CN106833358B - The multifunctional polyurethane acrylate composition of dual cure - Google Patents
The multifunctional polyurethane acrylate composition of dual cure Download PDFInfo
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
- C08G18/677—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups
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- C—CHEMISTRY; METALLURGY
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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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
- C09D5/24—Electrically-conducting paints
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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Abstract
The present invention provides a kind of multifunctional polyurethane acrylate composition of dual cure, the component including following quality proportioning: 100 parts of oligomer (1), 10~200 parts of oligomer (2), 10~200 parts of polymer polyatomic alcohol, 10~200 parts of reactive diluent, 0~0.5 part of stabilizer and 1.5~15 parts of photoinitiator；The multifunctional polyurethane acrylate composition of the dual cure is used as film forming agent, has the function of hydrophilic nmature, antibacterial functions of killing livestock, cation and anion exchange, conducting function by polyurethane acrylate resin made of optical and thermal dual cure.
Description
Technical field
The present invention relates to a kind of multifunctional polyurethane acrylate compositions of dual cure, it is characterised in that including following
Component: it is carried out in polyisocyanates and chemical structure containing the function polyalcohol of schiff base of salicylaldehyde complex and quaternary ammonium cation
Oligomer (2) made from oligomer made from sudden reaction (1), polyisocyanates and hydroxy-ethyl acrylate progress sudden reaction,
Polymer polyatomic alcohol, reactive diluent, photoinitiator and stabilizer, belong to functional polymer material field.
Technical background
Urethane acrylate (polyurethane acrylate, PUA) is by polyisocyanates, polyalcohol and propylene
A kind of photoresist that sour hydroxy ester is synthesized through two-step reaction has photocuring and heat curing process feature.Due to its raw material
May be selected multiplicity, by MOLECULE DESIGN again can synthesize set performance oligomer, therefore be the current photoresist trade mark most
More oligomer is widely used in coating, ink, in adhesive.A lot of research and application proves that PUA is prepared as prepolymer
High molecular material have the following characteristics that 1. PUA has ammonia ester bond, the high-polymer molecule interchain can form a variety of hydrogen bonds so that
Polyurethane film has excellent mechanical endurance and flexibility, and elongation at break is high.2. its cured coating film has excellent resistance toization
Learn performance and high and low temperature resistance.3. its cured coating film has preferable adhesive force to the substrate for being difficult to be bonded, such as plastics.4. passing through
The polyalcohol and polyisocynate monomer kind and dosage, the available wide different resins of performance range adjusted in PUA produces
Product.However how to assign urethane acrylate ion exchanging function, chemical catalysis performance, kill livestock antibacterial functions or conductive heat transfer
Performance, correlative study is not much with report to be seen.
Ship and marine worker equipment in ocean pass through marine antifouling coating coating, can effectively prevent marine biofouling.
Marine antifouling coating used at present mainly has polyurethane-based paints and polyacrylic acid ester group coating.In the marine antifouling coating
Middle add introduces antibacterial agent of killing livestock on kill livestock antibacterial anti-fouling agent or polymer macromolecule chain, be the manufacture marine antifouling coating
Main method.Quaternary ammonium salt is the sterilization antibacterial agent using nearly half a century, has simple production process, uses safe and effective spy
Point, so marine antifouling coating has been turned to grinding for quaternary ammonium salt-modified polyurethane coating or polyacrylate coating by people in recent years
Study carefully.US5084096 in 1992 discloses the high-performance marine antifouling paint of quaternary ammonium salt-modified polyurethane coating；
US20080181862 reports the excellent from polishing and anti-marime fouling effect of quaternary ammonium salt modified polysiloxane polyurethane coating coating
It is different；CN201110143379.8 and CN201110143380.0 also proposes quaternary ammonium salt modified polysiloxane polyurethane coating simultaneously
Antifouling multipurpose.However that there are marine anti-pollution polyurethane coating film forming matters is non-renewable, sterilization antibacterial for techniques described above
Act on the defect that single, raw material are expensive and production technology is complicated.The present inventor develops quaternary ammonium salt and water in early-stage study
Poplar aldehyde and complex modified polyurethane or modified polyacrylate, thus form the marine antifouling coating of multiple kinds.Example
Such as ZL201202020, ZL201202020, ZL201202020, ZL201202020 and ZL201121021, macromolecular is disclosed
Vegetable fat based polyurethanes, organosilicon acrylic resin or the polyacrylic acid of quaternary ammonium cation and bigcatkin willow aldehyde radical and complex are connected on side chain
Ester is used as marine antifouling coating, has raw material sources wide, technology of preparing is simple；Realize salicylide, quaternary ammonium salt, heavy metal ion
Antibacterial is killed livestock the synergy of efficiency between complex.But the above belongs to solvent type marine antifouling coating.It develops low
Pollution, environmental-friendly marine antifouling coating have become one of the Main way of current marine functional coatings industry development.
For existing marine antifouling coating technology there are problem and defect, the present inventor is in earlier antibacterial polyurethane or poly-
On the Research foundation of acrylate, using the multi-curing technology characteristics of urethane acrylate, a kind of dual cure is devised
Multifunctional polyurethane acrylate composition, the multifunctional polyurethane acrylate composition of the dual cure, molecule
Contain quaternary ammonium cation, schiff base of salicylaldehyde complex in structure, be used as solvent-free marine antifouling coating film forming agent, both there is parent
Aqueous energy, antibacterial functions of killing livestock, splendid weatherability, adhesive force and wearability, and there are excellent inhibition marine organisms to adhere to function
Energy.
Summary of the invention
The present invention provides a kind of multifunctional polyurethane acrylate composition of dual cure, it is characterised in that including following
The component of quality proportioning: 100 parts of oligomer (1), 10~200 parts of oligomer (2), 10~200 parts of polymer polyatomic alcohol,
10~200 parts of reactive diluent, 0~0.5 part of stabilizer and 1.5~15 parts of photoinitiator；
Wherein the oligomer (1) refers to using function polyalcohol and polyisocyanates as raw material, by sudden reaction system
The oligomer obtained；
The oligomer (1) refers to that polyisocyanates and function polyalcohol carry out oligomer made from sudden reaction；Institute
It states function polyalcohol and refers to function polyalcohol in chemical structure containing schiff base of salicylaldehyde complex and quaternary ammonium cation, tool
There is structure shown in logical formula (I):
R in the logical formula (I)1And R2It is respectively selected from C1~C20Alkyl, M be selected from Zn2+、Cu2+、Co2+、Ni2+、Ag+Or
Hg2+One or more of, X-Selected from Cl-、Br-、F-、SO4 2-、NO3 -Or CH3COO-One or more of.
The allyl contained in structure function polyol structure shown in the logical formula (I) can participate in esters of acrylic acid or benzene
The free radicals copolymerization reaction of ethylene (commonly referred to as reactive diluent)；The primary hydroxyl contained can participate in the addition of isocyanates
Polymerization reaction forms carbamic acid ester chain；The quaternary ammonium cation and salicylaldoxime complex contained has cation and anion exchange function
Can, and the two has the antibacterial efficacy of killing livestock of different mechanisms；
The function polyalcohol of structure shown in logical formula (I) can be by N, N- dialkyl allyl amine, 5- chloromethyl salicylaldehyde, ethyl alcohol
Amine and alcohol-soluble MX2Heavy metallic salt is raw material, is made by nucleophilic substitution, addition condensation reaction and complex reaction；
Referring to following reaction equations:
The wherein R in the reaction equation1And R2It is respectively selected from C1~C20Alkyl, M be selected from Zn2+、Co2+、Cu2+、Ni2+、Ag+
Or Hg2+One or more of, X-Selected from Cl-、Br-、F-、SO4 2-、NO3 -Or CH3COO-One or more of.
The polyisocyanates refers to toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, own diisocyanate
Ester, isophorone diisocyanate, dicyclohexyl methyl hydride diisocyanate vinegar, naphthalene diisocyanate, polymethylene polyphenyl isocyanide
One of acid esters, triphenylmethane triisocyanate, tri o cresyl thiophosphate (4- phenyl isocyanate)；
The oligomer (2) refers to using Hydroxyethyl Acrylate and polyisocyanates as raw material, by sudden reaction system
The oligomer obtained；
The polymer polyatomic alcohol refers in commercial goods polyether polyol, polyolefin polyhydric alcohol or polyester polyol
One kind；
The reactive diluent refers to methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, third
Olefin(e) acid monooctyl ester, dodecylacrylate, acrylic acid trifluoromethyl ester, acrylic acid trifluoro ethyl ester, hexafluorobutyl acrylate, acrylic acid
Ten difluoro monooctyl esters, styrene, methyl styrene, divinylbenzene, acrylonitrile, acrylic acid, vinylacetate, diacrylate second two
Alcohol ester, 1,2-PD diacrylate, diacrylate 1,3-PD ester, 1,4-butanediol diacrylate, diacrylate
1,6- hexylene glycol ester, diacrylate diethylene glycol (DEG) ester, glycerol tri-acrylate, pentaerythritol triacrylate or trimethylolpropane
One or more of triacrylate；
The stabilizer refers to one of hydroquinone or p methoxy phenol；
The photoinitiator be selected from Darocure1173, Darocure184, Darocure2959, Ingacure819,
Ingacure907, Ingacure369,4- methyl benzophenone, 2,4,6- tri-methyl benzophenones or 2,4,6 trimethylbenzene first
One or more of aminosulfonylphenyl phosphinic acid ethyl ester；
The following institute of the specific preparation method of the multifunctional polyurethane acrylate composition of dual cure provided by the invention
It states:
Step 1: the preparation of oligomer (1)
It weighs polyisocyanates and catalyst is added in reaction kettle, stir the lower continuous function for putting into structure shown in logical formula (I)
Energy polyalcohol, and it is warming up to 40~140 DEG C simultaneously, it reacts 2~12 hours, is made oligomer (1).
Wherein the function polyalcohol has structure shown in logical formula (I):
The wherein R in the general formula (I)1And R2It is respectively selected from C1~C20Alkyl, M be selected from Zn2+、Cu2+、Co2+、Ni2+、
Ag+Or Hg2+One or more of, X-Selected from Cl-、Br-、F-、SO4 2-、NO3 -Or CH3COO-One or both of with
On.
The polyisocyanates refers to toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, own diisocyanate
Ester, isophorone diisocyanate, dicyclohexyl methyl hydride diisocyanate vinegar, naphthalene diisocyanate, polymethylene polyphenyl isocyanide
One of acid esters, triphenylmethane triisocyanate, tri o cresyl thiophosphate (4- phenyl isocyanate)；The polyisocyanates
Mole dosage is 1.5~2.5 times of function polyalcohol；
The catalyst refers to dibutyltin dilaurate, stannous octoate, stannous oxalate, two maleic acid of dialkyl group
Tin, two (dodecyl sulphur) dibutyl tins, dibutyltin diacetate, dimethylethanolamine, n,N-Dimethylformamide, triethylene
Diamines, dialkylpiperazines, alkyl imidazole, 1,8- diazabicyclo [5.4.0], 11 carbon -7- alkene, triethylene diamine carboxylate, two
One or more of alkyl piperazine carboxylate or alkyl imidazole carboxylate；The quality dosage of the catalyst is polyisocyanate cyanogen
Acid esters 1~5%.
Step 2: the preparation of oligomer (2)
It weighs polyisocyanates and catalyst is added in reaction kettle, Hydroxyethyl Acrylate is continuously added under stirring, and same
When be warming up to 40~140 DEG C, react 2~12 hours, be made oligomer (2).
Wherein the polyisocyanates refers to that toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, oneself is two different
Cyanate, isophorone diisocyanate, dicyclohexyl methyl hydride diisocyanate vinegar, naphthalene diisocyanate, polymethylene polyphenyl
One of isocyanates, triphenylmethane triisocyanate, tri o cresyl thiophosphate (4- phenyl isocyanate)；The polyisocyanic acid
The mole dosage of ester is 1.0~2.0 times of Hydroxyethyl Acrylate；
The catalyst refers to dibutyltin dilaurate, stannous octoate, stannous oxalate, two maleic acid of dialkyl group
Tin, two (dodecyl sulphur) dibutyl tins, dibutyltin diacetate, dimethylethanolamine, n,N-Dimethylformamide, triethylene
Diamines, dialkylpiperazines, alkyl imidazole, 1,8- diazabicyclo [5.4.0], 11 carbon -7- alkene, triethylene diamine carboxylate, two
One or more of alkyl piperazine carboxylate or alkyl imidazole carboxylate；The quality dosage of the catalyst is polyisocyanate cyanogen
The 1~5% of acid esters.
Step 3: the preparation of dual cure multifunctional polyurethane acrylate composition
It is matched according to the constituent mass, successively weighs the pure and mild photoinitiator of polymer polyol and be added in reaction kettle, room temperature
Under stir evenly obtained solution A；It is matched according to the constituent mass, successively weighs reactive diluent, stabilizer, step 1 and be made
Oligomer (1) and step 2 made from oligomer (2), after mixing, obtained solution B is stirred evenly, by the solution A when use
It is uniformly mixed with solution B, is dual cure multifunctional polyurethane acrylate composition；
The polymer polyatomic alcohol refers to commercial goods polyether polyol, polybutadiene polyol or polyester polyol
One of；
The photoinitiator be selected from Darocure1173, Darocure184, Darocure2959, Ingacure819,
Ingacure907, Ingacure369,4- methyl benzophenone, 2,4,6- tri-methyl benzophenones or 2,4,6 trimethylbenzene first
One or more of aminosulfonylphenyl phosphinic acid ethyl ester；
The reactive diluent refers to methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, third
Olefin(e) acid monooctyl ester, dodecylacrylate, acrylic acid trifluoromethyl ester, acrylic acid trifluoro ethyl ester, hexafluorobutyl acrylate, acrylic acid
Ten difluoro monooctyl esters, styrene, methyl styrene, divinylbenzene, acrylonitrile, acrylic acid, vinylacetate, diacrylate second two
Alcohol ester, 1,2-PD diacrylate, diacrylate 1,3-PD ester, 1,4-butanediol diacrylate, diacrylate
1,6- hexylene glycol ester, diacrylate diethylene glycol (DEG) ester, three glycerol acrylates, pentaerythritol triacrylate or trimethylolpropane
The one or more of triacrylate；
The stabilizer refers to one of hydroquinone or p methoxy phenol；
The oligomer (1): oligomer (2): polymer polyatomic alcohol: reactive diluent: stabilizer: the quality of photoinitiator
Amount ratio is 100: 10~200: 10~200: 10~200: 0~0.5: 1.5~15.
Dual cure multifunctional polyurethane acrylate composition provided by the invention has the feature that
1. the method for preparing dual cure multifunctional polyurethane acrylate composition of the present invention is simple and easy, former material
Expect abundance, it is low in cost.
2. with dual cure multifunctional polyurethane acrylate composition provided by the invention, by made of dual cure
Polyurethane acrylate resin has the function of amphipathic characteristic, antibacterial functions of killing livestock, cation and anion exchange, conducting function.
Specific embodiment
By following example to dual cure multifunctional polyurethane acrylate composition provided by the invention and system
Preparation Method further illustrates that its object is to more fully understand the contents of the present invention.
The preparation of 1 dual cure multifunctional polyurethane acrylate composition (1) of embodiment
Step 1: the preparation of oligomer (1-a)
Weigh the function polyalcohol, 5 grams of triethylene diamines and 1.8 grams of dibutyltindilaurylmercaptides of structure shown in 135 grams of formulas (I-a)
Cinnamic acid ester is added in reaction kettle, stirs lower separately 110 grams of isophorone diisocyanate of investment, and be warming up to 60~80 DEG C simultaneously,
Reaction was down to room temperature after 4 hours, was made oligomer (1-a).
The wherein function polyalcohol of structure shown in the formula (I-a) are as follows:
Step 2: the preparation of oligomer (2-a)
It weighs 53 grams of Hydroxyethyl Acrylates and 0.8 gram of dibutyltin dilaurate is added in reaction kettle, it is another under stirring
55 grams of isophorone diisocyanate are put into, and are warming up to 60~80 DEG C simultaneously, reaction was down to room temperature after 4 hours, added 2 grams
P methoxy phenol, 60 grams of methyl acrylate and 80 grams of styrene, stir evenly and obtain oligomer (2-a).
Step 3: the preparation of dual cure multifunctional polyurethane acrylate composition (1)
Successively weigh 102 grams of the polyether-tribasic alcohol, 10 that hydroxyl value is 56mgKOH/g, average molecular weight is 3000~4000
Gram of Darocure1173 and 5 gram 4- methyl benzophenone is added in reaction kettle, stirs evenly obtained solution A-1 at room temperature；It will step
Oligomer (2-a) made from oligomer made from rapid one (1-a) and step 2 is uniformly mixed and obtains solution B -1；It will be described molten
Liquid A-1 and the solution B -1 are uniformly mixed, after vacuum defoamation, dual cure multifunctional polyurethane acrylate composition
(1)。
The preparation of 2 dual cure multifunctional polyurethane acrylate composition (2) of embodiment
According to the method and operating procedure of embodiment 1, by the function of structure shown in the formula (I-a) in 1 step 1 of embodiment
Polyalcohol change is the function polyalcohol of structure shown in formula (I-b), obtains dual cure multifunctional polyurethane acrylate group
It closes object (2)；
The preparation of 3 dual cure multifunctional polyurethane acrylate composition (3) of embodiment
According to the method and operating procedure of embodiment 1, by the function of structure shown in the formula (I-a) in 1 step 1 of embodiment
Polyalcohol change is the function polyalcohol of structure shown in formula (I-c), obtains dual cure multifunctional polyurethane acrylate group
It closes object (3)；
The filming performance of 4 dual cure multifunctional polyurethane acrylate composition (1)~(3) of embodiment
Each 30 grams of dual cure multifunctional polyurethane acrylate composition (1)~(3) are taken respectively, and even application is in cleaning
On 26*10cm rectangle A3 steel plate after polishing, at room temperature after ultraviolet light 1 minute, rear 60-80 DEG C of curing and drying 24 is small
When, referring to the method measurement film hardness and film adhesive force of GB1730-1993 and GB1720-1993 defined, it the results are shown in Table 1.
1 dual cure multifunctional polyurethane acrylate composition (1) of table~(3) film forming characteristics
Claims (2)
1. a kind of multifunctional polyurethane acrylate composition of dual cure, it is characterised in that the group including following quality proportioning
Point: 100 parts of oligomer (1), 10~200 parts of oligomer (2), 10~200 parts of polymer polyatomic alcohol, 10~200 parts
Reactive diluent, 0~0.5 part of stabilizer and 1.5~15 parts of photoinitiator；
Wherein the oligomer (1) refers to that polyisocyanates and function polyalcohol carry out oligomer made from sudden reaction；Institute
It states function polyalcohol and refers to function polyalcohol in chemical structure containing schiff base of salicylaldehyde complex and quaternary ammonium cation, tool
There is structure shown in logical formula (I):
The wherein R in the general formula (I)1And R2It is respectively selected from C1~C20Alkyl, M be selected from Zn2+、Cu2+、Co2+、Ni2+、Ag+Or
Hg2+One or more of, X-Selected from Cl-、Br-、F-、NO3 -Or CH3COO-One or more of；
The oligomer (2) refers to using Hydroxyethyl Acrylate and polyisocyanates as raw material, by made from sudden reaction
Oligomer；
Wherein the polyisocyanates refers to toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, own diisocyanate
Ester, isophorone diisocyanate, dicyclohexyl methyl hydride diisocyanate vinegar, naphthalene diisocyanate, polymethylene polyphenyl isocyanide
One of acid esters, triphenylmethane triisocyanate, tri o cresyl thiophosphate (4- phenyl isocyanate)；
The polymer polyatomic alcohol refers to one in commercial goods polyether polyol, polyolefin polyhydric alcohol or polyester polyol
Kind；
The reactive diluent refers to methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid
Monooctyl ester, dodecylacrylate, acrylic acid trifluoromethyl ester, acrylic acid trifluoro ethyl ester, hexafluorobutyl acrylate, acrylic acid 12
Fluorine monooctyl ester, styrene, methyl styrene, divinylbenzene, acrylonitrile, acrylic acid, vinylacetate, diacrylate ethylene glycol
Ester, 1,2-PD diacrylate, diacrylate 1,3-PD ester, 1,4-butanediol diacrylate, diacrylate 1,
6- hexylene glycol ester, diacrylate diethylene glycol (DEG) ester, three glycerol acrylates, pentaerythritol triacrylate or trimethylolpropane tris
One or more of acrylate；
The stabilizer refers to one of hydroquinone or p methoxy phenol；
The photoinitiator is selected from Darocure1173, Darocure184, Darocure2959,4- methyl benzophenone, 2,
4,6- tri-methyl benzophenones or 2, one or more of 4,6 trimethylbenzoyl phenyl phosphinic acid ethyl esters.
2. the preparation method of the multifunctional polyurethane acrylate composition according to dual cure described in claim 1, special
Sign is as described below:
Step 1: the preparation of oligomer (1)
It weighs polyisocyanates and catalyst is added in reaction kettle, stir the lower function polyalcohol for putting into structure shown in logical formula (I),
And it is warming up to 40~140 DEG C simultaneously, it reacts 2~12 hours, is made oligomer (1)；
Wherein the function polyalcohol has structure shown in logical formula (I):
The wherein R in the general formula (I)1And R2It is respectively selected from C1~C20Alkyl, M be selected from Zn2+、Cu2+、Co2+、Ni2+、Ag+Or
Hg2+One or more of, X-Selected from Cl-、Br-、F-、NO3 -Or CH3COO-One or more of；
The polyisocyanates refers to toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, hexamethylene diisocyanate, different
Isophorone diisocyanate, dicyclohexyl methyl hydride diisocyanate vinegar, naphthalene diisocyanate, polymethylene multi-phenenyl isocyanate,
One of triphenylmethane triisocyanate, tri o cresyl thiophosphate (4- phenyl isocyanate)；Mole of the polyisocyanates
Dosage is 1.5~2.5 times of function polyalcohol；
The catalyst refer to dibutyltin dilaurate, stannous octoate, stannous oxalate, two maleic acid tin of dialkyl group,
Two (dodecyl sulphur) dibutyl tins, dibutyltin diacetate, dimethylethanolamine, n,N-Dimethylformamide, triethylene two
Amine, dialkylpiperazines, alkyl imidazole, 1,8- diazabicyclo [5.4.0], 11 carbon -7- alkene, triethylene diamine carboxylate, dioxane
One or more of base piperazine carboxylic acid salt or alkyl imidazole carboxylate；The quality dosage of the catalyst is polyisocyanic acid
Ester 1~5%；
Step 2: the preparation of oligomer (2)
It weighs polyisocyanates and catalyst is added in reaction kettle, Hydroxyethyl Acrylate is continuously added under stirring, and rise simultaneously
Temperature is reacted 2~12 hours to 40~140 DEG C, is made oligomer (2)；
Wherein the polyisocyanates refers to toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, own diisocyanate
Ester, isophorone diisocyanate, dicyclohexyl methyl hydride diisocyanate vinegar, naphthalene diisocyanate, polymethylene polyphenyl isocyanide
One of acid esters, triphenylmethane triisocyanate, tri o cresyl thiophosphate (4- phenyl isocyanate)；The polyisocyanates
Mole dosage is 1.0~2.0 times of Hydroxyethyl Acrylate；
The catalyst refer to dibutyltin dilaurate, stannous octoate, stannous oxalate, two maleic acid tin of dialkyl group,
Two (dodecyl sulphur) dibutyl tins, dibutyltin diacetate, dimethylethanolamine, n,N-Dimethylformamide, triethylene two
Amine, dialkylpiperazines, alkyl imidazole, 1,8- diazabicyclo [5.4.0], 11 carbon -7- alkene, triethylene diamine carboxylate, dioxane
One or more of base piperazine carboxylic acid salt or alkyl imidazole carboxylate；The quality dosage of the catalyst is polyisocyanic acid
The 1~5% of ester；
Step 3: the preparation of dual cure multifunctional polyurethane acrylate composition
According to quality proportioning described in component, successively weighs the pure and mild photoinitiator of polymer polyol and be added in reaction kettle, stir at room temperature
Mix uniform obtained solution A；According to quality proportioning described in component, reactive diluent, stabilizer, low made from step 1 are successively weighed
Oligomer (2) made from polymers (1) and step 2 after mixing, stirs evenly obtained solution B, by the solution A and B when use
Solution is uniformly mixed, and is dual cure multifunctional polyurethane acrylate composition；
The polymer polyatomic alcohol refers in commercial goods polyether polyol, polybutadiene polyol or polyester polyol
It is a kind of；
The photoinitiator is selected from Darocure1173, Darocure184, Darocure2959,4- methyl benzophenone, 2,
4,6- tri-methyl benzophenones or 2, one or more of 4,6 trimethylbenzoyl phenyl phosphinic acid ethyl esters；
The reactive diluent refers to methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid
Monooctyl ester, dodecylacrylate, acrylic acid trifluoromethyl ester, acrylic acid trifluoro ethyl ester, hexafluorobutyl acrylate, acrylic acid 12
Fluorine monooctyl ester, styrene, methyl styrene, divinylbenzene, acrylonitrile, acrylic acid, vinylacetate, diacrylate ethylene glycol
Ester, 1,2-PD diacrylate, diacrylate 1,3-PD ester, 1,4-butanediol diacrylate, diacrylate 1,
6- hexylene glycol ester, diacrylate diethylene glycol (DEG) ester, three glycerol acrylates, pentaerythritol triacrylate or trimethylolpropane tris
One or more of acrylate；
The stabilizer refers to one of hydroquinone or p methoxy phenol；
The oligomer (1): oligomer (2): polymer polyatomic alcohol: reactive diluent: stabilizer: the quality dosage of photoinitiator
Than being 100: 10~200: 10~200: 10~200: 0~0.5: 1.5~15.
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| CN109776754B (en) * | 2017-11-13 | 2022-02-08 | 湖南大学 | Preparation method of cationic waterborne UV polyurethane acrylate self-antibacterial resin |
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