CN105885009A - Preparation method of organic silicon modified waterborne UV curable polyurethane (PU) with high poly-alkenyl activity - Google Patents
Preparation method of organic silicon modified waterborne UV curable polyurethane (PU) with high poly-alkenyl activity Download PDFInfo
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- CN105885009A CN105885009A CN201410783244.1A CN201410783244A CN105885009A CN 105885009 A CN105885009 A CN 105885009A CN 201410783244 A CN201410783244 A CN 201410783244A CN 105885009 A CN105885009 A CN 105885009A
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Abstract
The invention discloses a preparation method of organic silicon modified waterborne UV curable polyurethane (PU) with high poly-alkenyl activity. The method comprises the following reactions: I. firstly subjecting polyether or polyester polyol, hydroxy-terminated silicone oil and a diisocyanate trimer to reaction to obtain a hydroxy-terminated solution; II. reacting DMPA with aromatic or aliphatic diisocyanate to obtain a -NCO-blocked solution, then dropwise adding the reactant I to the reactant II to obtain an organic silicon modified prepolymer subjected to chain extension, and then carrying out blocking reaction on the organic silicon modified prepolymer subjected to chain extension by using hydroxyethyl methylacrylate, hydroxyethyl acrylate or pentaerythritol triacrylate, thus obtaining an organic silicon modified PU prepolymer; and finally carrying out neutralization reaction on a system by using a triethylamine neutralizer, adding water for dilution and carrying out stirring and emulsification, thus obtaining the organic silicon modified waterborne UV curable PU emulsion. A UV curable film has better water resistance, hardness and adhesion and can be used for environmental protection, buildings, household appliances, and the like.
Description
Technical field
The present invention relates to the preparation method of a kind of organic silicon modified aqueous light-cured polyurethane of polyene-based high activity,
The invention belongs to polyene-based high activity, weatherability, the preparation method of resistance to water, all well light-cured resin.
Background introduction
In recent years, along with people are to the energy and the attention of environmental conservation, countries in the world are waved in solvent based coating
The discharge of the property sent out organic constituents (VOC) is increasingly any limitation as, and develops the water paint of low stain environment-friendly type
Have become as the Main way of coating development.Aqueous photo-curing system is inherited and has developed UV-curing technology
And the plurality of advantages of aqueous technology, as little in curing of coating shrinkage factor, adhesive force is good so that it is can to have concurrently high hard
Degree and toughness, also environmentally safe or pollute the feature such as the least, missing of ignition, be to be worth Devoting Major Efforts To Developing
Coating variety.And, ultraviolet-curing paint is easily-controllable with its prominent environmental protection, high-efficiency low energy consumption, rheological characteristic
The advantages such as system are increasingly subject to pay attention to.
But the hardness of aqueous photo-curing coating is the highest, and resistance to water also has much room for improvement.Therefore aqueous light is improved solid
The hardness of change coating and resistance to water become current focus.Organosilicon, due to the chemical constitution of its uniqueness, has
The excellent specific properties such as surface energy low, gas permeability is high, high-low temperature resistant, resistance to oxidation, good weatherability, extensively should
It is used in the industries such as chemical industry, weaving, Aero-Space, building, light industry, medical treatment.Utilize organic silicon modified aqueous
Polyurethane, the material obtained has preferable hydrophobicity, low-temperature flexibility and surface enrichment etc., deeply by domestic
The favor of outer research worker.Chinese patent 200610035457.6 discloses a kind of poly-ammonia of UV-curable water-borne
Ester acrylate paint resin and preparation method thereof, what in this patent, reaction obtained is two degree of functionality linearity blocks
Urethane acrylate (PUA), there are some negative effects in the performance of film, the hardness such as coating is the highest, resistance to
High temperature resistance to water is poor, limits its application in a lot of industries.Along with resource and environment pressure day by day
Increase, improve the performance of environment-friendly type aqueous curable urethane acrylate resin, expand its application.
Summary of the invention
A kind of coating of the organic silicon modified aqueous light-cured polyurethane of polyene-based high activity of gained of the present invention, with
With polyester diol as soft segment centered by diisocyanate trimer, it is possible to well improve polyurethane
Compliance, has more excellent mechanical property, hydrolytic resistance, thermostability, oxidative resistance, rub resistance simultaneously
Property and chemical-resistant, simultaneously on its strand, introduce siliconoxygen bond (-Si-O-Si-), due to siliconoxygen bond
The bond distance comparing carbon-carbon bond (-C-C-) is much bigger so that the compliance of chain is greatly improved, and too increases polyurethane
Resistance to water and thermostability.
The technical scheme is that
The preparation method of a kind of organic silicon modified aqueous light-cured polyurethane of polyene-based high activity, including walking as follows
Rapid:
(1) under nitrogen atmosphere polyester diol, hydroxy silicon oil and catalyst are joined in there-necked flask,
In 60～80 DEG C of temperature ranges, agitation and dropping diisocyanate trimer reaction 3～5h, obtains solution A；
(2) under nitrogen atmosphere diisocyanate, multi-hydroxy carboxy acid and catalyst are joined in there-necked flask,
In 30～50 DEG C of temperature ranges, stirring reaction 2～4h, obtains solution B；
(3) the B solution temperature obtained is increased to 60～80 DEG C, then solution A is slowly added drop-wise in B,
Reaction 4～6h, uses the viscosity of acetone regulation system, obtains solution C；
(4) in solution C, some polymerization inhibitors are just added, then by hydroxyl one end, one end photosensitive base Han ultraviolet
Being added drop-wise in solution C of dough compound, keeps temperature-resistant, the response time 2～4h；
(5) solution D that obtains is reduced temperature to 40～60 DEG C, adds amine and neutralize, add deionized water,
Stirring 1～1.5h, prepares organic-silicon-modified aqueous photo-curing polyurethane.
In solution A described in step (1), diisocyanate trimer is hexamethylene diisocyanate (HDI) trimerization
One in body, toluene di-isocyanate(TDI) (TDI) trimer, different Buddhist diisocyanates (IPDI) trimer
Or several mixture, end hydroxyalkyl silicone oil is end methylol silicone oil, end ethoxy silicone oil, end hydroxypropyl silicon
Oil, end hydroxyl butyl silicone oil in the mixture of one or more, the molecular weight of end hydroxyl silicone oil 500～2000,
Polyester diol is the one in PCDL, polycaprolactone diols, adipate polyester dihydroxylic alcohols
Or several mixture, the ratio of hydroxy silicon oil and the amount of the material of dihydroxylic alcohols: n (hydroxy silicon oil)/n (polyester binary
Alcohol or polyether Glycols)=(1: 5)～9, and the ratio of the amount of dihydroxylic alcohols and the material of hydroxy silicon oil: n (two isocyanides
Acid esters)/n (dihydroxylic alcohols and hydroxy silicon oil)=1: (1.1～1.3), catalyst is dibutyl tin laurate
(DBTDL), the weight/mass percentage composition of catalyst is 0.1～0.3%；
Diisocyanate in step (2) is toluene di-isocyanate(TDI) (TDI), different Buddhist diisocyanates
(IPDI), hexamethylene diisocyanate (HDI), 4, one or more in 4 '-methyl diphenylene diisocyanate mixed
Compound；Multi-hydroxy carboxy acid is 2,2 '-dihydromethyl propionic acid (DMPA), 2,2 '-dimethylolpropionic acid (DMBA)
In the mixture of one or more, the amount of diisocyanate and the material of multi-hydroxy carboxy acid compares: n (two isocyanides
Acid esters)/n (multi-hydroxy carboxy acid)=(1.1～1.5): 1；
The mass fraction of the acetone addition described in step (3) is 5～20%；
Hydroxyl one end, one end photosensitive group compound Han ultraviolet in described in step (4) is tetramethylolmethane three
Acrylate (PETA) or hydroxyethyl methylacrylate (HEMA) or 2-(Acryloyloxy)ethanol (HEA) is a kind of or
Several mixture, polymerization inhibitor is hydroquinone or to the mixture of one or more in methoxyl group phenol, hydroxyl
Base acrylate with the amount ratio of organic-silicon-modified resinous substances is: n (hydroxy acrylic acid): n (organosilicon
Modified resin)=(1～4): 1；
In step (5), amine is the mixture of one or more in triethylamine or dimethylaminoethanol, triethylamine
The mol ratio of amount and carboxyl of material: n (triethylamine)/n (carboxyl-content)=0.6～(1.1: 1)；Deionization
The mass fraction of the addition of water is the 30～60% of resin.
The invention has the beneficial effects as follows: by above reaction, synthesis obtain hardness and weatherability, resistance to water,
The water borne UV curing resin that wearability is greatly improved.This resin can be used for improving the weatherability of coating, it is possible to big
Improve greatly water-oil resistance, can be widely used for environmental protection, building, household electrical appliance, ink, coating etc..
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further illustrated, but embodiment is not intended that the present invention
The restriction of claimed scope:
The toluene di-isocyanate(TDI) of all uses in embodiment, isophorone diisocyanate, oneself two isocyanides
Acid esters etc., and hydroxyethyl methylacrylate, Hydroxypropyl methacrylate all through decompression distillation obtain,
Polyethers or polyester diol process through evacuation, and catalysts and solvents is processed by molecular sieve, dihydroxymethyl
Propanoic acid toasts 2h at 120 DEG C of baking ovens, and other modifying agent such as end hydroxyalkyl silicone oil is all that evacuation processes.
Embodiment 1
(1) in there-necked flask, 6.65g PCDL (PCDL) and 1g end hydroxyl silicone oil are added, then
Adding 0.15g dibutyl tin laurate (DBTDL) catalyst, open stirring, regulation reaction temperature is
70 DEG C, after temperature arrives 70 DEG C, it is slowly added dropwise 2.52g HDI trimer reacts, stopped reaction after 4h.
(2) adding 2.15g 2 in there-necked flask, 2 '-dihydromethyl propionic acid (DMPA) and 0.04g DBTDL urge
Agent, opens stirring, and regulation reaction temperature is 45 DEG C, is slowly added dropwise 7.09g different after temperature reaches 45 DEG C
Buddhist diisocyanates (IPDI) reacts, stopped reaction after 3h.
(3) temperature of (2) is increased to 70 DEG C, adds 0.15g dibutyl tin laurate (DBTDL)
The product of reaction in (1) is then added drop-wise in (2) by catalyst slowly, adds during reaction
The viscosity of acetone regulation system, response time 4h.
(4), after reaction completely, insulation keeps 70 DEG C again by hydroquinone of polymerization retarder and 3.48g 2-(Acryloyloxy)ethanol
(HEA) during mixture is added drop-wise to reaction bulb, the organic silicon modified polyurethane performed polymer after above-mentioned chain extension is carried out
End capping reaction, reacts 5h, and wherein hydroquinone of polymerization retarder accounts for the 0.05% of mixture weight, prepares after reaction completely
The end group organic silicon modified polyurethane performed polymer containing acrylic double bond, solid content is about 70%.
(5) by polyurethane prepolymer solvent revolve has steamed after, after being cooled to 50 DEG C add 1.48g triethylamine and
The end group base polyurethane prepolymer for use as containing acrylic double bond occurs to neutralize reaction, is subsequently adding the dilution of 20g water, regulation system
PH value be 7, stir 1.5h, emulsifying, prepared solid content is the pale yellow transparent organic silicon modified polyurethane of 50%
Aqueous dispersions, is obtained final resin.
Embodiment 2
(1) in there-necked flask, add 5.5g polycaprolactone diols and 0.8g end hydroxyl silicone oil, add
0.15g dibutyl tin laurate (DBTDL) catalyst, opens stirring, and regulation reaction temperature is 75 DEG C,
After temperature arrives 75 DEG C, it is slowly added dropwise 3.12g IPDI trimer react, stopped reaction after 4h.
(2) adding 2.15g 2 in there-necked flask, 2 '-dihydromethyl propionic acid (DMPA) and 0.04g DBTDL urge
Agent, opens stirring, and regulation reaction temperature is 50 DEG C, is slowly added dropwise 7.09g different after temperature reaches 50 DEG C
Buddhist diisocyanates (IPDI) reacts, stopped reaction after 3h.
(3) temperature of (2) is increased to 70 DEG C, adds 0.15g dibutyl tin laurate (DBTDL)
The product of reaction in (1) is then added drop-wise in (2) by catalyst slowly, adds during reaction
The viscosity of acetone regulation system, response time 4h.
(4), after reaction completely, insulation keeps 80 DEG C again by hydroquinone of polymerization retarder and 8.06g tetramethylolmethane 3 third
Olefin(e) acid ester (PETA) mixture is added drop-wise in reaction bulb the organic silicon modified polyurethane pre-polymerization after above-mentioned chain extension
Body carries out end capping reaction, reacts 4h, and wherein hydroquinone of polymerization retarder accounts for the 0.05% of mixture weight, and reaction is completely
The rear end group for preparing contains the organic silicon modified polyurethane performed polymer of acrylic double bond, and solid content is about 70%.
(5) by polyurethane prepolymer solvent revolve has steamed after, after being cooled to 50 DEG C add 1.63g triethylamine and
The end group base polyurethane prepolymer for use as containing acrylic double bond occurs to neutralize reaction, is subsequently adding the dilution of 50g water, regulation system
PH value be 8, stir 2h, emulsifying, prepared solid content is the organic-silicon-modified poly-ammonia of pale yellow transparent of about 30%
Ester aqueous dispersions, is obtained final resin.
Claims (6)
- The preparation method of the most organic-silicon-modified polyfunctionality aqueous photo-curing polyurethane coating, its characterization step is such as Under:(1) under nitrogen atmosphere polyester diol, hydroxy silicon oil and catalyst are joined in there-necked flask, In 60～80 DEG C of temperature ranges, agitation and dropping diisocyanate trimer reaction 3～5h, obtains solution A；(2) under nitrogen atmosphere diisocyanate, multi-hydroxy carboxy acid and catalyst are joined in there-necked flask, In 30～50 DEG C of temperature ranges, stirring reaction 2～4h, obtains solution B；(3) the B solution temperature obtained is increased to 60～80 DEG C, then solution A is slowly added drop-wise in B, Reaction 4～6h, uses the viscosity of acetone regulation system, obtains solution C；(4) in solution C, some polymerization inhibitors are just added, then by one end with hydroxyl or amino, one end band There is the compound of ultraviolet photosensitive group, be added drop-wise in solution C, keep temperature-resistant, the response time 2～4h；(5) solution D that obtains is reduced temperature to 40～60 DEG C, adds amine and neutralize, add deionized water, Stirring 1～1.5h, prepares organic-silicon-modified aqueous photo-curing polyurethane.
- It is characterized in that the most as claimed in claim 1: diisocyanate trimerization in the solution A described in step (1) Body is hexamethylene diisocyanate (HDI) trimer, toluene di-isocyanate(TDI) (TDI) trimer, different Buddhist diketone two isocyanide The mixture of one or more in acid esters (IPDI) trimer, end hydroxyalkyl silicone oil is end methylol silicone oil, end The mixture of one or more in ethoxy silicone oil, end hydroxypropyl silicone oil, end hydroxyl butyl silicone oil, terminal hydroxy group The molecular weight of silicone oil 500～2000, polyester diol be PCDL, polycaprolactone diols, The amount of the material of the mixture of one or more in adipate polyester dihydroxylic alcohols, hydroxy silicon oil and dihydroxylic alcohols Ratio: n (hydroxy silicon oil)/n (polyester diol or polyether Glycols)=(1: 5)～9, diisocyanate and dihydroxylic alcohols and The ratio of the amount of the material of hydroxy silicon oil: n (diisocyanate)/n (dihydroxylic alcohols and hydroxy silicon oil)=(1: 1.1)～1.3, urges Agent is dibutyl tin laurate (DBTDL), and the weight/mass percentage composition of catalyst is 0.1～0.3%.
- It is characterized in that the most as claimed in claim 1: the diisocyanate in step (2) is toluene di-isocyanate(TDI) (TDI), different Buddhist diisocyanates (IPDI), hexamethylene diisocyanate (HDI), 4,4 '-diphenyl methane two The mixture of one or more in isocyanates (MDI)；Multi-hydroxy carboxy acid is 2,2 '-dihydromethyl propionic acid (DMPA), 2, the mixture of one or more in 2 '-dimethylolpropionic acid (DMBA), diisocyanate with The amount ratio of the material of multi-hydroxy carboxy acid: n (diisocyanate)/n (multi-hydroxy carboxy acid)=(1.1～1.5): 1.
- It is characterized in that the most as claimed in claim 1: the mass fraction of the acetone addition described in step (3) is 5～20%.
- It is characterized in that the most as claimed in claim 1: the one end in described in step (4) with hydroxyl or amino, One end is with the compound of ultraviolet photosensitive group, for pentaerythritol triacrylate (PETA) or methacrylic acid The mixture of one or more in hydroxyl ethyl ester (HEMA) or 2-(Acryloyloxy)ethanol (HEA), polymerization inhibitor is to benzene Diphenol or to the mixture to one or more in methoxyl group phenol, hydroxy acrylate is with organic-silicon-modified The amount ratio of resinous substances is: n (hydroxy acrylic acid): n (organic-silicon-modified resin)=(1～4): 1.
- It is characterized in that the most as claimed in claim 1: in step (5), amine is in triethylamine or dimethylaminoethanol The mixture of one or more, the amount of the material of triethylamine is with the mol ratio of carboxyl: n (triethylamine)/(carboxyl contains n Amount)=0.6～(1.1: 1)；The mass fraction of the addition of deionized water is the 30～60% of resin.
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| CN107090076A (en) * | 2017-06-15 | 2017-08-25 | 盐城工学院 | A kind of organic-silicon-modified watersoluble closed type polyisocyanate crosslinking agent and preparation method thereof |
| CN107236108A (en) * | 2017-07-17 | 2017-10-10 | 江苏三木化工股份有限公司 | The preparation method of aqueous polyurethane acrylate |
| CN108264630A (en) * | 2017-12-29 | 2018-07-10 | 广东博海化工科技有限公司 | Cured modified waterborne, polycarbonate polyaminoester emulsion and preparation method thereof after a kind of UV |
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| CN107090076A (en) * | 2017-06-15 | 2017-08-25 | 盐城工学院 | A kind of organic-silicon-modified watersoluble closed type polyisocyanate crosslinking agent and preparation method thereof |
| CN107236108A (en) * | 2017-07-17 | 2017-10-10 | 江苏三木化工股份有限公司 | The preparation method of aqueous polyurethane acrylate |
| CN108264630A (en) * | 2017-12-29 | 2018-07-10 | 广东博海化工科技有限公司 | Cured modified waterborne, polycarbonate polyaminoester emulsion and preparation method thereof after a kind of UV |
| CN108912830A (en) * | 2018-07-17 | 2018-11-30 | 芜湖倍思科创园有限公司 | A kind of modified water-soluble ink and preparation method thereof |
| CN109293846A (en) * | 2018-09-19 | 2019-02-01 | 江苏三木化工股份有限公司 | The preparation method of fluorinated silicone modified multi-arm type polyurethane-hydroxy acrylate lotion |
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| CN109438654A (en) * | 2018-11-06 | 2019-03-08 | 天津科技大学 | A kind of preparation of new polyurethane film |
| CN110818878A (en) * | 2019-10-31 | 2020-02-21 | 上海交通大学 | Preparation method of waterproof high-strength transparent waterborne polyurethane |
| CN110818878B (en) * | 2019-10-31 | 2021-11-12 | 上海交通大学 | Preparation method of waterproof high-strength transparent waterborne polyurethane |
| CN111019083A (en) * | 2019-12-20 | 2020-04-17 | 珠海展辰新材料股份有限公司 | Photocuring resin, preparation method thereof and iodine tincture-resistant anti-doodling coating |
| CN111410732A (en) * | 2020-05-06 | 2020-07-14 | 深圳市前海博扬研究院有限公司 | Water-based UV resin and preparation method thereof |
| CN111410732B (en) * | 2020-05-06 | 2022-06-10 | 深圳市前海博扬研究院有限公司 | Water-based UV resin and preparation method thereof |
| CN114605646A (en) * | 2022-03-31 | 2022-06-10 | 四川大学 | Thermosetting polyurethane modified polysiloxane material capable of being repeatedly processed and used and preparation method thereof |
| CN114605646B (en) * | 2022-03-31 | 2023-03-10 | 四川大学 | Thermosetting polyurethane modified polysiloxane material capable of being repeatedly processed and used and preparation method thereof |
| CN115029059A (en) * | 2022-07-04 | 2022-09-09 | 广东省蜂巢纳米材料有限公司 | Ultraviolet-curing water-based anti-graffiti coating and preparation method thereof |
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Application publication date: 20160824 |