CN109403048A - A kind of cotton hydrophilic block polyethers amido silicon oil and preparation method thereof - Google Patents
A kind of cotton hydrophilic block polyethers amido silicon oil and preparation method thereof Download PDFInfo
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- CN109403048A CN109403048A CN201811266723.0A CN201811266723A CN109403048A CN 109403048 A CN109403048 A CN 109403048A CN 201811266723 A CN201811266723 A CN 201811266723A CN 109403048 A CN109403048 A CN 109403048A
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- amido silicon
- silicon oil
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- hydrophilic block
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- -1 amido silicon Chemical compound 0.000 title claims abstract description 59
- 239000003921 oil Substances 0.000 title claims abstract description 58
- 229920000570 polyether Polymers 0.000 title claims abstract description 56
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 53
- 239000010703 silicon Substances 0.000 title claims abstract description 53
- 229920000742 Cotton Polymers 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229920002545 silicone oil Polymers 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 239000004593 Epoxy Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 3
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims description 47
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 32
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 29
- 238000010792 warming Methods 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000013067 intermediate product Substances 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 14
- 150000007524 organic acids Chemical class 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 150000003254 radicals Chemical class 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005639 Lauric acid Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical group CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 3
- WPWHSFAFEBZWBB-UHFFFAOYSA-N 1-butyl radical Chemical compound [CH2]CCC WPWHSFAFEBZWBB-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000004744 fabric Substances 0.000 abstract description 32
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 15
- 230000010148 water-pollination Effects 0.000 abstract description 13
- 125000001302 tertiary amino group Chemical group 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 8
- 239000000675 fabric finishing Substances 0.000 abstract description 6
- 238000009962 finishing (textile) Methods 0.000 abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 abstract description 3
- 229920013822 aminosilicone Polymers 0.000 abstract description 3
- 238000005956 quaternization reaction Methods 0.000 abstract description 3
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 2
- 239000004902 Softening Agent Substances 0.000 abstract description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- OBFQBDOLCADBTP-UHFFFAOYSA-N aminosilicon Chemical compound [Si]N OBFQBDOLCADBTP-UHFFFAOYSA-N 0.000 description 3
- 238000009940 knitting Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000009736 wetting Methods 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
- D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences
-
- 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
-
- 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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- 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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Silicon Polymers (AREA)
Abstract
The present invention relates to a kind of fabric finishing agent more particularly to a kind of cotton hydrophilic block polyethers amido silicon oils and preparation method thereof.The present invention carries out quaternization reaction with chlorocarbon base silane coupling agent and epoxy terminated polyethers to hold tertiary amine groups closure agent to hold tertiary amine groups silicone oil accordingly as Material synthesis, then respectively, and polynary alkoxy end-capped block polyether amino silicone oil has been made.Compared with existing main chain block amino-silicone oil softening agent, feel is more excellent, smaller on the whiteness of fabric, hydrophily influence, and product can be concentrated into very high content, can be obviously improved the operating environment of fabric post-treatment technique, with good application prospect.
Description
Technical field
The present invention relates to a kind of fabric finishing agent more particularly to a kind of cotton hydrophilic block polyethers amido silicon oil and its preparations
Method.
Background technique
With the improvement of living standards, more stringent requirements are proposed for snugness of fit of the people to fabric.Fabric of organosilicon
Post-finishing agent also requires the fabric after arranging to have certain hydrophily, no other than the fluffy feel of soft and smooth property to be met
Normal moisture absorption sweat discharging functions are influenced, this is particularly important to the value promotion of pure cotton and commingled yarn fabric.Common cotton is with hydrophilic
There are mainly two types of amido silicon oils: one is quaternised modified common amido silicon oils；Another kind is that quaternised modified block is poly-
Ether amido silicon oil.The latter's stability is good, and has given full play to the synergistic effect of quaternary ammonium salt and polyether segment, the fabric after arrangement
Hydrophily is more preferably.Quaternized and polymerization reaction system is occurred under the catalysis of organic acid for the polyethers that epoxy silicon oil and tertiary amine groups block
Standby block polyether hydrophile amino silicon oil is widespread practice in current industry.But this method equally exists disadvantage, used in
Tertiary amine groups end capped polyether unstable product quality, and price is higher；The structure of silicone oil is more single, is unable to satisfy diversified hand
Sense.
Patent Office of the People's Republic of China discloses a kind of patent of invention of the preparation method of hydrophilic silicone oil on June 29th, 2018, authorization
Notification number is CN108219147A, the invention by common tri-block polyethers amido silicon oil be added hydrophilic modifier (2,
3- epoxypropyltrimethylchloride chloride etc.) hydrophile amino silicon oil is prepared, the epoxy group in hydrophilic modifier can be with block
Amino in polyethers amido silicon oil reacts, to introduce quaternary ammonium salt group in silicone oil.The defect of the invention is, block
Polyethers amido silicon oil is macromolecular, and amino reactivity thereon is lower, and the conversion ratio of reaction is lower.
Summary of the invention
Corresponding Amino End Group silicon is made using amino closure agent as raw material to solve the above problems, the invention proposes one kind
Oil, then by quaternized and polymerization reaction, polynary alkoxy end-capped block polyether amino silicone oil has been made.
To achieve the above object, the invention adopts the following technical scheme:
A kind of cotton hydrophilic block polyethers amido silicon oil, the structural formula of the amido silicon oil are as follows:
A:
B:
C:
Wherein, the R in the B1For-H ,-CH2CH2CH3,-CH2CH2CH2CH3,-CH2CH(OH)CH2OCH2CH=CH2
Or-CH2CH(OH)CH2OCH2CH2CH2CH3, R in the C2For-CH3Or-OCH3, a is the integer between 1~40, b
For the integer between 50~500, m is the integer between 5~50, and n is the integer between 0~40.
There is hydrophilic polyether segment and quaternary ammonium salt group on main chain of the present invention, it is higher can to guarantee that amido silicon oil has
Hydrophily, it is white also, since the distribution of quaternary ammonium salt group and polyether segment in silicone molecule is to the feel of fabric after arrangement
Degree and hydrophily have significant impact, and therefore, it is necessary to the positions of strict control quaternary ammonium salt group and polyether segment in strand
The length with segment is set, to balance each performance, can just obtain feel, whiteness and all good block polyether amino silicone oil of hydrophily
Kind fabric finishing agent.
The cotton includes raw material a, raw material b and original with the raw material that hydrophilic block polyethers amido silicon oil synthesizes the amido silicon oil
Expect that c, the raw material a are epoxy radicals end-blocking polyethers, structural formula are as follows:The raw material b is amino closure agent, structural formula are as follows:The raw material c
For gamma-chloropropylmethyldimethoxysilane or γ-r-chloropropyl trimethoxyl silane, preparation method includes the following steps:
(1) raw material b, dimethyl siloxane ring body and basic catalyst are added into system, are warming up to 80~120 DEG C, reaction 8
System is then warming up to 140~150 DEG C by~16h, is reacted 1~2h, is then kept the temperature, vacuumizing is greater than vacuum degree
0.098Mpa is distilled, and faint yellow intermediate product 1: Amino End Group silicone oil is obtained；
(2) Amino End Group silicone oil made from step (1) is uniformly mixed in a solvent with raw material c, is warming up to 60 DEG C~120 DEG C reactions
8~12h obtains intermediate product 2；
(3) organic acid and raw material a are added in intermediate product 2,8~16h is reacted after being warming up to 60 DEG C~120 DEG C, is concentrated into institute
The concentration needed, obtains hydrophilic block polyethers amido silicon oil.
The present invention is in innovation and creation by that will hold tertiary amine groups silicone oil and end ring oxygen end capped polyether under the catalysis of organic acid
It carries out quaternized polymerization reaction and obtains amido silicon oil, present invention uses the epoxy-capped polyethers of cheaper as raw material,
It avoids using tertiary amine groups end capped polyether, and using the tertiary amine groups silicone oil of double amino structures as raw material, the polarity of product is more
By force, for the cotton of preparation with hydrophilic block polyethers amido silicon oil compared with existing main chain block amino-silicone oil softening agent, feel is more excellent,
The whiteness of fabric, hydrophily are influenced smaller, and product can be concentrated into very high content, can be obviously improved whole after fabric
The operating environment of science and engineering skill, and technique is relatively simple, reaction condition is relatively mild, is convenient for commercial applications and industrialization promotion.
Preferably, raw material b described in step (1) and the mass ratio of dimethyl siloxane ring body are 1:10~60.
Preferably, the basic catalyst is (CH3)4NOH alkali glue or (n-C4H9)4POH alkali glue, basic catalyst have
Imitate 0.03wt%~0.1wt% that content is system gross mass.
Preferably, the mass ratio of the material of raw material c and Amino End Group oxygen silicone oil is 0.05~1:1 in the step (2), it is more excellent
It is selected as 0.2~0.6:1.
Preferably, solvent described in step (2) is isopropanol, ethylene glycol monobutyl ether, ethylene glycol ether, ethylene glycol
The combination of one or more of the tertiary butyl ether of single ether, glycol monoethyl ether, ethylene glycol and diethylene glycol monomethyl ether, the use of solvent
Amount is 30wt%~80wt% of reaction system.
Preferably, organic acid described in step (3) is at least one of acetic acid or lauric acid.
Preferably, raw material a described in step (3) and Amino End Group silicone oil mass ratio are 0.5~0.975:1, more preferably
0.7~0.9:1.
Preferably, the mass ratio of the material of organic acid described in step (3) and raw material a are greater than 2.
Preferably, the content of product can achieve 80wt%~95wt% after concentration in step (3).
The present inventor wants to emphasize that the present invention is not only simply to mix each component to be used as polymerization reaction, is obtained
Amido silicon oil with specific structure performance needs to carry out each component stringent proportion and limits, such as the present inventor is testing
Middle discovery amino content in amido silicon oil is smaller, and whiteness is higher, is less susceptible to xanthochromia, quaternary ammonium salt content more high-hydrophilic more
It is good, and to a certain extent, the bigger feel of molecular weight is better, therefore the proportion between the selection and each component of raw material limits
There is important influence to the whiteness, hydrophily and feel of amido silicon oil, in order to which each performance reaches balance, obtain comprehensive performance
All good amido silicon oil, it is by no means easy for common those skilled in the art.
Advantageous effect of the invention is: (1) compared with prior art, the present invention will be by that will hold tertiary amine groups silicone oil and end ring oxygen
End capped polyether carries out quaternized polymerization reaction under the catalysis of organic acid and obtains amido silicon oil, the feel of product, whiteness and hydrophilic
The performances such as property are more preferable, and product quality is more stable, and raw material has used the epoxy-capped polyethers of cheaper as raw material
To replace tertiary amine groups end capped polyether；(2) select the tertiary amine groups silicone oil of double amino structures as raw material, so that the polarity of product is more
By force, the oriented attachment ability on fiber is more preferable；(3) with the end ring of the chlorocarbon base silane coupling agent of single functionality and bifunctionality
The collaboration of oxygroup polyethers carries out quaternization, and the quaternization degree of silicone oil is high, and initial molecular weight is smaller, when emulsification phase inversion viscosity compared with
It is small, higher content can be concentrated into；(4) end structure of amido silicon oil of the present invention is polyfunctional alkoxy, and fabric is in height
When temperature bakes, silicone molecule can further condensation cross-linking, improve the film forming of silicone oil on the fabric, make the feel of product more
Add it is excellent, it is more diversified.
Specific embodiment
The present invention program is more clearly and completely described below in conjunction with specific embodiment, it is clear that described implementation
Example is only a part of the embodiment of the present invention, rather than whole embodiments.Based on the embodiments of the present invention, ordinary skill
Personnel's every other embodiment obtained without making creative work, belongs to protection scope of the present invention.
Embodiment 1: cotton is as follows with hydrophilic block polyethers amido silicon oil preparation step:
(1) by 28g amino closure agent (raw material b, Mn=794g/mol), 380g dimethyl siloxane ring body and 0.4g (CH3)4NOH is added into system, is warming up to 90 DEG C, reacts 8h, and system is then warming up to 140 DEG C, reacts 2h, then keeps the temperature
Degree, vacuumizing makes vacuum degree 0.098MPa, is distilled, and faint yellow intermediate product 1: Amino End Group silicone oil is obtained；
(2) by the gamma-chloropropylmethyldimethoxysilane of Amino End Group silicone oil made from step (1) and 1.4g, (raw material c) exists
It is uniformly mixed in 230g isopropanol, is warming up to 60 DEG C of reaction 8h, obtains intermediate product 2；
(3) 4g acetic acid and 16g epoxy radicals end-blocking polyethers (raw material a, molecular weight 500g/mol) are added in intermediate product 2, rises
Temperature obtains hydrophilic block polyethers amido silicon oil to 8h is reacted after 70 DEG C.
Embodiment 2: cotton is as follows with hydrophilic block polyethers amido silicon oil preparation step:
(1) by 20g amino closure agent (raw material b, Mn=566g/mol), 705g dimethyl siloxane ring body and 0.6g (CH3)4NOH is added into system, is warming up to 98 DEG C, reacts 10h, and system is then warming up to 144 DEG C, reacts 1.5h, then keeping should
Temperature, vacuumizing makes vacuum degree 0.098MPa, is distilled, and obtains faint yellow intermediate product 1: Amino End Group silicone oil；
(2) by the gamma-chloropropylmethyldimethoxysilane of Amino End Group silicone oil made from step (1) and 3.5g, (raw material c) exists
It is uniformly mixed in 510g ethylene glycol monobutyl ether, is warming up to 70 DEG C of reaction 9h, obtains intermediate product 2；
(3) 3.8g acetic acid and 26.8g epoxy radicals end-blocking polyethers (raw material a, molecular weight 1000g/ are added in intermediate product 2
Mol), 11h is reacted after being warming up to 75 DEG C, obtains hydrophilic block polyethers amido silicon oil.
Embodiment 3: cotton is as follows with hydrophilic block polyethers amido silicon oil preparation step:
(1) by 11.5g amino closure agent (raw material b, Mn=650g/mol), 570g dimethyl siloxane ring body and 0.5g (n-
C4H9)4POH is added into system, is warming up to 110 DEG C, reacts 12h, and system is then warming up to 150 DEG C, reacts 2h, then protects
The temperature is held, vacuumizing makes vacuum degree 0.098MPa, is distilled, and faint yellow intermediate product 1: Amino End Group silicone oil is obtained；
(2) by γ-r-chloropropyl trimethoxyl silane of Amino End Group silicone oil made from step (1) and 1.8g, (raw material c) is different in 420g
It is uniformly mixed in propyl alcohol, is warming up to 80 DEG C of reaction 10h, obtains intermediate product 2；
(3) 6.6g lauric acid and 20g epoxy radicals end-blocking polyethers (raw material a, molecular weight 1500g/ are added in intermediate product 2
Mol), 16h is reacted after being warming up to 80 DEG C, obtains hydrophilic block polyethers amido silicon oil.
Embodiment 4: cotton is as follows with hydrophilic block polyethers amido silicon oil preparation step:
(1) by 12g amino closure agent (raw material b, Mn=678g/mol), 350g dimethyl siloxane ring body and 0.4g (n-C4H9)4POH is added into system, is warming up to 100 DEG C, reacts 10h, and system is then warming up to 140 DEG C, reacts 2h, then keeping should
Temperature, vacuumizing makes vacuum degree 0.098MPa, is distilled, and obtains faint yellow intermediate product 1: Amino End Group silicone oil；
(2) by γ-r-chloropropyl trimethoxyl silane of Amino End Group silicone oil made from step (1) and 1.4g, (raw material c) is in 400g second
It is uniformly mixed in the tertiary butyl ether of glycol, is warming up to 75 DEG C of reaction 8h, obtains intermediate product 2；
(3) 6.8g lauric acid and 21g epoxy radicals end-blocking polyethers (molecular weight 1500g/mol), heating are added in intermediate product 2
12h is reacted after to 80 DEG C, obtains hydrophilic block polyethers amido silicon oil.
Comparative example:
Quaternized and polymerization reaction preparation is carried out under the catalysis of organic acid using the polyethers that epoxy silicon oil and tertiary amine groups block
Route.By 36.2g epoxy double-seal head, 796g organosiloxane ring body and 0.8g (CH3)4Reaction system, heating is added in NOH alkali glue
To 100 DEG C, 8h is balanced；140 DEG C or so decomposition catalyst 2h are then heated to, vacuum distillation removes solvent and low-boiling-point substance, obtains
Appearance is colourless or flaxen epoxy-terminated silicone oil；By epoxy-terminated silicone oil made from upper step, 100g tertiary amine groups end capped polyether
(Mn=1000g/mol), 12g acetic acid and 560g isopropanol are uniformly mixed, and in 70 DEG C of reaction 10h, comparison product is made.
Above-described embodiment and comparative example are prepared into finishing agent and are used to handle all-cotton knitting cloth, and carries out performance comparison.
Finishing agent preparation and processing all-cotton knitting cloth method are as follows: by amido silicon oil product made from embodiment and comparative example
It is stirred evenly with a small amount of nonionic emulsifier, then slowly adds water while stirring, open dilute lotion for being 10wt% at silicone oil,
Finishing agent finally is made with glacial acetic acid tune pH to 6 or so, finishing agent obtained is handled into all-cotton knitting cloth, dosage 30g/L, one
Immersing and rolling (pick-up: 70%) → drying and shaping (180 DEG C × 90S) → cooling resurgence → performance evaluation.
Performance test methods are as follows: feel: touching rating method using more manpowers, be divided into 1~5 grade, the bigger numerical value the more soft；It is white
Degree: being measured by whiteness instrument, smaller with the difference of original cloth, illustrates that yellowing resistance is better；Hydrophily: with standard dropper from certain
Height drips water in fabric surface, observes the time required for water droplet is permeated in fabric surface complete wetting, the time is shorter, says
Bright hydrophily is better；Test result see the table below.
| Sample serial number | Feel rank | Whiteness | Hydrophily |
| Original cloth | 1 | 92.6 | 0.3s |
| Embodiment 1 | 4 | 83.3 | 1s |
| Embodiment 2 | 5 | 85.1 | 1.8s |
| Embodiment 3 | 4~5 | 88.3 | 2.9s |
| Embodiment 4 | 4~5 | 87.9 | 1.6s |
| Comparative example | 3~4 | 81.1 | 2.6s |
As shown above, after being handled using fabric finishing agent made of amido silicon oil of the present invention fabric, compared to
Original cloth and comparative example, fabric feeling is more soft, meanwhile, after product of the invention, the whiteness of fabric and the whiteness of original cloth
Difference is smaller, illustrates the amido silicon oil relative to comparative example, treated for fabric finishing agent made of amido silicon oil of the invention
Fabric yellowing resistance is more preferable, and influence of the fabric finishing agent made of amido silicon oil of the present invention to fabric hydrophilic is smaller, makes
Obtaining the hydrophily that fabric remains original cloth to a greater extent, wherein embodiment 4 is the embodiment that performance is best in the present invention, though
So for some performance, embodiment 4 is not best, but feel, Baidu and the hydrophily of comprehensive fabric, is implemented
The performance of example 4 is more prominent, however, the proportion, reaction condition between each raw material of product are for the comprehensive performance of fabric
Not show it is obviously regular, when inventor change some raw material proportioning or reaction condition make fabric certain
When one performance is prominent, the other performance of fabric will may decline therewith, therefore the innovation and creation that inventor is done are in original
The innovation and creation that material proportion and reaction condition are completed in the case where not having visible trend to product comprehensive performance, in order to obtain synthesis
The preferable amino silane of performance, is not easy to those skilled in the art.
Claims (10)
1. a kind of cotton hydrophilic block polyethers amido silicon oil, which is characterized in that the structural formula of the amido silicon oil is as follows:
Wherein, the R in the B1For-H ,-CH2CH2CH2CH3,-CH2CH(OH)CH2OCH2CH=CH2,-CH2CH2CH3,
Or-CH2CH(OH)CH2OCH2CH2CH2CH3, R in the C2For-CH3Or-OCH3, a is the integer between 1~40, b
For the integer between 50~500, m is the integer between 5~50, and n is the integer between 0~40.
2. a kind of preparation method of cotton described in claim 1 hydrophilic block polyethers amido silicon oil, which is characterized in that synthesis institute
The raw material for stating amido silicon oil includes raw material a, raw material b and raw material c, the raw material a are epoxy radicals end-blocking polyethers, structural formula are as follows:The raw material b is amino closure agent, structural formula are as follows:The raw material c
For gamma-chloropropylmethyldimethoxysilane or γ-r-chloropropyl trimethoxyl silane, preparation method includes the following steps:
(1) raw material b, dimethyl siloxane ring body and basic catalyst are added into system, are warming up to 80~120 DEG C, reaction 8
System is then warming up to 140~150 DEG C by~16h, is reacted 1~2h, is then kept the temperature, vacuumizing is greater than vacuum degree
0.098Mpa is distilled, and faint yellow intermediate product 1: Amino End Group silicone oil is obtained；
(2) Amino End Group silicone oil made from step (1) is uniformly mixed in a solvent with raw material c, is warming up to 60 DEG C~120 DEG C reactions
8~12h obtains intermediate product 2；
(3) organic acid and raw material a are added in intermediate product 2,8~16h is reacted after being warming up to 60 DEG C~120 DEG C, is concentrated into institute
The concentration needed, obtains hydrophilic block polyethers amido silicon oil.
3. a kind of preparation method of cotton hydrophilic block polyethers amido silicon oil according to claim 2, which is characterized in that step
Suddenly raw material b described in (1) and the mass ratio of dimethyl siloxane ring body are 1:10~60.
4. a kind of preparation method of cotton hydrophilic block polyethers amido silicon oil according to claim 2, which is characterized in that institute
Stating basic catalyst is (CH3)4NOH alkali glue or (n-C4H9)4POH alkali glue, the effective content of basic catalyst are system gross mass
0.03wt%~0.1wt%.
5. a kind of preparation method of cotton hydrophilic block polyethers amido silicon oil according to claim 2, which is characterized in that institute
Stating the mass ratio of the material of raw material c and Amino End Group oxygen silicone oil in step (2) is 0.05~1:1.
6. a kind of preparation method of cotton hydrophilic block polyethers amido silicon oil according to claim 2, which is characterized in that step
Suddenly solvent described in (2) is isopropanol, ethylene glycol monobutyl ether, ethylene glycol ether, ethylene glycol monoethyl ether, ethylene glycol list first
The combination of one or more of the tertiary butyl ether of ether, ethylene glycol and diethylene glycol monomethyl ether, the dosage of solvent are reaction system
30wt%~80wt%.
7. a kind of preparation method of cotton hydrophilic block polyethers amido silicon oil according to claim 2, which is characterized in that step
Suddenly organic acid described in (3) is at least one of acetic acid or lauric acid.
8. a kind of preparation method of cotton hydrophilic block polyethers amido silicon oil according to claim 2, which is characterized in that step
Suddenly raw material a described in (3) and Amino End Group silicone oil mass ratio are 0.5~0.975:1.
9. a kind of preparation method of cotton hydrophilic block polyethers amido silicon oil according to claim 2, which is characterized in that step
Suddenly the mass ratio of the material of organic acid described in (3) and raw material a are greater than 2.
10. a kind of preparation method of cotton hydrophilic block polyethers amido silicon oil according to claim 2, which is characterized in that
The content of product can achieve 80wt%~95wt% after concentration in step (3).
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| CN116355222A (en) * | 2021-12-20 | 2023-06-30 | 山东东岳有机硅材料股份有限公司 | A kind of washable amino, polyether co-modified polysiloxane and its preparation method |
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| CN114775291B (en) * | 2022-05-16 | 2023-06-27 | 杭州美高华颐化工有限公司 | Preparation method of novel quaternized modified block silicone oil |
| CN115182169A (en) * | 2022-06-29 | 2022-10-14 | 浙江科峰有机硅股份有限公司 | A kind of special hydrophilic silicone oil and preparation method thereof |
| CN116239778A (en) * | 2023-02-16 | 2023-06-09 | 南京自一界科技研发有限公司 | Soft finishing agent capable of improving soaping resistance of fabric |
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Effective date of registration: 20210514 Address after: No.6 Chunchao Road, Haining hi tech Industrial Park, Jiaxing, Zhejiang Applicant after: ZHEJIANG KEFENG SILICONE Co.,Ltd. Address before: No.107, Weiye Road, Wukang Town, Deqing County, Huzhou City, Zhejiang Province Applicant before: ZHEJIANG KEFENG NEW MATERIAL Co.,Ltd. |
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