CN107857862A - A kind of preparation method of dication type organic silicon modified aqueous polyurethane color fixing agent - Google Patents
A kind of preparation method of dication type organic silicon modified aqueous polyurethane color fixing agent Download PDFInfo
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- CN107857862A CN107857862A CN201711286021.4A CN201711286021A CN107857862A CN 107857862 A CN107857862 A CN 107857862A CN 201711286021 A CN201711286021 A CN 201711286021A CN 107857862 A CN107857862 A CN 107857862A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/02—After-treatment
- D06P5/04—After-treatment with organic compounds
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of preparation method of dication type organic silicon modified aqueous polyurethane color fixing agent, cation type organic silicon, diisocyanate, polymer polyatomic alcohol, cationic hydrophilic chain extender, acid neutralizing agent, the end-capping reagent blocked by the double hydroxyl alkyls rolled into a ball containing tertiary sulfonium tegmen is raw material, by prepolymerization reaction, end capping reaction and emulsification is neutralized, obtains dication type organic silicon modified aqueous polyurethane color fixing agent.The present invention introduces cation using the cation type organic silicon of double hydroxyl alkyls end-blocking containing ternary sulphonium group in soft segment；From tertiary amine cationoid chain extender, cation is introduced in hard section, two distinct types of cation group has been incorporated herein, cationic strength enhancing, the active force of anionic dye has been strengthened.The introducing of polysiloxanes segment simultaneously, improve the pliability of fabric after arranging.
Description
Technical field
The present invention relates to fabric post-treatment field, and in particular to a kind of dication type organic silicon modified aqueous polyurethane is consolidated
The preparation method of toner.
Background technology
After anionic dye dyed fabric, generally require and arranged with color fixing agent, to improve fabric color moisture resistant fastness.
As piece market proposes new requirement to the green problem of product, traditional color fixing agent release formaldehyde and dyeing is knitted
Change and feel is looked for have a great influence.Although in the market there are many color fixing agent products in recent years, also exist many
Problems demand solves, and such as current color fixing agent most on the market is anionic or nonionic structure, and it is to cellulose fiber
The anionic group of peacekeeping dyestuff has repulsion left and right, therefore adsorption capacity is not high.In order to improve such color fixing agent on dyed fabric
Content, generally require to add more auxiliary agent, cause the waste of resource.
Aqueous polyurethane has nonflammable, non-toxic, environment-friendly, resources conservation and easily added using water as decentralized medium
The advantages that work, for polyurethane as aldehyde-free colour stabilizer, it forms film by being adhered to dye molecule surface, and can be with dyestuff and fiber
Upper active group reacts, but in general polyurethane has more shortcoming, and such as poor water resistance, heat endurance is not good enough, gloss
Spend not good enough, feel is not good enough etc..
Organosiloxane has the characteristic of organic compound and inorganic compound concurrently, has a relatively low surface energy, thus into
Silicon-containing group it is dirty to assign good low temperature resistant, the weather-proof, Waterproofing/oilproofing of polymer-modified film to table to enrichment in membrane process
With good mechanical performance, polysiloxanes is combined by the Silicon Oligomer-polyuretyane Block Copolymer that soft segment synthesizes of polysiloxanes
With both polyurethane advantage, the flexibility of fabric can be improved and reduce surface energy, combined the effect such as absorption, film forming, improve dye
The fastness to wet rubbing of yarn dyed fabric.
China Patent Publication No. CN105113255A discloses a kind of organic silicon modified polyurethane color fixing agent and its preparation side
Method, by hydroxy-terminated polysiloxane, polypropylene glycol (PPG), IPDI (IPDI), N methyldiethanol amine, three
Hydroxymethyl-propane (TMP), acetone, glacial acetic acid, methyl ethyl ketoxime are Material synthesis organic silicon modified polyurethane, and this method is the same as most
Number organic silicon modified polyurethanes are similar, and using hydroxy-terminated polysiloxane modified polyurethane, this method is to the polysiloxanes of introducing
Content and molecular weight have compared with big limitation, and polysiloxane molecule amount is less than 1000 in the invention, and the improvement to feel is made
With smaller.
The content of the invention
It is organic silicon modified aqueous poly- it is an object of the invention to overcome the deficiencies of the prior art and provide a kind of dication type
The preparation method of urethane color fixing agent, it is applied to fabric printing fixation last handling process using color fixing agent made from this method, can
Effectively improve fabric dry and wet colorfastness to rubbing.
To achieve the above object, the present invention adopts the following technical scheme that：
With containing ternary sulphonium group double hydroxyl alkyls block cation type organic silicon, diisocyanate, polymer polyatomic alcohol,
Cationic hydrophilic chain extender, end-capping reagent, acid neutralizing agent are raw material, by prepolymerization reaction, end capping reaction and neutralize emulsification, obtain double
Cation type organic silicon modified water-borne polyurethane color fixing agent.
Specifically comprise the following steps：
(1) ring-opening reaction：In flask, α is sequentially added, ω-bis-epoxy terminated polysiloxane, dipropyl sulfide and acetic acid,
Reaction system is warming up to 70 DEG C, now system heat release is obvious, if temperature of reaction system more than 80 DEG C, should be carried out with ice bath in time
Cooling；After heat release terminates, 8h is reacted at this temperature, the terminating reaction when reaction system acid number is less than 5, is obtained double ended type and is contained
The hydroxyl alkyl blocking silicone of ternary sulphonium group
(2) prepolymerization reaction：Cation type organic silicon, the polymer polyatomic alcohol that double hydroxyl alkyls containing ternary sulphonium group are blocked
Add in reactor, temperature is 100~110 DEG C, and vacuum is that 1~1.5h is removed water under -0.05~-0.08MPa, surveys moisture
＜ 0.1%, cooling add diisocyanate, are reacted 1~4 hour at 50~90 DEG C, when isocyanate group content reaches theoretical value
When, cationic hydrophilic chain extender is added, reacts 0.5~2 hour, obtains dication type organic silicon modified polyurethane performed polymer.
(3) end capping reaction：The dication type organic silicon modified polyurethane performed polymer that step (2) obtains adds a certain amount of
End-capping reagent reacts 0.5~2 hour, reacts to isocyanate-free group, obtains dication type organic silicon modified polyurethane；
(4) emulsification is neutralized：The dication type organic silicon modified polyurethane that step (3) obtains, add in a certain amount of acid
With 0.5 hour, under the conditions of high-speed stirred, add deionized water, acetone is removed under reduced pressure, it is organic-silicon-modified to obtain dication type
Polyaminoester emulsion.
Cation type organic silicon its structure of double hydroxyl alkyls end-blocking containing ternary sulphonium group is as follows：
Wherein, the hydroxyl alkyl blocking silicone containing ternary sulphonium group is with α, ω-bis-epoxy terminated polysiloxane, propyl sulfide
Ether and acetic acid are initiation material, are obtained through epoxy ring opening reaction；Epoxide group carries out the synthesis of ring-opening reaction with sulfide compound
Method has similar relevant report (to refer in foreign language literature：《Langmuir》2000, volume 16,3214-3220 pages), it is closed
This patent is incorporated by reference into method.
α, ω-bis-epoxy terminated polysiloxane：Dipropyl sulfide：Acetic acid mol ratio=1:2:2.
Containing ternary sulphonium group double hydroxyl alkyls end-blocking cation type organic silicon content range be：10%~30%, containing tertiary sulfonium
Cation type organic silicon molecular weight Mn=1000~5000 of double hydroxyl alkyls end-blocking of group.The polymer polyol alcohol content model
Enclose for：30%~70%, the cationic hydrophilic chain extender content scope is：3%~10%, the cation type organic silicon,
Polymer polyatomic alcohol and cationic hydrophilic chain extender content are respectively cation type organic silicon, polymer polyatomic alcohol and cation parent
Water chain extender quality accounts for the percentage of total solid quality.
The amount of diisocyanate is cation type organic silicon, the polymer polyol blocked according to double hydroxyl alkyls of ternary sulphonium group
Total hydroxyl determines in alcohol, cationic hydrophilic chain extender, control n (NCO):N (OH)=1.1~1.4.
The amount of end-capping reagent is residual isocyanate base 100%~110%.
Diisocyanate is selected from IPDI (IPDI), toluene di-isocyanate(TDI) (TDI), diphenyl-methane two
Isocyanates (MDI), hexamethylene diisocyanate (HDI), one kind in dicyclohexyl methyl hydride diisocyanate (HMDI) or
It is a variety of.
Polymer polyatomic alcohol be PolyTHF dihydric alcohol, polyoxyethylene glycol, Polyoxypropylene diol, gather oneself
Diacid hexylene glycol ester dihydric alcohol, poly adipate succinic acid ester dihydric alcohol, polyethylene glycol adipate dihydric alcohol, polyadipate new penta
Any one in diol ester dihydric alcohol, poly- phthalic acid hexylene glycol ester dihydric alcohol or any two kinds and two or more mixing
Thing.
Cationic hydrophilic chain extender is N methyldiethanol amine, one kind in N butyl diethanol amine or mixture.
End-capping reagent is diacetylmonoxime, phenol, one kind in 3,5- methylimidazoles or mixture.
The amount of deionized water is to make solid content be 20%~40%.
The beneficial effects of the invention are as follows：
1) cation type organic silicon blocked from double hydroxyl alkyls of ternary sulphonium group, cation is introduced in soft segment, from uncle
Amine cation chain extender, cation is introduced in hard section, two distinct types of cation group has been incorporated herein, cation is strong
Degree enhancing, the active force of anionic dye is strengthened.
2) the dication type modified aqueous polyurethane of synthesis, ternary sulphonium group and tertiary amine group can provide hydrophily, have
Beneficial to the silicone segments for introducing high level and larger molecular weight, so as to preferably improve feel, and stabilization can be formed
Emulsion.
Embodiment
With reference to specific embodiment, the invention will be further described.Following examples are only used for clearly saying
Bright technical scheme, and can not be limited the scope of the invention with this.
Embodiment 1
Silicone content 10%, molecular weight Mn=1000, polymer polyatomic alcohol 70%, tertiary amine cation hydrophile content
3%, NCO：Hydroxyl=1.1.
(1) ring-opening reaction
In four-necked bottle, 384g α are sequentially added, ω-bis-epoxy terminated polysiloxane, 59g dipropyl sulfides and 60g acetic acid,
Reaction system is warming up to 70 DEG C, now system heat release is obvious, if temperature of reaction system more than 80 DEG C, should be carried out with ice bath in time
Cooling；After heat release terminates, 8h is reacted at this temperature, the terminating reaction when reaction system acid number is less than 5, is obtained double ended type and is contained
The hydroxyl alkyl blocking silicone (Mn=1000) of ternary sulphonium group.
(2) prepolymerization reaction：Cation type organic silicon (the Mn=that the 15g double hydroxyl alkyls for containing ternary sulphonium group are blocked
1000), 100g PolyTHFs dihydric alcohol (PTMG2000) add reactor in, temperature be 100~110 DEG C, vacuum for-
1h is removed water under 0.05~-0.08MPa, surveys moisture ＜ 0.1%, cooling adds 25g IPDIs (IPDI),
Reacted 1 hour at 90 DEG C, when isocyanate group content reaches theoretical value, add 4.46g cationic hydrophilic chain extender N- methyl two
Monoethanolamine, react 0.5 hour, obtain dication type organic silicon modified polyurethane performed polymer.
(3) end capping reaction：The dication type organic silicon modified polyurethane performed polymer that step (2) obtains adds 1.83g fourths
Ketoxime reacts 0.5 hour, reacts to isocyanate-free group, obtains dication type organic silicon modified polyurethane；
(4) emulsification is neutralized：The dication type organic silicon modified polyurethane that step (3) obtains, add 2.51g acetic acid and neutralize
0.5 hour, under the conditions of high-speed stirred, add 578 deionized waters, acetone be removed under reduced pressure, obtain solid content for the 20% pair of sun from
Subtype organic silicon modified polyurethane emulsion.
Embodiment 2
Silicone content 23%, molecular weight Mn=3000, polymer polyatomic alcohol 50%, tertiary amine cation hydrophile content
6%, NCO：Hydroxyl=1.2.
(1) ring-opening reaction (mol ratio α, ω-bis- silicon hydrogen terminated polysiloxane：Dipropyl sulfide：Acetic acid=1：2：2) in four necks
In bottle, 691g α are sequentially added, ω-bis-epoxy terminated polysiloxane, 59g dipropyl sulfides and 60g acetic acid, reaction system are heated up
To 70 DEG C, now system heat release is obvious, if temperature of reaction system should be cooled with ice bath in time more than 80 DEG C；Heat release terminates
Afterwards, 8h is reacted at this temperature, the terminating reaction when reaction system acid number is less than 5, obtains the hydroxyl that double ended type contains ternary sulphonium group
Hydroxyl-terminated silicone (Mn=3000).
(2) prepolymerization reaction：Cation type organic silicon (the Mn=that the 45g double hydroxyl alkyls for containing ternary sulphonium group are blocked
3000), 100g poly adipate succinic acid esters dihydric alcohol (PBA2000) is added in reactor, and temperature is 100~110 DEG C, vacuum
To remove water 1.5h under -0.05~-0.08MPa, moisture ＜ 0.1% is surveyed, cooling adds 33.6gHDI, small in 50 DEG C of reactions 4
When, when isocyanate group content reaches theoretical value, add 11.9g cationic hydrophilic chain extender N methyldiethanol amines, reaction 1
Hour, obtain dication type organic silicon modified polyurethane performed polymer.
(3) end capping reaction：The dication type organic silicon modified polyurethane performed polymer that step (2) obtains adds 7.4g3,5-
Dimethyl pyrazole reacts hour, reacts to isocyanate-free group, obtains dication type organic silicon modified polyurethane；
(4) emulsification is neutralized：The dication type organic silicon modified polyurethane that step (3) obtains, add 6.6g acetic acid and neutralize
0.5 hour, under the conditions of high-speed stirred, add 453 deionized waters, acetone be removed under reduced pressure, obtain solid content for the 30% pair of sun from
Subtype organic silicon modified polyurethane emulsion.
Embodiment 3
Silicone content 30%, molecular weight Mn=5000, polymer polyatomic alcohol 30%, tertiary amine cation hydrophile content
10%, NCO：Hydroxyl=1.4.
(1) ring-opening reaction (mol ratio α, ω-bis- silicon hydrogen terminated polysiloxane：Dipropyl sulfide：Acetic acid=1：2：2) in four necks
In bottle, 1250g α are sequentially added, ω-bis-epoxy terminated polysiloxane, 59g dipropyl sulfides and 60g acetic acid, reaction system are heated up
To 70 DEG C, now system heat release is obvious, if temperature of reaction system should be cooled with ice bath in time more than 80 DEG C；Heat release terminates
Afterwards, 8h is reacted at this temperature, the terminating reaction when reaction system acid number is less than 5, obtains the hydroxyl that double ended type contains ternary sulphonium group
Hydroxyl-terminated silicone (Mn=5000).
(2) prepolymerization reaction：Cation type organic silicon (the Mn=that the 100g double hydroxyl alkyls for containing ternary sulphonium group are blocked
5000), 100g Polyoxypropylene diols (PPG3000) add reactor in, temperature be 100~110 DEG C, vacuum for-
1~1.5h is removed water under 0.05~-0.08MPa, surveys moisture ＜ 0.1%, cooling adds 91.7gHMDI, small in 80 DEG C of reactions 3
When, when isocyanate group content reaches theoretical value, add 32.25g cationic hydrophilic chain extender N butyl diethanol amines, reaction 2
Hour, obtain dication type organic silicon modified polyurethane performed polymer.
(3) end capping reaction：The dication type organic silicon modified polyurethane performed polymer that step (2) obtains adds 18g phenol
Hour is reacted, reacts to isocyanate-free group, obtains dication type organic silicon modified polyurethane；
(4) emulsification is neutralized：The dication type organic silicon modified polyurethane that step (3) obtains, add 12g acetic acid and neutralize
0.5 hour, under the conditions of high-speed stirred, add 486 deionized waters, acetone be removed under reduced pressure, obtain solid content for the 40% pair of sun from
Subtype organic silicon modified polyurethane emulsion.
Product obtained by above-described embodiment is subjected to fixation treatment to textile, application effect is tested as follows
And evaluation：
Color fixing process：Bafta → two soak two and roll (color fixing agent, pick-up 80%) → preliminary drying after reactive brilliant blue K-GR dyeing
(temperature 45 C, time 3min → baking (150 DEG C of temperature, time 3min), contrasted with solid content.
1. crock fastness method of testing presses GB/T3920-2008《Textile color stability tests colour fastness to rubbing》Method is surveyed
It is fixed；
2. soaping fastness method of testing presses GB/T3921-2008《Textile color stability tests color fastness to washing》Method is surveyed
It is fixed.
The fabric WASHING COLOR FASTNESS after color fixing agent of the present invention arrangement improves 2-3 levels, dry friction jail as can be seen from the above table
Degree improves 1-2 levels, and fastness to wet rubbing improves 2-3 levels, and fabric feeling softens after arrangement.
It is described above, it is only the preferred embodiments of the present invention, not limits the present invention, appoints
What what those skilled in the art was changed or be modified as possibly also with the technology contents of the disclosure above to change on an equal basis etc.
Imitate embodiment.It is every without departing from the present invention program content, the technical spirit according to the present invention is to made for any of the above embodiments any
Simple modification, equivalent variations and remodeling, all fall within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of dication type organic silicon modified aqueous polyurethane color fixing agent, it is characterised in that to contain uncle
Cation type organic silicon, diisocyanate, polymer polyatomic alcohol, the cationic hydrophilic chain extension of double hydroxyl alkyls end-blocking of sulfonium group
Agent, end-capping reagent, acid neutralizing agent are raw material, by prepolymerization reaction, end capping reaction and neutralize emulsification, obtain dication type organosilicon
Modified aqueous polyurethane color fixing agent.
2. the preparation method of dication type organic silicon modified aqueous polyurethane color fixing agent according to claim 1, it is special
Sign is, comprises the following steps：
S1) ring-opening reaction：In four-necked bottle, α is sequentially added, ω-bis-epoxy terminated polysiloxane, dipropyl sulfide and acetic acid will
Reaction system is warming up to 70 DEG C, and now system heat release is obvious, if temperature of reaction system should be dropped with ice bath in time more than 80 DEG C
Temperature；After heat release terminates, 8h is reacted at this temperature, the terminating reaction when reaction system acid number is less than 5, is obtained double ended type and is contained uncle
The hydroxyl alkyl blocking silicone of sulfonium group；
S2) prepolymerization reaction：Cation type organic silicon, the polymer polyatomic alcohol that double hydroxyl alkyls containing ternary sulphonium group are blocked add
In reactor, temperature is 100~110 DEG C, and vacuum is that 1~1.5h is removed water under -0.05~-0.08MPa, surveys moisture ＜
0.1%, cooling adds diisocyanate, is reacted 1~4 hour at 50~90 DEG C, when isocyanate group content reaches theoretical value,
Cationic hydrophilic chain extender is added, reacts 0.5~2 hour, obtains dication type organic silicon modified polyurethane performed polymer；
S3) end capping reaction：Step S2) obtained dication type organic silicon modified polyurethane performed polymer adds a certain amount of end-blocking
Agent is reacted 0.5~2 hour, is reacted to isocyanate-free group, is obtained dication type organic silicon modified polyurethane；
S4 emulsification) is neutralized：Step S3) obtained dication type organic silicon modified polyurethane, add a certain amount of acetic acid and neutralize
0.5 hour, under the conditions of high-speed stirred, deionized water is added, acetone is removed under reduced pressure, it is organic-silicon-modified poly- to obtain dication type
Urethane emulsion.
3. the preparation method of dication type organic silicon modified aqueous polyurethane color fixing agent according to claim 1, it is special
Sign is, the described cation type organic silicon of double hydroxyl alkyls end-blocking its structure containing ternary sulphonium group is as follows：
4. the preparation method of dication type organic silicon modified aqueous polyurethane color fixing agent according to claim 2, it is special
Sign is, α, ω-bis-epoxy terminated polysiloxane：Dipropyl sulfide：Acetic acid mol ratio=1:2:2.
5. the preparation method of dication type organic silicon modified aqueous polyurethane color fixing agent according to claim 2, it is special
Sign is that the cation type organic silicon content range of double hydroxyl alkyls end-blocking of the ternary sulphonium group is：10%~30%, the uncle
Molecular weight Mn=1000~5000 of the cation type organic silicon of double hydroxyl alkyls end-blocking of sulfonium group, the polymer polyatomic alcohol contain
Measuring scope is：30%~70%, the cationic hydrophilic chain extender content scope is：3%~10%, the cationic is organic
Silicon, polymer polyatomic alcohol and cationic hydrophilic chain extender content be respectively cation type organic silicon, polymer polyatomic alcohol and sun from
Sub- hydrophilic chain extender quality accounts for the percentage of total solid quality.
6. the preparation method of dication type organic silicon modified aqueous polyurethane color fixing agent according to claim 2, it is special
Sign is, the amount of diisocyanate is by the cation type organic silicon, the polymer polyol that are blocked according to double hydroxyl alkyls of ternary sulphonium group
Total hydroxyl determines in alcohol, cationic hydrophilic chain extender, control n (NCO):N (OH)=1.1~1.4.
7. the preparation method of dication type organic silicon modified aqueous polyurethane color fixing agent according to claim 2, it is special
Sign is that the amount of the end-capping reagent is residual isocyanate base 100%~110%.
8. the preparation side of dication type organic silicon modified aqueous polyurethane color fixing agent according to any one of claims 1 to 7
Method, it is characterised in that the diisocyanate be selected from IPDI (IPDI), toluene di-isocyanate(TDI) (TDI),
'-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), dicyclohexyl methyl hydride diisocyanate (HMDI)
In one or more.
9. the preparation side of dication type organic silicon modified aqueous polyurethane color fixing agent according to any one of claims 1 to 7
Method, it is characterised in that the polymer polyatomic alcohol is PolyTHF dihydric alcohol, polyoxyethylene glycol, PPOX
Dihydric alcohol, polyadipate hexylene glycol ester dihydric alcohol, poly adipate succinic acid ester dihydric alcohol, polyethylene glycol adipate dihydric alcohol,
In polyneopentyl glycol adipate dihydric alcohol, poly- phthalic acid hexylene glycol ester dihydric alcohol any one or it is any two kinds and two
The mixture of the kind above.
10. the preparation side of dication type organic silicon modified aqueous polyurethane color fixing agent according to any one of claims 1 to 7
Method, it is characterised in that the cationic hydrophilic chain extender be N methyldiethanol amine, one kind in N butyl diethanol amine or
Mixture；The end-capping reagent is diacetylmonoxime, phenol, one kind in 3,5- methylimidazoles or mixture；The deionized water
Amount make solid content be 20%~40%.
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Cited By (4)
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| EP3744758A1 (en) | 2019-05-31 | 2020-12-02 | Henkel AG & Co. KGaA | Onium-functionalized siloxanes |
| CN112219842A (en) * | 2020-07-24 | 2021-01-15 | 华南农业大学 | Waterborne polyurethane drug-loaded slow-release spray with opposite charges and preparation method and application thereof |
| CN115073703A (en) * | 2022-06-29 | 2022-09-20 | 江西辙炜新材料科技有限公司 | Ultraviolet light curing water-based colorant, preparation method and application thereof |
| CN116396464A (en) * | 2023-05-10 | 2023-07-07 | 杭州美高华颐化工有限公司 | Preparation method of isophorone diisocyanate blocked block silicone oil |
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| US6555612B1 (en) * | 1999-01-28 | 2003-04-29 | Basf Coatings Ag | Aqueous coating material and modular system for producing same |
| CN104017158A (en) * | 2014-06-10 | 2014-09-03 | 山东省农业科学院农业质量标准与检测技术研究所 | Preparation method of organic silicon modified amphiprotic polyurethane aqueous dispersion |
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| US6555612B1 (en) * | 1999-01-28 | 2003-04-29 | Basf Coatings Ag | Aqueous coating material and modular system for producing same |
| CN104017158A (en) * | 2014-06-10 | 2014-09-03 | 山东省农业科学院农业质量标准与检测技术研究所 | Preparation method of organic silicon modified amphiprotic polyurethane aqueous dispersion |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3744758A1 (en) | 2019-05-31 | 2020-12-02 | Henkel AG & Co. KGaA | Onium-functionalized siloxanes |
| WO2020239615A1 (en) | 2019-05-31 | 2020-12-03 | Henkel Ag & Co. Kgaa | Onium-functionalized siloxanes |
| CN112219842A (en) * | 2020-07-24 | 2021-01-15 | 华南农业大学 | Waterborne polyurethane drug-loaded slow-release spray with opposite charges and preparation method and application thereof |
| CN115073703A (en) * | 2022-06-29 | 2022-09-20 | 江西辙炜新材料科技有限公司 | Ultraviolet light curing water-based colorant, preparation method and application thereof |
| CN115073703B (en) * | 2022-06-29 | 2023-05-23 | 江西辙炜新材料科技有限公司 | Ultraviolet light curing water-based colorant, and preparation method and application thereof |
| CN116396464A (en) * | 2023-05-10 | 2023-07-07 | 杭州美高华颐化工有限公司 | Preparation method of isophorone diisocyanate blocked block silicone oil |
| CN116396464B (en) * | 2023-05-10 | 2024-04-16 | 杭州美高华颐化工有限公司 | Preparation method of isophorone diisocyanate blocked block silicone oil |
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