CN118206947A - Curing method for microwave initiated curing - Google Patents
Curing method for microwave initiated curing Download PDFInfo
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- CN118206947A CN118206947A CN202410326258.4A CN202410326258A CN118206947A CN 118206947 A CN118206947 A CN 118206947A CN 202410326258 A CN202410326258 A CN 202410326258A CN 118206947 A CN118206947 A CN 118206947A
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- curing
- diisocyanate
- hot melt
- melt adhesive
- polyurethane hot
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- 238000001723 curing Methods 0.000 title claims abstract description 44
- 239000004814 polyurethane Substances 0.000 claims abstract description 43
- 239000004831 Hot glue Substances 0.000 claims abstract description 39
- 229920002635 polyurethane Polymers 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 20
- 230000005855 radiation Effects 0.000 claims abstract description 14
- 238000013008 moisture curing Methods 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- 230000003078 antioxidant effect Effects 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 229920005906 polyester polyol Polymers 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 12
- 229920000570 polyether Polymers 0.000 claims description 12
- 229920005862 polyol Polymers 0.000 claims description 12
- 150000003077 polyols Chemical class 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- ZMSQJSMSLXVTKN-UHFFFAOYSA-N 4-[2-(2-morpholin-4-ylethoxy)ethyl]morpholine Chemical compound C1COCCN1CCOCCN1CCOCC1 ZMSQJSMSLXVTKN-UHFFFAOYSA-N 0.000 claims description 10
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 claims description 10
- 150000002009 diols Chemical class 0.000 claims description 10
- -1 polyoxypropylene Polymers 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- 238000004806 packaging method and process Methods 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- 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 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229920005992 thermoplastic resin Polymers 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 229920001610 polycaprolactone Polymers 0.000 claims description 6
- 239000004632 polycaprolactone Substances 0.000 claims description 6
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 claims description 2
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 claims description 2
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 2
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- TWLCPLJMACDPFF-UHFFFAOYSA-N cyclohexane;1,2-diisocyanatoethane Chemical compound C1CCCCC1.O=C=NCCN=C=O TWLCPLJMACDPFF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920005749 polyurethane resin Polymers 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002530 phenolic antioxidant Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 239000000203 mixture Substances 0.000 description 28
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 15
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 238000009472 formulation Methods 0.000 description 7
- 230000000977 initiatory effect Effects 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a curing method for microwave-initiated curing, and relates to the technical field of polyurethane hot melt adhesives. The microwave initiated curing method provided by the invention comprises the following steps: coating polyurethane hot melt adhesive, humidifying the coated material, and assisting in moisture curing through microwave radiation; the microwave frequency in the microwave radiation is 2450+/-5 MHz, and the output power is 800W. The polyurethane hot melt adhesive adopted by the invention is assisted in moisture curing through a specific microwave radiation wave band, so that an excellent curing effect is achieved in a short time, and meanwhile, the polyurethane hot melt adhesive has excellent adhesive property.
Description
The application discloses a polyurethane hot melt adhesive for microwave initiated curing, which is applied for the application of 2022, 01 and 07, CN202210012623.5 and a preparation method and a curing method thereof.
Technical Field
The invention belongs to the technical field of polyurethane hot melt adhesives, and particularly relates to a curing method for microwave-initiated curing.
Background
The reactive moisture-curable polyurethane hot melt adhesive (PUR) has a terminal-NCO polyurethane prepolymer which can react with water molecules adsorbed in the air or on the surface of an adhesive material to form a network structure at room temperature. The adhesive strength, water resistance, heat resistance and chemical resistance of the adhesive after being cured by the reaction with moisture are all superior to those of the traditional hot melt adhesive, and the adhesive is widely used in textile, automobile, woodworking, electronic and other industries.
Although the moisture-cured polyurethane hot melt adhesive has high bonding strength after curing, the curing process is slow, and at least 24 hours or even days are often required to be cured completely to reach the highest strength, so that the requirements of some quick process occasions cannot be met. In recent years, new curing methods have been developed to address this problem, such as the introduction of UV light curing methods. Such methods, which greatly increase the cure rate by initiating an accelerated curing reaction with UV radiation, are not suitable for all materials to be bonded, and have limited application when the bonded materials cannot be cured by UV penetration.
Microwaves are an electromagnetic wave energy form, the frequency is 0.3-300GHz, the electromagnetic wave energy form is widely used in the universe, and materials containing polar molecules can absorb microwave radiation and be rapidly heated, so that great convenience can be provided for our daily life, the electromagnetic wave energy form can be applied to chemical reaction, and the organic reaction process is accelerated; if the curing rate of the PUR is too high, the adhesive layer is overheated and a large number of bubbles are generated, which is unfavorable for the bonding effect. Therefore, how to develop a polyurethane hot melt adhesive capable of being cured by microwave initiation to realize the combination of the excellent performance of the polyurethane hot melt adhesive and the advantage of efficient curing by microwave radiation is a problem to be solved.
Disclosure of Invention
In view of this, the present invention provides a method of curing by microwave initiation, which employs a polyurethane hot melt adhesive cured by microwave initiation, and can accelerate the curing process by a specific microwave radiation band.
The technical scheme for solving the technical problems is as follows:
A method of curing by microwave initiated curing comprising the steps of: coating polyurethane hot melt adhesive, humidifying the coated material, and assisting in moisture curing through microwave radiation; the microwave frequency in the microwave radiation is 2450+/-5 MHz, and the output power is 800W; the polyurethane hot melt adhesive comprises the following raw material components in parts by weight:
The reactive thermoplastic resin is selected from one or more of hydroxyl-terminated polyurethane resin, polycaprolactone resin and hydroxyl-containing acrylic resin; the weight average molecular weight of the reactive thermoplastic resin is 5000-150000g/mol, and the glass transition temperature Tg is-60-80 ℃.
Preferably, the polyether polyol is selected from one or more of polyoxypropylene diol, polyoxyethylene diol, polytrimethylene ether diol and polyoxypropylene triol, and has a hydroxyl value of 50-150mgKOH/g.
Preferably, the polyester polyol is selected from one or more of conventional polyester diol, polycaprolactone diol, and polycarbonate diol, and the hydroxyl value of the polyester polyol is 20 to 120mgKOH/g.
Preferably, the polyester polyol is a polyester polyol formed by polycondensing one or more of ethylene glycol, diethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, 1, 4-cyclohexanedimethanol and 3-methyl-1, 5-pentanediol with one or more of epsilon-caprolactone, 1, 6-adipic acid, phthalic acid, terephthalic acid, isophthalic acid, sebacic acid and dodecanedioic acid.
Preferably, the isocyanate is one or more of diphenylmethane diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, tetramethyl m-xylylene diisocyanate, norbornane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1, 4-cyclohexane diisocyanate, cyclohexane dimethylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate and methylcyclohexyl diisocyanate.
Preferably, the latent curing agent comprises an oxazolidine-based latent curing agent, which is effective in preventing the problem of blistering of the subbing layer due to an excessively fast curing rate.
Preferably, the catalyst is one or more of dimorpholinodiethyl ether, dibutyltin dilaurate, stannous octoate, tetrabutyl titanate and triethylenediamine. More preferably, the catalyst is dimorpholinodiethyl ether. The catalyst is used for catalyzing the reaction of isocyanate groups with active hydrogen atoms.
Preferably, the antioxidant is selected from at least one of hindered phenol antioxidants and phosphite antioxidants. The antioxidant is used for preventing the molecular structure of the adhesive from being damaged due to local overheating in the curing process.
Preferably, the preparation method of the polyurethane hot melt adhesive comprises the following steps:
Step 1: polyether polyol, polyester polyol and reactive thermoplastic resin are put into a reactor, heated and dissolved under normal pressure and stirred uniformly;
Step 2: stirring the reactor for 1-3h at 120-140 ℃ under the vacuum condition of-0.1 Mpa, and cooling to 70-80 ℃ after the water content of the material is lower than 200 ppm;
step 3: under the protection of inert gas, adding isocyanate into a reactor, and stirring and reacting for 1-3h at 90-120 ℃ and-0.1 Mpa;
Step 4: when NCO content of a reaction system reaches theoretical value +/-0.2 w%, adding a latent curing agent, a catalyst and an antioxidant under the protection of inert gas, uniformly stirring under-0.1 Mpa, discharging, sealing and packaging to obtain the polyurethane hot melt adhesive capable of being cured by microwave initiation.
Compared with the prior art, the invention has the following beneficial effects:
(1) The polyurethane hot melt adhesive has moisture curing characteristics, can accelerate the curing process of the terminal-NCO prepolymer after absorbing microwave radiation of a specific wave band, achieves the best strength in a short time, and is suitable for bonding the surfaces of various polar materials;
(2) The polyurethane hot melt adhesive prepared by the invention realizes rapid solidification under the action of microwave radiation, has excellent adhesive property, and is beneficial to accelerating the process flow and improving the economic benefit.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
The polyester polyol is purchased from Yu Xuchuan chemical (Suzhou) Inc., shanghai Critical chemical Co., ltd., and Ying-Critical chemical (Shanghai) Co., ltd., in the examples of the invention; the reactive thermoplastic resin is purchased from Shanghai gold soup plastic technology Co., ltd, shanghai Boril chemical Co., ltd and Shanghai Hui chemical Co., ltd respectively; incozol EH is selected as the oxazolidine latent fixing agent. The antioxidants selected are the commercial products of hindered phenol antioxidant 1076 and phosphite antioxidant 168.
Example 1 preparation of polyurethane Hot melt adhesive
Table 1 raw material formulation used in example 1
According to the raw material proportion and the composition in the table 1, polyether polyol, polyester polyol and thermoplastic polyurethane resin are added into a reactor, heated and stirred uniformly, and kept at 140 ℃ for 2 hours; cooling the reactor to 70 ℃ after the water content of the materials is lower than 200 ppm; after diphenylmethane diisocyanate MDI-100 is added under the protection of nitrogen, the reactor is controlled to stir and react for 2 hours under the pressure of minus 0.1Mpa and the temperature of 100 ℃ until NCO percent reaches theoretical value +/-0.2 w%; under the protection of nitrogen, oxazolidine Incozol EH, DMDEE and an antioxidant mixture are added, wherein the antioxidant mixture consists of an antioxidant 1076 and an antioxidant 168, and the proportion of the antioxidant 1076 to the antioxidant 168 is 1:1 to 3:1, a step of; continuously stirring uniformly under-0.1 Mpa, discharging, and sealing and packaging to obtain the polyurethane hot melt adhesive.
Example 2 preparation of polyurethane Hot melt adhesive
TABLE 2 raw material formulation used in example 2
According to the raw material proportion and the composition in the table 2, polyether polyol, polyester polyol and acrylic resin are added into a reactor, heated and stirred uniformly, and kept at 140 ℃ for 2 hours; cooling the reactor to 70 ℃ after the water content of the materials is lower than 200 ppm; after diphenylmethane diisocyanate is added under the protection of nitrogen, the reactor is controlled to stir and react for 2 hours at minus 0.1Mpa and 100 ℃ until NCO% reaches theoretical value +/-0.2 w%; under the protection of nitrogen, oxazolidine Incozol EH, DMDEE and an antioxidant mixture are added, wherein the antioxidant mixture consists of an antioxidant 1076 and an antioxidant 168, and the proportion of the antioxidant 1076 to the antioxidant 168 is 1:1 to 3:1, a step of; continuously stirring uniformly under-0.1 Mpa, discharging, and sealing and packaging to obtain the polyurethane hot melt adhesive.
Example 3 preparation of polyurethane Hot melt adhesive
TABLE 3 raw material formulation for example 3
According to the raw material proportion and the composition in the table 3, polyether polyol, polyester polyol and thermoplastic polyurethane resin are added into a reactor, heated and stirred uniformly, and kept at 140 ℃ for 2 hours; cooling the reactor to 70 ℃ after the water content of the materials is lower than 200 ppm; after diphenylmethane diisocyanate is added under the protection of nitrogen, the reactor is controlled to stir and react for 2 hours at minus 0.1Mpa and 100 ℃ until NCO% reaches theoretical value +/-0.2 w%; under the protection of nitrogen, oxazolidine Incozol EH, DMDEE and an antioxidant mixture are added, wherein the antioxidant mixture consists of an antioxidant 1076 and an antioxidant 168, and the proportion of the antioxidant 1076 to the antioxidant 168 is 1:1 to 3:1, a step of; continuously stirring uniformly under-0.1 Mpa, discharging, and sealing and packaging to obtain the polyurethane hot melt adhesive.
Example 4 preparation of polyurethane Hot melt adhesive
TABLE 4 raw material formulation for example 4
Adding polyether polyol, polyester polyol and polycaprolactone resin into a reactor according to the raw material proportion and the composition in Table 4, heating and stirring uniformly, and keeping at 140 ℃ for 2 hours; cooling the reactor to 70 ℃ after the water content of the materials is lower than 200 ppm; after diphenylmethane diisocyanate is added under the protection of nitrogen, the reactor is controlled to stir and react for 2 hours at minus 0.1Mpa and 100 ℃ until NCO% reaches theoretical value +/-0.2 w%; under the protection of nitrogen, oxazolidine Incozol EH, DMDEE and an antioxidant mixture are added, wherein the antioxidant mixture consists of an antioxidant 1076 and an antioxidant 168, and the proportion of the antioxidant 1076 to the antioxidant 168 is 1:1 to 3:1, a step of; continuously stirring uniformly under-0.1 Mpa, discharging, and sealing and packaging to obtain the polyurethane hot melt adhesive.
Example 5 preparation of polyurethane Hot melt adhesive
TABLE 5 raw material formulation for example 5
Adding polyether polyol, polyester polyol and polycaprolactone resin into a reactor according to the raw material proportion and the composition in Table 5, heating and stirring uniformly, and keeping at 140 ℃ for 2 hours; cooling the reactor to 70 ℃ after the water content of the materials is lower than 200 ppm; after diphenylmethane diisocyanate is added under the protection of nitrogen, the reactor is controlled to stir and react for 2 hours at minus 0.1Mpa and 100 ℃ until NCO% reaches theoretical value +/-0.2 w%; under the protection of nitrogen, oxazolidine Incozol EH, DMDEE and an antioxidant mixture are added, wherein the antioxidant mixture consists of an antioxidant 1076 and an antioxidant 168, and the proportion of the antioxidant 1076 to the antioxidant 168 is 1:1 to 3:1, a step of; continuously stirring uniformly under-0.1 Mpa, discharging, and sealing and packaging to obtain the polyurethane hot melt adhesive.
Example 6 preparation of polyurethane Hot melt adhesive
TABLE 6 raw material formulation for example 6
According to the raw material proportion and the composition in Table 6, polyether polyol, polyester polyol and thermoplastic polyurethane resin are added into a reactor, heated and stirred uniformly, and kept at 140 ℃ for 2 hours; cooling the reactor to 70 ℃ after the water content of the materials is lower than 200 ppm; after MDI-100 is added under the protection of nitrogen, the reactor is controlled to stir and react for 2 hours at minus 0.1Mpa and 100 ℃ until the NCO percent reaches theoretical value +/-0.2 w%; under the protection of nitrogen, oxazolidine Incozol EH, DMDEE and an antioxidant mixture are added, wherein the antioxidant mixture consists of an antioxidant 1076 and an antioxidant 168, and the proportion of the antioxidant 1076 to the antioxidant 168 is 1:1 to 3:1, a step of; continuously stirring uniformly under-0.1 Mpa, discharging, and sealing and packaging to obtain the polyurethane hot melt adhesive.
Example 7 preparation of polyurethane Hot melt adhesive
TABLE 7 raw material formulation for example 7
Adding polyether polyol, polyester polyol and acrylic resin into a reactor according to the raw material proportion and the composition in Table 7, heating and stirring uniformly, and keeping at 140 ℃ for 2 hours; cooling the reactor to 70 ℃ after the water content of the materials is lower than 200 ppm; after MDI-100 is added under the protection of nitrogen, the reactor is controlled to stir and react for 2 hours at minus 0.1Mpa and 100 ℃ until the NCO percent reaches theoretical value +/-0.2 w%; under the protection of nitrogen, oxazolidine Incozol EH, DMDEE and an antioxidant mixture are added, wherein the antioxidant mixture consists of an antioxidant 1076 and an antioxidant 168, and the proportion of the antioxidant 1076 to the antioxidant 168 is 1:1 to 3:1, a step of; continuously stirring uniformly under-0.1 Mpa, discharging, and sealing and packaging to obtain the polyurethane hot melt adhesive.
Control group
Two PUR products of quick drying type and slow drying type for textile of a certain company in China are selected as comparison groups, and the serial numbers are PU-1 and PU-2.
Performance testing
The polyurethane hot melt adhesives prepared in the above examples 1to 7 and two commercial PUR products of the control group PU-1 and PU-2 were used for bonding PVC films and polyurethane fabric base materials, respectively. After the polyurethane hot melt adhesive is coated, accelerating the curing process by a microwave oven, wherein the conditions of the microwave oven are as follows: the microwave frequency is 2450+/-5 MHz, the output power is 800W, and all the coated materials are humidified before being cured. The curing time and peel strength for each of the two materials, each achieving the best peel force, were tested using a tensile machine and the specific test results are shown in table 8.
TABLE 8 Performance test results
As shown by the test results of examples 1-7 and the control group in Table 8, the curing rate of the experimental examples 1-7 is obviously accelerated after microwave irradiation of a microwave oven is carried out, and the two substrates of PVC film and spandex are kept with good bonding strength; the comparative commercial products, however, showed an increase in cure rate after microwave irradiation, but were still significantly lower than those of examples 1-7, and had poor adhesion properties, failing to ensure adequate peel strength in a short period of time.
In summary, the polyurethane hot melt adhesive cured by microwave initiation can achieve an excellent curing effect in a short time by microwave radiation assisted moisture curing, and has a better bonding effect.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Variations in various forms will be apparent to those skilled in the art in light of the foregoing description. It is not necessary here nor exhaustive, but rather that all embodiments extend or inspire from this to the scope of the invention.
Claims (8)
1. A method of curing by microwave initiated curing comprising the steps of: coating polyurethane hot melt adhesive, humidifying the coated material, and assisting in moisture curing through microwave radiation; the microwave frequency in the microwave radiation is 2450+/-5 MHz, and the output power is 800W;
The polyurethane hot melt adhesive comprises the following raw material components in parts by weight:
The reactive thermoplastic resin is selected from one or more of hydroxyl-terminated polyurethane resin, polycaprolactone resin and hydroxyl-containing acrylic resin; the weight average molecular weight of the reactive thermoplastic resin is 5000-150000g/mol, and the glass transition temperature Tg is-60-80 ℃.
2. The curing method according to claim 1, wherein the polyether polyol is one or more selected from the group consisting of polyoxypropylene diol, polyoxyethylene diol, polytrimethylene ether diol and polyoxypropylene triol, and the polyether polyol has a hydroxyl value of 50-150mgKOH/g.
3. The curing method of claim 1, wherein the polyester polyol is selected from one or more of a conventional polyester diol, a polycaprolactone diol, and a polycarbonate diol, and the polyester polyol has a hydroxyl value of 20 to 120mgKOH/g.
4. The curing process of claim 1, wherein the isocyanate is one or more of diphenylmethane diisocyanate, toluene diisocyanate, terephthal-diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, tetramethyl-m-xylylene diisocyanate, norbornane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1, 4-cyclohexane diisocyanate, cyclohexane dimethylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, and methylcyclohexyl diisocyanate.
5. The method of curing according to claim 1, wherein the latent curing agent comprises an oxazolidine-based latent curing agent.
6. The method of curing according to claim 1, wherein the catalyst is one or more of dimorpholinodiethyl ether, dibutyltin dilaurate, stannous octoate, tetrabutyl titanate, and triethylenediamine.
7. The curing method of claim 1, wherein the antioxidant is selected from at least one of hindered phenolic antioxidants and phosphite antioxidants.
8. The curing method according to any one of claims 1 to 8, characterized in that the preparation method of the polyurethane hot melt adhesive comprises the following steps:
Step 1: polyether polyol, polyester polyol and reactive thermoplastic resin are put into a reactor, heated and dissolved under normal pressure and stirred uniformly;
Step 2: stirring the reactor for 1-3h at 120-140 ℃ under the vacuum condition of-0.1 Mpa, and cooling to 70-80 ℃ after the water content of the material is lower than 200 ppm;
step 3: under the protection of inert gas, adding isocyanate into a reactor, and stirring and reacting for 1-3h at 90-120 ℃ and-0.1 Mpa;
Step 4: when NCO content of a reaction system reaches theoretical value +/-0.2 w%, adding a latent curing agent, a catalyst and an antioxidant under the protection of inert gas, uniformly stirring under-0.1 Mpa, discharging, and sealing and packaging to obtain the polyurethane hot melt adhesive.
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| US6632873B2 (en) * | 2001-11-19 | 2003-10-14 | Ashland, Inc. | Two-part polyurethane adhesives for structural finger joints and method therefor |
| US7494540B2 (en) * | 2004-12-15 | 2009-02-24 | Dow Global Technologies, Inc. | System for bonding glass into a structure |
| DE102005017912A1 (en) * | 2005-04-18 | 2006-10-19 | Henkel Kgaa | Low temperature hardening of 1-component polyurethane adhesives or sealants for bonding plastics especially in headlamp manufacture involves exposure to microwave irradiation |
| DE102006025769A1 (en) * | 2006-05-31 | 2007-12-06 | Henkel Kgaa | Adhesive / sealant composition with double cure mechanism |
| WO2009061580A1 (en) * | 2007-11-07 | 2009-05-14 | Dow Global Technologies Inc. | Polyurethane adhesive compositions having high filler levels |
| EP2123443A1 (en) * | 2008-05-21 | 2009-11-25 | Alcan Technology & Management Ltd. | Process for manufacturing a flexible laminate for packaging |
| CN107987778B (en) * | 2017-12-08 | 2019-04-12 | 杭州之江有机硅化工有限公司 | A kind of household electrical appliances reaction type polyurethane hot-melt adhesive and preparation method thereof |
| CN109536055B (en) * | 2018-12-06 | 2021-06-04 | 福建中裕新材料技术有限公司 | Lettering film and preparation method thereof |
| CN109777336B (en) * | 2019-01-23 | 2020-04-24 | 杭州之江新材料有限公司 | Reactive polyurethane hot melt adhesive for PVC and preparation method thereof |
| CN110845983B (en) * | 2019-12-19 | 2021-11-19 | 万果新材料科技(上海)有限公司 | Epoxy modified polyurethane hot melt adhesive and preparation method thereof |
| CN112248566B (en) * | 2020-10-22 | 2021-07-06 | 深圳市汇坤科技有限公司 | Anti-blue-light eye protection terminal screen protection film for children |
| CN113337237A (en) * | 2021-05-18 | 2021-09-03 | 旭川化学（苏州）有限公司 | Reactive polyurethane hot melt adhesive for laminating wood-plastic plate and PVC (polyvinyl chloride) film and preparation method thereof |
| CN113736417B (en) * | 2021-09-29 | 2022-09-13 | 韦尔通(厦门)科技股份有限公司 | Polyether ester type polyurethane hot melt adhesive with good heat resistance and preparation method thereof |
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