CN105175650A - Benzene-free modified acrylic resin for PP substrate and preparation method thereof - Google Patents
Benzene-free modified acrylic resin for PP substrate and preparation method thereof Download PDFInfo
- Publication number
- CN105175650A CN105175650A CN201510627835.4A CN201510627835A CN105175650A CN 105175650 A CN105175650 A CN 105175650A CN 201510627835 A CN201510627835 A CN 201510627835A CN 105175650 A CN105175650 A CN 105175650A
- Authority
- CN
- China
- Prior art keywords
- acrylic resin
- benzene
- solvent
- acid
- free type
- 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.)
- Granted
Links
Abstract
The invention provides benzene-free modified acrylic resin for a PP substrate. The benzene-free modified acrylic resin for the PP substrate is prepared from, by mass, 3%-10% of double-bond epoxy intermediates, 3%-10% of rosin resin or hydrogenated rosin resin, 3%-10% of chlorinated polypropylene, 30%-55% of acrylic ester monomers, 0.5%-1.5% of initiator and 35%-60% of solvent. Correspondingly, the invention further provides a preparation method of the benzene-free modified acrylic resin for the PP substrate. According to the benzene-free modified acrylic resin for the PP substrate, the grafting rate of the chlorinated polypropylene is high, and the resin is good in stability and storing performance and not prone to layering. A paint film prepared from the benzene-free modified acrylic resin has excellent adhesive force to the PP substrate, pretreatment on the substrate or addition of adhesion promoter are not needed, the resin is stable in performance and good in storing performance, the application property is good, silver powder distribution is excellent, the high temperature resistance and the high humidity resistance are excellent, the alcohol resistance and the water resistance are excellent, benzene solvent is not contained, and the market prospect is wide.
Description
Technical field
The present invention relates to acrylic coating technical field, it is acrylic resin modified and preparation method thereof to be specifically related to a kind of PP ground benzene-free type.
Background technology
Polypropylene (PP) material source is abundant, low price, in recent years, along with the adjustment of polypropylene (PP) plastics product quality develops, performance improves constantly, and acrylic plastering component obtain large-scale popularization and application in fields such as household electric appliances, automobile industry, toy industries.But polypropylene material degree of crystallinity is high, solvent resistance is strong, surface polarity and surface energy low, film is difficult to attachment, add the multi items of acrylic plastering, thus the coating of polypropylene (PP) plastics and application thereof become the problem that everybody extremely pays close attention to.
Chlorinated Polypropylene III (CPP) has good sticking power to non-polar plastic polypropylene (PP), has been widely used in polypropylene (PP) coating.But along with diversification and the Focus development gradually of polypropylene (PP) material applications, the performance of Chlorinated Polypropylene III (CPP) is had higher requirement, therefore the research that Chlorinated Polypropylene III (CPP) carries out modification is also increased gradually.But, current PP ground resin ubiquity such as poor adhesive force on the market (need beat PP water, or other pre-treatments), poor, the poor storage stability of application property bad, silver powder arrangement, easy layering, the problems such as ground bad adaptability, limit its range of application, and mostly adopting toluene or dimethylbenzene as solvent, toxicity is larger.
A kind of environment friendly chlorinated polypropylene modified acrylic acid resin primer and preparation method thereof disclosed in Chinese patent CN101914337A, adopt non-benzene kind solvent synthetic environment-friendly chlorinated polypropylene modified acrylic acid resin, synthesis technique adopts and once feeds intake, though simple to operate, but side reaction is more, the more difficult control of exothermic heat of reaction, and still need to add the sticking power of adhesion promoter raising to PP ground.
Summary of the invention
For above-mentioned technical problem, the invention provides a kind of PP ground benzene-free type acrylic resin modified, by first synthesizing double bond epoxy intermediate, add Gum Rosin or hydrogenated rosin resin carries out composite modified, increase substantially the percentage of grafting of acrylic ester monomer to Chlorinated Polypropylene III, improve the sticking power to PP ground, resin stability is good, not easily layering.
Technical problem to be solved by this invention is also, additionally provides the preparation method that a kind of PP ground benzene-free type is acrylic resin modified.
In order to realize technical purpose of the present invention, the present invention adopts following technical scheme:
A kind of PP ground benzene-free type is acrylic resin modified, by mass percentage, by the double bond epoxy intermediate of 3%-10%, the Gum Rosin of 3%-10% or hydrogenated rosin resin, the Chlorinated Polypropylene III of 3%-10%, the acrylic monomer of 30%-55% or acrylic ester monomer, the solvent composition of 0.5%-1.5% initiator and 50%-60%.
Preferably; described double bond epoxy intermediate is by the epoxy resin of (mass percent) 30%-50%; the polyprotonic acid of 8%-20% or multi-anhydride; after the solvent of 40%-60% and the oxalic acid of 0.005%-0.015% mix in a kettle.; be heated to reflux temperature reaction under nitrogen protection, to acid number≤60mgKOH/g.
Preferably, described epoxy resin is tertiary carbonic acid glycidyl ester, one or more in bisphenol A epoxide resin E20, E44, E51 mix with arbitrary proportion.
Preferably, described polyprotonic acid or multi-anhydride are cis-butenedioic anhydrides, one or more in fumaric acid, Succinic anhydried mix with arbitrary proportion.
Preferably, described acrylic monomer is methacrylic acid, one or both in vinylformic acid mix with arbitrary proportion; Described acrylic ester monomer is methyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, Tert-butyl Methacrylate, cyclohexyl methacrylate, lauryl methacrylate(LMA), isobutyl acrylate, tert-butyl acrylate, hydroxyethyl methylacrylate one or more mix with arbitrary proportion.
Preferably, described initiator is benzoyl peroxide, one or more in peroxidized t-butyl perbenzoate, the peroxidation 2 ethyl hexanoic acid tert-butyl ester, di-t-butyl peroxide mix with arbitrary proportion.
Preferably, described solvent is vinyl acetic monomer, one or more in N-BUTYL ACETATE, 2-butyl acetate, methyl iso-butyl ketone (MIBK), acetone mix with arbitrary proportion.
Accordingly, present invention also offers the preparation method that a kind of PP ground benzene-free type is acrylic resin modified, adopt following steps:
A the solvent of the double bond epoxy intermediate of whole proportioning, Gum Rosin or hydrogenated rosin resin, Chlorinated Polypropylene III and total solvent quality 10%-20% joins in reactor by (), stir, under nitrogen protection, 1-2 hour is reacted under being warming up to reflux temperature;
B acrylic ester monomer that () then drips whole proportioning and the mixture be made up of total initiator quality 40%-70% and total solvent quality 5%-10%, time for adding is 2-4 hour, drips rear continuation reaction 2-4 hour;
C () adds the mixture be made up of total initiator quality 15%-20% and total solvent quality 2%-4%, continue reaction 1-3 hour;
D () adds the mixture be made up of the initiator of residue proportioning and total solvent quality 2%-4%, continue reaction 4-6 hour;
E () is lowered the temperature, add the solvent of residue proportioning, discharging after stirring.
The beneficial effect that the present invention has: the present invention has the double bond epoxy intermediate of high reaction activity by first synthesis, carry out composite modified by introducing double bond epoxy intermediate, Gum Rosin or hydrogenated rosin resin to Chlorinated Polypropylene III again, compared with prior art, the percentage of grafting of acrylic ester monomer to Chlorinated Polypropylene III has been increased substantially.With the present invention prepare acrylic resin modified, grafted chlorinated polypropylene rate is high, resin stability, and storage characteristics is good, not easily layering, the paint film standby by resin-made of the present invention is excellent to PP substrate adhesion, and without the need to doing pre-treatment to ground or adding adhesion promoter, resin property is stablized, storage characteristics is good, application property is good, silver powder arrangement is excellent, high-temp resisting high-humidity resisting performance is excellent, alcohol resistance and excellent water resistance, not containing benezene solvent, and cheap, wide market.
Embodiment
For a better understanding of the present invention, be described in detail invention below in conjunction with embodiment, following component all by percentage to the quality.
Embodiment 1:
(1) double bond epoxy intermediate is prepared; using the bisphenol A epoxide resin E51 of 35%, 10% cis-butenedioic anhydride, the vinyl acetic monomer of 30%, the N-BUTYL ACETATE of 24.995% and 0.005% oxalic acid join in reactor as catalyzer; be uniformly mixed; pass into nitrogen air is discharged; heated and stirred is to reflux temperature under nitrogen protection; reaction, to acid number≤60mgKOH/g, obtains this double bond epoxy intermediate.
(2) prepare acrylic resin modified, each raw material add-on of step (a) ~ (e) is in table 1.
The acrylic resin modified each step raw material of table 1 embodiment 1 adds scale
Dropped in reactor by raw material in step (a), stir, logical nitrogen gas stirring is heated to reflux temperature and reacts 1 hour; Drip step (b) Raw, time for adding is 3 hours, after dropwising, and reacts 3 hours at a reflux temperature; Add step (c) Raw, be then incubated 2 hours at a reflux temperature; Add step (d) Raw, continue reaction 5 hours; Cooling, adds remaining raw material in step (e), stopped reaction after stirring, obtains a kind of PP ground benzene-free type of the present invention acrylic resin modified.
Embodiment 2:
(1) double bond epoxy intermediate is prepared; the mixture that the bisphenol A epoxide resin E44 of 40%, the fumaric acid of 8% and Succinic anhydried are formed using arbitrary proportion, the vinyl acetic monomer of 30%, the acetone of 21.995% and 0.005% oxalic acid join in reactor as catalyzer; be uniformly mixed; pass into nitrogen air is discharged; heated and stirred is to reflux temperature under nitrogen protection; reaction, to acid number≤60mgKOH/g, obtains this double bond epoxy intermediate.
(2) prepare acrylic resin modified, each raw material add-on of step (a) ~ (e) is in table 2.
The acrylic resin modified each step raw material of table 2 embodiment 2 adds scale
Dropped in reactor by raw material in step (a), stir, logical nitrogen gas stirring is heated to reflux temperature and reacts 2 hours; Drip step (b) Raw, time for adding is 4 hours, after dropwising, and reacts 2 hours at a reflux temperature; Add step (c) Raw, be then incubated 3 hours at a reflux temperature; Add step (d) Raw, continue reaction 6 hours; Cooling, adds remaining raw material in step (e), stopped reaction after stirring, obtains a kind of PP ground benzene-free type of the present invention acrylic resin modified.
Embodiment 3:
(1) double bond epoxy intermediate is prepared; the mixture that the mixture formed by bisphenol A epoxide resin E44 and E20 of the arbitrary proportion of 50%, the fumaric acid of 9.99% and Succinic anhydried form using arbitrary proportion, the 2-butyl acetate of 20%, the methyl iso-butyl ketone (MIBK) of 20% and 0.010% oxalic acid join in reactor as catalyzer; be uniformly mixed; pass into nitrogen air is discharged; heated and stirred is to reflux temperature under nitrogen protection; reaction, to acid number≤60mgKOH/g, obtains this double bond epoxy intermediate.
(2) prepare acrylic resin modified, each raw material add-on of step (a) ~ (e) is in table 3.
The acrylic resin modified each step raw material of table 3 embodiment 3 adds scale
Dropped in reactor by raw material in step (a), stir, logical nitrogen gas stirring is heated to reflux temperature and reacts 2 hours; Drip step (b) Raw, time for adding is 2 hours, after dropwising, and reacts 4 hours at a reflux temperature; Add step (c) Raw, be then incubated 1 hour at a reflux temperature; Add step (d) Raw, continue reaction 4 hours; Cooling, adds remaining raw material in step (e), stopped reaction after stirring, obtains a kind of PP ground benzene-free type of the present invention acrylic resin modified.
Embodiment 4:
(1) double bond epoxy intermediate is prepared; the mixture that the bisphenol A epoxide resin E20 of 30%, the cis-butenedioic anhydride of 9.985% and Succinic anhydried are formed using arbitrary proportion, the 2-butyl acetate of 35%, the methyl iso-butyl ketone (MIBK) of 25% and 0.015% oxalic acid join in reactor as catalyzer; be uniformly mixed; pass into nitrogen air is discharged; heated and stirred is to reflux temperature under nitrogen protection; reaction, to acid number≤60mgKOH/g, obtains this double bond epoxy intermediate.
(2) prepare acrylic resin modified, each raw material add-on of step (a) ~ (e) is in table 4.
The acrylic resin modified each step raw material of table 4 embodiment 4 adds scale
Dropped in reactor by raw material in step (a), stir, logical nitrogen gas stirring is heated to reflux temperature and reacts 2 hours; Drip step (b) Raw, time for adding is 3 hours, after dropwising, and reacts 2 hours at a reflux temperature; Add step (c) Raw, be then incubated 3 hours at a reflux temperature; Add step (d) Raw, continue reaction 6 hours; Cooling, adds remaining raw material in step (e), stopped reaction after stirring, obtains a kind of PP ground benzene-free type of the present invention acrylic resin modified.
Embodiment 5:
(1) double bond epoxy intermediate is prepared; the mixture, the N-BUTYL ACETATE of 41.99% and the oxalic acid of 0.01% that the tertiary carbonic acid glycidyl ester of 38%, the cis-butenedioic anhydride of 20% and Succinic anhydried are formed using arbitrary proportion join in reactor as catalyzer; be uniformly mixed; pass into nitrogen air is discharged; heated and stirred is to reflux temperature under nitrogen protection; reaction, to acid number≤60mgKOH/g, obtains this double bond epoxy intermediate.
(2) prepare acrylic resin modified, each raw material add-on of step (a) ~ (e) is in table 5.
The acrylic resin modified each step raw material of table 5 embodiment 5 adds scale
Dropped in reactor by raw material in step (a), stir, logical nitrogen gas stirring is heated to reflux temperature and reacts 1 hour; Drip step (b) Raw, time for adding is 3 hours, after dropwising, and reacts 4 hours at a reflux temperature; Add step (c) Raw, be then incubated 3 hours at a reflux temperature; Add step (d) Raw, continue reaction 5 hours; Cooling, adds remaining raw material in step (e), stopped reaction after stirring, obtains a kind of PP ground benzene-free type of the present invention acrylic resin modified.
Carry out paint film experiment test to the acrylic resin modified thermosetting acrylic resin of PP ground benzene-free type obtained by embodiment 1-5, test result is as shown in table 6.
Table 6 embodiment 1-5 test result
Note: detect above, ground is PP material.
Can obviously find out according to data in table 6, acrylic resin provided by the invention, grafted chlorinated polypropylene rate is high, resin stability, storage characteristics is good, not easily layering, and the paint film standby by resin-made of the present invention is excellent to PP substrate adhesion, without the need to doing pre-treatment to ground or adding adhesion promoter, resin property is stablized, and storage characteristics is good, and application property is good, silver powder arrangement is excellent, high-temp resisting high-humidity resisting performance is excellent, alcohol resistance and excellent water resistance, not containing benezene solvent, and cheap, wide market.
Should be appreciated that invention which is intended to be protected is not limited to non-limiting embodiments, should be appreciated that non-limiting embodiments is described as just example.The protection domain of the essence required by the application is more embodied in the scope that independent claim and its dependent claims provide.
Claims (9)
1. a PP ground benzene-free type is acrylic resin modified, it is characterized in that: by mass percentage, by the double bond epoxy intermediate of 3%-10%, the Gum Rosin of 3%-10% or hydrogenated rosin resin, the Chlorinated Polypropylene III of 3%-10%, the acrylic monomer of 30%-55% or acrylic ester monomer, the solvent composition of 0.5%-1.5% initiator and 35%-60%.
2. a kind of PP ground benzene-free type according to claim 1 is acrylic resin modified, it is characterized in that: described double bond epoxy intermediate is by the epoxy resin of (by percentage to the quality) 30%-50%, the polyprotonic acid of 8%-20% or multi-anhydride, after the solvent of 40%-60% and the oxalic acid of 0.005%-0.015% mix in a kettle., react to acid number≤60mgKOH/g.
3. a kind of PP ground benzene-free type according to claim 2 is acrylic resin modified, it is characterized in that: described epoxy resin is one or more in tertiary carbonic acid glycidyl ester, bisphenol A epoxide resin E20, E44, E51.
4. a kind of PP ground benzene-free type according to claim 2 is acrylic resin modified, it is characterized in that: described polyprotonic acid or multi-anhydride are one or more in cis-butenedioic anhydride, fumaric acid, Succinic anhydried.
5. a kind of PP ground benzene-free type according to claim 2 is acrylic resin modified, it is characterized in that: described solvent is one or more in vinyl acetic monomer, N-BUTYL ACETATE, 2-butyl acetate, methyl iso-butyl ketone (MIBK), acetone.
6. a kind of PP ground benzene-free type according to claim 1 is acrylic resin modified, it is characterized in that: described acrylic monomer is one or both in methacrylic acid, vinylformic acid, and described acrylic ester monomer is one or more in methyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, Tert-butyl Methacrylate, cyclohexyl methacrylate, lauryl methacrylate(LMA), isobutyl acrylate, tert-butyl acrylate, hydroxyethyl methylacrylate.
7. a kind of PP ground benzene-free type according to claim 1 is acrylic resin modified, it is characterized in that: described initiator is one or more in benzoyl peroxide, peroxidized t-butyl perbenzoate, the peroxidation 2 ethyl hexanoic acid tert-butyl ester, di-t-butyl peroxide.
8. a kind of PP ground benzene-free type according to claim 1 is acrylic resin modified, it is characterized in that: described solvent is one or more in vinyl acetic monomer, N-BUTYL ACETATE, 2-butyl acetate, methyl iso-butyl ketone (MIBK), acetone.
9. the preparation method that the PP ground benzene-free type as described in claim 1-8 is acrylic resin modified, is characterized in that, comprise the following steps:
A the solvent of the double bond epoxy intermediate of whole proportioning, Gum Rosin or hydrogenated rosin resin, Chlorinated Polypropylene III and total solvent quality 10%-20% joins in reactor by (), stir, under nitrogen protection, react 1-2 hour under being warming up to reflux temperature;
B acrylic ester monomer that () then drips whole proportioning and the mixture be made up of total initiator quality 40%-70% and total solvent quality 5%-10%, time for adding is 2-4 hour, drips rear continuation reaction 2-4 hour;
C () adds the mixture be made up of total initiator quality 15%-20% and total solvent quality 2%-4%, continue reaction 1-3 hour;
D () adds the mixture be made up of the initiator of residue proportioning and total solvent quality 2%-4%, continue reaction 4-6 hour;
E () is lowered the temperature, add the solvent of residue proportioning, discharging after stirring.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510627835.4A CN105175650B (en) | 2015-09-25 | 2015-09-25 | A kind of PP grounds benzene-free type is acrylic resin modified and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510627835.4A CN105175650B (en) | 2015-09-25 | 2015-09-25 | A kind of PP grounds benzene-free type is acrylic resin modified and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105175650A true CN105175650A (en) | 2015-12-23 |
| CN105175650B CN105175650B (en) | 2018-05-04 |
Family
ID=54898140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510627835.4A Active CN105175650B (en) | 2015-09-25 | 2015-09-25 | A kind of PP grounds benzene-free type is acrylic resin modified and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105175650B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105733390A (en) * | 2016-04-20 | 2016-07-06 | 湖南省金海科技有限公司 | Water-based two-component transparent finish paint for PP plastic and preparation method of finish paint |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0297555A2 (en) * | 1987-06-29 | 1989-01-04 | Sakata Inkusu Kabushiki Kaisha | Modified chlorinated polypropylene, process for producing the same and use thereof |
| CN101914337A (en) * | 2010-08-13 | 2010-12-15 | 广东省石油化工研究院 | Environment friendly chlorinated polypropylene modified acrylic acid resin primer and preparation method thereof |
| CN104610890A (en) * | 2015-01-07 | 2015-05-13 | 江苏斯德瑞克化工有限公司 | Preparation method of modified chlorinated polypropylene adhesive |
-
2015
- 2015-09-25 CN CN201510627835.4A patent/CN105175650B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0297555A2 (en) * | 1987-06-29 | 1989-01-04 | Sakata Inkusu Kabushiki Kaisha | Modified chlorinated polypropylene, process for producing the same and use thereof |
| CN101914337A (en) * | 2010-08-13 | 2010-12-15 | 广东省石油化工研究院 | Environment friendly chlorinated polypropylene modified acrylic acid resin primer and preparation method thereof |
| CN104610890A (en) * | 2015-01-07 | 2015-05-13 | 江苏斯德瑞克化工有限公司 | Preparation method of modified chlorinated polypropylene adhesive |
Non-Patent Citations (4)
| Title |
|---|
| 刘丹丹: "聚合松香改性丙烯酸酯微乳液的制备与表征", 《中国优秀硕士学位论文全文数据库（工程科技Ⅰ辑）》 * |
| 尉晓丽: "双组分水性丙烯酸酯压敏胶的制备及其粘接机理", 《中国优秀硕士学位论文全文数据库（工程科技Ⅰ辑）》 * |
| 张春: "APP接枝丙烯酸酯的合成及其性能研究", 《中国优秀硕士学位论文全文数据库（工程科技Ⅰ辑）》 * |
| 肖坤立等: "CPP-g-GMA对聚丙烯及其复合材料涂装性能的改善", 《玻璃钢/复合材料》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105733390A (en) * | 2016-04-20 | 2016-07-06 | 湖南省金海科技有限公司 | Water-based two-component transparent finish paint for PP plastic and preparation method of finish paint |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105175650B (en) | 2018-05-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lomège et al. | Fatty acid-based radically polymerizable monomers: from novel poly (meth) acrylates to cutting-edge properties | |
| CN101974194B (en) | Epoxy modified styrene-acrylate emulsion and preparation method thereof | |
| CN101921357B (en) | High-solid low-viscosity hydroxy acrylic resin and preparation process thereof | |
| CN102952362B (en) | Metallic super-toughened PMMA (polymethyl methacrylate) composite material and preparation method thereof | |
| CN107286854A (en) | Polyolefin packaging adhesive film and its preparation method and application | |
| CN101805570A (en) | Room-temperature curing water-based mono-component metal-plate-covered hide glue | |
| CN112442318A (en) | Bio-based self-repairing photocureable coating and preparation method and application thereof | |
| CN103304736B (en) | A kind of preparation method of water soluble dispersing agent | |
| CN104877058A (en) | Polyacrylate resin 3D printing material and preparation method thereof | |
| CN104098767B (en) | The preparation method of polyaniline and ring oxygen grafted and mofiied acrylic ester mixture | |
| CN111171239A (en) | ABS resin and preparation method thereof | |
| CN109517102A (en) | Vinyl acetate-ester-vinyl multi-copolymer emulsion and preparation method thereof | |
| CN104946154A (en) | Packaging adhesive tape | |
| CN114316854A (en) | Acrylic acid adhesive with high solid content and low viscosity and preparation method thereof | |
| CN103865451A (en) | Neoprene adhesive subjected to secondary graft modification and preparation method of neoprene adhesive | |
| CN105175650A (en) | Benzene-free modified acrylic resin for PP substrate and preparation method thereof | |
| CN104892821A (en) | Preparation method of vinyl acetate-vinyl versatate copolymer emulsion | |
| WO2022157585A1 (en) | Polyethylene copolymer and terpolymer hotmelt adhesive compositions, articles and methods of preparing same | |
| CN113308092A (en) | Environment-friendly thermosetting plastic powder and production process thereof | |
| CN101705066B (en) | Pressure sensitive adhesive composite with wide temperature applicable range and preparation method thereof | |
| CN102060964B (en) | Preparation method and application of amino acrylic resin | |
| CN102775943A (en) | Acrylate pressure-sensitive adhesive containing crystalline polyester and preparation method thereof | |
| CN115572344A (en) | High-weather-resistance acrylic resin and preparation method thereof | |
| CN104356289A (en) | Tetrafluoroethylene fluorocarbon coating resin special for solar backboard and preparation method thereof | |
| CN103396750A (en) | Preparation of water-based adhesive and preparation method of metal/polypropylene composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |