CN113773653A - Preparation method of modified novolac epoxy resin - Google Patents
Preparation method of modified novolac epoxy resin Download PDFInfo
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- CN113773653A CN113773653A CN202111047475.2A CN202111047475A CN113773653A CN 113773653 A CN113773653 A CN 113773653A CN 202111047475 A CN202111047475 A CN 202111047475A CN 113773653 A CN113773653 A CN 113773653A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
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- 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
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
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- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- 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
- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C09D187/005—Block or graft polymers not provided for in groups C09D101/00 - C09D185/04
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- 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
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- 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
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- Engineering & Computer Science (AREA)
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Abstract
The invention relates to the field of epoxy resin, in particular to a preparation method of modified novolac epoxy resin. Selecting hydroxyl-terminated polysiloxane with the number average molecular weight of 400-800, firstly, carrying out chain extension on the hydroxyl-terminated polysiloxane by using diisocyanate to obtain modified hydroxyl-terminated polysiloxane with a specific structure and alternating soft and hard segments, and then grafting the modified hydroxyl-terminated polysiloxane to a side chain of novolac epoxy resin through reaction to obtain modified novolac epoxy resin I; carrying out graft modification on phenolic aldehyde by using tris (3-trimethoxysilylpropyl) isocyanurate to obtain modified phenolic epoxy resin II; and uniformly mixing the modified novolac epoxy resin I and the modified novolac epoxy resin II according to a proportion. The modified novolac epoxy resin has high adhesion, high corrosion resistance, high temperature resistance and high toughness after being cured. Can be widely used for coating high-temperature valves, high-temperature boilers and heat exchangers.
Description
Technical Field
The invention relates to the field of epoxy resin, and in particular relates to a preparation method of modified novolac epoxy resin.
Background
Bisphenol F epoxy resin is widely applied to the industries of transportation, machinery, electronics and electricity and the like due to low viscosity, high electrical insulation, corrosion resistance and good adhesion, and a cured product has excellent mechanical properties. However, bisphenol F epoxy resins still have the disadvantages of high crosslinking density after curing, large internal stress, poor impact resistance, poor cracking resistance, poor moist heat resistance and the like, and therefore, the modification of bisphenol F epoxy resins is attracting more and more attention of researchers. Chinese patent CN106893448B discloses a high-temperature ceramic organosilicon-novolac epoxy anticorrosive paint and a preparation method thereof, the paint adopts a chemical grafting method to synthesize organosilicon-novolac epoxy resin, the resin has an organosilicon chain segment and a novolac epoxy chain segment, on one hand, the resin not only has the characteristics of heat resistance, weather resistance, wear resistance, flexibility and the like of the organosilicon chain segment, but also has the advantages that the adhesive force of the novolac epoxy chain segment on the resin molecule to a metal base material is far higher than that of the organosilicon chain segment, and the corrosion resistance effect of the novolac epoxy chain segment after being crosslinked with a curing agent is also far higher than that of the organosilicon chain segment, thereby solving the problems of low adhesive force and poor corrosion resistance effect of the organosilicon paint; on the other hand, the residual carbon rate of the novolac epoxy chain segment in a high-temperature environment is high, and the novolac epoxy chain segment and a thermal degradation product of the organic silicon chain segment in the high-temperature environment can generate a secondary film forming effect, so that the ceramic effect of the coating in the high-temperature environment is improved. The organic silicon-phenolic epoxy resin obtained by the patent has the problems of poor adhesive force and toughness and the like.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of modified novolac epoxy resin, and the modified novolac epoxy resin prepared by the method has excellent adhesion to base materials such as glass, metal and the like, and also has high corrosion resistance, high temperature resistance and high toughness. Can be widely used for coating high-temperature valves, high-temperature boilers and heat exchangers.
In order to achieve the purpose, the invention adopts the following technical scheme:
on one hand, the invention provides a preparation method of modified novolac epoxy resin, which is characterized by comprising the following steps:
step one, adding hydroxyl-terminated polysiloxane with the number average molecular weight of 400-800 into a three-neck flask, performing vacuum dehydration for 1-2h at 110 ℃, introducing nitrogen, dropwise adding diisocyanate while stirring, and obtaining an intermediate product I after the reaction is finished;
adding novolac epoxy resin into a three-neck flask, adding a certain amount of tetraisopropyl titanate, introducing nitrogen, heating and keeping the temperature at 120 ℃, dropwise adding the intermediate product I prepared in the step one while stirring, keeping the temperature for reacting for 2-3 hours after dropwise adding, and obtaining an intermediate product II after the reaction is finished;
adding novolac epoxy resin into a three-neck flask, heating to 80-95 ℃, then introducing nitrogen, dropwise adding tris (3-trimethoxysilylpropyl) isocyanurate while stirring, preserving heat for reacting for 2 hours after dropwise adding is completed, and obtaining an intermediate product III after the reaction is finished;
step four, uniformly mixing the intermediate product II and the intermediate product III according to a certain mass ratio to obtain modified novolac epoxy resin;
in the first step, the molar ratio of hydroxyl groups to isocyanate groups is 2: 1;
in the second step, the mass ratio of the novolac epoxy resin to the intermediate product I is about 80-85: 15-20;
in the third step, the mass ratio of the aldehyde epoxy resin to the tris (3-trimethoxysilylpropyl) isocyanurate is 90-95: 5-10;
in the fourth step, the mass ratio of the intermediate product II to the intermediate product III is about 70-85: 15-25. .
In one embodiment, the hydroxyl-terminated polysiloxane has a number average molecular weight of 500-700.
In one embodiment, the diisocyanate is one or more of toluene diisocyanate, hexamethylene diisocyanate.
In one embodiment, in the second step, the mass ratio of the novolac epoxy resin to the intermediate product I is 80: 20.
In one embodiment, the mass ratio of the aldehyde epoxy resin to tris (3-trimethoxysilylpropyl) isocyanurate in step three is 95: 5.
In one embodiment, the mass ratio of intermediate II to intermediate III in step four is 85: 15.
In one embodiment, the novolac epoxy resin is one or more of phenol novolac epoxy resin, o-cresol novolac epoxy resin, bisphenol a novolac epoxy resin.
On the other hand, the invention also provides the modified novolac epoxy resin prepared by the method.
On the other hand, the invention also provides the application of the modified novolac epoxy resin in the high-temperature resistant coating.
In another aspect, the invention also provides the use of the modified novolac epoxy resin in the coating of high temperature valves, high temperature boilers and heat exchangers.
The invention selects hydroxyl-terminated polysiloxane with specific molecular weight, firstly uses diisocyanate to carry out chain extension on the hydroxyl-terminated polysiloxane, introduces a soft-segment and hard-segment alternating structure, and then grafts the hydroxyl-terminated polysiloxane on a side chain of novolac epoxy resin through reaction to obtain modified novolac epoxy resin I; carrying out graft modification on phenolic aldehyde by using tris (3-trimethoxysilylpropyl) isocyanurate to obtain modified phenolic epoxy resin II; the modified novolac epoxy resin of the invention is obtained by uniformly mixing the modified novolac epoxy resin I and the modified novolac epoxy resin II according to a proportion. The modified novolac epoxy resin has high adhesion, high corrosion resistance, high temperature resistance and high toughness after being cured. Can be widely used for coating high-temperature valves, high-temperature boilers and heat exchangers.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention is described in further detail with reference to a number of tests performed in sequence, and a part of the test results are used as reference, and the following detailed description is given with reference to specific examples.
Example 1
The preparation method of the modified novolac epoxy resin comprises the following steps:
step one, adding hydroxyl-terminated polysiloxane with number average molecular weight of 400 into a three-neck flask, dehydrating for 1h in vacuum at 110 ℃, then introducing nitrogen, dropwise adding toluene diisocyanate while stirring, and obtaining an intermediate product I after the reaction is finished;
adding novolac epoxy resin into a three-neck flask, adding a certain amount of tetraisopropyl titanate, introducing nitrogen, heating and keeping the temperature at 120 ℃, dropwise adding the intermediate product I prepared in the step one while stirring, preserving heat for reacting for 2 hours after dropwise adding is completed, and obtaining an intermediate product II after the reaction is completed;
adding novolac epoxy resin into a three-neck flask, heating to 80 ℃, introducing nitrogen, dropwise adding tris (3-trimethoxysilylpropyl) isocyanurate while stirring, preserving heat for reacting for 2 hours after dropwise adding is completed, and obtaining an intermediate product III after the reaction is finished;
step four, uniformly mixing the intermediate product II and the intermediate product III according to a certain mass ratio to obtain modified novolac epoxy resin;
in the first step, the molar ratio of hydroxyl groups to isocyanate groups is 2: 1;
in the second step, the mass ratio of the novolac epoxy resin to the intermediate product I is 80: 20;
in the third step, the mass ratio of the aldehyde epoxy resin to the tris (3-trimethoxysilylpropyl) isocyanurate is 90: 10;
in the fourth step, the mass ratio of the intermediate product II to the intermediate product III is 70: 25.
Example 2
The preparation method of the modified novolac epoxy resin comprises the following steps:
the preparation method of the modified novolac epoxy resin is characterized by comprising the following steps:
step one, adding hydroxyl-terminated polysiloxane with the number average molecular weight of 800 into a three-neck flask, dehydrating for 2 hours in vacuum at 110 ℃, introducing nitrogen, dropwise adding hexamethylene diisocyanate while stirring, and obtaining an intermediate product I after the reaction is finished;
adding novolac epoxy resin into a three-neck flask, adding a certain amount of tetraisopropyl titanate, introducing nitrogen, heating and keeping the temperature at 120 ℃, dropwise adding the intermediate product I prepared in the step one while stirring, preserving heat for reacting for 3 hours after dropwise adding is completed, and obtaining an intermediate product II after the reaction is finished;
adding novolac epoxy resin into a three-neck flask, heating to 95 ℃, introducing nitrogen, dropwise adding tris (3-trimethoxysilylpropyl) isocyanurate while stirring, preserving heat for reacting for 2 hours after dropwise adding is completed, and obtaining an intermediate product III after the reaction is finished;
step four, uniformly mixing the intermediate product II and the intermediate product III according to a certain mass ratio to obtain modified novolac epoxy resin;
in the first step, the molar ratio of hydroxyl groups to isocyanate groups is 2: 1;
in the second step, the mass ratio of the novolac epoxy resin to the intermediate product I is 85: 15;
in the third step, the mass ratio of the aldehyde epoxy resin to the tris (3-trimethoxysilylpropyl) isocyanurate is 95: 5;
in the fourth step, the mass ratio of the intermediate product II to the intermediate product III is 85: 15.
Example 3
The preparation method of the modified novolac epoxy resin comprises the following steps:
step one, adding hydroxyl-terminated polysiloxane with number average molecular weight of 600 into a three-neck flask, dehydrating for 1.5h at 110 ℃ in vacuum, introducing nitrogen, dropwise adding toluene diisocyanate while stirring, and obtaining an intermediate product I after the reaction is finished;
adding novolac epoxy resin into a three-neck flask, adding a certain amount of tetraisopropyl titanate, introducing nitrogen, heating and keeping the temperature at 120 ℃, dropwise adding the intermediate product I prepared in the step one while stirring, keeping the temperature for reacting for 2.5 hours after dropwise adding, and obtaining an intermediate product II after the reaction is finished;
adding novolac epoxy resin into a three-neck flask, heating to 90 ℃, introducing nitrogen, dropwise adding tris (3-trimethoxysilylpropyl) isocyanurate while stirring, preserving heat for reacting for 2 hours after dropwise adding is completed, and obtaining an intermediate product III after the reaction is finished;
step four, uniformly mixing the intermediate product II and the intermediate product III according to a certain mass ratio to obtain modified novolac epoxy resin;
in the first step, the molar ratio of hydroxyl groups to isocyanate groups is 2: 1;
in the second step, the mass ratio of the novolac epoxy resin to the intermediate product I is 83: 17;
in the third step, the mass ratio of the aldehyde epoxy resin to the tris (3-trimethoxysilylpropyl) isocyanurate is 93: 7;
in the fourth step, the mass ratio of the intermediate product II to the intermediate product III is 80: 20.
Comparative example 1
The organic silicon-phenolic epoxy resin is prepared according to the technical scheme of the example 1 in Chinese patent CN 106893448B.
TABLE 1 modified Novolac epoxy product parameters
The modified novolac epoxy resins prepared in examples 1-3 and the organosilicon-novolac epoxy resin of comparative example 1 are cured by using 4-functional PAMAM as a curing agent in the same amount to obtain coating test pieces, and the coating test pieces are tested according to corresponding national and industrial standards, wherein the testing standards comprise adhesion (circle marking method GB/T1720), impact resistance (GB/T1732-93) and salt spray resistance (GB/T1771).
TABLE 2 comparison of Properties of curable silicon-based hybrid resins
| Test items | Example 1 | Example 2 | Example 3 | Comparative example 1 |
| Grade of adhesion | 1 | 1 | 1 | 4 |
| Impact resistance/cm | 72 | 68 | 71 | 34 |
| Salt spray resistance/h | ≥2861 | ≥2469 | ≥2613 | ≤1200 |
As can be seen from Table 2, the modified novolac epoxy resin provided by the invention has high adhesion level (the best grade 1, the worst grade 7), and good impact resistance and salt spray resistance. Can be widely used for coating high-temperature valves, high-temperature boilers and heat exchangers.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The preparation method of the modified novolac epoxy resin is characterized by comprising the following steps:
step one, adding hydroxyl-terminated polysiloxane with the number average molecular weight of 400-800 into a three-neck flask, performing vacuum dehydration for 1-2h at 110 ℃, introducing nitrogen, dropwise adding diisocyanate while stirring, and obtaining an intermediate product I after the reaction is finished;
adding novolac epoxy resin into a three-neck flask, adding a certain amount of tetraisopropyl titanate, introducing nitrogen, heating and keeping the temperature at 120 ℃, dropwise adding the intermediate product I prepared in the step one while stirring, keeping the temperature for reacting for 2-3 hours after dropwise adding, and obtaining an intermediate product II after the reaction is finished;
adding novolac epoxy resin into a three-neck flask, heating to 80-95 ℃, then introducing nitrogen, dropwise adding tris (3-trimethoxysilylpropyl) isocyanurate while stirring, preserving heat for reacting for 2 hours after dropwise adding is completed, and obtaining an intermediate product III after the reaction is finished;
step four, uniformly mixing the intermediate product II and the intermediate product III according to a certain mass ratio to obtain modified novolac epoxy resin;
in the first step, the molar ratio of hydroxyl groups to isocyanate groups is 2: 1;
in the second step, the mass ratio of the novolac epoxy resin to the intermediate product I is about 80-85: 15-20;
in the third step, the mass ratio of the aldehyde epoxy resin to the tris (3-trimethoxysilylpropyl) isocyanurate is 90-95: 5-10;
in the fourth step, the mass ratio of the intermediate product II to the intermediate product III is about 70-85: 15-25.
2. The method as set forth in claim 1, wherein the hydroxyl-terminated polysiloxane has a number average molecular weight of 500-700.
3. The method according to claim 1, wherein the diisocyanate is one or more of toluene diisocyanate, hexamethylene diisocyanate, and isophorone.
4. The preparation method according to claim 1, wherein in the second step, the mass ratio of the novolac epoxy resin to the intermediate product I is 80: 20.
5. The method according to claim 1, wherein the mass ratio of the aldehyde epoxy resin to the tris (3-trimethoxysilylpropyl) isocyanurate in step three is 95: 5.
6. The method according to claim 1, wherein in the fourth step, the mass ratio of the intermediate product II to the intermediate product III is 85: 15.
7. The method according to claim 1, wherein the novolac epoxy resin is one or more of phenol novolac epoxy resin, o-cresol novolac epoxy resin, and bisphenol a novolac epoxy resin.
8. A modified novolac epoxy resin, characterized in that it is prepared by the process according to any one of claims 1 to 7.
9. Use of the modified novolac epoxy resin of claim 8 in high temperature resistant coatings.
10. Use of the modified novolac epoxy resin of claim 8 in coating of high temperature valves, high temperature boilers and heat exchangers.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001247749A (en) * | 2000-03-06 | 2001-09-11 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| JP2005023220A (en) * | 2003-07-03 | 2005-01-27 | Hitachi Chem Co Ltd | Flame-retardant epoxy resin composition, electric or electronic component insulated by using the same, and method for producing the same |
| JP2006008808A (en) * | 2004-06-24 | 2006-01-12 | Uchiyama Mfg Corp | Adhesive composition |
| CN104448329A (en) * | 2014-12-05 | 2015-03-25 | 四川东材科技集团股份有限公司 | Preparation methods of phenolic epoxy-organic silicone resin and heat-resistant insulating impregnating varnish thereof |
| JP2018203943A (en) * | 2017-06-08 | 2018-12-27 | 日立化成株式会社 | Epoxy resin composition for sealing electronic component |
| CN109293880A (en) * | 2018-09-06 | 2019-02-01 | 苏州兴业材料科技股份有限公司 | A kind of preparation method of modified o-cresol formaldehyde epoxy resin |
-
2021
- 2021-09-08 CN CN202111047475.2A patent/CN113773653B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001247749A (en) * | 2000-03-06 | 2001-09-11 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| JP2005023220A (en) * | 2003-07-03 | 2005-01-27 | Hitachi Chem Co Ltd | Flame-retardant epoxy resin composition, electric or electronic component insulated by using the same, and method for producing the same |
| JP2006008808A (en) * | 2004-06-24 | 2006-01-12 | Uchiyama Mfg Corp | Adhesive composition |
| CN104448329A (en) * | 2014-12-05 | 2015-03-25 | 四川东材科技集团股份有限公司 | Preparation methods of phenolic epoxy-organic silicone resin and heat-resistant insulating impregnating varnish thereof |
| JP2018203943A (en) * | 2017-06-08 | 2018-12-27 | 日立化成株式会社 | Epoxy resin composition for sealing electronic component |
| CN109293880A (en) * | 2018-09-06 | 2019-02-01 | 苏州兴业材料科技股份有限公司 | A kind of preparation method of modified o-cresol formaldehyde epoxy resin |
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