CN113512361A - High-adhesion-strength shellac and preparation method thereof - Google Patents
High-adhesion-strength shellac and preparation method thereof Download PDFInfo
- Publication number
- CN113512361A CN113512361A CN202110198600.3A CN202110198600A CN113512361A CN 113512361 A CN113512361 A CN 113512361A CN 202110198600 A CN202110198600 A CN 202110198600A CN 113512361 A CN113512361 A CN 113512361A
- Authority
- CN
- China
- Prior art keywords
- shellac
- strength
- cooh
- adhesion
- product
- 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; DRIERS (SICCATIVES); TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
- C09J193/02—Shellac
Abstract
The invention discloses high-adhesion-strength shellac and a preparation method thereof, and belongs to the field of application of natural adhesives. The invention puts carboxylic acid and/or alcohol containing sulfydryl, shellac, initiator and solvent into a reaction vessel, and reacts for 2-48 hours under heating condition; and precipitating and filtering the product in deionized water, and drying the precipitate in a vacuum oven to obtain a purified product. The preparation method provided by the invention is easy to operate and control, efficient in reaction and easy to purify, and the obtained shellac is stable in chemical property and has high bonding performance to polar materials such as metal, wood, ceramic, glass and the like.
Description
Technical Field
The invention belongs to the technical field of environment-friendly natural polymer adhesives, relates to a high-adhesion-strength shellac and a preparation method thereof, and particularly relates to a preparation method and application of a high-adhesion-strength shellac containing multiple polar groups.
Background
The shellac is a low molecular weight natural resin with a molecular weight of about 900g/mol, which is prepared by removing impurities and wax from lacca secretion and is harmless to human and livestock. Dissolving shellac in anhydrous ethanol to form pasty solution with certain viscosity, and regulating viscosity of cosmetic or skin care product. Because the shellac resin has a higher softening point, it naturally forms a film after ethanol in the shellac ethanol solution is volatilized. Because of this property, shellac is commonly used as a film former in cosmetics. In addition, the shellac is also used as a glazing agent for desserts such as food preservatives, chocolate and the like, and enteric coating of medicaments; due to the chromophore contained in its molecular structure, it is also commonly used as an environmentally friendly weakly acidic industrial stain. Besides the purposes, the shellac has good bonding strength due to polar functional groups such as carboxyl and hydroxyl contained in the molecular structure, and is mainly used as an adhesive for wood and applied to splicing purposes of wooden furniture.
With the improvement of health and environmental protection awareness of people and the continuous deepening of shellac research, the application range of shellac is wider and wider, and the application range of shellac is continuously expanded from the initial wood processing field to the production and processing processes of high-performance products such as metal, glass, ceramic parts and the like. In these new fields of application, the requirement for the bonding strength between shellac and base material is becoming more and more demanding. The existing natural shellac resin is directly used as an adhesive, and the bonding strength of the natural shellac resin can not meet the process requirements.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides the high-adhesion-strength shellac and the preparation method thereof. The invention adopts the mercapto-alkene addition reaction to introduce functional groups such as carboxyl, hydroxyl, amine (ammonium salt) group and the like into the shellac resin molecule, thereby improving the bonding force between the shellac resin and the base material and obtaining high bonding strength.
One of the objects of the present invention is to provide a high adhesion strength shellac, comprising formula I and formula II,
wherein R is selected from- (CH)2)n-COOH、-(CH2)n’-OH、-(CH2)n’-NH2、-(CH2)n-NH3Cl、-CH(CH2)2-(OH)2、-CH(CH2)2-(COOH)2、-C6H5-COOH、-C6H5-OH，
And n 'are integers, n is 2-11, and n' is 2-12.
The invention also aims to provide a preparation method of the high-adhesion-strength shellac, which comprises the following steps:
1) the shellac and the terminal mercapto compound are mixed according to a molar ratio of 1: 0.5-2.0 of feeding and adding into excessive organic solvent, then adding initiator with 1-5% of the mass of the thiol-terminated compound, then introducing nitrogen for protection and heating to 50-80 ℃ for oil bath reaction for 2-48 hours;
wherein the content of the first and second substances,
the shellac is shellac or white shellac,
the mercapto-terminated compound is selected from HS- (CH)2)n-COOH、HS-(CH2)n’-OH、HS-(CH2)n’-NH2、HS-(CH2)n-NH3Cl、HS-(CH2)n-N(CH3)2、HS-CH(CH2)2-(OH)2、HS-CH(CH2)2-(COOH)2、HS-C6H5-COOH、HS-C6H5-OH, wherein n, n 'are integers, n-2-11, n' -2-12,
the initiator is at least one of azobisisobutyronitrile, azobisisoheptonitrile, azobiscyanovaleric acid and dimethyl azobisisobutyrate;
2) and (3) dropwise adding the product after the reaction is finished into deionized water for precipitation, and drying the obtained precipitate in a vacuum oven at the temperature of 30 ℃ until the weight is constant to obtain the high-adhesion-strength shellac containing a plurality of polar groups.
Preferably, the organic solvent in step 1) is at least one of 1, 4-dioxane, tetrahydrofuran, ethanol and methanol.
Advantageous effects
Compared with the existing shellac, the shellac with high bonding strength provided by the invention has the advantages that the bonding property is improved by more than 2 times, and the shellac with high bonding strength provided by the invention has improved solubility and is convenient for construction. In addition, the high-adhesion-strength shellac provided by the invention has excellent stability, solves the problems of poor storage stability, severe storage conditions and the like of the existing shellac resin, and avoids economic loss and waste of shellac resources caused by improper storage of the shellac resin.
In addition, the preparation method of the shellac resin provided by the invention is easy to operate and control, efficient in reaction and easy to purify, and the obtained shellac with high bonding strength is stable in chemical property and has good storage performance.
The invention provides application of high-adhesion-strength shellac containing a plurality of polar groups such as carboxyl, hydroxyl, amino, ammonium and the like in an environment-friendly adhesive used in the processing process of materials such as metal, wood, ceramic, glass and the like.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is an infrared (FTIR) spectrum of shellac and the product of example 1.
FIG. 2(a) is a graph showing the results of Differential Scanning Calorimeter (DSC) measurement of shellac.
FIG. 2(b) is a graph showing the results of Differential Scanning Calorimeter (DSC) measurement of the product of example 1.
Figure 3 is a FTIR plot of shellac and the product of example 2.
FIG. 4 is a graph showing the results of Differential Scanning Calorimeter (DSC) measurements of the product of example 2.
Detailed Description
The present invention will now be described in more detail with reference to the accompanying drawings, in which preferred embodiments of the invention are shown, it being understood that one skilled in the art may modify the invention herein described while still achieving the beneficial results of the present invention. Thus, the following description of the multiple heat-useable shellac should be understood as being broadly known to those skilled in the art and not as limiting the invention.
Example 1:
1.5001g (1.685mmol) of shellac were weighed out accurately and dissolved in 3.00g of tetrahydrofuran, then 0.0893g (0.843mmol) of 3-mercaptopropionic acid and 4.5mg of azobisisobutyronitrile were added. Introduction of N2After the gas is aerated for 30min, the mixture is put into an oil bath kettle at the temperature of 60 ℃ for reaction for 24 h. The resulting product was precipitated with deionized water. The precipitate was collected by high speed centrifugation and dried in a vacuum oven at 30 ℃ to give the final product.
The chemical structures of shellac before and after modification with 3-mercaptopropionic acid were tested by infrared spectroscopy, and the results are shown in FIG. 1. In FIG. 1, unmodified shellac is shown at 1188 and 1151cm wavenumbers-1The absorption peak is the in-plane bending vibration absorption peak of the carbon-hydrogen bond (C-H) in the olefin; after the thiopropionic acid is added with the vinyl double bond, the double bond absorption peak disappears, which indicates that the modification reaction is successful. Meanwhile, in FIG. 1, at a chemical shift of 3435cm-1And a new high-intensity absorption peak appears, namely an-OH absorption peak in carboxyl, namely, the carboxyl with high polarity is additionally introduced into shellac molecules.
The thermal properties of the mercaptopropionic acid modified shellac before and after the test were measured by Differential Scanning Calorimeter (DSC) and the results are shown in fig. 2: the unmodified shellac undergoes thermal polymerization of vinyl groups during the temperature rise, with the heat of reaction being 55.17J/g (FIG. 2 a). After the modification by mercaptopropionic acid, the product obtained in example 1 only has a glass transition temperature (79.5 ℃) in the temperature rising process, and basically has no thermal effect (fig. 2b), which indicates that double bonds in shellac raw materials are consumed, and indirectly proves that the thermal stability or storage stability of the product can be improved after the addition modification of the mercaptopropionic acid to shellac.
The adhesion performance of the shellac A and the shellac to the steel plate and the glass was measured with an electronic tensile machine, and the stretching rate was set to 10 mm/min. The experimental result shows that the tensile forces of the unmodified shellac-bonded steel plate and the glass sample are respectively 2.25MPa and 2.52MPa, the tensile shear strengths of the product of the example 1 are respectively 4.37MPa and 4.55MPa and are about 2 times of the tensile shear strength of the unmodified shellac, and the product is proved to be capable of obviously improving the bonding strength.
Example 2:
1.5011g (1.687mmol) of shellac were weighed out accurately and dissolved with 6.02g of 1, 4-dioxane, then 0.3650g (3.373mmol) of thioglycerol and 3.7mg of azobisisoheptonitrile were added. Introduction of N2After the gas is aerated for 30min, the mixture is put into an oil bath kettle at the temperature of 80 ℃ for reaction for 12 h. The resulting product was precipitated with deionized water. The precipitate was collected by high speed centrifugation and dried in a vacuum oven at 30 ℃ to give the final product.
The chemical structures of shellac before and after thioglycerol modification were tested by infrared spectroscopy and the results are shown in fig. 3. In the infrared spectrogram of the modified shellac, the chemical shift is 3200-3450cm-1an-OH absorption peak appears, and the introduction of polar hydroxyl in the shellac molecule is proved.
The thermal properties of the thioglycerol modified shellac were tested using a Differential Scanning Calorimeter (DSC) and the results are shown in figure 4: the heat of vinyl polymerization of the unmodified shellac during the temperature increase was 55.17J/g (FIG. 2 a). The heat of polymerization of the product obtained in example 2 after modification with thioglycerol is 3.72J/g (fig. 4), which indicates that most of the double bonds in the shellac raw material are consumed, and indirectly indicates that the thermal stability or storage stability of the product of shellac after addition modification with mercaptopropionic acid is significantly improved.
The adhesion performance of the shellac A and the shellac to the steel plate and the glass was measured with an electronic tensile machine, and the stretching rate was set to 10 mm/min. The experimental results show that the tensile forces of the unmodified shellac-bonded steel plate and the glass sample are respectively 2.25MPa and 2.52MPa, the tensile shear strengths of the product of example 4 are respectively 4.79MPa and 4.92MPa, and are about 2 times or more of the tensile shear strength of the unmodified shellac, and the product is proved to be capable of remarkably improving the bonding strength.
Example 3:
1.5007g (1.687mmol) of white shellac were weighed out accurately and dissolved in 4.55g of methanol and ethanol (1: 1 by mass), then 0.1915g (1.686mmol) of 3-mercaptopropylamine hydrochloride were added, 2.0mg of azobisisoheptonitrile and 2.0mg of azobiscyanovaleric acid were added. After sealing, the mixture is put into an oil bath kettle at 50 ℃ for reaction for 48 hours. The resulting product was precipitated with deionized water. The precipitate was collected by high speed centrifugation and dried in a vacuum oven at 30 ℃ to give the final product.
The adhesion performance of the shellac A and the shellac to the steel plate and the glass was measured with an electronic tensile machine, and the stretching rate was set to 10 mm/min. The experimental result shows that the tensile forces of the unmodified shellac bonded steel plate and the glass sample are respectively 2.11MPa and 2.34MPa, and the tensile shear strengths of the products obtained in example 3 are respectively 3.52MPa and 3.58MPa, which are about 1.67 times of the tensile shear strength of the unmodified shellac, so that the product can obviously improve the bonding strength.
Example 4:
1.5031g (1.689mmol) of white shellac were weighed out accurately and dissolved in 6.10g of tetrahydrofuran and ethanol (mass ratio 2:1), then 0.1844g (2.027mmol) of 3-mercaptopropylamine, 2.0mg of azobisisoheptonitrile and 2.0mg of dimethyl azobisisobutyrate were added. After sealing, the mixture is put into an oil bath kettle at the temperature of 58-60 ℃ for reaction for 24 hours. The resulting product was precipitated with deionized water. The precipitate was collected by high speed centrifugation and dried in a vacuum oven at 30 ℃ to give the final product.
The adhesion performance of the shellac A and the shellac to the steel plate and the glass was measured with an electronic tensile machine, and the stretching rate was set to 10 mm/min. The experimental result shows that the tensile forces of the unmodified shellac-bonded steel plate and the glass sample are respectively 2.11MPa and 2.34MPa, the tensile shear strengths of the product of the example 4 are respectively 5.81MPa and 5.96MPa and are about 3 times of the tensile shear strength of the unmodified shellac, and the product is proved to be capable of obviously improving the bonding strength.
The embodiments 1 to 4 are products obtained by modifying carboxyl, hydroxyl, amino and ammonium groups respectively, and the specific embodiments also prove that the prepared high-adhesion-strength shellac has the adhesion property remarkably improved by more than 2 times compared with the existing shellac, and the shellac prepared by the invention contains more carboxyl, hydroxyl, amino, ammonium and other groups to remarkably improve the adhesion strength on metal and other base materials, so that the requirement of processing technologies such as large-size metal pieces, glass ceramic products and the like on the adhesion strength of the shellac can be met. In addition, the polar group is introduced into the high-adhesion-strength shellac, so that the solubility of the shellac can be obviously improved, and the high-adhesion-strength shellac is convenient to construct. On the other hand, the terpene double bonds in the shellac resin structure are completely converted into saturated carbon-carbon single bonds by adopting the mercapto-alkene addition reaction, so that the problems of poor storage stability, severe storage conditions and the like of the shellac resin are solved, and the economic loss and the waste of shellac resources caused by improper storage of the shellac resin are avoided.
Therefore, the high-adhesion-strength shellac containing a plurality of polar groups such as carboxyl, hydroxyl, amino, ammonium and the like provided by the invention is used as an environment-friendly adhesive in the processing process of materials such as metal, wood, ceramic, glass and the like.
Although the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the details of the embodiments, and various equivalent modifications can be made within the technical spirit of the present invention, and the scope of the present invention is also within the scope of the present invention. It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition. In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (3)
1. A high-adhesion-strength shellac, characterized in that the shellac comprises formula I and formula II,
wherein R is selected from- (CH)2)n-COOH、-(CH2)n’-OH、-(CH2)n’-NH2、-(CH2)n-NH3Cl、-CH(CH2)2-(OH)2、-CH(CH2)2-(COOH)2、-C6H5-COOH、-C6H5-OH, and n, n 'are integers, n-2-11, n' -2-12.
2. The preparation method of the shellac with high bonding strength is characterized by comprising the following steps:
1) the shellac and the terminal mercapto compound are mixed according to a molar ratio of 1: 0.5-2.0 of feeding and adding into excessive organic solvent, then adding initiator with 1-5% of the mass of the thiol-terminated compound, then introducing nitrogen for protection and heating to 50-80 ℃ for oil bath reaction for 2-48 hours;
wherein the content of the first and second substances,
the shellac is shellac or white shellac,
the mercapto-terminated compound is selected from HS- (CH)2)n-COOH、HS-(CH2)n’-OH、HS-(CH2)n’-NH2、HS-(CH2)n-NH3Cl、HS-(CH2)n-N(CH3)2、HS-CH(CH2)2-(OH)2、HS-CH(CH2)2-(COOH)2、HS-C6H5-COOH、HS-C6H5-OH, wherein n, n 'are integers, n-2-11, n' -2-12,
the initiator is at least one of azobisisobutyronitrile, azobisisoheptonitrile, azobiscyanovaleric acid and dimethyl azobisisobutyrate;
2) and (3) dropwise adding the product after the reaction is finished into deionized water for precipitation, and drying the obtained precipitate in a vacuum oven at the temperature of 30 ℃ until the weight is constant to obtain the high-adhesion-strength shellac containing a plurality of polar groups.
3. The method according to claim 2, wherein the organic solvent in step 1) is at least one of 1, 4-dioxane, tetrahydrofuran, ethanol, and methanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110198600.3A CN113512361B (en) | 2021-02-22 | 2021-02-22 | High-adhesion-strength shellac and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110198600.3A CN113512361B (en) | 2021-02-22 | 2021-02-22 | High-adhesion-strength shellac and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113512361A true CN113512361A (en) | 2021-10-19 |
| CN113512361B CN113512361B (en) | 2022-10-04 |
Family
ID=78061026
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110198600.3A Active CN113512361B (en) | 2021-02-22 | 2021-02-22 | High-adhesion-strength shellac and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113512361B (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB300956A (en) * | 1927-11-21 | 1929-11-07 | Walter Dux | Manufacture of shellac substitutes |
| GB370323A (en) * | 1930-09-08 | 1932-04-07 | British Thomson Houston Co Ltd | Improvements in and relating to the manufacture of laminated materials |
| US5844047A (en) * | 1993-07-16 | 1998-12-01 | Ciba Specialty Chemicals Corporation | Single component, heat curing compositions which are stable when stored at room temperature and which comprise polymers containing anhydride groups and powdered crosslinking agents, and their method of manufacture and use |
| US5932680A (en) * | 1993-11-16 | 1999-08-03 | Henkel Kommanditgesellschaft Auf Aktien | Moisture-curing polyurethane hot-melt adhesive |
| WO1999048990A1 (en) * | 1998-03-24 | 1999-09-30 | Nippon Zeon Co., Ltd. | Adhesive resin composition |
| WO2003014236A2 (en) * | 2001-08-03 | 2003-02-20 | Henkel Kommanditgesellschaft Auf Aktien | Binding agent component for surface coating agents with improved adhesive properties |
| US20140065079A1 (en) * | 2012-09-05 | 2014-03-06 | d-ANTAEUS | Method for de-coloring shellac, de-colored shellac, compositions comprising same, and uses therefor |
| CN103936962A (en) * | 2014-04-11 | 2014-07-23 | 烟台大学 | Epoxy curing agent synthesized through mercapto-vinyl addition |
| WO2016178244A2 (en) * | 2015-05-05 | 2016-11-10 | Asian Paints Ltd. | Water borne cross linked and hydrophobic shellac-pu-acrylic hybrid for glossy enamel and wood finish |
| EP3205751A1 (en) * | 2014-10-06 | 2017-08-16 | Nitto Denko Corporation | Masking sheet for anodizing |
| JP2018009153A (en) * | 2016-06-16 | 2018-01-18 | 荒川化学工業株式会社 | Tackifier resin, tackifier resin emulsion, aqueous adhesive composition, and polychloroprene latex adhesive composition |
| CN110643027A (en) * | 2019-10-07 | 2020-01-03 | 烟台大学 | Wetting defoaming auxiliary agent and preparation method thereof |
-
2021
- 2021-02-22 CN CN202110198600.3A patent/CN113512361B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB300956A (en) * | 1927-11-21 | 1929-11-07 | Walter Dux | Manufacture of shellac substitutes |
| GB370323A (en) * | 1930-09-08 | 1932-04-07 | British Thomson Houston Co Ltd | Improvements in and relating to the manufacture of laminated materials |
| US5844047A (en) * | 1993-07-16 | 1998-12-01 | Ciba Specialty Chemicals Corporation | Single component, heat curing compositions which are stable when stored at room temperature and which comprise polymers containing anhydride groups and powdered crosslinking agents, and their method of manufacture and use |
| US5932680A (en) * | 1993-11-16 | 1999-08-03 | Henkel Kommanditgesellschaft Auf Aktien | Moisture-curing polyurethane hot-melt adhesive |
| WO1999048990A1 (en) * | 1998-03-24 | 1999-09-30 | Nippon Zeon Co., Ltd. | Adhesive resin composition |
| WO2003014236A2 (en) * | 2001-08-03 | 2003-02-20 | Henkel Kommanditgesellschaft Auf Aktien | Binding agent component for surface coating agents with improved adhesive properties |
| US20140065079A1 (en) * | 2012-09-05 | 2014-03-06 | d-ANTAEUS | Method for de-coloring shellac, de-colored shellac, compositions comprising same, and uses therefor |
| CN103936962A (en) * | 2014-04-11 | 2014-07-23 | 烟台大学 | Epoxy curing agent synthesized through mercapto-vinyl addition |
| EP3205751A1 (en) * | 2014-10-06 | 2017-08-16 | Nitto Denko Corporation | Masking sheet for anodizing |
| WO2016178244A2 (en) * | 2015-05-05 | 2016-11-10 | Asian Paints Ltd. | Water borne cross linked and hydrophobic shellac-pu-acrylic hybrid for glossy enamel and wood finish |
| JP2018009153A (en) * | 2016-06-16 | 2018-01-18 | 荒川化学工業株式会社 | Tackifier resin, tackifier resin emulsion, aqueous adhesive composition, and polychloroprene latex adhesive composition |
| CN110643027A (en) * | 2019-10-07 | 2020-01-03 | 烟台大学 | Wetting defoaming auxiliary agent and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| TANG,B: "Deep Eutectic Solvent-Based HS-SME Coupled with GC for the Analysis of Bioactive Terpenoids in Chamaecyparis obtusa leaves", 《CHROMATOGRAPHIA》 * |
| 陈奇等: "紫胶树脂在氨水中的溶解性及其铵盐的理化性质", 《食品科学》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113512361B (en) | 2022-10-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2018058816A1 (en) | Method for manufacturing polyoxazoline chain extending agent | |
| CN114316854B (en) | Acrylic acid adhesive with high solid content and low viscosity and preparation method thereof | |
| CN105175644A (en) | Preparation method for dual-curing resin monomer based on castor oil | |
| CN113512361B (en) | High-adhesion-strength shellac and preparation method thereof | |
| CN108017937B (en) | Preparation method of silane modified polyether sealant calcium carbonate | |
| CN105418861B (en) | One kind is based on polyaminoacid molecule cross-link hydrogel and preparation method thereof | |
| JPS61500851A (en) | Copolymer using isoimide and method for producing the same | |
| Xu et al. | Customized thermoplastic polyhydroxyurethanes synthesized from ene-containing cyclic carbonates, dithiols and diamines: design, mechanical properties and applications in adhesives | |
| CN110435170B (en) | Modification method for improving shape memory performance of gutta percha | |
| Yin et al. | Mussel-inspired fabrication of pH-sensitive biomimetic hydrogels based on greenhouse gas carbon dioxide | |
| CN114702936B (en) | Water-based adhesive and preparation method and application thereof | |
| CN108003337B (en) | Hyperbranched star polymer of uV curable and its preparation method and application | |
| Yu et al. | Difunctional initiator based on 1, 3‐diisopropenylbenzene. IV. Synthesis and modification of poly (alkyl methacrylate‐b‐styrene‐b‐butadiene‐b‐styrene‐b‐alkyl methacrylate (MSBSM)) thermoplastic elastomers | |
| US20200071433A1 (en) | Hyperbranched cationic mussel-imitated polymer and method of preparing the same | |
| CN110126161A (en) | A kind of production technology of melamine dishware | |
| CN115286761A (en) | High-water-resistance water-based acrylic polyurethane and preparation method thereof | |
| CN113493665A (en) | Palm oil-based underwater adhesive and preparation method thereof | |
| CN105440222B (en) | A kind of polyaminoacid nonionic macromolecules cross-linking agent and preparation method thereof | |
| JP2781264B2 (en) | Manufacturing method of gel base powder | |
| CN1935866A (en) | CS petroleum resin quick-functionizing method | |
| CN117683184B (en) | Reversible cross-linked covalent sulfur-containing polymer elastomer and preparation method thereof | |
| CN109514964A (en) | A kind of preparation method of modified asphalt waterproof coiled material | |
| CN115850714B (en) | POSS modified nitrile rubber compound and preparation method and application thereof | |
| SU672859A1 (en) | Oligomers of 2-aminoethylvinyl ester as hardener for epoxy resins and method of producing same | |
| CN113667274B (en) | Tough epoxy composite material and preparation method thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |