CN106632964B - A kind of preparation method of the side chain of silicone oil containing dissaving structure aqueous polyurethane - Google Patents
A kind of preparation method of the side chain of silicone oil containing dissaving structure aqueous polyurethane Download PDFInfo
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- 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
- 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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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- 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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- C08G18/00—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
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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
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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Abstract
The present invention provides a kind of hyperbranched silicone oil modified side chain water-based polyurethane polymers and preparation method thereof, polymer is obtained containing hyperbranched silicone oil side chain by 100 parts of polyether polyols and 10-50 parts of hyperbranched amido silicon oils and 20-80 parts of di-isocyanate reactions and is had isocyanate-terminated base polyurethane prepolymer for use as；It is added 2-19 part small molecule polyol chain extenders and 0.1-10 parts of dihydric alcohols of small molecule containing amino progress chain extensions in performed polymer, it is quaternized and further emulsify and hyperbranched silicone oil modified side chain polyurethane copolymer emulsion is made.Of the invention containing uses hyperbranched siloxane segment in hyperbranched silicone oil modified side chain aqueous polyurethane emulsion, improve its water contact angle, reduce the water absorption rate of polyurethane；It can be used as no fluoro water proofing agent, be applied to chemical fibre fabric or cotton；Preparation method, technique is relatively simple, and reaction speed is moderate, and operating condition is easily controllable；This product belongs to water-based emulsion, meets environmentally protective developing direction.
Description
Technical field
The invention belongs to field of fine chemical, and in particular to a kind of system of the side chain of silicone oil containing dissaving structure aqueous polyurethane
Preparation Method.
Background technique
Aqueous polyurethane has excellent comprehensive performance, and has the feature of environmental protection, thus is widely used in textile printing and dyeing and adds
Work, leather processing, adhesive, furniture lacquer, electrophoretic paint, electrocoating paint, building coating, paper process coating, glass fibre apply
Many fields such as material.But in general, aqueous polyurethane still has some disadvantages needs to overcome, as strand contain hydrophilic chain link or
The problems such as ionic group of person's side chain causes water resistance bad；The problems such as inadequate because of heat resistance caused by based on linear molecule.Needle
To these problems, existing distinct methods approach solves it.Organic siloxane modified aqueous polyurethane be wherein approach it
One, polyurethane can improve the oil resistivity of polysiloxane emulsion, and polysiloxane emulsion can improve the water-fast of aqueous polyurethane
And solvent resistance, the two, which is blended, can get the effect learnt from other's strong points to offset one's weaknesses, available water-fast, resistance to greasy dirt performance and high-low temperature resistant
The water-base polyurethane material of equal excellent combination properties.
Currently, can be divided into blending and modifying and modification by copolymerization according to the different preparation methods of modification, wherein blending and modifying is maximum
The shortcomings that both be exactly poor compatibility, often result in that microphase separation degree is excessive, the mechanical strength of material caused to decline.In order to
Improve this problem, one of them is exactly to pass through copolymerization process.And modification by copolymerization can be divided into small molecule silicon according to the structure of organosilicon
Alkane coupling agent and macromolecular polysiloxanes (it is silanol-modified, aminoalkyl is silicon oil modified, hydroxyalkyl is silicon oil modified and alkoxyl silicone oxygen
Alkane is cross-linking modified etc.).
Polysiloxanes can assign many Zhuos such as good waterproof, anti-pollution and solvent resistance for polyurethane-modified
Characteristic more, main reason is that polysiloxanes and polyurethane are mutual exclusive two kinds of polymer, therefore, polysiloxanes segment
Polymeric outer layer can be gradually moved to, allows material surface to be enriched with organosilicon, has apparent surface modifying function to material in this way, make
The performances such as its water resistance, steam permeability, heat resistance, chemical-resistant reagent improve, and the variation of ontology mechanical property is little.However, due to
Polysiloxane chain is easily wrapped up wherein in the main chain of copolymer, and migration is difficult, thus the characteristic of polysiloxanes show it is unknown
It shows, especially random copolymer.More preferable performance in order to obtain, it is necessary to increase additive amount, result in the two phase separation degree in this way
Increase, it is not ideal enough to will lead to its mechanical property instead.96 years, one researcher of Pennsylvania Pennsylvania closed
Polyamide polymer at branch with polysiloxane finds that the polymer has good hydrophobicity, and contact angle reaches 100
Degree left and right, keeps hydrophobic stability (Chapman, T. M. in 30 days; Marra, K. G. Macromolecules
1995,28, (6), 2081-2085.).
Qilu University of Technology Zhang in 2010 et al. also indicates that the polyurethane copolymer of branch chain belt polysiloxanes than main chain class
Type have more low water absorption and preferably it is hydrophobic with oleophobic property, this is because the polyurethane copolymer of branch chain belt polysiloxanes
Middle polysiloxanes segment is easier to migrate to superficial layer, causes film surface silicon content higher reason (Zong, J.; Zhang,
Q.; Sun, H.; Yu, Y.; Wang, S.; Liu, Y. Polymer bulletin 2010, 65, (5), 477-
493.).2014, Yu etc. was respectively synthesized the polyurethane-polysiloxane copolymer of block and grafting, when content of siloxane is from 0
When increasing to 5%, the tensile strength of block polyurethane copolymer film is gradually reduced, graft modified aqueous polyurethane polysiloxanes
The tensile strength of copolymer film but improves；When polysiloxanes is in 3% or more water, the tension of grafted polyurethane copolymer film
Intensity is declined；In addition, graft modified aqueous polyurethane water absorption rate decline degree is also bigger than block modified polyurethane, respectively
17.3% and 40.2%(Xiahou, G. are fallen to from 163.9; Liu, W.; Yan, Z.; Su, K.; Wang, H.
Journal of Macromolecular Science, Part A 2014,51, (12), 966-975.).Although poly- ammonia
Polysiloxanes branch segment is more easy to migrate to superficial layer in ester copolymer, the hydrophobic performance of material is effectively improved, however, still cannot
The strong-hydrophobicity energy having is played to greatest extent.
Summary of the invention
It is to be solved to ask it is an object of that present invention to provide a kind of hyperbranched silicone oil modified side chain water-based polyurethane polymer
Topic is the hydrophobic performance in order to further increase organic silicon modified polyurethane,.
Another object of the present invention is to provide the preparations of above-mentioned hyperbranched silicone oil modified side chain water-based polyurethane polymer
Method.
The purpose of the invention is achieved by the following technical solution: a kind of hyperbranched silicone oil modified side chain aqueous polyurethane polymerization
Object, which is characterized in that including component are as follows: hyperbranched amido silicon oil 10-50 parts, 20-80 parts of diisocyanate, polyether-type is polynary
100 parts of alcohol, 2-10 parts of small molecule polyol chain extender, 0.1-10 parts of amino-containing small molecule dihydric alcohol, quaternizing agent are measured and are
The 60-110% of amino-containing small molecule dihydric alcohol molal quantity.
The hyperbranched amido silicon oil has the general structure that is shown below:
Wherein, in general formula X, Y, Z be respectively 10~100 natural number.
The diisocyanate is selected from isofoer diisocyanate, hexamethylene diisocyanate, two isocyanide of ditolyl methane
Acid esters, sub- one of xylylene diisocyanate or toluene di-isocyanate(TDI) or no less than two kinds of combination.
The polyether polyol be one of polyethylene glycol, polypropylene glycol or polytetrahydrofuran ether glycol or
No less than two kinds of combination, molecular weight 300-6000.
The small molecule polyol chain extender is selected from 1,4-butanediol, 1,2-PD, ethylene glycol, a contracting diethyl two
One of alcohol, glycerine or trimethylolpropane or no less than two kinds of combination.
The amino-containing small molecule dihydric alcohol is N- phenyldiethanol-amine, N butyl diethanol amine, N- propyl diethyl
One of hydramine, N- ethyldiethanolamine and N methyldiethanol amine.
The quaternizing agent is benzyl chloride, dimethyl carbonate, dimethyl suflfate, bromobutane, iodomethane, epoxy chloropropionate
One of alkane.
The preparation method of hyperbranched silicone oil modified side chain water-based polyurethane polymer, it is characterised in that:
Step 1: 100 parts of polyether polyols, 10-50 parts of hyperbranched silicone oil and 20-80 parts of diisocyanate are being catalyzed
It is stirred to react in 65-100 DEG C 1-3 hours under the conditions of agent；
Step 2: 2-10 parts of small molecule polyol chain extenders, 0.1-10 parts of amino-containing small molecule dihydric alcohols and the are added
A kind of solvent is stirred to react 2-6 hours at 45-80 DEG C, is analyzed residual isocyanate groups content with di-n-butylamine method, is then dropped
Temperature adds to being lower than 30 DEG C and carries out quaternized, room temperature holding reaction 1-3 with the diluted quaternizing agent of second of Solvents Solvent
Hour, obtain the isocyanate-terminated base polyurethane prepolymer for use as of quaternized cationic type；
Step 3: the base polyurethane prepolymer for use as of the quaternized cationic type being stirred, 5-25 DEG C of deionization is at the uniform velocity added
Until being uniformly dispersed then at the same temperature, the polynary amine aqueous solution of the 5-20% containing mass percentage concentration is slowly added dropwise in water, stirring
Reaction 0.5-2 hours is obtained containing hyperbranched silicone oil modified side chain aqueous polyurethane emulsion.
Catalyst described in step 1 is one of organotin catalysts, organozinc catalyst and organic bismuth catalyst.
The catalyst is organotin catalysts, and the organotin catalysts are dibutyltin dilaurate, and dosage is
Diisocyanate, polyether polyol, amido silicon oil and small molecule polyol gross mass 0.1-0.5%.
The first solvent described in step 2 is one of acetone, methyl butyl ketone, ethyl acetate, butyl acetate, and dosage is
0.5-2 times of small molecule polyol chain extender and amino-containing small molecule dihydric alcohol gross mass.
One of second of solvent acetone, methyl butyl ketone, ethyl acetate, butyl acetate described in step 2, dosage are season
The 10-30% of ammonium reagent gross mass.
Deionized water dosage described in step 3 is 2-4 times of polyurethane prepolymer weight.
Polyamine described in step 3 is ethylenediamine, diethylenetriamine, triethylene triamine, hexamethylene diamine or isophorone two
One of amine, dosage are that the molar ratio of reactive hydrogen and isocyanate groups in cation polyurethane performed polymer in diamine is
0.8-1.1:1.
Compared with prior art, the present invention having the following advantages that and effect:
(1) preparation method of the invention containing hyperbranched silicone oil modified side chain aqueous polyurethane emulsion, technique is relatively simple,
Reaction speed is moderate, and operating condition is easily controllable, can flexibly be controlled by source chemicals ratio and reaction time and temperature
The extent of reaction of entire reaction process is suitable for industrialized production.
It is (2) of the invention containing using hyperbranched siloxane segment in hyperbranched silicone oil modified side chain aqueous polyurethane emulsion,
Compared to the surface property that more can effectively improve material in original technology using single siloxane chain, its water contact angle is improved, is dropped
The water absorption rate of oligourethane material can be used as the application of polyurethanes waterproofing agent, therefore have better market prospects.
Detailed description of the invention
Fig. 1 is the infrared spectrum containing hyperbranched silicone oil modified side chain aqueous polyurethane emulsion in embodiment 1；
Fig. 2 is containing hyperbranched silicone oil modified side chain aqueous polyurethane emulsion on a glass after dried coating film in embodiment 5
Contact angle test figure；
Fig. 3 be comparative example in containing hyperbranched silicone oil modified side chain aqueous polyurethane emulsion on a glass dried coating film after
Contact angle test figure.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
By diisocyanate and hyperbranched amido silicon oil, polyether polyol, small molecule polyol and contain amino first
Small molecule dihydric alcohol carry out step-reaction polymerization, then be added quaternizing agent be amino formed quaternary ammonium salt, obtain containing over-expense
The performed polymer, is finally dispersed in water by SiClx oil modified side chain base polyurethane prepolymer for use as, is made and changes containing hyperbranched silicone oil side chain
Property aqueous polyurethane emulsion.
The preparation method containing hyperbranched silicone oil modified side chain aqueous polyurethane emulsion, the specific steps are as follows:
1) by 100 parts of polyether polyols, 10-50 parts of hyperbranched silicone oil and 20-80 parts of diisocyanate in catalyst item
It is stirred to react in 65-100 DEG C 1-3 hours under part, obtains isocyanate-terminated base polyurethane prepolymer for use as；
Wherein,
In step (1), the polyether polyol be selected from one of polypropylene glycol or polytetrahydrofuran ether glycol or
Person is no less than two kinds of combination, molecular weight 300-6000；
In step (1), the hyperbranched amido silicon oil has the general structure as shown in following formula (I):
Formula (I)
Wherein, in formula (I), X, Y, Z are respectively 10~100 natural number；
In step (1), the diisocyanate is selected from isofoer diisocyanate (IPDI), hexamethylene diisocyanate
(HDI), ditolyl methane diisocyanate (MDI), sub- xylylene diisocyanate (XDI) or toluene di-isocyanate(TDI)
Or no less than two kinds of combination one of (TDI)；
In step (1), the catalyst is one in organotin catalysts, organozinc catalyst and organic bismuth catalyst
Kind, wherein preferred organotin catalysts are dibutyltin dilaurate, dosage is diisocyanate, polyether polyol, ammonia
The 0.1-0.5% of base silicone oil and small molecule polyol gross mass；
2) among the above base polyurethane prepolymer for use as be added 2-10 parts of small molecule polyol chain extenders, 0.1-10 parts it is amino-containing
Small molecule dihydric alcohol and solvent 1 are stirred to react 2-6 hours at 45-80 DEG C, analyze residual NCO content with di-n-butylamine method, so
After be down to room temperature (lower than 30 DEG C), add and carried out with the diluted quaternizing agent of solvent 2 quaternized, room temperature keeps reacting 1-3
Hour, obtain the isocyanate-terminated base polyurethane prepolymer for use as of quaternized cationic type；
Wherein,
In step (2), the small molecule polyol chain extender is selected from 1,4-butanediol, 1,2-PD, ethylene glycol, one
One of diglycol ethylene, glycerine or trimethylolpropane (TMP) or no less than two kinds of combination；
In step (2), the amino-containing small molecule dihydric alcohol be N- phenyldiethanol-amine, N butyl diethanol amine,
One of N- propyl diethanol amine, N- ethyldiethanolamine and N methyldiethanol amine (MDEA)；
In step (2), the solvent 1 is one of acetone, methyl butyl ketone, ethyl acetate, butyl acetate, and dosage is small
0.5-2 times of molecular polylol chain extender and amino-containing small molecule dihydric alcohol gross mass；
In step (2), the quaternizing agent is benzyl chloride, dimethyl carbonate, dimethyl suflfate, bromobutane, iodine first
One of alkane, epoxychloropropane, dosage are the 60-110% of amino-containing small molecule dihydric alcohol molal quantity；
In step (2), the solvent 2 is one of acetone, methyl butyl ketone, ethyl acetate, butyl acetate, and dosage is season
The 10-30% of ammonium reagent gross mass；
3) base polyurethane prepolymer for use as of quaternized cationic type among the above is stirred, 5-25 DEG C of deionization is at the uniform velocity added
Until being uniformly dispersed then at the same temperature, the polynary amine aqueous solution of the 5-20% containing mass percentage concentration is slowly added dropwise in water, stirring
Reaction 0.5-2 hours is obtained containing hyperbranched silicone oil modified side chain aqueous polyurethane emulsion；
Wherein,
In step (3), the deionized water dosage is 2-4 times of polyurethane prepolymer weight；
In step (3), it is ethylenediamine, diethylenetriamine, triethylene triamine, hexamethylene diamine or different Buddhist that the polyamine, which is selected from,
A kind of in your ketone diamines, dosage is mole of reactive hydrogen and isocyanate groups in cation polyurethane performed polymer in diamine
Than for 0.8-1.1:1；
This aqueous polyurethane emulsion solid content > 18%, Ph=5.5-7.0, appearance are translucent blue light or milky.
Embodiment 1
The 100 hyperbranched amido silicon oils of g PPG1000 and 50g (stepping figure, SF1921) are added to equipped with thermometer and reflux
In the three-necked flask of condenser pipe, under agitation, 36g toluene di-isocyanate(TDI) and dibutyltin dilaurate is added
0.25g is stirred to react 3 hours in 65 DEG C, obtains isocyanate-terminated base polyurethane prepolymer for use as；Then, in poly- ammonia among the above
5g trimethylolpropane chain extender, 5gN- methyl diethanolamine chain extender is added in ester performed polymer, is diluted with acetone 50g, at 45 DEG C
It is stirred to react 6 hours, analyzes residual NCO content with di-n-butylamine method, wait after reaching calculated value, be then down to room temperature (lower than 30
DEG C), add carried out with the diluted dimethyl suflfate of 2.8g acetone (5.5g) it is quaternized, room temperature keep reaction 1 hour, obtain season
The isocyanate-terminated base polyurethane prepolymer for use as of ammonium cationic；By the base polyurethane prepolymer for use as of quaternized cationic type among the above
It is stirred, 25 DEG C of deionized water 800g is at the uniform velocity added and then at the same temperature, are slowly added dropwise containing matter until being uniformly dispersed
The ethylenediamine solution 42g for measuring percentage concentration 5%, is stirred to react 1 hour, obtains containing hyperbranched silicone oil modified side chain aqueous polyurethane
Lotion.
From the stretching vibration peak that can be seen that in attached drawing 1 from 3320cm-1 for associate hydrogen bond (O-H), the stretching vibration of N-H
Peak is overlapped with it.The NCO characteristic absorption peak not occurred within the scope of 2280-2240 cm-1 shows in the lotion of preparation without trip
From CNO exist.In the deformation vibration the absworption peak that the peak that 1530 cm-1 occur should be N-H group in CO-NH, in 1698 cm-1
The peak of appearance should be the stretching vibration peak of C=O group in CO-NH, and the above two o'clock is the eigen vibration peak of carbamate groups, table
Bright surveyed substance is polyurethane.2 peaks that 1097 cm-1 and 1032 cm-1 occur should be the asymmetric stretch of C-O-C in polyethers
Shock absorption peak.A peak that 780 cm-1 and 1242 cm-1 occur should be the characteristic absorption peak of Si-O-Si and Si-C, illustrate poly-
There are silicone ingredients in urethane.Find out in attached drawing 2, water contact angle is greater than 90 degree, reaches hydrophobic effect.In attached drawing 3, test knot
Fruit, which shows, is made lotion average grain diameter in 104.4nm.
Embodiment 2
45 g PPG300,55Gppg6000 and the hyperbranched amido silicon oil of 10g (stepping figure, SF1708) are added to equipped with temperature
In the three-necked flask of degree meter and reflux condensing tube, under agitation, 80g isophorone diisocyanate and dibutyl is added
Tin dilaurate 1g is stirred to react 1 hour in 100 DEG C, obtains isocyanate-terminated base polyurethane prepolymer for use as；Then, upper
The agent of 1g chain expansion of succinic acid, 20gN- phenyldiethanol-amine chain extender is added in base polyurethane prepolymer for use as in stating, dilute with propyl acetate 20g
It releases, is stirred to react at 80 DEG C 2 hours, analyze residual NCO content with di-n-butylamine method, wait after reaching calculated value, be then down to room
Temperature (be lower than 30 DEG C) adds and is carried out with the diluted iodomethane of 46g propyl acetate (23g) quaternized, and room temperature keeps reacting 3 small
When, obtain the isocyanate-terminated base polyurethane prepolymer for use as of quaternized cationic type；By the poly- of quaternized cationic type among the above
Urethane performed polymer is stirred, and 25 DEG C of deionized water 500g are at the uniform velocity added, and until being uniformly dispersed, then at the same temperature, is delayed
It is slow that the isophorone diamine solution 62g containing mass percentage concentration 20% is added dropwise, it is stirred to react 3 hours, obtains containing hyperbranched silicone oil side
Chain modified aqueous polyurethane emulsion.
Embodiment 3
The 100 hyperbranched amido silicon oils of g PTMG1000 and 15g (stepping figure, SF1706) are added to equipped with thermometer and are returned
In the three-necked flask for flowing condenser pipe, under agitation, 35g hexamethylene diisocyanate and dibutyltindilaurylmercaptide osmanthus is added
Acid esters 0.3g is stirred to react 2 hours in 85 DEG C, obtains isocyanate-terminated base polyurethane prepolymer for use as；Then, poly- among the above
1g butanediol and 3g trimethylolpropane chain extender, 5gN- methyl diethanolamine chain extender is added in urethane performed polymer, with acetone 30g
Dilution, is stirred to react 3 hours at 60 DEG C, analyzes residual NCO content with di-n-butylamine method, waits after reaching calculated value, be then down to
Room temperature (be lower than 30 DEG C) adds and is carried out with the diluted epoxychloropropane of 4g acetone (2.5g) quaternized, and room temperature keeps reacting 2 small
When, obtain the isocyanate-terminated base polyurethane prepolymer for use as of quaternized cationic type；By the poly- of quaternized cationic type among the above
Urethane performed polymer is stirred, and 25 DEG C of deionized water 800g are at the uniform velocity added, and until being uniformly dispersed, then at the same temperature, is delayed
It is slow that the ethylenediamine solution 16g containing mass percentage concentration 10% is added dropwise, it is stirred to react 2 hours, obtains containing hyperbranched silicone oil modified side chain
Aqueous polyurethane emulsion
Embodiment 4
45 g PPG300,55 PTMG1000 and the hyperbranched amido silicon oil of 50g (stepping figure, SF1706) are added to equipped with temperature
In the three-necked flask of degree meter and reflux condensing tube, under agitation, 75g toluene di-isocyanate(TDI) and dibutyl tin two is added
Laurate 1g is stirred to react 2 hours in 75 DEG C, obtains isocyanate-terminated base polyurethane prepolymer for use as；Then, among the above
2g trimethylolpropane, 18gN- methyl diethanolamine chain extender is added in base polyurethane prepolymer for use as, is diluted with acetone 20g, is stirred at 60 DEG C
Reaction 3 hours is mixed, residual NCO content is analyzed with di-n-butylamine method, waits after reaching calculated value, be then down to room temperature (lower than 30
DEG C), add carried out with the diluted dimethyl suflfate of 30g acetone (18g) it is quaternized, room temperature keep reaction 3 hours, obtain quaternary ammonium
Change the isocyanate-terminated base polyurethane prepolymer for use as of cationic；By the base polyurethane prepolymer for use as of quaternized cationic type among the above into
Row stirring is at the uniform velocity added 25 DEG C of deionized water 800g and then at the same temperature, is slowly added dropwise containing quality until being uniformly dispersed
The isophorone diamine solution 60g of percentage concentration 20%, is stirred to react 3 hours, obtains aqueous poly- containing hyperbranched silicone oil modified side chain
Urethane lotion.
Embodiment 5
45 g PPG300,55 PTMG1000 and the hyperbranched amido silicon oil of 50g (stepping figure, SF1706) are added to equipped with temperature
In the three-necked flask of degree meter and reflux condensing tube, under agitation, 35g isophorone diisocyanate, 50g toluene is added
Diisocyanate and dibutyltin dilaurate 1g are stirred to react 2 hours in 75 DEG C, obtain isocyanate-terminated polyurethane
Performed polymer；Then, 2g trimethylolpropane, 18gN- methyl diethanolamine chain extender is added in base polyurethane prepolymer for use as among the above,
It is diluted, is stirred to react at 80 DEG C 2 hours with acetone 20g, analyzed residual NCO content with di-n-butylamine method, wait after reaching calculated value,
Then it is down to room temperature (lower than 30 DEG C), adds and carries out quaternized, room temperature guarantor with the diluted dimethyl suflfate of 30g acetone (18g)
Reaction 3 hours is held, the isocyanate-terminated base polyurethane prepolymer for use as of quaternized cationic type is obtained；By among the above it is quaternized sun from
The base polyurethane prepolymer for use as of subtype is stirred, and 25 DEG C of deionized water 800g are at the uniform velocity added, until being uniformly dispersed, then in same temperature
Under degree, the isophorone diamine solution 44g containing mass percentage concentration 10% is slowly added dropwise, is stirred to react 3 hours, obtains containing over-expense
SiClx oil modified side chain aqueous polyurethane emulsion.
Comparative example
It is changed to according to by the hyperbranched amido silicon oil (stepping figure, SF1706) in embodiment 5 according to document (Zong, J.;
Zhang, Q.; Sun, H.; Yu, Y.; Wang, S.; Liu, Y. Polymer bulletin 2010, 65, (5),
477-493.) make silicone oil by oneself, other components are constant, obtain silicate-containing oil modified side chain aqueous polyurethane emulsion.
Characterization method
Infrared spectroscopy (IR): 470 FT IR infrared spectrometer of Nicolet company, U.S. NEXUS exists a small amount of emulsion droplets
Test is dried on potassium bromide chip.
Infrared (Fig. 1) the result shows that, in 3340cm-1There is the stretching vibration peak of NH at place, in 1740 cm-1There is the C of CO-NH at place
=O stretching vibration peak, in 1547 cm-1Place is its NH deformation vibration peak, these three peaks are the features of carbamate in polyurethane
Vibration peak illustrates that the aqueous polyurethane emulsion of synthesis has polyurethanes generation, 1100 cm really-1Place has that Si-O-Si's is curved
Bent vibration peak, 1250 cm-1Place is Si-CH2Flexural vibrations peak, it was demonstrated that contain silicone ingredients really in the lotion.
Contact angle test: taking 100 microlitres of emulsion droplets on the glass sheet, at drying at room temperature 12 hours, then in 80 DEG C of dryings
24 hours, water droplet contact angle test is then carried out by contact angle instrument.
The sample contact angle for scheming hyperbranched silicone oil is stepped than sample in comparative example it is obvious that adding from contact angle picture
The contact angle of product is big, it was demonstrated that hyperbranched silicone oil is effectively improved the surface property of material, improves its water contact angle.
Water absorption rate test: glue film is cut into the fritter of about 0.2g weight, impregnates in water after correct amount m1, is taken after 24 hours
Out, the moisture on surface is wiped rapidly, and the quality m2 of precise glue film calculates its water absorption rate.
The water absorption rate of 1 polyurethane film of table
| Sample | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Water absorption rate (%) | 18.7 | 27.2 | 19.3 | 18.0 | 20.2 | 25.4 |
As seen from Table 1, addition steps the sample water absorption rate of the hyperbranched silicone oil of figure generally than the water suction of sample in comparative example
Rate is low, it was demonstrated that the water absorption rate of polyurethane film is effectively reduced in hyperbranched silicone oil.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (8)
1. a kind of preparation method of the side chain of silicone oil containing dissaving structure aqueous polyurethane, it is characterised in that: silicon containing dissaving structure
The component that oily side chain water-based polyurethane polymer includes are as follows: hyperbranched amido silicon oil 10-50 parts, 20-80 parts of diisocyanate, gather
100 parts of ether type polyalcohol, 2-10 parts of small molecule polyol chain extender, 0.1-10 parts of amino-containing small molecule dihydric alcohol, it is quaternized
Reagent is measured as the 60-110% of amino-containing small molecule dihydric alcohol molal quantity；
Hyperbranched amido silicon oil has the general structure that is shown below:
Wherein, in general formula X, Y, Z be respectively 10~100 natural number；
The preparation method of the hyperbranched silicone oil modified side chain water-based polyurethane polymer the following steps are included:
Step 1: by 100 parts of polyether polyols, 10-50 parts of hyperbranched silicone oil and 20-80 parts of diisocyanate in catalyst item
It is stirred to react in 65-100 DEG C 1-3 hours under part；
Step 2: be added 2-10 parts of small molecule polyol chain extenders, 0.1-10 parts of amino-containing small molecule dihydric alcohols and the first
Solvent is stirred to react 2-6 hours at 45-80 DEG C, is analyzed residual isocyanate groups content with di-n-butylamine method, is then cooled to
Lower than 30 DEG C, add carried out with the diluted quaternizing agent of second of Solvents Solvent it is quaternized, room temperature keep reaction 1-3 it is small
When, obtain the isocyanate-terminated base polyurethane prepolymer for use as of quaternized cationic type；
Step 3: the base polyurethane prepolymer for use as of the quaternized cationic type is stirred, 5-25 DEG C of deionized water is at the uniform velocity added,
Until being uniformly dispersed, then at the same temperature, the polynary amine aqueous solution of the 5-20% containing mass percentage concentration is slowly added dropwise, stirring is anti-
It answers 0.5-2 hours, obtains containing hyperbranched silicone oil modified side chain aqueous polyurethane emulsion.
2. preparation method as described in claim 1, it is characterised in that: the diisocyanate is selected from different Fu Er ketone diisocyanate
In ester, hexamethylene diisocyanate, ditolyl methane diisocyanate, sub- xylylene diisocyanate or toluene di-isocyanate(TDI)
A kind of or no less than two kinds of combination.
3. preparation method as described in claim 1, it is characterised in that: the polyether polyol is polyethylene glycol, poly- the third two
One of alcohol or polytetrahydrofuran ether glycol or no less than two kinds of combination, molecular weight 300-6000.
4. preparation method as described in claim 1, it is characterised in that: the small molecule polyol chain extender is selected from Isosorbide-5-Nitrae-fourth
One of glycol, 1,2-PD, ethylene glycol, diglycol, glycerine or trimethylolpropane or no less than two
The combination of kind；The amino-containing small molecule dihydric alcohol is N- phenyldiethanol-amine, N butyl diethanol amine, N- propyl diethanol
One of amine, N- ethyldiethanolamine and N methyldiethanol amine；The quaternizing agent is benzyl chloride, carbonic acid diformazan
One of ester, dimethyl suflfate, bromobutane, iodomethane, epoxychloropropane.
5. preparation method as described in claim 1, it is characterised in that: catalyst described in step 1 be organotin catalysts,
One of organozinc catalyst and organic bismuth catalyst.
6. preparation method as claimed in claim 5, it is characterised in that: the catalyst is organotin catalysts, the organotin
Catalyst is dibutyltin dilaurate, and dosage is diisocyanate, polyether polyol, amido silicon oil and small molecule polyol
The 0.1-0.5% of gross mass.
7. preparation method as described in claim 1, it is characterised in that: the first solvent described in step 2 is acetone, first fourth
One of ketone, ethyl acetate, butyl acetate, dosage are that small molecule polyol chain extender and amino-containing small molecule dihydric alcohol are total
0.5-2 times of quality；
One of second of solvent acetone, methyl butyl ketone, ethyl acetate, butyl acetate described in step 2, dosage are quaternized
The 10-30% of reagent gross mass.
8. preparation method as described in claim 1, it is characterised in that: deionized water dosage described in step 3 is that polyurethane is pre-
2-4 times of aggressiveness quality；
Polyamine described in step 3 is in ethylenediamine, diethylenetriamine, triethylene triamine, hexamethylene diamine or isophorone diamine
One kind, dosage is that the molar ratio of isocyanate groups in reactive hydrogen and cation polyurethane performed polymer in diamine is 0.8-
1.1:1.
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| CN108034228A (en) * | 2017-12-12 | 2018-05-15 | 东莞市雄林新材料科技股份有限公司 | A kind of TPU film of surface super hydrophobic and preparation method thereof |
| CN108129636B (en) * | 2017-12-19 | 2021-01-01 | 传化智联股份有限公司 | Preparation method of amphiphilic comb-structure organic silicon-polyurethane graft copolymer |
| CN108752563B (en) * | 2018-05-24 | 2020-12-15 | 哈尔滨工业大学无锡新材料研究院 | Waterborne hyperbranched structure modified polyurethane polymer, preparation method thereof and self-repairing diffuse reflection coating composition |
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| KR20210135275A (en) | 2019-03-05 | 2021-11-12 | 다우 글로벌 테크놀로지스 엘엘씨 | Aqueous polyurethane dispersion and method for preparing same |
| CN110156948B (en) * | 2019-04-25 | 2021-02-19 | 陕西科技大学 | Preparation method of amino-terminated hyperbranched polysiloxane modified waterborne polyurethane |
| CN111748271A (en) * | 2020-07-17 | 2020-10-09 | 安徽开林新材料股份有限公司 | High-performance waterborne polyurethane coating |
| CN113322000B (en) * | 2021-06-10 | 2022-07-29 | 广州大学 | Organic silicon coating and preparation method and application thereof |
| CN113430833A (en) * | 2021-07-09 | 2021-09-24 | 福可新材料(上海)有限公司 | Fluoride-free waterproof finishing liquid for ready-made clothes and application thereof |
| CN113956434B (en) * | 2021-10-29 | 2023-05-23 | 山东圳谷新材料科技有限公司 | Hyperbranched organic amino silicon post-chain extension modified waterborne polyurethane and preparation method thereof |
| CN114311861A (en) * | 2021-12-28 | 2022-04-12 | 浙江东进新材料有限公司 | Waterproof and antibacterial composite functional fabric |
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