CN108976425A - A kind of preparation method of polyurethane-epoxy resin block copolymerization water-base resin - Google Patents
A kind of preparation method of polyurethane-epoxy resin block copolymerization water-base resin Download PDFInfo
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- CN108976425A CN108976425A CN201810615076.3A CN201810615076A CN108976425A CN 108976425 A CN108976425 A CN 108976425A CN 201810615076 A CN201810615076 A CN 201810615076A CN 108976425 A CN108976425 A CN 108976425A
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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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/4465—Polyurethanes
Abstract
A kind of preparation method of polyurethane-epoxy resin block copolymerization water-base resin, comprising the following steps: (1) oligomer dihydric alcohol and di-isocyanate reaction are obtained into base polyurethane prepolymer for use as；(2) epoxy resin, piperazine and water-soluble solvent is added, reaction to epoxide number is 0, obtains mixture；(3) deionized water with quality such as added water-soluble solvents is added, stirs evenly, then staticly settle out polymer, washes polymer, obtains precursor resin；(4) gained precursor resin is heated up, be added organic acid, stirring, be added deionized water, stir 20-35min to get.The present invention realizes the block copolymerization of polyurethane resin and epoxy resin, overcomes limitation of the synthetic method of common polyurethane epoxy material to epoxy resin introduction volume；And the present invention can adjust the performance of products obtained therefrom by adjusting formulation parameter.
Description
Technical field
The present invention relates to polyurethane-epoxy resin Material Fields, relate in particular to a kind of polyurethane-epoxy resin block
The preparation method of copolymerized waterborne resin, particularly suitable for making cathode electrophoresis dope.
Background technique
Epoxy resin is many kinds of, and application field is extensive.However non-modified epoxy resin cure post-crosslinking density is high,
Cause internal stress excessive, the defects of that there are matter is crisp, easy to crack for product, poor impact resistance, limits its application field.And polyurethane
It with good flexibility, with itself and epoxy resin modification by copolymerization, can accomplish have complementary advantages, it is more excellent to obtain service performance
Polyurethane epoxy material.The method for usually preparing polyurethane epoxy material has mechanical blending method, direct grafting copolymerization process and ring
Three kinds of methods such as oxygen open loop method.
Mechanical blending method is to wrap up epoxy resin with hydrophilic base polyurethane prepolymer for use as, and then aquation, obtains epoxy-modified
Ester-polyurethane resin emulsion.The advantages of this method be easily prepare stable resin emulsion, but have insufficient place at two, first,
This method is simple blend physically, and there is no the links of chemical bond for two kinds of resins, it is thus impossible to make two kinds of trees well
The mutual supplement with each other's advantages of rouge, to hardly result in the paint film of function admirable；Second, epoxy resin is by point stable by package ability
It is scattered in lotion, therefore, epoxy resin increases, and obtained resin emulsion partial size becomes larger or even part epoxy can not be wrapped
It covers, influences the stability of resin emulsion, lead to that less epoxy resin modification polyurethane can only be used, to affect answering for product
Use range.
Direct grafting copolymerization process is first to synthesize base polyurethane prepolymer for use as, and then the secondary hydroxyl in performed polymer and epoxy resin is anti-
It answers, polyurethane is introduced into epoxy resin.The advantages of this method is that obtained paint film properties are obtained better than mechanical blending method
The paint film arrived, the disadvantage is that more difficult prepare stable resin emulsion, because in the polymerization, epoxy resin participates in meeting after reaction
Branched chain is generated, therefore, when dosage is more than a certain range, the molecular weight of reactant can be made to increased dramatically, resin is caused to be difficult
By aquation or cannot be stable lotion.
Epoxy addition method is to carry out ring-opening reaction with epoxy resin first with small molecule acid, amine or alcohol etc., generates terminal hydroxy group
Epoxy resin, then as a kind of polyalcohol and di-isocyanate reaction.Party's legal system improves the dosage of epoxy resin,
The paint film property being prepared is excellent.But insufficient place is, the reaction process of epoxy resin open loop is more difficult to control and cannot
Therefore complete open loop containing epoxy group and small molecule ring opening agent (such as acid, amine) in obtained modified resin lotion, influences cream
The storage stability of liquid.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a kind of better simply poly- ammonia of technique
Ester-epoxy resin block copolymerization water-base resin preparation method, the storage of gained polyurethane-epoxy resin block copolymerization water-base resin
Stability is preferable.
The technical solution used to solve the technical problems of the present invention is that a kind of polyurethane-epoxy resin block copolymerization is aqueous
The preparation method of resin, comprising the following steps:
(1) by oligomer dihydric alcohol and diisocyanate investment reaction flask, reaction temperature is 50 DEG C ~ 80 DEG C, reacts 1 ~ 3h, system
It is standby to obtain base polyurethane prepolymer for use as；
The ratio of the oligomer dihydric alcohol and diisocyanate, should make the substance of the isocyanate group in diisocyanate
The ratio between amount and the amount of substance of [OH] in oligomer dihydric alcohol are 1.5-2 ︰ 1；
(2) epoxy resin, piperazine and water-soluble solvent is added into step (1) gained base polyurethane prepolymer for use as, stirs evenly, heats up
To 30 DEG C ~ 70 DEG C, 3 ~ 8 h are reacted, reaction to epoxide number is 0, obtains mixture；
The additional amount of the water-soluble solvent, be base polyurethane prepolymer for use as, epoxy resin, piperazine gross mass 60-100%；
The proportion of epoxy resin and piperazine is controlled with chain extension parameter Rt and hard segment content H%；
Control chain extension parameter Rt=1.2 ~ 1.6, Rt={ n (amino)/[n (epoxy group)+n (isocyanate group)] }, n expression thing
The amount (molal quantity) of matter.Rt is controlled in this range, can control the molecular weight of synthetic resin, general Rt > 1.0, it is ensured that block is total
Polymers is blocked with amido；Amino is the secondary amine in piperazine, and epoxy group is the epoxy group in epoxy resin, and isocyanate group is poly- ammonia
Isocyanate group in ester performed polymer.
Control hard segment content H% is the preferred 20-50% of 10 ~ 60%()；H%={ [m (epoxy resin)+m (piperazine)]/[m
(epoxy resin)+m (piperazine)+m (base polyurethane prepolymer for use as)] }, m indicates the quality of substance.Hard segment content H% is hard segment content,
The flexibility of adjustable synthetic resin.
(3) deionized water with quality such as added water-soluble solvents is added into step (2) gained mixture, stirring is equal
It is even, then polymer is staticly settled out, polymer is washed, precursor resin is obtained；
(4) precursor resin obtained by step (3) is warming up to 40-55 DEG C, it is excellent that addition is equivalent to 1.2 ~ 16.0%(of precursor resin quality
Select 2.8-10.0%) organic acid, stir 3-10min, be added and be equivalent to the deionized water of 1-3 times of precursor resin quality, stir
20-35min(emulsification) to get arrive polyurethane-epoxy resin block copolymerization water-base resin.
Further, in step (1), the oligomer dihydric alcohol is polycaprolactone diols, one contracting diethyl two of polyadipate
At least one of alcohol ester, polytetrahydrofuran dihydric alcohol, wherein it is preferred that polycaprolactone diols.
Further, in step (1), the oligomer dihydric alcohol molecular weight is 400-4000, and wherein preferred molecular weight is
1000-2000。
Further, in step (1), the diisocyanate is toluene di-isocyanate(TDI) (TDI), isophorone diisocyanate
At least one of ester (IPDI), methyl diphenylene diisocyanate (MDI), hexamethylene diisocyanate (HDI), wherein excellent
Select at least one of toluene di-isocyanate(TDI) (TDI), isophorone diisocyanate (IPDI).
Further, in step (2), the epoxy resin is epoxy E-51, in epoxy E-44, epoxy E-20, epoxy E-12
At least one, preferably epoxy E-44, E-20.Epoxide number is lower, then the amine value in water-base resin is smaller.
Further, in step (2), the water-soluble solvent is n,N-Dimethylformamide, tetrahydrofuran, acetone, N- first
One or both of base pyrrolidones, wherein it is preferred that at least one of n,N-Dimethylformamide, tetrahydrofuran.
Water-soluble solvent is added in reaction, reason there are following three points: first, dissolution reactant, fills reactant molecule
Tap touching, so that reaction is more abundant；Second, can reduce the viscosity of reaction system, be conducive to the heat transfer and heat dissipation of system；Its
Three, it is water-soluble solvent, therefore after reacting and stopping, deionized water, which only need to be added, can be settled out precursor resin, and solvent and water
Mixed liquor, it is only necessary to be dehydrated, can recycle through simple distillation, therefore, eliminate in general water-base resin preparation process take off
The step of except solvent.
Further, in step (2), control reaction is 45-60 DEG C of temperature.
Further, in step (2), the control reaction time is 4-6h.
Further, in step (4), the organic acid is at least one in glacial acetic acid, lactic acid, formic acid, propionic acid, oxalic acid etc.
Kind.
Design principle of the invention: with oligomer dihydric alcohol and diisocyanate synthesis of polyurethane performed polymer, by itself and piperazine
Piperazine and epoxy resin carry out chain-extension polymerization reaction, adjusted by controlling the material proportion of copolymer synthetic resin molecular weight and
Flexibility prepares serial linear polyblock macromolecular resin.
The present invention has following two o'clock using the purpose of piperazine chain extension: 1. piperazine is cyclic structure substance, modified with its chain extension,
Synthetic resin film strength can be improved；2. piperazine both ends are secondary amines, there is following two o'clock advantage with its chain extension, first, to synthesis
While resin introducing can be ionized amido, make the amine value of resin in lower range.Second, it at a lower temperature may be used
With isocyanate group, epoxy reaction, speed is much larger than the reaction speed of secondary hydroxyl and isocyanate group on epoxy, therefore,
Reaction process is simple, economical.
The present invention uses the purpose of base polyurethane prepolymer for use as chain extension to have at following 3 points: 1. isocyanic acid is in base polyurethane prepolymer for use as both ends
Ester group can be reacted with the secondary amino group in piperazine at a lower temperature；2. the introducing of base polyurethane prepolymer for use as can make to synthesize
Resin have certain flexibility；3. containing hydrophobic segment in base polyurethane prepolymer for use as, blocked isocyanate can be coated
Curing agent, so as to make curing agent proportionally electrophoresis synchronous with resin to electrode surface.
For the present invention using epoxy resin as hard section, base polyurethane prepolymer for use as is soft segment, using piperazine as chain extender, by adjusting chain extension
Parameter (Rt) controls the molecular weight of synthetic resin, adjusts the flexibility of synthetic resin, essence by adjusting hard segment content (H%)
It is embedding to obtain Series of Polyurethane-epoxy resin for quasi- preparation Series of Polyurethane-epoxy resin line-type block polymer, neutralized aquation
Section copolymerized waterborne resin, the precursor resin of synthesis can also be compounded, cathode electrophoresis dope is made with blocked isocyanate.
The polyurethane-epoxy resin block copolymerization water-base resin preparation process reaction equation of the present invention is as follows:
Compared with prior art, advantage of the present invention is as follows:
(1) for the present invention using epoxy resin as hard section, base polyurethane prepolymer for use as is soft segment, using piperazine as chain extender, by adjusting chain extension
Parameter controls the molecular weight of synthetic resin, by adjusting hard segment content adjusts the flexibility for synthesizing resin.This synthesis
Method realizes the block copolymerization of polyurethane resin and epoxy resin, overcomes the synthesis side of common polyurethane-epoxy resin material
Limitation of the method to epoxy resin introduction volume；And the present invention can adjust products obtained therefrom by adjusting the material proportion of copolymer
Performance.
(2) base polyurethane prepolymer for use as, epoxy resin and piperazine of the invention carry out chain-extension polymerization reaction, and wherein piperazine both ends are
Secondary amine, at a lower temperature just can with isocyanate group, epoxy reaction, therefore, reaction process simple process, economy,
And its two amino be secondary amine the characteristics of, make the amine value of the polyurethane-epoxy resin block copolymerization water-base resin synthesized compared with
It is low.
(3) present invention uses water-soluble solvent, and water-soluble solvent energy and water are miscible with arbitrary proportion, and therefore, water is in this hair
The mixed liquor of precipitating reagent can be done in bright, be settled out precursor resin from reaction solution, and generated solvent and water, it is de- through simple distillation
Water can recycle.The method eliminates the step of solvent is removed in traditional water-base resin preparation process, while neutralizing aquation
Water-base resin afterwards, achievees the purpose that Diamond Search.
Specific embodiment
Below in conjunction with specific embodiment, invention is further described in detail.
Embodiment 1 (comparative example)
With formulation parameter Rt=1.10, for H%=30w%, the preparation method of polyurethane-epoxy resin block copolymerization water-base resin is such as
Under:
(1) polycaprolactone diols (molecular weight Mn=2000) removed water 25.39 g and 5.64 g isophorone diisocyanates
Ester (IPDI) is put into reaction flask, and reaction temperature is 80 DEG C, reacts 2h, base polyurethane prepolymer for use as 31.03g is prepared；
The ratio of the oligomer dihydric alcohol and diisocyanate, so that the amount of the substance of the isocyanate group in diisocyanate
It is 2 ︰ 1 with the ratio between amount of substance of [OH] in oligomer dihydric alcohol；
(2) 10.00 g epoxy E-44,3.30 g piperazines and 40.21 gN, N- are added into step (1) gained base polyurethane prepolymer for use as
Dimethylformamide stirs evenly, and is warming up to 55 DEG C, reacts 5 h；Reaction to epoxide number is 0, obtains mixture；
(3) deionized water with quality such as added water-soluble solvents is added into step (2) gained mixture, stirs evenly, then
Polymer is staticly settled out, polymer is washed, obtains precursor resin；
(4) precursor resin obtained by step (3) is warming up to 45 DEG C, the glacial acetic acid for being equivalent to precursor resin quality 2.9% is added, stirs
5min is mixed, addition is equivalent to 2 times of precursor resin quality of deionized water, and stirring 30min emulsifies to arrive polyurethane-asphalt mixtures modified by epoxy resin
Rouge block copolymerization water-base resin.
Embodiment 2
With formulation parameter Rt=1.20, for H%=30w%, the preparation method of polyurethane-epoxy resin block copolymerization water-base resin is such as
Under:
(1) polycaprolactone diols (molecular weight Mn=2000) removed water 30.05 g and 6.69 g isophorone diisocyanates
Ester (IPDI) is put into reaction flask, and reaction temperature is 80 DEG C, reacts 2h, base polyurethane prepolymer for use as 36.74g is prepared；
The ratio of the oligomer dihydric alcohol and diisocyanate, so that the amount of the substance of the isocyanate group in diisocyanate
It is 2 ︰ 1 with the ratio between amount of substance of [OH] in oligomer dihydric alcohol；
(2) 11.59 g epoxy E-44,4.16 g piperazines and 41.98 gN, N- are added into step (1) gained base polyurethane prepolymer for use as
Dimethylformamide stirs evenly, and is warming up to 55 DEG C, reacts 5 h；Reaction to epoxide number is 0, obtains mixture；
(3) deionized water with quality such as added water-soluble solvents is added into step (2) gained mixture, stirs evenly, then
Polymer is staticly settled out, polymer is washed, obtains precursor resin；
(4) precursor resin obtained by step (3) is warming up to 45 DEG C, the glacial acetic acid for being equivalent to precursor resin quality 3.6% is added, stirs
5min is mixed, addition is equivalent to 2 times of precursor resin quality of deionized water, and stirring 30min emulsifies to arrive polyurethane-asphalt mixtures modified by epoxy resin
Rouge block copolymerization water-base resin.
Embodiment 3
With formulation parameter Rt=1.25, for H%=30w%, the preparation method of polyurethane-epoxy resin block copolymerization water-base resin is such as
Under:
(1) polycaprolactone diols (molecular weight Mn=2000) removed water 27.90 g and 6.21 g isophorone diisocyanates
Ester (IPDI) is put into reaction flask, and reaction temperature is 80 DEG C, reacts 2h, base polyurethane prepolymer for use as 34.11g is prepared；
The ratio of the oligomer dihydric alcohol and diisocyanate, so that the amount of the substance of the isocyanate group in diisocyanate
It is 2 ︰ 1 with the ratio between amount of substance of [OH] in oligomer dihydric alcohol；
(2) 10.63 g epoxy E-44,3.99 g piperazines and 38.98 gN, N- are added into step (1) gained base polyurethane prepolymer for use as
Dimethylformamide stirs evenly, and is warming up to 55 DEG C, reacts 5 h；Reaction to epoxide number is 0, obtains mixture；
(3) deionized water with quality such as added water-soluble solvents is added into step (2) gained mixture, stirs evenly, then
Polymer is staticly settled out, polymer is washed, obtains precursor resin；
(4) precursor resin obtained by step (3) is warming up to 45 DEG C, the glacial acetic acid for being equivalent to precursor resin quality 3.7% is added, stirs
5min is mixed, addition is equivalent to 2 times of precursor resin quality of deionized water, and stirring 30min emulsifies to arrive polyurethane-asphalt mixtures modified by epoxy resin
Rouge block copolymerization water-base resin.
Embodiment 4
With formulation parameter Rt=1.30, for H%=30w%, the preparation method of polyurethane-epoxy resin block copolymerization water-base resin is such as
Under:
(1) polycaprolactone diols (molecular weight Mn=2000) removed water 28.86 g and 6.42 g isophorone diisocyanates
Ester (IPDI) is put into reaction flask, and reaction temperature is 80 DEG C, reacts 2h, base polyurethane prepolymer for use as 35.28g is prepared；
The ratio of the oligomer dihydric alcohol and diisocyanate, so that the amount of the substance of the isocyanate group in diisocyanate
It is 2 ︰ 1 with the ratio between amount of substance of [OH] in oligomer dihydric alcohol；
(2) 10.86 g epoxy E-44,4.26g piperazines and 40.32 gN, N- are added into step (1) gained base polyurethane prepolymer for use as
Dimethylformamide stirs evenly, and stirring is warming up to 55 DEG C, reacts 5 h；Reaction to epoxide number is 0, obtains mixture；
(3) deionized water with quality such as added water-soluble solvents is added into step (2) gained mixture, stirs evenly, then
Polymer is staticly settled out, polymer is washed, obtains precursor resin；
(4) precursor resin obtained by step (3) is warming up to 45 DEG C, the glacial acetic acid for being equivalent to precursor resin quality 3.9% is added, stirs
5min is mixed, addition is equivalent to 2 times of precursor resin quality of deionized water, and stirring 30min emulsifies to arrive polyurethane-asphalt mixtures modified by epoxy resin
Rouge block copolymerization water-base resin.
Embodiment 5
With formulation parameter Rt=1.30, for H%=40w%, the preparation method of polyurethane-epoxy resin block copolymerization water-base resin is such as
Under:
(1) polycaprolactone diols (molecular weight Mn=2000) removed water 30.44 g and 6.55 g isophorone diisocyanates
Ester (IPDI) is put into reaction flask, and reaction temperature is 80 DEG C, reacts 2h, base polyurethane prepolymer for use as 36.99g is prepared；
The ratio of the oligomer dihydric alcohol and diisocyanate, so that the amount of the substance of the isocyanate group in diisocyanate
It is 2 ︰ 1 with the ratio between amount of substance of [OH] in oligomer dihydric alcohol；
(2) 18.51 g epoxy E-44,6.25 g piperazines and 49.41 gN, N- are added into step (1) gained base polyurethane prepolymer for use as
Dimethylformamide stirs evenly, and is warming up to 55 DEG C, reacts 5 h；Reaction to epoxide number is 0, obtains mixture；
(3) deionized water with quality such as added water-soluble solvents is added into step (2) gained mixture, stirs evenly, then
Polymer is staticly settled out, polymer is washed, obtains precursor resin；
(4) precursor resin obtained by step (3) is warming up to 45 DEG C, the glacial acetic acid for being equivalent to precursor resin quality 5.0% is added, stirs
5min is mixed, addition is equivalent to 2 times of precursor resin quality of deionized water, and stirring 30min emulsifies to arrive polyurethane-asphalt mixtures modified by epoxy resin
Rouge block copolymerization water-base resin.
Embodiment 6
With formulation parameter Rt=1.30, for H%=50w%, the preparation method of polyurethane-epoxy resin block copolymerization water-base resin is such as
Under:
(1) polycaprolactone diols (molecular weight Mn=2000) removed water 25.00 g and 5.41 g isophorone diisocyanates
Ester (IPDI) is put into reaction flask, and reaction temperature is 80 DEG C, reacts 2h, base polyurethane prepolymer for use as 30.41g is prepared；
The ratio of the oligomer dihydric alcohol and diisocyanate, so that the amount of the substance of the isocyanate group in diisocyanate
It is 2 ︰ 1 with the ratio between amount of substance of [OH] in oligomer dihydric alcohol；
(2) 23.30 g epoxy E-44,7.16 g piperazines and 48.70 gN, N- are added into step (1) gained base polyurethane prepolymer for use as
Dimethylformamide stirs evenly, and is warming up to 55 DEG C, reacts 5 h；Reaction to epoxide number is 0, obtains mixture；
(3) deionized water with quality such as added water-soluble solvents is added into step (2) gained mixture, stirs evenly, then
Polymer is staticly settled out, polymer is washed, obtains precursor resin；
(4) precursor resin obtained by step (3) is warming up to 45 DEG C, the glacial acetic acid for being equivalent to precursor resin quality 6.4% is added, stirs
5min is mixed, addition is equivalent to 2 times of precursor resin quality of deionized water, and stirring 30min emulsifies to arrive polyurethane-asphalt mixtures modified by epoxy resin
Rouge block copolymerization water-base resin.
Embodiment 7
With formulation parameter Rt=1.25, for H%=50w%, the preparation method of polyurethane-epoxy resin block copolymerization water-base resin is such as
Under:
(1) polycaprolactone diols (molecular weight Mn=1000) removed water 13.40 g and 3.50g toluene di-isocyanate(TDI)
(TDI) it puts into reaction flask, reaction temperature is 60 DEG C, reacts 2h, base polyurethane prepolymer for use as 16.9g is prepared；
The ratio of the oligomer dihydric alcohol and diisocyanate, so that the amount of the substance of the isocyanate group in diisocyanate
It is 1.5 ︰ 1 with the ratio between amount of substance of [OH] in oligomer dihydric alcohol；
(2) 12.48 g epoxy E-51,4.42g piperazines and 27.04 g tetrahydros are added into step (1) gained base polyurethane prepolymer for use as
Furans is added in reaction flask, stirs evenly, and is warming up to 50 DEG C, reacts 6 h；Reaction to epoxide number is 0, obtains mixture；
(3) deionized water with quality such as added water-soluble solvents is added into step (2) gained mixture, stirs evenly, then
Polymer is staticly settled out, polymer is washed, obtains precursor resin；
(4) precursor resin obtained by step (3) is warming up to 45 DEG C, the lactic acid for being equivalent to precursor resin quality 10.0%, stirring is added
5min, addition are equivalent to 3 times of precursor resin quality of deionized water, and stirring 30min emulsifies to arrive polyurethane-epoxy resin
Block copolymerization water-base resin.
Embodiment 8
With formulation parameter Rt=1.25, for H%=50w%, the preparation method of polyurethane-epoxy resin block copolymerization water-base resin is such as
Under:
(1) by the 17.18g polyadipate diglycol ester (molecular weight Mn=2000) removed water and 2.60g hexa-methylene two
Isocyanates (HDI) is put into reaction flask, and reaction temperature is 50 DEG C, reacts 2h, base polyurethane prepolymer for use as 11.61g is prepared；
The ratio of the oligomer dihydric alcohol and diisocyanate, so that the amount of the substance of the isocyanate group in diisocyanate
It is 1.8 ︰ 1 with the ratio between amount of substance of [OH] in oligomer dihydric alcohol；
(2) 17.02g epoxy E-20,2.76g piperazine and 31.65gN- methyl is added into step (1) gained base polyurethane prepolymer for use as
Pyrrolidones stirs evenly, and is warming up to 45 DEG C, reacts 7h；Reaction to epoxide number is 0, obtains mixture；
(3) deionized water with quality such as added water-soluble solvents is added into step (2) gained mixture, stirs evenly, then
Polymer is staticly settled out, polymer is washed, obtains precursor resin；
(4) precursor resin obtained by step (3) is warming up to 45 DEG C, the propionic acid for being equivalent to precursor resin quality 4.4%, stirring is added
5min, addition are equivalent to 1.5 times of precursor resin quality of deionized water, and stirring 30min emulsifies to arrive polyurethane-asphalt mixtures modified by epoxy resin
Rouge block copolymerization water-base resin.
Polyurethane-epoxy resin block copolymerization water-base resin performance detection embodiment obtained by each embodiment:
Before detection, polyurethane-epoxy resin block copolymerization water-base resin to be detected is prepared into solidfied material: the poly- ammonia that will be obtained
Ester-epoxy resin block copolymerization water-base resin is with BL3370 MPA by n(active hydrogen): n(isocyanate group)=2 compound, then fall
Enter Teflon mould, it is dry to water volatilization, it is put into 120 DEG C of baking ovens and toasts 20min to get solidfied material print is arrived.
Application of the polyurethane-epoxy resin block copolymerized resin obtained by each embodiment in ability cathode electrophoresis, can use with
Lower method:
Prepared polyurethane-epoxy resin block copolymerized resin is first taken, it is added by a certain percentage with blocked isocyanate
Enter into container, is stirred with dispersion machine to homogeneous, then suitable organic acid is added in mixing speed 600r/min, continue to stir
5min is mixed, deionized water is then added into container, after stirring 30min, emulsion solid content is adjusted to 20w% to get dispersion is arrived
Uniform electrophoresis lotion；Make cathode with tinplate or other metal plates, the electrophoresis 30-150s at electrophoretic voltage 40-120V；Terminate
Afterwards, metal plate is taken out, deposition layer surface is rinsed with deionized water, toasts 30min at 120 DEG C, finally obtain smooth coating light
Sliding exemplar.
Experimental result and characterization
The research of 1 ~ embodiment 8 through the foregoing embodiment, explore formulation parameter to resin structure parameter, water-base resin performance,
The influence of water-base resin condensate performance, resin ability cathode electrophoresis liquid and paint film property.Its characterization result is as described below.
(1) influence of the formulation parameter to resin structure parameter
Influence of the Rt to synthesis resin molecular weight is probed into.Experimental result is as shown in table 1.
As shown in Table 1, Rt increases, and the molecular weight of synthetic resin reduces, and molecular weight distribution (D) totally becomes larger.Because Rt is got over
Greatly, amino material is excessive more, it is more to form Amino End Group macromolecular quantity, therefore resin molecular weight is smaller；When point of synthetic resin
Son amount is small, i.e. degree of polymerization hour, and the relative mistakes of two adjacent intermolecular molecular weight of the degree of polymerization is away from becoming larger, therefore molecular weight distribution
It broadens.
(2) influence of the formulation parameter to water-base resin performance
Influence of the formulation parameter to water-base resin performance is probed into.Experimental result such as table 2.
As shown in Table 2, when H% is constant, and Rt is 1.10, synthetic resin cannot be by aquation；As Rt >=1.20, the partial size of lotion
Reducing with the increase of Rt, this is primarily due to, and the molecular weight of synthetic resin reduces, and amine value increases, therefore in identical degree of neutralization
In the case where, the amido being ionized increases, resin increased hydrophilicity.
When Rt is constant, the partial size of lotion reduces with the increase of H%, this is primarily due to H% increase, synthetic resin amine value
Increase, in the case where identical degree of neutralization, the amido that resin is ionized increases, resin increased hydrophilicity.
(3) influence of the formulation parameter to condensate performance
Influence of the formulation parameter to the mechanical property of synthesis resin cured matter is probed into.Experimental result such as table 3.
As known from Table 3, when the constant Rt of H% becomes larger, tensile strength becomes smaller, and elongation at break becomes larger, and is primarily due to one
Aspect Rt is big, and the molecular weight of synthetic resin is small, i.e., strand is short, and the physical entanglement point between strand is few；Another aspect Rt is big,
The active hydrogen amount of resin is few, causes the chemical crosslinking point of resin few.
When the constant H% of Rt becomes larger, tensile strength increases, and elongation at break reduces, and is primarily due to one side H% increase,
The rigid structure of modified resin increases, and increases solidfied material cohesive force；Another aspect H% increases, and the active hydrogen amount of resin increases,
The chemical crosslinking point of resin increases.
(4) influence of the formulation parameter to resin ability cathode electrophoresis fluidity energy
Influence of the formulation parameter to resin ability cathode electrophoresis fluidity energy is probed into.Experimental result such as table 4.
As shown in Table 4, when H% is constant, and Rt is 1.20, the ability cathode electrophoresis liquid that synthetic resin is prepared is milky turbidity liquid
Body, and mechanical stability and storage stability be not up to standard, it is big that this is primarily due to synthetic resin molecular weight, and can be ionized
Amido it is less, therefore, hydrophily is poor, wrap up blocked curing agent after, poor (such situation of the dispersion stabilization of lotion
Under resin can only be used as water paint)；As Rt >=1.25, the conductivity and pH value of electrophoresis liquid increase with the increase of Rt
Adding, this molecular weight for being primarily due to synthetic resin reduces, and amine value increases, therefore in the case where identical degree of neutralization, by ion
The amido of change increases, and amido is both salt forming group and basic group, and therefore, Rt increases, and the conductivity and pH of electrophoresis liquid are all
It increases.
When Rt is constant, and H% content increases, the conductivity and pH value of electrophoresis liquid increase with the increase of H%, this is mainly
Because H% increases, the amine groups number that synthetic resin introduces increases, i.e., amine value becomes larger, therefore, in the case where identical degree of neutralization,
The amido being ionized increases, and amido is both the group that can be ionized and basic group, therefore H% increases, the electricity of electrophoresis liquid
Conductance and pH are increased.
(5) influence of the formulation parameter to electrodeposited paint film performance
Influence of the formulation parameter to electrodeposited paint film performance is probed into.Experimental result such as table 5.
Known by table 5, under identical deposition condition, when the constant Rt of H% increases, the hardness of paint film reduces, thickness and glossiness
Increase, water resistance and resistance to acid and alkali reduce, and in Rt=1.25, paint film alkali resistance is stronger than acid resistance very much.This is to be mainly
Because one side Rt increases, the molecular weight of modified resin is small, i.e., strand is short, and the physical entanglement point between strand is few, and
The active hydrogen amount of resin is few, causes the chemical crosslinking point of resin few, therefore hardness of paint film, water resistance and resistance to acid and alkali reduce；
One side Rt increases, and the amine value of synthetic resin increases, and amido is both salt forming group and hydrophilic radical, and therefore, amine value increases
While making the conductivity increase of synthetic resin ability cathode electrophoresis liquid, the water resistance of synthetic resin is reduced, therefore in identical electrophoresis strip
The thickness of paint film increases under part, and the water resistance of paint film reduces.On the other hand positively charged micelle in OH- and is analysed near cathode
Out, it is solidified into paint film after the coating baking obtained, therefore, in acid condition, the amido in paint film is ionized, and easily makes paint film
There is anti-molten phenomenon, however is then not in this phenomenon in alkaline condition, therefore in Rt=1.25, the alkali resistance ratio of paint film
Acid resistance is many by force.
Known by table, under identical deposition condition, the constant H% of Rt increases, and thickness, hardness and the alkali resistance of paint film increase,
Glossiness and water resistance reduce, and generally alkali resistance is stronger than acid resistance, this is to be primarily due to one side H% increase, synthesis tree
The rigid structure of rouge increases, and increases solidfied material cohesive force, and the active hydrogen amount of resin increases, and the chemical crosslinking point of resin increases
More, therefore, H% is increased, and hardness of paint film and alkali resistance increase；On the one hand, H% increases, and the amine value of synthetic resin increases, and amido was both
Be salt forming group it is hydrophilic radical again, therefore, while the conductivity of ability cathode electrophoresis liquid increases, reduces the resistance to of synthetic resin
It is aqueous, and under identical deposition condition, the speed of charged colloidal particles migration increases, i.e. the speed of electro-deposition increases, but electro-deposition speed
It when degree is more than certain speed, is easy to keep paint film roughening or even packing phenomenon occurs, therefore, H% is increased, and film thickness becomes larger, light
Damp degree and water resistance reduce.On the other hand positively charged micelle is near cathode by OH-It neutralizes and is precipitated, it is solid after obtained coating baking
It is melted into paint film, therefore, in acid condition, the amido in paint film is ionized, and so that paint film anti-molten phenomenon is occurred, however in alkali
It is then not in this phenomenon in property condition, therefore the alkali resistance of generally paint film is stronger than acid resistance.
Attached detection method:
1, the electrophoresis liquid performance test of water-base resin and its preparation
(1) measurement of epoxide number
0.5000-1.5000 g resin is weighed, is placed in the conical flask of 150 ml, it is (dense that 20.0 ml hydrochloric acid-acetone soln is added
Hydrochloric acid l ml is dissolved in 40 ml acetone, matching while using), bottle stopper is stoppered, is shaken up, sample is completely dissolved.In Shade 1 is small
When, 2-3 drop methyl red indicator is added dropwise, is then titrated with 0.2 mol/LNa0H standard solution, when solution colour is by red flavescence
For terminal, blank assay is equally done, calculation method is as follows:
In formula: E---- epoxide number (mol/100g)；
V0Na0H liquor capacity (ml) consumed by ----blank；
V1NaOH solution volume (ml) consumed by ----sample；
The quality (g) of W---- sample；
NNaOH--- the concentration (mol/L) of the solution of-NaOH；
(1) emulsion appearance: emulsion state made from visual observations.Example: color, transparency, whether there is or not cohesions etc.；
(2) emulsion solid content: referring to " measurement of GB/T 1725-2007 colored paint, varnish and plastic cement non-volatile content "；
(3) lotion mechanical stability: associated test standards there is no for the mechanical stability of lotion, with reference to existing experimental method
It is tentative that it is as shown in the table.
Mechanical stability rank and stage division
| Rank | Stage division |
| 1 grade | Not split-phase under the min of 1500 r/min × 20 |
| 2 grades | Not split-phase under the min of 2000 r/min × 20 |
| 3 grades | Not split-phase under the min of 2500 r/min × 20 |
| 4 grades | Not split-phase under the min of 3000 r/min × 20 |
| 5 grades | Not split-phase under the min of 3500 r/min × 20 |
| 6 grades | Not split-phase under the min of 4000 r/min × 20 |
Wherein, rank is higher, indicates that electrophoretic coating emulsion intercalation method is better.Generally 20 are centrifuged at 3000 r/min
Split-phase can not think that room temperature stands 6 months lotions not split-phase to min.
(4) electrophoresis liquid pH is measured: being measured using PHS-3C type pH meter；
(5) electrophoresis liquid conductance measurement: referring to HG/T3335-1997 (1985) " electrophoretic paint conductance measurement method "；
(6) emulsion particle diameter measures: using Malvern company of Britain Zetasizer Nano ZS type particles distribution instrument measurement lotion
Partial size and distribution.
, condensate performance test
With reference to ASTM D2707-1985, solidfied material is cut into standard batten, at room temperature with tester for elongation with 90mm/min
Tensile speed carry out tension test, test the tensile strength and elongation at break of solidfied material.
, coating performance test
(1) pencil hardness: referring to " it is hard that GB/T 6739-2006/ISO 15184:1998 paint and varnish pencil method measures paint film
Degree "；
(2) adhesive force: referring to " cross cut test of GB/T 9286-1998/ISO 2409:1992 paint and varnish paint film "；
(3) flexibility: referring to " GB/T 1731-1993 paint film flexibility measuring method "；
(4) it the measurement of paint film film thickness: is measured using DR-330 coating thickness detector；
(5) measurement of gloss of film degree: referring to " GB/T9754-2007 paint and varnish, the colored paint paint film without metallic pigments it
The measurement of 20 °, 60 ° and 85 ° bright lusters ".
Claims (10)
1. a kind of preparation method of polyurethane-epoxy resin block copolymerization water-base resin, which comprises the following steps:
(1) by oligomer dihydric alcohol and diisocyanate investment reaction flask, reaction temperature is 50 DEG C ~ 80 DEG C, reacts 1 ~ 3h, system
It is standby to obtain base polyurethane prepolymer for use as；
(2) epoxy resin, piperazine and water-soluble solvent is added into step (1) gained base polyurethane prepolymer for use as, stirs evenly, heats up
To 30 DEG C ~ 70 DEG C, 3 ~ 8 h are reacted, reaction to epoxide number is 0, obtains mixture；
(3) deionized water with quality such as added water-soluble solvents is added into step (2) gained mixture, stirs evenly, then
Polymer is staticly settled out, polymer is washed, obtains precursor resin；
(4) precursor resin obtained by step (3) is warming up to 40-55 DEG C, addition is equivalent to having for precursor resin quality 1.2 ~ 16.0%
Machine acid, stirs 3-10min, and the deionized water for being equivalent to 1-3 times of precursor resin quality is added, and it is poly- to get arriving to stir 20-35min
Urethane-epoxy resin block copolymerization water-base resin.
2. the preparation method of polyurethane-epoxy resin block copolymerization water-base resin according to claim 1, feature exist
In, in step (1), the ratio of the oligomer dihydric alcohol and diisocyanate, so that the isocyanate group in diisocyanate
Substance amount and the ratio between the amount of substance of [OH] in oligomer dihydric alcohol be 1.5-2 ︰ 1.
3. the preparation method of polyurethane-epoxy resin block copolymerization water-base resin according to claim 1 or 2, feature
Be, in step (2), the additional amount of the water-soluble solvent, be base polyurethane prepolymer for use as, epoxy resin, piperazine gross mass 60-
100%；
The proportion of epoxy resin and piperazine is controlled with chain extension parameter Rt and hard segment content H%；
Control chain extension parameter Rt=1.2 ~ 1.6, Rt={ n (amino)/[n (epoxy group)+n (isocyanate group)] }, n expression thing
The amount of matter；Amino is the secondary amine in piperazine, and epoxy group is the epoxy group in epoxy resin, and isocyanate group is base polyurethane prepolymer for use as
In isocyanate group；
Controlling hard segment content H% is 10 ~ 60%；H%={ [m (epoxy resin)+m (piperazine)]/[m (epoxy resin)+m (piperazine)
+ m (base polyurethane prepolymer for use as)] }, m indicates the quality of substance；Hard segment content H% is hard segment content, adjustable synthetic resin
Flexibility.
4. the preparation method of polyurethane-epoxy resin block copolymerization water-base resin according to claim 1 or 2, feature
It is, in step (1), the oligomer dihydric alcohol is polycaprolactone diols, polyadipate diglycol ester, poly- tetrahydro
At least one of furans dihydric alcohol.
5. the preparation method of polyurethane-epoxy resin block copolymerization water-base resin according to claim 1 or 2, feature
It is, in step (1), the oligomer dihydric alcohol molecular weight is 400-4000.
6. the preparation method of polyurethane-epoxy resin block copolymerization water-base resin according to claim 1 or 2, feature
It is, in step (1), the diisocyanate is toluene di-isocyanate(TDI), isophorone diisocyanate, diphenyl methane two
At least one of isocyanates, hexamethylene diisocyanate.
7. the preparation method of polyurethane-epoxy resin block copolymerization water-base resin according to claim 1 or 2, feature
It is, in step (2), the epoxy resin is at least one of epoxy E-51, epoxy E-44, epoxy E-20, epoxy E-12.
8. the preparation method of polyurethane-epoxy resin block copolymerization water-base resin according to claim 1 or 2, feature
It is, in step (2), the water-soluble solvent is n,N-Dimethylformamide, tetrahydrofuran, acetone, N-Methyl pyrrolidone
One or both of.
9. the preparation method of polyurethane-epoxy resin block copolymerization water-base resin according to claim 1 or 2, feature
It is, in step (2), control reaction is 45-60 DEG C of temperature；The control reaction time is 4-6h.
10. the preparation method of polyurethane-epoxy resin block copolymerization water-base resin according to claim 1 or 2, feature
It is, in step (4), the organic acid is at least one of glacial acetic acid, lactic acid, formic acid, propionic acid, oxalic acid.
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| CN114230749A (en) * | 2021-11-29 | 2022-03-25 | 西安交通大学 | Epoxy resin cured material capable of being quickly self-repaired, preparation method and application |
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