CN117866208A - Synthesis method of cationic block silicone oil - Google Patents
Synthesis method of cationic block silicone oil Download PDFInfo
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- CN117866208A CN117866208A CN202311682748.XA CN202311682748A CN117866208A CN 117866208 A CN117866208 A CN 117866208A CN 202311682748 A CN202311682748 A CN 202311682748A CN 117866208 A CN117866208 A CN 117866208A
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- silicone oil
- block silicone
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- betaine
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- 229920002545 silicone oil Polymers 0.000 title claims abstract description 69
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 43
- 238000001308 synthesis method Methods 0.000 title claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 43
- 229920000570 polyether Polymers 0.000 claims abstract description 43
- 229960003237 betaine Drugs 0.000 claims abstract description 35
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims abstract description 28
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims abstract description 28
- -1 polysiloxane Polymers 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 21
- 125000000129 anionic group Chemical group 0.000 claims abstract description 15
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 13
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims abstract description 9
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012972 dimethylethanolamine Substances 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims description 29
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 27
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 23
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 23
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 4
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 4
- RBGLVWCAGPITBS-UHFFFAOYSA-L bis(trifluoromethylsulfonyloxy)tin Chemical compound [Sn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F RBGLVWCAGPITBS-UHFFFAOYSA-L 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- QYYZHXHYNLXWAW-UHFFFAOYSA-N trimethyl(2-phenylethynyl)stannane Chemical compound C[Sn](C)(C)C#CC1=CC=CC=C1 QYYZHXHYNLXWAW-UHFFFAOYSA-N 0.000 claims description 4
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims 1
- 239000004744 fabric Substances 0.000 abstract description 16
- 241000894006 Bacteria Species 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000000243 solution Substances 0.000 description 16
- 239000000839 emulsion Substances 0.000 description 14
- 239000003921 oil Substances 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000004753 textile Substances 0.000 description 7
- 230000000844 anti-bacterial effect Effects 0.000 description 6
- 229920000742 Cotton Polymers 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229920013822 aminosilicone Polymers 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000520 microinjection Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000012224 working solution Substances 0.000 description 2
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- 241000222122 Candida albicans Species 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000003797 alkaloid derivatives Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000675 fabric finishing Substances 0.000 description 1
- 238000009962 finishing (textile) Methods 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexamethylene diamine Natural products NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000008041 oiling agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- LYRCQNDYYRPFMF-UHFFFAOYSA-N trimethyltin Chemical compound C[Sn](C)C LYRCQNDYYRPFMF-UHFFFAOYSA-N 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Abstract
The invention discloses a method for synthesizing cationic block silicone oil, which comprises the steps of synthesizing isophorone diisocyanate (IPDI), N-Dimethylethanolamine (DMEA) and 1, 3-propane sultone (1, 3-PS) to obtain betaine (NCO-betaine). And (3) reacting betaine (NCO-betaine) with self-made multiport polyether modified polysiloxane, and finally synthesizing the silicone oil with anionic and cationic groups. By adjusting the length of the polyether chain, a series of anionic-cationic block silicone oils can be obtained. The method is simple in synthesis, and the anionic/cationic block silicone oil has the effects of resisting bacteria and softening fabrics.
Description
Technical Field
The invention relates to a method for synthesizing block silicone oil, in particular to a method for preparing novel anionic and cationic block silicone oil, which is used in the fields of textile auxiliaries and daily chemical care.
Background
The organic silicon is used for various processes of fiber, fabric and dyeing and finishing in the textile processing process, has the functions of softening, lubricating, waterproofing, antistatic, elastic, non-ironing, mildew-proof, antibacterial and the like of finished fabrics, and can also be applied to defoaming equipment, textile dyeing equipment lubrication and the like.
Quaternary Ammonium Salts (QAS), also known as quaternary ammonium salts, are readily soluble in water and aqueous solutions thereof have conductivity, are a class of disinfectants and preservatives, also known as cationic detergents, and are widely used in medical disinfection, cleaning, deodorizing, and the like. The quaternary ammonium groups with positive charges in the quaternary ammonium salts adsorb bacteria with negative charges on the surfaces through the actions of static electricity and the like, damage the cell walls of the bacteria, inactivate proteins and finally damage the cell structures, thereby leading to the dissolution and death of the bacteria. The quaternary ammonium group has strong cationic property and thus better stability, but has poor binding force with textile fibers and thus needs to be modified. The quaternary ammonium salt type organic silicon has yellowing resistance, oxidation resistance and good antibacterial property, and can be widely applied to the fields of fiber fabric treatment and biomedical materials.
Betaine is an amphoteric alkaloid containing anionic and cationic groups, has good antibacterial performance and hygroscopicity, and has good heat stability, good cleaning effect, and wide application in the fields of textiles and the like. Chen et al (ACS Applied Materials & Interfaces,2011,3 (4): 1154-1162) designed and synthesized a novel environment-friendly betaine SSPB containing active siloxane groups, which has excellent antibacterial properties to bacteria such as E.coli, S.aureus, C.albican and the like after being subjected to covalent bonding and finishing on the surface of cotton textiles, obviously improves the hydrophilicity and breaking strength, and has no toxicity and no irritation to skin. Meanwhile, a nontoxic and safe siloxane antibacterial agent SSB (Surface Science,2011,605 (11-12): L25-L28) is synthesized, and is adhered to the Surface of glass, the antibacterial rate of E.coli and S.aureus is more than 99.9%, and the antibacterial rate of the novel quaternized modified block silicone oil still reaches 95% after standard washing.
Paper "study of the synthesis and properties of hydrophilic block silicone oils" (organosilicon materials, 2020,34 (2) 51-54) describes the preparation of quaternized hydrophilic block silicone oils by reacting an epoxy-terminated silicone oil with 4 alkyl tertiary amines (tetramethyl ethylenediamine, tetramethyl propylenediamine, tetramethyl hexamethylenediamine, bis (dimethylaminoethyl) ether), which have excellent whiteness, hydrophilicity, hand feel and water washing resistance when applied to cotton and polyester cotton; patent CN201610783241.7 discloses a quaternized modified block polyether amino silicone oil and a preparation method thereof, firstly, DMC and an epoxy end capping agent are used for preparing end epoxy silicone oil under alkaline conditions, then the end epoxy end capped block polyether amino silicone oil prepolymer is prepared by reacting with polyetheramine, and then the quaternized modified block polyether amino silicone oil is prepared by reacting with a tertiary amine compound, so that the end cap epoxy end capped block polyether amino silicone oil has excellent hand feeling when being applied to polyester cotton, and has small influence on whiteness and hydrophilicity of fabrics. When the block silicone oil is applied to fabrics, the block silicone oil is mainly combined with the fabrics through ionic bonds, although ideal effects can be achieved, the problem that the performances such as hydrophilicity, handfeel and antistatic performance are seriously reduced often occurs after multiple times of water washing is solved, the block silicone oil is lack of effective active groups in the structure of the block silicone oil, so that weak bond interaction cannot be generated between the block silicone oil and the active groups such as hydroxyl groups, carboxyl groups, amido groups and amino groups on fibers, and the block silicone oil cannot be crosslinked, so that the block silicone oil of the structure is greatly discounted in the selection of the type of the fabrics to be applied, and further application directions of the block silicone oil are limited.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of novel anionic/cationic block silicone oil, which is simple to synthesize, and the anionic/cationic block silicone oil has the effects of resisting bacteria and softening fabrics.
The invention provides a production process of anionic/cationic block silicone oil, which firstly synthesizes isophorone diisocyanate, N-dimethylethanolamine and 1, 3-propane sultone to obtain betaine. And (3) reacting betaine with self-made multiport polyether modified polysiloxane, and finally synthesizing the silicone oil with the anionic and cationic groups. By adjusting the length of the polyether chain, a series of anionic-cationic block silicone oils can be obtained.
A preparation method of cationic block silicone oil comprises the following steps:
(1) Preparation of the multiport polyether modified polysiloxane: under the protection of nitrogen, tetramethyl siloxane and allyl polyether are dissolved in an organic solvent, a catalyst is added after the temperature is raised, the temperature is raised to 80-100 ℃ to react to a terminal point, and the multiport polyether modified polysiloxane is obtained through vacuum rotary evaporation. The reaction formula is as follows:
in some embodiments, the solvent of step (1) is one of the starting materials 400 allyl polyether, 600 allyl polyether, 800 allyl polyether, with 400 allyl polyether being particularly preferred. The feeding mass ratio/mole ratio of the allyl polyether to the tetramethyl siloxane is 2-3:1, preferably 2:1.
preferably, the catalyst of step (1) is one of Speier's, karstedt's catalyst or other platinum catalyst, with Speier's catalyst being particularly preferred. It is foreseeable to the person skilled in the art that the amount of catalyst used is such that the above-mentioned reaction is carried out in the forward direction, and is generally in the range of 1 to 100ppm.
The organic solvent is selected from one of tetrahydrofuran, DMF, acetone and isopropanol.
(2) Preparation of cationic block silicone oil: the multiport polyether modified polysiloxane solution is injected into betaine solution and is stirred vigorously, catalyst is added, after temperature rising reaction, the mixture is cooled to room temperature, and the cationic block silicone oil is obtained, wherein the reaction formula is as follows:
the preparation method of the betaine in the structural formula comprises the following steps: in an organic solvent, isophorone diisocyanate, N-dimethylethanolamine and 1, 3-propane sultone are used as raw materials to react under the condition of a catalyst, the catalytic reaction temperature is 50-60 ℃, the reaction time is 0.1-24h, and betaine is prepared, wherein the reaction formula is as follows:
in some embodiments, the solvent is one of tetrahydrofuran, acetonitrile, acetone, and particularly tetrahydrofuran is preferred.
In some embodiments, the catalyst is one of dibutyltin dilaurate (DBTDL), stannous isooctanoate, tin trifluoromethane sulfonate, and trimethyltin (phenylethynyl), with dibutyltin dilaurate (DBTDL) being particularly preferred. It is foreseeable to the person skilled in the art that the amount of catalyst used is such that the above-mentioned reaction is carried out in the forward direction, typically the amount of catalyst is from 1 to 100mg/g of starting material.
Aiming at the technical scheme of the step (2), the formed multi-terminal polyether modified polysiloxane solution or the solvent of the betaine solution is selected from one of tetrahydrofuran, acetone, DMF and isopropanol;
in the technical scheme of the step (2), the catalyst is selected from one of dibutyl tin dilaurate (DBTDL), stannous isooctanoate, tin trifluoromethane sulfonate, trimethyl (phenylethynyl) tin and dibutyl tin diacetate, and especially preferably one of dibutyl tin dilaurate (DBTDL).
Aiming at the technical scheme of the step (2), the feeding mass ratio/mole ratio of the betaine to the multiport polyether modified polysiloxane is 2:1.
the catalytic reaction temperature is 50-60 ℃ and the reaction time is 0.1-20h.
The invention has the beneficial effects that: compared with the existing block silicone oil, the method for preparing the anionic-cationic block silicone oil is prepared by utilizing betaine and multiport polyether modified polysiloxane to react, the self-emulsifying property of the silicone oil and the heat-resistant storage stability of emulsion are greatly improved, the application end of secondary processing of the silicone oil is reduced, and the use of high-shear equipment is reduced, so that the industrialized cost is reduced. The anionic-cationic block silicone oil solves the problem of instability of the traditional cationic silicone oil emulsion in an anionic application system, and expands the application range of the product emulsion. In addition, the quaternary cationic block silicone oil has the functions of resisting bacteria and endowing fabric with softness and low yellowing, and a series of cationic block silicone oils can be obtained by adjusting the length of polyether chains.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the patent claims is not limited to the scope of the examples.
EXAMPLE 1 preparation of betaine
4.44g (20 mmol) of isophorone diisocyanate (IPDI) is added into a round-bottom flask, and dissolved in 60mL of Tetrahydrofuran (THF), after the dissolution is completed, 1.78g (20 mmol) of N, N-Dimethylethanolamine (DMEA) is slowly added dropwise by using a constant pressure funnel, 120 mu L of dibutyltin dilaurate (DBTDL) is added as a catalyst, uniformly mixed at 60 ℃ and magnetically stirred at constant temperature for 2h; 2.44g (20 mmol) of 1, 3-propane sultone (1, 3-PS) was added at 50℃and magnetically stirred at constant temperature for 2h, resulting in a large amount of white precipitate; after the reaction, the mixture is filtered by suction and washed by anhydrous diethyl ether for a plurality of times, and is placed in a vacuum drying oven to be dried for 12 hours at a constant temperature of 40 ℃ to obtain the white solid compound (betaine, molecular weight 418.5) with the yield of 86.0 percent and the purity of 95.1 percent.
EXAMPLE 2 preparation of betaine
4.44g (20 mmol) of isophorone diisocyanate (IPDI) is added into a round-bottom flask and dissolved in 60mL of acetone, after the dissolution is completed, 1.78g (20 mmol) of N, N-Dimethylethanolamine (DMEA) is slowly added dropwise by using a constant pressure funnel, 120 mu L of dibutyltin dilaurate (DBTDL) is added as a catalyst, uniformly mixed at 60 ℃ and magnetically stirred at constant temperature for 2h; 2.44g (20 mmol) of 1, 3-propane sultone (1, 3-PS) was added at 50℃and magnetically stirred at constant temperature for 2h, resulting in a large amount of white precipitate; after the reaction, the mixture is filtered by suction and washed by anhydrous diethyl ether for a plurality of times, and is placed in a vacuum drying oven to be dried for 12 hours at a constant temperature of 40 ℃ to obtain the white solid compound (betaine, molecular weight 418.5) with the yield of 70.0 percent and the purity of 65.3 percent.
EXAMPLE 3 preparation of betaine
4.44g (20 mmol) of isophorone diisocyanate (IPDI) is added into a round-bottom flask, and dissolved in 60mL of acetone, after the dissolution is completed, 1.78g (20 mmol) of N, N-Dimethylethanolamine (DMEA) is slowly added dropwise by using a constant pressure funnel, 40mg of trimethyl (phenylethynyl) tin is added as a catalyst, and the mixture is uniformly mixed at 60 ℃ and magnetically stirred at constant temperature for 2 hours; 2.44g (20 mmol) of 1, 3-propane sultone (1, 3-PS) was added at 50℃and magnetically stirred at constant temperature for 2h, resulting in a large amount of white precipitate; after the reaction, the mixture is filtered by suction and washed by anhydrous diethyl ether for a plurality of times, and is placed in a vacuum drying oven to be dried for 12 hours at a constant temperature of 40 ℃ to obtain the white solid compound (betaine, molecular weight 418.5) with the yield of 28.4 percent and the purity of 78.9 percent.
EXAMPLE 4 preparation of Multi-terminal polyether modified polysiloxanes
Under nitrogen protection, 1g of tetramethyldisiloxane and 4.05g of allyl polyether (molecular weight 400) were added to a vessel (as generally understood from a four-necked flask equipped with a rotor, thermometer, condenser), 15. Mu.L of isopropyl chloroplatinate solution (0.8 mg/mL) was added, and the oil bath magnetic stirrer was heated to 60℃and activated for 30 minutes, and the temperature was further raised to 100℃to react for 7 hours. Isopropanol was removed by rotary evaporation in vacuo to give a colourless oily liquid (molecular weight 900) with a conversion of 65.4%.
EXAMPLE 5 preparation of Multi-terminal polyether modified polysiloxanes
Under the protection of nitrogen, 4.05g of allyl polyether (molecular weight 400) is added into a four-neck flask with a rotor, a thermometer and a condenser, 15 mu L of chloroplatinic acid isopropanol solution (0.8 mg/mL) is added, an oil bath magnetic stirrer is heated to 60 ℃, activation is carried out for 30min, the temperature is further raised to 100 ℃, 1g of tetramethyl disiloxane is added dropwise, and the reaction is carried out for 7h. Isopropanol was removed by rotary evaporation in vacuo to give a colourless oily liquid (molecular weight 900) with a conversion of 95.8%.
EXAMPLE 6 preparation of Multi-terminal polyether modified polysiloxanes
Under the protection of nitrogen, 4.05g of allyl polyether (molecular weight 800) is added into a four-neck flask with a rotor, a thermometer and a condenser, 15 mu L of chloroplatinic acid isopropanol solution (0.8 mg/mL) is added, an oil bath magnetic stirrer is heated to 60 ℃, activation is carried out for 30min, the temperature is further raised to 100 ℃, 1g of tetramethyl disiloxane is added dropwise, and the reaction is carried out for 7h. The isopropanol was removed by rotary evaporation in vacuo to give a colourless oily liquid (molecular weight 1700) with a conversion of 90.5%.
EXAMPLE 7 preparation of cationic block Silicone oil
Under the protection of nitrogen, adding betaine (NCO-betaine) prepared in the example 1 into a four-neck flask, heating to 50 ℃, slowly dripping the multi-terminal polyether modified polysiloxane acetone solution prepared in the example 5 by a microinjection pump, vigorously stirring, keeping the stirring state for 2 hours, adding a catalyst (dibutyl tin dilaurate), heating to 60 ℃ and reacting for 30 minutes. Cooling to room temperature to obtain anionic/cationic block silicone oil (molecular weight 1300), with a conversion rate of 96.1%.
EXAMPLE 8 preparation of cationic block Silicone oil
Under the protection of nitrogen, the betaine (NCO-betaine) prepared in the example 1 and the multiport polyether modified polysiloxane prepared in the example 5 are respectively dissolved in acetone, added into a four-neck flask, heated to 50 ℃, kept in a stirring state for 2h to finish dripping, and then added with a catalyst dibutyltin dilaurate, heated to 60 ℃ to react for 30min. Cooling to room temperature to obtain anionic/cationic block silicone oil (molecular weight 1300), with a conversion rate of 86.3%.
EXAMPLE 9 preparation of cationic block Silicone oil
Under the protection of nitrogen, adding betaine (NCO-betaine) prepared in the example 1 into a four-neck flask, heating to 50 ℃, slowly dripping the multi-terminal polyether modified polysiloxane tetrahydrofuran solution prepared in the example 5 by a microinjection pump, vigorously stirring, keeping the stirring state for 2 hours, adding a catalyst dibutyltin dilaurate, heating to 60 ℃ and reacting for 30 minutes. Cooling to room temperature to obtain anionic/cationic block silicone oil (molecular weight 1300), with a conversion rate of 88.5%.
EXAMPLE 10 preparation of cationic block Silicone oil
Under the protection of nitrogen, adding betaine (NCO-betaine) prepared in the example 1 into a four-neck flask, heating to 50 ℃, slowly dripping the multi-terminal polyether modified polysiloxane tetrahydrofuran solution prepared in the example 5 by a microinjection pump, vigorously stirring, keeping the stirring state for 2 hours, adding a catalyst dibutyltin diacetate, heating to 60 ℃ and reacting for 30 minutes. Cooling to room temperature to obtain anionic/cationic block silicone oil (molecular weight 1300), and the conversion rate is 72.1%.
Evaluation of cationic block silicone oil application:
table 1 laboratory apparatus
| Instrument name | Instrument model |
| Laboratory padder | EL-400B |
| Sample shaping dryer | LD-360 |
| Whiteness color instrument | DRK-130B |
| High-speed dispersing machine | MICCRAos-40HS |
Isophorone diisocyanate-terminated block silicone oil or the cationic block silicone oil prepared in example 7 was emulsified to an emulsion having a solids content of 30wt%, and the amount of HAC was 2wt% of the solids content of the emulsion. Water is gradually added in the stirring and emulsifying process until emulsion is formed. And (3) forming a transparent solution after the cationic block silicone oil emulsion is static, and performing cloth beating test:
the preparation method of isophorone diisocyanate blocked block silicone oil comprises the following steps: 2000 g of double-end epoxy silicone oil with the number average molecular weight of 20000, 35 g of diethylenediamine and 650 g of isopropanol are added into a reaction vessel equipped with a condensation reflux device, the reaction vessel is heated to 90 ℃, and the reaction is carried out for 5 hours under the condition of heat preservation within the temperature range, so that piperazine-terminated polysiloxane is prepared; the reaction vessel is cooled to 40 ℃, 50 g of isophorone diisocyanate is added into the reaction vessel, and the reaction is carried out for 2 hours with heat preservation, thus obtaining isophorone diisocyanate end-capped block silicone oil.
The application test process comprises the following steps: the fabric toweling cloth, flannel and pure cotton woven cloth are padded in the transparent solution (the dosage is 6.67 g/L) formed in the above, baked for 70 seconds at 160 ℃, cooled and tested.
Smooth and silky feel: the hand feeling is evaluated by adopting a touch method, and particularly 10 professionals are grouped to carry out touch scoring to give average division, 100 division is adopted, and a high score indicates that the better the smoothness is and the stronger the real silk feeling is.
Centrifugal stability test: centrifuging the multifunctional finishing agent and storing for 24 hours to check whether layering occurs; the centrifugation conditions were 8000r/min,30min.
Whiteness is tested by adopting a whiteness instrument DRK-130B; softness and smoothness are tested by a fabric style meter YG821L, and the greater the bending stiffness is, the worse the fabric softness is represented; the higher the liveness value, the softer the representation; the lower the coefficient of friction value, the better the representative slip. The hand comparison samples have fine phase differences, and the higher the whiteness value is, the lower the yellowing is.
Heat resistance stability: 200mL of 3% silicone oil working solution is prepared in a 250mL closed container, the mixture is placed in a constant temperature oven with the temperature being adjusted to 80 ℃ for 4 hours, the stability of the working solution in a cup is observed, and whether phenomena such as oil bleaching and oil bloom exist or not is recorded.
Alkali resistance 3g of organosilicon sample emulsion is weighed in a 150mL beaker, 97mL of sodium carbonate solution (the pH value is adjusted to be 12-13) is added, the mixture is stood for 4 hours, the stability of the emulsion in the beaker is observed, and the phenomena of drifting and layering are recorded.
Anion-resistant: a3 g sample of the silicone emulsion was weighed in a 150mL beaker and placed in a 97mL rest position if a 0.3% fluorescent whitening agent VBU solution. Observations were made once at 4h and 24h, respectively, and the phenomena of oil drift and delamination in the cup were recorded.
Electrolyte (magnesium chloride): a sample of 3g of the silicone emulsion was weighed into a 150mL beaker and 2% MgCl was added 2 Standing 97mL of 6H2O solution, observing once in 4H and 24H respectively, and recording the phenomena of oil drifting and layering in the cup.
Acid resistance: 3g of the silicone emulsion sample was weighed into a 150mL beaker, then 97mL of acetic acid solution (adjusted to pH 2-3) was added, the mixture was allowed to stand for 4 hours, the stability of the emulsion in the beaker was observed, and the presence or absence of delamination of the oil was recorded.
By comparing with isophorone diisocyanate end-capped block silicone oil and market conventional Kefeng block silicone oil, the anionic and cationic block silicone oil of the invention has particularly obvious fabric finishing effect and excellent emulsion storage stability, and is particularly in the aspects of anion resistance and heat resistance storage.
Compared with the current quaternary ammonium salt cationic block silicone oil, the cationic block silicone oil has the advantages of simple process, high yield, low industrialization cost, strong handfeel controllability of product structural design and the like. The product can be mainly used in the fields of daily chemical care additives, textile printing and dyeing after-finishing assistants, high-performance carbon fiber oiling agents and the like.
Claims (9)
1. The synthesis method of the cationic block silicone oil is characterized by comprising the following steps of:
(1) Preparation of the multiport polyether modified polysiloxane: under the protection of nitrogen, tetramethyl siloxane and allyl polyether are dissolved in an organic solvent, a catalyst is added after the temperature is raised, the temperature is raised to 80-100 ℃ to react to a terminal point, and the multi-terminal polyether modified polysiloxane is obtained by vacuum rotary evaporation;
(2) Preparation of betaine NCO-betaine: dissolving isophorone diisocyanate IPDI, N-dimethylethanolamine DMEA and 1, 3-propane sultone 1,3-PS in an organic solvent, and adding a catalyst to synthesize betaine;
(3) Preparation of cationic block silicone oil: and (3) injecting the multi-terminal polyether modified polysiloxane solution into the betaine solution, stirring vigorously, adding a catalyst, heating to react, and cooling to room temperature to obtain the anionic/cationic block silicone oil.
2. The method for synthesizing the cationic block silicone oil according to claim 1, wherein the method comprises the following steps: the allyl polyether in the step (1) is selected from one of 400 allyl polyether, 600 allyl polyether and 800 allyl polyether, and particularly preferably the raw material is 400 allyl polyether; the feeding mass ratio/mole ratio of the allyl polyether to the tetramethyl siloxane is 2-3:1.
3. the method for synthesizing the cationic block silicone oil according to claim 1, wherein the method comprises the following steps: the catalyst in step (1) is selected from one of Speier's, karstedt's catalyst or other platinum catalysts, with Speier's catalyst being particularly preferred;
the organic solvent is selected from one of tetrahydrofuran, DMF, acetone and isopropanol.
4. The method for synthesizing the cationic block silicone oil according to claim 1, wherein the method comprises the following steps: in the step (2), the betaine is prepared by reacting isophorone diisocyanate, N-dimethylethanolamine and 1, 3-propane sultone serving as raw materials in an organic solvent under the condition of a catalyst.
5. The method for synthesizing the cationic block silicone oil according to claim 1, wherein the method comprises the following steps: the organic solvent in the step (3) is selected from one of tetrahydrofuran, DMF, acetone and isopropanol; the catalyst is selected from one of dibutyl tin dilaurate DBTDL, stannous isooctanoate, tin trifluoromethane sulfonate, trimethyl (phenylethynyl) tin and dibutyl tin diacetate, and especially preferably one of dibutyl tin dilaurate DBTDL.
6. The method for synthesizing the cationic block silicone oil according to claim 5, wherein the method comprises the following steps: the catalytic reaction temperature is 50-60 ℃ and the reaction time is 0.1-24h.
7. The method for synthesizing the cationic block silicone oil according to claim 1, wherein the method comprises the following steps: the multi-terminal polyether modified polysiloxane solution formed in the step (1), the step (2) or the solvent of the betaine solution is selected from one of tetrahydrofuran, acetone, DMF and isopropanol;
the catalyst is selected from one of dibutyl tin dilaurate (DBTDL), stannous octoate, tin trifluoromethane sulfonate, trimethyl (phenylethynyl) tin and dibutyl tin diacetate, and especially preferably one of dibutyl tin dilaurate (DBTDL).
8. The method for synthesizing the cationic block silicone oil according to claim 1, wherein the method comprises the following steps: the feeding mass ratio/mole ratio of the betaine to the multiport polyether modified polysiloxane is 2:1.
9. the method for synthesizing the cationic block silicone oil according to claim 1, wherein the method comprises the following steps: the catalytic reaction temperature in the step (3) is 50-60 ℃ and the reaction time is 0.1-20h.
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