CN116854593B - Esterified acetylenic hydrosilylation inhibitor, preparation method and liquid silicone rubber - Google Patents
Esterified acetylenic hydrosilylation inhibitor, preparation method and liquid silicone rubber Download PDFInfo
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- CN116854593B CN116854593B CN202311126801.8A CN202311126801A CN116854593B CN 116854593 B CN116854593 B CN 116854593B CN 202311126801 A CN202311126801 A CN 202311126801A CN 116854593 B CN116854593 B CN 116854593B
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- acetylenic
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- hydrosilylation inhibitor
- hydrosilylation
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- 239000003112 inhibitor Substances 0.000 title claims abstract description 102
- 238000006459 hydrosilylation reaction Methods 0.000 title claims abstract description 92
- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 38
- 239000004944 Liquid Silicone Rubber Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000012295 chemical reaction liquid Substances 0.000 claims description 30
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 19
- 239000013067 intermediate product Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 16
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical group C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 claims description 15
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 14
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 12
- -1 diisopropyl titanate Chemical compound 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000011976 maleic acid Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 229920005601 base polymer Polymers 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims 1
- 238000005886 esterification reaction Methods 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 5
- 239000004945 silicone rubber Substances 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 10
- 230000005764 inhibitory process Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 5
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical group COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000004513 sizing Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 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
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000006961 mixed inhibition Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
- C07C69/40—Succinic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/62—Halogen-containing esters
- C07C69/65—Halogen-containing esters of unsaturated acids
- C07C69/657—Maleic acid esters; Fumaric acid esters; Halomaleic acid esters; Halofumaric acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The application belongs to the technical field of silicone rubber, and particularly relates to an esterified acetylenic hydrosilylation inhibitor, a preparation method and liquid silicone rubber; the application provides an esterified acetylenic hydrosilylation inhibitor which is an inhibitor with a new chemical structure, wherein all functional groups in the chemical structure can cooperate with each other to effectively inhibit hydrosilylation reaction, so that the storage time and the operation time of addition type liquid silicone rubber are greatly prolonged, and meanwhile, the esterified acetylenic hydrosilylation inhibitor also has the advantages of low volatility and good compatibility, thereby solving the technical problem of lacking multifunctional hydrosilylation inhibitor in the prior art.
Description
Technical Field
The application belongs to the technical field of silicone rubber, and particularly relates to an esterified acetylenic hydrosilylation inhibitor, a preparation method and liquid silicone rubber.
Background
The hydrosilylation inhibitor added in the addition type liquid silicone rubber can inhibit the hydrosilylation reaction in a wider temperature range, lose the inhibition activity at the vulcanization temperature of the liquid silicone rubber, quickly cause the hydrosilylation reaction and solidify the liquid silicone rubber; thereby meeting the technological stage requirements of the addition type liquid silicone rubber in pouring, coating or injection molding and the like.
The hydrosilylation inhibitor used for the addition type liquid silicone rubber mainly comprises maleate and alkynol inhibitors; the maleic acid ester hydrosilylation inhibitor has lower volatility, but has limited activity of inhibiting hydrosilylation reaction, and the alkynol hydrosilylation inhibitor has better inhibition effect and is commonly used in industrial production; however, the 2-methyl-3-butyn-2-ol in the alkynol hydrosilylation inhibitor is extremely volatile and has larger toxicity, the compatibility with an organic silicon system is poor, the storage stability of the sizing material is easy to be greatly reduced, the volatilization is carried out in the heating and vulcanization process, so that the surface of sulfide is wrinkled, compared with the 2-methyl-3-butyn-2-ol, the ethynyl cyclohexanol has better inhibition effect and relatively lower volatility, but is easy to solidify at room temperature, and is separated out from the sizing material, the storage stability of the sizing material is influenced, the toxicity is not ignored, so that the alkynol hydrosilylation inhibitor has high activity of inhibiting hydrosilylation, but has the defects of volatility and poor compatibility with an addition reaction system; the existing maleate hydrosilylation inhibitor and alkynol hydrosilylation inhibitor have the defects that volatility, compatibility and inhibition activity cannot be achieved simultaneously, and the multifunctional hydrosilylation inhibitor for the maleate hydrosilylation inhibitor and the alkynol hydrosilylation inhibitor has the technical problem that the multifunctional hydrosilylation inhibitor is lacking at present.
Disclosure of Invention
In view of the above, the present application provides an esterified acetylenic hydrosilylation inhibitor, a preparation method thereof and a liquid silicone rubber, which are used for solving the technical problem that the prior art lacks a multifunctional hydrosilylation inhibitor.
The first aspect of the application provides an esterified acetylenic hydrosilylation inhibitor, the chemical structure of which is shown as a formula I;
a formula I;
in the formula I, the compound (I),
r1 is、/>、/>、/>、/>、Or->；
R2 is、/>、/>、/>、/>、、/>Methyl, ethyl, isopropyl, long chain alkyl, phenyl, benzyl, vinyl, allyl or (2, 3-glycidoxy) propyl;
a is、/>Phenyl or naphthyl, and->，/>，。
In a second aspect, the present application provides a process for the preparation of an esterified acetylenic hydrosilylation inhibitor of the first aspect, the process comprising the steps of:
step S1, mixing an alkynol hydrosilylation inhibitor, dicarboxylic acid or carboxylic ester, a catalyst and a solvent for reaction to obtain an intermediate product reaction solution;
and S2, cooling the intermediate product reaction liquid, and removing precipitated insoluble matters to obtain the reaction liquid of the esterified acetylenic hydrosilylation inhibitor.
Preferably, after step S2, step S3 is further included to distill the reaction solution of the esterified acetylenic hydrosilylation inhibitor under reduced pressure.
Preferably, in the step S2, the intermediate product reaction liquid is cooled at room temperature, and the pressure of reduced pressure distillation is 95 kPa-99.9 kPa, and the temperature is 30-50 ℃.
Preferably, in step S2, the way to remove the precipitated insoluble matter includes filtration or centrifugation.
Preferably, in the step S1, the reaction temperature is 40-120 ℃ and the reaction time is 2-24 hours.
Preferably, in the step S1, the molar ratio of the alkynol hydrosilylation inhibitor to the dicarboxylic acid or the carboxylic acid ester to the solvent is 1:1-4:10-20.
Preferably, in step S1, the alkynol hydrosilylation inhibitor is selected from 2-methyl-3-butyn-2-ol and/or 1-ethynyl cyclohexanol.
Preferably, in step S1, the dicarboxylic acid is selected from maleic acid and/or phthalic acid;
the carboxylic acid ester is selected from monomethyl maleate and/or dimethyl succinate.
Preferably, in step S1, the catalyst is selected from at least one of dicyclohexylcarbodiimide/4-dimethylaminopyridine system, tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetra-tert-butyl titanate and diisopropyl di (acetylacetonate) titanate;
the solvent is at least one selected from toluene, benzene, acetone, chloroform, dimethylformamide and dimethyl sulfoxide.
In a third aspect the present application provides a liquid silicone rubber, which is an addition type liquid silicone rubber, comprising a silicone base polymer, a cross-linking agent, a catalyst, an auxiliary agent and an esterified acetylenic hydrosilylation inhibitor according to the first or second aspect.
Preferably, the silicone base polymer is selected from vinyl silicone oils;
the cross-linking agent is selected from hydrogen-containing silicone oil;
the catalyst is selected from a cassiterite catalyst;
the auxiliary agent is selected from gas-phase white carbon black and hexamethyldisilazane.
The novel esterified acetylenic hydrosilylation inhibitor is added into the liquid silicone rubber, so that hydrosilylation reaction can be effectively inhibited below vulcanization temperature, the operation time of the two-component addition type liquid silicone rubber after mixing can be prolonged, the storage time of the single-component addition type liquid silicone rubber can be prolonged, and compared with the existing addition type liquid silicone rubber added with the maleate hydrosilylation inhibitor and the acetylenic alcohol hydrosilylation inhibitor, the performance is more excellent.
In summary, the present application provides an esterified acetylenic hydrosilylation inhibitor, a preparation method thereof and a liquid silicone rubber, wherein the esterified acetylenic hydrosilylation inhibitor combines the advantages of maleate, phthalic acid and alkynol hydrosilylation inhibitor, is a multifunctional hydrosilylation inhibitor, can reduce the volatility of the acetylenic inhibitor, improve the compatibility in a reaction system, and has ester groups and unsaturated bonds to increase the adhesive force between a sizing material and a base material; more importantly, compared with maleate, phthalic acid and alkynol, the preparation method can effectively inhibit the hydrosilylation reaction of the addition type liquid silicone rubber, prolong the storage time and the operation time of the addition type liquid silicone rubber, and has the advantages of low volatility, good compatibility and high inhibition activity, thereby solving the technical problem of lacking the multifunctional hydrosilylation inhibitor in the prior art.
Detailed Description
The application provides an esterified acetylenic hydrosilylation inhibitor, a preparation method and liquid silicone rubber, which are used for solving the technical problem that the prior art lacks a multifunctional hydrosilylation inhibitor.
The following description of the present application will be made clearly and fully, and it is apparent that the embodiments described are some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
Example 1
Example 1 of the present application provides a method for preparing an esterified acetylenic hydrosilylation inhibitor, comprising preparing an intermediate reaction solution and preparing an esterified acetylenic hydrosilylation inhibitor reaction solution.
The preparation of the intermediate reaction liquid comprises the following steps: under the protection of nitrogen, the reactants maleic acid and ethynyl cyclohexanol are dissolved in dry solvent toluene, catalysts DCC and DMAP are respectively added, the reaction is heated to 80 ℃, and the reaction is stirred for 2 hours to obtain intermediate product reaction liquid; the reactants used in the reaction were 0.1 mole of 11.6 grams of maleic acid and 0.2 mole of 24.8 grams of ethynyl cyclohexanol, the solvent used was 250 milliliters of toluene, and the catalyst used was 0.22 mole of 45.5 grams of dicyclohexylcarbodiimide and 0.038 mole of 4.6 grams of 4-dimethylaminopyridine, respectively.
The preparation of the reaction liquid of the esterified acetylenic hydrosilylation inhibitor comprises the following steps: cooling the intermediate product reaction liquid to room temperature, precipitating a large amount of white solids, and filtering to obtain an esterified acetylenic hydrosilylation inhibitor reaction liquid; washing the filter cake with toluene, and distilling the filtrate under reduced pressure to obtain light yellow liquid 30.9, g, so as to obtain maleic acid bis (1-ethynyl cyclohexyl) ester; the filtrate was distilled under reduced pressure at a pressure of 95 kPa and a temperature of 30 ℃.
The product light yellow liquid is subjected to nuclear magnetic resonance hydrogen spectrum test, and the data are that 1 H-NMR(CDCl 3 ) δ ppm: 6.71(d, 2H), 2.53(s, 2H), 2.04(m, 4H), 1.88(m, 4H), 1.68(m, 8H), 1.54(m, 4H)。
Example 2
Example 2 of the present application provides a method for preparing an esterified acetylenic hydrosilylation inhibitor, comprising preparing an intermediate reaction solution and preparing an esterified acetylenic hydrosilylation inhibitor reaction solution.
The preparation of the intermediate reaction liquid comprises the following steps: dissolving reactants of monomethyl maleate and ethynyl cyclohexanol in dry solvent toluene under the protection of nitrogen, respectively adding catalysts DCC and DMAP, heating to 80 ℃ for reaction, and stirring for 2 hours to obtain intermediate product reaction liquid; the reactants used in the reaction were 0.05 mole of monomethyl maleate and 0.05 mole of ethynyl cyclohexanol, 130 ml of toluene as solvent, 11.4 grams of dicyclohexylcarbodiimide and 0.0095 mole of 4-dimethylaminopyridine, respectively.
The preparation of the reaction liquid of the esterified acetylenic hydrosilylation inhibitor comprises the following steps: cooling the intermediate product reaction liquid to room temperature, precipitating a large amount of white solids, and filtering to obtain an esterified acetylenic hydrosilylation inhibitor reaction liquid; washing the filter cake with toluene, and distilling the filtrate under reduced pressure to obtain pale yellow liquid 10.1. 10.1 g, thereby obtaining maleic acid (1-ethynyl cyclohexyl) methyl ester; the filtrate was distilled under reduced pressure at a pressure of 95 kPa and a temperature of 30 ℃.
The product light yellow liquid is subjected to nuclear magnetic resonance hydrogen spectrum test, and the data are that 1 H-NMR(CDCl 3 ) δ ppm: 6.73(d, 2H), 3.74(s, 3H), 2.53(s, 1H), 2.04(m, 2H), 1.88(m, 2H), 1.68(m, 4H), 1.54(m, 2H)。
Example 3
Example 3 of the present application provides a method for preparing an esterified acetylenic hydrosilylation inhibitor, comprising preparing an intermediate reaction solution and preparing an esterified acetylenic hydrosilylation inhibitor reaction solution.
The preparation of the intermediate reaction liquid comprises the following steps: dissolving reactants maleic acid and 2-methyl-3-yn-2-ol in dry solvent toluene under the protection of nitrogen, respectively adding catalysts DCC and DMAP, heating to 80 ℃ for reaction, and stirring for 2 hours to obtain intermediate product reaction liquid; the reactants used in the reaction were 0.1 mole of 11.6 grams of maleic acid and 0.22 mole of 18.5 grams of 2-methyl-3-yn-2-ol, the solvent used was 250 milliliters of toluene, and the catalyst used was 0.24 mole of 49.5 grams of dicyclohexylcarbodiimide and 0.04 mole of 4.8 grams of 4-dimethylaminopyridine, respectively.
The preparation of the reaction liquid of the esterified acetylenic hydrosilylation inhibitor comprises the following steps: cooling the intermediate product reaction liquid to room temperature, precipitating a large amount of white solids, and filtering to obtain an esterified acetylenic hydrosilylation inhibitor reaction liquid; washing the filter cake with toluene, and distilling the filtrate under reduced pressure to obtain pale yellow liquid 25.4. 25.4 g, thereby obtaining maleic acid bis (2-methylbutan-3-yn-2-yl) ester; the filtrate was distilled under reduced pressure at a pressure of 95 kPa and a temperature of 30 ℃.
The product light yellow liquid is subjected to nuclear magnetic resonance hydrogen spectrum test, and the data are that 1 H-NMR(CDCl 3 ) δ ppm : 6.76(d, 2H), 2.43(s, 2H), 1.67(s, 12H)。
Example 4
Example 4 of the present application provides a method for preparing an esterified acetylenic hydrosilylation inhibitor, comprising preparing an intermediate reaction solution and preparing an esterified acetylenic hydrosilylation inhibitor reaction solution.
The preparation of the intermediate reaction liquid comprises the following steps: the reactants of monomethyl maleate and 2-methyl-3-alkyne-2-alcohol are dissolved in dry solvent toluene under the protection of nitrogen, catalysts DCC and DMAP are respectively added, the reaction is heated to 80 ℃, and the reaction is stirred for 2 hours to obtain intermediate product reaction liquid; the reactants used in the reaction were 0.05 mole of monomethyl maleate and 0.05 mole of 4.63 grams of ethynyl cyclohexanol, 125 milliliters of toluene as solvent, 11.4 grams of dicyclohexylcarbodiimide and 0.0095 mole of 4-dimethylaminopyridine as catalyst, respectively.
The preparation of the reaction liquid of the esterified acetylenic hydrosilylation inhibitor comprises the following steps: cooling the intermediate product reaction liquid to room temperature, precipitating a large amount of white solids, and filtering to obtain an esterified acetylenic hydrosilylation inhibitor reaction liquid; washing the filter cake with toluene, and distilling the filtrate under reduced pressure to obtain 9.5. 9.5 g as pale yellow liquid, thereby obtaining maleic acid (2-methylbut-3-yn-2-yl) methyl ester; the filtrate was distilled under reduced pressure at a pressure of 95 kPa and a temperature of 30 ℃.
The product light yellow liquid is subjected to nuclear magnetic resonance hydrogen spectrum test, and the data are that 1 H-NMR(CDCl 3 ) δ ppm: 6.72(d, 2H), 3.74(s, 3H), 2.43(s, 1H), 1.67(s, 6H)。
Example 5
Example 5 of the present application provides a method for preparing an esterified acetylenic hydrosilylation inhibitor, comprising preparing an intermediate reaction solution and preparing an esterified acetylenic hydrosilylation inhibitor reaction solution.
The preparation of the intermediate reaction liquid comprises the following steps: reactants of dimethyl succinate, ethynyl cyclohexanol and tetrabutyl titanate are dissolved in dry solvent toluene under the protection of nitrogen, catalysts of DCC and DMAP are respectively added, the reaction is heated to 80 ℃, and stirring reaction is carried out for 3 hours, so that an intermediate product reaction solution is obtained; the reactants used in the reaction were 0.075 mole of dimethyl succinate, 0.15 mole of 18.8 grams of ethynyl cyclohexanol, 0.1 mole of 0.3 grams of tetrabutyl titanate, 125 milliliters of toluene solvent, 0.055 mole of 11.4 grams of dicyclohexylcarbodiimide, and 0.0095 mole of 1.15 grams of 4-dimethylaminopyridine, respectively.
The preparation of the reaction liquid of the esterified acetylenic hydrosilylation inhibitor comprises the following steps: cooling the intermediate product reaction liquid to room temperature, precipitating a large amount of white solids, and filtering to obtain an esterified acetylenic hydrosilylation inhibitor reaction liquid; washing the filter cake with toluene, and distilling the filtrate under reduced pressure to obtain pale yellow liquid 24.3-g, thereby obtaining bis (1-ethynyl cyclohexyl) succinate; the filtrate was distilled under reduced pressure at a pressure of 95 kPa and a temperature of 30 ℃.
The product light yellow liquid is subjected to nuclear magnetic resonance hydrogen spectrum test, and the data are that 1 H-NMR(CDCl 3 ) δ ppm: 2.72(m, 4H), 2.42(s, 2H), 2.01(m, 4H), 1.88(m, 4H), 1.69(m, 8H), 1.54(m ,4H)。
Experimental example 1
The performance of the esterified acetylenic hydrosilylation inhibitor, the conventional 2-methyl-3-butyn-2-ol inhibitor and the ethynyl cyclohexanol inhibitor prepared in examples 1-5 is tested, so that the effects of the hydrosilylation inhibitor are compared, an addition type liquid silicone rubber sample is prepared in the experimental process, the performance is tested, and the test results are shown in table 1.
The preparation of the addition type liquid silicone rubber sample comprises: 0.0 g of a hydrosilylation inhibitor, 0.1 g of a 2-methyl-3-butyn-2-ol inhibitor, 0.1 g of an ethynyl cyclohexanol inhibitor, 0.1 g of an esterified acetylenic hydrosilylation inhibitor prepared in examples 1-5, 720 g of 2000 cp vinyl silicone oil, 250 g of 200 specific surface area fumed silica, 50 g of hexamethyldisilazane, 30 g of 0.5% hydrogen-containing silicone oil are respectively added into a kneader, kneaded uniformly at room temperature, 1g of 3000 ppm of a Kasite catalyst is added, stirred uniformly, and placed into a vacuum drying oven at room temperature for full foam discharging for standby, thus obtaining a test sample.
Testing the properties of the addition-type liquid silicone rubber samples included: gel time at room temperature, gel time at 50℃and scorch time (t 10 ) Flat, maximum, highest torque or force (MH) and minimum torque or force (ML) reached within a specified time.
The room temperature gel time method for testing the addition type liquid silicone rubber sample comprises the following steps: the prepared sample was placed in a vacuum oven and set at 25℃and the flow state of the composition was visually checked at regular intervals to record the time when solid precipitation occurred as gel time.
The 50 ℃ gel time method for testing the addition type liquid silicone rubber sample comprises the following steps: placing the prepared liquid silicone rubber into a PTFE container, sealing and placing the PTFE container in an oven, setting the temperature to 50 ℃, picking and hanging the silicone rubber by a glass rod at regular time, and recording the time when the glass rod cannot pick out wires from the silicone rubber, namely the gel time of the liquid silicone rubber at 50 ℃;
test of scorch time (t) of addition type liquid silicone rubber sample 10 ) The flat, maximum, highest torque or force (MH) and minimum torque or force (ML) methods achieved in a specified time include: the vulcanization curve of the liquid silicone rubber at 120℃was measured using a JK-321 rotor-less vulcanizer.
TABLE 1
As can be seen from table 1, after adding the alkynol inhibitor such as 2-methyl-3-butyn-2-ol or ethynyl cyclohexanol, the gel time of the addition type liquid silicone rubber at room temperature is 5-9 days, and the gel time of 50 ℃ is 46-92 hours, which indicates that the inhibition activity of the alkynol inhibitor can inhibit the hydrosilylation reaction of the liquid silicone rubber, and the addition type liquid silicone rubber is beneficial to the technological operations such as pouring after the alkynol inhibitor is added; compared with alkynol inhibitors such as 2-methyl-3-butyn-2-ol or ethynyl cyclohexanol, the esterified acetylenic hydrosilylation inhibitor such as maleic acid bis (1-ethynyl cyclohexyl) ester provided by the application can reach 23 days at room temperature gel time and 92 hours at 50 ℃ under the condition of the same addition amount (0.1 g), and meanwhile, the inhibition activity of the esterified acetylenic hydrosilylation inhibitor is far higher than that of the single alkynol inhibitor such as 2-methyl-3-butyn-2-ol or ethynyl cyclohexanol, and meanwhile, the inhibition activity of the maleate inhibitor is far lower than that of the alkynol inhibitor, so that the esterified acetylenic hydrosilylation inhibitor is far higher than that of the single maleate inhibitor under the condition of the same addition amount (0.1 g), namely, the inhibition activity of the 0.1 g esterified acetylenic hydrosilylation inhibitor is higher than that of the mixed inhibition activity of the 0.05 g maleate inhibitor and the 0. 0.05 g alkynol inhibitor, which indicates that the novel chemical structure compound shown in the formula I provided by the application can exert synergistic activity on the addition of the alkynol.
In summary, referring to examples 1-5 and nmr hydrogen spectrum data thereof, the preparation provided in the examples of the present application can prepare an esterified acetylenic hydrosilylation inhibitor, which is a new chemical structure hydrosilylation inhibitor, and has the advantages of low volatility, good compatibility and high inhibition activity, and meanwhile, the chemical structure of the inhibitor introduces ester groups and unsaturated bonds, so that the adhesion between sizing material and base material can be improved, and the preparation process has relatively mild reaction conditions and simple process, thereby being beneficial to industrial mass production.
The above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.
Claims (7)
1. An esterified acetylenic hydrosilylation inhibitor is characterized in that the chemical structure is shown as a formula I;
formula I.
2. A process for the preparation of an esterified acetylenic hydrosilylation inhibitor as recited in claim 1 comprising the steps of:
step S1, mixing an alkynol hydrosilylation inhibitor, dicarboxylic acid, a catalyst and a solvent for reaction to obtain an intermediate product reaction solution;
s2, cooling the intermediate product reaction liquid, and removing precipitated insoluble matters to obtain an esterified acetylenic hydrosilylation inhibitor reaction liquid;
the alkynol hydrosilylation inhibitor is selected from ethynyl cyclohexanol;
the dicarboxylic acid is selected from maleic acid.
3. The method for preparing an esterified acetylenic hydrosilylation inhibitor according to claim 2, wherein the step of mixing and reacting the acetylenic alcohol hydrosilylation inhibitor, dicarboxylic acid, catalyst and solvent to obtain an intermediate reaction solution specifically comprises the following steps:
the alkynol hydrosilylation inhibitor, dicarboxylic acid, catalyst and solvent are mixed and then reacted at 80 ℃ for 2 h, thus obtaining an intermediate product reaction solution.
4. The method for preparing an esterified acetylenic hydrosilylation inhibitor according to claim 2, characterized in that in step S1, the catalyst is selected from at least one of dicyclohexylcarbodiimide/4-dimethylaminopyridine system, tetraethyltitanate, tetraisopropyl titanate, tetrabutyltitanate, tetra-tert-butyl titanate and di (acetylacetonate) diisopropyl titanate;
the solvent is at least one selected from toluene, benzene, acetone, chloroform, dimethylformamide and dimethyl sulfoxide.
5. The method for producing an esterified acetylenic hydrosilylation inhibitor according to claim 2, further comprising a step S3 of distilling the esterified acetylenic hydrosilylation inhibitor reaction solution under reduced pressure after the step S2.
6. The method for producing an esterified acetylenic hydrosilylation inhibitor according to claim 5, characterized in that the reduced pressure distillation of the esterified acetylenic hydrosilylation inhibitor reaction liquid specifically comprises: and (3) distilling the esterification acetylenic hydrosilylation inhibitor reaction solution under reduced pressure at a pressure of 95-99.9 kPa and a temperature of 30-50 ℃.
7. A liquid silicone rubber comprising a silicone base polymer, a cross-linking agent, a catalyst, an auxiliary agent, and an esterified acetylenic hydrosilylation inhibitor of claim 1.
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| US5506289A (en) * | 1993-07-23 | 1996-04-09 | Gen Electric | Liquid injection molding inhibitors for curable compositions |
| CN105418669A (en) * | 2015-12-07 | 2016-03-23 | 武汉大学 | Alkoxy silane acetylenic silicon hydrogen addition inhibitor and preparation method thereof |
| CN107541070A (en) * | 2017-10-11 | 2018-01-05 | 成都硅宝科技股份有限公司 | A kind of thixotroping foam silicone rubber and preparation method thereof |
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| US5506289A (en) * | 1993-07-23 | 1996-04-09 | Gen Electric | Liquid injection molding inhibitors for curable compositions |
| CN105418669A (en) * | 2015-12-07 | 2016-03-23 | 武汉大学 | Alkoxy silane acetylenic silicon hydrogen addition inhibitor and preparation method thereof |
| CN107541070A (en) * | 2017-10-11 | 2018-01-05 | 成都硅宝科技股份有限公司 | A kind of thixotroping foam silicone rubber and preparation method thereof |
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