CN117736688A - Photo/moisture dual-curing reactive polyurethane hot melt adhesive and preparation method thereof - Google Patents
Photo/moisture dual-curing reactive polyurethane hot melt adhesive and preparation method thereof Download PDFInfo
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- JWKHMHXHTMFJKG-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C.OOC(=O)C=C JWKHMHXHTMFJKG-UHFFFAOYSA-N 0.000 claims abstract description 13
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- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 13
- CQHKDHVZYZUZMJ-UHFFFAOYSA-N [2,2-bis(hydroxymethyl)-3-prop-2-enoyloxypropyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(CO)COC(=O)C=C CQHKDHVZYZUZMJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
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- -1 polyoxypropylene Polymers 0.000 claims description 5
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- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- ZMSQJSMSLXVTKN-UHFFFAOYSA-N 4-[2-(2-morpholin-4-ylethoxy)ethyl]morpholine Chemical compound C1COCCN1CCOCCN1CCOCC1 ZMSQJSMSLXVTKN-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 3
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical group CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 claims description 2
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 claims description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 2
- FXIVKZGDYRLHKF-UHFFFAOYSA-N C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 Chemical group C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 FXIVKZGDYRLHKF-UHFFFAOYSA-N 0.000 claims description 2
- GQPVFBDWIUVLHG-UHFFFAOYSA-N [2,2-bis(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(CO)COC(=O)C(C)=C GQPVFBDWIUVLHG-UHFFFAOYSA-N 0.000 claims description 2
- JUDXBRVLWDGRBC-UHFFFAOYSA-N [2-(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(COC(=O)C(C)=C)COC(=O)C(C)=C JUDXBRVLWDGRBC-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims 1
- 238000001723 curing Methods 0.000 description 24
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- LZDXRPVSAKWYDH-UHFFFAOYSA-N 2-ethyl-2-(prop-2-enoxymethyl)propane-1,3-diol Chemical compound CCC(CO)(CO)COCC=C LZDXRPVSAKWYDH-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
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Abstract
The invention discloses a photo/moisture dual curing reaction type polyurethane hot melt adhesive and a preparation method thereof. The reactive polyurethane hot melt adhesive is prepared from the following raw materials in parts by weight: 20-60 parts of liquid polyester polyol, 10-30 parts of polyether polyol, 0.3-4 parts of dihydroxyl diacrylate, 0.002-0.1 part of polymerization inhibitor, 10-45 parts of isocyanate, 0.5-3 parts of adhesion promoter, 0.5-6 parts of hydroxyl triacrylate, 1-5 parts of photoinitiator and 0.01-0.2 part of catalyst. The light/wet dual-curing PUR prepared by the invention has the characteristics of low melt viscosity, high initial bonding strength, long opening time, high temperature and humidity resistance, excellent comprehensive performance and the like.
Description
Technical Field
The invention relates to the technical field of hot melt adhesives, in particular to a light/moisture dual-curing reaction type polyurethane hot melt adhesive and a preparation method thereof.
Background
The reactive polyurethane hot melt adhesive (PUR) mainly refers to polyurethane hot melt adhesive which is crosslinked and solidified by utilizing moisture in air, has the characteristics of common hot melt adhesive and reactive adhesive, has lower application temperature than common hot melt adhesive, has high bonding strength after solidification, heat resistance and good chemical resistance durability, can have good bonding performance on wood, ceramic, fabric, metal, glass, plastic, rubber and other substrates, and has been rapidly developed in the fields of building, automobiles, electronic appliances, wood processing, book binding, food packaging and the like in recent years.
The curing of PUR is divided into two stages, firstly PUR is melt-sized on a substrate, then cooled and condensed to generate initial adhesive strength, and then-NCO in the system is subjected to moisture curing reaction with moisture in the air to reach final viscosity strength. However, the initial bond strength is generally low due to the slower penetration of moisture in the air after PUR sizing, and often requires days for complete curing. In order to improve the initial bonding strength of PUR, methods such as improving the proportion of solid polyester, high Tg resin and high molecular weight thermoplastic resin in a system are mainly adopted at present. However, since polyester has poor hydrolysis resistance, high Tg resins have large brittleness, and large molecular weight thermoplastic resins have large melt viscosity and mostly have no reactivity, increasing initial adhesive strength by these methods tends to cause problems such as high melt viscosity, short open time, poor hydrolysis resistance, unstable adhesive effect, etc. of PUR products.
Disclosure of Invention
Based on this, the present invention aims to provide a reactive polyurethane hot melt adhesive having high initial adhesive strength.
In order to achieve the above purpose, the invention comprises the following technical scheme.
The light/wet dual-curing reaction type polyurethane hot melt adhesive is prepared from the following raw materials in parts by weight: 20-60 parts of liquid polyester polyol, 10-30 parts of polyether polyol, 0.3-4 parts of dihydroxyl diacrylate, 0.002-0.1 part of polymerization inhibitor, 10-45 parts of isocyanate, 0.5-3 parts of adhesion promoter, 0.5-6 parts of hydroxyl triacrylate, 1-5 parts of photoinitiator and 0.01-0.2 part of catalyst.
In some embodiments, the light/moisture dual-curing reactive polyurethane hot melt adhesive is prepared from the following raw materials in parts by weight: 30-55 parts of liquid polyester polyol, 15-30 parts of polyether polyol, 1-3 parts of dihydroxyl diacrylate, 0.005-0.08 part of polymerization inhibitor, 14-25 parts of isocyanate, 1-2.5 parts of adhesion promoter, 1-4.5 parts of hydroxyl triacrylate, 2-4 parts of photoinitiator and 0.05-0.15 part of catalyst.
In some embodiments, the light/moisture dual-curing reactive polyurethane hot melt adhesive is prepared from the following raw materials in parts by weight: 48-52 parts of liquid polyester polyol, 18-22 parts of polyether polyol, 1.5-2.5 parts of dihydroxyl diacrylate, 0.008-0.015 part of polymerization inhibitor, 20-24 parts of isocyanate, 1.5-2.2 parts of adhesion promoter, 3.5-4.5 parts of hydroxyl triacrylate, 2-4 parts of photoinitiator and 0.05-0.15 part of catalyst.
In some embodiments, the dihydroxydiacrylate is one or both of pentaerythritol diacrylate and pentaerythritol dimethacrylate.
In some embodiments, the hydroxy triacrylate is one or both of pentaerythritol triacrylate and pentaerythritol trimethacrylate.
In some of these embodiments, the liquid polyester polyol has a hydroxyl number of from 10 to 112mg KOH/g.
In some of these embodiments, the liquid polyester polyol has a hydroxyl number of 18 to 60mgKOH/g.
In some of these embodiments, the liquid polyester polyol has a hydroxyl number of 18 to 34mgKOH/g.
In some of these embodiments, the liquid polyester polyol is7230 and/or->7250。
In some of these embodiments, the liquid polyester polyol is in a mass ratio of 3 to 5:1, 17230 and method for producing the same7250.
In some of these embodiments, the polyether polyol is a polyoxypropylene diol having a number average molecular weight of 1000-3000.
In some of these embodiments, the isocyanate is one or more of 4,4' -diphenylmethane diisocyanate (MDI), carbodiimide modified MDI, and MDI-50.
In some of these embodiments, the adhesion promoter is one or more of 3-isocyanatopropyl triethoxysilane, 3-isocyanatopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane.
In some of these embodiments, the polymerization inhibitor is 2, 5-di-tert-butylhydroquinone.
In some of these embodiments, the catalyst is at least one of dibutyltin dilaurate (DBTDL), triethylenediamine, dimorpholinodiethyl ether (DMDEE).
In some of these embodiments, the photoinitiator is ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate.
The invention also provides a preparation method of the light/moisture dual-curing reaction type polyurethane hot melt adhesive, which comprises the following steps:
(1) Putting the liquid polyester polyol, polyether polyol and polymerization inhibitor into a reaction kettle, heating to 110-130 ℃, and vacuum dehydrating for 60-180 minutes under stirring, wherein the vacuum degree is-0.095-0.05 MPa;
(2) Adding the isocyanate, stirring and reacting for 60-180 minutes at 110-130 ℃ under the protection of inert gas;
(3) Adding the dihydroxyl diacrylate, stirring and reacting for 30-60 minutes at 110-130 ℃ under the protection of inert gas;
(4) Adding the hydroxy triacrylate, and stirring and reacting for 30-60 minutes at 110-130 ℃ under the protection of inert gas;
(5) Sequentially adding the adhesion promoter, the catalyst and the photoinitiator under the light-shielding condition, and stirring and mixing for 20-40 minutes at 110-130 ℃ under the protection of inert gas;
(6) And (3) maintaining the temperature at 110-130 ℃, vacuumizing until no bubbles appear, and discharging to obtain the product.
In some embodiments, the preparation method of the light/moisture dual curing reaction type polyurethane hot melt adhesive comprises the following steps:
(1) Putting the liquid polyester polyol, polyether polyol and polymerization inhibitor into a reaction kettle, heating to 115-125 ℃, and vacuum dehydrating for 100-140 minutes under stirring, wherein the vacuum degree is-0.095 to-0.08 MPa;
(2) Adding the isocyanate, stirring and reacting for 100-140 minutes at 115-125 ℃ under the protection of inert gas;
(3) Adding the dihydroxyl diacrylate, and stirring and reacting for 35-45 minutes at 115-125 ℃ under the protection of inert gas;
(4) Adding the hydroxy triacrylate, and stirring and reacting for 35-45 minutes at 115-125 ℃ under the protection of inert gas;
(5) Sequentially adding the adhesion promoter, the catalyst and the photoinitiator under the light-shielding condition, and stirring and mixing for 25-35 minutes at 115-125 ℃ under the protection of inert gas;
(6) And (3) maintaining the temperature at 115-125 ℃, vacuumizing until no bubbles appear, and discharging to obtain the product.
According to the photo/wet dual-curing reaction type polyurethane hot melt adhesive (PUR), a proper amount of dihydroxyl diacrylate is sequentially added as a chain extender and a proper amount of hydroxytriacrylate is sequentially added as a blocking agent in the preparation process, carbon-carbon double bonds can be respectively introduced into part of main chain side groups and end groups of polyurethane prepolymer in a photo/wet dual-curing PUR system, and when ultraviolet light curing is carried out, trifunctional carbon-carbon double bonds of side chain multiple functions and end groups can participate in photo-curing reaction, so that the crosslinking density of photo-curing is greatly improved, and better initial bonding strength is provided; meanwhile, after moisture curing, the cured and crosslinked structure of the system is more compact, and the final bonding strength is better; the coupling agent with active groups isocyanic acid or mercapto is added as an adhesion promoter, the coupling agent with mercapto can react with-NCO, the coupling agent with isocyanic acid can participate in moisture curing reaction during PUR moisture curing reaction, both can be introduced into a crosslinking curing system, and simultaneously the attached alkoxy forms hydrogen bond with the surface of the bonded substrate or reacts chemically, so that the adhesion of the PUR to the substrate can be improved; because no raw materials such as crystalline polyester polyol, amorphous polyester polyol, high molecular weight thermoplastic resin and the like are added in the light/moisture dual-curing PUR system, the obtained light/moisture dual-curing PUR has longer opening time and lower melt viscosity.
Compared with the prior art, the invention has the following beneficial effects:
1. the components are reasonably matched according to a certain proportion, so that the prepared light/wet dual-curing PUR has the characteristics of low melt viscosity, high initial bonding strength, long opening time, high temperature and high humidity resistance, excellent comprehensive performance and the like, and has good market prospect.
2. The preparation process of the reactive polyurethane hot melt adhesive is simple, easy to operate and easy to industrialize.
Detailed Description
The technical scheme of the invention is further described by the following specific examples. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The terms "comprising" and "having" and any variations thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, apparatus, article, or device that comprises a list of steps is not limited to the elements or modules listed but may alternatively include additional steps not listed or inherent to such process, method, article, or device.
In the present invention, the term "plurality" means two or more. "and/or", describes an association relationship of an association object, and indicates that there may be three relationships, for example, a and/or B, and may indicate: a exists alone, A and B exist together, and B exists alone. The character "/" generally indicates that the context-dependent object is an "or" relationship.
The viscosity in the present invention refers to the viscosity under the test condition of 25 ℃.
The following are specific examples.
The liquid polyester polyol used in the examples of the present invention was purchased from Yingchuang corporation7200 series, specifically as follows:
7230, hydroxyl value is 27-34 mgKOH/g;
7250, the hydroxyl value is 18-24 mgKOH/g.
Polyether polyol: polyoxypropylene diol (PPG 2000) was purchased from Jiangsu bell mountain chemical Co., ltd, mn=2000, and hydroxyl number of 54-58 mgKOH/g.
Pentaerythritol diacrylate and pentaerythritol triacrylate were purchased from Shanghai Michael Biochemical Co.
The rest raw material components are all common commercial products.
The raw materials used for the photo/moisture dual curing reactive polyurethane hot melt adhesives of the examples and comparative examples of the present invention are shown in the following table 1.
Table 1: the proportions of the components (parts by weight) in each example
Note that: in comparative example 5, the pentaerythritol triacrylate of example 3 was replaced with the polydipentaerythritol pentacrylate in equal amounts; in comparative example 6, the pentaerythritol triacrylate of example 3 was replaced with an equal amount of hydroxyethyl methacrylate; in comparative example 7, pentaerythritol diacrylate in example 3 was replaced with equal amounts of trimethylolpropane monoallyl ether.
The photo/moisture dual curing reaction type polyurethane hot melt adhesives of the above examples 1 to 3 were prepared by the following preparation method, except that the kinds of raw materials and the amounts of raw materials were changed as shown in table 1:
(1) Putting the liquid polyester polyol, polyether polyol and polymerization inhibitor into a reaction kettle, heating to 120 ℃, and vacuum dehydrating for 120 minutes under stirring, wherein the vacuum degree is-0.09 MPa;
(2) Adding isocyanate in N 2 Stirring and reacting for 120 minutes at 120 ℃ under the protection;
(3) Adding dihydroxydiacrylate to N 2 Stirring and reacting for 40 minutes at 120 ℃ under the protection;
(4) Adding hydroxy triacrylate, in N 2 Stirring and reacting for 40 minutes at 120 ℃ under the protection;
(5) Sequentially adding adhesion promoter and catalyst under light-shielding conditionA chemical agent, a photoinitiator, in N 2 Stirring and mixing for 30 minutes at 120 ℃ under the protection;
(6) Vacuum pumping at 120 ℃ until no bubbles appear, and discharging.
The preparation methods of the photo/moisture dual curing reaction type polyurethane hot melt adhesives provided in comparative examples 1 to 4 are different from the above examples in that when the corresponding components are not added, the corresponding steps are omitted; the other steps are the same as in the examples.
The preparation method of the light/moisture dual curing reaction type polyurethane hot melt adhesive provided in comparative examples 5 to 7 is different from the above examples in that the step (4) of comparative example 5 is to replace pentaerythritol triacrylate with polydipentaerythritol pentaacrylate; comparative example 6 step (4) was the substitution of hydroxyethyl methacrylate for pentaerythritol triacrylate; comparative example 7 in step (3), pentaerythritol diacrylate was replaced with trimethylolpropane monoallyl ether; the other steps are the same as in the examples.
And (3) effect test:
taking the reactive polyurethane hot melt adhesives prepared in examples 1-3 and comparative examples 1-7, and testing the melt viscosity of the hot melt adhesives according to HG/T3660-1999; testing the open time of the hot melt adhesive according to HG/T3716-2003; the hot melt adhesive was tested according to GB/T7124-2008 for initial adhesive strength (the sample substrate was Polycarbonate (PC) & PC, tensile shear strength tested after 5min of sample placement after uv irradiation), final adhesive strength (the sample substrate was PC, tensile shear strength tested after 7d of moisture cure at 25 ℃/50% rh after uv irradiation of the sample) and tensile shear strength tested after high temperature and high humidity (the sample substrate was PC, tensile shear strength tested after 7d of moisture cure at 25 ℃/50% rh after uv irradiation of the sample and after 7d of placement at 85 ℃/85% rh).
The test results are shown in Table 2.
TABLE 2 results of reactive polyurethane Hot melt adhesive related Performance test for examples 1-3 and comparative examples 1-7
As can be seen from the comparison of the performances of examples 1 to 3 and comparative examples 1 to 3 in Table 2, examples 1 to 3 of the photo/moisture dual curing reactive polyurethane hot melt adhesives added with pentaerythritol diacrylate and pentaerythritol triacrylate simultaneously have a larger improvement in both initial bonding strength and final bonding strength than comparative examples 1 to 3, and the photo/moisture dual curing reactive polyurethane hot melt adhesives added with pentaerythritol diacrylate and pentaerythritol triacrylate simultaneously have both initial bonding strength and final bonding strength superior to those of the photo/moisture dual curing reactive polyurethane hot melt adhesives added with pentaerythritol diacrylate or pentaerythritol triacrylate alone.
As can be seen from the comparison of the properties of examples 1 to 3 and comparative example 4 in Table 2, examples 1 to 3 with the adhesion promoter added have significantly improved final bond strength and bond strength after high temperature and high humidity, compared with comparative example 4 without the adhesion promoter added.
As can be seen from the comparison of the properties of examples 1-3 and comparative examples 5-7 in Table 2, comparative example 5 replaces the pentaerythritol triacrylate of example 3 with an equal amount of polydipentaerythritol pentacrylate, and the initial bond strength of the resulting polyurethane hot melt adhesive is substantially lower than that of example 3, although it is comparable to that of example 3; comparative example 6 was a similar substitution of hydroxyethyl methacrylate for pentaerythritol triacrylate in example 3, comparative example 7 was a similar substitution of trimethylolpropane monoallyl ether for pentaerythritol diacrylate in example 3, and the initial bond strength and final bond strength of the polyurethane hot melt adhesives obtained in comparative examples 6-7 were much lower than in example 3.
It can be seen that the specific types of chain extender and end capping agent have a great influence on the initial bonding strength and the final bonding strength of the obtained polyurethane hot melt adhesive; the addition of the specific adhesion promoter has obvious promotion effect on the final bonding strength and the bonding strength after high temperature and high humidity. The photo/moisture dual-curing reaction type polyurethane hot melt adhesive prepared by simultaneously adding components such as pentaerythritol diacrylate and pentaerythritol triacrylate and matching with an adhesion promoter in the embodiments 1-3 has the characteristics of low melt viscosity, high initial bonding strength, long open time, high temperature and high humidity resistance, excellent comprehensive performance and the like. Among them, the reactive polyurethane hot melt adhesive of example 3 was most excellent in combination properties.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail, but are not to be construed as limiting the scope of the invention
Is limited by the number of (a). It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The light/wet dual-curing reaction type polyurethane hot melt adhesive is characterized by being prepared from the following raw materials in parts by weight: 20-60 parts of liquid polyester polyol, 10-30 parts of polyether polyol, 0.3-4 parts of dihydroxyl diacrylate, 0.002-0.1 part of polymerization inhibitor, 10-45 parts of isocyanate, 0.5-3 parts of adhesion promoter, 0.5-6 parts of hydroxyl triacrylate, 1-5 parts of photoinitiator and 0.01-0.2 part of catalyst.
2. The light/moisture dual curing reaction type polyurethane hot melt adhesive according to claim 1, which is characterized by being prepared from the following raw materials in parts by weight: 30-55 parts of liquid polyester polyol, 15-30 parts of polyether polyol, 1-3 parts of dihydroxyl diacrylate, 0.005-0.08 part of polymerization inhibitor, 14-25 parts of isocyanate, 1-2.5 parts of adhesion promoter, 1-4.5 parts of hydroxyl triacrylate, 2-4 parts of photoinitiator and 0.05-0.15 part of catalyst.
3. The light/moisture dual curing reaction type polyurethane hot melt adhesive according to claim 2, which is characterized by being prepared from the following raw materials in parts by weight: 48-52 parts of liquid polyester polyol, 18-22 parts of polyether polyol, 1.5-2.5 parts of dihydroxyl diacrylate, 0.008-0.015 part of polymerization inhibitor, 20-24 parts of isocyanate, 1.5-2.2 parts of adhesion promoter, 3.5-4.5 parts of hydroxyl triacrylate, 2-4 parts of photoinitiator and 0.05-0.15 part of catalyst.
4. A light/moisture dual cure reactive polyurethane hot melt adhesive as claimed in any one of claims 1 to 3, wherein said dihydroxy diacrylate is one or both of pentaerythritol diacrylate and pentaerythritol dimethacrylate; and/or the number of the groups of groups,
the hydroxyl triacrylate is one or two of pentaerythritol triacrylate and pentaerythritol trimethacrylate.
5. A light/moisture dual cure reactive polyurethane hot melt adhesive according to any one of claims 1 to 3, wherein the liquid polyester polyol has a hydroxyl value of 10 to 112mgKOH/g, preferably 18 to 60mgKOH/g, more preferably 18 to 34mgKOH/g.
6. The light/moisture dual cure reactive polyurethane hot melt adhesive of claim 5, wherein the liquid polyester polyol is7230 and/or->7250。
7. The light/moisture dual curing reaction type polyurethane hot melt adhesive according to claim 6, wherein the liquid polyester polyol has a mass ratio of 3 to 5:1, 17230 and->7250.
8. A light/moisture dual cure reactive polyurethane hot melt adhesive as claimed in any one of claims 1 to 3, wherein said polyether polyol is a polyoxypropylene diol having a number average molecular weight of 1000 to 3000; and/or the number of the groups of groups,
the isocyanate is one or more of 4,4' -diphenylmethane diisocyanate, carbodiimide modified MDI and MDI-50; and/or the number of the groups of groups,
the adhesion promoter is one or more of 3-isocyanatopropyl triethoxysilane, 3-isocyanatopropyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane and 3-mercaptopropyl triethoxysilane; and/or the number of the groups of groups,
the polymerization inhibitor is 2, 5-di-tert-butylhydroquinone; and/or the number of the groups of groups,
the catalyst is at least one of dibutyl tin dilaurate, triethylenediamine and dimorpholinodiethyl ether; and/or the number of the groups of groups,
the photoinitiator is ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate.
9. A process for preparing a photo/moisture dual cure reactive polyurethane hot melt adhesive as claimed in any one of claims 1 to 8, comprising the steps of:
(1) Putting the liquid polyester polyol, polyether polyol and polymerization inhibitor into a reaction kettle, heating to 110-130 ℃, and vacuum dehydrating for 60-180 minutes under stirring, wherein the vacuum degree is-0.095-0.05 MPa;
(2) Adding the isocyanate, stirring and reacting for 60-180 minutes at 110-130 ℃ under the protection of inert gas;
(3) Adding the dihydroxyl diacrylate, stirring and reacting for 30-60 minutes at 110-130 ℃ under the protection of inert gas;
(4) Adding the hydroxy triacrylate, and stirring and reacting for 30-60 minutes at 110-130 ℃ under the protection of inert gas;
(5) Sequentially adding the adhesion promoter, the catalyst and the photoinitiator under the light-shielding condition, and stirring and mixing for 20-40 minutes at 110-130 ℃ under the protection of inert gas;
(6) And (3) maintaining the temperature at 110-130 ℃, vacuumizing until no bubbles appear, and discharging to obtain the product.
10. The method for preparing the photo/moisture dual curing reaction type polyurethane hot melt adhesive according to claim 9, comprising the following steps:
(1) Putting the liquid polyester polyol, polyether polyol and polymerization inhibitor into a reaction kettle, heating to 115-125 ℃, and vacuum dehydrating for 100-140 minutes under stirring, wherein the vacuum degree is-0.095 to-0.08 MPa;
(2) Adding the isocyanate, stirring and reacting for 100-140 minutes at 115-125 ℃ under the protection of inert gas;
(3) Adding the dihydroxyl diacrylate, and stirring and reacting for 35-45 minutes at 115-125 ℃ under the protection of inert gas;
(4) Adding the hydroxy triacrylate, and stirring and reacting for 35-45 minutes at 115-125 ℃ under the protection of inert gas;
(5) Sequentially adding the adhesion promoter, the catalyst and the photoinitiator under the light-shielding condition, and stirring and mixing for 25-35 minutes at 115-125 ℃ under the protection of inert gas;
(6) And (3) maintaining the temperature at 115-125 ℃, vacuumizing until no bubbles appear, and discharging to obtain the product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311731544.0A CN117736688A (en) | 2023-12-15 | 2023-12-15 | Photo/moisture dual-curing reactive polyurethane hot melt adhesive and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311731544.0A CN117736688A (en) | 2023-12-15 | 2023-12-15 | Photo/moisture dual-curing reactive polyurethane hot melt adhesive and preparation method thereof |
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| CN117736688A true CN117736688A (en) | 2024-03-22 |
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| CN202311731544.0A Pending CN117736688A (en) | 2023-12-15 | 2023-12-15 | Photo/moisture dual-curing reactive polyurethane hot melt adhesive and preparation method thereof |
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| Country | Link |
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| CN (1) | CN117736688A (en) |
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