CN112159504A - Preparation method of defoaming agent for silicone rubber - Google Patents
Preparation method of defoaming agent for silicone rubber Download PDFInfo
- Publication number
- CN112159504A CN112159504A CN202011108457.6A CN202011108457A CN112159504A CN 112159504 A CN112159504 A CN 112159504A CN 202011108457 A CN202011108457 A CN 202011108457A CN 112159504 A CN112159504 A CN 112159504A
- Authority
- CN
- China
- Prior art keywords
- solution
- silicone oil
- graft
- stirring
- silicone rubber
- 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
- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 70
- 239000004945 silicone rubber Substances 0.000 title claims abstract description 47
- 239000002518 antifoaming agent Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920002545 silicone oil Polymers 0.000 claims abstract description 84
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 84
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 56
- 238000003756 stirring Methods 0.000 claims description 50
- 239000003054 catalyst Substances 0.000 claims description 43
- 238000002156 mixing Methods 0.000 claims description 42
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 28
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 21
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 21
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 15
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical group [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 14
- 239000007806 chemical reaction intermediate Substances 0.000 claims description 14
- 239000011261 inert gas Substances 0.000 claims description 14
- 239000012312 sodium hydride Substances 0.000 claims description 14
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 10
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052754 neon Inorganic materials 0.000 claims description 4
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011787 zinc oxide Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004073 vulcanization Methods 0.000 description 7
- 239000006260 foam Substances 0.000 description 6
- 230000002401 inhibitory effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000013530 defoamer Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- -1 methyl vinyl phenyl Chemical group 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 229920005560 fluorosilicone rubber Polymers 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- HPOKESDSMZRZLC-UHFFFAOYSA-N propan-2-one;hydrochloride Chemical compound Cl.CC(C)=O HPOKESDSMZRZLC-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a preparation method of a defoaming agent for silicon rubber; relates to the technical field of zinc oxide, comprising: (1) preparing a graft; (2) pretreating silicone oil; (3) grafting silicone oil; after the defoaming agent is adopted, the mechanical property of the silicone rubber can be obviously improved, and the application range of the silicone rubber can be further improved.
Description
Technical Field
The invention belongs to the technical field of zinc oxide, and particularly relates to a preparation method of a defoaming agent for silicone rubber.
Background
Silicone rubber refers to rubber having a backbone composed of alternating silicon and oxygen atoms, with the silicon atoms typically having two organic groups attached to them. Conventional silicone rubbers consist predominantly of siloxane segments containing methyl groups and small amounts of vinyl groups. The introduction of phenyl can improve the high and low temperature resistance of the silicone rubber, and the introduction of trifluoropropyl and cyano can improve the temperature resistance and oil resistance of the silicone rubber. The silicon rubber has good low-temperature resistance and can still work at the temperature of minus 55 ℃. After the introduction of phenyl, a temperature of-73 ℃ can be reached. The silicon rubber has outstanding heat resistance, can work for a long time at 180 ℃, can still have elasticity for a plurality of weeks or more even at the temperature slightly higher than 200 ℃, and can instantaneously resist the high temperature of more than 300 ℃. Silicone rubber has good gas permeability, and oxygen transmission rate is the highest among synthetic polymers. In addition, the silicon rubber also has the outstanding characteristics of physiological inertia and no coagulation, so the silicon rubber is widely applied in the medical field.
The silicone rubber is classified into a heat vulcanization type (high temperature vulcanized silicone HTV) and a room temperature vulcanization type (RTV), wherein the room temperature vulcanization type is also classified into a polycondensation reaction type and an addition reaction type. The high-temperature silicon rubber is mainly used for manufacturing various silicon rubber products, and the room-temperature silicon rubber is mainly used as an adhesive, a potting material or a mold. The heat vulcanization type is the most used, and the heat vulcanization type is divided into methyl silicone rubber (MQ), methyl vinyl silicone rubber (VMQ, the most used amount and product brand), methyl vinyl phenyl silicone rubber PVMQ (low temperature resistant and radiation resistant), other silicone rubber, fluorosilicone rubber and the like.
However, in the vulcanization process of the silicone rubber, the vulcanized rubber tends to generate bubbles, and more bubbles will affect the physical properties of the silicone rubber and greatly reduce the physical properties of the silicone rubber, so that the bubble suppression treatment needs to be performed in the re-vulcanization process of the silicone rubber.
Disclosure of Invention
The invention aims to provide a preparation method of a defoaming agent for silicon rubber, which aims to overcome the defects in the prior art.
The technical scheme adopted by the invention is as follows:
a preparation method of a defoaming agent for silicone rubber comprises the following steps:
(1) preparing a graft:
sequentially adding epoxy chloropropane and allyl polyoxyethylene ether into a reaction kettle, heating to 90-95 ℃, keeping the temperature and stirring for 15-20min, then adding an active catalyst, continuing to keep the temperature and react for 2-3 h, then carrying out reduced pressure to remove unreacted epoxy chloropropane, naturally cooling to 35-40 ℃, then adding a sodium hydroxide solution into the reaction kettle, stirring and reacting for 40min, standing for 30min, then carrying out reduced pressure suction filtration and rotary evaporation to remove moisture, and thus obtaining the required graft;
(2) pretreatment of silicone oil:
uniformly mixing silicone oil and isopropanol according to the mass ratio of 10:1-1.5, heating to 60 ℃, and stirring for 40min under the condition of heat preservation to obtain pretreated silicone oil;
(3) grafting silicone oil:
sequentially adding the pretreated silicone oil and toluene into a reaction kettle, uniformly stirring, adding a catalyst solution, introducing inert gas, discharging air in the reaction kettle, heating to 80-90 ℃, preserving heat and stirring for 10min to obtain a reaction intermediate solution;
dissolving the graft in toluene to obtain a graft solution;
dissolving diethylaminoethyl methacrylate in toluene to obtain a diethylaminoethyl methacrylate solution;
and (3) dropwise adding the graft solution into the reaction intermediate solution, after dropwise adding, adjusting the temperature to 100 ℃, keeping the temperature and stirring for reaction for 30-40min, then dropwise adding the diethylaminoethyl methacrylate solution, continuously heating to 125 ℃, keeping the temperature and reacting for 10-14 h, standing for 1 h, and then carrying out reduced pressure drying to remove the solvent to obtain the catalyst.
The mixing mass ratio of the epichlorohydrin to the allyl polyoxyethylene ether is 1.5-1.8: 1.
The active catalyst is sodium hydride;
the mass ratio of the sodium hydride to the allyl polyoxyethylene ether is 1: 120-150.
The silicone oil is dimethyl silicone oil.
The mixing ratio of the pretreated silicone oil to the toluene is 80-110 g: 400 mL.
The preparation method of the catalyst solution comprises the following steps:
dripping chloroplatinic acid into isopropanol, and uniformly stirring to obtain a chloroplatinic acid isopropanol solution;
the mixing molar ratio of the chloroplatinic acid to the isopropanol is 1: 2;
the catalyst solution and the pretreated silicone oil are mixed according to the mass ratio: 1:50-60.
The inert gas is nitrogen or neon.
The mass fraction of the graft solution is 10-12%;
the mass fraction of the diethylaminoethyl methacrylate solution is 4-5%;
the mixing mass ratio of the graft solution to the pretreated silicone oil is 1: 2-3;
the mixing mass ratio of the diethylaminoethyl methacrylate solution to the pretreated silicone oil is 1: 1.8-2.
When the silicon rubber is used as the defoaming agent, the optimal weight ratio of the silicon rubber to the raw rubber is 0.02: 90.
Has the advantages that:
the high epoxy value content of the grafted species prepared by the method indicates that the end capping rate of the grafted species in the preparation process is high, so that a better foundation can be laid for the subsequent grafting reaction with the pretreated silicone oil.
After the defoaming agent is adopted, the mechanical property of the silicon rubber can be obviously improved, the application range of the silicon rubber can be further improved, the defoaming agent is not adopted, the mechanical property of the silicon rubber is obviously and greatly reduced, and under the condition that the defoaming agent is not added, more bubbles are generated in the silicon rubber, so that the mechanical property of the silicon rubber is directly reduced, the silicon rubber defoaming agent prepared by the method can better improve the mechanical property of the silicon rubber, because the silicon oil is subjected to a series of grafting modification treatment by the method, the surface active groups of the silicon oil are increased, the defoaming and foam inhibiting properties of the silicon rubber are greatly improved, in addition, the continuous foam inhibiting time is long, the foam inhibiting effect is good, the generation of bubbles in the silicon rubber is greatly inhibited, the mechanical property of the silicon rubber is improved, but the mechanical property of the silicon rubber can be also influenced by the amount of other addition of the defoaming agent, excessive addition of the defoamer can adversely reduce the mechanical properties of the silicone rubber.
Detailed Description
A preparation method of a defoaming agent for silicone rubber comprises the following steps:
(1) preparing a graft:
sequentially adding epoxy chloropropane and allyl polyoxyethylene ether into a reaction kettle, heating to 90-95 ℃, keeping the temperature and stirring for 15-20min, then adding an active catalyst, continuing to keep the temperature and react for 2-3 h, then carrying out reduced pressure to remove unreacted epoxy chloropropane, naturally cooling to 35-40 ℃, then adding a sodium hydroxide solution into the reaction kettle, stirring and reacting for 40min, standing for 30min, then carrying out reduced pressure suction filtration and rotary evaporation to remove moisture, and thus obtaining the required graft;
(2) pretreatment of silicone oil:
uniformly mixing silicone oil and isopropanol according to the mass ratio of 10:1-1.5, heating to 60 ℃, and stirring for 40min under the condition of heat preservation to obtain pretreated silicone oil;
(3) grafting silicone oil:
sequentially adding the pretreated silicone oil and toluene into a reaction kettle, uniformly stirring, adding a catalyst solution, introducing inert gas, discharging air in the reaction kettle, heating to 80-90 ℃, preserving heat and stirring for 10min to obtain a reaction intermediate solution;
dissolving the graft in toluene to obtain a graft solution;
dissolving diethylaminoethyl methacrylate in toluene to obtain a diethylaminoethyl methacrylate solution;
and (3) dropwise adding the graft solution into the reaction intermediate solution, after dropwise adding, adjusting the temperature to 100 ℃, keeping the temperature and stirring for reaction for 30-40min, then dropwise adding the diethylaminoethyl methacrylate solution, continuously heating to 125 ℃, keeping the temperature and reacting for 10-14 h, standing for 1 h, and then carrying out reduced pressure drying to remove the solvent to obtain the catalyst.
Epoxy chloropropane
Molar refractive index: 20.37, respectively;
molar volume (cm 3/mol): 76.7;
isospecific volume (90.2K): 187.4;
surface tension (dyne/cm): 35.6;
dipole moment (. times.10-30 Cm): 6.0;
polarizability: 8.07;
refractive index: 1.43805 (20 ℃); 1.4358 (25 ℃);
relative steam density (air = 1): 3.29;
the mixing mass ratio of the epichlorohydrin to the allyl polyoxyethylene ether is 1.5-1.8: 1.
The active catalyst is sodium hydride;
the mass ratio of the sodium hydride to the allyl polyoxyethylene ether is 1: 120-150.
The silicone oil is dimethyl silicone oil.
Dimethyl silicone oil
Viscosity (25 ℃ cp) 1000;
a dielectric constant of 2.76;
flash point 300 deg.C;
relative density 0.966;
a refractive index of 21.2;
the mixing ratio of the pretreated silicone oil to the toluene is 80-110 g: 400 mL.
The preparation method of the catalyst solution comprises the following steps:
dripping chloroplatinic acid into isopropanol, and uniformly stirring to obtain a chloroplatinic acid isopropanol solution;
the mixing molar ratio of the chloroplatinic acid to the isopropanol is 1: 2;
the catalyst solution and the pretreated silicone oil are mixed according to the mass ratio: 1:50-60.
The inert gas is nitrogen or neon.
The mass fraction of the graft solution is 10-12%;
the mass fraction of the diethylaminoethyl methacrylate solution is 4-5%;
the mixing mass ratio of the graft solution to the pretreated silicone oil is 1: 2-3;
the mixing mass ratio of the diethylaminoethyl methacrylate solution to the pretreated silicone oil is 1: 1.8-2.
The following will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a defoaming agent for silicone rubber comprises the following steps:
(1) preparing a graft:
sequentially adding epoxy chloropropane and allyl polyoxyethylene ether into a reaction kettle, heating to 90 ℃, preserving heat and stirring for 15min, then adding an active catalyst, continuing to react for 2 hours under the condition of preserving heat, then removing unreacted epoxy chloropropane under reduced pressure, naturally cooling to 35 ℃, then adding a sodium hydroxide solution into the reaction kettle, stirring and reacting for 40min, standing for 30min, then carrying out reduced pressure suction filtration and rotary evaporation to remove moisture, and thus obtaining the required graft; the mixing mass ratio of the epichlorohydrin to the allyl polyoxyethylene ether is 1.5: 1. The active catalyst is sodium hydride; the mass ratio of the sodium hydride to the allyl polyoxyethylene ether is 1: 120.
(2) Pretreatment of silicone oil:
uniformly mixing silicone oil and isopropanol according to a mass ratio of 10:1, heating to 60 ℃, and stirring for 40min under the condition of heat preservation to obtain pretreated silicone oil; the silicone oil is dimethyl silicone oil.
(3) Grafting silicone oil:
sequentially adding the pretreated silicone oil and toluene into a reaction kettle, uniformly stirring, adding a catalyst solution, introducing inert gas, discharging air in the reaction kettle, heating to 80 ℃, preserving heat and stirring for 10min to obtain a reaction intermediate solution; dissolving the graft in toluene to obtain a graft solution; dissolving diethylaminoethyl methacrylate in toluene to obtain a diethylaminoethyl methacrylate solution; and (3) dropwise adding the graft solution into the reaction intermediate solution, adjusting the temperature to 100 ℃ after dropwise adding, keeping the temperature, stirring and reacting for 30min, then dropwise adding the diethylaminoethyl methacrylate solution, continuously heating to 120 ℃, keeping the temperature, reacting for 10 h, standing for 1 h, and then drying under reduced pressure to remove the solvent to obtain the catalyst. The mixing ratio of the pretreated silicone oil to the toluene is 80 g: 400 mL. The preparation method of the catalyst solution comprises the following steps: dripping chloroplatinic acid into isopropanol, and uniformly stirring to obtain a chloroplatinic acid isopropanol solution; the mixing molar ratio of the chloroplatinic acid to the isopropanol is 1: 2; the catalyst solution and the pretreated silicone oil are mixed according to the mass ratio: 1:50. The inert gas is nitrogen. The mass fraction of the graft solution is 10 percent; the mass fraction of the diethylaminoethyl methacrylate solution is 4%; the mixing mass ratio of the graft solution to the pretreated silicone oil is 1: 2; the mixing mass ratio of the diethylaminoethyl methacrylate solution to the pretreated silicone oil is 1: 1.8.
Example 2
A preparation method of a defoaming agent for silicone rubber comprises the following steps:
(1) preparing a graft:
sequentially adding epoxy chloropropane and allyl polyoxyethylene ether into a reaction kettle, heating to 95 ℃, preserving heat and stirring for 15-20min, then adding an active catalyst, continuing to react for 3 h under heat preservation, then removing unreacted epoxy chloropropane under reduced pressure, naturally cooling to 40 ℃, then adding a sodium hydroxide solution into the reaction kettle, stirring and reacting for 40min, standing for 30min, then carrying out reduced pressure suction filtration and rotary evaporation to remove moisture, and thus obtaining the required graft; the mixing mass ratio of the epichlorohydrin to the allyl polyoxyethylene ether is 1.8: 1. The active catalyst is sodium hydride; the mass ratio of the sodium hydride to the allyl polyoxyethylene ether is 1: 150.
(2) Pretreatment of silicone oil:
uniformly mixing silicone oil and isopropanol according to the mass ratio of 10:1.5, heating to 60 ℃, and stirring for 40min under the condition of heat preservation to obtain pretreated silicone oil; the silicone oil is dimethyl silicone oil.
(3) Grafting silicone oil:
sequentially adding the pretreated silicone oil and toluene into a reaction kettle, uniformly stirring, adding a catalyst solution, introducing inert gas, discharging air in the reaction kettle, heating to 90 ℃, preserving heat and stirring for 10min to obtain a reaction intermediate solution; dissolving the graft in toluene to obtain a graft solution; dissolving diethylaminoethyl methacrylate in toluene to obtain a diethylaminoethyl methacrylate solution; and (3) dropwise adding the graft solution into the reaction intermediate solution, adjusting the temperature to 100 ℃ after dropwise adding, keeping the temperature, stirring and reacting for 40min, then dropwise adding the diethylaminoethyl methacrylate solution, continuously heating to 125 ℃, keeping the temperature, reacting for 14 h, standing for 1 h, and then drying under reduced pressure to remove the solvent to obtain the catalyst. The mixing ratio of the pretreated silicone oil to the toluene is 110 g: 400 mL. The preparation method of the catalyst solution comprises the following steps: dripping chloroplatinic acid into isopropanol, and uniformly stirring to obtain a chloroplatinic acid isopropanol solution; the mixing molar ratio of the chloroplatinic acid to the isopropanol is 1: 2; the catalyst solution and the pretreated silicone oil are mixed according to the mass ratio: 1:60. The inert gas is nitrogen. The mass fraction of the graft solution is 12 percent; the mass fraction of the diethylaminoethyl methacrylate solution is 5%; the mixing mass ratio of the graft solution to the pretreated silicone oil is 1: 3; the mixing mass ratio of the diethylaminoethyl methacrylate solution to the pretreated silicone oil is 1:2.
Example 3
A preparation method of a defoaming agent for silicone rubber comprises the following steps:
(1) preparing a graft:
sequentially adding epoxy chloropropane and allyl polyoxyethylene ether into a reaction kettle, heating to 92 ℃, preserving heat and stirring for 16min, then adding an active catalyst, continuing to react for 2.5 h under heat preservation, then removing unreacted epoxy chloropropane under reduced pressure, naturally cooling to 38 ℃, then adding a sodium hydroxide solution into the reaction kettle, stirring and reacting for 40min, standing for 30min, then carrying out reduced pressure suction filtration and rotary evaporation to remove moisture, and thus obtaining the required graft; the mixing mass ratio of the epichlorohydrin to the allyl polyoxyethylene ether is 1.6: 1. The active catalyst is sodium hydride; the mass ratio of the sodium hydride to the allyl polyoxyethylene ether is 1: 130.
(2) Pretreatment of silicone oil:
uniformly mixing silicone oil and isopropanol according to the mass ratio of 10:1.2, heating to 60 ℃, and stirring for 40min under the condition of heat preservation to obtain pretreated silicone oil; the silicone oil is dimethyl silicone oil.
(3) Grafting silicone oil:
sequentially adding the pretreated silicone oil and toluene into a reaction kettle, uniformly stirring, adding a catalyst solution, introducing inert gas, discharging air in the reaction kettle, heating to 82 ℃, preserving heat and stirring for 10min to obtain a reaction intermediate solution; dissolving the graft in toluene to obtain a graft solution; dissolving diethylaminoethyl methacrylate in toluene to obtain a diethylaminoethyl methacrylate solution; and (3) dropwise adding the graft solution into the reaction intermediate solution, adjusting the temperature to 100 ℃ after dropwise adding, keeping the temperature and stirring for reaction for 34min, then dropwise adding the diethylaminoethyl methacrylate solution, continuously heating to 121 ℃, keeping the temperature and reacting for 12 h, standing for 1 h, and then drying under reduced pressure to remove the solvent to obtain the catalyst. The mixing ratio of the pretreated silicone oil to the toluene is 90 g: 400 mL. The preparation method of the catalyst solution comprises the following steps: dripping chloroplatinic acid into isopropanol, and uniformly stirring to obtain a chloroplatinic acid isopropanol solution; the mixing molar ratio of the chloroplatinic acid to the isopropanol is 1: 2; the catalyst solution and the pretreated silicone oil are mixed according to the mass ratio: 1:53. The inert gas is neon. The mass fraction of the graft solution is 11%; the mass fraction of the diethylaminoethyl methacrylate solution is 4.5%; the mixing mass ratio of the graft solution to the pretreated silicone oil is 1: 2.3; the mixing mass ratio of the diethylaminoethyl methacrylate solution to the pretreated silicone oil is 1: 1.9.
Example 4
A preparation method of a defoaming agent for silicone rubber comprises the following steps:
(1) preparing a graft:
sequentially adding epoxy chloropropane and allyl polyoxyethylene ether into a reaction kettle, heating to 94 ℃, preserving heat and stirring for 20min, then adding an active catalyst, continuing to react for 3 hours under heat preservation, then removing unreacted epoxy chloropropane under reduced pressure, naturally cooling to 35 ℃, then adding a sodium hydroxide solution into the reaction kettle, stirring and reacting for 40min, standing for 30min, then carrying out reduced pressure suction filtration and rotary evaporation to remove moisture, and thus obtaining the required graft; the mixing mass ratio of the epichlorohydrin to the allyl polyoxyethylene ether is 1.6: 1. The active catalyst is sodium hydride; the mass ratio of the sodium hydride to the allyl polyoxyethylene ether is 1: 142.
(2) Pretreatment of silicone oil:
uniformly mixing silicone oil and isopropanol according to the mass ratio of 10:1.2, heating to 60 ℃, and stirring for 40min under the condition of heat preservation to obtain pretreated silicone oil; the silicone oil is dimethyl silicone oil.
(3) Grafting silicone oil:
sequentially adding the pretreated silicone oil and toluene into a reaction kettle, uniformly stirring, adding a catalyst solution, introducing inert gas, discharging air in the reaction kettle, heating to 85 ℃, preserving heat and stirring for 10min to obtain a reaction intermediate solution; dissolving the graft in toluene to obtain a graft solution; dissolving diethylaminoethyl methacrylate in toluene to obtain a diethylaminoethyl methacrylate solution; and (3) dropwise adding the graft solution into the reaction intermediate solution, adjusting the temperature to 100 ℃ after dropwise adding, keeping the temperature, stirring and reacting for 36min, then dropwise adding the diethylaminoethyl methacrylate solution, continuously heating to 122 ℃, keeping the temperature, reacting for 12 h, standing for 1 h, and then drying under reduced pressure to remove the solvent to obtain the catalyst. The mixing ratio of the pretreated silicone oil to the toluene is 100 g: 400 mL. The preparation method of the catalyst solution comprises the following steps: dripping chloroplatinic acid into isopropanol, and uniformly stirring to obtain a chloroplatinic acid isopropanol solution; the mixing molar ratio of the chloroplatinic acid to the isopropanol is 1: 2; the catalyst solution and the pretreated silicone oil are mixed according to the mass ratio: 1:55. The inert gas is nitrogen. The mass fraction of the graft solution is 11%; the mass fraction of the diethylaminoethyl methacrylate solution is 5%; the mixing mass ratio of the graft solution to the pretreated silicone oil is 1: 2; the mixing mass ratio of the diethylaminoethyl methacrylate solution to the pretreated silicone oil is 1: 1.9.
Test of
The epoxy value content of the graft is measured by referring to GB/T1677-1981 determination of epoxy value of plasticizer (hydrochloric acid-acetone method), and the end capping rate of the product is characterized;
TABLE 1
| Epoxy value content% | |
| Example 1 | 86.41 |
| Example 2 | 85.34 |
| Example 3 | 88.75 |
| Example 4 | 90.53 |
As can be seen from Table 1, the grafted species prepared by the method of the present invention has a higher epoxy value content, which indicates that the graft in the method of the present invention has a higher end capping rate during the preparation process, thereby better laying a better foundation for the subsequent grafting reaction with the pretreated silicone oil.
Kinematic viscosity test:
measuring the kinematic viscosity of the sample under the constant temperature condition by adopting an LVDV-III Fourier viscometer, detecting each sample for 5 times, and taking an average value;
TABLE 2
| Kinematic viscosity mm/s | |
| Example 1 | 34.73 |
| Example 2 | 34.54 |
| Example 3 | 35.05 |
| Example 4 | 36.12 |
As can be seen from Table 2, the defoaming agent for silicone rubber prepared by the method of the present invention has a better kinematic viscosity.
Testing refractive index;
determining the refractive index of the sample by adopting a WAY-IS Abbe refractometer;
TABLE 3
| Refractive index nD25 | |
| Example 1 | 1.4187 |
| Example 2 | 1.4165 |
| Example 3 | 1.4204 |
| Example 4 | 1.4283 |
As can be seen from Table 3, the defoaming agent for silica gel prepared by the method of the invention has higher refractive index.
90 parts of raw rubber, 8 parts of precipitated silica, 1.2 parts of silane coupling agent and 1.5 parts of deionized water are put into a kneader, and the mixture is kneaded into a mass and then heated to 150 ℃ for kneading for 1 hour. Thinly passing the mixture on a two-roller open mill for 5 times, putting the mixture into dimethylbenzene for swelling to prepare a dispersion liquid with the mass fraction of 15%, adding 0.8 part of methyl vinyl silicone rubber, 0.1 part of isopropanol-Pt catalyst and 0.02 part of defoaming agents of examples and comparative examples into the dispersion liquid, uniformly stirring the mixture, injecting the mixture into a polytetrafluoroethylene plate groove, putting the polytetrafluoroethylene plate groove into an oven, and curing and molding the mixture at the temperature of 140 ℃ to obtain a sample;
and (3) detecting the sample:
and (2) carrying out performance detection comparison on the test sample by adopting a CMT4000 type electronic universal testing machine (the tensile strength is referred to GB/T1692-:
TABLE 4
| Tensile strength MPa | Tear Strength KN/m | |
| Example 1 | 3.04 | 3.31 |
| Example 2 | 3.03 | 3.26 |
| Example 3 | 3.08 | 3.45 |
| Example 4 | 3.12 | 3.53 |
| Comparative example 1 | 2.81 | 2.54 |
| Comparative example 2 | 2.93 | 2.87 |
| Comparative example 3 | 2.95 | 2.96 |
Comparative example 1: blank control group, no defoamer was added;
comparative example 2: the defoaming agent adopts dimethyl silicone oil;
comparative example 3: the defoaming agent of example 1 was used, and the weight portion of the defoaming agent was 0.03 portion;
as can be seen from Table 4, after the defoaming agent is adopted, the mechanical property of the silicone rubber can be obviously improved, and the application range of the silicone rubber can be further improved, the mechanical property of the silicone rubber is obviously and greatly reduced, and under the condition of not adopting the defoaming agent, more bubbles can be generated in the silicone rubber, so that the mechanical property of the silicone rubber is directly reduced, the silicone rubber defoaming agent prepared by the method can better improve the mechanical property of the silicone rubber, because the silicone oil is subjected to a series of grafting modification treatment by the method of the invention, the surface active groups are increased, the defoaming and foam inhibiting properties of the silicone rubber are greatly improved, the continuous foam inhibiting time is long, the foam inhibiting effect is good, the generation of bubbles in the silicone rubber is greatly inhibited, so that the mechanical property of the silicone rubber is improved, but the mechanical property of the silicone rubber can be also influenced by the amount of other addition of the defoaming agent, excessive addition of the defoamer can adversely reduce the mechanical properties of the silicone rubber.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention, and the present invention is not limited to the illustrated embodiments, and all the modifications and equivalents of the embodiments may be made without departing from the spirit of the present invention.
Claims (8)
1. A preparation method of a defoaming agent for silicone rubber is characterized by comprising the following steps:
(1) preparing a graft:
sequentially adding epoxy chloropropane and allyl polyoxyethylene ether into a reaction kettle, heating to 90-95 ℃, keeping the temperature and stirring for 15-20min, then adding an active catalyst, continuing to keep the temperature and react for 2-3 h, then carrying out reduced pressure to remove unreacted epoxy chloropropane, naturally cooling to 35-40 ℃, then adding a sodium hydroxide solution into the reaction kettle, stirring and reacting for 40min, standing for 30min, then carrying out reduced pressure suction filtration and rotary evaporation to remove moisture, and thus obtaining the required graft;
(2) pretreatment of silicone oil:
uniformly mixing silicone oil and isopropanol according to the mass ratio of 10:1-1.5, heating to 60 ℃, and stirring for 40min under the condition of heat preservation to obtain pretreated silicone oil;
(3) grafting silicone oil:
sequentially adding the pretreated silicone oil and toluene into a reaction kettle, uniformly stirring, adding a catalyst solution, introducing inert gas, discharging air in the reaction kettle, heating to 80-90 ℃, preserving heat and stirring for 10min to obtain a reaction intermediate solution;
dissolving the graft in toluene to obtain a graft solution;
dissolving diethylaminoethyl methacrylate in toluene to obtain a diethylaminoethyl methacrylate solution;
and (3) dropwise adding the graft solution into the reaction intermediate solution, after dropwise adding, adjusting the temperature to 100 ℃, keeping the temperature and stirring for reaction for 30-40min, then dropwise adding the diethylaminoethyl methacrylate solution, continuously heating to 125 ℃, keeping the temperature and reacting for 10-14 h, standing for 1 h, and then carrying out reduced pressure drying to remove the solvent to obtain the catalyst.
2. The method for preparing an antifoaming agent for silicone rubber according to claim 1, wherein: the mixing mass ratio of the epichlorohydrin to the allyl polyoxyethylene ether is 1.5-1.8: 1.
3. The method for preparing an antifoaming agent for silicone rubber according to claim 1, wherein: the active catalyst is sodium hydride;
the mass ratio of the sodium hydride to the allyl polyoxyethylene ether is 1: 120-150.
4. The method for preparing an antifoaming agent for silicone rubber according to claim 1, wherein: the silicone oil is dimethyl silicone oil.
5. The method for preparing the defoaming agent for silicone rubber according to claim 1, characterized in that: the mixing ratio of the pretreated silicone oil to the toluene is 80-110 g: 400 mL.
6. The method for preparing an antifoaming agent for silicone rubber according to claim 1, wherein: the preparation method of the catalyst solution comprises the following steps:
dripping chloroplatinic acid into isopropanol, and uniformly stirring to obtain a chloroplatinic acid isopropanol solution;
the mixing molar ratio of the chloroplatinic acid to the isopropanol is 1: 2;
the catalyst solution and the pretreated silicone oil are mixed according to the mass ratio: 1:50-60.
7. The method for preparing an antifoaming agent for silicone rubber according to claim 1, wherein: the inert gas is nitrogen or neon.
8. The method for preparing an antifoaming agent for silicone rubber according to claim 1, wherein: the mass fraction of the graft solution is 10-12%;
the mass fraction of the diethylaminoethyl methacrylate solution is 4-5%;
the mixing mass ratio of the graft solution to the pretreated silicone oil is 1: 2-3;
the mixing mass ratio of the diethylaminoethyl methacrylate solution to the pretreated silicone oil is 1: 1.8-2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011108457.6A CN112159504A (en) | 2020-10-16 | 2020-10-16 | Preparation method of defoaming agent for silicone rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011108457.6A CN112159504A (en) | 2020-10-16 | 2020-10-16 | Preparation method of defoaming agent for silicone rubber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112159504A true CN112159504A (en) | 2021-01-01 |
Family
ID=73867320
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011108457.6A Pending CN112159504A (en) | 2020-10-16 | 2020-10-16 | Preparation method of defoaming agent for silicone rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112159504A (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101637708A (en) * | 2009-09-01 | 2010-02-03 | 陕西科技大学 | Method for preparing solvent-free polyether grafting organosilico/diamide compound emulsion defoamer |
| CN101698705A (en) * | 2007-12-13 | 2010-04-28 | 吴江市方霞企业信息咨询有限公司 | Synthesis of polyether silicone oil |
| CN101928389A (en) * | 2010-08-24 | 2010-12-29 | 浙江皇马科技股份有限公司 | Method for preparing glycidol ether terminated propenol polyoxyethylene ether |
| US20110190190A1 (en) * | 2010-01-29 | 2011-08-04 | Frank Schubert | Novel Linear Polydimethylsiloxane-Polyether Copolymers with Amino and/or Quaternary Ammonium Groups and Use Thereof |
| CN102153759A (en) * | 2011-03-16 | 2011-08-17 | 齐齐哈尔大学 | Method for synthesizing amphoteric polysiloxane used as flax softener |
| CN103214679A (en) * | 2013-05-06 | 2013-07-24 | 江南大学 | Preparation method of aminopolyether modified polysiloxane deforming agent |
| CN104650363A (en) * | 2015-02-05 | 2015-05-27 | 南通斯恩特纺织科技有限公司 | Preparation method of hyperbranched ternary polymerization organic silicon |
| CN106215465A (en) * | 2016-08-12 | 2016-12-14 | 中国海洋石油总公司 | A kind of Oil-gas Separation defoamer |
| CN106751880A (en) * | 2016-12-09 | 2017-05-31 | 成都硅宝科技股份有限公司 | The calcium carbonate-filled RTV silicon rubber and preparation method of a kind of silicone oil of alkyl containing carboxylic |
| CN107880564A (en) * | 2017-12-13 | 2018-04-06 | 四川锦盛油田技术服务有限公司 | A kind of preparation method of composite organic defoamer, its product and application |
-
2020
- 2020-10-16 CN CN202011108457.6A patent/CN112159504A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101698705A (en) * | 2007-12-13 | 2010-04-28 | 吴江市方霞企业信息咨询有限公司 | Synthesis of polyether silicone oil |
| CN101637708A (en) * | 2009-09-01 | 2010-02-03 | 陕西科技大学 | Method for preparing solvent-free polyether grafting organosilico/diamide compound emulsion defoamer |
| US20110190190A1 (en) * | 2010-01-29 | 2011-08-04 | Frank Schubert | Novel Linear Polydimethylsiloxane-Polyether Copolymers with Amino and/or Quaternary Ammonium Groups and Use Thereof |
| CN101928389A (en) * | 2010-08-24 | 2010-12-29 | 浙江皇马科技股份有限公司 | Method for preparing glycidol ether terminated propenol polyoxyethylene ether |
| CN102153759A (en) * | 2011-03-16 | 2011-08-17 | 齐齐哈尔大学 | Method for synthesizing amphoteric polysiloxane used as flax softener |
| CN103214679A (en) * | 2013-05-06 | 2013-07-24 | 江南大学 | Preparation method of aminopolyether modified polysiloxane deforming agent |
| CN104650363A (en) * | 2015-02-05 | 2015-05-27 | 南通斯恩特纺织科技有限公司 | Preparation method of hyperbranched ternary polymerization organic silicon |
| CN106215465A (en) * | 2016-08-12 | 2016-12-14 | 中国海洋石油总公司 | A kind of Oil-gas Separation defoamer |
| CN106751880A (en) * | 2016-12-09 | 2017-05-31 | 成都硅宝科技股份有限公司 | The calcium carbonate-filled RTV silicon rubber and preparation method of a kind of silicone oil of alkyl containing carboxylic |
| CN107880564A (en) * | 2017-12-13 | 2018-04-06 | 四川锦盛油田技术服务有限公司 | A kind of preparation method of composite organic defoamer, its product and application |
Non-Patent Citations (1)
| Title |
|---|
| 杨杏 等编: "《化学工业标准汇编》", 31 July 1993, 化学工业出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103665885B (en) | A kind of High tear resistance silicon rubber and preparation method thereof | |
| CN109776804B (en) | Cross-linkable POSS reinforced polyurethane nano hybrid material and preparation method thereof | |
| CN104004191A (en) | Fluorosiloxane copolymer and preparing method thereof | |
| CN112457462A (en) | Non-ionic waterborne polyurethane and preparation method and application thereof | |
| CN110358299B (en) | Hybrid modified silicone rubber and preparation method and application thereof | |
| CN112159497A (en) | Preparation method of fluorine-silicon modified butyronitrile latex applied to medical butyronitrile gloves | |
| CN115181270A (en) | Ternary polymerization fluorosilicone rubber and preparation method thereof | |
| CN113930077A (en) | High-strength wide-temperature-range low-pressure-change silicone rubber composite material and preparation method thereof | |
| CN112159504A (en) | Preparation method of defoaming agent for silicone rubber | |
| CN113980300A (en) | Polypropylene with low gel content and high melt strength, preparation method and application thereof | |
| CN107216658B (en) | Water-resistant silicone rubber and preparation method thereof | |
| CN110330654B (en) | Methyl vinyl silicone rubber and application thereof | |
| CN109517126B (en) | Polyurethane modified epoxy resin diluent and low-viscosity high-toughness epoxy resin composition composed of same | |
| CN109535369B (en) | Preparation method of high-low temperature resistant mixing type polyurethane raw rubber | |
| CN112646145A (en) | Low-dielectric-constant TPEE elastomer and preparation method and application thereof | |
| CN110698613A (en) | Preparation method of high-crosslinking organic silicon rubber | |
| CN115073741A (en) | Preparation method of low-temperature-resistant silicone rubber | |
| CN113004517B (en) | Modified epoxy resin, adhesive, preparation method and application thereof | |
| CN109575203B (en) | High-toughness automobile waterproof sealing strip and preparation method thereof | |
| CN116396443B (en) | Synthesis method of polytetrahydrofuran ether glycol modified polymer polyol | |
| CN114410090B (en) | Preparation method of packaging film | |
| CN115572483A (en) | Addition type liquid silicone rubber plastic dipping liquid and preparation method thereof | |
| CN111138625B (en) | Polyurethane material for flaw detection of outer wheel film and preparation method thereof | |
| CN114517016B (en) | High-resilience low-pressure variable rubber compound and preparation method thereof | |
| CN116836368B (en) | Epoxy resin containing carbamate 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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210101 |
|
| RJ01 | Rejection of invention patent application after publication |