CN102250424B - Low-smoke halogen-free flame-retardant ethylene-propylene-diene mischpolymere rubber - Google Patents
Low-smoke halogen-free flame-retardant ethylene-propylene-diene mischpolymere rubber Download PDFInfo
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- CN102250424B CN102250424B CN 201110235534 CN201110235534A CN102250424B CN 102250424 B CN102250424 B CN 102250424B CN 201110235534 CN201110235534 CN 201110235534 CN 201110235534 A CN201110235534 A CN 201110235534A CN 102250424 B CN102250424 B CN 102250424B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 31
- 239000000779 smoke Substances 0.000 title claims abstract description 24
- 229920001971 elastomer Polymers 0.000 title claims abstract description 22
- 239000005060 rubber Substances 0.000 title claims abstract description 22
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007822 coupling agent Substances 0.000 claims abstract description 9
- 229910001853 inorganic hydroxide Inorganic materials 0.000 claims abstract description 9
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011787 zinc oxide Substances 0.000 claims abstract description 9
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 8
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 8
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 229920001897 terpolymer Polymers 0.000 claims description 13
- 229920002943 EPDM rubber Polymers 0.000 claims description 11
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical group [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical group C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 235000019504 cigarettes Nutrition 0.000 description 4
- 235000012254 magnesium hydroxide Nutrition 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000032696 parturition Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses low-smoke halogen-free flame-retardant ethylene-propylene-diene mischpolymere rubber, which is prepared from ethylene-propylene-diene mischpolymere rubber, a halogen-free composite flame-retardant system, a processing aid and a vulcanizing agent, wherein the processing aid consists of zinc oxide and a titanate coupling agent. The low-smoke halogen-free flame-retardant ethylene-propylene-diene mischpolymere rubber comprises the following components in part by weight: 100 parts of ethylene-propylene-diene mischpolymere rubber, 5 to 9 parts of red phosphorus, 80 to 120 parts of inorganic hydroxide, 10 to 30 parts of antimonous oxide, 10 to 20 parts of kaolin, 3 parts of zinc oxide, 1 to 1.5 parts of titanate coupling agent and 2.5 parts of vulcanizing agent. The low-smoke halogen-free flame-retardant ethylene-propylene-diene mischpolymere rubber has good flame-retardant effect, the oxygen index (O.I.) of more than 32 percent, the maximum smoke density (MSD) of less than 50, and the smoke density rating (SDR) of less than 30.
Description
Technical field
The present invention relates to a kind of macromolecular material, be specifically related to a kind of low smoke halogen-free flame retardant ethylene-propylene-diene rubber.
Background technology
Terpolymer EP rubber is a kind of important elastomeric material, and it is widely used in the industries such as automobile, electronic apparatus.But this rubber belongs to inflammable material, and oxygen index is lower, and living cigarette amount is larger in combustion processes, becomes the carbon amount very low.Therefore, it is very important carrying out fire-retardant to terpolymer EP rubber.
It is a lot of at present terpolymer EP rubber to be carried out fire-retardant document, but or have that following some is not enough: (1) is that American and French NBS smoke box or the smoke box of ISO all can not effectively be simulated the living cigarette situation in the actual fire, therefore, real flame-retarding is that spreading of flame controlled and composition and the growing amount of flue gas are controlled.And prior art is to improve the oxygen index of rubber mostly, and flame retardant effect is limited like this.(2) contain softening agent in the prescription, because the smog that softening agent produces is very large, like this so that smoke density is higher, so that flame retardant effect is not good, even adopt SUNPAR 2280 paraffin oils of high flash point low volatility also obviously to have above-mentioned deficiency when burning.(3) particle diameter of metal hydroxides is had relatively high expectations, usually need nano level.(4) adopt oxidizing acid or rare earth to carry out although can eliminate the decomposition that oxidation brings, can help spreading of flame, thereby so that life cigarette amount being larger when fire-retardant.
Summary of the invention
The object of the invention is to overcome the problems referred to above, all lower low smoke halogen-free flame retardant ethylene-propylene-diene rubbers of a kind of maximum smoke density and smoke density grade are provided.
Technical conceive of the present invention is: real flame-retarding is that spreading of flame controlled and composition and the growing amount of flue gas are controlled, therefore any material (such as some micromolecular low viscosity paraffin oils) that causes volatilization and in combustion processes, can cause quick chain degradation can not be adopted, thereby those in combustion processes, can fully the burn growing amount that reduces carbon monoxide and materials that can not cause again propagation of flame should be selected.
Realize that the object of the invention technical scheme is: a kind of low smoke halogen-free flame retardant ethylene-propylene-diene rubber, it is to be made by terpolymer EP rubber, Halogen composite flame retardant system, processing aid and vulcanizing agent; Described Halogen composite flame retardant system is comprised of red phosphorus, inorganic hydroxide, antimonous oxide and kaolin; Described processing aid is comprised of zinc oxide and titanate coupling agent.
The weight part of each component is as follows: 100 parts of terpolymer EP rubbers, 5～9 parts in red phosphorus, 80～120 parts of inorganic hydroxides, 10～30 parts of antimonous oxides, 10～20 parts of kaolin, 3 parts in zinc oxide, 1～1.5 part of titanate coupling agent, 2.5 parts of vulcanizing agents.
The 3rd monomer of described terpolymer EP rubber is ethylidene norbornene, therein ethylene content 〉=60wt%, mooney viscosity ML(1+4) 100 ℃ 〉=80.
The purity of described red phosphorus＞85%, point of ignition＞340 ℃, the order number is 800 orders～1250 orders.
Described inorganic hydroxide is magnesium hydroxide, aluminium hydroxide or layered double-hydroxide LDH.
Described vulcanizing agent is DCP vulcanizing agent or BIBP vulcanizing agent.
The positively effect that the present invention has: the flame retardant effect of (1) low smoke halogen-free flame retardant ethylene-propylene-diene rubber of the present invention is very good, its oxygen index (O.I.)＞32%, maximum smoke density (MSD)＜50, smoke density grade (SDR)＜30.(2) the present invention adopts red phosphorus, inorganic hydroxide, antimonous oxide and kaolin to form Halogenless composite fire retardant, wherein to the particle diameter no requirement (NR) of inorganic hydroxide, only need it in terpolymer EP rubber, to disperse to get final product, be 800 orders～1250 orders and red phosphorus is required its purity＞85%, point of ignition＞340 ℃, order number, when can avoiding burning, this red phosphorus produces too much carbon monoxide, make rubber fully sinter the dense char shell into after the burning at short notice, can not cause propagation of flame, thereby greatly reduce the cigarette amount of giving birth to.(3) shape of the component of the present invention's employing is iris or rhombus laminated structure, like this so that the escape difficult of flue gas has improved flame retardant effect.(4) plasticizer-containing not in the prescription of the present invention, thus can be so that flame retardant effect be unaffected.
Embodiment
(embodiment 1)
The low smoke halogen-free flame retardant ethylene-propylene-diene rubber of present embodiment is made by the component of following weight parts:
100 parts of terpolymer EP rubbers, 9 parts in red phosphorus, 120 parts of magnesium hydroxides, 24 parts of antimonous oxides, 20 parts of kaolin, 3 parts in zinc oxide, 1 part of titanate coupling agent, 2.5 parts of DCP vulcanizing agents.Wherein red phosphorus, magnesium hydroxide, antimonous oxide and kaolin form the Halogen composite flame retardant system.Zinc oxide and titanate coupling agent are processing aid.
Wherein the 3rd monomer of terpolymer EP rubber is ethylidene norbornene, its ethylene content 〉=60wt%, mooney viscosity ML(1+4) 100 ℃ 〉=80.
The purity of red phosphorus＞85%, point of ignition＞340 ℃, the order number is 1000 orders.
The preparation method of above-mentioned low smoke halogen-free flame retardant ethylene-propylene-diene rubber is ordinary method: after soon terpolymer EP rubber is plasticated fully, it is abundant to add red phosphorus, magnesium hydroxide, antimonous oxide, kaolin, zinc oxide and titanate coupling agent banburying under 95～105 ℃ temperature, add at ambient temperature the DCP vulcanizing agent after parking 24h, three slices of thin-pass get final product.
The performance of the low smoke halogen-free flame retardant ethylene-propylene-diene rubber of present embodiment sees Table 1.
(embodiment 2～embodiment 4)
Each embodiment is substantially the same manner as Example 1, and difference sees Table 1.
Claims (3)
1. a low smoke halogen-free flame retardant ethylene-propylene-diene rubber is characterized in that being made by terpolymer EP rubber, Halogen composite flame retardant system, processing aid and vulcanizing agent; Described Halogen composite flame retardant system is comprised of red phosphorus, inorganic hydroxide, antimonous oxide and kaolin; Described processing aid is comprised of zinc oxide and titanate coupling agent;
The weight part of each component is as follows:
100 parts of terpolymer EP rubbers, 5～9 parts in red phosphorus, 80～120 parts of inorganic hydroxides, 10～30 parts of antimonous oxides, 10～20 parts of kaolin, 3 parts in zinc oxide, 1～1.5 part of titanate coupling agent, 2.5 parts of vulcanizing agents;
The 3rd monomer of described terpolymer EP rubber is ethylidene norbornene, therein ethylene content 〉=60wt%, mooney viscosity ML(1+4) 100 ℃ 〉=80;
The purity of described red phosphorus＞85%, point of ignition＞340 ℃, the order number is 800 orders～1250 orders.
2. low smoke halogen-free flame retardant ethylene-propylene-diene rubber according to claim 1, it is characterized in that: described inorganic hydroxide is magnesium hydroxide, aluminium hydroxide or layered double-hydroxide LDH.
3. low smoke halogen-free flame retardant ethylene-propylene-diene rubber according to claim 1, it is characterized in that: described vulcanizing agent is DCP vulcanizing agent or BIBP vulcanizing agent.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201110235534 CN102250424B (en) | 2011-08-17 | 2011-08-17 | Low-smoke halogen-free flame-retardant ethylene-propylene-diene mischpolymere rubber |
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| CN 201110235534 CN102250424B (en) | 2011-08-17 | 2011-08-17 | Low-smoke halogen-free flame-retardant ethylene-propylene-diene mischpolymere rubber |
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| CN102250424A CN102250424A (en) | 2011-11-23 |
| CN102250424B true CN102250424B (en) | 2013-05-01 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601982A (en) * | 2013-10-30 | 2014-02-26 | 安徽嘉木橡塑工业有限公司 | Flame retardant ethylene-propylene-diene monomer rubber material |
| CN105153550A (en) * | 2015-07-31 | 2015-12-16 | 安徽太平洋电缆股份有限公司 | Modified nanometer LDHs low-smoke zero-halogen flame-retardation EPDM (ethylene propylene diene monomer) rubber and preparation method thereof |
| CN106589626A (en) * | 2016-12-21 | 2017-04-26 | 上海精橡胶科技有限公司 | Environmental protection like flame-retardant elastomer material for electric appliance |
| CN107057199B (en) * | 2017-05-09 | 2019-12-10 | 浙江省仙居县博达异型橡塑有限公司 | Low-smoke halogen-free flame-retardant sealing strip and preparation method thereof |
| CN108410070A (en) * | 2018-03-19 | 2018-08-17 | 上海利物盛企业集团有限公司 | A kind of heat conductive insulating rubber sheet gasket and preparation method thereof |
| CN114456507A (en) * | 2022-03-18 | 2022-05-10 | 临朐瑞星塑胶制品有限公司 | Flame-retardant foaming adhesive tape and preparation process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831115A (en) * | 2010-04-29 | 2010-09-15 | 江苏远洋东泽电缆股份有限公司 | Ethylene propylene rubber insulation material for longitudinal high-voltage watertight cable of ships and warships and production method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831115A (en) * | 2010-04-29 | 2010-09-15 | 江苏远洋东泽电缆股份有限公司 | Ethylene propylene rubber insulation material for longitudinal high-voltage watertight cable of ships and warships and production method thereof |
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Correction item: Applicant Correct: Mi Yueqi|213149 No. 10, fruit Road, Wujin Economic Development Zone, Jiangsu, Changzhou, China False: Mi Yueqi|213149 No. 10, fruit Road, Wujin Economic Development Zone, Jiangsu, Changzhou, China Number: 47 Volume: 27 Correction item: Inventor Correct: Mi Yueqi False: Mi Yueqi Number: 47 Volume: 27 |
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Correction item: Name of applicant and inventor Correct: Mi Yueqi False: Mi Yueqi Number: 47 Page: The title page Volume: 27 |
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Free format text: CORRECT: APPLICANT; FROM: FEI YUEQI:213149 NO.10, GUOXIANG ROAD, WUJIN ECONOMIC DEVELOPMENT ZONE, CHANGZHOU CITY, JIANGSU PROVINCE TO: MI YUEQI:213149 NO.10, GUOXIANG ROAD, WUJIN ECONOMIC DEVELOPMENT ZONE, CHANGZHOU CITY, JIANGSU PROVINCE Free format text: CORRECT: INVENTOR; FROM: FEI YUEQI TO: MI YUEQI |
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Assignee: CHANGZHOU SANYOU DIOR INSULATION MATERIALS MFG Co.,Ltd. Assignor: Mi Yueqi Contract record no.: 2012320000509 Denomination of invention: Low smoke halogen-free flame retardant ethylene-propylene-diene rubber and preparation method by extrusion molding thereof License type: Exclusive License Open date: 20111123 Record date: 20120420 |
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Effective date of registration: 20150821 Address after: 213000 Jiangsu city of Changzhou province Wujin fruit Road Economic Development Zone No. 10 Patentee after: CHANGZHOU SANYOU DIOR INSULATION MATERIALS MFG Co.,Ltd. Address before: 213149 No. 10, fruit Road, Wujin Economic Development Zone, Jiangsu, Changzhou, China Patentee before: Mi Yueqi |
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Address after: 213000 No. 10, fruit Road, Wujin Economic Development Zone, Jiangsu, Changzhou, China Patentee after: Jiangsu Shanyou Diao Energy Saving New Material Co.,Ltd. Address before: 213000 No. 10, fruit Road, Wujin Economic Development Zone, Jiangsu, Changzhou, China Patentee before: CHANGZHOU SANYOU DIOR INSULATION MATERIALS MFG Co.,Ltd. |
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