CN114605717A - Halogen-free environment-friendly flame-retardant rubber and preparation method thereof - Google Patents
Halogen-free environment-friendly flame-retardant rubber and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 115
- 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 100
- 229920001971 elastomer Polymers 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 26
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 25
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 25
- 229920001194 natural rubber Polymers 0.000 claims abstract description 25
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000006229 carbon black Substances 0.000 claims abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 18
- 239000011593 sulfur Substances 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims description 30
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 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
- 238000004073 vulcanization Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000003801 milling Methods 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- 230000003712 anti-aging effect Effects 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- CZGWDPMDAIPURF-UHFFFAOYSA-N (4,6-dihydrazinyl-1,3,5-triazin-2-yl)hydrazine Chemical compound NNC1=NC(NN)=NC(NN)=N1 CZGWDPMDAIPURF-UHFFFAOYSA-N 0.000 claims description 4
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims description 3
- VRFNYSYURHAPFL-UHFFFAOYSA-N [(4-methylphenyl)sulfonylamino]urea Chemical compound CC1=CC=C(S(=O)(=O)NNC(N)=O)C=C1 VRFNYSYURHAPFL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- LSNDGFYQJRXEAR-UHFFFAOYSA-N benzenesulfonamidourea Chemical compound NC(=O)NNS(=O)(=O)C1=CC=CC=C1 LSNDGFYQJRXEAR-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims 3
- 239000000779 smoke Substances 0.000 abstract description 7
- 231100000956 nontoxicity Toxicity 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical group C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- ZRMMVODKVLXCBB-UHFFFAOYSA-N 1-n-cyclohexyl-4-n-phenylbenzene-1,4-diamine Chemical group C1CCCCC1NC(C=C1)=CC=C1NC1=CC=CC=C1 ZRMMVODKVLXCBB-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000013040 rubber vulcanization Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- -1 aminopropyl Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- 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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Landscapes
- 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 discloses a halogen-free environment-friendly flame-retardant rubber and a preparation method thereof, wherein the flame-retardant rubber is prepared from the following raw materials in parts by mass: 90-110 parts of natural rubber, 4.5-14 parts of solid auxiliary agent, 20-60 parts of carbon black, 1-3 parts of sulfur, 1.5-3.5 parts of accelerator, 3-12 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 2-10 parts of organic silsesquioxane flame retardant. The flame-retardant rubber with flame retardance is formed by combining natural rubber, a solid auxiliary agent, carbon black, sulfur, an accelerant, a flame retardant and the like, the added flame retardant is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and organic silsesquioxane, and the two flame retardants form a flame-retardant phosphorus-silicon synergistic effect, so that the flame retardance of the rubber can be effectively improved, low smoke and no toxicity are generated, and further damage of a burning object or gas to a human body and other objects is reduced.
Description
Technical Field
The invention relates to flame retardant rubber, in particular to halogen-free environment-friendly flame retardant rubber and a preparation method thereof.
Background
Natural Rubber (NR) is an important rubber material, and has excellent properties such as resilience, insulation, water barrier property, and plasticity, and also has valuable properties such as oil resistance, acid resistance, alkali resistance, heat resistance, cold resistance, pressure resistance, and wear resistance after being appropriately processed, and thus, it has a wide range of applications. However, the oxygen index of the natural rubber is only 17-18, and the natural rubber is a polymer material which is extremely easy to burn, so that the flame retardant modification of the natural rubber is of great significance.
The traditional inorganic metal hydroxide flame retardant (such as micron magnesium hydroxide, aluminum hydroxide and the like) has large particle size, low flame retardant efficiency and large filling amount, influences the physical and mechanical properties and the forming and processing properties of the NR material, and in addition, because of the environmental protection requirement, the halogen-containing flame retardant is aversive during combustion and halogen-containing steam has certain corrosivity, particularly has certain damage to rescue workers and people needing to be rescued in the case of fire, and greatly hinders the fire extinguishing and evacuation work of people. Therefore, the flame retardant modification is developing towards low smoke, non-toxicity, halogen-free and environment-friendly direction, which makes the halogen-antimony system flame retardant not to be used, and the pursuit of new flame retardant system is very important necessity.
Disclosure of Invention
In order to solve the problems, the invention provides halogen-free environment-friendly flame-retardant rubber and a preparation method thereof, the flame-retardant rubber is prepared by adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and organic silsesquioxane into natural rubber as a flame retardant, so that a flame-retardant phosphorus-silicon synergistic effect is formed, the flame-retardant property of the natural rubber is improved, and the flame-retardant rubber material is developed in the direction of low smoke, no toxicity, no halogen and environmental friendliness.
In order to achieve the above purpose, the invention provides a halogen-free environment-friendly flame retardant rubber, which is prepared from the following raw materials in parts by mass: 90-110 parts of natural rubber, 4.5-14 parts of solid auxiliary agent, 20-60 parts of carbon black, 1-3 parts of sulfur, 1.5-3.5 parts of accelerator, 3-12 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 2-10 parts of organic silsesquioxane flame retardant.
In the technical scheme, the flame retardant is a halogen-free environment-friendly flame retardant which is respectively 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and organic silsesquioxane, the two flame retardant phosphorus-silicon synergistic effect is formed, after rubber is ignited, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide can decompose metaphosphoric acid to remove water in a base material to form a phosphorus-containing carbon layer, the organic silsesquioxane flame retardant is preheated and decomposed, silicon elements in the organic silsesquioxane can migrate to the surface of the rubber on fire to form a silicon-containing protective layer to form a multilayer structure, the carbon blocking effect is achieved, the thermal decomposition strength of a base material is reduced, the release of gas in rubber combustible is reduced, the flame retardance of the rubber can be effectively improved, and low smoke, low smoke and low smoke are generated, No toxicity, and reduced further damage of burning matter or gas to human body and other objects.
The carbon black has super wear resistance and can reinforce the wear resistance of rubber.
Specifically, the accelerator is an accelerator M (2-mercaptobenzothiazole) or an accelerator DM (dibenzothiazyl disulfide).
Specifically, the solid auxiliary agent comprises 2-6 parts of zinc oxide, 0.5-2 parts of stearic acid and 2-6 parts of an anti-aging agent. Wherein the antioxidant is antioxidant 4010 (N-cyclohexyl-N' -phenyl-p-phenylenediamine) or antioxidant RD (2,2, 4-trimethyl-1, 2-dihydro-p-quinoline dimer).
Specifically, the organic silsesquioxane flame retardant is a cage type silsesquioxane, such as octaphenyl cage type polysilsesquioxane, unfilled corner phenyl cage type silsesquioxane, cage type aminopropyl silsesquioxane, epoxy cage type silsesquioxane and the like. The cage type silsesquioxane is internally composed of a silica inorganic core, the periphery of the cage type silsesquioxane is surrounded by reactive or non-reactive organic groups, the inorganic silica core endows the cage type silsesquioxane with excellent heat resistance and excellent rigidity and oxidation resistance, the peripheral non-reactive organic groups can increase the compatibility between the cage type silsesquioxane and an organic matrix, and the reactive groups can form covalent bonds with the matrix to strengthen the bonding force.
Further, the rubber also comprises the following preparation raw materials: 3-10 parts of halogen-free flame retardant auxiliary agent.
Specifically, the halogen-free flame retardant auxiliary agent is one or more of trihydrazinotriazine, barium azodicarboxylate, p-toluenesulfonylaminourea, 4' -oxybis (benzenesulfonylaminourea) and 5-phenyltetrazole.
According to the technical scheme, a small amount of halogen-free flame retardant auxiliary is added into a rubber system, and a rubber vulcanization system is matched, so that a blow-out effect in flame retardance can be formed, namely in the combustion process of a rubber material, a gas-phase product which can be decomposed in advance by the added flame retardant auxiliary can quickly form large internal bubbles in matrix rubber, the bubbles contain flame retardant components with high concentration, namely nitrogen and carbon dioxide, when pyrolysis gas in the bubbles in the carbon layer reaches the integrated volume and pressure, an alternating current structure formed by the carbon layer and a rubber vulcanizing agent and generated by the synergistic effect of a flame retardant can be broken in a very short time, the alternating current structure is sprayed outwards at a high speed, and high-speed gas with the flame retardant components is released in a concentrated mode, so that the flame is quickly extinguished.
The second aspect of the invention provides a preparation method of halogen-free environment-friendly flame retardant rubber, which comprises the following steps: fully milling natural rubber, a solid auxiliary agent, carbon black, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, an organic silsesquioxane flame retardant, sulfur and an accelerator, and then vulcanizing to obtain the flame retardant;
the flame retardant is prepared from the following raw materials, by mass, 90-110 parts of natural rubber, 4.5-14 parts of a solid auxiliary agent, 20-60 parts of carbon black, 1-3 parts of sulfur, 1.5-3.5 parts of an accelerator, 3-12 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 2-10 parts of an organic silsesquioxane flame retardant.
The preparation method is simple, and the prepared flame-retardant rubber has good flame-retardant property.
Specifically, the natural rubber is plasticated, the solid auxiliary agent is added for even milling, the carbon black is added for even milling, then the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the organic silsesquioxane flame retardant are added for even milling, the sulfur and the accelerator are added after the complete milling, and the vulcanization is carried out after the even milling.
Further plasticating the natural rubber, adding a solid auxiliary agent, uniformly mixing, adding carbon black, mixing, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, an organic silsesquioxane flame retardant and a halogen-free flame retardant auxiliary agent, mixing, adding sulfur and an accelerator after mixing is sufficient, and vulcanizing after uniform mixing; wherein the dosage of the halogen-free flame retardant auxiliary agent is 3-10 parts.
The halogen-free flame retardant auxiliary agent is one or more of trihydrazinotriazine, barium azodicarboxylate, p-toluenesulfonyl semicarbazide, 4' -oxo-bis (benzenesulfonylamino urea) and 5-phenyltetrazole.
Specifically, the vulcanization temperature was 140-.
Further, after the components are uniformly mixed, the components are firstly molded and vulcanized on a pressure molding machine, then the components are taken out of a vulcanizing press and vulcanized for about 10 min.
Through the technical scheme, the invention has the following beneficial effects:
1. the flame-retardant rubber with flame retardance is formed by combining natural rubber, a solid auxiliary agent, carbon black, sulfur, an accelerator, a flame retardant and the like, the added flame retardant is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and organic silsesquioxane, and the two flame-retardant phosphorus-silicon synergistic effect is formed; and sulfur and an accelerator are added to improve the crosslinking degree of the rubber and the heat resistance of the rubber.
2. In a preferred technical scheme of the invention, a small amount of halogen-free flame retardant auxiliary agent is added into a rubber system, and a rubber vulcanization system is matched to form a blow-out effect in flame retardance, so that the flame retardant property of the rubber is further improved.
3. In the invention, inorganic metal hydroxide flame retardant with a large addition amount is not used, and halogen-containing flame retardant is not added, so that the flame retardant is suitable for the currently pursued flame retardant development direction with low smoke, no toxicity, no halogen and environmental friendliness.
Detailed Description
The following examples are provided to explain the present invention in detail. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
Example 1
Plasticating 90 parts of natural rubber on an open mill, adding 2 parts of zinc oxide, 0.5 part of stearic acid and 2 parts of an anti-aging agent, uniformly mixing, adding 20 parts of carbon black, mixing, adding 3 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 2 parts of octaphenyl cage polysilsesquioxane, fully mixing, adding 1 part of sulfur and 1.5 parts of an accelerator, uniformly mixing, vulcanizing on a pressure forming machine, vulcanizing at the vulcanization temperature of 145 ℃, vulcanizing at 145 ℃ on a flat vulcanizing machine for 10min, and discharging. The prepared rubber has the flame retardant property reaching V-1 level and the LOI coefficient of 29.
Example 2
Plasticating 110 parts of natural rubber on an open mill, adding 6 parts of zinc oxide, 2 parts of stearic acid and 6 parts of anti-aging agent, uniformly mixing, adding 60 parts of carbon black, mixing, adding 12 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10 parts of octaphenyl cage-shaped polysilsesquioxane, fully mixing, adding 3 parts of sulfur and 3.5 parts of accelerator, vulcanizing on a pressure forming machine after uniform mixing, vulcanizing at the vulcanization temperature of 145 ℃, vulcanizing at 145 ℃ on a flat vulcanizing machine for 10min, and discharging. The prepared rubber has the flame retardant property reaching V-1 level and the LOI coefficient of 30.
Example 3
Plasticating 100 parts of natural rubber on an open mill, adding 5 parts of zinc oxide, 1 part of stearic acid and 4 parts of anti-aging agent, uniformly mixing, adding 50 parts of carbon black, fully mixing, adding 8 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 7 parts of octaphenyl cage-shaped polysilsesquioxane, fully mixing, adding 2 parts of sulfur and 2.5 parts of accelerator, uniformly mixing, vulcanizing on a pressure forming machine, vulcanizing at the vulcanization temperature of 145 ℃, vulcanizing at 145 ℃ on a flat vulcanizing machine for 10min, and discharging.
Example 4
Plasticating 100 parts of natural rubber on an open mill, adding 5 parts of zinc oxide, 1 part of stearic acid and 4 parts of anti-aging agent, uniformly mixing, adding 50 parts of carbon black, mixing, adding 8 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 7 parts of octaphenyl cage polysilsesquioxane and 5 parts of trihydrazinotriazine, mixing fully, adding 2 parts of sulfur and 2.5 parts of accelerator, uniformly mixing, vulcanizing on a pressure forming machine, vulcanizing at the vulcanization temperature of 145 ℃, vulcanizing on a flat vulcanizing machine for 10min, and discharging the sheet.
The other conditions are the same as example 4, and the effects of different flame retardant additive amounts and types on the flame retardant rubber performance are verified, and the results are shown in tables 1 and 2.
TABLE 1 Effect of different flame-retardant auxiliary amounts on the flame-retardant rubber Properties
As can be seen from Table 1, a small amount of flame retardant additive is added, the vertical combustion flame retardant rating is only V-2 level, and the flame retardant coefficients added by more than 3 parts are all V-0 level; as seen from the oxygen index data, the LOI value is continuously improved along with the increase of the part of the flame retardant additive, and the improvement of the flame retardant property is not obvious when 10 parts and 15 parts are used, so that 3-10 parts of the flame retardant additive is preferably used in the invention in view of saving the cost.
TABLE 2 influence of different flame-retardant auxiliary classes on the flame-retardant rubber Properties
As can be seen from Table 2, the flame retardant rubber prepared by using different flame retardant additives of the invention has excellent flame retardant property, and can reach V-0 level.
The other conditions were the same as in example 4, and the effects of different flame retardants and flame retardant auxiliaries on the performance of the flame-retardant rubber were verified, and the results are shown in Table 3.
TABLE 3 influence of different flame retardants and flame-retardant auxiliaries on the properties of the flame-retardant rubber
As can be seen from Table 3, the flame retardant property of the rubber can only reach V-1 grade when one flame retardant and/or flame retardant auxiliary agent is used alone, the LOI coefficient is basically maintained within 30, the flame retardant property of the rubber reaches V-1 grade and the LOI coefficient reaches 30 when two flame retardants are used simultaneously (example 3), and the flame retardant property of the rubber reaches V-0 grade and the LOI coefficient also rises to about 38 when the flame retardant and the flame retardant auxiliary agent are used simultaneously (example 4), so that the flame retardant property is excellent.
The preferred embodiments of the present invention have been described in detail with reference to the examples, but the present invention is not limited to the details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. The halogen-free environment-friendly flame-retardant rubber is characterized by being prepared from the following raw materials in parts by mass: 90-110 parts of natural rubber, 4.5-14 parts of solid auxiliary agent, 20-60 parts of carbon black, 1-3 parts of sulfur, 1.5-3.5 parts of accelerator, 3-12 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 2-10 parts of organic silsesquioxane flame retardant.
2. The halogen-free environment-friendly flame retardant rubber according to claim 1, wherein the organic silsesquioxane flame retardant is cage type silsesquioxane.
3. The halogen-free environment-friendly flame retardant rubber according to claim 1, wherein the solid auxiliary comprises 2-6 parts of zinc oxide, 0.5-2 parts of stearic acid and 2-6 parts of an anti-aging agent.
4. The halogen-free environment-friendly flame retardant rubber according to any one of claims 1 to 3, characterized in that the rubber further comprises the following preparation raw materials: 3-10 parts of halogen-free flame retardant auxiliary agent.
5. The halogen-free environment-friendly flame retardant rubber according to claim 4, wherein the halogen-free flame retardant auxiliary agent is one or more of trihydrazinotriazine, barium azodicarboxylate, p-toluenesulfonylaminourea, 4' -oxybis (benzenesulfonylaminourea) and 5-phenyltetrazole.
6. The preparation method of the halogen-free environment-friendly flame retardant rubber is characterized by comprising the following steps of: fully milling natural rubber, a solid auxiliary agent, carbon black, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, an organic silsesquioxane flame retardant, sulfur and an accelerator, and then vulcanizing to obtain the organic silsesquioxane flame retardant;
the flame retardant is prepared from the following raw materials, by mass, 90-110 parts of natural rubber, 4.5-14 parts of a solid auxiliary agent, 20-60 parts of carbon black, 1-3 parts of sulfur, 1.5-3.5 parts of an accelerator, 3-12 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 2-10 parts of an organic silsesquioxane flame retardant.
7. The method for preparing halogen-free environment-friendly flame retardant rubber according to claim 6, wherein the natural rubber is plasticated, the solid auxiliary agent is added for even mixing, then the carbon black is added for even mixing, then the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the organic silsesquioxane flame retardant are added for even mixing, after the even mixing, the sulfur and the accelerator are added, and after the even mixing, the vulcanization is carried out.
8. The method for preparing halogen-free environment-friendly flame retardant rubber according to claim 6, wherein the natural rubber is plasticated, the solid auxiliary agent is added for even mixing, then the carbon black is added for even mixing, then the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, the organic silsesquioxane flame retardant and the halogen-free flame retardant auxiliary agent are added for even mixing, after the even mixing, the sulfur and the accelerator are added for vulcanization;
wherein the dosage of the halogen-free flame retardant auxiliary agent is 3-10 parts.
9. The method for preparing halogen-free environment-friendly flame retardant rubber according to any one of claims 6 to 8, wherein the vulcanization temperature is 140-145 ℃.
10. The preparation method of the halogen-free environment-friendly flame retardant rubber according to claim 9, wherein the components are uniformly mixed and then molded and vulcanized, and then sheet vulcanization is carried out.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106750317A (en) * | 2017-01-13 | 2017-05-31 | 山东船舶技术研究院 | One kind is based on caged polysilsesquioxane phosphonium flame retardant and preparation method thereof |
| CN107868255A (en) * | 2017-11-17 | 2018-04-03 | 厦门大学 | The preparation method and applications of POSS DOPO triazine derivative flame retardants with self assembly humidification |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106750317A (en) * | 2017-01-13 | 2017-05-31 | 山东船舶技术研究院 | One kind is based on caged polysilsesquioxane phosphonium flame retardant and preparation method thereof |
| CN107868255A (en) * | 2017-11-17 | 2018-04-03 | 厦门大学 | The preparation method and applications of POSS DOPO triazine derivative flame retardants with self assembly humidification |
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| WENCHAO ZHANG等: "Study of the synergistic effect of silicon and phosphorus on the blowing-out effect of epoxy resin composites" * |
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