CN113152102A - High-oil-emulsion-ratio amino modified macromolecular organic silicon emulsion and preparation method thereof - Google Patents
High-oil-emulsion-ratio amino modified macromolecular organic silicon emulsion and preparation method thereof Download PDFInfo
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- 239000000839 emulsion Substances 0.000 title claims abstract description 91
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 83
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000010703 silicon Substances 0.000 title claims abstract description 62
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000004945 emulsification Methods 0.000 title description 7
- 239000000203 mixture Substances 0.000 claims abstract description 66
- 229920002545 silicone oil Polymers 0.000 claims abstract description 55
- 229920002521 macromolecule Polymers 0.000 claims abstract description 47
- 239000003921 oil Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000010779 crude oil Substances 0.000 claims abstract description 26
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 239000003381 stabilizer Substances 0.000 claims abstract description 12
- 239000004753 textile Substances 0.000 claims abstract description 12
- 239000007957 coemulsifier Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 9
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 11
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 11
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- -1 polydimethylsiloxane Polymers 0.000 claims description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 229920002379 silicone rubber Polymers 0.000 claims description 4
- 239000004945 silicone rubber Substances 0.000 claims description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical group C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000000373 fatty alcohol group Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 229920013822 aminosilicone Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
-
- 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
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a high oil emulsion ratio type amino modified macromolecule organic silicon emulsion and a preparation method thereof, wherein the high oil emulsion ratio type amino modified macromolecule organic silicon emulsion is used as a hand feeling finishing agent of textiles, and the method comprises the following steps: adding an organic silicon cross-linking agent and amino modified macromolecule organic silicon crude oil into a reaction kettle according to the mass ratio of 0-1: 3, starting stirring, and reacting for 0-2 hours at 50-100 ℃ to obtain a silicone oil mixture; adding a co-emulsifier accounting for 20-100% of the silicone oil mixture, an emulsifier accounting for 5-10%, a silicone oil stabilizer accounting for 0-2% and an acid accounting for 0.5-3% by mass ratio, and emulsifying with water to obtain the high oil emulsion ratio type amino modified macromolecule silicone emulsion. The high-oil emulsion ratio amino modified macromolecule organic silicon emulsion prepared by the invention has the advantages of stable, smooth and soft emulsion, fine hand feeling, good skin-friendly feeling and wide market prospect.
Description
Technical Field
The invention relates to the field of polymer chemistry, in particular to a high-oil emulsion type amino modified macromolecular organic silicon emulsion and a preparation method thereof.
Background
In recent years, along with the improvement of the quality of life, people have higher requirements on the hand feeling of textiles, most of the hand feeling finishing agents of the textiles are amino modified organic silicon polysiloxane polymer emulsion products (such as amino silicone oil, ternary copolymer silicone oil and the like), and sometimes a certain amount of macromolecular modified silicone oil needs to be introduced in order to achieve a better smoothing effect. However, the amino silicone oil can not be directly used, a certain proportion of emulsifier is required to be added to form a relatively stable amino silicone oil emulsion, the introduction of the emulsifier reduces the hand feeling of the amino silicone oil on the textile to a certain extent, particularly, an excessive amount of emulsifier is often added into the amino modified macromolecular organic silicone emulsion, and in the textile hand feeling finishing, a large amount of emulsifier also remains on the cloth cover, so that the hand feeling of the textile is greatly influenced. The block silicone oil for replacing amino silicone oil products is relatively complex in synthetic process, high in solvent content (generally between 30-50%), harmless to human bodies, but brings about a great deal of adverse effects on the after-finishing processing environment, the safety of transportation and storage is greatly reduced, and meanwhile, a polyether chain segment in the block silicone oil is located on a main chain segment of an organic silicon polymer, so that the hand feeling of textiles is influenced to a certain extent. Therefore, the development of amino modified silicone oil with high oil emulsion ratio and emulsion thereof, especially amino modified macromolecule silicone and emulsion thereof is very necessary.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide the high-oil-emulsion-ratio amino modified macromolecular organic silicon emulsion and the preparation method thereof.
The technical scheme of the invention is as follows:
a preparation method of a high oil emulsion ratio type amino modified macromolecule organic silicon emulsion used as a hand feeling finishing agent of textiles comprises the following steps:
adding an organic silicon cross-linking agent and amino modified macromolecule organic silicon crude oil into a reaction kettle according to the mass ratio of 0-1: 3, starting stirring, and reacting for 0-2 hours at 50-100 ℃ to obtain a silicone oil mixture;
adding a co-emulsifier accounting for 20-100% of the silicone oil mixture, an emulsifier accounting for 5-10%, a silicone oil stabilizer accounting for 0-2% and an acid accounting for 0.5-3% by mass ratio, and emulsifying with water to obtain the high oil emulsion ratio type amino modified macromolecule silicone emulsion.
Optionally, the amino modified macromolecular silicone crude oil is prepared by the following process:
mixing the organic silicon ring body and the amino end capping agent according to the mass ratio of 100: 3-100: 15 to obtain a first mixture, adding an alkaline catalyst accounting for 0.3-0.4% of the first mixture according to the mass ratio, and carrying out equilibrium reaction at 90-140 ℃ for 2-6 hours;
adding a silane coupling agent accounting for 0.2-10% of the first mixture according to the mass ratio, and reacting for 2-4 hours at 90-140 ℃;
and adding the super-large molecular linear silicone oil accounting for 1-50% of the first mixture according to the mass ratio, and reacting at 100-140 ℃ for 2-4 hours to obtain the amino modified macromolecular organic silicon crude oil.
Further optionally, the silicone ring body is octamethylcyclotetrasiloxane or dimethylcyclosiloxane.
Further optionally, the amino capping agent is QH-612.
Further optionally, the basic catalyst is any one of tetramethylammonium hydroxide, potassium hydroxide, sodium hydroxide and lithium hydroxide.
Further optionally, the silane coupling agent is one or more of KBM602, QH-121, and QH-110.
Further optionally, the ultra-large molecular linear silicone oil is one or more of hydroxy dimethyl siloxy terminated polydimethylsiloxane with a molecular weight of 50-500 ten thousand and methyl vinyl silicone rubber with a molecular weight of 50-500 ten thousand.
Optionally, the emulsifier is fatty alcohol-polyoxyethylene ether, isomeric tridecanol polyoxypropylene ether or a compound thereof;
the auxiliary emulsifier is a mixture of ethylene glycol monobutyl ether and glycerol in any proportion.
Optionally, the silicone oil stabilizer is AEO80-68S and the acid is one or more of glacial acetic acid, formic acid, or citric acid.
The invention relates to a high-oil-emulsion-ratio amino modified macromolecular organic silicon emulsion, which is prepared by the preparation method of the high-oil-emulsion-ratio amino modified macromolecular organic silicon emulsion.
Has the advantages that: the high-oil emulsion ratio amino modified macromolecule organic silicon emulsion prepared by the invention has the advantages of stable, smooth and soft emulsion, fine hand feeling, good skin-friendly feeling and wide market prospect.
Detailed Description
The invention provides a high oil emulsion ratio type amino modified macromolecule organic silicon emulsion and a preparation method thereof, and the invention is further explained in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a preparation method of a high-oil emulsion ratio type amino modified macromolecular organic silicon emulsion, which is used as a hand feeling finishing agent of textiles, and the method comprises the following steps:
s1, adding the organic silicon cross-linking agent and the amino modified macromolecule organic silicon crude oil into a reaction kettle according to the mass ratio of 0-1: 3, starting stirring, and reacting for 0-2 hours at 50-100 ℃ to obtain a silicone oil mixture;
s2, adding a co-emulsifier accounting for 20-100% of the silicone oil mixture, an emulsifier accounting for 5-10%, a silicone oil stabilizer accounting for 0-2% and an acid accounting for 0.5-3% by mass ratio, and emulsifying with water to obtain the high oil emulsion ratio type amino modified macromolecule organic silicon emulsion.
In the embodiment of the invention, firstly, an organosilicon crosslinking agent and amino modified macromolecule organosilicon crude oil are added into a reaction kettle according to the mass ratio of 0-1: 3, stirring is started, and the macromolecule chain segment and amino in the amino modified macromolecule organosilicon crude oil chain segment are reacted through the organosilicon crosslinking agent so as to improve the water solubility of the organosilicon crosslinking agent, an organosilicon elastomer is easily formed due to improper control of reaction conditions and is not beneficial to emulsification into emulsion, and the ideal reaction conditions are as follows: the reaction temperature is 50-100 ℃, and the reaction time is not more than 2 hours, so that the silicone oil mixture is obtained. Then, adding a co-emulsifier which accounts for 20-100% of the silicone oil mixture and an emulsifier which accounts for 5-10% of the silicone oil mixture according to the mass ratio, wherein the addition of the co-emulsifier can obviously reduce the viscosity of the silicone oil emulsification phase inversion, improve the phase inversion consistency of the emulsion, emulsifying with water, and finally adding 0-2% of a silicone oil stabilizer and 0.5-3% of acid to prepare the stable high oil emulsion ratio type amino modified macromolecular organic silicon emulsion.
According to the embodiment of the invention, amino modified macromolecule organic silicon crude oil and an organic silicon cross-linking agent are added with a proper amount of emulsifier, co-emulsifier, silicon oil stabilizer and acid according to a certain proportion, and the high oil emulsion ratio amino modified macromolecule organic silicon emulsion is prepared by water emulsification. The high-oil emulsion ratio amino modified macromolecule organic silicon emulsion prepared by the embodiment of the invention has the advantages of stable, smooth and soft emulsion, fine hand feeling, good skin-friendly feeling and wide market prospect. Wherein the high oil emulsion ratio refers to the mass ratio of the amino modified macromolecule organic silicon crude oil to the emulsifier being more than 10, and the specific mass ratio is 10-20.
In step S1, in one embodiment, the amino-modified macromolecular silicone crude oil is prepared as follows:
s11, mixing the organic silicon ring body and the amino end socket agent according to the mass ratio of 100: 3-100: 15 to obtain a first mixture, adding an alkaline catalyst accounting for 0.3-0.4% of the first mixture according to the mass ratio, and carrying out equilibrium reaction at 90-140 ℃ for 2-6 hours;
s12, adding a silane coupling agent accounting for 0.2-10% of the first mixture according to the mass ratio, and reacting for 2-4 hours at 90-140 ℃;
and S13, adding the super-large molecular linear silicone oil accounting for 1-50% of the first mixture according to the mass ratio, and reacting at 100-140 ℃ for 2-4 hours to obtain the amino modified macromolecular organic silicon crude oil.
In step S11, in one embodiment, the silicone ring body is octamethylcyclotetrasiloxane (D4) or Dimethylcyclosiloxane (DMC).
In one embodiment, the amino capping agent is QH-612, which has a major component of-CH2CH2NHCH2O(CH2CH2O)2(CH(CH3)CH2O)2(CH2)3Si(CH3)2O-。
In one embodiment, the basic catalyst is any one of tetramethylammonium hydroxide, potassium hydroxide, sodium hydroxide, and lithium hydroxide.
In step S12, in one embodiment, the silane coupling agent is KBM602 (chemical formula NH)2CH2CH2NH2CH2CH2CH2SiCH3(OCH3)2) QH-121 (chemical structural formula is CH)3(CH3O)2SiCH2CH2CH2NHCH2CH2CH2N(CH3)2) And QH-110 (chemical structural formula
) One or more of (a).
In an embodiment, in step S13, the linear ultra-large molecular silicone oil is one or more of hydroxy dimethylsilyloxy terminated polydimethylsiloxane having a molecular weight of 50 to 500 ten thousand and methyl vinyl silicone rubber having a molecular weight of 50 to 500 ten thousand.
In step S1, the preparation process of the organosilicon crosslinking agent is the same as that in the patent "an organosilicon high-elasticity smoothing agent and its preparation method" (ZL201710074185.4), and is not repeated here.
In step S2, in an embodiment, the emulsifier is one or more of fatty alcohol polyoxyethylene ether, isomeric tridecanol polyoxyethylene ether, and isomeric tridecanol polyoxypropylene ether.
In one embodiment, the co-emulsifier is a mixture of ethylene glycol monobutyl ether and glycerol in any proportion. Further, the mass ratio of the ethylene glycol monobutyl ether to the glycerol is 0-5: 10.
In one embodiment, the silicone oil stabilizer is a linear C16-18 fatty alcohol ethoxylate (55EO), also known as AEO 80-68S.
In one embodiment, the acid is one or more of glacial acetic acid, formic acid, citric acid, or the like.
The embodiment of the invention provides a high-oil-emulsion-ratio amino modified macromolecular organic silicon emulsion, which is prepared by the preparation method of the high-oil-emulsion-ratio amino modified macromolecular organic silicon emulsion.
The invention is further illustrated by the following specific examples.
Example 1:
the preparation process of the amino modified macromolecule organic silicon crude oil comprises the following steps: mixing an organosilicon ring body D4 and an amino end capping agent QH-612 according to the mass ratio of 100:3 to obtain a first mixture, adding a basic catalyst tetramethylammonium hydroxide accounting for 0.3 percent of the first mixture according to the mass ratio at 90 ℃ to perform equilibrium reaction for 4 hours, then adding a silane coupling agent QH-121 accounting for 2 percent of the first mixture to perform reaction for 2 hours at 100 ℃, then adding a hydroxydimethylsiloxy-terminated polydimethoxysilane accounting for 30 percent of the first mixture and having the average molecular weight of 500 ten thousand to perform equilibrium reaction for 2 hours at 120 ℃, thereby preparing the amino modified macromolecular organosilicon crude oil.
The preparation process of the high oil emulsion ratio type amino modified macromolecule organic silicon emulsion comprises the following steps: emulsifying by using 30% of silicone oil in percentage by mass, adding the organosilicon crosslinking agent and the amino modified macromolecule organosilicon crude oil into a reaction kettle according to the mass ratio of 1:19, starting stirring, and reacting for 0.5 hour at 100 ℃ to obtain a silicone oil mixture; adding co-emulsifier propylene glycol accounting for 45% of the silicone oil mixture and 5% of ethylene glycol monobutyl ether, emulsifier accounting for 8% of the silicone oil mixture and silicone oil stabilizer AEO80-68S accounting for 2% of the silicone oil mixture according to the mass ratio, stirring uniformly, adding glacial acetic acid accounting for 1% of the silicone oil mixture, and adding water accounting for 172.3% of the silicone oil mixture under the stirring condition, thereby preparing the high-oil emulsion ratio type amino modified macromolecular organic silicon emulsion with 30% of silicon content. Wherein the emulsifier comprises isomeric tridecanol polyoxyethylene ether TO-5 and TO-7, and the mass ratio of the isomeric tridecanol polyoxyethylene ether TO-5 TO the isomeric TO-7 is 1: 1.
The material composition is as follows 1:
TABLE 1 materials ratio
Example 2:
the preparation process of the amino modified macromolecule organic silicon crude oil comprises the following steps: mixing organic silicon ring DMC and amino end capping agent QH-612 according to the mass ratio of 100:15 to obtain a first mixture, adding alkaline catalyst KOH accounting for 0.5% of the first mixture according to the mass ratio at 140 ℃ to perform equilibrium reaction for 6 hours, then adding silane coupling agent QH-110 accounting for 1% of the first mixture to perform reaction for 2 hours at 100 ℃, then adding methyl vinyl silicone rubber accounting for 10% of the first mixture and having the average molecular weight of 60 ten thousand to perform equilibrium reaction for 2 hours at 110 ℃, thereby preparing the high oil emulsion ratio type amino modified macromolecular organic silicon crude oil.
The preparation process of the high oil emulsion ratio type amino modified macromolecule organic silicon emulsion comprises the following steps: emulsifying by using 30% silicon content, adding the organosilicon crosslinking agent and the high oil emulsion ratio type amino modified macromolecule organosilicon crude oil into a reaction kettle according to the mass ratio of 1:3, starting stirring, and reacting for 2 hours at 50 ℃ to obtain a silicone oil mixture; adding co-emulsifier glycerol accounting for 100% of the silicone oil mixture, emulsifier accounting for 5% of the silicone oil mixture and silicone oil stabilizer AEO80-68S accounting for 1% of the silicone oil mixture according to the mass ratio, stirring uniformly, adding glacial acetic acid accounting for 2% of the silicone oil mixture, and adding water accounting for 125.3% of the silicone oil mixture under the stirring condition, thereby preparing the high-oil emulsion ratio type amino modified macromolecular organic silicon emulsion with the silicon content of 30%. Wherein the emulsifier comprises isomeric tridecanol polyoxyethylene ether TO-5.
The material composition is as follows 2:
TABLE 2 materials ratio
Example 3:
the preparation process of the amino modified macromolecule organic silicon crude oil comprises the following steps: mixing organic silicon ring DMC and amino end capping agent QH-612 according to the mass ratio of 100:3 to obtain a first mixture, adding an alkaline catalyst NaOH accounting for 0.3% of the first mixture according to the mass ratio at 100 ℃ to perform equilibrium reaction for 6 hours, then adding silane coupling agent KBM-602 accounting for 8% of the first mixture to perform reaction for 2 hours at 100 ℃, then adding hydroxydimethylsiloxy-terminated polydimethoxysilane accounting for 50% of the first mixture and having an average molecular weight of 200 ten thousand to perform reaction for 4 hours at 120 ℃, thereby preparing the amino modified macromolecular organic silicon crude oil.
The preparation process of the amino modified macromolecule organic silicon emulsion with high oil emulsion ratio is as follows: emulsifying by using 30% of silicon content, adding the organosilicon crosslinking agent and the amino modified macromolecule organosilicon crude oil into a reaction kettle according to the mass ratio of 1:9, starting stirring, and reacting for 1 hour at 70 ℃ to obtain a silicone oil mixture; adding propylene glycol accounting for 95% of the silicone oil mixture, ethylene glycol monobutyl ether accounting for 5% of the silicone oil mixture and an emulsifier accounting for 10% of the silicone oil mixture according to the mass ratio, uniformly stirring, adding formic acid accounting for 3% of the silicone oil mixture, and adding water accounting for 120.3% of the silicone oil mixture under the stirring condition, thereby preparing the high-oil emulsion ratio amino modified macromolecular organic silicon emulsion with the silicon content of 30%. The emulsifier comprises isomeric tridecanol polyoxyethylene ether TO-5 and TO-7, wherein the mass ratio of the isomeric tridecanol polyoxyethylene ether TO-5 TO the isomeric TO-7 is 2: 1.
The material formulation is as follows 3:
TABLE 3 materials ratio
Example 4:
the preparation process of the amino modified macromolecule organic silicon crude oil comprises the following steps: mixing organosilicon ring DMC and amino end capping agent QH-612 according to the mass ratio of 100:8 to obtain a first mixture, adding a basic catalyst LiOH accounting for 0.4% of the first mixture according to the mass ratio at 130 ℃ to perform equilibrium reaction for 4 hours, then adding silane coupling agent QH-121 accounting for 0.2% of the first mixture to perform reaction for 4 hours at 130 ℃, then adding hydroxydimethylsiloxy-terminated polydimethoxysilane accounting for 25% of the first mixture and having the average molecular weight of 500 ten thousand to perform equilibrium reaction for 2 hours at 130 ℃, thereby preparing the amino modified macromolecular organosilicon crude oil.
The preparation process of the amino modified macromolecule organic silicon emulsion with high oil emulsion ratio is as follows: adding 20% of co-emulsifier glycerol and 10% of ethylene glycol monobutyl ether, 10% of emulsifier and 2% of silicone oil stabilizer AEO80-68S into amino modified macromolecule organic silicon crude oil by using 30% of silicon content for emulsification, adding citric acid accounting for 0.5% of silicone oil mixture after uniformly stirring, and adding water accounting for 190.83% of silicone oil mixture under the stirring condition, thereby preparing the high oil emulsion ratio type amino modified macromolecule organic silicon emulsion with 30% of silicon content. The emulsifier comprises isomeric tridecanol polyoxyethylene ether TO-5 and TO-7, wherein the mass ratio of the isomeric tridecanol polyoxyethylene ether TO-5 TO the isomeric TO-7 is 4: 1.
The material composition is as follows 4:
TABLE 4 materials ratio
Evaluation of hand feeling
Comparison standard: preparing the high-oil emulsion ratio type amino modified macromolecule organic silicon emulsion with the silicon content of 30% into 80g/L working solution, finishing pure white mercerized stentering cloth, and adopting a one-dipping one-rolling process to shape at 160 ℃ for 90 seconds.
The evaluation method comprises the following steps: the hand feeling is mainly examined from the aspects of softness, smoothness and fineness and is blindly touched by multiple experts, the grade 5 is the best, and the grade 1 is the worst. The comparison results are shown in table 5 below:
TABLE 5 comparative results
The handfeel fineness of the textile finished by the high-oil emulsion ratio type amino modified macromolecular organic silicon emulsion is obviously better than that of the textile finished by the organic silicon in the traditional emulsification process, and simultaneously, various indexes such as softness, smoothness and the like are obviously enhanced.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of high oil emulsion ratio type amino modified macromolecule organic silicon emulsion used as hand feeling finishing agent of textile is characterized by comprising the following steps:
adding an organic silicon cross-linking agent and amino modified macromolecule organic silicon crude oil into a reaction kettle according to the mass ratio of 0-1: 3, starting stirring, and reacting for 0-2 hours at 50-100 ℃ to obtain a silicone oil mixture;
adding a co-emulsifier accounting for 20-100% of the silicone oil mixture, an emulsifier accounting for 5-10%, a silicone oil stabilizer accounting for 0-2% and an acid accounting for 0.5-3% by mass ratio, and emulsifying with water to obtain the high oil emulsion ratio type amino modified macromolecule silicone emulsion.
2. The method for preparing high oil emulsion ratio type amino modified macromolecule organosilicon emulsion according to claim 1, wherein the amino modified macromolecule organosilicon crude oil is prepared by the following steps:
mixing the organic silicon ring body and the amino end capping agent according to the mass ratio of 100: 3-100: 15 to obtain a first mixture, adding an alkaline catalyst accounting for 0.3-0.4% of the first mixture according to the mass ratio, and carrying out equilibrium reaction at 90-140 ℃ for 2-6 hours;
adding a silane coupling agent accounting for 0.2-10% of the first mixture according to the mass ratio, and reacting for 2-4 hours at 90-140 ℃;
and adding the super-large molecular linear silicone oil accounting for 1-50% of the first mixture according to the mass ratio, and reacting at 100-140 ℃ for 2-4 hours to obtain the amino modified macromolecular organic silicon crude oil.
3. The method for preparing high oil emulsion ratio amino modified macromolecule silicone emulsion according to claim 2, wherein the silicone ring body is octamethylcyclotetrasiloxane or dimethylcyclosiloxane.
4. The method for preparing high oil emulsion ratio type amino modified macromolecule organosilicon emulsion according to claim 2, wherein the amino end capping agent is QH-612.
5. The method for preparing high oil emulsion ratio type amino modified macromolecule silicone emulsion according to claim 2, characterized in that the basic catalyst is any one of tetramethyl ammonium hydroxide, potassium hydroxide, sodium hydroxide and lithium hydroxide.
6. The method for preparing high oil emulsion ratio type amino modified macromolecule organosilicon emulsion according to claim 2, wherein the silane coupling agent is one or more of KBM602, QH-121 and QH-110.
7. The method for preparing the high oil emulsion ratio type amino modified macromolecule silicone emulsion according to claim 2, wherein the ultra-large molecule linear silicone oil is one or more of hydroxy dimethyl silyl terminated polydimethylsiloxane with a molecular weight of 50-500 ten thousand and methyl vinyl silicone rubber with a molecular weight of 50-500 ten thousand.
8. The method for preparing high oil emulsion ratio type amino modified macromolecule organosilicon emulsion according to claim 1, wherein the emulsifier is fatty alcohol polyoxyethylene ether, isomeric tridecanol polyoxypropylene ether or their compound;
the auxiliary emulsifier is a mixture of ethylene glycol monobutyl ether and glycerol in any proportion.
9. The method for preparing high oil emulsion ratio type amino modified macromolecule organosilicon emulsion according to claim 1, wherein the silicone oil stabilizer is AEO80-68S, and the acid is one or more of glacial acetic acid, formic acid or citric acid.
10. The high-oil-emulsion-ratio amino modified macromolecular silicone emulsion is characterized by being prepared by the preparation method of the high-oil-emulsion-ratio amino modified macromolecular silicone emulsion according to any one of claims 1 to 9.
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