CN114702387A - Isobornyl (meth) acrylate and process for its preparation - Google Patents
Isobornyl (meth) acrylate and process for its preparation Download PDFInfo
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- CN114702387A CN114702387A CN202210407287.4A CN202210407287A CN114702387A CN 114702387 A CN114702387 A CN 114702387A CN 202210407287 A CN202210407287 A CN 202210407287A CN 114702387 A CN114702387 A CN 114702387A
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- isobornyl
- acrylate
- acrylic acid
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 38
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000008569 process Effects 0.000 title claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 41
- 241000779819 Syncarpia glomulifera Species 0.000 claims abstract description 31
- 239000001739 pinus spp. Substances 0.000 claims abstract description 31
- 229940036248 turpentine Drugs 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- 239000003112 inhibitor Substances 0.000 claims abstract description 19
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- 230000035484 reaction time Effects 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 37
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical group C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 24
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 24
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical group C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 22
- 239000007795 chemical reaction product Substances 0.000 claims description 17
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- 238000004519 manufacturing process Methods 0.000 claims description 9
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- 239000012952 cationic photoinitiator Substances 0.000 claims description 8
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 4
- 125000005520 diaryliodonium group Chemical group 0.000 claims description 4
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- 229950000688 phenothiazine Drugs 0.000 claims description 4
- 125000005409 triarylsulfonium group Chemical group 0.000 claims description 3
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- 229920001577 copolymer Polymers 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
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- 238000001228 spectrum Methods 0.000 description 18
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Chemical class C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 14
- 238000009835 boiling Methods 0.000 description 12
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical class CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 12
- PXRCIOIWVGAZEP-UHFFFAOYSA-N Primaeres Camphenhydrat Natural products C1CC2C(O)(C)C(C)(C)C1C2 PXRCIOIWVGAZEP-UHFFFAOYSA-N 0.000 description 9
- 229930006739 camphene Natural products 0.000 description 9
- ZYPYEBYNXWUCEA-UHFFFAOYSA-N camphenilone Natural products C1CC2C(=O)C(C)(C)C1C2 ZYPYEBYNXWUCEA-UHFFFAOYSA-N 0.000 description 9
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- 238000005286 illumination Methods 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical class C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 5
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Chemical class C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 5
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Chemical class C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 5
- 229930006722 beta-pinene Chemical class 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Chemical class C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 5
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- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
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- AWUMFQREGHLKJB-UHFFFAOYSA-N (7-oxocyclohepta-1,3,5-trien-1-yl) 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC1=CC=CC=CC1=O AWUMFQREGHLKJB-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the technical field of photocatalytic organic synthesis, and discloses isobornyl (meth) acrylate and a preparation method thereof. The preparation method comprises the following steps: mixing oleum Terebinthinae, acrylic acid or methacrylic acid, polymerization inhibitor and catalyst uniformly, placing under UV light irradiation, stirring for reaction, and performing rotary evaporation under reduced pressure after reaction. The method adopts a photocatalysis method to prepare the isobornyl (meth) acrylate, has mild reaction conditions, short reaction time, basically no side reaction and by-product, no conditions of high temperature, high pressure and the like, simple separation and purification and easy operation. The invention adopts the natural renewable resource turpentine to prepare the isobornyl (meth) acrylate, opens up a new application direction for the natural renewable resource vegetable oil, improves the economic value of the isobornyl (meth) acrylate, and has good popularization effect on the development of agriculture and forestry economy.
Description
Technical Field
The invention belongs to the technical field of photocatalytic organic synthesis, and particularly relates to isobornyl (meth) acrylate and a preparation method thereof.
Background
Turpentine is a liquid extracted from resin of plant of Pinaceae by distillation or other method, and contains pinene as main ingredient. The pinene has two isomers of alpha-pinene and beta-pinene, and the turpentine contains 58-65% of alpha-pinene and 30% of beta-pinene. Alpha-pinene and beta-pinene can be obtained by fractional distillation of turpentine under reduced pressure. Camphene is an isomer of pinene, is obtained by catalytic isomerization of pinene, and generally adopts super acid as a catalyst. The alpha-pinene is treated with acid to produce Vargner-milweifen rearrangement reaction and can be isomerized into camphene. Beta-pinene is easily isomerized into alpha-pinene by heating, and can also be hydrated and isomerized into camphene. The important application of turpentine in the field of fine chemicals at present is to prepare isobornyl (meth) acrylate, and the preparation method comprises the following steps: firstly, turpentine is subjected to reduced pressure distillation to prepare pinene, then the pinene is isomerized into camphene under the catalysis of super acid, and isobornyl (meth) acrylate is prepared from camphene and (meth) acrylic acid through super acid catalytic addition reaction. Therefore, the prior art preparation of isobornyl (meth) acrylate from turpentine requires a multi-step process, in which at least three distillation operations are performed, with high energy consumption.
Isobornyl (meth) acrylate is an important acrylate monomer, and has a unique bridged ring structure, so that the acrylate monomer has the special physicochemical properties of low viscosity, high boiling point, low surface tension, low shrinkage, high glass transition temperature, low chroma, high refractive index, good hydrophobicity, good compatibility with various resins, solvents and pigments and fillers, low toxicity, nonflammability and the like. At present, isobornyl (meth) acrylate is mainly used as an active diluent in photocuring coatings, printing ink and adhesives, and is characterized in that the hardness of a film-forming substance is increased, the elasticity of the film-forming substance can be maintained and increased, and the gloss, the brilliance, the adhesive force, the leveling property, the friction resistance, the aging resistance, the corrosion resistance and the like of a polymer can be improved. In addition, the high boiling point and low volatility of the isobornyl (meth) acrylate monomer reduce toxicity in application and reduce environmental pollution. When the isobornyl (meth) acrylate is used as a polymerization monomer, the viscosity of the emulsion can be reduced on the basis of ensuring the molecular weight of the polymer and the solid content of the emulsion. Isobornyl (meth) acrylate has a structure in which the double bond of the acrylic moiety is copolymerizable with many other unsaturated monomers by radical polymerization, and the ester alkoxy moiety is a bulky nonpolar bicycloalkyl group which gives strong steric protection to the polymer chain, resulting in excellent UV, water and chemical resistance. The huge nonpolar side group on the polymer chain weakens the acting force between the molecular chains, so that the viscosity of the polymer solution is reduced, and the compatibility with other resins and solvents is improved. Due to these excellent properties, isobornyl (meth) acrylate is becoming more and more popular and the range of applications is expanding. The methods developed so far for synthesizing isobornyl (meth) acrylate generally use a strong acid catalyst under heating, and have problems of long reaction time, low efficiency, uneven heating, and the like.
Disclosure of Invention
The first object of the present invention is to provide a process for producing isobornyl (meth) acrylate, and the second object of the present invention is to provide isobornyl (meth) acrylate produced by the process.
According to a first aspect of the present invention, there is provided a process for producing isobornyl (meth) acrylate, comprising the steps of:
uniformly mixing turpentine, (methyl) acrylic acid, a catalyst and a polymerization inhibitor, placing under UV (ultraviolet) light irradiation, stirring for reaction, and performing rotary evaporation after the reaction is finished to obtain the turpentine-acrylic acid-vinyl acetate copolymer;
the (meth) acrylic acid referred to in the present invention is acrylic acid or methacrylic acid; when the (meth) acrylic acid is acrylic acid, the product obtained is isobornyl acrylate; when the (meth) acrylic acid is methacrylic acid, the resulting product is isobornyl methacrylate.
In some embodiments, the catalyst is a cationic photoinitiator.
The basic action characteristic of the cationic photoinitiator is that the molecules are activated by light to be in an excited state, and the molecules are subjected to serial decomposition reactions to finally generate the super-strong protonic acid. In the invention, pinene in the turpentine is isomerized to generate camphene under the catalysis of a cationic photoinitiator. The electron cloud of the double bond in camphene is affected by a large alkyl group having an electron-repelling effect, the electron cloud density at the double bond increases, and the carbocation ions formed by the reaction with acrylic acid or methacrylic acid are unstable and immediately undergo rearrangement to form isobornyl acrylate or isobornyl methacrylate under the catalytic action of an electrophilic catalyst, which is a mechanism of electrophilic addition reaction of olefins.
In some embodiments, the cationic photoinitiator is at least one of an aryl diazonium salt, a diaryl iodonium salt, a triarylsulfonium salt, an alkyl sulfonium salt, an iron arene salt, a sulfonyloxy ketone, and a triarylsiloxy ether.
In some embodiments, the amount of the catalyst is1 to 10% of the sum of the mass of the turpentine and the mass of the (meth) acrylic acid.
In some embodiments, the molar ratio of turpentine to (meth) acrylic acid is 1: (0.5 to 1.5).
In some embodiments, the polymerization inhibitor is at least one of hydroquinone, p-hydroxyanisole and phenothiazine, and the amount of the polymerization inhibitor is 0.1-0.5% of the mass of the (meth) acrylic acid.
In some embodiments, the power of the UV light is 100W to 500W.
In some embodiments, the stirring speed is 100 to 500r/min, and the stirring reaction time is10 to 30 min.
In some embodiments, the reaction raw materials are added to a transparent reactor, thereby facilitating irradiation of the reaction system with UV light.
In some embodiments, the crude product is subjected to rotary evaporation under reduced pressure to obtain a transparent liquid, i.e., isobornyl acrylate or isobornyl methacrylate.
In some embodiments, when the (meth) acrylic acid is acrylic acid, the reaction product is subjected to rotary evaporation to collect 119-121 ℃ components, and when the (meth) acrylic acid is methacrylic acid, the reaction product is subjected to rotary evaporation to collect 127-129 ℃ components.
The boiling point of the alpha-pinene is 156 ℃, the boiling point of the beta-pinene is 164 ℃, the boiling point of the camphene is 159-160 ℃, the boiling point of the acrylic acid is 140.9 ℃, the boiling point of the methacrylic acid is 163 ℃, the boiling point of the isobornyl acrylate is 119-121 ℃, and the boiling point of the isobornyl methacrylate is 127-129 ℃, so the boiling point of the product is far lower than that of the reactant. According to the invention, by utilizing the difference of the boiling points of the reactants and the product, simple decompression rotary evaporation is adopted, and the components at 119-121 ℃ or 127-129 ℃ are collected, so that the pure product isobornyl acrylate or isobornyl methacrylate can be obtained.
According to a second aspect of the present invention, there is provided isobornyl (meth) acrylate obtained by the above-mentioned production process.
The beneficial effects of the invention include:
(1) the invention adopts a one-pot method to directly prepare the isobornyl (methyl) acrylate by the reaction of turpentine, does not need to prepare pinene by the turpentine firstly and then prepare camphene by the pinene, only needs one-step distillation operation in the whole reaction process, greatly saves the operation steps and reduces the energy consumption.
(2) The invention directly takes turpentine as raw material to carry out photocatalytic reaction with acrylic acid or methacrylic acid to synthesize isobornyl (meth) acrylate. The method adopts a photocatalysis method to prepare the isobornyl (meth) acrylate, has mild reaction conditions, short reaction time, basically no side reaction and by-product, no conditions of high temperature, high pressure and the like, simple separation and purification and easy operation. The invention utilizes the larger boiling point difference between the reactants and the reaction products, and adopts the reduced pressure distillation method to obtain the high-purity isobornyl (meth) acrylate, thereby greatly saving the steps of separation operation and reducing the cost.
(3) According to the invention, the biomass resource turpentine is introduced into the UV curing material system, so that the dependence on petroleum-based raw materials is reduced, and the effect of saving resources is achieved. The invention adopts the natural renewable resource turpentine to prepare the isobornyl (meth) acrylate, opens up a new application direction for the natural renewable resource vegetable oil, improves the economic value of the isobornyl (meth) acrylate, and has good popularization effect on the development of agriculture and forestry economy.
Drawings
FIG. 1 is a Fourier transform infrared spectrum of isobornyl methacrylate obtained in example 1 of the present invention.
FIG. 2 is a nuclear magnetic hydrogen spectrum of isobornyl methacrylate obtained in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto. The materials referred to in the following examples are commercially available.
In the following embodiments, the method for measuring the yield of isobornyl acrylate or isobornyl methacrylate is: when the reaction raw material is acrylic acid, collecting 119-121 ℃ components when the reaction product is subjected to rotary evaporation, when the reaction raw material is methacrylic acid, collecting 127-129 ℃ components when the reaction product is subjected to rotary evaporation, and calculating the ratio of the mass of the collected components to the mass of the theoretical product to obtain the yield.
The purity detection method comprises the following steps: measuring a standard sample diluted by a certain multiple by using a gas chromatograph to obtain a peak area and retention time; and (3) diluting the reaction product into a certain multiple, measuring the gas phase, obtaining the peak area of the reaction product according to the retention time of a standard product, and then calculating the purity of the reaction product according to the peak area of the reaction product, the purity and content of the standard product and the peak area.
Example 1
The preparation method of isobornyl methacrylate of this example includes the following steps:
adding 150g of turpentine (1.1mol) into 129g of methacrylic acid (1.5mol), dissolving, uniformly stirring, adding 27.9g of catalyst cation photoinitiator aryl diazonium salt (diphenylamine-4-diazonium salt) (the dosage of the catalyst is10 percent of the mass sum of the turpentine and the methacrylic acid) and 0.129g of polymerization inhibitor hydroquinone (the dosage of the polymerization inhibitor is 0.1 percent of the mass of the methacrylic acid), uniformly stirring, placing under a 100W UV light source for illumination, stirring and reacting at the rotating speed of 100r/min, stopping the reaction after 10min, reducing pressure, performing rotary evaporation, collecting components at 127-129 ℃, and obtaining a pure and transparent reaction product.
The molecular weight of the synthesized product was measured by an Agilent 7250GC/Q-TOF GC/MS system, which is a model of Agilent corporation, USA, and the relative molecular weight of the product was determined to be 222, which is the same as the theoretical relative molecular weight of isobornyl methacrylate.
The IR spectrum of the synthesized product was measured by a Thermo-Nicolet iS10 Fourier Infrared spectrometer of Nicolet corporation, USA, and the result iS shown in FIG. 1. As can be seen from FIG. 1, at 3010cm-1The peak is the stretching vibration absorption peak of the tail end C ═ C at 2880cm-1～2960cm-1C-H stretching vibration absorption peak at 1720cm, of methyl group and methylene group-1The peak is the stretching vibration peak of ester carbonyl C ═ O, 1640cm-1The peak of stretching vibration is 1390cm-1～1460cm-1Bending vibration peaks of methyl and methylene C-H, 1050cm-1974cm at the C-O stretching vibration peak-1Where is RCH ═ CH2Characteristic absorption peak of (1). This indicates that isobornyl methacrylate was successfully synthesized.
In addition, the nuclear magnetic spectrum data of the synthesized product is tested and recorded by a Bruker AV600 nuclear magnetic resonance spectrometer under the test conditions of room temperature and the solvent of deuterated chloroform (CDCl)3) The nuclear magnetic hydrogen spectrum obtained by detection is shown in fig. 2, wherein the characteristic peaks are as follows: a (6.06ppm), b (5.51ppm), c (4.72ppm), d (1.93ppm), e (1.82to 1.86ppm), f (1.78to 1.79ppm), g (1.74to 1.76ppm), h (1.68to 1.72ppm), i (1.59ppm), j (1.15to 1.20ppm), k (1.08to 1.12ppm), l (1.01ppm), m (0.86ppm), n (0.85 ppm). This also indicates the successful synthesis of isobornyl methacrylate.
The isobornyl methacrylate yield of this example was found to be 92.9% with a product purity of 99.6%.
Example 2
The preparation method of isobornyl acrylate of the embodiment comprises the following steps:
adding 150g of turpentine (1.1mol) into 72g of acrylic acid (1.0mol), dissolving, uniformly stirring, adding 2.22g of catalyst cationic photoinitiator triarylsulfonium salt (UVI 6976 of the Dow chemical company) (the dosage of the catalyst is1 percent of the sum of the mass of the turpentine and the mass of the acrylic acid) and 0.144g of polymerization inhibitor p-hydroxyanisole (the dosage of the polymerization inhibitor is 0.2 percent of the mass of the acrylic acid), uniformly stirring, placing under 200W of UV light source for illumination, stirring and reacting at the rotating speed of 200r/min for 20min, stopping reaction, reducing pressure and rotating for evaporation, collecting components at 119-121 ℃, and obtaining a pure and transparent reaction product.
The molecular weight of the synthesized product was measured by an Agilent 7250GC/Q-TOF GC/MS system, a relative molecular mass of 208, which is the same as the theoretical relative molecular mass of isobornyl acrylate.
The infrared spectrum of the synthesized product was measured by a Thermo-Nicolet iS10 Fourier infrared spectrometer of Nicolet corporation, USA, and the characteristic peak on the obtained spectrum iS similar to that in FIG. 1, thereby indicating that isobornyl acrylate was successfully synthesized. In addition, the nuclear magnetic spectrum data of the synthesized product was tested and recorded by a Bruker AV600 nuclear magnetic resonance spectrometer, and the characteristic peaks on the obtained spectrum were similar to those in FIG. 2, thereby also indicating that the isobornyl acrylate was successfully synthesized.
The isobornyl acrylate yield of this example was found to be 93.5% with a product purity of 99.4%.
Example 3
The preparation method of isobornyl methacrylate of this example includes the following steps:
adding 150g of turpentine (1.1mol) into 43g of methacrylic acid (0.5mol), dissolving, uniformly stirring, adding 9.65g of catalyst cation photoinitiator diaryl iodonium salt (4,4' -ditolyl iodonium hexafluorophosphate) (the dosage of the catalyst is 5 percent of the mass sum of the turpentine and the methacrylic acid) and 0.129g of polymerization inhibitor phenothiazine (the dosage of the polymerization inhibitor is 0.3 percent of the mass of the methacrylic acid), uniformly stirring, placing under a 300W UV light source for illumination, reacting while stirring at the rotating speed of 300r/min, stopping the reaction after 30min, carrying out reduced pressure rotary evaporation, and collecting components at 127-129 ℃ to obtain a pure and transparent reaction product.
The molecular weight of the synthesized product was measured by an Agilent 7250GC/Q-TOF GC/MS system, which is a model of Agilent corporation, USA, and the relative molecular weight of the product was determined to be 222, which is the same as the theoretical relative molecular weight of isobornyl methacrylate.
The infrared spectrum of the synthesized product was measured by a Thermo-Nicolet iS10 Fourier infrared spectrometer of Nicolet corporation, USA, and the characteristic peak on the obtained spectrum iS similar to that in FIG. 1, thereby indicating that isobornyl methacrylate was successfully synthesized. In addition, the nuclear magnetic spectrum data of the synthesized product was tested and recorded by a Bruker AV600 nuclear magnetic resonance spectrometer, and the characteristic peaks on the obtained spectrum were similar to those in FIG. 2, thereby also indicating that the isobornyl methacrylate was successfully synthesized.
The isobornyl methacrylate yield of this example was found to be 92.4% with a product purity of 99.3%.
Example 4
The preparation method of isobornyl acrylate of the embodiment comprises the following steps:
adding 150g of turpentine (1.1mol) into 108g of acrylic acid (1.5mol), dissolving, uniformly stirring, adding 18.06g of catalyst cation photoinitiator alkyl sulfonium salt (dialkyl (4-hydroxyphenyl) sulfonium salt) (the dosage of the catalyst is 7 percent of the total mass of the turpentine and the acrylic acid) and 0.432g of polymerization inhibitor p-hydroxyanisole (the dosage of the polymerization inhibitor is 0.4 percent of the mass of the acrylic acid), uniformly stirring, placing under a 400W UV light source for illumination, stirring and reacting at the rotating speed of 400r/min for 10min, stopping the reaction, performing reduced pressure rotary evaporation, collecting components at 119-121 ℃, and obtaining a pure and transparent reaction product.
The molecular weight of the synthesized product was measured by an Agilent 7250GC/Q-TOF GC/MS system, a relative molecular mass of 208, which is the same as the theoretical relative molecular mass of isobornyl acrylate.
The infrared spectrum of the synthesized product was measured by a Thermo-Nicolet iS10 Fourier infrared spectrometer of Nicolet corporation, USA, and the characteristic peak on the obtained spectrum iS similar to that in FIG. 1, thereby indicating that isobornyl acrylate was successfully synthesized. In addition, the nuclear magnetic spectrum data of the synthesized product was tested and recorded by a Bruker AV600 nuclear magnetic resonance spectrometer, and the characteristic peaks on the obtained spectrum were similar to those in FIG. 2, thereby also indicating that the isobornyl acrylate was successfully synthesized.
The isobornyl acrylate yield of this example was found to be 93.2% with a product purity of 99.5%.
Example 5
The preparation method of isobornyl methacrylate of this example includes the following steps:
adding 150g of turpentine (1.1mol) into 86g of methacrylic acid (1.0mol), dissolving, uniformly stirring, adding 7.08g of catalyst cation photoinitiator diaryl iodonium salt (didodecyl benzene iodonium hexafluoroantimonate) (the dosage of the catalyst is 3 percent of the mass sum of the turpentine and the methacrylic acid) and 0.172g of polymerization inhibitor hydroquinone (the dosage of the polymerization inhibitor is 0.2 percent of the mass of the methacrylic acid), uniformly stirring, placing under a 500W UV light source for illumination, stirring and reacting at the rotating speed of 500r/min, stopping the reaction after 20min, reducing pressure and performing rotary evaporation, and collecting components at 127-129 ℃ to obtain a pure and transparent reaction product.
The molecular weight of the synthesized product was measured by an Agilent 7250GC/Q-TOF GC/MS system, which is a model of Agilent corporation, USA, and the relative molecular weight of the product was determined to be 222, which is the same as the theoretical relative molecular weight of isobornyl methacrylate.
The infrared spectrum of the synthesized product was measured by a Thermo-Nicolet iS10 Fourier infrared spectrometer of Nicolet corporation, USA, and the characteristic peak on the obtained spectrum iS similar to that in FIG. 1, thereby indicating that isobornyl methacrylate was successfully synthesized. In addition, the nuclear magnetic spectrum data of the synthesized product was tested and recorded by a Bruker AV600 nuclear magnetic resonance spectrometer, and the characteristic peaks on the obtained spectrum were similar to those in FIG. 2, thereby also indicating that the isobornyl methacrylate was successfully synthesized.
The isobornyl methacrylate yield of this example was found to be 92.8% with a product purity of 99.4%.
Example 6
The preparation method of isobornyl acrylate of the embodiment comprises the following steps:
adding 150g of turpentine (1.1mol) into 36g of acrylic acid (0.5mol), dissolving, uniformly stirring, adding 9.30g of catalyst cationic photoinitiator (2-p-toluenesulfonyloxy cycloheptatrienone) (the amount of the catalyst is 5% of the sum of the mass of the turpentine and the mass of the acrylic acid) and 0.18g of polymerization inhibitor phenothiazine (the amount of the polymerization inhibitor is 0.5% of the mass of the acrylic acid), uniformly stirring, placing under a 300W UV light source for illumination, stirring while reacting at the rotating speed of 300r/min, stopping the reaction after 30min, performing reduced pressure rotary evaporation, and collecting components at 119-121 ℃ to obtain a pure and transparent reaction product.
The molecular weight of the synthesized product was measured by an Agilent 7250GC/Q-TOF GC/MS system, a relative molecular mass of 208, which is the same as the theoretical relative molecular mass of isobornyl acrylate.
The infrared spectrum of the synthesized product was measured by a Thermo-Nicolet iS10 Fourier infrared spectrometer of Nicolet corporation, USA, and the characteristic peak on the obtained spectrum iS similar to that in FIG. 1, thereby indicating that isobornyl acrylate was successfully synthesized. In addition, the nuclear magnetic spectrum data of the synthesized product was tested and recorded by a Bruker AV600 nuclear magnetic resonance spectrometer, and the characteristic peaks on the obtained spectrum were similar to those in FIG. 2, thereby also indicating that the isobornyl acrylate was successfully synthesized.
The isobornyl acrylate yield of this example was found to be 93.6% with a product purity of 99.2%.
What has been described above are merely some embodiments of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept thereof, and these changes and modifications can be made without departing from the spirit and scope of the invention.
Claims (10)
- A process for the preparation of isobornyl (meth) acrylate, characterized by comprising the steps of:uniformly mixing turpentine, (methyl) acrylic acid, a catalyst and a polymerization inhibitor, placing under UV (ultraviolet) light irradiation, stirring for reaction, and performing rotary evaporation after the reaction is finished to obtain the turpentine-acrylic acid-vinyl acetate copolymer;the (meth) acrylic acid is acrylic acid or methacrylic acid; when the (meth) acrylic acid is acrylic acid, the resulting product is isobornyl acrylate; when the (meth) acrylic acid is methacrylic acid, the resulting product is isobornyl methacrylate.
- 2. The method for producing isobornyl (meth) acrylate according to claim 1, characterized in that the catalyst is a cationic photoinitiator.
- 3. The method for producing isobornyl (meth) acrylate according to claim 2, wherein the cationic photoinitiator is at least one of aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, alkylsulfonium salts, iron arene salts, sulfonyloxy ketones, and triarylsiloxy ethers.
- 4. The process for producing isobornyl (meth) acrylate according to any one of claims 1 to 3, wherein the amount of the catalyst is1 to 10% of the sum of the mass of turpentine and the mass of (meth) acrylic acid.
- 5. The method for producing isobornyl (meth) acrylate according to claim 4, wherein the molar ratio of the turpentine to the (meth) acrylic acid is 1: (0.5 to 1.5).
- 6. The method for producing isobornyl (meth) acrylate according to any one of claims 1 to 3, wherein the polymerization inhibitor is at least one of hydroquinone, p-hydroxyanisole and phenothiazine, and the amount of the polymerization inhibitor is 0.1 to 0.5% by mass of (meth) acrylic acid.
- 7. The isobornyl (meth) acrylate production method according to any one of claims 1 to 3, wherein the power of the UV light is 100 to 500W.
- 8. The method for producing isobornyl (meth) acrylate according to any one of claims 1 to 3, wherein the stirring speed is 100 to 500r/min and the stirring reaction time is10 to 30 min.
- 9. The method for producing isobornyl (meth) acrylate according to any one of claims 1 to 3, wherein when the (meth) acrylic acid is acrylic acid, the component at 119 to 121 ℃ is collected when the reaction product is subjected to rotary evaporation, and when the (meth) acrylic acid is methacrylic acid, the component at 127 to 129 ℃ is collected when the reaction product is subjected to rotary evaporation.
- 10. Isobornyl (meth) acrylate obtained by the production process according to any one of claims 1 to 9.
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