CN116478461A - Rubber sealing material and preparation method thereof - Google Patents
Rubber sealing material and preparation method thereof Download PDFInfo
- Publication number
- CN116478461A CN116478461A CN202310413129.4A CN202310413129A CN116478461A CN 116478461 A CN116478461 A CN 116478461A CN 202310413129 A CN202310413129 A CN 202310413129A CN 116478461 A CN116478461 A CN 116478461A
- Authority
- CN
- China
- Prior art keywords
- sealing material
- parts
- triethylamine
- rubber sealing
- diethyl ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003566 sealing material Substances 0.000 title claims abstract description 46
- 229920001971 elastomer Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 16
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 15
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 11
- 229920005989 resin Polymers 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 239000011593 sulfur Substances 0.000 claims abstract description 8
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 81
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 66
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- QGFSQVPRCWJZQK-UHFFFAOYSA-N 9-Decen-1-ol Chemical compound OCCCCCCCCC=C QGFSQVPRCWJZQK-UHFFFAOYSA-N 0.000 claims description 16
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 16
- 239000002041 carbon nanotube Substances 0.000 claims description 16
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 16
- 239000003607 modifier Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 10
- 238000004513 sizing Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- -1 sodium 9-decen-1-ol Chemical compound 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 239000007821 HATU Substances 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- DYHSDKLCOJIUFX-UHFFFAOYSA-N tert-butoxycarbonyl anhydride Chemical compound CC(C)(C)OC(=O)OC(=O)OC(C)(C)C DYHSDKLCOJIUFX-UHFFFAOYSA-N 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000003801 milling Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000004073 vulcanization Methods 0.000 claims description 5
- LNPMZQXEPNWCMG-UHFFFAOYSA-N 4-(2-aminoethyl)aniline Chemical compound NCCC1=CC=C(N)C=C1 LNPMZQXEPNWCMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000002386 leaching Methods 0.000 claims description 4
- 239000012044 organic layer Substances 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- 239000012047 saturated solution Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 239000002109 single walled nanotube Substances 0.000 abstract description 12
- 238000007789 sealing Methods 0.000 abstract description 10
- 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 abstract description 8
- 239000003063 flame retardant Substances 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 abstract description 7
- 230000003014 reinforcing effect Effects 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 230000009471 action Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009827 uniform distribution 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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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 rubber sealing material and a preparation method thereof, which belong to the technical field of sealing materials and comprise the following raw materials in parts by weight: 70 parts of nitrile rubber, 25-35 parts of polyvinyl chloride resin, 3-4 parts of anti-aging agent, 15-20 parts of modified carbon nano tube and 2-3 parts of sulfur; the sealing material is prepared by mixing, plasticizing, vulcanizing and the like the raw materials according to the proportion. The sealing material adopts the nitrile rubber and the polyvinyl chloride resin as the matrix, and has high toughness, elasticity and friction resistance and sealing performance; by adding the modified single-wall carbon nanotubes, the uniform dispersion of the single-wall carbon nanotubes in the material can be promoted, the reinforcing effect can be better exerted, and the stable reticular structure can be promoted to be formed, so that the sealing material has excellent wear resistance, and in addition, the sealing material can be endowed with high-efficiency, stable and durable flame retardant performance, so that the application range of the sealing material is improved.
Description
Technical Field
The invention belongs to the technical field of sealing materials, and particularly relates to a rubber sealing material and a preparation method thereof.
Background
For moving seals, friction is an important factor in relation to the moving mass. While sealing and friction are always constrained to each other. Generally, improving the tightness brings about an increase in friction force, which directly leads to a decrease in movement capacity and mass; and friction may accelerate wear of the seal.
Most of the current common sealing elements adopt ethylene propylene rubber or nitrile rubber and the like, but the friction performance of the sealing element is still required to be further improved as one of the sealing element materials; plastics generally have a lower coefficient of friction, more excellent barrier properties and higher strength and hardness than rubber, and during friction, the abrasive particles of the plastics wear less due to the higher hardness of the plastics. In order to improve the sealing performance of the rubber sealing piece, the advantages of combining high-performance special plastic and rubber are provided, and the friction and sealing performance of the rubber are greatly improved while the toughness and elasticity of a rubber matrix are not weakened.
However, the improvement effect on the wear resistance and mechanical properties of the sealing material is limited, so that the performance of the sealing material can be further improved by adopting reinforcing filler in the prior art. However, the general reinforcing filler belongs to inorganic filler, is difficult to uniformly disperse, not only reduces the reinforcing effect, but also can negatively influence the mechanical properties of the material. In addition, because the rubber is composed of C element and H element, the oxygen index is lower, the rubber is easy to ignite in the air, and micromolecules decomposed after ignition can be burnt with oxygen to generate a large amount of heat, so that the combustion is further intensified, the rubber cannot self-extinguish in the air, and the application of the rubber in sealing materials in a limited space is limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a rubber sealing material and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
the rubber sealing material comprises the following raw materials in parts by weight: 70 parts of nitrile rubber, 25-35 parts of polyvinyl chloride resin, 3-4 parts of anti-aging agent, 15-20 parts of modified carbon nano tube and 2-3 parts of sulfur;
the preparation method of the rubber sealing material comprises the following steps:
firstly, adding nitrile rubber and polyvinyl chloride resin into an internal mixer for plasticating for 3-4min, then adding an anti-aging agent for mixing for 2-4min, then adding a modified carbon nano tube for mixing for 3-5min, and standing for 50-60min to obtain a mixed material;
secondly, adding the mixed materials into an open mill, carrying out heat refining for 2-4min at the temperature of 40-60 ℃, adding sulfur, adjusting the roll gap to 1-2mm after the powder is eaten, and releasing the roll gap to obtain the sizing material after triangular wrapping for 5-6 times;
and thirdly, the sizing material is subjected to open mill milling through an open mill, and then the rubber sealing material is obtained through preforming and vulcanization molding processes.
Further, the antioxidant is any one of an antioxidant RD, an antioxidant 4010NA, and an antioxidant 445.
Further, the modified carbon nanotube is prepared by the steps of:
s1, reacting 9-decen-1-ol with sodium hydroxide to obtain 9-decen-1-sodium alkoxide for later use; introducing N 2 Removing air in a four-neck flask, dissolving hexachlorocyclotriphosphazene in tetrahydrofuran, placing the flask in an ice bath, slowly and uniformly dropwise adding a tetrahydrofuran mixed solution (the dropwise acceleration is controlled at 2 mL/min) in which 9-decen-1-sodium alkoxide and triethylamine are dissolved under stirring, reacting for 4 hours under the ice water bath after the dropwise adding is finished, removing generated salt (NaCl) through suction filtration, collecting filtrate, removing solvent and excessive triethylamine through reduced pressure distillation, washing for a plurality of times with chloroform and distilled water respectively, taking an organic layer, performing rotary evaporation and vacuum drying to obtain a phosphazene derivative; the ratio of the amounts of hexachlorocyclotriphosphazene, 9-decen-1-ol sodium and triethylamine was 0.03mol:0.09mol:0.1mol;
nucleophilic substitution reaction is carried out on-Cl group on hexachlorocyclotriphosphazene molecule and 9-decen-1-ol, and the trisubstituted reaction is carried out under the action of steric hindrance by controlling the mol ratio of the-Cl group to the 9-decen-1-ol to be 1:3, wherein the process is as follows:
s2, dissolving p-aminophenyl ethylamine in methanol, adding triethylamine as a catalyst, dissolving tert-butoxycarbonyl anhydride in diethyl ether, dropwise dripping the mixture into the three-necked flask through a constant pressure funnel, stirring the mixture for reaction for 10 hours at the constant temperature of 3-5 ℃, adding water and diethyl ether, extracting, taking diethyl ether phase, removing diethyl ether through rotary evaporation, and finally carrying out recrystallization purification by using a mixed solution of dichloromethane and diethyl ether (the volume ratio of dichloromethane to diethyl ether is 1:1) to obtain a grafting agent; the dosage ratio of the para-aminophenyl ethylamine, the triethylamine and the tert-butoxycarbonyl anhydride is 0.1mol:0.11mol:0.1mol;
by tert-butoxycarbonyl anhydride with-NH 2 Reaction of p-aminophenylamine with one-NH on the molecule 2 Protecting by tert-butyl (Boc) to obtain a grafting agent;
s3, adding dichloromethane into a four-neck flask, introducing nitrogen, continuously (removing air in the flask) for 10min, adding a phosphazene derivative and triethylamine, stirring and mixing uniformly, dropwise adding a dichloromethane solution dissolved with a grafting agent by adopting a constant pressure funnel, reacting for 4h under normal temperature after the dropwise addition is finished, removing generated triethylamine hydrochloride by suction filtration after the reaction is finished, and distilling filtrate under reduced pressure to obtain a primary product; the ratio of the phosphazene derivative, triethylamine and grafting agent is 35.3g to 15.3g to 35.4g;
-Cl on phosphazene derivative molecule and-NH on grafting agent molecule 2 Nucleophilic substitution reaction is carried out to obtain an initial product, and the reaction process is as follows:
s4, mixing the initial product with saturated hydrogen chloride solution of THF (tetrahydrofuran) according to a solid-to-liquid ratio of 1g to 8mL, stirring for 5 hours at room temperature, filtering, leaching a filter cake with diethyl ether, and vacuum drying to obtain a modifier;
removing Boc protecting group from initial product under acidic condition to obtain-NH 2 A modifier of the structure shown below was obtained:
s5, mixing the carboxylated carbon nanotubes with anhydrous dichloromethane, performing ultrasonic dispersion for 30min, adding HATU (2- (7-azabenzotriazol) -tetramethyluronium hexafluorophosphate) and DIPEA (N, N-diisopropylethylamine), continuing ultrasonic treatment for 20min, adding a modifier, stirring for reacting for 12h, and finally centrifuging, washing and drying to obtain the modified carbon nanotubes; the dosage ratio of carboxylated carbon nano tube, HATU, DIPEA and modifier is 1g to 2.8g to 2.2mL to 8.9g;
carboxylated carbon nanotube surface-COOH and modifier molecule-NH under the action of HATU and DIPEA 2 And carrying out amidation reaction, and chemically bonding a modifier molecular chain on the surface of the carbon nano tube to obtain the modified carbon nano tube.
After the single-wall carbon nano tube is modified, an organic molecular layer is formed on the surface, so that the interface compatibility of the single-wall carbon nano tube and a polymer matrix (nitrile rubber and polyvinyl chloride) can be effectively improved; in addition, the grafted modifier molecular chain contains a long fatty carbon chain, the tail end of the fatty carbon chain is an unsaturated carbon-carbon double bond, the long fatty carbon chain has extremely high similar compatibility with the molecular main chain of the polymer matrix, and the long fatty carbon chain can freely penetrate and insert between high molecular chains due to high flexibility, so that the uniform dispersion of the carbon nano tube in the material can be further improved, the reinforcing effect is better exerted, the wear resistance of the material is further improved, and when the single-wall carbon nano tube is oriented at 90 degrees in a composite system, a large number of NBR and PVC molecular chains can be adsorbed due to the extremely strong adsorption performance and the stronger van der Waals force effect on the surface, so that the material matrix is extremely stable, and the surface substances are less shed in the friction process, so that the wear resistance of the material is improved; in addition, unsaturated carbon-carbon double bonds at the end can participate in the melt polymerization process of NBR and PVC, and a plurality of unsaturated carbon-carbon double bonds can play a role in crosslinking, so that not only can the effect between NBR and PVC be improved, but also the stable reticular structure can be promoted to be formed, the binding force between internal molecular chains of the sealing material is increased, the relative sliding between the molecular chains is reduced, the sealing material has excellent wear resistance, and the service life of a sealing piece made of the sealing material is prolonged;
it should be further described that the grafted modifier molecule contains cyclophosphazene group, belongs to P-N synergistic flame retardant component, and can not only endow good flame retardant property to the sealing material along with the uniform distribution of the carbon nanotubes in the sealing material, but also has lasting and stable flame retardant effect due to strong interaction force with the material matrix, and improves the application range of the sealing material.
Further, the carboxylated carbon nanotubes are prepared by the steps of:
placing the single-wall carbon nano tube into a conical flask, adding strong acid (obtained by mixing 98% by mass of concentrated sulfuric acid and 37.5% by mass of concentrated hydrochloric acid according to a volume ratio of 5:1) according to a solid-to-liquid ratio of 1g to 12mL, performing ultrasonic treatment for 6 hours in a water bath at 50 ℃, cooling the mixture to room temperature, adding deionized water for dilution, performing centrifugal separation, washing with ethanol and deionized water for 3 times in sequence, drying to constant weight in a vacuum oven at 60 ℃, grinding, and sieving with a 200-mesh sieve to obtain the carboxylated carbon nano tube.
Oxidizing the single-wall carbon nanotube with strong acid to introduce-COOH functional group to the surface of the carbon nanotube, so as to lay the reaction site for subsequent modification.
Further, in step S1, the specific process of the reaction of 9-decen-1-ol and sodium hydroxide is as follows:
sequentially adding 20g (0.5 mol) of solid sodium hydroxide and 207.4g (1.4 mol) of 9-decen-1-ol into a four-mouth bottle provided with a thermometer, a rectifying column and a water separator, magnetically stirring under the protection of nitrogen, heating to reflux temperature, collecting water generated by azeotropy by the water separator until no obvious water drops fall down in the water separator, and obtaining 9-decen-1-sodium alkoxide after the reaction; the molar ratio of sodium hydroxide to 9-decen-1-ol was 1:1.
The invention has the beneficial effects that:
the sealing material adopts the nitrile rubber and the polyvinyl chloride resin as the matrix, can combine the advantages of the nitrile rubber and the polyvinyl chloride resin to form a rubber-plastic composite material, and has high toughness, elasticity and friction resistance and sealing performance; by adding the modified single-wall carbon nanotubes, the uniform dispersion of the single-wall carbon nanotubes in the material can be promoted, the reinforcing effect can be better exerted, and the stable reticular structure can be promoted to be formed, so that the binding force between internal molecular chains of the sealing material is increased, the relative sliding between the molecular chains is reduced, the sealing material has excellent wear resistance, and in addition, the sealing material can be endowed with high-efficiency, stable and durable flame retardant performance, so that the application range of the sealing material is improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparing carboxylated carbon nanotubes:
placing 10g of carbon nano tube into a conical flask, adding 120mL of strong acid (100 mL of concentrated sulfuric acid with the mass fraction of 98% and 20mL of concentrated hydrochloric acid with the mass fraction of 37.5%), performing ultrasonic treatment in a water bath at 50 ℃ for 6 hours, cooling the mixture to room temperature, adding 300mL of deionized water for dilution, performing centrifugal separation, washing with ethanol and deionized water for 3 times in sequence, drying in a vacuum oven at 60 ℃ to constant weight, grinding, and sieving with a 200-mesh sieve to obtain carboxylated carbon nano tube.
Example 2
Preparation of sodium 9-decen-1-olate:
8g of solid sodium hydroxide and 31.2g of 9-decen-1-ol are sequentially added into a four-mouth bottle provided with a thermometer, a rectifying column and a water separator, the mixture is magnetically stirred and heated to reflux temperature under the protection of nitrogen, water generated by azeotropy is collected by the water separator until no obvious water drops fall down in the water separator, and the reaction is finished, so that the 9-decen-1-ol sodium is obtained.
Example 3
Preparing a modified carbon nano tube:
s1, leading in N 2 Removing air in a four-neck flask, dissolving 10.4g of hexachlorocyclotriphosphazene in 100mL of tetrahydrofuran, placing the flask in an ice bath, slowly and uniformly dropwise adding 40mL of a tetrahydrofuran mixed solution containing 16g of 9-decen-1-ol sodium (prepared in example 2) and 10.1g of triethylamine under stirring, reacting for 4 hours in the ice bath after the completion of the dropwise addition for 20 minutes, removing generated salt (NaCl) by suction filtration after the completion of the reaction, collecting filtrate, removing the solvent and excessive triethylamine by reduced pressure distillation, washing with chloroform and distilled water for a plurality of times respectively, taking an organic layer, performing rotary evaporation and vacuum drying to obtain a phosphazene derivative;
s2, in a three-necked bottle, dissolving 13.7g of p-aminophenyl ethylamine in 80mL of methanol, adding 11.1g of triethylamine as a catalyst, dissolving 19.4g of tert-butoxycarbonyl anhydride in 50mL of diethyl ether, dropwise dripping the mixture into the three-necked bottle through a constant pressure funnel, stirring the mixture at the constant temperature of 3 ℃ for reaction for 10 hours, adding water and diethyl ether, extracting, taking diethyl ether phase, removing diethyl ether through rotary evaporation, and finally carrying out recrystallization purification by using a mixed solution of dichloromethane and diethyl ether (the volume ratio of dichloromethane to diethyl ether is 1:1) to obtain a grafting agent;
s3, adding 150mL of dichloromethane into a four-necked flask, introducing nitrogen, continuously adding 35.3g of phosphazene derivative and 15.3g of triethylamine after continuously heating for 10min (removing air in the flask), stirring and uniformly mixing, dropwise adding 60mL of dichloromethane solution dissolved with 35.4g of grafting agent by adopting a constant pressure funnel, reacting for 4h under normal temperature after the dropwise adding is completed, removing generated triethylamine hydrochloride by suction filtration after the reaction is completed, and obtaining a primary product after reduced pressure distillation of filtrate;
s4, mixing 60g of an initial product with 480mL of saturated hydrogen chloride solution of THF (tetrahydrofuran), stirring for 5 hours at room temperature, filtering, leaching a filter cake with diethyl ether, and drying in vacuum to obtain a modifier;
s5, mixing 5g of carboxylated carbon nanotubes (prepared in example 1) with 200mL of anhydrous dichloromethane, performing ultrasonic dispersion for 30min, adding 14g of HATU and 11mL of DIPEA, continuing ultrasonic treatment for 20min, adding 44.5g of modifier, stirring and reacting for 12h, and finally centrifuging, washing with ethanol and deionized water for 4 times in sequence, and drying to obtain the modified carbon nanotubes.
Example 4
Preparing a modified carbon nano tube:
s1, leading in N 2 Removing air in a four-neck flask, dissolving 20.8g of hexachlorocyclotriphosphazene in 200mL of tetrahydrofuran, placing the flask in an ice bath, slowly and uniformly dropwise adding 80mL of a tetrahydrofuran mixed solution containing 32g of 9-decen-1-ol sodium (prepared in example 2) and 20.2g of triethylamine under stirring, reacting for 4 hours in the ice bath after the completion of dropwise adding, removing generated salt (NaCl) by suction filtration after the completion of the reaction, collecting filtrate, removing the solvent and excessive triethylamine by reduced pressure distillation, washing with chloroform and distilled water for a plurality of times respectively, taking an organic layer, performing rotary evaporation and vacuum drying to obtain a phosphazene derivative;
s2, in a three-necked bottle, dissolving 27.4g of p-aminophenyl ethylamine in 160mL of methanol, adding 22.2g of triethylamine as a catalyst, dissolving 38.8g of tert-butoxycarbonyl anhydride in 100mL of diethyl ether, dropwise dripping the solution into the three-necked bottle through a constant pressure funnel, stirring and reacting for 10 hours at a constant temperature of 5 ℃, adding water and diethyl ether, extracting, taking diethyl ether phase, removing diethyl ether by rotary evaporation, and finally carrying out recrystallization and purification by using a mixed solution of dichloromethane and diethyl ether (the volume ratio of dichloromethane to diethyl ether is 1:1) to obtain a grafting agent;
s3, adding 300mL of dichloromethane into a four-necked flask, introducing nitrogen, continuously adding 70.6g of phosphazene derivative and 30.6g of triethylamine after continuously heating for 10min (removing air in the flask), stirring and uniformly mixing, dropwise adding 120mL of dichloromethane solution dissolved with 70.8g of grafting agent by adopting a constant pressure funnel, reacting for 4h at normal temperature after the dropwise addition is completed, removing generated triethylamine hydrochloride by suction filtration after the reaction is completed, and obtaining a primary product after reduced pressure distillation of filtrate;
s4, mixing 120g of the initial product with 960mL of saturated solution of THF (tetrahydrofuran) in hydrogen chloride, stirring for 5 hours at room temperature, filtering, leaching a filter cake with diethyl ether, and drying in vacuum to obtain a modifier;
s5, mixing 10g of carboxylated carbon nanotubes (prepared in example 1) with 400mL of anhydrous dichloromethane, performing ultrasonic dispersion for 30min, adding 28g of HATU and 22mL of DIPEA, continuing ultrasonic treatment for 20min, adding 89g of modifier, stirring and reacting for 12h, and finally centrifuging, washing with ethanol and deionized water for 4 times sequentially, and drying to obtain the modified carbon nanotubes.
Example 5
Preparing a rubber sealing material:
firstly, adding 700g of nitrile rubber and 250g of polyvinyl chloride resin into an internal mixer for plasticating for 3min, then adding 30g of antioxidant RD for mixing for 2min, then adding 150g of modified carbon nano tube prepared in example 3 for mixing for 3min, and standing for 50min to obtain a mixed material;
secondly, adding the mixed materials into an open mill, carrying out heat refining for 2min at the temperature of 40 ℃, adding 20g of sulfur, adjusting the roll gap to 1mm after the powder is eaten, and releasing the roll gap to obtain a sizing material after a triangular bag is opened for 5 times;
and thirdly, the sizing material is subjected to open mill milling through an open mill, and then the rubber sealing material is obtained through preforming and vulcanization molding processes.
Example 6
Preparing a rubber sealing material:
firstly, adding 700g of nitrile rubber and 300g of polyvinyl chloride resin into an internal mixer for plasticating for 3.5min, then adding 35g of anti-aging agent 4010NA for mixing for 3min, then adding 175g of modified carbon nano tube prepared in example 4 for mixing for 4min, and standing for 55min to obtain a mixed material;
secondly, adding the mixed materials into an open mill, carrying out heat refining for 3min at 50 ℃, adding 25g of sulfur, adjusting the roll gap to 2mm after the powder is eaten, and releasing the roll gap to obtain a sizing material after a triangular bag is opened for 6 times;
and thirdly, the sizing material is subjected to open mill milling through an open mill, and then the rubber sealing material is obtained through preforming and vulcanization molding processes.
Example 7
Preparing a rubber sealing material:
firstly, adding 700g of nitrile rubber and 350g of polyvinyl chloride resin into an internal mixer for plasticating for 4min, then adding 40g of anti-aging agent 445 for mixing for 4min, then adding 200g of modified carbon nano tube prepared in example 3 for mixing for 5min, and standing for 60min to obtain a mixing material;
secondly, adding the mixed materials into an open mill, carrying out heat refining for 4min at the temperature of 60 ℃, adding 30g of sulfur, adjusting the roll gap to 2mm after the powder is eaten, and releasing the roll gap to obtain the sizing material after 6 times of triangular wrapping;
and thirdly, the sizing material is subjected to open mill milling through an open mill, and then the rubber sealing material is obtained through preforming and vulcanization molding processes.
Comparative example
The modified carbon nanotube material in example 5 was replaced with a normal single-walled carbon nanotube, and the remaining materials and the preparation process were kept unchanged, to obtain a rubber sealing material.
The rubber sealing materials obtained in examples 5 to 7 and comparative example were cut into test samples, and the following performance tests were conducted:
tensile properties and hardness were measured according to GB/T528-2009 and GB/T531.1-2008, respectively;
compression set is measured by a test method in GB/T7759, wherein the measurement condition is that the temperature is 70 ℃, the compression ratio is 25% after 24 hours;
the wear resistance is characterized by an acle wear value;
testing the flame retardant property of the material according to the UL-94 standard;
the results are shown in the following table:
as can be seen from the data in the table, the rubber sealing material obtained by the invention has higher mechanical property, elasticity and wear resistance, and simultaneously has excellent flame retardant property; according to the data of the comparative example, after the single-walled carbon nanotubes are modified, the single-walled carbon nanotubes can be uniformly distributed in the material to exert the reinforcing effect, so that the mechanical property is improved, the formation of a crosslinked network structure is promoted, the wear resistance is improved, and the material is endowed with high-efficiency flame retardant property.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (7)
1. The rubber sealing material comprises the following raw materials in parts by weight: 70 parts of nitrile rubber, 25-35 parts of polyvinyl chloride resin, 3-4 parts of anti-aging agent, 15-20 parts of modified carbon nano tube and 2-3 parts of sulfur, and is characterized in that the modified carbon nano tube is prepared by the following steps:
s1, reacting 9-decen-1-ol with sodium hydroxide to obtain 9-decen-1-sodium alkoxide for later use; introducing N 2 Removing air in the four-mouth flask, dissolving hexachlorocyclotriphosphazene in tetrahydrofuran, placing the flask in ice bath, slowly and uniformly dropwise adding a tetrahydrofuran mixed solution in which 9-decen-1-sodium alkoxide and triethylamine are dissolved under stirring, reacting for 4 hours in the ice bath after the dropwise adding is completed, and purifying to obtain a phosphazene derivative after the reaction is finished;
s2, dissolving p-aminophenyl ethylamine in methanol, adding triethylamine as a catalyst, dissolving tert-butoxycarbonyl anhydride in diethyl ether, dropwise dripping the mixture into the three-necked flask through a constant pressure funnel, stirring the mixture for reaction for 10 hours at the constant temperature of 3-5 ℃, adding water and diethyl ether, extracting, taking diethyl ether phase, removing diethyl ether by rotary evaporation, and finally carrying out recrystallization purification by using a mixed solution of dichloromethane and diethyl ether to obtain a grafting agent;
s3, adding dichloromethane into a four-neck flask, introducing nitrogen, continuously adding phosphazene derivatives and triethylamine after 10min, stirring and mixing uniformly, dropwise adding a dichloromethane solution dissolved with a grafting agent by adopting a constant pressure funnel, reacting for 4h under normal temperature after the dropwise adding is finished, removing generated triethylamine hydrochloride by suction filtration after the reaction is finished, and obtaining a primary product after reduced pressure distillation of filtrate;
s4, mixing the initial product with saturated solution of THF (tetrahydrofuran) in a solid-to-liquid ratio of 1g to 8mL, stirring for 5h at room temperature, filtering, leaching a filter cake with diethyl ether, and drying in vacuum to obtain a modifier;
s5, mixing the carboxylated carbon nanotubes with anhydrous dichloromethane, performing ultrasonic dispersion for 30min, adding HATU and DIPEA, continuing ultrasonic treatment for 20min, adding a modifier, stirring for reaction for 12h, and finally centrifuging, washing and drying to obtain the modified carbon nanotubes.
2. The rubber sealing material according to claim 1, wherein the purification process in step S1 is: removing generated salt by suction filtration, collecting filtrate, removing solvent and excessive triethylamine by reduced pressure distillation, washing with chloroform and distilled water for several times respectively, taking an organic layer, rotary steaming, and vacuum drying to complete the purification process.
3. The rubber sealing material according to claim 1, wherein the ratio of hexachlorocyclotriphosphazene, sodium 9-decen-1-ol and triethylamine in step S1 is 0.03mol:0.09mol:0.1mol.
4. The rubber sealing material according to claim 1, wherein the amount ratio of p-aminophenylamine, triethylamine and t-butoxycarbonyl anhydride in step S2 is 0.1mol:0.11mol:0.1mol.
5. The rubber sealing material according to claim 1, wherein the ratio of the phosphazene derivative, triethylamine and grafting agent used in step S3 is 35.3g to 15.3g to 35.4g.
6. The rubber sealing material according to claim 1, wherein the ratio of the amounts of carboxylated carbon nanotubes, HATU, DIPEA, and modifier in step S5 is 1 g/2.8 g/2.2 ml/8.9 g.
7. The method for producing a rubber sealing material according to claim 1, comprising the steps of:
firstly, adding nitrile rubber and polyvinyl chloride resin into an internal mixer for plasticating for 3-4min, then adding an anti-aging agent for mixing for 2-4min, then adding a modified carbon nano tube for mixing for 3-5min, and standing for 50-60min to obtain a mixed material;
secondly, adding the mixed materials into an open mill, carrying out heat refining for 2-4min at the temperature of 40-60 ℃, adding sulfur, adjusting the roll gap to 1-2mm after the powder is eaten, and releasing the roll gap to obtain the sizing material after triangular wrapping for 5-6 times;
and thirdly, the sizing material is subjected to open mill milling through an open mill, and then the rubber sealing material is obtained through preforming and vulcanization molding processes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310413129.4A CN116478461A (en) | 2023-04-18 | 2023-04-18 | Rubber sealing material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310413129.4A CN116478461A (en) | 2023-04-18 | 2023-04-18 | Rubber sealing material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116478461A true CN116478461A (en) | 2023-07-25 |
Family
ID=87214986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310413129.4A Pending CN116478461A (en) | 2023-04-18 | 2023-04-18 | Rubber sealing material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116478461A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117341006A (en) * | 2023-12-04 | 2024-01-05 | 江苏零界科技集团有限公司 | Wood fire retardant and preparation method thereof |
-
2023
- 2023-04-18 CN CN202310413129.4A patent/CN116478461A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117341006A (en) * | 2023-12-04 | 2024-01-05 | 江苏零界科技集团有限公司 | Wood fire retardant and preparation method thereof |
| CN117341006B (en) * | 2023-12-04 | 2024-02-20 | 江苏零界科技集团有限公司 | Wood fire retardant and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102071539B (en) | Double-layer water-adsorption and moisture-transfer non-woven fabric and preparation method thereof | |
| CN116478461A (en) | Rubber sealing material and preparation method thereof | |
| CN105504352B (en) | A kind of phosphorus nitrogen system dendritic macromole functionalization graphene fire retardant and its application | |
| CN109403014B (en) | High-strength wear-resistant modified polypropylene material | |
| CN116285318B (en) | Light heat conduction engineering plastic and preparation method thereof | |
| CN105820438A (en) | Thermoplastic vulcanized rubber material for automobile steering dedusting cover and preparation method of thermoplastic vulcanized rubber material | |
| CN105418971B (en) | The preparation method of phosphorus nitrogen high load Graphene fire retardant | |
| CN114891451B (en) | Compound thermoplastic polymer TPO waterproofing membrane | |
| CN116462923B (en) | Flame-retardant modified PVC film | |
| CN110452525A (en) | A kind of modified antistatic TPU membrane of graphene | |
| CN110128634B (en) | Preparation method of graphene modified polyester chip | |
| CN117050523B (en) | Wear-resistant polyphenylene sulfide material and preparation method thereof | |
| CN109880180A (en) | Nano-cellulose/cellulose composite, enhancing polylactic acid 3D printing material and preparation method thereof | |
| CN109206677A (en) | A kind of dissaving polymer modified carbon black surface and its application in rubber processing | |
| CN106673043B (en) | Polyethersulfone resin filling anti-oxidant nano-calcium carbonate of toughness reinforcing uvioresistant and its production and use | |
| CN115073861B (en) | Stretch-resistant polyvinyl chloride communication tube and preparation method thereof | |
| CN111303616A (en) | Graphene oxide grafted phosphorus-containing maleic acid flame-retardant auxiliary agent and preparation method and application thereof | |
| CN114437459A (en) | Composite material for double-wall corrugated pipe | |
| CN105237822A (en) | Formula of shoe sole material synthesized by natural rubber and SBS and preparation method for shoe sole material | |
| CN113817299B (en) | PLA-based blended composite material with ion and chemical double-crosslinking structure and preparation method thereof | |
| CN109679173A (en) | A kind of solution polymerized butadiene styrene rubber composite material and preparation method | |
| CN112745780B (en) | Super strong cohesiveness self-adhesion waterproofing membrane | |
| CN117304661B (en) | Polyester composition, preparation method and application thereof | |
| CN110204797A (en) | A kind of rubber spring sizing material and preparation method thereof that high temperature resistant is ageing-resistant | |
| CN116574369B (en) | Modified polyamide PA flame-retardant material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |