CN100434468C - Preparation method of inflaming retarding ternary ethylene-propylene rubber without halogen - Google Patents
Preparation method of inflaming retarding ternary ethylene-propylene rubber without halogen Download PDFInfo
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- CN100434468C CN100434468C CNB2006101160183A CN200610116018A CN100434468C CN 100434468 C CN100434468 C CN 100434468C CN B2006101160183 A CNB2006101160183 A CN B2006101160183A CN 200610116018 A CN200610116018 A CN 200610116018A CN 100434468 C CN100434468 C CN 100434468C
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Abstract
The invention discloses a preparing method of halide-free flame-proof ternary ethylen-propylene rubber (EPDM), which is characterized by the following: blending EPT rubber, metal hydroxide, unsaturated carboxylate and peroxidase; sulfurizing to obtain the product; improving extending strength with oxygen index at 37; fitting for automobile and wire cable.
Description
Technical field:
The present invention relates to a kind of preparation method's of macromolecular material, particularly a kind of Halogen Free Flame Retardant EPDM preparation method.
Background technology:
The halogen flame of widespread use now is few because of its consumption, flame retarding efficiency is high and wide adaptability, has developed into the main product in fire retardant market.But the critical defect of halogen flame is when burning to generate a large amount of cigarette and poisonous and acrid gas, can cause merely the corrosion of the Circuits System switch that can not be caused by fire institute and other metal objects to reach pollution to environment; To the harm of human respiratory tract and other organ even because of the life-threatening safety of suffocating.In recent years, the U.S., Britain, Norway, Australia formulate or promulgate a decree, some goods is carried out the combustion toxicity test or the sour gas that use discharged of some goods is stipulated that the exploitation halogen-free flame retardants replaces the trend that halogen flame has become world's flame retardant area.
Metal hydroxides (magnesium hydroxide, aluminium hydroxide etc.) source is abundant, cheap, but its flame retardant effect is relatively poor, addition is big, mechanical property influence to goods is bigger, a kind of method that wherein solves the goods mechanical property is that metal hydroxides is carried out surface treatment, now the main coupling agent of metal hydroxides surface-treated is had silane coupling agent (Chinese patent application number 02124390.5), titanate coupling agent (Chinese patent application number 02124390.5) and sodium stearate (EP327660).In existing document and patent, these methods are mainly used in polyolefin plastics.
Generally have only 6-8MPa with its tensile strength of micron order magnesium hydroxide flame retardant terpolymer EP rubber, do not have (Zhang, the Q. of raising substantially with silane coupling agent surface-treated magnesium hydroxide/terpolymer EP rubber system tensile strength; Tian, M.; Wu., Y.; Lin, G.; Zhang, L.J Appl Polym Sci 2004,94,2341.) generally do not reach service requirements.Aluminium hydroxide/terpolymer EP rubber system tensile strength with silane coupling agent surface treatment aluminium hydroxide does not improve substantially yet.(Yang Qingzhi etc., rubber industry, 1995; (42); 72).
Summary of the invention:
The object of the invention is to solve the relatively poor problem of Halogen Free Flame Retardant EPDM mechanical property, and the interface interaction that adopts the method that adds salt unsaturated carboxylic acid to improve rubber and metal hydroxides improves the mechanical property of Halogen Free Flame Retardant EPDM.
A kind of preparation method of Halogen Free Flame Retardant EPDM is characterized in that the preparation method is as follows, below all represents with mass parts:
In mixing facilities, add 100 parts of terpolymer EP rubbers, metal hydroxides 50-300 part, salt unsaturated carboxylic acid 1-100 part, superoxide 0.1-10 part, descended mixing 5～30 minutes at 20-100 ℃, then on vulcanizing press in 150～200 ℃ of sulfurations 1～30 minute, obtain Halogen Free Flame Retardant EPDM.
Terpolymer EP rubber the 3rd monomer that the present invention uses is ethylidene norbornene, dicyclopentadiene or 1, and 4-hexadiene, therein ethylene content are 40～80%, and mooney viscosity (125 ℃) is 40～100.
The metal hydroxides that the present invention uses is magnesium hydroxide or aluminium hydroxide, and wherein particle diameter is 10nm-1mm.
The salt unsaturated carboxylic acid that the present invention uses is magnesinm methacrylate, zinc methacrylate or zinc acrylate resin.。
The superoxide that the present invention uses is dicumyl peroxide or 2,5-dimethyl-2,5 (di-t-butyl peroxide) hexane.
The mixing facilities that the present invention uses is mill, Banbury mixer, single screw extrusion machine or twin screw extruder.
Among the preparation method of a kind of Halogen Free Flame Retardant EPDM of the present invention, obviously improved the mechanical property of metal hydroxides/terpolymer EP rubber by the adding salt unsaturated carboxylic acid.Critical effect has been played in the raising of unsaturated carboxylic acid salt pair tensile strength, adds to improve terpolymer EP rubber behind the salt unsaturated carboxylic acid and combine with the interface of metal hydroxides, thereby has improved the mechanical property of terpolymer EP rubber.Add under the situation of 150 parts of magnesium hydroxides in 100 parts of terpolymer EP rubbers, adding 5 parts of magnesinm methacrylate tensile strengths can bring up to 12.3MPa from 5.5MPa, has improved 122%.100 parts of ternarys add under the situation of 40 parts of magnesium hydroxides in third rubber, add the silane coupling agent tensile strength and only improve 6%.100 parts of ternarys add under the situation of 100 parts of magnesium hydroxides in third rubber, add silane coupling agent back draft intensity and drop to 9.6MPa from 9.7MPa.Prepared its flame retardant properties of metal hydroxide halogen-free anti-flaming terpolymer EP rubber, mechanical property etc. can reach the requirement of products such as wire cable insulating skin.
Embodiment:
Following examples are that the present invention is further described, rather than limit the scope of the invention.
In following examples, the tensile property test is all carried out according to the GB528-82 standard, and the tear strength test is all carried out according to the GB530-81 standard.
Terpolymer EP rubber (keltan5508, DSM N. V.) the 3rd monomer used in the following example is an ethylidene norbornene, and ethylene content is 70%, and mooney viscosity (125 ℃) is 55.Be untreated in magnesium hydroxide (H5, Albemarle Corporation) surface, median size is 1.25-1.65um.
1. embodiment 1-5: press each constituent mass proportioning in table 1 prescription, in Banbury mixer, add terpolymer EP rubber, magnesium hydroxide, magnesinm methacrylate and dicumyl peroxide successively, 60 ℃ were descended mixing 8 minutes, vulcanized 12 minutes down in 170 ℃ then, obtained Halogen Free Flame Retardant EPDM.As can be seen from Table 1, behind the adding magnesinm methacrylate, the tensile strength and the tear strength of cross-linked rubber obviously improve, and oxygen index changes less.
2. Comparative Examples 1: prescription sees Table 1, and processing mode is identical with the processing mode of embodiment 1-3
Table 1
3. embodiment 6-9: press each constituent mass proportioning in table 2 prescription, in Banbury mixer, add terpolymer EP rubber, magnesium hydroxide, magnesinm methacrylate and dicumyl peroxide successively, 60 ℃ were descended mixing 8 minutes, vulcanized 12 minutes down in 170 ℃ then, obtained Halogen Free Flame Retardant EPDM.As can be seen from Table 2, behind the adding magnesinm methacrylate, the tensile strength and the tear strength of cross-linked rubber obviously improve, and oxygen index changes less.
Table 2
Claims (1)
1. the preparation method of a Halogen Free Flame Retardant EPDM is characterized in that the preparation method is as follows, below all represents with mass parts:
In mixing facilities, add 100 parts of terpolymer EP rubbers, metal hydroxides 50-300 part, salt unsaturated carboxylic acid 1-100 part, superoxide 0.1-10 part, 20-100 ℃ was descended mixing 5～30 minutes, then on vulcanizing press in 150～200 ℃ of sulfurations 1～30 minute, obtain Halogen Free Flame Retardant EPDM; Terpolymer EP rubber the 3rd monomer is ethylidene norbornene, dicyclopentadiene or 1, and 4-hexadiene, ethylene content are that the mooney viscosity under 40～80%, 125 ℃ is 40～100; Metal hydroxides is magnesium hydroxide or aluminium hydroxide, and wherein particle diameter is 10nm-1mm; Salt unsaturated carboxylic acid is magnesinm methacrylate, zinc methacrylate or zinc acrylate resin; Superoxide is dicumyl peroxide or 2,5-dimethyl-2,5 (di-t-butyl peroxide) hexane; Mixing facilities is mill, Banbury mixer, single screw extrusion machine or twin screw extruder.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006101160183A CN100434468C (en) | 2006-09-14 | 2006-09-14 | Preparation method of inflaming retarding ternary ethylene-propylene rubber without halogen |
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| CNB2006101160183A CN100434468C (en) | 2006-09-14 | 2006-09-14 | Preparation method of inflaming retarding ternary ethylene-propylene rubber without halogen |
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| CN1923884A CN1923884A (en) | 2007-03-07 |
| CN100434468C true CN100434468C (en) | 2008-11-19 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2522693A1 (en) * | 2011-05-12 | 2012-11-14 | Lapp Engineering & Co. | Composite material |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100480286C (en) * | 2006-07-20 | 2009-04-22 | 上海交通大学 | Preparation method of halogen less fire retardant trielement ethylene-propylene rubber |
| CN101220185B (en) * | 2008-01-29 | 2011-08-31 | 北京理工大学 | Expansion type flame-proof ethylene propylene terpolymer for fire resistant flame |
| CN101638501B (en) * | 2008-07-29 | 2011-08-17 | 比亚迪股份有限公司 | Flame retardant composition and thermoplastic elastomer containing same |
| CN101613506B (en) * | 2009-07-25 | 2011-07-20 | 四川明星电缆股份有限公司 | High temperature resistance non halogen flame retardant cable sheath material and preparation method thereof |
| CN103756223B (en) * | 2013-12-31 | 2017-05-10 | 杭州顺豪橡胶工程有限公司 | High temperature resisting halogen-free flame retardant conveyer belt covering adhesive and preparation method thereof |
| CN103980838A (en) * | 2014-05-16 | 2014-08-13 | 沈阳化工大学 | Adhesive preparation method for improving adhesion strength of ethylene-propylene-diene-terpolymer rubber |
| CN115873364A (en) * | 2022-12-08 | 2023-03-31 | 中绿新材料（江苏）有限公司 | Halogen-free rubber material with high damping and low hardness and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2522693A1 (en) * | 2011-05-12 | 2012-11-14 | Lapp Engineering & Co. | Composite material |
| EP2522694A1 (en) | 2011-05-12 | 2012-11-14 | Lapp Engineering & Co. | Composite material |
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