CN111320930A - Solvent-free polyurethane moisture curing coating and preparation method thereof - Google Patents

Solvent-free polyurethane moisture curing coating and preparation method thereof Download PDF

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Publication number
CN111320930A
CN111320930A CN202010274333.9A CN202010274333A CN111320930A CN 111320930 A CN111320930 A CN 111320930A CN 202010274333 A CN202010274333 A CN 202010274333A CN 111320930 A CN111320930 A CN 111320930A
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Prior art keywords
solvent
free polyurethane
filler
polyol
mass
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陈俊
刘倩
范亮亮
焦海山
苏平
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Wuhan Shiquanxing Polyurethane Technology Co ltd
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Wuhan Shiquanxing Polyurethane Technology Co ltd
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    • 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
    • C09D175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F118/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F120/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/675—Low-molecular-weight compounds
    • 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
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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    • 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
    • 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
    • C09D175/06—Polyurethanes from polyesters
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2272—Ferric oxide (Fe2O3)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a solvent-free polyurethane moisture curing coating and a preparation method thereof, belonging to the technical field of coatings, and the coating comprises the steps of modifying polyisocyanate by enol or acrylate, carrying out unsaturated double bond copolymerization under the action of an initiator to obtain a modified polyisocyanate prepolymer, mixing and reacting the modified polyisocyanate prepolymer with hydroxyl polyol containing pigment and filler, dispersing and uniformly grinding the mixture, and then continuously carrying out dehydration treatment to obtain the solvent-free polyurethane moisture curing coating. The coating has high peel strength and high viscosity.

Description

Solvent-free polyurethane moisture curing coating and preparation method thereof
Technical Field
The invention relates to a polyurethane coating, belongs to the technical field of coatings, and particularly relates to a solvent-free polyurethane moisture curing coating and a preparation method thereof.
Background
Polyurethane coatings are the common coatings at present and can be divided into two-component polyurethane coatings and one-component polyurethane coatings. Two-component polyurethane coatings are generally composed of two parts, usually referred to as a hardener component and a base component, of an isocyanate prepolymer (also called a low molecular urethane polymer) and a hydroxyl group-containing resin. The coating has a plurality of varieties and wide application range, generally has good mechanical property, higher solid content and better performances in all aspects, and is a coating variety with development prospect at present. Through the improvement of the formula, the coating film of the polyurethane can be made into a high-hardness coating film and also can be made into an elastic coating film with excellent flexibility, thereby greatly enhancing the application range of the polyurethane coating. The polyurethane paints produced at present can be classified according to different standards and methods, such as the type of isocyanate, the drying process of the paint or the dispersion medium. However, the film composition and curing mechanism are conventionally used for classification, and the classification can be roughly divided into the following five major categories.
1. An oxygen-curable polyurethane modified oil coating; 2. moisture-curable polyurethane coatings; 3. a blocked polyurethane coating; 4. catalytic curing polyurethane coating; 5. two-component hydroxyl curing type polyurethane coating. The moisture-curing polyurethane coating is a prepolymer containing a stone end group, is cured into a film through a urea bond generated by the reaction with moisture in the air, is mainly used for preparing moisture-curing polyurethane paint, has good wear resistance, and is usually used as floor varnish. Such coatings have a high tolerance to harsh climatic conditions, such as low temperatures and temperature variations, and surface moisture.
However, as the solid content of 1, most of the moisture-cured polyurethane coating is 30-75%, and the rest is ester, ether and aromatic solvent, a large amount of VOC (volatile organic compounds) is discharged in the using process, so that the environment is polluted; 2. the conventional solvent-based moisture-cured polyurethane coating is a hazardous chemical substance and is not beneficial to transportation and storage; 3. in the construction process, a large amount of solvent is volatilized, so that the construction environment is large in irritation and toxicity, and great in harm to human bodies; 4. in the conventional solvent-based moisture-cured polyurethane coating, the curing of a paint film is greatly influenced by the environment and is slow; 5. the common solvent-based moisture-cured polyurethane coating has too high viscosity and is not suitable for construction.
Disclosure of Invention
The invention discloses a solvent-free polyurethane moisture curing coating and a preparation method thereof, the coating is solvent-free and stable in storage, and solves the problems of high pollution, strong smell, high toxicity, difficult construction and the like of the traditional solvent-based polyurethane moisture curing coating.
In order to achieve the aim, the invention discloses a preparation method of a solvent-free polyurethane moisture curing type coating, which is characterized by comprising the following steps:
1) preparation of modified polyisocyanate monomer: reacting polyisocyanate, a polymerization inhibitor and enol or acrylate under the protection of inert gas to obtain a modified polyisocyanate monomer;
2) preparing a modified polyisocyanate prepolymer: placing part of the modified polyisocyanate monomer prepared in the step 1) into a reaction container, slowly dropwise adding a mixture of the rest of the modified polyisocyanate monomer and an initiator which are uniformly mixed into the reaction container, and reacting to obtain a modified polyisocyanate prepolymer;
3) preparation of hydroxyl polyol containing pigment and filler: uniformly mixing hydroxyl polyol, pigment filler and coating auxiliary agent, grinding and discharging to obtain hydroxyl polyol containing pigment filler;
4) preparing a solvent-free polyurethane moisture curing type coating: and (3) reacting the hydroxyl polyol containing the pigment and filler prepared in the step 3) with the modified polyisocyanate prepolymer prepared in the step 2) and a polyurethane catalyst to prepare the solvent-free polyurethane moisture curing coating.
Further, in the step 1), the mass of the enol or the acrylate is 15-40% of that of the solvent-free blocked colored polyisocyanate curing agent, the enol comprises at least one of allyl alcohol, 2-butenol, 1, 4-butenediol, 3-methyl-2-buten-1-ol, cis-2-penten-1-ol, trans-2-hexenol, 3-phenyl-2-propenol and 1-cyclohexyl-2-butenol, and the acrylate comprises one or more of hydroxyethyl acrylate, β -hydroxyethyl (meth) acrylate, β -hydroxypropyl (meth) acrylate or 2-hydroxy-3-phenoxypropyl acrylate.
Preferably, the enol is a mixture of allyl alcohol and 1-cyclohexyl-2-butenol in a molar ratio of 1: 1. The prepared coating has good stripping resistance and low viscosity.
Preferably, the acrylate is a mixture of hydroxyethyl acrylate and (methyl) acrylic acid- β -hydroxyethyl ester, the molar ratio of the hydroxyethyl acrylate to the (methyl) acrylic acid- β -hydroxyethyl ester is 1: 1.
Further, the specific reaction process of step 1) is as follows:
heating the polyisocyanate and the polymerization inhibitor in the formula ratio to 60-80 ℃, slowly dripping enol or acrylic ester, reacting for 2-4 hours in a heat preservation manner after dripping is finished, and cooling and discharging when the measured NCO value is reduced to a theoretical value to obtain the modified polyisocyanate monomer.
Further, the mass ratio of the modified polyisocyanate monomers mixed in two steps in the step 2) is 1: 1-6: 1.
In step 3), the mass of the hydroxyl polyol is 20-85% of that of the hydroxyl polyol containing the pigment and the filler, and the hydroxyl polyol contains one or more of polyester polyol, polyether polyol, polyolefin polyol, vegetable oil polyol, rosin ester polyol, amine-terminated polyether, fatty acid dimer diol or dimer polyester diol.
Further, in the step 3), the coating auxiliary agent mainly comprises a dispersing agent, an antifoaming agent and a thickening agent, wherein the mass of the dispersing agent is 0.3-4.5% of the mass of the hydroxyl polyol containing the pigment and filler, and the mass of the antifoaming agent is 0.2-4.5% of the mass of the hydroxyl polyol containing the pigment and filler; the mass of the thickening agent is 0.3-5.0% of that of the hydroxyl polyalcohol containing the pigment and the filler.
Further, the specific reaction process of step 4) is as follows:
adding the measured hydroxyl polyalcohol containing the pigment and the filler into a reaction bottle bottom with stirring, dehydrating for 2 hours at 120 ℃ in vacuum, reducing the vacuum degree to be more than or equal to 0.045Kpa, cooling to 65-85 ℃, adding the measured modified polyisocyanate prepolymer and the polyurethane catalyst, reacting for 2.5 hours, cooling and discharging to obtain the solvent-free polyurethane moisture curing coating.
Further, the mass of the polyurethane catalyst accounts for 0.01-4.0% of the mass of the solvent-free polyurethane moisture curing coating.
In addition, the invention also discloses a solvent-free polyurethane moisture curing type coating which is characterized by being prepared by the preparation method.
Further, the solvent-free polyurethane moisture-curable coating has a viscosity of 1000 to 1350mPa · s at room temperature and a peel strength of 90 to 140 kN/m.
Advantageous effects
According to the preparation method disclosed by the invention, through the reaction of the isocyanate group and the enol containing hydroxyl or the unsaturated ester compound containing hydroxyl, unsaturated double bonds are introduced on the polyisocyanate, and then the unsaturated double bonds are utilized for carrying out free radical copolymerization, so that the viscosity of the curing agent is reduced while the content of NCO is provided, and meanwhile, the hydroxyl component is further introduced, so that the solvent-free polyurethane moisture curing colored paint with stable storage is prepared, the application field of the single-component polyurethane moisture curing paint is greatly expanded, and the preparation method has a very wide market prospect in an environment-friendly society.
Detailed Description
The invention discloses a preparation method of a solvent-free closed colored polyisocyanate curing agent, which comprises the following steps:
1) preparation of modified polyisocyanate monomer (K)
Under the protection of nitrogen, adding polyisocyanate (A) and a polymerization inhibitor (B) with a designed formula ratio into a four-opening reactor with a thermometer and a condenser pipe and stirring, heating to 60-80 ℃ by using an electrothermal sleeve, slowly dripping enol or acrylic ester (C) for about 1 hour, carrying out heat preservation reaction for 2-4 hours, then beginning to measure the NCO content, and cooling and discharging when the NCO value is reduced to a theoretical value to obtain a modified polyisocyanate monomer (K);
2) preparation of modified polyisocyanate prepolymer (L)
Under the protection of nitrogen, placing part of modified polyisocyanate monomer (K) at the bottom of a reaction bottle, stirring and mixing the rest of modified polyisocyanate monomer (K) and an initiator (D) uniformly, slowly dropwise adding into the reaction bottle (dropwise adding is completed within about 3 hours), reacting at 70-80 ℃, preserving heat for 1 hour after dropwise adding, and discharging to obtain modified polyisocyanate prepolymer (L);
3) preparation of a hydroxy polyol (E) containing pigments and fillers
Sequentially adding the measured hydroxyl polyol, the dispersing agent, the defoaming agent and the thickening agent into a container, keeping the dispersing speed at 800-1200 r/min, and stirring for 10-15 min; adding a pigment and a filler, keeping the dispersion speed at 1200-2000 r/min, dispersing for 15-25 min, putting the slurry into a sand mill for grinding, and discharging when the fineness is reduced to below 25 mu m to obtain hydroxyl polyol (E) containing the pigment and the filler;
4) preparation of solvent-free polyurethane moisture-curable coating (A)
Adding metered hydroxyl polyol (E) containing pigment and filler into a reaction bottle bottom with stirring, dehydrating for 2 hours at 120 ℃ in vacuum, reducing the vacuum degree to be more than or equal to 0.045Kpa, cooling to 65-85 ℃, adding metered modified polyisocyanate prepolymer (L) and a certain amount of polyurethane catalyst (F), reacting for 2.5 hours, cooling and discharging to obtain solvent-free polyurethane moisture curing coating (A);
wherein the dosage of the enol or the acrylate is 15-40% of the solvent-free blocked colored polyisocyanate curing agent.
The enol comprises at least one of allyl alcohol, 2-butenol, 1, 4-butenediol, 3-methyl-2-buten-1-ol, cis-2-penten-1-ol, trans-2-hexenol, 3-phenyl-2-propenol and 1-cyclohexyl-2-butenol, and the acrylate comprises one or more of hydroxyethyl acrylate, β -hydroxyethyl (meth) acrylate, β -hydroxypropyl (meth) acrylate or 2-hydroxy-3-phenoxypropyl acrylate, preferably 3-methyl-2-buten-1-ol or β -hydroxyethyl (meth) acrylate.
The polyisocyanate comprises diisocyanate or one of dimer or trimer thereof, and the amount of the polyisocyanate accounts for 55-80% of the mass of the solvent-free closed colored polyisocyanate curing agent.
The polyisocyanate includes Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymeric diphenylmethane diisocyanate (PAPI), Hexamethylene Diisocyanate (HDI), HDI biuret, HDI trimer, isophorone diisocyanate (IPDI), IPDI trimer, Xylylene Diisocyanate (XDI), 4-dicyclohexylmethane diisocyanate (H)12MDI), cyclohexanedimethylene diisocyanate (H)6XDI) or tetramethylxylylene diisocyanate (TMXDI). Preferably TDI, MDI, IPDI, HDI, H12MDI。
The polymerization inhibitor comprises p-methylol anisole or hydroquinone.
The dosage of the initiator is 0.05-5.0% of enol or acrylate, and the initiator comprises one or more of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butyl peroxy-3, 5, 5-trimethylacetate, 2, 5-dimethyl-2, 5-di-tert-butyl peroxy hexane, dilauroyl peroxide or cumene hydroperoxide. Azobisisobutyronitrile is preferred.
The hydroxyl polyol (G) mainly comprises: polyester polyol (molecular weight 500-2500), polyether polyol (molecular weight 500-2500), polyolefin polyol, vegetable oil polyol, rosin ester polyol, amine-terminated polyether, fatty acid dimer diol, dimer polyester diol, and the like; the dosage of the pigment-filler-containing hydroxyl polyol E is 20-85% of the mass of the pigment-filler-containing hydroxyl polyol E;
the polyurethane catalyst is 0.01-3.0% of the mass of the solvent-free closed colored polyisocyanate curing agent and mainly comprises an organic metal compound or organic tertiary amine, wherein the organic metal compound comprises one or more of stannous octoate, dibutyltin dilaurate, lead octoate and iron octoate, and the organic tertiary amine comprises at least one of triethylamine, N-dimethylcyclohexylamine, triethylenediamine, N-dimethylbenzylamine or N, N-dimethylbutylamine. In the invention, an organic metal compound catalyst such as dibutyltin dilaurate is preferably used, and the using amount of the organic metal compound catalyst is 0.01-3.0% of the mass of the solvent-free closed type colored polyurethane moisture curing coating A.
The environment-friendly color paste mainly comprises epoxidized soybean oil, pigment fillers and coating additives. Wherein the amount of the epoxidized soybean oil is 30-85% of the mass of the environment-friendly color paste; the pigment and filler mainly comprises: titanium dioxide, zinc oxide, iron oxide red, iron oxide yellow, carbon black, phthalocyanine blue, phthalocyanine green, talcum powder, calcium carbonate, barium sulfate, quartz powder and the like, and the dosage of the titanium dioxide, the zinc oxide, the iron oxide red, the iron oxide yellow, the carbon black, the phthalocyanine blue, the phthalocyanine green, the talcum powder, the calcium carbonate, the barium sulfate, the quartz powder and the like is 25-80% of the total. The coating auxiliary agent comprises: dispersants, defoamers, thickeners, and the like. The dispersing agent in the coating auxiliary agent is one or more of macromolecular polycarboxylate, polyacrylate, long-chain polyaminoamide and salt of macromolecular acid ester, phosphate salt and macromolecular unsaturated polycarboxylic acid, and the dosage of the dispersing agent is 0.3-4.5% of the mass of the environment-friendly color paste. The defoaming agent comprises the following components: lower alcohol and ester, higher fatty acid metal soap, lower alkyl phosphate, organic silicon resin, modified organic silicon resin, silicon dioxide and organic silicon mixture, organic high molecular polymer, oligomer derivative, etc. Preferably, polysiloxane defoaming agent is selected, and the dosage of the defoaming agent is 0.2-4.5% of the mass of the environment-friendly color paste. The thickening agent in the paint auxiliary agent comprises the following components: cellulose, polyurethane-associated, organobentonite, castor oil derivatives, and polyethylene wax. Preferably, organic bentonite is selected, and the dosage of the organic bentonite is 0.3-5.0% of the mass of the environment-friendly color paste.
In order to better illustrate the preparation process of the present invention, the following description is given with reference to specific examples.
Example 1
Under the protection of nitrogen, 1578 parts of Hexamethylene Diisocyanate (HDI) and 1.5 parts of polymerization inhibitor (p-hydroxymethyl anisole) are added into a four-opening reactor which is provided with a thermometer, a condenser pipe and a stirrer, the reactor is heated to 60-80 ℃ by an electric heating jacket, 416 parts of hydroxyethyl acrylate is slowly dripped, dripping is completed within about 1 hour, the temperature is kept for 2-4 hours, then the NCO content is measured, when the NCO value is less than or equal to 32.78% (according to the experimental design, the NCO content when hydroxyl in the raw materials is completely reacted accounts for the percentage of the total amount of the resin), the temperature is reduced, discharging is carried out, and the modified polyisocyanate monomer is obtained.
Under the protection of nitrogen, 399 parts of the prepared modified polyisocyanate monomer is placed at the bottom of a reaction bottle, 1595 parts of the prepared modified polyisocyanate monomer and 9 parts of azodiisobutyronitrile are stirred and mixed uniformly, the mixture is slowly dripped into the reaction bottle (after dripping is finished for about 3 hours), the reaction is carried out at the temperature of 70-80 ℃, heat is preserved for 1 hour after dripping is finished, and the modified polyisocyanate prepolymer is obtained.
Preparation of hydroxyl polyol containing pigment and filler: sequentially adding 60 parts of polyether polyol (with the molecular weight of 1000 and the hydroxyl value of 112), 3 parts of dispersing agent (KENT 180), 0.5 part of defoaming agent (BYK-052) and 1.5 parts of organic bentonite into a container, keeping the dispersing speed at 800-1200 r/min, and stirring for 10-15 min; 2. adding 30 parts of titanium dioxide and 5 parts of talcum powder, keeping the dispersion speed at 1200-2000 r/min, dispersing for 15-25 min, putting the slurry into a sand mill for grinding, and discharging when the fineness is reduced to below 25 mu m to obtain hydroxyl polyol containing pigment and filler;
60 parts of the prepared hydroxyl polyol containing the pigment and filler is added into a reaction bottle bottom with stirring, vacuum dehydration is carried out for 2 hours at 120 ℃, the vacuum degree is more than or equal to 0.045Kpa, the temperature is reduced to 65-85 ℃, 140 parts of modified polyisocyanate prepolymer and 1.2 parts of dibutyltin dilaurate are added, the reaction is carried out for 2.5 hours, the temperature is reduced and the material is discharged, and the solvent-free polyurethane moisture curing type coating is obtained, wherein the theoretical NCO of the coating is 21.43 percent.
Example 2
Under the protection of nitrogen, adding 1145 parts of Hexamethylene Diisocyanate (HDI) and 2 parts of a polymerization inhibitor (p-hydroxymethyl anisole) into a four-opening reactor with a thermometer, a condenser and a stirrer, heating the reactor to 60-80 ℃ by using an electrothermal sleeve, slowly dripping 478 parts of hydroxyethyl methacrylate for about 1 hour, carrying out heat preservation reaction for 2-4 hours, then beginning to measure the NCO content, and when the NCO value is less than or equal to 26.37% (according to the experimental design, the NCO content of the raw materials when hydroxyl is completely reacted accounts for the percentage of the total amount of resin), cooling and discharging to obtain the modified polyisocyanate monomer.
Under the protection of nitrogen, 325 parts of the prepared modified polyisocyanate monomer is placed at the bottom of a reaction bottle, 1298 parts of the prepared modified polyisocyanate monomer and 7 parts of azodiisobutyronitrile are stirred and mixed uniformly, the mixture is slowly dripped into the reaction bottle (after dripping is finished for about 3 hours), the reaction is carried out at the temperature of 70-80 ℃, and the mixture is subjected to heat preservation for 1 hour after dripping is finished, so that the modified polyisocyanate prepolymer is obtained.
Preparation of hydroxyl polyol containing pigment and filler: sequentially adding 70 parts of polyether polyol (with the molecular weight of 500 and the hydroxyl value of 112), 3.5 parts of dispersing agent (KENT 180), 0.5 part of defoaming agent (BYK-052) and 2 parts of organic bentonite into a container, keeping the dispersing speed at 800-1200 r/min, and stirring for 10-15 min; 2. adding 10 parts of carbon black, 5 parts of barium sulfate and 9 parts of calcium carbonate, keeping the dispersion speed at 1200-2000 r/min, dispersing for 15-25 min, putting the slurry into a sand mill for grinding, and discharging when the fineness is reduced to below 25 mu m to obtain hydroxyl polyol containing pigment and filler;
60 parts of the prepared hydroxyl polyol containing the pigment and filler is added into a reaction bottle bottom with stirring, vacuum dehydration is carried out for 2 hours at 120 ℃, the vacuum degree is more than or equal to 0.045Kpa, the temperature is reduced to 65-85 ℃, 140 parts of modified polyisocyanate prepolymer and 1.5 parts of dibutyltin dilaurate are added, the reaction is carried out for 2.5 hours, the temperature is reduced and the material is discharged, and the solvent-free polyurethane moisture curing type coating is obtained, wherein the theoretical NCO of the coating is 14.93 percent.
Example 3
Under the protection of nitrogen, 1245 parts of isophorone diisocyanate (IPDI) and 2 parts of polymerization inhibitor (hydroquinone) are added into a four-opening reactor with a thermometer, a condenser and a stirrer, the reactor is heated to 60-80 ℃ by an electrothermal sleeve, 413 parts of hydroxyethyl methacrylate is slowly dripped, the dripping is finished within about 1 hour, the reaction is carried out for 2-4 hours under the condition of heat preservation, then the determination of NCO content is started, when the NCO value is less than or equal to 20.85 percent (according to the experimental design, the NCO content of hydroxyl in the raw materials during the complete reaction accounts for the percentage of the total amount of resin), the temperature is reduced, and the material is discharged, so that the modified polyisocyanate monomer is obtained.
Under the protection of nitrogen, 332 parts of the prepared modified polyisocyanate monomer is placed at the bottom of a reaction bottle, 1326 parts of the prepared modified polyisocyanate monomer and 9 parts of azodiisobutyronitrile are stirred and mixed uniformly, the mixture is slowly dripped into the reaction bottle (after dripping is finished for about 3 hours), the reaction is carried out at the temperature of 70-80 ℃, heat is preserved for 1 hour after dripping is finished, and the modified polyisocyanate prepolymer is obtained.
Preparation of hydroxyl polyol containing pigment and filler: sequentially adding 60 parts of polyether polyol (with the molecular weight of 400 and the hydroxyl value of 112), 3 parts of dispersing agent (KENT 180), 0.5 part of defoaming agent (BYK-058) and 2 parts of organic bentonite into a container, keeping the dispersing speed at 800-1200 r/min, and stirring for 10-15 min; 2. adding 20 parts of iron oxide red, 10 parts of barium sulfate and 4.5 parts of calcium carbonate, keeping the dispersion speed at 1200-2000 r/min, dispersing for 15-25 min, putting the slurry into a sand mill for grinding, and discharging when the fineness is reduced to below 25 mu m to obtain hydroxyl polyol containing pigment and filler;
60 parts of the prepared hydroxyl polyol containing the pigment and filler is added into a reaction bottle bottom with stirring, vacuum dehydration is carried out for 2 hours at 120 ℃, the vacuum degree is more than or equal to 0.045Kpa, the temperature is reduced to 65-85 ℃, 140 parts of modified polyisocyanate prepolymer and 1.5 parts of dibutyltin dilaurate are added, the reaction is carried out for 2.5 hours, the temperature is reduced and the material is discharged, and the solvent-free polyurethane moisture curing type coating is obtained, wherein the theoretical NCO of the coating is 10.82%.
Example 4
Under the protection of nitrogen, 1365 parts of hexamethylene diisocyanate (IPDI) and 2 parts of polymerization inhibitor (hydroquinone) are added into a four-opening reactor with a thermometer and a condenser pipe and stirring, heated to 60-80 ℃ by an electrothermal sleeve, slowly dropped with 420 parts of hydroxyethyl acrylate, dropped for about 1 hour, subjected to heat preservation reaction for 2-4 hours, and then the determination of NCO content is started, when the NCO value is less than or equal to 20.90% (according to the experimental design, the NCO content of the raw materials when hydroxyl groups are completely reacted accounts for the percentage of the total amount of resin), the temperature is reduced, and discharging is carried out, thus obtaining the modified polyisocyanate monomer.
Under the protection of nitrogen, 357 parts of the prepared modified polyisocyanate monomer is placed at the bottom of a reaction bottle, 1428 parts of the prepared modified polyisocyanate monomer and 8 parts of azobisisobutyronitrile are stirred and mixed uniformly, the mixture is slowly dripped into the reaction bottle (after dripping is finished for about 3 hours), the reaction is carried out at 70-80 ℃, heat is preserved for 1 hour after dripping is finished, and the modified polyisocyanate prepolymer is obtained.
Preparation of hydroxyl polyol containing pigment and filler: sequentially adding 70 parts of polyether polyol (with the molecular weight of 1000 and the hydroxyl value of 168), 2 parts of dispersing agent (KENT 180), 0.5 part of defoaming agent (BYK-052) and 2 parts of organic bentonite into a container, keeping the dispersing speed at 800-1200 r/min, and stirring for 10-15 min; 2. adding 10 parts of phthalocyanine blue, 5.5 parts of barium sulfate and 10 parts of calcium carbonate, keeping the dispersion speed at 1200-2000 r/min, dispersing for 15-25 min, putting the slurry into a sand mill, grinding, and discharging when the fineness is reduced to below 25 mu m to obtain hydroxyl polyol containing pigment and filler;
60 parts of the prepared hydroxyl polyol containing the pigment and the filler is added into a reaction bottle bottom with stirring, vacuum dehydration is carried out for 2 hours at 120 ℃, the vacuum degree is more than or equal to 0.045Kpa, the temperature is reduced to 65-85 ℃, 140 parts of modified polyisocyanate prepolymer and 1.5 parts of stannous octoate are added, the reaction is carried out for 2.5 hours, the temperature is reduced and the material is discharged, and the solvent-free polyurethane moisture curing type coating is obtained, wherein the theoretical NCO of the coating is 11.98%.
Example 5 in order to replace hydroxyethyl acrylate by the amount of β -hydroxyethyl (meth) acrylate used in a pair on the basis of example 1, the rest was the same as in example 1.
Example 6 in order to replace hydroxyethyl acrylate by the amount of 2-hydroxy-3-phenoxypropyl acrylate used in a pair on the basis of example 1, the rest remains the same as in example 1.
Example 7 in order to replace hydroxyethyl methacrylate by the amount of 3-methyl-2-buten-1-ol applied in pairs on the basis of example 2, the rest was the same as in example 2.
Example 8 in order to replace the amount of 2-butenol used in pairs with hydroxyethyl methacrylate on the basis of example 2, the rest remains the same as in example 2.
Example 9 in order to replace hydroxyethyl methacrylate by the amount of 1, 4-butenediol used in pairs on the basis of example 2, the rest of the procedure was the same as in example 2.
Example 10 in order to replace hydroxyethyl methacrylate by the amount of cis-2-penten-1-ol used in pairs on the basis of example 2, the rest remained the same as in example 2.
Example 11 in order to replace hydroxyethyl methacrylate by the amount of trans-2-hexenol applied in pairs on the basis of example 2, the rest remains the same as in example 2.
Example 12 in order to replace the amount of 3-phenyl-2-propenol used in pairs with hydroxyethyl methacrylate on the basis of example 2, the rest remains the same as in example 1.
Example 13 in order to replace hydroxyethyl methacrylate by the amount of 1-cyclohexyl-2-butenol used in pairs on the basis of example 2, the rest remains the same as in example 1.
Example 14 in order to replace Hexamethylene Diisocyanate (HDI) with the HDI biuret in the amount applied on the basis of example 1, the rest remained the same as in example 1.
Example 15 in order to replace Hexamethylene Diisocyanate (HDI) with the applied amount of HDI trimer on the basis of example 1, the rest remained the same as in example 1.
Examples 16 to 20 were carried out in the same manner as in example 1 except that the amounts of the initiators used in example 1 were adjusted to 0.05%, 0.1%, 0.5%, 1% and 3% of the enol or the acrylate, respectively.
Examples 21 to 23 are obtained by replacing polyether polyol with polyester polyol having a molecular weight of 500, 1000 or 2000 in an amount applied in addition to example 1.
Example 24 the polyether polyol was replaced with the polyolefin polyol in the application-specific amount on the basis of example 1.
Example 25 the polyether polyol was replaced with the vegetable oil polyol in the application-specific amount on the basis of example 1.
Example 26 the polyether polyol was replaced on the basis of example 1 by the rosin ester polyol in the amount applied in pairs.
Example 27 the polyether polyol was replaced on the basis of example 1 by the amino-terminated polyether in the amount applied in pairs.
Example 28 the polyether polyol was replaced on the basis of example 1 by the amino-terminated polyether in the amount applied in pairs.
Example 29 the polyether polyol was replaced on the basis of example 1 by the fatty acid dimer diol in the amount applied in pairs.
Example 30 the polyether polyol was replaced on the basis of example 1 by the dimeric polyester diol in the application-specific amount.
Example 31 example 1 is based on the replacement of hydroxyethyl acrylate by a mixture of allyl alcohol and 1-cyclohexyl-2-butenol in a molar ratio of 1:1, applied in pairs.
Example 32 in addition to example 1, hydroxyethyl acrylate was replaced by a mixture of hydroxyethyl acrylate and- β -hydroxyethyl (meth) acrylate in a molar ratio of 1:1, applied in pairs.
Wherein, the performance lists of the polyurethane coatings prepared in examples 5-32 are shown in the following table 1
Figure BDA0002444243610000111
Figure BDA0002444243610000121
The peel strength test in table 1 includes placing a sample mold on a vulcanizing machine, heating to 130 °, placing a metal iron sheet, uniformly coating the coating prepared by the method on the surface of the metal iron sheet, adhering a PU elastomer, solidifying for 40min, pressurizing for 30min, and then removing the mold. Experiments show that the paint has good peel strength and short curing period, so that the cured colored paint prepared by the benzene can be used in the technical fields of terraces, steel, plastics, ships, engineering machinery and the like.
In addition, as can be seen from table 1, the polyurethane coating prepared according to the present invention has a low viscosity while maintaining a relatively high solid content, so that the coating has a certain viscosity advantage.

Claims (10)

1. A preparation method of solvent-free polyurethane moisture curing type paint is characterized by comprising the following steps:
1) preparation of modified polyisocyanate monomer: reacting polyisocyanate, a polymerization inhibitor and enol or acrylate under the protection of inert gas to obtain a modified polyisocyanate monomer;
2) preparing a modified polyisocyanate prepolymer: putting part of the modified polyisocyanate monomer prepared in the step 1) into a reaction container, dropwise adding a mixture of the rest of the modified polyisocyanate monomer and an initiator which are uniformly mixed into the reaction container, and reacting to obtain a modified polyisocyanate prepolymer;
3) preparation of hydroxyl polyol containing pigment and filler: uniformly mixing hydroxyl polyol, pigment filler and coating auxiliary agent, grinding and discharging to obtain hydroxyl polyol containing pigment filler;
4) preparing a solvent-free polyurethane moisture curing type coating: and (3) reacting the hydroxyl polyol containing the pigment and filler prepared in the step 3) with the modified polyisocyanate prepolymer prepared in the step 2) and a polyurethane catalyst to prepare the solvent-free polyurethane moisture curing coating.
2. The method for preparing the solvent-free polyurethane moisture-curable coating according to claim 1, wherein in the step 1), the mass of the enol or the acrylate is 15-40% of that of the solvent-free blocked colored polyisocyanate curing agent, the enol comprises at least one of allyl alcohol, 2-butenol, 1, 4-butenediol, 3-methyl-2-buten-1-ol, cis-2-penten-1-ol, trans-2-hexenol, 3-phenyl-2-propenol and 1-cyclohexyl-2-butenol, and the acrylate comprises one or more of hydroxyethyl acrylate, β -hydroxyethyl (meth) acrylate, β -hydroxypropyl (meth) acrylate or 2-hydroxy-3-phenoxypropyl acrylate.
3. The method for preparing the solvent-free polyurethane moisture-curable coating according to claim 1 or 2, wherein the specific reaction process of step 1) is as follows:
heating the polyisocyanate and the polymerization inhibitor in the formula ratio to 60-80 ℃, slowly dripping enol or acrylic ester, reacting for 2-4 hours in a heat preservation manner after dripping is finished, and cooling and discharging when the measured NCO value is reduced to a theoretical value to obtain the modified polyisocyanate monomer.
4. The method for preparing the solvent-free polyurethane moisture-curable coating material according to claim 1 or 2, wherein the modified polyisocyanate monomers are mixed in two steps in step 2) in a mass ratio of 1: 1-6: 1.
5. The method for preparing the solvent-free polyurethane moisture-curable coating according to claim 1 or 2, wherein in the step 3), the mass of the hydroxyl polyol is 20-85% of the mass of the hydroxyl polyol containing the pigment and the filler, and the hydroxyl polyol contains one or more of polyester polyol, polyether polyol, polyolefin polyol, vegetable oil polyol, rosin ester polyol, amine-terminated polyether, fatty acid dimer diol or dimer polyester diol.
6. The preparation method of the solvent-free polyurethane moisture-curable coating according to claim 1 or 2, wherein in the step 3), the coating auxiliary agent mainly comprises a dispersing agent, a defoaming agent and a thickening agent, wherein the mass of the dispersing agent is 0.3-4.5% of the mass of the hydroxyl polyol containing the pigment and filler, and the mass of the defoaming agent is 0.2-4.5% of the mass of the hydroxyl polyol containing the pigment and filler; the mass of the thickening agent is 0.3-5.0% of that of the hydroxyl polyalcohol containing the pigment and the filler.
7. The method for preparing the solvent-free polyurethane moisture-curable coating according to claim 1 or 2, wherein the specific reaction process of the step 4) is as follows:
adding the measured hydroxyl polyalcohol containing the pigment and the filler into a reaction bottle bottom with stirring, dehydrating for 2 hours at 120 ℃ in vacuum, reducing the vacuum degree to be more than or equal to 0.045Kpa, cooling to 65-85 ℃, adding the measured modified polyisocyanate prepolymer and the polyurethane catalyst, reacting for 2.5 hours, cooling and discharging to obtain the solvent-free polyurethane moisture curing coating.
8. The method for preparing the solvent-free polyurethane moisture-curable coating according to claim 7, wherein the mass of the polyurethane catalyst accounts for 0.01-4.0% of the mass of the solvent-free polyurethane moisture-curable coating.
9. A solvent-free polyurethane moisture-curable coating which is obtained by the production process according to claim 1.
10. The solvent-free polyurethane moisture-curable coating material according to claim 8, wherein the viscosity at room temperature is 1000 to 1350 mPa-s, and the peel strength is 90 to 140 kN/m.
CN202010274333.9A 2020-04-09 2020-04-09 Solvent-free polyurethane moisture curing coating and preparation method thereof Pending CN111320930A (en)

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CN105669990A (en) * 2016-03-01 2016-06-15 武汉仕全兴聚氨酯科技股份有限公司 Preparation method of water dispersive acrylate modified polyisocyanate curing agent
CN109651998A (en) * 2018-11-01 2019-04-19 襄阳精信汇明科技股份有限公司 A kind of low viscosity single-component solvent-free polyurethane adhesive and its preparation method and application

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1778826A (en) * 2004-11-25 2006-05-31 拜尔材料科学股份公司 Polyisocyanate mixtures, process for their preparation and their use in coating compositions
WO2009005835A2 (en) * 2007-07-03 2009-01-08 Henkel Corporation Acrylated urethanes, processes for making the same and curable compositions including the same
CN102167794A (en) * 2010-02-26 2011-08-31 大日精化工业株式会社 Polyurethane prepolymer
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