CN105418669A - Alkoxy silane acetylenic silicon hydrogen addition inhibitor and preparation method thereof - Google Patents
Alkoxy silane acetylenic silicon hydrogen addition inhibitor and preparation method thereof Download PDFInfo
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- CN105418669A CN105418669A CN201510900212.XA CN201510900212A CN105418669A CN 105418669 A CN105418669 A CN 105418669A CN 201510900212 A CN201510900212 A CN 201510900212A CN 105418669 A CN105418669 A CN 105418669A
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
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Abstract
本发明涉及烷氧基硅烷化炔属硅氢加成抑制剂及其制备方法。本发明以炔醇和烷氧基硅烷为主要原料，在催化剂作用下生成烷氧基硅烷化炔属硅氢加成的抑制剂。本发明制备方法简单，获得的硅氢加成抑制剂可以改善炔醇类抑制剂与基胶相容性差、易挥发以及残留物的毒性等缺点。在加成型液体硅橡胶中使用，可延长室温下保存期限，而且固化后硅橡胶表面光滑，同时抑制剂所连接的有机基团可以改善与基材的粘接，赋予胶料更好的粘接力。The present invention relates to alkoxysilylated acetylenic hydrosilylation inhibitors and processes for their preparation. The invention uses acetylenic alcohol and alkoxysilane as main raw materials to generate an alkoxysilylated acetylenic hydrosilylation inhibitor under the action of a catalyst. The preparation method of the invention is simple, and the obtained hydrosilylation inhibitor can improve the disadvantages of poor compatibility between the acetylenic alcohol inhibitor and the rubber base, easy volatilization, toxicity of residues, and the like. Used in addition-type liquid silicone rubber, it can prolong the shelf life at room temperature, and the surface of the silicone rubber is smooth after curing. At the same time, the organic group connected by the inhibitor can improve the adhesion to the substrate and give the rubber better adhesion. force.
Description
Technical field
The present invention relates to organosilicon material field, be specifically related to a kind of multifunction alkoxyl silicone alkanisation acetylene series Si―H addition reaction inhibitor and preparation method thereof.
Background technology
Addition reaction of silicon with hydrogen is from the people such as Sommer (SommerLH, PietruszaEW, WhitmoreFC.Peroxide-catalyzedadditionoftrichlorosilaneto 1-octene [J] .JournaloftheAmericanChemicalSociety, 1947,69 (1): 188-188.) since finding, become one of most important reaction in organosilicon chemistry, had a wide range of applications in synthesis carbon official energy silicoorganic compound/polymkeric substance, Carbonsilane dendrimer and addition-type silicon rubber sulfuration etc.Addition reaction of silicon with hydrogen speed needs to need to carry out appropriate regulation according to use.Such as in addition-type silicon rubber, for adapting to perfusion, coating or injection molding technique needs, after two the component mixing of dual composition addition type liquid silastic, require the serviceable time having more than 4 hours at least; Single-component add-on type liquid silicon rubber, under room temperature can long time stored ability meaningful.And must complete fast once generation hydrosilation reaction.In order to reach such object, modal is also that the most practical method adds Si―H addition reaction inhibitor exactly in hydrosilation system.Si―H addition reaction inhibitor effectively can suppress catalyst hydrosilation reaction in certain temperature range, and after being heated to curing temperature, Si―H addition reaction inhibitor loses inhibit feature and hydrosilation reaction is occurred fast.
At present, alkynol compound is use the most general Si―H addition reaction inhibitor as methylbutynol and ethynylcyclohexanol, at room temperature has good restraining effect.Si―H addition reaction inhibitor is can be used as United States Patent (USP) (US3445420) discloses alkynol compound.But these alkynol compound have easy volatile and the problem such as organosilicon systems poor compatibility and toxicity.Wherein easy volatile can cause in the mixing deaeration technique of inhibitor before two-component silicone rubber uses volatile, makes inhibitor content unstable, and after causing sulfuration, rubber surface wrinkle is uneven, also result in waste of raw materials and environment murder by poisoning.And due to the fusing point (30-33 DEG C) of ethynylcyclohexanol lower, at room temperature can solidify precipitation, affect sizing material stability in storage.Therefore, some obtain application to the mode that alkynol carries out modification.As the volatility in order to reduce alkynol compound, Dow Corning Corporation discloses a kind of silylated acetylenic inhibitor
(US3445420), this compounds can well be dissolved in sizing material, also reduces the yellow of reaction product simultaneously.But owing to losing the hydroxyl of alkynol, its volatility is still larger.The acetylene series inhibitor of the polysiloxane that methylhydrogenpolysi,oxane and alkynol are obtained by dehydrogenation reaction
(US3933882) volatility, toxicity and and the compatibility problem of sizing material, is completely solved.But its remaining silicon hydrogen will cause A glue stability in storage in two-component silicone rubber to be deteriorated.
In order to overcome current technological difficulties, the invention discloses a class multifunction alkoxyl silicone alkanisation acetylene series Si―H addition reaction inhibitor, significantly can reduce the volatility of alkynol class inhibitor, reduce the toxicity of residue, increase and the consistency of sizing material; Simultaneously active silicon alkoxyl group can react or self hydrolytic crosslinking with the white carbon black in sizing material or other compound containing activity hydroxy, participates in solidification; Also can react with base material the bonding force increasing sizing material and base material.
Summary of the invention
The present invention, in conjunction with the technical foundation of existing acetylene series Si―H addition reaction inhibitor, discloses class multifunction alkoxyl silicone alkanisation acetylene series Si―H addition reaction inhibitor and preparation method thereof.
Multifunction alkoxyl silicone alkanisation acetylene series Si―H addition reaction inhibitor provided by the present invention can significantly reduce alkynol class inhibitor volatility, increase and the consistency of sizing material, simultaneously active silicon alkoxyl group can react or self hydrolytic crosslinking with the white carbon black in sizing material or other compound containing activity hydroxy, participates in solidification.Also can react with base material the bonding force increasing sizing material and base material.
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 is as follows:
Wherein: R
1for methyl or ethyl; R
2for methoxyl group, oxyethyl group or methyl, ethyl, n-propyl, phenyl or vinyl; R
3for methoxyl group, oxyethyl group, methyl, ethyl, n-propyl, chain alkyl (C
nh
2n+1-, its n>3), phenyl, methacryloxypropyl or (2,3-epoxy third oxygen) propyl group.
The present invention also provides the method preparing above-mentioned multifunction alkoxyl silicone alkanisation acetylene series Si―H addition reaction inhibitor, step is as follows: with methylbutynol or ethynylcyclohexanol for raw material, mix with organoalkoxysilane, add catalyzer, react 6-24 hour under 20-100 degree condition after, removing low-boiling-point substance, obtains product after directly obtaining product or distillation;
Wherein the molar feed ratio of alkoxysilane compound containing trialkylsilyl group in molecular structure and methylbutynol or ethynylcyclohexanol compound is 0.25 ~ 4;
Described catalyzer is one or more in tin compound, titanate ester compound, alkaline carbonate or basic metal organic acid salt.
Described tin compound is dibutyl tin dilaurate; Described titanate ester compound is tetrabutyl titanate; Described alkaline carbonate is salt of wormwood, described basic metal organic acid salt is sodium acetate.
Beneficial effect of the present invention is embodied in:
1, multifunction alkoxyl silicone alkanisation acetylene series Si―H addition reaction inhibitor overcomes methylbutynol and ethynylcyclohexanol as Si―H addition reaction inhibitor consistency and volatile problem, makes the sizing material smooth surface after solidification smooth.
2, multifunction alkoxyl silicone alkanisation acetylene series Si―H addition reaction inhibitor can participate in other reaction and combine together with sizing material, the toxicity problem solving volatility and remain and cause while suppression hydrosilation reaction.
3, the organic group that multifunction alkoxyl silicone alkanisation acetylene series Si―H addition reaction inhibitor connects can improve the bonding problem with base material, gives sizing material better bonding force.
4, synthetic route is simple, and generate without side reaction product, raw material is cheaply easy to get, reaction favorable reproducibility.
Embodiment
Following examples further illustrate content of the present invention, but should not be construed as limitation of the present invention.Without departing from the spirit and substance of the case in the present invention, the amendment do the inventive method, step or condition or replacement, all belong to scope of the present invention.
Embodiment one,
preparation
Magneton is being housed, reflux condensing tube, 8.4g (0.1mol) methylbutynol is added successively, 30.4g (0.2mol) tetramethoxy-silicane, 0.1g dibutyl tin dilaurate in three mouthfuls of round-bottomed flasks of the 250ml of bubbler and logical nitrogen device.React 6 hours at 60 degree of temperature, obtain weak yellow liquid.Be cooled to room temperature, oil pump underpressure distillation removing low-boiling-point substance, underpressure distillation obtains colourless transparent liquid 21.7g.
1H-NMR(CDCl
3)δ[ppm]:3.59(s,9H,OCH
3),2.45(s,1H,-C≡C-H),1.58(s,6H,-CH
3)
Embodiment two,
preparation
Magneton is being housed, reflux condensing tube, is adding successively in 250ml tri-mouthfuls of round-bottomed flasks of bubbler and logical nitrogen device, 12.4g (0.1mol) ethynylcyclohexanol, 30.4g (0.2mol) tetramethoxy-silicane, 0.1g butyl (tetra) titanate.React 24 hours at 60 degree of temperature, obtain blood red liquid.Cooling, oil pump underpressure distillation removing low-boiling-point substance, then be warming up to 90 degree, extract product, obtain colourless transparent liquid 24.0g.
1H-NMR(CDCl
3,300MHz)δ[ppm]:3.60(s,9H,OCH
3)，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
Magneton is being housed, reflux condensing tube, adds 12.6g (0.15mol) methylbutynol, 44.4g (0.3mol) vinyltrimethoxy silane in 250ml tri-mouthfuls of round-bottomed flasks of bubbler and logical nitrogen device successively, 0.15g stannous iso caprylate, 90 degree of reactions 6 hours.After cooling, obtain weak yellow liquid, oil pump underpressure distillation removing low-boiling-point substance, then be warming up to 60 degree of extraction products, obtain colourless transparent liquid 29.5g.
1H-NMR(CDCl
3,300MHz)δ[ppm]:6.16-5.88(m,3H,-CH＝CH
2),3.58(s,6H,OCH
3),2.45(s,1H,-C≡C-H),1.59(s,6H,-CH
3)
Embodiment 4,
preparation
Magneton is being housed, reflux condensing tube, 14.2g ethynylcyclohexanol (0.11mol) successively in 250ml tri-mouthfuls of round-bottomed flasks of bubbler and logical nitrogen device, 33.8g (0.23mol) vinyltrimethoxy silane, 0.12g salt of wormwood, 20 degree of reactions 20 hours.After cooling, centrifuging removing salt of wormwood.Oil pump underpressure distillation removing low-boiling-point substance, then be warming up to 90 degree of extraction products, obtain colourless transparent liquid 25.9g.
1H-NMR(CDCl
3,300MHz)δ[ppm]:6.11-5.89(m,3H，-CH＝CH
2),3.54(s,9H,OCH
3),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
Magneton is being housed, reflux condensing tube, in 250ml tri-mouthfuls of round-bottomed flasks of bubbler and logical nitrogen device, is adding 25.2g (0.3mol) methylbutynol successively, 40.8g (0.3mol) methyltrimethoxy silane, 0.3g sodium acetate.20 degree of reactions 18 hours.After cooling, centrifuging removing sodium acetate.Water pump underpressure distillation removing low-boiling-point substance, then the 90 degree of extraction products that heat up, obtain water white transparency product 55.41g.
1H-NMR(CDCl
3,300MHz)δ[ppm]:3.55(s,6H,OCH
3),2.45(s,1H,-C≡C-H),1.57(s,6H,-CH
3),0.22(s,3H,Si-CH
3)
Embodiment 6,
preparation
Magneton is being housed, reflux condensing tube, 12.4g (0.1mol) ethynylcyclohexanol is added successively in 250ml tri-mouthfuls of round-bottomed flasks of bubbler and logical nitrogen device, 27.2g (0.2mol) methyltrimethoxy silane, 0.1g dibutyl tin dilaurate, 40 degree of reactions 24 hours.After cooling, obtain yellow liquid, oil pump underpressure distillation removing is low boil after, then be warming up to 90 degree and extract product, obtain colourless transparent liquid 22.60g.
1H-NMR(CDCl
3,300MHz)δ[ppm]:3.55(s,6H,OCH
3),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-CH
3)
Embodiment 7,
preparation
Magneton is being housed, reflux condensing tube, adds 25.2g (0.3mol) methylbutynol, 25.0g (0.126mol) phenyltrimethoxysila,e in 250ml tri-mouthfuls of round-bottomed flasks of bubbler and logical nitrogen device successively, 0.2g stannous iso caprylate, 90 degree of reactions 24 hours.Obtain yellow liquid.Oil pump 90 degree of underpressure distillation go out low boiling, then heat up 120 degree, distill out product, obtain colourless transparent liquid 30g.
1H-NMR(CDCl
3,300MHz)δ[ppm]:7.70-7.68(m,2H,Ar-H),7.44-7.37(m,3H,Ar-H),3.63(s,6H,OCH
3),2.42(s,1H,-C≡C-H),1.61(s,6H,-CH
3).
Embodiment 8,
preparation
Magneton is being housed, reflux condensing tube, adds 49.6g (0.4mol) ethynylcyclohexanol, 19.6g (0.1mol) phenyltrimethoxysila,e in 250ml tri-mouthfuls of round-bottomed flasks of bubbler and logical nitrogen device successively, 0.2g Sodium Propionate, 90 degree of reactions 20 hours.Cooled and filtered removing Sodium Propionate, obtain transparent liquid again 150 degree, oil pump extract low-boiling-point substance, obtain colourless transparent liquid 27.2g.
1H-NMR(CDCl
3,300MHz)δ[ppm]:7.68-7.65(m,2H,Ar-H),7.40-7.35(m,3H,Ar-H),3.59(s,6H,OCH
3),2.46(s,1H,-C≡C-H),1.90(br,2H),1.66-1.56(m,5H),1.22(br,1H).
Embodiment 9,
preparation
Magneton is being housed, reflux condensing tube, 24.8g (0.2mol) ethynylcyclohexanol is added successively in 250ml tri-mouthfuls of round-bottomed flasks of bubbler and logical nitrogen device, 30.4g (0.2mol) ethyl trimethoxy silane, 0.2g sodium carbonate, 70 degree of reactions 15 hours, cooled and filtered removing sodium carbonate, obtain transparent liquid and extract low boiling with oil pump 60 degree of underpressure distillation again, then the 90 degree of extraction products that heat up.
1H-NMR(CDCl
3,300MHz)δ[ppm]:3.57(s,6H,Si-OCH
3),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,-CH
3),0.602(q,2H,-SiCH
2-).
Embodiment 10,
preparation
Magneton is being housed, reflux condensing tube, 16.8g (0.2mol) methylbutynol is added successively in 250ml tri-mouthfuls of round-bottomed flasks of bubbler and logical nitrogen device, 41.6g (0.2mol) n-propyl triethoxyl silane, 0.2g dibutyl tin laurate, 0.15g stannous iso caprylate.Obtain yellow liquid.80 degree of reactions 12 hours, oil pump 50 degree of underpressure distillation removings are low boils, 80 degree extraction products.Obtain colourless transparent liquid 42.6g.
1H-NMR(CDCl
3,300MHz)δ[ppm]:3.95-3.84(q,4H,OCH
2-),2.44(s,1H,-C≡C-H),1.61(s,6H,-CH
3),1.45(m,2H,-CH
2-),1.22(s,6H,-CH
3),0.96(t,3H,-CH
3),0.69-0.62(m,2H,Si-CH
2-).
Embodiment 11,
preparation
Magneton is being housed, reflux condensing tube, 25.2g (0.3mol) methylbutynol is added successively, 25.0g (0.1mol) γ-methacryloxypropyl trimethoxy silane, 0.1g sodium propylate in 250ml tri-mouthfuls of round-bottomed flasks of bubbler and logical nitrogen device.90 degree of reactions 24 hours.Reaction terminates rear cooling, crosses and filters sodium propylate.Extract low boiling with 150 degree, oil pump again, obtain colourless transparent liquid 27g.
1H-NMR(CDCl
3,300MHz)δ[ppm]:6.09(s,1H),5.54(s,1H),4.11(t,2H,-CH
2-),3.57(s,6H,OCH
3),2.45(s,1H,-C≡C-H),1.93(s,3H,-CH
3),1.83-1.73(m,2H,-CH
2-),1.57(s,6H,-CH
3),0.77-0.66(m,2H,Si-CH
2-).
Embodiment 12,
preparation
Magneton is being housed, reflux condensing tube, adds 25.3g (0.3mol) methylbutynol, 23.6g (0.1mol) (2 in 250ml tri-mouthfuls of round-bottomed flasks of bubbler and logical nitrogen device successively, 3-epoxy third oxygen) propyl trimethoxy silicane, 0.1g salt of wormwood.90 degree of reactions 24 hours.Reaction terminates rear cooling, crosses and filters salt of wormwood.150 degree, oil pump pumps low boiling, and obtains colourless transparent liquid 26.4g.
1H-NMR(CDCl3,300MHz)δ[ppm]:3.62(d,1H,-CH
2-),3.57-3.40(m,9H),3.14(br,1H,-CH-),2.79-2.59(m,2H,-CH
2-),2.46(s,1H,-C≡C-H),1.67-1.69(m,2H,-CH
2),1.57(s,6H,-CH
3),0.64-0.70(m,2H,Si-CH
2-).
Embodiment 13,
preparation
Magneton is being housed, reflux condensing tube, adds 20.8g (0.1mol) tetraethoxysilane, 16.8g (0.2mol) methylbutynol in 250ml tri-mouthfuls of round-bottomed flasks of bubbler and logical nitrogen device successively, 0.1g butyl (tetra) titanate, 90 degree of reactions 12 hours.Obtain yellow liquid, go low boiling with oil pump 50 degree of underpressure distillation, then be warming up to 70 degree of extraction products, obtain colourless transparent liquid 24.8g.
1H-NMR(CDCl
3,300MHz)δ[ppm]:3.90-3.84(q,6H,OCH
2-),2.43(s,1H,-C≡C-H),1.59(s,6H,-CH
3),1.48(m,6H,-CH
2-)1.24(t,9H,-CH
3).
Embodiment 14,
preparation
Magneton is being housed, reflux condensing tube, 12.4g (0.1mol) ethynylcyclohexanol is added successively, 76.8g (0.4mol) ethyl triethoxysilane, 0.1g Dibutyltin oxide in 250ml tri-mouthfuls of round-bottomed flasks of bubbler and logical nitrogen device.60 degree of reactions 24 hours.Cooled and filtered removing Dibutyltin oxide, low boiling is gone in oil pump 60 degree of underpressure distillation, and 110 degree are extracted product, obtain colourless transparent liquid 28.1g.
1H-NMR(CDCl
3,300MHz)δ[ppm]:3.85-3.77(q,4H,OCH
2-),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,-CH
2-),1.30(br,1H),1.22(t,6H,-CH
3),1.03(t,3H,-CH
3),0.63(q,2H,Si-CH
2-).
Embodiment 15,
preparation
Magneton is being housed, reflux condensing tube, 12.4g (0.1mol) ethynylcyclohexanol is added successively, 39.6g (0.3mol) dimethoxymethylvinylchlane, 0.1g butyl (tetra) titanate in 250ml tri-mouthfuls of round-bottomed flasks of bubbler and logical nitrogen device.40 degree of reactions 24 hours.Cooling rear pump or output pump 50 degree goes low boiling, and 90 degree are extracted product, obtain water white transparency product 22.3g.
1H-NMR(CDCl
3,300MHz)δ[ppm]:6.08-5.84(m,3H,-CH＝CH
2),3.58(s,3H,OCH
3),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-CH
3).
Embodiment 16,
preparation
Magneton is being housed, reflux condensing tube, 25.2g (0.3mol) methylbutynol is added successively in 250ml tri-mouthfuls of round-bottomed flasks of bubbler and logical nitrogen device, 22.0g (0.1mol) 3-[(2,3)-epoxy third oxygen] hydroxypropyl methyl dimethoxysilane, 0.1g sodium acetate, 90 degree of reaction 36h.Reaction terminates cooling, and cross and filter sodium acetate, 120 degree, oil pump goes low boiling, and obtains colourless transparent liquid 25.8g.
1H-NMR(CDCl
3,300MHz)δ[ppm]:3.62(d,1H,-CH
2-),3.57-3.40(m,6H),3.14(br,1H,-CH-),2.79-2.59(m,2H,-CH
2-),2.46(s,1H,-C≡C-H),1.67-1.69(m,2H,-CH
2-),1.57(s,6H,-CH
3),0.64-0.70(m,2H,-CH
2-),0.20(s,3H,Si-CH
3).
Embodiment 17,
preparation
Magneton is being housed, reflux condensing tube, adds 25.2g (0.3mol) methylbutynol in the 250ml there-necked flask of bubbler and logical nitrogen device, 23.2g (0.1mol) γ-methacryloxypropyl trimethoxy silane, 0.1g salt of wormwood, 90 degree of reactions 24 hours.Reaction terminates rear cooling, and cross and filter salt of wormwood, 120 degree, oil pump pumps low boiling, and obtains colourless transparent liquid 27.2g.
1H-NMR(CDCl
3,300MHz)δ[ppm]:6.09(s,1H),5.54(s,1H),4.11(t,2H),3.57(s,3H,OCH
3),2.45(s,1H,-C≡C-H),1.93(s,3H,-CH
3),1.83-1.73(m,2H,-CH
2-),1.567(s,6H,-CH
3),0.77-0.66(m,2H,-CH
2-),0.21(s,3H,-CH
3).
Embodiment 18,
preparation
Magneton is being housed, reflux condensing tube, in the 250ml there-necked flask of bubbler and logical nitrogen device, is adding 16.8g (0.2mol) methylbutynol, 18.2g (0.1mol) aminomethyl phenyl and methoxy silane, 0.1g dibutyl tin laurate.60 degree of reactions 24 hours.Oil pump 100 degree of underpressure distillation pump low boiling, and 120 degree are extracted product, obtain colourless transparent liquid 29.0g.
1H-NMR(CDCl
3,300MHz)δ[ppm]:7.65-7.60(m,2H,Ar-H),7.41-7.35(m,3H,Ar-H),3.60(s,6H,OCH
3),2.43(s,1H,-C≡C-H),1.61(s,3H,-CH
3),0.21(s,3H,-CH
3).
Embodiment 19,
preparation
Magneton is being housed, reflux condensing tube, 8.4g (0.1mol) methylbutynol is added in the 250ml there-necked flask of bubbler and logical nitrogen device, 24.4g (0.1mol) dimethoxydiphenylsilane, 0.1g butyl (tetra) titanate, 60 degree of reactions 24 hours, obtain yellow liquid, low boiling is gone in oil pump 120 degree of underpressure distillation, being warming up to 160 degree of extraction products, obtains colourless transparent liquid 27.9g.
1H-NMR(CDCl
3,300MHz)δ[ppm]:7.65-7.60(m,4H,Ar-H),7.41-7.35(m,6H,Ar-H),3.61(s,3H,OCH
3),2.43(s,1H,-C≡C-H),1.63(s,3H,-CH
3),0.21(s,3H,Si-CH
3).
Embodiment 20,
preparation
Magneton is being housed, reflux condensing tube, 12.4g (0.1mol) ethynylcyclohexanol is added in the 250ml there-necked flask of bubbler and logical nitrogen device, 48g (0.4mol) dimethyldimethoxysil,ne, 0.1g stannous iso caprylate, 20 degree of reactions 24 hours, obtain yellow liquid, 60 degree, oil pump goes low boiling, and the 80 degree of underpressure distillation that heat up obtain colourless transparent liquid 22.1g.
1H-NMR(CDCl
3,300MHz)δ[ppm]:3.55(s,3H,OCH
3),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-CH
3).
Embodiment 21,
preparation
Magneton is being housed, reflux condensing tube, the 250ml there-necked flask of bubbler and logical nitrogen device adds 8.4g (0.1mol) methylbutynol successively, 26.8g (0.2mol) methylethyl dimethoxysilane, 0.1g sodium carbonate.60 degree of reactions 12 hours.Cold filtration removing sodium carbonate, low boiling is gone in water pump 60 degree of underpressure distillation, and 90 degree are extracted product, obtain colourless transparent liquid 19.0g.
1H-NMR(CDCl
3,300MHz)δ[ppm]:3.51(s,3H,OCH
3),2.46(s,1H,-C≡C-H),1.59(6H,-CH
3),1.00(t,3H,-CH
3),0.65(q,2H,-CH
2-),0.19(3H,Si-CH
3).
Embodiment 22,
preparation
Magneton is being housed, reflux condensing tube, the 250ml there-necked flask of bubbler and logical nitrogen device adds 8.4g (0.1mol) methylbutynol successively, 14.8g (0.1mol) trimethoxysilyl propyl methacrylate TMOS, 0.1g stannous iso caprylate.80 degree of reactions 24 hours, obtain yellow liquid, 60 degree, water pump goes low boiling, and 90 degree are extracted products, obtain colourless transparent liquid 19.2g.
1H-NMR(CDCl
3,300MHz)δ[ppm]:3.60(s,3H,OCH
3)2.47(s,1H,-C≡C-H),1.61(s,6H,-CH
3)，1.50(m,2H,-CH
2-),0.96(t,3H,-CH
3),0.69-0.62(m,2H,-CH
2-),0.19(s,3H,Si-CH
3).
Embodiment 23,
preparation
Magneton is being housed, reflux condensing tube, the 250ml there-necked flask of bubbler and logical nitrogen device adds 8.4g (0.1mol) methylbutynol successively, 29.6g (0.2mol) diethyldimethoxysilane, 0.1g butyl (tetra) titanate.90 degree of reactions 12 hours, obtain yellow liquid, low boiling is gone in water pump 60 degree of underpressure distillation, and 90 degree are extracted products, obtain colourless transparent liquid 19.7g.
1H-NMR(CDCl
3,300MHz)δ[ppm]:3.57(s,3H,OCH
3),2.45(s,1H,-C≡C-H),1.58(6H,-CH
3),1.00(t,6H,-CH
3),0.67(q,4H,Si-CH
2-)。
Claims (3)
1. a multifunction alkoxyl silicone alkanisation acetylene series Si―H addition reaction inhibitor, is characterized in that: structural formula is as follows:
Wherein: R
1for methyl or ethyl; R
2for methoxyl group, oxyethyl group or methyl, ethyl, n-propyl, phenyl or vinyl; R
3for methoxyl group, oxyethyl group, methyl, ethyl, n-propyl, chain alkyl (C
nh
2n+1-, its n>3), phenyl, methacryloxypropyl or (2,3-epoxy third oxygen) propyl group.
2. prepare the method for multifunction alkoxyl silicone alkanisation acetylene series Si―H addition reaction inhibitor as claimed in claim 1 for one kind, it is characterized in that: step is as follows: with methylbutynol or ethynylcyclohexanol for raw material, mix with organoalkoxysilane, add catalyzer, react 6-24 hour under 20-100 degree condition after, removing low-boiling-point substance, obtains product after directly obtaining product or distillation; Wherein the molar feed ratio of alkoxysilane compound containing trialkylsilyl group in molecular structure and methylbutynol or ethynylcyclohexanol compound is 0.25 ~ 4;
Described catalyzer is one or more in tin compound, titanate ester compound, alkaline carbonate or basic metal organic acid salt.
3. preparation method as claimed in claim 2, is characterized in that: described tin compound is dibutyl tin dilaurate; Described titanate ester compound is tetrabutyl titanate; Described alkaline carbonate is salt of wormwood, described basic metal organic acid salt is sodium acetate.
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| CN105778516A (en) * | 2016-03-30 | 2016-07-20 | 武汉大学 | Addition type solidifiable polysiloxane composition |
| CN108841005A (en) * | 2018-05-21 | 2018-11-20 | 山东省科学院新材料研究所 | Si―H addition reaction type silicone resin high-temperature catalytic inhibition system and its preparation method and application |
| CN109851629A (en) * | 2019-01-09 | 2019-06-07 | 上海交通大学 | A kind of preparation method of single-component silicon rubber silanization alkynyl inhibitor |
| 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 |
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