CN103274967B - Tri-functional polyurethane acrylate, and preparation method and application thereof - Google Patents
Tri-functional polyurethane acrylate, and preparation method and application thereof Download PDFInfo
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 32
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 29
- 150000002148 esters Chemical class 0.000 claims abstract description 29
- 229920000570 polyether Polymers 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 22
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 20
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 16
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 13
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000853 adhesive Substances 0.000 claims abstract description 7
- 230000001070 adhesive effect Effects 0.000 claims abstract description 7
- 239000000976 ink Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 32
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000004927 clay Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000004280 Sodium formate Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 claims description 6
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 6
- 235000019254 sodium formate Nutrition 0.000 claims description 6
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 5
- 235000010235 potassium benzoate Nutrition 0.000 claims description 5
- 239000004300 potassium benzoate Substances 0.000 claims description 5
- 229940103091 potassium benzoate Drugs 0.000 claims description 5
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 5
- 235000010234 sodium benzoate Nutrition 0.000 claims description 5
- 239000004299 sodium benzoate Substances 0.000 claims description 5
- 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 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 238000003825 pressing Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000003848 UV Light-Curing Methods 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 description 15
- 238000001723 curing Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 description 7
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000012043 crude product Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical group COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000011085 pressure filtration Methods 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- -1 aliphatic urethane acrylates Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the field of materials, and relates to tri-functional polyurethane acrylate, and a preparation method and an application thereof. The tri-functional polyurethane acrylate is prepared by the following steps of reacting 2,2-bis(hydroxymethyl)propionic acid with ethylene oxide or propylene oxide in presence of a catalyst to obtain a trihydroxyl polyether ester; and then reacting the trihydroxyl polyether ester with diisocyanate, hydroxyethyl acrylate or hydroxypropyl acrylate. The tri-functional UV-curing polyurethane acrylate has excellent properties such as high hardness, wear resistance, scratch resistance, thermal resistance, weather resistance and the like after being cured, can be used as raw materials for UV coatings, inks and adhesives.
Description
Technical Field
The invention belongs to the field of materials, and relates to 3-functionality-degree polyurethane acrylate, and a preparation method and application thereof.
Background
With the rapid development of science and technology and the strict limitation of environmental regulations on solvents, UV light-cured polymer materials are receiving more and more attention from people. The UV light curing material has the excellent performances of fast curing, low energy consumption, less pollution, high efficiency and the like, so the UV light curing material is widely applied to the fields of coatings, printing, electronic industry and the like, and is rapidly developed in recent years. Polyurethane acrylate (PUA) is an important photocurable oligomer, has excellent properties such as low irritation, high curing speed, high transparency, stretch resistance, high cohesive energy and the like, is widely used in the fields of photocurable ink, coating, adhesive and the like, and is widely applied in developed countries of the united states, japan and europe. In recent years, with the rise of ultraviolet curing technology in China, the novel light curing material has wider and wider application as a raw material of UV coating, printing ink and adhesive, and the usage amount is increased year by year.
Disclosure of Invention
The object of the present invention is to provide a 3-functional urethane acrylate which addresses the above-mentioned deficiencies of the prior art.
Another object of the present invention is to provide a process for the preparation of the 3-functional urethane acrylates.
It is a further object of the present invention to provide the use of the 3-functional urethane acrylates.
The purpose of the invention can be realized by the following technical scheme:
a3-functionality polyurethane acrylate prepared by the following method: trihydroxy polyether ester is first prepared through the reaction of 2, 2-dimethylolpropionic acid and epoxy ethane or epoxy propane under the action of catalyst, and then reacted with diisocyanate and hydroxyethyl acrylate or hydroxypropyl acrylate to prepare 3-functionality polyurethane acrylate.
Wherein,
the first step reaction route is as follows:
when n =2, -R is-H is ethylene oxide reacted with 2, 2-dimethylolpropionic acid; when n =3, -R is-CH3During the reaction, propylene oxide reacts with 2, 2-dimethylolpropionic acid; wherein a + b + c = 4~ 8.
The preparation of trihydroxy polyether ester comprises the following steps: dropwise adding 4-8 mol of ethylene oxide or propylene oxide into 1mol of 2, 2-dimethylolpropionic acid in a high-pressure reaction kettle at 155-165 ℃ under the action of a catalyst for reaction, controlling the reaction pressure at 0.2-0.6MPa, preserving heat for 1-3 hours at 155-165 ℃ after the ethylene oxide or the propylene oxide is dropwise added, cooling to below 80 ℃, adding activated clay, stirring for 30 minutes, and performing circulating filter pressing until the mixture is clear and transparent to obtain trihydroxy polyether ester.
The catalyst is one or a mixture of two or more of sodium formate, potassium formate, sodium benzoate and potassium benzoate in any proportion, and the dosage of the catalyst is 1 to 5 weight percent of the total mass of the 2, 2-dimethylolpropionic acid and the ethylene oxide or the propylene oxide. The dosage of the activated clay is 1 to 5 weight percent of the total mass of the 2, 2-dimethylolpropionic acid and the ethylene oxide or the propylene oxide.
In the 3-functionality-degree polyurethane acrylate, 1mol of trihydroxy polyether ester, 3-3.5 mol of diisocyanate and 3-5 mol of hydroxyethyl acrylate or hydroxypropyl acrylate react at 60-95 ℃ preferably to prepare the 3-functionality-degree polyurethane acrylate.
According to the 3-functionality-degree polyurethane acrylate, 1mol of the prepared trihydroxy polyether ester and 3-3.5 mol of diisocyanate are preferably heated to 60-65 ℃ under the catalysis of dibutyltin dilaurate serving as a catalyst, stirred and react for 2-3 hours in a heat preservation manner to obtain an intermediate compound shown in formula (III), and the intermediate compound shown in formula (III) and 3-5 mol of hydroxyethyl acrylate or hydroxypropyl acrylate are slowly heated to 80-85 ℃ for 0.5-1 hour under the action of a polymerization inhibitor and dibutyltin dilaurate serving as a catalyst, and react for 4-5 hours in a heat preservation manner to obtain the 3-functionality-degree polyurethane acrylate. Wherein the polymerization inhibitor can be p-hydroxyanisole or hydroquinone, the dosage of the polymerization inhibitor is 5000ppm, and the dosage of the catalyst dibutyltin dilaurate is 3000ppm each time.
The diisocyanate is selected from one of TDI, HDI, IPDI, HMDI and MDI.
The second reaction route is as follows:
and (3) carrying out reaction on trihydroxy polyether ester and diisocyanate to obtain an intermediate:
(intermediate (III))
The intermediate reacts with hydroxyethyl acrylate to obtain 3-functionality polyurethane acrylate:
(intermediate (III))
The reaction for preparing trihydroxy polyether ester in the first step is a ring-opening addition reaction (anionic polymerization) of 1 carboxyl and 2 hydroxyls in 2, 2-dimethylolpropionic acid and epoxypropane (ethane), which is a known organic chemical reaction, under the reaction conditions of the invention, the epoxypropane (ethane) is gaseous, the continuous feeding is finished, the reaction is kept at the temperature for 1-3 hours, the pressure in a high-pressure reaction kettle is reduced to be constant, namely the epoxypropane (ethane) is completely reacted, and the conversion rate is more than 99.9%; the second reaction is the reaction of isocyanate groups with hydroxyl groups in diisocyanate, which is a well-known polyurethane (polyurethane) synthesis reaction.
The preparation method of the 3-functionality polyurethane acrylate is prepared by the following steps: trihydroxy polyether ester is prepared by reacting 2, 2-dimethylolpropionic acid with ethylene oxide or propylene oxide under the action of a catalyst, and then reacting with diisocyanate and hydroxyethyl acrylate or hydroxypropyl acrylate to prepare the 3-functionality polyurethane acrylate (namely the compound of the formula (II)).
The preparation method of the trihydroxy polyether ester comprises the following steps: dropwise adding 4-8 mol of ethylene oxide or propylene oxide into 1mol of 2, 2-dimethylolpropionic acid in a high-pressure reaction kettle at 155-165 ℃ under the action of a catalyst for reaction, controlling the reaction pressure at 0.2-0.6MPa, preserving heat for 1-3 hours at 155-165 ℃ after the ethylene oxide or the propylene oxide is dropwise added, cooling to below 80 ℃, adding activated clay, stirring for 30 minutes, and performing circulating pressure filtration until the mixture is clear and transparent to obtain trihydroxy polyether ester (formula (I)).
The catalyst is one or a mixture of two or more of sodium formate, potassium formate, sodium benzoate and potassium benzoate in any proportion, and the dosage of the catalyst is 0.5-3 wt% of the total mass of the 2, 2-dimethylolpropionic acid and the ethylene oxide or the propylene oxide.
According to the preparation method of the 3-functionality polyurethane acrylate, 1mol of the prepared trihydroxy polyether ester reacts with 3-3.5 mol of diisocyanate and 3-5 mol of hydroxyethyl acrylate or hydroxypropyl acrylate at the temperature of 60-95 ℃ to prepare the 3-functionality polyurethane acrylate; the diisocyanate is preferably one of TDI, HDI, IPDI, HMDI and MDI.
The invention relates to the use of 3-functional urethane acrylates for producing UV coatings, inks or adhesives.
Has the advantages that:
the catalyst used for preparing the polyether ester is different from the traditional method, the catalyst used in the traditional method is sodium hydroxide and potassium hydroxide, after the polymerization reaction is finished, phosphoric acid aqueous solution is added for neutralization treatment, and then high vacuum dehydration and filter pressing are carried out to obtain the polyether ester; the invention adopts one or a mixture of two or more than two of sodium formate, potassium formate, sodium benzoate and potassium benzoate in any proportion, after polymerization, acid is not needed to be added, water is not needed to be added for neutralization, high vacuum dehydration is not needed, only activated clay is needed to be added for filtration, filter residue is subjected to water dissolution, catalyst is dissolved, the activated clay is filtered, the water solution of the catalyst is evaporated and crystallized to realize recycling, and the reaction process belongs to green catalysis and clean production.
The invention discloses a novel 3-functionality-degree UV (ultraviolet) photocuring polyurethane acrylate and a preparation method thereof. After being cured, the 3-functionality-degree UV photocuring polyurethane acrylate has high hardness, excellent wear resistance, excellent scratch resistance, excellent heat resistance, excellent weather resistance and the like, and can be used as a raw material of UV coatings, printing ink and adhesives.
Detailed Description
Example 1:
1340 g of 2, 2-dimethylolpropionic acid (C) was charged in a 6L autoclave5H10O4Molecular weight 134), 40 g of sodium formate, heating to 155 ℃, and beginning to drop ethylene oxide (C)2H4O, molecular weight 44) 2200 g, controlling the temperature to 155-165 ℃ and the pressure to 0.2-0.6MPa, dropwise adding for 3-4 hours, preserving the heat for 2-3 hours at 155-165 ℃ after finishing dropping, then cooling to below 80 ℃, and discharging to obtain a crude product; adding 40 g of active clay into the crude product, stirring for 30 minutes, and performing circulating pressure filtration to obtain clear and transparent trihydroxy polyether ester (C)15H30O9Molecular weight 354) 3469.2 g, and has the structure shown in formula (I), wherein: n =2, a + b + c = 5.
Into a 3000mL four-necked flask was charged trihydroxy polyether ester (C)15H30O9The molecular weight is 354) 177 g, IPDI333 g (1.5 mol), dibutyltin dilaurate as a catalyst 0.2 g, heating to 60-65 ℃, stirring, carrying out heat preservation reaction for 2-3 hours, then adding 1 g of p-hydroxyanisole as a polymerization inhibitor, dibutyltin dilaurate as a catalyst 0.2 g, hydroxyethyl acrylate 185 g, slowly heating to 80-85 ℃ for 0.5-1 hour, carrying out heat preservation reaction for 4-5 hours, and discharging to obtain the 3-functionality polyurethane acrylate, wherein the structure is shown as the formula (II):
R1comprises the following steps:
n=2，a+b+c=5，
R2comprises the following steps:
example 2:
1340 g of 2, 2-dimethylolpropionic acid (C) was charged in a 6L autoclave5H10O4Molecular weight 134), 60 g of potassium formate, heating to 155 ℃, and starting to dropwise add propylene oxide (C)3H6O, molecular weight 58) 3480 g, controlling the temperature to 155-165 ℃ and the pressure to 0.2-0.6MPa, dropwise adding for 3-4 hours, keeping the temperature at 155-165 ℃ for 2-3 hours after dropwise adding, then cooling to below 80 ℃, and discharging to obtain a crude product; adding 60 g of active clay into the crude product, stirring for 30 minutes, and performing circulating pressure filtration to obtain clear and transparent trihydroxy polyether ester (C)23H46O10482) 4723.6 g, having the structure shown in formula (I), wherein: n =3, a + b + c = 6.
Into a 3000mL four-necked flask was charged trihydroxy polyether ester (C)23H46O10482) 241 g, 261 g of TDI (toluene diisocyanate, molecular weight 174), 0.2 g of dibutyltin dilaurate serving as a catalyst, heating to 60-65 ℃, stirring, carrying out heat preservation reaction for 2-3 hours, then adding 1 g of p-hydroxyanisole, 0.2 g of dibutyltin dilaurate serving as a catalyst, 185 g of hydroxyethyl acrylate, slowly heating to 80-85 ℃ for 0.5-1 hour, carrying out heat preservation reaction for 4-5 hours, and discharging to obtain the 3-functionality polyurethane acrylate, wherein the structure is shown as a formula (II):
R1comprises the following steps:
n=3，a+b+c=6，
R2comprises the following steps:
example 3
Raw material
UV resin: 3 functional aliphatic urethane acrylate prepared in example 1; difunctional aliphatic urethane acrylates (F5202, science and technology of Jiangsu Ritian).
UV monomer: dipentaerythritol hexaacrylate (DPHA, jiangsu lika); 1, 6-hexanediol diacrylate (HDDA, Jiangsu Rida).
Photoinitiator (2): 1173, Nanjing Waals chemical technology, Inc.
Auxiliary agent: tego432, Tego92, Germany Digao.
Mixing solvent: butyl acetate, toluene and methyl isobutyl ketone in a mass ratio of 1: 1: 1 and mixing.
Apparatus and device
LT-1002 type ultraviolet curing machine, blue sky lamp development Co., Ltd; QFZ type paint film adhesion tester, Tianjin department union materials testing machine factory; RCA paper tape wear-resisting instrument, Shanghai modern environmental engineering technical research institute; a water bath kettle; and (4) a cold-hot circulating device. Preparation of coating
Weighing a certain mass of UV resin, then adding a UV monomer, a photoinitiator and an auxiliary agent, uniformly stirring, and preparing the coating. The coating formulation is shown in Table I.
Table 1: proportion of coating
Preparation and curing of coating films
Selecting an ABS plastic plate of 10cm multiplied by 10cm, firstly spraying a layer of thermoplastic acrylic resin white primer on the surface of the ABS plastic plate, baking the ABS plastic plate for 3 hours at the temperature of 60 ℃, then spraying UV finish on the surface of the ABS plastic plate, wherein the thickness of the coating film is about 20 mu m, curing the ABS plastic plate on a photocuring machine to ensure that the cured film reaches surface dryness, characterizing the ABS plastic plate by a finger-touch dry method, and recording the curing time.
Performance testing
Curing time: the test was conducted by a dry-to-touch method in which the surface of the paint film was touched with a finger and was considered to be cured if it did not feel sticky.
Pencil hardness: the test is carried out according to a GB 6739-86 coating pencil hardness method.
Adhesion force: the test is carried out according to a GB/T1720-88 coating adhesion test method. The classification is 7 grades, the best grade 1 and the worst grade 7.
Wear resistance: RCA test, 175g, 500. + -. 50 times.
Boiling in water: refer to the national standard GB/T1733 "determination of Water resistance of paint film".
Cold and heat cycle resistance:
(1) scope and description: the tendency of plastic paints to crack, due to damp heat cycles or loss of plasticizer, or both, is determined by the alternating exposure of the paint films to hot and cold chambers, and the extent of cracking.
(2) The instrument comprises the following steps: the device comprises a wet and hot box, a freezing box, a color measuring instrument and a grid drawing device.
(3) The determination method comprises the following steps: putting the test sample into an incubator hot box with the relative temperature of 100% and the temperature of 38 ℃ for 24 hours. The sample plates should be placed at an angle of 0-30 degrees from the vertical and the plates should not touch each other during the test. ② after 24h, immediately transferring the sample plate into a freezer at (-23 +/-1.5) DEG C for 20h, wherein the transfer time is not more than 30S at most. Thirdly, the sample plate is taken out and placed for 4 hours at room temperature, so that 48 hours in total are a cycle, and the period can be subjected to stage evaluation. Fourthly, 15 cycles are carried out, and then the appearance, the color and the adhesive force of the sample plate are tested.
(4) The results show that: the coating should be free of cracking, discoloration, adhesion loss, or other defects.
(5) Reference standard: U.S. Standard AAMA615-02 trade Specification, Performance requirements and test methods for high Performance organic coatings for Plastic profiles.(1)
Results and discussion of the Effect of the resin on coating Performance
The UV resin is the main body of the UV coating, and the performance of the UV resin basically determines the main performance of a coating film after being cured. In the experiment, 3 functional group aliphatic polyurethane acrylate and difunctional aliphatic polyurethane acrylate resin are adopted to form different formulas, the dosage of various components is shown in table 1, and the coating performance is shown in table 2.
Table 2: influence of different proportions of 3-functional polyurethane acrylate and difunctional polyurethane acrylate on coating performance
Reference documents:
(1) yu yingying, inspection methods and instruments for paint industry are all the same, Beijing: chemical industry publishers, 2007: 525.
description of additional photoinitiator 1173:
the manufacturer: nanjing Wa chemical technology Co Ltd
Chemical name: 2-hydroxy-2-methyl-1-phenyl-1-propanone
English name: 2-Hydroxy-2-methyl-1-phenyl-propan-1-one
CAS NO：7473-98-5
Molecular formula of C10H12O
Molecular weight 164.2
Chemical structural formula:
the technical indexes are as follows:
appearance: colorless to pale yellow transparent liquid
The purity is more than or equal to 99.0 percent
Boiling point: 80-81 deg.C (centigrade)
The light transmittance is more than or equal to 99.0 percent at 425nm and more than or equal to 99.3 percent at 500nm
Volatile components: less than or equal to 0.2 percent
Ash content is less than or equal to 0.10 percent
The application comprises the following steps:
1173 are suitable for use in acrylic photocurable varnish systems, such as the varnishes of wood, metal, paper, plastics, and the like. 1173 it is particularly recommended that in UV-curable coatings which are resistant to yellowing and which are subjected to long-term exposure to sunlight, 1173 is suitable for use in combination with other photoinitiators, since it is a liquid, very easy to blend, and recommended to add in an amount of 1-4% w/w.
Claims (1)
1. A3-functional urethane acrylate, which is characterized by being prepared by the following method: trihydroxy polyether ester is prepared by the reaction of 2, 2-dimethylolpropionic acid with ethylene oxide or propylene oxide under the action of a catalyst, and then the trihydroxy polyether ester is reacted with diisocyanate and hydroxyethyl acrylate or hydroxypropyl acrylate to prepare 3-functionality polyurethane acrylate; the preparation of the trihydroxy polyether ester comprises the following steps: dropwise adding 4-8 mol of ethylene oxide or propylene oxide into 1mol of 2, 2-dimethylolpropionic acid in a high-pressure reaction kettle at 155-165 ℃ under the action of a catalyst for reaction, controlling the reaction pressure to be 0.2-0.6MPa, preserving heat for 1-3 hours at 155-165 ℃ after the ethylene oxide or the propylene oxide is dropwise added, cooling to be below 80 ℃, adding activated clay, stirring for 30 minutes, and performing circulating filter pressing until the mixture is clear and transparent to obtain trihydroxy polyether ester; the catalyst is one or a mixture of more than one of sodium formate, potassium formate, sodium benzoate and potassium benzoate in any proportion, and the dosage of the catalyst is 0.5-3 wt% of the total mass of the 2, 2-dimethylolpropionic acid and the ethylene oxide or the propylene oxide.
2. The 3-functional urethane acrylate according to claim 1, characterized in that: 1mol of the prepared trihydroxy polyether ester reacts with 3-3.5 mol of diisocyanate and 3-5 mol of hydroxyethyl acrylate or hydroxypropyl acrylate at the temperature of 60-95 ℃ to prepare the 3-functionality polyurethane acrylate.
3. The 3-functional urethane acrylate according to claim 1 or 2, characterized in that: the diisocyanate is selected from one of HDI, IPDI, HMDI and MDI.
4. The process for preparing a 3-functional urethane acrylate according to claim 1, wherein: trihydroxy polyether ester is prepared by the reaction of 2, 2-dimethylolpropionic acid with ethylene oxide or propylene oxide under the action of a catalyst, and then the trihydroxy polyether ester is reacted with diisocyanate and hydroxyethyl acrylate or hydroxypropyl acrylate to prepare 3-functionality polyurethane acrylate; the preparation of the trihydroxy polyether ester comprises the following steps: dropwise adding 4-8 mol of ethylene oxide or propylene oxide into 1mol of 2, 2-dimethylolpropionic acid in a high-pressure reaction kettle at 155-165 ℃ under the action of a catalyst for reaction, controlling the reaction pressure to be 0.2-0.6MPa, preserving heat for 1-3 hours at 155-165 ℃ after the ethylene oxide or the propylene oxide is dropwise added, cooling to be below 80 ℃, adding activated clay, stirring for 30 minutes, and performing circulating filter pressing until the mixture is clear and transparent to obtain trihydroxy polyether ester; the catalyst is one or a mixture of more than one of sodium formate, potassium formate, sodium benzoate and potassium benzoate in any proportion, and the dosage of the catalyst is 0.5-3 wt% of the total mass of the 2, 2-dimethylolpropionic acid and the ethylene oxide or the propylene oxide.
5. The method for preparing a 3-functional urethane acrylate according to claim 4, wherein: 1mol of the prepared trihydroxy polyether ester reacts with 3-3.5 mol of diisocyanate and 3-5 mol of hydroxyethyl acrylate or hydroxypropyl acrylate at the temperature of 60-95 ℃ to prepare the 3-functionality polyurethane acrylate; the diisocyanate is preferably one of HDI, IPDI, HMDI and MDI.
6. Use of the 3-functional urethane acrylates according to claim 1 for the preparation of UV coatings, inks or adhesives.
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| JP6425048B2 (en) * | 2014-03-25 | 2018-11-21 | 日産化学株式会社 | Compound having polymerizable group and crosslinkable group and method for producing the same |
| CN104018352B (en) * | 2014-05-20 | 2016-05-25 | 江苏利田科技股份有限公司 | UV photocuring Camouflage painting and its preparation method and application for a kind of fabric |
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Denomination of invention: A 3-functional polyurethane acrylate and its preparation method and Application Effective date of registration: 20211230 Granted publication date: 20141112 Pledgee: Nantong Branch of Industrial Bank Co.,Ltd. Pledgor: JIANGSU LITIAN TECHNOLOGY Co.,Ltd. Registration number: Y2021980017285 |
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Address after: 226408 Jiangsu city of Nantong province Rudong county new Feng Li Zhen Road No. 120 Patentee after: Jiangsu Litian Technology Co.,Ltd. Address before: 226408 Jiangsu city of Nantong province Rudong county new Feng Li Zhen Road No. 120 Patentee before: JIANGSU LITIAN TECHNOLOGY Co.,Ltd. |