CN106750152A - The preparation method of novel aqueous polyurethane-urea acrylate composite emulsion - Google Patents

The preparation method of novel aqueous polyurethane-urea acrylate composite emulsion Download PDF

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CN106750152A
CN106750152A CN201611125420.8A CN201611125420A CN106750152A CN 106750152 A CN106750152 A CN 106750152A CN 201611125420 A CN201611125420 A CN 201611125420A CN 106750152 A CN106750152 A CN 106750152A
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added
emulsion
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composite emulsion
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王耀斌
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Shaanxi Gaoxin Industry Co Ltd
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Abstract

The preparation method of the novel aqueous polyurethane-urea acrylate composite emulsion of the present invention is related to polyurethane industrial field, and in particular to the preparation method of novel aqueous polyurethane-urea acrylate composite emulsion, comprises the following steps：Pretreatment of raw material, PTMG is in 120 degree of vacuum dehydration 2h；Ethylene urea dries 24h under 90 degree of baking oven；Innovation of the present invention is, first using a kind of new chain extender ethylene urea, polyurethane backbone structure to be designed, and introduces urea bond or biuret structure, and aqueous polyurethaneurea emulsion is prepared with traditional synthesis technique；Secondly, the method being modified using interpenetrating polymer networks, by butyl acrylate, methyl propenoic acid glycidyl ether copolymerization in aqueous polyurethaneurea emulsion, later stage is crosslinked using ethylenediamine to methyl propenoic acid glycidyl ether, prepares the aqueous polyurethaneurea acrylate composite emulsion of function admirable.

Description

The preparation method of novel aqueous polyurethane-urea-acrylate composite emulsion
Technical field
The present invention relates to polyurethane industrial field, and in particular to novel aqueous polyurethane-urea acrylate composite emulsion Preparation method.
Background technology
Aqueous polyurethane is because with low content of volatile organic compounds, pollution-free, wearability, good mechanical performance, being easy to change The advantages of property, it is widely used in the industries such as leather finishing agent, adhesive, coating.Due to its rate of drying, water resistance, film Hardness and strength character are not as good as solvent borne polyurethane so that the popularization and application of aqueous polyurethane are restricted.And acrylate Emulsion has the advantages that preferable mechanical property, weatherability, water resistance, and aqueous polyurethane is modified using acrylate, The two performance can be had complementary advantages, be obtained the aqueous polyurethane acrylate emulsion of high comprehensive performance.
The content of the invention
It is a kind of simple to operate present invention aim at providing, convenient processing, and product quality is can guarantee that, enhance product performance Novel aqueous polyurethane-urea acrylate composite emulsion preparation method.
The preparation method of the novel aqueous polyurethane-urea acrylate composite emulsion of the present invention, comprises the following steps：
The first step, pretreatment of raw material
PTMG is in 120 degree of vacuum dehydration 2h；Ethylene urea dries 24h under 90 degree of baking oven；Dihydromethyl propionic acid After grinding to form fine powder, in drying 24h under 100 degree；Acetone, N, the 4A types after N dimethylformamides, triethylamine high-temperature activation Molecular sieve is processed 7 days；
Second step, the synthesis of aqueous polyurethaneurea emulsion
Under nitrogen protection, PTMG, IPDI are added and agitator, reflux condensation mode is housed In pipe, the four-hole boiling flask of thermometer, and catalyst dibutyltin dilaurylate 3-5 drops are added, in 90 degree of lower prepolymerization reaction 3-4h, NCO content is titrated with di-n-butylamine toluene method；Dibutyl tin laurate and IPDI are added, is warming up to 100 degree carry out chain extending reaction 3h, add cosolvent；Then 65 degree are cooled to, dihydromethyl propionic acid powder is added into reaction system In, continue chain extending reaction, period adds acetone viscosity reduction, reacts complete after 3-4h；The system for the treatment of is down to room temperature and adds triethylamine into salt 15min, afterwards pours into aqueous beaker and in high speed shear emulsified dispersion 1h performed polymer, is extracted after standing froth breaking 24h Acetone, obtains aqueous polyurethaneurea emulsion；
3rd step, the synthesis of aqueous polyurethaneurea acrylate composite emulsion
Under nitrogen protection, PTMG, IPDI are added and agitator, reflux condensation mode is housed In pipe, the four-hole boiling flask of thermometer, and catalyst dibutyltin dilaurylate 3-5 drops are added, in 90 degree of lower prepolymerization reaction 3-4h, NCO content is titrated with di-n-butylamine toluene method；Dibutyl tin laurate and IPDI are added, is warming up to 100 degree carry out chain extending reaction 3h, add cosolvent；First add dihydromethyl propionic acid and butyl acrylate, Glycidyl methacrylate Glycerin ether, reaction adds butyl acrylate, methyl propenoic acid glycidyl ether after terminating；Then treat that system is down to room temperature and adds three Ethamine is into salt 15min；Under 78 degree, ammonium persulfate constant pressure funnel is added drop-wise to the aqueous polyurethane dissolved with acrylate monomer Radical polymerization is carried out in emulsion, 1.5-2h is added dropwise to complete, be incubated 3h, be cooled to room temperature and add ethylenediamine to be crosslinked, prepared Aqueous polyurethane-urea acrylate composite emulsion.
Preferably, cosolvent is N, N dimethylformamides.
Preferably, the consumption of ammonium sulfate is the 1% of acrylate monomer.
Innovation of the present invention is, first using a kind of new chain extender ethylene urea, polyurethane backbone structure to be set Meter, introduces urea bond or biuret structure, and aqueous polyurethaneurea emulsion is prepared with traditional synthesis technique；Secondly, using IPN The modified method of polymer network, butyl acrylate, methyl propenoic acid glycidyl ether is common in aqueous polyurethaneurea emulsion Poly-, the later stage is crosslinked using ethylenediamine to methyl propenoic acid glycidyl ether, prepares the aqueous polyurethaneurea of function admirable Acrylate composite emulsion.
Specific embodiment
Embodiment one：
The preparation method of the novel aqueous polyurethane-urea acrylate composite emulsion of the present invention, comprises the following steps：
The first step, pretreatment of raw material
PTMG is in 120 degree of vacuum dehydration 2h；Ethylene urea dries 24h under 90 degree of baking oven；Dihydromethyl propionic acid After grinding to form fine powder, in drying 24h under 100 degree；Acetone, N, the 4A types after N dimethylformamides, triethylamine high-temperature activation Molecular sieve is processed 7 days；
Second step, the synthesis of aqueous polyurethaneurea emulsion
Under nitrogen protection, PTMG, IPDI are added and agitator, reflux condensation mode is housed In pipe, the four-hole boiling flask of thermometer, and catalyst dibutyltin dilaurylate 3-5 drops are added, in 90 degree of lower prepolymerization reaction 3-4h, NCO content is titrated with di-n-butylamine toluene method；Dibutyl tin laurate and IPDI are added, is warming up to 100 degree carry out chain extending reaction 3h, add cosolvent；Then 65 degree are cooled to, dihydromethyl propionic acid powder is added into reaction system In, continue chain extending reaction, period adds acetone viscosity reduction, reacts complete after 3-4h；The system for the treatment of is down to room temperature and adds triethylamine into salt 15min, afterwards pours into aqueous beaker and in high speed shear emulsified dispersion 1h performed polymer, is extracted after standing froth breaking 24h Acetone, obtains aqueous polyurethaneurea emulsion；
3rd step, the synthesis of aqueous polyurethaneurea acrylate composite emulsion
Under nitrogen protection, PTMG, IPDI are added and agitator, reflux condensation mode is housed In pipe, the four-hole boiling flask of thermometer, and catalyst dibutyltin dilaurylate 3-5 drops are added, in 90 degree of lower prepolymerization reaction 3-4h, NCO content is titrated with di-n-butylamine toluene method；Dibutyl tin laurate and IPDI are added, is warming up to 100 degree carry out chain extending reaction 3h, add cosolvent；First add dihydromethyl propionic acid and butyl acrylate, Glycidyl methacrylate Glycerin ether, reaction adds butyl acrylate, methyl propenoic acid glycidyl ether after terminating；Then treat that system is down to room temperature and adds three Ethamine is into salt 15min；Under 78 degree, ammonium persulfate constant pressure funnel is added drop-wise to the aqueous polyurethane dissolved with acrylate monomer Radical polymerization is carried out in emulsion, 1.5-2h is added dropwise to complete, be incubated 3h, be cooled to room temperature and add ethylenediamine to be crosslinked, prepared Aqueous polyurethane-urea acrylate composite emulsion.
Embodiment two：
The preparation method of the novel aqueous polyurethane-urea acrylate composite emulsion of the present invention, comprises the following steps：
The first step, pretreatment of raw material
PTMG is in 120 degree of vacuum dehydration 2h；Ethylene urea dries 24h under 90 degree of baking oven；Dihydromethyl propionic acid After grinding to form fine powder, in drying 24h under 100 degree；Acetone, N, the 4A types after N dimethylformamides, triethylamine high-temperature activation Molecular sieve is processed 7 days；
Second step, the synthesis of aqueous polyurethaneurea emulsion
Under nitrogen protection, PTMG, IPDI are added and agitator, reflux condensation mode is housed In pipe, the four-hole boiling flask of thermometer, and catalyst dibutyltin dilaurylate 3-5 drops are added, in 90 degree of lower prepolymerization reaction 3-4h, NCO content is titrated with di-n-butylamine toluene method；Dibutyl tin laurate and IPDI are added, is warming up to 100 degree carry out chain extending reaction 3h, add cosolvent；Then 65 degree are cooled to, dihydromethyl propionic acid powder is added into reaction system In, continue chain extending reaction, period adds acetone viscosity reduction, reacts complete after 3-4h；The system for the treatment of is down to room temperature and adds triethylamine into salt 15min, afterwards pours into aqueous beaker and in high speed shear emulsified dispersion 1h performed polymer, is extracted after standing froth breaking 24h Acetone, obtains aqueous polyurethaneurea emulsion；
3rd step, the synthesis of aqueous polyurethaneurea acrylate composite emulsion
Under nitrogen protection, PTMG, IPDI are added and agitator, reflux condensation mode is housed In pipe, the four-hole boiling flask of thermometer, and catalyst dibutyltin dilaurylate 3-5 drops are added, in 90 degree of lower prepolymerization reaction 3-4h, NCO content is titrated with di-n-butylamine toluene method；Dibutyl tin laurate and IPDI are added, is warming up to 100 degree carry out chain extending reaction 3h, add cosolvent；First add dihydromethyl propionic acid and butyl acrylate, Glycidyl methacrylate Glycerin ether, reaction adds butyl acrylate, methyl propenoic acid glycidyl ether after terminating；Then treat that system is down to room temperature and adds three Ethamine is into salt 15min；Under 78 degree, ammonium persulfate constant pressure funnel is added drop-wise to the aqueous polyurethane dissolved with acrylate monomer Radical polymerization is carried out in emulsion, 1.5-2h is added dropwise to complete, be incubated 3h, be cooled to room temperature and add ethylenediamine to be crosslinked, prepared Aqueous polyurethane-urea acrylate composite emulsion.
Cosolvent is N, N dimethylformamides.
The consumption of ammonium sulfate is the 1% of acrylate monomer.
Innovation of the present invention is, first using a kind of new chain extender ethylene urea, polyurethane backbone structure to be set Meter, introduces urea bond or biuret structure, and aqueous polyurethaneurea emulsion is prepared with traditional synthesis technique；Secondly, using IPN The modified method of polymer network, butyl acrylate, methyl propenoic acid glycidyl ether is common in aqueous polyurethaneurea emulsion Poly-, the later stage is crosslinked using ethylenediamine to methyl propenoic acid glycidyl ether, prepares the aqueous polyurethaneurea of function admirable Acrylate composite emulsion.

Claims (3)

1. a kind of preparation method of novel aqueous polyurethane-urea acrylate composite emulsion, it is characterised in that including following step Suddenly：
The first step, pretreatment of raw material
PTMG is in 120 degree of vacuum dehydration 2h；Ethylene urea dries 24h under 90 degree of baking oven；Dihydromethyl propionic acid After grinding to form fine powder, in drying 24h under 100 degree；Acetone, N, the 4A types after N dimethylformamides, triethylamine high-temperature activation Molecular sieve is processed 7 days；
Second step, the synthesis of aqueous polyurethaneurea emulsion
Under nitrogen protection, PTMG, IPDI are added and agitator, reflux condensation mode is housed In pipe, the four-hole boiling flask of thermometer, and catalyst dibutyltin dilaurylate 3-5 drops are added, in 90 degree of lower prepolymerization reaction 3-4h, NCO content is titrated with di-n-butylamine toluene method；Dibutyl tin laurate and IPDI are added, is warming up to 100 degree carry out chain extending reaction 3h, add cosolvent；Then 65 degree are cooled to, dihydromethyl propionic acid powder is added into reaction system In, continue chain extending reaction, period adds acetone viscosity reduction, reacts complete after 3-4h；The system for the treatment of is down to room temperature and adds triethylamine into salt 15min, afterwards pours into aqueous beaker and in high speed shear emulsified dispersion 1h performed polymer, is extracted after standing froth breaking 24h Acetone, obtains aqueous polyurethaneurea emulsion；
3rd step, the synthesis of aqueous polyurethaneurea acrylate composite emulsion
Under nitrogen protection, PTMG, IPDI are added and agitator, reflux condensation mode is housed In pipe, the four-hole boiling flask of thermometer, and catalyst dibutyltin dilaurylate 3-5 drops are added, in 90 degree of lower prepolymerization reaction 3-4h, NCO content is titrated with di-n-butylamine toluene method；Dibutyl tin laurate and IPDI are added, is warming up to 100 degree carry out chain extending reaction 3h, add cosolvent；First add dihydromethyl propionic acid and butyl acrylate, Glycidyl methacrylate Glycerin ether, reaction adds butyl acrylate, methyl propenoic acid glycidyl ether after terminating；Then treat that system is down to room temperature and adds three Ethamine is into salt 15min；Under 78 degree, ammonium persulfate constant pressure funnel is added drop-wise to the aqueous polyurethane dissolved with acrylate monomer Radical polymerization is carried out in emulsion, 1.5-2h is added dropwise to complete, be incubated 3h, be cooled to room temperature and add ethylenediamine to be crosslinked, prepared Aqueous polyurethane-urea acrylate composite emulsion.
2. as claimed in claim 1 novel aqueous polyurethane-urea acrylate composite emulsion preparation method, it is characterised in that The cosolvent is N, N dimethylformamides.
3. as claimed in claim 2 novel aqueous polyurethane-urea acrylate composite emulsion preparation method, it is characterised in that The consumption of the ammonium sulfate is the 1% of acrylate monomer.
CN201611125420.8A 2016-12-09 2016-12-09 The preparation method of novel aqueous polyurethane-urea acrylate composite emulsion Pending CN106750152A (en)

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CN110655828A (en) * 2018-06-29 2020-01-07 理想科学工业株式会社 Oil-based ink-jet ink and method for producing oil-based ink-jet ink
CN114031738A (en) * 2021-11-25 2022-02-11 杭州每步材料科技有限公司 Polyurethane grouting material capable of repeatedly expanding in water and preparation method thereof
CN117209876A (en) * 2023-09-26 2023-12-12 无锡哈威新材料科技有限公司 Ageing-resistant polyethylene cable material and preparation process thereof

Cited By (5)

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Publication number Priority date Publication date Assignee Title
CN110655828A (en) * 2018-06-29 2020-01-07 理想科学工业株式会社 Oil-based ink-jet ink and method for producing oil-based ink-jet ink
CN110655828B (en) * 2018-06-29 2021-09-28 理想科学工业株式会社 Oil-based ink-jet ink and method for producing oil-based ink-jet ink
CN114031738A (en) * 2021-11-25 2022-02-11 杭州每步材料科技有限公司 Polyurethane grouting material capable of repeatedly expanding in water and preparation method thereof
CN117209876A (en) * 2023-09-26 2023-12-12 无锡哈威新材料科技有限公司 Ageing-resistant polyethylene cable material and preparation process thereof
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