CN101240057A - Sulfonic acid type hydrophilic chain extender and preparation method thereof - Google Patents
Sulfonic acid type hydrophilic chain extender and preparation method thereof Download PDFInfo
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- CN101240057A CN101240057A CNA2008101021048A CN200810102104A CN101240057A CN 101240057 A CN101240057 A CN 101240057A CN A2008101021048 A CNA2008101021048 A CN A2008101021048A CN 200810102104 A CN200810102104 A CN 200810102104A CN 101240057 A CN101240057 A CN 101240057A
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Abstract
A hydrophilic chain extender of sulfonic acid type which pertains to chemical product, and preparation thereof. The invention mainly aims to solve the problems of slow reaction rate of hydrophilic chain extender used in aqueous polyurethanel industry, low content of aqueous resin, low heat resistance, low adhesion strength when applying to adhesive. The eligible product is obtained by fully dissolving multi-amine such as 0.5-1.5 parts of ethylenediamine into solvent, reacting with olefin sulfonate such as 5-9 parts of vinyl sodium sulfonate solution with about 25% of water for 4-30 hours at the temperature of 40-100 DEG C., vacuum distilling to remove solvent, dissolving with water, alcohol or ketone, vacuum distilling to remove all solvent for another time after deposition and filter. Stability treatment for storage is further carried out by adding water. The final product is slightly turbid vicous liquid in light yellow color and oil state, with density at 1.16-1.21 g/ml, pH at 11-12, content of ammonia at 6.9+-0.9g NH<SUB>3</SUB>/100g, effective content 40-55%. The invention can widely used into production of aqueous polyurethane of different fields, which has a fast reaction rate, high yield, highly enhanced content of solid in prepared aqueous resin, and obviously improved resistance of heat, acid, alkali, hard water, and is greatly beneficial for preparation of adhesive.
Description
Technical field
The invention belongs to chemical and preparation method thereof field, relate to sulfonic acid type hydrophilic chain extender and preparation method thereof.
Background technology
The popular hydrophilic chain extender mostly is a carboxylic acid type in the aqueous polyurethane industry at present, as DMPA---be 2.2-dihydroxyl methylpropanoic acid, DMBA-is a 2.2-dihydroxyl methylbutyric etc., its reactive group is a hydroxyl, the hydroxyl reaction activity is lower, the water-based group is a carboxyl, carboxylated hydrophilic is very low, molten water is slow, just can finish the chain extension process in about 6 hours at need under 50 ℃ of conditions, because the wetting ability of carboxyl is very low, therefore, the solid content of prepared water-base resin is generally all lower, if will improve solid content, needs to consume a large amount of chainextenders, simultaneously, because it is acid that carboxylic acid shows, the positive group of carboxyl, therefore, after finishing, chain extension generally needs to neutralize with triethylamine, and triethylamine is volatile, thereby makes prepared water-base resin heat-resisting, acid and alkali-resistance and stability in hard water can be not high, and the polarity of carboxylic acid is on the low side, make that also sticking power was low when prepared water-base resin was applied to tackiness agent, bonding strength is low.
Summary of the invention
The technical problem that solves:
Adopt polyamine and alkenyl sulphonate to synthesize, the preparation sulfonic acid type hydrophilic chain extender, can overcome the deficiencies in the prior art, the reactive group of this product is amino, than hydroxyl higher reactive behavior is arranged, the chain extension process substep of urethane is also finished rapidly, the water-based group of this product is the sulfonic acid negative ion, wetting ability is far above carboxyl, the solid content of water-base resin is improved greatly, and maximum value is increased to 65% from 50%, and sulfonate has the neutral characteristics simultaneously, and the stability of sulfonic acid group is very high, therefore need not neutralization after chain extension is finished, and prepared water-base resin is heat-resisting, acid and alkali-resistance and stability in hard water can have clear improvement, in addition because the polarity of sulfonate is higher than carboxylic acid, strong adhesion when prepared water-base resin is applied to tackiness agent, the bonding strength height.
The technical scheme that adopts:
The preparation method of sulfonic acid type hydrophilic chain extender, the first step, the preparation head product, after umber is dissolved among the corresponding solvent W cmpletely in accordance with regulations with selected feed composition polyamine, place in the reactor, to material heat temperature raising to 40～100 ℃, the feed composition olefin sulfonic acid salt brine solution that under agitation adds the regulation umber, and reacted 4～30 hours, stopped reaction carries out underpressure distillation except that desolvating, pressure-controlling is at 0.01～0.005MPa, wherein water can have 0～3 part of residue, promptly obtains head product, is slightly muddy light yellow of outward appearance, oily, thick liquid;
Second step, head product is removed impurity to be handled, the head product that the first step is obtained is dissolved among the complex solvent S cmpletely, and fully stir, make insoluble contamination precipitation and fully ageing, filter with 350～500 order net filtration equipment then, online is light yellow hard solid impurity, afterwards the clear liquid that filters out is carried out underpressure distillation once more, pressure-controlling is at 0.01～0.005MPa, after all solvents are removed in distillation, but promptly obtain qualified application product, be clarifying light yellow, the oily of outward appearance, thick liquid;
The 3rd step, but qualified application product is carried out package stability to be handled, because the sulfonic acid type hydrophilic chain extender that does not have solvent to surround is stable inadequately, store browning, rotten, sclerosis gradually after a couple of days, therefore, need to add and be no less than 1 part enough water, but stirring is dissolved qualified application product cmpletely, then with 400～500 order net filtration equipment filterings macrobead insolubles wherein, promptly obtain the product that can use and can store, be slightly muddy light yellow, the oily of outward appearance, thick liquid.
With the sulfonic acid type hydrophilic chain extender of above-mentioned preparation method preparation, outward appearance is muddiness slightly or clarifying light yellow, oily, thick liquid, density 1.16～1.21g/ml, PH11～12, ammonia value 6.9 ± 0.9gNH
3/ 100g, effective ingredient 40～55%; General structure is (NH
2) mR '-NH-R-SO
3Y, m is 1～3, Y is the metal ion on the ordinary meaning that constitutes raw materials used component alkenyl sulphonate, R is fat or the alicyclic ring class saturated hydrocarbyl identical with the number of institute's carbon atoms in the raw materials used component alkenyl sulphonate, R ' be with raw materials used component polyamine in the identical fats alkyl of number of institute's carbon atoms; Raw materials used component and portion rate, feed composition polyamine are 0.5～1.5 part, and described polyamine is meant diamine and above fats polyamine thereof, and general structure is Cn ' Hx (NH
2) m ', n ' is 2～10, m ' is 2～4, m '≤n ', x for the number n of carbon atom ' number of the hydrogen atom that is complementary; Polyamine solvent for use W is 5～8 parts, to dissolve polyamine cmpletely is principle, the effect of solvent W is fully to disperse polyamine, so that the system internal reaction is even, avoiding local crosses strong and influences finished product quality and yield, solvent W is water or other polar solvent, perhaps be wherein two or more composite the forming of compound that comprises water, the methyl alcohol of other polar solvent such as alcohols, ethanol, the acetone of ketone, the dioxane of ethers, tetrahydrofuran (THF), the ethyl acetate of ester class, the methylene dichloride of halogenated hydrocarbon, chloroform, the N of amides, dinethylformamide, the methyl-sulphoxide of sulfone class; The feed composition alkenyl sulphonate is that concentration is 5～9 parts of 20～30% olefin sulfonic acid salt brine solutions, and described alkenyl sulphonate is meant the derivative that contains vinylsulfonate, and with the direct-connected carbon of vinyl double bond be saturated carbon, general structure is Cn-C=C-SO
3Y, n are 0～30, and Cn is fat or alicyclic ring class saturated hydrocarbyl, and Y is the metal ion on the ordinary meaning that constitutes alkenyl sulphonate.Second step head product being removed that used complex solvent S is 8～30 parts in the impurity treatment step, is principle to dissolve head product cmpletely, and complex solvent S is C
1～4Alcohol, C
3～5Ketone or water perhaps are two or more composite the forming of compound wherein.
Beneficial effect:
The sulfonic acid type hydrophilic chain extender of the present invention's preparation can be applied to the production of various fields aqueous polyurethane at large, and can improve the respective performances and the quality of stability of aqueous polyurethane, needn't get final product relieved use by a batch test to every batch of product; Compare with carboxylic acid type wetting ability chainextender such as DMPA, DMBA etc., the reactive behavior height, speed of response is fast, the water-base resin solid content of preparing improves greatly, maximum value is increased to 65% from 50%, when synthesizing the water-base resin of identical solid content, the consumption of chainextender is few, reduce production cost, and water-base resin is heat-resisting, acid and alkali-resistance and stability in hard water can obviously improve, because the polarity of sulfonate is higher than carboxylic acid, the prepared water-base resin sticking power that goes out improves greatly, is very beneficial for preparing tackiness agent and is used for special dimension; Simultaneously, chainextender production technique of the present invention is easy to control, and required starting material extensively are easy to get, and can satisfy the multiple needs in market, and the price appropriateness, is suitable for by market and accepts.
Embodiment
Preferred version is:
The feed composition polyamine is 0.8～1.2 part; Preferred quadrol, propylene diamine, hexanediamine, third triamine or 1,3, the own triamine of 6-;
Polyamine solvent for use W is 6～7 parts, and solvent W preferably forms as shown in Table 1:
Table one
The feed composition alkenyl sulphonate is that concentration is 6～8 parts of 25 ± 2% olefin sulfonic acid salt brine solutions, preferred vinyl sodium sulfonate, methyl ethylene sodium sulfonate, ethyl vinyl sodium sulfonate, propyl ethylene base sodium sulfonate, butyl vinyl sodium sulfonate, cyclohexyl sodium vinyl sulfonate, vinyl sulfonic acid potassium, propyl ethylene base potassium sulfonate, butyl vinyl potassium sulfonate or cyclohexyl vinyl sulfonic acid potassium;
The first step prepares that temperature of reaction is 60～80 ℃ in the head product step, and the reaction times is 12～20 hours; The adding of olefin sulfonic acid salt brine solution uniform continuity; Heating means are water-bath, oil bath or gas bath;
Second step head product removed that used complex solvent S is 12～24 parts in the impurity treatment step, complex solvent S preferably forms as shown in Table 2:
Table two
But the 3rd step carried out in the package stability treatment step qualified application product, added 1.4～3 parts in water, but stir qualified application product was dissolved cmpletely;
The product of using and storing that after the 3rd step handled, obtains, make with extra care as required, with 1.5～3 parts of toluene described product is extracted, underpressure distillation then, pressure-controlling is at 0.01～0.005MPa, after removing the toluene that remains in aqueous phase, promptly obtain having the sulfonic acid type hydrophilic chain extender purified product of package stability, be clarifying light yellow, the oily of outward appearance, thick liquid.
Embodiment 1
The first step, the preparation head product, 1 part of quadrol is dissolved in cmpletely among 6.5 parts the solvent W, solvent W is mixed by 50% water and 50% ethanol, and place in the reactor, warming-in-water to 75 ℃, under agitation the adding concentration of uniform continuity is 7.5 parts of 25% vinyl sulfonic acid sodium water solutions, and reacted 16 hours, stopped reaction carries out underpressure distillation afterwards except that desolvating, pressure-controlling is at 0.008MPa, wherein contain 1.2 parts of surplus waters, head product, be slightly muddy light yellow, the oily of outward appearance, thick liquid;
Second step, head product is removed impurity to be handled, the head product that the first step is obtained is dissolved among 18 parts the complex solvent S cmpletely, complex solvent S is mixed by 70% ethanol and 30% water, fully stir, after treating insoluble contamination precipitation and abundant ageing, filter with 400 order net filtration equipment, remove online light yellow hard solid impurity, then the clear liquid that filters out is carried out underpressure distillation once more, pressure-controlling is at 0.008MPa, after all solvents are removed in distillation, but promptly obtain qualified application product quadrol base ethyl sulfonic acid sodium, structural formula is
Yield is 2.4 parts, is clarifying light yellow, the oily of outward appearance, thick liquid;
The 3rd step, but qualified application product is carried out package stability to be handled, add 2.4 parts of water, but stirring is dissolved qualified application product cmpletely, then with 400 order net filtration equipment filterings macrobead insolubles wherein, promptly obtain the product that to use and can store, be outward appearance slightly light yellow, oily, the thick liquid of muddy (small-particle organic suspension thing), density 1.17g/ml, PH11, ammonia value 7.1g NH
3/ 100g, effective constituent 50%;
The 4th step, refining, with 2 parts of toluene the product that can use and can store is extracted, underpressure distillation then, pressure-controlling is at 0.008MPa, after removing the toluene that remains in aqueous phase, promptly obtain having the quadrol base ethyl sulfonic acid sodium purified product of package stability, be clarifying light yellow, the oily of outward appearance, thick liquid.
The method steps of embodiment 2～8 is with embodiment 1, the when corresponding processing parameter of related feed composition, coordinative solvent, umber, yield and product property, title as shown in Table 3:
Table three
Table three (continuing)
Product is outward appearance slightly muddy (refining) or clarifying light yellow, oily, thick liquid.
Yield (part) in the table three (continuing) is the umber of resulting " but qualified application product " in second step of preparation method, and yield accounts for the per-cent of resulting " can use the product that can store " in the 3rd step and is " effective constituent " in this table.
Prepare in the head product step in the first step, the judgement that the reaction of reactant system finishes: get 5～6 of reactants, be added drop-wise to 10ml concentration and be in 50% the aqueous ethanolic solution, directly produce white particulate material if splash into the back, illustrate that reaction does not finish, if splash into slightly adularescent milk generation of back, but under agitation disappear immediately, illustrate that reaction finishes; For the certain reaction objects system, in certain reaction times, temperature of reaction is high more, and then speed of response is fast more, the easy more balance that reaches, but reach certain temperature, and after reaching balance, if temperature continues to raise, the meeting destruction of balance, reversed reaction is accelerated, and the transformation efficiency of alkenyl sulphonate can reduce on the contrary.
In second step head product is removed in the impurity treatment step, the judgement that all solvents finish is removed in underpressure distillation: when no longer producing bubble in the distilland system, solvent promptly all is distilled and removes.
Raw materials used be commercial.
With the prepared corresponding product of the foregoing description 1,2,5,6, to use and the corresponding aqueous polyurethane prepared as chainextender, its solid content is 55～65%, under 65 ℃ of conditions, still keeps mass conservation after 24 hours; When preparing the corresponding aqueous polyurethane that is applied to use when using as tackiness agent as chainextender, tackiness agent with preparation will be tested with two skin test spares and bond together, after the drying, in the tear test, be torn until two skin test spares, and adhesive linkage does not at all ftracture;
Comparing test-results with hydrophilic chain extender DMPA of the prior art and DMBA is: the corresponding aqueous polyurethane of preparing, and its solid content is up to 50%, under 65 ℃ of conditions, promptly goes bad less than 10 hours, demulsifying phenomenon occurs; And be applied to tackiness agent when contrast, and in the tear test, adhesive linkage ftractures fully, and two skin test spares are intactly torn and are separated.
Above-mentioned comparing result shows that product of the present invention can improve solid content, thermotolerance and the sticking power of water-base resin greatly; Form and the reaction mechanism analysis from feed composition, structure, product of the present invention can make water-base resin resistance to acids and bases, stability in hard water obviously improve, speed of response is obviously accelerated, test shows, product of the present invention is used for chain extension, give chain extension from 20 ℃ and be warming up to 50 ℃ of about half an hour, under 50 ℃, can finish the chain extension process in 3 minutes.
Claims (4)
1, the preparation method of sulfonic acid type hydrophilic chain extender, the first step, the preparation head product, after umber is dissolved among the corresponding solvent W cmpletely in accordance with regulations with selected feed composition polyamine, place in the reactor, to material heat temperature raising to 40～100 ℃, the feed composition olefin sulfonic acid salt brine solution that under agitation adds the regulation umber, and reacted 4～30 hours, stopped reaction carries out underpressure distillation except that desolvating, pressure-controlling is at 0.01～0.005MPa, wherein water can have 0～3 part of residue, promptly obtains head product, is slightly muddy light yellow of outward appearance, oily, thick liquid;
Second step, head product is removed impurity to be handled, the head product that the first step is obtained is dissolved among the complex solvent S cmpletely, and fully stir, make insoluble contamination precipitation and fully ageing, filter with 350～500 order net filtration equipment then, online is light yellow hard solid impurity, afterwards the clear liquid that filters out is carried out underpressure distillation once more, pressure-controlling is at 0.01～0.005MPa, after all solvents are removed in distillation, but promptly obtain qualified application product, be clarifying light yellow, the oily of outward appearance, thick liquid;
The 3rd step, but qualified application product is carried out package stability to be handled, because the sulfonic acid type hydrophilic chain extender that does not have solvent to surround is stable inadequately, store browning, rotten, sclerosis gradually after a couple of days, therefore, need to add and be no less than 1 part enough water, but stirring is dissolved qualified application product cmpletely, then with 400～500 order net filtration equipment filterings macrobead insolubles wherein, promptly obtain the product that can use and can store, be slightly muddy light yellow, the oily of outward appearance, thick liquid.
2, the preparation method of sulfonic acid type hydrophilic chain extender according to claim 1, it is characterized in that: make with extra care for the sulfonic acid type hydrophilic chain extender product of using and storing that outward appearance is slightly muddy, with 1.5～3 parts of toluene described product is extracted, underpressure distillation then, pressure-controlling is at 0.01～0.005MPa, after removing the toluene that remains in aqueous phase, promptly obtain the sulfonic acid type hydrophilic chain extender purified product that package stability was clarified and had to outward appearance.
3, the sulfonic acid type hydrophilic chain extender of preparing with the described method of claim 1, outward appearance is slightly muddy or clarifying light yellow, oily, thick liquid, density 1.16～1.21g/ml, PH11～12, ammonia value 6.9 ± 0.9gNH
3/ 100g, effective ingredient 40～55%; General structure is (NH
2) mR '-NH-R-SO
3Y, m is 1～3, Y is the metal ion on the ordinary meaning that constitutes raw materials used component alkenyl sulphonate, R is fat or the alicyclic ring class saturated hydrocarbyl identical with the number of institute's carbon atoms in the raw materials used component alkenyl sulphonate, R ' be with raw materials used component polyamine in the identical fats alkyl of number of institute's carbon atoms; Raw materials used component and portion rate, feed composition polyamine are 0.5～1.5 part, and described polyamine is meant diamine and above fats polyamine thereof, and general structure is Cn ' Hx (NH
2) m ', n ' is 2～10, m ' is 2～4, m '≤n ', x for the number n of carbon atom ' number of the hydrogen atom that is complementary; Polyamine solvent for use W is 5～8 parts, to dissolve polyamine cmpletely is principle, the effect of solvent W is fully to disperse polyamine, so that the system internal reaction is even, avoiding local crosses strong and influences finished product quality and yield, solvent W is water or other polar solvent, perhaps be wherein two or more composite the forming of compound that comprises water, the methyl alcohol of other polar solvent such as alcohols, ethanol, the acetone of ketone, the dioxane of ethers, tetrahydrofuran (THF), the ethyl acetate of ester class, the methylene dichloride of halogenated hydrocarbon, chloroform, the N of amides, dinethylformamide, the methyl-sulphoxide of sulfone class; The feed composition alkenyl sulphonate is that concentration is 5～9 parts of 20～30% olefin sulfonic acid salt brine solutions, and described alkenyl sulphonate is meant the derivative that contains vinylsulfonate, and with the direct-connected carbon of vinyl double bond be saturated carbon, general structure is Cn-C=C-SO
3Y, n are 0～30, and Cn is fat or alicyclic ring class saturated hydrocarbyl, and Y is the metal ion on the ordinary meaning that constitutes alkenyl sulphonate.Second step head product being removed that used complex solvent S is 8～30 parts in the impurity treatment step, is principle to dissolve head product cmpletely, and complex solvent S is C
1～4Alcohol, C
3～5Ketone or water perhaps are two or more composite the forming of compound wherein.
4, sulfonic acid type hydrophilic chain extender according to claim 3, feed composition polyamine are 0.8～1.2 part, preferred quadrol, propylene diamine, hexanediamine, third triamine or 1,3, the own triamine of 6-; Polyamine solvent for use W is 6～7 parts, and preferably water, ethanol, acetone, ethyl acetate, methyl-sulphoxide or tetrahydrofuran (THF) perhaps are two or more composite the forming of compound wherein; The feed composition alkenyl sulphonate is that concentration is 6～8 parts of 25 ± 2% olefin sulfonic acid salt brine solutions, preferred vinyl sodium sulfonate, methyl ethylene sodium sulfonate, ethyl vinyl sodium sulfonate, propyl ethylene base sodium sulfonate, butyl vinyl sodium sulfonate, cyclohexyl sodium vinyl sulfonate, vinyl sulfonic acid potassium or propyl ethylene base potassium sulfonate, head product removed used complex solvent S is 12～24 parts in the impurity treatment step, preferred alcohol, butanols, acetone or water, wherein two or more compound is composite forms.
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| CN102702037A (en) * | 2012-05-24 | 2012-10-03 | 福建创鑫科技开发有限公司 | Method for preparing ethylenediamino ethyl sulfonate |
| CN102766244A (en) * | 2012-06-27 | 2012-11-07 | 陕西科技大学 | Sulfonate-type hydrophilic chain extender and preparation method thereof |
| CN103665292A (en) * | 2013-11-29 | 2014-03-26 | 陕西科技大学 | Sulfonic acid type water-based polyurethane chain extender and preparation method thereof |
| CN105384900A (en) * | 2015-12-16 | 2016-03-09 | 武汉工程大学 | Method for preparing high solid content anionic aqueous polyurethane dispersion |
| CN106187829A (en) * | 2016-07-29 | 2016-12-07 | 万华化学集团股份有限公司 | A kind of method preparing ethylenediamine base esilate |
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| CN107935892A (en) * | 2017-11-24 | 2018-04-20 | 万华化学集团股份有限公司 | A kind of method for preparing ethylenediamine base ethyl sulfonic acid sodium |
| CN108558711A (en) * | 2018-05-31 | 2018-09-21 | 荆楚理工学院 | A kind of synthetic method of high-purity ethylenediamine base ethanesulfonic acid sodium |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102702037A (en) * | 2012-05-24 | 2012-10-03 | 福建创鑫科技开发有限公司 | Method for preparing ethylenediamino ethyl sulfonate |
| CN102766244A (en) * | 2012-06-27 | 2012-11-07 | 陕西科技大学 | Sulfonate-type hydrophilic chain extender and preparation method thereof |
| CN103665292A (en) * | 2013-11-29 | 2014-03-26 | 陕西科技大学 | Sulfonic acid type water-based polyurethane chain extender and preparation method thereof |
| CN103665292B (en) * | 2013-11-29 | 2015-06-03 | 陕西科技大学 | Sulfonic acid type water-based polyurethane chain extender and preparation method thereof |
| CN105384900A (en) * | 2015-12-16 | 2016-03-09 | 武汉工程大学 | Method for preparing high solid content anionic aqueous polyurethane dispersion |
| CN106187829B (en) * | 2016-07-29 | 2017-12-15 | 万华化学集团股份有限公司 | A kind of method for preparing ethylenediamine base esilate |
| CN106187829A (en) * | 2016-07-29 | 2016-12-07 | 万华化学集团股份有限公司 | A kind of method preparing ethylenediamine base esilate |
| CN107418644A (en) * | 2017-06-02 | 2017-12-01 | 太原理工大学 | A kind of briquette binder preparation method and application |
| CN107418644B (en) * | 2017-06-02 | 2019-11-01 | 太原理工大学 | A kind of application of briquette binder |
| CN107935892A (en) * | 2017-11-24 | 2018-04-20 | 万华化学集团股份有限公司 | A kind of method for preparing ethylenediamine base ethyl sulfonic acid sodium |
| CN107935892B (en) * | 2017-11-24 | 2020-06-02 | 万华化学集团股份有限公司 | Method for preparing ethylenediamine ethanesulfonic acid sodium salt |
| CN108558711A (en) * | 2018-05-31 | 2018-09-21 | 荆楚理工学院 | A kind of synthetic method of high-purity ethylenediamine base ethanesulfonic acid sodium |
| CN110183609A (en) * | 2019-04-23 | 2019-08-30 | 合肥科天水性科技有限责任公司 | A kind of solvent-free polyurethane resin and its application |
| CN110183609B (en) * | 2019-04-23 | 2021-12-24 | 合肥科天水性科技有限责任公司 | Solvent-free polyurethane resin and application thereof |
| CN117430534A (en) * | 2023-11-01 | 2024-01-23 | 张望清 | Sulfamate chain extender, preparation method and application thereof, and preparation method of waterborne polyurethane |
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