CN106117516A - A kind of epoxy resin modification amine flame retardant curing agent and preparation method thereof - Google Patents
A kind of epoxy resin modification amine flame retardant curing agent and preparation method thereof Download PDFInfo
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- CN106117516A CN106117516A CN201610549218.1A CN201610549218A CN106117516A CN 106117516 A CN106117516 A CN 106117516A CN 201610549218 A CN201610549218 A CN 201610549218A CN 106117516 A CN106117516 A CN 106117516A
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- Prior art keywords
- epoxy resin
- flame retardant
- curing agent
- resin modification
- retardant curing
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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
- C08G59/5046—Amines heterocyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
Abstract
A kind of epoxy resin modification amine flame retardant curing agent and preparation method thereof, relates to a kind of chemosynthesis agent and preparation method thereof, and raw material of the present invention includes: phosphorus oxychloride (POCl3), tetramethylolmethane (PER) and 1,3 hexamethylene dimethylamine (1,3 BAC), the method preparing this fire retardant is divided into two steps to carry out, and the first step, by POCl3The phosphorous intermediate SPDPC of generation is reacted under certain condition with PER；Second step, by first step gained intermediate and 1,3 BAC are stirring reaction certain time under noble gas imports, and product, through process such as filtering, wash, be dried, obtains white solid powder.This compound has good dispersibility at epoxy resin, can be cured as one with epoxy resin, both can be effectively improved again the fire resistance of epoxy resin as the firming agent of epoxy resin.Present invention process working condition is simple, product purity and productivity is higher, last handling process is easy.
Description
Technical field
The present invention relates to a kind of chemosynthesis agent and preparation method thereof, particularly relate to a kind of epoxy resin modification amine resistance
Combustion firming agent and preparation method thereof.
Background technology
Epoxy resin is that a class has the performances such as the bonding of excellence, anticorrosion, insulating properties, molding processibility, high intensity
Thermosetting polymer synthetic material, the performance in terms of mechanics, electrical equipment, heat and chemical-resistant resistance is the most superior.Due to have with
Upper described premium properties, epoxy resin is widely used in the manufacture of binding agent, coating, insulant etc..And at electronics, electricity
Playing an important role in gas, optical-mechanical, Aero-Space, Shipping and other many industrial circles, its application is almost time
And all of industrial circle.But, the disadvantage that epoxy resin exists in the application is exactly inflammable, and inflammability is also great majority
The common fault that has of macromolecular material.The existence of this shortcoming makes the range of application of epoxy resin be greatly limited.
Therefore, the research to the fire resistance of epoxy resin has emphatically in application electric, aerospace field for expanding it
The meaning wanted.
In recent years, the problem that fire-retardant academia is the most popular is exactly the problem of Halogen material environmental pollution, Yi Jiwei
Halogenated flame retardant finds suitable substitute products.Along with the analysis and research to material combustion product, a large amount of scholars think, halogen system hinders
To discharge two a small amount of English or dibenzofurans during combustion agent burning, this is also that the plastic containing halogenated flame retardant cannot return
The major reason received or destroy.Owing to carrying out replacing whole halogen containing flame-retardant currently without enough succedaneum, Europe and day simultaneously
This disables halogen containing flame-retardant the most comprehensively.This cause some manufacturers for " environmental problem " and the dual reason of Cost Problems,
Stop using fire retardant.Therefore, this way for reducing production cost and " response environmental regulation " of manufacturer has caused sternly
The disaster hidden-trouble of weight.This makes minimum incendiary source just can cause many people to lose the sustained combustion without fire-retardant television set
Raw.Subsequently, relevant electronic electric equipment treatment of wastes produced specification has been promulgated in Europe, it is stipulated that halogen system refuse needs to carry out special place
Reason, on the one hand this promoted the use of halogen-free flame retardants.
The direction of the fire-retardant research of epoxy resin increasingly tends to non-halogen.How to replace halogen, develop efficiently, low toxicity,
The halogen-free environment-friendly type flame-proof agent of low cigarette and novel flame-retardant epoxide resin material become the study hotspot of Chinese scholars.
The membership that adds of additive flame retardant produces extreme influence to the mechanical property of epoxy resin, and anti-flammability firming agent can
To react with epoxy resin, it is linked in epoxy resin with the form of chemical bond, the shadow to the mechanical property of epoxy resin
Ring the less or mechanical property of reinforced epoxy.In addition the mechanical property except additive flame retardant can be overcome to bring reduces
Problem, the fire resistance of epoxy resin can be dramatically increased simultaneously.
Summary of the invention
It is an object of the invention to provide a kind of epoxy resin modification amine flame retardant curing agent and preparation method thereof, the present invention
Prepare product and contain phosphorus, two kinds of ignition-proof elements of nitrogen, both can participate in the solidification of epoxy resin, meanwhile, have flame retarding efficiency high and
The features such as Halogen, low cigarette, low toxicity, meet the requirement that current people preserve the ecological environment, and this flame retardant curing agent is in combustion process
In greatly reduce the generation of toxic gas and corrosive gas.
It is an object of the invention to be achieved through the following technical solutions:
A kind of epoxy resin modification amine flame retardant curing agent, described firming agent raw material includes: phosphorus oxychloride (POCl3), Ji Wusi
Alcohol (PER) and 1,3-hexamethylene dimethylamine (1,3-BAC), flame retardant curing agent has a following structure:
A kind of epoxy resin modification amine flame retardant curing agent preparation method, described preparation method is that two steps are carried out, the first step,
By phosphorus oxychloride (POCl3) and tetramethylolmethane (PER) in a solvent react generation phosphorus, nitrogen intermediate SPDPC；Second step, in inciting somebody to action
Mesosome and 1,3-hexamethylene dimethylamine is stirring reaction under noble gas imports, and product, through filtration, washing, dried, obtains white
Pressed powder；
Said process chemical equation is expressed as:
。
Described a kind of epoxy resin modification amine flame retardant curing agent preparation method, synthesizes phosphorus, nitrogen intermediate in the first step
In, POCl3It is 2:1 to 3:1 with PER molar ratio；Solvent for use is 1,4-dioxane, chlorobenzene, benzene, toluene, acetonitrile
In a kind of or the mixture of its arbitrary proportion, AlCl3For catalyst.
Described a kind of epoxy resin modification amine flame retardant curing agent preparation method, synthesizes phosphorus, nitrogen intermediate in the first step
In, reaction temperature controls at 60 ~ 100 DEG C；Response time is 8 ~ 24h.
Described a kind of epoxy resin modification amine flame retardant curing agent preparation method, in second step, noble gas used
For the one in nitrogen, argon or helium.
Described a kind of epoxy resin modification amine flame retardant curing agent preparation method, in second step, reacts and is using 1,
Carry out under any one solvent condition in 4-dioxane, acetonitrile, chlorobenzene, oxolane.
Described a kind of epoxy resin modification amine flame retardant curing agent preparation method, in second step, reaction temperature is 20 ~
80 DEG C, intermediate SPDPC and 1,3-BAC proportioning is between 1:2 ~ 1:2.2, and needs to add acid binding agent triethylamine or pyridine.
Described a kind of epoxy resin modification amine flame retardant curing agent preparation method, in second step, the response time is 5 ~
12h。
Described a kind of epoxy resin modification amine flame retardant curing agent preparation method, in second step, cleaning solvent is two
The mixture of any one or its arbitrary proportion in chloromethanes, chloroform, benzene.
Described a kind of epoxy resin modification amine flame retardant curing agent preparation method, in second step, baking temperature is 60 ~
120℃.Advantages of the present invention with effect is:
1, a kind of epoxy resin modification amine flame retardant curing agent that the present invention provides, both can be as the solidification of a kind of epoxy resin
Agent, has again flame retardant effect.
2, a kind of epoxy resin modification amine flame retardant curing agent that the present invention provides, the advantage with low toxicity, high-efficiency environment friendly,
Be conducive to sustainable development.
3, the preparation method that the present invention provides is simple, mild condition, it is easy to control, and the product purity of gained is high, post processing
Convenient.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail.
Embodiment 1:
The first step: to equipped with reflux condensing tube, thermometer, N2The 500ml there-necked flask of ingress pipe and magneton adds 300ml acetonitrile
As solvent, then it is separately added into 20.4gPER, 23.0g POCl3And 0.61gAlCl3.It is passed through N2Protection, is warming up to 80 DEG C of reactions
6h, 100 DEG C of reaction 4h, reaction carries out filtering after terminating, washs, is dried, obtains white solid powder, be intermediate SPDPC.
Second step: equipped with magnetic agitation, Dropping funnel, N2The 250ml four-hole bottle of ingress pipe and thermometer adds
100ml acetonitrile, as solvent, adds 5.94g intermediate SPDPC and 4.15g triethylamine；By 5.90g1,3-BAC Yu 20ml second
Nitrile mixes, and transfers the solution in constant pressure funnel, starts dropping, be warming up to 50 DEG C after 2.0h dropping under room temperature,
Insulation reaction 10h, terminates reaction, through processing to obtain white solid powder.
Embodiment 2:
The first step: the synthetic method of intermediate is with embodiment 1.
Second step: equipped with magnetic agitation, Dropping funnel, N2The 500ml four-hole bottle of ingress pipe and thermometer adds 300ml
Acetonitrile, as solvent, adds 18.0g intermediate SPDPC and 12.5g triethylamine；18.0g1,3-BAC with 50ml acetonitrile is mixed
Closing, and be transferred in constant pressure funnel, start dropping, be warming up to 70 DEG C after 2.0h dropping under room temperature, insulation is anti-
Answer 6h, terminate reaction, through processing to obtain white solid powder.
Embodiment 3
The first step: the synthetic method of intermediate is with embodiment 1.
Second step: equipped with magnetic agitation, Dropping funnel, N2The 250ml four-hole bottle of ingress pipe and thermometer adds
100ml acetonitrile, as solvent, adds 5.94g intermediate SPDPC and 4.15g triethylamine；By 5.90g1,3-BAC Yu 20ml second
Nitrile mixes, and transfers the solution in constant pressure funnel, starts dropping, be warming up to 60 DEG C after 2.0h dropping under room temperature,
Insulation reaction 10h, terminates reaction, through processing to obtain white solid powder.
Embodiment 4
The first step: the synthetic method of intermediate is with embodiment 1.
Second step: equipped with magnetic agitation, Dropping funnel, N2The 250ml four-hole bottle of ingress pipe and thermometer adds
100ml acetonitrile, as solvent, adds 5.94g intermediate SPDPC and 4.15g triethylamine；By 6.30g1,3-BAC Yu 20ml second
Nitrile mixes, and transfers the solution in constant pressure funnel, starts dropping, be warming up to 50 DEG C after 2.0h dropping under room temperature,
Insulation reaction 12h, terminates reaction, through processing to obtain white solid powder.
Embodiment 5
The first step: the synthetic method of intermediate is with embodiment 1.
Second step: equipped with magnetic agitation, Dropping funnel, N2The 250ml four-hole bottle of ingress pipe and thermometer adds
100ml acetonitrile, as solvent, adds 5.94g intermediate SPDPC and 4.15g triethylamine；By 6.13g1,3-BAC Yu 20ml second
Nitrile mixes, and transfers the solution in constant pressure funnel, starts dropping, be warming up to 70 DEG C after 2.0h dropping under room temperature,
Insulation reaction 8h, terminates reaction, through processing to obtain white solid powder.
Claims (10)
1. an epoxy resin modification amine flame retardant curing agent, it is characterised in that described firming agent raw material includes: phosphorus oxychloride
(POCl3), tetramethylolmethane (PER) and 1,3-hexamethylene dimethylamine (1,3-BAC), flame retardant curing agent has a following structure:
。
2. an epoxy resin modification amine flame retardant curing agent preparation method, it is characterised in that described preparation method is two steps
Suddenly carry out, the first step, by phosphorus oxychloride (POCl3) and tetramethylolmethane (PER) in a solvent react generation phosphorus, nitrogen intermediate
SPDPC；Second step, by intermediate and 1,3-hexamethylene dimethylamine is stirring reaction under noble gas imports, and product is through filtering, washing
Wash, dried, obtain white solid powder；
Said process chemical equation is expressed as:
。
A kind of epoxy resin modification amine flame retardant curing agent preparation method the most according to claim 2, it is characterised in that
In the first step synthesis phosphorus, nitrogen intermediate, POCl3It is 2:1 to 3:1 with PER molar ratio；Solvent for use is 1,4-dioxy six
The mixture of a kind of or its arbitrary proportion in ring, chlorobenzene, benzene, toluene, acetonitrile, AlCl3For catalyst.
A kind of epoxy resin modification amine flame retardant curing agent preparation method the most according to claim 2, it is characterised in that
In the first step synthesis phosphorus, nitrogen intermediate, reaction temperature controls at 60 ~ 100 DEG C；Response time is 8 ~ 24h.
A kind of epoxy resin modification amine flame retardant curing agent preparation method the most according to claim 2, it is characterised in that
In second step, noble gas used is the one in nitrogen, argon or helium.
A kind of epoxy resin modification amine flame retardant curing agent preparation method the most according to claim 2, it is characterised in that
In second step, react and carry out under any one solvent condition in using Isosorbide-5-Nitrae-dioxane, acetonitrile, chlorobenzene, oxolane.
A kind of epoxy resin modification amine flame retardant curing agent preparation method the most according to claim 2, it is characterised in that
In second step, reaction temperature is 20 ~ 80 DEG C, and intermediate SPDPC and 1,3-BAC proportioning is between 1:2 ~ 1:2.2, and needs to add
Acid binding agent triethylamine or pyridine.
A kind of epoxy resin modification amine flame retardant curing agent preparation method the most according to claim 2, it is characterised in that
In second step, the response time is 5 ~ 12h.
A kind of epoxy resin modification amine flame retardant curing agent preparation method the most according to claim 1, it is characterised in that
In second step, cleaning solvent is the mixture of any one or its arbitrary proportion in dichloromethane, chloroform, benzene.
A kind of epoxy resin modification amine flame retardant curing agent preparation method the most according to claim 2, it is characterised in that
In second step, baking temperature is 60 ~ 120 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610549218.1A CN106117516A (en) | 2016-07-13 | 2016-07-13 | A kind of epoxy resin modification amine flame retardant curing agent and preparation method thereof |
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| CN201610549218.1A CN106117516A (en) | 2016-07-13 | 2016-07-13 | A kind of epoxy resin modification amine flame retardant curing agent and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107400196A (en) * | 2017-08-04 | 2017-11-28 | 武汉工程大学 | A kind of application process of new reaction-type flame-retarding epoxy curing agent in epoxy-resin systems |
| CN109943193A (en) * | 2019-03-21 | 2019-06-28 | 匡礼彬 | Composite environmental-friendly coating based on diatomite modified and preparation method thereof |
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|---|---|---|---|---|
| CN102731790A (en) * | 2012-07-10 | 2012-10-17 | 合肥工业大学 | Phosphorus-nitrogen-carbon intumescent flame retardant and preparation method thereof |
| CN104788647A (en) * | 2015-04-02 | 2015-07-22 | 沈阳化工大学 | Phosphorous-containing epoxy resin amine curing agent and preparation method thereof |
| CN104817685A (en) * | 2015-03-25 | 2015-08-05 | 沈阳化工大学 | Reactive epoxy resin flame-retardant curing agent containing phosphorus and nitrogen and preparation method thereof |
| CN105111687A (en) * | 2015-09-01 | 2015-12-02 | 沈阳化工大学 | Halogen-free epoxy resin flame retardant and preparation method thereof |
-
2016
- 2016-07-13 CN CN201610549218.1A patent/CN106117516A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731790A (en) * | 2012-07-10 | 2012-10-17 | 合肥工业大学 | Phosphorus-nitrogen-carbon intumescent flame retardant and preparation method thereof |
| CN104817685A (en) * | 2015-03-25 | 2015-08-05 | 沈阳化工大学 | Reactive epoxy resin flame-retardant curing agent containing phosphorus and nitrogen and preparation method thereof |
| CN104788647A (en) * | 2015-04-02 | 2015-07-22 | 沈阳化工大学 | Phosphorous-containing epoxy resin amine curing agent and preparation method thereof |
| CN105111687A (en) * | 2015-09-01 | 2015-12-02 | 沈阳化工大学 | Halogen-free epoxy resin flame retardant and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107400196A (en) * | 2017-08-04 | 2017-11-28 | 武汉工程大学 | A kind of application process of new reaction-type flame-retarding epoxy curing agent in epoxy-resin systems |
| CN109943193A (en) * | 2019-03-21 | 2019-06-28 | 匡礼彬 | Composite environmental-friendly coating based on diatomite modified and preparation method thereof |
| CN109943193B (en) * | 2019-03-21 | 2021-06-04 | 广西弗士特资源综合利用有限公司 | Composite environment-friendly coating based on diatomite modification and preparation method thereof |
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