CN107556483A - A kind of linear both sexes end carboxyl polyethers amido silicon oil, its crosslinking both sexes carboxyl polyethers amino silicone breast softening agent prepared and preparation method - Google Patents
A kind of linear both sexes end carboxyl polyethers amido silicon oil, its crosslinking both sexes carboxyl polyethers amino silicone breast softening agent prepared and preparation method Download PDFInfo
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Abstract
The invention discloses a kind of linear both sexes end carboxyl polyethers amido silicon oil, it is prepared by the mixture comprising amine terminated polyether silicone oil, dibasic acid anhydride；Wherein, amine terminated polyether silicone oil is prepared by the mixture comprising end ring oxygen polyether silicone oil, polyetheramine and isopropanol.The invention also discloses a kind of crosslinking both sexes carboxyl polyethers amino silicone breast softening agent based on prepared by linear end carboxyl polyethers amido silicon oil and preparation method thereof.Silicon breast softening agent is made in the crosslinking both sexes carboxyl polyethers amido silicon oil nonionic surfactant emulsification of the present invention, for fabric post-treatment, the soft hydrophilic performance and feel of fabric can not only be improved, moreover it is possible to assign the good bullet property endured of fabric with bath usability.
Description
Technical field
The invention belongs to textile finshing agent technical field, and in particular to a kind of linear both sexes end carboxyl polyethers amido silicon oil,
Its crosslinking both sexes carboxyl polyethers amino silicone breast softening agent prepared and preparation method.
Background technology
Polyethers amino silicone, the multiple excellent properties of Hydrophilicrto polyether group and amido silicon oil are had concurrently, after fabric
Arrange, soft, the smooth performance and feel of fabric can not only be obviously improved, and can assign the good moisture absorption of fabric, thoroughly
Gas and antistatic property, thus turn into a kind of soft after-treating auxiliary most popular in recent years.But limited by cationic,
Polyethers amino silicone is only applicable to sun, nonionic system；Anion systems use, cation polyether amino silicone because with system institute band
Electrically on the contrary, therefore easily causing very much system demulsification, floating oil or layering.
Carboxylic group is introduced in polyethers amino silicon structure, amino is changed into amphion group, is not reducing or is lacking
Amount is reduced under the precondition of flexibility, can be expanded the application of polyethers amino silicone, it is can be used not only for positive non-ionic precursor
System, and anion systems such as preparation of shampoo, acrylic resin coating etc. can be used for, and with resin anion (R.A.) auxiliary agent such as
Brightening agent VBL, dyestuff equally bathe use without producing demulsification, precipitation or oil spill.And if make both sexes carboxyl polyethers with reactant
The further crosslinked, branched of linear structure energy of amino silicone, then while the soft and smooth bullet for improving both sexes polyethers amino silicone endures performance,
Target silicone oil can also be made to produce comfortable active feel.
In consideration of it, present invention two-step synthesis method --- i.e. first with the linear both sexes end carboxyl polyethers amino of chemical reactive synthesis
Silicone oil, then end carboxyl polyethers amino silicone is modified with branched both sexes polyether-polyurethane performed polymer again, friendship has not only been made
It is coupled structure, the both sexes carboxyl polyethers amino silicone breast used can be bathed together with anions and canons resin/auxiliary agent, and both sexes carboxyl is gathered
Ether amino silicone breast is used for the soft final finishing of fabric, in the premise bar for keeping fabric to possess improved flexibility and moment hydrophilicity
Under part, also obtain fabric it is desirable that crease-resistant endure effect with bullet.
The content of the invention
It is an object of the invention to disclose a kind of linear both sexes end carboxyl polyethers amido silicon oil, cross-linked structure prepared therefrom
Both sexes carboxyl polyethers amino silicone breast softening agent and preparation method thereof.It is whole after the newborn softness for fabric of silicone oil, silicon of this method preparation
Reason, good soft, the hydrophilic and bullet of fabric can not only be assigned and endure performance, and with the same bath of anions and canons resin additive using not
Produce demulsification, floating oil.
Therefore, present invention employs following technical scheme：
The present invention first synthesizes amine terminated polyether silicone oil using the aminolysis ring-opening reaction of end ring oxygen polyether-based silicone oil and polyetheramine
Precursor, precursor and binary aliphatic anhydride reaction, first synthetic molecules end group are then carried into polyethers amino, carboxyl simultaneously again
With the linear both sexes end carboxyl polyethers amido silicon oil (α, ω-CPEAS) of the functional group such as carbon hydroxyl；Secondly, by diisocyanate with
Successively the branched poly- ammonia of both sexes polyethers is made in reaction to PPG, triethanolamine-dihydromethyl propionic acid equimolar mixture etc.
Ester performed polymer (PU), is then again reacted α, ω-CPEAS with PU, so as to which the friendship that a kind of polyether-polyurethane is modified be made
It is coupled structure both sexes carboxyl polyethers amido silicon oil, corresponding silicon breast softening agent can be obtained after emulsification.
(1) preparation of solvent Linear both sexes end carboxyl polyethers amido silicon oil：By end ring oxygen polyether-based silicone oil (α, ω-
EPS it is) 1 with polyetheramine (PEA) mol ratio:2 weigh α, ω-EPS and PEA successively, stir and evenly mix, and add with α, ω-EPS+
PEA mass meters 20-200% isopropanol (IPA) solvent, stirring, is heated to 80-85 DEG C of successive reaction 4-24h, then subtracts
Pressure is distilled to recover IPA solvents, obtains amine terminated polyether silicone oil (α, ω-PEAS) precursor；Stirring, by precursor α, ω-PEAS quality is again
20-30% polarity alcohol ether solvents A is added, adjusts reaction temperature then, to be rubbed to 70-125 DEG C by α, ω-PEAS with dibasic acid anhydride
You are than being 1:2, which add dibasic acid anhydride, carries out carboxylation reaction 1-4h, and reaction terminates, and obtains slightly muddy to transparency liquid, i.e. solvent
Linear both sexes end carboxyl polyethers amido silicon oil (α, ω-CPEAS), silicone oil is about 77.0-85.0%.
(2) preparation of branched both sexes polyether-polyurethane performed polymer：Diisocyanate (DIC) is taken to be stirred in dry reactor
Mix and be heated to 35-80 DEG C, by diisocyanate:PPG (PEPO) mol ratio is 2:1-1.25:1 is added dropwise to polyether polyols
The non-reactive polar solvent B of alcohol and the 20-50% in terms of DIC+PEPO mass, 35-80 DEG C of reaction 0.5-1h of temperature control, then,
Add the equimolar mixture of 0.5-1% triethanolamines and dihydromethyl propionic acid in terms of DIC+PEPO mass, temperature control 35-80
DEG C continue to react 0.5-2h, products therefrom, i.e., branched both sexes polyether-polyurethane performed polymer (PU).
(3) preparation of cross-linked structure both sexes carboxyl polyethers amino silicone breast softening agent：Take solvent Linear α, ω-CPEAS with
Branched both sexes PU mixing, the two dosage of control is so that the mass ratio of α in system, ω-CPEAS silicone oil and PU solid contents is 1:1-
0.3, stirring, 30-70 DEG C of temperature control carries out reaction 0.5-2h, products therefrom, i.e. cross-linked structure both sexes carboxyl polyethers amido silicon oil again
(PUCS) solution.
PUCS solution is taken, by institute's silicate-containing oil quality, adds the AEO of the 30-50% in terms of silicone oil quality
Emulsifying agent, 30min is stirred, adds acetic acid (HAc) and adjust system pH=5-6, then stirred while adding water to carry out breast
Change, obtain translucent-clear microemulsion, i.e. cross-linked structure both sexes carboxyl polyethers amino silicone breast softening agent, solid content is about 15-30%.
Described end ring oxygen polyether silicone oil (α, ω-EPS), shown in structure such as formula (1), main chain be dimethyl silicone polymer,
End group is epoxidized polyether group：
In formula (1), n is the degree of polymerization of dimethyl siloxane chain link, span 25-270；A, b is oxygen ethene, oxygen third
The degree of polymerization of alkene chain link, a, b span are 0-30, and a+b spans are 3-30.
Described polyetheramine, it is that molecule both ends are connected with aliphatic primary amino radical, centre is polyoxyethylene poly-oxygen propylene aether segment
Binary aliphatic organic amine, structure is：
H2N(C3H6O)x(C2H4O)y(C3H6O)zC3H6NH2 (2)
In formula, x, y, z is positive number, and x+z spans are 2.5-33.1, and y spans are 0-39, and the number of polyetheramine is divided equally
Son amount (Mn) be 230-2000, selection polyetheramine D230 (x+z=2.5, y=0, Mn=230), D400 (y=0, x+z=5.5,
Mn=400), D2000 (x+z=33.1, y=0, Mn=2000), ED600 (x+z=3.6, y=9, Mn=600), ED900 (x+
Z=6, y=12.5, Mn=900), one kind in ED2003 (x+z=6, y=39, Mn=2000) etc. or any two kinds of mixing
Thing.
Described dibasic acid anhydride is binary aliphatic acid anhydrides, choose maleic anhydride, succinic anhydride, itaconic anhydride,
One kind in adipic anhydride, glutaric anhydride etc..
The reaction of described end ring oxygen polyether silicone oil and polyetheramine, α, ω-EPS are 1 with PEA mol ratios:2, reaction temperature
For 80-85 DEG C, reaction time 4-24h, products therefrom is precursor --- amine terminated polyether silicone oil (α, ω-PEAS)；Described
The mol ratio of α, ω-PEAS and dibasic acid anhydride carboxylation reaction, α, ω-PEAS and dibasic acid anhydride is 1:2 (in α, ω-PEAS
The mol ratio of contained polyetheramine and dibasic acid anhydride is 1:1), reaction temperature is 70-125 DEG C, reaction time 1-4h, products therefrom
For shown in both sexes end carboxyl polyethers amido silicon oil (α, ω-CPEAS), structure such as formula (3)；Other product amine terminated polyether silicone oil
(α, ω-PEAS), shown in structure such as formula (4)：
In formula (3) and formula (4), pe1, pe2, pe3 are polyether-based, and pe1 comes from raw material α, ω-EPS, and pe2, pe3 come
It is may be the same or different from polyetheramine, pe2 with pe3；In addition, in formula (3), (4), the same formula of n, a, b span (1), and x, y, z
The same polyetheramine of span.
Described diisocyanate, predominantly intramolecular contain the aliphatic or aromatic diisocyanates of two NCO groups
Ester, choose hexamethylene diisocyanate (HDI), IPDI (IPDI), 4, the isocyanide of 4 '-diphenyl methane two
One kind in acid esters (MDI), toluene di-isocyanate(TDI) (TDI) etc.；Described PPG (PEPO), choose number-average molecular weight
For one kind in 200-2000 polyethylene glycol (PEG), PTMG (PTHG) etc., mean molecule quantity is preferentially chosen
For 200,400,600,1000,2000 polyethylene glycol such as PEG-200, PEG-400, PEG-600, PEG-1000, PEG-2000
One kind or any two kinds of mixture in.
Described polarity alcohol ether solvents A, generally to precursor amine terminated polyether silicone oil, binary aliphatic acid anhydrides and follow-up anti-
Polyether-polyurethane in answering has good hydrotropy effect and alcohol ether soluble in water, ether ester compound, preferential to choose the fourth of ethylene glycol two
Ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dibutyl ethylene glycol ether, dimethyl ether, DPG diethyl
One kind or any two kinds of mixture in ether, DPG butyl oxide, glycol methyl ether acetate etc., alcohol ether solvents A dosages
The generally 20-30% of amine terminated polyether silicone oil quality；Described non-reactive solvent B, with polarity alcohol ether solvents A can it is identical or
Difference, chooses alcohol ether solvents A, acetone or one kind in dioxane or any two kinds of mixture, dosage are generally DIC+
The 20-50% of PEPO mass.
It is described that prepared cross-linked structure both sexes carboxyl polyethers amido silicon oil is reacted by α, ω-CPEAS and PU, if reacting
The crosslinking of journey system is excessively or product is placed long afterwards, easily forms elastomer and leads to not use；To avoid this phenomenon from occurring, instead
(without removing solvent), which should be finished, directly to add emulsifying agent to be emulsified in system, and silicone oil can be changed into stable silicon micro emulsion
Storage.
Described cross-linked structure both sexes carboxyl polyethers amino silicone breast softening agent, solid content 15-30%, after being diluted with water with
Dipping or an immersing and rolling technique are used for fabric sofetening final finishing, then baked solidification, and fabric is with excellent after can not only assigning processing
Softness and feel, and the static water absorption time of fabric can be made (to have absorbed 1 with fabric face to drip timetable used
Show) it shorten to several seconds (1.87s), the bullet property endured --- represent and (determined with fabric crease elasticity test instrument) to reach with warp+latitude creasy recovery angle
To 302 °.
Described cross-linked structure both sexes carboxyl polyethers amino silicone breast softening agent, because the molecule carries carboxyl and amino simultaneously
Both sexes functional group, can be not only stabilized in the range of wider pH value (pH=1-14), and with yin, yang, non-, amphion resin
Or auxiliary agent is demulsified with bath use without generation, oil spill.
The cross-linked structure both sexes carboxyl polyethers amino silicone breast softening agent, with anions and canons resin additive with bath using not
Demulsification, oil spill are produced, for the final finishing of fabric, good soft, the hydrophilic and bullet of fabric can be assigned and endure performance.
Beneficial effects of the present invention are：
Before the amine terminated polyether silicone oil that the present invention is formed with end ring oxygen polyether silicone oil and polyetheramine aminolysis ring-opening reaction is made
Body raw material, it and binary aliphatic acid anhydrides are reacted, it is releasable while forming acid amides using primary amine groups and anhydride reaction
The characteristics of carboxyl, synthesize first in molecule while be connected with polyethers amino, carboxylic alkyl and C-OH linear both sexes end carboxyl polyethers
Amido silicon oil (α, ω-CPEAS)；
Secondly, it is the effect endured up to bullet, the present invention is again reacted diisocyanate and Hydrophilicrto polyether polyalcohol, so
Chain extension-crosslinking is carried out than blend with the equimolar of latency both sexes TEOA and dihydromethyl propionic acid again afterwards, and then has synthesized NCO
End-blocking, intramolecular are in the both sexes polyether-polyurethane performed polymer (PU) of the branched crosslinking of multiple spot；Macromolecular reaction agent is made with this, utilizes PU
The characteristics of amino, C-OH can react in middle residual-NCO chances α, ω-CPEAS is so as to branched by carboxyl polyethers amino silicone and elasticity
Polyether-polyurethane performed polymer be chemically bound together, have soft hydrophilic and bullet concurrently so as to be made and endure performance, polyurethane-modified
Cross-linked structure carboxyl polyethers amino silicone PUCS；
In addition, under the effect of AEO nonionic surfactant, PUCS is emulsified into stable silicon breast, used
In the soft final finishing of fabric, as a result find, PUCS emulsions can not only bathe use together with zwitterion resin additive, and whole through its
The fabric of reason, the static water absorption time is water-based to shorten to 1.87s, can reach 302 ° through+latitude creasy recovery angle, shows very
Good soft, hydrophilic and bullet endures effect.
Embodiment
With reference to embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.
Embodiment 1
(1) preparation of solvent Linear end carboxyl polyethers amido silicon oil：There are thermometer, reflux condensing tube and electricity in device
In the three-necked bottle of dynamic agitator, by end ring oxygen polyether silicone oil：Polyetheramine mol ratio is 1:2 weigh 0.01mol (203.58g) successively
Shown in structure such as formula (1), n=270, a=3, b=0, Mn=20358 α, ω-EPS-1 and 0.02mol (4.6g) mean molecule
It is H to measure as 230, x+z=2.5, y=0 structure2NC3H6O(C3H6O)2.5C3H6NH2Polyetheramine D230, stir and evenly mix, add
With α, ω-EPS-1+D230 quality meter 20%, about 41.64g isopropanol solvents, stirring, 80 DEG C of successive reaction 4h are heated to,
Then IPA solvents are recovered under reduced pressure in 80 DEG C, 0.2MPa, obtain 0.01mol, total amount about 208.18g amine terminated polyethers silicone oil (α, ω-
PEAS-1)；Then, by α, ω-PEAS-1 quality adds 20%, about 41.64g butyl cellosolve solvents, adjusts reaction temperature
To 70 DEG C, stirring, then 0.02mol, about 1.96g maleic anhydride (α, ω-PEAS-1 is added portionwise:Maleic anhydride mol ratio is
1:2) carboxylation reaction 1h is carried out, reaction terminates, and obtains light yellow clear liquid, i.e. structure solvent-borne type both sexes end as shown in (3-1)
Carboxyl polyethers amido silicon oil, it is denoted as α, ω-CPEAS-1, silicone oil about 83.46%.
(2) both sexes polyether-polyurethane performed polymer PU-1 preparation：Take 0.03mol, 6.66g IPDI
(IPDI) have in device in the drying three-necked bottle of thermometer, reflux condensing tube and electric mixer, be heated with stirring to 80 DEG C, so
Afterwards, by IPDI:PPG mol ratio is 2:1 ratio is added dropwise to polyethylene glycol after 0.015mol that is, 30g drying process
PEG-2000 and 20% in terms of IPDI+PEG-2000 mass, about 7.33g diethylene glycol dimethyl ether solvents, 80 DEG C of reactions of temperature control
0.5h, then it is added dropwise to again 0.5% in terms of IPDI+PEG-2000 mass, about 0.18gTEOA and dihydromethyl propionic acid equimolar ratio
35 DEG C of mixture temperature control continue react 2h, obtain total amount about 43.99g products, i.e. both sexes polyether-polyurethane performed polymer (PU-1), contain
Gu amount about 83.74%.
(3) preparation of cross-linked structure both sexes carboxyl polyethers amino silicone breast softening agent：Take 20g, the solvent that content is 83.46%
Type α, ω-CPEAS-1 (silicate-containing oil 16.69g) mixes with 19.93g, the PU-1 (containing solid 16.69g) that solid content is 83.74%,
The mass ratio of α in system, ω-CPEAS-1 silicone oil and PU-1 solid contents is 1:1, stirring, 30 DEG C of temperature control carries out reaction 0.5h again,
Cross-linked structure both sexes carboxyl polyethers amido silicon oil (PUCS-1) solution that products therefrom, i.e. polyether-polyurethane are modified, silicone oil
About 83.59%.
It is 83.59%PUCS-1 solution to take 30g, silicone oil, add 30% in terms of silicone oil quality, about 7.52g it is different
(the mass ratio 1 of structure tridecanol polyoxyethylene ether 1350/1390:2) emulsifying agent, mechanical agitation mixing 30min, adds HAc and adjusts body
It is pH=5-6, then stirs and emulsified while adding 71.14g deionized waters, obtain transparence micro emulsion, i.e. cross-linked structure
Both sexes carboxyl polyethers amino silicone breast (PUCS-1) softening agent, solid content is about 30%.
Embodiment 2
(1) preparation of end carboxyl polyethers amido silicon oil：There are thermometer, reflux condensing tube and electric mixer in device
In three-necked bottle, by end ring oxygen polyether-based silicone oil:Polyetheramine mol ratio is 1:2 weigh 0.01mol (48.50g) structure such as formula successively
(1) the end ring oxygen polyether silicone oil (α, ω-EPS-2) and 0.02mol that shown, n=25, a=30, b=0, Mn are about 4850
(40.00g) mean molecule quantity is 2000, y=39, x+z=6, structure H2NC3H6O(C3H6O)6(C2H4O)39C3H6NH2It is poly-
Ether amines ED2003, is stirred and evenly mixed, and is added with α, ω-EPS-2+ED2003 quality meter 200%, about 177.0g IPA solvents, is stirred
Mix, be heated to 85 DEG C of successive reaction 24h, then remove IPA solvents under reduced pressure, obtain 0.01mol, total amount is about 88.50g ends ammonia
Base polyether silicone oil (α, ω-PEAS-2)；Then, 30%, about 26.55g diethylene glycol two is added by α, ω-PEAS-2 quality
Butyl ether solvent, stirring, reaction temperature is adjusted to 125 DEG C, then 0.02mol, about 2.0g succinic anhydrides (α, ω-PEAS-2 is added portionwise:
Succinic anhydride mol ratio is 1:2) carboxylation reaction 4h and in 125 DEG C is carried out, reaction terminates, and it is light yellow to obtain total amount about 117.05g
Transparency liquid, i.e. structure the solvent-borne type both sexes carboxyl polyethers amido silicon oil (α, ω-CPEAS-2) as shown in (3-2), silicone oil is about
77.32%.
(2) preparation of both sexes polyether-polyurethane performed polymer (PU-2)：Take 0.05mol, 8.41g hexamethylene diisocyanate
(HDI) have in device in the drying three-necked bottle of thermometer, reflux condensation mode and electric mixer, be heated with stirring to 35 DEG C, then, press
HDI:PPG mol ratio mol ratio is 1.25:1 is added dropwise to the PEG-200 after 0.04mol that is, 8g drying process
(Mn200) and 50% in terms of HDI+PEG-200 mass, about 8.21g non-reactive dibutyl ethylene glycol ether solvents, 35 DEG C of temperature control
React 1h, be then added dropwise to again 1% in terms of HDI+PEG-200 mass, about 0.16gTEOA and dihydromethyl propionic acid equimolar than
Mixture, 80 DEG C of temperature control continue to react 0.5h, obtain total amount about 24.78g products, i.e. both sexes polyether-polyurethane performed polymer (PU-2),
Solid content 66.89%.
(3) preparation of cross-linking modified both sexes carboxyl polyethers amino silicone breast softening agent：Take the molten of 30g, solid content about 77.32%
Formulation α, ω-CPEAS-2 and 10.40g, the both sexes polyether-polyurethane performed polymer PU-2 of solid content about 66.89% are mixed, in system
The mass ratio of α, ω-CPEAS-2 silicone oil and PU-2 solid contents is 1:0.3, stir and evenly mix, be heated to 70 DEG C and reacted again
2h, obtain total amount about 40.40g products, i.e., the cross-linked structure both sexes carboxyl polyethers amido silicon oil (PUCS-2) that polyether-polyurethane is modified
Solution, solid content are about 74.62%.
Take 20.0g, the PUCS-2 solution (silicate-containing oil 14.92g) that silicone oil is 74.62%, add with silicone oil quality
Meter 50%, about 7.46g AEO emulsifying agent AEO-3/AEO-9 (mass ratioes 1:3) 30min, is stirred, then
Add HAc and adjust system pH=5-6, then stir while add 121.81g deionized waters, obtain clear microemulsion, that is, be crosslinked and tie
Structure both sexes carboxyl polyethers amino silicone breast (PUCS-2) softening agent, solid content is about 15%.
Embodiment 3
(1) preparation of solvent-borne type end carboxyl polyethers amido silicon oil：There are thermometer, reflux condensing tube and electric stirring in device
In the three-necked bottle of device, by end ring oxygen polyether-based silicone oil：Polyetheramine mol ratio is 1:2 weigh 0.02mol (211.4g) structure successively
As shown in formula (1), the end ring oxygen polyether silicone oil (α, ω-EPS-3) and 0.04mol that n=133, a=7, b=3, Mn are about 10570
(24.0g) mean molecule quantity is 600, y=9, x+z=3.6, structure H2NC3H6O(C3H6O)3.6(C2H4O)9C3H6NH2Polyethers
Amine ED600, is stirred and evenly mixed, and is added and is risen with α, ω-EPS-3+ED-600 quality meter 60%, about 141.24g IPA solvents, heating
Temperature is to 80 DEG C of successive reaction 8h, and then vacuum distillation recovered solvent IPA, obtains 0.02mol, total amount about 235.4g amine terminated polyether silicon
Oily (α, ω-PEAS-3)；Then, by α, it is molten that ω-PEAS-3 quality adds 25%, about 58.85g dimethyl ether
Agent, reaction temperature is adjusted to 75 DEG C, then 0.04mol, about 4.48g itaconic anhydrides (α, ω-PEAS-3 is added portionwise:Methylene
Base succinic anhydride mol ratio is 1:2) and 75 DEG C of progress carboxylation reaction 2h of temperature control, reaction terminate, and it is pale yellow to obtain total amount about 298.75g
Color transparency liquid, i.e. structure solvent-borne type both sexes carboxyl polyethers amido silicon oil (α, ω-CPEAS-3), silicone oil as shown in (3-3)
About 80.29%.
(2) preparation of both sexes polyether-polyurethane performed polymer (PU-3)：Take 0.03mol, 7.51g 4,4 '-diphenyl methane two
Isocyanates (MDI) has in the drying three-necked bottle of thermometer, reflux condensing tube and electric mixer in device, is heated with stirring to 60
DEG C, then, by MDI:PPG mol ratio is 1.5:After 1 ratio is added dropwise to 0.02mol that is, 12g drying process
PEG-600 and 25% in terms of MDI+PEG-600 mass, 4.88g DPG butyl oxides, 70 DEG C of reaction 50min of temperature control, then
It is added dropwise to 0.6% in terms of MDI+PEG-600 mass, about 0.12g TEOA- dihydromethyl propionic acids equimolar mixtures and controls again
60 DEG C of temperature continues to react 1.5h, obtains total amount about 24.51g products, i.e., (PU-3, solid content are about both sexes polyether-polyurethane performed polymer
80.09%.
(3) preparation of cross-linking modified both sexes carboxyl polyethers amino silicone breast softening agent
21.83g, silicone oil is taken to be 80.29% solvent-borne type α, ω-CPEAS-3 (silicate-containing oil 17.53g) and 10.94g, contain
Gu the polyether-polyurethane performed polymer PU-3 mixing of amount about 80.09% (containing solid 8.77g), α in system, ω-CPEAS-3 silicone oil with
The mass ratio of PU-3 solid contents is 1：0.5, stir and evenly mix, be again heated to 40 DEG C of reaction 2h, obtain total amount about 32.77g products, i.e., it is poly-
Polyurethane-modified cross-linked structure both sexes carboxyl polyethers amido silicon oil (PUCS-3) solution of ether, silicone oil about 80.26%.
The PUCS-3 (silicate-containing oil 16.05g) of 20g, silicone oil about 80.26% is taken, add 40% in terms of silicone oil quality,
About 6.42g heterogeneous ten alcohol polyoxyethylene ether XP-30/XP-90 (mass ratioes 1:2.5) emulsifying agent, 30min is stirred, then added
Enter HAc and adjust system pH=5-6, then stir while add 85.93g deionized waters, obtain clear microemulsion, i.e. cross-linked structure two
Property newborn (PUCS-3) softening agent of carboxyl polyethers amino silicone, solid content is about 20%.
Embodiment 4
(1) preparation of solvent-borne type end carboxyl polyethers amido silicon oil：There are thermometer, reflux condensing tube and electric mixing in device
In the three-necked bottle for mixing device, by end ring oxygen polyether-based silicone oil：Polyetheramine mol ratio is 1:2 weigh 0.005mol (39.5g) knots successively
Structure such as formula (1) is shown, n=90, a=10, b=0 end ring oxygen polyether silicone oil α, ω-EPS-4 and 0.01mol (9.0g) average mark
Son amount is 900, y=12.5, x+z=6, structure H2NC3H6O(C3H6O)6(C2H4O)12.5C3H6NH2Polyetheramine ED900, then
Add with α, ω-EPS-4+PEA quality meter 100%, about 48.5g IPA solvents, stir and evenly mix, be heated to 82 DEG C continuously instead
12h is answered, IPA solvents are then recovered under reduced pressure, obtains 0.005mol, total amount is about 48.5g amine terminated polyethers silicone oil (α, ω-PEAS-
4)；Then, by α, ω-PEAS-4 quality add 20%, about 9.7g by butyl cellosolve and ethylene glycol monobutyl ether acetic acid
Ester (mass ratio 2:1) solvent formed, adjust reaction temperature to 70 DEG C, add 0.01mol, about 1.14g glutaric anhydrides (α,
ω-PEAS-4:The mol ratio of glutaric anhydride is 1:2) and 70 DEG C of progress carboxylation reaction 1.5h of temperature control, reaction terminate, and obtain total amount
About 59.34g is colourless-light yellow clear liquid, i.e., structure as shown in (3-4) solvent-borne type both sexes carboxyl polyethers amido silicon oil (α,
ω-CPEAS-4), silicone oil about 83.65%.
(2) preparation of both sexes polyether-polyurethane performed polymer (PU-4)：Take 0.04mol, 6.97g toluene di-isocyanate(TDI)
(TDI) have in device in the drying three-necked bottle of thermometer, reflux condensing tube and electric mixer, be heated with stirring to 60 DEG C, so
HDI is pressed afterwards:PPG mol ratio is 1.8:The polyethylene glycol that 1 ratio is added after 0.0222mol, 22.22g drying process
PEG-1000 and 28% in terms of TDI+PEG-1000 mass (total amount 29.19g), about 8.17g is by DPG butyl oxide and two
Ring (the mass ratio 1 of oxygen six:1) solvent of composition, 50 DEG C of reaction 45min of temperature control, is then added dropwise to TDI+PEG-1000 mass again
(29.19g) meter 0.5%, about 0.146gTEOA and dihydromethyl propionic acid equimolar than mixture continue to react 1h, gained production
Thing, i.e. both sexes polyether-polyurethane performed polymer (PU-4), solid content about 77.23%.
(3) preparation of cross-linking modified both sexes carboxyl polyethers amino silicone breast softening agent
21.83g, silicone oil is taken to be 83.65% solvent-borne type α, ω-CPEAS-4 (silicate-containing oil 18.26g) and 18.92g, contain
Gu the polyether-polyurethane performed polymer PU-4 mixing of amount about 77.23% (containing solid 14.61g), α in system, ω-CPEAS-4 silicone oil with
The mass ratio of PU-4 solid contents is 1：0.8, stirring, then 40 DEG C of reaction 2h of temperature control, obtain total amount about 40.75g products, the i.e. poly- ammonia of polyethers
Ester modified cross-linked structure both sexes carboxyl polyethers amido silicon oil (PUCS-4) solution, silicone oil is about 80.66%.
The PUCS-3 solution (silicate-containing oil 16.13g) that 20g, silicone oil are about 80.66% is taken, is added with silicone oil quality
Meter 35%, about 5.64g heterogeneous ten alcohol polyoxyethylene ether XL-40/XL90 (mass ratioes 1:3) emulsifying agent, 30min is stirred,
Add HAc and adjust system pH=5-6, then stir while add 83.21g deionized waters, obtain clear microemulsion, that is, be crosslinked and tie
Soft dose of structure both sexes carboxyl polyethers amino silicone breast soft (PUCS-4), solid content is about 20%.
Embodiment 5
(1) preparation of solvent-borne type end carboxyl polyethers amido silicon oil：There are thermometer, reflux condensing tube and electric mixing in device
In the three-necked bottle for mixing device, by end ring oxygen polyether-based silicone oil:Polyetheramine mol ratio is 1:2 weigh 0.006mol (89.62g) knots successively
Structure such as formula (1) is shown, n=174, a=14, b=6 end ring oxygen polyether silicone oil α, ω-EPS-5 and 0.006mol (2.4g) are average
Molecular weight is 400, x=5.5, y=z=0, structure H2NC3H6O(C3H6O)5.5C3H6NH2Polyetheramine D400 and 0.006mol
(5.4g) mean molecule quantity is 900, y=12.5, x+z=6, structure H2NC3H6O(C3H6O)6(C2H4O)12.5C3H6NH2It is poly-
Ether amines ED900, is stirred and evenly mixed, and is added with α, ω-EPS-5+D400+ED900 quality meter 75%, about 73.07g IPA solvents,
Stir and evenly mix, be heated to 80 DEG C of successive reaction 10h, solvent IPA is then recovered under reduced pressure, obtain 0.06mol, total amount about 97.42g
Amine terminated polyether silicone oil (α, ω-PEAS-5)；Then, then by silicone oil α, ω-PEAS-5 quality add 23%, the two of about 22.41g
Ethylene glycol diethyl ether solvent, reaction temperature is adjusted to add 0.012mol, about 1.54g adipic anhydrides (α, ω-PEAS-5 to 80 DEG C：
Adipic anhydride mol ratio is 1:2) and 80 DEG C of progress carboxylation reaction 1h of temperature control, reaction terminate, and it is colourless-shallow to obtain total amount 121.37g
Yellow transparent liquid, i.e. structure solvent-borne type both sexes end carboxyl polyethers amido silicon oil (α, ω-CPEAS-5), silicone oil as shown in (3-5)
Content is about 81.54%.
(2) preparation of both sexes polyether-polyurethane performed polymer (PU-5)
0.05mol, 11.11g IPDI IPDI is taken to have thermometer, reflux condensing tube and electronic in device
In the drying three-necked bottle of agitator, 50 DEG C are heated with stirring to, then by IPDI:PPG mol ratio is 1.25:1 ratio adds
Enter the PEG-400 (Mn400) after 0.04mol, the about 16.0g drying process and 20%, 5.42g in terms of IPDI+PEG-400 mass
By diethylene glycol diethyl ether and acetone (mass ratio 1:2) mixed solvent of composition, 70 DEG C of temperature control reaction 1h, be then added dropwise to again with
IPDI+PEG-400 mass meter 0.8%, about 0.22gTEOA and dihydromethyl propionic acid equimolar than mixture continue to react
0.5h, obtain total amount about 32.75g products, i.e. both sexes polyether-polyurethane performed polymer (PU-5), solid content 83.45%.
(3) preparation of cross-linking modified both sexes carboxyl polyethers amino silicone softener
30.0g, silicone oil is taken to be 81.54% solvent-borne type α, ω-CPEAS-5 (silicate-containing oil 24.46g) and 19.05g, contain
Admittedly 83.45% (solid 15.89g) polyether-polyurethane performed polymer PU-5 mixing is measured, α, ω-CPEAS-5 silicone oil and PU- in system
The mass ratio of 5 solid contents is 1：0.65, stir and evenly mix, then 40 DEG C of reaction 2h of temperature control, obtain total amount about 49.05g products, i.e. polyurethane
Modified cross-linked structure both sexes carboxyl polyethers amido silicon oil (PUCS-5) solution, solid content about 82.26%.
Take the PUCS-5 solution of 25g, silicone oil 82.26%, add 35% in terms of silicone oil quality, about 7.20g it is different
The alcohol APEO XL-40/XL90 (mass ratioes 1 of structure ten:3) emulsifying agent, 30min is stirred, adds HAc and adjust system pH=
5-6, then stir and emulsified while adding 88.54g deionized waters, obtain clear microemulsion, i.e. cross-linked structure both sexes carboxyl
Polyethers amino silicone breast (PUCS-5) softening agent, solid content is about 23.0%.
Embodiment 6
The PEG-1000 in embodiment 4 is replaced with PTMG PTHG-1000, remaining raw material dosage and technique
It is soft with embodiment 4, the translucent micro emulsion of last gained, i.e. cross-linked structure both sexes carboxyl polyethers amino silicone newborn (PUCS-6)
Agent, solid content are about 20%.
Embodiment 7
The PEG-2000 in embodiment 1 is replaced with PTMG PTHG-2000, remaining raw material, dosage and work
Skill is soft with embodiment 1, the translucent micro emulsion of last gained, i.e. cross-linked structure both sexes carboxyl polyethers amino silicone newborn (PUCS-7)
Agent, solid content are about 30%.
Cross-linked structure both sexes carboxyl polyethers amino silicone breast softening agent prepared by Example 1-7, being converted into solid content is
30% silicon micro emulsion, then be diluted in the ratio of 1g silicon micro emulsion+100g water, prepare work body lotion.Then, learn from else's experience × filling face product
For 16.3cm × 12.6cm whites cotton (specification 21 × 21 × 108 × 98), it is impregnated into work body lotion and is rolled with laboratory room small-sized
The immersing and rolling of car one is arranged, padding machine pressure about 0.4MPa, pick-up about 70%, and fabric then is dried into 5min at 100 DEG C, existed again
165 DEG C of solidification 90s, and after 25 ± 2 DEG C of room temperature, humidity are 48% balance 24h, carry out performance test.
Flexibility is represented with bending stiffness, is determined with DC-RRY1000 type computer observing and controlling pliabilitys instrument, and bending stiffness is smaller,
Represent that the flexibility of fabric is better；Water imbibition represents that having absorbed 1 with stopwatch measure fabric face drips with the static water absorption time
Time used in (25 drops=1mL)；The bullet property endured is represented with [passing through (w)+latitude (f)] to creasy recovery angle, with YG54 fabric pincher bullets
Property instrument measure；With bath usability measure：Example 1-7 silicon breast, is diluted with water to and test specimens identical solid content or quality
Concentration, then silicon breast after dilution is mixed in equal volume with test specimens again, stood, whether observation test specimens mode of appearance becomes
Change, reference is the amine terminated polyether silicon PEAS silicon breast in embodiment, the results are shown in Table 1-2.Wherein, table 1 is cross-linked structure both sexes carboxylic
Base polyethers amino silicone breast softening agent handles the application performance of fabric, and table 2 is that PUCS and anions and canons resin additive same bath use
Property measurement result.
Table 1
* BR --- bending stiffness, WA --- creasy recovery angle
Table 2
◎ --- without significant change
From table 1-2, both sexes PUCS silicon breast and yin, yang, non-ionic resin/additive compatibility using do not produce demulsification and
Floating oil, with the fabric hydrophilic of PUCS arrangements is good, the bullet property endured is strong, flexibility increase.
Claims (10)
1. a kind of linear both sexes end carboxyl polyethers amido silicon oil, it is characterised in that prepared by the mixture comprising following components：
Amine terminated polyether silicone oil α, ω-PEAS
Dibasic acid anhydride AD every 1 mole of α, ω-PEAS add 2 moles；
Amine terminated polyether the silicone oil α, ω-PEAS are prepared by the mixture comprising following components：
End ring oxygen polyether silicone oil α, ω-EPS
Polyetheramine PEA every 1 mole of α, ω-EPS add 2 moles
Its addition of isopropanol IPA solvents is α, the 20-200% of ω-EPS+PEA quality sums.
A kind of 2. linear both sexes end carboxyl polyethers amido silicon oil according to claim 1, it is characterised in that：The end ring oxygen
Polyether silicone oil α, ω-EPS, shown in structure such as formula (1)：
In formula, n span is 25-270, and a, b span are 0-30, and a+b span is 3-30.
A kind of 3. linear both sexes end carboxyl polyethers amido silicon oil according to claim 1, it is characterised in that：The polyetheramine
PEA, shown in structure such as formula (2)：
H2NC3H6O(C3H6O)x(C2H4O)y(C3H6O)zC3H6NH2 (2)
In formula, x, y, z is positive number, and x+z spans are 2.5-33.1, y span 0-39, and the number-average molecular weight of polyetheramine is
230-2000, including polyetheramine D230, D400, D2000, ED600, ED900, ED2003 and its mixture.
A kind of 4. linear both sexes end carboxyl polyethers amido silicon oil according to claim 1, it is characterised in that：The binary acid
Acid anhydride is binary aliphatic acid anhydrides, including maleic anhydride, succinic anhydride, itaconic anhydride, glutaric anhydride, adipic anhydride.
A kind of 5. linear both sexes end carboxyl polyethers amido silicon oil according to claim 1, it is characterised in that：The linear both sexes
End carboxyl polyethers amido silicon oil is reacted by amine terminated polyether silicone oil α, ω-PEAS and dibasic acid anhydride in polarity alcohol ether solvents A
Arrive, polarity alcohol ether solvents A dosage is α, the 20-30% of ω-PEAS quality；Described polarity alcohol ether solvents A includes diethyl two
Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dibutyl ethylene glycol ether, dimethyl ether, dipropylene glycol diethyl ether, DPG
Butyl oxide, butyl cellosolve, glycol methyl ether acetate and its mixture.
A kind of 6. linear both sexes end carboxyl polyethers amido silicon oil according to any one of Claims 1 to 5, it is characterised in that：
The linear both sexes end carboxyl polyethers amido silicon oil, shown in major constituent structure such as formula (3)：
In formula, pe1Come from raw material α, ω-EPS, pe2、pe3Come from polyetheramine PEA, pe2With pe3It is identical or different.
7. a kind of cross-linked structure both sexes carboxyl polyethers amino silicone breast softening agent, it is characterised in that it is mixing comprising following components
Compound：
Cross-linked structure both sexes carboxyl polyethers amido silicon oil PUCS
Its addition of AEO emulsifying agent is 30~50% of silicone oil quality in PUCS
Acetic acid HAc regulations pH is 5~6；
The cross-linked structure both sexes carboxyl polyethers amido silicon oil PUCS is prepared by the mixture comprising following components：
The mass parts of solvent-borne type both sexes end carboxyl polyethers amido silicon oil α, ω-CPEAS 1
The mass parts of both sexes polyether-polyurethane performed polymer PU 1~0.3.
A kind of 8. cross-linked structure both sexes carboxyl polyethers amino silicone breast softening agent according to claim 7, it is characterised in that：Institute
AEO emulsifying agent is stated, including AEO, isomerous tridecanol polyoxyethylene ether, the alcohol of isomery ten gather
Oxygen vinethene etc..
A kind of 9. cross-linked structure both sexes carboxyl polyethers amino silicone breast softening agent according to claim 7, it is characterised in that：Institute
Both sexes polyether-polyurethane performed polymer PU is stated, is prepared by the mixture comprising following components：
The PPG PEPO, including polyethylene glycol PEG, the PTMG two that number-average molecular weight is 200-2000
Alcohol；
The diisocyanate DIC, including hexamethylene diisocyanate, IPDI, 4,4 '-diphenylmethyl
Alkane diisocyanate, toluene di-isocyanate(TDI)；
Described non-reactive solvent B, including diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dibutyl ethylene glycol ether, dipropyl
Glycol dimethyl ether, dipropylene glycol diethyl ether, DPG butyl oxide, butyl cellosolve, glycol methyl ether acetate, acetone,
Dioxane.
10. a kind of preparation method of cross-linked structure both sexes carboxyl polyethers amino silicone breast softening agent, it is characterised in that including following step
Suddenly：
1) preparation of solvent-borne type both sexes end carboxyl polyethers amido silicon oil：By end ring oxygen polyether silicone oil α, ω-EPS and polyetheramine PEA
Mol ratio is 1:2 weigh α, ω-EPS and PEA successively, stir and evenly mix, and add with α, ω-EPS+PEA quality meters 20-200%
Isopropanol IPA solvents, stirring, be heated to 80-85 DEG C reaction 4-24h, IPA solvents are then recovered under reduced pressure, obtain Amino End Group
Polyether silicone oil α, ω-PEAS precursors；Stirring, by α, ω-PEAS quality adds 20-30% polarity alcohol ether solvents A, adjusts reaction
Temperature is to 70-125 DEG C, and then, then by α, ω-PEAS and dibasic acid anhydride mol ratio are 1:2 addition dibasic acid anhydrides continue carboxylic
Glycosylation reaction 1-4h, reaction terminate, obtain it is slightly muddy to transparency liquid, i.e., solvent-borne type both sexes end carboxyl polyethers amido silicon oil α, ω-
CPEAS, silicone oil are about 77.0-85.0%；
2) preparation of branched both sexes polyether-polyurethane performed polymer：Diisocyanate DIC is taken, is heated with stirring to 35-80 DEG C, it is different by two
Cyanate:PPG PEPO mol ratios are 2:1-1.25:1 is added dropwise to PPG and in terms of DIC+PEPO mass
20-50% non-reactive solvent B, 35-80 DEG C of reaction 0.5-1h of temperature control, then, adds the 0.5- in terms of DIC+PEPO mass
1% triethanolamine and dihydromethyl propionic acid equimolar than mixture, 35-80 DEG C of temperature control continues to react 0.5-2h, products therefrom,
I.e. branched both sexes polyether-polyurethane performed polymer PU；
3) preparation of cross-linked structure both sexes carboxyl polyethers amino silicone breast softening agent：Solvent-borne type α, ω-CPEAS is taken to gather with branched both sexes
Ether base polyurethane prepolymer for use as mixes, and the two dosage of control is so that the mass ratio of α in system, ω-CPEAS silicone oil and PU solid contents is 1:
1-0.3, stirring, 30-70 DEG C of temperature control carry out reaction 0.5-2h, as products therefrom, cross-linked structure both sexes carboxyl polyethers amino again
Silicone oil PUCS solution；
PUCS solution is taken, the isomery AEO breast of the 30-50% in terms of silicone oil quality is added by institute's silicate-containing oil quality
Agent, 30min is stirred, adds acetic acid and adjust system pH=5-6, then stir while add water to be emulsified, obtain partly
Transparent-clear microemulsion, i.e. cross-linked structure both sexes carboxyl polyethers amino silicone breast softening agent, solid content is about 15-30%.
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