CN113816963A - Modified photobase generator, preparation method thereof and light-moisture dual-curing polyurethane hot melt adhesive applying modified photobase generator - Google Patents
Modified photobase generator, preparation method thereof and light-moisture dual-curing polyurethane hot melt adhesive applying modified photobase generator Download PDFInfo
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Abstract
A modified photobase generator, a preparation method thereof and a light-moisture dual-curing polyurethane hot melt adhesive applying the same. The invention provides a modified photobase generator obtained by a compound shown as a general formula I: general formula I:
wherein, at least one of R0, R1 and R2 is selected from the following groups: -OH, - (CH)2)mOH，‑O‑(CH2)nOH，‑(CH2)xCOOH，‑O‑(CH2)yCOOH, wherein m, n, x and y are integers selected from 1 to 5. The modified photobase generator of the invention has active groups connected to the alkyl branched chain in the molecule, and can react with isocyanate groups to polymerize into the main chain molecular structure, so that the modified photobase generator and the polyurethane hot melt adhesive system are changed from physical mixing into chemical bonding, and the solubility and the dispersion uniformity of the photobase generator in the polyurethane hot melt adhesive system are obviously enhanced.
Description
Technical Field
The invention belongs to the field of adhesive materials, and particularly relates to a modified photobase generator, a preparation method thereof and a light-moisture dual-curing polyurethane hot melt adhesive using the same.
Background
The reactive polyurethane hot melt adhesive is a solvent-free environment-friendly pollution-free hot melt adhesive, has high final bonding strength, good flexibility and weather resistance, and is suitable for bonding various materials. The method is widely applied to the fields of consumer electronics, household appliance assembly, fabric bonding, woodworking bonding and the like. After the conventional reactive polyurethane hot melt adhesive is applied, the initial bonding strength of the product is lower, the pressure maintaining time is longer, and the pressure maintaining can be stopped only by overcoming the resilience force of the base material through chemical curing. Longer pressurize time had both increased the cost of pressurize tool, had reduced the circulation speed of product again, and then improved user's use cost. Photoinitiators play an important role in many areas, such as coatings, adhesives, dental materials, microelectronic materials, and 3D printing. Photobase generators (Photobase generators) are a class of photoinitiators which are newly developed in recent years, and are compounds which can release alkaline active substances after being excited by irradiation, and can realize effective alkali catalytic reaction under certain conditions. The photopolymerization reaction system catalyzed by alkali has the advantages of small polymerization shrinkage rate of materials, no oxygen inhibition, no corrosion to base materials and the like. In the prior art, a photobase generator is introduced into a reactive polyurethane hot melt adhesive, and generates alkali after illumination, and the generated alkali can catalyze isocyanate groups to react with moisture quickly, so that high initial bonding strength can be obtained in a short time.
However, conventional photobase generators are all partial ion type compounds, cannot be dissolved in a system mainly comprising covalent bonds, such as a reactive polyurethane hot melt adhesive, and can only be dispersed in the system in the form of fillers, so that the dispersion uniformity and transparency of the photobase generators in the system are seriously affected, and the photobase generators cannot be sufficiently excited to play a role. In addition, the photolysis product of the photobase can also be dissociated in the system besides the organic base with catalytic activity, thus objectively reducing the comprehensive performance of the product.
Disclosure of Invention
The invention aims to provide a modified photobase generator, a preparation method thereof and a light-moisture dual-curing polyurethane hot melt adhesive using the same.
According to a first aspect of the present invention, there is provided a modified photobase generator and a method for preparing the same.
In order to achieve the purpose, the invention adopts the following technical scheme:
a modified photobase generator comprising a compound of formula I:
general formula I:
wherein, at least one of R0, R1 and R2 is selected from the following groups: -OH, - (CH)2)mOH，-O-(CH2)nOH，-(CH2)xCOOH，-O-(CH2)yCOOH, wherein m, n, x and y are integers selected from 1-5.
Preferably, at least one of R1 and R2 is selected from the following groups: -OH, - (CH)2)mOH，-O-(CH2)nOH，-(CH2)xCOOH，-O-(CH2)yCOOH。
Preferably, R1, R2 are selected from-H, -CH3。
Preferably, R1 is-CH2OH。
Preferably, the structural formula of the modified photobase generator is as follows:
preferably, R0 is selected from the following groups: -OH, - (CH)2)mOH，-O-(CH2)nOH，-(CH2)xCOOH，-O-(CH2)yCOOH。
Preferably, R0 is selected from-H, -CH3。
Preferably, the chemical structure of Chr is selected from one of general formula II, structural formula 2 and structural formula 3;
general formula II:
wherein X is selected from sulfur atom and oxygen atom, Y is selected from oxygen atom and sulfur atom, s and t are selected from but not limited to 0, 1;
the structure of structural formula 2 is:
the structure of structural formula 3 is:
preferably, Chr may be selected from any one of the following structural formulae:
preferably, the organic base B may be selected from:
1, 8-diazabicycloundecen-7-ene (DBU), 1, 5-diazabicyclono-5-ene (DBN), Triazabicyclo (TBD), Tributylamine (TBA), Triethylamine (TEA), triethylenediamine, piperidine derivatives, morpholine derivatives, imidazole derivatives, piperazine derivatives, tetramethylalkylenediamine, cyclohexylmethyl tertiary amine, bis (dimethylaminoethyl) ether and analogues, tris (dimethylaminopropyl) amine, N-dimethylbenzylamine, N-dimethyl (hexadecyl) amine.
Preferably, the organic base B has the formula:
preferably, the structure of the modified photobase generator may be selected from compounds of the following structures:
the invention also provides a preparation method of the modified photobase generator, which comprises the following steps:
(1) cyclization reaction: adding the raw material B into the mixed solution of the raw material A and concentrated sulfuric acid, and generating reaction liquid containing the intermediate C under the catalytic action of the concentrated sulfuric acid; and then dropwise adding the reaction liquid of the intermediate C into boiling water to convert the intermediate C into yellow precipitate, wherein the A, B, C substance has a general formula:
at least one of R3, R4, R5 and R6 is selected from-OH, - (CH)2)mOH，-(CH2)xCOOH；
(2) Alkali neutralization reaction: and dissolving the intermediate C in tetrahydrofuran, and dropwise adding organic alkali to generate the photobase generator.
Preferably, when at least one of R3, R4, R5 and R6 in the structural formula of the intermediate C is selected from-OH, the cyclization reaction further comprises the following substitution reaction steps: dissolving the product C, KOH and KI in deionized water, and dropwise adding the substance D to obtain an intermediate E, wherein the substance D and the intermediate E respectively correspond to the following structural formulas:
wherein u is an integer of 1-5, at least one of R7, R8, R9 and R10 is selected from O- (CH)2)nOH，-O-(CH2)yCOOH；
In the base neutralization reaction: and dissolving the intermediate E in tetrahydrofuran instead of the intermediate C, and dropwise adding 1, 8-diazabicycloundecen-7-ene (DBU) to generate the photobase generator.
Preferably, the photobase generator is generated by the structure:
preferably, the structure of the raw material a is:
preferably, the structure of the raw material B is:
preferably, the raw material B (55-60 parts) is added into a mixed solution of the raw material A (15-20 parts) and concentrated sulfuric acid (800-1000 parts) in batches, stirred for one hour at room temperature, then stirred for 6-10 hours at 80 ℃, filtered and dried to obtain the intermediate C with the following chemical structure:
preferably, the intermediate C (8-13 parts), KOH (35-40 parts) and KI (3-4 parts) are dissolved in deionized water, the substance D (22-27 parts) is dropwise added under the heating condition, and the reaction is refluxed and cooled to room temperature. Dropwise adding hydrochloric acid (12mol/L) until no precipitate is separated out, and then recrystallizing the precipitate with a solvent (ethanol/water ═ 2:8) to obtain an intermediate E;
the structural formula of the intermediate E is as follows:
preferably, the intermediate E (7-12 parts) is dissolved in tetrahydrofuran, 1, 8-diazabicycloundecen-7-ene (DBU) (7-12 parts) is dropwise added after the solution is clarified, when brown viscous liquid appears at the bottom of a flask, the supernatant is poured out, and after a certain volume of tetrahydrofuran is added for washing, the washing is repeated for three times, so that the modified photobase generator G is obtained.
Preferably, the structural formula of the modified photobase generator G is as follows:
the parts of each substance are parts of the substance.
The invention also provides a light-moisture dual-curing polyurethane hot melt adhesive prepared based on the modified light alkali-producing agent.
A light-moisture dual-curing polyurethane hot melt adhesive based on a modified light alkali-producing agent comprises the modified light alkali-producing agent; the components of the light-moisture dual-curing polyurethane hot melt adhesive also comprise a polyol polymer and an isocyanate monomer; the modified photobase generator comprises the following components in percentage by weight: polyol polymer: tackifying resin: isocyanate monomer is 0.5-10: 40-70: 10-30: 10 to 30.
Preferably, the light-moisture dual-curing polyurethane hot melt adhesive based on the modified light alkali-producing agent comprises the following raw materials in parts by weight:
preferably, the polyol is one or more of polyester polyol, polyether polyol, polyacrylate polyol, polyolefin polyol and bio-based polyol.
Preferably, the molecular weight of the polymeric polyol is 500-10000, the water content is < 0.5%, and the acid value is <1mg KOH/g.
Preferably, the polyester polyol is one or more of conventional polyester polyol, polycaprolactone polyol and polycarbonate polyol obtained by copolymerizing dihydric alcohol and dibasic acid.
Preferably, the conventional polyester polyol refers to solid or liquid polyester polyol prepared by reacting one or more diol compositions of 1, 4-butanediol, 1, 6-hexanediol, 1, 5-pentanediol, neopentyl glycol, 1, 2-propanediol, 1, 3-propanediol, dodecanediol, 3-methyl-1, 5-pentanediol, diethylpentanediol, trimethylpentanediol, diethylene glycol, ethylene glycol, diethylene glycol, cyclohexanediol, and cyclohexanediol with one or more dibasic acids of terephthalic acid, isophthalic acid, phthalic anhydride, 1, 6-adipic acid, succinic acid, sebacic acid, dodecanedioic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, dimer acid, mixed dicarboxylic acids, and 1, 4-cyclohexanedicarboxylic acid. Can be synthesized autonomously, or can be a commercial product. The commercial products have the common brands of CMA-44 and CMA-3044 of Huada chemical, 5400-3000, 5600 and 5400-200 of Changxing chemical, dynacoll series polyol won in Germany and the like.
The polycaprolactone polyol is preferably a polycaprolactone diol obtained by using one or more of 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, diethylene glycol and ethylene glycol as a starter, and may be synthesized autonomously or commercially available products such as placcel series of Japan xylonite and CAPA series of Perstorp.
Preferably, the polycarbonate polyol refers to one or more of polycarbonate diols synthesized from a combination of one or more of 1, 6-hexanediol, 1, 4-butanediol, 1, 4-cyclohexanedimethanol, 1, 5-pentanediol, 1-methylpentanediol, low molecular weight polytetrahydrofuran diol, and caprolactone and one or more of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate. Can be synthesized autonomously, or can be a commercial product. The common brands of the commercial products include Duranol series of Japan Asahi Kasei, UH series of Japan department, UC series, etc.
Preferably, the polyether polyol refers to one or more of polyethylene glycol, polypropylene glycol, polybutylene glycol, polytrimethylene ether glycol, bisphenol a/propylene oxide polyether glycol, bisphenol a/ethylene oxide polyether glycol, copolyether glycol, and the like. Preferred molecular weights are 400-4000, water contents < 0.5%, common commercial designations are DL2000D, DL1000D, DL400, Voranol WD2104, 2110Tb 2120, 2140 of the Dow chemical company, PTMEG2000 of the Korean PTG, PTMEG2000 of the Wawa trade.
Preferably, the tackifying resin is one or more of rosin or modified rosin resin, rosin pentaerythritol ester, petroleum resin, hydrogenated petroleum resin, terpene phenol resin, monomer resin and thermoplastic resin.
Preferably, the thermoplastic resin refers to one of thermoplastic acrylic resin, ethylene-vinyl acetate resin, random polyolefin resin, and the like, or a combination thereof. The preferable thermoplastic acrylic resin has Tg of 45 deg.C or higher, molecular weight of 5000-50 ten thousand, and commonly used brands such as Mitsubishi BR-106, MB-2660, BR-113, MB2592, DYNACOLL AC series 1630, 1750, 1920, etc.; the EVA resin is preferably EVA or modified EVA with a VA value of more than 28% and an MI value of more than 30g/10min (190 ℃, 2.16kg), and the preferred brands are Elvax 40W, 220, 210, 150 and the like of Dupont;
preferably, the isocyanate monomer can be one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and the like. Diphenylmethane diisocyanate is chosen, the common product being pure MDI from Wanhua, Jinhu and BASF.
Preferably, the antioxidant is one or a combination of several of antioxidant 245, antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 1330 and antioxidant 3114. Preferred is Irganon 245, marketed under the trade name BASF, Germany, Lowinox GP45, commercially available from Gekko, USA.
Preferably, the defoamer is a non-silicone polymer defoamer; the preferable brands are BYK one or a combination of more of A-500, A-501, A-550, A-555 and A-535, and the preferable dosage is 0-0.5%.
Preferably, the coupling agent is one of KH550, KH560, KH570, KH590 or a combination thereof.
Preferably, the catalyst is one or more of dibutyltin dilaurate, stannous octoate, tetramethylethylenediamine, triethylenediamine, dimorpholinodiethylether and dimorpholinodiethylether.
The invention also provides a preparation method of the light-moisture dual-curing polyurethane hot melt adhesive based on the modified light alkali-producing agent, which comprises the following steps:
(1) mixing 40-70 parts of polyol, 0.5-10 parts of modified photobase generator, 10-30 parts of tackifying resin, 0.01-3 parts of antioxidant and 0-1 part of defoaming agent to form a reaction mixture, and removing water until the water content of the reaction mixture is below 500 ppm;
(2) cooling to 70-90 ℃, continuously adding 10-30 parts of isocyanate monomer, reacting for 1-3 hours, and detecting the free NCO to a theoretical value of 2% -4%;
(3) and adding 0-2 parts of coupling agent and 0-0.5 part of catalyst, and reacting for 0.5-1 h to prepare the light-moisture dual-curing polyurethane hot melt adhesive.
The parts of the components are parts by weight.
Preferably, the free NCO is detected to a theoretical value of 3% to 4%.
The invention has the beneficial effects that:
(1) the modified photobase generator of the invention has active groups connected to the alkyl branched chain in the molecule, and can react with isocyanate groups to polymerize into the main chain molecular structure, so that the physical mixing of the modified photobase generator and the polyurethane hot melt adhesive system is changed into chemical bonding, and the solubility and the dispersion uniformity of the modified photobase generator in the polyurethane hot melt adhesive system are obviously enhanced. Therefore, the quantum reaction rate of the polymerization reaction is improved, the organic base can be efficiently released, the curing reaction of the reactive polyurethane hot melt adhesive is accelerated, the initial bonding force is improved, and the pressure maintaining time of the conventional reactive polyurethane hot melt adhesive is shortened or even cancelled.
(2) The chromophore in the modified photobase generator molecule of the invention is connected with an active group, and after the reaction, the chromophore can be bonded in a main chain molecular structure, thereby reducing the byproducts dissociated in the reaction system and improving the comprehensive performance of the product, such as: the tensile strength of the polyurethane hot melt adhesive product is enhanced, the adhesion performance to the base material is improved, and the aging resistance is improved.
(3) The modified photobase generator provided by the invention obviously increases the reaction efficiency of the polyurethane hot melt adhesive, so that the photocatalytic reaction can be efficiently carried out without adopting a photosensitizer. Therefore, the photosensitizer which is necessary in the prior formula technology can be omitted in the design of the product formula, and the cost and the complexity of the product composition are reduced.
(4) The process of first illumination and then adhesion enables the reactive polyurethane hot melt adhesive product to be used for connecting opaque substrates, solves the limitation of use of the opaque products, and enlarges the application range of the products.
Detailed Description
The present invention will be further described with reference to the following examples, but the embodiments of the present invention are not limited thereto.
Example 1
(1) Mixing 19 parts by weight of polyhexamethylene adipate diol (winning creation Dynacoll7360) with a molecular weight of 3500, 19 parts by weight of mixed polyester diol (winning creation Dynacoll7255) with a molecular weight of 3500, 29 parts by weight of propylene oxide polyether diol (Lanxingdong large DL2000D) with a molecular weight of 2000, 5 parts by weight of modified photobase generator, 11 parts by weight of thermoplastic propylene ester resin (Mitsubishi BR113), 0.2 parts by weight of antioxidant 1010 and 0.1 part by weight of defoaming agent (BYK-A535) to form a reaction mixture, and stopping when the water content of the reaction mixture is below 500ppm by removing water;
(2) cooling to 80 ℃, continuously adding 16 parts of isocyanate monomer (Wanhua MDI-100), and reacting for 1-3 hours until the theoretical value of free NCO is 3.2-3.3% by detection;
(3) and adding 0.5 part of coupling agent and 0.2 part of catalyst (dimorpholinyl diethyl ether) to react for 0.8h to prepare the light-moisture dual-curing polyurethane hot melt adhesive.
Wherein, the structural formula of the modified photobase generator is as follows:
the modified photobase generator is prepared by the following reaction route:
the specific reaction steps comprise:
(1) 58.5 parts of the raw material B are added into a mixed solution of 19.5 parts of the raw material A and 900 parts of concentrated sulfuric acid in batches according to the mass amount, stirred for 1 hour at room temperature, then stirred for 8 hours at 80 ℃, filtered and dried to obtain an intermediate product C.
(2) And (2) dissolving 10 parts of the intermediate product C in tetrahydrofuran, after the solution is clarified, dropwise adding 10 parts of 1, 8-diazabicycloundecen-7-ene (DBU), pouring out a supernatant after a brown viscous liquid appears at the bottom of a flask, adding a certain volume of tetrahydrofuran for washing, and repeating for three times to obtain the modified photobase generator D.
Example 2
(1) Mixing 20 parts by weight of polyhexamethylene adipate glycol (winning Dynacoll7360) with a molecular weight of 3500, 16 parts by weight of polytetrahydrofuran ether glycol (PTMEG2000) with a molecular weight of 2000, 14 parts by weight of propylene oxide polyether glycol (DL 2000D David Lanxingdong) with a molecular weight of 2000, 5 parts by weight of modified photobase generator, 30 parts by weight of rosin resin (145 rosin resin), 1.5 parts by weight of antioxidant 1010 and 0.5 part by weight of defoaming agent (BYK-A535) to form a reaction mixture, and stopping water removal until the water content of the reaction mixture is below 500 ppm;
(2) cooling to 80 ℃, continuously adding 12 parts of isocyanate monomer (Wanhua MDI-100), and reacting for 1-3 hours until the theoretical value of the free NCO is 2.2-2.3%;
(3) and adding 0.5 part of coupling agent and 0.5 part of catalyst (dimorpholinyl diethyl ether) to react for 0.8h to prepare the light-moisture dual-curing polyurethane hot melt adhesive.
Wherein, the structural formula of the modified photobase generator is as follows:
the modified photobase generator is prepared by the following reaction route:
the specific reaction steps comprise:
(1) 58.5 parts of the raw material B are added into a mixed solution of 19.5 parts of the raw material A and 900 parts of concentrated sulfuric acid in batches according to the mass amount, stirred for 1 hour at room temperature, then stirred for 8 hours at 80 ℃, filtered and dried to obtain an intermediate product C.
(2) Dissolving 10 parts of the intermediate product C, 40 parts of KOH and 3 parts of KI into liquid by using 1600 parts of deionized water, heating the reaction liquid to 110 ℃, dropwise adding 25 parts of the raw material D, reacting and refluxing for 8 hours, cooling to room temperature, and dropwise adding hydrochloric acid (12mol/L) until no precipitate is separated out. The precipitate was recrystallized from ethanol/water 2:8 to yield intermediate E as a pale yellow solid powder.
(3) And (3) dissolving 10 parts of the intermediate product E in tetrahydrofuran, clarifying the solution, dropwise adding 10 parts of 1, 8-diazabicycloundecen-7-ene (DBU), pouring out the supernatant when brown viscous liquid appears at the bottom of the flask, adding a certain volume of tetrahydrofuran for washing, and repeating the steps for three times to obtain the photobase generator F.
Example 3
(1) Mixing 20 parts by weight of polyhexamethylene adipate diol (winning creation Dynacoll7360) with a molecular weight of 3500, 8 parts by weight of mixed polyester diol (winning creation Dynacoll7255) with a molecular weight of 3500, 24 parts by weight of propylene oxide polyether diol (Lanxingdong large DL400D) with a molecular weight of 400, 10 parts by weight of modified photobase generator, 10 parts by weight of thermoplastic propylene ester resin (Mitsubishi BR113), 1.5 parts by weight of antioxidant 1010 and 0.5 part by weight of defoamer (BYK-A535) to form a reaction mixture, and stopping when the water content of the reaction mixture is below 500ppm by removing water;
(2) cooling to 80 ℃, continuously adding 25 parts of isocyanate monomer (Wanhua MDI-100), and reacting for 1-3 hours until the theoretical value of the free NCO is 2.6-2.8%;
(3) and adding 0.5 part of coupling agent and 0.5 part of catalyst (dimorpholinyl diethyl ether) to react for 0.8h to obtain the light-moisture dual-curing polyurethane hot melt adhesive.
Wherein, the structural formula of the modified photobase generator is as follows:
example 4
Mixing 25 parts by weight of polyhexamethylene adipate diol (winning creation Dynacoll7360) with a molecular weight of 3500, 5 parts by weight of polyhexamethylene dodecanoate diol (winning creation Dynacoll7380) with a molecular weight of 3500, 30 parts by weight of propylene oxide polyether diol (Lanxingdong large DL2000D) with a molecular weight of 2000, 5 parts by weight of modified photobase generator, 20 parts by weight of thermoplastic propylene ester resin (Mitsubishi BR113), 0.2 part by weight of antioxidant 1010 and 0.1 part by weight of defoamer (BYK-A535) to form a reaction mixture, and removing water until the water content of the reaction mixture is below 500 ppm;
(2) cooling to 80 ℃, continuously adding 14 parts of isocyanate monomer (Wanhua MDI-100), and reacting for 1-3 hours until the theoretical value of the free NCO is 2.7-2.8%;
(3) and adding 0.5 part of coupling agent and 0.2 part of catalyst (dimorpholinyl diethyl ether), and reacting for 0.8h to obtain the light-moisture dual-curing polyurethane hot melt adhesive.
Example 4 has the same chemical structure as the modified photobase generator in example 1.
Comparative example 1
Mixing 20 parts by weight of polyhexamethylene adipate diol (winning creation Dynacoll7360) with a molecular weight of 3500, 20 parts by weight of mixed polyester diol (winning creation Dynacoll7255) with a molecular weight of 3500, 30 parts by weight of propylene oxide polyether diol (Lanxingdao DL2000D) with a molecular weight of 2000, 12 parts by weight of thermoplastic propylene ester resin (Mitsubishi BR113), 0.2 part by weight of antioxidant 1010 and 0.1 part by weight of defoaming agent (BYK-A535) to form a reaction mixture, and stopping when the water content of the reaction mixture is below 500ppm by removing water;
(2) cooling to 80 ℃, continuously adding 17 parts of isocyanate monomer (Wanhua MDI-100), and reacting for 1-3 hours until the theoretical value of free NCO is 3.5-3.6%;
(3) and adding 0.5 part of coupling agent and 0.2 part of catalyst (dimorpholinyl diethyl ether), and reacting for 0.8h to obtain the light-moisture dual-curing polyurethane hot melt adhesive.
Comparative example 2
Mixing 18.5 parts by weight of polyhexamethylene adipate diol (winning creation Dynacoll7360) with a molecular weight of 3500, 18.5 parts by weight of mixed polyester diol (winning creation Dynacoll7255) with a molecular weight of 3500, 28 parts by weight of propylene oxide polyether diol (Lanxingdong large DL2000D) with a molecular weight of 2000, 5 parts by weight of modified photobase generator, 10 parts by weight of thermoplastic propylene ester resin (Mitsubishi BR113), 0.2 parts by weight of antioxidant 1010, 0.1 part by weight of defoaming agent (BYK-A535), and 3 parts by weight of photosensitizer (2-isopropyl thioxanthone) to form a reaction mixture, and removing water until the water content of the reaction mixture is below 500 ppm;
(2) cooling to 80 ℃, continuously adding 16 parts of isocyanate monomer (Wanhua MDI-100), and reacting for 1-3 hours until the theoretical value of free NCO is 3.4 percent;
(3) and adding 0.5 part of coupling agent and 0.2 part of catalyst (dimorpholinyl diethyl ether), and reacting for 0.8h to obtain the light-moisture dual-curing polyurethane hot melt adhesive.
The structure of the photobase generator added in comparative example 2 is as follows:
comparative example 3
Comparative example 3 differs from example 1 in that the added photobase generator has the following structure:
and (3) performance testing: taking the samples prepared in the examples 1-4 and the comparative examples 1-3 as reference to a single-cylinder rotational viscometer method for measuring the viscosity of GB/T2794-; the tensile strength test is carried out according to GB/T528-2009 determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber; refer to GB/T7124-2008 adhesive tensile shear strength test (rigid material to rigid material).
Table one example and comparative example sample performance test comparison table
From table one it can be found that:
(1) by combining the examples 1-4 and the comparative example 1 (common reactive polyurethane hot melt adhesive), it can be seen that the adhesive strength of the examples 1-4 after being cured for 15min, 30min and 1h after being irradiated by UV light is rapidly improved and far exceeds that of the comparative example 1, and the adhesive strength is close to the maximum adhesive strength value after being cured for 2 h. In contrast, the adhesive strength of comparative example 1 after being cured for 15min, 30min and 1h under UV light is not obviously improved under the same curing conditions. The invention has higher curing speed and higher initial bonding strength compared with the traditional reaction type polyurethane hot melt adhesive.
(2) By combining examples 1-4 with comparative example 2 (polyurethane hot melt adhesive prepared based on unmodified photobase generator and photosensitizer) and comparative example 3 (polyurethane hot melt adhesive prepared based on unmodified photobase generator and no photosensitizer), it can be seen that the adhesive strength of examples 1-4 after being cured by UV light for 15min, 30min and 1h is greatly higher than that of comparative example 2 and comparative example 3. The results of the performance tests of examples 1-4 and comparative examples 2 and 3 demonstrate that: the polyurethane hot melt adhesive prepared based on the modified photobase generator without adding the photosensitizer has higher reaction efficiency than the polyurethane hot melt adhesive prepared based on the unmodified photobase generator with the photosensitizer. Therefore, the polyurethane hot melt adhesive prepared based on the modified photobase generator can achieve the effect of obtaining higher curing speed without adding a photosensitizer. And further illustrates: the polyurethane hot melt adhesive prepared on the basis of the modified photobase generator without adding the photosensitizer has higher curing speed because the molecules of the modified photobase generator contain active groups, so that the solubility and the dispersion uniformity of photobase generator molecules in a polyurethane hot melt adhesive system are greatly improved, the transparency of the system is improved, and the photoreaction efficiency is improved.
Claims (12)
1. A modified photobase generator comprising a compound of formula I:
general formula I:
wherein, at least one of R0, R1 and R2 is selected from the following groups: -OH, - (CH)2)mOH，-O-(CH2)nOH，-(CH2)xCOOH，-O-(CH2)yCOOH, wherein m, n, x and y are integers selected from 1-5.
2. The modified photobase generator of claim 1, wherein at least one of R1 and R2 is selected from the group consisting of: -OH, - (CH)2)mOH，-O-(CH2)nOH，-(CH2)xCOOH，-O-(CH2)yCOOH。
3. The modified photobase generator of claim 2, wherein R1 is-CH2OH。
4. The modified photobase generator of claim 3, wherein the modified photobase generator has the formula:
structural formula 1
5. The modified photobase generator of claim 1, wherein R0 is selected from the group consisting of: -OH, - (CH)2)mOH，-O-(CH2)nOH，-(CH2)xCOOH，-O-(CH2)yCOOH。
6. The modified photobase generator of claim 1, wherein:
the chemical structure of the Chr is selected from one of a general formula II, a structural formula 2 and a structural formula 3;
the structure of formula II is as follows:
wherein X is selected from sulfur atom and oxygen atom, Y is selected from oxygen atom and sulfur atom, s and t are selected from but not limited to 0, 1;
the structure of structural formula 2 is:
the structure of structural formula 3 is:
7. the modified photobase generator of claim 6 wherein Chr has a formula selected from the group consisting of:
8. the modified photobase generator of claim 1 wherein the organic base B has a formula selected from the group consisting of:
9. the modified photobase generator of any of claims 7 or 8, having a structure selected from the group consisting of:
10. a method for preparing any one of the modified photobase generators of claim 9, comprising the steps of:
(1) cyclization reaction: adding the raw material B into a mixed solution of the raw material A and concentrated sulfuric acid, and generating a reaction solution containing the intermediate C under the catalytic action of the concentrated sulfuric acid; then dropwise adding the reaction liquid containing the intermediate C into boiling water to convert the intermediate C into yellow precipitate, wherein the A, B, C substance has a general formula:
at least one of R3, R4, R5 and R6 is selected from-OH, - (CH)2)mOH，-(CH2)xCOOH；
(2) Acid-base neutralization reaction: and dissolving the intermediate C in tetrahydrofuran, and dropwise adding organic alkali to generate the modified photobase generator.
11. The utility model provides a light moisture dual cure polyurethane hot melt adhesive which characterized in that: the modified photobase generator of claim 1; in addition, the components of the light-moisture dual-curing polyurethane hot melt adhesive also comprise a polyol polymer and an isocyanate monomer; the modified photobase generator comprises the following components in percentage by weight: the polymeric polyol: the tackifying resin: the isocyanate monomer is 0.5-10: 40-70: 10-30.
12. The preparation method of the light-moisture dual-curing polyurethane hot melt adhesive according to claim 11, which is characterized by comprising the following steps:
(1) mixing 40-70 parts of the polyhydric alcohol, 0.5-10 parts of the modified photobase generator, 10-30 parts of tackifying resin, 0.01-3 parts of antioxidant and 0-1 part of defoaming agent to form a reaction mixture, and dewatering until the water content of the reaction mixture is less than 500 ppm;
(2) cooling to 70-90 ℃, continuously adding 10-30 parts of isocyanate monomer, and reacting for 1-3 hours until the theoretical value of free NCO reaches 2% -4%;
(3) and adding 0-2 parts of coupling agent and 0-0.5 part of catalyst, and reacting for 0.5-1 h to obtain the light-moisture dual-curing polyurethane hot melt adhesive.
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| CN105938208A (en) * | 2015-03-06 | 2016-09-14 | 三星Sdi株式会社 | Device including barrier layer and patterning method of the barrier layer |
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| CN112724915A (en) * | 2020-12-29 | 2021-04-30 | 厦门韦尔通科技有限公司 | Reactive polyurethane hot melt adhesive with multiple curing modes and preparation method thereof |
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