CN110563890B - Preparation and application of polynorbornene containing hyperbranched structure - Google Patents
Preparation and application of polynorbornene containing hyperbranched structure Download PDFInfo
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- CN110563890B CN110563890B CN201910847278.5A CN201910847278A CN110563890B CN 110563890 B CN110563890 B CN 110563890B CN 201910847278 A CN201910847278 A CN 201910847278A CN 110563890 B CN110563890 B CN 110563890B
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- norbornene
- polynorbornene
- hyperbranched structure
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- 229920000636 poly(norbornene) polymer Polymers 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 229920001971 elastomer Polymers 0.000 claims abstract description 22
- 239000010426 asphalt Substances 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims abstract description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 6
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 claims description 7
- 150000002848 norbornenes Chemical class 0.000 claims description 6
- 229960004050 aminobenzoic acid Drugs 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- FYGUSUBEMUKACF-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carboxylic acid Chemical compound C1C2C(C(=O)O)CC1C=C2 FYGUSUBEMUKACF-UHFFFAOYSA-N 0.000 claims description 3
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 claims description 3
- IGHHPVIMEQGKNE-UHFFFAOYSA-N [3-(hydroxymethyl)-2-bicyclo[2.2.1]hept-5-enyl]methanol Chemical compound C1C2C=CC1C(CO)C2CO IGHHPVIMEQGKNE-UHFFFAOYSA-N 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims 1
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000005886 esterification reaction Methods 0.000 abstract 1
- 239000003973 paint Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004078 waterproofing Methods 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011387 rubberized asphalt concrete Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D121/00—Coating compositions based on unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D195/00—Coating compositions based on bituminous materials, e.g. asphalt, tar, pitch
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention relates to the field of high polymer materials, in particular to preparation and application of polynorbornene containing a hyperbranched structure. Firstly, pentaerythritol and dimethylolpropionic acid are subjected to esterification reaction, then norbornene or derivatives thereof are introduced to carry out ring-opening metathesis polymerization reaction to prepare polynorbornene containing a hyperbranched structure, and then the polynorbornene is added into the non-cured rubber asphalt waterproof coating to improve the heat resistance of the waterproof coating.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to preparation of polynorbornene containing a hyperbranched structure and improvement of heat resistance of a non-cured rubber asphalt waterproof coating.
Background
The non-cured rubber asphalt waterproof coating is an asphalt-based waterproof coating which is modified by rubber and has the advantages of high solid content, no curing for a long time, better self-healing capability, difficult peeling, good low-temperature viscosity and the like. The waterproof layer cracking and other problems caused by base layer strain can be solved well. Meanwhile, the paint can be used as a primer adhesion paint to be matched with a waterproof coiled material to form a composite waterproof layer.
The main components of the non-cured rubber asphalt waterproof coating are asphalt, rubber, a softening agent, a tackifier, a stabilizer, a filler and the like. In order to facilitate construction, the waterproof coating is generally designed to have higher fluidity at high temperature, so that the problems of poor heat resistance, easy flowing at high temperature, easy sagging in facade construction and the like are caused.
The invention prepares polynorbornene by ROMP method, and applies it to the modification of non-solidified rubber asphalt waterproof paint. The polynorbornene molecule prepared by the ROMP method contains a large number of double bonds, and can react with rubber components in the non-cured rubber asphalt waterproof coating to form a huge network, so that the purposes of reducing the system fluidity and improving the heat resistance are achieved.
Disclosure of Invention
In order to solve the defect of poor heat resistance of the non-cured rubber asphalt waterproof coating, the invention provides polynorbornene containing a hyperbranched structure.
The invention also provides a preparation method of the polynorbornene containing the hyperbranched structure.
The polynorbornene containing hyperbranched structure is realized by the following steps.
The method comprises the following steps: adding a certain amount of pentaerythritol and dimethylolpropionic acid into a four-neck flask, adding a catalyst of p-toluenesulfonic acid, heating to 140 ℃ for reaction for 4h, then adding a certain amount of p-aminobenzoic acid, and keeping the reaction conditions to continuously reflect for 4h to obtain the amino-terminated hyperbranched resin, wherein the structural formula is shown as follows.
Step two: adding a certain amount of amino-terminated hyperbranched resin into a four-mouth bottle, adding 5-norbornene-2, 3-dicarboxylic anhydride and toluene as a solvent, and refluxing for 48 hours at 110 ℃. The toluene was then distilled off, dissolved in dichloromethane and Grubbs III catalyst was added. Then norbornene or norbornene derivative is dissolved in dichloromethane and added dropwise to the reaction system, and after 10 minutes of reaction, ethyl vinyl ether is added to stop the reaction. Namely, the reaction process of the polynorbornene containing hyperbranched structure is shown as follows.
The dosage of the p-toluenesulfonic acid is 0.1-0.6% of the total mass of reactants.
The norbornene derivative is one or more than two of 5-norbornene-2-formic acid, 5-norbornene-2, 3-dimethanol, 5-norbornene-2, 3-dicarboxylic acid and 5-norbornene-2, 3-dicarboxylic anhydride.
Compared with the prior art, the polynorbornene containing the hyperbranched structure for improving the heat resistance of the non-cured rubber asphalt waterproof coating prepared by the invention has the following advantages.
The preparation method of the polynorbornene containing the hyperbranched structure is simple, and raw materials are easy to obtain; meanwhile, the heat resistance of the non-cured rubber asphalt waterproof coating is greatly improved, and the non-cured rubber asphalt waterproof coating is blended and stirred uniformly without adding an additional process, so that the cost is favorably controlled.
Detailed Description
The following is a more detailed description of the embodiments of the present invention, which is intended to illustrate the concepts and features of the invention, and not to limit the scope of the invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
The first embodiment is as follows:
the method comprises the following steps: adding 1.36g of pentaerythritol and 16.08g of dimethylolpropionic acid into a four-neck flask, adding 0.087g of catalyst p-toluenesulfonic acid, heating to 140 ℃ for reaction for 4 hours, then adding 21.92g of p-aminobenzoic acid, and keeping the reaction conditions to continuously reflect for 4 hours to obtain the amino-terminated hyperbranched resin.
Step two: 2g of amino-terminated hyperbranched resin is added into a four-neck flask, 1.53g of 5-norbornene-2, 3-dicarboxylic anhydride and toluene are added as a solvent, and the mixture is refluxed for 48 hours at 110 ℃. Thereafter, toluene was distilled off, methylene chloride was added to dissolve the toluene, and 0.152g of Grubbs III catalyst was added. Then, 20g of norbornene was dissolved in methylene chloride and added dropwise to the reaction system, and after reacting for 10 minutes, 2mL of ethyl vinyl ether was added to stop the reaction. Namely the polynorbornene containing hyperbranched structure.
Example two:
the method comprises the following steps: adding 1.36g of pentaerythritol and 16.08g of dimethylolpropionic acid into a four-neck flask, adding 0.087g of catalyst p-toluenesulfonic acid, heating to 140 ℃ for reaction for 4 hours, then adding 21.92g of p-aminobenzoic acid, and keeping the reaction conditions to continuously reflect for 4 hours to obtain the amino-terminated hyperbranched resin.
Step two: 2g of amino-terminated hyperbranched resin is added into a four-neck flask, 1.53g of 5-norbornene-2, 3-dicarboxylic anhydride and toluene are added as a solvent, and the mixture is refluxed for 48 hours at 110 ℃. Thereafter, toluene was distilled off, methylene chloride was added to dissolve the toluene, and 0.152g of Grubbs III catalyst was added. Then, 20g of 5-norbornene-2-carboxylic acid was dissolved in methylene chloride and added dropwise to the reaction system, and after reacting for 10 minutes, 2mL of ethyl vinyl ether was added to stop the reaction. Namely the polynorbornene containing hyperbranched structure.
Example three:
the method comprises the following steps: adding 1.36g of pentaerythritol and 16.08g of dimethylolpropionic acid into a four-neck flask, adding 0.087g of catalyst p-toluenesulfonic acid, heating to 140 ℃ for reaction for 4 hours, then adding 21.92g of p-aminobenzoic acid, and keeping the reaction conditions to continuously reflect for 4 hours to obtain the amino-terminated hyperbranched resin.
Step two: 2g of amino-terminated hyperbranched resin is added into a four-neck flask, 1.53g of 5-norbornene-2, 3-dicarboxylic anhydride and toluene are added as a solvent, and the mixture is refluxed for 48 hours at 110 ℃. Thereafter, toluene was distilled off, methylene chloride was added to dissolve the toluene, and 0.152g of Grubbs III catalyst was added. Then, 20g of 5-norbornene-2, 3-dicarboxylic acid was dissolved in methylene chloride and added dropwise to the reaction system, and after reacting for 10 minutes, 2mL of ethyl vinyl ether was added to stop the reaction. Namely the polynorbornene containing hyperbranched structure.
Performance testing
To illustrate the practical effects of the present invention, it is described that polynorbornene containing hyperbranched structure obtained in the examples of the present invention is added to the non-curable rubberized asphalt waterproofing paint. The test is carried out according to the method in JC/T2428-2017 non-cured rubber asphalt waterproof paint, and the test results are as follows:
TABLE 1 heat resistance of non-curing rubber asphalt waterproofing paint.
It can be seen from table 1 that the heat resistance of the non-cured rubber asphalt waterproof coating material is significantly improved after the addition of the polynorbornene containing hyperbranched structure prepared by the present invention. The main components of the non-solidified rubber asphalt are asphalt and rubber, the asphalt contains a large number of active groups, the rubber contains a large number of unreacted double bonds, both the asphalt and the rubber can react with the double bonds in the polynorbornene containing a hyperbranched structure, and the selected norbornene derivative monomer also has the active groups. The heat resistance significantly increases with increasing addition amount. The effect of the norbornene derivative is different among the three examples due to the different number of the active groups, wherein in terms of the content of the active groups, the third example > the second example > the first example, the amount of the active groups also plays a certain role in the process of modifying the non-cured rubber asphalt, so the effect of the third example is shown.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the embodiments, and any other changes, modifications, combinations, substitutions and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and fall within the scope of the present invention.
Claims (3)
1. A preparation method of polynorbornene containing a hyperbranched structure is characterized in that the preparation method of the polynorbornene containing the hyperbranched structure is realized by the following steps:
the method comprises the following steps: adding a certain amount of pentaerythritol and dimethylolpropionic acid into a four-neck flask, adding a catalyst of p-toluenesulfonic acid, heating to 140 ℃ for reaction for 4h, then adding a certain amount of p-aminobenzoic acid, and keeping the reaction condition for continuous reaction for 4h to obtain amino-terminated hyperbranched resin;
step two: adding a certain amount of amino-terminated hyperbranched resin into a four-neck flask, adding 5-norbornene-2, 3-dicarboxylic anhydride, using toluene as a solvent, refluxing for 48 hours at 110 ℃, then evaporating to remove the toluene, adding dichloromethane for dissolving, adding a Grubbs III catalyst, dissolving norbornene or norbornene derivatives in dichloromethane, dropwise adding the dichloromethane into a reaction system, reacting for 10 minutes, adding ethyl vinyl ether, and stopping the reaction to obtain the polynorbornene containing a hyperbranched structure.
2. The method according to claim 1, wherein the norbornene derivative is one or more selected from the group consisting of 5-norbornene-2-carboxylic acid, 5-norbornene-2, 3-dimethanol, 5-norbornene-2, 3-dicarboxylic acid and 5-norbornene-2, 3-dicarboxylic anhydride.
3. The application of the polynorbornene containing hyperbranched structure obtained by the preparation method according to claim 1, wherein the polynorbornene containing hyperbranched structure is used for improving the heat resistance of the non-cured rubber asphalt waterproof coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910847278.5A CN110563890B (en) | 2019-09-09 | 2019-09-09 | Preparation and application of polynorbornene containing hyperbranched structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201910847278.5A CN110563890B (en) | 2019-09-09 | 2019-09-09 | Preparation and application of polynorbornene containing hyperbranched structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110563890A CN110563890A (en) | 2019-12-13 |
| CN110563890B true CN110563890B (en) | 2021-09-24 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201910847278.5A Expired - Fee Related CN110563890B (en) | 2019-09-09 | 2019-09-09 | Preparation and application of polynorbornene containing hyperbranched structure |
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| CN114672111B (en) * | 2022-04-29 | 2023-04-07 | 杭州泰德机电有限公司 | Production process of high-strength explosion-proof wear-resistant PVC composite pipe |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030884A (en) * | 2010-10-26 | 2011-04-27 | 华南理工大学 | High-solid-content UV (Ultraviolet)-curing aqueous urethane acrylate dispersion liquid and preparation method thereof |
| EP3080170A1 (en) * | 2013-12-13 | 2016-10-19 | Transfert Plus, S.E.C. | Insertion polynorbornene-based thermoset resins |
| CN109824909A (en) * | 2019-02-27 | 2019-05-31 | 济南大学 | A kind of preparation and its application of organic-silicon-modified hyper-branched polyester-amide resin |
-
2019
- 2019-09-09 CN CN201910847278.5A patent/CN110563890B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030884A (en) * | 2010-10-26 | 2011-04-27 | 华南理工大学 | High-solid-content UV (Ultraviolet)-curing aqueous urethane acrylate dispersion liquid and preparation method thereof |
| EP3080170A1 (en) * | 2013-12-13 | 2016-10-19 | Transfert Plus, S.E.C. | Insertion polynorbornene-based thermoset resins |
| CN109824909A (en) * | 2019-02-27 | 2019-05-31 | 济南大学 | A kind of preparation and its application of organic-silicon-modified hyper-branched polyester-amide resin |
Non-Patent Citations (1)
| Title |
|---|
| Synthesis of Hyperbranched Polymers with Pendent Norbornene Functionalities via RAFT Polymerization of a Novel Asymmetrical Divinyl Monomer;Zhong-min Dong等;《Macromolecules》;20090609;第42卷(第13期);4596-4603 * |
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| CN110563890A (en) | 2019-12-13 |
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