-speed mixer for uniform mixing at 800rpm for 10min to obtain a mixed material;
(3) And (3) putting the mixed material obtained in the step (2) into a double-screw extruder, carrying out melt blending at 130 ℃ for 10min, and granulating to obtain a modified EVA material which can be used as a flame-retardant EVA cable material.
Example 3
The embodiment provides a modified EVA material, and the preparation method thereof is as follows:
(1) Per 100 parts by weight of ammonium polyphosphate: melamine: pentaerythritol ratio is 3:1:1 weight part of silane coupling agent kh550 is added on the basis of the mass ratio of 1, and uniformly mixed by a high-speed mixer at 500rpm for 5min to prepare an Intumescent Flame Retardant (IFR);
(2) According to the weight ratio, 12 parts of IFR, 1.5 parts of FeOOH, 6 parts of silane modified nano silicon dioxide R106 and 80 parts of EVA2803 are put into a high-speed mixer to be evenly mixed, and the rotating speed is 1000rpm for 8 minutes, so as to obtain a mixed material;
(3) And (3) putting the mixed material obtained in the step (2) into a double-screw extruder, carrying out melt blending at 120 ℃ for 15min, and granulating to obtain a modified EVA material which can be used as a flame-retardant EVA cable material.
Experimental example
The modified EVA material (EVA-2) prepared in example 1 is taken as a control (EVA-1), and the mechanical property, the water contact angle and the water absorption are detected. The detection results are shown in FIGS. 1-5. According to the detection result, the tensile strength of the modified EVA material provided by the invention is 20.3MPa, and the elongation at break reaches 685% (shown in figure 1); the water contact angle is 99 degrees (figure 2), the water absorption is reduced to 0.1 percent (figure 3), and the water absorption is greatly reduced; in addition, the heat release rate is reduced to 537.2kW/m 2 (FIG. 4) the total heat release was reduced to 148.6MJ/m 2 (FIG. 5) was reduced by 23.3% and 6%, respectively, compared to EVA cable material without added nanosilica.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (9)

1. The preparation method of the modified ethylene-vinyl acetate copolymer is characterized by comprising the following steps of: providing raw materials, wherein the raw materials comprise the following components in parts by weight: 80 parts of ethylene-vinyl acetate copolymer, 5 parts of silane modified nano silicon dioxide, 1 part of ferric hydroxide and 14 parts of intumescent flame retardant; uniformly mixing the raw materials to obtain a mixed material; and sequentially carrying out melt blending and extrusion granulation on the mixed materials to obtain the modified ethylene-vinyl acetate copolymer.
2. The method of preparing as claimed in claim 1, wherein the raw materials for preparing the intumescent flame retardant comprise: ammonium polyphosphate, melamine, pentaerythritol.
3. The preparation method according to claim 2, wherein the mass ratio of the ammonium polyphosphate, the melamine and the pentaerythritol is 3-2:1:1.
4. the method of claim 1, wherein the mixing is performed by a high speed mixer; the mixing conditions include: the rotating speed is 800-1000rpm, and the time is 5-10min.
5. The method of claim 1, wherein the melt blending is performed by a kneader.
6. The method of claim 1, wherein the extrusion granulation is performed by a twin screw extruder.
7. The method of claim 1, wherein the melt blending is performed at a temperature of 110 to 130 ℃ for a time of 10 to 15 minutes.
8. A modified ethylene vinyl acetate copolymer prepared according to the method of any one of claims 1-7.
9. Use of the modified ethylene vinyl acetate copolymer of claim 8 in the preparation of a cable material.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5291792A (en) * 1976-01-29 1977-08-02 Mitsubishi Rayon Co Ltd Production of water treating sheet material
EP1086982A1 (en) * 1999-09-22 2001-03-28 Toda Kogyo Corporation Resin composition and laminated film
CN102492214A (en) * 2011-12-21 2012-06-13 西北师范大学 Ethylene-vinyl acetate-based halogen-free flame retardant conductive high molecular composite material
CN103788451A (en) * 2014-01-07 2014-05-14 苏州奥凯材料技术有限公司 PE (polyethylene) flame-retardant cable material and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1541640A1 (en) * 2003-12-05 2005-06-15 Rohm and Haas Company Induction cured power coatings for temperature sensitive substrates

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5291792A (en) * 1976-01-29 1977-08-02 Mitsubishi Rayon Co Ltd Production of water treating sheet material
EP1086982A1 (en) * 1999-09-22 2001-03-28 Toda Kogyo Corporation Resin composition and laminated film
CN102492214A (en) * 2011-12-21 2012-06-13 西北师范大学 Ethylene-vinyl acetate-based halogen-free flame retardant conductive high molecular composite material
CN103788451A (en) * 2014-01-07 2014-05-14 苏州奥凯材料技术有限公司 PE (polyethylene) flame-retardant cable material and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Influence of Different Metal Oxides on the Thermal, Combustion Properties and Smoke Suppression in Ethylene-Vinyl Acetate;Wang, L 等;《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》;第52卷(第23期);8062-8069 *
Simultaneously improving mechanical strength, hydrophobic property and flame retardancy of ethylene vinyl acetate copolymer/intumescent flame retardant/FeOOH by introducing modified fumed silica;Xu, SY 等;《MATERIALS TODAY COMMUNICATIONS》;第26卷;文献号102114 *
聚乙烯—醋酸乙烯酯/铁氧化物复合材料制备及其火安全性研究;汪磊;《中国博士学位论文全文数据库 工程科技Ⅰ辑(月刊)》(第10期);B020-14 *

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