CN111072887A - 1, 4-xylylenediamine and formaldehyde phenol under alkaline condition to generate thermosetting modified phenolic resin - Google Patents
1, 4-xylylenediamine and formaldehyde phenol under alkaline condition to generate thermosetting modified phenolic resin Download PDFInfo
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- CN111072887A CN111072887A CN201911242080.0A CN201911242080A CN111072887A CN 111072887 A CN111072887 A CN 111072887A CN 201911242080 A CN201911242080 A CN 201911242080A CN 111072887 A CN111072887 A CN 111072887A
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- phenolic resin
- xylylenediamine
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- phenol
- modified phenolic
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 59
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 title claims abstract description 27
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 14
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 48
- 239000005011 phenolic resin Substances 0.000 claims abstract description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- 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
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 claims description 2
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 claims description 2
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 229920002866 paraformaldehyde Polymers 0.000 claims description 2
- 229940044654 phenolsulfonic acid Drugs 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 13
- 239000011347 resin Substances 0.000 abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- 238000002485 combustion reaction Methods 0.000 abstract description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- -1 aldehyde compound Chemical class 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 241001411320 Eriogonum inflatum Species 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
1, 4-xylylenediamine reacts with phenol formaldehyde to modify the phenolic resin, 1, 4-xylylenediamine is introduced into the phenolic resin, a large number of benzene rings can improve the heat resistance of the phenolic resin, and simultaneously, the structure that only methylene is connected among the resins is changed. The mechanical property, particularly the toughness, of the modified resin is greatly improved, the carbon residue rate after combustion is also improved, the application range of the improved phenolic resin is wide, and the improved phenolic resin has remarkable social and economic benefits.
Description
Technical Field
The invention relates to preparation of a thermosetting modified phenolic resin, in particular to a thermosetting modified phenolic resin prepared by reacting 1, 4-xylylenediamine with formaldehyde phenol under an alkaline condition.
Background
Phenolic resin is a kind of high molecular compound formed by condensation polymerization of phenolic compound and aldehyde compound under the catalysis of acid or alkali, and is one of the earliest industrialized high molecular materials. Because of its good mechanical properties, water resistance, heat resistance, weather resistance, flame retardancy and wear resistance, etc., it is widely used in the fields of electrical appliances, machinery, automobiles, communication, aerospace, etc. For example, phenolic resins used in spacecraft such as launch vehicles, satellites and airships often need to have special properties such as instantaneous high temperature resistance, ablation resistance, ultra-low temperature resistance, and special medium resistance. However, phenolic hydroxyl groups in the phenolic resin structure are easily oxidized, and the heat resistance needs to be improved; the rigid aromatic rings linked by structural methylene groups are tightly packed and toughness is also affected. Therefore, in order to meet the requirements of high and new technical fields such as automobiles, electronics, aviation, aerospace, national defense industry and the like, the development direction of phenolic resin is to modify phenolic resin and improve the toughness and heat resistance of the phenolic resin.
Chinese patent CN106543390A relates to a preparation method of a tetrahydroxy polyhedral silsesquioxane heat-resistant phenolic resin. The heat resistance of the prepared modified phenolic resin is obviously improved. The proposal only improves the heat resistance of the resin, does not solve the problem of poor toughness of the resin, and does not relate to the mechanical property of the modified phenolic resin.
The invention introduces the new 1, 4-xylylenediamine group on the molecular main chain, which can not only react with phenolic hydroxyl to improve the aging resistance of the resin, but also introduce the benzene ring structure and improve the heat resistance of the phenolic resin. Meanwhile, the cross-linked structure of the resin which is originally connected only by methylene is changed, and the toughness of the phenolic resin is improved.
Disclosure of Invention
The invention aims to provide a thermosetting modified phenolic resin formed by 1, 4-xylylenediamine and formaldehyde phenol under alkaline conditions, wherein a new 1, 4-xylylenediamine group is introduced into a molecular main chain, so that the aging resistance of the resin can be improved by reacting with phenolic hydroxyl, a cross-linked structure of the resin which is originally connected by methylene can be changed, and the toughness of the phenolic resin is improved. In addition, the introduced benzene ring structure can improve the heat resistance of the phenolic resin.
The purpose of the invention is realized by the following technical scheme:
1, 4-xylylenediamine and formaldehyde phenol are reacted under alkaline condition to generate thermosetting modified phenolic resin, and the generation and preparation of the thermosetting modified phenolic resin comprises the following processes:
a. preparing phenolic resin from the following raw materials in parts by weight:
15-25 parts of 1, 4-xylylenediamine;
80 parts of phenol;
50 parts of paraformaldehyde;
1 part of sodium hydroxide;
b. the thermosetting modified phenolic resin is prepared from the following raw materials in parts by weight:
100 parts of phenolic resin;
8-10 parts of a curing agent;
reacting 1, 4-xylylenediamine with phenol formaldehyde under alkaline conditions to generate a modified thermosetting phenol-formaldehyde resin:
the 1, 4-xylylenediamine and formaldehyde phenol generate thermosetting modified phenolic resin under alkaline condition, and the curing agent is one or more of p-toluenesulfonic acid, xylenesulfonic acid, phenolsulfonic acid and benzenesulfonic acid.
The invention has the advantages and effects that:
the modified phenolic resin of the invention is added with 1, 4-xylylenediamine group, thus improving the toughness of the phenolic resin and the impact strength of the resin.
According to the invention, 1, 4-xylylenediamine modified phenol reacts with formaldehyde, 1, 4-xylylenediamine groups are introduced to react with phenolic hydroxyl groups, so that the aging resistance of the phenolic resin is improved, and the heat resistance is improved.
According to the invention, 1, 4-xylylenediamine and phenol formaldehyde react to modify the phenolic resin, 1, 4-xylylenediamine groups are introduced into the phenolic resin, a large number of benzene rings can improve the heat resistance of the phenolic resin, and simultaneously, the structure that only methylene is connected among the resins is changed. The mechanical property, particularly the toughness of the modified resin is greatly improved, and the carbon residue rate after combustion is also improved.
Detailed Description
The present invention will be described in detail with reference to examples.
The present invention is further described in the following description of the specific embodiments, which is not intended to limit the invention, but various modifications and improvements can be made by those skilled in the art according to the basic idea of the invention, within the scope of the invention, as long as they do not depart from the basic idea of the invention.
Example 1
1, 4-xylylenediamine: phenol: the formaldehyde is 1: 6: 4, adding the mixture into a three-neck flask, and then weighing 1% sodium hydroxide of phenol by using an electronic balance to add into the three-neck flask. Putting the three-neck flask into a water bath kettle with the set temperature of 65 ℃, installing a stirring paddle and a condenser pipe, plugging a bottle stopper, and opening a condensed water switch and a stirring rod switch. Starting the reaction, raising the temperature to 95 ℃ after 2 hours of reaction, and continuously stirring to obtain the 1, 4-xylylenediamine modified phenolic resin after 2 hours. And adding the obtained modified phenolic resin solution and 10 parts of p-toluenesulfonic acid into the mixture, stirring for 15 seconds, transferring the mixed material into a mold, reacting for 10 hours in an oven at 90 ℃, and demolding to obtain the required phenolic resin.
Example 2
1, 4-xylylenediamine: phenol: the formaldehyde is added into the three-neck flask in the amount of 1:7:5, and then the 1% sodium hydroxide of the phenol is weighed by an electronic balance and added into the three-neck flask. Putting the three-neck flask into a water bath kettle with the set temperature of 65 ℃, installing a stirring paddle and a condenser pipe, plugging a bottle stopper, and opening a condensed water switch and a stirring rod switch. Starting the reaction, raising the temperature to 95 ℃ after 2 hours of reaction, and continuously stirring to obtain the 1, 4-xylylenediamine modified phenolic resin after 2 hours. And adding the obtained modified phenolic resin solution and 10 parts of p-toluenesulfonic acid into the mixture, stirring for 15 seconds, transferring the mixed material into a mold, reacting for 10 hours in an oven at 90 ℃, and demolding to obtain the required phenolic resin.
Example 3
1, 4-xylylenediamine: phenol: the formaldehyde is added into the three-neck flask in the proportion of 1:8:6, and then the sodium hydroxide with the concentration of 1% of the phenol is weighed by an electronic balance and added into the three-neck flask. Putting the three-neck flask into a water bath kettle with the set temperature of 65 ℃, installing a stirring paddle and a condenser pipe, plugging a bottle stopper, and opening a condensed water switch and a stirring rod switch. Starting the reaction, raising the temperature to 95 ℃ after 2 hours of reaction, and continuously stirring to obtain the 1, 4-xylylenediamine modified phenolic resin after 2 hours. And adding the obtained modified phenolic resin solution and 10 parts of p-toluenesulfonic acid into the mixture, stirring for 15 seconds, transferring the mixed material into a mold, reacting for 10 hours in an oven at 90 ℃, and demolding to obtain the required phenolic resin.
Example 4
1, 4-xylylenediamine: phenol: the formaldehyde is added into the three-neck flask in the proportion of 1:9:7, and then the 1% sodium hydroxide of the phenol is weighed by an electronic balance and added into the three-neck flask. Putting the three-neck flask into a water bath kettle with the set temperature of 65 ℃, installing a stirring paddle and a condenser pipe, plugging a bottle stopper, and opening a condensed water switch and a stirring rod switch. Starting the reaction, raising the temperature to 95 ℃ after 2 hours of reaction, and continuously stirring to obtain the 1, 4-xylylenediamine modified phenolic resin after 2 hours. And adding the obtained modified phenolic resin solution and 10 parts of p-toluenesulfonic acid into the mixture, stirring for 15 seconds, transferring the mixed material into a mold, reacting for 10 hours in an oven at 90 ℃, and demolding to obtain the required phenolic resin.
The performance pairs of the phenolic resins prepared in examples 1 to 4 of the present invention and the conventional phenolic resins are as follows:
as can be seen from the above table, the impact strength of the 1, 4-xylylenediamine-modified phenol resin was improved by 2 times as compared with the base resin. The reason is that 1, 4-xylylenediamine is introduced into the phenolic resin, so that the toughness of the material is improved, the steric hindrance of a system is increased, the network compactness of the phenolic resin is reduced, and the phenolic resin is not easy to break. The increase of the 1, 4-xylylene diamine group changes the condition that only methylene is connected between the phenolic resins, so that the 1, 4-xylylene diamine group is introduced into the phenolic resins to improve the toughness of the material.
The carbon residue rate results of the 1, 4-xylylenediamine modified phenolic resin and the common phenolic resin are compared, so that the carbon residue rate of the modified phenolic resin is improved by about 9-14% compared with that of the common phenolic resin. The volatilization of benzene ring methyl derivatives, phenols, methyl derivatives thereof and the like is reduced, and the carbon residue rate of the resin is greatly improved. The thermal deformation temperature of the 1, 4-xylylenediamine modified phenolic resin is up to 230.7 ℃, which is increased by nearly 37 ℃ compared with the common phenolic resin; the thermal decomposition peak temperature of the 1, 4-xylylenediamine modified phenolic resin is as high as 513.2 ℃, which is improved by nearly 98 ℃ compared with the common phenolic resin, and the stability is obviously improved.
In conclusion, the phenolic resin generated by 1, 4-xylylenediamine and phenol formaldehyde greatly improves the mechanical property and the heat resistance of the phenolic resin, improves the carbon residue rate and the thermal decomposition peak temperature, and improves the comprehensive performance of the product.
Claims (2)
1, 4-xylylenediamine and formaldehyde phenol under alkaline condition to generate thermosetting modified phenolic resin, which is characterized in that the generation and preparation of the thermosetting modified phenolic resin comprises the following processes:
a. preparing phenolic resin from the following raw materials in parts by weight:
15-25 parts of 1, 4-xylylenediamine;
80 parts of phenol;
50 parts of paraformaldehyde;
1 part of sodium hydroxide;
b. the thermosetting modified phenolic resin is prepared from the following raw materials in parts by weight:
100 parts of phenolic resin;
8-10 parts of a curing agent;
reacting 1, 4-xylylenediamine with phenol formaldehyde under alkaline conditions to generate a modified thermosetting phenol-formaldehyde resin:
2. the 1, 4-xylylenediamine of claim 1, wherein the curing agent is one or more of p-toluenesulfonic acid, xylenesulfonic acid, phenolsulfonic acid, and benzenesulfonic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911242080.0A CN111072887A (en) | 2019-12-06 | 2019-12-06 | 1, 4-xylylenediamine and formaldehyde phenol under alkaline condition to generate thermosetting modified phenolic resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911242080.0A CN111072887A (en) | 2019-12-06 | 2019-12-06 | 1, 4-xylylenediamine and formaldehyde phenol under alkaline condition to generate thermosetting modified phenolic resin |
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| Publication Number | Publication Date |
|---|---|
| CN111072887A true CN111072887A (en) | 2020-04-28 |
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| CN201911242080.0A Pending CN111072887A (en) | 2019-12-06 | 2019-12-06 | 1, 4-xylylenediamine and formaldehyde phenol under alkaline condition to generate thermosetting modified phenolic resin |
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| CN (1) | CN111072887A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111363110A (en) * | 2020-05-18 | 2020-07-03 | 营口理工学院 | Synthesis method of Co-modified high-carbon-residue-rate phenolic resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4209429A (en) * | 1977-08-29 | 1980-06-24 | Hitachi Chemical Company, Ltd. | Process for producing internally plasticized phenolic resins |
| CN109679041A (en) * | 2018-12-10 | 2019-04-26 | 沈阳化工大学 | A kind of benzidine modified phenolic resin material and preparation method thereof |
| CN109851732A (en) * | 2018-12-10 | 2019-06-07 | 沈阳化工大学 | N- hydroxymethyl acetamide modified pnenolic aldehyde foam material |
-
2019
- 2019-12-06 CN CN201911242080.0A patent/CN111072887A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4209429A (en) * | 1977-08-29 | 1980-06-24 | Hitachi Chemical Company, Ltd. | Process for producing internally plasticized phenolic resins |
| CN109679041A (en) * | 2018-12-10 | 2019-04-26 | 沈阳化工大学 | A kind of benzidine modified phenolic resin material and preparation method thereof |
| CN109851732A (en) * | 2018-12-10 | 2019-06-07 | 沈阳化工大学 | N- hydroxymethyl acetamide modified pnenolic aldehyde foam material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111363110A (en) * | 2020-05-18 | 2020-07-03 | 营口理工学院 | Synthesis method of Co-modified high-carbon-residue-rate phenolic resin |
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Application publication date: 20200428 |
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