CN102585149B - High-solid-content sulfonate type amphoteric waterborne polyurethane and preparation method thereof - Google Patents
High-solid-content sulfonate type amphoteric waterborne polyurethane and preparation method thereof Download PDFInfo
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- CN102585149B CN102585149B CN 201210008478 CN201210008478A CN102585149B CN 102585149 B CN102585149 B CN 102585149B CN 201210008478 CN201210008478 CN 201210008478 CN 201210008478 A CN201210008478 A CN 201210008478A CN 102585149 B CN102585149 B CN 102585149B
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Abstract
The invention discloses high-solid-content sulfonate type amphoteric waterborne polyurethane and a preparation method thereof. The polyurethane is prepared by the following steps of: pre-polymerizing dihydric alcohol and diisocyanate which are polymers; then adding an amphoteric hydrophilic chain extender and/or non-hydrophilic chain extender; and finally carrying out hydro-emulsification. Because anionic hydrophilic groups and cationic hydrophilic groups are further introduced, the obtained waterborne polyurethane has the advantage of simpleness in synthesis, good stability and stronger mechanical property and water and solvent resistance and can be applied to various fields of coatings, adhesive, clothing, bags, leather, biomedicine and the like.
Description
Technical field
The present invention relates to the waterborne polyurethane resin field, relate in particular to sulfonate amphoteric aqueous polyurethane of a kind of high solids content and preparation method thereof.
Background technology
Two waterborne polyurethanes structurally contain positively charged ion and anionic group simultaneously, can store under wider pH scope, have good stability.But also have preferably mechanical property, water-fast solvent resistance, and good biocompatibility, can be used for the fields such as coating, sizing agent, clothes, case and bag, leather goods, biomedicine.
At present, research report about two waterborne polyurethanes is less, and anionic hydrophilic group and the cationic hydrophilic group of two waterborne polyurethanes of report are introduced respectively by two kinds of wetting ability chainextenders, containing the wetting ability chainextender of anionic hydrophilic group and the wetting ability chainextender of cation hydrophilic radical when synthetic needs to add at twice, and the reaction times is longer.The people such as Yuan Jiang such as Nanjing University successively add N, and N-dimethylethanolamine and propane sultone synthesize sulphur ammonium amphotenic polkyurethanes.The people such as the Lan Yunjun of Wenzhou University add N methyldiethanol amine first in base polyurethane prepolymer for use as, by obtaining amphotenic polkyurethanes after the S-WAT sulfonation.Dong's bank of University Of Tianjin is outstanding to wait the people to adopt 3-dimethylamino-1,2-PD and dimethylol propionic acid to prepare amphotenic polkyurethanes.The people such as the Xu Gewen of University of Anhui have prepared sulfonate type two type polyurethanes take N methyldiethanol amine and quadrol base ethyl sulfonic acid sodium as hydrophilic chain extender.
The solid content of the aqueous polyurethane of producing at present mostly is about 30%, because evaporation of water latent heat is higher than the vaporization heat of organic solvent commonly used, exists the shortcoming that time of drying is long, energy consumption is high, can not adapt to the requirement of allegro modern production line.
Summary of the invention
First purpose of the present invention is the shortcoming and defect that exists in order to overcome prior art, and a kind of sulfonate amphoteric aqueous polyurethane that synthesizes efficiently simple and high solids content is provided
Another object of the present invention provides the preparation method of the sulfonate amphoteric aqueous polyurethane of above-mentioned high solids content.
For realizing first purpose of the present invention, technical scheme of the present invention is to comprise following component, in mass fraction:
10 ~ 30 parts of polymer polyatomic alcohols
6 ~ 15 parts of vulcabond
0 ~ 2 part of non-wetting ability chainextender
1 ~ 2 part of wetting ability chainextender
Surplus is water,
Wherein, the structural formula of wetting ability chainextender is:
It is that tertiary amine group and anionic hydrophilic group are sulfonate groups that this wetting ability chainextender has cationic hydrophilic groups simultaneously, a=1 ~ 20 wherein, b=1 ~ 20, c=1 ~ 20, M=metal ion or ammonium ion.
Further arrange is that described polymer polyatomic alcohol is at least a in the pure and mild polyether glycol of polyester polyols, polyester polyol is at least a in the polyethylene glycol adipate, poly adipate succinic acid ester of number-average molecular weight 500 ~ 3000, poly-hexanodioic acid hexylene glycol ester, poly-adipate glycol butanediol ester, polycaprolactone polyol, the polycarbonate polyol, and the polyether glycol number is at least a in the polyoxyethylene glycol, polypropylene glycol, PTMG of number-average molecular weight 500 ~ 3000.
Further arrange is that described vulcabond is at least a in hexamethylene diisocyanate, hydrogenated diphenyl methane diisocyanate, the hydrogenated tolylene diisocyanate.
Further arranging is that described non-wetting ability chainextender is ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol, glycol ether, 1, at least a in the 3-cyclohexanediol.
Further arranging is that described wetting ability chainextender accounts for 2 ~ 12% of total solids quality.
Second purpose of the present invention is achieved through the following technical solutions, and may further comprise the steps, and following umber is in mass fraction:
(1) 10 ~ 30 parts of polymer polyatomic alcohols is joined in the reaction vessel, start stirring, at 110 ℃ ~ 120 ℃ lower vaccum dewatering 2h;
(2) be cooled to 80 ℃ ~ 90 ℃, 6 ~ 15 parts of vulcabond and 0.2 ~ 0.5 part of catalyzer dropped into reaction vessel, at N
2The lower reaction 1 ~ 3h of protection is cooled to 60 ~ 80 ℃ again, adds 0 ~ 2 part of non-wetting ability chainextender, reaction 1 ~ 2h; Perhaps (2') is cooled to 80 ℃ ~ 90 ℃, 6 ~ 15 parts of vulcabond, 0 ~ 2 part of non-wetting ability chainextender and 0.2 ~ 0.5 part of catalyzer dropped into reaction vessel, at N
2The lower reaction 1 ~ 3h of protection obtains performed polymer;
(3) be cooled to 50 ℃ ~ 60 ℃, drop into 1 ~ 2 part of hydrophilic chain extender with 4 ~ 7 parts of solvent I dissolvings, at N
2The lower reaction 2 ~ 4h of protection.Can add 0 ~ 30 part of solvent II dilution according to viscosity in the reaction process, obtain from aggressiveness;
(4) step (3) gained in aggressiveness, add 10 ~ 45 parts of water, carry out emulsification by high-speed stirring, steam and to desolventize behind the II to such an extent that solid content is 50 ± 5% high solids content sulfonic acid type two waterborne polyurethanes,
Described solvent I is at least a in dimethyl formamide, the dimethyl sulfoxide (DMSO), and described solvent II is acetone.
Further arranging is that described catalyzer is dibutyl tin laurate or stannous octoate.
The content of the sulfonate amphoteric aqueous polyurethane reduction water of high solids content provided by the present invention namely improves solid content (〉=50%) and can effectively reduce the moisture evaporation load, shorten film forming and time of drying.The advantage such as simultaneously, high-solid content water-based polyurethane has also that plant factor is high, transportation cost and unit product energy expenditure are low.
The present invention compared with prior art has advantages of following several respects:
(1) has simultaneously anionic hydrophilic group and cationic hydrophilic groups on the wetting ability chainextender that adopts, therefore when synthetic two waterborne polyurethane, need not substep and add anionic hydrophilic chainextender and cationic hydrophilic chainextender, two kinds of hydrophilic radicals have been introduced by disposable, reduce synthesis step, shortened generated time.
(2) the wetting ability chainextender that adopts contains the primary hydroxyl of two isoreactivities, has suitable reactive behavior, the control that is conducive to react; Utilize simultaneously the space arm effect of a plurality of methylene radical, give full play to the characteristics of sulfonate groups.Gentle, the easy control of reaction conditions when the preparation high-solid content water-based polyurethane, the aqueous polyurethane of acquisition has satisfactory stability.
(3) combine cationic and advantage anion-type water-thinned polyurethane, two waterborne polyurethanes of preparation have good mechanical property and water tolerance preferably.
(4) high-solid content water-based polyurethane has short, the advantage such as energy consumption is low, plant factor is high, transportation cost is low time of drying.
Below in conjunction with embodiment the present invention is done further introduction.
Embodiment
Below by embodiment the present invention is carried out concrete description; only be used for the present invention is further specified; can not be interpreted as the restriction to protection domain of the present invention, the technician in this field can make some nonessential improvement and adjustment to the present invention according to the content of foregoing invention.
Embodiment 1
With N, N-(2-hydroxyethyl)-2-aminoethyl sulfonic acid sodium (being a=b=c=2, M=Na) is as the wetting ability chainextender.
With the poly adipate succinic acid ester of 20g number average molecular mass 2000 at 110 ℃ of lower vaccum dewatering 2h.Be cooled to 85 ℃, N
2Lower 7.6g isophorone diisocyanate and the 0.2g dibutyl tin laurate reaction 1.5h of adding of protection; be cooled to 80 ℃; add 0.64g 1; 4-butyleneglycol reaction 1h; be cooled to again 60 ℃, add the N that 1.44g has been dissolved in the 5mL methyl-sulphoxide, N-(2-hydroxyethyl)-2-aminoethyl sulfonic acid sodium reaction 3h; in order to reduce system viscosity, can add the 15mL acetone diluted.Be cooled to 40 ℃ behind the sufficient reacting, add distilled water 25mL, with strong shearing force emulsification 30min, remove acetone under reduced pressure, get solid content and be about 50%, the translucent polyaminoester emulsion of outward appearance.
Embodiment 2
With N, the amino fourth sodium sulfonate of N-(2-hydroxyethyl)-2-(being a=b=2, c=4, M=Na) is as the wetting ability chainextender.
With the polyoxyethylene glycol of 20g number average molecular mass 2000 at 110 ℃ of lower vaccum dewatering 2h.Be cooled to 80 ℃, N
2Lower 7.3g isophorone diisocyanate and the 0.2g dibutyl tin laurate reaction 2h of adding of protection; add again 0.60g 1; 4-butyleneglycol reaction 1h; be cooled to 60 ℃; adding 1.50g has been dissolved in the N of 5mL methyl-sulphoxide; the amino fourth sodium sulfonate reaction of N-(2-hydroxyethyl)-2-3h in order to reduce system viscosity, can add the 20mL acetone diluted.Be cooled to 40 ℃ behind the sufficient reacting, add distilled water 25mL, with strong shearing force emulsification 30min, remove acetone under reduced pressure, get solid content and be about 50% polyaminoester emulsion.
Embodiment 3
With N, N-(2-hydroxyethyl)-2-aminoethyl sulfonic acid lithium (being a=b=c=2, M=Li) is as the wetting ability chainextender.
With the PTMG of 20g number average molecular mass 2000 at 110 ℃ of lower vaccum dewatering 2h.Be cooled to 80 ℃, N
2Lower 6.0g hexamethylene diisocyanate and the 0.2g dibutyl tin laurate reaction 2h of adding of protection; add again 0.80g 1; 4-butyleneglycol reaction 1h; be cooled to 60 ℃; adding 1.4g has been dissolved in the N of 4mL methyl-sulphoxide; the amino fourth Sulfonic Lithium reaction of N-(2-hydroxyethyl)-2-2.5h in order to reduce system viscosity, can add the 20mL acetone diluted.Be cooled to 40 ℃ behind the sufficient reacting, add distilled water 25mL, with strong shearing force emulsification 30min, remove acetone under reduced pressure, get solid content and be about 50% polyaminoester emulsion.
Embodiment 4
With N, N-(2-hydroxyethyl)-2-aminoethyl sulfonic acid lithium (being a=b=c=2, M=Li) is as the wetting ability chainextender.
With the poly adipate succinic acid ester of 20g number average molecular mass 2000 at 110 ℃ of lower vaccum dewatering 2h.Be cooled to 80 ℃, N
2Lower 6.5g hexamethylene diisocyanate, the 0.60g 1 of adding of protection; 4-butyleneglycol and 0.2g dibutyl tin laurate reaction 2h; be cooled to again 60 ℃; add again 1.35g and be dissolved in the N of 4mL methyl-sulphoxide; N-(2-hydroxyethyl)-2-aminoethyl sulfonic acid lithium reaction 3h; in order to reduce system viscosity, can add the 15mL acetone diluted.Be cooled to 40 ℃ behind the sufficient reacting, add distilled water 25mL, with strong shearing force emulsification 30min, remove acetone under reduced pressure, get solid content and be about 50% oyster white aqueous polyurethane emulsion.
Embodiment 5
With N, the amino fourth sodium sulfonate of N-(2-hydroxyethyl)-2-(being a=b=2, c=4, M=Na) is as the wetting ability chainextender.
With the poly adipate succinic acid ester of 30g number average molecular mass 3000 at 110 ℃ of lower vaccum dewatering 2h.Be cooled to 80 ℃, N
2Lower 10.0g isophorone diisocyanate, the 0.65g 1 of adding of protection; 4-butyleneglycol and 0.2g dibutyl tin laurate reaction 2h; be cooled to again 60 ℃; add again 1.6g and be dissolved in the N of 6mL methyl-sulphoxide; the amino fourth sodium sulfonate reaction of N-(2-hydroxyethyl)-2-4h; in order to reduce system viscosity, can add the 15mL acetone diluted.Be cooled to 40 ℃ behind the sufficient reacting, add distilled water 35mL, with strong shearing force emulsification 30min, remove acetone under reduced pressure, get solid content and be about 50% aqueous polyurethane emulsion.
Claims (7)
1. the sulfonate amphoteric aqueous polyurethane of a high solids content is characterized in that comprising following component, in mass fraction:
10 ~ 30 parts of polymer polyatomic alcohols
6 ~ 15 parts of vulcabond
0 ~ 2 part of non-wetting ability chainextender
1 ~ 2 part of wetting ability chainextender
Surplus is water,
Wherein, the structural formula of wetting ability chainextender is:
It is that tertiary amine group and anionic hydrophilic group are sulfonate groups that this wetting ability chainextender has cationic hydrophilic groups simultaneously, a=1 ~ 20 wherein, b=1 ~ 20, c=1 ~ 20, M=metal ion or ammonium ion.
2. the sulfonate amphoteric aqueous polyurethane of a kind of high solids content according to claim 1, it is characterized in that: described polymer polyatomic alcohol is at least a in the pure and mild polyether glycol of polyester polyols, polyester polyol is the polyethylene glycol adipate of number-average molecular weight 500 ~ 3000, poly adipate succinic acid ester, poly-hexanodioic acid hexylene glycol ester, poly-adipate glycol butanediol ester, polycaprolactone polyol, at least a in the polycarbonate polyol, the polyether glycol number is the polyoxyethylene glycol of number-average molecular weight 500 ~ 3000, polypropylene glycol, at least a in the PTMG.
3. the sulfonate amphoteric aqueous polyurethane of a kind of high solids content according to claim 1 is characterized in that: described vulcabond is at least a in hexamethylene diisocyanate, hydrogenated diphenyl methane diisocyanate, the hydrogenated tolylene diisocyanate.
4. the sulfonate amphoteric aqueous polyurethane of a kind of high solids content according to claim 1, it is characterized in that: described non-wetting ability chainextender is ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol, glycol ether, 1, at least a in the 3-cyclohexanediol.
5. the sulfonate amphoteric aqueous polyurethane of a kind of high solids content according to claim 1, it is characterized in that: described wetting ability chainextender accounts for 2 ~ 12% of total solids quality.
6. a preparation method who prepares the sulfonate amphoteric aqueous polyurethane of high solids content as claimed in claim 1 is characterized in that may further comprise the steps, and following umber is in mass fraction:
(1) 10 ~ 30 parts of polymer polyatomic alcohols is joined in the reaction vessel, start stirring, at 110 ℃ ~ 120 ℃ lower vaccum dewatering 2h;
(2) be cooled to 80 ℃ ~ 90 ℃, 6 ~ 15 parts of vulcabond and 0.2 ~ 0.5 part of catalyzer dropped into reaction vessel, at N
2The lower reaction 1 ~ 3h of protection is cooled to 60 ~ 80 ℃ again, adds 0 ~ 2 part of non-wetting ability chainextender, reaction 1 ~ 2h; Perhaps (2') is cooled to 80 ℃ ~ 90 ℃, 6 ~ 15 parts of vulcabond, 0 ~ 2 part of non-wetting ability chainextender and 0.2 ~ 0.5 part of catalyzer dropped into reaction vessel, at N
2The lower reaction 1 ~ 3h of protection obtains performed polymer;
(3) be cooled to 50 ℃ ~ 60 ℃, drop into 1 ~ 2 part of hydrophilic chain extender with 4 ~ 7 parts of solvent I dissolvings, at N
2The lower reaction 2 ~ 4h of protection; Add 0 ~ 30 part of solvent II dilution according to viscosity in the reaction process, obtain from aggressiveness;
(4) step (3) gained in aggressiveness, add 10 ~ 45 parts of water, carry out emulsification by high-speed stirring, steam and to desolventize behind the II to such an extent that solid content is 50 ± 5% high solids content sulfonic acid type two waterborne polyurethanes,
Described solvent I is at least a in dimethyl formamide, the dimethyl sulfoxide (DMSO), and described solvent II is acetone.
7. the preparation method of the sulfonate amphoteric aqueous polyurethane of a kind of high solids content according to claim 6, it is characterized in that: described catalyzer is dibutyl tin laurate or stannous octoate.
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| CN101638468A (en) * | 2009-09-04 | 2010-02-03 | 安徽大学 | Preparation method of sulfonate amphoteric polyurethane emulsion |
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