CN115572420B - Nitrile rubber-heat-resistant resin heat-insulating material with cross-linked interpenetrating network structure and preparation method thereof - Google Patents
Nitrile rubber-heat-resistant resin heat-insulating material with cross-linked interpenetrating network structure and preparation method thereof Download PDFInfo
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- CN115572420B CN115572420B CN202211193729.6A CN202211193729A CN115572420B CN 115572420 B CN115572420 B CN 115572420B CN 202211193729 A CN202211193729 A CN 202211193729A CN 115572420 B CN115572420 B CN 115572420B
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- 239000011810 insulating material Substances 0.000 title claims abstract description 56
- 229920006015 heat resistant resin Polymers 0.000 title claims abstract description 38
- 150000002825 nitriles Chemical class 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 31
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 18
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 14
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims abstract description 14
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 14
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008117 stearic acid Substances 0.000 claims abstract description 14
- 239000011787 zinc oxide Substances 0.000 claims abstract description 14
- 239000000835 fiber Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000006229 carbon black Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920001971 elastomer Polymers 0.000 claims description 66
- 150000001875 compounds Chemical class 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 239000012774 insulation material Substances 0.000 claims description 17
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 claims description 14
- 239000004014 plasticizer Substances 0.000 claims description 13
- 229920006231 aramid fiber Polymers 0.000 claims description 12
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 229920001721 polyimide Polymers 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 9
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 8
- 229920001944 Plastisol Polymers 0.000 claims description 8
- 239000004999 plastisol Substances 0.000 claims description 8
- 239000009719 polyimide resin Substances 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 8
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 7
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 6
- 239000004917 carbon fiber Substances 0.000 claims description 6
- 229910021485 fumed silica Inorganic materials 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 claims description 3
- -1 accelerator DM Chemical compound 0.000 claims description 3
- 238000010009 beating Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims description 3
- ICXAPFWGVRTEKV-UHFFFAOYSA-N 2-[4-(1,3-benzoxazol-2-yl)phenyl]-1,3-benzoxazole Chemical compound C1=CC=C2OC(C3=CC=C(C=C3)C=3OC4=CC=CC=C4N=3)=NC2=C1 ICXAPFWGVRTEKV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 229920006376 polybenzimidazole fiber Polymers 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims 4
- 230000003078 antioxidant effect Effects 0.000 claims 4
- 238000004073 vulcanization Methods 0.000 claims 4
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 claims 1
- 239000004693 Polybenzimidazole Substances 0.000 claims 1
- 238000002679 ablation Methods 0.000 abstract description 35
- 239000000463 material Substances 0.000 abstract description 16
- 239000011159 matrix material Substances 0.000 abstract description 3
- 238000011010 flushing procedure Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000002184 metal Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 238000009991 scouring Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 235000015842 Hesperis Nutrition 0.000 description 2
- 235000012633 Iberis amara Nutrition 0.000 description 2
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- QFXZANXYUCUTQH-UHFFFAOYSA-N ethynol Chemical group OC#C QFXZANXYUCUTQH-UHFFFAOYSA-N 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- QAPVYZRWKDXNDK-UHFFFAOYSA-N P,P-Dioctyldiphenylamine Chemical compound C1=CC(CCCCCCCC)=CC=C1NC1=CC=C(CCCCCCCC)C=C1 QAPVYZRWKDXNDK-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 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
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000012546 transfer 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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
-
- 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
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- 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
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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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 provides a nitrile rubber-heat-resistant resin heat-insulating material with a cross-linked interpenetrating network structure and a preparation method thereof, wherein the heat-insulating material is prepared from the following raw materials in parts by mass: 100 parts of nitrile rubber, 20-30 parts of dioctyl phthalate, 20-75 parts of heat-resistant resin, 30-60 parts of white carbon black, 6-16 parts of fiber, 4-9 parts of zinc oxide, 0.5-3 parts of anti-aging agent, 1-4 parts of stearic acid, 1-6 parts of accelerator, 2-4 parts of vulcanizing agent and 0.2-1 part of resin curing catalyst. The heat insulating material prepared by the invention has an interpenetrating structure of a nitrile rubber crosslinked network and a resin crosslinked network, the resin crosslinked network is used as an ablation-resistant matrix skeleton, the nitrile rubber crosslinked network is used as a mechanical flexible skeleton, and fibers are used for further improving the ablation resistance and the flushing resistance of the material, the ablation resistance of the material is obviously superior to that of a single nitrile rubber heat insulating material, and simultaneously, the mechanical property and the interface bonding property of the material are greatly improved.
Description
Technical Field
The invention belongs to the technical field of aerospace ablation-resistant composite materials, and particularly relates to a nitrile rubber-heat-resistant resin heat-insulating material with a cross-linked interpenetrating network structure and a preparation method thereof.
Background
The heat insulation layer of the solid rocket engine is a heat insulation protective material between the inner surface of the shell and the propellant, and has the main functions of taking away most of heat through continuous decomposition and ablation of the heat insulation protective material to relieve the heat transfer from high-temperature fuel gas to the shell, avoiding the shell from reaching the temperature endangering the structural integrity of the shell and ensuring the normal operation of the engine in the running process.
At present, a rubber-based material such as ethylene propylene diene monomer, nitrile rubber or silicon rubber-based heat insulating material is mainly adopted as the heat insulating material in the solid rocket engine, and the nitrile rubber has excellent high and low temperature resistance and physical and mechanical properties, and simultaneously has higher carbon residue rate in the thermal decomposition process. However, with the development of ultra weapons in recent years, the mechanical properties, ablation resistance, erosion resistance and the like of the traditional rubber-based heat insulating material tend to be limited, and particularly, the compactness and hardness degree of a carbon layer after the ablation of the nitrile rubber heat insulating material are not high, the capability of bearing the two-phase erosion of particles and gas in the working process of a solid engine is poor, and the internal heat protection requirement of a weapon power system with stronger future maneuverability, higher energy, longer range and more severe heat flow environment is difficult to meet.
Therefore, there is a need to develop a novel heat insulating material which improves the ablation resistance and the anti-scouring performance of the heat insulating material.
Disclosure of Invention
In order to overcome the defects in the prior art, the inventor conducts intensive research and provides a nitrile rubber-heat-resistant resin heat-insulating material with a cross-linked interpenetrating network structure and a preparation method thereof, and the heat-insulating material has the cross-linked interpenetrating network structure, and the two polymers have good cross-linked network compatibility and stable performance, so that the ablation resistance, the mechanical property, the heat-insulating property and the anti-scouring property are excellent, thereby completing the invention.
The technical scheme provided by the invention is as follows:
in the first aspect, the nitrile rubber-heat-resistant resin heat-insulating material with the cross-linked interpenetrating network structure is prepared from the following raw materials in parts by mass:
in a second aspect, a method for preparing a nitrile rubber-heat-resistant resin heat-insulating material with a cross-linked interpenetrating network structure comprises the following steps:
proportioning according to the heat insulating material components, wherein before mixing nitrile rubber, plasticating the nitrile rubber and a plasticizer dioctyl phthalate on an open mill according to a proportion, and standing the plasticated rubber for more than 16 hours;
uniformly mixing nitrile rubber plastisol, heat-resistant resin, white carbon black, fibers, zinc oxide and stearic acid in an internal mixer, wherein the discharge temperature of the rubber compound is less than or equal to 120 ℃ to obtain a first section of rubber compound, standing for 16-48 hours, uniformly mixing an anti-aging agent, an accelerator, a vulcanizing agent, a resin curing catalyst and the first section of rubber compound in the internal mixer, wherein the discharge temperature of the rubber compound is less than or equal to 80 ℃ to obtain a second section of rubber compound, standing for 16-48 hours, and then, beating the rubber compound on an open mill to form triangular bags and thin through sheets;
and vulcanizing the mixed rubber on a plate vulcanizing machine to obtain the molded heat insulation material.
According to the nitrile rubber-heat-resistant resin heat-insulating material with the cross-linked interpenetrating network structure and the preparation method thereof, the nitrile rubber-heat-resistant resin heat-insulating material has the following beneficial effects:
(1) The book is provided withThe invention provides a nitrile rubber-heat-resistant resin heat-insulating material with a cross-linked interpenetrating network structure, wherein the linear ablation rate of the heat-insulating material is 0.01-0.03 mm/s, the mass ablation rate is 0.01-0.08 g/s, the heat conductivity is lower than 0.20W/m.K, the tensile strength is 9-15 MPa, the elongation at break is 250-450%, and the density is not higher than 1.20g/cm -3 The hardness is 84-92, the bonding strength with metal is 4-8 MPa, the adhesive has excellent ablation resistance and heat insulation performance, the adhesive is formed in a certain pre-grinding engine, and the forming quality is good;
(2) Compared with the ablation-resistant heat-insulating material reported in the literature, the nitrile rubber/heat-resistant resin heat-insulating material with the cross-linked interpenetrating network structure provided by the invention adopts a composite material system of a non-inflammable agent, improves the strength of a carbon layer after the ablation of the nitrile rubber/heat-resistant resin cross-linked interpenetrating system, and endows the nitrile rubber/heat-resistant resin heat-insulating material with excellent high-temperature particle scouring resistance;
(3) The nitrile rubber-heat-resistant resin heat-insulating material with the cross-linked interpenetrating network structure provided by the invention has a stable interpenetrating network structure, and the nitrile rubber and the heat-resistant resin have better compatibility of two cross-linked systems, can not generate phase separation phenomenon, and has excellent and stable performance, so that the heat-insulating material has excellent heat resistance and mechanical property. Meanwhile, the material and metal have excellent bonding performance, can be applied to heat prevention of a high-speed aircraft structure in a large heat flow environment, and provide support for the technical development of future carrier rockets and hypersonic rockets.
Drawings
FIG. 1 is a surface topography (SEM) of a material according to example 1 of the present invention;
FIG. 2 is the profile of the ablated test piece in example 1 of the present invention;
FIG. 3 is a cross-sectional profile of the ablated material of example 1 of the present invention.
Detailed Description
The features and advantages of the present invention will become more apparent and clear from the following detailed description of the invention.
The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. Although various aspects of the embodiments are illustrated in the accompanying drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
According to the first aspect of the invention, a nitrile rubber-heat-resistant resin heat-insulating material with a cross-linked interpenetrating network structure is provided, ablation-resistant resin capable of self-polymerizing at high temperature is introduced into a nitrile rubber matrix, the curing temperature of the resin is reduced by adding a resin curing catalyst, the formed heat-insulating material is of a structure of interpenetrating nitrile rubber cross-linked network and resin cross-linked network, the resin cross-linked network is taken as an ablation-resistant matrix skeleton, the nitrile rubber cross-linked network is taken as a mechanical flexible skeleton, and fibers are used for further improving the ablation resistance and the scouring resistance of the material, the ablation resistance of the material is obviously superior to that of an independent nitrile rubber heat-insulating material, and meanwhile, the mechanical property and the interface bonding property of the material are greatly improved.
In the invention, the heat insulation material is prepared from the following raw materials in parts by mass:
preferably, the heat insulating material is prepared from the following raw materials in parts by mass:
in a preferred embodiment, the heat-resistant resin is selected from one or more of a boron phenolic resin, a polyimide resin, an oxazine resin, an epoxy resin, a cyanate resin, or a bismaleimide resin, and preferably one or more of a polyimide resin or an oxazine resin. Polyimide resins and oxazine resins have higher char yields than the remaining few resins.
In a preferred embodiment, the white carbon black is selected from one or both of fumed silica, precipitated silica, or nanosilica.
In a preferred embodiment, the fibers are selected from one or both of aramid fibers, polyimide fibers, carbon fibers, polybenzimidazole fibers or poly-p-phenylene benzobisoxazole fibers, preferably one or both of aramid fibers or carbon fibers.
In a preferred embodiment, the anti-aging agent is selected from one or two of anti-aging agent D (N-phenyl-2-naphthylamine), anti-aging agent RD (2, 4-trimethyl-1, 2-dihydroquinoline polymer), anti-aging agent ODA (4, 4 ' -dioctyl diphenylamine), anti-aging agent 4020 (N- (1, 3-dimethyl) butyl-N ' -phenyl-p-phenylenediamine) or anti-aging agent 4010NA (N-isopropyl-N ' -phenyl-p-phenylenediamine).
In a preferred embodiment, the accelerator is selected from one or more of accelerator TMTD (tetramethylthiuram disulfide, tetramethyldithiothiuram disulfide), accelerator DM (dibenzothiazyl disulfide), accelerator CZ (N-cyclohexyl-2-benzothiazole sulfenamide) or accelerator M (2-mercaptobenzothiazole).
In a preferred embodiment, the vulcanizing agent is selected from any one or more of dicumyl peroxide (DCP), benzoyl Peroxide (BPO), bis-t-butyldiisopropylbenzene peroxide (BIPB), and sulfur (S).
In a preferred embodiment, the resin curing catalyst is selected from either or both of 2-methylimidazole or 4-methylimidazole.
According to a second aspect of the present invention, there is provided a method for producing a nitrile rubber-heat resistant resin heat insulating material of a crosslinked interpenetrating network structure, comprising the steps of:
proportioning according to the heat insulating material components, wherein before mixing nitrile rubber, plasticating the nitrile rubber and a plasticizer dioctyl phthalate on an open mill according to a proportion, and standing the plasticated rubber for more than 16 hours;
uniformly mixing nitrile rubber plastisol, heat-resistant resin, white carbon black, fibers, zinc oxide and stearic acid in an internal mixer, wherein the discharge temperature of the rubber compound is less than or equal to 120 ℃ to obtain a first section of rubber compound, standing for 16-48 hours, uniformly mixing an anti-aging agent, an accelerator, a vulcanizing agent, a resin curing catalyst and the first section of rubber compound in the internal mixer, wherein the discharge temperature of the rubber compound is less than or equal to 80 ℃ to obtain a second section of rubber compound, standing for 16-48 hours, and then, beating the rubber compound on an open mill to form triangular bags and thin through sheets;
vulcanizing the mixed rubber on a plate vulcanizing machine at the vulcanizing temperature of 150-180 ℃ for 20-60 min and the vulcanizing pressure of 5-15 MPa to obtain the molded heat insulation material.
Examples
Examples 1 to 5 provide nitrile rubber-heat resistant resin insulation materials of crosslinked interpenetrating network structure and a method for preparing the same, and the prepared insulation materials were tested for the items mentioned below.
(1) Tensile strength and elongation at break:
the test was carried out on a WDW-5J-type electronic tensile machine according to QJ 916-1985 at a test speed of 100mm/min, and the tensile strength and elongation at break of the material were recorded. The better the mechanical properties of the sample with greater tensile strength and elongation at break.
(2) Density:
testing the material density was recorded as tested on a mertrehler XS-204 density balance in switzerland according to QJ917A-1997 standard.
(3) Ablation resistance
The test is carried out in a multi-station oxyacetylene ablation tester according to GJB 323B-2018 standard, and oxyacetylene flame vertically acts on the surface of a sample during the test, the diameter of a nozzle is 2mm, the oxygen flow rate is 1512L/h, the acetylene flow rate is 1116L/h, and the heat flow density is 4196.4Kw/m 2 The ablation distance was 10mm. The thermal insulation material having smaller line and mass ablation rates has better ablation resistance.
(4) Thermal insulation properties
Testing was performed according to the heat flow meter method, according to the Q/Rs 193-2017 standard. The better the thermal insulation of a material having a smaller thermal conductivity.
Example 1
The nitrile rubber/heat-resistant resin heat-insulating material comprises 100 parts of nitrile rubber, 25 parts of plasticizer DOP, 75 parts of oxazine resin, 40 parts of fumed silica, 10 parts of aramid fiber, 5 parts of zinc oxide, 2.5 parts of anti-aging agent D, 1.5 parts of stearic acid, 2.5 parts of accelerator TMTD, 2.5 parts of vulcanizing agent DCP and 0.4 part of 2-methylimidazole.
The preparation of the heat insulating material comprises the following steps:
firstly, plasticating on an open mill according to 100 parts of nitrile rubber and 25 parts of plasticizer DOP, and standing the plasticated rubber for 16 hours;
mixing 125 parts of nitrile rubber plastisol, 75 parts of oxazine resin, 40 parts of fumed silica, 10 parts of aramid fiber, 5 parts of zinc oxide and 1.5 parts of stearic acid uniformly in an internal mixer, wherein the discharge temperature of the mixed rubber is 100 ℃ to obtain a first section of mixed rubber, after 24 hours for use, mixing 2.5 parts of an anti-aging agent D, 2.5 parts of an accelerator TMTD, 2.5 parts of a vulcanizing agent DCP and 0.4 part of 2-methylimidazole uniformly with the first section of mixed rubber in the internal mixer, wherein the discharge temperature of the mixed rubber is 70 ℃ to obtain a second section of mixed rubber, and after 24 hours for use, making triangular bags and thin-pass sheets on an open mill;
step three, vulcanizing the mixed rubber on a plate vulcanizing machine under the vulcanizing conditions: the temperature is 160 ℃, the time is 30min, and the pressure is 10MPa, so that the molded heat insulation material is obtained.
The linear ablation rate of the molded heat insulating material is 0.022mm/s, the mass ablation rate is 0.045g/s, the heat conductivity coefficient is lower than 0.189W/m.K, the tensile strength is 10.2MPa, the elongation at break is 392%, and the density is 1.18g/cm -3 Hardness 84, and adhesion strength with metal 5.8MPa. FIG. 1 is an SEM image of a cured insulation material, wherein the nitrile rubber and the resin have no obvious phase separation interface, which shows that the cured insulation material has better compatibility between two crosslinked networks. Fig. 2 is a graph of the shape of the test piece after ablation, the carbon layer formed on the surface is compact and not easy to fall off,the heat insulating material has excellent ablation resistance and anti-scouring performance. FIG. 3 is a cross-sectional morphology of the ablated material, and shows that the ablated carbon layer has a dense cross section and no obvious loose holes, and the ablated carbon layer has high compactness and excellent scouring resistance.
Example 2
The nitrile rubber/heat-resistant resin heat-insulating material of the embodiment comprises 100 parts of nitrile rubber, 25 parts of plasticizer DOP, 20 parts of polyimide resin, 40 parts of oxazine resin, 10 parts of fumed silica, 30 parts of precipitated silica, 10 parts of carbon fiber, 4 parts of zinc oxide, 2 parts of anti-aging agent D, 1 part of stearic acid, 2 parts of accelerator TMTD, 0.5 part of accelerator M, 2 parts of vulcanizing agent DCP, 0.5 part of sulfur and 0.4 part of 2-methylimidazole.
The preparation of the heat insulating material comprises the following steps:
firstly, plasticating on an open mill according to 100 parts of nitrile rubber and 25 parts of plasticizer DOP, and standing the plasticated rubber for 16 hours;
mixing 125 parts of nitrile rubber plastisol, 20 parts of polyimide resin, 40 parts of oxazine resin, 10 parts of fumed silica, 30 parts of precipitation method silica, 10 parts of carbon fiber, 4 parts of zinc oxide and 1 part of stearic acid uniformly in an internal mixer, wherein the discharge temperature of the mixed rubber is 100 ℃, obtaining a section of mixed rubber, after 24 hours for use, mixing uniformly the 2 parts of an anti-aging agent D, 2 parts of an accelerator TMTD, 0.5 part of an accelerator M, 2 parts of a vulcanizing agent DCP, 0.5 part of sulfur and 0.4 part of 2-methylimidazole with the section of mixed rubber in the internal mixer, the discharge temperature of the mixed rubber is 70 ℃, obtaining a second section of mixed rubber, and after 24 hours for use, making triangular bags and thin-pass sheets on an open mill;
step three, vulcanizing the mixed rubber on a plate vulcanizing machine under the vulcanizing conditions: the temperature is 160 ℃, the time is 60min, and the pressure is 10MPa, so that the molded heat insulation material is obtained.
The linear ablation rate of the molded heat insulating material is 0.025mm/s, the mass ablation rate is 0.046g/s, the heat conductivity coefficient is lower than 0.176W/m.K, the tensile strength is 13.1MPa, the elongation at break is 414 percent, and the density is 1.16g/cm -3 The hardness is 84, and the bonding strength with metal is 6.2MPa.
Example 3
The components of the nitrile rubber/heat-resistant resin heat-insulating material of the embodiment comprise 100 parts of nitrile rubber, 25 parts of plasticizer DOP, 30 parts of oxazine resin, 20 parts of polyimide resin, 30 parts of precipitated silica, 16 parts of aramid fiber, 5 parts of zinc oxide, 1.5 parts of anti-aging agent RD, 1 part of stearic acid, 2.5 parts of accelerator DM, 2.5 parts of vulcanizing agent BIPB, 0.5 part of sulfur and 0.4 part of 4-methylimidazole.
The preparation of the heat insulating material comprises the following steps:
firstly, plasticating on an open mill according to 100 parts of nitrile rubber and 25 parts of plasticizer DOP, and standing the plasticated rubber for 16 hours;
mixing 125 parts of nitrile rubber plastisol, 30 parts of oxazine resin and 20 parts of polyimide resin, 30 parts of precipitated silica, 16 parts of aramid fiber, 5 parts of zinc oxide and 1 part of stearic acid uniformly in an internal mixer, wherein the discharging temperature of the mixed rubber is 100 ℃ to obtain a first section of mixed rubber, after the mixed rubber is used for 36 hours, mixing uniformly the first section of mixed rubber, 2.5 parts of vulcanizing agent BIPB, 0.5 part of sulfur and 0.4 part of 4-methylimidazole with the first section of mixed rubber in the internal mixer, the discharging temperature of the mixed rubber is 80 ℃ to obtain a second section of mixed rubber, and after the mixed rubber is used for 48 hours, performing triangular package and thin-pass sheet forming on the mixed rubber on an open mill;
step three, vulcanizing the mixed rubber on a plate vulcanizing machine under the vulcanizing conditions: the temperature is 155 ℃, the time is 60min, and the pressure is 15MPa, so that the molded heat insulation material is obtained.
The linear ablation rate of the molded heat insulating material is 0.030mm/s, the mass ablation rate is 0.041g/s, the heat conductivity coefficient is lower than 0.182W/m.K, the tensile strength is 9.8MPa, the elongation at break is 396%, and the density is 1.19g/cm -3 Hardness 88, and adhesion strength with metal 5.2MPa.
Example 4
The components of the nitrile rubber/heat-resistant resin heat-insulating material of the embodiment comprise 100 parts of nitrile rubber, 20 parts of plasticizer DOP, 40 parts of oxazine resin, 50 parts of precipitated silica, 10 parts of aramid fiber, 4 parts of zinc oxide, 1.5 parts of anti-aging agent RD, 1 part of stearic acid, 2.5 parts of accelerator DM, 2.5 parts of vulcanizing agent BIPB, 0.5 part of sulfur and 0.4 part of 2-methylimidazole.
The preparation of the heat insulating material comprises the following steps:
firstly, plasticating on an open mill according to 100 parts of nitrile rubber and 20 parts of plasticizer DOP, and standing the plasticated rubber for 16 hours;
step two, mixing 120 parts of nitrile rubber plastisol, 40 parts of oxazine resin, 1.5 parts of anti-aging agent RD, 50 parts of precipitation method silicon dioxide, 10 parts of aramid fiber, 4 parts of zinc oxide and 1 part of stearic acid uniformly in an internal mixer, wherein the discharge temperature of the mixed rubber is 100 ℃, a first section of mixed rubber is obtained, after 36 hours of use, 2.5 parts of accelerator DM, 2.5 parts of vulcanizing agent BIPB, 0.5 part of sulfur and 0.4 part of 2-methylimidazole are mixed uniformly with the first section of mixed rubber in the internal mixer, the discharge temperature of the mixed rubber is 80 ℃, a second section of mixed rubber is obtained, and after 48 hours of use, the mixed rubber is subjected to triangular package and thin-pass sheet forming on an open mill;
step three, vulcanizing the mixed rubber on a plate vulcanizing machine under the vulcanizing conditions: the temperature is 165 ℃, the time is 40min, and the pressure is 10MPa, so that the molded heat insulation material is obtained.
The linear ablation rate of the molded heat insulating material is 0.013mm/s, the mass ablation rate is 0.019g/s, the heat conductivity coefficient is lower than 0.196W/m.K, the tensile strength is 9.4MPa, the elongation at break is 396%, and the density is 1.16g/cm -3 Hardness 90 and bonding strength with metal 5.2MPa.
Example 5
The components of the nitrile rubber/heat-resistant resin heat-insulating material of the embodiment comprise 100 parts of nitrile rubber, 30 parts of plasticizer DOP, 60 parts of oxazine resin, 30 parts of nano silicon dioxide, 10 parts of silane coupling agent modified grafting pretreatment aramid fiber, 4 parts of zinc oxide, 2 parts of anti-aging agent D, 1 part of stearic acid, 2 parts of accelerator TMTD, 0.5 part of accelerator M, 1.5 parts of vulcanizing agent DCP, 0.5 part of sulfur and 0.4 part of 2-methylimidazole.
The preparation of the heat insulating material comprises the following steps:
firstly, plasticating on an open mill according to 100 parts of nitrile rubber and 30 parts of plasticizer DOP, and standing the plasticated rubber for 16 hours;
mixing 130 parts of nitrile rubber plastisol, 20 parts of boron phenolic resin, 40 parts of oxazine resin, 30 parts of nano silicon dioxide, 10 parts of pretreated aramid fiber, 4 parts of zinc oxide and 1 part of stearic acid uniformly in an internal mixer, wherein the discharge temperature of the mixed rubber is 100 ℃, obtaining a first section of mixed rubber, after 24 hours for use, mixing uniformly 1.5 parts of vulcanizing agent DCP, 0.5 part of sulfur and 0.4 part of 2-methylimidazole with the first section of mixed rubber in the internal mixer, the discharge temperature of the mixed rubber is 80 ℃, obtaining a second section of mixed rubber, and after 24 hours for use, making triangular bags and thin-pass sheets on an open mill;
step three, vulcanizing the mixed rubber on a plate vulcanizing machine under the vulcanizing conditions: the temperature is 160 ℃, the time is 60min, and the pressure is 15MPa, so that the molded heat insulation material is obtained.
The linear ablation rate of the molded heat insulating material is 0.026mm/s, the mass ablation rate is 0.044g/s, the heat conductivity coefficient is 0.181W/m.K, the tensile strength is 12.0MPa, the elongation at break is 369 percent, and the density is 1.20g/cm -3 The hardness is 89, and the bonding strength with metal is 6.8MPa.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
What is not described in detail in the present specification is a well known technology to those skilled in the art.
Claims (9)
1. The nitrile rubber-heat-resistant resin heat-insulating material with the cross-linked interpenetrating network structure is characterized by being prepared from the following raw materials in parts by mass:
the heat-resistant resin is one or two of polyimide resin and oxazine resin;
the fiber is selected from one or two of aramid fiber, polyimide fiber, carbon fiber, polybenzimidazole fiber or poly-p-phenylene benzobisoxazole fiber.
2. The crosslinked interpenetrating network structured nitrile rubber-heat resistant resin insulation material according to claim 1, wherein said white carbon black is one or two selected from fumed silica, precipitated silica and nanosilica.
3. The crosslinked interpenetrating network structured nitrile rubber-heat resistant resin insulation material according to claim 1, wherein said fiber is one or both of an aramid fiber and a carbon fiber.
4. The nitrile rubber-heat-resistant resin insulating material of crosslinked interpenetrating network structure according to claim 1, wherein the antioxidant is one or two selected from the group consisting of antioxidant D, antioxidant RD, antioxidant ODA, antioxidant 4020 and antioxidant 4010 NA.
5. The nitrile rubber-heat-resistant resin insulating material with a crosslinked interpenetrating network structure according to claim 1, wherein the accelerator is one or more selected from the group consisting of accelerator TMTD, accelerator DM, accelerator CZ and accelerator M.
6. The cross-linked interpenetrating network structure nitrile rubber-heat-resistant resin heat-insulating material according to claim 1, wherein the vulcanizing agent is any one or more selected from dicumyl peroxide DCP, benzoyl peroxide BPO, (1, 4) -di-tert-butyl dicumyl peroxide BIPB and sulfur S.
7. The nitrile rubber-heat resistant resin insulation material of crosslinked interpenetrating network structure according to claim 1, wherein said resin curing catalyst is selected from either one or two of 2-methylimidazole or 4-methylimidazole.
8. A method for producing the nitrile rubber-heat-resistant resin heat-insulating material of crosslinked interpenetrating network structure according to any one of claims 1 to 7, comprising the steps of:
proportioning according to the heat insulating material components, wherein before mixing nitrile rubber, plasticating the nitrile rubber and a plasticizer dioctyl phthalate on an open mill according to a proportion, and standing the plasticated rubber for more than 16 hours;
uniformly mixing nitrile rubber plastisol, heat-resistant resin, white carbon black, fibers, zinc oxide and stearic acid in an internal mixer, wherein the discharge temperature of the rubber compound is less than or equal to 120 ℃ to obtain a first section of rubber compound, standing for 16-48 hours, uniformly mixing an anti-aging agent, an accelerator, a vulcanizing agent, a resin curing catalyst and the first section of rubber compound in the internal mixer, wherein the discharge temperature of the rubber compound is less than or equal to 80 ℃ to obtain a second section of rubber compound, standing for 16-48 hours, and then, beating the rubber compound on an open mill to form triangular bags and thin through sheets;
and vulcanizing the mixed rubber on a plate vulcanizing machine to obtain the molded heat insulation material.
9. The method for producing a nitrile rubber-heat resistant resin heat insulating material of crosslinked interpenetrating network structure according to claim 8, wherein the vulcanization conditions include: the vulcanization temperature is 150-180 ℃, the vulcanization time is 20-60 min, and the vulcanization pressure is 5-15 MPa.
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| CN114957818A (en) * | 2022-04-19 | 2022-08-30 | 华南理工大学 | Nitrile rubber-phenolic resin composite material and preparation method and application thereof |
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| CN106928512A (en) * | 2017-04-11 | 2017-07-07 | 湖北三江航天江河化工科技有限公司 | A kind of silicon carbide fibre strengthens nitrile rubber and preparation method |
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