CN101475789B - Preparation of PU binder resin for synthetic leather - Google Patents
Preparation of PU binder resin for synthetic leather Download PDFInfo
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- CN101475789B CN101475789B CN2009100955789A CN200910095578A CN101475789B CN 101475789 B CN101475789 B CN 101475789B CN 2009100955789 A CN2009100955789 A CN 2009100955789A CN 200910095578 A CN200910095578 A CN 200910095578A CN 101475789 B CN101475789 B CN 101475789B
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Abstract
The invention relates to a method for manufacturing PU adhesive resin for synthetic leather. The method comprises the following steps that: (i) AA and MPD are heated to undergo esterification and polycondensation reaction, when reaction is carried out till acid value is less than or equal to 25 mgKOH/g, reactant is vacuumized, residual water is removed, the acid value is reduced, when the reaction is carried out till the acid value is less than or equal to 2.5mgKOH/g, the vacuum degree is enlarged, and the reaction is continuously carried out to prepare hydroxyl-end capped MPD type polylol; and (ii) the MPD type polylol prepared in step (i) and a chain extender MPD are mixed, added with DMF, evenly stirred, added with MDI, heated and reacted, and polymerized to generate polyurethane; the polyurethane is added with the DMF and MEK; and the viscosity is adjusted between 12*10<4> MPa.s/25 DEG C. The adhesive resin prepared by the method is a semiliquid type PU adhesive, has the advantages of high connecting strength, peeling performance, hot dry pasting, good resin permeability, and the like, can be used for common synthetic leather, and is in particular suitable for ultrafine fiber leather and mirror face rear pasting leather.
Description
Technical field
The present invention relates to a kind of manufacture method of PU binder resin for synthetic leather,
Background technology
The employed polyvalent alcohol of PU resin glue is ethylene glycol, 1 normally, 4-butyleneglycol, glycol ether, hot pentanediol, 1, and the polyester polyol of these types of 6-hexylene glycol, chainextender only makes spent glycol, 1, the 4-butyleneglycol.The PU leather cohesive strength that the PU resin glue production of use straight chain polyvalent alcohol is general is passable, but adopts the binding agent of these types that various limitation are always arranged to pasting high-grade synthetic leather such as leather behind special superfiber leather, the minute surface.
When synthetic leather is produced, usually on separate-type paper, be coated with most 3000～6000cps/25 ℃ and add the dry method surface layer PU resin of colorant of one deck solvent cut viscosity earlier, and oven dry; And then be coated with most 6000～20000cps/25 ℃ and add the PU resin glue of colorant of last layer solvent cut viscosity, adopt technologies such as wet combining, half-dried subsides, hot dry doubling, the superfine fibre soaking cloth that embryo at the bottom of the wet method or decrement treatment are crossed is fitted with certain pressure, promptly peel off after the solvent oven dry then or maturation after non-ly promptly peel off.
Producing the employed PU binding agent of synthetic leather on the market, all is a liquid type binding agent and binary liquid shape binding agent basically.In the manufacture method of these two kinds of binding agents and the use, can there be various drawbacks usually.
Domestic manufacturer all uses a liquid type binding agent basically at present, can separate-type paper be separated then and there with synthetic leather at the production line end, is referred to as promptly to peel off.Can only accomplish 50% but the type binding agent solid content is generally the highest, under the environment, resin becomes muddy or caking easily in the winter time, and the synthetic leather bonding strength of production is low, and poor flexibility is not suitable for the applying of microfiber synthetic leather; And,, be not suitable for the dry doubling technology of pasting the class synthetic leather behind the minute surface usually more than 160 ℃ because its softening temperature is all very high.Japan, Korea S and the large-scale synthetic leather of domestic minority enterprise typically use binary liquid shape PU binding agent, the type binding agent has overcome the shortcoming of a liquid type binding agent, performance is excellent at aspects such as bonding strength, elasticity, resin transparent is good, can accomplish the high solids content more than 50%, but binary liquid shape PU resin glue is because soft section more, and viscosity stability is poor when reaction end, and viscosity descends easily during storage; The synthetic leather that uses binary liquid shape PU resin glue to produce, need be after leaving standstill 24～48 hours in 60 ℃～80 ℃ the greenhouse, just can carry out separate-type paper separates with synthetic leather, usually like this, can bring several problems, a problem is that energy consumption is big, need to build the homothermic greenhouse, and output is big more in the unit time, the greenhouse area requirements is big more; The use turnover that second problem is separate-type paper is slow, needs the more separate-type paper of deposit; The use that the 3rd problem is separate-type paper has limitation, and the separate-type paper of a part of non-refractory can not be used, and separate-type paper and synthetic leather are peeled off difficulty, and the access times of separate-type paper obviously descend; The 4th defective product rubbed the line weak effect.
Summary of the invention
Purpose of the present invention aim to provide a kind ofly have the strength of joint height, can promptly peel off, can hot dry doubling, the manufacture method of PU binder resin for synthetic leather that the resin permeability is good.
The manufacture method of this PU binder resin for synthetic leather may further comprise the steps:
(i) with the reaction of AA (hexanodioic acid) and MPD (2-methyl isophthalic acid, ammediol) heating carrying out esterifying polycondensation, when reacting, vacuumize to acid value≤25mgKOH/g, remove remainder water, reduce acid value; When reacting, strengthen vacuum tightness and continue reaction and make hydroxy-end capped MPD type polyvalent alcohol to acid value≤2.5mgKOH/g;
(ii) MPD type polyvalent alcohol and the chainextender MPD that (i) step is made mixes, add DMF (dimethyl formamide), after stirring, add MDI (4 again, 4 '-diphenylmethanediisocyanate), the reacting by heating polymerization generates urethane, add DMF and MEK (methylethylketone) more therein, adjust viscosity to 6～12 * 10
4MPas/25 ℃.
In the manufacture method of this PU binder resin for synthetic leather, polyvalent alcohol has used MPD type polyvalent alcohol, and chainextender has also used MPD separately, because the MPD monomer has a methyl, can effectively reduce the crystallinity of molecule, the cohesive force of raising and base material.The resin glue of making in this way is a liquid half mould PU binding agent between a liquid type and binary liquid shape, have the strength of joint height, can promptly peel off, can hot dry doubling, advantage such as the resin permeability is good.
Embodiment
The manufacture method of this PU binder resin for synthetic leather is:
(i) with the reaction of AA and MPD heating carrying out esterifying polycondensation, when reacting, begin to vacuumize (I section) to acid value≤25mgKOH/g, remove remainder water, reduce acid value; When reacting, strengthen vacuum tightness (II section) to acid value≤2.5mgKOH/g, continue to react to acid value and molecular weight control within the specific limits, promptly make hydroxy-end capped MPD type polyvalent alcohol.The charging capacity of MPD can be 1.05～1.15 times of theoretical value (in mass) in this step; The final acid value of polyvalent alcohol can be controlled in the scope of 0.1～0.8mgKOH/g; The final molecular weight of polyvalent alcohol can be controlled in 1000～4000 the scope.
(ii) MPD type polyvalent alcohol and the chainextender MPD that (i) step is made mixes, and adds DMF, after stirring, adds MDI again, and reacting by heating, polymerization generate urethane, add DMF and MEK more therein, adjust viscosity to 6～12 * 10
4MPas/25 ℃.The mol number of input amount of MDI can be counted 1～1.05 times of sum for the mol of polyvalent alcohol and MPD in this step, and the mass ratio of polyvalent alcohol and chainextender can be controlled at 12.5: 1～25: 1.The mass ratio of DMF and MEK can be chosen in 2: 1 to 9: 1 scope in the solvent.
In the manufacture method of this PU binder resin for synthetic leather, (i) Bu temperature of reaction is controlled at 210～230 ℃, and (ii) Bu temperature of reaction is controlled at 75～85 ℃.
With the prepared resin glue of the manufacture method of this PU binder resin for synthetic leather, viscosity is 6～12 * 10
4MPas/25 ℃, solid content is in 50%～70%, and when temperature 〉=-5 ℃, resin is colourless or light yellow transparent liquid, is an a kind of liquid half mould PU binding agent between a liquid type and binary liquid shape.When in the process hides process, using, in resin, add 4%～10% bridging agent, in the baking oven of production line, finish bridge formation after, can remove from office and promptly the peeling off of separate-type paper.With the synthetic leather that this PU resin glue is made, feel is full, good springiness, the cohesive strength height, do not exist the turnover and the high-temperature maturing of separate-type paper to hinder problems such as paper, except that can be used for general synthetic leather, also be specially adapted to the production of pasting high-grade synthetic leather products such as leather behind superfiber leather, the minute surface.
The specific operation process of the manufacture method of this PU binder resin for synthetic leather is:
(i) prepare MPD type polyvalent alcohol earlier, the molecular weight of design polyvalent alcohol can be chosen in 1000～4000 scope.Molecular weight as requested calculates the Theoretical Mass of AA and MPD earlier, the MPD charging capacity is chosen in 1.05～1.15 scope of theoretical value, when reacting to acid value≤25mgKOH/g for 210～230 ℃, begins to vacuumize (I section), remove remainder water, reduce acid value; When reacting, strengthen vacuum tightness (II section), continue to react to acid value being controlled in the scope of 0.1～0.8mgKOH/g to acid value≤2.5mgKOH/g; The final molecular weight of polyvalent alcohol can be controlled in the scope of design molecular weight ± 50.
(ii) use the MPD type polyvalent alcohol manufacturing urethane resin that the step makes: the amount of MPD type polyvalent alcohol and MPD chainextender is chosen in 12.5: 1～25: 1 scope by mass ratio; By hydroxyl and isocyanate group mol ratio is to calculate theoretical MDI charging capacity at 1: 1; Solid content is chosen in 50%～70% scope; The mass ratio of DMF and MEK can be chosen in 2: 1 to 9: 1 scope in the solvent.Drop into the DMF of certain mass and the MPD type polyvalent alcohol and the MPD chainextender of designing quality earlier, after stirring, gradation drops into the theoretical amount of MDI again, reacted sticking at 75～85 ℃, behind the isocyanate group sufficient reacting, add a small amount of MDI and make viscosity continue to rise, gradation drops into remaining DMF and MEK according to the viscosity situation simultaneously, and finally transfers to viscosity 6～12 * 10
4MPas/25 ℃, solid content is controlled at design solid content ± 1%.
Embodiment 1:
(i) the preparation molecular weight is 1000 ± 50 MPD type polyvalent alcohol:
Get the AA500 gram, MPD432.4 gram (be theoretical value 1.15 times), 210 ℃ of reactions 5 hours, acid value reaches 18KOH/g, begins to vacuumize, after 1.5 hours, acid value reaches 1.35KOH/g, strengthen vacuum tightness and continue reaction 30 minutes, acid value reaches 0.25KOH/g, obtains MPD type polyvalent alcohol 639.8 grams (theoretical value is 752.7 grams).Measuring hydroxyl value is 110.84, and final molecular weight is 1010.
(ii) polyreaction:
By the polyvalent alcohol 360 gram preparation chainextender MPD18 grams (1/20) of (i) step gained, MDI143 gram, solvent DMF 201 grams, MEK22.3 gram, (solid content is controlled at 70 ± 1%, and the mass ratio of DMF and MEK is 9: 1 in the solvent).
Restrain DMF and polyvalent alcohol and MPD with 150 earlier and mix, divide input three times with 140 gram MDI then, reacted sticking at 75～85 ℃, reacted 3 hours, viscosity stops to rise, and divides and adds MDI 3 times, each 1 gram that adds makes viscosity continue to rise, and reacts 3 hours, when viscosity rises to 40,000 cps/75 ℃, add 51 gram DMF viscosity reductions, continue reaction 1 hour, viscosity rises to 30,000 cps/75 ℃ again, add MEK, reacted 30 minutes, transferring to viscosity is 10 * 10
4MPas/25 ℃, finally obtain product 744.3 grams, solid content is 70%.
Embodiment 2:
(i) the preparation molecular weight is 1500 ± 50 MPD type polyvalent alcohol:
Get the AA500 gram, MPD404.7 gram (be theoretical value 1.15 times), 210 ℃ of reactions 5 hours, acid value reaches 19KOH/g, begins to vacuumize, after 1.5 hours, acid value reaches 1.42KOH/g, strengthen vacuum tightness and continue reaction 1 hour, acid value reaches 0.28KOH/g, obtains MPD type polyvalent alcohol 612.1 grams (theoretical value is 728.7 grams).Measuring hydroxyl value is 73.83, and final molecular weight is 1517.
(ii) polyreaction:
By the polyvalent alcohol 390 gram preparation chainextender MPD15.6 grams (1/25) of (i) step gained, MDI111.3 gram, solvent DMF 222.6 grams, MEK55.7 gram, (solid content is controlled at 65 ± 1%, and the mass ratio of DMF and MEK is 4: 1 in the solvent).
Restrain DMF and polyvalent alcohol and MPD with 150 earlier and mix, divide input three times with 108.3 gram MDI then, reacted sticking at 75～85 ℃, reacted 3 hours, viscosity stops to rise, and divides and adds MDI 2 times, each 1.5 grams that add make viscosity continue to rise, and react 4 hours, when viscosity rises to 50,000 cps/75 ℃, add 72.6 gram DMF viscosity reductions, continue reaction 1 hour, viscosity rises to 30,000 cps/75 ℃ again, add MEK, reacted 30 minutes, transferring to viscosity is 8 * 10
4MPas/25 ℃, finally obtain product 795.2 grams, solid content is 65%.
Embodiment 3:
(i) the preparation molecular weight is 2000 MPD type polyvalent alcohol:
Get the AA500 gram, MPD374.5 gram (be theoretical value 1.1 times), 215 ℃ of reactions 6 hours, acid value reaches 21.5KOH/g, begins to vacuumize, after 4 hours, acid value reaches 1.9KOH/g, strengthen vacuum tightness and continue reaction 2 hours, acid value reaches 0.42KOH/g, obtains MPD type polyvalent alcohol 595.3 grams (theoretical value is 717.2 grams).Measuring hydroxyl value is 56.43, and final molecular weight is 1985.
(ii) polyreaction:
By 360 gram MPD type polyvalent alcohol preparation chainextender MPD, 20 grams (1/18) of (i) step gained, MDI100.6 gram, solvent DMF 267 grams, MEK53.4 gram, (solid content is controlled at 60 ± 1%, and the mass ratio of DMF and MEK is 5: 1 in the solvent).
Restrain DMF and polyvalent alcohol and MPD with 180 earlier and mix, divide input three times with 97.6 gram MDI then, reacted sticking at 75～85 ℃, reacted 3 hours, viscosity stops to rise, and divides and adds MDI 3 times, each 1 gram that adds makes viscosity continue to rise, and reacts 3 minutes, when viscosity rises to 50,000 cps/75 ℃, add 87 gram DMF viscosity reductions, continue reaction 1.5 hours, viscosity rises to 40,000 cps/75 ℃ again, add MEK, reacted 30 minutes, transferring to viscosity is 12 * 10
4MPas/25 ℃, finally obtain product 801 grams, solid content is 60%.
Embodiment 4:
(i) the preparation molecular weight is 2000 MPD type polyvalent alcohol:
Get the AA500 gram, MPD374.5 gram (be theoretical value 1.1 times), 215 ℃ of reactions 6 hours, acid value reaches 21.5KOH/g, begins to vacuumize, after 4 hours, acid value reaches 1.9KOH/g, strengthen vacuum tightness and continue reaction 2 hours, acid value reaches 0.42KOH/g, obtains MPD type polyvalent alcohol 595.3 grams (theoretical value is 717.2 grams).Measuring hydroxyl value is 56.43, and final molecular weight is 1985.
(ii) polyreaction:
By 300 gram MPD type polyvalent alcohol preparation chainextender MPD24 grams (1/12.5) of (i) step gained, MDI104.2 gram, solvent DMF 321.1 grams, MEK107.1 gram, (solid content is controlled at 50 ± 1%, and the mass ratio of DMF and MEK is 3: 1 in the solvent).
Restrain DMF and polyvalent alcohol and MPD with 200 earlier and mix, divide input three times with 100.2 gram MDI then, reacted sticking at 75～85 ℃, reacted 4 hours, viscosity stops to rise, and divides and adds MDI 4 times, each 1 gram that adds makes viscosity continue to rise, and reacts 4 hours, when viscosity rises to 80,000 cps/75 ℃, add 121.1 gram DMF viscosity reductions, continue reaction 2 hours, viscosity rises to 60,000 cps/75 ℃ again, add MEK, reacted 30 minutes, transferring to viscosity is 7 * 10
4MPas/25 ℃, finally obtain product 856.4 grams, solid content is 50%.
Embodiment 5:
(i) the preparation molecular weight is 2500 MPD type polyvalent alcohol:
Get the AA500 gram, MPD367.2 gram (be theoretical value 1.1 times), 220 ℃ of reactions 7 hours, acid value reaches 20.2KOH/g, begins to vacuumize, after 4 hours, acid value reaches 1.78KOH/g, strengthen vacuum tightness and continue reaction 2 hours, acid value reaches 0.36KOH/g, obtains MPD type polyvalent alcohol 582.6 grams (theoretical value is 710.5 grams).Measuring hydroxyl value is 45.12, and final molecular weight is 2482.
(ii) polyreaction:
By 400 gram MPD type polyvalent alcohol preparation chainextender MPD20 grams (1/20) of (i) step gained, MDI98.6 gram, solvent DMF 248.3 grams, MEK31 gram, (solid content is controlled at 65 ± 1%, and the mass ratio of DMF and MEK is 8: 1 in the solvent).
Restrain DMF and polyvalent alcohol and MPD with 160 earlier and mix, divide input three times with 95.6 gram MDI then, reacted sticking at 75～85 ℃, reacted 3 hours, viscosity stops to rise, and divides and adds MDI 3 times, each 1 gram that adds makes viscosity continue to rise, and reacts 3 hours, when viscosity rises to 50,000 cps/75 ℃, add 88.3 gram DMF viscosity reductions, continue reaction 1 hour, viscosity rises to 30,000 cps/75 ℃ again, add MEK, reacted 30 minutes, transferring to viscosity is 11 * 10
4MPas/25 ℃, finally obtain product 797.9 grams, solid content is 65%.
Embodiment 6:
(i) the preparation molecular weight is 3000 MPD type polyvalent alcohol:
Get the AA500 gram, MPD355.8 gram (be theoretical value 1.08 times), 220 ℃ of reactions 7 hours, acid value reaches 21.3KOH/g, begins to vacuumize, after 4 hours, acid value reaches 1.98KOH/g, strengthen vacuum tightness and continue reaction 3 hours, acid value reaches 0.34KOH/g, obtains MPD type polyvalent alcohol 579 grams (theoretical value is 706.1 grams).Measuring hydroxyl value is 37.06, and final molecular weight is 3022.
(ii) polyreaction:
By 360 gram MPD type polyvalent alcohol preparation chainextender MPD20 grams (1/18) of (i) step gained, MDI89.8 gram, solvent DMF 268.5 grams, MEK44.7 gram, (solid content is controlled at 60 ± 1%, and the mass ratio of DMF and MEK is 6: 1 in the solvent).
Restrain DMF and polyvalent alcohol and MPD with 180 earlier and mix, divide input three times with 85.6 gram MDI then, reacted sticking at 75～85 ℃, reacted 3 hours, viscosity stops to rise, and divides and adds MDI 3 times, each 1.4 grams that add make viscosity continue to rise, and react 4 hours, when viscosity rises to 50,000 cps/75 ℃, add 88.5 gram DMF viscosity reductions, continue reaction 1 hour, viscosity rises to 30,000 cps/75 ℃ again, add MEK, reacted 30 minutes, transferring to viscosity is 9.5 * 10
4MPas/25 ℃, finally obtain product 783 grams, solid content is 60%.
Embodiment 7:
(i) the preparation molecular weight is 3500 MPD type polyvalent alcohol:
Get the AA500 gram, MPD352.4 gram (be theoretical value 1.08 times), 225 ℃ of reactions 8 hours, acid value reaches 20.2KOH/g, begins to vacuumize, after 5 hours, acid value reaches 2.06KOH/g, strengthen vacuum tightness and continue reaction 4 hours, acid value reaches 0.39KOH/g, obtains MPD type polyvalent alcohol 569.4 grams (theoretical value is 703.0 grams).Measuring hydroxyl value is 31.86, and final molecular weight is 3515.
(ii) polyreaction:
By 350 gram MPD type polyvalent alcohol preparation chainextender MPD17.5 grams (1/20) of (i) step gained, MDI77.2 gram, solvent DMF 272.8 grams, MEK91 gram, (solid content is controlled at 55 ± 1%, and the mass ratio of DMF and MEK is 3: 1 in the solvent).
Restrain DMF and polyvalent alcohol and MPD with 200 earlier and mix, divide input three times with 73.6 gram MDI then, reacted sticking at 75～85 ℃, reacted 3 hours, viscosity stops to rise, and divides and adds MDI 3 times, each 1.2 grams that add make viscosity continue to rise, and react 4 hours, when viscosity rises to 50,000 cps/75 ℃, add 72.8 gram DMF viscosity reductions, continue reaction 2 hours, viscosity rises to 40,000 cps/75 ℃ again, add MEK, reacted 30 minutes, transferring to viscosity is 8 * 10
4MPas/25 ℃, finally obtain product 808.5 grams, solid content is 55%.
Embodiment 8:
(i) the preparation molecular weight is 4000 MPD type polyvalent alcohol:
Get the AA500 gram, MPD340.2 gram (be theoretical value 1.05 times), 230 ℃ of reactions 8 hours, acid value reaches 19.2KOH/g, begins to vacuumize, after 6 hours, acid value reaches 1.95KOH/g, strengthen vacuum tightness and continue reaction 4 hours, acid value reaches 0.33KOH/g, obtains MPD type polyvalent alcohol 560.6 grams (theoretical value is 700.7 grams).Measuring hydroxyl value is 27.92, and final molecular weight is 4012.
(ii) polyreaction:
By 320 gram MPD type polyvalent alcohol preparation chainextender MPD, 16 grams (1/20) of (i) step gained, MDI67.4 gram, solvent DMF 268.9 grams, MEK134.5 gram, (solid content is controlled at 50 ± 1%, and the mass ratio of DMF and MEK is 2: 1 in the solvent).
Restrain DMF and polyvalent alcohol and MPD with 180 earlier and mix, divide input three times with 64.4 gram MDI then, reacted sticking at 75～85 ℃, reacted 4 hours, viscosity stops to rise, and divides and adds MDI 3 times, each 1 gram that adds makes viscosity continue to rise, when viscosity rises to 50,000 cps/75 ℃, add 88.9 gram DMF viscosity reductions, continue reaction 3 hours, when viscosity rises to 50,000 cps/75 ℃ again, add MEK, reacted 30 minutes, transferring to viscosity is 7.5 * 10
4MPas/25 ℃, finally obtain product 806.8 grams, solid content is 50%.
The resin glue made from the manufacture method of this PU binder resin for synthetic leather has that bridge formation speed is fast, good, the prevented from caking of resin transparent, low, the hot dry doubling intensity of softening temperature height, characteristics such as can promptly peel off.Wherein the product of embodiment 4,7,8 gained is specially adapted to paste behind the minute surface high-grade synthetic leather products such as leather, and the product of embodiment 1,2,3,5,6 gained is specially adapted to high-grade synthetic leather products such as the irregular ultra-fine fibre of coating surface.
The every performance index of the resin of the foregoing description gained are as shown in the table:
| Performance index | Bridge formation speed | The transparency | Softening temperature | Hot dry doubling intensity | Promptly peel off |
| Embodiment 1 | Hurry up | Generally | Low | High | Can |
| Embodiment 2 | Hurry up | Generally | Low | High | Can |
| Embodiment 3 | Hurry up | Good | Lower | High | Can |
| Embodiment 4 | Generally | Good | Low | High | Can |
| Embodiment 5 | Hurry up | Generally | Low | High | Can |
| Embodiment 6 | Hurry up | Good | Lower | High | Can |
| Embodiment 7 | Generally | Good | Low | High | Can |
| Embodiment 8 | Generally | Good | Low | High | Can |
Claims (4)
1. the manufacture method of a PU binder resin for synthetic leather is characterized in that:
(i) with hexanodioic acid and 2-methyl isophthalic acid, the esterifying polycondensation reaction is carried out in ammediol heating, when reacting to acid value≤25mgKOH/g, vacuumizes, and removes remainder water, reduces acid value; When reacting, strengthen vacuum tightness and continue reaction and make hydroxy-end capped 2-methyl isophthalic acid, ammediol type polyvalent alcohol to acid value≤2.5mgKOH/g;
(ii) (i) gone on foot the 2-methyl isophthalic acid that makes, ammediol type polyvalent alcohol and chainextender 2-methyl isophthalic acid, ammediol mixes, and adds dimethyl formamide, after stirring, add 4 again, 4 '-diphenylmethanediisocyanate, reacting by heating, polymerization generate urethane, add dimethyl formamide and methylethylketone more therein, adjust viscosity to 6～12 * 10
4MPas/25 ℃.
2. the manufacture method of PU binder resin for synthetic leather as claimed in claim 1, it is characterized in that 2-methyl isophthalic acid in (i) step, the ammediol charging capacity is 1.05～1.15 times of theoretical value in mass, the final acid value of polyvalent alcohol is controlled in the scope of 0.1～0.8mgKOH/g, and the final molecular weight control of polyvalent alcohol is in 1000～4000 scope.
3. the manufacture method of PU binder resin for synthetic leather as claimed in claim 1 or 2, in it is characterized in that (ii) going on foot 4,4 '-the mol number of the add-on of diphenylmethanediisocyanate is polyvalent alcohol and 2-methyl isophthalic acid, the mol of ammediol counts 1～1.05 times of sum, the mass ratio of polyvalent alcohol and chainextender was controlled at 12.5: 1～25: 1, and the mass ratio of dimethyl formamide and methylethylketone is chosen in 2: 1 to 9: 1 scope.
4. the manufacture method of PU binder resin for synthetic leather as claimed in claim 3 is characterized in that the temperature of reaction in (i) step is controlled at 210～230 ℃, and (ii) Bu temperature of reaction is controlled at 75～85 ℃.
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| CN2009100955789A CN101475789B (en) | 2009-01-22 | 2009-01-22 | Preparation of PU binder resin for synthetic leather |
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| CN2009100955789A CN101475789B (en) | 2009-01-22 | 2009-01-22 | Preparation of PU binder resin for synthetic leather |
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| CN101475789B true CN101475789B (en) | 2011-11-30 |
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| CN102978966A (en) * | 2012-12-31 | 2013-03-20 | 浙江科一合成革有限公司 | Superfine suede fiber leather and preparation method thereof |
| CN112342795A (en) * | 2020-10-27 | 2021-02-09 | 浙江大峰合成革有限公司 | Processing technology of PU synthetic leather |
| CN113897167A (en) * | 2021-11-19 | 2022-01-07 | 合肥安利聚氨酯新材料有限公司 | Poly (propylene carbonate) type polyurethane adhesive as well as preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6355317B1 (en) * | 1997-06-19 | 2002-03-12 | H. B. Fuller Licensing & Financing, Inc. | Thermoplastic moisture cure polyurethanes |
| CN1624067A (en) * | 2004-10-29 | 2005-06-08 | 东华大学 | Dry type compound polyurethane adhesive and its preparation method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6355317B1 (en) * | 1997-06-19 | 2002-03-12 | H. B. Fuller Licensing & Financing, Inc. | Thermoplastic moisture cure polyurethanes |
| CN1624067A (en) * | 2004-10-29 | 2005-06-08 | 东华大学 | Dry type compound polyurethane adhesive and its preparation method |
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