CN104629060B - Self-dispersal polyurethane acrylate water-based copolymer, preparation method and aqueous emulsion prepared from self-dispersal urethane acrylate water-based copolymer - Google Patents
Self-dispersal polyurethane acrylate water-based copolymer, preparation method and aqueous emulsion prepared from self-dispersal urethane acrylate water-based copolymer Download PDFInfo
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Abstract
The invention belongs to the technical field of water-based paints and discloses a self-dispersal polyurethane acrylate water-based copolymer, a preparation method and self-dispersal polyurethane acrylate aqueous emulsion prepared from the self-dispersal polyurethane acrylate water-based copolymer. The preparation method of the self-dispersal polyurethane acrylate water-based copolymer comprises the following steps: (1) preparing polyurethane prepolymer; (2) preparing polyacrylate prepolymer solution; and (3) preparing polyurethane acrylate water-based copolymer. Alkali is added to the self-dispersal polyurethane acrylate water-based copolymer to be neutralized to be neutral under the conditions of high temperature and high-speed dispersal, and deionized water is added to disperse for 15 min at high speed to obtain the self-dispersal polyurethane acrylate aqueous emulsion. The polyurethane acrylate water-based copolymer is dispersed per se in water, and particles with particle size of nanoscale can be obtained. Compared with a water-based disperse system prepared by the current most commonly used externally added emulgator method, reduction of extnerally added emulgator is avoided, the particle size is small, and the performance is exellent.
Description
Technical field
The invention belongs to technical field of aqueous paint, more particularly to a kind of self-dispersing polyurethane acrylic ester water copolymer
With preparation method and its self-dispersing urethane acrylate aqueous emulsion being prepared from.
Background technology
Coating is an indispensable supplementary material of contemporary industry.It is with plastics, adhesive, synthetic rubber, synthesis
Fiber is referred to as five big synthetic materials.The volatilization that coating is distributed in manufacture, construction, dry, solidification and film forming procedure in air
Property organic compound (VOC) pollution serious to health and environment structure and threat.For this purpose, countries in the world are all formulated
Corresponding environmental regulation, limits the discharge of VOC in coating.The progress and development of water-base resin production technology so that water paint
Progressively substitute solvent based coating to be possibly realized.
At present, aqueous emulsion of polyurethane, Polyacrylate Emulsion, epoxy resin aqueous emulsion etc. are widely used in water paint
Field.Wherein, the application of aqueous emulsion of polyurethane is especially extensive.But its chemical-resistant, solvent resistance be not good enough, hardness and glossiness
Relatively low, poor to non-polar substrate wettability, adhesion strength is low, and initial bonding strength is low, it is impossible to meet the needs of multiple fields.
Polyacrylate Emulsion has that anti-corrosion, alkaline-resisting, fast light, weather-proof, good film-forming property, colour retention be good, pollution-free, application property
Can it is good, using it is safe the features such as.Polyurethane is modified using acrylate, so as to the polyurethane third of excellent
Olefin(e) acid ester aqueous emulsion, is to study one of widest method at present.At present, the method for modifying for industrially generally adopting is by propylene
Acid esters aqueous emulsion is modified with aqueous emulsion of polyurethane physical mixed, but aqueous emulsion film modified in this way, and film easily goes out
The problems such as existing split-phase.Chemical modification is carried out if taking the method for general emulsion polymerization, core-shell emulsion polymerization, the breast added in system
The auxiliary agents such as agent, dispersant, can to a certain extent reduce emulsion property.
The content of the invention
In order to overcome the shortcoming and deficiency of above-mentioned prior art, the primary and foremost purpose of the present invention is to provide a kind of self-dispersing to gather
Urethane acrylate aqueous copolymer.
Another object of the present invention is to provide a kind of preparation side of above-mentioned self-dispersing polyurethane acrylic ester water copolymer
Method.
It is still another object of the present invention to provide what above-mentioned self-dispersing polyurethane acrylic ester water copolymer was prepared from
Self-dispersing urethane acrylate aqueous emulsion.
A further object of the present invention is the preparation method for providing above-mentioned self-dispersing urethane acrylate aqueous emulsion.
The purpose of the present invention is realized by following proposal：
A kind of self-dispersing polyurethane acrylic ester water copolymer, the copolymer has the structure being shown below：
Wherein, R1Represent H or CH3, R2Represent In one kind, x be between 1～10 from
So count, y is the natural number between 5～30, z is the natural number between 1～20, and a is the natural number between 1～4, and m is 5～200
Between natural number, n is the natural number between 1～18.
The preparation method of above-mentioned self-dispersing polyurethane acrylic ester water copolymer, including following operating procedure：
(1) preparation of polyurethane prepolymer：By 100 weight portion polyether Glycols of eliminating water, 50～65 DEG C are warming up to, are added
12～50 weight portion diisocyanate, are uniformly mixed, and are warming up to 70～80 DEG C, obtain polyurethane after 3～7h of reaction pre-
Polymers；
(2) preparation of polyacrylate pre-polymer solution：By the acrylate or methacrylate of 60～90 weight portions,
The crylic acid hydroxy ester or methacrylic acid hydroxy ester of 5～10 weight portions, the acrylic or methacrylic acid of 5～30 weight portions,
100 parts by weight solvent, the initiator of 2～3 weight portions, are uniformly mixed, and after reacting 10～15h at 80～100 DEG C, are obtained
Polyacrylate pre-polymer solution；
(3) preparation of polyurethane acrylic ester water copolymer：The polyurethane prepolymer of 20～40 weight portions, stirring are risen
Temperature adds the polyacrylate pre-polymer solution of 80～120 weight portions and the catalyst of 0.01～0.10 weight portion to 40 DEG C, stirs
Mix and be warming up to after mix homogeneously 60～70 DEG C, reaction obtains polyurethane acrylic ester water polymer solution after 2～7 hours；Make
The organic solvent in polyurethane acrylic ester water polymer solution is removed with rotary evaporator, self-dispersing polyurethane propylene is obtained
Acid esters aqueous copolymer.
The molecular weight of the polyether Glycols described in step (1) is 300～10000.
Diisocyanate described in step (1) is that toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, benzene two are sub-
Methyl diisocyanate, naphthalene diisocyanate, 1,3-Diisocyanatomethylcyclohexane, dicyclohexyl methyl hydride diisocyanate, oneself two
One or more in isocyanates, isophorone diisocyanate.
Alkyl acrylate described in step (2) is acrylic acid methyl ester., ethyl acrylate, propyl acrylate, acrylic acid
One or more of different monooctyl ester, butyl acrylate, octadecyl acrylate, lauryl acrylate, benzyl acrylate；
Described alkyl methacrylate be methyl methacrylate, ethyl methacrylate, propyl methacrylate,
2-Propenoic acid, 2-methyl-, isooctyl ester, butyl methacrylate, octadecyl methacrylate, lauryl methacrylate, methacrylic acid
One or more of benzyl ester.
Crylic acid hydroxy ester described in step (2) is 2-(Acryloyloxy)ethanol, Hydroxypropyl acrylate, acrylic acid 4- hydroxyl fourths
One or more of ester；
Described methacrylic acid hydroxy ester is hydroxyethyl methylacrylate, Hydroxypropyl methacrylate, methacrylic acid
One or more of 4- hydroxybutyls；
Described initiator is azodiisobutyronitrile, AMBN, 2,2'-Azobis(2,4-dimethylvaleronitrile) and azo dicyclohexyl first
One or more of nitrile；
Described solvent is one or more of toluene, dimethylbenzene, dioxane, Ketohexamethylene and glycol monoethyl ether.
Catalyst described in step (3) is trimethylamine class and organo-metallic compound；Step (1), (2) and (3) is
Stirring in the environment of logical nitrogen is carried out.
Described catalyst is tetramethyl butane diamine, dimethyl cyclohexyl amine, pentamethyl-diethylenetriamine, dibutyl tin osmanthus
One or more of sour stannum, lead octoate.
A kind of self-dispersing polyurethane propylene being prepared from by above-mentioned self-dispersing polyurethane acrylic ester water copolymer
Acid esters aqueous emulsion.
The preparation method of above-mentioned self-dispersing urethane acrylate aqueous emulsion, including following operating procedure：By self-dispersing
Polyurethane acrylic ester water copolymer, at normal temperatures with the rotating speed dispersed with stirring of 1500r/min under conditions of, add triethylamine
Neutrality is neutralized to, is subsequently adding after deionized water again with rotating speed dispersed with stirring 15min of 1500r/min, obtain the poly- ammonia of self-dispersing
Ester Polyacrylate Emulsion.
The present invention mechanism be：
The present invention by being chemically synthesized polyurethane acrylic ester water copolymer, in the side chain of acrylic ester prepolymer
Middle introducing aqueouss group, while there is hydrophilic polyether segment in polyurethane prepolymer structure, makes urethane acrylate be polymerized
Thing can under the conditions of emulsifier-free in water self-dispersing.Acrylic acid ester emulsion have against weather, resistance to ag(e)ing, non-oxidizability and
A series of features such as elongation at break is high compared with high, adhesive strength, adhesive linkage cohesiveness is big, resistance to water is good, environmental friendliness, can be fast
Rapid-curing cutback is dry, with mono-component polyurethane aqueous emulsion performance complement, after being combined aqueous emulsion can be made to have Polyacrylate Emulsion and poly- ammonia concurrently
The characteristics of ester aqueous emulsion.Containing abundant ester group and alkyl structure in polyurethane acrylic ester water copolymer structure, can with not
Active force is formed between the interface of same polarity.Self-dispersion type polyurethane acrylic ester water co-polymer has stronger cohesiveness, system
It is more excellent with the performance of aqueous emulsion of polyurethane physical blending system and more stable than Polyacrylate Emulsion when using into coating
Property.
The present invention has the following advantages and beneficial effect relative to prior art：
The present invention introduces aqueouss group in polyacrylate prepolymer, and end-product is using water as solvent, environmental friendliness；
Coating equipment and container can be cleaned with aqueous rinsing liquid, production safety, be capable of achieving shallow layer coating, be applicable to various applications
Equipment.The self-dispersion type polyurethane acrylic ester water copolymer that the present invention is obtained, in plastic sheeting, fibre board, sheet glass table
Face film, spreading property and adhesive property it is excellent.The self-dispersing urethane acrylate water obtained by the method for the present invention
Property copolymer be dispersed in water, particle diameter is little, compared with water-base disperse system prepared by present the most frequently used additional emulsifying agent method, keeps away
Exempt from the hydraulic performance decline that additional emulsifying agent causes, and particle diameter is less, performance is more excellent.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Performance testing standard is as follows in the following example：
Annular initial adhesive strength：Determine by FINAT FTM 9-2003；
180 ° of peel strengths：Determine by GB/2792-1998；
Hold viscosity：Determine by GB/4851-1998.
Adhesive force：Determined using 3M600# test tape.
Embodiment 1：
The preparation of polyurethane prepolymer：To polyethers N210 (molecular weight is 1000) vacuum under the conditions of 120 DEG C of vacuum drying oven
It is dried eliminating water 4h.By weight, 100 parts of polyethers N210 being dehydrated are added in equipped with agitator, the reactor of thermometer, is risen
Temperature adds 12 parts of toluene di-isocyanate(TDI) to 50 DEG C, and the mix homogeneously under conditions of stirring is warming up to 70 DEG C, and reaction 7 is little
When after obtain polyurethane prepolymer PU1.
The preparation of polyacrylate pre-polymer solution：By weight, equipped with agitator, thermometer, reflux condensing tube
60 parts of isobutyl methacrylates, 10 parts of hydroxyethyl methylacrylates, 30 parts of methacrylic acids, 100 parts of first are added in reactor
Benzene, 2 parts of azo diisopropyl imidazoline hydrochlorides, is uniformly mixed, and after being warming up to 80 DEG C of reaction 15h, polyacrylate prepolymer is obtained
PA1 solution.
The preparation of polyurethane acrylic ester water copolymer：The PU1 of 20 weight portions is placed in reactor, stirring is warming up to
40 DEG C, the PA1 solution of 120 weight portions and the tetramethyl butane diamine of 0.01 weight portion are added, 60 are warming up to after being uniformly mixed
DEG C, reaction obtains polyurethane acrylic ester water polymer solution after 2 hours；Polyurethane acroleic acid is removed using rotary evaporator
Toluene in ester aqueous polymer solution, obtains self-dispersing polyurethane acrylic ester water copolymer J1.
The preparation of self-dispersing urethane acrylate aqueous emulsion：J1 is placed in beaker, in room temperature turning with 1500r/min
Under the conditions of fast high speed is scattered, add triethylamine to be neutralized to neutrality, add after the deionized water of 100 weight portions again with 1500r/
The rotating speed of min disperses at a high speed 15min, obtains self-dispersing urethane acrylate aqueous emulsion.
According to 30g/m2Amount by self-dispersing urethane acrylate aqueous emulsion in BOPP film surface coating, treat water volatilize
Afterwards, the polyurethane acrylic ester water polymer-coated layer performance for obtaining is as follows：
Annular initial bonding strength 12.38N/25mm, 180 ° of peel strengths are 12.03N/25mm, hold viscous 3.82h；Adhesive force：Coating
Do not fall off；Transparency：Transparency is without significant change before and after film.
Embodiment 2：The preparation of polyurethane acrylic ester water polymer
The preparation of polyurethane prepolymer：To polyethers N220 (molecular weight is 2000) vacuum under the conditions of 120 DEG C of vacuum drying oven
It is dried eliminating water 4h.By weight, 100 parts of polyethers N220 being dehydrated are added in equipped with agitator, the reactor of thermometer, is risen
Temperature adds 50 parts of methyl diphenylene diisocyanate to 65 DEG C, and the mix homogeneously under conditions of stirring is warming up to 80 DEG C, instead
Answer and obtain polyurethane prepolymer PU2 after 3 hours.
The preparation of polyacrylate pre-polymer solution：By weight, equipped with agitator, thermometer, reflux condensing tube
90 parts of 2-Propenoic acid, 2-methyl-, isooctyl esters of addition in reactor, 5 parts of Hydroxypropyl methacrylates, 5 parts of acrylic acid, 100 parts of dimethylbenzene, 3
Part 2,2'-Azobis(2,4-dimethylvaleronitrile), is uniformly mixed, and after being warming up to 100 DEG C of reaction 10h, polyacrylate prepolymer PA2 solution is obtained.
The preparation of polyurethane acrylic ester water copolymer：The PU2 of 30 weight portions is placed in reactor, stirring is warming up to
40 DEG C, the PA2 solution of 120 weight portions and the dimethyl cyclohexyl amine of 0.1 weight portion are added, 70 are warming up to after being uniformly mixed
DEG C, reaction obtains polyurethane acrylic ester water polymer solution after 7 hours；Polyurethane acroleic acid is removed using rotary evaporator
Dimethylbenzene in ester aqueous polymer solution, obtains self-dispersing polyurethane acrylic ester water copolymer J2.
The preparation of self-dispersing urethane acrylate aqueous emulsion：J2 is placed in beaker, in room temperature turning with 1500r/min
Under the conditions of fast high speed is scattered, add triethylamine to be neutralized to neutrality, add after the deionized water of 100 weight portions again with 1500r/
The rotating speed of min disperses at a high speed 15min, obtains self-dispersing urethane acrylate aqueous emulsion.
According to 30g/m2Amount by self-dispersing urethane acrylate aqueous emulsion in BOPP film surface coating, treat water volatilize
Afterwards, the polyurethane acrylic ester water polymer-coated layer performance for obtaining is as follows：
Annular initial bonding strength 12.81N/25mm, 180 ° of peel strengths are 12.09N/25mm, hold viscous 3.09h；Adhesive force：Coating
Do not fall off；Transparency：Transparency is without significant change before and after film.
Embodiment 3：The preparation of polyurethane acrylic ester water polymer
The preparation of polyurethane prepolymer：To polyethers PEG300 (molecular weight is 300) vacuum under the conditions of 120 DEG C of vacuum drying oven
It is dried eliminating water 4h.By weight, 100 parts of polyethers PEG300 being dehydrated are added in equipped with agitator, the reactor of thermometer,
60 DEG C are warming up to, 15 parts of isoflurane chalcone diisocyanate, 15 parts of XDI, in the condition of stirring is added
Lower mix homogeneously, is warming up to 75 DEG C, and after 5 hours of reaction polyurethane prepolymer PU3 is obtained.
The preparation of polyacrylate pre-polymer solution：By weight, equipped with agitator, thermometer, reflux condensing tube
70 parts of propyl methacrylates, 8 parts of acrylic acid 4- hydroxybutyls, 22 parts of methacrylic acids, 100 parts of dioxies six are added in reactor
Ring, 2.5 parts of AMBNs, is uniformly mixed, and after being warming up to 90 DEG C of reaction 12h, polyacrylate prepolymer PA3 is obtained
Solution.
The preparation of polyurethane acrylic ester water copolymer：The PU3 of 40 weight portions is placed in reactor, stirring is warming up to
40 DEG C, the PA3 solution of 80 weight portions and the pentamethyl-diethylenetriamine of 0.05 weight portion are added, be warming up to after being uniformly mixed
65 DEG C, reaction obtains polyurethane acrylic ester water polymer solution after 5 hours；Polyurethane propylene is removed using rotary evaporator
Dioxane in acid esters aqueous polymer solution, obtains self-dispersing polyurethane acrylic ester water copolymer J3.
The preparation of self-dispersing urethane acrylate aqueous emulsion：J3 is placed in beaker, in room temperature turning with 1500r/min
Under the conditions of fast high speed is scattered, add triethylamine to be neutralized to neutrality, add after the deionized water of 100 weight portions again with 1500r/
The rotating speed of min disperses at a high speed 15min, obtains self-dispersing urethane acrylate aqueous emulsion.
According to 30g/m2Amount by self-dispersing urethane acrylate aqueous emulsion in BOPP film surface coating, treat water volatilize
Afterwards, the polyurethane acrylic ester water polymer-coated layer performance for obtaining is as follows：
Annular initial bonding strength 12.89N/25mm, 180 ° of peel strengths are 12.63N/25mm, hold viscous 3.87h；Adhesive force：Coating
Do not fall off；Transparency：Transparency is without significant change before and after film.
Embodiment 4：The preparation of polyurethane acrylic ester water polymer
The preparation of polyurethane prepolymer：To polyethers PEG600 (molecular weight is 600) vacuum under the conditions of 120 DEG C of vacuum drying oven
It is dried eliminating water 4h.By weight, 100 parts of polyethers PEG600 being dehydrated are added in equipped with agitator, the reactor of thermometer,
55 DEG C are warming up to, 40 parts of naphthalene diisocyanate is added, the mix homogeneously under conditions of stirring is warming up to 78 DEG C, and reaction 4 is little
When after obtain polyurethane prepolymer PU4.
The preparation of polyacrylate pre-polymer solution：By weight, equipped with agitator, thermometer, reflux condensing tube
80 parts of propyl methacrylates of addition in reactor, 10 parts of hydroxyethyl methylacrylates, 10 parts of acrylic acid, 100 parts of Ketohexamethylene,
2.8 parts of azodiisobutyronitriles, are uniformly mixed, and after being warming up to 95 DEG C of reaction 13h, polyacrylate prepolymer PA4 are obtained molten
Liquid.
The preparation of polyurethane acrylic ester water copolymer：The PU4 of 25 weight portions is placed in reactor, stirring is warming up to
40 DEG C, the PA4 solution of 100 weight portions and the dibutyl tin dilaurate of 0.05 weight portion are added, heated up after being uniformly mixed
To 68 DEG C, reaction obtains polyurethane acrylic ester water polymer solution after 4 hours；Polyurethane third is removed using rotary evaporator
Ketohexamethylene in olefin(e) acid ester aqueous polymer solution, obtains self-dispersing polyurethane acrylic ester water copolymer J4.
The preparation of self-dispersing urethane acrylate aqueous emulsion：J4 is placed in beaker, in room temperature turning with 1500r/min
Under the conditions of fast high speed is scattered, add triethylamine to be neutralized to neutrality, add after the deionized water of 100 weight portions again with 1500r/
The rotating speed of min disperses at a high speed 15min, obtains self-dispersing urethane acrylate aqueous emulsion.
According to 30g/m2Amount by self-dispersing urethane acrylate aqueous emulsion in BOPP film surface coating, treat water volatilize
Afterwards, the polyurethane acrylic ester water polymer-coated layer performance for obtaining is as follows：
Annular initial bonding strength 12.92N/25mm, 180 ° of peel strengths are 12.64N/25mm, hold viscous 3.87h；Adhesive force：Coating
Do not fall off；Transparency：Transparency is without significant change before and after film.
Embodiment 5：The preparation of polyurethane acrylic ester water polymer
The preparation of polyurethane prepolymer：To polyethers PEG10000 under the conditions of 120 DEG C of vacuum drying oven (molecular weight is 10000)
Vacuum drying eliminating water 4h.By weight, 100 parts of polyethers being dehydrated are added in equipped with agitator, the reactor of thermometer
PEG10000, is warming up to 58 DEG C, adds 20 parts of 1,3-Diisocyanatomethylcyclohexane, and the mix homogeneously under conditions of stirring rises
Temperature obtains polyurethane prepolymer PU5 to 75 DEG C after 5 hours of reaction.
The preparation of polyacrylate pre-polymer solution：By weight, equipped with agitator, thermometer, reflux condensing tube
65 parts of 2-Propenoic acid, 2-methyl-, isooctyl esters, 10 parts of 2-(Acryloyloxy)ethanols, 25 parts of methacrylic acids, 100 parts of ethylene glycol are added in reactor
Monomethyl ether, 2.5 parts of azodiisobutyronitriles, is uniformly mixed, and after being warming up to 85 DEG C of reaction 14h, polyacrylate pre-polymerization is obtained
Thing PA5 solution.
The preparation of polyurethane acrylic ester water copolymer：The PU5 of 35 weight portions is placed in reactor, stirring is warming up to
40 DEG C, the PA5 solution of 110 weight portions and the lead octoate of 0.08 weight portion are added, 65 DEG C are warming up to after being uniformly mixed, reaction
Polyurethane acrylic ester water polymer solution is obtained after 3 hours；Polyurethane acrylic ester water is removed using rotary evaporator
Glycol monoethyl ether in polymer solution, obtains self-dispersing polyurethane acrylic ester water copolymer J5.
The preparation of self-dispersing urethane acrylate aqueous emulsion：J5 is placed in beaker, in room temperature turning with 1500r/min
Under the conditions of fast high speed is scattered, add triethylamine to be neutralized to neutrality, add after the deionized water of 100 weight portions again with 1500r/
The rotating speed of min disperses at a high speed 15min, obtains self-dispersing urethane acrylate aqueous emulsion.
According to 30g/m2Amount by self-dispersing urethane acrylate aqueous emulsion in BOPP film surface coating, treat water volatilize
Afterwards, the polyurethane acrylic ester water polymer-coated layer performance for obtaining is as follows：
Annular initial bonding strength 12.68N/25mm, 180 ° of peel strengths are 12.65N/25mm, hold viscous 3.24h；Adhesive force：Coating
Do not fall off；Transparency：Transparency is without significant change before and after film.
Embodiment 6：The preparation of polyurethane acrylic ester water polymer
The preparation of polyurethane prepolymer：It is true to polyethers PEG6000 (molecular weight is 6000) under the conditions of 120 DEG C of vacuum drying oven
Sky is dried eliminating water 4h.By weight, 100 parts of polyethers being dehydrated are added in equipped with agitator, the reactor of thermometer
PEG6000, is warming up to 60 DEG C, adds 25 parts of dicyclohexyl methyl hydride diisocyanate, and the mix homogeneously under conditions of stirring rises
Temperature obtains polyurethane prepolymer PU6 to 70 DEG C after 6 hours of reaction.
The preparation of polyacrylate pre-polymer solution：By weight, equipped with agitator, thermometer, reflux condensing tube
75 parts of isobutyl methacrylates, 5 parts of Hydroxypropyl acrylates, 20 parts of acrylic acid, 100 parts of dimethylbenzene, 3 parts of idols are added in reactor
Nitrogen diisoamyl nitrile, is uniformly mixed, and after being warming up to 100 DEG C of reaction 10h, polyacrylate prepolymer PA6 solution is obtained.
The preparation of polyurethane acrylic ester water copolymer：The PU6 of 25 weight portions is placed in reactor, stirring is warming up to
40 DEG C, the PA6 solution of 90 weight portions and the dibutyl tin dilaurate of 0.08 weight portion are added, be warming up to after being uniformly mixed
65 DEG C, reaction obtains polyurethane acrylic ester water polymer solution after 6 hours；Polyurethane propylene is removed using rotary evaporator
Dimethylbenzene in acid esters aqueous polymer solution, obtains self-dispersing polyurethane acrylic ester water copolymer J6.
The preparation of self-dispersing urethane acrylate aqueous emulsion：J6 is placed in beaker, in room temperature turning with 1500r/min
Under the conditions of fast high speed is scattered, add triethylamine to be neutralized to neutrality, add after the deionized water of 100 weight portions again with 1500r/
The rotating speed of min disperses at a high speed 15min, obtains self-dispersing urethane acrylate aqueous emulsion.
According to 30g/m2Amount by self-dispersing urethane acrylate aqueous emulsion in BOPP film surface coating, treat water volatilize
Afterwards, the polyurethane acrylic ester water polymer-coated layer performance for obtaining is as follows：
Annular initial bonding strength 12.61N/25mm, 180 ° of peel strengths are 12.62N/25mm, hold viscous 3.78h；Adhesive force：Coating
Do not fall off；Transparency：Transparency is without significant change before and after film.
Embodiment 7：The preparation of polyurethane acrylic ester water polymer
The preparation of polyurethane prepolymer：To polyethers N220 (molecular weight is 2000) vacuum under the conditions of 120 DEG C of vacuum drying oven
It is dried eliminating water 4h.By weight, 100 parts of polyethers N220 being dehydrated are added in equipped with agitator, the reactor of thermometer, is risen
Temperature adds 25 parts of hexamethylene diisocyanate to 65 DEG C, and the mix homogeneously under conditions of stirring is warming up to 70 DEG C, reacts 6 hours
After obtain polyurethane prepolymer PU7.
The preparation of polyacrylate pre-polymer solution：By weight, equipped with agitator, thermometer, reflux condensing tube
80 parts of isopropyl methacrylates, 5 parts of 2-(Acryloyloxy)ethanols, 15 parts of methacrylic acids, 100 parts of dioxies six are added in reactor
Ring, 2 parts of 2,2'-Azobis(2,4-dimethylvaleronitrile), is uniformly mixed, and after being warming up to 90 DEG C of reaction 15h, polyacrylate prepolymer PA7 is obtained molten
Liquid.
The preparation of polyurethane acrylic ester water copolymer：The PU7 of 35 weight portions is placed in reactor, stirring is warming up to
40 DEG C, the PA7 solution of 100 weight portions and the tetramethyl butane diamine of 0.1 weight portion are added, 70 are warming up to after being uniformly mixed
DEG C, reaction obtains polyurethane acrylic ester water polymer solution after 6 hours；Polyurethane acroleic acid is removed using rotary evaporator
Dioxane in ester aqueous polymer solution, obtains self-dispersing polyurethane acrylic ester water copolymer J7.
The preparation of self-dispersing urethane acrylate aqueous emulsion：J7 is placed in beaker, in room temperature turning with 1500r/min
Under the conditions of fast high speed is scattered, add triethylamine to be neutralized to neutrality, add after the deionized water of 100 weight portions again with 1500r/
The rotating speed of min disperses at a high speed 15min, obtains self-dispersing urethane acrylate aqueous emulsion.
According to 30g/m2Amount by self-dispersing urethane acrylate aqueous emulsion in BOPP film surface coating, treat water volatilize
Afterwards, the polyurethane acrylic ester water polymer-coated layer performance for obtaining is as follows：
Annular initial bonding strength 12.81N/25mm, 180 ° of peel strengths are 12.64N/25mm, hold viscous 3.85h；Adhesive force：Coating
Do not fall off；Transparency：Transparency is without significant change before and after film.
From the urethane acrylate coating layer characteristic on BOPP film surface in embodiment, it is polymerized using different monomers
The annular initial adhesive strength of the polyurethane acrylic ester water polymer for obtaining, 180 ° of peel strengths and to hold viscosity good.Using water
As solvent, environmental friendliness, it is easy to regulation system viscosity, it is easy to processing.Due in the strand of polyacrylate and polyurethane
There is abundant ester group, the interaction force between chain and chain is strong so that urethane acrylate coat has good interior
Poly- power.Due to containing abundant polyether segment in structure, therefore polymer has good mobility, to BOPP film base material
Spreadability is good, and cohesive force is good, so as to reach the effect of the technology of the present invention raising.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention not by above-described embodiment
Limit, other any spirit without departing from the present invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (9)
1. a kind of self-dispersing polyurethane acrylic ester water copolymer, it is characterised in that：The copolymer has what is be shown below
Structure：
Wherein, R1Represent H or CH3, R2Represent In one kind, x be between 1～10 from
So count, y is the natural number between 5～30, z is the natural number between 1～20, and a is the natural number between 1～4, and m is 5～200
Between natural number, n is the natural number between 1～18.
2. the preparation method of a kind of self-dispersing polyurethane acrylic ester water copolymer according to claim 1, its feature
It is to include following operating procedure：
(1) preparation of polyurethane prepolymer：By 100 weight portion polyether Glycols of eliminating water, 50～65 DEG C are warming up to, add 12～
50 weight portion diisocyanate, are uniformly mixed, and are warming up to 70～80 DEG C, and after 3～7h of reaction polyurethane prepolymer is obtained；
(2) preparation of polyacrylate pre-polymer solution：By the acrylate or methacrylate of 60～90 weight portions, 5～
The crylic acid hydroxy ester or methacrylic acid hydroxy ester of 10 weight portions, the acrylic or methacrylic acid of 5～30 weight portions, 100
Parts by weight solvent, the initiator of 2～3 weight portions, is uniformly mixed, and after reacting 10～15h at 80～100 DEG C, is obtained poly-
Acrylic ester prepolymer solution；
(3) preparation of polyurethane acrylic ester water copolymer：The polyurethane prepolymer of 20～40 weight portions, stirring are warming up to
40 DEG C, the polyacrylate pre-polymer solution of 80～120 weight portions and the catalyst of 0.01～0.10 weight portion are added, stirring is mixed
60～70 DEG C are warming up to after closing uniformly, reaction obtains polyurethane acrylic ester water polymer solution after 2～7 hours；Using rotation
Turn the organic solvent that vaporizer is removed in polyurethane acrylic ester water polymer solution, obtain self-dispersing urethane acrylate
Aqueous copolymer.
3. preparation method according to claim 2, it is characterised in that：Diisocyanate described in step (1) is toluene
Diisocyanate, methyl diphenylene diisocyanate, XDI, naphthalene diisocyanate, dicyclohexyl first
One or more in alkane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate.
4. preparation method according to claim 2, it is characterised in that：Alkyl acrylate described in step (2) is third
E pioic acid methyl ester, ethyl acrylate, propyl acrylate, Isooctyl acrylate monomer, butyl acrylate, octadecyl acrylate, the acrylic acid moon
One or more of osmanthus ester；
Described alkyl methacrylate is methyl methacrylate, ethyl methacrylate, propyl methacrylate, methyl
One or more of Isooctyl acrylate monomer, butyl methacrylate, octadecyl methacrylate, lauryl methacrylate.
5. preparation method according to claim 2, it is characterised in that：Crylic acid hydroxy ester described in step (2) is third
One or more of olefin(e) acid hydroxyl ethyl ester, Hydroxypropyl acrylate, acrylic acid 4- hydroxybutyls；
Described methacrylic acid hydroxy ester is hydroxyethyl methylacrylate, Hydroxypropyl methacrylate, methacrylic acid 4- hydroxyls
One or more of base butyl ester；
Described initiator is in azodiisobutyronitrile, AMBN, 2,2'-Azobis(2,4-dimethylvaleronitrile) and azo diisopropyl imidazoline hydrochloride
More than one；
Described solvent is one or more of toluene, dimethylbenzene, dioxane, Ketohexamethylene and glycol monoethyl ether.
6. preparation method according to claim 2, it is characterised in that：Catalyst described in step (3) is trimethylamine
Class and organo-metallic compound；Step (1), (2) and (3) is to stir to carry out in the environment of logical nitrogen.
7. preparation method according to claim 6, it is characterised in that：Described catalyst is tetramethyl butane diamine, diformazan
One or more of basic ring hexylamine, pentamethyl-diethylenetriamine, dibutyl tin dilaurate, lead octoate.
8. the poly- ammonia of self-dispersing that a kind of self-dispersing polyurethane acrylic ester water copolymer by described in claim 1 is prepared from
Ester Polyacrylate Emulsion.
9. the preparation method of self-dispersing urethane acrylate aqueous emulsion according to claim 8, it is characterised in that include
Following operating procedure：By self-dispersing polyurethane acrylic ester water copolymer, at normal temperatures with the rotating speed stirring point of 1500r/min
Under conditions of dissipating, add triethylamine to be neutralized to neutrality, be subsequently adding after deionized water again with the rotating speed dispersed with stirring of 1500r/min
15min, obtains self-dispersing urethane acrylate aqueous emulsion.
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| CN104974656B (en) * | 2015-06-26 | 2017-10-27 | 中科院广州化学有限公司南雄材料生产基地 | Moisturecuring one-component polyacrylate modified polyurethane water-repellent paint and its preparation |
| CN106543881A (en) * | 2016-10-27 | 2017-03-29 | 中科院广州化学有限公司南雄材料生产基地 | A kind of water polyacrylic acid modified polyurethane water-repellent paint and its preparation method and application |
| CN111849338B (en) * | 2020-07-30 | 2021-07-27 | 佛山(华南)新材料研究院 | Self-dispersion aqueous electric heating slurry and preparation method thereof |
| CN112852286A (en) | 2021-01-13 | 2021-05-28 | 浙江佑谦特种材料有限公司 | Water-based polyurethane acrylate emulsion, preparation method thereof and water-based matte paint |
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