CN110862651A - Preparation method of zero-shrinkage epoxy resin - Google Patents
Preparation method of zero-shrinkage epoxy resin Download PDFInfo
- Publication number
- CN110862651A CN110862651A CN201911186709.4A CN201911186709A CN110862651A CN 110862651 A CN110862651 A CN 110862651A CN 201911186709 A CN201911186709 A CN 201911186709A CN 110862651 A CN110862651 A CN 110862651A
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- epoxy resin
- zero
- preparing
- room temperature
- shrink
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1483—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Emergency Medicine (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a preparation method of zero-shrinkage epoxy resin, which is characterized in that liquid epoxy resin is stirred and mixed uniformly at room temperature; stirring and mixing the prepared mixed solution and a certain amount of hollow glass beads completely at room temperature; adding a proper amount of expansion monomer; adding a proper amount of curing agent, stirring and mixing uniformly at room temperature; adding a certain amount of accelerator, stirring and mixing uniformly at room temperature. The invention can prepare the epoxy resin with zero shrinkage by offsetting the volume shrinkage of the epoxy resin in the curing process by the volume expansion generated in the polymerization process of the expansion monomer. The density of the epoxy resin prepared by the method is kept unchanged before and after the epoxy resin is cured, zero shrinkage is realized in a real sense, and the method has high application value.
Description
Technical Field
The invention relates to the field of composite materials, in particular to a preparation method of zero-shrinkage epoxy resin.
Background
Epoxy resin is a resin which is most widely applied in polymer matrix composite materials due to wide variety of raw materials, strong designability and the like. However, during the curing process of the epoxy resin, a certain volume shrinkage is inevitably generated when the liquid phase is changed into the solid phase, and the volume shrinkage generates a certain residual stress. The reason why the epoxy resin undergoes volume shrinkage is that the molecules behave as monomer molecules acting as van der waals force between themselves before curing, and become chemical bonds in the form of covalent bonds after curing. The distance between covalent bonds is significantly smaller than the gap between van der waals force molecules, and thus volume shrinkage occurs before and after curing, which leads to residual stress. Residual stresses in the resin are a potential damaging factor, and cause considerable stresses between the resin and the fibre interface (when used as a matrix of a composite material) or the glued joint (when used as an adhesive) when no external load is applied, thereby causing a reduction in strength and even cracking of the composite material, dimensional instability, or debonding of the glued joint.
The swelling monomer is a monomer capable of generating volume expansion in the polymerization process, and the corresponding polymerization reaction is called swelling polymerization reaction.
Disclosure of Invention
The invention aims to provide a preparation method of zero-shrinkage epoxy resin, which is characterized in that an expansion monomer is copolymerized with epoxy resin to prepare the zero-shrinkage epoxy resin, so that the internal stress caused by volume shrinkage can be reduced or even eliminated, the strength of an epoxy resin-based composite material or an adhesive is improved, and high-performance composite materials and adhesives are obtained.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a preparation method of zero-shrinkage epoxy resin comprises the following steps:
1) taking liquid epoxy resin, stirring and mixing uniformly at room temperature;
2) stirring and mixing the liquid epoxy resin obtained in the step 1) and a certain amount of hollow glass microspheres completely at room temperature;
3) adding a proper amount of expansion monomer into the mixed solution prepared in the step 2);
4) adding a proper amount of curing agent into the mixed solution prepared in the step 3), and stirring and mixing uniformly at room temperature;
5) adding a certain amount of accelerator into the mixed solution prepared in the step 4), and stirring and mixing uniformly at room temperature.
The liquid epoxy resin is one or more of bisphenol A type 128 epoxy resin, bisphenol F type epoxy resin, TDE-85 epoxy resin, AFG-90 epoxy resin and AG-80 epoxy resin.
The hollow glass microspheres are one or more of 3M hollow glass microspheres S60HS, iM16K and iM 30K.
The swelling monomer is one or more of 1, 4, 6-trioxaspiro [4,4] nonane, 3, 9-dimethylol-3 ', 9' -diethyl-1, 5, 7, 11-tetraoxaspiro [5, 5] undecane, and 3, 9-dimethylol-3, 9-bis (dimethylethylthio) -1, 5, 7, 11-tetraoxaspiro [5, 5] undecane.
The curing agent is one or more of isophorone diamine, polyether amine D-230 and polyether amine D-400.
The accelerant is BF3·OEt2And tert-butyl peroxybenzoate.
The particle size of the hollow glass beads is 1-70 mu m.
The adding amount of the hollow glass beads in the step 2) is as follows: 100 to 200 weight percent of the total amount of the resin
The addition amount of the swelling monomer is as follows: 5 to 30 weight percent of the total amount of the resin
The addition amount of the curing agent is as follows: 20-70 wt% of the total resin, and the addition amount of the accelerant is as follows: 1 to 10 weight percent of the total amount of the resin
Compared with the prior art, the invention has the beneficial effects that:
the invention can prepare the epoxy resin with zero shrinkage by offsetting the volume shrinkage of the epoxy resin in the curing process by the volume expansion generated in the polymerization process of the expansion monomer. The density of the epoxy resin prepared by the method is kept unchanged before and after the epoxy resin is cured, zero shrinkage is realized in a real sense, and the method has high application value.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
1) Uniformly mixing 45 g of 128-epoxy resin, 40 g of bisphenol F type epoxy resin and 15 g of TDE-85 epoxy resin in a beaker at room temperature;
2) adding 150g of 3M hollow glass microspheres S60HS into the mixed solution 1, and uniformly mixing at room temperature;
3) 15 g of 3, 9-dimethylol-3 ', 9' -diethyl-1, 5, 7, 11-tetraoxaspiro [5, 5] undecane was added to the mixed solution 2 in the above step, and stirred at room temperature for 10min to obtain a mixture 1.
4) 50g of polyetheramine D-400 was added to the mixture 3 in the above step and stirred at room temperature for 10min to obtain a mixture 4.
5) 2 g of BF3 OEt was added to the mixture 42Stirring for 10min at room temperature to obtain a zero-shrinkage epoxy resin system;
the zero-shrinkage epoxy resin system is defoamed in a vacuum drying oven, the density of the resin system before curing is tested by using a density bottle, and the test result is 1.64g/cm3. Curing the epoxy resin after the defoaming treatment at 90 ℃ for 2h, testing the cured epoxy resin by using a hydrostatic method, and testing the cured epoxy resin to obtain a test result of 1.64g/cm3The shrinkage before and after curing was calculated to be 0%.
Comparative example 1
This comparative example 1 is a conventional epoxy formulation.
1) Uniformly mixing 45 g of 128-epoxy resin, 40 g of bisphenol F type epoxy resin and 15 g of TDE-85 epoxy resin in a beaker at room temperature;
2) adding 50g of polyetheramine D-400 into the mixture obtained in the previous step, and stirring at room temperature for 10min to obtain a conventional epoxy resin system;
the conventional epoxy resin system was defoamed in a vacuum oven, and the density of the resin system before curing was measured using a density bottle, and the measurement result was 1.08g/cm3. Curing the epoxy resin after the defoaming treatment at 90 ℃ for 2h, testing the cured epoxy resin by using a hydrostatic method, and testing the cured epoxy resin to obtain a test result of 1.16g/cm3The shrinkage before and after curing was calculated to be 7.4%.
As can be seen from example 1 and comparative example 1, the curing shrinkage of the zero-shrinkage epoxy resin obtained by the present invention is 0%. The prepared epoxy resin can eliminate internal stress caused by volume shrinkage, and improve the strength of the epoxy resin-based composite material or adhesive, thereby obtaining high-performance composite materials and adhesives.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention in any way, and any person skilled in the art can make any simple modification, equivalent replacement, and improvement on the above embodiment without departing from the technical spirit of the present invention, and still fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of zero-shrinkage epoxy resin is characterized by comprising the following steps: the method comprises the following steps:
1) taking liquid epoxy resin, stirring and mixing uniformly at room temperature;
2) stirring and mixing the liquid epoxy resin obtained in the step 1) and a certain amount of hollow glass microspheres completely at room temperature;
3) adding a proper amount of expansion monomer into the mixed solution prepared in the step 2);
4) adding a proper amount of curing agent into the mixed solution prepared in the step 3), and stirring and mixing uniformly at room temperature;
5) adding a certain amount of accelerator into the mixed solution prepared in the step 4), and stirring and mixing uniformly at room temperature.
2. The method for preparing the zero-shrink epoxy resin according to claim 1, wherein: the liquid epoxy resin is one or more of bisphenol A type 128 epoxy resin, bisphenol F type epoxy resin, TDE-85 epoxy resin, AFG-90 epoxy resin and AG-80 epoxy resin.
3. The method for preparing the zero-shrink epoxy resin according to claim 1, wherein: the hollow glass microspheres are one or more of 3M hollow glass microspheres S60HS, iM16K and iM 30K.
4. The method for preparing the zero-shrink epoxy resin according to claim 1, wherein: the swelling monomer is one or more of 1, 4, 6-trioxaspiro [4,4] nonane, 3, 9-dimethylol-3 ', 9' -diethyl-1, 5, 7, 11-tetraoxaspiro [5, 5] undecane, and 3, 9-dimethylol-3, 9-bis (dimethylethylthio) -1, 5, 7, 11-tetraoxaspiro [5, 5] undecane.
5. The method for preparing the zero-shrink epoxy resin according to claim 1, wherein: the curing agent is one or more of isophorone diamine, polyether amine D-230 and polyether amine D-400.
6. The method for preparing the zero-shrink epoxy resin according to claim 1, wherein: the accelerant is BF3·OEt2And tert-butyl peroxybenzoate.
7. The method for preparing the zero-shrink epoxy resin according to claim 1, wherein: the particle size of the hollow glass beads is 1-70 mu m.
8. The method for preparing the zero-shrink epoxy resin according to claim 1, wherein: the adding amount of the hollow glass beads in the step 2) is as follows: 100 wt% -200 wt% of the total resin.
9. The method for preparing the zero-shrink epoxy resin according to claim 1, wherein: the addition amount of the swelling monomer is as follows: 5 wt% -30 wt% of the total resin.
10. The method for preparing the zero-shrink epoxy resin according to claim 1, wherein: the addition amount of the curing agent is as follows: 20-70 wt% of the total resin, and the addition amount of the accelerant is as follows: 1 wt% -10 wt% of the total resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911186709.4A CN110862651A (en) | 2019-11-28 | 2019-11-28 | Preparation method of zero-shrinkage epoxy resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911186709.4A CN110862651A (en) | 2019-11-28 | 2019-11-28 | Preparation method of zero-shrinkage epoxy resin |
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| CN110862651A true CN110862651A (en) | 2020-03-06 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113817290A (en) * | 2021-09-28 | 2021-12-21 | 重庆大学 | Anti-shrinkage self-repairing epoxy resin/microcapsule composite material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5556896A (en) * | 1993-07-01 | 1996-09-17 | The Curators Of The University Of Missouri | Polymeric compositions and composites prepared from spiroortho-carbonates and epoxy monomers |
| CN1718632A (en) * | 2005-07-27 | 2006-01-11 | 武汉理工大学 | Hollow microbead reinforced epoxy resin composite material and its preparation method |
| CN108641066A (en) * | 2018-04-17 | 2018-10-12 | 中国科学院化学研究所 | A kind of composition epoxy resin and preparation method thereof |
-
2019
- 2019-11-28 CN CN201911186709.4A patent/CN110862651A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5556896A (en) * | 1993-07-01 | 1996-09-17 | The Curators Of The University Of Missouri | Polymeric compositions and composites prepared from spiroortho-carbonates and epoxy monomers |
| CN1718632A (en) * | 2005-07-27 | 2006-01-11 | 武汉理工大学 | Hollow microbead reinforced epoxy resin composite material and its preparation method |
| CN108641066A (en) * | 2018-04-17 | 2018-10-12 | 中国科学院化学研究所 | A kind of composition epoxy resin and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113817290A (en) * | 2021-09-28 | 2021-12-21 | 重庆大学 | Anti-shrinkage self-repairing epoxy resin/microcapsule composite material and preparation method thereof |
| CN113817290B (en) * | 2021-09-28 | 2022-10-21 | 重庆大学 | Anti-shrinkage self-repairing epoxy resin/microcapsule composite material and preparation method thereof |
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Application publication date: 20200306 |
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