CN112280041A - Preparation method of amino silicone oil with low organosilicon ring body content - Google Patents
Preparation method of amino silicone oil with low organosilicon ring body content Download PDFInfo
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- 229920013822 aminosilicone Polymers 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000000463 material Substances 0.000 claims abstract description 44
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 27
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 22
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 22
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 20
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 230000007062 hydrolysis Effects 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 7
- LBKJNHPKYFYCLL-UHFFFAOYSA-N potassium;trimethyl(oxido)silane Chemical compound [K+].C[Si](C)(C)[O-] LBKJNHPKYFYCLL-UHFFFAOYSA-N 0.000 claims description 6
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- YLBPOJLDZXHVRR-UHFFFAOYSA-N n'-[3-[diethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CCO[Si](C)(OCC)CCCNCCN YLBPOJLDZXHVRR-UHFFFAOYSA-N 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 2
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 2
- LPJGNMYFZQJTPW-UHFFFAOYSA-N diethoxy-methyl-(3-piperazin-1-ylpropyl)silane Chemical compound CCO[Si](C)(OCC)CCCN1CCNCC1 LPJGNMYFZQJTPW-UHFFFAOYSA-N 0.000 claims description 2
- CTLDFURRFMJGON-UHFFFAOYSA-N dimethoxy-methyl-(3-piperazin-1-ylpropyl)silane Chemical compound CO[Si](C)(OC)CCCN1CCNCC1 CTLDFURRFMJGON-UHFFFAOYSA-N 0.000 claims description 2
- GFQRGIBXEJMWJM-UHFFFAOYSA-N [SiH3]O.[K] Chemical compound [SiH3]O.[K] GFQRGIBXEJMWJM-UHFFFAOYSA-N 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 12
- 239000003921 oil Substances 0.000 description 58
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 229920001296 polysiloxane Polymers 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000005227 gel permeation chromatography Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 7
- 125000003277 amino group Chemical group 0.000 description 6
- 230000000379 polymerizing effect Effects 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 4
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical group C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- IUMSDRXLFWAGNT-UHFFFAOYSA-N Dodecamethylcyclohexasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 IUMSDRXLFWAGNT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229940008099 dimethicone Drugs 0.000 description 2
- 239000000413 hydrolysate Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000013022 venting Methods 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000000490 cosmetic additive Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The invention relates to a preparation method of amino silicone oil with low organosilicon ring body content, wherein the preparation method comprises the following steps: s100, stirring and mixing 100 parts by weight of hydroxyl-terminated polydimethylsiloxane, 1-50 parts by weight of amino monomer with siloxy and 1-25 parts by weight of end-capping agent at the temperature of 50-100 ℃ to obtain a stirred and mixed material; s200, adding 1-5 parts by weight of water into the stirred and mixed material obtained in the step S100 for hydrolysis, and introducing nitrogen to remove moisture and alcohol to obtain a hydrolyzed material; s300, adding an alkaline catalyst into the hydrolyzed material, and carrying out polymerization reaction at the temperature of 50-110 ℃ to obtain a polymerization reaction material; s400, removing the polymerization reaction material to obtain the amino silicone oil. The amino silicone oil prepared by the preparation method has more uniform amino distribution, low organosilicon ring body content and low volatile component.
Description
Technical Field
The invention belongs to the technical field of organic silicon, and particularly relates to a preparation method of amino silicone oil with low organic silicon ring body content.
Background
The amino silicone oil is a product of dimethyl silicone oil with lateral and terminal methyl groups substituted by amino hydrocarbon groups, has strong amino polarity, high reactivity, adsorbability, intermiscibility and easy emulsibility, and is widely used for fiber after-finishing agents, resin modifiers, paint additives, brightening agents, cosmetic additives and the like.
Aminosilicones can be classified into reactive aminosilicones and non-reactive aminosilicones, depending on whether or not the polysiloxane backbone contains reactive groups other than amino groups. The reactive amino silicone oil can be crosslinked to form a film on the surface of the fiber due to the introduction of reactive groups such as hydroxyl, alkoxy and the like on the main chain of the amino polysiloxane, and has better soft lubricating capability, rebound capability and bonding fastness to the fiber than non-reactive amino silicone oil.
At present, the industrially synthesized amino silicone oil is mainly prepared by polymerizing octamethylcyclotetrasiloxane (D4) or dimethyl cyclosiloxane mixture (DMC) and amino monomers, and the obtained product is generally a random copolymer, and has uneven amino distribution and low conversion rate. In addition, mixed silicone ring bodies which are difficult to remove exist in the product, and the silicone ring bodies have continuous harm to the environment.
Chinese patent application CN108676165A discloses a preparation method of amino silicone oil, which comprises the steps of premixing a dimethyl cyclosiloxane mixture and a blocking agent, premixing a silane coupling agent and KOH, polycondensing the two mixtures in a container at the reaction temperature of 100-200 ℃, and finally removing the solvent to obtain the amino silicone oil. However, in the preparation method disclosed in chinese patent application CN108676165A, the conversion rate of the raw material is about 93.55%, and the product obtained by the condensation reaction contains a large amount of organosilicon ring bodies, such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane, and the organosilicon ring bodies need to be recovered and processed before being used. In addition, in the preparation method disclosed in this patent application, the polycondensation reaction temperature is relatively high, the time is long, and the energy consumption is high.
Chinese patent application CN108912333A discloses a preparation method of amino silicone oil with high transmittance, which comprises a step of preparing a coupling agent hydrolysate; a step of preparing amino silicone oil by dehydrating octamethylcyclotetrasiloxane; then adding a catalyst to dissolve under normal pressure; then adding the coupling agent hydrolysate under reduced pressure and mixing; then reducing the pressure, adding a blocking agent for reaction, and heating to deactivate the catalyst; then heating to remove low molecular compounds; standing and cooling to obtain the amino silicone oil with high transmittance. In the scheme, a technical route that amino silane coupling agent and water are hydrolyzed and alcohols are removed, and then the amino silane coupling agent and octamethylcyclotetrasiloxane are subjected to polymerization reaction to synthesize amino silicone oil is adopted, and compared with a method for preparing amino silicone oil by directly reacting amino silane coupling agent and octamethylcyclotetrasiloxane, the amino silicone oil has improved amino distribution uniformity. However, a polycondensation reaction may occur between the hydrolysates of the coupling agent, resulting in a relatively low degree of improvement in the uniformity of the amino group distribution.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing amino silicone oil with low silicone ring content, which has more uniform amino group distribution, low silicone ring content and low volatile component.
The purpose of the invention is realized by the following technical scheme.
The invention provides a preparation method of amino silicone oil with low organosilicon ring body content, wherein the preparation method comprises the following steps:
s100, stirring and mixing 100 parts by weight of hydroxyl-terminated polydimethylsiloxane, 1-50 parts by weight of amino monomer with siloxy and 1-25 parts by weight of end-capping agent at the temperature of 50-100 ℃ to obtain a uniformly mixed material;
s200, adding 1-5 parts by weight of water into the stirred and mixed material obtained in the step S100 for hydrolysis, and introducing nitrogen to remove moisture and alcohol to obtain a hydrolyzed material;
s300, adding an alkaline catalyst into the hydrolyzed material, and carrying out polymerization reaction at the temperature of 50-110 ℃ to obtain a polymerization reaction material;
s400, removing the polymerization reaction material to obtain the amino silicone oil.
The inventor of the present application finds that firstly, hydroxyl-terminated polydimethylsiloxane, amino monomer with siloxy and end-capping agent are stirred and mixed at 50-100 ℃ (step S100), then hydrolysis and polymerization are carried out (steps S200 and S300), and finally amino silicone oil is obtained through reduction, wherein amino groups in the amino silicone oil are uniformly distributed, volatile components are low, and the content of silicone ring bodies of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane is less than 0.1%. Furthermore, an end-capping reagent is added before hydrolysis, so that the polymerization degree of a linear body (hydroxyl-terminated polydimethylsiloxane) and an amino monomer can be effectively controlled, the viscosity of the amino silicone oil product is prevented from being excessively increased, and the product meeting the quality requirement is obtained.
According to the preparation method provided by the invention, the viscosity of the hydroxyl-terminated polydimethylsiloxane (linear body) in the step S100 is 20-200 cst. The viscosity of the hydroxyl-terminated polydimethylsiloxane is directly related to its molecular weight (hydroxyl content). When the viscosity is too high, the content of hydroxyl groups is too low, and polycondensation is not easily performed. In some embodiments, the hydroxyl terminated polydimethylsiloxane has a viscosity of from 20 to 100cst, and in some embodiments from 50 to 80 cst.
According to the preparation method provided by the invention, the amino monomer with the siloxy group is provided with an aminosilane coupling agent. Examples of amino monomers having a siloxy group suitable for use in the present invention include, but are not limited to: n-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldiethoxysilane, 3-piperazinopropylmethyldimethoxysilane, 3-piperazinopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane and 3-aminopropylmethyldiethoxysilane. In some embodiments, the amino monomer having a siloxy group in step S100 is N- β - (aminoethyl) - γ -aminopropylmethyldimethoxysilane.
According to the production method provided by the present invention, an example of a capping agent suitable for use in the present invention is a low-viscosity methyl silicone oil.
In the present invention, the term "low viscosity dimethylsilicone fluid" refers to methyl-terminated polydimethylsiloxane having a viscosity of 0.65 to 20 cst. In addition, the term "viscosity" refers to the viscosity at 25 ℃. For example, in some embodiments, the low viscosity dimethicone has a viscosity of 10 to 20cst, and in some embodiments the low viscosity dimethicone is hexamethyldisiloxane.
According to the preparation method provided by the invention, in the step S100, the amino content of the prepared amino silicone oil can be controlled by adjusting the using amount of the amino monomer with the siloxy group, and the viscosity of the amino silicone oil can be controlled by adjusting the using amount of the end-capping agent.
In some embodiments, the weight ratio of the hydroxyl-terminated polydimethylsiloxane, the amino monomer having a siloxy group, and the capping agent in step S100 is 100:2 to 10, and in some embodiments, 100:2.5 to 5:2.5 to 6.
According to the preparation method provided by the invention, the temperature for stirring and mixing in the step S100 is 80-90 ℃.
According to the preparation method provided by the invention, the stirring and mixing time in the step S100 is 0.5-5 hours, preferably 1-2 hours.
According to the preparation method provided by the invention, the using amount of the water in the step S200 is 2-3 parts by weight. In the present invention, water may be added to the stirred and mixed material at once or in portions. For example, in some embodiments, the water is added to the stirred and mixed material in two portions in step S200 at intervals of 20 to 40 minutes, and in some embodiments, the ratio of the first addition of water to the second addition of water is 1:0.5 to 1.
According to the preparation method provided by the invention, the hydrolysis in the step S200 can be performed at a temperature of 10 to 30 ℃, for example, at room temperature, and the hydrolysis time can be 1 to 2 hours.
According to the preparation method provided by the invention, the mixed materials are stirred in the step S200 to perform hydrolysis reaction, so that methanol or ethanol is generated. After the hydrolysis reaction, nitrogen is introduced into the reaction system to remove residual water and methanol or ethanol generated by hydrolysis. In some embodiments, the nitrogen is introduced in the step S200 in an amount of 1 to 100L/min, and in some embodiments, 20 to 30L/min, based on 100g of the reaction system.
According to the preparation method provided by the invention, in the step S200, the introduction time of the nitrogen gas may be 30 to 90 minutes, for example, 60 minutes.
The preparation method provided according to the present invention, wherein examples of the basic catalyst suitable for use in the present invention include, but are not limited to: KOH solid, KOH aqueous solution, potassium trimethylsilanolate, and tetramethylammonium hydroxide. In some embodiments, the basic catalyst in step S300 is KOH solid or potassium trimethylsilanolate.
According to the preparation method provided by the invention, the amount of the basic catalyst used in the step S300 is 0.01-0.1 part by weight. In some embodiments, the basic catalyst is used in an amount of 0.03 to 0.08 parts by weight in step S300; and in some embodiments, from 0.03 to 0.05 parts by weight.
According to the preparation method provided by the invention, in the step S300, the polymerization reaction is carried out under the condition of introducing nitrogen into the reaction system. The nitrogen is introduced to facilitate the removal of by-products such as water and the like, thereby facilitating the polymerization reaction.
In some embodiments, the nitrogen is introduced in the step S300 in an amount of 1 to 100L/min, and in some embodiments 30 to 50L/min, based on 100g of the reaction system.
According to the preparation method provided by the invention, in the step S300, the polymerization reaction is carried out at the temperature of 75-90 ℃. In addition, in step S300, the termination of the reaction can be determined by measuring that the viscosity of the reaction system does not increase any more within 10 minutes.
According to the preparation method provided by the invention, the reduction in the step S400 is carried out at the temperature of 130-170 ℃ and the vacuum degree of 0.097-0.099 MPa. In some embodiments, the temperature of the reduction in step S400 is from 140 to 150 ℃.
The preparation method of the invention has the following advantages:
(1) the amino silicone oil prepared by the preparation method has high oil content, uniform amino distribution and narrow molecular weight distribution. In the invention, the hydroxyl-terminated polydimethylsiloxane, the amino monomer with the siloxy group and the end-capping agent are stirred and mixed at 50-100 ℃, the materials are uniformly mixed, the stirred and mixed materials are hydrolyzed to obtain the silanol, then the silanol is subjected to polycondensation at the temperature of 50-110 ℃ (particularly at the temperature of 75-90 ℃) in the presence of an alkaline catalyst, and nitrogen is introduced for dehydration, so that the reaction conditions are mild, the amino group of the obtained amino silicone oil is uniformly distributed, and the molecular weight distribution is narrow.
(2) In the preparation method, the amino silicone oil is prepared by stirring, mixing, hydrolyzing, polymerizing and reducing, the amino group is uniformly distributed, the volatile component is small, and the content of organosilicon ring bodies such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and decadimethylcyclohexasiloxane is less than 0.1%. In particular, the preparation method of the invention uses a linear body to replace D4 or DMC to prepare amino silicone oil, which can effectively avoid the defect of residual organosilicon cyclic body impurities in reaction products. Further, without wishing to be bound by theory, it is believed that the possible presence of D4 or DMC may also be hydrolyzed and polymerized to reduce the content of silicone rings by hydrolysis reaction followed by nitrogen gas venting to remove moisture and alcohol (step S200) and polymerization reaction under nitrogen gas venting (step S300).
(3) The preparation method has the advantages of simple process, mild conditions, low equipment requirement, short production time and low production cost.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. Wherein,
FIG. 1 is an infrared spectrum of amino silicone oil prepared by the preparation method of the present invention; and
FIG. 2 is a gas chromatogram of an amino silicone oil obtained by the production method according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The specific techniques or conditions are not indicated in the examples, and are performed according to the techniques or conditions described in the literature in the field or according to the product specifications. The reagents or instruments used are conventional products available from regular distributors, not indicated by the manufacturer.
Infrared spectroscopic analysis
And (3) carrying out qualitative analysis on the amino silicone oil by adopting an FT-IR (FT-infrared) spectrometer.
Gel permeation chromatography determination of molecular weight distribution
The molecular weight distribution of the amino silicone oil was analyzed by gel permeation chromatography using a company Showa Denko K.K. under the trade name "SHODEX GPC system 21". Wherein the mobile phase is toluene, the flow rate is 1.0ml/min, and the column temperature is 40 ℃.
Volatile component
The volatile content of the amino silicone oil was measured by oven method. Specifically, 2g of the sample was weighed, dried at a temperature of 150 ℃ for 2 hours, and the weight of the sample before and after drying was measured, respectively, and the volatile content was calculated via formula I:
wherein，m0Is the weight of the sample before drying, m1Is the weight of the sample after drying.
Content of organosilicon ring bodies
Measuring the content of the organosilicon ring body by GC-FID chromatography based on an internal standard method, and calculating according to formula II:
in the formula:
wi represents the mass fraction of the organosilicon ring body, mu g/g;
fi represents a correction factor for the silicone ring body;
a2 represents the peak area of the silicone ring body in the sample;
m represents the sample mass, g.
Example 1
1. Stirring and mixing.
100g of hydroxyl-terminated polydimethylsiloxane with the viscosity of 80cst at 25 ℃, 2.56g of N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane and 3.52g of low-viscosity dimethylsilicone with the viscosity of 10cst at 25 ℃, namely hexamethyldisiloxane, are sequentially added into a reaction kettle, the temperature is increased to 90 ℃, stirring is carried out, and the mixture is mixed for 1 hour to obtain a uniformly mixed material.
2. And (4) hydrolyzing.
1g of water was added to a reaction vessel containing the stirred and mixed materials at 20 ℃ to conduct a reaction with stirring for 0.5 hour, and 1g of water was added to conduct a reaction with stirring for 0.5 hour. And introducing nitrogen for 1 hour to drive out excessive water and methanol to obtain a hydrolyzed material, wherein the introduction amount of the nitrogen is 25L/min.
3. And (4) polymerizing.
Adding 0.04g of potassium trimethylsilanolate into a reaction kettle filled with the hydrolyzed material, reacting at the temperature of 75 ℃, simultaneously introducing nitrogen until the viscosity of the reaction system does not increase within 10 minutes, and stopping introducing the nitrogen to obtain a polymerization reaction material, wherein the introduction amount of the nitrogen is 40L/min.
4. Removing low.
And (3) performing reduction treatment on the polymerization reaction material at the temperature of 140 ℃ and the vacuum degree of 0.099MPa to obtain colorless and transparent amino silicone oil with the viscosity of 3000 mPa.S.
The prepared low-ring amino silicone oil is characterized by an infrared method, and the result is shown in figure 1. In the infrared spectrum of FIG. 1, 3767cm-1、3701cm-1、3648cm-1Is the free-OH peak; 2963cm-1CH (A) of3The left side of the peak has a protrusion of-NH peak at 1595cm-1、1445cm-1Is the-NH peak; 2963cm-1、2905cm-1Is CH3A peak; 1261cm-1Is Si-CH3A peak; 1097cm-1The peak with the polymerization degree more than 5 chain Si-O chain links; 801cm-1、864cm-1Is Si (CH)3)2Peak(s). As can be seen from FIG. 1, the amino silicone oil, the target product, was obtained in example 1.
The aminosilicone oil was further characterized by GC-FID method, and the results are shown in FIG. 2, and the retention time and content of various silicone ring bodies are shown in tables 1 and 2.
In addition, the amino silicone oil was characterized by gel permeation chromatography, and the results are shown in Table 3.
Example 2
1. Stirring and mixing.
100g of hydroxyl-terminated polydimethylsiloxane with the viscosity of 70cst at 25 ℃, 4.05g of N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane and 5.41g of low-viscosity dimethylsilicone-hexamethyldisiloxane with the viscosity of 10cst at 25 ℃ are sequentially added into a reaction kettle, heated to 80 ℃ and mixed for 2 hours to obtain a uniformly mixed material.
2. And (4) hydrolyzing.
1.5g of water was added to a reaction vessel containing the stirred and mixed materials at 20 ℃ to conduct a reaction with stirring for 0.5 hour, and 1.5g of water was added to conduct a reaction with stirring for 0.5 hour. And introducing nitrogen for 1 hour to drive out excessive water and methanol to obtain a hydrolyzed material, wherein the introduction amount of the nitrogen is 25L/min.
3. And (4) polymerizing.
And (3) adding 0.05g of potassium trimethylsilanolate into the reaction kettle filled with the hydrolyzed material, reacting at the temperature of 90 ℃, simultaneously introducing nitrogen until the viscosity of the reaction system does not increase within 10 minutes, and stopping introducing the nitrogen to obtain a polymerization reaction material, wherein the introduction amount of the nitrogen is 40L/min.
4. Removing low.
And (3) performing reduction treatment on the polymerization reaction material at the temperature of 150 ℃ and the vacuum degree of 0.098MPa to obtain colorless and transparent amino silicone oil with the viscosity of 2400 mPa.S.
The prepared low-ring amino silicone oil is characterized by an infrared method, and the result is basically the same as that in figure 1. Thus, example 2 produced the subject amino silicone oil.
The aminosilicone oil and gel permeation chromatography were further characterized by GC-FID method, and the results are shown in tables 2-3.
Example 3
1. Stirring and mixing.
100g of hydroxyl-terminated polydimethylsiloxane with the viscosity of 50cst at 25 ℃, 4.74g of N-beta- (aminoethyl) -gamma-aminopropylmethyldiethoxysilane and 2.63g of low-viscosity dimethylsilicone oil with the viscosity of 10cst at 25 ℃ are sequentially added into a reaction kettle, the temperature is increased to 80 ℃, and the materials are mixed for 1.5 hours to obtain a uniformly mixed material.
2. And (4) hydrolyzing.
1.2g of water was added to a reaction vessel containing the stirred and mixed materials at 20 ℃ to conduct a reaction with stirring for 0.5 hour, and 1.2g of water was added to conduct a reaction with stirring for 0.5 hour. And introducing nitrogen for 1 hour to remove excessive water and ethanol to obtain a hydrolyzed material, wherein the introduction amount of the nitrogen is 25L/min.
3. And (4) polymerizing.
Adding 0.03g of potassium trimethylsilanolate into a reaction kettle filled with the hydrolyzed material, reacting at the temperature of 80 ℃, simultaneously introducing nitrogen until the viscosity of the reaction system does not increase within 10 minutes, and stopping introducing the nitrogen to obtain a polymerization reaction material, wherein the introduction amount of the nitrogen is 40L/min.
4. Removing low.
And (3) performing reduction treatment on the polymerization reaction material at the temperature of 150 ℃ and the vacuum degree of 0.099MPa to obtain colorless and transparent amino silicone oil with the viscosity of 3500 mPa.S.
The prepared low-ring amino silicone oil is characterized by an infrared method, and the result is basically the same as that in figure 1. Thus, example 3 produced the subject amino silicone oil.
The aminosilicone oil and gel permeation chromatography were further characterized by GC-FID method, and the results are shown in tables 2-3.
Comparative example 1
Mixing Dimethylcyclosiloxane Mixture (DMC), hexamethyldisiloxane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane and potassium hydroxide according to the mass ratio of 39: 1.5: 1: 0.01, adding into a reaction kettle in sequence, mixing, heating to 140 ℃, reacting for 12 hours, adding hydrochloric acid for neutralization, and stopping reaction.
And after neutralization, carrying out first reduced pressure distillation at 140 ℃ and under the vacuum degree of 0.08MPa, ending the distillation when the mass change is less than 1% of the total mass within 10min, immediately carrying out second distillation at 160 ℃ and under the vacuum degree of 0.08MPa for 1 hour, and cooling to 30 ℃ to obtain the colorless and transparent amino silicone oil with the viscosity of 3100 mPa.S.
The aminosilicone oil and gel permeation chromatography were further characterized by GC-FID method, and the results are shown in tables 2-3.
Comparative example 2
An amino silicone oil was prepared by substantially the same method as in example 2 except that: without the step 1 (mixing), 100g of hydroxyl-terminated polydimethylsiloxane having a viscosity of 70cst at 25 ℃, 4.05g of N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane and 5.41g of low-viscosity dimethylsilicone fluid having a viscosity of 10cst at 25 ℃ were sequentially added to the reaction kettle, and the mixture was directly subjected to the step 2 for hydrolysis, thereby obtaining a translucent aminosilicone fluid having a viscosity of 2200 mPa.S.
The prepared amino silicone oil and gel permeation chromatography were further characterized by GC-FID method, and the results are shown in tables 2-3.
Comparative example3
An amino silicone oil was prepared by substantially the same method as in example 2 except that: and (3) the step 2 (hydrolysis) operation is not carried out, the stirred and mixed materials directly enter the step 3 for hydrolysis, and the semitransparent amino silicone oil with the viscosity of 2050mPa.S is obtained.
The prepared amino silicone oil and gel permeation chromatography were further characterized by GC-FID method, and the results are shown in tables 2-3.
Comparative example 4
An amino silicone oil was prepared by substantially the same method as in example 2 except that: and the semitransparent amino silicone oil with the viscosity of 8000mPa.S is obtained without adopting low-viscosity dimethyl silicone oil as an end sealing agent.
The prepared amino silicone oil and gel permeation chromatography were further characterized by GC-FID method, and the results are shown in tables 2-3.
TABLE 1 Retention time of various Silicone Ring bodies
| Composition of | Retention time/min |
| D3 | 5.799 |
| D4 | 9.252 |
| D5 | 11.24 |
| D6 | 12.931 |
TABLE 2 Properties of amino silicone oils
As can be seen from Table 2, the aminosilicone prepared by the present invention has a low content of silicone rings and a low volatile content. Further, as can be seen from example 2 and comparative examples 2 to 3, in the present invention, the combination of stirring, mixing, hydrolysis and polymerization is advantageous in reducing the content of silicone rings and volatile components.
TABLE 3 molecular weight distribution
| Hydroxy-terminated polydimethylsiloxanes | Amino silicone oil | |
| Example 1 | 1.81 | 1.94 |
| Example 2 | 1.76 | 1.82 |
| Example 3 | 1.92 | 2.07 |
| Comparative example 1 | - | 2.65 |
| Comparative example 2 | 1.76 | 2.16 |
| Comparative example 3 | 1.76 | 2.23 |
| Comparative example 4 | 1.73 | 2.05 |
As can be seen from Table 3, the aminosilicone prepared by the present invention has a narrow molecular weight distribution.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of amino silicone oil with low organosilicon ring body content comprises the following steps:
s100, stirring and mixing 100 parts by weight of hydroxyl-terminated polydimethylsiloxane, 1-50 parts by weight of amino monomer with siloxy and 1-25 parts by weight of end-capping agent at the temperature of 50-100 ℃ to obtain a stirred and mixed material;
s200, adding 1-5 parts by weight of water into the stirred and mixed material obtained in the step S100 for hydrolysis, and introducing nitrogen to remove moisture and alcohol to obtain a hydrolyzed material;
s300, adding an alkaline catalyst into the hydrolyzed material, and carrying out polymerization reaction at the temperature of 50-110 ℃ to obtain a polymerization reaction material;
s400, removing the polymerization reaction material to obtain the amino silicone oil.
2. The method according to claim 1, wherein the hydroxyl-terminated polydimethylsiloxane in step S100 has a viscosity of 20 to 200cst, preferably 20 to 100cst, and more preferably 50 to 80 cst;
preferably, the amino monomer having a siloxy group is one or more selected from the group consisting of N- β - (aminoethyl) - γ -aminopropylmethyldimethoxysilane, N- β - (aminoethyl) - γ -aminopropylmethyldiethoxysilane, 3-piperazinopropylmethyldimethoxysilane, 3-piperazinopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane and 3-aminopropylmethyldiethoxysilane;
preferably, the end-capping agent is a low viscosity methyl silicone oil;
more preferably, the viscosity of the low-viscosity dimethyl silicone oil is 0.65-20 cst, and preferably 10-20 cst.
3. The production method according to claim 1 or 2, wherein the weight ratio of the hydroxyl-terminated polydimethylsiloxane, the amino monomer having a siloxy group, and the end-capping agent in step S100 is 100:2 to 10, preferably 100:2.5 to 5:2.5 to 6.
4. The production method according to any one of claims 1 to 3, wherein the temperature of the stirring and mixing in step S100 is 80 to 90 ℃;
preferably, the stirring and mixing time in step S100 is 0.5 to 5 hours, preferably 1 to 2 hours.
5. The production method according to any one of claims 1 to 4, wherein the amount of water used in step S200 is 2 to 3 parts by weight;
preferably, in the step S200, water is added into the stirred and mixed material in two batches, the time interval is 20-40 minutes, and the ratio of the water added for the first time to the water added for the second time is preferably 1: 0.5-1;
preferably, the hydrolysis in step S200 is performed at a temperature of 10-30 ℃ for 1-2 hours.
6. The preparation method according to any one of claims 1 to 5, wherein the nitrogen is introduced in the amount of 1 to 100L/min, preferably 20 to 30L/min, based on 100g of the reaction system in step S200;
preferably, the nitrogen gas is introduced for 30 to 90 minutes in the step S200.
7. The production method according to any one of claims 1 to 6, wherein the basic catalyst in step S300 is KOH solid, an aqueous KOH solution, potassium silanol or tetramethylammonium hydroxide, preferably KOH solid or potassium trimethylsilanolate;
preferably, the amount of the basic catalyst used in step S300 is 0.01 to 0.1 part by weight, preferably 0.03 to 0.08 part by weight, and more preferably 0.03 to 0.05 part by weight.
8. The production method according to any one of claims 1 to 7, wherein the polymerization reaction in step S300 is carried out under a condition of introducing nitrogen into the reaction system;
preferably, the amount of nitrogen introduced in step S300 is 1-100L/min, preferably 30-50L/min, based on 100g of the reaction system.
9. The production method according to any one of claims 1 to 8, wherein the polymerization reaction in step S300 is carried out at a temperature of 75 to 90 ℃.
10. The production method according to any one of claims 1 to 9, wherein the reduction in step S400 is performed at a temperature of 130 to 170 ℃, preferably 140 to 150 ℃, and a vacuum degree of 0.097 to 0.099 MPa.
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