CN105418669B - A kind of multifunction alkoxyl silicone alkanisation acetylene series Si―H addition reaction inhibitor and preparation method thereof - Google Patents
A kind of multifunction alkoxyl silicone alkanisation acetylene series Si―H addition reaction inhibitor and preparation method thereof Download PDFInfo
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000007259 addition reaction Methods 0.000 title claims abstract description 20
- 239000002683 reaction inhibitor Substances 0.000 title claims abstract description 17
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 16
- 125000003545 alkoxy group Chemical group 0.000 title claims abstract description 15
- -1 alkoxy silane Chemical compound 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 229910000077 silane Inorganic materials 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 40
- JQZGUQIEPRIDMR-UHFFFAOYSA-N 3-methylbut-1-yn-1-ol Chemical compound CC(C)C#CO JQZGUQIEPRIDMR-UHFFFAOYSA-N 0.000 claims description 21
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 150000003606 tin compounds Chemical class 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical group [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 125000004665 trialkylsilyl group Chemical group 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 36
- 239000000463 material Substances 0.000 abstract description 20
- 238000004513 sizing Methods 0.000 abstract description 12
- 239000003112 inhibitor Substances 0.000 abstract description 11
- 229920002379 silicone rubber Polymers 0.000 abstract description 6
- 238000007711 solidification Methods 0.000 abstract description 5
- 230000008023 solidification Effects 0.000 abstract description 5
- 230000001988 toxicity Effects 0.000 abstract description 5
- 231100000419 toxicity Toxicity 0.000 abstract description 5
- 229920001971 elastomer Polymers 0.000 abstract description 2
- 125000000962 organic group Chemical group 0.000 abstract description 2
- 229920000260 silastic Polymers 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 46
- 238000005160 1H NMR spectroscopy Methods 0.000 description 23
- 229910052757 nitrogen Inorganic materials 0.000 description 23
- 238000010992 reflux Methods 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000000047 product Substances 0.000 description 20
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 18
- 239000003921 oil Substances 0.000 description 18
- 238000009835 boiling Methods 0.000 description 17
- 238000000605 extraction Methods 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 238000005292 vacuum distillation Methods 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical group [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical class CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 235000011091 sodium acetates Nutrition 0.000 description 2
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical class [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 2
- 235000010334 sodium propionate Nutrition 0.000 description 2
- RCOSUMRTSQULBK-UHFFFAOYSA-N sodium;propan-1-olate Chemical compound [Na+].CCC[O-] RCOSUMRTSQULBK-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- LMVLVUPTDRWATB-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-ol Chemical compound CO[Si](C)(OC)CCCO LMVLVUPTDRWATB-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- QNEFNFIKZWUAEQ-UHFFFAOYSA-N carbonic acid;potassium Chemical compound [K].OC(O)=O QNEFNFIKZWUAEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- VSYLGGHSEIWGJV-UHFFFAOYSA-N diethyl(dimethoxy)silane Chemical compound CC[Si](CC)(OC)OC VSYLGGHSEIWGJV-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- HTSRFYSEWIPFNI-UHFFFAOYSA-N ethyl-dimethoxy-methylsilane Chemical compound CC[Si](C)(OC)OC HTSRFYSEWIPFNI-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000010412 perfusion Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000004324 sodium propionate Substances 0.000 description 1
- 229960003212 sodium propionate Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- C07F7/045—
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The present invention relates to alkoxyl silicone alkanisation acetylene series Si―H addition reaction inhibitor and preparation method thereof.The present invention generates the inhibitor of alkoxyl silicone alkanisation acetylene series Si―H addition reaction using alkynol and alkoxy silane as primary raw material under catalyst action.Preparation method of the present invention is simple, and the Si―H addition reaction inhibitor of acquisition can improve the shortcomings of alkynol class inhibitor is with base rubber poor compatibility, volatile and residue toxicity.Used in add-on type liquid silicon rubber, the pot-life at room temperature can be extended, and silastic surface is smooth after solidification, while the organic group that inhibitor is connected can improve bonding with base material, the imparting more preferable bonding force of sizing material.
Description
Technical field
The present invention relates to organosilicon material field, and in particular to a kind of multifunction alkoxyl silicone alkanisation acetylene series Si―H addition reaction
Inhibitor and preparation method thereof.
Background technology
Hydrosilylation is from Sommer et al. (Sommer L H, Pietrusza E W, Whitmore F
C.Peroxide-catalyzed addition of trichlorosilane to 1-octene[J].Journal of
the American Chemical Society,1947,69(1):Since 188-188.) finding, organosilicon chemistry is had become
In it is most important reaction one of, synthesis carbon function organo-silicon compound/polymer, Carbonsilane dendrimer and add-on type
Silicon rubber vulcanization etc. has a wide range of applications.Hydrosilylation speed needs to be needed to carry out appropriate regulation according to use.
Such as in addition-type silicon rubber, to adapt to perfusion, coating or injection molding technique needs, dual composition addition type liquid silastic
After two component mixing, it is desirable at least 4 up times more than hour；One-component add-on type liquid silicon rubber, room temperature
Under can be significant with long time stored.And it must be rapidly completed when silicon hydrogenation occurs.It is such in order to reach
Purpose, most common also most practical method are exactly the addition Si―H addition reaction inhibitor in silicon hydro genation system.Si―H addition reaction presses down
Preparation effectively can suppress catalyst silicon hydrogenation in certain temperature range, and after curing temperature is heated to, silicon
Hydrogen addition inhibitor, which loses, to be suppressed function and silicon hydrogenation is quickly occurred.
At present, alkynol compound such as methyl butynol and ethynylcyclohexanol is suppressed using most common Si―H addition reaction
Agent, at room temperature with good inhibitory action.It can be used as silicon as United States Patent (USP) (US3445420) discloses alkynol compound
Hydrogen addition inhibitor.But these alkynol compounds have effumability and organosilicon systems poor compatibility and toxicity etc.
Problem.Wherein effumability can cause volatile in mixing deaeration technique of the inhibitor before two-component silicone rubber use, make suppression
Formulation content is unstable, and rubber surface wrinkle is uneven after causing vulcanization, also result in waste of raw materials and environment is poisoned.And by
It is relatively low in the fusing point (30-33 DEG C) of ethynylcyclohexanol, it solidification can separate out at room temperature, influence sizing material storage stability.Therefore,
Some are applied to the mode that alkynol is modified.Such as in order to reduce the volatility of alkynol compound, Dow Corning Corporation is public
A kind of silylated acetylenic inhibitor is opened(US3445420), such compound can be very
Good is dissolved in sizing material, while also reduces the yellow of reaction product.But due to losing the hydroxyl of alkynol, its volatility is still
It is so larger.By methylhydrogenpolysi,oxane and the acetylene series inhibitor of alkynol polysiloxanes as obtained from dehydrogenation reaction(US3933882) volatility, toxicity and the consistency problem with sizing material, are completely solved.So
And its remaining silicon hydrogen will cause A glue storage stability in two-component silicone rubber to be deteriorated.
In order to overcome current technology difficult point, the invention discloses a kind of multifunction alkoxyl silicone alkanisation acetylene series silicon hydrogen to add
Into inhibitor, the compatible of the volatility of alkynol class inhibitor, the toxicity for reducing residue, increase and sizing material can be greatly lowered
Property；While the silane epoxide of activity can be reacted with the white carbon in sizing material or other compounds containing activity hydroxy or oneself
Body hydrolytic crosslinking, participate in solidification；Also the bonding force of increase sizing material and base material can be reacted with base material.
The content of the invention
The present invention combines the technical foundation of existing acetylene series Si―H addition reaction inhibitor, discloses a kind of multifunction alkoxyl silicone
Alkanisation acetylene series Si―H addition reaction inhibitor and preparation method thereof.
Alkynes can be greatly lowered in multifunction alkoxyl silicone alkanisation acetylene series Si―H addition reaction inhibitor provided by the present invention
The compatibility of the volatility of alcohols inhibitor, increase and sizing material, at the same the silane epoxide of activity can with the white carbon in sizing material or
The other compounds containing activity hydroxy of person react or itself hydrolytic crosslinking, participate in solidification.Also increase glue can be reacted with base material
The bonding force of material and base material.
The concrete technical scheme of the present invention is as follows：
A kind of multifunction alkoxyl silicone alkanisation acetylene series Si―H addition reaction inhibitor, structural formula are as follows：
Wherein：R1For methyl or ethyl；R2For methoxyl group, ethyoxyl or methyl, ethyl, n-propyl, phenyl or ethene
Base；R3For methoxyl group, ethyoxyl, methyl, ethyl, n-propyl, chain alkyl (CnH2n+1-, its n>3), phenyl, methacryl
Oxygen propyl group or (oxygen of 2,3- epoxies third) propyl group.
The present invention also provides the method for preparing above-mentioned multifunction alkoxyl silicone alkanisation acetylene series Si―H addition reaction inhibitor, step
It is as follows：Using methyl butynol or ethynylcyclohexanol as raw material, mixed with alkoxy silane, catalyst is added, in 20-100 degree
Under the conditions of react 6-24 hours after, remove low-boiling-point substance, directly obtain product or distillation after obtain product；
The molar feed ratio of wherein alkoxysilane compound containing trialkylsilyl group in molecular structure and methyl butynol or ethynylcyclohexanol compound is
0.25~4；
The catalyst is in tin compound, titanate ester compound, alkali carbonate or alkali metal acylate
It is one or more of.
The tin compound is dibutyl tin dilaurate；The titanate ester compound is butyl titanate；The alkali
Metal carbonate is potassium carbonate, the alkali metal acylate is sodium acetate.
Beneficial effects of the present invention are embodied in：
1st, multifunction alkoxyl silicone alkanisation acetylene series Si―H addition reaction inhibitor overcomes methyl butynol and acetenyl hexamethylene
Alcohol makes the sizing material surface after solidification smooth as Si―H addition reaction inhibitor compatibility and volatile problem.
2nd, multifunction alkoxyl silicone alkanisation acetylene series Si―H addition reaction inhibitor can join while silicon hydrogenation is suppressed
With it is other reaction and combined together with sizing material, solve volatility and residual caused by toxicity problem.
3rd, the organic group that multifunction alkoxyl silicone alkanisation acetylene series Si―H addition reaction inhibitor is connected can improve and base
The bonding problem of material, assign the more preferable bonding force of sizing material.
4th, synthetic route is simple, and no side reaction product generation, raw material is cheap and easily-available, reacts favorable reproducibility.
Embodiment
Following examples further illustrate present disclosure, but should not be construed as limiting the invention.Without departing substantially from
In the case of of the invention spirit and essence, the modifications or substitutions made to the inventive method, step or condition belong to the present invention
Scope.
Embodiment one,Preparation
Equipped with magneton, reflux condensing tube, in the 250ml of bubbler and logical nitrogen device three neck round bottom flask successively plus
Enter 8.4g (0.1mol) methyl butynol, 30.4g (0.2mol) tetramethoxy-silicane, 0.1g dibutyl tin dilaurates.60 degree
At a temperature of react 6 hours, obtain weak yellow liquid.Room temperature is cooled to, oil pump, which is evaporated under reduced pressure, removes low-boiling-point substance, and vacuum distillation obtains
Colourless transparent liquid 21.7g.1H-NMR(CDCl3)δ[ppm]:3.59(s,9H,OCH3),2.45(s,1H,-C≡C-H),1.58
(s,6H,-CH3)
Embodiment two,Preparation
Equipped with magneton, reflux condensing tube, in the 250ml three neck round bottom flask of bubbler and logical nitrogen device successively plus
Enter, 12.4g (0.1mol) ethynylcyclohexanol, 30.4g (0.2mol) tetramethoxy-silicane, 0.1g butyl titanates.60 degree of temperature
Lower reaction 24 hours, obtains blood red liquid.Cooling, oil pump, which is evaporated under reduced pressure, removes low-boiling-point substance, then is warming up to 90 degree, extraction production
Product, obtain colourless transparent liquid 24.0g.1H-NMR(CDCl3,300MHz)δ[ppm]:3.60(s,9H,OCH3), 2.53 (s ,-C
≡ C-H), 1.95 (br, 2H), 1.69-1.59 (m, 5H), 1.58-1.49 (m, 2H), 1.26 (br, 1H)
Embodiment three,Preparation
Equipped with magneton, reflux condensing tube, sequentially add in the 250ml three neck round bottom flask of bubbler and logical nitrogen device
12.6g (0.15mol) methyl butynol, 44.4g (0.3mol) vinyltrimethoxy silane, 0.15g stannous iso caprylates, 90 degree
Reaction 6 hours.After cooling, weak yellow liquid is obtained, oil pump, which is evaporated under reduced pressure, removes low-boiling-point substance, then is warming up to 60 degree of extraction products,
Obtain colourless transparent liquid 29.5g.1H-NMR(CDCl3,300MHz)δ[ppm]:6.16-5.88 (m, 3H ,-CH=CH2),3.58
(s,6H,OCH3),2.45(s,1H,-C≡C-H), 1.59(s,6H,-CH3)
Embodiment 4,Preparation
Equipped with magneton, reflux condensing tube, in the 250ml three neck round bottom flask of bubbler and logical nitrogen device successively
14.2g ethynylcyclohexanols (0.11mol), 33.8g (0.23mol) vinyltrimethoxy silane, 0.12g potassium carbonate, 20 degree
Reaction 20 hours.After cooling, centrifugal filtration removes potassium carbonate.Oil pump, which is evaporated under reduced pressure, removes low-boiling-point substance, then is warming up to 90 degree of extractions
Product, obtain colourless transparent liquid 25.9g.1H-NMR(CDCl3,300MHz)δ[ppm]:6.11-5.89 (m, 3H ,-CH=
CH2),3.54(s,9H,OCH3),2.49(s,-C≡C-H),1.89(br,2H),1.68-1.57(m,5H),1.55-1.48(m,
2H),1.26(br,1H)
Embodiment 5,Preparation
Equipped with magneton, reflux condensing tube, sequentially add in the 250ml three neck round bottom flask of bubbler and logical nitrogen device
25.2g (0.3mol) methyl butynol, 40.8g (0.3mol) MTMS, 0.3g sodium acetates.20 degree of reactions 18 are small
When.After cooling, centrifugal filtration removes sodium acetate.Water pump, which is evaporated under reduced pressure, removes low-boiling-point substance, then the 90 degree of extraction products that heat up, and obtains nothing
Color opaque products 55.41g.1H-NMR(CDCl3,300MHz)δ[ppm]:3.55(s,6H,OCH3),2.45(s,1H,-C≡C-
H),1.57(s,6H,-CH3),0.22(s,3H,Si-CH3)
Embodiment 6,Preparation
Equipped with magneton, reflux condensing tube, sequentially add in the 250ml three neck round bottom flask of bubbler and logical nitrogen device
12.4g (0.1mol) ethynylcyclohexanol, 27.2g (0.2mol) MTMS, 0.1g dibutyl tin dilaurates,
40 degree are reacted 24 hours.After cooling, yellow liquid is obtained, after oil pump is evaporated under reduced pressure removing low boiling, then 90 degree is warming up to and extracts
Product, obtain colourless transparent liquid 22.60g.1H-NMR(CDCl3,300MHz)δ[ppm]:3.55(s,6H,OCH3),2.52(s,
1H,-C≡C-H),1.91(br,2H),1.66-1.57(m,5H),1.56-1.48(m,2H),1.25(br,2H),0.22(s,
3H,Si-CH3)
Embodiment 7,Preparation
Equipped with magneton, reflux condensing tube, sequentially add in the 250ml three neck round bottom flask of bubbler and logical nitrogen device
25.2g (0.3mol) methyl butynol, 25.0g (0.126mol) phenyltrimethoxysila,e, 0.2g stannous iso caprylates, 90 degree anti-
Answer 24 hours.Obtain yellow liquid.90 degree of oil pump is evaporated under reduced pressure out low boiling, then heats up 120 degree, distills out product, obtains colourless
Transparency liquid 30g.1H-NMR(CDCl3,300MHz)δ[ppm]:7.70-7.68(m,2H,Ar-H),7.44-7.37(m,3H,Ar-
H),3.63(s,6H,OCH3),2.42(s,1H,-C≡C-H),1.61(s,6H,-CH3).
Embodiment 8,Preparation
Equipped with magneton, reflux condensing tube, sequentially add in the 250ml three neck round bottom flask of bubbler and logical nitrogen device
49.6g (0.4mol) ethynylcyclohexanol, 19.6g (0.1mol) phenyltrimethoxysila,e, 0.2g sodium propionates, 90 degree of reactions 20
Hour.Cooled and filtered removes sodium propionate, and obtaining transparency liquid, 150 degree of oil pump extracts low-boiling-point substance again, obtains colourless transparent liquid
27.2g。1H-NMR(CDCl3,300MHz)δ[ppm]:7.68-7.65(m,2H,Ar-H),7.40-7.35(m,3H,Ar-H),
3.59(s,6H,OCH3),2.46(s,1H,-C≡C-H),1.90(br,2H),1.66-1.56(m,5H),1.22(br,1H).
Embodiment 9,Preparation
Equipped with magneton, reflux condensing tube, sequentially add in the 250ml three neck round bottom flask of bubbler and logical nitrogen device
24.8g (0.2mol) ethynylcyclohexanol, 30.4g (0.2mol) ethyl trimethoxy silane, 0.2g sodium carbonate, 70 degree of reactions 15
Hour, cooled and filtered removes sodium carbonate, obtains transparency liquid and extracts low boiling with 60 degree of vacuum distillations of oil pump again, then heats up 90 degree
Extract product.1H-NMR(CDCl3,300MHz)δ[ppm]:3.57(s,6H,Si-OCH3),2.51(s,1H,-C≡C-H),1.89
(br,2H),1.66-1.56(m,5H),1.55-1.48(m,2H),1.26(br,1H),1.01(t,3H,-CH3),0.602(q,
2H,-SiCH2-).
Embodiment 10,Preparation
Equipped with magneton, reflux condensing tube, sequentially add in the 250ml three neck round bottom flask of bubbler and logical nitrogen device
16.8g (0.2mol) methyl butynol, 41.6g (0.2mol) n-propyl triethoxysilane, 0.2g dibutyl tin laurates,
0.15g stannous iso caprylates.Obtain yellow liquid.80 degree are reacted 12 hours, and 50 degree of oil pump, which is evaporated under reduced pressure, removes low boiling, 80 degree of extractions
Product.Obtain colourless transparent liquid 42.6g.1H-NMR(CDCl3,300MHz)δ[ppm]:3.95-3.84(q,4H,OCH2-),
2.44(s,1H,-C≡C-H),1.61(s,6H,-CH3),1.45(m,2H,-CH2-),1.22(s,6H,-CH3),0.96(t,
3H,-CH3),0.69-0.62(m,2H,Si-CH2-).
Embodiment 11,Preparation
Equipped with magneton, reflux condensing tube, in the 250ml three neck round bottom flask of bubbler and logical nitrogen device successively plus
Enter 25.2g (0.3mol) methyl butynol, 25.0g (0.1mol) γ-methacryloxypropyl trimethoxy silane, 0.1g
Sodium propoxide.90 degree are reacted 24 hours.Reaction cools down after terminating, and is filtered to remove sodium propoxide.Again with oil pump 150 degree extract low boiling, obtain
To colourless transparent liquid 27g.1H-NMR(CDCl3,300MHz)δ[ppm]:6.09(s,1H),5.54(s,1H),4.11(t,2H,-
CH2-),3.57(s,6H,OCH3),2.45(s,1H,-C≡C-H),1.93(s,3H,-CH3),1.83-1.73(m,2H,-
CH2-),1.57(s,6H,-CH3),0.77-0.66(m,2H,Si-CH2-).
Embodiment 12,Preparation
Equipped with magneton, reflux condensing tube, sequentially add in the 250ml three neck round bottom flask of bubbler and logical nitrogen device
25.3g (0.3mol) methyl butynol, 23.6g (0.1mol) (2,3- the third oxygen of epoxy) propyl trimethoxy silicane, 0.1g carbonic acid
Potassium.90 degree are reacted 24 hours.Reaction cools down after terminating, and is filtered to remove potassium carbonate.150 degree of oil pump pumps low boiling, obtains colourless
Prescribed liquid 26.4g.1H-NMR(CDCl3,300MHz)δ[ppm]:3.62(d,1H,-CH2-),3.57-3.40(m,9H),3.14
(br,1H,-CH-),2.79-2.59(m,2H,-CH2-),2.46(s,1H,-C≡C-H),1.67-1.69(m,2H,-CH2),
1.57(s,6H,-CH3),0.64-0.70(m,2H,Si-CH2-).
Embodiment 13,Preparation
Equipped with magneton, reflux condensing tube, sequentially add in the 250ml three neck round bottom flask of bubbler and logical nitrogen device
20.8g (0.1mol) tetraethoxysilane, 16.8g (0.2mol) methyl butynol, 0.1g butyl titanates, 90 degree of reactions 12 are small
When.Yellow liquid is obtained, low boiling is gone with 50 degree of vacuum distillations of oil pump, then is warming up to 70 degree of extraction products, obtains water white transparency liquid
Body 24.8g.1H-NMR(CDCl3,300MHz)δ[ppm]:3.90-3.84(q,6H,OCH2-),2.43(s,1H,-C≡C-H),
1.59(s,6H,-CH3),1.48(m,6H,-CH2-)1.24(t,9H,-CH3).
Embodiment 14,Preparation
Equipped with magneton, reflux condensing tube, sequentially add in the 250ml three neck round bottom flask of bubbler and logical nitrogen device
12.4g (0.1mol) ethynylcyclohexanol, 76.8g (0.4mol) ethyl triethoxysilane, 0.1g Dibutyltin oxides.60 degree
Reaction 24 hours.Cooled and filtered removes Dibutyltin oxide, and 60 degree of vacuum distillations of oil pump are gone low boiling, 110 degree of extraction products, obtained
To colourless transparent liquid 28.1g.1H-NMR(CDCl3,300MHz)δ[ppm]:3.85-3.77(q,4H,OCH2-),2.51(s,
1H,-C≡C-H),1.89(br,2H),1.68-1.59(m,5H),1.58-1.49(m,2H),1.45(m,4H,-CH2-),1.30
(br,1H),1.22(t,6H,-CH3),1.03(t,3H,-CH3),0.63(q,2H,Si-CH2-).
Embodiment 15,Preparation
Equipped with magneton, reflux condensing tube, sequentially add in the 250ml three neck round bottom flask of bubbler and logical nitrogen device
12.4g (0.1mol) ethynylcyclohexanol, 39.6g (0.3mol) dimethoxymethylvinylchlane, 0.1g butyl titanates.40
Degree reaction 24 hours.50 degree of rear pump or output pump of cooling goes low boiling, 90 degree of extraction products, obtains water white transparency product 22.3g.1H-NMR
(CDCl3,300MHz)δ[ppm]:6.08-5.84 (m, 3H ,-CH=CH2),3.58(s,3H,OCH3),2.52(s,1H,-C≡C-
H),1.95(br,2H),1.68-1.59(m,5H),1.58-1.47(m,2H),1.27(br,1H),0.22(s,3H,Si-CH3).
Embodiment 16,Preparation
Equipped with magneton, reflux condensing tube, sequentially add in the 250ml three neck round bottom flask of bubbler and logical nitrogen device
25.2g (0.3mol) methyl butynol, 22.0g (0.1mol) 3- [oxygen of (2,3)-epoxy third] hydroxypropyl methyl dimethoxysilane,
0.1g sodium acetates, 90 degree of reaction 36h.Reaction terminates cooling, is filtered to remove sodium acetate, 120 degree of oil pump goes low boiling, obtained colourless
Prescribed liquid 25.8g.1H-NMR(CDCl3,300MHz)δ[ppm]:3.62(d,1H,-CH2-),3.57-3.40(m,6H),3.14
(br,1H,-CH-),2.79-2.59(m,2H,-CH2-),2.46(s,1H,-C≡C-H),1.67-1.69(m,2H,-CH2-),
1.57(s,6H,-CH3),0.64-0.70(m,2H,-CH2-),0.20(s,3H,Si-CH3).
Embodiment 17,Preparation
Equipped with magneton, reflux condensing tube, 25.2g is added in the 250ml three-necked flasks of bubbler and logical nitrogen device
(0.3mol) methyl butynol, 23.2g (0.1mol) γ-methacryloxypropyl trimethoxy silane, 0.1g potassium carbonate,
90 degree are reacted 24 hours.Reaction cools down after terminating, and is filtered to remove potassium carbonate, 120 degree of oil pump pumps low boiling, obtains water white transparency liquid
Body 27.2g.1H-NMR(CDCl3,300MHz)δ[ppm]:6.09(s,1H),5.54(s,1H),4.11(t,2H),3.57(s,3H,
OCH3),2.45(s,1H,-C≡C-H),1.93(s,3H,-CH3),1.83-1.73(m,2H,-CH2-),1.567(s,6H,-
CH3),0.77-0.66(m,2H, -CH2-),0.21(s,3H,-CH3).
Embodiment 18,Preparation
Equipped with magneton, reflux condensing tube, 16.8g is added in the 250ml three-necked flasks of bubbler and logical nitrogen device
(0.2mol) methyl butynol, 18.2g (0.1mol) aminomethyl phenyls and methoxy silane, 0.1g dibutyl tin laurates.60
Degree reaction 24 hours.100 degree of vacuum distillations of oil pump pump low boiling, 120 degree of extraction products, obtain colourless transparent liquid 29.0g.1H-NMR(CDCl3,300MHz)δ[ppm]:7.65-7.60(m,2H,Ar-H),7.41-7.35(m,3H,Ar-H),3.60(s,
6H,OCH3),2.43(s,1H,-C≡C-H),1.61(s,3H,-CH3),0.21(s,3H,-CH3).
Embodiment 19,Preparation
Equipped with magneton, reflux condensing tube, 8.4g is added in the 250ml three-necked flasks of bubbler and logical nitrogen device
(0.1mol) methyl butynol, 24.4g (0.1mol) dimethoxydiphenylsilane, 0.1g butyl titanates, 60 degree of reactions 24 are small
When, yellow liquid is obtained, low boiling is gone in 120 degree of vacuum distillations of oil pump, is being warming up to 160 degree of extraction products, is being obtained water white transparency liquid
Body 27.9g.1H-NMR(CDCl3,300MHz)δ[ppm]:7.65-7.60(m,4H,Ar-H),7.41-7.35(m,6H,Ar-H),
3.61(s,3H,OCH3),2.43(s,1H,-C≡C-H),1.63(s,3H,-CH3),0.21(s,3H,Si-CH3).
Embodiment 20,Preparation
Equipped with magneton, reflux condensing tube, 12.4g is added in the 250ml three-necked flasks of bubbler and logical nitrogen device
(0.1mol) ethynylcyclohexanol, 48g (0.4mol) dimethyldimethoxysil,ne, 0.1g stannous iso caprylates, 20 degree of reactions 24
Hour, yellow liquid is obtained, 60 degree of oil pump goes low boiling, and 80 degree of vacuum distillations of heating obtain colourless transparent liquid 22.1g.1H-NMR
(CDCl3,300MHz)δ[ppm]:3.55(s,3H,OCH3),2.50(s,1H,-C≡C-H),1.87(br,2H),1.63-1.55
(m,5H),1.54-1.46(m,2H),1.27(br,1H),0.20(s,6H,Si-CH3).
Embodiment 21,Preparation
Equipped with magneton, reflux condensing tube, the 250ml three-necked flasks of bubbler and logical nitrogen device sequentially add 8.4g
(0.1mol) methyl butynol, 26.8g (0.2mol) Methylethyl dimethoxysilane, 0.1g sodium carbonate.60 degree of reactions 12 are small
When.Cold filtration removes sodium carbonate, and 60 degree of vacuum distillations of water pump go low boiling, 90 degree of extraction products, obtain colourless transparent liquid
19.0g。 1H-NMR(CDCl3,300MHz)δ[ppm]:3.51(s,3H,OCH3),2.46(s,1H,-C≡C-H),1.59(6H,-
CH3),1.00(t,3H,-CH3),0.65(q,2H,-CH2-),0.19(3H,Si-CH3).
Embodiment 22,Preparation
Equipped with magneton, reflux condensing tube, the 250ml three-necked flasks of bubbler and logical nitrogen device sequentially add 8.4g
(0.1mol) methyl butynol, 14.8g (0.1mol) trimethoxysilyl propyl methacrylate TMOS, 0.1g stannous iso caprylates.80 degree of reactions
24 hours, yellow liquid is obtained, 60 degree of water pump goes low boiling, 90 degree of extraction products, obtains colourless transparent liquid 19.2g.1H-NMR
(CDCl3,300MHz)δ[ppm]:3.60(s,3H,OCH3)2.47(s,1H,-C≡C-H),1.61(s,6H,-CH3), 1.50 (m,
2H,-CH2-),0.96(t,3H,-CH3),0.69-0.62(m,2H,-CH2-),0.19(s,3H,Si-CH3).
Embodiment 23,Preparation
Equipped with magneton, reflux condensing tube, the 250ml three-necked flasks of bubbler and logical nitrogen device sequentially add 8.4g
(0.1mol) methyl butynol, 29.6g (0.2mol) diethyldimethoxysilane, 0.1g butyl titanates.90 degree of reactions 12 are small
When, yellow liquid is obtained, 60 degree of vacuum distillations of water pump go low boiling, 90 degree of extraction products, obtain colourless transparent liquid 19.7g.1H-NMR(CDCl3,300MHz)δ[ppm]:3.57(s,3H,OCH3),2.45(s,1H,-C≡C-H),1.58(6H,-CH3),
1.00(t,6H,-CH3),0.67(q,4H,Si-CH2-)。
Claims (3)
- A kind of 1. multifunction alkoxyl silicone alkanisation acetylene series Si―H addition reaction inhibitor, it is characterised in that：Structural formula is as follows：Wherein：R1For methyl or ethyl；R2For methoxyl group, ethyoxyl or methyl, ethyl, n-propyl, phenyl or vinyl；R3 For methoxyl group, ethyoxyl, methyl, ethyl, n-propyl, chain alkyl, phenyl, methacryloxypropyl or (2,3- epoxies third Oxygen) propyl group；The chain alkyl is CnH2n+1-, wherein n is positive integer, and n>3.
- 2. a kind of method for preparing multifunction alkoxyl silicone alkanisation acetylene series Si―H addition reaction inhibitor as claimed in claim 1, It is characterized in that：Step is as follows：Using methyl butynol or ethynylcyclohexanol as raw material, mixed with alkoxy silane, addition is urged Agent, after reacting 6-24 hours under the conditions of 20-100 degree, low-boiling-point substance is removed, product is obtained after directly obtaining product or distillation； Wherein alkoxysilane compound containing trialkylsilyl group in molecular structure and methyl butynol or the molar feed ratio of ethynylcyclohexanol compound are 0.25~4；The catalyst is one kind in tin compound, titanate ester compound, alkali carbonate or alkali metal acylate It is or several.
- 3. preparation method as claimed in claim 2, it is characterised in that：The tin compound is dibutyl tin dilaurate；Institute It is butyl titanate to state titanate ester compound；The alkali carbonate is potassium carbonate, the alkali metal acylate is second Sour sodium.
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| CN105778516B (en) * | 2016-03-30 | 2019-04-09 | 武汉大学 | A kind of add-on type curable silicone compositions |
| CN108841005B (en) * | 2018-05-21 | 2021-01-15 | 山东省科学院新材料研究所 | Hydrosilylation type silicone resin high-temperature catalysis inhibition system and preparation method and application thereof |
| CN109851629B (en) * | 2019-01-09 | 2020-08-25 | 上海交通大学 | Preparation method of silanized alkynyl inhibitor for single-component silicone rubber |
| JP7175249B2 (en) * | 2019-09-06 | 2022-11-18 | 信越化学工業株式会社 | Alkynyl group-containing organopolysiloxane and hydrosilylation reaction control agent |
| CN110628221A (en) * | 2019-09-16 | 2019-12-31 | 东莞新东方科技有限公司 | Silanization inhibitor and preparation method thereof |
| CN111100297A (en) * | 2020-01-08 | 2020-05-05 | 东莞新东方科技有限公司 | Preparation method of addition type liquid silicone rubber inhibitor silanized acetylene cyclohexanol |
| CN113444286B (en) * | 2021-08-13 | 2022-05-27 | 新元化学(山东)股份有限公司 | Addition type liquid fluorosilicone rubber inhibitor and preparation method thereof |
| CN114921220A (en) * | 2022-06-17 | 2022-08-19 | 惠州市浩明科技股份有限公司 | Pressure-sensitive adhesive and protective film suitable for polylactic acid resin base material and preparation method thereof |
| CN116854593B (en) * | 2023-09-04 | 2024-04-02 | 佛山市天宝利硅工程科技有限公司 | Esterified acetylenic hydrosilylation inhibitor, preparation method and liquid silicone rubber |
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