CN109957083B - Unsaturated polyol, photocurable polyurethane prepared from unsaturated polyol and preparation methods of unsaturated polyol and photocurable polyurethane - Google Patents
Unsaturated polyol, photocurable polyurethane prepared from unsaturated polyol and preparation methods of unsaturated polyol and photocurable polyurethane Download PDFInfo
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Abstract
The present invention relates to an unsaturated polyol, a photocurable polyurethane prepared therefrom, and a method for producing the same. The unsaturated polyol comprises units of unsaturated double bonds and coinitiator tertiary amine, the photocurable polyurethane is prepared from the polyol, the main chain of the photocurable polyurethane contains tertiary amine groups, the side chain of the photocurable polyurethane has unsaturated double bond groups and photosensitive group units, and the content ratio of the unsaturated double bond groups to the photosensitive groups is (4-10): (8-25), the polyurethane can be spontaneously polymerized, crosslinked and cured under the irradiation of ultraviolet light without an external photoinitiator. The polyurethane structure of the invention is designed more flexibly, the molecule has a plurality of cross-linking sites, and the polyurethane coating with photoinitiation efficiency, high cross-linking curing degree and large peel strength can be obtained by adjusting the proportion of unsaturated double bond groups of unsaturated polyol and polyol containing photosensitive groups in the polymerization monomer.
Description
Technical Field
The invention belongs to the technical field of photocuring, and particularly relates to unsaturated polyol and photocurable polyurethane prepared from the same.
Background
The ultraviolet light curing technology is a process technology which gives consideration to both environmental and economic benefits, has the characteristics of short curing time, simple and convenient equipment, excellent coating performance, environmental friendliness and the like compared with the traditional curing technology, and is widely applied to the fields of aerospace, electronics, medical health and the like. As a typical representative of the application of the technology, ultraviolet-curable coatings such as photocurable polyurethane have the characteristics of low energy consumption, high curing speed, excellent coating performance and the like, so that rapid development is achieved.
The formula of the ultraviolet curing coating is generally composed of an oligomer, a reactive diluent monomer, a photoinitiator and the like, and under the condition of illumination, the photoinitiator generates a reactive free radical to initiate the polymerization of the oligomer and the monomer, so that the aim of crosslinking and curing is fulfilled. However, lower molecular weight initiators and diluents remain in the polymer network after curing and are slowly migrated and diffused to the substrate surface over time into the surrounding environment. In addition, small molecular substances such as catalysts and auxiliary agents added in the curing process often have certain toxicity and irritation, and the use of these coatings in certain fields (such as the biomedical field) is limited due to safety considerations.
The appearance and the use of the macromolecular photoinitiator are expected to make up and solve the defects of the existing micromolecular photoinitiator, and when the macromolecular photoinitiator is used, the problems of residue, migration to the surface and volatilization can be reduced. This has been reported in a number of documents in recent years. For example, J.Wei et al have synthesized a series of benzophenone-based macrophotoinitiators (J.Polym.Sci., Part A: Polym.Chem.,2007(45), 576; Macromolecules,2007(40), 2344; Macromolecules,2009(42),5486) and used them to initiate polymerization of acrylate monomers. Patent document 1 discloses a method for producing a polyurethane-based polymeric photoinitiator, which reduces or even eliminates migration and leaching of the photoinitiator and its by-products during use. Patent document 2 prepares a photosensitive polyurethane by reacting an isocyanate group and a hydroxyl group-substituted photosensitive small molecule compound. Patent document 3 discloses a photosensitive polyurethane containing sulfur and benzophenone in the side chain and co-initiator amine in the main chain, which can be used as a macro-molecular photoinitiator alone without adding a micro-molecular co-initiator.
Because the polyurethane has better elasticity and adhesiveness and strong coating recoating performance, researchers often use the polyurethane as a precoating material of the coating of the medical instrument and prepares various polyurethanes capable of being photocured by combining a photocuring technology with the characteristics of short curing time, simple and convenient equipment, environmental friendliness and the like. Most of the light-curable polyurethane structures described in the prior art only contain photosensitive groups or unsaturated double bond groups, the photosensitive groups or the unsaturated double bond groups cannot be organically combined, and active crosslinking monomers or micromolecular auxiliaries and the like still need to be added in the subsequent curing process. Patent document 4 discloses that a spontaneously curable polyurethane is prepared by introducing benzophenone into a side chain of polyurethane and capping with a hydroxy acrylate, but the photoinitiation efficiency and the crosslinking curing degree of the polyurethane structure are still limited because of a small number of double bond molecules contained per unit mass.
Patent document 2: US6031044A
Patent document 3: CN1884333A
Patent document 4: CN106366277A
Disclosure of Invention
Problems to be solved by the invention
In order to solve the above problems of the prior art, the present invention has devised a novel unsaturated polyol, and provides photocurable polyurethanes prepared therefrom and a method for producing the same. The main chain of the light-curable polyurethane contains tertiary amine groups, the side chain of the light-curable polyurethane contains unsaturated double bond groups and photosensitive group units, and the content ratio of the unsaturated double bond groups to the photosensitive groups is (4-10): (8-25) by1H NMR measurement; the light-curable polyurethane can be spontaneously polymerized and crosslinked for curing under the irradiation of ultraviolet light. The polyurethane of the invention has flexible structural design, a plurality of crosslinking sites exist in molecules, and the polyurethane coating with high photoinitiation efficiency, crosslinking curing degree and peeling strength can be obtained by adjusting the proportion of unsaturated polyol and photosensitive group-containing polyol in a polymerization monomer.
Means for solving the problems
The present invention provides, first, an unsaturated polyol having the following structural formula:
wherein:
x is- (CH)2)p-or-CH (CH)3)CH2-，p＝1～3；
Y is O or NH;
z is H or CH3；
A is- (CH)2)q-or-CH (CH)3)CH2-，q＝1～3。
The unsaturated polyol as set forth above wherein: y is O.
The unsaturated polyol as set forth above wherein: p is 2, and Z is H; further, wherein q is 2.
Further, the present invention provides a method for preparing the unsaturated polyol according to the above, comprising the steps of: reacting hydroxyalkyl (meth) acrylate or hydroxyalkyl (meth) acrylamide with halogen acetyl halide to synthesize an intermediate product containing halogen and unsaturated bonds; and then reacting the intermediate product with an amino compound to obtain the polyol.
The method for producing an unsaturated polyol as described above, wherein the hydroxyalkyl (meth) acrylate is any one selected from hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; the hydroxyalkyl (meth) acrylamide is selected from any one of N-hydroxymethyl acrylamide, N-hydroxyethyl acrylamide and N-hydroxypropyl acrylamide; the amino compound is selected from any one of diethanolamine and diisopropanolamine; the halogen acetyl halide is selected from any one of bromoacetyl bromide and chloroacetyl chloride.
Further, the present invention provides a photocurable polyurethane obtained by reacting components including a polyol and an isocyanate, characterized in that: the polyol includes the unsaturated polyol described above in the present invention or the polyol prepared by the method for preparing the unsaturated polyol described above.
A photocurable polyurethane as described above wherein said polyol further comprises a photosensitive group-containing polyol.
The photocurable polyurethane comprises a tertiary amine group on a main chain, an unsaturated double bond group and a photosensitive group unit on a side chain, wherein the content ratio of the unsaturated double bond group to the photosensitive group is (4-10): (8-25) by1H NMR measurement.
Further, the photocurable polyurethane has the following structural formula:
wherein the content of the first and second substances,
x is- (CH)2)p-or-CH (CH)3)CH2-，p＝1～3；
Y is O or NH;
z is H or CH3；
A is- (CH)2)q-or-CH (CH)3)CH2-，q＝1～3；
R is a polymeric polyol;
R1is the residue of a diisocyanate;
R2is- (CH)2)k-，k＝1-4；
m, n, e and f are the number of repeating units and are integers not equal to 0; preferably, m and n are integers from 1 to 200, and e and f are integers from 1 to 100.
In addition, the invention also provides a preparation method of the light-curable polyurethane, which comprises the following steps:
(1) under the protection of inert gas, dissolving polyalcohol and isocyanate in an organic solvent to react to obtain a polyurethane prepolymer-1;
(2) dissolving the unsaturated polyol, the polyol containing a benzophenone group and the catalyst in a solvent, adding the mixture into a polyurethane prepolymer-1, and heating to react to obtain a polyurethane prepolymer-2 with a side chain containing a photosensitive group and an unsaturated double bond group;
(3) and adding the micromolecular dihydric alcohol into the polyurethane prepolymer-2 to carry out chain extension and end capping to obtain the light-curable polyurethane.
The preparation method of the photocurable polyurethane comprises the steps of (1) preparing a polyol, wherein the polyol is one or a mixture of polyether diol, polyester diol, polyacetal diol and polythioether diol; the isocyanate is diisocyanate or polyisocyanate, preferably one or two of aliphatic diisocyanate or aromatic diisocyanate; the molar ratio of the unsaturated polyol to the benzophenone group-containing polyol is 2:1 to 1: 5.
ADVANTAGEOUS EFFECTS OF INVENTION
The invention designs and synthesizes novel unsaturated polyol and ultraviolet light-curable polyurethane, and simultaneously introduces unsaturated double bonds, photosensitive groups and co-initiation groups into a polyurethane chain segment, thereby avoiding the use of micromolecular photoinitiator and auxiliary agents with pungent odor and solving the problems of migration and leaching caused by the use of micromolecular substances. According to the invention, the content of double bonds and photosensitive groups in the polyurethane can be controlled by adjusting the ratio of unsaturated polyol and benzophenone group-containing polyol, so that the polyurethane with different structures, performances and molecular weights can be synthesized, and the controllability of the whole structure is enhanced. In addition, the unsaturated polyol structure contains a coinitiator tertiary amine structure, and the introduction of the tertiary amine group enhances the energy transfer in the polyurethane chain segment molecule, enhances the initiation efficiency of the photosensitive group, and improves the curing rate and the bonding strength of the polyurethane.
Drawings
FIG. 1: 2- (N, N-dihydroxyethyl) -2-acetoxyethyl acrylate Nuclear magnetic Hydrogen Spectrum (1H NMR) spectrum.
FIG. 2: example 1 ultraviolet-curable polyurethane Nuclear magnetic Hydrogen Spectrum prepared (1H NMR) spectrum.
Detailed Description
The technical solution of the present invention will be described in detail with reference to the following examples.
The term "unit" in the present invention means not only a functional group (e.g., photosensitive group) but also an additional chemical group having a small influence on the functional group, such as an alkyl group, an alkylene group, etc.
In the present invention, the term "(meth) acrylamide" is understood to encompass both acryloyl and methacryloyl compounds or derivatives and mixtures thereof, as well as the term "(meth) acrylate".
The photocuring process in the present invention takes place by methods known per se, via irradiation with light or UV radiation in the wavelength range from 100 to 600 nm. Illumination sources that may be used are sunlight or artificial lamps or lasers. For example, high, medium or low pressure mercury lamps and xenon and tungsten lamps are advantageous. Also excimer, solid state and diode based lasers are advantageous. Diode-based light sources are generally advantageous for initiating chemical reactions.
< unsaturated polyol >
The unsaturated polyol of the present invention has the following structural formula:
wherein:
x is- (CH)2)p-or-CH (CH)3)CH2-，p＝1～3；
Y is O or NH;
z is H or CH3；
A is- (CH)2)q-or-CH (CH)3)CH2-，q＝1～3。
Compared with the conventional dihydric alcohol (such as MDEA) containing amino, the unsaturated polyhydric alcohol designed by the invention can introduce a longer side chain containing unsaturated double bonds into the polyurethane, greatly increases the content of C-C double bonds of the polyurethane, improves the ultraviolet curing crosslinking density, and in addition, polar groups in the unsaturated polyhydric alcohol, such as ester groups and amide groups, can improve the coating force of the polyurethane on polar materials and the coating hydrophilicity.
In the unsaturated polyol of the present invention, preferably Y is O; more preferably, p ═ 2, q ═ 2, and Z is H, i.e., the unsaturated polyols described in the present invention are preferably of the formula:
Further, the present invention provides a method for preparing the unsaturated polyol according to the above, comprising the steps of: 1) reacting hydroxyalkyl (meth) acrylate or hydroxyalkyl (meth) acrylamide with halogen acetyl halide to synthesize an intermediate product containing halogen and unsaturated bonds; 2) and then reacting the intermediate product with an amino compound to obtain the unsaturated polyol.
Preferably, the step 1) is to dissolve the hydroxyalkyl (meth) acrylate or hydroxyalkyl (meth) acrylamide in a solvent, dropwise add halogen acetyl halide at low temperature, and react under the action of a catalyst to obtain an intermediate product. The hydroxyalkyl (meth) acrylate is selected from one or more of hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; the hydroxyalkyl (meth) acrylamide is selected from one or more of N-methylolacrylamide, N-hydroxyethyl acrylamide and N-hydroxypropyl acrylamide; the halogen acetyl halide is selected from any one of bromoacetyl bromide and chloroacetyl chloride; the molar ratio of the haloacetyl halide to the hydroxyalkyl (meth) acrylate or hydroxyalkyl (meth) acrylamide is 1.5:1 to 1.1:1, more preferably 1.1: 1. The solvent is selected from the group consisting of ethyl acetate, dichloromethane, chloroform and tetrahydrofuran, more preferably the solvent is dichloromethane. The catalyst is a basic catalyst, such as inorganic bases such as sodium hydroxide, potassium hydroxide and sodium carbonate, and organic bases such as triethylamine and pyridine.
The reaction temperature of the step 1) is 20-40 ℃, the reaction can be directly carried out at room temperature, and the preferable temperature is 25-30 ℃; the reaction time is 10 to 20 hours, and more preferably 15 to 18 hours.
Step 2) preferably, mixing and dissolving the intermediate product obtained in the step 1) and the amino compound in a molar ratio of 1: 1-1:2 (more preferably, the molar ratio of the intermediate product to the amino compound is 1: 1.2-1: 1.5) in a solvent, and heating and reacting under a catalyst to obtain the unsaturated polyol. More preferably, the amino compound is selected from any one or more of diethanolamine and diisopropanolamine; the solvent used in the step is dioxane, and the catalyst is triethylamine; the reaction temperature is 40-80 ℃, preferably 50-70 ℃, and the reaction time is 3-8 hours, preferably 5-6 hours.
Without limitation, in one embodiment of the present invention, the unsaturated polyol is prepared by the following method: reacting hydroxyethyl acrylate with bromoacetyl bromide to synthesize 2- (2-bromoacetoxyl) ethyl acrylate; then reacting with diethanol amine to obtain 2- (N, N-dihydroxyethyl) -2-acetoxyl ethyl acrylate.
Specifically, the preparation method of the 2- (N, N-dihydroxyethyl) -2-acetoxyl ethyl acrylate comprises the following steps:
(1) synthesis of 2- (2-bromoacetoxy) ethyl acrylate:
dissolving hydroxyethyl acrylate in a solvent, dropwise adding bromoacetyl bromide into the solution at a low temperature, reacting for 0.2-1 h under the action of a catalyst, heating to 25-30 ℃, continuing to react for 15-18 h, and purifying and drying to obtain 2- (2-bromoacetoxyl) ethyl acrylate; the molar ratio of bromoacetyl bromide to hydroxyethyl acrylate is 1.1: 1;
(2) synthesis of 2- (N, N-dihydroxyethyl) -2-acetoxyethyl acrylate:
and (3) dissolving the product obtained in the first step and diethanol amine in dioxane, reacting for 5-6 h at 50-70 ℃ under the action of triethylamine, and separating, purifying and drying to obtain the product. The molar ratio of the 2- (2-bromoacetoxyl) ethyl acrylate to the diethanolamine is preferably 1:1.2 to 1: 1.5.
< light-curable polyurethane >
Polyurethanes are typically prepared by the reaction of a polyol with an isocyanate. The unsaturated polyol of the present invention described above can be used to prepare the photocurable polyurethane of the present invention.
In order to make the polyurethane itself photosensitive, it is preferable that the polyol for preparing the polyurethane further includes a polyol containing a photosensitive group. The photoactive group is derived from benzophenone, phenylaminoalkyl ketones, thioxanthones, benzil ketals, phenylhydroxyalkyl ketones, α -dialkoxy-acetophenones, α -hydroxy-alkyl-phenones, α -amino-alkyl-phenones, acyl-phosphine oxides, phenylcoumarin ketones, silanes, camphorquinones, maleimides and derivatives thereof, and further preferably the photoactive group-containing polyol is a benzophenone group-containing polyol such as 4- {3- [ bis (2-hydroxyethyl) amino ] propoxy } benzophenone, 4- { [ bis (2-hydroxyethyl) amino ] methyl } benzophenone, 4- { [ bis (2-hydroxyethyl) amino ] ethyl } benzophenone, 4- [ bis (2-hydroxyethyl) amino ] benzophenone, benzil ketals, phenyl hydroxyalkyl ketones, α -dialkoxy-acetophenones, α -hydroxy-alkyl-phenones, α -amino-alkyl-phenones, acyl-phosphine oxides, phenylcoumarin ketones, silanes, camphor, 4- [ bis (2-hydroxypropyl) amino ] benzophenone and the like, more preferably 4- {3- [ bis (2-hydroxyethyl) amino ] propoxy } benzophenone, and the specific preparation method is described in example 1 of WO 2012/062333A.
Other conventional polyols may also be added to the present invention. For example, the polyurethane prepolymer-1 can be synthesized by using a polymeric polyol. The molecular weight of the polymeric polyol is not particularly limited, and the number average molecular weight is preferably not more than 5000, preferably not more than 2000, more preferably not more than 1000. Examples of the polyhydric polyol include polyester polyol, polyether polyol, polyacetal diol, polythioether diol, polybutadiene polyol, silicon polyol, and polyacrylate polyol, and combinations thereof, and preferably one or a mixture of several of polyether diol, polyester diol, polyacetal diol, and polythioether diol. Suitable polyether polyols include polyethylene glycol, polypropylene glycol and polytetramethylene glycol or block copolymers thereof. Suitable polyester polyols are preferably the hydroxylation reaction products of dihydric alcohols with polycarboxylic acids, preferably dicarboxylic acids, or their corresponding anhydrides, and also the products obtained by ring-opening polymerization of lactones. The polycarboxylic acids which can be used to form these polyester polyols can be aliphatic, cycloaliphatic, aromatic and/or heterocyclic and they can be substituted, saturated or unsaturated. Examples of dicarboxylic acids are succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, isophthalic acid, terephthalic acid, phthalic acid, and the like; dihydric alcohols include ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 1, 4-cyclohexanedimethanol, bisphenol A and the like. The polyester polyol may also use polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane and pentaerythritol. In addition, small-molecule polyols such as ethylene glycol, diethylene glycol, propylene glycol, 1, 4-butanediol or 1, 6-hexanediol, etc. can also be used as blocking agents for polyurethanes.
In the present invention, aliphatic and aromatic diisocyanates and polyisocyanates are used to prepare polyurethane prepolymer-1 and photocurable polyurethane. Preferably a diisocyanate; however, it is within the scope of the present invention to include a small amount, i.e., no greater than about 20 mole percent, of trifunctional isocyanates or higher functionality isocyanates. Preferred isocyanates include, but are not limited to: aliphatic linear isocyanates including, for example, α, ω alkylene diisocyanates having 5 to 20 carbon atoms, preferably tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc.; cycloaliphatic diisocyanates, such as isophorone diisocyanate, cyclohexane diisocyanate, preferably 1, 4-cyclohexane diisocyanate, fully hydrogenated aromatic diisocyanates, such as hydrogenated tetramethylxylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated methylenediphenylene diisocyanate; aromatic diisocyanates such as toluene diisocyanate, particularly its 2, 4-isomer, methylene diphenylene diisocyanate, tetramethylxylene diisocyanate, and the like. The aromatic diisocyanates may also include polymethylene polyphenylene polyisocyanates having a functionality greater than 2. More than one isocyanate may be used in the present invention. Particular preference is given to using one or more of tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, dicyclohexyl diisocyanate, isophorone diisocyanate, tetramethylxylylene diisocyanate.
Without limitation, in one embodiment of the present invention, the main chain of the photocurable polyurethane of the present invention contains tertiary amine groups, the side chain has unsaturated double bond groups and photosensitive group units, and the introduction of unsaturated double bonds and photosensitive group units into the side chain can realize effective control of crosslinking curing and photoinitiation efficiency. Preferably, the content ratio of the unsaturated double bond group to the photosensitive group is (4-10): (8-25) by1H NMR determination, and calculating the respective mol percent (mol%) of the unsaturated double bond group and the photosensitive group by utilizing a nuclear magnetic spectrum to obtain the content ratio. To obtainObtaining the polyurethane coating with optimal crosslinking performance and peeling strength, and further preferably, the content ratio of unsaturated double bond groups to photosensitive groups is (5-7): (10-23), further in an embodiment of the present invention, the photocurable polyurethane preferably has a double bond molar percentage of 5-6.5% and a photosensitive group molar percentage of 10-23%.
Further, the photocurable polyurethane of the present invention is preferably of the formula:
wherein X, Y, Z, A is as defined above for the unsaturated polyol of the present invention;
r is a polymeric polyol;
R1is the residue of a diisocyanate;
R2is- (CH)2)k-，k＝1-4；
m, n, e and f are the number of repeating units and are integers not equal to 0; preferably, m and n are integers from 1 to 200, and e and f are integers from 1 to 100.
The main chain of the polyurethane with the structure is provided with a plurality of tertiary amine groups, and the tertiary amine auxiliary agent with low molecular weight can be partially or completely replaced; the polyurethane has a photosensitive group on its side chain, and the aromatic ketone moiety can abstract the tertiary amine proton from the carbon atom adjacent to the amino nitrogen, and can generate a reactive group for initiating polymerization or crosslinking; in addition, the unsaturated double bonds in the side chains can lead to a good spontaneous crosslinking function of the polyurethane.
Preferably, the photocurable polyurethane of the present invention is prepared by the following method:
(1) under the protection of inert gas, dissolving polyalcohol and isocyanate in an organic solvent to react to obtain a polyurethane prepolymer-1;
(2) dissolving the unsaturated polyol, the polyol containing the photosensitive group and the catalyst in a solvent, adding the solution into a polyurethane prepolymer-1, and heating to react to obtain a polyurethane prepolymer-2 with a side chain containing the photosensitive group and an unsaturated double bond group;
(3) and adding the micromolecular dihydric alcohol into the polyurethane prepolymer-2 to carry out chain extension and end capping to obtain the light-curable polyurethane.
Further preferably, the reaction in step (1) is always carried out under the protection of nitrogen, and the polymeric polyol is preferably one or a mixture of several of polyether diol, polyester diol, polyacetal diol and polythioether diol; the organic solvent is one or two of acetone, butanone, 1, 4-dioxane, cyclohexanone, 4-methyl-2-pentanone, N, N-dimethylformamide and N-methylpyrrolidone, and the reaction in the step (1) is preferably carried out at 60-90 ℃ for 1-4 hours. In the step (2), dibutyltin dilaurate is used as a catalyst, the polyol containing a photosensitive group is preferably a polyol containing a benzophenone group, the molar ratio of the unsaturated polyol to the polyol containing the benzophenone group is 2:1-1:5, and is further preferably 2:1-1:2, and a polyurethane coating film with good crosslinking degree and peeling strength can be obtained by adopting the proportion range; the reaction in the step (2) is carried out for 2 to 5 hours at the temperature of between 70 and 90 ℃. The reaction of step (3) is preferably carried out at 50 to 70 ℃ for 1 to 3 hours; the small molecular diol in the step (3) is preferably ethylene glycol or 1, 4-butanediol.
The photocurable polyurethane of the present invention can be cured by exposure to UV radiation using a radiation source having a wavelength of at least 300nm, preferably 320-500 nm. Curing may be carried out in solution. The photocurable polyurethane according to the invention can be dissolved in a suitable solvent and sprayed, for example, onto a tube and subsequently exposed to UV radiation. The solvent may then be evaporated or remain in the coating and act as a swelling medium providing the desired gel.
The photocurable polyurethanes of the present invention are preferably used for the preparation of coatings, adhesives, sealants and the like. The photocurable polyurethane of the present invention may also be used in combination with additives commonly used in the art, depending on the particular application, including but not limited to: dispersing agents, flow aids, thickeners, defoamers, deaerators, pigments, fillers, matting agents and wetting agents. Preferably, the photocurable polyurethane of the present invention can be directly used as a photocurable coating. The photocurable polyurethanes of the present invention can be applied to a variety of substrates by any method known to those skilled in the art, including but not limited to spraying, roll coating, knife coating, casting, brushing, dipping, putty knife coating, or doctor blade coating, and the time for which the coated substrate is irradiated depends on the spectral overlap of the lamp emission spectrum and the absorption spectrum of the photoinitiator, the distance from the radiation source, and the lamp intensity, solvent content of the formulation, temperature and humidity of the curing environment, but is typically as little as 10 minutes and as little as 0.1 second.
The invention is further illustrated, but not limited, by the following examples.
Examples
The present invention is described below by way of examples, which are not exhaustive, as those skilled in the art will appreciate that the examples are illustrative only. The preparation examples are compound synthesis examples, and the related chemical raw materials and reagents are all sold in the market or synthesized according to the published documents.
The content of double bonds and the content of photosensitive groups are determined by1H NMR spectroscopy.
The degree (%) of crosslinking of the coating was determined by soxhlet extraction: weighing a certain mass of cured coating sample, cutting the coating sample, extracting the cut coating sample for 12 hours at 120 ℃ by using a Soxhlet extractor, performing vacuum drying after extraction, weighing, and calculating the crosslinking degree of the coating.
The peel strength (N/mm) of the polyurethane coating was tested according to GB/T8808-1988.
Preparation example 1: synthesis of unsaturated polyols
Dissolving hydroxyethyl acrylate (11.5mL, 0.1mol) in dichloromethane, dropwise adding bromoacetyl bromide (9.6mL, 0.11mol) into the solution at low temperature, wherein the molar ratio of the bromoacetyl bromide to the hydroxyethyl acrylate is 1.1:1, reacting for 0.5h under the action of sodium hydroxide (4g, 0.1mol), heating to 30 ℃, continuing to react for 16h, and obtaining 2- (2-bromoacetoxy) ethacrylic acid after purification and dryingEster (16.5g, 70% yield); then, 2- (2-bromoacetoxy) ethyl acrylate (11.8g, 0.05mol) and diethanolamine (6.3g, 0.06mol) were dissolved in dioxane, reacted at 60 ℃ for 5h under the catalysis of triethylamine (6.1g, 0.06mol), separated, purified, and dried to obtain 2- (N, N-dihydroxyethyl) -2-acetoxy ethyl acrylate (10.2g, yield 78%). The nuclear magnetic spectrum of the product is shown in figure 1,1H NMR(δ/ppm):2.51(m,4H,CH2),3.35(s,2H,CH2),3.52(m,4H,CH2),4.28(m,2H,CH2),4.38(m,2H,CH2),5.83(m，H,CH＝CH2),6.12(m,H,CH＝CH2),6.45(m,H,CH＝CH2). The attribution and integral area of each characteristic peak are consistent with the structure of a target product.
Example 1: synthesis of light-curable polyurethane
(1) Under the protection of nitrogen, 3.5g of toluene diisocyanate was added into a round-bottomed flask equipped with a thermometer, a condenser and a stirrer, the flask was put in an oil bath at 75 ℃, 10g of polypropylene glycol was dropped into a four-necked reaction flask by using a constant-pressure funnel, and the mixture was allowed to react for 2.5 hours while maintaining the temperature, and the viscosity of the reaction solution was adjusted with acetone to obtain polyurethane prepolymer-1.
(2) 2.6g of the unsaturated polyol obtained in preparation example 1 and 1.7g of 4- {3- [ bis (2-hydroxyethyl) amino ] propoxy } benzophenone (molar ratio of these two is 2/1) were dissolved in DMF, and added to prepolymer-1, and 0.1g of dibutyltin dilaurate as a catalyst was added thereto, and the mixture was reacted at 65 ℃ for 3 hours to obtain polyurethane prepolymer-2 having a side chain containing a photosensitive group and an unsaturated double bond group.
(3) And cooling to 50 ℃, adding 1.6g of 1, 4-butanediol into the prepolymer-2 by using a dropping funnel, reacting for 2 hours at 60 ℃, and carrying out chain extension and end capping to obtain the light-curable polyurethane. The nuclear magnetic spectrum of the resulting photocurable polyurethane is shown in FIG. 2. As can be seen from FIG. 2, the characteristic peak corresponding to the main chain structure of polyurethane at 1.2-4.6ppm, the characteristic peak at the position of 7.43-7.85ppm proves that benzene rings exist in the polyurethane, the peak at the position of 5.72-5.79ppm proves that double bonds exist in the polyurethane, and the molar percentage of unsaturated double bonds is 8.4% and the molar percentage of benzophenone groups is 10.0% through measurement.
Example 2:
(1) under the protection of nitrogen, 3.5g of toluene diisocyanate was added into a round-bottomed flask equipped with a thermometer, a condenser and a stirrer, the flask was put in an oil bath at 80 ℃, 10g of polypropylene glycol was dropped into a four-necked reaction flask by using a constant-pressure funnel, and the mixture was allowed to react for 2.5 hours while maintaining the temperature, and the viscosity of the reaction solution was adjusted with acetone to obtain polyurethane prepolymer-1.
(2) 1.95g of the unsaturated polyol obtained in preparation example 1 and 1.7g of 4- {3- [ bis (2-hydroxyethyl) amino ] propoxy } benzophenone (molar ratio of 1.5/1) were dissolved in DMF, and added to prepolymer-1, 0.15g of dibutyltin dilaurate as a catalyst was added thereto, and the mixture was reacted at 70 ℃ for 3 hours to obtain polyurethane prepolymer-2 having a photosensitive group and an unsaturated double bond group in a side chain.
(3) Cooling to 50 ℃, adding 2.0g of 1, 4-butanediol into the prepolymer-2 by using a dropping funnel, reacting for 2 hours at 65 ℃, chain extending and end capping to obtain the light-curable polyurethane, wherein the molar percentage of unsaturated double bonds is 6.5 percent and the molar percentage of benzophenone groups is 10.0 percent.
Example 3:
(1) under the protection of nitrogen, 3.5g of toluene diisocyanate was added into a round-bottomed flask equipped with a thermometer, a condenser and a stirrer, the flask was put in an oil bath at 70 ℃, 10g of polypropylene glycol was dropped into a four-necked reaction flask by using a constant-pressure funnel, and the mixture was allowed to react for 2.5 hours while maintaining the temperature, and the viscosity of the reaction solution was adjusted with acetone to obtain polyurethane prepolymer-1.
(2) 1.3g of the unsaturated polyol obtained in preparation example 1 and 1.7g of 4- {3- [ bis (2-hydroxyethyl) amino ] propoxy } benzophenone (molar ratio of these two is 1/1) were dissolved in DMF, and added to prepolymer-1, to which 0.1g of dibutyltin dilaurate as a catalyst was added, followed by reaction at 70 ℃ for 3 hours to obtain polyurethane prepolymer-2 having a side chain containing a photosensitive group and an unsaturated double bond group.
(3) Cooling to 50 ℃, adding 1.8g of 1, 4-butanediol into the prepolymer-2 by using a dropping funnel, reacting for 2 hours at 50 ℃, carrying out chain extension and end capping to obtain the light-curable polyurethane, wherein the molar percentage of unsaturated double bonds is 5.0 percent and the molar percentage of benzophenone groups is 10.0 percent.
Example 4:
(1) under the protection of nitrogen, 3.5g of toluene diisocyanate was added into a round-bottomed flask equipped with a thermometer, a condenser and a stirrer, the flask was put in an oil bath at 70 ℃, 10g of polypropylene glycol was dropped into a four-necked reaction flask by using a constant-pressure funnel, the reaction was maintained for 2 hours, and the viscosity of the reaction solution was adjusted with acetone to obtain polyurethane prepolymer-1.
(2) 1.3g of the unsaturated polyol obtained in preparation example 1 and 3.4g of 4- {3- [ bis (2-hydroxyethyl) amino ] propoxy } benzophenone (molar ratio of these two is 1/2) were dissolved in DMF, and added to prepolymer-1, to which 0.15g of dibutyltin dilaurate as a catalyst was added, followed by reaction at 80 ℃ for 3 hours to obtain polyurethane prepolymer-2 having a side chain containing a photosensitive group and an unsaturated double bond group.
(3) Cooling to 60 ℃, adding 1.5g of 1, 4-butanediol into the prepolymer-2 by using a dropping funnel, reacting for 2 hours at 60 ℃, carrying out chain extension and end capping to obtain the light-curable polyurethane, wherein the molar percentage of unsaturated double bonds is 5.0 percent and the molar percentage of benzophenone groups is 17.2 percent.
Example 5:
(1) under the protection of nitrogen, 3.5g of toluene diisocyanate was added into a round-bottomed flask equipped with a thermometer, a condenser and a stirrer, the flask was put in an oil bath at 85 ℃, 10g of polypropylene glycol was dropped into a four-necked reaction flask by using a constant-pressure funnel, the reaction was maintained for 2 hours, and the viscosity of the reaction solution was adjusted with acetone to obtain polyurethane prepolymer-1.
(2) The temperature was reduced to 60 ℃, 1.3g of the unsaturated polyol obtained in preparation example 1, 8.5g of 4- {3- [ bis (2-hydroxyethyl) amino ] propoxy } benzophenone (the molar ratio of the two was 1/5) was dissolved in acetone, and added to prepolymer-1, 0.18g of dibutyltin dilaurate (mass fraction was 0.5% of the total amount of the reaction solution) as a catalyst was added thereto, and the temperature was raised to 80 ℃ and reacted for 2.5 hours to obtain polyurethane prepolymer-2 having a side chain containing a photosensitive group and an unsaturated double bond group.
(3) Cooling to 60 ℃, adding 1.4g of 1, 4-butanediol into the prepolymer-2 by using a dropping funnel, reacting for 2 hours at 60 ℃, carrying out chain extension and end capping to obtain the light-curable polyurethane, wherein the molar percentage of unsaturated double bonds is 5.0 percent and the molar percentage of benzophenone groups is 22.3 percent.
Application example
The light-curable polyurethane prepared in the embodiment 1-5 is compounded with a BOPP film-aluminum foil, or the polyurethane is coated on a tinplate and is cured for 2-3 min by ultraviolet light, wherein the curing distance is 20cm, and the light intensity is 20-30 mw/cm2The peel strength and the degree of crosslinking of the cured film were measured.
TABLE 1 Photocurable polyurethane compositions and coating Properties thereof
It can be seen from the above examples that in the case where the content of the photosensitive group in the polyurethane composition is constant (examples 1 to 3), the density of the crosslinking points increases with the increase of the double bond content, and thus the degree of crosslinking of the polyurethane coating layer increases. In the case of a certain double bond content in the polyurethane composition (examples 3 to 5), the degree of crosslinking of the polyurethane coating increases to a certain extent with increasing content of photosensitive groups, since free-radical coupling crosslinking can likewise take place between the photosensitive groups in the polyurethane structure of the invention. Furthermore, as the double bond and photosensitive group content increases, the peel strength of the coating decreases, which may be related to polyurethane shrinkage during curing. Therefore, the relative amounts of the unsaturated polyol and the polyol containing a photosensitive group in the invention need to be reasonably regulated and controlled so that the contents of the photosensitive group and the double bond in the prepared photocurable polyurethane structure are equivalent, and then the polyurethane coating with optimal crosslinking performance and peel strength can be obtained.
However, the above description is only a preferred embodiment of the present invention, and it is natural that those skilled in the art can change the present invention based on the actual requirement after understanding the technical means of the present invention. Therefore, all equivalent changes and modifications made in accordance with the claims of the present invention should still fall within the scope of the present invention.
Claims (11)
1. An unsaturated polyol characterized in that:
has the following structural formula:
wherein:
x is- (CH)2)p-or-CH (CH)3)CH2-，p＝1～3；
Y is O or NH;
z is H or CH3；
A is- (CH)2)q-or-CH (CH)3)CH2-，q＝1～3。
2. The unsaturated polyol of claim 1, wherein: y is O.
3. The unsaturated polyol of claim 1 or 2, wherein: p is 2, q is 2 and Z is H.
4. The method for producing an unsaturated polyol according to any one of claims 1 to 3, wherein a hydroxyalkyl (meth) acrylate or hydroxyalkyl (meth) acrylamide and a halogen acetyl halide are reacted to synthesize an intermediate product containing a halogen and an unsaturated bond; and then reacting the intermediate product with an amino compound to obtain the unsaturated polyol.
5. The method for producing an unsaturated polyol according to claim 4, wherein said hydroxyalkyl (meth) acrylate is any one selected from the group consisting of hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; the hydroxyalkyl (meth) acrylamide is selected from any one of N-hydroxymethyl acrylamide, N-hydroxyethyl acrylamide and N-hydroxypropyl acrylamide; the amino compound is selected from any one of diethanolamine and diisopropanolamine; the halogen acetyl halide is selected from any one of bromoacetyl bromide and chloroacetyl chloride.
6. A photocurable polyurethane obtained by the reaction of components comprising a polyol and an isocyanate, characterized in that: the polyol includes the unsaturated polyol described in any one of claims 1 to 3 or the unsaturated polyol produced by the production method described in any one of claims 4 or 5.
7. A photocurable polyurethane as recited in claim 6, wherein: the polyols also include polyols containing photosensitive groups.
8. A photocurable polyurethane as claimed in claim 6 or 7, characterized in that: the main chain of the light-curable polyurethane contains tertiary amine groups, the side chain of the light-curable polyurethane contains unsaturated double-bond groups and photosensitive group units, and the content ratio of the unsaturated double-bond groups to the photosensitive groups is (4-10): (8-25) by1H NMR measurement.
9. A photocurable polyurethane according to claim 6 or 7, characterized in that said photocurable polyurethane has the following structural formula:
wherein X, Y, Z, A is as defined in claim 1;
r is the residue of a polymeric polyol;
R1is the residue of a diisocyanate;
R2is- (CH)2)k-，k＝1-4；
m, n, e and f are the number of repeating units and are integers not equal to 0.
10. A photocurable polyurethane according to claim 8, wherein said photocurable polyurethane has the following structural formula:
wherein X, Y, Z, A is as defined in claim 1;
r is the residue of a polymeric polyol;
R1is the residue of a diisocyanate;
R2is- (CH)2)k-，k＝1-4；
m, n, e and f are the number of repeating units and are integers not equal to 0.
11. The process for producing photocurable polyurethane according to any one of claims 6-10, characterized in that:
(1) under the protection of inert gas, dissolving polyalcohol and isocyanate in an organic solvent to react to obtain a polyurethane prepolymer-1;
(2) dissolving unsaturated polyol, polyol containing benzophenone groups and a catalyst in a solvent, adding the solution into a polyurethane prepolymer-1, and heating the solution to react to obtain a polyurethane prepolymer-2 with a side chain containing photosensitive groups and unsaturated double bond groups; the unsaturated polyol is the polyol according to any one of claims 1 to 3 or the polyol produced by the production method according to any one of claims 4 or 5;
(3) and adding the micromolecular dihydric alcohol into the polyurethane prepolymer-2 to carry out chain extension and end capping to obtain the light-curable polyurethane.
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