WO2019080700A1 - 一种环保聚氨酯固化剂及其制备方法和应用 - Google Patents

一种环保聚氨酯固化剂及其制备方法和应用

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Publication number
WO2019080700A1
WO2019080700A1 PCT/CN2018/108943 CN2018108943W WO2019080700A1 WO 2019080700 A1 WO2019080700 A1 WO 2019080700A1 CN 2018108943 W CN2018108943 W CN 2018108943W WO 2019080700 A1 WO2019080700 A1 WO 2019080700A1
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WO
WIPO (PCT)
Prior art keywords
curing agent
environmentally
polyurethane curing
small molecule
friendly polyurethane
Prior art date
Application number
PCT/CN2018/108943
Other languages
English (en)
French (fr)
Inventor
周建明
何绍群
刘晓鸿
Original Assignee
佛山市精信汇明科技有限公司
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Filing date
Publication date
Application filed by 佛山市精信汇明科技有限公司 filed Critical 佛山市精信汇明科技有限公司
Publication of WO2019080700A1 publication Critical patent/WO2019080700A1/zh

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes

Definitions

  • the invention relates to an environmentally-friendly polyurethane curing agent and a preparation method and application thereof.
  • Two-component polyurethane coatings and adhesives have the advantages of low film forming temperature, strong adhesion, high abrasion resistance, high hardness, solvent resistance and water resistance. They are used in large quantities in the market, and VOCs with national standards. The enforcement of restrictions on content has increased. Many companies have made a lot of efforts in developing high-performance and environmentally-friendly products: one is to minimize the amount of solvent used, and the other is to reduce the content of free diisocyanate monomer in the polyurethane curing agent. A waterborne hydroxy resin and a curing agent for low residual TDI and HDI monomers.
  • the currently water-dispersible curing agents are basically made of aliphatic isocyanates (HDI, IPDI). Their functional group NCO activity is relatively low, and the reaction rate with water is slow. When mixed with aqueous hydroxy resin, it has room temperature. 4 ⁇ 6 hours of use, the solution over the use period will slowly solidify and can only be discarded.
  • the baking paint industry and the high-temperature rubber industry are still solvent-based products, and the curing temperature is as high as 160 ° C or higher, that is, low-temperature baking paint.
  • the curing temperature also reached above 120 ° C, and the baking time is still relatively long.
  • the dual pressures of environmental protection and energy consumption are forcing such companies to be on the verge of bankruptcy. Therefore, the demand for water-based closed low-temperature curing agents is growing.
  • CN103554430A discloses blocking an isocyanate trimer with methyl ethyl ketone oxime to obtain compound A, reacting diisocyanate with polyethylene glycol monomethyl ether to obtain emulsifier B, mixing A and B, and then adding deionized water to obtain a blocked polyisocyanate.
  • CN104130375A discloses forming a diisocyanate into a semi-blocking substance, wherein the isocyanate group in the semi-block is reacted with a hydroxyl group of the hydroxy polyacrylate to obtain a polyacrylate-modified aqueous blocked isocyanate prepolymer, which is neutralized with an amine and emulsified with water.
  • CN101649036A discloses the reaction of a diisocyanate monomer with a diol and a triol to form a branched polyisocyanate, which is extended by a hydrophilic chain extender, then the NCO is blocked, and finally the amine is neutralized to form a salt.
  • the type of curing agent has the advantage of being hydrolyzable at normal temperature, and the disadvantage is that it can only be used for paving of sports venues.
  • the object of the present invention is to provide an environmentally-friendly polyurethane curing agent which can coexist with a hydroxy resin at a room temperature for a long period of time and can be cured by heating, and provides a method for preparing and applying an environmentally-friendly polyurethane curing agent.
  • An environmentally friendly polyurethane curing agent comprising a blocked polyisocyanate prepolymer containing a sulfonic acid group; the blocked polyisocyanate prepolymer containing a sulfonic acid group is a polyisocyanate prepolymer, a diisocyanate and a chain extender
  • the chain extension reaction is carried out, and the terminal isocyanate group is blocked by adding a blocking agent; the molar ratio of the isocyanate group of the polyisocyanate prepolymer to the isocyanate group of the diisocyanate is 1: (0.7 ⁇ 1.2); the chain extender is a small molecule sulfonate.
  • the salt of the acid salt diol, the small molecule sulfonate diol has a molecular weight of 350 to 1000, and the molar ratio of the hydroxyl group of the small molecule sulfonate diol to the isocyanate group of the diisocyanate is 1: (1.5 ⁇ 3);
  • the agent is a hydrogen-containing compound, and the molar ratio of the active hydrogen of the hydrogen-containing compound to the blocked isocyanate group is (1.05 to 1.2):1.
  • the polyisocyanate prepolymer is at least one of a prepolymer of a diisocyanate and a triol, a TDI trimer, an MDI trimer, an HDI trimer, an IPDI trimer, an HDI biuret, and a PAPI.
  • the diisocyanate is at least one of MDI, HMDI, TDI, HDI, and IPDI.
  • the small molecule sulfonate diol is obtained by esterification of a small molecule diol with a dicarboxy sulfonate.
  • the molar ratio of the hydroxyl group of the small molecule diol to the carboxyl group of the dicarboxy sulfonate is (2 ⁇ 3): 1; the small molecule diol is a diol having a molecular weight of less than 300, and the dicarboxy sulfonate is an alkali metal dicarboxy sulfonate.
  • Hydrogen-containing compounds are methanol, ethanol, isopropanol, tert-butanol, propylene glycol monomethyl ether, methyl ethyl ketone oxime, acetone oxime, methyl isobutyl hydrazine, imidazole, 2-methylpyrazole, 3,5-dimethyl Pyrazole, 3-methyl-5-ethylpyrazole, 3-ethyl-5-propylpyrazole, acetylacetone, ethyl acetoacetate, diethyl malonate, caprolactam, phenol, catechol At least one of them.
  • An environmentally-friendly polyurethane curing agent is prepared by adding a small molecule sulfonate glycol chain extender to a mixture of a polyisocyanate prepolymer and a diisocyanate to carry out a chain extension reaction to obtain a polyisocyanate containing a sulfonic acid group.
  • the prepolymer is further encapsulated with a hydrogen-containing compound blocking agent to block the terminal isocyanate group to obtain the above-mentioned environmentally-friendly polyurethane curing agent.
  • the preparation method of the above environmentally-friendly polyurethane curing agent comprises the following steps:
  • the temperature of the heating reaction is 50 to 90 ° C, and the reaction time is 3 to 9 hours; and the step c) is specifically to adjust the temperature of the reaction vessel to 50 to 70 ° C, and the addition is completed within 1 to 3 hours.
  • the hydrogen-containing compound is further incubated at 70-80 ° C for 2 to 5 hours, and then cooled and discharged to obtain an environmentally-friendly polyurethane curing agent.
  • the organic solvent is at least one of an alcohol, an ether, a ketone, a glycol ether ester, an acetate, and an amide solvent.
  • a polyurethane baking varnish or polyurethane high temperature adhesive comprising an environmentally friendly polyurethane curing agent as described above.
  • the polyurethane curing agent of the invention has good water dispersibility, good storage stability, wide deblocking temperature range, can significantly improve the performance of the water-based resin, is suitable for the preparation of water-based baking varnish and water-based high-temperature glue, and has the coating on the heat sensitive material. Good application prospects.
  • the present invention has the following advantages over the prior art:
  • the polyurethane curing agent of the present invention has good water dispersibility.
  • the anionic sulfonate has good hydrophilicity, low viscosity, easy to disperse in water, and -NCO has been blocked. It has a long storage period at room temperature after mixing with the aqueous resin, and can only be active after the deblocking temperature is reached.
  • Hydrogen cross-linking curing suitable for making water-based baking varnish and water-based high-temperature adhesive curing agent.
  • the deblocking temperature of the present invention is low. Different deisocyanate prepolymers and different diisocyanate ratios have different deblocking temperatures.
  • the minimum deblocking temperature of the curing agent made of MDI can reach about 80 °C, or there is only a short deblocking time at high temperature. It not only saves energy and reduces consumption, but also can be used for the coating of heat sensitive materials.
  • the product of the invention has high solid content and low solvent content, and the VOC content of the baking varnish and the high temperature glue after matching with the water-based resin can reach the national standard.
  • the NCO percentage of the invention is relatively high, the amount of addition in the aqueous resin is relatively low, and the utilization rate is relatively high, which is advantageous for reducing the cost and improving the strength property of the cured product.
  • the present invention can be produced by a device which generally produces a solvent-type curing agent without adding new equipment.
  • An environmentally friendly polyurethane curing agent comprising a blocked polyisocyanate prepolymer containing a sulfonic acid group; the blocked polyisocyanate prepolymer containing a sulfonic acid group is a polyisocyanate prepolymer, a diisocyanate and a chain extender
  • the chain extension reaction is carried out, and the terminal isocyanate group is blocked by adding a blocking agent; the molar ratio of the isocyanate group of the polyisocyanate prepolymer to the isocyanate group of the diisocyanate is 1: (0.7 ⁇ 1.2); the chain extender is a small molecule sulfonate.
  • the salt of the acid salt diol, the small molecule sulfonate diol has a molecular weight of 350 to 1000, and the molar ratio of the hydroxyl group of the small molecule sulfonate diol to the isocyanate group of the diisocyanate is 1: (1.5 ⁇ 3);
  • the agent is a hydrogen-containing compound, and the molar ratio of the active hydrogen of the hydrogen-containing compound to the blocked isocyanate group is (1.05 to 1.2):1.
  • the polyisocyanate prepolymer is at least one of a prepolymer of a diisocyanate and a triol, a TDI trimer, an MDI trimer, an HDI trimer, an IPDI trimer, an HDI biuret, and a PAPI.
  • the polyisocyanate prepolymer is a prepolymer of TDI/MDI/HDI/IPDI/HMDI and a triol, a TDI trimer, an MDI trimer, an HDI trimer, an IPDI trimer, At least one of HDI biuret and PAPI; still more preferably, the polyisocyanate prepolymer is TDI-TMP adduct, MDI-TMP adduct, HDI trimer, IPDI trimer, PAPI At least one.
  • the triol is at least one of trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, and glycerin; further preferably, the triol is trimethylolpropane .
  • the diisocyanate is at least one of MDI, HMDI, TDI, HDI, and IPDI.
  • the small molecule sulfonate diol is obtained by esterification of a small molecule diol with a dicarboxy sulfonate; preferably, the hydroxyl group of the small molecule diol and the carboxyl group of the dicarboxy sulfonate thereof
  • the molar ratio is (2 ⁇ 3):1.
  • the small molecule diol is a diol having a molecular weight of less than 300; further preferably, the small molecule diol is 3-methyl-1,5-pentanediol, neopentyl glycol, ethylene glycol, and Diethylene glycol, cyclohexanediol, methyl propylene glycol, TCD tricyclic diol, 1,3-propanediol, 1,4-dimethylolcyclohexane, 1,4-butanediol, 1,3 -butanediol, 1,5-pentanediol, diethyl pentanediol, 1,2-propanediol, diethylene glycol, tetrahydrofuran diol, 1,6-hexanediol, trimethylpentanediol, butyl At least one of ethyl ethyl propylene glycol, 2,2-bis
  • the dicarboxysulfonate is an alkali metal dicarboxysulfonate; further preferably, the dicarboxysulfonate is at least one of a potassium dicarboxysulfonate and a sodium dicarboxysulfonate; further preferred The dicarboxysulfonate is sodium isophthalate-5-sulfonate.
  • the hydrogen-containing compound is methanol, ethanol, isopropanol, tert-butanol, propylene glycol monomethyl ether, methyl ethyl ketone oxime, acetone oxime, methyl isobutyl hydrazine, imidazole, 2-methylpyrazole, 3, 5- Dimethylpyrazole, 3-methyl-5-ethylpyrazole, 3-ethyl-5-propylpyrazole, acetylacetone, ethyl acetoacetate, diethyl malonate, caprolactam, phenol, neighbor At least one of hydroquinone; further preferably, the hydrogen-containing compound is at least one of methyl ethyl ketone oxime, imidazole, and 3,5-dimethylpyrazole.
  • An environmentally-friendly polyurethane curing agent is prepared by adding a small molecule sulfonate glycol chain extender to a mixture of a polyisocyanate prepolymer and a diisocyanate to carry out a chain extension reaction to obtain a polyisocyanate containing a sulfonic acid group.
  • the prepolymer is further encapsulated with a hydrogen-containing compound blocking agent to block the terminal isocyanate group to obtain the above-mentioned environmentally-friendly polyurethane curing agent.
  • the preparation method of the above environmentally-friendly polyurethane curing agent comprises the following steps:
  • the step a) of the preparation method is specifically: in the esterification tank, the esterification reaction is carried out by using a small molecular diol and a dicarboxy sulfonate as raw materials, and the temperature is raised from 80 to 220 ° C to carry out esterification and water separation. Vacuuming was carried out to obtain a sulfonic acid group-containing small molecule diol having a molecular weight of 350 to 1,000.
  • the temperature of the heating reaction is 50 to 90 ° C, and the reaction time is 3 to 9 hours.
  • the step c) of the preparation method is specifically: adjusting the temperature of the reaction vessel to 50 to 70 ° C, adding the hydrogen-containing compound in 1 to 3 hours, and then holding the mixture at 70 to 80 ° C for 2 to 5 hours, and then cooling the material to obtain the material.
  • Environmentally friendly polyurethane curing agent is specifically: adjusting the temperature of the reaction vessel to 50 to 70 ° C, adding the hydrogen-containing compound in 1 to 3 hours, and then holding the mixture at 70 to 80 ° C for 2 to 5 hours, and then cooling the material to obtain the material.
  • the organic solvent is at least one of an alcohol, an ether, a ketone, a glycol ether ester, an acetate, and an amide solvent; further preferably, the organic solvent is acetic acid.
  • Ethyl ester butyl acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, acetone, methyl ethyl ketone, cyclohexanone, methanol, ethanol, isopropyl At least one of an alcohol, tert-butanol, dioxane, tetrahydrofuran, and N,N-dimethylformamide.
  • a polyurethane baking varnish or polyurethane high temperature adhesive comprising an environmentally friendly polyurethane curing agent as described above.
  • an application method of an environmentally-friendly polyurethane curing agent is specifically: mixing an environmentally-friendly polyurethane curing agent with a hydroxyl-containing water-based resin to obtain an aqueous polyurethane baking paint or an aqueous polyurethane high-temperature adhesive; or an environmentally-friendly polyurethane curing agent and a hydroxyl group-containing solvent type The resin is mixed to obtain a solvent-based polyurethane baking varnish or a solvent-based polyurethane high-temperature adhesive.
  • the polyurethane curing agent contains an active -NCO group
  • the -NCO of the curing agent has a competitive reaction with water and -OH
  • the aliphatic isocyanate - NCO activity is low, the reaction rate with water is slower than -OH, but it also consumes some -NCO over time
  • the -NCO activity for aromatic isocyanate is higher, and the reaction rate with water is faster than -OH It can hardly be used in combination with waterborne resins. Therefore, both the aliphatic and aromatic isocyanate curing agents have a problem of water consumption activity-NCO, so the active-NCO must be blocked.
  • the -NCO is blocked with a hydrogen-containing compound to obtain an urethane which is stable at normal temperature to prevent attack by a nucleophile such as water.
  • the urethane can be deblocked under certain temperature conditions, and the active -NCO is released again. At this time, the water has evaporated at a high temperature, leaving only the active -OH in the resin, so the two functional groups can play very much. Good cross-linking reaction.
  • the idea of the invention is to introduce a small molecule sulfonate glycol hydrophilic group in a mixture of a polyisocyanate prepolymer and a diisocyanate monomer, and design a reactant raw material ratio mainly to extend the hydrophilic group and the diisocyanate. Reaction, such that the linear molecules after chain extension are relatively small; try to reduce the reaction between the hydrophilic group and the polyisocyanate prepolymer, because the polyisocyanate prepolymer is a polymer, and the molecules of the hydrophilic group after chain extension Larger, the product has a high viscosity and poor water dispersion.
  • the prepolymer of the small molecular sulfonate diol designed by the invention has a relatively low viscosity, and the viscosity of the product after blocking the terminal-NCO with a hydrogen-containing compound is also relatively low.
  • Low-viscosity hydrophilic polyisocyanate prepolymers are easily dispersed in water. If the viscosity is too large, it is difficult to disperse in water. It is necessary to increase the solvent, lower the viscosity, and reduce the solid content. This does not meet the national environmental protection regulations for VOC restrictions. .
  • the invention adopts a small molecule sulfonate glycol as a hydrophilic group, and only a small amount of a sulfonic acid group can bring all the polyisocyanate prepolymer molecules into water to achieve the hydrophilic effect of the whole molecule, thereby reducing the NCO. Consumption.
  • the invention adopts a small molecular diol having a molecular weight of 350-1000 containing a sulfonic acid group, and is also for increasing the percentage of NCO per unit volume, and finally the number of -NCOs which are blocked and protected is large.
  • the detection viscosity is carried out according to the national standard "GB/T2794-1995 Determination of Adhesive Viscosity".
  • Reflux for 2 hours then increase the temperature by 10 ° C every 0.5 hours, collect the fraction in the water separator until the temperature reaches 210-220 ° C, keep warm for 1 hour, vacuum at 220 ° C 1KPa for 2 hours, cool down to 100 ° C, add 220 g of propylene glycol Ether acetate, stirred evenly, and then cooled to 60 ° C, discharged, to obtain 730 g of a small molecular sulfonate diol having a solid content of 70% and a number average molecular weight of 550;
  • the curing agent was tested to be a light yellow transparent viscous liquid having a solid content of 60% and a viscosity of 5200 mPa•s (25 ° C).
  • PAPI is a mixture of polyfunctional isocyanates containing 50% by weight of monomeric MDI
  • 73 g of propylene glycol methyl ether acetate and the procedure of Example 1 were added to the reactor.
  • Example 2 The curing agent product of Example 1 and the aqueous polyurethane dispersion were stirred and mixed to prepare an aqueous polyurethane baking varnish, which was sprayed and formed into a sample plate, and cured in an oven at 90 ° C for 40 minutes, and left at room temperature for 24 hours, and the properties of the obtained paint film were as follows. : Appearance of film (visual) smooth and smooth; gloss (60°): ⁇ 92%; hardness: Shore D55; impact strength: 58KJ/m2; adhesion: grade 1; flexibility: 1mm; water resistance (72h) abnormal.
  • Inspection method gloss (60 °) according to GB9754-2007, hardness according to GB1730-79, impact strength according to GB/T 2571-1995, adhesion according to GB1720-89, flexibility according to GB1731-79 standard, water resistance according to GB/T1733-1993.
  • the curing agent product of Example 1 and the polyurethane emulsion were stirred and mixed to prepare an aqueous polyurethane high temperature adhesive for PET film and PET film composite.
  • the coating machine applies the glue to a piece of PET film, and then bakes it in an oven at 150 ° C for 2 minutes, takes it out, and recombines another piece of PET film thereon, and presses the hot pressing compound at a temperature of 80 to 90 ° C. After standing at room temperature for 24 hours, the T-peel strength test was carried out according to /T2791-1995 "Adhesive T peel strength test method flexible material for flexible material", and the PET film was torn.
  • Example 2 The curing agent product of Example 1 and the polyurethane emulsion were stirred and mixed to prepare an aqueous polyurethane high-temperature glue.
  • the glue was applied to the cloth surface by a machine, woven and velvet, and then placed in an oven at 90 ° C for 30 minutes, and left at room temperature for 24 hours.
  • the tensile strength, elongation at break, wear resistance, dimensional stability of the washed flanion are all in accordance with the strength properties of the flannel, and the appearance, feel and comfort are also in accordance with the requirements of the flannel.
  • the curing agent product of Example 2 and the aqueous amino resin were stirred and mixed to prepare an aqueous amino baking varnish.
  • the sample was sprayed and formed into a sample, and cured in an oven at 120 ° C for 30 minutes. After standing at room temperature for 24 hours, the properties of the obtained film were as follows: The appearance of the paint film (visual) is smooth and smooth; gloss (60°): ⁇ 86%; hardness: Shore D63; impact strength: 42KJ/m2; adhesion: grade 1: flexibility: 1mm; water resistance (72h) without abnormality .
  • Example 3 The curing agent product of Example 3 and the aqueous acrylic resin were stirred and mixed to prepare an aqueous acrylic polyurethane baking varnish, which was sprayed and formed into a sample plate, and cured in an oven at 160 ° C for 30 minutes, and left at room temperature for 24 hours, and the properties of the obtained paint film were as follows. : Appearance of film (visual) smooth and smooth; gloss (60°): ⁇ 92%; hardness: Shore D54; impact strength: 52KJ/m2; adhesion: grade 1; flexibility: 1mm; water resistance (72h) abnormal.
  • the curing agent product of the embodiment 4 and the water-based epoxy resin are stirred and mixed to obtain a water-based epoxy high-temperature adhesive, which is used for reinforcing the socket sealing of the PP plastic tube, and is baked at a low temperature of 80 ° C after being applied at the joint.
  • the moisture is placed in an oven at 100 ° C for 30 minutes, and after standing at room temperature for 24 hours, the shear strength test after the test block is bonded according to GB6328-86 "Adhesive Shear Impact Strength Test Method", and the PP plastic pipe is reinforced.
  • the environmentally friendly curing agent of the present invention contains a hydrophilic sulfonic acid group in the molecular structure, and can bring the entire molecule of the polyisocyanate prepolymer into water to achieve water-soluble or water-dispersing effect, and does not require ammonia neutralization.
  • the disadvantages of the current neutralization of the hydrophilic anion carboxyl group by ammonia are avoided; the active-NCO of the present invention is blocked, and is stable at normal temperature, and can be stably coexisted at a normal temperature after mixing with the aqueous resin.
  • the NCO group is dissociated to react with the hydroxyl group, carboxyl group, amino group and the like on the molecular chain of the aqueous resin to form a crosslinked structure, which can significantly improve the performance of the aqueous resin, and is particularly suitable for some special processing.
  • the invention can avoid the phenomenon that the raw water curing agent is solidified and discarded after being mixed with the water-based resin and used up within a limited number of hours.
  • the invention can be used to prepare a low temperature deblocking aqueous curing agent with a highly active aromatic isocyanate, for example, an aqueous curing agent made of MDI can have a minimum deblocking temperature as low as 80 ° C or a high temperature rapid deblocking (Application Example 2, 150 ° C) Baking for 2 minutes), the low-temperature baking varnish made by it not only saves processing energy, but also avoids dimerization and trimerization of NCO groups at the time of high-temperature deblocking of NCO groups, and formation of allophanate or biuret. Consume useful -NCO.
  • Low-temperature deblocking or high-temperature rapid deblocking expands the range of application of curing agents, especially for coating heat-sensitive components, electronic components, plastic parts, etc. with low temperature resistance.
  • the invention can prepare a curing agent with high solid content (50-75%), low viscosity (25 ° C, 3000-6000 mPa ⁇ s) and high NCO%, because in the preparation method step b), the hydrophilic group is small Molecular sulfonate diols are mainly reacted with monomolecular diisocyanates, and the molecules after chain extension are still relatively small. This is because the molecules of the small molecule sulfonate diol and the diisocyanate are relatively small, the activity is relatively high, and it is easy to collide. Also, because the molar ratio of the two is designed, the NCO is greatly exceeded than the OH, and the diisocyanate has more collisions.
  • Molecular sulfonate diol reaction which is beneficial to control the molecular weight of the sulfonate after chain extension, so that the molecular weight after the NCO is blocked by the hydrogen-containing compound in the next step is not too high, so the product viscosity is relatively low, and the product can be made.
  • a high solids product that reduces the VOC content of the curing agent. At the same time, due to the high solid content, the NCO content of the product is relatively high, and the amount of NCO blocked is relatively large, so the environmentally friendly curing agent of the present invention has a high NCO% after deblocking.
  • the deblocking temperature of the environment-friendly curing agent prepared by selecting different diisocyanate and polyisocyanate prepolymers can be adjusted in the range of 80 to 200 ° C; the selected diisocyanate and polyisocyanate prepolymer can be of the same kind. It can also be a different kind.
  • the aliphatic polyisocyanate prepolymer and the aromatic diisocyanate can also be used together, but care should be taken to treat the residual monomers to meet the national standards. In short, they are selected according to the applicable objects and performance requirements.
  • the curing agent of the invention is mainly used for matching with polyurethane aqueous dispersion, acrylic emulsion, water-based alkyd resin, water-based amino resin, etc., and is made into water-based baking varnish and water-based high-temperature glue.
  • the invention has wide application range and good compatibility with various types of solvent-based hydroxy resins, and can be used for supporting solvent-based baking varnishes and high-temperature adhesives.
  • the invention can also be added to various water-based paints, printing pastes and styrene-butadiene latexes, and after heat treatment, the strength performance can be remarkably improved, and the water resistance and chemical corrosion resistance can be improved.

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Abstract

一种环保聚氨酯固化剂及其制备方法和应用。该环保聚氨酯固化剂包括含有磺酸基团的封闭多异氰酸酯预聚物；所述的含有磺酸基团的封闭多异氰酸酯预聚物是由多异氰酸酯预聚物、二异氰酸酯和扩链剂进行扩链反应，再加入封闭剂将端异氰酸酯基封闭而成。该聚氨酯固化剂水分散性好，贮存稳定性佳，解封温度范围广，可显著改善水性树脂的性能，适用于制作水性烤漆和水性高温胶，并在热敏感材料的涂装上有良好的应用前景。

Description

一种环保聚氨酯固化剂及其制备方法和应用
技术领域
本发明涉及一种环保聚氨酯固化剂及其制备方法和应用。
背景技术
双组分聚氨酯涂料和胶粘剂具有成膜温度低、附着力强、耐磨性高、硬度高、耐溶剂性和耐水性好等优点，在市场上用量很大，随着国家标准对其中的VOC含量进行限制的执法力度加大，许多企业在开发高性能环保型产品方面作了很多努力：一是最大限度地减少溶剂用量，二是减少聚氨酯固化剂中游离的二异氰酸酯单体含量，即开发水性羟基树脂和低残留TDI及HDI单体的固化剂。目前市场销售的水性羟基树脂品种比较多，而与之配套的可水溶或水分散的聚氨酯固化剂品种却比较少，一方面是从外国进口的品种有限，另一方面是国内很多品种还没有开发出来。例如：现在进口的可水分散的固化剂基本是脂肪族异氰酸酯（HDI、IPDI）制造的，它们的官能团NCO活性比较低，与水的反应速度比较慢，与水性羟基树脂混合后在室温下有4~6小时的使用期，超过使用期的溶液就缓慢固化了，只能废弃，因此，这类固化剂配制的涂料或胶粘剂无法完成大型部件的作业或非连续性生产，稍有不慎，则造成原料的极大浪费。而芳香族异氰酸酯（MDI、TDI）的官能团NCO活性比较高，若与水性羟基树脂混合，-NCO与水的反应速度比羟基快，有效使用期更短，基本不能应用，目前市场上基本无水性芳香族异氰酸酯固化剂。对于需要高温固化的单组分水性树脂，更是难以找到与之配套的封闭型固化剂，所以烤漆行业和高温胶行业仍然是溶剂型产品，固化温度高达160℃以上，即或是低温烤漆的固化温度也达到120℃以上，而且烘烤的时间还比较长。环保和能耗的双重压力迫使这类企业濒临倒闭的危险，因此，对水性封闭型低温固化剂的需求呼声日益强烈。
近几年聚氨酯业界人士在致力于聚氨酯固化剂水性化研究方面作了一些工作，但对可水溶的封闭型聚氨酯固化剂报道甚少。CN103554430A公开了将异氰酸酯三聚体用甲乙酮肟封闭得到化合物A，将二异氰酸酯与聚乙二醇单甲醚反应得到乳化剂B，将A和B混合后再加入去离子水乳化得到封闭型多异氰酸酯交联剂水乳液的制备方法，该方法采用的亲水剂是非离子型，制成的水性聚氨酯固化剂存在着水分散性差，稳定性差，制成品的耐水性差等缺点。CN104130375A公开了将二异氰酸酯制成半封闭物，半封闭物中的异氰酸酯基再与羟基聚丙烯酸酯的羟基反应，得到聚丙烯酸酯改性水性封闭异氰酸酯预聚体，再用胺中和，加水乳化，除去溶剂，制得聚丙烯酸酯改性水性封闭型异氰酸酯固化剂，该方法存在着胺类中和剂有臭味及易使制品变黄等缺陷。CN101649036A公开了用二异氰酸酯单体与二元醇和三元醇反应，生成支链多异氰酸酯，经亲水性扩链剂扩链后再封闭端NCO，最后加胺中和成盐，制成的封闭型固化剂的优点是在常温下可水解封，缺点是只能用于运动场地类的铺装。涂料工业2014年9月第44卷第9期发表的封闭型水性多异氰酸酯交联剂的制备及其性能研究，是用2,2-二羟甲基丙酸（DMPA）作为亲水基团，与HMDI反应后再与TMP反应合成支化结构的中间体，然后用咪唑类封闭剂将活性NCO封闭，最后用三乙胺中和，制得一系列封闭型水性多异氰酸酯交联剂，同样存在着亲水的羧基用胺类中和所带来的质量问题。目前专利和现有文献公开的制备封闭异氰酸酯水性固化剂的方法非常有限，而实际市场上并没有此类产品的销售，或极少有试用品销售，远远满足不了种类繁多的水性树脂对配套固化剂的品种需求。
发明内容
本发明的目的在于提供一种在室温下能与羟基树脂长期稳定共存，加热能固化的环保聚氨酯固化剂，同时提供一种环保聚氨酯固化剂的制备和应用方法。
本发明所采取的技术方案是：
一种环保聚氨酯固化剂，包括含有磺酸基团的封闭多异氰酸酯预聚物；所述的含有磺酸基团的封闭多异氰酸酯预聚物是由多异氰酸酯预聚物、二异氰酸酯和扩链剂进行扩链反应，再加入封闭剂将端异氰酸酯基封闭而成；多异氰酸酯预聚物的异氰酸酯基与二异氰酸酯的异氰酸酯基其摩尔比为1：（0.7~1.2）；扩链剂为小分子磺酸盐二元醇，小分子磺酸盐二元醇的分子量为350~1000，小分子磺酸盐二元醇的羟基与二异氰酸酯的异氰酸酯基其摩尔比为1：（1.5~3）；封闭剂为含氢化合物，含氢化合物的活性氢与被封闭的端异氰酸酯基其摩尔比为（1.05~1.2）：1。
多异氰酸酯预聚物为二异氰酸酯与三元醇的预聚物、TDI三聚体、MDI三聚体、HDI三聚体、IPDI三聚体、HDI缩二脲、PAPI中的至少一种。
二异氰酸酯为MDI、HMDI、TDI、HDI、IPDI中的至少一种。
小分子磺酸盐二元醇是由小分子二元醇与二羧基磺酸盐经酯化反应制得，小分子二元醇的羟基与二羧基磺酸盐的羧基其摩尔比为（2~3）：1；所述的小分子二元醇为分子量小于300的二元醇，二羧基磺酸盐为二羧基磺酸碱金属盐。
含氢化合物为甲醇、乙醇、异丙醇、叔丁醇、丙二醇单甲醚、甲乙酮肟、丙酮肟、甲基异丁基肟、咪唑、2-甲基吡唑、3,5-二甲基吡唑、3-甲基-5-乙基吡唑、3-乙基-5-丙基吡唑、乙酰丙酮、乙酰乙酸乙酯、丙二酸二乙酯、己内酰胺、苯酚、邻苯二酚中的至少一种。
一种环保聚氨酯固化剂的制备方法，是在多异氰酸酯预聚物和二异氰酸酯的混合物中，加入小分子磺酸盐二元醇扩链剂进行扩链反应，得到含有磺酸基团的多异氰酸酯预聚物，再加入含氢化合物封闭剂将端异氰酸酯基进行封闭，得到上述的环保聚氨酯固化剂。
上述一种环保聚氨酯固化剂的制备方法，包括以下步骤：
a）制备小分子磺酸盐二元醇：在酯化釜中，将小分子二元醇和二羧基磺酸盐进行酯化反应，制得小分子磺酸盐二元醇；
b）制备含有磺酸基团的多异氰酸酯预聚物：在反应釜中，将多异氰酸酯预聚物、二异氰酸酯、小分子磺酸盐二元醇和有机溶剂混合，加热反应；
c）制备环保聚氨酯固化剂：在反应釜中，继续加入含氢化合物，加热反应，出料，得到环保聚氨酯固化剂。
制备方法的步骤b）中，加热反应的温度为50~90℃，反应时间为3~9小时；步骤c）具体为，调节反应釜温度为50~70℃，在1~3小时内加完含氢化合物，再在70~80℃下保温2~5小时，然后降温出料，得到环保聚氨酯固化剂。
制备方法的步骤c）中，有机溶剂为醇类、醚类、酮类、二醇醚酯类、醋酸酯类、酰胺类溶剂中的至少一种。
一种聚氨酯烤漆或聚氨酯高温胶，包括上述的一种环保聚氨酯固化剂。
本发明的有益效果是：
本发明的聚氨酯固化剂水分散性好，贮存稳定性佳，解封温度范围广，可显著改善水性树脂的性能，适用于制作水性烤漆和水性高温胶，并在热敏感材料的涂装上有良好的应用前景。
具体而言，本发明与现有技术相比具有如下优点：
1、本发明的聚氨酯固化剂水分散性好。阴离子磺酸盐的亲水性好，产品粘度低，容易分散在水中，并且-NCO已被封闭，与水性树脂混合后在室温下有很长的贮存期，只有达到解封温度后才能与活性氢交联固化，适用于制作水性烤漆和水性高温胶的固化剂。
2、本发明的解封温度低。不同多异氰酸酯预聚物与不同二异氰酸酯配比制作的固化剂的解封温度不同，用MDI制作的固化剂的最低解封温度可达到80℃左右，或者在高温下只有很短的解封时间，不仅节能降耗效果明显，而且可用于热敏感材料的涂装。
3、本发明产品的固含量较高，溶剂含量较低，与水性树脂配套后的烤漆和高温胶的VOC含量能达到国家标准。
4、本发明的NCO百分含量比较高，在水性树脂中的加入量比较低，利用率比较高，有利于降低成本，提高固化物的强度性能。
5、本发明可用一般生产溶剂型固化剂的设备来生产，无需增加新设备。
具体实施方式
一种环保聚氨酯固化剂，包括含有磺酸基团的封闭多异氰酸酯预聚物；所述的含有磺酸基团的封闭多异氰酸酯预聚物是由多异氰酸酯预聚物、二异氰酸酯和扩链剂进行扩链反应，再加入封闭剂将端异氰酸酯基封闭而成；多异氰酸酯预聚物的异氰酸酯基与二异氰酸酯的异氰酸酯基其摩尔比为1：（0.7~1.2）；扩链剂为小分子磺酸盐二元醇，小分子磺酸盐二元醇的分子量为350~1000，小分子磺酸盐二元醇的羟基与二异氰酸酯的异氰酸酯基其摩尔比为1：（1.5~3）；封闭剂为含氢化合物，含氢化合物的活性氢与被封闭的端异氰酸酯基其摩尔比为（1.05~1.2）：1。
优选的，多异氰酸酯预聚物为二异氰酸酯与三元醇的预聚物、TDI三聚体、MDI三聚体、HDI三聚体、IPDI三聚体、HDI缩二脲、PAPI中的至少一种；进一步优选的，多异氰酸酯预聚物是TDI/MDI/HDI/IPDI/HMDI与三元醇的预聚物、TDI三聚体、MDI三聚体、HDI三聚体、IPDI三聚体、HDI缩二脲、PAPI中的至少一种；再进一步优选的，多异氰酸酯预聚物是TDI-TMP加成物、MDI-TMP加成物、HDI三聚体、IPDI三聚体、PAPI中的至少一种。
优选的，三元醇为三羟甲基丙烷、三羟甲基乙烷、1,2,6-己三醇、甘油中的至少一种；进一步优选的，三元醇为三羟甲基丙烷。
优选的，二异氰酸酯为MDI、HMDI、TDI、HDI、IPDI中的至少一种。
进一步的，小分子磺酸盐二元醇是由小分子二元醇与二羧基磺酸盐经酯化反应制得；优选的，小分子二元醇的羟基与二羧基磺酸盐的羧基其摩尔比为（2~3）：1。
优选的，小分子二元醇为分子量小于300的二元醇；进一步优选的，小分子二元醇为3-甲基-1,5-戊二醇、新戊二醇、乙二醇、一缩二乙二醇、环己二醇、甲基丙二醇、TCD三环二醇、1,3-丙二醇、1,4-二羟甲基环己烷、1,4-丁二醇、1,3-丁二醇、1,5-戊二醇、二乙基戊二醇、1,2-丙二醇、二甘醇、四氢呋喃二醇、1,6-己二醇、三甲基戊二醇、丁基乙基丙二醇、2,2-二（4-羟基苯基）丙烷、一缩二丙二醇、三丙二醇、乙基己二醇中的至少一种；再进一步优选的，小分子二元醇为1,4-丁二醇、新戊二醇中的至少一种。
优选的，二羧基磺酸盐为二羧基磺酸碱金属盐；进一步优选的，二羧基磺酸盐为二羧基磺酸钾盐、二羧基磺酸钠盐中的至少一种；再进一步优选的，二羧基磺酸盐为间苯二甲酸-5-磺酸钠。
优选的，含氢化合物为甲醇、乙醇、异丙醇、叔丁醇、丙二醇单甲醚、甲乙酮肟、丙酮肟、甲基异丁基肟、咪唑、2-甲基吡唑、3,5-二甲基吡唑、3-甲基-5-乙基吡唑、3-乙基-5-丙基吡唑、乙酰丙酮、乙酰乙酸乙酯、丙二酸二乙酯、己内酰胺、苯酚、邻苯二酚中的至少一种；进一步优选的，含氢化合物为甲乙酮肟、咪唑、3,5-二甲基吡唑中的至少一种。
一种环保聚氨酯固化剂的制备方法，是在多异氰酸酯预聚物和二异氰酸酯的混合物中，加入小分子磺酸盐二元醇扩链剂进行扩链反应，得到含有磺酸基团的多异氰酸酯预聚物，再加入含氢化合物封闭剂将端异氰酸酯基进行封闭，得到上述的环保聚氨酯固化剂。
上述一种环保聚氨酯固化剂的制备方法，包括以下步骤：
a）制备小分子磺酸盐二元醇：在酯化釜中，将小分子二元醇和二羧基磺酸盐进行酯化反应，制得小分子磺酸盐二元醇；
b）制备含有磺酸基团的多异氰酸酯预聚物：在反应釜中，将多异氰酸酯预聚物、二异氰酸酯、小分子磺酸盐二元醇和有机溶剂混合，加热反应；
c）制备环保聚氨酯固化剂：在反应釜中，继续加入含氢化合物，加热反应，出料，得到环保聚氨酯固化剂。
制备方法的步骤a）具体为：在酯化釜中，用小分子二元醇和二羧基磺酸盐为原料，进行酯化反应，从80～220℃经过阶段升温，进行酯化、分水、抽真空，得到分子量为350～1000的含磺酸基团的小分子二元醇。
制备方法的步骤b）中，优选的，加热反应的温度为50~90℃，反应时间为3~9小时。
制备方法的步骤c）具体为：调节反应釜温度为50~70℃，在1~3小时内加完含氢化合物，再在70~80℃下保温2~5小时，然后降温出料，得到环保聚氨酯固化剂。
制备方法的步骤c）中，优选的，有机溶剂为醇类、醚类、酮类、二醇醚酯类、醋酸酯类、酰胺类溶剂中的至少一种；进一步优选的，有机溶剂为醋酸乙酯、醋酸丁酯、乙二醇乙醚醋酸酯、丙二醇甲醚醋酸酯、碳酸二甲酯、碳酸二乙酯、碳酸二苯酯、丙酮、丁酮、环已酮、甲醇、乙醇、异丙醇、叔丁醇、二氧六环、四氢呋喃、N,N-二甲基甲酰胺中的至少一种。
一种聚氨酯烤漆或聚氨酯高温胶，包括上述的一种环保聚氨酯固化剂。
进一步的，一种环保聚氨酯固化剂的应用方法具体为：环保聚氨酯固化剂与含羟基的水性树脂混合，制得水性聚氨酯烤漆或水性聚氨酯高温胶；或者，环保聚氨酯固化剂与含羟基的溶剂型树脂混合，制得溶剂型聚氨酯烤漆或溶剂型聚氨酯高温胶。
下面对本发明的发明原理阐述如下：聚氨酯固化剂都含有活泼的-NCO基团，在与水性羟基树脂混合后，固化剂的-NCO存在着与水和-OH的竞争反应，脂肪族异氰酸酯的-NCO活性较低，与水的反应速度比-OH慢，但也会随着时间的延长而消耗掉一些-NCO；对于芳香族异氰酸酯的-NCO活性较高，与水的反应速度比-OH快，它几乎不能用于与水性树脂配套。因此，不论是脂肪族还是芳香族异氰酸酯固化剂都存在着水消耗活性-NCO的问题，所以必须对活性-NCO进行封闭保护。用含氢化合物将-NCO封闭后得到在常温下稳定的亚氨酯，以阻止水等亲核试剂的进攻。亚氨酯可以在一定的温度条件下解封，重新释放出活性的-NCO，此时水份已在高温下蒸发，只剩下树脂中的活性-OH，因此这两种官能团能起到很好的交联反应。
本发明的思路是在多异氰酸酯预聚物与二异氰酸酯单体的混合物中引入小分子磺酸盐二元醇亲水基团，设计反应物原料配比主要让亲水基团与二异氰酸酯扩链反应，这样扩链后的直链分子比较小；尽量减少亲水基团与多异氰酸酯预聚物反应，因为多异氰酸酯预聚物是多聚体，亲水基团对其扩链后的分子会比较大，产物粘度高，水分散性差。本发明设计的小分子磺酸盐二元醇扩链后的预聚物粘度比较低，再用含氢化合物封闭端头-NCO后的产物粘度也比较低。低粘度的亲水性多异氰酸酯预聚物容易在水中分散，如果粘度太大，在水中分散困难，势必要增加溶剂，降低粘度，减小固含量，这样就不符合国家环保法规对VOC的限制。
本发明采用小分子磺酸盐二元醇作为亲水基团，只需少量磺酸基就能将全部多异氰酸酯预聚物分子带入水中，达到整个分子亲水的效果，这样能减少NCO的消耗。本发明采用分子量为350～1000含磺酸基团的小分子二元醇，也是为了提高单位体积的NCO百分含量，最终使被封闭保护的-NCO数量较多。
以下通过具体的实施例对本发明的内容作进一步详细的说明。
以下实施例中：
1、检测粘度按国标《GB/T2794-1995胶粘剂粘度的测定》进行。
2、检测固含量按国标《GB/T 2793-1995胶粘剂不挥发物含量的测定》进行。
3、检测分子量采用GPC 凝胶色谱法。
实施例1：
a）制备小分子磺酸盐二元醇
在装有分馏装置的四口烧瓶中，加入300g间苯二甲酸-5-磺酸钠，360g新戊二醇，300g去离子水和0.568g钛酸四丁酯，通氮气保护，在160℃回流2小时，然后每0.5小时升温10℃，分水器中收集馏分，直到温度达到210～220℃，保温1小时，在220℃1KPa下抽真空2小时，降温至100℃，加入220g丙二醇甲醚醋酸酯，搅拌均匀，再降温至60℃，出料，得730g固含量为70%、数均分子量为550的小分子磺酸盐二元醇；
b）制备含有磺酸基团的多异氰酸酯预聚物
在反应釜中加入300g固含量为75%的MDI-TMP的加成物、44g丙二醇甲醚醋酸酯、110gMDI-50及步骤 a）得到的小分子磺酸盐二元醇120g，升温至60℃反应1小时，70℃反应1小时，80℃反应2.5小时，取样分析游离异氰酸酯含量；
c）制备环保型聚氨酯固化剂
降温至60~70℃，分五次加入124g甲乙酮肟，控制加料温度在60~70℃，1.5小时加完，加完料后在70~80℃下保温反应2小时，降温至60℃以下，出料，得环保型聚氨酯固化剂。经检测该固化剂外观为浅黄色透明粘稠液体，固含量为60%，粘度为5200mPa•s（25℃）。
实施例2：
a）采用实施例1制备的小分子磺酸盐二元醇
b）制备含有磺酸基团的多异氰酸酯预聚物
在反应釜中加入300g固含量为75%的TDI-TMP的加成物、24g丙二醇甲醚醋酸酯、120gMDI-50及实施例1步骤 a）得到的小分子磺酸盐二元醇130g，升温至60℃反应1小时，70℃反应1小时，80℃反应3小时；
c） 制备环保型聚氨酯固化剂
降温至60~70℃，分六次加入153g甲乙酮肟，控制加料温度在60~70℃，2小时加完，加完料后在70~80℃下保温反应2小时，降温至60℃以下，出料，得环保型聚氨酯固化剂。经检测该固化剂外观为浅黄色透明粘稠液体，固含量为60%，粘度为4800mPa•s（25℃）。
实施例3：
a）采用实施例1制备的小分子磺酸盐二元醇
b）制备含有磺酸基团的多异氰酸酯预聚物
在反应釜中加入150g固含量为100%的HDI三聚体、21g丙二醇甲醚醋酸酯、80gHMDI及实施例1步骤 a）得到的小分子磺酸盐二元醇114g，升温至60℃反应1小时，70℃反应1小时，80℃反应4小时，90℃反应3小时；
c）制备环保型聚氨酯固化剂
降温至60~70℃，分四次加入112g甲乙酮肟，控制加料温度在60~70℃，2小时加完，加完料后在70~80℃下保温反应3小时，降温至60℃以下，出料，得环保型聚氨酯固化剂。经检测该固化剂外观为浅黄色透明粘稠液体，固含量为60%，粘度为3600mPa•s（25℃）。
实施例4：
a）采用实施例1制备的小分子磺酸盐二元醇
b）制备含有磺酸基团的多异氰酸酯预聚物
在反应釜中加入300gPAPI（PAPI是多官能度异氰酸酯的混合物，其中含有占混合物总量50%的单体MDI）、73g丙二醇甲醚醋酸酯及实施例1步骤 a）得到的小分子磺酸盐二元醇185g，升温至60℃反应1小时，70℃反应1小时，80℃反应4小时；
c）制备环保型聚氨酯固化剂
降温至60~70℃，分六次加入157g甲乙酮肟，控制加料温度在60~70℃，2小时加完，加完料后在70~80℃下保温反应2小时，降温至60℃以下，出料，得环保型聚氨酯固化剂。经检测该固化剂外观为棕黄色粘稠液体，固含量为60%，粘度为5300 mPa•s（25℃）。
应用例1：
实施例1的固化剂产品和聚氨酯水分散液搅拌混合，制得水性聚氨酯烤漆，将其喷涂施工制成样板，在90℃烘箱固化40分钟，室温放置24小时后，制得的漆膜性能如下：漆膜外观（目测）平整光滑；光泽（60°）：≥92%；硬度：邵氏D55；冲击强度：58KJ/m2；附着力：1级；柔韧性：1mm；耐水性（72h）无异常。
检验方法：光泽（60°）按GB9754-2007、硬度按GB1730-79、冲击强度按GB/T 2571-1995、附着力按GB1720-89、柔韧性按GB1731-79标准、耐水性按GB/T1733-1993。
应用例2：
实施例1的固化剂产品和聚氨酯乳液搅拌混合，制得水性聚氨酯高温胶，用于PET薄膜与PET薄膜复合。涂布机将胶涂布到一片PET膜上，置于烘箱中150℃烘烤2分钟，取出，将另一片PET膜复合在其上，经压辊温度为80～90℃滚动热压复合，室温放置24小时后，按/T2791-1995《胶粘剂T剥离强度实验方法挠性材料对挠性材料》，进行T型剥离强度试验，PET薄膜被撕破。
应用例3：
实施例1的固化剂产品和聚氨酯乳液搅拌混合，制得水性聚氨酯高温胶，通过机器将胶涂布到布面上，织上绒，再放到烘箱90℃固化30分钟，室温放置24小时后，测试绒布的抗拉强度、断裂伸长率、耐磨性、水洗尺寸稳定性等均符合绒布的强度性能要求，外观、手感和舒适性也符合绒布的要求。
应用例4：
实施例2的固化剂产品和水性氨基树脂搅拌混合，制得水性氨基烤漆，将其喷涂施工制成样板，在120℃烘箱固化30分钟，室温放置24小时后，制得的漆膜性能如下：漆膜外观（目测）平整光滑；光泽（60°）：≥86%；硬度：邵氏D63；冲击强度：42KJ/m2；附着力：1级；柔韧性：1mm；耐水性（72h）无异常。
应用例5：
实施例3的固化剂产品和水性丙烯酸树脂搅拌混合，制得水性丙烯酸聚氨酯烤漆，将其喷涂施工制成样板，在160℃烘箱固化30分钟，室温放置24小时后，制得的漆膜性能如下：漆膜外观（目测）平整光滑；光泽（60°）：≥92%；硬度：邵氏D54；冲击强度：52KJ/m2；附着力：1级；柔韧性：1mm；耐水性（72h）无异常。
应用例6：
实施例4的固化剂产品和水性环氧树脂搅拌混合，制得水性环氧高温胶，将其用于增强PP塑料管的套接密封，在连接处涂胶后，低温80℃烘烤挥发掉水份，放在100℃烘箱固化30分钟，室温放置24小时后，按GB6328-86《胶粘剂剪切冲击强度试验方法》进行试块胶接后的剪切强度试验，增强PP塑料管被剪断。
本发明环保型固化剂的分子结构中含有亲水性好的磺酸基团，能将多异氰酸酯预聚物的整个分子带入水中，达到水溶或水分散的效果，而且不需要用氨中和，避免了目前亲水性的阴离子羧基用氨中和带来的弊端；本发明的活性-NCO已被封闭，在常温下是稳定的物质，与水性树脂混合后常温下可以长期稳定共存，使用时通过加热到解封温度，离解出NCO基团，才能与水性树脂分子链上的羟基、羧基、氨基等基团反应形成交联结构，可显著改善水性树脂性能，特别适合某些有特殊加工要求的水性产品。本发明能避免一般水性固化剂与水性树脂混合后在有限的几个小时内没有用完而造成原料固化报废的现象。
本发明可以用高活性的芳香族异氰酸酯制作低温解封的水性固化剂，例如用MDI制作的水性固化剂的最低解封温度可低至80℃，或者高温快速解封（应用例2，150℃烘烤2分钟），用其制作的低温烤漆不仅节省加工能源，而且可避免NCO基团在高温解封时发生NCO基团的二聚、三聚，生成脲基甲酸酯或缩二脲等消耗有用的-NCO。低温解封或高温快速解封使得固化剂的适用范围扩大，尤其是可用于涂装耐温较低的热敏感元件、电子元件、塑料件等。
本发明能制备出高固含量（50~75%）、低粘度（25℃，3000～6000mPa•s）、较高NCO%的固化剂，因为在制备方法步骤b）中，亲水基团小分子磺酸盐二元醇主要与单分子二异氰酸酯反应，扩链后的分子仍然比较小。这是因为小分子磺酸盐二元醇和二异氰酸酯的分子都比较小，活性都比较高，容易碰撞，还因为设计两者的摩尔比时NCO比OH大大超量，二异氰酸酯有更多碰撞到小分子磺酸盐二元醇的机率；而多异氰酸酯预聚物具有三官能度以上结构，体积庞大活动困难，其分子结构上的NCO活性比二异氰酸酯单分子的NCO活性低，所以难于与小分子磺酸盐二元醇反应，这有利于控制磺酸盐扩链后的分子量，以致于下一步用含氢化合物封端NCO后的分子量也不会太高，因此产物粘度比较低，可以制成高固含量的产品，即减少固化剂中的VOC含量。同时，由于固含量高，产物的NCO含量就比较高，被封闭的NCO数量就比较多，因此本发明环保型固化剂解封后有较高的NCO%。
本发明通过选择不同的二异氰酸酯及多异氰酸酯预聚物制备的环保型固化剂的解封温度可在80~200℃范围调节；选择的二异氰酸酯与多异氰酸酯预聚物的种类可以是同种，也可以是不同种，脂肪族多异氰酸酯预聚物与芳香族二异氰酸酯也可以搭配使用，但要注意处理残留单体以达到国家标准，总之，根据适用对象和性能要求的不同而选配。
本发明固化剂主要用于与聚氨酯水分散体、丙烯酸乳液、水性醇酸树脂、水性氨基树脂等配套，制成水性烤漆和水性高温胶。
本发明的适用范围广，与各种类型的溶剂型羟基树脂也有很好的相溶性，可用于配套溶剂型烤漆和高温胶。
本发明还可添加到多种水性涂料、印花浆料、丁苯类胶乳中，经热处理后可显著提高强度性能，改善耐水、耐化学腐蚀等性能。

Claims (10)

  1. 一种环保聚氨酯固化剂，其特征在于：包括含有磺酸基团的封闭多异氰酸酯预聚物；所述的含有磺酸基团的封闭多异氰酸酯预聚物是由多异氰酸酯预聚物、二异氰酸酯和扩链剂进行扩链反应，再加入封闭剂将端异氰酸酯基封闭而成；多异氰酸酯预聚物的异氰酸酯基与二异氰酸酯的异氰酸酯基其摩尔比为1：（0.7~1.2）；扩链剂为小分子磺酸盐二元醇，小分子磺酸盐二元醇的分子量为350~1000，小分子磺酸盐二元醇的羟基与二异氰酸酯的异氰酸酯基其摩尔比为1：（1.5~3）；封闭剂为含氢化合物，含氢化合物的活性氢与被封闭的端异氰酸酯基其摩尔比为（1.05~1.2）：1。
  2. 根据权利要求1所述的一种环保聚氨酯固化剂，其特征在于：多异氰酸酯预聚物为二异氰酸酯与三元醇的预聚物、TDI三聚体、MDI三聚体、HDI三聚体、IPDI三聚体、HDI缩二脲、PAPI中的至少一种。
  3. 根据权利要求1或2所述的一种环保聚氨酯固化剂，其特征在于：二异氰酸酯为MDI、HMDI、TDI、HDI、IPDI中的至少一种。
  4. 根据权利要求1所述的一种环保聚氨酯固化剂，其特征在于：小分子磺酸盐二元醇是由小分子二元醇与二羧基磺酸盐经酯化反应制得，小分子二元醇的羟基与二羧基磺酸盐的羧基其摩尔比为（2~3）：1；所述的小分子二元醇为分子量小于300的二元醇，二羧基磺酸盐为二羧基磺酸碱金属盐。
  5. 根据权利要求1所述的一种环保聚氨酯固化剂，其特征在于：含氢化合物为甲醇、乙醇、异丙醇、叔丁醇、丙二醇单甲醚、甲乙酮肟、丙酮肟、甲基异丁基肟、咪唑、2-甲基吡唑、3,5-二甲基吡唑、3-甲基-5-乙基吡唑、3-乙基-5-丙基吡唑、乙酰丙酮、乙酰乙酸乙酯、丙二酸二乙酯、己内酰胺、苯酚、邻苯二酚中的至少一种。
  6. 一种环保聚氨酯固化剂的制备方法，其特征在于：在多异氰酸酯预聚物和二异氰酸酯的混合物中，加入小分子磺酸盐二元醇扩链剂进行扩链反应，得到含有磺酸基团的多异氰酸酯预聚物，再加入含氢化合物封闭剂将端异氰酸酯基进行封闭，得到权利要求1~5任一项所述的环保聚氨酯固化剂。
  7. 根据权利要求6所述的一种环保聚氨酯固化剂的制备方法，其特征在于：包括以下步骤：
    a）制备小分子磺酸盐二元醇：在酯化釜中，将小分子二元醇和二羧基磺酸盐进行酯化反应，制得小分子磺酸盐二元醇；
    b）制备含有磺酸基团的多异氰酸酯预聚物：在反应釜中，将多异氰酸酯预聚物、二异氰酸酯、小分子磺酸盐二元醇和有机溶剂混合，加热反应；
    c）制备环保聚氨酯固化剂：在反应釜中，继续加入含氢化合物，加热反应，出料，得到环保聚氨酯固化剂。
  8. 根据权利要求7所述的一种环保聚氨酯固化剂的制备方法，其特征在于：步骤b）中，加热反应的温度为50~90℃，反应时间为3~9小时；步骤c）具体为，调节反应釜温度为50~70℃，在1~3小时内加完含氢化合物，再在70~80℃下保温2~5小时，然后降温出料，得到环保聚氨酯固化剂。
  9. 根据权利要求7所述的一种环保聚氨酯固化剂的制备方法，其特征在于：步骤c）中，有机溶剂为醇类、醚类、酮类、二醇醚酯类、醋酸酯类、酰胺类溶剂中的至少一种。
  10. 一种聚氨酯烤漆或聚氨酯高温胶，其特征在于：包括权利要求1~5任一项所述的一种环保聚氨酯固化剂。
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