CN104927308A - Epoxy resin toughening agent based on cyclotriphosphazene six-arm star polymer and preparation method for epoxy resin toughening agent - Google Patents
Epoxy resin toughening agent based on cyclotriphosphazene six-arm star polymer and preparation method for epoxy resin toughening agent Download PDFInfo
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Abstract
The present invention provides an epoxy resin toughening agent based on cyclotriphosphazene six-arm star polymer and a preparation method for the epoxy resin toughening agent, and belongs to the technical field of epoxy resin modification. The preparation method for the toughening agent comprises the following steps of: step I, in the presence of an acid scavenger, generating a nucleophilic substitution reaction in an oargnic solvent by utilizing hexachlorocyclotriphosphazene and p-hydroxybenzaldehyde, and obtaining a solid after separation and drying; step II, in the presence of a reductant, reducing a solid aldehyde group obtained in the step I to a hydroxyl group; and step III, by taking the solid obtained in the step II as an initiator, initiating ring-opening polymerization of caprolactone and obtaining the toughening agent after separation and drying. The epoxy resin toughening agent based on cyclotriphosphazene six-arm star polymer provided by the present invention has significant toughening effect on epoxy resin and can significantly improve impact resistance of the epoxy resin without sacrificing other mechanical properties and thermal properties of the material, thereby facilitating industrialized production.
Description
Technical field
The present invention relates to a kind of epoxy resin toughener, specifically a kind of epoxy resin toughener based on ring three phosphonitrile six arm star polymkeric substance.The invention further relates to the preparation method of described epoxy resin toughener.The invention belongs to epoxy resin modification technical field.
Technical background
Epoxy resin has good physics, chemical property, it has excellent bonding strength to the surface of metal and non-metallic material, dielectric properties are good, set shrinking percentage is little, product size good stability, hardness is high, and snappiness is better, to alkali and most of solvent-stable, be thus widely used in the field such as cast, dipping, lamination material, caking agent, coating.But in tridimensional network after epoxy resin cure, cross-linking density is high, the shortcoming such as have that internal stress is large, quality is firmly crisp, humidity resistance is poor and stripping strength is low.Thus toughening modifying carries out to epoxy resin particularly important.
Star-type polymer modified epoxy is utilized to be emerging Toughening Epoxy Resin method in recent years.Similar with hyperbranched polymer, this highly branched polymkeric substance is compared with the simple linear polymer of same molecular amount, and solubleness is high, and viscosity is lower, and have high chemical reactivity, a large amount of functional end-group can also improve required performance by further modification.These characteristics make star-type polymer the thermosetting resins such as epoxy resin toughness reinforcing in demonstrate tempting application prospect.Through finding the retrieval of existing scientific and technical literature, the U.S.'s " macromolecular chemistry and physics " periodical was in the 213rd volume 335-343 page (M.Morell in 2012, etal., New Improved Thermosets Obtained From Diglycidylether of Bisphenol A anda Multiarm Star Copolymer Based on Hyperbranched Poly (glycidol) Core andPoly (methyl methacrylate) Arms, Macromol.Chem.Phys., 2012, 213, 335-343) report a kind of with hyperbranched poly-(Racemic glycidol) for kernel, the star copolymer that poly-(methyl methacrylate) is side arm, use its Toughening Modification of Epoxy, shock strength can be promoted to 200%, Holland's " organic coating progress " periodical was at the 77th volume 1288-1298 page (C.Acebo in 2014, et al., Effect ofhydroxyl ended and end-capped multiarm star polymers on the curing process andmechanical, Prog.Org.Coat., 2014,77,1288-1298) report a kind of be kernel with hyperbranched poly-(ethyleneimine), poly-(6-caprolactone) star copolymer that is side arm, make the shock strength of epoxy-anhydride aathermoset resin system be promoted to 300% as toughner, the U.S.'s " polymkeric substance " periodical was in the 52nd volume 5723-5731 page (F. in 2011
et al., Hyperstar poly (ester-methacrylate) s asadditives in thermally and photocured epoxy resins, Polymer, 2011,52,5723-5731) report a kind of star copolymer, its side arm that there is aromatic polyester kernel and be made up of the segmented copolymer of poly-(methyl methacrylate) and poly-(hydroxyethyl methylacrylate), and this star copolymer is applied to the Formulaion of epoxy resin of photocuring and thermofixation as toughner.But existing star-type polymer while epoxy resin toughened, often causes the decline of other mechanical properties of material (as tensile strength) and thermal characteristics, or the reduction of processing characteristics.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of epoxy resin toughener based on ring three phosphonitrile six arm star polymkeric substance is provided.The present invention first with hexachlorocyclotriphosphazene and p-Hydroxybenzaldehyde for six (to aldehyde radical phenoxy group) ring three phosphonitrile prepared by raw material, be reduced to six (to hydroxy methyl phenyloxy) ring three phosphonitrile again, then with six (to hydroxy methyl phenyloxy) ring three phosphonitrile for initiator, cause 6-caprolactone ring-opening polymerization, prepare six arm star polycaprolactones.Epoxy resin toughener based on ring three phosphonitrile star-type polymer prepared by the present invention has obvious toughening effect to epoxy resin, while significantly improving the shock resistance of epoxy resin, tensile strength and the thermal characteristics of material can not be affected, be conducive to realizing suitability for industrialized production.
The present invention is achieved by the following technical solutions, and the present invention relates to a kind of epoxy resin toughener based on ring three phosphonitrile six arm star polymkeric substance, its chemical structure is as follows:
The preparation method of described epoxy resin toughener, comprises the steps:
Step one, under acid binding agent existent condition, utilizes hexachlorocyclotriphosphazene and p-Hydroxybenzaldehyde in organic solvent nucleophilic substitution reaction to occur, and obtains six (to aldehyde radical phenoxy group) ring three phosphonitrile after being separated drying;
Step 2, under reductive agent existent condition, there is reduction reaction in six (to aldehyde radical phenoxy group) ring three phosphonitrile in organic solvent, obtains six (to hydroxy methyl phenyloxy) ring three phosphonitrile after being separated drying;
Step 3, under catalyzer existent condition, with six (to hydroxy methyl phenyloxy) ring three phosphonitrile for initiator, makes 6-caprolactone generation ring-opening polymerization, obtains toughner after being separated drying.
In step one, described acid binding agent is the one in triethylamine, Tributylamine, pyridine, salt of wormwood.
In step one, described organic solvent is for being tetrahydrofuran (THF), acetonitrile, acetone, toluene, N, the mixed solvent of one or more in N '-dimethyl methane amide.
In step 2, described reductive agent is the one in sodium borohydride, lithium aluminum hydride, aluminum isopropylate.
In step 3, described catalyzer is the one in stannous octoate, stannous acetate, triethyl aluminum, tert.-butoxy aluminium.
In step 3, the mol ratio of six (to hydroxy methyl phenyloxy) ring three phosphonitrile and 6-caprolactone is 1:60 ~ 1:240.
Compared with prior art, the present invention has following beneficial effect: (1) epoxy resin toughener of the present invention has hub-and-spoke configuration, viscosity is low, good with the consistency of epoxy resin, and end is with hydroxyl, can participate in the curing reaction of epoxy resin, form the cured product of stable uniform; (2) in the structure of epoxy resin toughener of the present invention, not only there is a large amount of polycaprolactone flexible chain, and there is phosphonitrile ring and phenyl ring rigid element, while the toughness effectively improving epoxy resin, tensile strength and the thermal characteristics of material can not be affected; (3) epoxy resin toughener of the present invention has ring three phosphonitrile kernel, and while the effect of performance toughner, also having certain phosphorus-nitrogen cooperative flame retardant effect, is the agent of a kind of multifunctional type epoxy resin modification.
Accompanying drawing explanation
Fig. 1 is the route schematic diagram of embodiment 1 synthetic epoxy resin toughner;
Fig. 2 is the infrared spectrogram of embodiment 1 initiator six (to hydroxy methyl phenyloxy) ring three phosphonitrile obtained and the six arm star polycaprolactones obtained;
Fig. 3 is the nmr spectrum of the six arm star polycaprolactones that embodiment 1 obtains;
Fig. 4 is that the six arm star polycaprolactones that embodiment 1 obtains are added in E51 type epoxy resin, the resistance to impact shock test pattern after solidification.
Embodiment
Following instance will the invention will be further described by reference to the accompanying drawings.The present embodiment is implemented under premised on technical solution of the present invention, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiment.The experimental technique of unreceipted actual conditions in the following example, usually conveniently condition, or according to the condition that manufacturer advises.
Embodiment 1
In the there-necked flask of 250mL drying that magneton, thermometer, constant pressure funnel and condensation reflux unit are housed, add p-Hydroxybenzaldehyde 14.76g and tetrahydrofuran (THF) 50mL, then add triethylamine (TEA) 20mL.After being heated to 60 DEG C, stir lower tetrahydrofuran (THF) (40mL) solution dripping hexachlorocyclotriphosphazene 6.95g, keep stirring lower back flow reaction 8h and terminate.Six (to aldehyde radical phenoxy group) ring three phosphonitrile is obtained after recrystallization in ethyl acetate.
In 250mL there-necked flask, add six (to aldehyde radical phenoxy group) ring three phosphonitrile 4.31g, tetrahydrofuran (THF) 30mL, methyl alcohol 15mL successively, and stir.Add 2g sodium borohydride again, at 25 DEG C, react 14h.Revolve and steam except after desolventizing, washing, and recrystallization twice in ethanol, obtain six (to hydroxy methyl phenyloxy) ring three phosphonitrile.
In 50mL single port flask, add 6.84g 6-caprolactone, 0.291g six (to hydroxy methyl phenyloxy) ring three phosphonitrile and 3 stannous octoates, react 24h at 100 DEG C and obtain six arm star polycaprolactones.
Get 50g epoxy resin (E51), at 70 DEG C, add six arm star polycaprolactones of different mass, stir, then add 50g methyl hexahydrophthalic anhydride and a small amount of curing catalyst, curing reaction 4h at 140 DEG C, obtained Impact Test batten.
The implementation result of the present embodiment:
Fig. 1 is the synthetic route schematic diagram of epoxy resin toughener.
Fig. 2 is the infrared spectrogram of obtained initiator six (to hydroxy methyl phenyloxy) ring three phosphonitrile and six obtained arm star polycaprolactones.As shown in the figure, contrast initiator and product, product is at 3261cm
-1hydroxyl (OH) absorption peak at place disappears, 1714cm
-1carbonyl (C=O) absorption peak at place occurs, shows caprolactone success and initiator for reaction.
Fig. 3 is the nmr spectrum of six obtained arm star polymkeric substance.Chemical shift is the proton peak on phenyl ring at 7.2ppm and 6.9ppm place; Chemical shift is-Ph-at the unimodal of 5.1ppm
cH 2 the proton peak of O-methylene radical; Chemical shift is-CH at the triplet of 4.1ppm
2-
cH 2 the proton peak of-O-methylene radical; Chemical shift at the triplet of 3.7ppm is
cH 2 the proton peak of OH methylene radical; Chemical shift is-CO-at the triplet of 2.4ppm
cH 2 -CH
2the proton peak of methylene radical; Chemical shift is-CO-CH at the quintet of 1.6ppm
2-
cH 2 -CH
2-
cH 2 -CH
2the proton peak of-O two methylene radical; Chemical shift is-CO-CH at the quintet of 1.4ppm
2-CH
2-
cH 2 the proton peak of methylene radical.
Fig. 4 is that six obtained arm star polycaprolactones are added in E51 type epoxy resin, the resistance to impact shock test pattern after solidification.As shown in the figure, along with the increase of six arm star polymkeric substance additions, after solidification, the shock strength of resin increases gradually, can reach 250% of pure epoxy resin.
Embodiment 2
In the there-necked flask of 250mL drying that magneton, thermometer, constant pressure funnel and condensation reflux unit are housed, add p-Hydroxybenzaldehyde 14.76g and tetrahydrofuran (THF) 50mL, then add triethylamine (TEA) 20mL.After being heated to 60 DEG C, stir lower tetrahydrofuran (THF) (40mL) solution dripping hexachlorocyclotriphosphazene 6.95g, keep stirring lower back flow reaction 8h and terminate.Six (to aldehyde radical phenoxy group) ring three phosphonitrile is obtained after recrystallization in ethyl acetate.
In 250mL there-necked flask, add six (to aldehyde radical phenoxy group) ring three phosphonitrile 4.31g, tetrahydrofuran (THF) 30mL, methyl alcohol 15mL successively, and stir.Add 2g sodium borohydride again, at 25 DEG C, react 14h.Revolve and steam except after desolventizing, washing, and recrystallization twice in ethanol, obtain six (to hydroxy methyl phenyloxy) ring three phosphonitrile.
In 50mL single port flask, add 6.84g 6-caprolactone, 0.874g six (to hydroxy methyl phenyloxy) ring three phosphonitrile and 3 stannous octoates, react 24h at 100 DEG C and obtain six arm star polycaprolactones.
Get 50g epoxy resin (E51), at 70 DEG C, add six arm star polycaprolactones of different mass, stir, then add 50g methyl hexahydrophthalic anhydride and a small amount of curing catalyst, curing reaction 4h at 140 DEG C, obtained Impact Test batten.
Embodiment 3
In the there-necked flask of 250mL drying that magneton, thermometer, constant pressure funnel and condensation reflux unit are housed, add p-Hydroxybenzaldehyde 14.76g and tetrahydrofuran (THF) 50mL, then add triethylamine (TEA) 20mL.After being heated to 60 DEG C, stir lower tetrahydrofuran (THF) (40mL) solution dripping hexachlorocyclotriphosphazene 6.95g, keep stirring lower back flow reaction 8h and terminate.Six (to aldehyde radical phenoxy group) ring three phosphonitrile is obtained after recrystallization in ethyl acetate.
In 250mL there-necked flask, add six (to aldehyde radical phenoxy group) ring three phosphonitrile 4.31g, tetrahydrofuran (THF) 30mL, methyl alcohol 15mL successively, and stir.Add 2g sodium borohydride again, at 25 DEG C, react 14h.Revolve and steam except after desolventizing, washing, and recrystallization twice in ethanol, obtain six (to hydroxy methyl phenyloxy) ring three phosphonitrile.
In 50mL single port flask, add 6.84g 6-caprolactone, 0.437g six (to hydroxy methyl phenyloxy) ring three phosphonitrile and 3 stannous octoates, react 24h at 100 DEG C and obtain six arm star polycaprolactones.
Get 50g epoxy resin (E51), at 70 DEG C, add six arm star polycaprolactones of different mass, stir, then add 50g methyl hexahydrophthalic anhydride and a small amount of curing catalyst, curing reaction 4h at 140 DEG C, obtained Impact Test batten.
Embodiment 4
In the there-necked flask of 250mL drying that magneton, thermometer, constant pressure funnel and condensation reflux unit are housed, add p-Hydroxybenzaldehyde 14.76g and tetrahydrofuran (THF) 50mL, then add salt of wormwood 6g.After being heated to 60 DEG C, stir lower tetrahydrofuran (THF) (40mL) solution dripping hexachlorocyclotriphosphazene 6.95g, keep stirring lower back flow reaction 8h and terminate.(six pairs of aldehyde radical phenoxy groups) ring three phosphonitrile is obtained after recrystallization in ethyl acetate.
In 250mL there-necked flask, add six (to aldehyde radical phenoxy group) ring three phosphonitrile 4.31g, tetrahydrofuran (THF) 30mL, methyl alcohol 15mL successively, and stir.Add 2g sodium borohydride again, at 25 DEG C, react 14h.Revolve and steam except after desolventizing, washing, and recrystallization twice in ethanol, obtain six (to hydroxy methyl phenyloxy) ring three phosphonitrile.
In 50mL single port flask, add 6.84g 6-caprolactone, 0.218g six (to hydroxy methyl phenyloxy) ring three phosphonitrile and 3 stannous octoates, react 24h at 100 DEG C and obtain six arm star polycaprolactones.
Get 50g epoxy resin (E51), at 70 DEG C, add six arm star polycaprolactones of different mass, stir, then add 50g methyl hexahydrophthalic anhydride and a small amount of curing catalyst, curing reaction 4h at 140 DEG C, obtained Impact Test batten.
Claims (7)
1., based on an epoxy resin toughener for ring three phosphonitrile six arm star polymkeric substance, it is characterized in that, its chemical structure is as follows:
2. a preparation method for the epoxy resin toughener based on ring three phosphonitrile six arm star polymkeric substance according to claim 1, is characterized in that, comprise the steps:
Step one, under acid binding agent existent condition, utilizes hexachlorocyclotriphosphazene and p-Hydroxybenzaldehyde in organic solvent nucleophilic substitution reaction to occur, and obtains six (to aldehyde radical phenoxy group) ring three phosphonitrile after being separated drying;
Step 2, under reductive agent existent condition, there is reduction reaction in six (to aldehyde radical phenoxy group) ring three phosphonitrile in organic solvent, obtains six (to hydroxy methyl phenyloxy) ring three phosphonitrile after being separated drying;
Step 3, under catalyzer existent condition, with six (to hydroxy methyl phenyloxy) ring three phosphonitrile for initiator, makes 6-caprolactone generation ring-opening polymerization, obtains toughner after being separated drying.
3. the preparation method of a kind of epoxy resin toughener based on ring three phosphonitrile six arm star polymkeric substance according to claim 2, it is characterized in that, in step one, described acid binding agent is the one in triethylamine, Tributylamine, pyridine, salt of wormwood.
4. the preparation method of a kind of epoxy resin toughener based on ring three phosphonitrile six arm star polymkeric substance according to claim 2, it is characterized in that, in step, described organic solvent is tetrahydrofuran (THF), acetonitrile, acetone, toluene, N, the mixed solvent of one or more in N '-dimethyl methane amide.
5. the preparation method of a kind of epoxy resin toughener based on ring three phosphonitrile six arm star polymkeric substance according to claim 2, it is characterized in that, in step 2, described reductive agent is the one in sodium borohydride, lithium aluminum hydride, aluminum isopropylate.
6. the preparation method of a kind of epoxy resin toughener based on ring three phosphonitrile six arm star polymkeric substance according to claim 2, it is characterized in that, in step 3, described catalyzer is the one in stannous octoate, stannous acetate, triethyl aluminum, tert.-butoxy aluminium.
7. the preparation method of a kind of epoxy resin toughener based on ring three phosphonitrile six arm star polymkeric substance according to claim 2, it is characterized in that, in step 3, the mol ratio of six (to hydroxy methyl phenyloxy) ring three phosphonitrile and 6-caprolactone is 1:60 ~ 1:240.
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| CN105399959A (en) * | 2015-12-23 | 2016-03-16 | 江南大学 | Polyphosphazene microsphere-based phenolic resin molding plastic additive and preparation method thereof |
| CN107337692A (en) * | 2017-07-04 | 2017-11-10 | 西北工业大学 | The preparation method of the phosphonitrile type epoxy resin of ring three |
| CN108070072A (en) * | 2016-11-07 | 2018-05-25 | 无锡创达新材料股份有限公司 | A kind of imidazoles based epoxy resin latent curing agent based on three phosphonitrile of ring and preparation method thereof |
| CN108976418A (en) * | 2018-07-19 | 2018-12-11 | 中国科学院宁波材料技术与工程研究所 | A kind of three-dimensional structure fire retardant and preparation method thereof based on three phosphonitrile of furan derivatives and ring |
| CN111848952A (en) * | 2020-06-17 | 2020-10-30 | 扬州天启新材料股份有限公司 | Bisphenol A type cyanate ester resin prepolymer and preparation method thereof |
| CN113881376A (en) * | 2021-11-01 | 2022-01-04 | 江南大学 | Bio-based epoxy resin pouring sealant and preparation method thereof |
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Cited By (9)
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| CN105399959A (en) * | 2015-12-23 | 2016-03-16 | 江南大学 | Polyphosphazene microsphere-based phenolic resin molding plastic additive and preparation method thereof |
| CN105399959B (en) * | 2015-12-23 | 2018-07-13 | 江南大学 | A kind of alkyd resin moulding material additive and preparation method thereof based on polyphosphazene microspheres |
| CN108070072A (en) * | 2016-11-07 | 2018-05-25 | 无锡创达新材料股份有限公司 | A kind of imidazoles based epoxy resin latent curing agent based on three phosphonitrile of ring and preparation method thereof |
| CN107337692A (en) * | 2017-07-04 | 2017-11-10 | 西北工业大学 | The preparation method of the phosphonitrile type epoxy resin of ring three |
| CN108976418A (en) * | 2018-07-19 | 2018-12-11 | 中国科学院宁波材料技术与工程研究所 | A kind of three-dimensional structure fire retardant and preparation method thereof based on three phosphonitrile of furan derivatives and ring |
| CN108976418B (en) * | 2018-07-19 | 2021-01-05 | 中国科学院宁波材料技术与工程研究所 | Three-dimensional structure flame retardant based on furan derivative and cyclotriphosphazene and preparation method thereof |
| CN111848952A (en) * | 2020-06-17 | 2020-10-30 | 扬州天启新材料股份有限公司 | Bisphenol A type cyanate ester resin prepolymer and preparation method thereof |
| CN113881376A (en) * | 2021-11-01 | 2022-01-04 | 江南大学 | Bio-based epoxy resin pouring sealant and preparation method thereof |
| CN113881376B (en) * | 2021-11-01 | 2022-11-11 | 江南大学 | Bio-based epoxy resin pouring sealant and preparation method thereof |
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Application publication date: 20150923 |