CN102391123A - Light-cured tetrahydrophthalic anhydridized tung oil acrylate resin and preparation method thereof - Google Patents
Light-cured tetrahydrophthalic anhydridized tung oil acrylate resin and preparation method thereof Download PDFInfo
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- 238000005886 esterification reaction Methods 0.000 claims abstract description 13
- 238000005698 Diels-Alder reaction Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
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- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 claims description 62
- 238000000016 photochemical curing Methods 0.000 claims description 34
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- 239000002253 acid Substances 0.000 claims description 19
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- 238000010792 warming Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
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- 238000006243 chemical reaction Methods 0.000 claims description 12
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- -1 hydroxy ester Chemical class 0.000 claims description 10
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- TUOBEAZXHLTYLF-UHFFFAOYSA-N [2-(hydroxymethyl)-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(CC)COC(=O)C=C TUOBEAZXHLTYLF-UHFFFAOYSA-N 0.000 claims description 7
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 7
- 239000003921 oil Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 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 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XRCRJFOGPCJKPF-UHFFFAOYSA-N 2-butylbenzene-1,4-diol Chemical compound CCCCC1=CC(O)=CC=C1O XRCRJFOGPCJKPF-UHFFFAOYSA-N 0.000 claims description 3
- 101000823778 Homo sapiens Y-box-binding protein 2 Proteins 0.000 claims description 3
- 150000004054 benzoquinones Chemical class 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
The invention discloses light-cured tetrahydrophthalic anhydridized tung oil acrylate resin and a preparation method thereof. The preparation method comprises the followings steps: tung oil and a tetrahydrophthalic anhydride monomer are subjected to the Diels-Alder reaction so as to produce an intermediate product, namely, tetrahydrophthalic anhydridized tung oil; and the tetrahydrophthalic anhydridized tung oil and an acrylic hydroxy ester monomer are subjected to an esterification reaction so as to prepare the product, wherein the mass ratio of the used raw materials is that the tung oil/the tetrahydrophthalic anhydride monomer/the acrylic hydroxy ester monomer is equal to 100:(45 to 55):(10-40). The product disclosed by the invention has a main chain which is a longer flexible chain, and the structural characteristics of a bonded rigid double six-membered ring; and the light-cured tetrahydrophthalic anhydridized tung oil acrylate resin is applied to the fields, such as light-cured solvent-free inks and coatings and the like as matrix resin, the rigidity, the toughness, the glossiness, the adhesive force to a base material, the weather-resisting property and the like of the inks, the coatings and the like can be adjusted within a wider range, so that the application performance is convenient to optimize and the fossil resources can be saved.
Description
Technical field
The invention belongs to the light-cured resin technical field, particularly relate to a kind of photocuring THPA tung oil acrylate resin and preparation method thereof.
Background technology
Along with " energy-saving and emission-reduction, Sustainable development " implementation, many in the world countries all replace " fossil property " resource to prepare the technical research of Chemicals actively developing with the recyclability resource, and photo-curing material is one of key areas of paying close attention to of people.
Utilize the vegetables oil of natural reproducible to substitute " fossil property " resource such as oil and prepare photo-curing material, what the current research report was more is soybean oil modified light-cured resin.And being soybean oil based resin, new trend changes to the other plant oil-based resin.
China is the important place of origin of tung oil, and annual output is about 140,000 tons, accounts for more than 80% of worldwide production.The tung oil molecular structure has functional groups such as conjugated double bond, carboxyl, and number of chemical reactions such as Diels-Alder reaction, Friedel-Crafts reaction, radical polymerization, epoxidation, amidation and esterification can take place.Therefore, the research that utilizes tung oil particular chemical structure to prepare light-cured resin is reported more.For example: 1, CN 1028373C discloses the tung oil-modified resin of cis-butenedioic anhydride, and this resin is earlier by cis-butenedioic anhydride and tung oil reaction, reactant again and senecioate-hydroxyalkyl react, make the sensitization alkali soluble resins.2, application number is that 88101351.X, denomination of invention are the patent of invention of " the synthetic and photosensitive composition of phenolic group tung oil resin "; This patent discloses a kind of phenolic group tung oil photoresist; Be by tung oil and Resorcinol; Generate the tung oil resorcinol resin under certain condition, this resin can be applicable to imaging or Micrometer-Nanometer Processing Technology.
But, above-mentioned light-cured resin, because structural characteristics, sticking power, elasticity, glossiness and the weather resisteant of the coat that solidify to form as the photocuring system of matrix resin all do not have clear superiority, and material toxicity is big.Therefore, limited the application of this resinoid in packings such as food, medicine and agricultural byproducts.Hypotoxic THPA class monomer is one type of fine chemical product that development in recent years is got up; Use in growing field; Like the alkyd amino lacquer that replaces the aromatic series polyprotonic acid to produce with the tetrahydro-phthalic anhydride, amino polyester lacquer, polyester lacquer, polyurethane paint, powder coating etc., can significantly improve aquatic foods degree of reflecting, the gloss of coating, reduction viscosity; Improve solid content, especially can increase substantially the weather resisteant of coating.
Summary of the invention
The technical problem that the present invention will solve provides a kind of photocuring THPA tung oil acrylate resin and preparation method thereof.Technical scheme of the present invention is to adopt hypotoxic THPA class monomer and tung oil to react through Diels-Alder; Make THPA tung oil midbody; THPA tung oil carries out esterification with crylic acid hydroxy ester class monomer again, makes photocuring THPA tung oil acrylate resin.Product photocuring THPA tung oil acrylate resin of the present invention can be used as matrix resin and is applied to fields such as photocuring solventless ink and coating.
In order to address the above problem, the technical scheme that the present invention adopts is:
The present invention provides a kind of photocuring THPA tung oil acrylate resin, and the general structure of said photocuring THPA tung oil acrylate resin is:
Wherein, R
1For
R
2For-H or-CH
3
R
3For senecioate-hydroxyl ethyl ester except that-part the OH or be senecioate-hydroxypropyl acrylate except that-part the OH or for methylacrylic acid-beta-hydroxy ethyl ester remove-part OH or be methylacrylic acid-β-hydroxypropyl acrylate except that-part the OH be vinylformic acid-2-hydroxyl-3-phenoxy propyl ester except that-part the OH or for trimethylolpropane diacrylate except that-part the OH or for pentaerythritol triacrylate except that-part the OH; Below be R
3Structural formula explanation:
(senecioate-hydroxyl ethyl ester except that-part the OH),
(senecioate-hydroxypropyl acrylate except that-part the OH),
(methylacrylic acid-beta-hydroxy ethyl ester except that-part the OH),
(methylacrylic acid-β-hydroxypropyl acrylate except that-part the OH),
(vinylformic acid-2-hydroxyl-3-phenoxy propyl ester except that-part the OH)
(trimethylolpropane diacrylate except that-part the OH)
(pentaerythritol triacrylate except that-part the OH).
A kind of preparation method of above-mentioned photocuring THPA tung oil acrylate resin, said preparation method may further comprise the steps:
A, be basic raw material with tung oil and THPA class monomer, tung oil and THPA class monomer are that the ratio of 100:45～55 takes by weighing according to mass ratio; Earlier the tung oil that takes by weighing is added in the four-hole reactor drum of belt stirrer, TM and reflux exchanger; Oil bath is heated to 60～70 ℃, adds the THPA class monomer take by weighing then, is warming up under 120～180 ℃ the condition to carry out Diels-Alder reaction; Carrying out along with reaction; Generate midbody product THPA tung oil, the midbody product of generation is along with the carrying out of reaction, and its acid number increases gradually; When the acid number that reacts to midbody product THPA tung oil no longer changes, react and finish; Products therefrom is cooled to room temperature, washs successively then, freeze-day with constant temperature, obtain midbody product THPA tung oil after the drying;
B, THPA tung oil, backflow band aqua and stopper that step a is obtained join in the four-hole reactor drum of belt stirrer, TM and reflux exchanger; Being warming up to 65～75 ℃ melts; Fusing adds crylic acid hydroxy ester class monomer evenly and when condensing reflux occurring, is warming up to 80～140 ℃ and carries out esterification; Under this reflux conditions, react to the system acid number and no longer change, reaction finishes; Steam the band aqua that refluxes then, obtain product, products therefrom is washed,, carry out freeze-day with constant temperature at last, obtain product photocuring THPA tung oil acrylate resin after the drying to remove unreacted stopper;
Said THPA class monomer and crylic acid hydroxy ester class monomer between the two the mass ratio of add-on be 45～55:10～40; The add-on of said backflow band aqua is 80～130% of a tung oil quality; The add-on of said stopper is 0.1～0.2% of a tung oil quality.
According to the preparation method of above-mentioned photocuring THPA tung oil acrylate resin, the class of THPA described in step a monomer is THPA or methyl tetrahydro phthalic anhydride.
According to the preparation method of above-mentioned photocuring THPA tung oil acrylate resin, washing described in the step a is to adopt acetonitrile to wash, and washing times is 2～4 times, and the add-on of acetonitrile is 70～100% of a tung oil quality;
Drying temperature is 85 ℃ during said freeze-day with constant temperature, and be 1h time of drying.
According to the preparation method of above-mentioned photocuring THPA tung oil acrylate resin, the class of crylic acid hydroxy ester described in step b monomer is any in senecioate-hydroxyl ethyl ester, senecioate-hydroxypropyl acrylate, methylacrylic acid-beta-hydroxy ethyl ester, methylacrylic acid-β-hydroxypropyl acrylate, vinylformic acid-2-hydroxyl-3-phenoxy propyl ester, trimethylolpropane diacrylate and the pentaerythritol triacrylate.
According to the preparation method of above-mentioned photocuring THPA tung oil acrylate resin, the band aqua that refluxes described in the step b is any in benzene, toluene and the YLENE.
According to the preparation method of above-mentioned photocuring THPA tung oil acrylate resin, said stopper is any in Resorcinol, arylamine, benzoquinones, oil of mirbane, p methoxy phenol, Tert. Butyl Hydroquinone and the DBPC 2,6 ditertiary butyl p cresol.
Preparing method according to above-mentioned photocuring THPA tung oil acrylate resin; Described in the step b products therefrom is washed; Adopt 75～85 ℃ hot water to wash during washing, wash 2～4 times, the add-on of hot water is 40～50% of a tung oil quality;
Drying temperature is 105 ℃ during said freeze-day with constant temperature, and be 2h time of drying.
Positive beneficial effect of the present invention:
1, to adopt tung oil be one of raw material in the present invention, and the tung oil staple is the eleostearic acid Witepsol W-S 55, contains 9 conjugated double bonds, and the πDian Zi cloud between the conjugated double bond carbon atom hands over lid overlapping each other, polarization easily, and polymerization velocity is fast more than other vegetables oil.
There are two kinds of isomer in tung oil: α-type and β-type, α-type tung oil chemically reactive is high, take place than being easier to the monomeric Diels-Alder reaction of THPA class, and the position that reacts is 11,13.β-type tung oil chemically reactive is relatively low, and with the monomeric Diels-Alder reaction of THPA class relative difficult, the position that reacts is 9,11 or 11,13.Therefore; The structure of midbody THPA tung oil has diversified characteristics because of tung oil source, THPA class monomer type, proportioning raw materials and synthetic technological condition etc.; Select for use different crylic acid hydroxy ester class monomers and THPA tung oil to carry out esterification, the product THPA tung oil acrylate resin of also having given the present invention's preparation has structure, advantage that the performance degree of amplitude modulation is big in addition.
2, the present invention adopts THPA class monomer and tung oil to react through Diels-Alder, make can with the THPA tung oil midbody of crylic acid hydroxy ester class monomer reaction.The THPA class raw material monomer that the present invention adopted is compared with anhydride compounds such as maleic anhydrides; Its toxicity is lower, makes the product THPA tung oil acrylate resin of the present invention that makes be more suitable for being used to preparing the matrix resin of the field photocuring system such as photocuring solventless ink and coating of packages printings such as food, medicine, agricultural byproducts.
3, utilize the macromole of the product THPA tung oil acrylate resin of technical scheme preparation of the present invention to have two six-membered ring structures; And on ring, be linked with the constitutional features of the good long aliphatic chain of kindliness; Not only helping improving with THPA tung oil acrylate resin is the curing speed of the photocuring system of matrix; Make curing volume shrinkage ratio less, and can give cured product firm, the tough performance characteristic of Ji and excellent weather resistance etc. mutually.
Four, description of drawings:
The infrared analysis spectrogram of Fig. 1 embodiment 1 step a gained midbody product THPA tung oil.
Fig. 1 analyzes explanation: among Fig. 1 1839,1775,1183cm
-1Show and be linked with the anhydride functional group in the midbody.
The infrared analysis spectrogram of Fig. 2 embodiment 1 products obtained therefrom THPA tung oil senecioate-hydroxyl ethyl ester resin.
Fig. 2 analyzes explanation: among Fig. 2 1774,1413 and 2500～3000cm
-1The broad peak at place shows the existence of carboxylic acid functional; 1708,1262 and 1183cm
-1Show the existence of ester group.
The infrared analysis spectrogram of Fig. 3 embodiment 2 products obtained therefrom THPA tung oil methylacrylic acid-beta-hydroxy ethyl ester resins.
Fig. 3 analyzes explanation: among Fig. 3 1761,1435 and 2500～3000cm
-1The broad peak at place shows the existence of carboxylic acid functional; 1743,1296 and 1160cm
-1Show the existence of ester group; 2927,2855,1435 and 1380cm
-1Show the existence of methyl.
Five, embodiment:
Following examples have been merely and have further specified the present invention, do not limit content of the present invention.
Embodiment 1:
The preparation method of photocuring THPA tung oil acrylate resin of the present invention, said preparation method may further comprise the steps:
A, be basic raw material with tung oil and THPA, tung oil and the THPA mass ratio between the two is 100:45, at first the tung oil 100g that takes by weighing is added in the four-hole reactor drum of belt stirrer, TM and reflux exchanger; Oil bath is heated to 65 ℃, adds the THPA 45g that takes by weighing then, is warming up to 180 ℃; Under this temperature condition, carry out Diels-Alder reaction,, generate midbody product THPA tung oil along with the carrying out of reaction; The midbody product that generates is along with the carrying out of reaction; Its acid number increases gradually, when the acid number that reacts to midbody product THPA tung oil no longer changes, reacts and finishes; Products therefrom is cooled to room temperature, uses 100mL acetonitrile washed product 3 times then, tell oil phase,, obtain 130.5g midbody product THPA tung oil (the infrared analysis spectrogram of this midbody product sees Fig. 1 for details) after the drying at last at 85 ℃ of following freeze-day with constant temperature 1h;
B, THPA tung oil 106g, backflow water liquid benzene 100mL and hydroquinone of polymerization retarder 0.1g that step a is obtained join in the four-hole reactor drum of belt stirrer, TM and reflux exchanger; Being warming up to 70 ℃ melts; Fusing adds 10g senecioate-hydroxyl ethyl ester evenly and when condensing reflux occurring, is warming up to 80 ℃ and carries out esterification; Under this reflux conditions, react to the system acid number and no longer change, reaction finishes; Steam benzene then; Products therefrom is washed (adopting 40mL, 80 ℃ hot wash product 3 times); To remove unreacted stopper; At 105 ℃ of following freeze-day with constant temperature 2h, obtain the 114.0g product after the drying at last: THPA tung oil senecioate-hydroxyl ethyl ester resin (the infrared analysis spectrogram of this product sees Fig. 2 for details).
Embodiment 2: basic identical with embodiment 1, difference is:
Among the step b: the band aqua that refluxes is YLENE 100mL, and stopper is p methoxy phenol 0.1g, adds 15g methylacrylic acid-beta-hydroxy ethyl ester, is warming up to 138 ℃ and carries out esterification; Obtain the 118.8g product: THPA tung oil methylacrylic acid-beta-hydroxy ethyl ester resin (the infrared analysis spectrogram of this product sees Fig. 3 for details).
Embodiment 3: basic identical with embodiment 1, difference is:
Among the step b: the band aqua that refluxes is YLENE 100mL, and stopper is oil of mirbane 0.1g, adds 10g senecioate-hydroxypropyl acrylate, is warming up to 138 ℃ and carries out esterification; Obtain the 113.7g product: THPA tung oil senecioate-hydroxypropyl acrylate resin.
Embodiment 4: basic identical with embodiment 1, difference is:
Among the step a: add the THPA 50g that takes by weighing then; Make midbody product THPA tung oil 135.5g;
Among the step b: the band aqua that refluxes is benzene 100mL, and stopper is Tert. Butyl Hydroquinone 0.12g, adds 30g vinylformic acid-2-hydroxyl-3-phenoxy propyl ester, is warming up to 80 ℃ and carries out esterification; Obtain the 133.7g product: THPA tung oil vinylformic acid-2-hydroxyl-3-phenoxy propyl ester resin.
Embodiment 5: basic identical with embodiment 1, difference is:
Among the step a: add the methyl tetrahydro phthalic anhydride 50g that takes by weighing then, be warming up to 180 ℃, make midbody product methyl tetrahydro phthalic anhydride tung oil 133.7g;
Among the step b: the band aqua that refluxes is YLENE 100mL, and stopper is arylamine 0.1g, adds the 30g pentaerythritol triacrylate, is warming up to 138 ℃ and carries out esterification; Obtain the 132.5g product: methyl tetrahydro phthalic anhydride tung oil pentaerythritol triacrylate resin.
Embodiment 6: basic identical with embodiment 1, difference is:
Among the step a: add the methyl tetrahydro phthalic anhydride 50g that takes by weighing then, be warming up to 120 ℃, make midbody product methyl tetrahydro phthalic anhydride tung oil 132.3g;
Among the step b: the band aqua that refluxes is toluene 100mL, and stopper is DBPC 2,6 ditertiary butyl p cresol 0.1g, adds 17g methylacrylic acid-β-hydroxypropyl acrylate, is warming up to 110 ℃ and carries out esterification; Obtain the 121.8g product: methyl tetrahydro phthalic anhydride tung oil methylacrylic acid-β-hydroxypropyl acrylate resin.
Embodiment 7: basic identical with embodiment 1, difference is:
Among the step a: add the methyl tetrahydro phthalic anhydride 55g that takes by weighing then, be warming up to 150 ℃, make midbody product methyl tetrahydro phthalic anhydride tung oil 137.0g;
Among the step b: the band aqua that refluxes is benzene 100mL, and stopper is benzoquinones 0.1g, adds the 30g trimethylolpropane diacrylate, is warming up to 80 ℃ and carries out esterification; Obtain the 132.5g product: methyl tetrahydro phthalic anhydride tung oil trimethylolpropane diacrylate resin.
The product THPA tung oil acrylate resin outward appearance of the present invention that embodiment 1～7 prepares is faint yellow transparence.With it is matrix resin, and composite with the suitable light trigger and the photocuring system of other auxiliary agents, the performance of its light-cured performance and cured coating film is following:
Surface drying time: according to the regulation test of standard GB/T 13477.5-2002, the surface drying time of filming is in 30s.
Determination of pencil hardness: according to the regulation test of standard GB/T 6739-1986, the pencil hardness of cured coating film reaches 1H-4H.
Sticking power is measured: according to the regulation test of standard GB/T 9286-1988, the sticking power of cured coating film reaches first three level.
Water tolerance is measured: according to the regulation test of standard GB/T 1733-1993, the having excellent water-resistance of cured coating film, in water, soak 48h non-foaming, wrinkle resistant, do not come off.
Claims (8)
1. a photocuring THPA tung oil acrylate resin is characterized in that, the general structure of said photocuring THPA tung oil acrylate resin is:
Wherein, R
1For
R
2For-H or-CH
3
R
3For senecioate-hydroxyl ethyl ester except that-part the OH or be senecioate-hydroxypropyl acrylate except that-part the OH or for methylacrylic acid-beta-hydroxy ethyl ester remove-part OH or be methylacrylic acid-β-hydroxypropyl acrylate except that-part the OH be vinylformic acid-2-hydroxyl-3-phenoxy propyl ester except that-part the OH or for trimethylolpropane diacrylate except that-part the OH or for pentaerythritol triacrylate except that-part the OH.
2. the preparation method of the said photocuring THPA of claim 1 a tung oil acrylate resin is characterized in that said preparation method may further comprise the steps:
A, be basic raw material with tung oil and THPA class monomer, tung oil and THPA class monomer are that the ratio of 100:45～55 takes by weighing according to mass ratio; Earlier the tung oil that takes by weighing is added in the four-hole reactor drum of belt stirrer, TM and reflux exchanger; Oil bath is heated to 60～70 ℃, adds the THPA class monomer take by weighing then, is warming up under 120～180 ℃ the condition to carry out Diels-Alder reaction; Carrying out along with reaction; Generate midbody product THPA tung oil, the midbody product of generation is along with the carrying out of reaction, and its acid number increases gradually; When the acid number that reacts to midbody product THPA tung oil no longer changes, react and finish; Products therefrom is cooled to room temperature, washs successively then, freeze-day with constant temperature, obtain midbody product THPA tung oil after the drying;
B, THPA tung oil, backflow band aqua and stopper that step a is obtained join in the four-hole reactor drum of belt stirrer, TM and reflux exchanger; Being warming up to 65～75 ℃ melts; Fusing adds crylic acid hydroxy ester class monomer evenly and when condensing reflux occurring, is warming up to 80～140 ℃ and carries out esterification; Under this reflux conditions, react to the system acid number and no longer change, reaction finishes; Steam the band aqua that refluxes then, obtain product, products therefrom is washed,, carry out freeze-day with constant temperature at last, obtain product photocuring THPA tung oil acrylate resin after the drying to remove unreacted stopper;
Said THPA class monomer and crylic acid hydroxy ester class monomer between the two the mass ratio of add-on be 45～55:10～40; The add-on of said backflow band aqua is 80～130% of a tung oil quality; The add-on of said stopper is 0.1～0.2% of a tung oil quality.
3. the preparation method of photocuring THPA tung oil acrylate resin according to claim 2 is characterized in that: the class of THPA described in step a monomer is THPA or methyl tetrahydro phthalic anhydride.
4. the preparation method of photocuring THPA tung oil acrylate resin according to claim 2; It is characterized in that: washing described in the step a is to adopt acetonitrile to wash; Washing times is 2～4 times, and the add-on of acetonitrile is 70～100% of a tung oil quality;
Drying temperature is 85 ℃ during said freeze-day with constant temperature, and be 1h time of drying.
5. the preparation method of photocuring THPA tung oil acrylate resin according to claim 2 is characterized in that: the class of crylic acid hydroxy ester described in step b monomer is any in senecioate-hydroxyl ethyl ester, senecioate-hydroxypropyl acrylate, methylacrylic acid-beta-hydroxy ethyl ester, methylacrylic acid-β-hydroxypropyl acrylate, vinylformic acid-2-hydroxyl-3-phenoxy propyl ester, trimethylolpropane diacrylate and the pentaerythritol triacrylate.
6. the preparation method of photocuring THPA tung oil acrylate resin according to claim 2 is characterized in that: the band aqua that refluxes described in the step b is any in benzene, toluene and the YLENE.
7. the preparation method of photocuring THPA tung oil acrylate resin according to claim 2; It is characterized in that: said stopper is any in Resorcinol, arylamine, benzoquinones, oil of mirbane, p methoxy phenol, Tert. Butyl Hydroquinone and the DBPC 2,6 ditertiary butyl p cresol.
8. the preparation method of photocuring THPA tung oil acrylate resin according to claim 2; It is characterized in that: described in the step b products therefrom is washed; Adopt 75～85 ℃ hot water to wash during washing; Wash 2～4 times, the add-on of hot water is 40～50% of a tung oil quality;
Drying temperature is 105 ℃ during said freeze-day with constant temperature, and be 2h time of drying.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102746157A (en) * | 2012-07-13 | 2012-10-24 | 河南金誉包装科技股份有限公司 | Photocuring tetrahydrophthalic-anhydridized tung oil acrylic acid/vinyl ether ester prepolymer and preparation method thereof |
| CN102746158A (en) * | 2012-07-13 | 2012-10-24 | 河南金誉包装科技股份有限公司 | Photocuring tetrahydrophthalic-anhydridized tung oil acrylic acid/propenyl ether ester prepolymer and preparation method thereof |
| CN110092884A (en) * | 2019-04-28 | 2019-08-06 | 上海嘉宝莉涂料有限公司 | A kind of haze tallow oleoresin and high rigidity color inhibition wood wax oil |
| CN111349037A (en) * | 2018-12-21 | 2020-06-30 | 中国石油化工股份有限公司 | Monoacid type aviation fuel antiwear agent and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746157A (en) * | 2012-07-13 | 2012-10-24 | 河南金誉包装科技股份有限公司 | Photocuring tetrahydrophthalic-anhydridized tung oil acrylic acid/vinyl ether ester prepolymer and preparation method thereof |
| CN102746158A (en) * | 2012-07-13 | 2012-10-24 | 河南金誉包装科技股份有限公司 | Photocuring tetrahydrophthalic-anhydridized tung oil acrylic acid/propenyl ether ester prepolymer and preparation method thereof |
| CN111349037A (en) * | 2018-12-21 | 2020-06-30 | 中国石油化工股份有限公司 | Monoacid type aviation fuel antiwear agent and preparation method thereof |
| CN111349037B (en) * | 2018-12-21 | 2021-10-08 | 中国石油化工股份有限公司 | Monoacid type aviation fuel antiwear agent and preparation method thereof |
| CN110092884A (en) * | 2019-04-28 | 2019-08-06 | 上海嘉宝莉涂料有限公司 | A kind of haze tallow oleoresin and high rigidity color inhibition wood wax oil |
| CN110092884B (en) * | 2019-04-28 | 2021-09-28 | 上海嘉宝莉涂料有限公司 | Wood wax oil resin and high-hardness yellowing-resistant wood wax oil |
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