CN113816963B - Modified photo-alkali generating agent, preparation method thereof and photo-moisture dual-curing polyurethane hot melt adhesive using same - Google Patents
Modified photo-alkali generating agent, preparation method thereof and photo-moisture dual-curing polyurethane hot melt adhesive using same Download PDFInfo
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Abstract
A modified photo-alkali generating agent, a preparation method thereof and photo-moisture dual-curing polyurethane hot melt adhesive using the same. The present invention provides a modified photobase generator comprising a compound represented by the general formula I: general formula I:
wherein at least one of R0, R1 and R2 is selected from the following groups: -OH, - (CH) 2 ) m OH，‑O‑(CH 2 ) n OH，‑(CH 2 ) x COOH，‑O‑(CH 2 ) y COOH, wherein m, n, x, y are selected from integers from 1 to 5. The alkyl branched chain in the modified photobase generator molecule is connected with the active group, and can react with the isocyanate group to polymerize into the main chain molecular structure, so that the physical mixing of the modified photobase generator and the polyurethane hot melt colloid system is changed into chemical bonding, and the solubility and the dispersion uniformity of the photobase generator in the polyurethane hot melt colloid system are obviously enhanced.
Description
Technical Field
The invention belongs to the field of adhesive materials, and particularly relates to a modified photo-alkali generating agent, a preparation method thereof and photo-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 adhesive is widely applied in the fields of consumer electronics, household appliance assembly, fabric adhesion, woodworking adhesion and the like. After the conventional reactive polyurethane hot melt adhesive is applied, the pressure maintaining time is generally longer because the initial adhesive strength of the product is lower, and the pressure maintaining can be stopped only by overcoming the resilience force of the base material through chemical curing. Longer dwell time has both increased the cost of pressurize tool, has reduced the circulation speed of product again, and then has improved user's use cost. Photoinitiators have important roles in many fields, such as coatings, adhesives, dental materials, microelectronic materials, and 3D printing. The photo-alkaline agent (Photobase generator) is a photoinitiator which is newly developed in recent years, is a compound which can release alkaline active substances after being excited by irradiation, and can realize effective alkali catalytic reaction under certain conditions. The base catalyzed photopolymerization reaction system has the advantages of small material polymerization shrinkage, no oxygen inhibition, no corrosion to the base material and the like. In the prior art, a photo-alkali generating agent is introduced into a reactive polyurethane hot melt adhesive, alkali is generated after illumination, and the generated alkali can catalyze isocyanate groups to react with moisture rapidly, so that higher initial bonding strength can be obtained in a shorter time.
However, the conventional photobase generator is an offset compound, cannot be dissolved in a system mainly comprising covalent bonds such as the reactive polyurethane hot melt adhesive, can only be dispersed in the system in a filler form, and seriously affects the uniformity of the dispersion of the photobase generator in the system and the transparency of the system, so that the photobase generator cannot be sufficiently excited to play a role. In addition, besides the organic base with catalytic activity, other products can be dissociated in the system, and the comprehensive performance of the product is objectively reduced.
Disclosure of Invention
The invention aims to provide a modified photo-alkali agent, a preparation method thereof and photo-moisture dual-curing polyurethane hot melt adhesive using the same, and the compatibility of the photo-alkali agent and the polyurethane hot melt adhesive is improved by modifying the photo-alkali agent.
According to a first aspect of the present invention, there is provided a modified photobase generator and a method of preparing the same.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a modified photobase generator comprising a compound represented by the general formula I:
general formula I:
wherein at least one of R0, R1 and R2 is selected from the following groups: -OH, - (CH) 2 ) m OH，-O-(CH 2 ) n OH，-(CH 2 ) x COOH，-O-(CH 2 ) y COOH, wherein m, n, x, y are selected from integers from 1 to 5.
Preferably, at least one of R1 and R2 is selected from the following groups: -OH, - (CH) 2 ) m OH，-O-(CH 2 ) n OH，-(CH 2 ) x COOH，-O-(CH 2 ) y COOH。
Preferably, R1, R2 are selected from the group consisting of-H, -CH 3 。
Preferably, R1 is-CH 2 OH。
Preferably, the modified photobase generator has the structural formula:
preferably, R0 is selected from the following groups: -OH, - (CH) 2 ) m OH，-O-(CH 2 ) n OH，-(CH 2 ) x COOH，-O-(CH 2 ) y COOH。
Preferably, R0 is selected from the group consisting of-H, -CH 3 。
Preferably, the chemical structure of Chr is selected from one of the general formula II, the structural formula 2 and the structural formula 3;
general formula II:
wherein X is selected from the group consisting of sulfur atoms, oxygen atoms, Y is selected from the group consisting of oxygen atoms, sulfur atoms, s, t is 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 formulas:
preferably, the organic base B may be selected from:
1, 8-diazabicyclo undec-7-ene (DBU), 1, 5-diazabicyclo non-5-ene (DBN), triazabicyclo (TBD), tributylamine (TBA), triethylamine (TEA), triethylenediamine, piperidine derivatives, morpholine derivatives, imidazole derivatives, piperazine derivatives, tetramethylalkylenediamines, cyclohexylmethyl tertiary amines, bis (dimethylaminoethyl) ether and base analogues, tris (dimethylaminopropyl) amine, N-dimethylbenzylamine, N-dimethyl (hexadecyl) amine.
Preferably, the organic base B has the structural formula:
preferably, the structure of the modified photobase generator may be selected from compounds of the following structure:
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 the concentrated sulfuric acid, and generating a reaction solution containing an intermediate C under the catalysis of the concentrated sulfuric acid; then the reaction solution of the intermediate C is dropwise added into boiling water to convert the intermediate C into yellow precipitate, wherein the substance A, B, C has the general formula:
at least one of R3, R4, R5 and R6 is selected from-OH, - (CH) 2 ) m OH，-(CH 2 ) x COOH；
(2) And (3) alkali neutralization reaction: dissolving the intermediate C in tetrahydrofuran, and dropwise adding organic base to generate the photobase generator.
Preferably, when at least one of R3, R4, R5, R6 in the above structural formula of 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 a substance D to obtain an intermediate E, wherein the structural formulas corresponding to the substance D and the intermediate E are respectively as follows:
wherein u is an integer from 1 to 5, and at least one of R7, R8, R9 and R10 is selected from O- (CH) 2 ) n OH，-O-(CH 2 ) y COOH；
In the base neutralization reaction: dissolving the intermediate E instead of the intermediate C in tetrahydrofuran, and dropwise adding 1, 8-diazabicyclo undec-7-ene (DBU) to generate the photobase generator.
Preferably, the structure of the photobase generator is:
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 the mixed solution of the raw material A (15-20 parts) and the concentrated sulfuric acid (800-1000 parts) in batches, and stirred for 6-10 hours at 80 ℃ after stirring for one hour at room temperature, filtered and dried to obtain the chemical structure of the intermediate C as follows:
preferably, the above intermediate C (8-13 parts), KOH (35-40 parts) and KI (3-4 parts) are dissolved in deionized water, and the substance D (22-27 parts) is dropwise added under heating, reacted and refluxed, and cooled to room temperature. Dropwise adding hydrochloric acid (12 mol/L) until no precipitate is separated out, and 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 taken and dissolved in tetrahydrofuran, after the solution is clarified, 1, 8-diazabicyclo undec-7-ene (DBU) (7-12 parts) is dropwise added, when brown viscous liquid appears at the bottom of a flask, the supernatant is poured off, and the solution is washed by adding a certain volume of tetrahydrofuran and repeated three times, thus obtaining the modified photobase generator G.
Preferably the modified photobase generator G has the structural formula:
the parts of the components are the parts by weight of the components.
The invention also provides a photo-moisture dual-curing polyurethane hot melt adhesive prepared based on the modified photo-alkali generating agent.
A photo-moisture dual-curing polyurethane hot melt adhesive based on modified photo-alkali generating agent comprises the modified photo-alkali generating agent; the components of the photo-moisture dual-curing polyurethane hot melt adhesive also comprise polyalcohol and isocyanic acid monomer; the modified photobase generator comprises the following components in percentage by weight: polyol: tackifying resin: isocyanate monomer=0.5-10:40-70:10-30: 10 to 30 percent.
Preferably, the photo-moisture dual-curing polyurethane hot melt adhesive based on the modified photo-alkali generator comprises the following raw materials in parts by weight:
preferably, the polyol refers to one or more of polyester polyols, polyether polyols, polyacrylate polyols, polyolefin polyols and bio-based polyols.
Preferably, the polyol has a molecular weight of 500-10000, a water content of <0.5% and an acid value of <1mg KOH/g.
Preferably, the polyester polyol is one or more of conventional polyester polyol, polycaprolactone polyol, polycarbonate polyol obtained by copolymerizing a diol with a diacid.
Preferably, conventional polyester polyols refer to solid or liquid polyester polyols 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 with one or more diacid compositions 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 acid, 1, 4-cyclohexanedicarboxylic acid. Can be synthesized autonomously or by using commercial products. The commercial products are commonly named CMA-44, CMA-3044, 5400-3000, 5600, 5400-200, dynacoll series polyols, which are won by Germany.
Preferably, the polycaprolactone polyol is polycaprolactone diol which takes one or more of 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, diethylene glycol and ethylene glycol as an initiator, can be synthesized autonomously, and can also be a commercially available product, wherein the commercially available product is commonly used in the plastcel series of Japanese cellophane, the CAPA series of Perston company and the like.
Preferably, the polycarbonate polyol refers to one or more of polycarbonate diols synthesized from one or more diol compositions of 1, 6-hexanediol, 1, 4-butanediol, 1, 4-cyclohexanedimethanol, 1, 5-pentanediol, 1-methylpentanediol, low molecular weight polytetrahydrofuran diol, caprolactone and one or more esters of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate. Can be synthesized autonomously or by using commercial products. Common trade marks of commercial products are Duranol series of Asahi Kabushiki Kaisha, UH series of Japanese Kogyo, UC series, and the like.
Preferably, the polyether polyol refers to one or more of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytrimethylene ether glycol, bisphenol A/propylene oxide polyether glycol, bisphenol A/ethylene oxide polyether glycol, and copolyether glycol. Preferred molecular weights are 400-4000, water content <0.5%, common commercial brands are DL2000D, DL1000D, DL400, voranol WD2104, 2110tb,2120, 2140, etc. of the dow chemical, PTMEG2000 of korean PTG, PTMEG2000 of the guanghua industry.
Preferably, the tackifying resin is one or more of rosin or modified rosin resins, pentaerythritol rosin esters, petroleum resins, hydrogenated petroleum resins, terpene phenol resins, monomer resins, and thermoplastic resins.
Preferably, the thermoplastic resin refers to one of thermoplastic propylene resin, ethylene-vinyl acetate resin, random polyolefin resin, etc., or a combination thereof. The preferable thermoplastic acrylic resin preferably has Tg above 45deg.C, and molecular weight of 5000-50 ten thousand, and common brands are Mitsubishi BR-106, MB-2660, BR-113,MB2592,DYNACOLL AC series 1630, 1750, 1920, etc.; EVA resin is preferably EVA with VA value above 28%, MI value above 30g/10min (190 deg.C, 2.16 kg) or modified EVA, and is preferably Elvax 40W,220, 210, 150 etc. of DuPont;
preferably, the isocyanate monomer may be one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and the like. The diphenylmethane diisocyanate is selected, and the common products are pure MDI of Wanhua, jinhu and BASF.
Preferably, the antioxidant is one or more of antioxidant 245, antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 1330 and antioxidant 3114. Irganon 245, commercially available from BASF, germany, lowinox GP45, from Polyya, U.S.A., is preferred.
Preferably, the defoamer is a non-silicone polymer defoamer; the preferred composition is one or more of A-500, A-501, A-550, A-555, A-535 having the BYK designation, preferably in an amount of 0 to 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 dibutyl tin dilaurate, stannous octoate, tetramethyl ethylenediamine, triethylenediamine, dimorpholinodiethyl ether and dimorpholinotriethyl ether.
The invention also provides a preparation method of the photo-moisture dual-curing polyurethane hot melt adhesive based on the modified photo-alkali generator, which comprises the following steps:
(1) Mixing 40-70 parts of poly polyol, 0.5-10 parts of modified photo-alkali generating agent, 10-30 parts of tackifying resin, 0.01-3 parts of antioxidant and 0-1 part of defoamer to form a reaction mixture, and stopping dewatering until the water content of the reaction mixture is below 500ppm;
(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) Adding 0-2 parts of coupling agent, 0-0.5 part of catalyst, and reacting for 0.5-1 h to obtain the photo-moisture dual-curing polyurethane hot melt adhesive.
The parts of the components are weight parts.
Preferably, the free NCO is detected to a theoretical value of 3% to 4%.
The invention has the beneficial effects that:
(1) The alkyl branched chain in the modified photobase generator molecule is connected with the active group, and can react with the isocyanate group to polymerize into the main chain molecular structure, so that the physical mixing of the modified photobase generator and the polyurethane hot melt colloid system is changed into chemical bonding, and the solubility and the dispersion uniformity of the modified photobase generator in the polyurethane hot melt colloid system are obviously enhanced. Therefore, the quantum reaction rate of the polymerization reaction is improved, the organic alkali can be efficiently released, the curing reaction of the reactive polyurethane hot melt adhesive is accelerated, the initial adhesion 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 is connected with active groups, after the reaction, the chromophore can be bonded into a main chain molecular structure, so that byproducts free in a reaction system are reduced, and the comprehensive performance of products is improved, for example: the tensile strength of the polyurethane hot melt adhesive product is enhanced, the adhesion performance to a base material is improved, and the ageing 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 photocatalysis reaction can be efficiently carried out without adopting a photosensitizer. Therefore, the photosensitizer which is indispensable 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 firstly illuminating and then bonding enables the reactive polyurethane hot melt adhesive product to be used for connecting opaque substrates, solves the use limitation of opaque products and expands the application range of the products.
Detailed Description
The present invention will be further described with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
(1) In parts by weight, 19 parts of a polyhexamethylene adipate glycol having a molecular weight of 3500 (winning Dynacoll 7360), 19 parts of a mixed polyester glycol having a molecular weight of 3500 (winning Dynacoll 7255), 29 parts of a propylene oxide polyether glycol having a molecular weight of 2000 (blue eastern large DL 2000D), 5 parts of a modified photobase generator, and 11 parts of a thermoplastic propylene resin (mitsubishi BR 113), 0.2 parts of an antioxidant 1010, 0.1 parts of a defoamer (BYK-a 535), were mixed to form a reaction mixture, and water was removed until the water content of the reaction mixture was 500ppm or less;
(2) Cooling to 80 ℃, continuously adding 16 parts of isocyanate monomer (Wanhua MDI-100), and reacting for 1-3 hours until the free NCO is detected to be 3.2-3.3% of theoretical value;
(3) Adding 0.5 part of coupling agent and 0.2 part of catalyst (dimorpholinodiethyl ether) to react for 0.8h to prepare the photo-moisture double-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) According to the amount of the substances, 58.5 parts of raw material B is added into a mixed solution of 19.5 parts of raw material A and 900 parts of concentrated sulfuric acid in batches, and the mixture is stirred for 1h at room temperature, then stirred for 8h at 80 ℃, filtered and dried to obtain an intermediate product C.
(2) 10 parts of intermediate product C is dissolved in tetrahydrofuran, 10 parts of 1, 8-diazabicyclo undec-7-ene (DBU) is dropwise added after the solution is clarified, the supernatant is poured off when brown viscous liquid appears at the bottom of the flask, and the solution is washed by adding a certain volume of tetrahydrofuran and repeated three times to obtain the modified photobase generator D.
Example 2
(1) 20 parts by weight of a polyhexamethylene adipate glycol (winning Dynacoll 7360) having a molecular weight of 3500, 16 parts by weight of a polytetrahydrofuran ether glycol (PTMEG 2000) having a molecular weight of 2000, 14 parts by weight of a propylene oxide polyether glycol (DL 2000D) having a molecular weight of 2000, 5 parts by weight of a modified photobase generator and 30 parts by weight of a rosin resin (145 rosin resin), 1.5 parts by weight of an antioxidant 1010, and 0.5 part by weight of a defoamer (BYK-a 535) are mixed to form a reaction mixture, and water is removed until the water content of the reaction mixture is 500ppm or less;
(2) Cooling to 80 ℃, continuously adding 12 parts of isocyanate monomer (Wanhua MDI-100), and reacting for 1-3 hours until the free NCO is detected to be 2.2-2.3% of theoretical value;
(3) Adding 0.5 part of coupling agent and 0.5 part of catalyst (dimorpholinodiethyl ether) to react for 0.8h to prepare the photo-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) According to the amount of the substances, 58.5 parts of raw material B is added into a mixed solution of 19.5 parts of raw material A and 900 parts of concentrated sulfuric acid in batches, and the mixture is stirred for 1h at room temperature, then stirred for 8h at 80 ℃, filtered and dried to obtain an intermediate product C.
(2) 10 parts of the intermediate C, 40 parts of KOH and 3 parts of KI are dissolved into liquid by 1600 parts of deionized water, the reaction liquid is heated to 110 ℃, 25 parts of raw material D is dropwise added, the reaction is refluxed for 8 hours, and hydrochloric acid (12 mol/L) is dropwise added until no precipitate is precipitated after cooling to room temperature. The above precipitate was recrystallized from ethanol/water=2:8 to give intermediate E as a pale yellow solid powder.
(3) 10 parts of the intermediate E is dissolved in tetrahydrofuran, 10 parts of 1, 8-diazabicyclo undec-7-ene (DBU) is dropwise added after the solution is clarified, the supernatant is poured off when brown viscous liquid appears at the bottom of the flask, and the solution is washed by adding a certain volume of tetrahydrofuran and repeated three times to obtain the photobase generator F.
Example 3
(1) 20 parts by weight of a polyhexamethylene adipate glycol having a molecular weight of 3500 (winning Dynacoll 7360), 8 parts by weight of a mixed polyester glycol having a molecular weight of 3500 (winning Dynacoll 7255), 24 parts by weight of a propylene oxide polyether glycol having a molecular weight of 400 (blue eastern large DL 400D), 10 parts by weight of a modified photobase generator, and 10 parts by weight of a thermoplastic propylene resin (mitsubishi BR 113), 1.5 parts by weight of an antioxidant 1010, 0.5 part by weight of an antifoaming agent (BYK-a 535) are mixed to form a reaction mixture, and water is removed until the water content of the reaction mixture is 500ppm or less;
(2) Cooling to 80 ℃, continuously adding 25 parts of isocyanate monomer (Wanhua MDI-100), and reacting for 1-3 hours until the free NCO is detected to be 2.6-2.8% of theoretical value;
(3) Adding 0.5 part of coupling agent and 0.5 part of catalyst (dimorpholinodiethyl ether) to react for 0.8h to prepare the photo-moisture double-curing polyurethane hot melt adhesive.
Wherein, the structural formula of the modified photobase generator is as follows:
example 4
25 parts by weight of a polyhexamethylene adipate glycol having a molecular weight of 3500 (winning Dynacoll 7360), 5 parts by weight of a polyhexamethylene dodecanoate glycol having a molecular weight of 3500 (winning Dynacoll 7380), 30 parts by weight of a propylene oxide polyether glycol having a molecular weight of 2000 (blue star east DL 2000D), 5 parts by weight of a modified photobase generator, and 20 parts by weight of a thermoplastic propylene resin (mitsubishi BR 113), 0.2 parts by weight of an antioxidant 1010, 0.1 parts by weight of an antifoaming agent (BYK-a 535) were mixed to form a reaction mixture, and water was removed until the water content of the reaction mixture was 500ppm or less;
(2) Cooling to 80 ℃, continuously adding 14 parts of isocyanate monomer (Wanhua MDI-100), and reacting for 1-3 hours until the free NCO is detected to be 2.7-2.8% of theoretical value;
(3) Adding 0.5 part of coupling agent and 0.2 part of catalyst (dimorpholinodiethyl ether) to react for 0.8h to prepare the photo-moisture dual-curing polyurethane hot melt adhesive.
Example 4 has the same chemical structure as the modified photobase generator of example 1.
Comparative example 1
20 parts by weight of a polyhexamethylene adipate glycol having a molecular weight of 3500 (winning Dynacoll 7360), 20 parts by weight of a mixed polyester glycol having a molecular weight of 3500 (winning Dynacoll 7255), 30 parts by weight of a propylene oxide polyether glycol having a molecular weight of 2000 (blue star DL 2000D), and 12 parts by weight of a thermoplastic propylene resin (mitsubishi BR 113), 0.2 part by weight of an antioxidant 1010, 0.1 part by weight of an antifoaming agent (BYK-a 535) are mixed to form a reaction mixture, and water is removed until the water content of the reaction mixture is 500ppm or less;
(2) Cooling to 80 ℃, continuously adding 17 parts of isocyanate monomer (Wanhua MDI-100), and reacting for 1-3 hours until the free NCO is detected to be 3.5-3.6% of theoretical value;
(3) Adding 0.5 part of coupling agent and 0.2 part of catalyst (dimorpholinodiethyl ether) to react for 0.8h to prepare the photo-moisture dual-curing polyurethane hot melt adhesive.
Comparative example 2
In parts by weight, 18.5 parts of a polyhexamethylene adipate glycol having a molecular weight of 3500 (winning Dynacoll 7360), 18.5 parts of a mixed polyester glycol having a molecular weight of 3500 (winning Dynacoll 7255), 28 parts of a propylene oxide polyether glycol having a molecular weight of 2000 (blue eastern large DL 2000D), 5 parts of a modified photobase generator, 10 parts of a thermoplastic propylene resin (mitsubishi BR 113), 0.2 part of an antioxidant 1010, 0.1 part of an antifoaming agent (BYK-a 535), 3 parts of a photosensitizer (2-isopropylthioxanthone) are mixed to form a reaction mixture, and water is removed until the water content of the reaction mixture is 500ppm or less;
(2) Cooling to 80 ℃, continuously adding 16 parts of isocyanate monomer (Wanhua MDI-100), and reacting for 1-3 hours until the free NCO is detected to be 3.4% of theoretical value;
(3) Adding 0.5 part of coupling agent and 0.2 part of catalyst (dimorpholinodiethyl ether) to react for 0.8h to prepare the photo-moisture dual-curing polyurethane hot melt adhesive.
The photobase generator added in comparative example 2 has the following structure:
comparative example 3
Comparative example 3 differs from example 1 in that the structure of the photobase generator added is as follows:
performance test: the samples prepared in examples 1-4 and comparative examples 1-3 were subjected to viscosity testing by a high temperature viscometer, a 27# rotor and a 120 ℃ reference to a single cylinder rotational viscometer method for measuring viscosity of GB/T2794-2013 adhesive; tensile strength test is carried out by referring to GB/T528-2009 determination of tensile stress strain properties of vulcanized rubber or thermoplastic rubber; the shear strength test was performed with reference to GB/T7124-2008 determination of adhesive tensile shear strength (rigid material to rigid material).
Table one example and comparative example sample performance test comparative table
From table one can be found that:
(1) It can be seen from the combination of examples 1 to 4 and comparative example 1 (ordinary reactive polyurethane hot melt adhesive), that the adhesive strength of examples 1 to 4 after curing for 15min, 30min, and 1h by UV irradiation was rapidly improved and far exceeded comparative example 1, and the adhesive strength at the time of curing for 2h was already close to the maximum adhesive strength value. And the bonding strength of comparative example 1 after being cured for 15min, 30min and 1h under the same curing conditions is not obviously improved. Compared with the traditional reactive polyurethane hot melt adhesive, the invention has higher curing speed and higher initial bonding strength.
(2) In combination with examples 1 to 4 and 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 without photosensitizer added), it can be seen that the adhesive strength of examples 1 to 4 after curing for 15min, 30min, 1h after UV irradiation greatly exceeded that of comparative examples 2 and 3. The results of the performance tests of examples 1 to 4 and comparative examples 2 and 3 demonstrate that: the polyurethane hot melt adhesive prepared without adding the photosensitizer based on the modified photo-alkali generating agent has higher reaction efficiency than the polyurethane hot melt adhesive prepared with the unmodified photo-alkali generating agent and the photosensitizer. Therefore, the polyurethane hot melt adhesive prepared based on the modified photobase generator can achieve the effect of obtaining a faster curing speed without adding a photosensitizer. And further illustrate: the polyurethane hot melt adhesive prepared based on the modified photo-alkaline agent under the condition of no photosensitizer is higher in curing speed, and the modified photo-alkaline agent molecules contain active groups, so that the solubility and the dispersion uniformity of the photo-alkaline agent molecules in the polyurethane hot melt adhesive system are greatly improved, the transparency of the system is improved, and the photoreaction efficiency is improved.
Claims (10)
1. A modified photobase generator comprising a compound of formula i:
general formula I:
in the general formula I, at least one of R0, R1 and R2 is selected from the following groups: -OH, - (CH) 2 ) m OH，
-O-(CH 2 ) n OH，-(CH 2 ) x COOH，-O-(CH 2 ) y COOH, wherein m, n, x, y are selected from integers from 1 to 5;
the chemical structure of the Chr is shown as a general formula II, and the general formula II has the following structure:
in the general formula II, X is selected from sulfur atoms, oxygen atoms, Y is selected from oxygen atoms, sulfur atoms, s and t are selected from but not limited to 0,1 at the same time;
the structural formula of the organic base B is selected from:
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 ) m OH，-O-(CH 2 ) n OH，-(CH 2 ) x COOH，-O-(CH 2 ) y COOH。
3. The modified photobase generator of claim 2, wherein R1 is-CH 2 OH。
4. The modified photobase generator of claim 3, wherein said modified photobase generator has the structural formula:
structure 1
5. The modified photobase generator of claim 1, wherein R0 is selected from the group consisting of: -OH, - (CH) 2 ) m OH，-O-(CH 2 ) n OH，-(CH 2 ) x COOH，-O-(CH 2 ) y COOH。
6. The modified photobase generator of claim 5, wherein said Chr has a formula selected from the group consisting of:
7. the modified photobase generator of any one of claims 1 or 6, having a structure selected from the group consisting of:
8. a method of preparing the modified photobase generator of claim 7, comprising the steps of:
(1) Cyclization reaction: adding the raw material B into the mixed solution of the raw material A and the concentrated sulfuric acid, and generating a reaction solution containing an intermediate C under the catalysis of the concentrated sulfuric acid; the reaction solution containing the intermediate C is then added dropwise to boiling water to convert the intermediate C into a 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 ) m OH，-(CH 2 ) x COOH；
(2) Acid-base neutralization reaction: and dissolving the intermediate C in tetrahydrofuran, and dropwise adding organic base to generate the modified photobase generator.
9. A photo-moisture dual-curing polyurethane hot melt adhesive is characterized in that: a composition comprising the modified photobase generator of claim 1; in addition, the components of the photo-moisture dual-curing polyurethane hot melt adhesive also comprise polyalcohol and isocyanic acid monomers; the modified photobase generator comprises the following components in percentage by weight: the polyol: the tackifying resin: isocyanate monomer=0.5-10:40-70:10-30:10-30.
10. A method for preparing the photo-moisture dual-curing polyurethane hot melt adhesive as claimed in claim 9, which comprises the following steps:
(1) Mixing 40-70 parts of the poly polyol, 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 defoamer to form a reaction mixture, and removing water until the water content of the reaction mixture is less than 500ppm;
(2) Cooling to 70-90 ℃, continuously adding 10-30 parts of the isocyanate monomer, and reacting for 1-3 hours until the theoretical value of free NCO reaches 2% -4%;
(3) Adding 0-2 parts of coupling agent, 0-0.5 part of catalyst, and reacting for 0.5-1 h to obtain the photo-moisture dual-curing polyurethane hot melt adhesive.
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