CN104262631A - Low molecular weight linear amino-terminated silicon oil and synthetic method thereof - Google Patents
Low molecular weight linear amino-terminated silicon oil and synthetic method thereof Download PDFInfo
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Abstract
The invention discloses low molecular weight linear amino-terminated silicon oil and a synthetic method thereof. The synthetic method comprises the following steps: taking dried and dehydrated cyclomethylsiloxane, amino head sealing agent, functionalized cyclosiloxane and a basic catalyst as reaction raw materials in a ratio of parts by mass of 100 to (5.0-30.0) to (0-20.0), wherein the basic catalyst accounts for 0.001-0.01% of total mass of cyclomethylsiloxane, amino head sealing agent and functionalized cyclosiloxane; then, mixing the reaction raw materials, and then reacting for 6-12 hours at 80-120 DEG C under protection of dried nitrogen; and then, removing the basic catalyst, decompressing and distilling to remove low-boiling-point substances under protection of nitrogen, and cooling to room temperature to obtain the low molecular weight linear amino-terminated silicon oil. The molecular weight of the low molecular weight linear amino-terminated silicon oil synthesized by the synthetic method is less than 4000, and the viscosity is less than 100mm<2>/s.
Description
[technical field]
The present invention relates to a kind of amido silicon oil and synthetic method thereof, particularly the linear Amino End Group silicone oil of a kind of lower molecular weight and synthetic method thereof.
[background technology]
Amido silicon oil is containing amino polydimethylsiloxane in side chain or end group.Amido silicon oil is except having the intrinsic hydrophobicity of dimethyl silicone oil and release property, its reactivity, adsorptivity, oilness, flexibilities etc. are also given in the existence of ammonia alkyl, are extensively used as fibre trimmer, modifier, releasing agent, daily cosmetics additive etc.
Current domestic and international market has the amido silicon oil compared with multi items, but these amido silicon oils are nearly all with amino on side chain, and end group with amino linear silicone oils because of its structure unique, have special performance in developing at urethane, polyureas, novel elastomer and become the novel product of amido silicon oil gradually, its application is by increasingly extensive.
Present researchist has done much research in the preparation of Amino End Group silicone oil, in patent CN103087323A, disclose a kind of synthetic method of double-end amino silicone oil, the method comprises two steps, first catalyzer is joined together with chlorallylene in end hydrogen silicone oil, reacting by heating, steams fugitive constituent, obtains two chloropropyl siloxanes; Then above-mentioned material is transferred in autoclave, import liquefied ammonia, compressive reaction, then decompression steams fugitive constituent, obtains target product double-end amino silicone oil.Need condition of high voltage in this patent reaction process, pressure is 5 ~ 8MPa.In patent CN102796265A, disclose a kind of preparation method of linear amino-silicone oil, the method comprises two steps, first by the obtained amido silicon oil of silicon oil of low hydrogen content, solvent, organic amine and platinum catalyst reaction, then amido silicon oil and epoxy compounds reaction are obtained epoxy-modified linear amino-silicone oil.The molecular weight of this linear amino-silicone oil is high, and the viscosity of linear amino-silicone oil obtained in embodiment is at more than 10000mPas; The mass percentage 0.05 ~ 1% of platinum in the platinum catalyst used, the mass percent that the consumption of platinum catalyst accounts for total charging capacity is 0.1 ~ 2%.In patent CN103172867A, disclose the preparation method of a kind of long chain alkane and epoxy co-modified double-end amino silicone oil, first the method has obtained by octamethylcyclotetrasiloxane, long chain alkane silane coupling agent, double-end amino silane end-cappers the modification double-end amino silicone oil that side chain contains long chain alkane under the effect of basic catalyst, and then and epichlorohydrin reaction, epoxide modified group is introduced by the amino of both-end, thus obtaining long chain alkane and epoxy co-modified double-end amino silicone oil, the viscosity of this silicone oil under 25 DEG C of conditions is 1000 ~ 10000mPs.
In US Patent No. 5276122A, disclose a kind of method preparing the amido silicon oil with homogeneous molecular weight, in the method, adopt cyclosiloxane, the ring-opening polymerization under the effect of basic catalyst of low-molecular-weight Amino End Group polysiloxane obtains amido silicon oil.Low-molecular-weight Amino End Group polysiloxane end socket yet there are no commercial product, must synthesize voluntarily, and the molecular weight of silicone oil obtained in embodiment is higher, all more than 8000.
In the modification of organosilicon sealant and the preparation of organosilicon new polymers, need a kind of low-molecular-weight Amino End Group silicone oil, molecular weight lower than 4000 or viscosity lower than 100mm
2/ s, as chainextender and reaction prepolymer.The present invention selects cyclosiloxane for this reason, amino closure agent is main raw material, synthesizes the linear Amino End Group silicone oil of a kind of lower molecular weight by the method for base catalysis anionic ring-opening polymerization.
[summary of the invention]
[technical problem that will solve]
The object of this invention is to provide the synthetic method of the linear Amino End Group silicone oil of a kind of lower molecular weight;
Another object of the present invention is to provide the linear Amino End Group silicone oil of a kind of lower molecular weight.
[technical scheme]
The present invention is achieved through the following technical solutions.
Technical scheme of the present invention is: select methyl cyclosiloxane, amino closure agent, functionalized cyclosiloxane to be main raw material, adopts the method for base catalysis anionic ring-opening polymerization to prepare the linear Amino End Group silicone oil of a kind of lower molecular weight.
The invention provides the synthetic method of the linear Amino End Group silicone oil of a kind of lower molecular weight, the step of this synthetic method is as follows:
A, raw material mixing and building-up reactions: according to mass parts than 100:5.0 ~ 30.0:0 ~ 20.0 get drying dewater after methyl cyclosiloxane, amino closure agent, functionalized cyclosiloxane and basic catalyst as reaction raw materials, wherein the quality of basic catalyst is 0.001% ~ 0.01% of methyl cyclosiloxane, amino closure agent and functionalized cyclosiloxane total mass; Then under drying nitrogen protection, at temperature 80 ~ 120 DEG C, 6 ~ 12h is reacted after being mixed by reaction raw materials;
B, remove basic catalyst and remove low-boiling-point substance: reacted for steps A product is removed basic catalyst, then underpressure distillation removing low-boiling-point substance under nitrogen protection, is cooled to room temperature, namely obtains the linear Amino End Group silicone oil of described lower molecular weight.
According to the preferred embodiment of the present invention, described functionalized cyclosiloxane is that one or more are selected from the functionalized cyclosiloxane of t etram-ethyltetravinylcyclotetrasiloxane, tetramethyl tetraphenyl cyclotetrasiloxane, octaphenylcyclotetrasiloxane.
According to the preferred embodiment of the present invention, described methyl cyclosiloxane is that one or more are selected from hexamethyl cyclotrisiloxane (abbreviation D
3), octamethylcyclotetrasiloxane (be called for short D
4), decamethylcyclopentaandoxane (be called for short D
5) or the methyl cyclosiloxane of dimethyl siloxane mixed methylcyclosiloxane (be called for short DMC).
According to the preferred embodiment of the present invention, described amino closure agent is that one or more are selected from two (the 3-aminopropyl)-1 of 1,3-, 1,3,3-tetramethyl disiloxane, 1, two (the N-β-aminoethyl-γ-aminopropyl)-1,1,3 of 3-, 3-tetramethyl disiloxane, 1,3-two (n-formyl sarcolysine base-3-aminopropyl)-1,1,3,3-tetramethyl disiloxane, 1,3-two (pyridyl-3-aminopropyl)-1, the amino closure agent of 1,3,3-tetramethyl disiloxane.
According to the preferred embodiment of the present invention, described basic catalyst is that one or more are selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, Tetramethylammonium hydroxide or lithium hydroxide, sodium hydroxide, potassium hydroxide, Tetramethylammonium hydroxide react obtained silicon alkoxide respectively basic catalyst with methyl cyclosiloxane.
According to the preferred embodiment of the present invention, raw material mixing described in steps A and building-up reactions are a step feeding method or substep feeding method, a described step feeding method be according to mass parts than 100:5.0 ~ 30.0:0 ~ 20.0 get drying dewater after methyl cyclosiloxane, amino closure agent, functionalized cyclosiloxane mix with basic catalyst, wherein the quality of basic catalyst is 0.001% ~ 0.01% of methyl cyclosiloxane, amino closure agent and functionalized cyclosiloxane total mass; Then under drying nitrogen protection, at temperature 80 ~ 120 DEG C, 6 ~ 12h is reacted;
Described substep feeding method be according to mass parts than 100:5.0 ~ 30.0:0 ~ 20.0 get drying dewater after methyl cyclosiloxane, amino closure agent, functionalized cyclosiloxane and basic catalyst as reaction raw materials, wherein the quality of basic catalyst is 0.001% ~ 0.01% of methyl cyclosiloxane, amino closure agent and functionalized cyclosiloxane total mass; Then by the methyl cyclosiloxane of 40 ~ 60%, whole amino closure agents, whole functionalized cyclosiloxane, 40 ~ 60% basic catalyst mixing or the amino closure agent of 40% ~ 60%, whole methyl cyclosiloxane, whole functionalized cyclosiloxane, 50 ~ 80% basic catalyst mixing; then under drying nitrogen protection, at temperature 80 ~ 120 DEG C, react 2 ~ 4h, then continue after remaining reaction raw materials being added mixing at temperature 80 ~ 120 DEG C, to react 3 ~ 8h under drying nitrogen protection.
According to the preferred embodiment of the present invention, the method that the drying described in steps A dewaters to dewater 1 ~ 3h or pass into drying nitrogen and to dewater under temperature 40 ~ 60 DEG C, vacuum tightness-0.095 ~-0.08MPa 0.5 ~ 1h for passing into drying nitrogen at temperature 80 ~ 120 DEG C.
According to the preferred embodiment of the present invention, the method for the removal basic catalyst described in step B be add with the mineral acid of basic catalyst equivalent, organic acid in and basic catalyst, or by be warming up to 130 ~ 160 DEG C remove basic catalysts.
According to the preferred embodiment of the present invention, the method removing low-boiling-point substance described in step B is under nitrogen protection in temperature 110 ~ 150 DEG C, vacuum tightness-0.09MPa and carry out underpressure distillation, till oozing without low-boiling-point substance in 5min above.
Present invention also offers a kind of linear Amino End Group silicone oil of lower molecular weight adopting described synthetic method synthesis, it has following characteristic: molecular weight is lower than 4000; Viscosity is less than 100mm
2/ s.
The present invention is further illustrated below.
The invention provides the synthetic method of the linear Amino End Group silicone oil of a kind of lower molecular weight, the step of this synthetic method is as follows:
A, raw material mixing and building-up reactions: according to mass parts than 100:5.0 ~ 30.0:0 ~ 20.0 get drying dewater after methyl cyclosiloxane, amino closure agent, functionalized cyclosiloxane and basic catalyst as reaction raw materials, wherein the quality of basic catalyst is 0.001% ~ 0.01% of methyl cyclosiloxane, amino closure agent and functionalized cyclosiloxane total mass; Then under drying nitrogen protection, at temperature 80 ~ 120 DEG C, 6 ~ 12h is reacted after being mixed by reaction raw materials;
B, remove basic catalyst and remove low-boiling-point substance: reacted for steps A product is removed basic catalyst, then underpressure distillation removing low-boiling-point substance under nitrogen protection, is cooled to room temperature, namely obtains the linear Amino End Group silicone oil of described lower molecular weight;
Functionalized cyclosiloxane described in the present invention is the functionalized cyclosiloxane being selected from t etram-ethyltetravinylcyclotetrasiloxane, tetramethyl tetraphenyl cyclotetrasiloxane, octaphenylcyclotetrasiloxane.
In the present invention, functionalized cyclosiloxane is to introduce vinyl group or phenyl group at amido silicon oil molecule, making this amido silicon oil have more performance.
In the present invention, methyl cyclosiloxane prepares the main raw material of silicone oil, as main chain agent; Amino closure agent is molecular weight regulator, provides amino group simultaneously; The consumption of amino closure agent be amido silicon oil molecular weight in order to prepare in setting range, the consumption of functionalized cyclosiloxane is not affecting the suitable improvement to amido silicon oil under amido silicon oil performance.Therefore in the present invention, methyl cyclosiloxane, amino closure agent, functionalized cyclosiloxane are 100:5.0 ~ 30.0:0 ~ 20.0 according to mass parts ratio; According to the preferred embodiment of the present invention, methyl cyclosiloxane, amino closure agent, functionalized cyclosiloxane are 100:10.0 ~ 25.0:2.0 ~ 15.0 according to mass parts ratio; It is further preferred that methyl cyclosiloxane, amino closure agent, functionalized cyclosiloxane are 100:15.0 ~ 20.0:5.0 ~ 10.0 according to mass parts ratio.
When the quality of basic catalyst is less than 0.001% of methyl cyclosiloxane, amino closure agent and functionalized cyclosiloxane total mass, then catalyst levels is too low, and catalytic effect is bad; When the quality of basic catalyst is greater than 0.01% of methyl cyclosiloxane, amino closure agent and functionalized cyclosiloxane total mass, then catalyst levels is too high, and cost is high, causes the waste of catalyzer; Therefore the quality of basic catalyst be methyl cyclosiloxane, amino closure agent and functionalized cyclosiloxane total mass 0.001% ~ 0.01% be rational.
According to the preferred embodiment of the present invention, described methyl cyclosiloxane is selected from hexamethyl cyclotrisiloxane (to be called for short D
3), octamethylcyclotetrasiloxane (be called for short D
4), decamethylcyclopentaandoxane (be called for short D
5) or the methyl cyclosiloxane of dimethyl siloxane mixed methylcyclosiloxane (be called for short DMC).
In the present invention, hexamethyl cyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentaandoxane and dimethyl siloxane mixed methylcyclosiloxane are the product often sold on the market, and such as Dow corning, Jiangxi spark manufacturer produce.
According to the preferred embodiment of the present invention, described amino closure agent is selected from two (the 3-aminopropyl)-1 of 1,3-, 1,3,3-tetramethyl disiloxane, 1, two (the N-β-aminoethyl-γ-aminopropyl)-1,1,3 of 3-, 3-tetramethyl disiloxane, 1,3-two (n-formyl sarcolysine base-3-aminopropyl)-1,1,3,3-tetramethyl disiloxane, 1,3-two (pyridyl-3-aminopropyl)-1, the amino closure agent of 1,3,3-tetramethyl disiloxane.
According to the preferred embodiment of the present invention, described basic catalyst is that one or more are selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, Tetramethylammonium hydroxide or lithium hydroxide, sodium hydroxide, potassium hydroxide, Tetramethylammonium hydroxide react obtained silicon alkoxide respectively basic catalyst with methyl cyclosiloxane.
Silicon alkoxide described in the present invention be lithium hydroxide, sodium hydroxide, potassium hydroxide, Tetramethylammonium hydroxide respectively with D
4or the silicon alkoxide that DMC reaction is obtained, obtained silicon alkoxide is respectively lithium hydroxide silicon alkoxide, sodium hydroxide silicon alkoxide, potassium hydroxide silicon alkoxide, Tetramethylammonium hydroxide silicon alkoxide.
In the present invention, described Tetramethylammonium hydroxide silicon alkoxide is Tetramethylammonium hydroxide crystal and D
4or DMC is by certain mass ratio, at 80 ~ 100 DEG C, vacuum tightness-0.09MPa and more than, logical nitrogen reaction is to obtaining translucent viscous liquid.Other are also same.
According to the preferred embodiment of the present invention, raw material mixing described in steps A and building-up reactions are a step feeding method or substep feeding method, a described step feeding method be according to mass parts than 100:5.0 ~ 30.0:0 ~ 20.0 get drying dewater after methyl cyclosiloxane, amino closure agent, functionalized cyclosiloxane mix with basic catalyst, wherein the quality of basic catalyst is 0.001% ~ 0.01% of methyl cyclosiloxane, amino closure agent and functionalized cyclosiloxane total mass; Then under drying nitrogen protection, at temperature 80 ~ 120 DEG C, 6 ~ 12h is reacted;
Described substep feeding method be according to mass parts than 100:5.0 ~ 30.0:0 ~ 20.0 get drying dewater after methyl cyclosiloxane, amino closure agent, functionalized cyclosiloxane and basic catalyst as reaction raw materials, wherein the quality of basic catalyst is 0.001% ~ 0.01% of methyl cyclosiloxane, amino closure agent and functionalized cyclosiloxane total mass; Then by the methyl cyclosiloxane of 40 ~ 60%, whole amino closure agents, whole functionalized cyclosiloxane, 40 ~ 60% basic catalyst mixing or the amino closure agent of 40% ~ 60%, whole methyl cyclosiloxane, whole functionalized cyclosiloxane, 50 ~ 80% basic catalyst mixing; then under drying nitrogen protection, at temperature 80 ~ 120 DEG C, react 2 ~ 4h, then continue after remaining reaction raw materials being added mixing at temperature 80 ~ 120 DEG C, to react 3 ~ 8h under drying nitrogen protection.
In the present invention, the effect of substep feeding method first obtains pre-reaction thing, regulates the speed of reaction of each reactant in reaction system, reach higher balanced reaction degree.
According to the preferred embodiment of the present invention, the method that the drying described in steps A dewaters to dewater 1 ~ 3h or pass into drying nitrogen and to dewater under temperature 40 ~ 60 DEG C, vacuum tightness-0.095 ~-0.08MPa 0.5 ~ 1h for passing into drying nitrogen at temperature 80 ~ 120 DEG C.Methyl cyclosiloxane, amino closure agent, functionalized the cyclosiloxane before the reaction dry effect dewatered to get rid of in reaction raw materials micro-moisture to the impact of reaction.
According to the preferred embodiment of the present invention, the method for the removal basic catalyst described in step B be add with the mineral acid of basic catalyst equivalent, organic acid in and basic catalyst, or by be warming up to 130 ~ 160 DEG C remove basic catalysts.
According to the preferred embodiment of the present invention, the method removing low-boiling-point substance described in step B is under nitrogen protection in temperature 110 ~ 150 DEG C, vacuum tightness-0.09MPa and carry out underpressure distillation, till oozing without low-boiling-point substance in 5min above.
Present invention also offers the linear Amino End Group silicone oil of lower molecular weight of the synthetic method synthesis described in a kind of basis, it has following characteristic: molecular weight is lower than 4000; Viscosity is less than 100mm
2/ s.
According to a preferred embodiment of the invention, the linear Amino End Group silicone oil of described lower molecular weight, it has following characteristic: molecular weight is lower than 2000; Viscosity is less than 100mm
2/ s.
The low molecule linear silicone oils that the present invention obtains characterizes from following three aspects:
1) molecular weight and molecualr weight distribution index: the mensuration of being carried out this amido silicon oil molecular weight and molecular weight distribution by gel permeation chromatography (GPC).
2) viscosity: unit mm
2/ s, by the kinematic viscosity of this amido silicon oil of Ping Shi viscometer determining.
3) ammonia value: i.e. amino content, consume with 1g amido silicon oil the mmole number that volumetric molar concentration is the perchloric acid solution of 0.1mol/L in referring to, unit is mmol/g, by perchloric acid-glacial acetic acid solution solution titration.
[beneficial effect]
(1) this synthetic method is simple, is easy to suitability for industrialized production.
(2) the linear amino-silicone oil low-boiling-point substance synthesized is few, and cost is lower, quality better.
(3) molecular weight of this linear amino-silicone oil is lower and can design on demand.
(4) can design in amido silicon oil structure and add the functionalizing group such as phenyl, vinyl and improve amido silicon oil product performance further.
(5) the method need not be reacted under elevated pressure conditions, can not use expensive catalyzer, and aftertreatment technology is simple, and obtained amino silicone oil viscosity is low.And for the compound use of the selection of catalyzer, particularly catalyzer, common solves at the polyreaction initial stage, polymer viscosity this difficult problem uncontrollable.
[embodiment]
The present invention can be understood better by following embodiment.
Embodiment 1
In the 1000mL four-hole boiling flask that mechanical stirring, prolong, thermometer, nitrogen bulging pipe are housed, add octamethylcyclotetrasiloxane 488g, t etram-ethyltetravinylcyclotetrasiloxane 16g, 1, two (the 3-aminopropyl)-1 of 3-, 1,3,3-tetramethyl disiloxane 96g, is uniformly mixed, be warming up to 80 DEG C, logical drying nitrogen dewaters 2h; Then 4g Tetramethylammonium hydroxide silicon alkoxide (Tetramethylammonium hydroxide and D is added
41:100 is at 80 ~ 100 DEG C in mass ratio, vacuum tightness-0.09MPa and more than, logical nitrogen reaction is to obtaining translucent viscous liquid) and 0.01g potassium hydroxide, at temperature 100 DEG C, continue logical nitrogen and react 10h.Then decompose Tetramethylammonium hydroxide silicon alkoxide 30min at being warming up to 150 DEG C, then add with the acid of potassium hydroxide equivalent in and potassium hydroxide.Be cooled to 120 DEG C again, under vacuum tightness-0.09MPa, distill out low-boiling-point substance, be cooled to room temperature, obtain the linear Amino End Group silicone oil of lower molecular weight.The number-average molecular weight recording this amido silicon oil is 1572, and molecular weight distributing index is 2.38, and kinematic viscosity is 58mm
2/ s, ammonia value is 1.26mmol/g.
Embodiment 2
In the 1000mL four-hole boiling flask that mechanical stirring, prolong, thermometer, nitrogen bulging pipe are housed, add dimethyl siloxane mixed methylcyclosiloxane 480g, tetramethyl tetraphenyl cyclotetrasiloxane 38g, 1,3-two (3-aminopropyl)-1,1,3,3-tetramethyl disiloxane 52g, 1,3-two (N-β-aminoethyl-γ-aminopropyl)-1,1,3,3-tetramethyl disiloxane 30g, is uniformly mixed, be warming up to 120 DEG C, logical drying nitrogen dewaters 1h; Then (sodium hydroxide and DMC are in mass ratio for 1:200 is at 80 ~ 100 DEG C to add 2g Tetramethylammonium hydroxide silicon alkoxide and 2g sodium hydroxide silicon alkoxide, vacuum tightness-0.09MPa and more than, logical nitrogen reaction is to obtaining translucent viscous liquid), at temperature 120 DEG C, continue logical nitrogen reaction 6h.Then Tetramethylammonium hydroxide silicon alkoxide 30min is decomposed at being warming up to 150 DEG C, add with the acid of sodium hydroxide equivalent in sodium hydroxide silicon alkoxide in and sodium hydroxide, again temperature 150 DEG C, distill out low-boiling-point substance under vacuum tightness-0.09MPa, be cooled to room temperature, obtain the linear Amino End Group silicone oil of lower molecular weight.The number-average molecular weight recording this amido silicon oil is 1670, and molecular weight distributing index is 2.77, and kinematic viscosity is 93mm
2/ s, ammonia value is 1.12mmol/g.
Embodiment 3
In the 1000mL four-hole boiling flask that mechanical stirring, prolong, thermometer, nitrogen bulging pipe are housed, add octamethylcyclotetrasiloxane 485g, hexamethyl cyclotrisiloxane 15g, t etram-ethyltetravinylcyclotetrasiloxane 15g, tetramethyl tetraphenyl cyclotetrasiloxane 10g, 1, two (the N-β-aminoethyl-γ-aminopropyl)-1 of 3-, 1,3,3-tetramethyl disiloxane 50g, 1, two (the n-formyl sarcolysine base-3-aminopropyl)-1,1,3 of 3-, 3-tetramethyl disiloxane 25g, be uniformly mixed, at temperature 50 C, under vacuum tightness-0.09MPa, logical drying nitrogen dewaters 0.5h; Then add Tetramethylammonium hydroxide silicon alkoxide 3g and sodium hydroxide 0.01g, at temperature 80 DEG C, continue logical nitrogen reaction 12h.Then decompose Tetramethylammonium hydroxide silicon alkoxide 30min at being warming up to 150 DEG C, then add with the acid of sodium hydroxide equivalent in and sodium hydroxide.Under temperature 110 DEG C, vacuum tightness-0.09MPa, distill out low-boiling-point substance again, be cooled to room temperature, obtain the linear Amino End Group silicone oil of lower molecular weight.The kinematic viscosity recording this amido silicon oil is 86mm
2/ s, ammonia value is 0.96mmol/g.
Embodiment 4
In the 1000mL four-hole boiling flask that mechanical stirring, prolong, thermometer, nitrogen bulging pipe are housed, add drying nitrogen dewater after octamethylcyclotetrasiloxane 200g, octaphenylcyclotetrasiloxane 20g, 1, two (the N-β-aminoethyl-γ-aminopropyl)-1,1,3 of 3-, 3-tetramethyl disiloxane 80g, be uniformly mixed, be warming up to 90 DEG C, add Tetramethylammonium hydroxide 0.03g, at temperature 90 DEG C, continue logical nitrogen reaction 4h.Add again drying nitrogen dewater after dimethyl siloxane mixed methylcyclosiloxane 300g, sodium hydroxide silicon alkoxide 3g, maintains the temperature at 90 DEG C, continues logical nitrogen reaction 8h.Then Tetramethylammonium hydroxide 30min is decomposed at being warming up to 130 DEG C, then add with the acid of sodium hydroxide equivalent in sodium hydroxide silicon alkoxide in and sodium hydroxide, low-boiling-point substance is distilled out again under temperature 130 DEG C, vacuum tightness-0.09MPa, be cooled to room temperature, obtain the linear Amino End Group silicone oil of lower molecular weight.The number-average molecular weight recording this amido silicon oil is 1960, and molecular weight distributing index is 2.67, and kinematic viscosity is 75mm
2/ s, ammonia value is 1.07mmol/g.
Embodiment 5
In the 1000mL four-hole boiling flask that mechanical stirring, prolong, thermometer, nitrogen bulging pipe are housed, add drying nitrogen dewater after dimethyl siloxane mixed methylcyclosiloxane 480g, t etram-ethyltetravinylcyclotetrasiloxane 30g, tetramethyl tetraphenyl cyclotetrasiloxane 10g, 1, two (the 3-aminopropyl)-1,1,3 of 3-, 3-tetramethyl disiloxane 40g, be uniformly mixed, be warming up to 100 DEG C, add Tetramethylammonium hydroxide silicon alkoxide 2g, at temperature 100 DEG C, continue logical nitrogen reaction 4h.Add 1 again, two (the n-formyl sarcolysine base-3-aminopropyl)-1 of 3-, 1,3,3-tetramethyl disiloxane 40g, potassium hydroxide silicon alkoxide 2g (potassium hydroxide and DMC be in mass ratio 1:150 at 80 ~ 100 DEG C, vacuum tightness-0.09MPa and more than, logical nitrogen reaction is to obtaining translucent viscous liquid), maintain the temperature at 100 DEG C, continue logical nitrogen reaction 6h.Then Tetramethylammonium hydroxide silicon alkoxide 30min is decomposed at being warming up to 140 DEG C, then add with the acid of potassium hydroxide equivalent in potassium hydroxide silicon alkoxide in and potassium hydroxide, low-boiling-point substance is distilled out under temperature 140 DEG C, vacuum tightness-0.09MPa, be cooled to room temperature, obtain the linear Amino End Group silicone oil of lower molecular weight.The kinematic viscosity recording this amido silicon oil is 82mm
2/ s, ammonia value is 0.89mmol/g.
Embodiment 6
In the 1000mL four-hole boiling flask that mechanical stirring, prolong, thermometer, nitrogen bulging pipe are housed, add drying nitrogen dewater after octamethylcyclotetrasiloxane 460g, decamethylcyclopentaandoxane 20g, t etram-ethyltetravinylcyclotetrasiloxane 24g, octaphenylcyclotetrasiloxane 8g, 1, two (the 3-aminopropyl)-1 of 3-, 1,3,3-tetramethyl disiloxane 44g, be uniformly mixed, be warming up to 110 DEG C, add Tetramethylammonium hydroxide 0.05g, at temperature 110 DEG C, continue logical nitrogen reaction 3h.Add two (pyridyl-3-aminopropyl)-1,1,3,3-tetramethyl disiloxane 44g, the lithium hydroxide 0.01g of 1,3-again, maintain the temperature at 110 DEG C, continue logical nitrogen reaction 6h.Then Tetramethylammonium hydroxide 30min is decomposed at being warming up to 140 DEG C, then add with the acid of lithium hydroxide equivalent in and lithium hydroxide, under temperature 140 DEG C, vacuum tightness-0.09MPa, distill out low-boiling-point substance again, be cooled to room temperature, obtain the linear Amino End Group silicone oil of lower molecular weight.The kinematic viscosity measuring this amido silicon oil is 90mm
2/ s, ammonia value is 0.71mmol/g.
The above is only the preferred embodiment of the present invention, for those skilled in the art, without departing from the inventive concept of the premise, can also make some improvements and modifications, and these improvements and modifications also should in protection scope of the present invention.
Claims (10)
1. a synthetic method for the linear Amino End Group silicone oil of lower molecular weight, is characterized in that the step of this synthetic method is as follows:
A, raw material mixing and building-up reactions: according to mass parts than 100:5.0 ~ 30.0:0 ~ 20.0 get drying dewater after methyl cyclosiloxane, amino closure agent, functionalized cyclosiloxane and basic catalyst as reaction raw materials, wherein the quality of basic catalyst is 0.001% ~ 0.01% of methyl cyclosiloxane, amino closure agent and functionalized cyclosiloxane total mass; Then under drying nitrogen protection, at temperature 80 ~ 120 DEG C, 6 ~ 12h is reacted after being mixed by reaction raw materials;
B, remove basic catalyst and remove low-boiling-point substance: reacted for steps A product is removed basic catalyst, then underpressure distillation removing low-boiling-point substance under nitrogen protection, is cooled to room temperature, namely obtains the linear Amino End Group silicone oil of described lower molecular weight.
2. synthetic method according to claim 1, is characterized in that described functionalized cyclosiloxane is that one or more are selected from the functionalized cyclosiloxane of t etram-ethyltetravinylcyclotetrasiloxane, tetramethyl tetraphenyl cyclotetrasiloxane, octaphenylcyclotetrasiloxane.
3. synthetic method according to claim 1, is characterized in that described methyl cyclosiloxane is that one or more are selected from the methyl cyclosiloxane of hexamethyl cyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentaandoxane or dimethyl siloxane mixed methylcyclosiloxane.
4. synthetic method according to claim 1, it is characterized in that described amino closure agent is that one or more are selected from 1, two (the 3-aminopropyl)-1 of 3-, 1,3,3-tetramethyl disiloxane, 1, two (the N-β-aminoethyl-γ-aminopropyl)-1 of 3-, 1,3,3-tetramethyl disiloxane, 1, two (the n-formyl sarcolysine base-3-aminopropyl)-1 of 3-, 1,3,3-tetramethyl disiloxane, 1, two (pyridyl-3-aminopropyl)-1 of 3-, the amino closure agent of 1,3,3-tetramethyl disiloxane.
5. synthetic method according to claim 1, is characterized in that described basic catalyst is that one or more are selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, Tetramethylammonium hydroxide or lithium hydroxide, sodium hydroxide, potassium hydroxide, Tetramethylammonium hydroxide react obtained silicon alkoxide respectively basic catalyst with methyl cyclosiloxane.
6. synthetic method according to claim 1, it is characterized in that the raw material mixing described in steps A and building-up reactions are a step feeding method or substep feeding method, a described step feeding method be according to mass parts than 100:5.0 ~ 30.0:0 ~ 20.0 get drying dewater after methyl cyclosiloxane, amino closure agent, functionalized cyclosiloxane mix with basic catalyst, wherein the quality of basic catalyst is 0.001% ~ 0.01% of methyl cyclosiloxane, amino closure agent and functionalized cyclosiloxane total mass; Then under drying nitrogen protection, at temperature 80 ~ 120 DEG C, 6 ~ 12h is reacted;
Described substep feeding method be according to mass parts than 100:5.0 ~ 30.0:0 ~ 20.0 get drying dewater after methyl cyclosiloxane, amino closure agent, functionalized cyclosiloxane and basic catalyst as reaction raw materials, wherein the quality of basic catalyst is 0.001% ~ 0.01% of methyl cyclosiloxane, amino closure agent and functionalized cyclosiloxane total mass; Then by the methyl cyclosiloxane of 40 ~ 60%, whole amino closure agents, whole functionalized cyclosiloxane, 40 ~ 60% basic catalyst mixing or the amino closure agent of 40% ~ 60%, whole methyl cyclosiloxane, whole functionalized cyclosiloxane, 50 ~ 80% basic catalyst mixing; then under drying nitrogen protection, at temperature 80 ~ 120 DEG C, react 2 ~ 4h, then continue after remaining reaction raw materials being added mixing at temperature 80 ~ 120 DEG C, to react 3 ~ 8h under drying nitrogen protection.
7. synthetic method according to claim 1, is characterized in that step that the drying described in steps A dewaters to dewater 1 ~ 3h or pass into drying nitrogen and to dewater under temperature 40 ~ 60 DEG C, vacuum tightness-0.095 ~-0.08MPa 0.5 ~ 1h for passing into drying nitrogen at temperature 80 ~ 120 DEG C.
8. synthetic method according to claim 1, it is characterized in that the method for the removal basic catalyst described in step B be add with the mineral acid of basic catalyst equivalent, organic acid in and basic catalyst, or by be warming up to 130 ~ 160 DEG C remove basic catalysts.
9. synthetic method according to claim 1; it is characterized in that the method removing low-boiling-point substance described in step B is under nitrogen protection in temperature 110 ~ 150 DEG C, vacuum tightness-0.09MPa and carry out underpressure distillation, till oozing without low-boiling-point substance in 5min above.
10. the linear Amino End Group silicone oil of lower molecular weight of the synthetic method synthesis according to any one of claim 1-9 claim, is characterized in that it has following characteristic: molecular weight is lower than 4000; Viscosity is less than 100mm
2/ s.
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| CN106883413A (en) * | 2017-03-13 | 2017-06-23 | 广州市仲沅其新型材料有限公司 | A kind of double-end amino silicone oil and its production and use |
| CN107245147A (en) * | 2017-05-25 | 2017-10-13 | 广州道明研究院有限公司 | A kind of method for efficiently synthesizing linear Amino End Group silicone oil |
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