CN117185928A - Functional acrylic monomer and application thereof in photo-curing coating - Google Patents
Functional acrylic monomer and application thereof in photo-curing coating Download PDFInfo
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- CN117185928A CN117185928A CN202311158103.6A CN202311158103A CN117185928A CN 117185928 A CN117185928 A CN 117185928A CN 202311158103 A CN202311158103 A CN 202311158103A CN 117185928 A CN117185928 A CN 117185928A
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- diol
- acrylate monomer
- functional acrylate
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- 239000000178 monomer Substances 0.000 title claims abstract description 43
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000000576 coating method Methods 0.000 title claims abstract description 13
- 239000011248 coating agent Substances 0.000 title claims abstract description 11
- 238000000016 photochemical curing Methods 0.000 title abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- -1 acrylic ester Chemical class 0.000 claims description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 150000002009 diols Chemical class 0.000 claims description 4
- NDZAIJYMNAJWFJ-UHFFFAOYSA-N 2,9-dimethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(O)C#CC(O)CC(C)C NDZAIJYMNAJWFJ-UHFFFAOYSA-N 0.000 claims description 3
- YGMADCGBQRYLND-UHFFFAOYSA-N oct-4-yne-3,6-diol Chemical compound CCC(O)C#CC(O)CC YGMADCGBQRYLND-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- NUYADIDKTLPDGG-UHFFFAOYSA-N 3,6-dimethyloct-4-yne-3,6-diol Chemical compound CCC(C)(O)C#CC(C)(O)CC NUYADIDKTLPDGG-UHFFFAOYSA-N 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- DPWCXHJKJXRDBZ-UHFFFAOYSA-N dec-5-yne-4,7-diol Chemical compound CCCC(O)C#CC(O)CCC DPWCXHJKJXRDBZ-UHFFFAOYSA-N 0.000 claims description 2
- KDKYADYSIPSCCQ-UHFFFAOYSA-N ethyl acetylene Natural products CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 13
- 238000001723 curing Methods 0.000 abstract description 6
- 125000000304 alkynyl group Chemical group 0.000 abstract description 3
- 238000011417 postcuring Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 14
- 238000005406 washing Methods 0.000 description 12
- 238000005886 esterification reaction Methods 0.000 description 10
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 238000010146 3D printing Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000032050 esterification Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 4
- 229910001626 barium chloride Inorganic materials 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 4
- 235000019796 monopotassium phosphate Nutrition 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- RYIOLWQRQXDECZ-UHFFFAOYSA-N phosphinous acid Chemical compound PO RYIOLWQRQXDECZ-UHFFFAOYSA-N 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 101000720524 Gordonia sp. (strain TY-5) Acetone monooxygenase (methyl acetate-forming) Proteins 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- YFUQYYGBJJCAPR-UHFFFAOYSA-N 1,4-dimethoxybut-2-yne Chemical compound COCC#CCOC YFUQYYGBJJCAPR-UHFFFAOYSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical class C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a functional acrylic monomer and application thereof in a photo-curing coating, wherein the structure of the functional acrylic monomer is shown as a formula (I):wherein R is 1 Selected from H or CH3, R 2 Selected from H, alkyl, methoxy, aryl, m+n=2 to 4, m+n being an integer; the provided functional acrylate monomer contains an alkynyl structure with a pi electron cloud structure, and the structure endows the monomer with solidificationThe post-curing agent has good dimensional stability, almost no shrinkage and rigidity of a curing system, and provides a new material for application fields with requirements on a fine structure.
Description
Technical Field
The application belongs to the field of photo-curing coatings, and particularly relates to a functional acrylic monomer and application thereof in a photo-curing coating.
Background
The photocuring technology is widely applied to the fields of printing and packaging, woodware, plastic, 3D printing and the like for preparing coatings due to the advantages of energy conservation, environmental protection, high curing efficiency, good economic benefit, no VOCs emission and the like.
The photocuring 3D printing technology adopts high-power laser to photocuring liquid resin, can obtain a required three-dimensional shape, can build a high-quality prototype with fine features (thin walls, sharp angles and the like) and complex geometric figures, can reduce the thickness of a layer to 25mm, has the minimum feature size of 50-250 mm, but has limited material and color selection provided by the photocuring 3D printing technology, is usually black, white, gray or transparent material, and has higher requirements on the resin. In addition, since the photo-curing 3D printing technology has high printing precision, the material is required to have higher dimensional stability after curing, and the material has higher dimensional stability after curing and has better application prospect in the application field with fine structural requirements. Therefore, developing a material with high dimensional stability has certain market application value.
Disclosure of Invention
Aiming at the problem of poor dimensional stability of the monomer in the prior art, the application provides a functional acrylic ester monomer, the provided functional acrylic ester monomer contains an alkynyl structure with a pi electron cloud structure, the structure endows the monomer with good dimensional stability after curing, a curing system is hardly contracted and has rigid performance, and a new material is provided for application fields with requirements on a fine structure.
The application aims to provide a functional acrylic ester monomer, the structure of which is shown as a formula (I):
wherein R is 1 Selected from H or CH 3 ，R 2 Selected from H, alkyl, methoxy, aryl, m+n=2 to 4, m+n being an integer.
Preferably, the structure of the functional acrylic ester monomer is shown as a formula (I):
wherein R is 1 Selected from H, R 2 Selected from isopropyl or tert-butyl, m+n=2 to 4, m+n being an integer.
More preferably, the structure of the functional acrylate monomer is shown as a formula (I):
wherein R is 1 Selected from CH 3 ，R 2 Selected from methoxy, phenyl, m+n=2.
The application also provides a preparation method of the functional acrylic ester monomer, which comprises the following steps:
s1, mixing and reacting acetylenic diol, ethylene carbonate and an alkaline catalyst to obtain a low-hydroxyethyl product;
s2, mixing the acrylic compound with a strong acid catalyst, a polymerization inhibitor and a water-carrying agent for reaction to obtain a functional acrylic ester monomer;
the structure of the low-hydroxyethyl product is shown as a formula (II):
the structure of the acrylic compound is shown as a formula (III):
preferably, in S1, the molar ratio of the acetylenic diol to the ethylene carbonate is 1:1.5-6.
Preferably, in S1, the amount of the alkaline catalyst is 1000-5000 ppm of the total reaction raw materials.
Preferably, in S1, the alkyne diol includes at least one of butyne diol, 4-octyne-3, 6-diol, 2, 9-dimethyl-5-decyne-4, 7-diol, 3, 6-dimethyl-4-octyne-3, 6-diol, 5-decyne-4, 7-diol, 1, 2-bis (1, 1' -dicyclohexyl) acetylene.
Preferably, in S1, the basic catalyst includes at least one of potassium hydroxide, sodium hydroxide, and potassium tert-butoxide.
Preferably, in S1, the temperature of the reaction is 80-160 ℃ and the time is 4-12 hours.
Preferably, in S2, the molar ratio of the low-hydroxyl compound to the acrylic compound is 1:2-2.5.
Preferably, in S2, the strong acid catalyst is used in an amount of 1 to 3wt% based on the total reaction raw materials.
Preferably, in S2, the water-carrying agent is used in an amount of 30-50 wt% of the total reaction raw materials.
Preferably, in S2, the amount of the polymerization inhibitor is 1000-3000 ppm of the total reaction raw materials.
Preferably, in S2, the strong acid catalyst includes at least one of trifluoromethanesulfonic acid and methanesulfonic acid.
Preferably, in S2, the polymerization inhibitor includes at least one of para-hydroxyanisole, BHT, copper salt, aluminum salt, phenothiazine.
Preferably, in S2, the water-carrying agent includes at least one of cyclohexane and toluene.
Preferably, in S2, an antioxidant is also added to the reaction.
Preferably, in S2, the antioxidant comprises hypophosphorous acid.
Preferably, in S2, the antioxidant is used in an amount of 0.05-0.3 wt% of the total reaction raw materials.
Preferably, in S2, the reaction temperature is 80-110 ℃ and the reaction time is 8-16 hours.
The application also aims at providing a UV light-cured coating which is prepared from the functional acrylic monomer.
Compared with the prior art, the application has the following beneficial effects:
the functional acrylate monomer contains alkynyl with pi electron structure, the structure has rigidity, the system does not shrink after UV curing, and the functional acrylate monomer has good dimensional stability, and provides a new material for fields with fine structure fineness requirements, such as 3D printing, positioning optical adhesive and optical device manufacturing.
Detailed Description
In order to better understand the technical solutions of the present application, the following description will clearly and completely describe the technical solutions of the embodiments of the present application in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present application without making any inventive effort, shall fall within the scope of the present application.
TPO: diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide;
b-368: polyurethane acrylates purchased from the new materials science limited of bouxing, guangdong;
ACMO: acryloylmorpholine;
TPGDA: tripropylene glycol diacrylate;
4EO-BPADA: ethoxylated bisphenol a diacrylate;
IBOA: isobornyl acrylate;
the starting materials in the examples are all commercially available.
Example 1
The embodiment provides a functional acrylic monomer M 1 The specific process is as follows:
s1.250ml of straight four-neck flask, under the protection of nitrogen and 5MPa, butynediol (1 mol), potassium hydroxide (0.05 g) and ethylene carbonate (1.95 mol) are added, the temperature of the materials is controlled to be 100+/-2 ℃, the temperature is raised to 120 ℃ for continuous reaction after 2 hours, the ethylene carbonate content is determined by adopting a titration method after the reaction for 5 hours (the ethylene carbonate firstly reacts with sodium hydroxide and then adopts barium chloride to precipitate, finally hydrochloric acid is adopted for titration to measure excessive sodium hydroxide, and blank experiments are carried out at the same time, so that the content of the ethylene carbonate is obtained), when the ethylene carbonate is completely reacted, potassium dihydrogen phosphate is added, alkaline substances in the ethylene carbonate are absorbed, and solid impurities are filtered, so that clear transparent colorless liquid A1 is obtained;
s2.500ml of straight four-necked flask is added with acrylic acid (1 mol), clear transparent colorless liquid A1 (0.45 mol), p-hydroxyanisole (0.018 g), cupric chloride (0.05 g), hypophosphorous acid (0.12 g), trifluoromethanesulfonic acid (3.6 g) and cyclohexane (50 g), the temperature is slowly raised to 90 ℃, namely, the water carrying agent is refluxed for 10 hours, an esterification effluent is collected by a water separator, and when the esterification effluent is larger than or equal to the theoretical effluent rate, the esterification reaction is finished. Adding hydroxy phosphine lime to remove impurity acid in the reaction liquid, and filtering; washing with hot water to remove copper chloride in the reactant, washing with hot water for 2 times, and washing with saturated saline water to remove water in the product; adding 500ppm of para-hydroxyanisole, and spin-evaporating to remove the solvent to obtain a functional acrylate monomer M1;
the nuclear magnetic hydrogen spectrum of A1 is as follows:
1 H NMR(CDCl 3 ,400M Hz):4.04(s,4H),3.50～3.60(t,4H),3.30～3.40(t,4H).
the nuclear magnetic hydrogen spectrum of M1 is as follows:
1 H NMR(CDCl 3 ,400M Hz):6.30(d,2H),6.08(tert,2H),5.60(d,2H),4.30(d,4H),4.10(s,4H),3.60(d,4H).
wherein m=1, n=1;
example 2
The embodiment provides a functional acrylic monomer M 2 The specific process is as follows:
s1.500ml of straight four-necked flask, under the protection of nitrogen and 5MPa, adding 4-octyne-3, 6-diol (1 mol), potassium hydroxide (0.1 g) and ethylene carbonate (1.95 mol), controlling the temperature of the materials to be 100+/-2 ℃, heating to 120 ℃ for continuous reaction after 2 hours, determining the content of the ethylene carbonate by adopting a titration method (the ethylene carbonate firstly reacts with sodium hydroxide and then adopts barium chloride to precipitate, finally adopts hydrochloric acid to titrate and measure excessive sodium hydroxide, and simultaneously carries out a blank experiment to determine the content of the ethylene carbonate), adding monopotassium phosphate after the complete reaction of the ethylene carbonate, absorbing alkaline substances therein, and filtering to remove solid impurities to obtain clear transparent colorless liquid A2;
s2.500ml of straight four-necked flask is added with acrylic acid (1.05 mol), clear transparent colorless liquid A2 (0.50 mol), p-hydroxyanisole (0.023 g), copper chloride (0.010 g), hypophosphorous acid (0.26 g), trifluoromethanesulfonic acid (5.6 g) and cyclohexane (82-90 g), the temperature is slowly increased to 90 ℃, namely, the water carrying agent is refluxed for 10 hours, a water knockout vessel is adopted to collect esterified water, and when the esterified water is larger than or equal to the theoretical water yield, the esterification reaction is finished. Adding hydroxy phosphine lime to remove impurity acid in the reaction liquid, and filtering; washing with hot water to remove copper chloride in the reactant, washing with hot water for 2 times, and washing with saturated saline water to remove water in the product; adding 500ppm of para-hydroxyanisole, and spin-evaporating to remove the solvent to obtain a functional acrylate monomer M2;
the nuclear magnetic hydrogen spectrum of A2 is as follows:
1 H NMR(CDCl 3 ,400M Hz):3.90(t,2H),3.50～3.60(t,8H),1.65～1.62(dd,4H)，0.90～0.88(t,6H).
the nuclear magnetic hydrogen spectrum of M2 is as follows:
1 H NMR(CDCl 3 ,400M Hz):6.27(d,2H),6.05(tert,2H),5.63(d,2H),4.32(d,4H),3.88(t,2H)，3.68(t,4H),1.67(dd,4H),0.96(t,6H).
where m=1, n=1.
Example 3
S1.250ml of straight four-neck flask, 2, 9-dimethyl-5-decyne-4, 7-diol (1 mol), potassium hydroxide (0.1 g) and ethylene carbonate (1.95 mol) are added under the protection of nitrogen and 5MPa, the temperature of the materials is controlled to be 100+/-2 ℃, the reaction is carried out for 2 hours, the temperature is increased to 120 ℃ for continuous reaction, the titration method is adopted to measure the content of ethylene carbonate (the ethylene carbonate is firstly reacted with sodium hydroxide and then precipitated by barium chloride, finally, hydrochloric acid is adopted to titrate and measure excessive sodium hydroxide, and blank experiments are carried out simultaneously, so that the content of ethylene carbonate is obtained), after the complete reaction of ethylene carbonate is completed, potassium dihydrogen phosphate is added, alkaline substances in the ethylene carbonate are absorbed, and solid impurities are filtered and clear and transparent colorless liquid A3 is obtained;
into a straight four-necked flask of S2.500ml, acrylic acid (1.01 mol), clear transparent colorless liquid A3 (0.5 mol), p-hydroxyanisole (0.032 g), copper chloride (0.012 g), hypophosphorous acid (0.40 g), trifluoromethanesulfonic acid (4.05 g) and cyclohexane (96 g) are added, the temperature is slowly raised to 90 ℃, namely, a water carrying agent is refluxed for 10 hours, an esterification effluent is collected by a water separator, and when the esterification effluent is greater than or equal to the theoretical effluent rate, the esterification reaction is ended. Adding hydroxy phosphine lime to remove impurity acid in the reaction liquid, and filtering; washing with hot water to remove copper chloride in the reactant, washing with hot water for 2 times, and washing with saturated saline water to remove water in the product; adding 500ppm of para-hydroxyanisole, and spin-evaporating to remove the solvent to obtain a functional acrylate monomer M3;
the nuclear magnetic hydrogen spectrum of A3 is as follows:
1 H NMR(CDCl 3 ,400M Hz):3.86(t,2H),3.52～3.65(t,8H),1.65～1.55(m,6H)，0.90～0.88(d,12H).
the nuclear magnetic hydrogen spectrum of M3 is as follows:
1 H NMR(CDCl 3 ,400M Hz):6.25(d,2H),6.03(tert,2H),5.65(d,2H),4.32(d,4H),3.88(t,2H)，3.68(t,4H),1.67～1.60(dd,6H),0.90(t,12H).
where m=1, n=1.
Example 4
S1.250ml of straight four-neck flask, under the protection of nitrogen and 5MPa, adding 1, 4-dimethoxy-2-butyne (1 mol), potassium hydroxide (0.1 g) and ethylene carbonate (1.95 mol), controlling the temperature of the materials to be 100+/-2 ℃, heating to 120 ℃ for continuous reaction after 2 hours, measuring the content of ethylene carbonate by adopting a titration method (the ethylene carbonate reacts with sodium hydroxide firstly and then adopts barium chloride to precipitate, finally adopts hydrochloric acid to titrate and measure excessive sodium hydroxide, and simultaneously carries out a blank experiment, thereby obtaining the content of ethylene carbonate), adding monopotassium phosphate after the complete reaction of the ethylene carbonate, absorbing alkaline substances therein, and filtering to remove solid impurities, thus obtaining clear transparent colorless liquid A4;
into a straight four-necked flask of S2.500ml, methacrylic acid (1.01 mol), clear transparent colorless liquid A3 (0.5 mol), p-hydroxyanisole (0.032 g), copper chloride (0.012 g), hypophosphorous acid (0.40 g), trifluoromethanesulfonic acid (4.05 g) and cyclohexane (120 g) are added, the temperature is slowly raised to 90 ℃, namely, a water carrying agent is refluxed for 10 hours, an esterification effluent is collected by a water separator, and when the esterification effluent is greater than or equal to the theoretical effluent rate, the esterification reaction is ended. Adding hydroxy phosphine lime to remove impurity acid in the reaction liquid, and filtering; washing with hot water to remove copper chloride in the reactant, washing with hot water for 2 times, and washing with saturated saline water to remove water in the product; adding 500ppm of para-hydroxyanisole, and spin-evaporating to remove the solvent to obtain a functional acrylate monomer M4;
the nuclear magnetic hydrogen spectrum of A4 is as follows:
1 H NMR(CDCl 3 ,400M Hz):6.14(s,2H),3.70(t,4H),3.56(t,4H),3.30(s,6H).
the nuclear magnetic hydrogen spectrum of M4 is as follows:
1 H NMR(CDCl 3 ,400M Hz):6.48(s,2H),6.40(s,2H),6.15(s,2H),4.32(t,4H),3.65(t,4H),3.34(s,6H)，2.01(s,6H).
where m=1, n=1.
Preparation of photo-curing coating:
table 1. Composition of the coating.
Preparation and performance test of photo-curing coating: mixing 30g, B-368 50g, TPO 3g and ACMO 20g of the first monomer according to Table 1 to obtain samples of examples 5-8 and comparative examples 1-3 respectively, placing 3D printing formulas (i.e. samples of examples 5-8 and comparative examples 1-3) into a resin tank of a DLP type 3D printer respectively, setting a printing model and parameters, wherein the printing model is a mechanical model, the thickness of a printing layer is 0.05mm, the wavelength is 405nm, and the power of an ultraviolet light source is 6mW/cm 2 The bottom layer is printed for 10s, each layer is 1.5s, a 3D printing mechanical test sample is obtained, and the physical and mechanical property results after post-treatment are shown in Table 2.
Wherein, tensile sample model: determination of tensile Properties of plastics according to GB/T1040.2-2006 part 2: the dimensions of type 1BA as specified in test conditions for molding and extrusion of plastics.
Bending the sample model: the dimensions specified in GB/T9341-2008 determination of Plastic flexural Properties.
Table 2. Coating performance test results for examples 5-8 and comparative examples 1-3.
| Coating material | Viscosity at 30 ℃ (cps) | Tensile Strength (MPa) | Shrinkage (%) | Whether or not the print model is warped |
| Example 5 | 100 | 15.1 | 3.2 | Whether or not |
| Example 6 | 110 | 15.3 | 3.0 | Whether or not |
| Example 7 | 120 | 17.0 | 3.1 | Whether or not |
| Example 8 | 110 | 15.0 | 2.1 | Whether or not |
| Comparative example 1 | 90 | 14.0 | 9.8 | Slightly warp |
| Comparative example 2 | 160 | 15.8 | 8.8 | Whether or not |
| Comparative example 3 | 80 | 15.1 | 7.8 | Whether or not |
As is clear from Table 2, the functional acrylate monomers M1 to M4 prepared in examples 1 to 4 of the present application were used to prepare paints, and the shrinkage of the prepared paints was smaller than that of paints prepared with conventional monomers TPGDA, 4EO-BPADA, IBOA, thus demonstrating that the functional acrylate monomers M1 to M4 prepared in examples 1 to 4 of the present application were used to prepare paints, and the paints had good dimensional stability.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present application and not for limiting the same, and although the present application has been described in detail with reference to the above-mentioned embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made to the specific embodiments of the present application after reading the present specification, and these modifications and variations do not depart from the scope of the application as claimed in the pending claims.
Claims (10)
1. The functional acrylic ester monomer is characterized in that the structure of the functional acrylic ester monomer is shown as a formula (I):
wherein R is 1 Selected from H or CH 3 ，R 2 Selected from H, alkyl, methoxy, aryl, m+n=2 to 4, m+n being an integer.
2. The functional acrylate monomer according to claim 1, wherein the functional acrylate monomer has a structure as shown in formula (i):
wherein R is 1 Selected from H, R 2 Selected from isopropyl or tert-butyl, m+n=2 to 4, m+n being an integer.
3. The functional acrylate monomer according to claim 2, wherein the functional acrylate monomer has a structure as shown in formula (i):
wherein R is 1 Selected from CH 3 ，R 2 Selected from methoxy, phenyl, m+n=2.
4. A method for producing a functional acrylate monomer according to any one of claims 1 to 3, comprising the steps of:
s1, mixing and reacting acetylenic diol, ethylene carbonate and an alkaline catalyst to obtain a low-hydroxyethyl product;
s2, mixing the acrylic compound with a strong acid catalyst, a polymerization inhibitor and a water-carrying agent for reaction to obtain a functional acrylic ester monomer;
the structure of the low-hydroxyethyl product is shown as a formula (II):
the structure of the acrylic compound is shown as a formula (III):
5. the method for producing a functional acrylic monomer according to claim 4, wherein in S1, the molar ratio of the acetylenic diol to the ethylene carbonate is 1:1.5-6;
and/or the dosage of the alkaline catalyst is 1000-5000 ppm of the total reaction raw materials.
6. The method for producing a functional acrylate monomer according to claim 4 wherein in S1, the alkyne diol comprises at least one of butyne diol, 4-octyne-3, 6-diol, 2, 9-dimethyl-5-decyne-4, 7-diol, 3, 6-dimethyl-4-octyne-3, 6-diol, 5-decyne-4, 7-diol, and 1, 2-bis (1, 1' -dicyclohexyl) acetylene;
and/or the alkaline catalyst comprises at least one of potassium hydroxide, sodium hydroxide and potassium tert-butoxide.
7. The method for producing a functional acrylate monomer according to claim 4 wherein the reaction temperature in S1 is 80 to 160℃and the reaction time is 4 to 12 hours.
8. The method for producing a functional acrylic monomer according to claim 4, wherein in S2, the molar ratio of the low-hydroxyl compound to the acrylic compound is 1:2 to 2.5;
and/or the dosage of the strong acid catalyst is 1-3 wt% of the total reaction raw materials;
and/or the dosage of the water-carrying agent is 30-50wt% of the total reaction raw materials;
and/or the dosage of the polymerization inhibitor is 1000-3000 ppm of the total reaction raw materials.
9. The method for producing a functional acrylate monomer according to claim 4 wherein the reaction temperature in S2 is 80 to 110℃and the reaction time is 8 to 16 hours.
10. A UV light curable coating prepared from the functional acrylate monomer according to any one of claims 1 to 3.
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