CN109897273B - Composite flame retardant graft-modified EVA (ethylene-vinyl acetate) foam material and preparation method thereof - Google Patents
Composite flame retardant graft-modified EVA (ethylene-vinyl acetate) foam material and preparation method thereof Download PDFInfo
- Publication number
- CN109897273B CN109897273B CN201910200997.8A CN201910200997A CN109897273B CN 109897273 B CN109897273 B CN 109897273B CN 201910200997 A CN201910200997 A CN 201910200997A CN 109897273 B CN109897273 B CN 109897273B
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- eva
- parts
- modified
- dopo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a composite flame retardant graft modified EVA (ethylene-vinyl acetate) foam material and a preparation method thereof, belonging to the field of polymer composite foam materials. The EVA foam composite material is prepared from the following raw materials: the flame retardant is characterized by comprising EVA, a composite flame retardant, maleic anhydride grafted EVA, a foaming agent, stearic acid, zinc stearate, zinc oxide and a crosslinking agent, wherein the composite flame retardant is a modified DOPO/graphene oxide composite material, and a high-efficiency flame retardant EVA system is constructed. The foam material has the advantages of less addition of the flame retardant, no halogen and stable effect; also maintains stable mechanical property and has wide application prospect.
Description
Technical Field
The invention belongs to the field of polymer composite foaming materials, and particularly relates to a preparation method of a composite flame retardant graft-modified EVA (ethylene-vinyl acetate) foam material.
Background
The EVA foaming composite material has the advantages of low density, strong buffering and shock absorbing capacity, low temperature resistance and the like, and is widely applied to the fields of shoe materials, buildings, packaging and the like. However, EVA is a flammable material, is easy to cause fire in the using process, and has great threat to the property and personal safety of people, thereby limiting the application field of the EVA. Adding a flame retardant to EVA for improving its flame retardant properties is a common way of flame retardancy. Although the traditional halogen flame retardant can bring good flame retardant performance to materials, a large amount of smoke and toxic and corrosive hydrogen halide gas are generated in the combustion process, and the traditional halogen flame retardant does not meet the requirement of environment-friendly development and is forbidden to be used. The metal hydroxide is non-volatile, does not generate toxic and harmful gases, is considered to be the flame retardant with the most development prospect, and is favored by people. However, when the metal hydroxide is used for flame-retardant polyolefin, the flame-retardant property is required to reach a certain level, and the addition amount is usually over 60 percent, so that the processing property and the mechanical property of the composite material are seriously influenced by the large addition amount.
Compared with other organic and inorganic filling flame retardants, the DOPO-based flame retardant has the characteristics of high efficiency, environmental protection and the like when being used as a phosphorus flame retardant and graphene, and has a great application prospect. Therefore, the phosphorus system/graphene compound flame retardant is added into the EVA to synthesize the flame-retardant EVA foam composite material with stable flame-retardant effect.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the flame-retardant EVA foam composite material and the preparation method thereof, and the material has the advantages of less addition of a flame retardant, no halogen and stable effect; also maintains stable mechanical property and has wide application prospect.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the composite flame retardant graft modified EVA foam material comprises the following raw materials in parts by weight: 80-100 parts of ethylene-vinyl acetate copolymer EVA, 1-10 parts of composite flame retardant, 1-10 parts of maleic anhydride grafted EVA, 10-30 parts of talcum powder, 2.8-3.5 parts of foaming agent AC, 1.5 parts of stearic acid, 0.5 part of zinc stearate, 0.8 part of zinc oxide and 0.8 part of dicumyl peroxide DCP; the composite flame retardant is a modified DOPO/graphene oxide composite material.
The VA content of the ethylene-vinyl acetate copolymer EVA is 18-28 wt%. The grafting rate of the maleic anhydride grafted EVA is 2%.
The modified DOPO/graphene oxide composite flame-retardant material is obtained by compounding and modifying DOPO by using trihydroxymethyl phosphine oxide THPO and graphene oxide, and specifically comprises the following steps:
1) dissolving 2.0g of tris (hydroxymethyl) phosphine oxide (THPO) and 12.5g of DOPO in 200mL of ethanol at the temperature of ice bath below 5 ℃ and uniformly stirring;
2) after complete dissolution, 8.5g CCl4Slowly adding the solution into the solution obtained in the step 1), stirring for 6 hours in a water bath at 30 ℃, adding 0.6g of graphene oxide, and continuously reacting for 4 hours;
3) and filtering the obtained modified DOPO/graphene oxide composite material, centrifuging for 2-4 times to remove impurities, and drying in a vacuum oven.
The preparation method of the composite flame retardant graft-modified EVA foam material specifically comprises the following steps:
1) uniformly mixing ethylene-vinyl acetate copolymer EVA, a composite flame retardant, maleic anhydride grafted EVA, talcum powder, stearic acid, zinc stearate, zinc oxide, dicumyl peroxide DCP and a foaming agent AC, and then placing the mixture into a preheated extruder, wherein the temperature of each zone is 105-115 ℃, and the extrusion mixing is carried out at the rotating speed of 20 rpm;
2) quickly transferring the mixture obtained in the step 1) to an open mill, mixing for 10-20min, and pressing the materials into slices;
3) placing the sheet prepared in the step 2) in a preheated plate vulcanizing machine die cavity, and carrying out die pressing and foaming for 6min at 10MPa and 170 ℃ to obtain the composite flame retardant graft modified EVA foam material.
The invention has the beneficial effects that:
1. the modified DOPO has different P groups, free radicals such as PO & and the like can quench high-activity H & and OH & free radicals generated by pyrolysis and hinder free radical chain reaction, and gas-phase flame retardance is realized and enhanced. Compared with a single DOPO flame retardant, the flame retardant efficiency is improved.
2. Graphene oxide GO surface contains active group, improves system cohesion and stability, and GO is as synergist simultaneously, can generate compact and stable protective carbide layer when the material is tentatively burnt, and extension micromolecule migrates to the surface, with DOPO synergism, isolated oxygen and the heat of burning production are to the inside transmission of material, realize that the coacervate is fire-retardant, have constructed efficient fire-retardant system.
3. The maleic anhydride grafted EVA is adopted for dry grafting, so that the compatibility of each material, particularly a flame retardant in an EVA matrix is improved, and the material is not easy to agglomerate, thereby effectively improving the flame retardant property of the invention.
Drawings
Fig. 1 is an XRD pattern of graphene oxide (a) and modified DOPO/graphene oxide (b);
fig. 2 is an SEM image of graphene oxide (a) and modified DOPO/graphene oxide (b).
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.
Example 1
A preparation method of a composite flame retardant graft-modified EVA foam material specifically comprises the following steps:
1) dissolving 2.0g of tris (hydroxymethyl) phosphine oxide (THPO) and 12.5g of DOPO in 200mL of ethanol at the temperature of ice bath below 5 ℃ and uniformly stirring;
2) after complete dissolution, 8.5g CCl4Slowly adding the solution into the solution obtained in the step 1), stirring for 6 hours in a water bath at 30 ℃, adding 0.6g of graphene oxide, and continuously reacting for 4 hours;
3) filtering the obtained modified DOPO/graphene oxide composite flame retardant, centrifuging for 3 times to remove impurities, and drying in a vacuum oven;
4) uniformly mixing 90 parts by weight of EVA, 2 parts by weight of composite flame retardant, 6 parts by weight of maleic anhydride grafted EVA, 15 parts by weight of talcum powder, 1.5 parts by weight of stearic acid, 0.5 part by weight of zinc stearate, 0.8 part by weight of zinc oxide, 0.8 part by weight of dicumyl peroxide DCP and 3 parts by weight of foaming agent AC, and then placing the mixture in a preheated extruder, wherein the temperature of each zone is 110 ℃, and the rotating speed is 20rpm for extrusion and mixing;
5) quickly transferring the mixture obtained in the step 4) into an open mill, mixing for 15min, and pressing the materials into slices;
6) placing the sheet prepared in the step 5) in a preheated press vulcanizer die cavity, and carrying out die pressing and foaming for 6min at 10MPa and 170 ℃ to obtain the composite flame retardant graft modified EVA foam material.
Example 2
A preparation method of a composite flame retardant graft-modified EVA foam material specifically comprises the following steps:
1) dissolving 2.0g of tris (hydroxymethyl) phosphine oxide (THPO) and 12.5g of DOPO in 200mL of ethanol at the temperature of ice bath below 5 ℃ and uniformly stirring;
2) after complete dissolution, 8.5g CCl4Slowly adding the solution into the solution obtained in the step 1), stirring for 6 hours in a water bath at 30 ℃, adding 0.6g of graphene oxide, and continuously reacting for 4 hours;
3) filtering the obtained modified DOPO/graphene oxide composite flame retardant, centrifuging for 3 times to remove impurities, and drying in a vacuum oven;
4) uniformly mixing 90 parts by weight of EVA, 4 parts by weight of composite flame retardant, 8 parts by weight of maleic anhydride grafted EVA, 15 parts by weight of talcum powder, 1.5 parts by weight of stearic acid, 0.5 part by weight of zinc stearate, 0.8 part by weight of zinc oxide, 0.8 part by weight of dicumyl peroxide DCP and 3 parts by weight of foaming agent AC, placing the mixture in a preheated extruder, and extruding and mixing the mixture in each zone at the temperature of 110 ℃ and the rotating speed of 20 rpm;
5) quickly transferring the mixture obtained in the step 4) into an open mill, mixing for 15min, and pressing the materials into slices;
6) placing the sheet prepared in the step 5) in a preheated press vulcanizer die cavity, and carrying out die pressing and foaming for 6min at 10MPa and 170 ℃ to obtain the composite flame retardant graft modified EVA foam material.
Example 3
A preparation method of a composite flame retardant graft-modified EVA foam material specifically comprises the following steps:
1) dissolving 2.0g of tris (hydroxymethyl) phosphine oxide (THPO) and 12.5g of DOPO in 200mL of ethanol at the temperature of ice bath below 5 ℃ and uniformly stirring;
2) after complete dissolution, 8.5g CCl4Slowly adding the solution into the solution obtained in the step 1), stirring for 6 hours in a water bath at 30 ℃, adding 0.6g of graphene oxide, and continuously reacting for 4 hours;
3) the obtained modified DOPO/graphene oxide composite flame retardant is filtered and centrifuged for 2 times to remove impurities. Drying in a vacuum oven;
4) uniformly mixing 90 parts by weight of EVA, 6 parts by weight of composite flame retardant, 8 parts by weight of maleic anhydride grafted EVA, 15 parts by weight of talcum powder, 1.5 parts by weight of stearic acid, 0.5 part by weight of zinc stearate, 0.8 part by weight of zinc oxide, 0.8 part by weight of dicumyl peroxide DCP and 3 parts by weight of foaming agent AC, placing the mixture in a preheated extruder, and extruding and mixing the mixture in each zone at the temperature of 105 ℃ and the rotating speed of 20 rpm;
5) quickly transferring the mixture obtained in the step 4) into an open mill, mixing for 10min, and pressing the materials into slices;
6) placing the sheet prepared in the step 5) in a preheated press vulcanizer die cavity, and carrying out die pressing and foaming for 6min at 10MPa and 170 ℃ to obtain the composite flame retardant graft modified EVA foam material.
Example 4
A preparation method of a composite flame retardant graft-modified EVA foam material specifically comprises the following steps:
1) dissolving 2.0g of tris (hydroxymethyl) phosphine oxide (THPO) and 12.5g of DOPO in 200mL of ethanol at the temperature of ice bath below 5 ℃ and uniformly stirring;
2) after complete dissolution, 8.5g CCl4Slowly adding the solution into the solution obtained in the step 1), stirring for 6 hours in a water bath at 30 ℃, adding 0.6g of graphene oxide, and continuously reacting for 4 hours;
3) the obtained modified DOPO/graphene oxide composite flame retardant is filtered and centrifuged for 4 times to remove impurities. Drying in a vacuum oven;
4) uniformly mixing 90 parts by weight of EVA, 8 parts by weight of composite flame retardant, 10 parts by weight of maleic anhydride grafted EVA, 15 parts by weight of talcum powder, 1.5 parts by weight of stearic acid, 0.5 part by weight of zinc stearate, 0.8 part by weight of zinc oxide, 0.8 part by weight of dicumyl peroxide DCP and 3 parts by weight of foaming agent AC, placing the mixture in a preheated extruder, and extruding and mixing the mixture in each zone at the temperature of 115 ℃ and the rotating speed of 20 rpm;
5) quickly transferring the mixture obtained in the step 4) into an open mill, mixing for 20min, and pressing the materials into slices;
6) placing the sheet prepared in the step 5) in a preheated press vulcanizer die cavity, and carrying out die pressing and foaming for 6min at 10MPa and 170 ℃ to obtain the composite flame retardant graft modified EVA foam material.
Comparative example 1
A preparation method of an EVA foam material specifically comprises the following steps:
1) uniformly mixing 90 parts by weight of EVA, 15 parts by weight of talcum powder, 1.5 parts by weight of stearic acid, 0.5 part by weight of zinc stearate, 0.8 part by weight of zinc oxide, 0.8 part by weight of dicumyl peroxide (DCP) and 3 parts by weight of foaming Agent (AC), and then placing the mixture in a preheated extruder, wherein the temperature of each zone is 110 ℃, and the rotating speed is 20rpm for extrusion and mixing;
2) quickly transferring the mixture obtained in the step 2) to an open mill, mixing for 15min, and pressing the materials into slices;
3) placing the sheet prepared in the step 3) in a preheated press vulcanizer die cavity, and carrying out die pressing and foaming for 6min at 10MPa and 170 ℃ to obtain the composite flame retardant graft modified EVA foam material.
The products of examples 1-4 and the product of comparative example 1 were subjected to performance tests following the relevant standards, the results of which are shown in table 1:
TABLE 1 mechanical Properties of the products of the examples
Curve a in fig. 1 shows a sharp diffraction peak at 10.5 °, corresponding to the characteristic diffraction peak of graphene oxide, indicating that graphite has been oxidized to graphene oxide. The diffraction peak intensity of curve b is reduced and shifted to 9.2 ° to the left, indicating that the interlayer spacing is further increased due to the reaction of the modified DOPO with the oxygen-containing functional groups of GO, increasing the distance between GO sheets.
In fig. 2 a can see the lamellar structure of the folds contained in the GO surface, and the folds appearing in b in fig. 2 are more obvious because the modified DOPO is introduced to increase the degree of folds and the surface appears with some nodular shadows, indicating that the modified DOPO is grafted to the GO surface.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (2)
1. The EVA foam material grafted and modified by the composite flame retardant is characterized in that: the foam material comprises the following components in parts by weight: 80-100 parts of ethylene-vinyl acetate copolymer EVA, 1-10 parts of composite flame retardant, 3-10 parts of maleic anhydride grafted EVA, 10-30 parts of talcum powder, 2.8-3.5 parts of foaming agent AC, 1.5 parts of stearic acid, 0.5 part of zinc stearate, 0.8 part of zinc oxide and 0.8 part of dicumyl peroxide DCP; the composite flame retardant is a modified DOPO/graphene oxide composite material;
the VA content of the ethylene-vinyl acetate copolymer EVA is 18-28 wt%; the grafting rate of the maleic anhydride grafted EVA is 2%;
the modified DOPO/graphene oxide composite material is obtained by compounding and modifying DOPO by trihydroxymethyl phosphine oxide THPO and graphene oxide;
the specific preparation method of the modified DOPO/graphene oxide composite material comprises the following steps:
1) dissolving 2.0g of tris (hydroxymethyl) phosphine oxide (THPO) and 12.5g of DOPO in 200mL of ethanol at the temperature of ice bath below 5 ℃ and uniformly stirring;
2) after complete dissolution, 8.5g CCl4Slowly adding the solution into the solution obtained in the step 1), stirring for 6 hours in a water bath at 30 ℃, adding 0.6g of graphene oxide, and continuously reacting for 4 hours;
3) and filtering the obtained modified DOPO/graphene oxide composite material, centrifuging for 2-4 times to remove impurities, and drying in a vacuum oven.
2. A method for preparing the composite flame retardant graft-modified EVA foam of claim 1, characterized by: the method comprises the following steps:
1) uniformly mixing ethylene-vinyl acetate copolymer EVA, a composite flame retardant, maleic anhydride grafted EVA, talcum powder, stearic acid, zinc stearate, zinc oxide, dicumyl peroxide DCP and a foaming agent AC, and then placing the mixture into a preheated extruder, wherein the temperature of each zone is 105-115 ℃, and the extrusion mixing is carried out at the rotating speed of 20 rpm;
2) quickly transferring the mixture obtained in the step 1) to an open mill, mixing for 10-20min, and pressing the materials into slices;
3) placing the sheet prepared in the step 2) in a preheated plate vulcanizing machine die cavity, and carrying out die pressing and foaming for 6min at 10MPa and 170 ℃ to obtain the composite flame retardant graft modified EVA foam material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910200997.8A CN109897273B (en) | 2019-03-18 | 2019-03-18 | Composite flame retardant graft-modified EVA (ethylene-vinyl acetate) foam material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910200997.8A CN109897273B (en) | 2019-03-18 | 2019-03-18 | Composite flame retardant graft-modified EVA (ethylene-vinyl acetate) foam material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109897273A CN109897273A (en) | 2019-06-18 |
| CN109897273B true CN109897273B (en) | 2021-11-30 |
Family
ID=66952274
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910200997.8A Active CN109897273B (en) | 2019-03-18 | 2019-03-18 | Composite flame retardant graft-modified EVA (ethylene-vinyl acetate) foam material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109897273B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110408276B (en) * | 2019-08-10 | 2021-07-06 | 国网福建省电力有限公司 | Material for cable incoming line fireproof plugging |
| CN110938250A (en) * | 2019-11-14 | 2020-03-31 | 浙江恒诚鞋业有限公司 | Foamed sole and preparation method thereof |
| CN110964239B (en) * | 2019-12-25 | 2021-08-31 | 福州大学 | Environment-friendly wear-resistant flame-retardant EVA foam composite material |
| CN111303616B (en) * | 2020-04-22 | 2021-06-22 | 福州大学 | Graphene oxide grafted phosphorus-containing maleic acid flame-retardant auxiliary agent and preparation method and application thereof |
| EP3926001A1 (en) * | 2020-06-15 | 2021-12-22 | swisspor Management AG | Halogen-free, flame-retardant foamed thermoplastic polymer |
| CN114921227B (en) * | 2022-06-17 | 2024-04-19 | 陕西科技大学 | Flame-retardant dust suppressant for coal and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106883450A (en) * | 2017-02-20 | 2017-06-23 | 无锡市惠山区川大石墨烯应用研究中心 | A kind of rich phosphatization Graphene fire retardant and preparation method thereof |
| CN107245182A (en) * | 2017-06-21 | 2017-10-13 | 常州碳润新材料科技有限公司 | A kind of APP/graphene cooperative flame retardant EVA expanded materials and preparation method thereof |
| CN108976588A (en) * | 2018-08-02 | 2018-12-11 | 福州大学 | A kind of flame-retardant and anti-static eva foam composite material and preparation method |
-
2019
- 2019-03-18 CN CN201910200997.8A patent/CN109897273B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106883450A (en) * | 2017-02-20 | 2017-06-23 | 无锡市惠山区川大石墨烯应用研究中心 | A kind of rich phosphatization Graphene fire retardant and preparation method thereof |
| CN107245182A (en) * | 2017-06-21 | 2017-10-13 | 常州碳润新材料科技有限公司 | A kind of APP/graphene cooperative flame retardant EVA expanded materials and preparation method thereof |
| CN108976588A (en) * | 2018-08-02 | 2018-12-11 | 福州大学 | A kind of flame-retardant and anti-static eva foam composite material and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109897273A (en) | 2019-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109897273B (en) | Composite flame retardant graft-modified EVA (ethylene-vinyl acetate) foam material and preparation method thereof | |
| CN110218401B (en) | Flame-retardant smoke-inhibiting soft polyvinyl chloride composite material with good mechanical property and preparation method thereof | |
| WO2021129216A1 (en) | Pvc cable material and preparation method therefor | |
| CN1241207C (en) | Halogen-free non-phosphorus flame-retarded cable sheath material | |
| CN102643469B (en) | LDPE (Low-Density Polyethylene)/EVA (Ethylene Vinyl Acetate Copolymer) anti-flaming material and preparation method thereof | |
| CN104250391A (en) | Silane crosslinking halogen-free flame retardant polyolefin composite material and preparation method thereof | |
| CN107090120B (en) | ATH graphene synergistic flame-retardant EVA and preparation method thereof | |
| CN107286563A (en) | A kind of expansion type flame retardant and its preparation and application for ABS electric switch outer covers | |
| CN113667277B (en) | Low-heat-release, low-smoke and high-flame-retardance epoxy resin material and preparation method thereof | |
| CN112280100A (en) | Composite intumescent flame retardant and preparation method thereof | |
| CN108503895B (en) | Preparation method of lanthanum-loaded organic phosphorus-modified nitrogen-doped graphene and flame-retardant modified ABS thereof | |
| CN108676248A (en) | A kind of high fire-retardance polypropylene material and the preparation method and application thereof | |
| CN104262875B (en) | Intumescent flame-retardant cable material taking plant-based active carbon as synergist and preparation method thereof | |
| CN111690197B (en) | Melamine-containing direct intercalation g-C 3 N 4 Flame-retardant cable material and preparation method thereof | |
| CN110845779B (en) | Modified composite flame-retardant TPO resin and preparation method thereof | |
| CN109517279B (en) | Halogen-free phosphorus synergistic flame retardant and flame-retardant polymer composite material and preparation method thereof | |
| CN115536906B (en) | Modified hydrotalcite flame retardant and application thereof | |
| CN108250573B (en) | Thermo-oxidative aging resistant halogen-free environment-friendly flame-retardant polypropylene material and preparation method thereof | |
| CN108997615B (en) | Piperazine modified lignin/aluminum hydroxide double-coated red phosphorus flame retardant and application thereof in EVA | |
| CN100352859C (en) | Nano composite fire retardant parent material, preparation method and application | |
| CN107987316A (en) | A kind of anti-flaming smoke-inhibiting agent, its preparation method and PVC flame-retardant smoke inhibitions material prepared therefrom | |
| CN110903546B (en) | Flame-retardant high polymer material and preparation method and application thereof | |
| CN114891293A (en) | Halogen-free low-smoke flame-retardant cable material and preparation method thereof | |
| CN110256879B (en) | Environment-friendly water-based inorganic flame-retardant coating | |
| CN113801429A (en) | Impact-resistant heat-resistant flame-retardant ABS resin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |