CN115160543A - Preparation method and application of environment-friendly flame-retardant amine curing agent - Google Patents
Preparation method and application of environment-friendly flame-retardant amine curing agent Download PDFInfo
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- CN115160543A CN115160543A CN202210962288.5A CN202210962288A CN115160543A CN 115160543 A CN115160543 A CN 115160543A CN 202210962288 A CN202210962288 A CN 202210962288A CN 115160543 A CN115160543 A CN 115160543A
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/395—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing phosphorus
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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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a preparation method of an environment-friendly flame-retardant amine curing agent, which specifically comprises the following steps: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and epoxy-terminated polydimethylsiloxane are subjected to prepolymerization reaction under the action of a catalyst, and then excessive polyethylene polyamine is added for modification. The environment-friendly flame-retardant amine curing agent can fully perform a crosslinking reaction with epoxy resin, and has the characteristics of high flame retardant property, no halogen, high concrete adhesion, excellent appearance and the like. Can be widely applied to the fields of protection, corrosion prevention, reinforcement and the like of the civil engineering terrace. Specially adapted has the terrace place of fire prevention special requirement, for example: floor coating for underground civil air defense engineering ground and underground space of dense personnel area.
Description
Technical Field
The invention relates to the technical field of curing agent preparation, in particular to a preparation method and application of an environment-friendly flame-retardant amine curing agent.
Background
In recent decades, domestic epoxy floor coatings are rapidly developed from scratch, and various types of floors applied to different scenes are gradually developed. Including artistic terraces, colored terraces, self-leveling terrace, anti-static terraces and the like. In recent years, due to the fact that various organic compounds are increasingly used in modern society and fire easily occurs, the requirement on the fire-proof grade of the terrace is higher and higher, and the B-grade fire prevention of the common epoxy resin terrace can not meet the market requirement any more. The flame-retardant effect can reach B1 grade by adding special flame-retardant materials such as antimony trioxide, tetrabromobisphenol and other halogen-containing flame retardants into the resin. Such flame retardant materials can generate toxic and harmful gases during combustion. Therefore, the invention provides a preparation method and application of a novel environment-friendly flame-retardant amine curing agent, so that the flame retardant property of epoxy resin is effectively improved, and toxic and harmful gases are avoided.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method and application of an environment-friendly flame-retardant amine curing agent, so as to solve the problems in the background art. In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of an environment-friendly flame-retardant amine curing agent specifically comprises the following steps:
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and epoxy-terminated polydimethylsiloxane are subjected to prepolymerization reaction under the action of a catalyst, and then excessive polyethylene polyamine is added for modification.
Preferably, the prepolymerization reaction is as follows: mixing a proper amount of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and epoxy-terminated polydimethylsiloxane, heating to 155-160 ℃, adding a catalyst triphenylphosphine, and reacting for 2 hours.
Preferably, the specific contents of the modification are as follows: and adding excessive polyethylene polyamine into the material obtained by the prepolymerization reaction, continuously reacting for 1 hour, cooling to room temperature, and discharging.
Preferably, the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide refers to the following structural material:
preferably, the epoxy-terminated polydimethylsiloxane contains two or more epoxy groups. In particular to the following structural substances:
wherein n is an integer of 0 or more and 15 or less.
Preferably, the polyethylene polyamine is, but not limited to, one of ethylenediamine, diethylenetriamine and triethylenetetramine, and specifically refers to the following structural substances:
wherein n is an integer of 0 to 8.
The application of the environment-friendly flame-retardant amine curing agent in preparing the epoxy fireproof flame-retardant floor coating specifically comprises the following contents: weighing a certain mass part of liquid epoxy resin and an environment-friendly flame-retardant amine curing agent at room temperature, adding a certain amount of inorganic flame-retardant powder filler, stirring for 30 minutes, and uniformly mixing to obtain an epoxy base material; wherein the liquid epoxy resin and the amine curing agent account for 20-45 percent, and the inorganic flame-retardant powder filler accounts for 55-80 percent.
Preferably, the liquid epoxy resin is, but not limited to, one of liquid bisphenol a epoxy resin, liquid bisphenol F epoxy resin, resorcinol epoxy resin, liquid novolac epoxy resin.
Preferably, the inorganic flame-retardant powder filler is one or more of attapulgite, basic magnesium carbonate, aluminum hydroxide, hydrotalcite, montmorillonite and zinc oxide.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a preparation method of a modified fatty amine curing agent containing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a polydimethylsiloxane structure. Phosphorus and silicon atoms are introduced into polyethylene polyamine through a covalent bond and then are crosslinked and cured with epoxy resin, so that a synergistic effect is generated in the aspects of improving the flame retardant property and limiting oxygen index of a cured product. Phosphorus provides a tendency of forming a carbonized layer during combustion, silicon improves the thermal stability of the carbonized layer, and flame-retardant inorganic powder fillers such as attapulgite, basic magnesium carbonate and the like are matched to obtain the flame-retardant floor coating which does not contain halogen and antimony trioxide, has good apparent effect, high concrete adhesion and high oxygen index. Can be widely applied to the fields of protection, corrosion prevention, reinforcement and the like of the civil engineering terrace. Specially adapted has the terrace place of fire prevention special requirement, for example: floor coating for underground civil air defense engineering ground and underground space of dense personnel area.
Detailed Description
In order to make the technical means, the creation features, the work flow and the using method of the present invention easily understand and understand the purpose and the efficacy, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The first step is as follows: preparation of modified amine curing agent containing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and epoxy-terminated polydimethylsiloxane:
taking 7g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10 g of terminal epoxy polydimethylsiloxane DMS-E09 (viscosity: 10cps, weight average molecular weight 363) of Japan shin-Etsu company, heating to 155 ℃, adding 0.0035g of catalyst triphenylphosphine, reacting for 2 hours, then cooling to 70 ℃, dropwise adding 5.3 g of diethylenetriamine, continuing to react for 1 hour, cooling to room temperature, discharging, and obtaining the environment-friendly flame-retardant amine curing agent with the phosphorus content of 4.4 percent and the active hydrogen equivalent of 95 g/eq.
Example 2
The first step is as follows: preparation of modified amine curing agent containing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and epoxy-terminated polydimethylsiloxane:
5g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10 g of terminal epoxy polydimethylsiloxane DMS-E11 (viscosity: 15cps, weight average molecular weight 550) of Japan shin-Etsu company are taken, heated to 155 ℃, added with 0.0032g of catalyst triphenylphosphine and reacted for 2 hours, then cooled to 70 ℃, dropwise added with 2.6 g of triethylene tetramine and continuously reacted for 1 hour, cooled to room temperature and discharged to obtain the environment-friendly flame-retardant amine curing agent with the phosphorus content of 4.0 percent and the active hydrogen equivalent of 188 g/eq.
Example 3
The first step is as follows: preparation of modified amine curing agent containing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and epoxy-terminated polydimethylsiloxane:
taking 2g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10 g of terminal epoxy polydimethylsiloxane DMS-E12 (viscosity: 28cps, weight average molecular weight 1250) of Japan shin-Etsu corporation, heating to 155 ℃, adding 0.0030g of catalyst triphenylphosphine, reacting for 2 hours, then cooling to 70 ℃, dropwise adding 1.12 g of ethylenediamine, continuing to react for 1 hour, cooling to room temperature, discharging, and obtaining the environment-friendly flame-retardant amine curing agent with the phosphorus content of 2.1 percent and the active hydrogen equivalent of 193 g/eq.
Example 4
The first step is as follows: preparation of modified amine curing agent containing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and epoxy-terminated polydimethylsiloxane:
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 9g, terminal epoxy polydimethylsiloxane DMS-E09 (viscosity: 10cps, weight average molecular weight 363) 10 g of Japan Xinyue company are taken, heated to 155 ℃, added with 0.0035g of catalyst triphenylphosphine and reacted for 2 hours, then cooled to 70 ℃, 3.8 g of ethylenediamine is dripped, the reaction is continued for 1 hour, cooled to room temperature and discharged, and the environment-friendly flame-retardant amine curing agent with the phosphorus content of 5.5 percent and the active hydrogen equivalent of 95g/eq is obtained.
Example 5,6,7,8 and comparative examples 9,10
The second step is that: preparation of the environment-friendly flame-retardant floor coating:
according to the formula shown in the table 1, at room temperature, the epoxy resin and the obtained amine curing agent are sequentially mixed at a low speed, then the inorganic flame-retardant powder filler is added, the mixture is uniformly dispersed at a medium speed, then the mixture is cast on the surface of standard C30 concrete and is placed at 23 ℃ and 70% relative humidity for curing for 7 days, and the performance of the obtained paint film is shown in the table 1 below.
TABLE 1
Wherein, CYD 128: liquid bisphenol A epoxy resin, supplied by Yueyangbang Ba Ling petrochemical (epoxy equivalent EEW:195 g/eq); XY 694: resorcinol diglycidyl ether, anhui Mianjian (epoxy equivalent EEW:123 g/eq);
431: liquid bisphenol F epoxy resin, supplied by Olin, USA (epoxy equivalent EEW:170 g/eq);
438: liquid novolac epoxy resin, available from Olin corporation, USA (epoxy equivalent EEW:170 g/eq);
2771: modified polyetheramine curing agents, available from Evonic, germany (active hydrogen equivalent: 95 g/eq);
2883: a modified alicyclic amine curing agent supplied by Evonic, germany (active hydrogen equivalent: 76 g/eq); concrete tensile strength: test standard reference GB50367-2006; oxygen index: the test standard is referred to GB2406-93.
The performance detection results show that the cured floor coating has good appearance, high Shore D hardness and excellent concrete bonding strength by introducing a phosphorus and silicon containing structure into a polyethylene polyamine molecular structure in a chemical modification mode and adding an inorganic flame-retardant powder filler through a large amount of experimental screening. Meanwhile, compared with the traditional modified polyether amine and modified alicyclic amine curing agent, the oxygen index of the modified polyether amine and modified alicyclic amine curing agent is greatly improved, the flame retardant property is obviously improved, and the modified polyether amine and modified alicyclic amine curing agent is beneficial to wide application in fireproof floor coatings.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. The preparation method of the environment-friendly flame-retardant amine curing agent is characterized by comprising the following steps:
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and epoxy-terminated polydimethylsiloxane are subjected to prepolymerization reaction under the action of a catalyst, and then excessive polyethylene polyamine is added for modification.
2. The preparation method of the environment-friendly flame-retardant amine curing agent according to claim 1, characterized in that: the prepolymerization reaction comprises the following specific contents: mixing a proper amount of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and epoxy-terminated polydimethylsiloxane, heating to 155-160 ℃, adding a catalyst triphenylphosphine, and reacting for 2 hours.
3. The preparation method of the environment-friendly flame-retardant amine curing agent according to claim 2, characterized in that: the specific contents of the modification are as follows: and adding excessive polyethylene polyamine into the material obtained by the prepolymerization reaction, continuously reacting for 1 hour, cooling to room temperature, and discharging.
4. The preparation method of the environment-friendly flame-retardant amine curing agent according to claim 1, characterized in that: the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide refers to the following structural substances:
5. the preparation method of the environment-friendly flame-retardant amine curing agent according to claim 1, characterized in that: the epoxy-terminated polydimethylsiloxane contains two or more epoxy groups. In particular to the following structural substances:
wherein n is an integer of 0 or more and 15 or less.
6. The preparation method of the environment-friendly flame-retardant amine curing agent according to claim 1, characterized in that: the polyethylene polyamine is but not limited to one of ethylenediamine, diethylenetriamine and triethylene tetramine, and refers in particular to the following structural substances:
wherein n is an integer of 0 to 8.
7. The application of the environment-friendly flame-retardant amine curing agent is characterized by comprising the following specific components in percentage by weight: the application method in preparing the epoxy fireproof flame-retardant floor coating comprises the following steps: weighing a certain mass part of liquid epoxy resin and an environment-friendly flame-retardant amine curing agent at room temperature, adding a certain amount of inorganic flame-retardant powder filler, stirring for 30 minutes, and uniformly mixing to obtain an epoxy base material; wherein the liquid epoxy resin and the amine curing agent account for 20-45 percent, and the inorganic flame-retardant powder filler accounts for 55-80 percent.
8. The use of the environment-friendly flame retardant amine curing agent as defined in claim 7, wherein: the liquid epoxy resin is one of, but not limited to, liquid bisphenol a epoxy resin, liquid bisphenol F epoxy resin, resorcinol epoxy resin and liquid novolac epoxy resin.
9. The use of the environment-friendly flame retardant amine curing agent as defined in claim 7, wherein: the inorganic flame-retardant powder filler is one or a combination of more of attapulgite, basic magnesium carbonate, aluminum hydroxide, hydrotalcite, montmorillonite and zinc oxide.
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| CN202210962288.5A CN115160543A (en) | 2022-08-11 | 2022-08-11 | Preparation method and application of environment-friendly flame-retardant amine curing agent |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115746669A (en) * | 2022-12-22 | 2023-03-07 | 黄山天马新材料科技有限公司 | Epoxy resin anticorrosive floor paint and preparation method thereof |
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- 2022-08-11 CN CN202210962288.5A patent/CN115160543A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115746669A (en) * | 2022-12-22 | 2023-03-07 | 黄山天马新材料科技有限公司 | Epoxy resin anticorrosive floor paint and preparation method thereof |
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