CN102746158A - Photocuring tetrahydrophthalic-anhydridized tung oil acrylic acid/propenyl ether ester prepolymer and preparation method thereof - Google Patents
Photocuring tetrahydrophthalic-anhydridized tung oil acrylic acid/propenyl ether ester prepolymer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a photocuring tetrahydrophthalic-anhydridized tung oil acrylic acid/propenyl ether ester prepolymer and a preparation method thereof. The preparation method comprises the following steps: carrying out Diels-Alder reaction on tung oil and low-toxicity tetrahydrophthalic anhydride monomers to obtain tetrahydrophthalic anhydride modified tung oil, carrying out ring-opening esterification on propenyl ether with hydroxy group and the tetrahydrophthalic-anhydridized tung oil in a certain mol ratio to obtain tetrahydrophthalic-anhydridized tung oil propenyl ether half-ester, and carrying out esterification reaction on the acrylate or acrylic epoxy esters with hydroxy group and the carboxyl group on the tetrahydrophthalic-anhydridized tung oil propenyl ether half-ester to obtain the product tetrahydrophthalic-anhydridized tung oil acrylic acid/propenyl ether ester prepolymer. The preparation method disclosed by the invention has the advantage of simple technique; and the prepared prepolymer can be used for free radical-cation photocuring reaction, and can be used in the technical fields of inks, paints, adhesives and the like.
Description
Technical field
The invention belongs to the light-cured resin technical field, particularly relate to a kind of photocuring THPA tung oil vinylformic acid/propenyl ether-ether performed polymer and preparation method thereof.
Background technology
World today's coating, printing ink, tackiness agent, plastics and matrix material all a large amount of with Nonrenewable resources such as oil, Sweet natural gas, coals as basic raw material.For Sustainable development, stay some resources to the descendants, people have to seek low cost, safety and renewable resources and substitute Nonrenewable resources such as oil, Sweet natural gas, coal.Tung oil is as a kind of height polyunsaturated vegetable oil of China's special product, and its conjugated triple bond that has can carry out the number of chemical reaction, is a kind of ideal industrial chemicals.
Because most of tung oil through modification is applicable to solvent-based system, the influence to environment is very big equally in the use of a large amount of organic solvents; Though water-based system printing ink belongs to environmentfriendly products, it need consume a large amount of heat energy and remove moisture content to reach the purpose of dry solidification.Photocuring technology is because it is energy-conservation, low VOC, high-level efficiency and high performance outstanding advantage and become a kind of novel green chemical industry technology of hot topic gradually.Therefore, utilize natural tung oil resource, tung oil is carried out modification, coating, printing ink, then environmental protection at a low price of tackiness agent, the saving fossil resource designing a kind of modified tung oil base photocuring performed polymer and utilize this performed polymer to make.CN88105564.6 discloses a kind of employing maleic anhydride modified tung oil resin and has done the ultraviolet light polymerization etchingresistant printing material; By cis-butenedioic anhydride and tung oil reaction; Reactant again and senecioate-hydroxyalkyl reaction, advantages such as prepared etchingresistant printing material has that caustic solubility is good, curing speed fast, viscosity is lower, printing performance and good stability.CN201110093579.7 discloses the preparation method of the ester modified tung oil vinyl of a kind of ammonia light-cured resin, and this patent is raw material with tung oil, on the tung oil molecule, has connected the ammonia ester structure with the non-isocyanate technology, makes product environmental protection more.
Yet above-mentioned modified tung oil light-cured resin all is limited to radical photoinitiator to be solidified.Radical photoinitiator curing reaction speed is fast, but exist that shrinking percentage is big, problem such as oxygen inhibition, sticking power are relatively poor.Cation photocuring has that " living polymerization ", volumetric shrinkage are little, strong adhesion, wear-resisting, hardness advantages of higher, but its curing speed is slower.Therefore radical-cationic hybrid photocuring system then can be learnt from other's strong points to offset one's weaknesses, and widens the use range of photocuring system.Be that main raw material is prepared the performed polymer that is linked with free redical-cationic hybrid photocuring functional group on a part with tung oil; Not only can reduce pollution and saving Nonrenewable resources to environment; Also solved simultaneously the shortcoming that single photocuring brought, work beyond doubt with novelty.
Summary of the invention
The technical problem that the present invention will solve provides free redical-cationic hybrid photocuring THPA tung oil vinylformic acid/propenyl ether-ether performed polymer and preparation method thereof.The present invention carries out the acid anhydrides modification with tung oil; Again with hydroxyl propenyl ether, (methyl) acrylate reactions hydroxyl or the band epoxy group(ing); Be prepared into the performed polymer that not only has two keys of free redical polymerization but also have the propenyl ether structure of cationically polymerizable, product photocuring THPA tung oil vinylformic acid promptly of the present invention/propenyl ether-ether performed polymer.
In order to address the above problem, the technical scheme that the present invention adopts is:
Photocuring THPA tung oil vinylformic acid provided by the invention/propenyl ether-ether performed polymer, its general structure is:
Wherein, R
1Be
R
2Be-H or-CH
3
R
3Be 2-hydroxyethyl propenyl ether except that-part the OH, 3-hydroxypropyl propenyl ether except that-part the OH, 4-hydroxybutyl propenyl ether except that-part the OH or 6-hydroxyl hexyl propenyl ether except that-part the OH;
The concrete structure formula is following:
(during n=2 2-hydroxyethyl propenyl ether except that-part the OH; During n=3 3-hydroxypropyl propenyl ether except that-part the OH; Being 4-hydroxybutyl propenyl ether during n=4 except that-part the OH, is 6-hydroxyl hexyl propenyl ether during n=6 except that-part the OH);
R
4Be 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 the-part the OH, vinylformic acid-2, the part in part in the 3-epoxy propyl ester after the epoxide group open loop or the GMA after the epoxide group open loop;
The concrete structure formula is following:
((methyl) senecioate-hydroxyl ethyl ester or (methyl) senecioate-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),
(part after the open loop of (methyl) acrylic acid epoxy propyl ester epoxide group).
The preparation method of a kind of photocuring THPA tung oil vinylformic acid/propenyl ether-ether performed polymer, said preparation method may further comprise the steps:
A, be basic raw material with tung oil and THPA class monomer; At first tung oil is dewatered; Its water ratio of tung oil after the dehydration≤0.10%, tung oil after the dehydration and THPA class monomer carry out Diels-Alder reaction under heating condition, tung oil after the said dehydration and THPA class monomer between the two the mol ratio of add-on be 1:1～3; Temperature of reaction system is 110～150 ℃; Reaction times is 3～5h, does not become the foundation of reaction end with the content constant of Diels-Alder reaction product THPA tung oil, obtains having the THPA tung oil of twin nuclei after Diels-Alder reaction;
B, under the effect of catalyzer; The THPA tung oil that hydroxyl propenyl ether monomer and step a are obtained carries out the esterification by ring opening reaction; Temperature of reaction system is 90～140 ℃; Reaction times is 1～3h, and invariable with the acid number of this step reaction system is the foundation of reaction end, obtains THPA tung oil propenyl ether half ester after the esterification by ring opening reaction;
Said hydroxyl propenyl ether monomer and THPA tung oil carry out esterification by ring opening when reaction, and anhydride group on the THPA tung oil and the monomeric hydroxyl of the hydroxyl propenyl ether mol ratio between the two is 1:0.9～1.1; The add-on of said catalyzer accounts for 0.1～3.0% of hydroxyl propenyl ether monomer and the two total mass of THPA tung oil;
C, hydroxy acrylate class monomer is at first added stopper and refluxes the band aqua; The stopper consumption accounts for 0.01～1.00% of THPA tung oil propenyl ether half ester and the two total mass of hydroxy acrylate class monomer, and the add-on of said backflow band aqua accounts for 10～30% of THPA tung oil propenyl ether half ester and hydroxy acrylate class monomer total mass; The THPA tung oil propenyl ether half ester that obtains with step b behind the hydroxy acrylate class monomer adding stopper and the band aqua that refluxes carries out esterification; Carboxyl on the said THPA tung oil propenyl ether half ester and the mol ratio between the hydroxyl on the hydroxy acrylate class monomer are 1:0.9～1.1; Esterification reaction temperature is 90～140 ℃; Reaction times is 1～3h; Invariable with the acid number of this step reaction system is the foundation of reaction end, carries out underpressure distillation after reaction finishes and handles, and obtains product photocuring THPA tung oil vinylformic acid of the present invention/propenyl ether-ether performed polymer after the processing;
Perhaps acrylic acid epoxy ester class monomer is added stopper and catalyzer, the stopper consumption accounts for 0.01～1.00% of THPA tung oil propenyl ether half ester and the two total mass of acrylic acid epoxy ester class monomer; Catalyst consumption accounts for 0.1～3.0% of THPA tung oil propenyl ether half ester and the two total mass of acrylic acid epoxy ester class monomer; The THPA tung oil propenyl ether half ester that obtains with step b behind acrylic acid epoxy ester class monomer adding stopper and the catalyzer carries out esterification; Carboxyl on the said THPA tung oil propenyl ether half ester and the mol ratio between the epoxide group on the acrylic acid epoxy ester class monomer are 1:0.9～1.1; Esterification reaction temperature is 90～140 ℃; Reaction times is 1～3h; Invariable with the acid number of this step reaction system is the foundation of reaction end, and reaction promptly obtains product photocuring THPA tung oil vinylformic acid of the present invention/propenyl ether-ether performed polymer after finishing.
Adding stopper among the above-mentioned steps c in the hydroxy acrylate class monomer and be in order to stop the two keys on the hydroxy acrylate class monomer to carry out polymerization, add the reflux effect of band aqua is to isolate the water that generates in the reaction process, improves the transformation efficiency that reacts; Acrylic acid epoxy ester class monomer adds stopper and catalyzer, and wherein the adding of stopper is in order to stop the two keys on the acrylic acid epoxy ester class monomer to carry out polymerization, and the effect of catalyzer is in order to improve the speed of reaction of epoxy group(ing) and carboxyl.
According to the preparation method of above-mentioned photocuring THPA tung oil vinylformic acid/propenyl ether-ether performed polymer, 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 vinylformic acid/propenyl ether-ether performed polymer, hydroxyl propenyl ether monomer described in the step b is 2-hydroxyethyl propenyl ether, 3-hydroxypropyl propenyl ether, 4-hydroxybutyl propenyl ether or 6-hydroxyl hexyl propenyl ether.
According to the preparation method of above-mentioned photocuring THPA tung oil vinylformic acid/propenyl ether-ether performed polymer, catalyzer described in the step b is tosic acid, zinc oxide or sieve catalyst.
Preparing method according to above-mentioned photocuring THPA tung oil vinylformic acid/propenyl ether-ether performed polymer; Stopper described in the step c is any in Resorcinol, arylamine, benzoquinones, oil of mirbane, p methoxy phenol, Tert. Butyl Hydroquinone and the DBPC 2,6 ditertiary butyl p cresol.
According to the preparation method of above-mentioned photocuring THPA tung oil vinylformic acid/propenyl ether-ether performed polymer, the band aqua that refluxes described in the step c is any in benzene, toluene and the YLENE.
According to the preparation method of above-mentioned photocuring THPA tung oil vinylformic acid/propenyl ether-ether performed polymer, the class of hydroxy acrylate described in step c 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 vinylformic acid/propenyl ether-ether performed polymer, the monomer of acrylic acid epoxy ester described in the step c is a vinylformic acid-2,3-epoxy propyl ester or GMA.
Preparing method according to above-mentioned photocuring THPA tung oil vinylformic acid/propenyl ether-ether performed polymer; Catalyzer described in the step c is triethylamine, N; N-dimethyl benzylamine, N, any in accelerine, trimethyl benzyl ammonia chloride, triphenylphosphine, antimony triphenyl, chromium acetylacetonate and the tetraethylammonium bromide.
Positive beneficial effect of the present invention:
1, to adopt renewable plant resources tung oil be main raw material in the present invention.The staple of tung oil is the eleostearic acid Witepsol W-S 55; Contain 9 conjugated double bonds, the πDian Zi cloud between the conjugated double bond carbon atom hands over lid overlapping each other, easily polarization; Has very high reactive behavior; THPA class monomers easy and the two keys of band carry out the Diels-Alder reaction, and acquisition has the modified tung oil of anhydride group and twin nuclei, for further functionalization provides architecture basics.
2, the THPA class monomer that the present invention adopted is compared with anhydride compounds such as maleic anhydrides; Its toxicity is lower; And the product photocuring THPA tung oil vinylformic acid of the present invention/propenyl ether-ether performed polymer that makes has twin nuclei; The performed polymer performance of this structure is more excellent, is suitable for preparing photocuring solventless adhesive, printing ink and the coating in packages printing fields such as food, medicine, agricultural byproducts.
3, the present invention is linked with the long aliphatic chain of two keys of the good band of kindliness and band propenyl ether on the twin nuclei of a part respectively, can carry out radical-cationic hybrid photocuring, can comprehensively demonstrate the advantage of radical and cation photocuring.
Four, description of drawings:
The IR spectrogram of Fig. 1 THPA tung oil;
Among Fig. 1,1850,1780,929cm
-1The existence of absorption peak proof cyclic acid anhydride structure.
The IR spectrogram of the half ester that Fig. 2 THPA tung oil and 2-hydroxyethyl propenyl ether make;
Among Fig. 2,1159cm
-1The existence of absorption peak proof ether structure.
Fig. 3 is the IR spectrogram of photocuring THPA tung oil vinylformic acid/propenyl ether-ether performed polymer of making of main raw material with tung oil, THPA, 2-hydroxyethyl propenyl ether and senecioate-hydroxyl ethyl ester;
Among Fig. 3,1160cm
-1The existence of absorption peak proof ether structure, 1735,1181cm
-1The existence of proof ester group structure.
Five, embodiment:
Further set forth the present invention below in conjunction with embodiment, but do not limit content of the present invention.
Intermediate product or final performed polymer characterize structure with IR spectroscopy.
Prepared performed polymer is added an amount of free radical photo-initiation, cation light initiator and a certain amount of reactive thinner etc. be mixed with photocuring system, evenly be applied on the base material, on UV curing machine, solidify.
Surface drying time: according to the regulation test of GB/T 1728-1979.
Pencil hardness: according to the regulation test of GB/T 6739-2006.
Sticking power: according to the regulation test of GB/T 9286-1998.
Water tolerance: according to the regulation test of GB/T 1733-1993.
The preparation method of the raw material 2-hydroxyethyl propenyl ether that adopts among the following embodiment, 3-hydroxypropyl propenyl ether, 4-hydroxybutyl propenyl ether and 6-hydroxyl hexyl propenyl ether is following.
The preparation method of 2-hydroxyethyl propenyl ether
:37.24g (0.6mol) 1 and 85mL toluene are joined in the four-hole boiling flask, begin to stir the feeding nitrogen N
2When being warming up to 30 ℃, reaction system adds the 1.2g Tetrabutyl amonium bromide; Add 6g (0.15mol) sodium hydroxide when reaction system is warming up to 40 ℃, continue to rise to 65 ℃ and begin slowly evenly to drip 18.15g (0.15mol) allyl bromide 98 and 10mL toluene mixture liquid with constant pressure funnel, about 6h drips off; Stop heating after dripping Bi Jixu reaction 2h, feeding nitrogen N
2Be cooled to room temperature under the agitation condition; The reaction product that reaction obtains after finishing is removed solid through suction filtration, and rotary evaporation removes and desolvates the back underpressure distillation and collect cut, obtains the 2-hydroxyethyl allyl ether;
Getting above-mentioned 2-hydroxyethyl allyl ether 10.2g (0.1mol) and the 100mL DMSO 99.8MIN. that obtains joins in the there-necked flask; Begin to stir and heat up; Add 3.54g (0.03mol) potassium tert.-butoxide when being warming up to 80 ℃, continue intensification and under 100-110 ℃ of condition, react the 1h postcooling to room temperature; Reaction back products therefrom adds 400mL zero(ppm) water after removing by filter solid, use ether: the mixing solutions washing of normal hexane=1:1 (V:V is a volume ratio) 5-6 time, rotary evaporation removes and desolvates then, obtains product 2-hydroxyethyl propenyl ether.
The preparation method of 3-hydroxypropyl propenyl ether
:With 45.66g (0.6mol) 1, ammediol and 85mL toluene join in the four-hole boiling flask, begin to stir the feeding nitrogen N
2When being warming up to 30 ℃, reaction system adds the 1.2g Tetrabutyl amonium bromide; Add 6g (0.15mol) sodium hydroxide when reaction system is warming up to 40 ℃, continue to rise to 65 ℃ and begin slowly evenly to drip 18.15g (0.15mol) allyl bromide 98 and 10mL toluene mixture liquid with constant pressure funnel, about 6h drips off; Stop heating after dripping Bi Jixu reaction 2h, feeding nitrogen N
2Be cooled to room temperature under the agitation condition; The reaction product that obtains after the reaction is removed solid through suction filtration, and rotary evaporation removes and desolvates the back underpressure distillation and collect cut, obtains 3-hydroxypropyl allyl ethers;
Getting above-mentioned product 3-hydroxypropyl allyl ethers 11.6g (0.1mol) and the 100mL DMSO 99.8MIN. that obtains joins in the there-necked flask; Begin to stir and heat up; Add 3.54g (0.03mol) potassium tert.-butoxide when being warming up to 80 ℃, continue to heat up, reaction 1h postcooling is to room temperature under 100-110 ℃ of condition; Reaction back products therefrom adds 400mL zero(ppm) water through removing by filter solid, uses ether: the mixing solutions washing of normal hexane=1:1 (V:V is a volume ratio) 5-6 time, rotary evaporation removes and desolvates, and obtains product 3-hydroxypropyl propenyl ether.
The preparation method of 4-hydroxybutyl propenyl ether
:With 54.1g (0.6mol) 1,4-butyleneglycol and 85mL toluene join in the four-hole boiling flask, begin to stir the feeding nitrogen N
2When being warming up to 30 ℃, reaction system adds the 1.2g Tetrabutyl amonium bromide; Add 6g (0.15mol) sodium hydroxide when reaction system is warming up to 40 ℃, continue to rise to 65 ℃ and begin slowly evenly to drip 18.15g (0.15mol) allyl bromide 98 and 10mL toluene mixture liquid with constant pressure funnel, about 6h drips off; Stop heating after dripping Bi Jixu reaction 2h, feeding N
2Be cooled to room temperature under the agitation condition; Reaction back gained reaction product is removed solid through suction filtration, and rotary evaporation removes and desolvates the back underpressure distillation and collect cut, obtains product 4-hydroxybutyl allyl ethers;
Getting above-mentioned products therefrom 4-hydroxybutyl allyl ethers 13.0g (0.1mol) and 100mL DMSO 99.8MIN. joins in the there-necked flask; Begin to stir and heat up; Add 3.54g (0.03mol) potassium tert.-butoxide when being warming up to 80 ℃, continue to heat up, reaction 1h postcooling is to room temperature under 100-110 ℃ of condition; Products therefrom adds 400mL zero(ppm) water through removing by filter solid, uses ether: normal hexane=1:1 (V:V is a volume ratio) mixing solutions washing 5-6 time, rotary evaporation removes and desolvates, and obtains product 4-hydroxybutyl propenyl ether.
The preparation method of 6-hydroxyl hexyl propenyl ether
:With 70.9g (0.6mol) 1,6-pinakon and 85mL cyclohexane join in the four-hole boiling flask, begin to stir the feeding nitrogen N
2When being warming up to 30 ℃, reaction system adds the 1.2g Tetrabutyl amonium bromide; Add 6g (0.15mol) sodium hydroxide when reaction system is warming up to 40 ℃, continue to rise to 65 ℃ and begin slowly evenly to drip 18.15g (0.15mol) allyl bromide 98 and 10mL toluene mixture liquid with constant pressure funnel, about 6h drips off; Stop heating after dripping Bi Jixu reaction 2h, feeding nitrogen N
2Be cooled to room temperature under the agitation condition; Reaction back gained reaction product is removed solid through suction filtration, and rotary evaporation removes and desolvates the back underpressure distillation and collect cut, obtains product 6-hydroxyl hexyl allyl ethers;
Getting above-mentioned products therefrom 6-hydroxyl hexyl allyl ethers 15.8g (0.1mol) and 100mL DMSO 99.8MIN. joins in the there-necked flask; Begin to stir and heat up; Add 3.54g (0.03mol) potassium tert.-butoxide when being warming up to 80 ℃, continue to heat up, reaction 1h postcooling is to room temperature under 100-110 ℃ of condition; Reaction back products therefrom adds 400mL zero(ppm) water through removing by filter solid, uses ether: normal hexane=1:1 (V:V is a volume ratio) mixing solutions washing 5-6 time, rotary evaporation removes and desolvates, and obtains product 6-hydroxyl hexyl propenyl ether.
Embodiment 1:
With tung oil, THPA, 2-hydroxyethyl propenyl ether and senecioate-hydroxyl ethyl ester is main raw material, makes a kind of photocuring THPA of the present invention tung oil vinylformic acid/propenyl ether-ether performed polymer, and its concrete structure formula is:
The concrete preparation method of a kind of photocuring THPA of the invention described above tung oil vinylformic acid/propenyl ether-ether performed polymer may further comprise the steps:
A, be basic raw material with tung oil and THPA, at first in the there-necked flask of band magnetic agitation and TM, add 25.0g (0.028mol) tung oil, 60 ℃ of vacuum states dewater about 0.5h (its water ratio of the tung oil after the dehydration≤0.10%) down; Be warming up to 100 ℃ then; 13.0g (0.085mol) THPA is divided into three equal parts, and every equal portions 10min at interval add in the flask, and temperature can rise automatically therebetween; The control maximum temperature is not higher than 130 ℃; Make reaction system at 130 ℃ ± 2 ℃ about 4h of isothermal reaction behind reinforced the finishing, the detection reaction product has the content of the THPA tung oil of twin nuclei, no longer increases with content and promptly arrives reaction end;
The concrete structure formula that step a gained intermediate product has the THPA tung oil of twin nuclei is:
B, reaction system among the step a is cooled to 90 ℃ ± 2 ℃; Add catalyzer tosic acid 0.04g, under this temperature, stir 5min, in flask, drip 8.7g (0.085mol) 2-hydroxyethyl propenyl ether with constant pressure funnel; Rate of addition is as the criterion with the not obvious decline of temperature; Drip and finish, be warming up to and carry out the esterification by ring opening reaction under 110 ℃ ± 2 ℃, react about 2h; Detection reaction system acid number no longer changes i.e. reaction end, obtains the product THPA tung oil propenyl ether half ester of THPA tung oil and the reaction of 2-hydroxyethyl propenyl ether esterification by ring opening after reaction finishes;
The structural formula of products therefrom THPA tung oil propenyl ether half ester is:
C, reaction system among the step b is cooled to 90 ℃ ± 2 ℃; Add 10mL toluene, in flask, drip the mixture of 9.9g (0.085mol) senecioate-hydroxyl ethyl ester and 0.02g Resorcinol with constant pressure funnel, rate of addition is as the criterion with the not obvious decline of temperature; Drip and finish; Be warming up under 110 ℃ ± 2 ℃ and carry out esterification, react about 2h, detection reaction system acid number no longer changes and promptly arrives reaction end; Decompression at last steams toluene; Obtain the orange-yellow transparent thick liquid nano product of 43.8g, promptly have a kind of the product photocuring THPA tung oil vinylformic acid of the present invention/propenyl ether-ether performed polymer of said structure, productive rate is 79.5%
.
Embodiment 2:
With tung oil, methyl tetrahydro phthalic anhydride, 2-hydroxyethyl propenyl ether and senecioate-hydroxyl ethyl ester is main raw material, makes the another kind of photocuring THPA of the present invention tung oil vinylformic acid/propenyl ether-ether performed polymer, and its structural formula is:
The concrete preparation method of above-mentioned a kind of photocuring THPA tung oil vinylformic acid/propenyl ether-ether performed polymer, basic identical with embodiment 1, difference is:
A, be basic raw material with tung oil and methyl tetrahydro phthalic anhydride; At first in the there-necked flask of band magnetic agitation and TM, add 25.0g (0.028mol) tung oil; 60 ℃ of vacuum states dewater about 0.5h (its water ratio of the tung oil after the dehydration≤0.10%) down, are warming up to 65 ℃ then, and 14.2g (0.085mol) methyl tetrahydro phthalic anhydride is divided into three equal parts; Every equal portions 10min at interval add in the flask; Temperature can rise automatically therebetween, and the control maximum temperature is not higher than 130 ℃, makes reaction system at 130 ℃ ± 2 ℃ about 4h of isothermal reaction behind reinforced the finishing; The detection reaction product has the content of the methyl tetrahydro phthalic anhydride tung oil of twin nuclei, no longer increases with content and promptly arrives reaction end;
The concrete structure formula of step a gained intermediate product methyl tetrahydro phthalic anhydride tung oil is:
B, reaction system among the step a is cooled to 90 ℃ ± 2 ℃; Add catalyst oxidation zinc 0.04g, under this temperature, stir 5min, in flask, drip 8.7g (0.085mol) 2-hydroxyethyl propenyl ether with constant pressure funnel; Rate of addition is as the criterion with the not obvious decline of temperature; Drip and finish, be warming up to and carry out the esterification by ring opening reaction under 110 ℃ ± 2 ℃, react about 2h; Detection reaction system acid number no longer changes i.e. reaction end, obtains the product methyl tetrahydro phthalic anhydride tung oil propenyl ether half ester that the reaction of methyl tetrahydro phthalic anhydride tung oil and 2-hydroxyethyl propenyl ether esterification by ring opening forms;
The concrete structure formula of products therefrom methyl tetrahydro phthalic anhydride tung oil propenyl ether half ester is:
C, with adding 10mL YLENE in the step b reaction system, in flask, drip the mixture of 9.9g (0.085mol) senecioate-hydroxyl ethyl ester and 0.02g arylamine with constant pressure funnel, rate of addition is as the criterion with the not obvious decline of temperature; Drip and finish; Be warming up under 120 ℃ ± 2 ℃ and carry out esterification, react about 2h, detection reaction system acid number no longer changes and promptly arrives reaction end; Decompression at last steams YLENE; Obtain the orange-yellow transparent thick liquid nano product of 45.8g, promptly have another kind of the product THPA tung oil vinylformic acid of the present invention/propenyl ether-ether performed polymer of said structure, productive rate 81.3%
.
Embodiment 3:
With tung oil, THPA, 3-hydroxypropyl propenyl ether and senecioate-hydroxyl ethyl ester is main raw material, makes the another kind of photocuring THPA of the present invention tung oil vinylformic acid/propenyl ether-ether performed polymer, and its concrete structure formula is:
The concrete preparation method of above-mentioned a kind of photocuring THPA tung oil vinylformic acid/propenyl ether-ether performed polymer, basic identical with embodiment 1, difference is:
A, be basic raw material with tung oil and THPA; At first in the there-necked flask of band magnetic agitation and TM, add 25.0g (0.028mol) tung oil, 60 ℃ of vacuum states dewater about 0.5h (its water ratio of the tung oil after the dehydration≤0.10%) down, are warming up to 100 ℃ then; 13.0g (0.085mol) THPA is divided into three equal parts; Every equal portions 10min at interval add in the flask, and temperature can rise automatically therebetween, and the control maximum temperature is not higher than 130 ℃; Make reaction system at 130 ℃ ± 2 ℃ about 4h of isothermal reaction behind reinforced the finishing; The detection reaction product has the content of the THPA tung oil of twin nuclei, no longer increases with content and promptly arrives reaction end, and the concrete structure formula is with embodiment 1;
B, reaction system among the step a is cooled to 90 ℃ ± 2 ℃; Add sieve catalyst 0.04g, under this temperature, stir 5min, in flask, drip 9.9g (0.085mol) 3-hydroxypropyl propenyl ether with constant pressure funnel; Rate of addition is as the criterion with the not obvious decline of temperature; Drip and finish, be warming up to and carry out the esterification by ring opening reaction under 110 ℃ ± 2 ℃, react about 2h; Detection reaction system acid number no longer changes i.e. reaction end, obtains the product THPA tung oil propenyl ether half ester that the reaction of THPA tung oil and 3-hydroxypropyl propenyl ether esterification by ring opening forms;
The concrete structure formula of products therefrom THPA tung oil propenyl ether half ester is:
C, reaction system among the step b is cooled to 90 ℃ ± 2 ℃, adds 10mL toluene, in flask, drip the mixture of 9.9g (0.085mol) senecioate-hydroxyl ethyl ester and 0.02g benzoquinones with constant pressure funnel; Rate of addition is as the criterion with the not obvious decline of temperature, drips to finish, and is warming up under 110 ℃ ± 2 ℃ and carries out esterification; React about 2h; Detection reaction system acid number no longer changes and promptly arrives reaction end, and decompression at last steams toluene, obtains the orange-yellow transparent thick liquid nano product of 44.3g; Another kind that promptly has the product photocuring THPA tung oil vinylformic acid of the present invention/propenyl ether-ether performed polymer of said structure, productive rate 78.7%.
Embodiment 4:
With tung oil, THPA, 4-hydroxybutyl propenyl ether and senecioate-hydroxyl ethyl ester is main raw material, makes the another kind of photocuring THPA of the present invention tung oil vinylformic acid/propenyl ether-ether performed polymer, and its concrete structure formula is:
The concrete preparation method of above-mentioned a kind of photocuring THPA tung oil vinylformic acid/propenyl ether-ether performed polymer, basic identical with embodiment 1, difference is:
A, be basic raw material with tung oil and THPA; At first in the there-necked flask of band magnetic agitation and TM, add 25.0g (0.028mol) tung oil, 60 ℃ of vacuum states dewater about 0.5h (its water ratio of the tung oil after the dehydration≤0.10%) down, are warming up to 100 ℃ then; 13.0g (0.085mol) THPA is divided into three equal parts; Every equal portions 10min at interval add in the flask, and temperature can rise automatically therebetween, and the control maximum temperature is not higher than 130 ℃; Make reaction system at 130 ℃ ± 2 ℃ about 4h of isothermal reaction behind reinforced the finishing; The detection reaction product has the content of the THPA tung oil of twin nuclei, no longer increases with content and promptly arrives reaction end, and the concrete structure formula is with embodiment 1;
B, reaction system among the step a is cooled to 90 ℃ ± 2 ℃; Add catalyzer tosic acid 0.04g, under this temperature, stir 5min, in flask, drip 11.1g (0.085mol) 4-hydroxybutyl propenyl ether with constant pressure funnel; Rate of addition is as the criterion with the not obvious decline of temperature; Drip and finish, be warming up to and carry out the esterification by ring opening reaction under 110 ℃ ± 2 ℃, react about 2h; It is reaction end that detection reaction system acid number no longer changes, and obtains the product THPA tung oil propenyl ether half ester that the reaction of THPA tung oil and 4-hydroxybutyl propenyl ether esterification by ring opening forms;
The concrete structure formula of products therefrom THPA tung oil propenyl ether half ester is:
C, reaction system among the step b is cooled to 90 ℃ ± 2 ℃, adds 10mL toluene, in flask, drip the mixture of 9.9g (0.085mol) senecioate-hydroxyl ethyl ester and 0.02g oil of mirbane with constant pressure funnel; Rate of addition is as the criterion with the not obvious decline of temperature; Drip to finish, be warming up to and carry out the about 2h of esterification under 110 ℃ ± 2 ℃, detection reaction system acid number no longer changes and promptly arrives reaction end; Decompression at last steams toluene; Obtain the orange-yellow transparent thick liquid nano product of 44.7g, promptly have another kind of the product photocuring THPA tung oil vinylformic acid of the present invention/propenyl ether-ether performed polymer of said structure, productive rate 77.8%
.
Embodiment 5:
With tung oil, THPA, 6-hydroxyl hexyl propenyl ether and senecioate-hydroxyl ethyl ester is main raw material, makes the another kind of photocuring THPA of the present invention tung oil vinylformic acid/propenyl ether-ether performed polymer, and its concrete structure formula is:
The concrete preparation method of above-mentioned a kind of photocuring THPA tung oil vinylformic acid/propenyl ether-ether performed polymer, basic identical with embodiment 1, difference is:
A, be basic raw material with tung oil and THPA; At first in the there-necked flask of band magnetic agitation and TM, add 25.0g (0.028mol) tung oil, 60 ℃ of vacuum states dewater about 0.5h (its water ratio of the tung oil after the dehydration≤0.10%) down, are warming up to 100 ℃ then; 13.0g (0.085mol) THPA is divided into three equal parts; Every equal portions 10min at interval add in the flask, and temperature can rise automatically therebetween, and the control maximum temperature is not higher than 130 ℃; Make reaction system at 130 ℃ ± 2 ℃ about 4h of isothermal reaction behind reinforced the finishing; The detection reaction product has the content of the THPA tung oil of twin nuclei, no longer increases with content and promptly arrives reaction end, and the concrete structure formula is with embodiment 1;
B, reaction system among the step a is cooled to 90 ℃ ± 2 ℃; Add catalyzer tosic acid 0.04g, under this temperature, stir 5min, in flask, drip 13.5g (0.085mol) 6-hydroxyl hexyl propenyl ether with constant pressure funnel and carry out esterification; Rate of addition is as the criterion with the not obvious decline of temperature; Drip and finish, be warming up to and carry out the esterification by ring opening reaction under 110 ℃ ± 2 ℃, react about 2h; It is reaction end that detection reaction system acid number no longer changes, and obtains the product THPA tung oil propenyl ether half ester that the reaction of THPA tung oil and 6-hydroxyl hexyl propenyl ether esterification by ring opening forms;
The concrete structure formula of products therefrom THPA tung oil propenyl ether half ester is:
C, reaction system among the step b is cooled to 90 ℃ ± 2 ℃, adds 10mL toluene, in flask, drip the mixture of 9.9g (0.085mol) senecioate-hydroxyl ethyl ester and 0.02g p methoxy phenol with constant pressure funnel; Rate of addition is as the criterion with the not obvious decline of temperature; Drip to finish, be warming up to and carry out the about 2h of esterification under 110 ℃ ± 2 ℃, detection reaction system acid number no longer changes and promptly arrives reaction end; Decompression at last steams toluene; Obtain the orange-yellow transparent thick liquid nano product of 45.1g, promptly have another kind of the product photocuring THPA tung oil vinylformic acid of the present invention/propenyl ether-ether performed polymer of said structure, productive rate 75.3%.
Embodiment 6:
With tung oil, THPA, 2-hydroxyethyl propenyl ether and methylacrylic acid-beta-hydroxy ethyl ester is main raw material, makes the another kind of photocuring THPA of the present invention tung oil vinylformic acid/propenyl ether-ether performed polymer, and its concrete structure formula is:
The concrete preparation method of above-mentioned a kind of photocuring THPA tung oil vinylformic acid/propenyl ether-ether performed polymer, basic identical with embodiment 1, difference is:
A, be basic raw material with tung oil and THPA; At first in the there-necked flask of band magnetic agitation and TM, add 25.0g (0.028mol) tung oil, 60 ℃ of vacuum states dewater about 0.5h (its water ratio of the tung oil after the dehydration≤0.10%) down, are warming up to 100 ℃ then; 13.0g (0.085mol) THPA is divided into three equal parts; Every equal portions 10min at interval add in the flask, and temperature can rise automatically therebetween, and the control maximum temperature is not higher than 130 ℃; Make reaction system at 130 ℃ ± 2 ℃ about 4h of isothermal reaction behind reinforced the finishing; The detection reaction product has the content of the THPA tung oil of twin nuclei, no longer increases with content and promptly arrives reaction end, and the concrete structure formula is with embodiment 1;
B, reaction system among the step a is cooled to 90 ℃ ± 2 ℃, adds catalyzer tosic acid 0.04g, under this temperature, stir 5min; In flask, drip 8.7g (0.085mol) 2-hydroxyethyl propenyl ether with constant pressure funnel; Rate of addition is as the criterion with the not obvious decline of temperature, drips to finish, and is warming up to carry out the esterification by ring opening reaction under 110 ℃ ± 2 ℃; React about 2h; Detection reaction system acid number no longer changes i.e. reaction end, obtains the product THPA tung oil propenyl ether half ester of THPA tung oil and 2-hydroxyethyl propenyl ether esterification by ring opening reaction, and the concrete structure formula is with embodiment 1;
C, reaction system among the step b is cooled to 80 ℃ ± 2 ℃; Add 10mL benzene, in flask, drip the mixture of 11.1g (0.085mol) methylacrylic acid-beta-hydroxy ethyl ester and 0.02g Tert. Butyl Hydroquinone with constant pressure funnel, rate of addition is as the criterion with the not obvious decline of temperature; Constant temperature carries out the about 2h of esterification under 80 ℃ ± 2 ℃; Detection reaction system acid number no longer changes and promptly arrives reaction end, and decompression at last steams benzene, obtains the orange-yellow transparent thick liquid nano product of 45.2g; Another kind that promptly has the product photocuring THPA tung oil vinylformic acid of the present invention/propenyl ether-ether performed polymer of said structure, productive rate 80.3%.
Embodiment 7:
With tung oil, THPA, 2-hydroxyethyl propenyl ether and senecioate-hydroxypropyl acrylate is main raw material, makes the another kind of photocuring THPA of the present invention tung oil vinylformic acid/propenyl ether-ether performed polymer, and its concrete structure formula is:
The concrete preparation method of above-mentioned a kind of photocuring THPA tung oil vinylformic acid/propenyl ether-ether performed polymer, basic identical with embodiment 1, difference is:
A, be basic raw material with tung oil and THPA; At first in the there-necked flask of band magnetic agitation and TM, add 25.0g (0.028mol) tung oil, 60 ℃ of vacuum states dewater about 0.5h (its water ratio of the tung oil after the dehydration≤0.10%) down, are warming up to 100 ℃ then; 13.0g (0.085mol) THPA is divided into three equal parts; Every equal portions 10min at interval add in the flask, and temperature can rise automatically therebetween, and the control maximum temperature is not higher than 130 ℃; Make reaction system at 130 ℃ ± 2 ℃ about 4h of isothermal reaction behind reinforced the finishing; The detection reaction product has the content of the THPA tung oil of twin nuclei, no longer increases with content and promptly arrives reaction end, and the concrete structure formula is with embodiment 1;
B, reaction system among the step a is cooled to 90 ℃ ± 2 ℃, adds catalyzer tosic acid 0.04g, under this temperature, stir 5min; In flask, drip 8.7g (0.085mol) 2-hydroxyethyl propenyl ether with constant pressure funnel; Rate of addition is as the criterion with the not obvious decline of temperature, drips to finish, and is warming up to carry out the esterification by ring opening reaction under 110 ℃ ± 2 ℃; React about 2h; Detection reaction system acid number no longer changes i.e. reaction end, obtains the product THPA tung oil propenyl ether half ester of THPA tung oil and 2-hydroxyethyl propenyl ether esterification by ring opening reaction, and the concrete structure formula is with embodiment 1;
C, reaction system among the step b is cooled to 90 ℃ ± 2 ℃, adds 10mL toluene, in flask, drip 11.1g (0.085mol) senecioate-hydroxypropyl acrylate and 0.02g 2 with constant pressure funnel; The mixture of 6-ditertbutylparacresol; Rate of addition is as the criterion with the not obvious decline of temperature, carries out the about 2h of esterification under the constant temperature to 110 ℃ ± 2 ℃, and detection reaction system acid number no longer changes and promptly arrives reaction end; Decompression at last steams toluene; Obtain the orange-yellow transparent thick liquid nano product of 42.9g, promptly have another kind of the product photocuring THPA tung oil vinylformic acid of the present invention/propenyl ether-ether performed polymer of said structure, productive rate 76.1%.
Embodiment 8:
With tung oil, THPA, 2-hydroxyethyl propenyl ether and methylacrylic acid-β-hydroxypropyl acrylate is main raw material, makes the another kind of photocuring THPA of the present invention tung oil vinylformic acid/propenyl ether-ether performed polymer, and its concrete structure formula is:
The concrete preparation method of above-mentioned a kind of photocuring THPA tung oil vinylformic acid/propenyl ether-ether performed polymer, basic identical with embodiment 1, difference is:
A, be basic raw material with tung oil and THPA; At first in the there-necked flask of band magnetic agitation and TM, add 25.0g (0.028mol) tung oil, 60 ℃ of vacuum states dewater about 0.5h (its water ratio of the tung oil after the dehydration≤0.10%) down, are warming up to 100 ℃ then; 13.0g (0.085mol) THPA is divided into three equal parts; Every equal portions 10min at interval add in the flask, and temperature can rise automatically therebetween, and the control maximum temperature is not higher than 130 ℃; Make reaction system at 130 ℃ ± 2 ℃ about 4h of isothermal reaction behind reinforced the finishing; The detection reaction product has the content of the THPA tung oil of twin nuclei, no longer increases with content and promptly arrives reaction end, and the concrete structure formula is with embodiment 1;
B, reaction system among the step a is cooled to 90 ℃ ± 2 ℃, adds catalyzer tosic acid 0.04g, under this temperature, stir 5min; In flask, drip 8.7g (0.085mol) 2-hydroxyethyl propenyl ether with constant pressure funnel; Rate of addition is as the criterion with the not obvious decline of temperature, drips to finish, and is warming up to carry out the esterification by ring opening reaction under 110 ℃ ± 2 ℃; React about 2h; Detection reaction system acid number no longer changes i.e. reaction end, obtains the product THPA tung oil propenyl ether half ester of THPA tung oil and 2-hydroxyethyl propenyl ether esterification by ring opening reaction, and the concrete structure formula is with embodiment 1;
C, reaction system among the step b is cooled to 90 ℃ ± 2 ℃, adds 10mL toluene, in flask, drip the mixture of 12.3g (0.085mol) methylacrylic acid-β-hydroxypropyl acrylate and 0.02g Resorcinol with constant pressure funnel; Rate of addition is as the criterion with the not obvious decline of temperature; Drip to finish, be warming up to and carry out the about 2h of esterification under 110 ℃ ± 2 ℃, detection reaction system acid number no longer changes and promptly arrives reaction end; Decompression at last steams toluene; Obtain the orange-yellow transparent thick liquid nano product of 42.8g, promptly have another kind of the product photocuring THPA tung oil vinylformic acid of the present invention/propenyl ether-ether performed polymer of said structure, productive rate 74.5%.
Embodiment 9:
With tung oil, THPA, 2-hydroxyethyl propenyl ether and vinylformic acid-2-hydroxyl-3-phenoxy propyl ester is main raw material, makes the another kind of photocuring THPA of the present invention tung oil vinylformic acid/propenyl ether-ether performed polymer, and its concrete structure formula is:
The concrete preparation method of above-mentioned a kind of photocuring THPA tung oil vinylformic acid/propenyl ether-ether performed polymer, basic identical with embodiment 1, difference is:
A, be basic raw material with tung oil and THPA; At first in the there-necked flask of band magnetic agitation and TM, add 25.0g (0.028mol) tung oil, 60 ℃ of vacuum states dewater about 0.5h (its water ratio of the tung oil after the dehydration≤0.10%) down, are warming up to 100 ℃ then; 13.0g (0.085mol) THPA is divided into three equal parts; Every equal portions 10min at interval add in the flask, and temperature can rise automatically therebetween, and the control maximum temperature is not higher than 130 ℃; Make reaction system at 130 ℃ ± 2 ℃ about 4h of isothermal reaction behind reinforced the finishing; The detection reaction product has the content of the THPA tung oil of twin nuclei, no longer increases with content and promptly arrives reaction end, and the concrete structure formula is with embodiment 1;
B, reaction system among the step a is cooled to 90 ℃ ± 2 ℃, adds catalyzer tosic acid 0.04g, under this temperature, stir 5min; In flask, drip 8.7g (0.085mol) 2-hydroxyethyl propenyl ether with constant pressure funnel; Rate of addition is as the criterion with the not obvious decline of temperature, drips to finish, and is warming up to carry out the esterification by ring opening reaction under 110 ℃ ± 2 ℃; React about 2h; Detection reaction system acid number no longer changes i.e. reaction end, obtains the product THPA tung oil propenyl ether half ester of THPA tung oil and 2-hydroxyethyl propenyl ether esterification by ring opening reaction, and the concrete structure formula is with embodiment 1;
C, reaction system among the step b is cooled to 90 ℃ ± 2 ℃; Add 10mL toluene, in flask, drip the mixture of 19.0g (0.085mol) vinylformic acid-2-hydroxyl-3-phenoxy propyl ester and 0.02g Resorcinol with constant pressure funnel, rate of addition is as the criterion with the not obvious decline of temperature; Carry out the about 2h of esterification under the constant temperature to 110 ℃ ± 2 ℃; Detection reaction system acid number no longer changes and promptly arrives reaction end, and decompression at last steams toluene, obtains the orange-yellow transparent thick liquid nano product of 46.7g; Another kind that promptly has the product photocuring THPA tung oil vinylformic acid of the present invention/propenyl ether-ether performed polymer of said structure, productive rate 72.7%.
Embodiment 10:
With tung oil, THPA, 2-hydroxyethyl propenyl ether and trimethylolpropane diacrylate is main raw material, makes the another kind of photocuring THPA of the present invention tung oil vinylformic acid/propenyl ether-ether performed polymer, and its concrete structure formula is:
The concrete preparation method of above-mentioned a kind of photocuring THPA tung oil vinylformic acid/propenyl ether-ether performed polymer, basic identical with embodiment 1, difference is:
A, be basic raw material with tung oil and THPA; At first in the there-necked flask of band magnetic agitation and TM, add 25.0g (0.028mol) tung oil, 60 ℃ of vacuum states dewater about 0.5h (its water ratio of the tung oil after the dehydration≤0.10%) down, are warming up to 100 ℃ then; 13.0g (0.085mol) THPA is divided into three equal parts; Every equal portions 10min at interval add in the flask, and temperature can rise automatically therebetween, and the control maximum temperature is not higher than 130 ℃; Make reaction system at 130 ℃ ± 2 ℃ about 4h of isothermal reaction behind reinforced the finishing; The detection reaction product has the content of the THPA tung oil of twin nuclei, no longer increases with content and promptly arrives reaction end, and the concrete structure formula is with embodiment 1;
B, reaction system among the step a is cooled to 90 ℃ ± 2 ℃, adds catalyzer tosic acid 0.04g, under this temperature, stir 5min; In flask, drip 8.7g (0.085mol) 2-hydroxyethyl propenyl ether with constant pressure funnel; Rate of addition is as the criterion with the not obvious decline of temperature, drips to finish, and is warming up to carry out the esterification by ring opening reaction under 110 ℃ ± 2 ℃; React about 2h; Detection reaction system acid number no longer changes i.e. reaction end, obtains the product THPA tung oil propenyl ether half ester of THPA tung oil and 2-hydroxyethyl propenyl ether esterification by ring opening reaction, and the concrete structure formula is with embodiment 1;
C, reaction system among the step b is cooled to 90 ℃ ± 2 ℃, adds 10mL toluene, in flask, drip the mixture of 18.3g (0.855mol) trimethylolpropane diacrylate and 0.02g Resorcinol with constant pressure funnel; Rate of addition is as the criterion with the not obvious decline of temperature; Drip to finish, be warming up to and carry out the about 2h of esterification under 110 ℃ ± 2 ℃, detection reaction system acid number no longer changes and promptly arrives reaction end; Decompression at last steams toluene; Obtain the orange-yellow transparent thick liquid nano product of 44.6g, promptly have another kind of the product photocuring THPA tung oil vinylformic acid of the present invention/propenyl ether-ether performed polymer of said structure, productive rate 70.2%.
Embodiment 11:
With tung oil, THPA, 2-hydroxyethyl propenyl ether and pentaerythritol triacrylate is main raw material, makes the another kind of photocuring THPA of the present invention tung oil vinylformic acid/propenyl ether-ether performed polymer, and its concrete structure formula is:
The concrete preparation method of above-mentioned a kind of photocuring THPA tung oil vinylformic acid/propenyl ether-ether performed polymer, basic identical with embodiment 1, difference is:
A, be basic raw material with tung oil and THPA; At first in the there-necked flask of band magnetic agitation and TM, add 25.0g (0.028mol) tung oil, 60 ℃ of vacuum states dewater about 0.5h (its water ratio of the tung oil after the dehydration≤0.10%) down, are warming up to 100 ℃ then; 13.0g (0.085mol) THPA is divided into three equal parts; Every equal portions 10min at interval add in the flask, and temperature can rise automatically therebetween, and the control maximum temperature is not higher than 130 ℃; Make reaction system at 130 ℃ ± 2 ℃ about 4h of isothermal reaction behind reinforced the finishing; The detection reaction product has the content of the THPA tung oil of twin nuclei, no longer increases with content and promptly arrives reaction end, and the concrete structure formula is with embodiment 1;
B, reaction system among the step a is cooled to 90 ℃ ± 2 ℃, adds catalyzer tosic acid 0.04g, under this temperature, stir 5min; In flask, drip 8.7g (0.085mol) 2-hydroxyethyl propenyl ether with constant pressure funnel; Rate of addition is as the criterion with the not obvious decline of temperature, drips to finish, and is warming up to carry out the esterification by ring opening reaction under 110 ℃ ± 2 ℃; React about 2h; Detection reaction system acid number no longer changes i.e. reaction end, obtains the product THPA tung oil propenyl ether half ester of THPA tung oil and 2-hydroxyethyl propenyl ether esterification by ring opening reaction, and the concrete structure formula is with embodiment 1;
C, reaction system among the step b is cooled to 90 ℃ ± 2 ℃, adds 10mL toluene, in flask, drip the mixture of 25.5g (0.085mol) pentaerythritol triacrylate and 0.02g Resorcinol with constant pressure funnel; Rate of addition is as the criterion with the not obvious decline of temperature; Drip to finish, be warming up to and carry out the about 2h of esterification under 110 ℃ ± 2 ℃, detection reaction system acid number no longer changes and promptly arrives reaction end; Decompression at last steams toluene; Obtain the orange-yellow transparent thick liquid nano product of 48.4g, promptly have another kind of the product photocuring THPA tung oil vinylformic acid of the present invention/propenyl ether-ether performed polymer of said structure, productive rate 68.5%.
Embodiment 12:
With tung oil, THPA, 2-hydroxyethyl propenyl ether and vinylformic acid-2,3-epoxy propyl ester is a main raw material, makes the another kind of photocuring THPA of the present invention tung oil vinylformic acid/propenyl ether-ether performed polymer, and its concrete structure formula is:
The concrete preparation method of above-mentioned a kind of photocuring THPA tung oil vinylformic acid/propenyl ether-ether performed polymer, basic identical with embodiment 1, difference is:
A, be basic raw material with tung oil and THPA; At first in the there-necked flask of band magnetic agitation and TM, add 25.0g (0.028mol) tung oil, 60 ℃ of vacuum states dewater about 0.5h (its water ratio of the tung oil after the dehydration≤0.10%) down, are warming up to 100 ℃ then; 13.0g (0.085mol) THPA is divided into three equal parts; Every equal portions 10min at interval add in the flask, and temperature can rise automatically therebetween, and the control maximum temperature is not higher than 130 ℃; Make reaction system at 130 ℃ ± 2 ℃ about 4h of isothermal reaction behind reinforced the finishing; The detection reaction product has the content of the THPA tung oil of twin nuclei, no longer increases with content and promptly arrives reaction end, and the concrete structure formula is with embodiment 1;
B, reaction system among the step a is cooled to 90 ℃ ± 2 ℃, adds catalyzer tosic acid 0.04g, under this temperature, stir 5min; In flask, drip 8.7g (0.085mol) 2-hydroxyethyl propenyl ether with constant pressure funnel; Rate of addition is as the criterion with the not obvious decline of temperature, drips to finish, and is warming up to carry out the esterification by ring opening reaction under 110 ℃ ± 2 ℃; React about 2h; Detection reaction system acid number no longer changes i.e. reaction end, obtains the product THPA tung oil propenyl ether half ester of THPA tung oil and 2-hydroxyethyl propenyl ether esterification by ring opening reaction, and the concrete structure formula is with embodiment 1;
C, reaction system among the step b is cooled to 90 ℃ ± 2 ℃; In flask, drip 10.9g (0.085mol) vinylformic acid-2 with constant pressure funnel, the mixture of 3-epoxy propyl ester, 0.02g Resorcinol and 0.03g triphenylphosphine, rate of addition is as the criterion with the not obvious decline of temperature; Drip and finish; Be warming up to and carry out the about 2h of esterification under 110 ℃ ± 2 ℃, detection reaction system acid number no longer changes and promptly arrives reaction end, obtains the orange-yellow transparent thick liquid nano product of 43.4g; Another kind that promptly has the product photocuring THPA tung oil vinylformic acid of the present invention/propenyl ether-ether performed polymer of said structure, productive rate 75.3%.
Embodiment 13:
With tung oil, THPA, 2-hydroxyethyl propenyl ether and GMA is main raw material, makes another kind of photocuring THPA tung oil vinylformic acid/propenyl ether-ether performed polymer, and its concrete structure formula is:
The concrete preparation method of above-mentioned a kind of photocuring THPA tung oil vinylformic acid/propenyl ether-ether performed polymer, basic identical with embodiment 1, difference is:
A, be basic raw material with tung oil and THPA; At first in the there-necked flask of band magnetic agitation and TM, add 25.0g (0.028mol) tung oil, 60 ℃ of vacuum states dewater about 0.5h (its water ratio of the tung oil after the dehydration≤0.10%) down, are warming up to 100 ℃ then; 13.0g (0.085mol) THPA is divided into three equal parts; Every equal portions 10min at interval add in the flask, and temperature can rise automatically therebetween, and the control maximum temperature is not higher than 130 ℃; Make reaction system at 130 ℃ ± 2 ℃ about 4h of isothermal reaction behind reinforced the finishing; The detection reaction product has the content of the THPA tung oil of twin nuclei, no longer increases with content and promptly arrives reaction end, and the concrete structure formula is with embodiment 1;
B, reaction system among the step a is cooled to 90 ℃ ± 2 ℃, adds catalyzer tosic acid 0.04g, under this temperature, stir 5min; In flask, drip 8.7g (0.085mol) 2-hydroxyethyl propenyl ether with constant pressure funnel; Rate of addition is as the criterion with the not obvious decline of temperature, drips to finish, and is warming up to carry out the esterification by ring opening reaction under 110 ℃ ± 2 ℃; React about 2h; Detection reaction system acid number no longer changes i.e. reaction end, obtains the product THPA tung oil propenyl ether half ester of THPA tung oil and 2-hydroxyethyl propenyl ether esterification by ring opening reaction, and the concrete structure formula is with embodiment 1;
C, reaction system among the step b is cooled to 90 ℃ ± 2 ℃; In flask, drip the mixture of 12.1g (0.085mol) GMA, 0.02g Resorcinol and 0.03g tetraethylammonium bromide with constant pressure funnel; Rate of addition is as the criterion with the not obvious decline of temperature, drips to finish, and is warming up to and carries out the about 2h of esterification under 100 ℃ ± 2 ℃; Detection reaction system acid number no longer changes and promptly arrives reaction end; Obtain the orange-yellow transparent thick liquid nano product of 46.6g, promptly have another kind of the product photocuring THPA tung oil vinylformic acid of the present invention/propenyl ether-ether performed polymer of said structure, productive rate 79.2%.
The photocuring THPA tung oil vinylformic acid/propenyl ether-ether performed polymer that makes and light trigger, reactive thinner etc. are re-dubbed photocuring system according to certain prescription, illumination curing, test performance.Partial results is seen table 1:
| Performed polymer | Surface drying time | Pencil hardness | Sticking power | The water logging bubble |
| Embodiment 1 | <30s | H | 1 grade | No change |
| Embodiment 2 | <30s | H | 2 grades | No change |
| Embodiment 12 | <30s | HB | 1 grade | No change |
Claims (10)
1. photocuring THPA tung oil vinylformic acid/propenyl ether-ether performed polymer, it is characterized in that: the general structure of said photocuring THPA tung oil vinylformic acid/propenyl ether-ether performed polymer is:
Wherein, R
1Be
R
2Be-H or-CH
3
R
3Be 2-hydroxyethyl propenyl ether except that-part the OH, 3-hydroxypropyl propenyl ether except that-part the OH, 4-hydroxybutyl propenyl ether except that-part the OH or 6-hydroxyl hexyl propenyl ether except that-part the OH;
R
4Be 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 the-part the OH, vinylformic acid-2, the part in part in the 3-epoxy propyl ester after the epoxide group open loop or the GMA after the epoxide group open loop.
2. the preparation method of the described photocuring THPA of claim 1 tung oil vinylformic acid/propenyl ether-ether performed polymer is characterized in that said preparation method may further comprise the steps:
A, be basic raw material with tung oil and THPA class monomer; At first tung oil is dewatered; Its water ratio of tung oil after the dehydration≤0.10%, tung oil after the dehydration and THPA class monomer carry out Diels-Alder reaction under heating condition, tung oil after the said dehydration and THPA class monomer between the two the mol ratio of add-on be 1:1～3; Temperature of reaction system is 110～150 ℃; Reaction times is 3～5h, does not become the foundation of reaction end with the content constant of Diels-Alder reaction product THPA tung oil, obtains having the THPA tung oil of twin nuclei after Diels-Alder reaction;
B, under the effect of catalyzer; The THPA tung oil that hydroxyl propenyl ether monomer and step a are obtained carries out the esterification by ring opening reaction; Temperature of reaction system is 90～140 ℃; Reaction times is 1～3h, and invariable with the acid number of this step reaction system is the foundation of reaction end, obtains THPA tung oil propenyl ether half ester after the esterification by ring opening reaction;
Said hydroxyl propenyl ether monomer and THPA tung oil carry out esterification by ring opening when reaction, and anhydride group on the THPA tung oil and the monomeric hydroxyl of the hydroxyl propenyl ether mol ratio between the two is 1:0.9～1.1; The add-on of said catalyzer accounts for 0.1～3.0% of hydroxyl propenyl ether monomer and the two total mass of THPA tung oil;
C, hydroxy acrylate class monomer is at first added stopper and refluxes the band aqua; The stopper consumption accounts for 0.01～1.00% of THPA tung oil propenyl ether half ester and the two total mass of hydroxy acrylate class monomer, and the add-on of said backflow band aqua accounts for 10～30% of THPA tung oil propenyl ether half ester and hydroxy acrylate class monomer total mass; The THPA tung oil propenyl ether half ester that obtains with step b behind the hydroxy acrylate class monomer adding stopper and the band aqua that refluxes carries out esterification; Carboxyl on the said THPA tung oil propenyl ether half ester and the mol ratio between the hydroxyl on the hydroxy acrylate class monomer are 1:0.9～1.1; Esterification reaction temperature is 90～140 ℃; Reaction times is 1～3h; Invariable with the acid number of this step reaction system is the foundation of reaction end, carries out underpressure distillation after reaction finishes and handles, and obtains product photocuring THPA tung oil vinylformic acid of the present invention/propenyl ether-ether performed polymer after the processing;
Perhaps acrylic acid epoxy ester class monomer is added stopper and catalyzer, the stopper consumption accounts for 0.01～1.00% of THPA tung oil propenyl ether half ester and the two total mass of acrylic acid epoxy ester class monomer; Catalyst consumption accounts for 0.1～3.0% of THPA tung oil propenyl ether half ester and the two total mass of acrylic acid epoxy ester class monomer; The THPA tung oil propenyl ether half ester that obtains with step b behind acrylic acid epoxy ester class monomer adding stopper and the catalyzer carries out esterification; Carboxyl on the said THPA tung oil propenyl ether half ester and the mol ratio between the epoxide group on the acrylic acid epoxy ester class monomer are 1:0.9～1.1; Esterification reaction temperature is 90～140 ℃; Reaction times is 1～3h; Invariable with the acid number of this step reaction system is the foundation of reaction end, and reaction promptly obtains product photocuring THPA tung oil vinylformic acid of the present invention/propenyl ether-ether performed polymer after finishing.
3. the preparation method of photocuring THPA tung oil vinylformic acid according to claim 2/propenyl ether-ether performed polymer 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 vinylformic acid according to claim 2/propenyl ether-ether performed polymer is characterized in that: hydroxyl propenyl ether monomer described in the step b is 2-hydroxyethyl propenyl ether, 3-hydroxypropyl propenyl ether, 4-hydroxybutyl propenyl ether or 6-hydroxyl hexyl propenyl ether.
5. the preparation method of photocuring THPA tung oil vinylformic acid according to claim 2/propenyl ether-ether performed polymer, it is characterized in that: catalyzer described in the step b is tosic acid, zinc oxide or sieve catalyst.
6. the preparation method of photocuring THPA tung oil vinylformic acid according to claim 2/propenyl ether-ether performed polymer; It is characterized in that: stopper described in the step c is any in Resorcinol, arylamine, benzoquinones, oil of mirbane, p methoxy phenol, Tert. Butyl Hydroquinone and the DBPC 2,6 ditertiary butyl p cresol.
7. the preparation method of photocuring THPA tung oil vinylformic acid according to claim 2/propenyl ether-ether performed polymer is characterized in that: the band aqua that refluxes described in the step c is any in benzene, toluene and the YLENE.
8. the preparation method of photocuring THPA tung oil vinylformic acid according to claim 2/propenyl ether-ether performed polymer is characterized in that: the class of hydroxy acrylate described in step c 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.
9. the preparation method of photocuring THPA tung oil vinylformic acid according to claim 2/propenyl ether-ether performed polymer, it is characterized in that: the monomer of acrylic acid epoxy ester described in the step c is a vinylformic acid-2,3-epoxy propyl ester or GMA.
10. the preparation method of photocuring THPA tung oil vinylformic acid according to claim 2/propenyl ether-ether performed polymer; It is characterized in that: catalyzer described in the step c is triethylamine, N; N-dimethyl benzylamine, N, any in accelerine, trimethyl benzyl ammonia chloride, triphenylphosphine, antimony triphenyl, chromium acetylacetonate and the tetraethylammonium bromide.
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