Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of polyurethane wool anti-felting finish agent and preparation method thereof, to overcome the above-mentioned defective that prior art exists.To satisfy the needs of relevant field development.
Polyurethane wool anti-felting finish agent of the present invention is the reactive organic silicon modified aqueous polyurethane anti-felting finish agent of a kind of anionic, and its general structure is as follows:
NaSO
3OCHN——R——NHCOSO
3Na
R represents a kind of and polyether-modified organopolysiloxane in polyether glycol or the polyester polyol and the cross-linking reaction thing of isocyanate group;
Preferred polyurethane wool anti-felting finish agent is for comprising end-blocking emulsive aqueous solution behind isophorone diisocyanate, six methylene diisocyanates, Xylene Diisocyanate, modification diimine MDI and polyol compounds, the organosilicon polyol reaction.
The reactive organic silicon modified aqueous polyurethane anti-felting finish agent of anionic of the present invention can adopt infrared method to characterize, and every data are as shown in the table;
Absorption peak wave number/cm
-1 | Relative intensity | Ownership |
3250~3500 2940,2860 2240~2280 2120 1770~1785 1715~1750 1689~1710 1600~1615 1520~1560 1450~1470 1380 1225~1235 | In by force very strong stronger | The cis NH stretching vibration CH of OH stretching, NHCO
2,CH
3C=O in C=O ester group C=O in the stretching vibration NCO characteristic absorption peak N=C=N absworption peak urea diketone ring (dimer), acid amides I key (C=O) isocyanuric acid ester (tripolymer) (1408~1430 peak being arranged in addition) phenyl ring C=C skeleton stretching vibration acid amides II key (N-H deformation vibration) CH2Formation vibration, CH
3Asymmetrical deformation vibration CH
3Symmetrical deformation vibration polyester C-O stretches or the OH formation vibration
|
1060~1150 |
Wide strong |
C-O-C (fatty ether) absorption peak |
1000~1110 |
Extremely wide strong |
The Si-O-Si charateristic avsorption band |
3680±10 |
By force |
The Si-OH charateristic avsorption band |
Its number-average molecular weight is 2000~20000.
The preparation method of the reactive organic silicon modified aqueous polyurethane wool anti-felting finish agent of above-mentioned anionic comprises the steps:
With polyisocyanates and polyol compound and the reaction of polyether-modified polyorganosiloxane compounds, generating end group is the base polyurethane prepolymer for use as of isocyanate group, end-blocking emulsification in sodium sulfite solution and organic solvent then, with acid for adjusting pH to 2~6, make the reactive organic silicon modified aqueous polyurethane wool anti-felting finish agent of anionic at last;
Temperature of reaction is 30 ℃~140 ℃, and the reaction times is 1~8 hour;
Polyisocyanates, polyol compound, polyether-modified polyorganosiloxane compounds react according to following proportioning:
-NCO/OH=I.1~6, wherein :-NCO represents isocyanate group, OH represents: hydroxyl;
The mol ratio of polyol compound and polyether-modified polyorganosiloxane compounds is:
Polyol compound: polyether-modified polyorganosiloxane compounds=1: 1~9;
The add-on of sodium bisulfite is 1.1~1.2 times of free isocyanate molar weight;
The weight concentration of sodium sulfite solution is 10~40%;
Sodium sulfite solution with the volume of organic solvent ratio is:
Sodium sulfite solution: organic solvent=1: 1~5.
Said polyol compound comprises saturated or unsaturated polyol compound, preferred molecular weight is a kind of in affixture of 200~6000 polyethers, polyester, polycarbonate-based or dihydroxyphenyl propane and oxyethane, propylene oxide or butylene oxide ring etc., and its general structure is as follows:
N represents the polymerization degree, n=50~1000, and x represents functionality, x=5~1000, Y represents the initiator main chain, and it is 1~5 alkyl or hydrogen that R represents carbon atom;
Preferred polyether alcohol is selected from oxyethane, propylene oxide, tetrahydrofuran by polymerization product or its multipolymer or graft copolymer;
The polyether alcohol of being addressed adopts the commercially available prod;
Said polyester polyvalent alcohol is by ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,3-butyleneglycol, neopentyl glycol, pentanediol, ethylene glycol, ethohexadiol, 1, polyvalent alcohols such as saturated and undersaturated low-molecular-weight diol such as 4-butynediol, dihydroxyphenyl propane, glycol ether, Triethylene glycol, dipropylene glycol, tripropylene glycol or glycerol, TriMethylolPropane(TMP) and tetramethylolmethane and aliphatic dibasic acid and aromatic acid are or/and the polycondensation product of carboxylic acid anhydride, cyclic lactone etc., and its general structure is as follows:
N1 represents the polymerization degree, n1=50~1000, and it is 1~10 alkylidene group that R ' represents carbonatoms, it is 1~16 alkylidene group that R1 represents carbonatoms;
Preferred polyester class polyvalent alcohol is selected from ethylene glycol, 1,2-propylene glycol, 1, ammediol and aliphatic dibasic acid and polycondensation products such as aromatic acid or/and carboxylic acid anhydride, cyclic lactone;
The polyether alcohol of being addressed adopts the commercially available prod;
Said dihydroxyphenyl propane class polyol structure general formula is as follows:
M, N represents the polymerization degree, N=10~50, M=10~40, N>M
It is a kind of in 1000~4000 that preferred dihydroxyphenyl propane class polyvalent alcohol is selected from molecular weight;
The dihydroxyphenyl propane class polyvalent alcohol of being addressed adopts commercially available prod or document disclosed method to be prepared;
Said polyether-modified polyorganosiloxane compounds is that molecular weight is 200~6000 dibasic alcohol that contains silicon and polyol compound, and its general structure is as follows:
In the formula: n2 represents polyoxyethylene groups repeating segment number, n2=1~200, and x1 represents siloxanes continuous chain joint number, x1=1~100; M represents the methene chain joint number, m=1~100;
The polyether-modified polyorganosiloxane compounds of addressing adopts commercially available prod or document disclosed method to be prepared;
Said organic solvent comprises common organic solvent such as ketone, ethers, ester class or alcohols, one or more in preferred toluene, dimethylbenzene, acetone, methylethylketone, dimethyl formamide, ethanol, Virahol, ethyl acetate, butylacetate or the diethylene glycol ether etc.
Said polyisocyanates comprises aromatic polyisocyanate or aliphatic polyisocyante, preferred tolylene diisocyanate, diphenylmethanediisocyanate (MDI), blending MDI, polyether-modified MDI, carbodiimide modification MDI, poly methylene poly phenyl poly isocyanate (PAPI), 1, hexamethylene-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, naphthalene-1, the 5-vulcabond, Methylcyclohexyl diisocyanate, in dicyclohexyl methane diisocyanate or the tetramethylxylylene diisocyanate etc. one or more.
Water reactive based polyurethane anti-felting finish agent of the present invention can be used for the woolen antifelting treatment.
This anti-felting finish agent discharges-the NCO group after reaching the deblocking temperature, the crosslinked film forming of fiber surface or with the fibrous active radical reaction bonded, produce competent antifelting treatment effect, and do not discharge poisonous, deleterious material.
The reactive organic silicon modified aqueous polyurethane wool anti-felting finish agent that adopts the present invention to make, the preventing felting and shrinking of wood fabric effect of handling is remarkable, anti-felting effect can reach the IWS-TM31 standard, soft, not containing objectionable impuritiess such as organochlorine, is a kind of green ecotypical auxiliary agent, both can obtain to be satisfied with, can not damage simultaneously woolen softness, plentiful style again, have broad application prospects.
Embodiment
Embodiment 1
1. in the four-hole boiling flask of 500ml, add polyoxygenated third rare triol 9g, polyether-modified polyorganosiloxane compounds 19g; add isophorone diisocyanate 6g after the vacuum hydro-extraction, under nitrogen protection, 120 ℃ were reacted 5 hours; make base polyurethane prepolymer for use as ,-NCO content 4.1%.
2. in the four-hole boiling flask of 500ml, add methylethylketone 6g, stir adding aqueous solution of sodium bisulfite 45ml and the emulsification of trimethyl carbinol 45ml end-blocking after 10 minutes, add hydrochloric acid after 1 hour, regulate pH 4, obtain to contain the mixture of isophorone diisocyanate, solid content 37%.
Embodiment 2
1. in the four-hole boiling flask of 500ml, add polyoxygenated third rare glycol 10g, polyether-modified polyorganosiloxane compounds 18g; add six methylene diisocyanates (HDI) 9g after the vacuum hydro-extraction, under nitrogen protection, 120 ℃ were reacted 7 hours; make base polyurethane prepolymer for use as ,-NCO content 3.5%.
2. in the four-hole boiling flask of 500ml, add acetone 4g, stir adding aqueous solution of sodium bisulfite 45ml and the emulsification of Virahol 55ml end-blocking after 10 minutes, add hydrochloric acid after 1 hour, regulate PH 3~4, obtain to contain the mixture of six methylene diisocyanates, solid content 36%.
Embodiment 3
1. in the four-hole boiling flask of 500ml, add polyoxygenated third rare glycol 14g, polyether-modified polyorganosiloxane compounds 11g; add Xylene Diisocyanate (TDI) 8g after the vacuum hydro-extraction, under nitrogen protection, 80 ℃ were reacted 4 hours; make base polyurethane prepolymer for use as ,-NCO content 5.6%.
2. in the four-hole boiling flask of 500ml, add ethyl acetate 4g, stir adding aqueous solution of sodium bisulfite 50ml and the emulsification of ethanol 50ml end-blocking after 10 minutes, add hydrochloric acid after 1 hour, regulate PH 3~4, obtain to contain the mixture of Xylene Diisocyanate, solid content 35%.
Embodiment 4
1. in the four-hole boiling flask of 500ml, add polyoxygenated third rare glycol 14g, polyether-modified polyorganosiloxane compounds 11g; add modification diimine MDI10g after the vacuum hydro-extraction, under nitrogen protection, 80 ℃ were reacted 3 hours; make base polyurethane prepolymer for use as ,-NCO content 5.1%.
2. in the four-hole boiling flask of 500ml, add dimethyl formamide 4.5g, stir adding aqueous solution of sodium bisulfite 48ml and the emulsification of ethanol 62ml end-blocking after 10 minutes, add hydrochloric acid after 1 hour, regulate PH 3~4, obtain to contain the mixture of modification diimine MDI; Solid content 34%.
Embodiment 5
Wool fabric:
All woolen woman clothing (following machine grey cloth), yarn linear density 11.76tex * 2, weight 178g/m
2
The fabric anti-felting finishing technique:
1. working fluid is formed:
The anionic reactive organic silicon modified aqueous polyurethane wool anti-felting finish agent of 40 grams per liter embodiment 1,5 grams per liter sodium bicarbonate dressing liquids
2. technical process: adopt two soak two roll (mangle expression 95%), preliminary drying (80 ℃/3min), bake (160 ℃/4min).
Performance test:
1. felt proofing performance test
The mensuration of area felting rate is with reference to GB8628-88 testing standard and method.
2. yellowness index
Yellowness index bakes 1min with the style after handling at 180oC with reference to GB8424-87, the x of test fabric, y, z tristimulus values, the yellowness index of calculating fabric.The yellowness index calculation formula is YI=(X-Z)/Y) * 100%.
3. washing standard
With reference to AATCC 135-2000 standard.
4. feel test
The hand valuation of fabric adopts subjective sensory evaluation.
Table 1 Wool fabric anti-felting arrangement result
The experiment number | Area felting rate (%) | Yellowness index (%) | Hand valuation | Washing back size/cm |
Planeness | Pliability | Warp-wise | Broadwise |
1 2 3 | 0 -17.28 0.691 | 10.42 11.53 15.81 | Good job is good | Good job is good | 0 18.12 19.87 | 0 18.26 20.27 |
Annotate: 1-former state (not washing); 2-former state (1 washing); 3-former state anti-felting finish agent is handled (10 washings); The former state washing is preceding to be 20cm * 20cm through broadwise length
As shown in Table 1, wool fabric is handled through the reactive organic silicon modified aqueous polyurethane anti-felting finish agent of anionic, and repeatedly after the washing, soft, look diminishes, and anti-felting effect is remarkable.