CN109369872A - A kind of addition hollow microsphere aqueous polyurethane matting resin and preparation method - Google Patents

A kind of addition hollow microsphere aqueous polyurethane matting resin and preparation method Download PDF

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Publication number
CN109369872A
CN109369872A CN201811114985.5A CN201811114985A CN109369872A CN 109369872 A CN109369872 A CN 109369872A CN 201811114985 A CN201811114985 A CN 201811114985A CN 109369872 A CN109369872 A CN 109369872A
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hollow microsphere
polyureas
aqueous polyurethane
matting resin
preparation
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杨建军
丁琳
吴庆云
吴明元
张建安
刘久逸
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Anhui University
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Anhui University
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • 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
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/302—Water
    • 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
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
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    • 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
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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    • 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
    • C09D175/06—Polyurethanes from polyesters
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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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/65—Additives macromolecular
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/18—Spheres
    • C08L2205/20—Hollow spheres

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  • Polyurethanes Or Polyureas (AREA)
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Abstract

The present invention relates to a kind of aqueous polyurethane matting resins and preparation method for adding hollow microsphere.The hollow microsphere is polyureas hollow microsphere, and 200~600nm of average grain diameter, the quality of polyureas hollow microsphere is the 10~30% of the aqueous polyurethane matting resin quality；Aqueous polyurethane matting resin is dried in vacuo obtains glue film in a mold, and the glossiness that 60 ° of glue film is 2.5~4.0, and the tensile strength of glue film is 17.0~22.5MPa.The present invention is reacted using polyisocyanates with water, and amine cross-linking agent is added and generates polyureas core-shell particles, is dissolved out kernel under acetic acid solvent effect, is prepared polyureas hollow microsphere, be added in aqueous polyurethane emulsion, obtain aqueous polyurethane matting resin.Aqueous polyurethane matting resin of the present invention has good intensity, it will not cause to rupture under the effect of the powerful external force and high velocity impact of high-speed mixer and extruder, therefore the aqueous polyurethane glue film extinction formed is good, good mechanical performance improves the stability of aqueous polyurethane matting resin.

Description

A kind of addition hollow microsphere aqueous polyurethane matting resin and preparation method
Technical field
The invention belongs to aqueous low luster coating technical fields, and in particular to a kind of addition hollow microsphere aqueous polyurethane delustring The preparation method of resin.
Background technique
Aqueous low luster coating is not apparent soft dazzling because low gloss is presented by covering with paint body surface after its covering with paint, makes us easypro It is suitable, therefore pursued.As the main film forming component of low luster coating, the preparation of aqueous polyurethane matting resin becomes research Emphasis.The preparation method of most tradition low luster coatings is all by adding delustering agent, and in dried coating film, delustering agent floats on table Rough surface is caused in face, and diffusing reflection occurs for light, to achieve the effect that delustring.For example, a kind of indoor physics extinction type polyester tree Physics delustering agent and a variety of curing accelerators are added in coating, disappears in curing and drying for the preparation method of rouge and coating Photo etching can uniformly be attached to surface of the paint film and generate microcosmic out-of-flatness, reach extinction effect.This method cause auxiliary dosage increase and Glue film performance decline.Another kind has the preparation side of the aqueous polyurethane acrylate chemical quenching resin of reverse phase core-shell structure Method is enriched in aqueous polyether polyurethane macromolecular table using being added at one time acrylic ester monomer and reaching limting concentration Face is copolymerized in combination with one sodium vinyl sulfonate of reactive emulsifier and acrylic ester monomer, make to generate with polyurethane core, Acrylic acid is the aqueous polyurethane acrylate of the reverse phase core-shell structure of shell.Extinction effect caused by the resin is by resin itself Caused by film-forming rear surface forms micro- fold, specific fold situation is related with environmental factor when film forming, therefore gloss It spends more difficult to control.The preparation method of another extinction type aqueous polyurethane emulsion, passes through chemical bond for polyurethane molecular chain first The method of conjunction is coated to functionalized SiO2Or polyaminoester microball lotion is formed on polystyrene hollow microballoon, it is lesser with partial size Aqueous polyurethane emulsion mixing, obtains delustring aqueous polyurethane emulsion；But it is not discussed in detail wherein and how to divide polyurethane Subchain is bonded on tiny balloon, and the partial size of selected microballoon is in 1000 ~ 2000nm, and partial size is more after polyurethane is coated upper microballoon Greatly, uniform particle diameter is difficult to control.
Addition delustering agent low luster coating to reach extinction level, various auxiliary agents need to be added in coating, with help dispersion and Conducive to covering with paint.But also bring along simultaneously such as component easily condense, delustering agent disperse uneven easily settled, glue film appearance like seediness, apply The defects of layer brittleness is big.And be not added with the matting resin of delustering agent by increasing emulsion particle diameter, obtain after the drying rough surface with Reach extinction effect, stability of emulsion difference prepared in this way and glue film poor rigidity.
Summary of the invention
In order to improve the stability of polyurethane matting resin, the technical issues of solution in the presence of the above-mentioned prior art, more Caused performance deficiency after adding delustering agent is mended, the present invention provides a kind of addition hollow microsphere aqueous polyurethane matting resin, together When, the preparation method of addition hollow microsphere aqueous polyurethane matting resin is provided.
A kind of aqueous polyurethane matting resin adding hollow microsphere, sky microballoon therein is polyureas hollow microsphere, polyureas The average grain diameter of hollow microsphere is 200~600nm, and the quality of polyureas hollow microsphere is water in the aqueous polyurethane matting resin The 10~30% of property polyurethane matting resin quality；
One day will be stood under the aqueous polyurethane matting resin room temperature for adding hollow microsphere, the vacuum in polytetrafluoroethylene (PTFE) board mold It is dried to obtain glue film, the glossiness of 60 ° of the glue film is 2.5~4.0, and the tensile strength of glue film is 17.0~22.5MPa.
The operating procedure of the aqueous polyurethane matting resin of preparation addition hollow microsphere is as follows:
Step (1) prepares polyureas core-shell particles
20~30g polyisocyanates is slowly added in 280~480g acetone water mixed liquid reaction medium, keeps turning at 30 DEG C Fast 30rpm is slowly stirred reaction 3h, and the reaction of 8~12g amine cross-linking agent is added, polyureas core-shell particles dispersion liquid is made；
Step (2) prepares polyureas hollow microsphere
Polyureas core-shell particles dispersion liquid ultrasound 30min prepared by step (1) is uniformly dispersed, is centrifuged at a high speed, and will centrifugation Lower layer's microballoon afterwards is cleaned with acetone water mixed liquid, then is centrifuged, and such repeated centrifugation is washed 3 times, obtains centrifugation microballoon；It will centrifugation For microballoon ultrasonic disperse into acetic acid solvent, the additional amount for being centrifuged microballoon is the 2% of acetic acid solvent quality；In 80 DEG C of temperature, revolving speed It under 30rpm, stirs the 8h time, kernel dissolution, then centrifuge washing 3 times obtain polyureas hollow microsphere；The polyureas hollow microsphere Partial size in 200nm~600nm, yield is 83.65~86.79wt%；
Step (3) prepares aqueous polyurethane matting resin
The polyisocyanates of 14~22.5g, 25~30g polyvalent alcohol, 1.4~1.8g hydrophilic chain extender are mixed, in catalyst Under effect, 80 DEG C of reaction 3h are kept；1.5~2g small molecule chain extender 1,4-butanediol is added, 2h is reacted at 65 DEG C, obtains pre- Aggressiveness；In performed polymer be added 1~2g neutralizer in and 5min, stirred under the conditions of revolving speed 3000rpm, and be added 100~ 150g deionized water emulsifies 30min, obtains polyaminoester emulsion；It is subsequently added into polyureas hollow microsphere to be uniformly mixed, polyureas is hollow micro- The additional amount of ball is the 10~30% of polyaminoester emulsion quality, microsphere surface-NH2With residue-NCO in polyaminoester emulsion Reaction obtains the aqueous polyurethane matting resin of addition hollow microsphere.
The technical solution further limited is as follows:
In step (1), (2), acetone and water are uniformly mixed obtained acetone water mixed liquid by mass ratio 6~8:2~4.
In step (3), the polyisocyanates is toluene di-isocyanate(TDI), 1,6- hexamethylene diisocyanate, different Buddhist That ketone diisocyanate (IPDI), hexamethylene -1,4- diisocyanate, 4,4 '-dicyclohexyl methyl hydride diisocyanates, 4,4 ' - At least one of methyl diphenylene diisocyanate.
In step (3), the molecular weight of the polyvalent alcohol is 1000-2000；The polyvalent alcohol is polytetramethylene ether Glycol, polytetrahydrofuran ether glycol, polyoxypropyleneglycol, polybutylene glyool adipate, polyadipate hexylene glycol ester two At least one of alcohol, polycarbonate glycol；The polyvalent alcohol is dehydrated 2.5h using preceding vacuumize at 110 DEG C, hydrophilic Chain extender uses preceding dry 1h at 50 DEG C in a vacuum drying oven.
In step (3), the hydrophilic chain extender is dihydromethyl propionic acid, dimethylolpropionic acid, 2- [(2- aminoethyl) ammonia At least one of base] sodium sulfonate.
In step (3), the catalyst is stannous octoate.
In step (3), the small molecule chain extender is 1,4-butanediol.
In step (3), the neutralizer is triethylamine.
Advantageous effects of the invention embody in the following areas:
1. the present invention is reacted using polyisocyanates with water, amine cross-linking agent is added and generates polyureas core-shell particles, in acetic acid solvent Effect is lower to dissolve out kernel, prepares polyureas hollow microsphere, is added in aqueous polyurethane emulsion, obtains aqueous polyurethane delustring tree Rouge；Remaining-NH on polyureas hollow microsphere2It can be reacted with residue-NCO in aqueous polyurethane emulsion, the two forms stabilization Urea bond, therefore the aqueous polyurethane matting resin prepared of polyureas hollow microsphere is added there is good intensity, even if in height The aqueous polyurethane that will not be caused to rupture, therefore be formed under the effect of the powerful external force and high velocity impact of fast mixing machine and extruder Glue film extinction is good, good mechanical performance, improves the stability of aqueous polyurethane matting resin.
2. preparation method of the invention is not only environmentally friendly but also easy, microballoon reacts preparation, solvent acetic acid with water by polyisocyanates Also recyclable recycling；Hollow microsphere and aqueous polyurethane can form stable urea bond, avoid the two physical mixed compatibility The problem of difference.
Detailed description of the invention
Fig. 1 is polyureas hollow microsphere preparation process schematic diagram.
Fig. 2 is the TEM photo figure of polyureas hollow microsphere.
Specific embodiment
Hereinafter, preferred embodiments of the present invention will be described, it should be understood that preferred embodiment described herein is only used In the description and interpretation present invention, it is not intended to limit the present invention.
Embodiment 1:
The present embodiment is raw materials used and weight is described as follows:
Acetone and water are uniformly mixed by mass ratio 6:4 and are made third by toluene di-isocyanate(TDI) 20g, acetone water mixed liquid 480g( Ketone water mixed liquid), diethylenetriamine 8g, isophorone diisocyanate 15.5g, polybutylene glyool adipate 25g(molecule It measures 2000), stannous octoate 0.05g, dimethylolpropionic acid 1.4g, 1,4-butanediol 1.5g, triethylamine 1g, deionized water 100g.
Referring to Fig. 1, adding the preparation manipulation of the aqueous polyurethane matting resin of hollow microsphere, steps are as follows:
(1), 20g toluene di-isocyanate(TDI) is slowly added into 480g acetone water mixed liquid, keeps revolving speed at 30 DEG C 30rpm is slowly stirred reaction 3h, and 8g diethylenetriamine crosslinking agent is added and drips off in 3h, polyureas core-shell particles dispersion liquid is made；
(2), polyureas core-shell particles dispersion liquid ultrasound 30min is uniformly dispersed, high speed centrifugation under the conditions of revolving speed 10000rpm The polyureas core-shell particles that centrifugation obtains are cleaned with acetone water mixed liquid, then are centrifuged 10min by 10min, such repeated centrifugation washing 3 times, obtain centrifugation microballoon；Microballoon ultrasonic disperse will be centrifuged into acetic acid solvent, under the conditions of 80 DEG C of temperature, revolving speed 30rpm, stirring 8h microballoon kernel dissolution to be centrifuged；Then it repeats above-mentioned centrifuge washing process 3 times, obtains polyureas hollow microsphere, polyureas is hollow micro- The average grain diameter of ball is 400nm, sees Fig. 2；The yield of polyureas hollow microsphere is 86.68wt%.
(3), 25g polybutylene glyool adipate is vacuumized to dehydration 2.5h at 110 DEG C, is put into reactor, is risen Temperature is to 80 DEG C；15.5g isophorone diisocyanate and 1.4g dimethylolpropionic acid are added, it is sub- in 0.05g octoate catalyst 3h is reacted under the action of tin；It adds 1.5g small molecule chain extender 1,4-butanediol and reacts 2h at 65 DEG C, obtain performed polymer；When When performed polymer is cooled to 40 DEG C or less, into performed polymer be added 1g triethylamine in and 5min, in the stirring condition of revolving speed 3000rpm Lower addition 100g deionized water emulsifies 30min；It is subsequently added into polyureas hollow microsphere to be uniformly mixed, obtains addition hollow microsphere Aqueous polyurethane matting resin.
In this implementation, the quality of polyureas hollow microsphere is the 10% of aqueous polyurethane matting resin quality；It will add hollow micro- One day is stood under the aqueous polyurethane matting resin room temperature of ball, vacuum drying obtains glue film, glue in polytetrafluoroethylene (PTFE) board mold The glossiness that 60 ° of film is 4.0, and the tensile strength of glue film is 19.5MPa.
Embodiment 2
The present embodiment is raw materials used and weight is described as follows:
Acetone and water are uniformly mixed by mass ratio 7:3 and are made third by toluene di-isocyanate(TDI) 20g, acetone water mixed liquid 480g( Ketone water mixed liquid), triethylene tetramine 8.5g, isophorone diisocyanate 16g, polycarbonate glycol 25g(molecular weight 2000), stannous octoate 0.05g, dimethylolpropionic acid 1.4g, 1,4-butanediol 1.5g, triethylamine 1g, deionized water 100g.
Referring to Fig. 1, adding the preparation manipulation of the aqueous polyurethane matting resin of hollow microsphere, steps are as follows:
(1), 20g toluene di-isocyanate(TDI) is slowly added into 480g acetone water mixed liquid, keeps revolving speed at 30 DEG C 30rpm is slowly stirred reaction 3h, adds 8.5g diethylenetriamine crosslinking agent and drip off in 3h, polyureas core-shell particles point are made Dispersion liquid；
(2), polyureas core-shell particles dispersion liquid ultrasound 30min is uniformly dispersed, high speed centrifugation under the conditions of revolving speed 10000rpm The polyureas core-shell particles that centrifugation obtains are cleaned with acetone water mixed liquid, then are centrifuged 10min by 10min, such repeated centrifugation washing 3 times, obtain centrifugation microballoon；Microballoon ultrasonic disperse will be centrifuged into acetic acid solvent, under the conditions of 80 DEG C of temperature, revolving speed 30rpm, stirring 8h is dissolved out wait be centrifuged kernel in microballoon；Then it repeats above-mentioned centrifuge washing process 3 times, obtains polyureas hollow microsphere；Polyureas is hollow The average grain diameter of microballoon is 500nm, and the yield of polyureas hollow microsphere is 86.68wt%.
(3), 25g polycarbonate glycol is vacuumized to dehydration 2.5h at 110 DEG C, puts into reactor, is warming up to 80 ℃；16g isophorone diisocyanate and 1.4g dimethylolpropionic acid are added, in the effect of 0.05g octoate catalyst stannous Lower reaction 3h；It adds 1.5g small molecule chain extender 1,4-butanediol and reacts 2h at 65 DEG C, obtain performed polymer；When performed polymer drops It when temperature is to 40 DEG C or less, is added into performed polymer in 1g triethylamine and 5min, is added under the stirring condition of revolving speed 3000rpm 100g deionized water emulsifies 30min；It is subsequently added into polyureas hollow microsphere to be uniformly mixed, obtains the aqueous poly- of addition hollow microsphere Urethane matting resin.
In this implementation, the average grain diameter of polyureas hollow microsphere is 500nm, and the quality of polyureas hollow microsphere is aqueous polyurethane The 10% of matting resin quality；One day will be stood under the aqueous polyurethane matting resin room temperature for adding hollow microsphere, in polytetrafluoroethyl-ne Vacuum drying obtains glue film in alkene board mold, and the glossiness that 60 ° of glue film is 3.0, and the tensile strength of glue film is 17MPa.
Embodiment 3
The present embodiment is raw materials used and weight is described as follows:
Toluene di-isocyanate(TDI) 20g, acetone water mixed liquid 280g, the two mass ratio are 8:2, diethylenetriamine 8g, toluene two Isocyanates 14g, polybutylene glyool adipate 25g(molecular weight 2000), dihydromethyl propionic acid 1.4g, 1,4-butanediol 2g, triethylamine 1g, deionized water 120g.
Referring to Fig. 1, adding the preparation manipulation of the aqueous polyurethane matting resin of hollow microsphere, steps are as follows:
(1), 20g toluene di-isocyanate(TDI) is slowly added into 480g acetone water mixed liquid, keeps revolving speed at 30 DEG C 30rpm is slowly stirred reaction 3h, adds 8g diethylenetriamine crosslinking agent and drip off in 3h, and the dispersion of polyureas core-shell particles is made Liquid；
(2), polyureas core-shell particles dispersion liquid ultrasound 30min is uniformly dispersed, high speed centrifugation under the conditions of revolving speed 10000rpm The polyureas core-shell particles that centrifugation obtains are cleaned with acetone water mixed liquid, then are centrifuged 10min by 10min, such repeated centrifugation washing 3 times, obtain centrifugation microballoon；Microballoon ultrasonic disperse will be centrifuged into acetic acid solvent, under the conditions of 80 DEG C of temperature, revolving speed 30rpm, stirring Kernel dissolves out in 8h microballoon to be centrifuged；Then it repeats above-mentioned centrifuge washing process 3 times, obtains polyureas hollow microsphere；Polyureas is hollow The average grain diameter of microballoon is 350nm, and the yield of polyureas hollow microsphere is 83.65wt%.
(3), 25g polybutylene glyool adipate is vacuumized to dehydration 2.5h at 110 DEG C, is put into reactor, is risen Temperature is to 80 DEG C；14g toluene di-isocyanate(TDI) and 1.4g dihydromethyl propionic acid are added, in the work of 0.05g octoate catalyst stannous With lower reaction 3h；It adds 2g small molecule chain extender 1,4-butanediol and reacts 2h at 65 DEG C, obtain performed polymer；When performed polymer drops It when temperature is to 40 DEG C or less, is added into performed polymer in 1g triethylamine and 5min, is added under the stirring condition of revolving speed 3000rpm 120g deionized water emulsifies 30min；Be subsequently added into account for quality of the emulsion score be 15% polyureas hollow microsphere be uniformly mixed, obtain Add the aqueous polyurethane matting resin of hollow microsphere.
In this implementation, the quality of polyureas hollow microsphere is the 15% of aqueous polyurethane matting resin quality；It will add hollow micro- One day is stood under the aqueous polyurethane matting resin room temperature of ball, vacuum drying obtains glue film, glue in polytetrafluoroethylene (PTFE) board mold The glossiness that 60 ° of film is 6.5, and the tensile strength of glue film is 21MPa.
Embodiment 4
The present embodiment is raw materials used and weight is described as follows:
Acetone and water are uniformly mixed by mass ratio 6:4 and are made third by toluene di-isocyanate(TDI) 30g, acetone water mixed liquid 470g( Ketone water mixed liquid), diethylenetriamine 12g, isophorone diisocyanate 22.5g, polycarbonate glycol 30g(molecular weight 2000), stannous octoate 0.05g, dihydromethyl propionic acid 1.8g, 1,4-butanediol 2g, triethylamine 2g, deionized water 150g.
Referring to Fig. 1, adding the preparation manipulation of the aqueous polyurethane matting resin of hollow microsphere, steps are as follows:
(1), 30g toluene di-isocyanate(TDI) is slowly added into 470g acetone water mixed liquid, keeps revolving speed at 30 DEG C 30rpm is slowly stirred reaction 3h, adds 12g diethylenetriamine crosslinking agent and drip off in 3h, and the dispersion of polyureas core-shell particles is made Liquid；
(2), polyureas core-shell particles dispersion liquid ultrasound 30min is uniformly dispersed, high speed centrifugation under the conditions of revolving speed 10000rpm The polyureas core-shell particles that centrifugation obtains are cleaned with acetone water mixed liquid, then are centrifuged 10min by 10min, such repeated centrifugation washing 3 times, obtain centrifugation microballoon；Microballoon ultrasonic disperse will be centrifuged into acetic acid solvent, under the conditions of 80 DEG C of temperature, revolving speed 30rpm, stirring Kernel dissolves out in 8h microballoon to be centrifuged；Then it repeats above-mentioned centrifuge washing process 3 times, obtains polyureas hollow microsphere；Polyureas is hollow The average grain diameter of microballoon is 600nm, and the yield of polyureas hollow microsphere is 86.79wt%.
(3), 30g polycarbonate glycol is vacuumized to dehydration 2.5h at 110 DEG C, puts into reactor, is warming up to 80 ℃；22.5g isophorone diisocyanate and 1.8g dihydromethyl propionic acid are added, in the work of 0.05g octoate catalyst stannous With lower reaction 3h；It adds 2g small molecule chain extender 1,4- butanediol and reacts 2h at 65 DEG C and obtain performed polymer；When performed polymer drops It when temperature is to 40 DEG C or less, is added into performed polymer in 2g triethylamine and 5min, is added under the stirring condition of revolving speed 3000rpm 150g deionized water emulsifies 30min；It is subsequently added into polyureas hollow microsphere to be uniformly mixed, obtains the aqueous poly- of addition hollow microsphere Urethane matting resin.
In this implementation, the quality of polyureas hollow microsphere is the 20% of aqueous polyurethane matting resin quality；It will add hollow micro- One day is stood under the aqueous polyurethane matting resin room temperature of ball, vacuum drying obtains glue film, glue in polytetrafluoroethylene (PTFE) board mold The glossiness that 60 ° of film is 2.5, and the tensile strength of glue film is 22.5MPa.

Claims (9)

1. a kind of aqueous polyurethane matting resin for adding hollow microsphere, it is characterised in that: described to add the aqueous of hollow microsphere Hollow microsphere in polyurethane matting resin is polyureas hollow microsphere, and the average grain diameter of polyureas hollow microsphere is 200~600nm, The quality of polyureas hollow microsphere is the 10~30% of aqueous polyurethane matting resin quality in the aqueous polyurethane matting resin；
One day will be stood under the aqueous polyurethane matting resin room temperature for adding hollow microsphere, the vacuum in polytetrafluoroethylene (PTFE) board mold It is dried to obtain glue film, the glossiness of 60 ° of the glue film is 2.5~4.0, and the tensile strength of glue film is 17.0~22.5MPa.
2. preparing a kind of method for the aqueous polyurethane matting resin for adding hollow microsphere described in claim 1, it is characterised in that Operating procedure is as follows:
Step (1) prepares polyureas core-shell particles
20~30g polyisocyanates is slowly added in 280~480g acetone water mixed liquid reaction medium, keeps turning at 30 DEG C Fast 30rpm is slowly stirred reaction 3h, and the reaction of 8~12g amine cross-linking agent is added, polyureas core-shell particles dispersion liquid is made；
Step (2) prepares polyureas hollow microsphere
Polyureas core-shell particles dispersion liquid ultrasound 30min prepared by step (1) is uniformly dispersed, is centrifuged at a high speed, and will centrifugation Lower layer's microballoon afterwards is cleaned with acetone water mixed liquid, then is centrifuged, and such repeated centrifugation is washed 3 times, obtains centrifugation microballoon；It will centrifugation For microballoon ultrasonic disperse into acetic acid solvent, the additional amount for being centrifuged microballoon is the 2% of acetic acid solvent quality；In 80 DEG C of temperature, revolving speed It under 30rpm, stirs the 8h time, kernel dissolution, then centrifuge washing 3 times obtain polyureas hollow microsphere；The polyureas hollow microsphere Partial size in 200nm~600nm, yield is 83.65~86.79wt%；
Step (3) prepares aqueous polyurethane matting resin
The polyisocyanates of 14~22.5g, 25~30g polyvalent alcohol, 1.4~1.8g hydrophilic chain extender are mixed, in catalyst Under effect, 80 DEG C of reaction 3h are kept；1.5~2g small molecule chain extender 1,4-butanediol is added, 2h is reacted at 65 DEG C, obtains pre- Aggressiveness；In performed polymer be added 1~2g neutralizer in and 5min, stirred under the conditions of revolving speed 3000rpm, and be added 100~ 150g deionized water emulsifies 30min, obtains polyaminoester emulsion；It is subsequently added into polyureas hollow microsphere to be uniformly mixed, polyureas is hollow micro- The additional amount of ball is the 10~30% of polyaminoester emulsion quality, microsphere surface-NH2With residue-NCO in polyaminoester emulsion Reaction obtains the aqueous polyurethane matting resin of addition hollow microsphere.
3. preparation method according to claim 2, it is characterised in that: in step (1), (2), by 6~8:2 of mass ratio Acetone and water are uniformly mixed obtained acetone water mixed liquid by~4.
4. preparation method according to claim 2, it is characterised in that: in step (3), the polyisocyanates is toluene two Isocyanates, 1,6- hexamethylene diisocyanate, isophorone diisocyanate (IPDI), hexamethylene -1,4- diisocyanate At least one of ester, 4,4 '-dicyclohexyl methyl hydride diisocyanates, 4,4 '-methyl diphenylene diisocyanates.
5. preparation method according to claim 2, it is characterised in that: in step (3), the molecular weight of the polyvalent alcohol is 1000-2000；The polyvalent alcohol is polytetramethylene ether diol, polytetrahydrofuran ether glycol, polyoxypropyleneglycol, gathers oneself At least one of succinate adipate glycol, polyhexamethylene adipate glycol, polycarbonate glycol；The polyvalent alcohol Dehydration 2.5h is vacuumized at 110 DEG C using preceding, and hydrophilic chain extender uses preceding dry 1h at 50 DEG C in a vacuum drying oven.
6. preparation method according to claim 2, it is characterised in that: in step (3), the hydrophilic chain extender is dihydroxy first At least one of base propionic acid, dimethylolpropionic acid, 2- [(2- aminoethyl) amino] sodium sulfonate.
7. preparation method according to claim 2, it is characterised in that: in step (3), the catalyst is stannous octoate.
8. preparation method according to claim 2, it is characterised in that: in step (3), the small molecule chain extender is Isosorbide-5-Nitrae- Butanediol.
9. preparation method according to claim 2, it is characterised in that: in step (3), the neutralizer is triethylamine.
CN201811114985.5A 2018-09-25 2018-09-25 A kind of addition hollow microsphere aqueous polyurethane matting resin and preparation method Pending CN109369872A (en)

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CN110408313A (en) * 2019-06-21 2019-11-05 安徽大学 A kind of aqueous polyurethane matting resin and preparation method that polyacrylonitrile hollow microsphere is modified
CN112876958A (en) * 2019-11-29 2021-06-01 万华化学集团股份有限公司 Water-based leather finishing agent and application thereof
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