CN118652174A - Method for grafting hydroxyethyl acrylate compound on epsilon-caprolactone under catalysis of acid resin - Google Patents
Method for grafting hydroxyethyl acrylate compound on epsilon-caprolactone under catalysis of acid resin Download PDFInfo
- Publication number
- CN118652174A CN118652174A CN202411151241.6A CN202411151241A CN118652174A CN 118652174 A CN118652174 A CN 118652174A CN 202411151241 A CN202411151241 A CN 202411151241A CN 118652174 A CN118652174 A CN 118652174A
- Authority
- CN
- China
- Prior art keywords
- epsilon
- hydroxyethyl acrylate
- caprolactone
- acid resin
- grafting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011347 resin Substances 0.000 title claims abstract description 44
- 229920005989 resin Polymers 0.000 title claims abstract description 44
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000002253 acid Substances 0.000 title claims abstract description 32
- -1 hydroxyethyl acrylate compound Chemical class 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000006555 catalytic reaction Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical class OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000000741 silica gel Substances 0.000 claims description 8
- 229910002027 silica gel Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 229920001610 polycaprolactone Polymers 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000003456 ion exchange resin Substances 0.000 claims description 3
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229920000578 graft copolymer Polymers 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000013270 controlled release Methods 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000007142 ring opening reaction Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000001228 spectrum Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- 238000011085 pressure filtration Methods 0.000 description 5
- 229920001311 Poly(hydroxyethyl acrylate) Polymers 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical class [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052747 lanthanoid Chemical class 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for grafting an epsilon-caprolactone into a hydroxyethyl acrylate compound by using acid resin as a catalyst, wherein the hydroxyethyl acrylate compound is grafted while epsilon-caprolactone is subjected to ring opening under the heating condition, and the structural general formula of the product is as follows:
Description
Technical Field
The invention relates to the technical field of organic catalytic synthesis, in particular to a method for grafting an epsilon-caprolactone grafted hydroxyethyl acrylate compound by using acid resin.
Background
Acrylic resins have found wide application in the fields of coatings, adhesives and composites in terms of their excellent transparency, weatherability and chemical resistance. However, the hardness and toughness of these materials tend to be difficult to optimize simultaneously, limiting their use in higher end applications.
In conventional acrylic resins, increasing toughness tends to result in a decrease in hardness and vice versa. This tradeoff in properties limits the performance of the material in particular applications, especially in the field of 3C (computer, communication, and consumer electronics) product coatings where high abrasion and impact resistance are required.
The caprolactone is grafted to the hydroxyethyl acrylate compound, so that the length and complexity of a branched chain of a molecular chain can be effectively increased, and the hardness and wear resistance of the material are improved on the premise of not sacrificing toughness. However, the traditional grafting copolymerization method has the problems of low grafting efficiency, nonuniform molecular weight distribution, low yield and the like, and at present, zinc acetate or a lanthanide derivative is adopted as a catalyst in the grafting reaction of caprolactone and hydroxyethyl acrylate compounds, so that the search for a green and environment-friendly nonmetallic catalyst to optimize the grafting reaction conditions is imperative.
Disclosure of Invention
The invention aims to solve the technical problems of low grafting efficiency and low yield of the existing graft copolymerization method of caprolactone and hydroxyethyl acrylate compounds, and provides a synthesis method of epsilon-caprolactone grafted hydroxyethyl acrylate compounds by using acid resin, which is simple in process, green and safe.
According to the method for grafting the hydroxyethyl acrylate compound on the epsilon-caprolactone by using the acid resin as a catalyst, the hydroxyethyl acrylate compound is grafted while the epsilon-caprolactone is subjected to ring opening under the heating condition; the technical scheme comprises the following steps:
Mixing epsilon-caprolactone and hydroxyethyl acrylate compounds in a reaction vessel, adding acid resin, placing the reaction system under a heating condition, stirring and reacting for 20-75 hours until the reaction is finished, filtering the reaction system while the reaction system is hot to remove the acid resin, and obtaining oily liquid which is a product poly (epsilon-caprolactone) -poly (hydroxyethyl alkyl acrylate) graft copolymer, and solidifying the product into a solid after cooling, wherein the structural general formula is as follows:
wherein, the value of n is the mole ratio of epsilon-caprolactone to hydroxyethyl acrylate compound, and R is H or C1-C10 alkyl.
As a further preferred embodiment of the present invention, R is H or a saturated alkyl group of C1-C6.
Preferably, in the structural general formula of the product, n=1 to 10.
Preferably, the structural general formula of the hydroxyethyl acrylate compound is as follows:
Wherein r=h or CH 3.
Preferably, the acidic resin is macroporous acidic resin, hydrogen ion exchange resin or hydrogen adsorption resin with the hydrogen ion group capacity of 1.5-8 mmol/g.
Preferably, the molar ratio of the acid resin to the hydroxyethyl acrylate compound is 0.01-0.1:1.
Preferably, the heating is oil bath heating, and the heating temperature is 80-100 ℃. This is because the heating can accelerate the reaction process, and therefore, the grafting reaction is selected to be carried out at a suitably high temperature to accelerate the reaction process.
Preferably, the stirring adopts magnetic stirring, and the stirring rotating speed is 300-500r/min.
Preferably, the filtration is performed by transferring the reaction system to an empty silica gel column and pressurizing to remove the acidic resin.
Compared with the prior caprolactone-grafted acrylic acid hydroxy ester method, the method has the following beneficial effects:
1. The method does not need to use a solvent, has mild and simple reaction conditions, safe operation and low cost, and is suitable for large-scale production.
2. The catalyst used in the invention is acid resin, can be separated from products, and the resin can be regenerated and recycled, so that the discharge of waste water and waste materials in production is reduced, and the catalyst is more environment-friendly.
3. The reaction process of the invention does not need to add polymerization inhibitor.
4. The invention realizes the effective grafting of the hydroxyethyl acrylate compound on epsilon-caprolactone by optimizing the reaction condition and selecting a proper catalyst, improves the purity of the product, and the yield of the product can reach 100 percent.
5. The grafted product combines the excellent performance of epsilon-caprolactone and hydroxyethyl acrylate compounds, and can be widely applied to the fields of biomedicine, drug controlled release, tissue engineering and the like.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of the product of example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance spectrum of the product of example 2 of the present invention;
FIG. 3 is a nuclear magnetic resonance spectrum of the product of example 3 of the present invention;
FIG. 4 is a nuclear magnetic resonance spectrum of the product of example 4 of the present invention;
FIG. 5 is a nuclear magnetic resonance spectrum of the product of example 5 of the present invention;
FIG. 6 is a nuclear magnetic resonance spectrum of the product of example 6 of the present invention.
Detailed Description
The present invention will be described in detail with reference to the following examples. This example will enable one skilled in the art to more fully understand the invention and is not intended to limit it in any way.
Example 1
10G (0.07684 mol) of hydroxyethyl methacrylate, 8.771g (0.07684 mol) of epsilon-caprolactone and 0.2795g (0.07684 multiplied by 0.02 mol) of macroporous strong acid resin (Amberlite-15) (dry type, 5.5 mmol/g) are weighed into a round bottom flask, a magnetic rotor is added, the mixture is stirred and mixed at the rotating speed of 300r/min, the reaction flask is placed into an oil bath at 90 ℃ for heating reaction for 24 hours, the reaction system is transferred to an empty silica gel column for pressure filtration to remove the resin when the reaction is finished, 18.77g (yield 100% and purity is 98% through HPLC) of light yellow oily liquid, namely the product 2- (methacryloyloxy) -6-hydroxycaproic acid ethyl ester is solidified after cooling, and the structural formula is as follows:
The nuclear magnetic spectrum is shown in figure 1, and the nuclear magnetic hydrogen spectrum data is that ：1H NMR (600 MHz, Chloroform-d) δ 6.77 – 5.94 (m, 1H), 5.61 (q, J = 1.8 Hz, 1H), 4.71 – 3.97 (m, 4H), 4.03 – 3.19 (m, 2H), 2.33 (dtd, J = 24.6, 7.5, 2.2 Hz, 2H), 1.96 (dt, J = 9.2, 1.3 Hz, 3H), 1.78 – 1.52 (m, 4H), 1.40 (dddd, J = 12.7, 10.3, 5.8, 2.7 Hz, 2H).
Example 2
10G (0.08612 mol) of hydroxyethyl acrylate, 9.8295g (0.08612 mol) of epsilon-caprolactone and 0.3132g (0.08612 multiplied by 0.02 mol) of macroporous strong acid resin (Amberlite-15) (dry type, 5.5 mmol/g) are weighed into a round bottom flask, a magnetic rotor is added, the mixture is stirred and mixed at the rotating speed of 300r/min, the reaction flask is placed into an oil bath at 80 ℃ for heating reaction for 25 hours, the reaction system is transferred to an empty silica gel column while the reaction is still hot, the resin is removed by pressure filtration, and thus 19.81g (yield 100% and purity of the light yellow oily liquid is 98% through HPLC analysis) is obtained, the oily liquid is the product of ethyl 2- (acryloyloxy) -6-hydroxycaproate, and the product is solidified into a solid after cooling, and has the following structural formula:
the nuclear magnetic spectrum is shown in figure 2, and the nuclear magnetic hydrogen spectrum data is that ：1H NMR (600 MHz, Chloroform-d) δ 6.45 (dd,J= 17.3, 1.4 Hz, 1H),6.26-5.99 (m, 1H), 5.88 (dt,J =10.4,13 Hz,1H),4.88-4.15 (m,4H),4.08-3.82 (m, 1H),3.64 (d,J= 1.2 Hz, 1H),2.34 (dd, J=26.0,2.8 Hz,2H),1.88-1.51 (m, 4H),1.51-1.11 (m, 2H).
Example 3
10G (0.08612 mol) of hydroxyethyl acrylate, 19.659g (2X 0.08612 mol) of epsilon-caprolactone and 0.4533g (0.08612X 0.02 mol) of strong acid ion exchange resin (Amberlite-IR 120) (dry type, 3.8 mmol/g) are weighed into a round bottom flask, a magnetic rotor is added, stirring and mixing are carried out at the rotating speed of 400r/min, the reaction flask is placed into an oil bath at 80 ℃ for heating reaction for 40h, the reaction system is transferred to an empty silica gel column for pressure filtration to remove the resin after the reaction is finished, and 29.64g (yield 100% and purity is 98% through HPLC analysis) of light yellow oily liquid is the product poly (epsilon-caprolactone) -poly (hydroxyethyl acrylate) -2, and the product is solidified into solid after cooling, and has the following structural formula:
The nuclear magnetic spectrum is shown in figure 3, and the nuclear magnetic hydrogen spectrum data is that ：1H NMR (600 MHz, Chloroform-d) δ 6.45 (ddd, J = 17.3, 9.8, 1.4 Hz, 1H), 6.16 (dd, J = 13.9, 3.4 Hz, 1H), 5.88 (dd, J = 10.4, 1.4 Hz, 1H), 4.82 – 4.15 (m, 3H), 4.06 (t, J = 1.8 Hz, 3H), 3.90 – 3.42 (m, 2H), 2.31 (d, J = 3.3 Hz, 4H), 1.98 – 1.50 (m, 9H), 1.40 (d, J = 6.6 Hz, 4H).
Example 4
10G (0.08612 mol) of hydroxyethyl acrylate, 29.4885g (3X 0.08612 mol) of epsilon-caprolactone, 0.5556g (0.08612X 0.02 mol) of strong acid resin (Amberlite-15) (dry type, 3.1 mmol/g) are weighed into a round bottom flask, a magnetic rotor is added, stirring and mixing are carried out at the rotating speed of 400r/min, the reaction flask is placed into an oil bath at 90 ℃ for heating reaction for 48h, the reaction system is transferred to an empty silica gel column for pressurizing and filtering to remove the resin after the reaction is finished, so as to obtain 39.46g (yield 100 percent, purity is 98 percent through HPLC analysis) of light yellow oily liquid, namely the product poly (epsilon-caprolactone) -poly (hydroxyethyl acrylate) -3, and the product is solidified into light yellow solid after cooling, and the structural formula is as follows:
the nuclear magnetic spectrum is shown in figure 4, and the nuclear magnetic hydrogen spectrum data is that ：1H NMR (600 MHz, Chloroform-d) δ 6.44 (dd, J = 17.3, 1.4 Hz, 1H), 6.24–6.05 (m, 1H), 5.87 (dd, J = 10.5, 1.5 Hz, 1H), 4.47–4.15 (m, 3H), 4.06 (ddd, J = 6.7, 4.6, 2.1 Hz, 5H), 3.91–3.24 (m, 2H), 2.31 (s, 6H), 1.65 (dd, J = 7.6, 2.5 Hz, 12H), 1.47–1.14 (m, 6H).
Example 5
10G (0.08612 mol) of hydroxyethyl acrylate, 49.1475g (5X 0.08612 mol) of epsilon-caprolactone and 0.2153g (0.08612X 0.02 mol) of macroporous strong acid resin (Amberlite-15) (dry type, 8.0 mmol/g) are weighed into a round bottom flask, a magnetic rotor is added, the mixture is stirred and mixed at the rotating speed of 500r/min, the reaction flask is placed into an oil bath at 90 ℃ for heating reaction for 60h, the reaction system is transferred to an empty silica gel column for pressure filtration after the reaction is finished, resin is removed, 59.1g (yield 100% and purity is 98% through HPLC) of light yellow oily liquid is obtained, the oily liquid is the product poly (epsilon-caprolactone) -poly (hydroxyethyl acrylate) -5, and the product is solidified into white solid after cooling, and the structural formula is as follows:
the nuclear magnetic spectrum is shown in figure 5, and the nuclear magnetic hydrogen spectrum data is that ：1H NMR (600 MHz, Chloroform-d) δ 6.44 (d, J = 17.1 Hz, 1H), 6.27–5.98 (m, 1H), 5.87 (dd, J = 10.5, 1.5 Hz, 1H), 4.81–4.13 (m, 4H), 4.06 (s, 8H), 3.96–3.30 (m, 2H), 2.31 (s, 10H), 1.89–1.48 (m, 21H), 1.39 (dd, J = 7.5, 2.7 Hz, 10H).
Example 6
10G (0.08612 mol) of hydroxyethyl acrylate, 98.295g (10X 0.08612 mol) of epsilon-caprolactone and 0.3744g (0.08612X 0.02 mol) of D101 adsorption resin (hydrogen form, 4.6 mmol/g) are weighed into a round bottom flask, a magnetic rotor is added, the mixture is stirred and mixed at the rotating speed of 500r/min, the reaction flask is placed into an oil bath at 90 ℃ for heating reaction for 75 hours, the reaction system is transferred to an empty silica gel column for pressure filtration after the reaction is finished, resin is removed, and thus 108.22g (yield 100% and purity of the pale yellow oily liquid is 98% through HPLC analysis) is obtained, the oily liquid is the product poly (epsilon-caprolactone) -poly (hydroxyethyl acrylate) -10, and the product is solidified into white solid after cooling, and the structural formula is as follows:
The nuclear magnetic spectrum is shown in figure 6, and the nuclear magnetic hydrogen spectrum data is that ：1H NMR (600 MHz, Chloroform-d) δ 6.44 (dd, J = 17.4, 1.4 Hz, 1H), 6.14 (dd, J = 17.3, 10.4 Hz, 1H), 5.87 (dd, J = 10.5, 1.4 Hz, 1H), 4.52–4.21 (m, 4H), 4.06 (td, J = 6.7, 2.5 Hz, 18H), 3.65 (t, J = 6.5 Hz, 2H), 2.71–1.98 (m, 21H), 1.79 –1.52 (m,40H), 1.50–1.04 (m, 21H).
Claims (10)
1. The method for grafting the hydroxyethyl acrylate compound on the epsilon-caprolactone by using the acid resin is characterized by comprising the following steps of:
Mixing epsilon-caprolactone and hydroxyethyl acrylate compounds in a reaction vessel, adding acid resin, placing the reaction system under a heating condition, stirring and reacting for 20-75 hours until the reaction is finished, filtering the reaction system while the reaction system is hot to remove the acid resin, and obtaining oily liquid which is a product poly (epsilon-caprolactone) -poly (hydroxyethyl alkyl acrylate) graft copolymer, wherein the product is cooled or solidified into a solid, and the structural general formula is as follows:
wherein, the value of n is the mole ratio of epsilon-caprolactone to hydroxyethyl acrylate compound, and R is H or C1-C10 alkyl.
2. The method for grafting an epsilon-caprolactone onto a hydroxyethyl acrylate compound by using an acid resin according to claim 1, wherein R is H or saturated alkyl of C1-C6.
3. A method for acid resin catalyzed grafting of epsilon-caprolactone onto hydroxyethyl acrylate as claimed in claim 2, wherein n=1-10 in the structural formula of the product.
4. A method for grafting an epsilon-caprolactone into a hydroxyethyl acrylate compound by using acid resin as defined in any one of claims 1-3, wherein the hydroxyethyl acrylate compound has a structural general formula:
Wherein r=h or CH 3.
5. A method for grafting an epsilon-caprolactone into a hydroxyethyl acrylate compound by using an acid resin as claimed in any one of claims 1 to 3, wherein the acid resin is a macroporous acid resin, a hydrogen ion exchange resin or a hydrogen adsorption resin with a hydrogen ion group capacity of 1.5 to 8 mmol/g.
6. A method of acid resin catalyzed e-caprolactone grafting of hydroxyethyl acrylate compound according to any of claims 1-3, wherein the molar ratio of acid resin to hydroxyethyl acrylate compound is 0.01-0.1:1.
7. A method of acid resin catalyzed grafting of epsilon-caprolactone onto hydroxyethyl acrylate as claimed in any of claims 1 to 3 wherein the heating is oil bath heating.
8. The method for grafting an epsilon-caprolactone onto a hydroxyethyl acrylate compound with an acid resin as claimed in claim 7, wherein the heating temperature is 80-100 ℃.
9. A method for acid resin catalyzed grafting of epsilon-caprolactone onto hydroxyethyl acrylate compound as claimed in any of claims 1-3, wherein the stirring is magnetic stirring with a stirring speed of 300-500r/min.
10. A process for the acid resin catalyzed grafting of epsilon-caprolactone onto hydroxyethyl acrylate as claimed in any of claims 1 to 3, wherein the filtration is carried out by transferring the reaction system to an empty silica gel column and pressurizing to remove the acid resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411151241.6A CN118652174A (en) | 2024-08-21 | 2024-08-21 | Method for grafting hydroxyethyl acrylate compound on epsilon-caprolactone under catalysis of acid resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411151241.6A CN118652174A (en) | 2024-08-21 | 2024-08-21 | Method for grafting hydroxyethyl acrylate compound on epsilon-caprolactone under catalysis of acid resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118652174A true CN118652174A (en) | 2024-09-17 |
Family
ID=92707987
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202411151241.6A Pending CN118652174A (en) | 2024-08-21 | 2024-08-21 | Method for grafting hydroxyethyl acrylate compound on epsilon-caprolactone under catalysis of acid resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118652174A (en) |
Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4260813A (en) * | 1978-02-02 | 1981-04-07 | Showa Denko K.K. | Process for the continuous production of ethylene glycol monoethyl ether acetate |
| US4916254A (en) * | 1981-05-11 | 1990-04-10 | Daicel Chemical Industries, Inc. | Process for producing epsilon-caprolactone-modified hydroxyalkyl acrylate or methacrylate and coating copolymer from the same |
| JPH10298143A (en) * | 1997-04-23 | 1998-11-10 | Mitsubishi Rayon Co Ltd | Production of hydroxyalkyl mono(meth)acrylate |
| JP2001151998A (en) * | 1999-11-30 | 2001-06-05 | Daicel Chem Ind Ltd | Method of producing lactone modified reactive monomer composition with reduced lactone chain |
| JP2012126877A (en) * | 2010-11-24 | 2012-07-05 | Toyo Ink Sc Holdings Co Ltd | Pressure sensitive adhesive composition and pressure sensitive adhesive film using the same |
| CN103145699A (en) * | 2007-02-01 | 2013-06-12 | 泰博特克药品有限公司 | Processes and intermediates for preparing a macrocyclic protease inhibitor of hcv |
| CN104447324A (en) * | 2014-11-04 | 2015-03-25 | 大连东方创新科技有限公司 | Arylalkyl methacrylate as well as preparation method and application thereof |
| CN105246936A (en) * | 2013-05-27 | 2016-01-13 | 巴斯夫欧洲公司 | Method for producing urethane (meth)acrylates |
| WO2016043242A1 (en) * | 2014-09-19 | 2016-03-24 | 株式会社巴川製紙所 | Film laminate and polarization plate |
| US20160284450A1 (en) * | 2015-03-25 | 2016-09-29 | Fujifilm Corporation | Magnetic recording medium composition and method of manufacturing magnetic recording medium |
| WO2018038056A1 (en) * | 2016-08-26 | 2018-03-01 | クラレノリタケデンタル株式会社 | Photocurable resin composition |
| WO2018105441A1 (en) * | 2016-12-08 | 2018-06-14 | Dic株式会社 | Active-energy-beam-curable resin composition, and laminate |
| CN110028622A (en) * | 2017-12-22 | 2019-07-19 | 荒川化学工业株式会社 | Actinic energy ray curable resion composition antistatic agent, actinic energy ray curable resion composition, solidfied material and film |
| CN110590984A (en) * | 2019-07-12 | 2019-12-20 | 华伦纳路新材料有限公司 | Preparation method of acrylic resin for flexible plastic |
| JP2021042301A (en) * | 2019-09-10 | 2021-03-18 | 信越化学工業株式会社 | Polymerizable functional group-containing organosiloxane and photocurable composition |
| CN112694602A (en) * | 2020-12-24 | 2021-04-23 | 宁波窦氏化学科技有限公司 | Method for preparing biodegradable plastic PBS |
| CN112812265A (en) * | 2020-12-31 | 2021-05-18 | 安庆飞凯新材料有限公司 | Polyurethane acrylate oligomer, preparation method thereof, coating composition and application thereof |
-
2024
- 2024-08-21 CN CN202411151241.6A patent/CN118652174A/en active Pending
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4260813A (en) * | 1978-02-02 | 1981-04-07 | Showa Denko K.K. | Process for the continuous production of ethylene glycol monoethyl ether acetate |
| US4916254A (en) * | 1981-05-11 | 1990-04-10 | Daicel Chemical Industries, Inc. | Process for producing epsilon-caprolactone-modified hydroxyalkyl acrylate or methacrylate and coating copolymer from the same |
| JPH10298143A (en) * | 1997-04-23 | 1998-11-10 | Mitsubishi Rayon Co Ltd | Production of hydroxyalkyl mono(meth)acrylate |
| JP2001151998A (en) * | 1999-11-30 | 2001-06-05 | Daicel Chem Ind Ltd | Method of producing lactone modified reactive monomer composition with reduced lactone chain |
| CN103145699A (en) * | 2007-02-01 | 2013-06-12 | 泰博特克药品有限公司 | Processes and intermediates for preparing a macrocyclic protease inhibitor of hcv |
| JP2012126877A (en) * | 2010-11-24 | 2012-07-05 | Toyo Ink Sc Holdings Co Ltd | Pressure sensitive adhesive composition and pressure sensitive adhesive film using the same |
| CN105246936A (en) * | 2013-05-27 | 2016-01-13 | 巴斯夫欧洲公司 | Method for producing urethane (meth)acrylates |
| WO2016043242A1 (en) * | 2014-09-19 | 2016-03-24 | 株式会社巴川製紙所 | Film laminate and polarization plate |
| CN104447324A (en) * | 2014-11-04 | 2015-03-25 | 大连东方创新科技有限公司 | Arylalkyl methacrylate as well as preparation method and application thereof |
| US20160284450A1 (en) * | 2015-03-25 | 2016-09-29 | Fujifilm Corporation | Magnetic recording medium composition and method of manufacturing magnetic recording medium |
| WO2018038056A1 (en) * | 2016-08-26 | 2018-03-01 | クラレノリタケデンタル株式会社 | Photocurable resin composition |
| WO2018105441A1 (en) * | 2016-12-08 | 2018-06-14 | Dic株式会社 | Active-energy-beam-curable resin composition, and laminate |
| CN110028622A (en) * | 2017-12-22 | 2019-07-19 | 荒川化学工业株式会社 | Actinic energy ray curable resion composition antistatic agent, actinic energy ray curable resion composition, solidfied material and film |
| CN110590984A (en) * | 2019-07-12 | 2019-12-20 | 华伦纳路新材料有限公司 | Preparation method of acrylic resin for flexible plastic |
| JP2021042301A (en) * | 2019-09-10 | 2021-03-18 | 信越化学工業株式会社 | Polymerizable functional group-containing organosiloxane and photocurable composition |
| CN112694602A (en) * | 2020-12-24 | 2021-04-23 | 宁波窦氏化学科技有限公司 | Method for preparing biodegradable plastic PBS |
| CN112812265A (en) * | 2020-12-31 | 2021-05-18 | 安庆飞凯新材料有限公司 | Polyurethane acrylate oligomer, preparation method thereof, coating composition and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20110052742A (en) | N-(1-hydroxyethyl)carboxamide compound and process for producing same | |
| CN101423577B (en) | Method for preparing polyacrylic acid or sodium polyacrylate | |
| CN113278143B (en) | Efficient unsaturated carbon dioxide-based polyol and preparation method thereof | |
| CN112264095B (en) | Polymeric ionic liquid solid acid catalyst for catalyzing esterification reaction of pentaerythritol and oleic acid and preparation method thereof | |
| CN118652174A (en) | Method for grafting hydroxyethyl acrylate compound on epsilon-caprolactone under catalysis of acid resin | |
| JP4136886B2 (en) | Polymers of novel alicyclic vinyl ethers | |
| CN113912500A (en) | Method for preparing amine compound by using microchannel reactor | |
| CN111018711A (en) | Acrylate synthesis method with low polymerization inhibitor | |
| Jaswal et al. | Curing and decomposition behaviour of cresol novolac based vinyl ester resin | |
| CN114846033B (en) | Cyclic carbonate group-containing (meth) acrylate monomers and polymers | |
| CN101497569A (en) | Method for synthesizing allyl alcohol polyoxyethylene ether methacrylate | |
| CN118724705A (en) | Method for catalyzing epsilon-caprolactone to graft hydroxyethyl acrylate compound by using aromatic sulfonic acid | |
| CN101089028B (en) | Process of preparing oxyalkylene-base unsaturated ester polymer | |
| EP0151495B1 (en) | Polyfunctional acrylate derivatives of caprolactone-polyols | |
| CN118652175A (en) | Method for catalyzing epsilon-caprolactone to graft hydroxyethyl acrylate compound by using aromatic phosphate | |
| CN109704962A (en) | A kind of more acrylate monomers of water soluble polyhydroxy and preparation method thereof | |
| CN111013657A (en) | Polymeric ionic liquid solid acid catalyst for catalyzing esterification reaction of trimethylolpropane and oleic acid and preparation method thereof | |
| EP1185537B1 (en) | Benzylidenecyanoacetates and a method for making benzylidenecyanoacetates | |
| JPH02193944A (en) | Production of (meth)acrylic acid ester | |
| EP2892872B1 (en) | Liquid 1,3/1,4-alkoxylated cyclohexanedimethanol based diacrylates | |
| CN107827935B (en) | α -diimine nickel complex with butanedione skeleton and preparation method and application thereof | |
| JP3900313B2 (en) | Method for producing modified copolymer | |
| KR101178238B1 (en) | Method for preparing alkylacrylate by azetropic ester reaction | |
| JP3831822B2 (en) | Propenyl group-containing acrylic or methacrylic compound | |
| JPH0369337B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |