CN113444286B - Addition type liquid fluorosilicone rubber inhibitor and preparation method thereof - Google Patents
Addition type liquid fluorosilicone rubber inhibitor and preparation method thereof Download PDFInfo
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- CN113444286B CN113444286B CN202110928159.XA CN202110928159A CN113444286B CN 113444286 B CN113444286 B CN 113444286B CN 202110928159 A CN202110928159 A CN 202110928159A CN 113444286 B CN113444286 B CN 113444286B
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- 229920005560 fluorosilicone rubber Polymers 0.000 title claims abstract description 78
- 239000003112 inhibitor Substances 0.000 title claims abstract description 64
- 239000007788 liquid Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims description 31
- 239000001257 hydrogen Substances 0.000 claims description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 23
- 239000000706 filtrate Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 claims description 15
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- 230000003472 neutralizing effect Effects 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 10
- 229960001545 hydrotalcite Drugs 0.000 claims description 10
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- URZHQOCYXDNFGN-UHFFFAOYSA-N 2,4,6-trimethyl-2,4,6-tris(3,3,3-trifluoropropyl)-1,3,5,2,4,6-trioxatrisilinane Chemical compound FC(F)(F)CC[Si]1(C)O[Si](C)(CCC(F)(F)F)O[Si](C)(CCC(F)(F)F)O1 URZHQOCYXDNFGN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 8
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 claims description 8
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 239000002841 Lewis acid Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 150000007517 lewis acids Chemical class 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000011968 lewis acid catalyst Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 150000003384 small molecules Chemical class 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 13
- 230000005764 inhibitory process Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract 3
- 230000000996 additive effect Effects 0.000 abstract 3
- 229920001971 elastomer Polymers 0.000 description 14
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- JQZGUQIEPRIDMR-UHFFFAOYSA-N 3-methylbut-1-yn-1-ol Chemical compound CC(C)C#CO JQZGUQIEPRIDMR-UHFFFAOYSA-N 0.000 description 7
- 230000002401 inhibitory effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- -1 polyfluorosiloxane Polymers 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- 229910020038 Mg6Al2 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
-
- 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
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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- 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
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
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- 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
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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- 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
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Abstract
The invention discloses an addition type liquid fluorosilicone rubber inhibitor and a preparation method thereof. The additive liquid fluorosilicone rubber can be fully compatible with a fluorosilicone rubber system in the using process, has the advantage of difficult volatilization even in a high-temperature environment, has a good inhibition effect, effectively solves the problems of volatilization loss of an inhibitor, poor compatibility with the system and the like, provides sufficient operation time for the additive liquid fluorosilicone rubber, improves the storage stability of products, and ensures that fluorosilicone rubber products prepared from the additive liquid fluorosilicone rubber have smooth surfaces and excellent performance.
Description
Technical Field
The invention relates to the technical field of rubber materials, in particular to an addition type liquid fluorosilicone rubber inhibitor and a preparation method thereof.
Background
The addition type liquid fluorosilicone rubber is an elastomer with a three-dimensional network structure formed by hydrosilylation reaction under the action of a platinum catalyst by taking vinyl-containing polyfluorosiloxane as a base rubber and taking hydrogen-containing oligosiloxane as a cross-linking agent. In practical applications, it is often necessary to add reaction inhibitors to regulate the rate of cure, giving sufficient open time for construction. Generally, in order to meet the requirements of processes such as pouring, calendering, coating, injection molding and the like, the two-component addition type liquid fluorosilicone rubber requires at least four hours of operable time at room temperature after the two components are mixed; the storage stability period of the one-component addition type liquid fluorosilicone rubber at room temperature generally requires at least six months.
The fluorosilicone rubber inhibitor can form a coordination bond with platinum atoms in the catalyst at room temperature, so that silicon vinyl groups or silicon hydrogen groups can be prevented from participating in coordination at the same time, after the catalyst is heated to the vulcanization temperature, the coordination bond of the inhibitor is weakened or decomposed, and the silicon vinyl groups and the silicon hydrogen groups can quickly undergo an addition reaction for crosslinking.
At present, inhibitors related to addition type liquid fluorosilicone rubber mainly include alkynol compounds, polyvinyl polysiloxane, dibasic acid esters containing double bonds, nitrogen-containing compounds, etc., and the alkynol compounds are the most commonly used inhibitors, such as methylbutynol, ethynylcyclohexanol, etc. However, due to the low boiling point of the methylbutynol, the methylbutynol is easy to volatilize in the mixing, defoaming and construction processes, and the addition type fluorosilicone rubber prepared by the methylbutynol is scorched, so that the surface of a sulfide is uneven, and the mechanical property of a product is also influenced; although the ethynyl cyclohexanol is the most classical inhibitor, the ethynyl cyclohexanol has a high melting point, exists in a solid form at normal temperature, is easy to separate out from a formula at a low roller temperature, has poor compatibility with addition type fluorosilicone rubber, directly influences the inhibition effect, and reduces the operable time and the storage period of a product.
Therefore, it is of great significance to develop an inhibitor suitable for addition type liquid fluorosilicone rubber.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an addition type liquid fluorosilicone rubber inhibitor and a preparation method thereof, which can effectively solve the problems of volatilization loss of the inhibitor, poor compatibility with a fluorosilicone rubber system and the like. The inhibitor can be fully compatible with a system in the using process, has the advantage of difficult volatilization even in a high-temperature environment, has good inhibiting effect, provides sufficient operable time for addition type liquid fluorosilicone rubber, also improves the storage stability of products, and fluorosilicone rubber products prepared from the inhibitor have smooth surfaces and excellent performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
an addition type liquid fluorosilicone rubber inhibitor has a structure shown in a formula (I):
in the formula (I), m represents the average polymerization degree, and m is more than or equal to 0 and less than or equal to 30.
According to the invention, m can take the values 0, 3, 8, 12, 18, 22, 25, 28;
preferably, when m is 0, the addition type liquid fluorosilicone rubber inhibitor has a structure shown in a formula (III):
according to the invention, the preparation method of the addition type liquid fluorosilicone rubber inhibitor comprises the following steps:
(1) under the protection of protective gas, uniformly mixing an organic solvent, hydrogen-containing fluorosilicone oligomer and a Lewis acid catalyst, heating to 40-50 ℃, dropwise adding 2-methyl-3-butyne-2-alcohol into the mixture for dehydrogenation reaction, and continuously stirring for reaction for 1-2 h after dropwise adding;
or, under the protection of protective gas, uniformly mixing an organic solvent, tetramethyldisiloxane and a Lewis acid catalyst, heating to 40-50 ℃, dropwise adding 2-methyl-3-butyne-2-ol into the mixture to perform dehydrogenation reaction, and continuously stirring to react for 1-2 h after dropwise adding;
(2) adding a neutralizing agent and a filter aid into the reaction system, stirring and filtering;
(3) removing the solvent and low-boiling-point substances in the filtrate under negative pressure, and cooling to obtain the addition type liquid fluorosilicone rubber inhibitor.
According to the present invention, the hydrogen-containing fluorosilicone oligomer described in step (1) has a structure represented by formula (II):
in the formula (II), n represents the average degree of polymerization, and n is more than 0 and less than or equal to 30.
According to the present invention, the hydrogen-containing fluorosilicone oligomer described in step (1) is prepared as follows:
trimethyltris (3,3, 3-trifluoropropyl) cyclotrisiloxane (D)3F) Mixing with tetramethyl disiloxane uniformly, adding an acid catalyst to carry out cationic catalysis ring-opening polymerization reaction, neutralizing the system after the reaction is completed, filtering, then carrying out negative pressure and heating to remove low-boiling-point micromolecules, and cooling to obtain the catalyst.
According to the invention, preferably, the trimethyltris (3,3, 3-trifluoropropyl) cyclotrisiloxane (D)3F) And tetramethyldisiloxane in a feed molar ratio of 1: (0.1-5).
According to the invention, preferably, the acidic catalyst is concentrated sulfuric acid or trifluoromethanesulfonic acid, and the feeding amount is D30.2-2% of the total mass of the F and the tetramethyldisiloxane.
According to the invention, the ring-opening polymerization reaction temperature is preferably 0-50 ℃, and the reaction time is preferably 0.5-5 h.
According to the invention, sodium bicarbonate is preferably adopted for neutralization reaction, and the feeding amount of the sodium bicarbonate is 0.5-2.5 times of the feeding amount of the acidic catalyst.
According to the invention, the low-boiling micromolecules are preferably removed under the conditions of 160-180 ℃ and-0.09 MPa-0.1 MPa.
According to the present invention, it is preferable that the hydrogen-containing fluorosilicone oligomer and 2-methyl-3-butyn-2-ol are fed in a molar ratio of 1: (2.0-2.2).
According to the invention, the organic solvent in the step (1) is toluene, and the feeding amount of the organic solvent is 1-2 times of the feeding mass of the hydrogen-containing fluorosilicone oligomer.
According to the present invention, it is preferable that the protective gas in step (1) is nitrogen or argon.
According to the present invention, preferably, the lewis acid in step (1) is tris (pentafluorophenyl) borane, and the dosage amount is 0.1% to 1% of the total mass of the hydrogen-containing fluorosilicone oligomer and the 2-methyl-3-butyn-2-ol dosage.
According to the present invention, preferably, the neutralizing agent in the step (2) is hydrotalcite [ Mg6Al2(OH)16CO3.4H2O]The feeding amount of the catalyst is 5-10 times of the feeding mass of the Lewis acid.
According to the invention, preferably, the filter aid in the step (2) is diatomite, and the feeding amount of the diatomite is 0.5-2 times of the feeding mass of the hydrotalcite.
According to the invention, the time for the neutralization stirring in the step (2) is preferably 0.5h to 3 h.
According to the present invention, it is preferred that the conditions for removing the solvent and the low boiling substances in the step (3) are a temperature of 100 ℃ to 150 ℃ and a pressure of-0.09 MPa to-0.1 MPa.
According to the invention, under the protection of protective gas, an organic solvent, tetramethyldisiloxane and a Lewis acid catalyst are uniformly mixed, the temperature is raised to 40-50 ℃, 2-methyl-3-butyn-2-ol is dropwise added into the mixture for dehydrogenation reaction, and the mixture is continuously stirred and reacted for 1-2 h after the dropwise addition; the inhibitor with the structure of the formula (III) can be obtained. Namely: the inhibitor with the structure shown in the formula (III) is prepared by dehydrogenation reaction of tetramethyldisiloxane and 2-methyl-3-butyne-2-ol.
The present invention has not been described in detail, but is in accordance with conventional techniques in the art.
Compared with the prior art, the invention has the following technical characteristics and beneficial effects:
1. the addition type liquid fluorosilicone rubber inhibitor is very stable in the using process, has the advantage of difficult volatilization even in a high-temperature environment, has a good inhibiting effect, and effectively solves the problem of volatilization loss of the inhibitor.
2. The inhibitor has good compatibility with addition type liquid fluorosilicone rubber, can not be separated out from a formula in the mixing process, is fully compatible with a system, and avoids the defects of uneven mixing, influence on vulcanization and the like.
3. The inhibitor has obvious effect on addition type liquid fluorosilicone rubber, gives sufficient operation time, improves the storage stability of products, does not influence the deep vulcanization of the rubber, and also ensures the appearance and the mechanical property of products.
4. The preparation method of the invention has simple operation, high reaction efficiency and high yield of the product.
Drawings
FIG. 1 shows addition type liquid fluorosilicone rubber inhibitor prepared in example 1 of the present invention1H-NMR spectrum.
FIG. 2 shows addition type liquid fluorosilicone rubber inhibitor prepared in example 3 of the present invention1H-NMR spectrum.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
The starting materials described in the examples are conventional and are commercially available or prepared according to the prior art.
Example 1
An addition type liquid fluorosilicone rubber inhibitor has the following structure:
the preparation steps are as follows:
(1) under the protection of nitrogen, 1340g of tetramethyldisiloxane, 1500g of toluene and 12.6g of tris (pentafluorophenyl) borane are added into a reaction kettle provided with a mechanical stirrer, a thermometer, a condenser tube and a dropping funnel, the stirring is started, the temperature is raised to 40 ℃, 1764g of 2-methyl-3-butyn-2-ol is slowly dropped into the kettle for dehydrogenation reaction, a large amount of heat is released during the dropping, the kettle temperature is regulated and controlled through the dropping speed, the reaction temperature in the whole dropping process is maintained to be 40-50 ℃, and the stirring reaction is continued for 1 hour after the dropping is finished;
(2) the reaction system was cooled to room temperature and 76g of hydrotalcite [ Mg ] was added to the kettle6Al2(OH)16CO3.4H2O]Stirring and neutralizing with 80g of diatomite for 2 hours, then carrying out suction filtration under negative pressure, and collecting filtrate;
(3) heating the filtrate to 110-130 ℃ to remove the solvent, then maintaining the system pressure at-0.098 MPa by using a vacuum pump to carry out rectification purification, and collecting the fraction at 120-122 ℃ by controlling the reflux ratio to be 8: 1-10: 1 in the rectification process to obtain the addition type liquid fluorosilicone rubber inhibitor, wherein the yield is 88.5%.
The nuclear magnetic hydrogen spectrum of the product prepared in example 1 is shown in FIG. 1, wherein Si-CH is present at 0.22-0.24ppm3Chemical shift signal peak of middle H, C-CH at 1.56ppm3The chemical shift signal peak of H in-C [ identical to ] CH is at 2.42ppm, the chemical shift signal peak of H in-C [ identical to ] CH is at 7.28ppm, solvent deuterochloroform is at 7.28ppm, the integral area ratio of H in the three groups is 12:12:2, and data represented by the spectrogram can indicate the molecular structure of the addition type liquid fluorosilicone rubber inhibitor.
Example 2
An addition type liquid fluorosilicone rubber inhibitor has the following structure:
the preparation steps are as follows:
(1) under the protection of nitrogen, 1340g of tetramethyldisiloxane, 2000g of toluene and 17.5g of tris (pentafluorophenyl) borane are added into a reaction kettle provided with a mechanical stirrer, a thermometer, a condenser tube and a dropping funnel, the stirring is started, the temperature is raised to 40 ℃, 1848g of 2-methyl-3-butyn-2-ol is slowly dropped into the kettle for dehydrogenation reaction, a large amount of heat is released during the dropping, the kettle temperature is regulated and controlled through the dropping speed, the reaction temperature in the whole dropping process is maintained to be 40-50 ℃, and the stirring reaction is continued for 2 hours after the dropping is finished;
(2) the reaction system was cooled to room temperature and 105g of hydrotalcite [ Mg ] was added to the kettle6Al2(OH)16CO3.4H2O]Stirring and neutralizing with 100g of diatomite for 2 hours, then carrying out suction filtration under negative pressure, and collecting filtrate;
(3) heating the filtrate to 110-130 ℃ to remove the solvent, then maintaining the system pressure at-0.098 MPa by using a vacuum pump to carry out rectification purification, and collecting the fraction at 120-122 ℃ by controlling the reflux ratio to be 8: 1-10: 1 in the rectification process to obtain the addition type liquid fluorosilicone rubber inhibitor, wherein the yield is 87.9%.
Example 3
An addition type liquid fluorosilicone rubber inhibitor has the following structure:
the preparation steps are as follows:
(1) 468g of trimethyltris (3,3, 3-trifluoropropyl) cyclotrisiloxane (D) were added to a reaction vessel equipped with a mechanical stirrer, thermometer and condenser3F) 268g of tetramethyldisiloxane are stirred uniformly, and the temperature of the kettle is reduced to 10-15 ℃ by adopting an ice water bath; then slowly adding 3.6g of trifluoromethanesulfonic acid into the kettle to perform cationic catalytic ring-opening polymerization reaction, discharging heat, cooling by using an ice water bath, and after the temperature is increased, keeping the temperature of 10-20 ℃ and continuing stirring for reaction for 2 hours; adding 3.2g of sodium bicarbonate into the kettle, stirring for 3 hours for neutralization reaction, filtering, and collecting filtrate; heating to 160 ℃ under the pressure of-0.09 MPa to remove unreacted raw materials and low-boiling-point micromolecules, and cooling to obtain 570.5g of hydrogen-containing fluorosilicone oligomer;
(2) under the protection of nitrogen, adding 302g of the hydrogen-containing fluorosilicone oligomer, 302g of toluene and 1.56g of tris (pentafluorophenyl) borane into another reaction kettle provided with a mechanical stirrer, a thermometer, a condenser tube and a dropping funnel, starting stirring, heating to 40 ℃, then slowly dropwise adding 88g of 2-methyl-3-butyn-2-ol into the kettle for dehydrogenation reaction, wherein a large amount of heat is released during dropwise adding, the temperature of the kettle is regulated and controlled by the dropwise adding speed, the reaction temperature in the whole dropwise adding process is maintained at 40-50 ℃, and stirring reaction is continued for 1h after dropwise adding;
(3) will be reversedCooling the system to room temperature, adding 9.4g hydrotalcite [ Mg ] into the kettle6Al2(OH)16CO3.4H2O]Stirring and neutralizing the mixture for 2 hours with 15g of diatomite, then carrying out suction filtration under negative pressure, and collecting filtrate;
(4) and heating the filtrate to 110-130 ℃ to remove the solvent, then maintaining the pressure of-0.098 MPa to continuously remove low-boiling-point substances, and cooling to obtain 363g of addition type liquid fluorosilicone rubber inhibitor with the yield of 93.1%.
The nuclear magnetic hydrogen spectrum of the product prepared in example 3 is shown in FIG. 2, wherein Si-CH is present at 0.22-0.25ppm3Chemical shift signal peak of middle H, Si-CH at 0.84-0.89ppm2CH2CF3The chemical shift signal peak of methylene H connected with Si at 1.56ppm is C-CH3Chemical shift signal peak of middle H, Si-CH at 2.05-2.17ppm2CH2CF3Neutralization of-CF3Chemical shift signal peaks of connected methylene H are chemical shift signal peaks of H in-C ≡ CH at 2.41ppm, solvent deuterochloroform at 7.28ppm, the integral area ratio of H in the groups is 21:6:12:6:2, and data represented by the spectrogram can indicate the molecular structure of the addition type liquid fluorosilicone rubber inhibitor.
Example 4
An addition type liquid fluorosilicone rubber inhibitor has the following structure:
the preparation steps are as follows:
(1) 468g of trimethyltris (3,3, 3-trifluoropropyl) cyclotrisiloxane (D) were added to a reaction vessel equipped with a mechanical stirrer, thermometer and condenser3F) And 75g of tetramethyldisiloxane, stirring uniformly, and cooling the kettle to 10-20 ℃ by adopting an ice water bath; then slowly adding 2.8g of trifluoromethanesulfonic acid into the kettle to perform cationic catalytic ring-opening polymerization reaction, discharging heat, cooling by using an ice water bath, and after the temperature is increased, keeping the temperature at 20-30 ℃ and continuing stirring for reaction for 2 hours; then 2.4g of sodium bicarbonate is added into the kettle and stirred for 3 hours to neutralize the reaction andfiltering and collecting filtrate; under the pressure of-0.09 MPa, heating to 160 ℃ to remove unreacted raw materials and low-boiling-point micromolecules, and cooling to obtain 472.3g of hydrogen-containing fluorosilicone oligomer;
(2) under the protection of nitrogen, adding 356g of the hydrogen-containing fluorosilicone oligomer, 380g of toluene and 2.02g of tris (pentafluorophenyl) borane into another reaction kettle provided with a mechanical stirrer, a thermometer, a condenser tube and a dropping funnel, starting stirring, heating to 40 ℃, then slowly dropwise adding 46g of 2-methyl-3-butyn-2-ol into the kettle for dehydrogenation reaction, wherein a large amount of heat is released during dropwise adding, the temperature of the kettle is regulated and controlled by the dropwise adding speed, the reaction temperature in the whole dropwise adding process is maintained at 40-50 ℃, and stirring and reacting are continued for 2 hours after dropwise adding;
(3) the reaction system was cooled to room temperature and 12.2g of hydrotalcite [ Mg ] was added to the kettle6Al2(OH)16CO3.4H2O]Stirring and neutralizing with 20g of diatomite for 2 hours, then carrying out suction filtration under negative pressure, and collecting filtrate;
(4) and heating the filtrate to 110-130 ℃ to remove the solvent, then maintaining the pressure of-0.098 MPa to continuously remove low-boiling-point substances, and cooling to obtain 380g of addition type liquid fluorosilicone rubber inhibitor with the yield of 94.5%.
Example 5
An addition type liquid fluorosilicone rubber inhibitor has the following structure:
the preparation steps are as follows:
(1) 468g of trimethyltris (3,3, 3-trifluoropropyl) cyclotrisiloxane (D) were added to a reaction vessel equipped with a mechanical stirrer, thermometer and condenser3F) And 50g of tetramethyldisiloxane, stirring uniformly, and adjusting the temperature of the kettle to 30-40 ℃ by adopting a water bath; then slowly adding 7.8g of concentrated sulfuric acid into the kettle to perform a cationic catalysis ring-opening polymerization reaction, discharging heat, and after the temperature is flushed, keeping the temperature of the kettle at 40-50 ℃ through a water bath to continue stirring and reacting for 5 hours; then 15.6g of sodium bicarbonate is added into the kettle and stirred for 3 hours for neutralization reaction and filteredCollecting the filtrate; heating to 180 ℃ under the pressure of-0.09 MPa to remove unreacted raw materials and low-boiling-point micromolecules, and cooling to obtain 450.5g of hydrogen-containing fluorosilicone oligomer;
(2) under the protection of nitrogen, adding 400g of the hydrogen-containing fluorosilicone oligomer, 500g of toluene and 1.98g of tris (pentafluorophenyl) borane into another reaction kettle provided with a mechanical stirrer, a thermometer, a condenser tube and a dropping funnel, starting stirring, heating to 40 ℃, then slowly dropwise adding 36g of 2-methyl-3-butyn-2-ol into the kettle for dehydrogenation reaction, greatly releasing heat during dropwise adding, regulating and controlling the temperature of the kettle through the dropwise adding speed, maintaining the reaction temperature of the whole dropwise adding process at 40-50 ℃, and continuing stirring for reaction for 1h after dropwise adding;
(3) the reaction system was cooled to room temperature and 15.6g of hydrotalcite [ Mg ] was added to the kettle6Al2(OH)16CO3.4H2O]Stirring and neutralizing with 20g of diatomite for 2 hours, then carrying out suction filtration under negative pressure, and collecting filtrate;
(4) and heating the filtrate to 110-130 ℃ to remove the solvent, then maintaining the pressure of-0.098 MPa to continuously remove low-boiling-point substances, and cooling to obtain 408g of addition type liquid fluorosilicone rubber inhibitor with the yield of 93.6%.
Example 6
An addition type liquid fluorosilicone rubber inhibitor has the following structure:
the preparation steps are as follows:
(1) 468g of trimethyltris (3,3, 3-trifluoropropyl) cyclotrisiloxane (D) were added to a reaction vessel equipped with a mechanical stirrer, thermometer and condenser3F) And 32g of tetramethyldisiloxane, stirring uniformly, and adjusting the temperature of the kettle to 30-40 ℃ by adopting a water bath; then slowly adding 10g of concentrated sulfuric acid into the kettle to perform cationic catalysis ring-opening polymerization reaction, discharging heat, and after the temperature is completely flushed, keeping the temperature of the kettle at 40-50 ℃ through a water bath to continuously stir for reaction for 4 hours; then 18.3g of sodium bicarbonate is added into the kettle, stirred for 3 hours for neutralization reaction and filtered, and then collectedCollecting filtrate; heating to 180 ℃ under the pressure of-0.09 MPa to remove unreacted raw materials and low-boiling-point micromolecules, and cooling to obtain 438.6g of hydrogen-containing fluorosilicone oligomer;
(2) under the protection of nitrogen, adding 360g of the hydrogen-containing fluorosilicone oligomer, 400g of toluene and 2.24g of tris (pentafluorophenyl) borane into another reaction kettle provided with a mechanical stirrer, a thermometer, a condenser tube and a dropping funnel, starting stirring, heating to 40 ℃, then slowly dropwise adding 22g of 2-methyl-3-butyn-2-ol into the kettle for dehydrogenation reaction, wherein a large amount of heat is released during dropwise adding, the temperature of the kettle is regulated and controlled by the dropwise adding speed, the reaction temperature in the whole dropwise adding process is maintained at 40-50 ℃, and stirring reaction is continued for 2 hours after dropwise adding;
(3) the reaction system was cooled to room temperature and 18.2g of hydrotalcite [ Mg ] was added to the kettle6Al2(OH)16CO3.4H2O]Stirring and neutralizing the mixture for 2 hours with 30g of diatomite, then carrying out suction filtration under negative pressure, and collecting filtrate;
(4) and heating the filtrate to 110-130 ℃ to remove the solvent, then maintaining the pressure of-0.098 MPa to continuously remove low-boiling-point substances, and cooling to obtain 354g of addition type liquid fluorosilicone rubber inhibitor with the yield of 92.7%.
Test example 1
The products prepared in the examples 1 and 3 and the methyl butynol and the ethynyl cyclohexanol which are commonly used in the industry are taken as the inhibitor of the addition type liquid fluorosilicone rubber to carry out a formulation experiment, and the inhibiting effect of the inhibitor is characterized by the following method:
the formula of the addition type liquid fluorosilicone rubber mainly comprises the following components in parts by weight as shown in the following table 1:
TABLE 1
| Vinyl fluorosilicone oil (viscosity 30000cp, vinyl mass fraction 0.20%) | 100 portions of |
| Hydrophobic fumed silica (220 +/-25 m)2/g) | 25 portions of |
| Hydrogen-containing fluorosilicone oil (viscosity 80cp, hydrogen mass fraction 0.48%) | 2.2 parts of |
| Platinum catalyst (platinum content 3000ppm) | 0.5 portion |
In addition to the components shown in Table 1, the molar ratio of inhibitor to platinum atoms in the formulation was 100: 1.
And respectively placing the addition type liquid fluorosilicone rubber prepared by different inhibitors in a constant temperature oven at 50 ℃, and testing the viscosity change of the addition type liquid fluorosilicone rubber after initial, 4h and 8h so as to evaluate the effect of the inhibitors on rubber materials. The test instrument adopts a German HAAKE VTiQ intelligent rheometer, and the test method comprises the following steps: 20mm flat rotor, shear rate 10s-1The results of the test at 25 ℃ for 50 seconds are shown in Table 2.
TABLE 2
| Viscosity of the solution | Example 1 | Example 3 | Methyl butynol | Ethynyl cyclohexanol |
| initial/Pa.s | 780 | 775 | 778 | 783 |
| 4h/Pa.s | 788 | 779 | 1670 | 989 |
| 8h/Pa.s | 795 | 784 | Gelation | 1356 |
As can be seen from table 2, the inhibitors prepared in examples 1 and 3 of the present invention have an obvious effect of inhibiting addition-type liquid fluorosilicone rubber, and the rheological viscosity of fluorosilicone rubber prepared from the inhibitors is substantially unchanged even under a standing condition of 50 ℃, so that the method completely meets the operation time requirement of two-component liquid fluorosilicone rubber construction, and the effect is very significant.
The viscosity of the addition type fluorosilicone rubber prepared by adopting the methylbutinol is increased by more than 2 times after the addition type fluorosilicone rubber is placed for 4 hours, the placing time is continuously prolonged to 8 hours, the cross-linking of the rubber material obviously generates the phenomenon of gelation, the state of a semi-elastomer is formed, and the construction application cannot be carried out at all. The situation is mainly that the boiling point of the methylbutinol is low, and the defects of easy volatilization inevitably exist in the using process, so that the inhibiting effect of the methylbutinol is greatly damaged.
The addition type liquid fluorosilicone rubber prepared by adopting ethynyl cyclohexanol has a relatively obvious thickening phenomenon in the placing process, which needs to provide high injection pressure for the injection type liquid fluorosilicone rubber, thereby causing great adverse effect. The reason is that the ethynyl cyclohexanol has a high melting point and exists in a solid form at normal temperature, and when a three-roll grinder is used for mixing and dispersing rubber materials, the ethynyl cyclohexanol is easy to separate out from a formula at a low roll temperature, has poor compatibility with addition type fluorosilicone rubber, influences the inhibition effect of the ethynyl cyclohexanol, and therefore limits the operable time and the storage period of products.
Test example 2
The formulation experiment of the product prepared in the example 1 and the example 3, and the methyl butynol and the ethynylcyclohexanol serving as the addition type liquid fluorosilicone rubber inhibitor in the test example 1 is repeated, then the rubber compound prepared by different inhibitors is placed for 4 hours at room temperature, the mechanical properties and the apparent states of the rubber compound after the initial time and the 4 hours are respectively tested, and the action effect of different inhibitors on the fluorosilicone rubber is compared. The test method comprises the steps of vulcanizing the completely mixed addition type liquid fluorosilicone rubber at 120 ℃ for 15min to prepare a standard test piece of 2mm, and carrying out mechanical property test and surface observation on the test piece, wherein the test result is shown in Table 3. Wherein the hardness is measured according to ASTM D2240; tensile strength and elongation at break were measured according to ASTM D412.
TABLE 3
As can be seen from table 3, when the inhibitors prepared in examples 1 and 3 of the present invention are applied to addition type liquid fluorosilicone rubber, the fluorosilicone rubber has stable performance. After the rubber material is mixed in an initial state and is placed for 4 hours, the vulcanization reaction is carried out for 120 ℃ multiplied by 15min respectively, the hardness, the tensile strength and the elongation at break of the fluorosilicone rubber are basically unchanged, the surface of the fluorosilicone rubber also presents smooth appearance, the reaction effect is good, the action effect of an inhibitor is not influenced due to overlong placing time, and the mechanical property and the surface appearance of the fluorosilicone rubber are not damaged.
Although the addition type liquid fluorosilicone rubber prepared by adopting the methylbutinol can play a role in inhibiting when mixed initially, the action effect on the fluorosilicone rubber is gradually weakened along with the prolonging of the standing time. During the standing period, due to the volatilization loss of the methylbutynol, the rubber compound can slowly generate a crosslinking reaction, and the hardness and the viscosity are increased. When the rubber material is vulcanized at a high temperature of 120 ℃, the rubber generates scorching phenomenon due to the lack of the inhibitor, the surface of the test piece on one surface contacting with the mold is uneven, a large number of wrinkles appear, and the appearance and the mechanical strength of the product are influenced.
The addition type liquid fluorosilicone rubber prepared from ethynyl cyclohexanol also has the scorching problem, because ethynyl cyclohexanol is easy to separate out at low temperature, the ethynyl cyclohexanol has poor compatibility with the liquid fluorosilicone rubber, the problem of uneven dispersion is easy to occur during mixing, the inhibition effect of the ethynyl cyclohexanol is obviously damaged, wrinkles appear on the surface of a film in the high-temperature vulcanization process, and the tensile strength and the elongation at break of the fluorosilicone rubber are also influenced.
Claims (13)
1. An addition type liquid fluorosilicone rubber inhibitor is characterized in that the inhibitor has a structure shown as a formula (I):
in the formula (I), m represents the average polymerization degree, and m is more than 0 and less than or equal to 30.
2. The method for preparing the addition type liquid fluorosilicone rubber inhibitor according to claim 1, comprising the steps of:
(1) under the protection of protective gas, uniformly mixing an organic solvent, hydrogen-containing fluorosilicone oligomer and a Lewis acid catalyst, heating to 40-50 ℃, dropwise adding 2-methyl-3-butyne-2-ol into the mixture for dehydrogenation reaction, and continuously stirring for reaction for 1-2 h after dropwise adding;
(2) adding a neutralizing agent and a filter aid into the reaction system, stirring and filtering;
(3) removing the solvent and low-boiling-point substances in the filtrate under negative pressure, and cooling to obtain the addition type liquid fluorosilicone rubber inhibitor.
3. The method for preparing an addition type liquid fluorosilicone rubber inhibitor according to claim 2, wherein the hydrogen-containing fluorosilicone oligomer in the step (1) has a structure represented by formula (II):
in the formula (II), n represents the average degree of polymerization, and n is more than 0 and less than or equal to 30.
4. The method for preparing an addition type liquid fluorosilicone rubber inhibitor according to claim 2, wherein the hydrogen-containing fluorosilicone oligomer in the step (1) is prepared by the following method:
mixing trimethyltris (3,3, 3-trifluoropropyl) cyclotrisiloxane and tetramethyldisiloxane uniformly, adding an acid catalyst into the mixture to perform cationic catalysis ring-opening polymerization reaction, neutralizing the system after the reaction is completed, filtering, then performing negative pressure and temperature rise to remove low-boiling-point micromolecules, and cooling to obtain the catalyst.
5. The method for preparing a hydrofluorosiloxane oligomer of claim 4, wherein the molar ratio of trimethyltris (3,3, 3-trifluoropropyl) cyclotrisiloxane to tetramethyldisiloxane is 1: (0.1-5).
6. The method for preparing a hydrofluorosiloxane oligomer of claim 4, wherein the acidic catalyst is concentrated sulfuric acid or trifluoromethanesulfonic acid, and the amount of the acidic catalyst is 0.2% -2% of the total mass of the trimethyltris (3,3, 3-trifluoropropyl) cyclotrisiloxane and tetramethyldisiloxane feeds.
7. The method for preparing a fluorosilicone oligomer comprising hydrogen according to claim 4, wherein the ring-opening polymerization reaction temperature is 0 to 50 ℃ and the reaction time is 0.5 to 5 hours.
8. The method for preparing a hydrofluorosiloxane oligomer according to claim 4, wherein sodium bicarbonate is used for neutralization, and the amount of the added hydrogen fluorosilicone oligomer is 0.5-2.5 times of the amount of the added acidic catalyst.
9. The method for preparing hydrogen-containing fluorosilicone oligomer according to claim 4, wherein the conditions for removing the low-boiling small molecules are 160 ℃ to 180 ℃ and a pressure of-0.09 MPa to-0.1 MPa.
10. The method for preparing an addition type liquid fluorosilicone rubber inhibitor according to claim 2, wherein the molar ratio of the hydrogen-containing fluorosilicone oligomer and 2-methyl-3-butyn-2-ol fed in the step (1) is 1: (2.0-2.2); the organic solvent is toluene, and the feeding amount of the organic solvent is 1-2 times of the feeding mass of the hydrogen-containing fluorosilicone oligomer; the protective gas is nitrogen or argon.
11. The method for preparing the addition type liquid fluorosilicone rubber inhibitor according to claim 2, wherein the Lewis acid in the step (1) is tris (pentafluorophenyl) borane, and the dosage amount of the Lewis acid is 0.1% to 1% of the total mass of the hydrogen-containing fluorosilicone oligomer and the 2-methyl-3-butyn-2-ol.
12. The method for preparing the addition type liquid fluorosilicone rubber inhibitor according to claim 2, wherein the neutralizing agent in the step (2) is hydrotalcite [ Mg [ ]6Al2(OH)16CO3.4H2O]The feeding amount of the catalyst is 5-10 times of the feeding mass of the Lewis acid; the filter aid is diatomite, and the feeding amount of the filter aid is 0.5-2 times of the feeding mass of the hydrotalcite; the time for neutralizing and stirring is 0.5-3 h.
13. The method for preparing the addition type liquid fluorosilicone rubber inhibitor according to claim 2, wherein the conditions for removing the solvent and the low boiling residue in the step (3) are a temperature of 100 ℃ to 150 ℃ and a pressure of-0.09 MPa to-0.1 MPa.
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| CN110256853A (en) * | 2019-05-10 | 2019-09-20 | 肇庆皓明有机硅材料有限公司 | A kind of in-place molding foamed silastic sealing ring composition and preparation method thereof |
| CN111925526A (en) * | 2020-08-31 | 2020-11-13 | 威海新元新材料有限公司 | High-activity hydrogen-containing fluorosilicone oil cross-linking agent and preparation method thereof |
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| CN110256853A (en) * | 2019-05-10 | 2019-09-20 | 肇庆皓明有机硅材料有限公司 | A kind of in-place molding foamed silastic sealing ring composition and preparation method thereof |
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Denomination of invention: A kind of addition type liquid fluorosilicone rubber inhibitor and preparation method thereof Effective date of registration: 20220921 Granted publication date: 20220527 Pledgee: Weihai City Commercial Bank Limited by Share Ltd. high tech branch Pledgor: Xinyuan chemical (Shandong) Co.,Ltd.|Weihai Xinyuan New Material Co.,Ltd. Registration number: Y2022980015764 |