CN109734877A - A kind of new bio base phosphonitrile epoxy monomer and its biology base phosphorus nitrogen fire retarding epoxide resin obtained - Google Patents
A kind of new bio base phosphonitrile epoxy monomer and its biology base phosphorus nitrogen fire retarding epoxide resin obtained Download PDFInfo
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- CN109734877A CN109734877A CN201811589830.7A CN201811589830A CN109734877A CN 109734877 A CN109734877 A CN 109734877A CN 201811589830 A CN201811589830 A CN 201811589830A CN 109734877 A CN109734877 A CN 109734877A
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Abstract
The invention belongs to high molecular fire retardant technical fields, disclose a kind of new bio base phosphonitrile epoxy monomer and its biology base phosphorus nitrogen fire retarding epoxide resin obtained and application.The biology base phosphonitrile epoxy monomer is named as six [(4- glycidyl -2- methoxyl group) phenoxy group] rings, three phosphonitrile (EHEP), and molecular structural formula is as follows:The EHEP be by hexachlorocyclotriph,sphazene and eugenol in the organic solvent I of basic catalyst, substitution reaction occurs in nitrogen, three phosphonitrile (HEP) of synthetic intermediate six [(4- allyl -2- methoxyl group) phenoxy group] ring, HEP is dissolved in organic solvent II again, oxidant is added under the conditions of -10~5 DEG C, oxidation reaction is carried out under room temperature, nitrogen to be made.Biology base phosphorus nitrogen fire retarding epoxide resin is to mix EHEP, epoxy monomer and curing agent addition organic solvent III, is fed into mold after removing solvent, is made in 60~150 DEG C of progress curing moldings.
Description
Technical field
The invention belongs to high molecular fire retardant technical fields, more particularly, to a kind of new bio base phosphonitrile epoxy resin
Monomer and its biology base phosphorus nitrogen fire retarding epoxide resin obtained.
Background technique
Epoxy resin is because possess outstanding tensile strength, modulus, low cure shrinkage, and people are used as in life
Adhesive, clad and polymeric matrix.But epoxy resin easily burns (its limit oxygen index only has 21% or so), this
Performance short slab hinders its development in each application field.
There are many kinds of the modes for promoting ethoxyline resin antiflaming performance, and one's early years people reduce ring with halogen-containing flame-retardant additive
The combustibility of oxygen resin.But since there are certain toxicity for halogen additive, and it can be discharged into environment, so more later
Countries and regions disabling.In addition to this, on the market the raw material sources of most of epoxy resin in petroleum-based feedstock bisphenol-A, its valence
Lattice are cheap, and the manufactured resin come out has outstanding mechanical property.However, but there is bio-toxicity, part infants for bisphenol-A
Product has been forbidden to use or has added the resin of bisphenol A-type.The non-renewable of bisphenol-A has caused a deviation from sustainable development simultaneously
Theory.
It is believed that: the fire-retardant bisphenol A type epoxy resin of conventional halogen additive is to the disagreeableness material of environment.
In recent years, in order to may be implemented " Green Flammability ", the fire-retardant resin of biology base has become the research hotspot of material development personnel.But
It is that the research of present bio-based resin material is mainly limited to starch plastic, cellulosic-based material, PHBV, PLA, PBS, biology base
The thermoplastic materials such as PE, it is then relatively fewer to the research of thermosetting property bio-based materials.
Hexachlorocyclotriph,sphazene (HCCP) is a kind of heterocyclic compound for possessing phosphorus nitrogen, and structure is as shown in Figure 1, it can quilt
As insecticide, fertilizer, anti-tumor drug, phase transfer catalyst, radical polymerization initiator, light stabilizer, antioxidant, resistance
Fire agent etc..For cyclotrinitrile phosphide, phosphorus nitrogen skeleton is natural highly effective flame-retardant structure, it is only necessary to be introduced specific living
Property functional group can be obtained response type phosphonitrile fire retardant.Therefore, reactive flame retardant is prepared based on three phosphonitrile of ring with it
Natural advantage.Currently, researcher is by introducing ring three for functional groups such as Oxyranyle, amido, phenolic hydroxyl group, alkenyls
Phosphonitrile successfully prepares a large amount of reaction three phosphazene derivatives of type ring.These derivatives can be used as monomer, curing agent or copolymerization
Object participates in the curing reaction of epoxy resin, so that fire-retardant unit is introduced resin cross-linked network.
Eugenol (Eugenol) is a kind of simple aromatic compound, and structure is as shown in Fig. 2, it is the master of caryophyllus oil
Want ingredient.It has there are two functional group, hydroxyl and allyl, the two functional groups can further be modified to be formed with special
The epoxide of function, while its phenyl ring can give resin certain mechanical strength.Therefore, it is to prepare thermosetting property ring
A kind of very promising raw material of oxygen resin.This phenolic compound is a kind of weak yellow liquid oil, is occupied in medical field application
It is more, because it has analgesia, antibiotic, anti-corrosion, the anti-oxidant excellent performance waited.In addition, it is also used to manufacture fragrance, also conduct
Stabilizer and antioxidant in plastics industry.More importantly eugenol can be added to food with the dosage of low concentration
In, so being safe and reliable as the raw material for preparing green thermosetting material.
Summary of the invention
In order to solve above-mentioned the shortcomings of the prior art and disadvantage, the object of the present invention is to provide a kind of novel lifes
Object base phosphonitrile epoxy monomer.
Another object of the present invention is the provision of biology base phosphorus made from above-mentioned new bio base phosphonitrile epoxy monomer
Nitrogen fire retarding epoxide resin.
The purpose of the present invention is realized by following technical proposals:
A kind of new bio base phosphonitrile epoxy monomer, the new bio base phosphonitrile epoxy monomer are named as six
Three phosphonitrile of [(4- glycidyl -2- methoxyl group) phenoxy group] ring, is abbreviated as EHEP, molecular structural formula is as follows:
The new bio base phosphonitrile epoxy monomer EHEP is by hexachlorocyclotriph,sphazene and eugenol in base catalysis
In the organic solvent I of agent, 24~72h of substitution reaction, the [(4- allyl -2- first of synthetic intermediate six occur in nitrogen atmosphere
Oxygroup) phenoxy group] three phosphonitrile of ring, it is abbreviated as HEP, then intermediate HEP is dissolved in organic solvent II, under the conditions of -10~5 DEG C
Oxidant is added, oxidation reaction is carried out under room temperature, nitrogen and is made.
Preferably, the basic catalyst is potassium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, metallic sodium or metal
Potassium；The oxidant is m-chloro-benzoic acid peroxide, perbenzoic acid, Peracetic acid or oxygen.
Preferably, the temperature of the substitution reaction is 25~100 DEG C, and the time of the oxidation reaction is 2~7 days.
Preferably, the organic solvent I be tetrahydrofuran, Isosorbide-5-Nitrae-one of dioxane or diethylene glycol dimethyl ether with
On；The organic solvent II is one or more of methylene chloride, chloroform or carbon tetrachloride.
Preferably, the mass ratio of the hexachlorocyclotriph,sphazene, eugenol and basic catalyst is 5:(15~20): (2~
5)；The HEP and the mass ratio of oxidant are 10:(11~18)；Quality of the hexachlorocyclotriph,sphazene in organic solvent I is dense
Degree is 10~50g/L；Mass concentration of the HEP in organic solvent II is 50~150g/L.
Biology base phosphorus nitrogen fire retarding epoxide resin made from new bio base phosphonitrile epoxy monomer described in a kind of, it is described
Biology base phosphorus nitrogen fire retarding epoxide resin is that EHEP, epoxy monomer and curing agent are added in organic solvent III, is uniformly mixed,
It is fed into mold after removing solvent, solidifies 1~molding for 24 hours at 60~150 DEG C after drying and is made.
Preferably, the mass ratio of the EHEP, epoxy monomer and curing agent is (0~100): (100~0): (20
~50), the sum of the EHEP and epoxy monomer mass fraction are 100.
Preferably, the epoxy monomer is one or more of E51, E44, E42 or E31；The organic solvent III
For methylene chloride, acetone, ethyl acetate, ether or tetrahydrofuran.
Preferably, the curing agent is to replace alkane, aminated compounds or acid anhydrides.
It is further preferable that the substitution alkane is 4- diaminodiphenylmethane or diaminodiphenyl ether, the aminated compounds
For the graceful D230 of the polyetheramine Hensel or graceful T403 of Hensel, the acid anhydrides is hexahydrophthalic anhydride or tetrabydrophthalic anhydride.
Application of the biology base phosphorus nitrogen fire retarding epoxide resin in flame retardant area.
The present invention synthesizes the chemical reaction equation of six [(4- allyl -2- methoxyl group) phenoxy group] rings, three phosphonitrile (HEP) such as
Under:
The chemical reaction equation of synthesizing new biology base phosphonitrile epoxy monomer of the present invention is as follows:
Compared with prior art, the invention has the following advantages:
1. there are six epoxy groups for new bio base phosphonitrile epoxy monomer of the invention, epoxy resin is helped to improve
Crosslink density, obtain high performance epoxy resin product.
2. present invention preparation biology base phosphonitrile epoxy monomer material therefor eugenol derives from renewable resource, price
Cheap, abundant raw material；
3. biology base phosphonitrile epoxy resin of the invention has the characteristics that mechanical strength height, excellent fireproof performance；Biology base
Contain phosphorus nitrogen in phosphonitrile epoxy resin simultaneously, the flame retardant property of epoxy resin, and opposite addition halogen-type can be significantly improved
The epoxy resin of fire retardant, effect on environment is small, more environmentally protective.
Detailed description of the invention
Fig. 1 is hexachlorocyclotriph,sphazene (HCCP) chemical structure of the prior art.
Fig. 2 is eugenol (Eugenol) chemical structure of the prior art.
Fig. 3 is the chemical structure of six [(4- glycidyl -2- methoxyl group) phenoxy group] ring triphosphine nitriles (EHEP).
Specific embodiment
The contents of the present invention are further illustrated combined with specific embodiments below, but should not be construed as limiting the invention.
Unless otherwise specified, the conventional means that technological means used in embodiment is well known to those skilled in the art.Except non-specifically
Illustrate, reagent that the present invention uses, method and apparatus is the art conventional reagents, method and apparatus.
Embodiment 1
7.44g sodium hydride, 45.55g eugenol are taken, 18.87g hexachlorocyclotriph,sphazene dissolves in 140mL tetrahydrofuran, at 50 DEG C
It is passed through nitrogen, after reacting 36h, obtains six [(4- allyl -2- methoxyl group) phenoxy group] rings, three phosphonitrile (HEP).Again by intermediate
HEP reacts in methylene chloride with 20g Peracetic acid, leads under the conditions of 5 DEG C such as nitrogen, reaction 4 days, obtained six [(4- epoxies third
Base -2- methoxyl group) phenoxy group] three phosphonitrile (EHEP) of ring.
Embodiment 2
22.22g potassium carbonate, 44.45g eugenol are taken, 16.67g hexachlorocyclotriph,sphazene dissolves in 200mL diethylene glycol dimethyl ether,
It is passed through nitrogen at 100 DEG C, after reacting 36h, obtains six [(4- allyl -2- methoxyl group) phenoxy group] rings, three phosphonitrile (HEP).Again
Intermediate HEP is reacted in methylene chloride with 60g perbenzoic acid, nitrogen is led under the conditions of 5 DEG C, is reacted 4 days, is made six
Three phosphonitrile (EHEP) of [(4- glycidyl -2- methoxyl group) phenoxy group] ring, molecular structure is as shown in Figure 1.
Three phosphonitrile (HEP) of intermediate six [(4- allyl -2- methoxyl group) phenoxy group] ring obtained to the present embodiment carries out
Infrared spectrum analysis, characterization result are as follows: principal character peak is 914 and 816cm-1(stretching vibration of P-O), 1123cm-1,
1150cm-1, 1182cm-1(P=N) and 874cm-1(P-N), 1269cm-1(benzene oxygen key), 1638cm-1, 996cm-1And 904cm-1
(acrylic C=C).
HEP's1The characterization result of H-NMR: absorption peak be δ=6.6ppm, δ=6.5ppm, δ=6.9ppm (phenyl ring it is upper
Hydrogen).δ=3.6ppm (hydrogen of methoxyl group).δ=5.9ppm, δ=5.0ppm, δ=3.3ppm (three kinds of differences on allyl
Hydrogen)；HEP's31P-NMR.δ=9.1ppm.
EHEP's1The characterization result of H-NMR: absorption peak be δ=7.0ppm, δ=6.7ppm, δ=6.6ppm (phenyl ring it is upper
Hydrogen).δ=2.5ppm, δ=2.8ppm, δ=3.1ppm (3 kinds of hydrogen in glycidyl).δ=3.6ppm be (methoxyl group
Hydrogen).EHEP mass spectrum has the highest particle of abundance at m/z=1210.276, this also confirms that the monomer of synthesis is EHEP.
Embodiment 3
Bisphenol A type epoxy resin monomer (E51) 100g is taken, is stirred evenly, 40g D230 curing agent, vacuum under room temperature is added
Deaeration 2min.It pours into mold, is put into baking oven 80 DEG C/2 hours+110 DEG C/2 hours, obtain the cured E51 asphalt mixtures modified by epoxy resin of D230
Rouge is named as EHEP-0.
Embodiment 4
Bisphenol A type epoxy resin monomer (E51) 80g is taken, 20g EHEP made from embodiment 1 is added, stirs evenly, is added
40g D230 curing agent is again stirring for uniformly.Vacuum defoamation 2min under room temperature.It pours into mold, it is small to be put into baking oven 80 DEG C/2
When+110 DEG C/2 hours, obtain biology base phosphorus nitrogen fire retarding epoxide resin, be named as EHEP-20.
Embodiment 5
Bisphenol A type epoxy resin monomer (E51) 60g is taken, 40g EHEP made from embodiment 1 is added, stirs evenly, is added
40g D230 curing agent is again stirring for uniformly.Vacuum defoamation 2min under room temperature.It pours into mold, it is small to be put into baking oven 80 DEG C/2
When+110 DEG C/2 hours, obtain biology base phosphorus nitrogen fire retarding epoxide resin, be named as EHEP-40.
Embodiment 6
Bisphenol A type epoxy resin monomer (E51) 20g is taken, 80g EHEP made from embodiment 1 is added, stirs evenly, is added
40g D230 curing agent is again stirring for uniformly.Vacuum defoamation 2min under room temperature.It pours into mold, it is small to be put into baking oven 80 DEG C/2
When+110 DEG C/2 hours, obtain biology base phosphorus nitrogen fire retarding epoxide resin, be named as EHEP-80.
Embodiment 7
100g EHEP and q. s. methylene chloride, stir evenly, and 40g D230 curing agent made from embodiment 1 are added, again
It stirs evenly, is spin-dried for methylene chloride.Vacuum defoamation 2min under room temperature.It pours into mold, is put into baking oven 80 DEG C/2 hours+110
DEG C/2 hours, biology base phosphorus nitrogen fire retarding epoxide resin is obtained, EHEP-100 is named as.
Embodiment 8
Bisphenol A type epoxy resin monomer (E51) 100g is taken, 60 DEG C stir evenly, addition 40g HHPA curing agent, under room temperature
Vacuum defoamation 2min.It pours into mold, is put into baking oven 100 DEG C/2 hours+130 DEG C/2 hours, obtains hexahydrophthalic acid
The cured E51 epoxy resin of acid anhydride (HHPA), is named as EHEP-0 '.
Embodiment 9
Bisphenol A type epoxy resin monomer (E51) 75g is taken, 25g EHEP made from embodiment 2 is added, 60 DEG C stir evenly,
40g HHPA curing agent is added, is again stirring for uniformly.Vacuum defoamation 2min under room temperature.It pours into mold, 100 DEG C/2 hours+130
DEG C/2 hours, biology base phosphorus nitrogen fire retarding epoxide resin is obtained, EHEP-25 ' is named as.
Embodiment 10
Six [(4- glycidyl -2- methoxyl group) phenoxy group] rings, three phosphonitrile (EHEP) is made in a kind of above-mentioned preparation method
Using.Bisphenol A type epoxy resin monomer (E51) 50g is taken, 50g EHEP made from embodiment 2 is added, 60 DEG C stir evenly, and add
Enter 40g HHPA curing agent, is again stirring for uniformly.Vacuum defoamation 2min under room temperature.It pours into mold, 100 DEG C/2 hours+130
DEG C/2 hours, biology base phosphorus nitrogen fire retarding epoxide resin is obtained, EHEP-50 ' is named as.
Embodiment 11
Bisphenol A type epoxy resin monomer (E51) 25g is taken, 75g EHEP made from embodiment 2 is added, 60 DEG C stir evenly,
40g HHPA curing agent is added, is again stirring for uniformly.Vacuum defoamation 2min under room temperature.It pours into mold, 100 DEG C/2 hours+130
DEG C/2 hours, biology base phosphorus nitrogen fire retarding epoxide resin is obtained, EHEP-75 ' is named as.
Embodiment 12
100g EHEP and q. s. methylene chloride made from embodiment 2,40 DEG C stir evenly, and 40g HHPA solidification is added
Agent is again stirring for uniformly, being spin-dried for methylene chloride.Vacuum defoamation 2min under room temperature.It pours into mold, is put into 100 DEG C/2 in baking oven
+ 130 DEG C/2 hours hour, biology base phosphorus nitrogen fire retarding epoxide resin is obtained, EHEP-100 ' is named as.
Using the vertical oxygen index (OI) of GB/T 2408-2008 standard testing UL94, specimen size is 120 × 13 × 3mm3；The limit
Oxygen index (OI) (LOI) uses GB/T 2406-2009, and specimen size is 80 × 6.5 × 3mm3；Tensile property test uses GB/T
1040.2-2006 standard, specimen size are the 5A pattern item in standard；Bending property test is marked using GB/T 9341-2008
Standard, specimen size are 80 × 10 × 4mm3；Crooked test use GB/T 1843-2008 standard, specimen size be 80 × 10 ×
4mm3Non-notch impact batten.30 DEG C -700 DEG C of Range of measuring temp, heating rate 20K/min of thermogravimetric analysis (TGA),
Nitrogen atmosphere, as a result as follows:
The performance parameter of the biology base phosphorus nitrogen fire retarding epoxide resin prepared in 1 embodiment 3-12 of table
Table 1 is the new bio base phosphorus nitrogen fire retarding epoxide resin performance parameter prepared in embodiment 3-12.It can from table 1
Know, tensile strength, carbon yield and the flame retardant property of biology base phosphorus nitrogen fire retarding epoxide resin are mentioned with the increase of the content of EHEP
Height, but decomposition temperature and impact strength are declined.This illustrates that the epoxy resin that can be improved of EHEP stretches intensity and resistance
Performance is fired, while also bringing along certain brittleness；In addition, hexahydrophthalic anhydride curing agent is relative to the graceful D230 solidification of Hensel
Agent can bring preferable tensile strength and a degree of anti-flammability for resin, but graceful not as good as Hensel in impact strength
The cured resin of D230.This shows epoxy resin prepared by EHEP, can be by the change of curing agent type, thus centainly
The application that the performance for changing resin in degree is resin under different occasions provides flexibility.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by change, modification, substitution, combination and simplify,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of new bio base phosphonitrile epoxy monomer, which is characterized in that the new bio base phosphonitrile epoxy resin list
Body is named as six [(4- glycidyl -2- methoxyl group) phenoxy group] rings, three phosphonitrile, is abbreviated as EHEP, molecular structural formula is as follows:
The new bio base phosphonitrile epoxy monomer EHEP is by hexachlorocyclotriph,sphazene and eugenol in basic catalyst
In organic solvent I, 24~72h of substitution reaction, synthetic intermediate six [(4- allyl -2- methoxyl group) occur in nitrogen atmosphere
Phenoxy group] three phosphonitrile of ring, it is abbreviated as HEP, then intermediate HEP is dissolved in organic solvent II, is added under the conditions of -10~5 DEG C
Oxidant carries out oxidation reaction under room temperature, nitrogen and is made.
2. new bio base phosphonitrile epoxy monomer according to claim 1, which is characterized in that the basic catalyst
For potassium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, metallic sodium or metallic potassium；The oxidant is m-chloro benzoyl peroxide first
Acid, perbenzoic acid, Peracetic acid or oxygen.
3. new bio base phosphonitrile epoxy monomer according to claim 1, which is characterized in that the substitution reaction
Temperature is 25~100 DEG C, and the time of the oxidation reaction is 2~7 days.
4. new bio base phosphonitrile epoxy monomer according to claim 1, which is characterized in that the organic solvent I
For one or more of tetrahydrofuran, 1,4- dioxane or diethylene glycol dimethyl ether；The organic solvent II is methylene chloride, three
One or more of chloromethanes or carbon tetrachloride.
5. new bio base phosphonitrile epoxy monomer according to claim 1, which is characterized in that three phosphorus of chlordene ring
The mass ratio of nitrile, eugenol and basic catalyst is 5:(15~20): (2~5)；The HEP and the mass ratio of oxidant are 10:
(11~18)；Mass concentration of the hexachlorocyclotriph,sphazene in organic solvent I is 10~50g/L；The HEP is in organic solvent
Mass concentration in II is 50~150g/L.
6. biology base phosphorus made from a kind of new bio base phosphonitrile epoxy monomer according to claim 1-5
Nitrogen fire retarding epoxide resin, which is characterized in that the biology base phosphorus nitrogen fire retarding epoxide resin is by EHEP, epoxy monomer and to consolidate
Agent be added organic solvent III in, be uniformly mixed, remove solvent after be fed into mold, after drying 60~150 DEG C solidify 1~
Molding is made for 24 hours.
7. biology base phosphorus nitrogen fire retarding epoxide resin according to claim 6, which is characterized in that the EHEP, epoxy resin
The mass ratio of monomer and curing agent is (0~100): (100~0): (20~50), the EHEP and epoxy monomer quality point
The sum of number is 100.
8. biology base phosphorus nitrogen fire retarding epoxide resin according to claim 6, which is characterized in that the epoxy monomer is
One or more of E51, E44, E42 or E31；The organic solvent III is methylene chloride, acetone, ethyl acetate, ether or four
Hydrogen furans.
9. biology base phosphorus nitrogen fire retarding epoxide resin according to claim 6, which is characterized in that the curing agent is to replace
Alkane, aminated compounds or acid anhydrides.
10. biology base phosphorus nitrogen fire retarding epoxide resin according to claim 9, which is characterized in that the substitution alkane is 4- bis-
Diaminodiphenylmethane or diaminodiphenyl ether, the aminated compounds is the graceful D230 of polyetheramine Hensel or Hensel graceful T403, described
Acid anhydrides is hexahydrophthalic anhydride or tetrabydrophthalic anhydride.
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Cited By (1)
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| CN114957918A (en) * | 2022-05-31 | 2022-08-30 | 安徽大学 | Epoxy resin flame-retardant material and preparation method thereof |
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| CN102718802A (en) * | 2012-05-31 | 2012-10-10 | 四川东材绝缘技术有限公司 | Aryloxy substituted tripolyphosphazene epoxide and preparation method and application thereof |
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Application publication date: 20190510 |