CN102060974A - Synthesis method of organosilicon-modified aqueous polyurethane acrylate - Google Patents
Synthesis method of organosilicon-modified aqueous polyurethane acrylate Download PDFInfo
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Abstract
The invention provides a synthesis method of organosilicon-modified aqueous polyurethane acrylate, which takes different aliphatic diisocyanates, alcoholic hydroxyl-terminated polysiloxane and acrylic acid monomer as main raw materials, and utilizes a stepwise synthesis method. The stepwise synthesis method comprises the following steps of: synthesizing organosilicon-modified polyurethane, introducing a hydrophilic group, and introducing the acrylic acid monomer, wherein a mixed solution of dibutyl tin laurate and organic carboxylic acid rare earth is taken as a catalyst for reflowing at the certain temperature so as to optimize the reaction condition; therefore, the invention provides a synthesis method of photo-cured aqueous polyurethane acrylate with great performances of yellowing resistance, high hardness and the like. The invention has the characteristics of high yield, easy operation and control and the like.
Description
Technical field
The invention belongs to the field of chemical synthesis, specifically providing a kind of is main raw material with different aliphatic diisocyanates, the end capped polysiloxane of alcoholic extract hydroxyl group, acrylic monomer, adopt step synthesis, obtain the method for organic silicon modified aqueous polyurethane acrylate.
Background technology
Traditional oiliness urethane acrylate curing system exists deficiency, especially diluent monomer to the pungency of human body skin and eyes at aspects such as environment protection, health of human body, technological operation and film properties controls, and smell is poor, price is more expensive.And the advantage of traditional curing system is inherited and developed to the aqueous photo-curing polyurethane acrylate, than oiliness urethane acrylate curing system, have low cost, low viscosity, nontoxic advantage such as non-stimulated, characteristics such as its good wear resistance, chemicals-resistant, low temperature resistant and snappiness be good in addition, and receive much attention.For synthesizing of it, raw material generally contains vulcabond.Vulcabond has aromatic diisocyanate and aliphatic diisocyanate.The urethane of aromatic diisocyanate preparation is because the isocyanic ester building stone directly links to each other oxidation flavescence easily with phenyl ring.And the urethane of aliphatic diisocyanate preparation has anti-xanthochromic performance, but exists the low shortcoming of intensity with the urethane of aliphatics cyanate preparation.For this reason, need to propose a kind of synthetic method, can improve the novel curing system of the advantage of organic polymer high rigidity, anti-solvent and wear resistance when making product can keep organic macromolecule filming, the transparency again.
Very active to the research of aqueous photo-curing resin in recent years, roughly be divided into following a few class:
1, copolymer type acrylate resin
Copolymer type acrylate resin photocuring system, have cheap, preparation easily, glossiness is high
Characteristics, at present also many to the research of this system.It is by the monomer that contains special groups (as Hydroxyethyl acrylate, glycidyl acrylate, acrylic acid series etc.) copolymerization, and the hydroxyl of gained multipolymer or epoxy group(ing) are reacted with acrylic monomer again, make UV curable water-borne acrylate resin.
2, unsaturated polyester resin
Water-based UV solidifies the unsaturated polyester system, is to obtain not at traditional polyvalent alcohol and polyprotonic acid polycondensation
Introduce a certain amount of hydrophilic radical on the basis of saturated polyester, as polyoxyethylene glycol, trimellitic acid 1,2-anhydride or pyromellitic acid acid anhydride etc., thus make it to have water-soluble.
3, Epocryl
To have price low because of Epocryl, cured film hardness height, and sticking power is good, and glossiness is high and anti-
Advantages such as pharmaceutical chemicals is good and be subjected to the parent and look at are so the research of this respect is also many.Water-based epoxy acrylic ester resin is to obtain epoxy acrylate with Resins, epoxy and vinylformic acid reaction earlier, utilize hydroxyl in the epoxy acrylate and anhydride reaction (as cis-butenedioic anhydride, trimellitic acid 1,2-anhydride, pyromellitic acid acid anhydride, phthalic anhydride, succinyl oxide, tetrahydrophthalic anhydride etc.) introducing-COOH as hydrophilic radical again, obtain water-based epoxy acrylic ester resin with the alkali neutralization again.
4, urethane acrylate
Urethane acrylate class photocuring system is because of it has good wear resistance, chemicals-resistant, low temperature resistant
With characteristics such as snappiness are good, and receive much attention.Aqueous polyurethane acrylate ultraviolet light polymerization system is except having above-mentioned advantage, and is also because of it belongs to environmental protection product, many to its research.The urethane acrylate sorting technique is a lot, according to different emulsification methods it is divided into outer oil-in-water type and self-emulsifying type.
A. outer oil-in-water type: utilize the outer method that adds emulsifying agent, under the effect of high shear force, the polyurethane acrylate resin of common uV curable is scattered in the water, obtain the urethane acrylate emulsion.
B. self-emulsifying type: on hydrophobic polyurethane backbone, introduce hydrophilic radical, be scattered in the water then.
5, other
J. Odeberg etc. has reported the latex of several ultraviolet light polymerizations.They are by two step letex polymerizations, and to have synthesized with PS be nuclear, be the latex of shell with butyl acrylate (BA) and glycidyl methacrylate (GMA) multipolymer, utilize the epoxide group introducing ultraviolet curing group on emulsion particle surface then.
Summary of the invention
The objective of the invention is to select for use different aliphatic diisocyanate (hexamethylene diisocyanates, 4,4 '-vulcabond dicyclohexyl methyl hydride), the end capped polysiloxane of alcoholic extract hydroxyl group (DHPDMS), chainextender (dimethylene ethamine, the divinyl triamine), acrylic monomer (Hydroxyethyl acrylate, hydroxyethyl methylacrylate, pentaerythritol triacrylate), and by introducing organosilicon radical, adopting dibutyl tin laurate and organic carboxyl acid rare earth mixed solution is catalyzer, optimize reaction conditions, a kind of good anti-flavescence that has is provided, the high efficiency synthetic method of the organic-silicon-modified-photocuring aqueous polyurethane acrylate of premium propertiess such as high rigidity.
The general formula of this organic silicon modified aqueous polyurethane acrylate is:
R
1-O-CO-NH-R
2-[NH-CO-O-R
3-O-CO-R
2-]
n-NH-CO-O-R
1
Wherein: R
1Represent oleic series
R
2Representative-[R-NH-CO-O-R '-O-CO-NH-R-NH-CO-O-R ' '-O-CO-NH-R-]
m
Described R is aliphatic carbon chain or ring; R ' is a polyether glycol; R ' ' is pure terminal hydroxy group polysiloxane; )
R
3Representative is the glycol of hydrophilic group with the carboxylic acid.Described different aliphatic diisocyanate is hexamethylene diisocyanate or 4,4 '-vulcabond dicyclohexyl methyl hydride.
Technical scheme of the present invention is achieved in that with different aliphatic diisocyanates, the end capped polysiloxane of alcoholic extract hydroxyl group, acrylic monomer be main raw material, adopt step synthesis, promptly the urethane of the first step synthesizing organo-silicon modification, second step are introduced hydrophilic group, the 3rd step introducing Acrylic Acid Monomer.
Concrete steps are as follows:
The first step: the urethane of in synthesis of polyurethane, introducing the modification of organosilicon radical synthesizing organo-silicon; Preparation urethane: N2 exists down, 50-150
oC reflux vulcabond, polyether glycol, pure terminal hydroxy group polysiloxane mixed solution, the ratio of three raw materials is in the mixed solution: 1-6:1:1,
Every 60Minute survey NCO content, when NCO content no longer changes, stop heating; Cool to 50
oC;
Second step: introduce hydrophilic group by adding carboxylic dibasic alcohol; In the above-mentioned solution that is placed to room temperature, add proper amount of acetone,, add carboxylic dibasic alcohol then, add dimethylol propionic acid, be warmed up to 65 ℃ of backflows, disappear to the dimethylol propionic acid particle to reduce viscosity.
The 3rd step:, under dibutyl tin laurate and organic carboxyl acid rare earth mixed solution catalyst action, reflux and introduce Acrylic Acid Monomer by adding the oleic series monomer; In the solution of second step placement, add the oleic series monomer, dosage is 1.0-1.1 times that second step placed solution residual hydroxyl amount, catalyzer dibutyl tin laurate and organic carboxyl acid rare earth are pressed the 0.01%-1% of urethane solid content and Acrylic Acid Monomer total amount, 50 ~ 120 ℃ of reflux 50 ~ 60 minutes; 60-90
oThe C reflux was surveyed NCO content every 60 minutes, stopped heating when NCO content disappears;
The 4th step: in the solution of the 3rd step gained, add in the triethylamine and the carboxylic acid salify; Be neutralized to till the pH=6-7;
The 5th step: under vigorous stirring, slowly drip deionized water, be mixed with the acrylate of organic silicon modified aqueous polyurethane;
Wherein, all are reflected under the normal pressure carries out, described chainextender can add in the 3rd step, also can after adding distilled water, add in the 5th step, also can not add, chainextender is that dimethylene ethamine, divinyl triamine, acrylic monomer are: Hydroxyethyl acrylate, hydroxyethyl methylacrylate, pentaerythritol triacrylate; The amount of reactant adds according to the requirement of want synthetic polymer; The mole number of the vulcabond that adds in the reaction is greater than polyether glycol, polysiloxane, contains the dibasic alcohol of hydrophilic radical, Acrylic Acid Monomer.
Wherein: the first step reaction adopts vulcabond, polyether glycol, the end capped polysiloxane of alcoholic extract hydroxyl group to be made into mixed solution, obtains organic-silicon-modified isocyanate-terminated urethane through backflow; Wherein reflux temperature is 70-90
oC.
Wherein, the first step reaction adopts vulcabond, polyether glycol, the end capped polysiloxane of alcoholic extract hydroxyl group to be made into mixed solution, and the mole proportioning is a vulcabond: polyether glycol: the end capped polysiloxane proportioning of alcoholic extract hydroxyl group is 2-4:1:1.
The end capped polysiloxane of the alcoholic extract hydroxyl group that adds in the described first step is a DHPDMS.
Adopting dibutyl tin laurate and organic carboxyl acid rare earth mixed solution when described three-step reaction adds the oleic series monomer is catalyzer, and the reflux features temperature is 60 ~ 80 ℃.
The present invention has the following advantages: add the end capped polysiloxane of alcoholic extract hydroxyl group 1..
2. adopted dibutyl tin laurate and organic carboxyl acid rare earth mixed solution to substitute traditional dibutyl tin laurate catalyzer.
3. product is stronger than common aqueous polyurethane acrylate anti-yellowing property, and hardness is higher.
4. equipment requirements is not high, easy handling control.
Embodiment
The present invention is further illustrated by following examples.
Embodiment 1
Under the nitrogen atmosphere, in exsiccant three neck round-bottomed flasks, add hexamethylene diisocyanate, polyether glycol, DHPDMS, its molecular ratio was 2.5:1:1, is heated to 70 ℃ of backflows, surveyed NCO content every 1 hour, until no longer changing.Cool to 50 ℃, add dimethylol propionic acid, be warmed up to 65 ℃ of backflows, disappear to the dimethylol propionic acid particle.Add 0.2% dibutyl tin laurate and 0.1% cerous acetate mixture, Resorcinol, dropwise addition of acrylic acid hydroxyl ethyl ester continues to be heated to 75 ℃ of backflows, surveys NCO content every 1 hour, disappears until NCO content.Cool to room temperature, under agitation add triethylamine, be neutralized to about pH=6.5, under vigorous stirring, slowly drip a certain amount of deionized water, finally obtain organic-silicon-modified aqueous polyurethane acrylate.
Embodiment 2
Under the nitrogen atmosphere, in exsiccant three neck round-bottomed flasks, add 4,4 '-vulcabond dicyclohexyl methyl hydride, polyether glycol, DHPDMS, its molecular ratio is 2.5:1:1, is heated to 80 ℃ of backflows, surveyed NCO content every 1 hour, until no longer changing.Cool to 50 ℃, add dimethylol propionic acid, be warmed up to 65 ℃ of backflows, disappear to the dimethylol propionic acid particle.Add 0.1% dibutyl tin laurate and 0.2% cerous acetate mixture, Resorcinol, dropwise addition of acrylic acid hydroxyl ethyl ester continues to be heated to 75 ℃ of backflows, surveys NCO content every 1 hour, disappears until NCO content.Cool to room temperature, under agitation add triethylamine, be neutralized to about pH=6.5, under vigorous stirring, slowly drip a certain amount of deionized water, finally obtain organic-silicon-modified aqueous polyurethane acrylate.
Embodiment 3
Under the nitrogen atmosphere, in exsiccant three neck round-bottomed flasks, add 4,4 '-vulcabond dicyclohexyl methyl hydride, polyether glycol, DHPDMS, its molecular ratio is 2.5:1:1, is heated to 70 ℃ of backflows, surveyed NCO content every 1 hour, until no longer changing.Cool to 50 ℃, add dimethylol propionic acid, be warmed up to 65 ℃ of backflows, disappear to the dimethylol propionic acid particle.Add 0.3% dibutyl tin laurate and 0.2% yttium acetate, Resorcinol, drip hydroxyethyl methylacrylate, continue to be heated to 80 ℃ of backflows, surveyed NCO content, disappear until NCO content every 1 hour.Cool to room temperature, under agitation add triethylamine, be neutralized to about pH=6.5, under vigorous stirring, slowly drip a certain amount of deionized water, finally obtain organic-silicon-modified aqueous polyurethane acrylate.
Embodiment 4
Under the nitrogen atmosphere, in exsiccant three neck round-bottomed flasks, add hexamethylene diisocyanate, polyether glycol, DHPDMS, its molecular ratio was 3:1:1, is heated to 70 ℃ of backflows, surveyed NCO content every 1 hour, until no longer changing.Cool to 50 ℃, add dimethylol propionic acid, be warmed up to 65 ℃ of backflows, disappear to the dimethylol propionic acid particle.Add 0.2% dibutyl tin laurate and 0.2% cerous acetate mixture, Resorcinol, drip pentaerythritol triacrylate, continue to be heated to 75 ℃ of backflows, surveyed NCO content, disappear until NCO content every 1 hour.Cool to room temperature, under agitation add triethylamine, be neutralized to about pH=6.5, under vigorous stirring, slowly drip a certain amount of deionized water, finally obtain organic-silicon-modified aqueous polyurethane acrylate.
Embodiment 5
Under the nitrogen atmosphere, in exsiccant three neck round-bottomed flasks, add 4,4 '-vulcabond dicyclohexyl methyl hydride, polyether glycol, DHPDMS, its molecular ratio is 2.5:1:1, is heated to 70 ℃ of backflows, surveyed NCO content every 1 hour, until no longer changing.Cool to 50 ℃, add dimethylol propionic acid, be warmed up to 70 ℃ of backflows, disappear to the dimethylol propionic acid particle.Add 0.3% dibutyl tin laurate and 0.2% cerous acetate mixture, Resorcinol, drip pentaerythritol triacrylate, continue to be heated to 85 ℃ of backflows, surveyed NCO content, disappear until NCO content every 1 hour.Cool to room temperature, under agitation add triethylamine, be neutralized to about pH=6.5, under vigorous stirring, slowly drip a certain amount of deionized water, finally obtain organic-silicon-modified aqueous polyurethane acrylate.
The comparative example 1
Under the nitrogen atmosphere, in exsiccant three neck round-bottomed flasks, add hexamethylene diisocyanate, polyether glycol, its molecular ratio was 2.5:2, is heated to 70 ℃ of backflows, surveyed NCO content every 1 hour, until no longer changing.Cool to 50 ℃, add dimethylol propionic acid, be warmed up to 65 ℃ of backflows, disappear to the dimethylol propionic acid particle.Add 0.2% dibutyl tin laurate and 0.2% yttium acetate mixture, Resorcinol, drip hydroxyethyl methylacrylate, continue to be heated to 80 ℃ of backflows, surveyed NCO content, disappear until NCO content every 1 hour.Cool to room temperature, under agitation add triethylamine, be neutralized to about pH=6.5, under vigorous stirring, slowly drip a certain amount of deionized water, finally obtain organic-silicon-modified aqueous polyurethane acrylate.
The comparative example 2
Under the nitrogen atmosphere, in exsiccant three neck round-bottomed flasks, add hexamethylene diisocyanate, polyether glycol, DHPDMS, its molecular ratio was 1.5:1:1, is heated to 70 ℃ of backflows, surveyed NCO content every 1 hour, until no longer changing.Cool to 50 ℃, add dimethylol propionic acid, be warmed up to 65 ℃ of backflows, disappear to the dimethylol propionic acid particle.Add 0.2% dibutyl tin laurate and 0.2% yttium acetate mixture, Resorcinol, drip hydroxyethyl methylacrylate, continue to be heated to 80 ℃ of backflows, surveyed NCO content, disappear until NCO content every 1 hour.Cool to room temperature, under agitation add triethylamine, be neutralized to about pH=6.5, under vigorous stirring, slowly drip a certain amount of deionized water, finally obtain organic-silicon-modified aqueous polyurethane acrylate.
The comparative example 3
Under the nitrogen atmosphere, in exsiccant three neck round-bottomed flasks, add hexamethylene diisocyanate, polyether glycol, DHPDMS, its molecular ratio was 2.5:1:1, is heated to 60 ℃ of backflows, surveyed NCO content every 1 hour, until no longer changing.Cool to 50 ℃, add dimethylol propionic acid, be warmed up to 65 ℃ of backflows, disappear to the dimethylol propionic acid particle.Add 0.2% dibutyl tin laurate and 0.2% yttium acetate mixture, Resorcinol, drip hydroxyethyl methylacrylate, continue to be heated to 80 ℃ of backflows, surveyed NCO content, disappear until NCO content every 1 hour.Cool to room temperature, under agitation add triethylamine, be neutralized to about pH=6.5, under vigorous stirring, slowly drip a certain amount of deionized water, finally obtain organic-silicon-modified aqueous polyurethane acrylate.
The performance perameter table:
The above only is a better embodiment of the present invention, so all equivalences of doing according to the described structure of patent claim of the present invention, feature and principle change or modify, is included in the patent claim of the present invention.
Claims (7)
1. the synthetic method of organic silicon modified aqueous polyurethane acrylate, it is characterized in that: a kind of is main raw material with different aliphatic diisocyanates, the end capped polysiloxane of alcoholic extract hydroxyl group, acrylic monomer, adopt step synthesis, the urethane, second step that are the modification of the first step synthesizing organo-silicon are introduced hydrophilic group, the 3rd step introducing Acrylic Acid Monomer, and reaction obtains the method for organic silicon modified aqueous polyurethane acrylate; The general formula of this organic silicon modified aqueous polyurethane acrylate is:
R
1-O-CO-NH-R
2-[NH-CO-O-R
3-O-CO-R
2-]
n-NH-CO-O-R
1
Wherein: R
1Represent Acrylic Acid Monomer,
The R representative-[R-NH-CO-O-R '-O-CO-NH-R-NH-CO-O-R ' '-O-CO-NH-R-]
m
Described R-aliphatic carbon chain or ring; R '-polyether glycol; R ' '-pure terminal hydroxy group polysiloxane;
R
3Representative is the glycol of hydrophilic group with the carboxylic acid.
2. the synthetic method of organic silicon modified aqueous polyurethane acrylate according to claim 1 is characterized in that: described different aliphatic diisocyanate is hexamethylene diisocyanate or 4,4 '-vulcabond dicyclohexyl methyl hydride.
3. the synthetic method of organic silicon modified aqueous polyurethane acrylate according to claim 2 is characterized in that: synthetic by following steps:
The first step: the urethane of in synthesis of polyurethane, introducing the modification of organosilicon radical synthesizing organo-silicon; Preparation urethane:
N2 exists down, 50-150
oC reflux vulcabond, polyether glycol, pure terminal hydroxy group polysiloxane mixed solution, the ratio of three raw materials is in the mixed solution: 1-6:1:1, surveyed NCO content every 60 minutes, when no longer changing, NCO content stops heating; Cool to 50
oC;
Second step: introduce hydrophilic group by adding carboxylic dibasic alcohol; In the above-mentioned solution that is placed to room temperature, add proper amount of acetone, add carboxylic dibasic alcohol then, add dimethylol propionic acid, be warmed up to 65 ℃ of backflows, disappear to the dimethylol propionic acid particle to reduce viscosity;
The 3rd step:, under dibutyl tin laurate and organic carboxyl acid rare earth mixed solution catalyst action, reflux and introduce Acrylic Acid Monomer by adding the oleic series monomer; In the solution of second step placement, add the oleic series monomer, dosage is 1.0-1.1 times that second step placed solution residual hydroxyl amount, catalyzer dibutyl tin laurate and organic carboxyl acid rare earth are pressed the 0.01%-1% of urethane solid content and Acrylic Acid Monomer total amount, 50 ~ 120 ℃ of reflux 50 ~ 60 minutes; 60-90
oThe C reflux was surveyed NCO content every 60 minutes, stopped heating when NCO content disappears;
The 4th step: in the solution of the 3rd step gained, add in the triethylamine and the carboxylic acid salify; Be neutralized to till the pH=6-7;
The 5th step: under vigorous stirring, slowly drip deionized water, be mixed with the acrylate of organic silicon modified aqueous polyurethane;
Wherein, all are reflected under the normal pressure carries out, wherein chainextender can add in the 3rd step, also can after adding distilled water, add in the 5th step, also can not add, chainextender is that dimethylene ethamine, divinyl triamine, acrylic monomer are: Hydroxyethyl acrylate, hydroxyethyl methylacrylate, pentaerythritol triacrylate; The amount of reactant adds according to the requirement of want synthetic polymer; The mole number of the vulcabond that adds in the reaction is greater than polyether glycol, polysiloxane, contains the dibasic alcohol of hydrophilic radical, Acrylic Acid Monomer.
According to the described organic silicon modified aqueous polyurethane acrylate of claim 2 synthetic method, it is characterized in that: the first step reaction adopts vulcabond, polyether glycol, the end capped polysiloxane of alcoholic extract hydroxyl group to be made into mixed solution, obtains organic-silicon-modified isocyanate-terminated urethane through backflow; Wherein reflux temperature is 70-90
oC.
5. organic silicon modified aqueous polyurethane acrylate according to claim 2 synthetic method, it is characterized in that: the first step reaction adopts vulcabond, polyether glycol, the end capped polysiloxane of alcoholic extract hydroxyl group to be made into mixed solution, and the mole proportioning is a vulcabond: polyether glycol: the end capped polysiloxane proportioning of alcoholic extract hydroxyl group is 2-4:1:1.
6. organic silicon modified aqueous polyurethane acrylate according to claim 2 synthetic method, it is characterized in that: the end capped polysiloxane of the alcoholic extract hydroxyl group that adds in the first step is a DHPDMS.
7. according to claim 2 organic-silicon-modified-aqueous polyurethane acrylate synthetic method, it is characterized in that: adopting dibutyl tin laurate and organic carboxyl acid rare earth mixed solution when three-step reaction adds the oleic series monomer is catalyzer, and the reflux features temperature is 60 ~ 80 ℃.
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