CN1031882C - Preparation process of anion-type water-thinned polyurethane for tanning - Google Patents
Preparation process of anion-type water-thinned polyurethane for tanning Download PDFInfo
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- CN1031882C CN1031882C CN 91108102 CN91108102A CN1031882C CN 1031882 C CN1031882 C CN 1031882C CN 91108102 CN91108102 CN 91108102 CN 91108102 A CN91108102 A CN 91108102A CN 1031882 C CN1031882 C CN 1031882C
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Abstract
The present invention relates to a preparation method for anion-type water-based polyurethane for tanning. In the method, vegetable oil modified polylol is used for reacting with excessive polyisocyanate to generate polyurethane prepolymers with end groups of isocyanate, and then polyethylene-polyamine and halohydrin ring anhydrous carboxyl ester anhydride are used for chain extension; afterwards, a water solution of alkali is used for neutralization and turning emulsification, and anion-type reactive water-based polyurethane can be prepared after solvents are removed. Products obtained by adopting the present invention can be suitable for retanning and filling, level dyeing, color fixation, coating of leather, and the present invention can solve the problem of loose surfaces of cattle leather, sheep leather and pigskin. The present invention is especially suitable for the filling of full-grain upper leather, and can solve the problem of loose surfaces of cattle leather, sheep leather and pigskin; moreover, the present invention has the advantages of rapid speed of permeability, strong adhesive force, level dyeing and color fixing function.
Description
The present invention relates to the plant oil modified polyvalent alcohol of a kind of usefulness and prepare the anion-type water-thinned polyurethane method.
Generally as the leather retanning packing material, two kinds of organic and inorganic materials.Aspect organic materials, natural organic and synthetic organic material two big classes are arranged again.Aspect synthetic organic material, phenolic aldehyde, urea aldehyde, aminoresin, Resins, epoxy, unsaturated olefin resene etc. are arranged, especially in the majority with latter's acrylic copolymeric resin.But the performance of this resin is single, and retanning and filling are difficult to take into account.With regard to potting resin, because be emulsion-type, particle diameter is bigger, and filling effect is not good, especially can not solve the loose side problem of full grain.Add that the finished leather feel of filling with acrylic resin is harder, the adhesive property deficiency is unable to undergo to play with.The hot sticky cold crisp problem appears again in the finished leather with acrylic resin is covered with paint, lacquer, colour wash, etc., and passes through abundant stuffing exactly, can obtain soft clothes leather, but lack the body bone, is difficult to obtain to keep the feel of natural leather, obtains flexible and flexible balance.
Because urethane has many multiple carbamates
Structural unit, similar to amino acid structure contained in the natural leather fiber, the leather that makes arrangement is softness but also be rich in the body bone not only, obtains good flexibility and flexible balance, has the feel that exactly likes natural leather.Therefore, be widely used as synthetic leather and natural leather finishing composition.There are many emulsifying water types, water dispersant type polyaminoester hide finishes to develop operation in succession at present both at home and abroad.And be used for the aqueous polyurethane of leather retanning filling aspect, have only West Germany Beyer Co., Ltd to be useful on the patent (DE:3517803) of retanning oiling aspect.This patent is to be that raw material makes and contains the aqueous polyurethane that 15% hydroxyethyl is an end group with polyethers and polyester and polycarbonate polyol.
The objective of the invention is above-mentioned situation,, select for use resourceful, low-cost vegetables oil to come modified polyalcohol, make the aqueous polyurethane of reactive anionic in conjunction with the present situation and the characteristics of China's tanning industry.
The anion-type water-thinned polyurethane for tanning preparation takes following method to realize; Making isocyanic ester with plant oil modified polyvalent alcohol is that the urethane of end group gives aggressiveness (A), generate polyurethane-urea compound (B) with excessive polyethylene polyamine reaction, again with epihalohydrins react intermediate product (C), then with ring-type anhydrous carboxylic acid anhydride reactant, get addition polymer (D), with in the alkaline aqueous solution and addition polymer (D), turn to emulsification to make anion-type water-thinned polyurethane.
The vegetables oil that uses among the present invention can be selected non-drying oils, semi-drying oils, dryness oils for use.Can select for use non-drying oils as Viscotrol C, sweet oil, Oleum Cocois, plam oil, tea oil, peanut wet goods; Semi-drying oils is as Rice pollard oil, oleum gossypii seminis, sesame oil, Semen Maydis oil, sunflower oil, soya-bean oil, safflower oil, vegetable seeds wet goods; Dryness oils is as oleum lini, walnut oil, hempseed oil, tung oil etc., therefrom selects a kind ofly, perhaps severally comes modified poly ester or/and polyether glycol, vegetables oil and polyester or/and the weight ratio of polyether glycol can in 0～100/100～0 scope, select.According to the final performance of product, select appropriate proportional range.
As polyol compound, molecular weight can be from 200～10000, for example, well-known polyethers, polyester, polyesteramide class, polycarbonate-based, and the saturated and/or undersaturated multicomponent alcoholics compounds such as affixture of dihydroxyphenyl propane and oxyethane, propylene oxide, butylene oxide ring.
As polyether alcohol, for example: polymerisate such as tetrahydrofuran (THF), oxyethane, propylene oxide, butylene oxide ring, glycerol and multipolymer thereof or graft copolymer all can.
As the polyester polyvalent alcohol, for example: by ethylene glycol, 1,2 one propylene glycol, 1,3 one propylene glycol, 1,4 one butyleneglycols, 1,3 one butyleneglycols, new the eleventh of the twelve Earthly Branches glycol, the eleventh of the twelve Earthly Branches glycol, hexylene glycol, ethohexadiol, 1, saturated and undersaturated low-molecular-weight diol or glycerol such as 4 one butynediol, dihydroxyphenyl propane, glycol ether, Triethylene glycol, dipropylene glycol, tripropylene glycol, TriMethylolPropane(TMP) and season polyvalent alcohol such as the eleventh of the twelve Earthly Branches tetrol, with polycondensation products such as aliphatic dibasic acid or aromatic acid or/and carboxylic acid anhydride, cyclic lactones.
Above-mentioned plant oil modified polyester is or/and polyether glycol, and with excessive polyisocyanates reaction, the urethane that generates isocyanic ester and be end group gives aggressiveness (A).The equivalence ratio of polyisocyanates and polyol compound ,-NCO/-OH=1.3～2.3/1.50～100 ℃ of temperature of reaction, the reaction times is 1～8 hour.
As polyisocyanate compound aromatic polyisocyanate and aliphatic polyisocyante are arranged, for example: tolylene diisocyanate (2.4-and 2.6 one, and composition thereof), 4,4 ' one diphenylmethanediisocyanates, the xylyl vulcabond, isophorone diisocyanate, triphenylmethane triisocyanate, poly methylene poly phenyl poly isocyanate, hexamethylene diisocyanates etc. therefrom can be selected one or more, or their oligopolymer uses.
Urethane is given aggressiveness (A) and its equivalence ratio-NCO/ of polyethylene polyamine ketone solution reaction＞NH=1/2～6, temperature of reaction is-20 ℃～+ 70 ℃, reaction times is 0.5～2 hour, until generating no isocyano (till the polyurethane-urea compound (B) NCO).
Have as the polyethylene polyamine compound: diethylenetriamine, triethylene tetramine, tetraethylene pentamine etc., and composition thereof, in addition, quadrol, trolamine also can be selected for use.
Polyurethane-urea compound (8) and epihalohydrins reaction, its equivalence ratio,
/ 1～5, temperature of reaction is 5～70 ℃, and the reaction times is 1～8 hour, makes intermediate product (C).
As epihalohydrins, generally select Epicholorohydrin or epibromohydrin for use.
Except that the mode of above-mentioned this chain extending reaction, on the synthesis technique earlier with polyethylene polyamine compounds and epihalohydrins reaction, and then with isocyanic ester be that the urethane of end group gives aggressiveness and reacts.
Intermediate product (C) and cyclic carboxylic acids anhydride reactant, its equivalence ratio＞NH and/or-OH/-COOH=1/1～5, temperature of reaction is 20 ℃～70 ℃, the reaction times is 0.5～2.0 hour, generates the addition polymer (D) of band carboxyl.
Have as the cyclic carboxylic acids acid anhydride: maleic anhydride, Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, pyromellitic acid acid anhydrides etc. can therefrom be selected one or more mixture for use.
Addition polymer (D) neutralizes with the aqueous solution of alkali, and this alkali can be selected metal hydroxides for use, as: sodium hydroxide, potassium hydroxide, lithium hydroxide.Or carbonate, as: yellow soda ash, sodium bicarbonate, the aqueous solution of salt of wormwood is perhaps used ammoniacal liquor, organic amine R
3N (R is H in the formula, or the alkyl of 1～4 carbon atom, hydroxyethyl, hydroxypropyl).
Product after the neutralization falls after the agent through turning to emulsification, vacuum removal, regulates pH value and solid content, just can obtain the anionic reactive waterborne polyurethane of desired properties.
According to method of the present invention,, can make water-soluble, water dispersible, water and milk voltinism and wax shape waterborne polyurethane resin respectively with different ingredients and reaction conditions.
With the reactive polyurethane that the present invention makes, molecular weight is 2000～8000, can be used as retanning, filling, level dyeing, fixation on tanning industry, and as the properties-correcting agent of crylic acid resin finishing agent.Molecular weight be 8000～100000 can be used for the leather surface finishing agent.In addition, can also be used for industrial aspect such as weaving, papermaking, material of construction, plastics, as coating, tackiness agent, seal gum etc.
The cloudy release aqurous ployurethane leather retanning filler that adopts the present invention to make, can solve the loose side problem of ox, sheep, pigskin, be particularly suitable for the filling of full grain, it is fast to have seepage velocity, and cementability is strong, level dyeing, tint retention, gives finished leather natural leather feel, high resilience, obviously improve intensity, make the leather of filling improve 0.5～1.0 grade, also can be used as the properties-correcting agent of vinylformic acid finishing agent.
Below be specific embodiments of the invention:
Embodiment 1:
(1) in the four-hole of 500ml burns also, add oleum lini 105g, glycerine 33g, CaO0.02g under nitrogen protection, reacted one hour down in 230 ± 10 ℃, made reaction product (A).
(2) in the four-hole of 500ml burns also, add reaction product (A) 50g, polyoxyethylene glycol (400) 50g, after the toluene dehydration, add tolylene diisocyanate (80/20) 88g, benzene 60g, in 70 ℃ of down reactions 1.5 hours, make have-isocyanic ester of NCO%=6.7 is that the urethane of end group gives aggressiveness (B).
(3) the four-hole of 500ml burn and in, add the ketone solution of 5.0g diethylenetriamine and give aggressiveness (B) 30g, 55 ± 5 ℃ of reaction half an hour down, add maleic anhydride 14.3g, in 55 ± 5 ℃ of reactions 1.5 hours down, add NaOH/H
2The aqueous solution of O=8g/150g turns to emulsification, and the vacuum removal solvent makes brown transparent anionic aqurous ployurethane.PH value is 8～9, and solid content is 30%.
Embodiment 2:
(1) in the 500ml four-hole burns also, add product (A) 21g among the embodiment 1, poly-adipic acid glycol ester dibasic alcohol (molecular weight 2000) 8.6g, after the dehydration, add tolylene diisocyanate (80/20) 25g, add dimethyl formamide 30g, reacted 1.5 hours down in 80 ℃, the urethane that makes isocyanic ester and be end group gives aggressiveness (B) ,-RCO%=2.3%.
(2) the 500ml four-hole burn and in, 2g diethylenetriamine ketone solution and give aggressiveness (B) 35g is 55 ± 5 ℃ of reaction half an hour down, add Epicholorohydrin 18g again, react half an hour down, add maleic anhydride 14.3g again in 55 ± 5 ℃, reacted 1.5 hours down in 55 ± 5 ℃, again with NaOH/H
2The aqueous solution of O=8/150 turns to emulsification, behind the vacuum removal solvent, makes brown translucent anionic aqurous ployurethane, and pH value is that 8～9 solid contents are 30%.
Embodiment 3:
(1) the four-hole of 500ml burn and in, add Viscotrol C 50g, polyoxyethylene glycol (400) 50g after the vacuum hydro-extraction, adds tolylene diisocyanate (80/20) 76.5g, butanone 150g, in 80 ℃ down reaction to make isocyanic ester in one hour be that the urethane of end group gives aggressiveness.-NCO％＝4.9％。
(2) the 500ml four-hole burn and in, add 5g diethylenetriamine ketone solution and give aggressiveness 35g, 55 ± 5 ℃ of reaction half an hour down, add Epicholorohydrin 18g, reacted 1 hour down, add maleic anhydride 22g in 55 ± 5 ℃, react half an hour down in 55 ± 5 ℃, again with NaOH/H
2The aqueous solution of O=14g/100g turns to emulsification, behind the vacuum desolventizing, makes brown transparent anionic aqurous ployurethane, and pH value is 7～8, and solid content is 30%.
Embodiment 4:
(1) in the 500ml four-hole burns also, adds Viscotrol C 51.5g, poly-adipic acid glycol ester dibasic alcohol (molecular weight 500) 50g, after the vacuum hydro-extraction, add tolylene diisocyanate (80/20) 71g, butanone 100g, in 80 ℃ of down reactions 1 hour, the urethane that makes isocyanic ester and be end group gives aggressiveness.-NCO％＝4.3％。
(2) the 500ml four-hole burn and in add 5g diethylenetriamine ketone solution and give aggressiveness 40g, 55 ± 5 ℃ of reaction half an hour down, add Epicholorohydrin 18g, in 55 ± 5 ℃ of reactions 1 hour down, add maleic anhydride 22g again, reacted 1 hour down in 55 ± 5 ℃, with NaOH/H
2The aqueous solution of O=14g/100g, the vacuum desolventizing makes brown opaque anion-type water-thinned polyurethane solution, and pH value is 7～8, and solid content is 30%.
Claims (7)
1, a kind of preparation process of anion-type water-thinned polyurethane for tanning, it is characterized in that making isocyanic ester with plant oil modified polyvalent alcohol is that the urethane of end group gives aggressiveness (A), generate polyurethane-urea compound (B) with excessive polyethylene polyamine reaction, again with epihalohydrins react intermediate product (C), then with ring-type anhydrous carboxylic acid anhydride reactant, get addition polymer (D), use in the alkaline aqueous solution and addition polymer (D), turn to emulsification to make anion-type water-thinned polyurethane:
A, from vegetables oil, select one or several and come the modified poly ester polyvalent alcohol or/and polyether glycol, vegetables oil and polyester or and the weight ratio of polyether glycol, can in 0～100/100～0 scope, select;
8, with plant oil modified polyester or/and polyether glycol, with excessive polyisocyanates reaction, generation and isocyanic ester are that the urethane of end group gives aggressiveness (A), equivalence ratio-the NCO/-OH=1.3 of polyvalent alcohol and polyisocyanate compound～2.3/1,50～100 ℃ of temperature of reaction, the reaction times is 1～8 hour;
C, urethane give aggressiveness (A) and polyethylene polyamine ketone solution reaction, its equivalence ratio-NCO/＞NH=1/2～6, temperature of reaction is-20 °～+ 70 ℃, and the reaction times is 0.5～2 hour, until generating no isocyano (till the polyurethane-urea compound (B) NCO);
D, with the reaction of polyurethane-urea compound (B) and epihalohydrins, its equivalence ratio
=1/1～5, temperature of reaction is 5～70 ℃, and the reaction times is to make intermediate product (C) in 1～8 hour;
E, intermediate product (C) and cyclic carboxylic acids anhydride reactant, its equivalence ratio＞NH or-OH/-COOH=1/1～5, temperature of reaction is 20 ℃～70 ℃, the reaction times is 0.5～2.0 hour, generates the addition polymer (D) of band carboxyl;
F, with the aqueous solution neutralization of addition polymer (D) and alkali, the product after the neutralization through turning to emulsification, behind the vacuum removal solvent, is regulated pH value and solid content.
2, preparation process of anion-type water-thinned polyurethane for tanning according to claim 1 is characterized in that vegetables oil can select non-drying oils, semi-drying oils, dryness oils for use; Non-drying oils is as Viscotrol C, sweet oil, Oleum Cocois, plam oil, tea oil, peanut oil; Semi-drying oils is as Rice pollard oil, oleum gossypii seminis, sesame oil, Semen Maydis oil, sunflower oil, soya-bean oil, safflower oil, rape seed oil; Dryness oils is as oleum lini, walnut oil, hempseed oil, tung oil.
3, preparation process of anion-type water-thinned polyurethane for tanning according to claim 1, it is characterized in that polyethylene polyamine is: diethylenetriamine, triethylene tetramine, tetraethylene pentamine and composition thereof, quadrol and trolamine also can be selected for use.
4, preparation process of anion-type water-thinned polyurethane for tanning according to claim 1 is characterized in that epihalohydrins can adopt Epicholorohydrin or epibromohydrin.
5, preparation process of anion-type water-thinned polyurethane for tanning according to claim 1, it is characterized in that on the synthesis technique also can be earlier with polyethylene polyamine and epihalohydrins reaction, and then with isocyanic ester be end group give the aggressiveness reaction, carry out chain extension.
6, preparation process of anion-type water-thinned polyurethane for tanning according to claim 1 is characterized in that ring-type anhydrous carboxylic acid acid anhydride refers to Maleic Acid, Anhydrous acid anhydride, Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, pyromellitic acid acid anhydride.
7, preparation process of anion-type water-thinned polyurethane for tanning according to claim 1 is characterized in that neutralizing and can select the aqueous solution of sodium hydroxide, potassium hydroxide, lithium hydroxide, yellow soda ash, sodium bicarbonate, salt of wormwood for use or with ammoniacal liquor or organic amine R with the aqueous solution of alkali
3N (R is H in the formula, or the alkyl of 1～4 carbon atom, hydroxyethyl, hydroxypropyl).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91108102 CN1031882C (en) | 1991-07-08 | 1991-07-08 | Preparation process of anion-type water-thinned polyurethane for tanning |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91108102 CN1031882C (en) | 1991-07-08 | 1991-07-08 | Preparation process of anion-type water-thinned polyurethane for tanning |
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| Publication Number | Publication Date |
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| CN1068343A CN1068343A (en) | 1993-01-27 |
| CN1031882C true CN1031882C (en) | 1996-05-29 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 91108102 Expired - Fee Related CN1031882C (en) | 1991-07-08 | 1991-07-08 | Preparation process of anion-type water-thinned polyurethane for tanning |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880369A (en) * | 2010-07-23 | 2010-11-10 | 温州市宏得利树脂有限公司 | Polyurethane elastomer |
| CN101062997B (en) * | 2006-04-30 | 2011-01-12 | 王爱华 | Vegetable oil polyether polyatomic alcohol duromer polyurethane foam plastic pouring material |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1046952C (en) * | 1995-10-27 | 1999-12-01 | 王南 | Composite dubbing of polyurethane-polyacrylate for leather |
| CA2273289A1 (en) * | 1996-11-29 | 1998-06-04 | Takao Yoshikawa | Thermally conductive pressure-sensitive adhesive and adhesive sheet containing the same |
| CN107868204B (en) * | 2017-11-30 | 2020-06-26 | 上海大学 | Anionic waterborne polyurethane resin, preparation method and application thereof |
| CN112029064A (en) * | 2020-09-09 | 2020-12-04 | 四川亭江新材料股份有限公司 | Amino-terminated polyurethane of synthetic tanning agent and preparation method and application thereof |
| CN112725549A (en) * | 2020-11-30 | 2021-04-30 | 温州大学 | Hyperbranched polymer leather retanning agent capable of reducing content of free formaldehyde |
-
1991
- 1991-07-08 CN CN 91108102 patent/CN1031882C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101062997B (en) * | 2006-04-30 | 2011-01-12 | 王爱华 | Vegetable oil polyether polyatomic alcohol duromer polyurethane foam plastic pouring material |
| CN101880369A (en) * | 2010-07-23 | 2010-11-10 | 温州市宏得利树脂有限公司 | Polyurethane elastomer |
| CN101880369B (en) * | 2010-07-23 | 2011-07-20 | 温州市宏得利树脂有限公司 | Polyurethane elastomer |
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| Publication number | Publication date |
|---|---|
| CN1068343A (en) | 1993-01-27 |
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