CN102219886B - Preparation method of aqueous polyurethane emulsion with high solid content - Google Patents
Preparation method of aqueous polyurethane emulsion with high solid content Download PDFInfo
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Abstract
The invention relates to a preparation method of an aqueous polyurethane emulsion with a high solid content. The method comprises the following steps: first, adding polymer polyol, polyisocyanates, catalyst and chain extender into a reactor according to certain steps, and controlling hydrophilic groups to distribute on molecular chain ends; then adding polyisocyanates to form a performed polymer terminated with an NCO group; then reducing system temperature, adding a neutralizer for neutralization, adding deionized water, and stirring with high speed to carry out water dispersion; at last, adding a post chain extender to carry out chain extension in water; removing the solvents under a reduced pressure after reaction to obtain the aqueous polyurethane emulsion. According to the invention, hydrophilic efficiency of the hydrophilic groups is raised to lower intake amount of hydrophilic groups, and a small amount of solvents are added in the reaction to lower a system viscosity. The aqueous polyurethane emulsion prepared by the invention has characteristics of high solid content, low viscosity, good water resistance and stabile storage, and can be used in industries of paint, adhesive, leather finishing and fabric arrangement, etc.
Description
Technical field
The present invention relates to the Synthesis of Waterborne Polyurethane method, relate more specifically to a kind of preparation method of high solid content aqueous polyurethane emulsion.
Background technology
The solvent borne polyurethane product is widely used in fields such as coating, sizing agent with its superior performance.Evaporate in the atmosphere but have a large amount of volatile organic compounds (VOC) in its film process, cause environmental pollution, therefore develop the attention that environmentally friendly polyurethane products receive people day by day.Aqueous polyurethane emulsion replaces the dispersion medium of traditional organic solvent as system with water; Low temperature resistant, the premium properties such as snappiness good, bonding strength is big that not only have solvent borne polyurethane; And can significantly reduce and even finally eliminate the pollution of VOC fully environment, have do not fire, advantages such as smell is little, energy-conserving and environment-protective, easy modification easy to operate.
The POLYMETHYLENE POLYPHENYLISOCYANATE that is used to prepare aqueous polyurethane emulsion comprises two big types of aromatic series and aliphatics.Because the NCO activity on the aromatic isocyanate is higher, be prone to and water generation chain extending reaction in the water-dispersion process, influence each item performance of emulsification dispersion and product, the product light stability is poor simultaneously, xanthochromia easily, therefore application is restricted.NCO group activity on aliphatics (the comprising alicyclic) POLYMETHYLENE POLYPHENYLISOCYANATE is lower, can of short duration stable existence in water, favourable to the water-dispersion process, and its product good light stability, therefore xanthochromia is not widely used in the aqueous polyurethane field.
At present, preparation technology's broadly similar of aliphatics aqueous polyurethane performed polymer, its basic procedure is: polymer polyatomic alcohol at first reacts with POLYMETHYLENE POLYPHENYLISOCYANATE, adds wetting ability chainextender and small molecule chain extender afterwards.Above-mentioned technological operation is simple; But whole process lacks obvious conscious control; The final performance that embodies of product also is difficult to make an explanation and contrast from its microtexture; And the regularity of performed polymer molecular chain is relatively poor, and particularly the introducing quantity of hydrophilic radical produces very big influence to the product over-all properties.Hydrophilic radical was introduced the stability that the major general directly influences product, and the hydrophilic radical introducing too much will influence the solid content of product and the water tolerance of filming.Only under the prerequisite that guarantees the product storage stability, the introducing amount that reduces hydrophilic radical could further improve the overall performance of product.
In addition, some aqueous polyurethane product has used a large amount of high boiling points and expensive solvent in the preparation process, like (Nanda A K such as n-formyl sarcolysine base pyrrolidone; Wicks D A; Madbouly S A, et al. J Appl Polym Sci, 2005; 98 (6): 2514-2520), almost have no smell in preparation process relative environmental protection and the film process though the introducing of this kind solvent makes; But because its boiling point is higher, evaporation rate is very slow in film process, and particularly aspect the interior trim finishing, the organic solvent often low than those boiling points, that smell is big is the health of harm users more.
Summary of the invention
For addressing the above problem, the present invention provides a kind of preparation method of high solid content aqueous polyurethane emulsion on the basis that guarantees product stability.This method makes the two ends of the position of hydrophilic radical at the performed polymer molecular chain; Farthest improve the hydrophilic efficient of hydrophilic radical; Reduce the introducing amount of hydrophilic radical as far as possible, reduced boiling point height and expensive organic solvent simultaneously and prepared the consumption in the process, reduced production cost at performed polymer; And the environmental protection more of its product, meet the human health demand.
The present invention implements through following technical scheme:
(A) polymer polyatomic alcohol, POLYMETHYLENE POLYPHENYLISOCYANATE (I) and little solvent are added in the reactor drum, stir under 60 ℃, add catalyzer then, 60-90 ℃ of reaction 1-2 hour down;
(B) add small molecule chain extender and little solvent, 60-90 ℃ was reacted 1-2 hour down;
(C) add wetting ability chainextender and little solvent, 60-90 ℃ of following reaction 1-2 hour;
(D) add POLYMETHYLENE POLYPHENYLISOCYANATE (II), 60-90 ℃ was reacted 1-3 hour down, forms the base polyurethane prepolymer for use as of NCO group end capping;
(E) be cooled to 45-70 ℃, add the neutralizing agent neutralization, add deionized water then, high-speed stirring is carried out water-dispersion;
(F) add the back chainextender, constant temperature stirred 1-2 hour, and decompression removes solvent, promptly gets aqueous polyurethane emulsion.
Wherein, step (A) was reacted 1.5 hours down for preferred 70 ℃, and (B) preferred 70 ℃ were reacted 1.5 hours down; (C) preferred 75 ℃ were reacted 1.5 hours down; (D) preferred 85 ℃ were reacted 2 hours down, (E) preferably were cooled to 60 ℃, and (F) preferred constant temperature stirred 1.5 hours.
In the above-mentioned technology, the mass fraction that base polyurethane prepolymer for use as prepares the raw material consumption in the process is: 55 parts-80 parts of polymer polyatomic alcohols; POLYMETHYLENE POLYPHENYLISOCYANATE (I) and (II) 15 parts-40 parts; 1 part-10 parts of small molecule chain extenders; 3 parts-5 parts of wetting ability chainextenders; 0.01 part-0.1 part of catalyzer; 30% of the adding total amount≤performed polymer quality of solvent.
Above-mentioned POLYMETHYLENE POLYPHENYLISOCYANATE (I) and POLYMETHYLENE POLYPHENYLISOCYANATE (II) can for: 4,4 '-dicyclohexyl methane diisocyanate (H
12MDI), isophorone diisocyanate (IPDI), 1,6-hexane diisocyanate (HDI) and xylylene diisocyanate (XDI) and compsn thereof;
Above-mentioned polymer polyatomic alcohol can be polyester polyol, polyether glycol and compsn thereof;
Above-mentioned small molecule chain extender can be terepthaloyl moietie, 1,4-butyleneglycol, glycol ether, 1,6-pinakon, TriMethylolPropane(TMP) and compsn thereof;
Above-mentioned wetting ability chainextender can be dimethylol propionic acid (DMPA), dimethylolpropionic acid (DMBA) and compsn thereof;
Above-mentioned catalyzer can be dibutyl tin laurate, stannous octoate and compsn thereof;
Above-mentioned solvent can be acetone, butanone, N, dinethylformamide, N-Methyl pyrrolidone and compsn thereof;
Above-mentioned neutralizing agent can be triethylamine, trolamine and compsn thereof;
Above-mentioned back chainextender can be quadrol, tetramethylenediamine, isophorone diamine, hexanediamine and compsn thereof;
In the above-mentioned technology, the mol ratio of NCO/OH functional group is 1.0-2.0 before the aquation, in the back chain extension process behind the NCO/ chainextender functional group (like OH or NH
2) mol ratio be 1.1-2.0;
In the above-mentioned technology, the mol ratio of wetting ability chainextender and neutralizing agent is 0.9-1.1;
Do not use shielding gas such as nitrogen in the above-mentioned technological process.
The present invention compared with prior art has following advantage:
1, segmented structure is regular and farthest improve the hydrophilic efficient of hydrophilic radical
The aqueous polyurethane emulsion that technological process according to the invention is prepared, the position of its hydrophilic radical near end capped NCO group, have farthest improved the efficient of hydrophilic radical at the two ends of performed polymer molecular chain; Owing to adopt the method for fractional steps to add each component, entire reaction course is controlled simultaneously, and performed polymer molecular chain segmented structure is regular relatively, and the product over-all properties is improved.
2, the prescription regulation range is big, easy to operate, energy-conserving and environment-protective
Technology according to the invention; Applied widely; Only need reaction conditions is finely tuned; Can obtain the aqueous polyurethane emulsion product of various different performance requirements through changing prescription, and characteristics such as viscosity is low, water-tolerant, storage-stable are arranged, can be used for industries such as coating, sizing agent, leather finish, textile finishing.
And the preparation process need not the high boiling solvent of a large amount of high prices, only adopts a small amount of lower boiling solvent, and solvent load is controlled at below 30% of performed polymer quality, and it is easy that reaction finishes the back solvent removal, and it is convenient to reclaim in the industrial production, compliance with environmental protection requirements.
In system, add little amount of catalyst, the temperature of reaction of preparation process can be controlled in lower scope, and the reaction times also shortens a lot than the catalyst-free system, meet energy-conservation requirement.
3, solid content is higher
The solid content of the aqueous polyurethane emulsion finished product of effective sale is basically at 30-35% on the market.Preparation technology according to the invention under the prerequisite that guarantees product performance, can make the aqueous polyurethane emulsion of solid content at 35-45%, has saved transportation cost.
Embodiment
Following instance will further specify the present invention, be not in order to limit scope of the present invention.
Embodiment 1
PBA (40g), IPDI (9.18g) and acetone (account for performed polymer quality 4%) are added in the 500ml reactor drum, stir under 60 ℃, add catalyzer then, be warming up to 70 ℃ of reactions 1.5 hours; In system, add DEG (1.07g) and acetone (accounting for the 6-8% of performed polymer quality), isothermal reaction 1.5 hours; In system, add the DMPA (2.63g) that is dissolved in DMF, be warming up to 75 ℃ after stirring, constant temperature 1.5 hours; Add IPDI (4.59g), be warming up to 85 ℃, constant temperature 2 hours; Be cooled to 60 ℃, add TEA (1.94g) neutralization, add deionized water again and carry out water-dispersion, mixing speed is 900-1500r/min; Add massfraction and be 20% ethylenediamine solution (2.57g) and carry out back chain extension, constant temperature stirred after 1.5 hours, reduced pressure and removed solvent, promptly got aqueous polyurethane emulsion.The product median size is 95nm, solid content 40%, and viscosity is lower than 300mPa.s, and outward appearance is translucent dispersion liquid, and glued membrane 72h water-intake rate is 7.0%.
Comparative Examples (1)
In the 500ml reactor drum, after the PBA of homogenous quantities, DEG, DMPA, an amount of DMF and acetone stir in the adding instance 1, under 60 ℃ of conditions, add IPDI (13.77g); After stirring, add catalyzer, after reaction half a hour; Be warming up to 75 ℃, react after 4 hours, be cooled to 60 ℃; Add TEA (1.94g), stir after 20-30 minute, add deionized water and carry out water-dispersion; Mixing speed is 900-1500r/min, adds massfraction after the water-dispersion and is 20% ethylenediamine solution (2.57g) and carry out back chain extension, constant temperature stirring 1.5 hours.The product median size is 120nm, solid content 40%, and viscosity is lower than 300mpa.s, and outward appearance is the oyster white dispersion liquid.
Can find out from the median size result of above-mentioned two examples; Under the situation of using complete equivalent material; Obviously the particle diameter than Comparative Examples is little for product cut size among the embodiment 1, and promptly under the situation of equal storage stability and particle diameter requirement, the usage quantity of DMPA required for the present invention will be less than traditional technology; When reducing cost, improved the water resistance of product.
Comparative Examples (2)
Adopt technology in the Comparative Examples (1), through improving the DMPA add-on to 3.19g, obtain the emulsion with embodiment 1 same particle size and similar outward appearance, measuring its glued membrane 72h water-intake rate is 9.8%.
Embodiment 2
PBA (40g), IPDI (9.18g) and acetone (account for performed polymer quality 4%) are added in the 500ml reactor drum, stir under 60 ℃, add catalyzer then, be warming up to 70 ℃ of reactions 1.5 hours; In system, add BDO (0.95g) and acetone (accounting for the 6-8% of performed polymer quality), isothermal reaction 1.5 hours; In system, add the DMPA (2.21g) that is dissolved in DMF, be warming up to 75 ℃ after stirring, constant temperature 1.5 hours; Add H
12MDI (4.33g) is warming up to 85 ℃, constant temperature 2 hours; Be cooled to 60 ℃, add TEA (1.59g) neutralization, add deionized water again and carry out water-dispersion, mixing speed is 900-1500r/min; Add massfraction and be 20% ethylenediamine solution (2.11g) and carry out back chain extension, constant temperature stirred after 1.5 hours, and reducing pressure removes solvent.The median size of gained aqueous polyurethane emulsion product is 200nm, and solid content 41%, centrefuge experiment show, but product stable storage 6 months.
Comparative Examples (3)
In the 500ml reactor drum, after the PBA of homogenous quantities, DEG, DMPA, an amount of DMF and acetone stir among the adding embodiment 1, under 60 ℃ of conditions, add IPDI (9.18g) and H
12MDI (4.33g) after stirring, adds catalyzer, after reaction half a hour; Be warming up to 75 ℃, react after 4 hours, be cooled to 60 ℃; Add TEA (1.94g), stir after 20-30 minute, add deionized water and carry out water-dispersion; Mixing speed is 900-1500r/min, adds massfraction after the water-dispersion and is 20% ethylenediamine solution (2.57g) and carry out back chain extension, constant temperature stirring 1.5 hours.The product median size is 275nm, solid content 41%, and the product storage layering occurred after 7 days.
Embodiment 3
With PNA (40g), H
12MDI (10.48g) and acetone (account for performed polymer quality 4%) add in the 500ml reactor drum, stir under 60 ℃, add catalyzer then, are warming up to 70 ℃ of reactions 1.5 hours; In system, add BDO (0.77g) and acetone (accounting for the 6-8% of performed polymer quality), isothermal reaction 1.5 hours; In system, add the DMPA (3.03g) that is dissolved in DMF, be warming up to 75 ℃ after stirring, constant temperature 1.5 hours; Add XDI (4.33g), be warming up to 85 ℃, constant temperature 2 hours; Be cooled to 60 ℃, add TEA (2.21g) neutralization, add deionized water again and carry out water-dispersion, mixing speed is 900-1500r/min; Add massfraction and be 20% ethylenediamine solution (3.46g) and carry out back chain extension, constant temperature stirred after 1.5 hours, reduced pressure and removed solvent, promptly got aqueous polyurethane emulsion, solid content 39%.
Embodiment 4
PHA (40g), IPDI (9.18g) and acetone (account for performed polymer quality 4%) are added in the 500ml reactor drum, stir under 60 ℃, add catalyzer then, be warming up to 70 ℃ of reactions 1.5 hours; In system, add DEG (0.58g) and acetone (accounting for the 6-8% of performed polymer quality), isothermal reaction 1.5 hours; In system, add the DMPA (3.93g) that is dissolved in DMF, be warming up to 75 ℃ after stirring, constant temperature 1.5 hours; Add XDI (5.45g), be warming up to 85 ℃, constant temperature 2 hours; Be cooled to 60 ℃, add TEA (2.79g) neutralization, add deionized water again and carry out water-dispersion, mixing speed is 900-1500r/min; Add massfraction and be 20% ethylenediamine solution (4.36g) and carry out back chain extension, constant temperature stirred after 1.5 hours, reduced pressure and removed solvent, promptly got aqueous polyurethane emulsion, solid content 40%.
Embodiment 5
PHA (40g), IPDI (9.18g) and acetone (account for performed polymer quality 4%) are added in the 500ml reactor drum, stir under 60 ℃, add catalyzer then, be warming up to 80 ℃ of reactions 1 hour; In system, add DEG (0.58g) and acetone (accounting for the 6-8% of performed polymer quality), isothermal reaction 1 hour; In system, add the DMPA (3.93g) that is dissolved in DMF, be warming up to 85 ℃ after stirring, constant temperature 1 hour; Add XDI (5.45g), be warming up to 90 ℃, constant temperature 1.5 hours; Be cooled to 45 ℃, add TEA (2.79g) neutralization, add deionized water again and carry out water-dispersion, mixing speed is 900-1500r/min; Add massfraction and be 20% ethylenediamine solution (4.36g) and carry out back chain extension, constant temperature stirred after 2 hours, reduced pressure and removed solvent, promptly got aqueous polyurethane emulsion, solid content 38%.
The above is merely preferred embodiment of the present invention, and all equalizations of doing according to claim of the present invention change and modify, and all should belong to covering scope of the present invention.
Claims (10)
1. the preparation method of a high solid content aqueous polyurethane emulsion, it is characterized in that: said preparation method comprises the steps to carry out successively:
(A) polymer polyatomic alcohol, POLYMETHYLENE POLYPHENYLISOCYANATE (I) and solvent are added in the reactor drum, stir under 60 ℃, add catalyzer then, 60-90 ℃ of reaction 1-2 hour down;
(B) add small molecule chain extender and solvent, 60-90 ℃ was reacted 1-2 hour down; Said small molecule chain extender is selected from terepthaloyl moietie, 1,4-butyleneglycol, glycol ether, 1,6-pinakon and TriMethylolPropane(TMP);
(C) add wetting ability chainextender and solvent, 60-90 ℃ was reacted 1-2 hour down; Said wetting ability chainextender is selected from dimethylol propionic acid, dimethylolpropionic acid;
(D) add POLYMETHYLENE POLYPHENYLISOCYANATE (II), 60-90 ℃ was reacted 1-3 hour down, forms the base polyurethane prepolymer for use as of NCO group end capping;
(E) base polyurethane prepolymer for use as is cooled to 45-70 ℃, adds the neutralizing agent neutralization, add deionized water then, high-speed stirring is carried out water-dispersion;
(F) add the back chainextender, constant temperature stirred 1-2 hour, and decompression removes solvent, promptly gets described high solid content aqueous polyurethane emulsion; Said back chainextender is selected from quadrol, tetramethylenediamine, isophorone diamine and hexanediamine.
2. the preparation method of a kind of high solid content aqueous polyurethane emulsion according to claim 1 is characterized in that: reacted 1.5 hours under preferred 70 ℃ in the said step (B); Preferred 75 ℃ were reacted 1.5 hours down in the said step (C); Preferred 85 ℃ were reacted 2 hours down in the said step (D); Preferably be cooled to 60 ℃ in the said step (E); The preferred stirring 1.5 hours in the said step (F).
3. the preparation method of a kind of high solid content aqueous polyurethane emulsion according to claim 1, it is characterized in that: the mass fraction that said base polyurethane prepolymer for use as prepares the raw material consumption in the process is: 55 parts-80 parts of polymer polyatomic alcohols; POLYMETHYLENE POLYPHENYLISOCYANATE (I) and (II) 15 parts-40 parts; 1 part-10 parts of small molecule chain extenders; 3 parts-5 parts of wetting ability chainextenders; 0.01 part-0.1 part of catalyzer.
4. the preparation method of a kind of high solid content aqueous polyurethane emulsion according to claim 1, it is characterized in that: said polymer polyatomic alcohol is selected from polyester polyol, polyether glycol; Said POLYMETHYLENE POLYPHENYLISOCYANATE (I) and POLYMETHYLENE POLYPHENYLISOCYANATE (II) all are selected from 4,4 '-dicyclohexyl methane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate; Said catalyzer is selected from dibutyl tin laurate, stannous octoate.
5. the preparation method of a kind of high solid content aqueous polyurethane emulsion according to claim 1 is characterized in that: the interpolation total amount of solvent is not more than 30% of base polyurethane prepolymer for use as quality among said step (A), (B), (C).
6. the preparation method of a kind of high solid content aqueous polyurethane emulsion according to claim 5, it is characterized in that: said solvent is selected from acetone, butanone, N, dinethylformamide and N-Methyl pyrrolidone.
7. the preparation method of a kind of high solid content aqueous polyurethane emulsion according to claim 1, it is characterized in that: said neutralizing agent is selected from triethylamine, trolamine; The mol ratio of said wetting ability chainextender and neutralizing agent is 0.9-1.1.
8. the preparation method of a kind of high solid content aqueous polyurethane emulsion according to claim 1 is characterized in that: in the chain extension process of said back behind the NCO/ mol ratio of chainextender amido functional group be 1.1-2.0.
9. the preparation method of a kind of high solid content aqueous polyurethane emulsion according to claim 1 is characterized in that: the rotating speed that said step (E) high speed stirs is 750r/min-3000r/min.
10. the preparation method of a kind of high solid content aqueous polyurethane emulsion according to claim 9 is characterized in that: the preferred rotating speed that said step (E) high speed stirs is 900-1500r/min.
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