CN117843917A - Polyurethane acrylate oligomer for dry film and preparation method thereof - Google Patents
Polyurethane acrylate oligomer for dry film and preparation method thereof Download PDFInfo
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- CN117843917A CN117843917A CN202310703071.7A CN202310703071A CN117843917A CN 117843917 A CN117843917 A CN 117843917A CN 202310703071 A CN202310703071 A CN 202310703071A CN 117843917 A CN117843917 A CN 117843917A
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- acrylate oligomer
- oligomer
- polyurethane
- dry film
- polyol
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 44
- 239000004814 polyurethane Substances 0.000 title claims abstract description 44
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims abstract description 13
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- 229920005862 polyol Polymers 0.000 claims description 25
- 150000003077 polyols Chemical class 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 claims description 20
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 15
- 229920005906 polyester polyol Polymers 0.000 claims description 15
- 229920000570 polyether Polymers 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000006068 polycondensation reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000000016 photochemical curing Methods 0.000 abstract description 5
- 238000007039 two-step reaction Methods 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 description 8
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 238000007792 addition Methods 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- YGSFNCRAZOCNDJ-UHFFFAOYSA-N propan-2-one Chemical compound CC(C)=O.CC(C)=O YGSFNCRAZOCNDJ-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
Abstract
The invention discloses a polyurethane acrylate oligomer for a dry film and a preparation method thereof, comprising the steps of synthesizing a polyurethane oligomer 1; synthesis of urethane acrylate oligomer: and (3) performing chain extension reaction on the polyurethane oligomer 1 obtained in the step (1) and hydroxyethyl acrylate in the presence of a catalyst and hydroquinone to synthesize the polyurethane acrylate oligomer. The invention synthesizes the trifunctional polyurethane acrylate oligomer by a two-step reaction method. The oligomer contains photoreactive double bonds and has a functional number of 3, and also contains the chain length flexibility of the polyurethane oligomer. When participating in the subsequent photo-curing, provides excellent flexibility and adhesion to the dry film.
Description
Technical Field
The invention belongs to the field of resin, relates to polyurethane acrylate oligomer, and in particular relates to polyurethane acrylate oligomer for a dry film and a preparation method thereof.
Background
The acrylic dry film is prepared by coating a dry film glue solution on a PET film, drying the PET film by a baking oven and compounding the PE film, wherein the dry film glue solution consists of acrylic resin, a photoreaction monomer, a photoinitiator, other assistants and the like. The photoreactive monomer is a small molecular oligomer containing unsaturated double bonds, and most of photoreactive monomers used for dry films on the market are conventional acrylic monomers.
However, the conventional acrylic monomer is a small molecular monomer, and the photo-reaction to form a polymer has poor mechanical strength, affects the cap hole and adhesive force characteristics of the dry film of the PCB, and has a slow photo-polymerization efficiency of the general urethane acrylate.
Disclosure of Invention
In order to solve the problems, the invention provides a polyurethane acrylate oligomer for a dry film and a preparation method thereof. The oligomer contains photoreactive polymerized double bonds, has a functional number of 3, and also contains the chain length flexibility of the polyurethane oligomer, so that the polyurethane oligomer provides excellent flexibility and adhesive force for a dry film when participating in subsequent photocuring.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention firstly provides a preparation method of polyurethane acrylate oligomer for a dry film, which comprises the following steps:
1) Synthesizing polyurethane oligomer 1, namely, synthesizing polyurethane oligomer 1 by performing polycondensation reaction on HDI trimer and polyol in a solvent system through a catalyst;
2) Synthesis of urethane acrylate oligomer: and (3) performing chain extension reaction on the polyurethane oligomer 1 obtained in the step (1) and hydroxyethyl acrylate in the presence of a catalyst and hydroquinone to synthesize the polyurethane acrylate oligomer.
In the step 2), the catalyst is an organotin catalyst, and the addition amount of the organotin catalyst is 0.2-0.22% of the total mass of the reaction system of the HDI trimer and the polyol; the addition amount of hydroquinone is 0.1-0.12% of the total mass of the reaction system of HDI trimer and polyol.
As a preferred embodiment of the present invention, the organotin-based catalyst is dibutyltin dilaurate.
As a preferable scheme of the invention, the solvent system is a mixed solution of toluene and acetone, and 102-105 parts of toluene and 50-55 parts of acetone are added according to parts by weight.
As a preferred scheme of the invention, the specific steps of the step 1) are as follows: adding a solvent system into a reaction vessel, adding the HDI trimer into the solvent system, introducing dry nitrogen, dropwise adding polyol, and reacting for 2-3h at room temperature.
As a preferable scheme of the invention, the polyol comprises polyether polyol and polyester polyol, and the dripping time is 55-65min; wherein, 50 parts of HDI trimer, 100 parts of polyether polyol and 100 parts of polyester polyol are added according to parts by weight.
As a preferred scheme of the present invention, the specific steps of the step 2) are as follows: heating to 70-80 ℃, adding a catalyst and hydroquinone into a reaction container, dropwise adding hydroxyethyl acrylate into the reaction container for 85-95min, reacting for 4-5h, and cooling to room temperature to obtain polyurethane acrylate oligomer; 25-35 parts of hydroxyethyl acrylate are added according to weight fraction.
As a preferred embodiment of the present invention, the polyurethane oligomer 1 has the structural formula
The invention also provides a polyurethane acrylate oligomer for the dry film prepared by the preparation method.
In the present invention, the trifunctional urethane acrylate oligomer is synthesized by a two-step reaction process. The oligomer contains photoreactive double bonds and has a functional number of 3, and also contains the chain length flexibility of the polyurethane oligomer. When participating in the subsequent photo-curing, provides excellent flexibility and adhesion to the dry film.
The invention makes HDI trimer and polyol (polyether, polyester polyol) produce polycondensation reaction in the presence of solvent system by means of catalyst to synthesize polymer 1, and in the second step, the acrylate monomer containing hydroxyl group is undergone the process of dripping, and polymerized in the presence of organotin catalyst to form polyurethane acrylate oligomer. Wherein, polyether polyol PPG1000 and PPG2000, and polyester polyol is polyethylene glycol adipate and polyethylene glycol hexanedioldite.
Compared with the prior art, the invention has the following beneficial effects:
1) The invention synthesizes the trifunctional polyurethane acrylate oligomer by a two-step reaction method. The oligomer contains photoreactive double bonds and has a functional number of 3, and also contains the chain length flexibility of the polyurethane oligomer. When participating in the subsequent photo-curing, provides excellent flexibility and adhesion to the dry film.
2) The urethane acrylate oligomer of the present invention is excellent in flexibility and adhesion to a PCB.
Detailed Description
In order to facilitate understanding of the technical means, the creation characteristics, the achievement of the objects and the effects achieved by the present invention, the present invention is further described below with reference to specific examples, but the following examples are only preferred examples of the present invention, not all of which are described in detail below. Based on the examples in the embodiments, those skilled in the art can obtain other examples without making any inventive effort, which fall within the scope of the invention. The experimental methods in the following examples are conventional methods unless otherwise specified, and materials, reagents, etc. used in the following examples are commercially available unless otherwise specified.
The invention makes HDI trimer and polyol (polyether, polyester polyol) produce polycondensation reaction in the presence of solvent system by means of catalyst to synthesize polymer 1, and in the second step, the acrylate monomer containing hydroxyl group is undergone the process of dripping, and polymerized in the presence of organotin catalyst to form polyurethane acrylate oligomer.
Example 1
The present example provides a method for preparing a urethane acrylate oligomer for a dry film, comprising:
adding 100g of toluene, 50g of acetone solvent and HDI trimer into a three-necked bottle provided with a reflux condenser (with a drying pipe), a stirrer and a constant-pressure dropping funnel, mixing, introducing dry nitrogen, dropping the mixed solution of polyether polyol and polyester polyol by using the dropping funnel (the dropping is completed within 60 min), and reacting for 2 hours below room temperature; heating to 70 ℃, adding 0.2% of dibutyltin dilaurate and 0.1% of hydroquinone which are used for the total mass of the reaction system of HDI trimer, polyether polyol and polyester polyol into a three-necked bottle, adding 30g of hydroxyethyl acrylate (dropwise adding is controlled within 90 min) into the constant pressure drain, and reacting for 4 hours. Cooling to room temperature to obtain the polyurethane acrylate oligomer.
In this example, the polyether polyol was PPG1000 and the polyester polyol was polyethylene glycol adipate 2000. Wherein 50g (0.1 mol) of HDI trimer, 1000 100g (0.1 mol) of PPG, 2000 100g (0.05 mol) of PEA were weighed.
Example 2
The present example provides a method for preparing a urethane acrylate oligomer for a dry film, comprising:
105g of toluene and 52g of acetone solvent are added into a three-necked bottle provided with a reflux condenser (with a drying pipe), a stirrer and a constant-pressure dropping funnel to be mixed with HDI trimer, dry nitrogen is introduced, the mixed solution of polyether polyol and polyester polyol is dropped into the dropping funnel (the dropping is controlled to be completed within 55 min), and the reaction is carried out for 2.5h below room temperature; to the three-necked flask, dibutyltin dilaurate (0.22%) and hydroquinone (0.12%) were added in an amount of 0.22% based on the total mass of the reaction system of HDI trimer+polyether polyol and polyester polyol, and 25g of hydroxyethyl acrylate (dropwise addition was completed within 85 min) was added to the above-mentioned constant pressure flask, followed by a reaction for 4.5 hours. Cooling to room temperature to obtain the polyurethane acrylate oligomer.
In this example, PPG1000 is selected as the polyether polyol and polyethylene glycol adipate 2000 is selected as the polyester polyol. Wherein 50g (0.1 mol) of HDI trimer, 1000 100g (0.1 mol) of PPG, 2000 100g (0.05 mol) of PEA were weighed.
Example 3
The present example provides a method for preparing a urethane acrylate oligomer for a dry film, comprising:
adding 102g of toluene, 55g of acetone solvent and HDI trimer into a three-necked bottle provided with a reflux condenser (with a drying pipe), a stirrer and a constant-pressure dropping funnel, mixing, introducing dry nitrogen, dropping the mixed solution of polyether polyol and polyester polyol by using the dropping funnel (the dropping is controlled to be completed within 65 min), and reacting for 3 hours below room temperature; to the three-necked flask, dibutyltin dilaurate (0.21%) and hydroquinone (0.11%) were added, and 35g of hydroxyethyl acrylate (dropwise addition was completed within 95 min) was added to the constant pressure flask, followed by reaction for 5 hours. Cooling to room temperature to obtain the polyurethane acrylate oligomer.
In this example, PPG1000 is selected as the polyether polyol and polyethylene glycol adipate 2000 is selected as the polyester polyol. Wherein 50g (0.1 mol) of HDI trimer, 1000 100g (0.1 mol) of PPG, 2000 100g (0.05 mol) of PEA were weighed.
The urethane acrylate oligomer prepared in example 1 was used to prepare a dry film according to the formulation described in table 1 and a dry film prepared in the control group (without urethane acrylate oligomer added) by the prior art, and the adhesion and flexibility were measured, and the measurement results are shown in table 2.
TABLE 1 Dry film formulation
| Dry film formulation | Control group | Example 1 |
| Acrylic resin | 100 | 100 |
| HDDA | 20 | 20 |
| HDDMA | 30 | 20 |
| Polyurethane acrylate oligomers | 0 | 10 |
| Photoinitiator 184 | 1.2 | 1.2 |
| Pigment | 0.3 | 0.3 |
| Acetone (acetone) | 30 | 30 |
| Methanol | 20 | 20 |
TABLE 2 test results
| Test item | Control group | Example 1 |
| Dry film thickness | 40 | 40 |
| 20 th order energy | 35 | 35 |
| Analysis 1 (x/x) | 40 | 35 |
| Analysis 2 (x/400) | 40 | 35 |
| Adhesion force | 35 | 20 |
Therefore, the invention synthesizes the trifunctional polyurethane acrylate oligomer through a two-step reaction method. The oligomer contains photoreactive double bonds and has a functional number of 3, and also contains the chain length flexibility of the polyurethane oligomer. When participating in the subsequent photo-curing, provides excellent flexibility and adhesion to the dry film.
While the invention has been described with respect to preferred embodiments thereof, it will be understood by those skilled in the art that various modifications and additions may be made without departing from the scope of the invention. Equivalent embodiments of the present invention will be apparent to those skilled in the art having the benefit of the teachings disclosed herein, when considered in the light of the foregoing disclosure, and without departing from the spirit and scope of the invention; meanwhile, any equivalent changes, modifications and evolution of the above embodiments according to the essential technology of the present invention still fall within the scope of the technical solution of the present invention.
Claims (9)
1. A method for preparing a polyurethane acrylate oligomer for a dry film, the method comprising the steps of:
1) Synthesis of polyurethane oligomer 1 is synthesized by polycondensation of HDI trimer and polyol in a solvent system and with a catalyst
2) Synthesis of urethane acrylate oligomer: and (3) performing chain extension reaction on the polyurethane oligomer 1 obtained in the step (1) and hydroxyethyl acrylate in the presence of a catalyst and hydroquinone to synthesize the polyurethane acrylate oligomer.
2. The method for preparing polyurethane acrylate oligomer for dry film according to claim 1, wherein in the step 2), the catalyst is an organotin catalyst, and the addition amount of the organotin catalyst is 0.2-0.22% of the total mass of the reaction system of HDI trimer and polyol; the addition amount of hydroquinone is 0.1-0.12% of the total mass of the reaction system of HDI trimer and polyol.
3. The method for producing a urethane acrylate oligomer for dry films according to claim 2, wherein said organotin-based catalyst is dibutyltin dilaurate.
4. The method for preparing polyurethane acrylate oligomer for dry film according to claim 1, wherein the solvent system is a mixed solution of toluene and acetone, and 102-105 parts of toluene and 50-55 parts of acetone are added according to parts by weight.
5. The method for preparing a polyurethane acrylate oligomer for dry films according to claim 1, wherein the specific steps of step 1) are as follows: adding a solvent system into a reaction vessel, adding the HDI trimer into the solvent system, introducing dry nitrogen, dropwise adding polyol, and reacting for 2-3h at room temperature.
6. The method for preparing a polyurethane acrylate oligomer for a dry film according to claim 5, wherein the polyol comprises polyether polyol and polyester polyol, and the dripping time is 55-65min; wherein, 50 parts of HDI trimer, 100 parts of polyether polyol and 100 parts of polyester polyol are added according to parts by weight.
7. The method for preparing polyurethane acrylate oligomer for dry film according to claim 1, wherein the specific steps of the step 2) are as follows: heating to 70-80 ℃, adding a catalyst and hydroquinone into a reaction container, dropwise adding hydroxyethyl acrylate into the reaction container for 85-95min, reacting for 4-5h, and cooling to room temperature to obtain polyurethane acrylate oligomer; 25-35 parts of hydroxyethyl acrylate are added according to weight fraction.
8. The method for preparing a polyurethane acrylate oligomer for dry film according to claim 1, wherein the polyurethane oligomer 1 has a structural formula of
9. A urethane acrylate oligomer for a dry film, characterized by being prepared by the preparation method according to any one of claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310703071.7A CN117843917A (en) | 2023-06-14 | 2023-06-14 | Polyurethane acrylate oligomer for dry film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310703071.7A CN117843917A (en) | 2023-06-14 | 2023-06-14 | Polyurethane acrylate oligomer for dry film and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117843917A true CN117843917A (en) | 2024-04-09 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310703071.7A Pending CN117843917A (en) | 2023-06-14 | 2023-06-14 | Polyurethane acrylate oligomer for dry film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117843917A (en) |
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2023
- 2023-06-14 CN CN202310703071.7A patent/CN117843917A/en active Pending
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