CN117801209A - Polyurethane modified epoxy resin and preparation method thereof - Google Patents
Polyurethane modified epoxy resin and preparation method thereof Download PDFInfo
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- CN117801209A CN117801209A CN202311778615.2A CN202311778615A CN117801209A CN 117801209 A CN117801209 A CN 117801209A CN 202311778615 A CN202311778615 A CN 202311778615A CN 117801209 A CN117801209 A CN 117801209A
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- Prior art keywords
- epoxy resin
- modified epoxy
- polyurethane modified
- hours
- groups
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 49
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 49
- 239000004814 polyurethane Substances 0.000 title claims abstract description 34
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 150000003077 polyols Chemical class 0.000 claims abstract description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 229920000570 polyether Polymers 0.000 claims abstract description 10
- 229920005862 polyol Polymers 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000012948 isocyanate Substances 0.000 claims abstract description 8
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 239000000498 cooling water Substances 0.000 claims abstract description 7
- 125000000524 functional group Chemical group 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 8
- 229920001451 polypropylene glycol Polymers 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 8
- 239000000853 adhesive Substances 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
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- Epoxy Resins (AREA)
Abstract
The invention relates to the technical field of adhesives, in particular to polyurethane modified epoxy resin and a preparation method thereof, and the polyurethane modified epoxy resin comprises the following components in parts by weight: polyether polyol, epoxy resin, isocyanate containing at least two NCO functional groups and catalyst 0.06-0.1 parts. The preparation method comprises the following steps: adding the polyether polyol and isocyanate containing at least two NCO functional groups into a reaction kettle, introducing nitrogen, heating to 60-120 ℃, stirring for 2-3 hours, cooling by cooling water to below 20 ℃, adding the epoxy resin and the catalyst, stirring uniformly, heating to 100-140 ℃, and reacting for 3-6 hours to obtain the polyurethane modified epoxy resin. The polyurethane modified epoxy resin provided by the invention has good toughness and good wet heat resistance, and can be used as an adhesive.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to polyurethane modified epoxy resin and a preparation method thereof.
Background
The epoxy resin (EP) has the advantages of good adhesive property, high chemical stability, strong high and low temperature resistance, low curing shrinkage rate and the like, is a thermosetting resin with excellent comprehensive properties, and is widely applied to the fields of adhesives, coatings and the like after being introduced into the domestic market from the end of the twentieth century 50. The epoxy resin is cured to form a highly crosslinked network structure, so that the internal stress is increased, the quality is fragile, the impact resistance is poor, and the comprehensive application performance is improved through toughening modification.
The toughening modification methods of the epoxy resin are numerous, but Polyurethane (PU) modified epoxy resin (EP) materials have the problem that PU is not fully compatible with EP, the addition amount of PU cannot be too high, and the toughening effect is not ideal. The traditional polyurethane toughening modified epoxy resin method mainly comprises two methods: firstly, hydroxyl-terminated polyurethane is added into epoxy resin for blending, and polyurethane molecular chain flexibility is utilized to toughen the epoxy resin; and secondly, the isocyanate group in the polyurethane structure and the hydroxyl group in the epoxy resin structure are utilized to react, so that the adhesive property and the mechanical property of the toughening system are obviously improved. Among them, the first method is not very good in compatibility because of physical blending, and cannot have very high compatibility; the second method uses the reaction of hydroxyl and NCO, and has the advantages of low hydroxyl content, obvious steric effect in macromolecular epoxy, insufficient reaction and poor compatibility.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides polyurethane modified epoxy resin and a preparation method thereof.
The technical scheme for solving the technical problems is as follows:
the invention provides polyurethane modified epoxy resin, which comprises the following components in parts by weight:
polyether polyol, epoxy resin, isocyanate containing at least two NCO functional groups and catalyst 0.06-0.1 parts.
Based on the technical scheme, the invention can also make the following improvements:
further, the molar ratio of NCO groups to OH groups in the polyether polyol was 2.1:1, so that the OH groups were sufficiently reacted.
Further, the molar ratio of epoxy groups to NCO groups in the epoxy resin was 2.1:1 so that NCO groups were sufficiently reacted.
Further, the polyether polyol is selected from polypropylene glycol (PPG-400) or polytetrahydrofuran ether glycol (PTMG-1000).
Further, the epoxy resin is selected from E-51 or E-44.
Further, the isocyanate is selected from any one or more of MDI, HDI, TDI, IPDI.
Further, the catalyst is selected from one or a combination of two of triethanolamine and imidazole.
The invention also provides a preparation method of the polyurethane modified epoxy resin, which comprises the following steps: adding the polyether polyol and isocyanate containing at least two NCO functional groups into a reaction kettle, introducing nitrogen, heating to 60-120 ℃, stirring for 2-3 hours, cooling by cooling water to below 20 ℃, adding the epoxy resin and the catalyst, stirring uniformly, heating to 100-140 ℃, and reacting for 3-6 hours to obtain the polyurethane modified epoxy resin.
The process route of the invention involves the following two steps of reactions:
the first step of reaction:
and the second step of reaction:
compared with the prior art, the invention has the following technical effects:
under the action of a catalyst, synthesizing a five-membered heterocyclic ring structure by isocyanate groups and epoxy functional groups, wherein the five-membered ring is a rigid five-membered ring structure composed of C, N, O elements, has larger cohesive energy, and has larger bond energy of carbon-oxygen double bonds and good high temperature resistance;
the invention utilizes the reaction of NCO and epoxy groups to synthesize the front-stage modified resin with one epoxy group at both ends, fully utilizes the reactivity of the two materials, improves the compatibility, and the polyurethane modified epoxy resin prepared by adding the polyol chain segment has good toughness and good wet heat resistance and can be used as an adhesive.
Detailed Description
Further advantages and effects of the present invention will become apparent to those skilled in the art from the disclosure of the present specification, by describing the embodiments of the present invention with specific examples. While the description of the invention will be described in connection with the preferred embodiments, it is not intended to limit the inventive features to the implementation. Rather, the purpose of the invention described in connection with the embodiments is to cover other alternatives or modifications, which may be extended by the claims based on the invention. The following description contains many specific details for the purpose of providing a thorough understanding of the present invention. The invention may be practiced without these specific details. Furthermore, some specific details are omitted from the description in order to avoid obscuring the invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
Example 1
Polytetrahydrofuran ether glycol (PTMG-1000) and IPDI are added into a reaction kettle according to the proportion of (NCO): R (OH) =2.1:1, nitrogen is introduced, the temperature is raised to 60 ℃, after stirring for 3 hours, cooling water is introduced to below 20 ℃, and according to epoxy groups: and adding 0.06 part of E-44 and imidazole in the ratio of NCO=2.1:1, uniformly stirring, heating to 100 ℃, and reacting for 3 hours to obtain the polyurethane modified epoxy resin after the reaction is finished.
Example 2
Polypropylene glycol (PPG-400) and MD I are added into a reaction kettle according to the proportion of (NCO): R (OH) =2.1:1, nitrogen is introduced, the temperature is raised to 120 ℃, after stirring for 2 hours, cooling water is introduced to below 20 ℃, and according to epoxy groups: and adding 0.1 part of E-44 and 0.1 part of imidazole in the ratio of NCO=2.1:1, uniformly stirring, heating to 140 ℃, and reacting for 3 hours to obtain the polyurethane modified epoxy resin after the reaction is finished.
Example 3
Polypropylene glycol (PPG-400) and HD I are added into a reaction kettle according to the proportion of (NCO): R (OH) =2.1:1, nitrogen is introduced, the temperature is raised to 90 ℃, after stirring for 2 hours, cooling water is introduced to below 20 ℃, and according to epoxy groups: and adding 0.08 part of E-51 and imidazole in the ratio of NCO=2.1:1, uniformly stirring, heating to 120 ℃, and reacting for 4 hours to obtain the polyurethane modified epoxy resin after the reaction is finished.
Example 4
Polytetrahydrofuran ether glycol (PTMG-1000) and TDI are added into a reaction kettle according to the proportion of (NCO): R (OH) =2.1:1, nitrogen is introduced, the temperature is raised to 100 ℃, stirring is carried out for 2.5 hours, cooling water is introduced to below 20 ℃, and epoxy groups are formed: and adding 0.1 part of E-44 and 0.1 part of imidazole in the ratio of NCO=2.1:1, uniformly stirring, heating to 140 ℃, and reacting for 3 hours to obtain the polyurethane modified epoxy resin after the reaction is finished.
Comparative example 1
And (3) a commercially available epoxy resin packaging material.
The testing method comprises the following steps:
shear strength test: manufacturing a standard shearing sample piece by referring to a method specified in GB/T7124, selecting a bonding material for test according to an actual bonding surface material, wherein the thickness is required to be consistent with that of the groups, and is 0.2mm, and the standard shearing sample piece can be controlled by using a spacing wire (an iron wire or a copper wire with fixed thickness or a pressure-sensitive adhesive tape with fixed thickness) or a small glass ball, and if the spacing wire is a wire, the wire is parallel to the direction of the applied force so as to avoid error in the test;
after the sample is manufactured, the sample is placed in a constant temperature and humidity box (25 ℃/50%RH) for curing for 7 days;
selecting proper parameters of a tension machine: the breaking load is between 10% and 80% of the maximum load of the tensile machine, and the response time of the testing machine is short enough to ensure the accuracy of the breaking time judgment, and the stretching speed is 10mm/min.
Elongation at break test: preparing and measuring a sample strip by referring to GB/T528, preparing an adhesive sample sheet with the thickness of 2mm, and placing the sample sheet into a constant temperature and humidity box (25 ℃/50%RH) for curing for 7 days;
after the sample is completely solidified, standing for 3 hours in a laboratory environment, and cutting out standard sample strips by using an I-shaped dumbbell cutter;
for a sample which is not easy to cut, a standard die is used for preparing the sample;
selecting proper parameters of a tension machine: the breaking load is between 10% and 80% of the maximum load of the tensile machine, and the response time of the testing machine is short enough to ensure the accuracy of the breaking time judgment, and the stretching speed is 100mm/min.
Tensile shear strength after double 85 x 1000 hours: samples of each form were tested after being left to cure in laboratory conditions, see "GB/T2423.3 environmental test second part: test method test Cab: constant damp-heat test, putting the sample into a constant temperature and humidity box with the temperature set at 85+/-3 ℃ and the humidity set at 82% -88% RH for 1000 hours, taking out, and putting the sample at normal temperature for 24 hours for testing.
The properties of the encapsulating material are shown in table 1.
TABLE 1
Note that: double 85 means double 85 test, in which the test body is subjected to an aging test under conditions that the ambient temperature is set to 85 ℃ and the humidity is 85%, usually for 1000 hours.
As can be seen from the data in Table 1, the polyurethane modified epoxy resin material prepared by the invention has no obvious attenuation after double 85 ageing. In conclusion, the polyurethane modified epoxy resin material prepared by the invention has the advantages of air tightness and adhesiveness of the traditional epoxy, capability of improving the wet heat resistance and good toughness.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (8)
1. The polyurethane modified epoxy resin is characterized by comprising the following components in parts by weight:
polyether polyol, epoxy resin, isocyanate containing at least two NCO functional groups and catalyst 0.06-0.1 parts.
2. The polyurethane modified epoxy resin of claim 1, wherein the molar ratio of NCO groups to OH groups in the polyether polyol is 2.1:1.
3. The polyurethane modified epoxy resin of claim 1, wherein the molar ratio of epoxy groups to NCO groups in the epoxy resin is 2.1:1.
4. The polyurethane modified epoxy resin of claim 1, wherein the polyether polyol is selected from polypropylene glycol (PPG-400) or polytetrahydrofuran ether glycol (PTMG-1000).
5. The polyurethane modified epoxy resin of claim 1, wherein the epoxy resin is selected from the group consisting of E-51 and E-44.
6. The polyurethane modified epoxy resin of claim 1, wherein the isocyanate is selected from any one or more of MDI, HDI, TDI, IPDI.
7. The polyurethane modified epoxy resin of claim 1, wherein the catalyst is selected from one or a combination of two of triethanolamine and imidazole.
8. A method for preparing the polyurethane modified epoxy resin as claimed in any one of claims 1 to 7, comprising the steps of: adding the polyether polyol and isocyanate containing at least two NCO functional groups into a reaction kettle, introducing nitrogen, heating to 60-120 ℃, stirring for 2-3 hours, cooling by cooling water to below 20 ℃, adding the epoxy resin and the catalyst, stirring uniformly, heating to 100-140 ℃, and reacting for 3-6 hours to obtain the polyurethane modified epoxy resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311778615.2A CN117801209A (en) | 2023-12-22 | 2023-12-22 | Polyurethane modified epoxy resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311778615.2A CN117801209A (en) | 2023-12-22 | 2023-12-22 | Polyurethane modified epoxy resin and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117801209A true CN117801209A (en) | 2024-04-02 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311778615.2A Pending CN117801209A (en) | 2023-12-22 | 2023-12-22 | Polyurethane modified epoxy resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117801209A (en) |
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2023
- 2023-12-22 CN CN202311778615.2A patent/CN117801209A/en active Pending
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