CN102161746A - Synthesis method of spiro orthoester-epoxy resin copolymer - Google Patents
Synthesis method of spiro orthoester-epoxy resin copolymer Download PDFInfo
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- CN102161746A CN102161746A CN 201110033649 CN201110033649A CN102161746A CN 102161746 A CN102161746 A CN 102161746A CN 201110033649 CN201110033649 CN 201110033649 CN 201110033649 A CN201110033649 A CN 201110033649A CN 102161746 A CN102161746 A CN 102161746A
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- epoxy resin
- spiro orthoester
- spiro
- toluene
- butyrolactone
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Abstract
The invention relates to a synthesis method of a spiro orthoester-epoxy resin copolymer, which comprises the following steps: synthesis of spiro orthoester: adding phenylmethane and gamma-butyrolactone into a three-neck flask, sufficiently dissolving E-54 in phenylmethane, pouring the reaction liquid into a separating funnel, washing out excessive gamma-butyrolactone, washing with deionized water to neutral, drying by adding anhydrous magnesium sulfate into the solution, filtering, and distilling under reduced pressure to remove phenylmethane, thereby obtaining the milky waxy spiro orthoester monomer; preparation of modified epoxy resin: taking the spiro orthoester, respectively adding to the epoxy resin E-44, adding mixed resin BF3.NH2Et, evenly mixing, and cooling to room temperature for later use; and evenly spreading the prepared modified epoxy resin between two potassium bromide salt flakes, and after the two potassium bromide salt flakes are fixed, curing by putting the two potassium bromide salt flakes into a baking oven which is preheated to 120 DEG C. The tensile strength and shear strength of the spiro orthoester-epoxy resin copolymer are on the rise, the rising trend of the shear strength is especially obvious, and thus, the mechanical properties of the modified epoxy resin matrix are enhanced.
Description
Technical field
The present invention relates to a kind of synthetic method of multipolymer, particularly relate to the synthetic method of a kind of spiro orthoester and epoxy resin copolymer.
Background technology
When professor Bailey finds that spiro orthoester class monomer carries out two ring-opening polymerization under the cationic initiator effect, be accompanied by volumetric expansion
(1), this phenomenon has caused macromolecular material scholar's very big interest.Common monomer and the prepolymer resin volumetric shrinkage that when polymerization, invariably accompanies, particularly thermosetting resin after gelation further curing and the volumetric shrinkage that causes makes the inner string stress that produces of resin material, being easy to generate stress concentration, is to cause the one of the main reasons that material mechanical performance degenerates, reduce work-ing life.Often reduce shrinking percentage, to reach the purpose that improves material mechanical performance by adding certain filler.This can only reduce and can not offset contraction fully, and the discovery of Expanding Monomer not only can thoroughly address this problem, and has opened up the new Application Areas of macromolecular material, thereby its research and application become increasingly active.For example, utilize the spiro orthocarbonate modified epoxy with the preparation carbon-fibre composite, the toughness of material is significantly improved, and shearing resistance and other mechanical property are constant substantially, even slightly improves
(2)This is because the volumetric shrinkage of modified epoxy resin system reduces, and has improved the bonding interface situation between fiber and the resin, has improved the cause of interfacial adhesion power.And for example, with containing a kind of tackiness agent that the unitary prepolymer modified epoxy of spiro orthocarbonate is made, owing to reduced volumetric shrinkage in the solidification process, its bonding strength improves a lot
(3)For another example, with a kind of particular adhesive that the spiro orthocarbonate modified epoxy is made, come adhering glass, its optical property is constant substantially
(4)Resins, epoxy is a kind of thermoset macromolecule material of widespread use, because its volumetric shrinkage (although less) when solidifying has limited its application under some special occasions.With swelling property volution monomer to its modification with prepare non-contraction or a little the expansible macromolecular material be an important use direction.
Summary of the invention
The object of the present invention is to provide the synthetic method of a kind of spiro orthoester and epoxy resin copolymer.This method provides the resin additive that contains the spiro orthoester structural unit Modification effect to Resins, epoxy, and this additive has improved the mechanical property of modified epoxy material to the influence of epoxide group transformation efficiency.
The objective of the invention is to be achieved through the following technical solutions:
The synthetic method of a kind of spiro orthoester and epoxy resin copolymer, the synthetic method of described spiro orthoester and epoxy resin copolymer comprise the synthetic of spiro orthoester, its synthesis step: add toluene g-butyrolactone in there-necked flask; Get E-54 and fully dissolve, in the dropping funnel of packing into toluene; Get catalyst B F
3OEt
2Be dissolved in the toluene, divide three addings, each 40min at interval; Bathe with cryosel and to be cooled to-12 ℃, begin to drip the Resins, epoxy toluene solution after adding first catalyzer, the control drop rate behind the reaction 2h, is warming up to-5 ℃, reacts 3h again; Adding triethylamine stops; Reaction solution is poured in the separating funnel, the g-butyrolactone that flush away is excessive, extremely neutral with deionized water wash then, add anhydrous magnesium sulfate drying in the solution, filter underpressure distillation again, steam toluene, the oyster white thick liquid, vacuum-drying, oyster white wax shape spiro orthoester monomer; Again to the preparation of modified epoxy: get spiro orthoester, add respectively in the epoxy resin E-44, add the BF of hybrid resin weight 3% again
3NH
2Et stirs evenly postcooling to room temperature, standby; The above-mentioned modified epoxy for preparing is evenly coated between two bromination sylvite sheets, fixing after, put into preheating and solidify at 120 ℃ baking oven and get final product.
The synthetic method of described a kind of spiro orthoester and epoxy resin copolymer, the g-butyrolactone that its described flush away is excessive is to use the 8%NaOH solution washing.
The synthetic method of described a kind of spiro orthoester and epoxy resin copolymer, its described adding hybrid resin BF
3NH
2Et is to stir evenly postcooling to room temperature, standby at 60 ℃.
Advantage of the present invention and effect are:
The present invention has synthesized a new spiro orthoester monomer, promptly has the Resins, epoxy of spiro orthoester structural unit.With this monomer Resins, epoxy is carried out modification, can reduce the epoxide group that remains in the resin matrix, this illustrates the copolymerization curing reaction has taken place between this monomer and the Resins, epoxy, and the bonding strength of modified epoxy in the finite concentration scope then the increase with the add-on of prepolymer increase.Show that along with the increase of add-on, its tensile strength and shearing resistance are all in rising trend, particularly the shearing resistance rising is more obvious, and the mechanical property of modified epoxy matrix gets a promotion.
Description of drawings
Fig. 1 is the reaction equation figure of spiro orthoester of the present invention;
Fig. 2 is the influence figure of volution content of the present invention to the epoxide group transformation efficiency;
Fig. 3 is the graph of a relation of shrinking percentage of the present invention and bonding tensile strength and shearing resistance.
Embodiment
The present invention is described in detail with reference to the accompanying drawings.
Raw material of the present invention and reagent are Resins, epoxy (E-54, E-44) chemical plant, Shenyang product; Boron trifluoride mono aminoethane (BF
3-NH
2Et, analytical pure) for the Tokyo changes into Industrial Co., Ltd's product, g-butyrolactone (chemical pure); Boron trifluoride diethyl etherate (analytical pure).
At first carry out the synthetic of spiro orthoester, reaction equation is seen Fig. 1.
Its synthesis step: in there-necked flask, add 140ml toluene 25ml g-butyrolactone; Get 25g E-54 and fully dissolve, in the dropping funnel of packing into 45ml toluene; Get catalyst B F
3OEt
20.66ml be dissolved in the 20ml toluene, divide three addings, each 40min at interval.Bathe with cryosel and to be cooled to about-12 ℃, begin to drip the Resins, epoxy toluene solution after adding first catalyzer, the control drop rate behind the reaction 2h, is warming up to-5 ℃, reacts 3h again.Add 1.32ml triethylamine termination reaction.
Reaction solution is poured in the separating funnel, with the 8%NaOH solution washing for several times, with the excessive g-butyrolactone of flush away, extremely neutral with deionized water wash then, add anhydrous magnesium sulfate drying in the solution, filter, underpressure distillation is to steam toluene again, get the oyster white thick liquid, vacuum-drying 3h gets oyster white wax shape spiro orthoester monomer (productive rate 72.6%).
The test result of product is as follows:
Infrared spectra: at 913cm
-1Place's epoxy characteristic peak disappears substantially, and the g-butyrolactone is at 1780～1760cm
-1The lactone characteristic peak completely dissolve at place is at 1230cm
-1The volution characteristic peak appears in the place, proves that the spiro orthoester monomer generates.
Ultimate analysis: C
29H
36O
8,(Wt%) calculated value: C, 67.97; H, 7.03.
Measured value: C, 67.18; H, 6.85.
Again to the preparation of modified epoxy: get spiro orthoester, add respectively in the epoxy resin E-44, add the BF of hybrid resin weight 3% again
3NH
2Et stirs evenly about 60 ℃, is cooled to room temperature, and is standby.The above-mentioned modified epoxy for preparing is evenly coated between two bromination sylvite sheets, fixing after, put into preheating and solidify 3h at 120 ℃ baking oven.Behind the cool to room temperature, its infrared spectra of test on day island proper Tianjin IR-435 infrared spectrometer.According to epoxide group at 913cm
-1Characteristic absorbance peak height (the A at place
913) height (being directly proportional) with the content of epoxide group in the system, with 1610cm
-1Place's phenyl ring skeletal vibration absorbs peak height (A
1610, in polyreaction, remain unchanged .) as standard, the transformation efficiency of 1 ring oxygen groups (a) by formula
(5)
Subscript 0 and t refer to that respectively polymerization time is 0 and t in the formula.
Specimen surface is polished smooth, use washing with acetone, after then the different modified epoxy of proportioning being coated in the surface equably, two samples are glued together, after it is firmly fixed, put into constant temperature and solidify 3h at 120 ℃ baking oven, slowly behind the cool to room temperature, test its tensile strength and shearing resistance on universal testing machine, the chuck spacing is 50 ± 2mm, rate of extension is 6mm/min, gets five sample parallel testing results' mean value.
Get the modified epoxy for preparing and put into steel (45#) molding jig that is of a size of 90mm * 10mm * 10mm, de-bubbled 2h under the vacuum puts into 140 ℃ baking oven again, solidifies 4h, after the cooling sample is tested on universal testing machine.The chuck spacing is 50 ± 2mm, and rate of extension is 6mm/min, gets 5 sample parallel testing results' mean value.
The curing reaction of pure epoxy resin is that epoxide group is at F
3B-NH
2The cationic ring-opening polymerization that carries out under the katalysis of Et, because the crosslinking structure that forms behind the gelation point has limited the activity of epoxide group, thereby the whole open loops of epoxide group to carry out polymerization be impossible, also have the part epoxide group to be present in the resin matrix behind the curing reaction, and in polymerization process, be accompanied by volumetric shrinkage.The spiro orthoester structural unit can carry out ring-opening polymerization equally under the effect of this catalyzer, this is confirmed (at 1230cm by Infrared spectroscopy
-1The volution group charateristic avsorption band at place disappears, generation be at 1736cm
-1The charateristic avsorption band that ester carbonyl group occurs), by selecting Latence catalyst (F
3B-NH
2Et, in the time of 90 ℃, emit the spike catalyzed reaction, thereby be easy to carry out pre-treatment under the normal temperature), can make both carry out copolyreaction effectively, but comparatively speaking, epoxide group is more active, and the reaction of curing reaction epoxide group in early stage is more, so after epoxide group is crosslinked substantially, also have considerable volution group to be present in the system.Since this moment the volution group reactivity, it can continue and epoxide group collision and copolyreaction takes place, and generates side chain or crosslinking structure, thereby the monomeric adding of volution can improve the transformation efficiency of epoxide group, test-results has also confirmed this point.
Table 1 volution content is to the influence of modified epoxy tensile strength and shearing resistance
————————————————————————————
No. prepolymer tensile strength shearing resistance
(wt%) (MPa) (MPa)
————————————————————————————
1 0 30.60 10.80
2 5 31.90 13.60
3 10 33.30 15.30
4 15 34.50 17.10
5 20 35.20 17.80
6 30 35.05 17.50
————————————————————————————
The add-on of spiro orthoester is to the influence of bonding tensile strength and adhesive shear strength, and the result shows that along with the increase of add-on, its tensile strength and shearing resistance are all in rising trend, and particularly shearing resistance rises more obvious.Its reason is: the adding of spiro orthoester has reduced the volumetric shrinkage in the polymerization process, after particularly the cross linking of epoxy resin structure basically forms, the reduction of volumetric shrinkage can reduce the string stress between the bonded part greatly, so increase along with add-on, volumetric shrinkage reduces, cause the bonding strength of Resins, epoxy to increase, test has also confirmed this point; But when the spiro orthoester add-on is big (for example 30%), bonding strength decreases, this be since this moment resin system viscosity bigger, cause the test specimen surface wettability is bad.
The mechanical property of table 2 modified epoxy matrix
——————————————————————————————
No spiro orthoester Young's modulus tensile strength elongation at break
(wt%) (MPa) (MPa) (%)
——————————————————————————————
1 0 882 56.8 8.90
2 20 665 53.9 9.60
——————————————————————————————
As can be seen from Table 2, be added with the monomeric modified epoxy matrix of spiro orthoester, its Young's modulus greatly reduces, and tensile strength also decreases, elongation at break has increase slightly, and this is because introduced the result of the lower carboxylic acid ester groups unit chain link of cohesive strength in the main chain.Can reach a conclusion thus, the modulus of modified epoxy matrix itself may cause cohesive strength to reduce, thereby the raising of cohesive strength is that reduction owing to the system shrinking percentage causes.
Claims (3)
1. the synthetic method of spiro orthoester and epoxy resin copolymer, it is characterized in that, the synthetic method of described spiro orthoester and epoxy resin copolymer comprises the synthetic of spiro orthoester, its synthesis step: add toluene g-butyrolactone in there-necked flask; Get E-54 and fully dissolve, in the dropping funnel of packing into toluene; Get catalyst B F
3OEt
2Be dissolved in the toluene, divide three addings, each 40min at interval; Bathe with cryosel and to be cooled to-12 ℃, begin to drip the Resins, epoxy toluene solution after adding first catalyzer, the control drop rate behind the reaction 2h, is warming up to-5 ℃, reacts 3h again; Adding triethylamine stops; Reaction solution is poured in the separating funnel, the g-butyrolactone that flush away is excessive, extremely neutral with deionized water wash then, add anhydrous magnesium sulfate drying in the solution, filter underpressure distillation again, steam toluene, the oyster white thick liquid, vacuum-drying, oyster white wax shape spiro orthoester monomer; Again to the preparation of modified epoxy: get spiro orthoester, add respectively in the epoxy resin E-44, add the BF of hybrid resin weight 3% again
3NH
2Et stirs evenly postcooling to room temperature, standby; The above-mentioned modified epoxy for preparing is evenly coated between two bromination sylvite sheets, fixing after, put into preheating and solidify at 120 ℃ baking oven and get final product.
2. the synthetic method of a kind of spiro orthoester according to claim 1 and epoxy resin copolymer is characterized in that, the g-butyrolactone that described flush away is excessive is to use the 8%NaOH solution washing.
3. the synthetic method of a kind of spiro orthoester according to claim 1 and epoxy resin copolymer is characterized in that, described adding hybrid resin BF
3NH
2Et is to stir evenly postcooling to room temperature, standby at 60 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108641066A (en) * | 2018-04-17 | 2018-10-12 | 中国科学院化学研究所 | A kind of composition epoxy resin and preparation method thereof |
| CN110862652A (en) * | 2019-11-29 | 2020-03-06 | 南京航空航天大学 | Low-shrinkage resin cured at room temperature and preparation method thereof |
-
2011
- 2011-01-31 CN CN 201110033649 patent/CN102161746A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 《辽宁工程技术大学学报》 20051225 王长松，曲明哲，史航，刘刚，于智 一种螺环原酸酯与环氧树脂的共聚改性研究 第917也第1列第1行-第2列第1行 1-3 第24卷, 第6期 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108641066A (en) * | 2018-04-17 | 2018-10-12 | 中国科学院化学研究所 | A kind of composition epoxy resin and preparation method thereof |
| CN110862652A (en) * | 2019-11-29 | 2020-03-06 | 南京航空航天大学 | Low-shrinkage resin cured at room temperature and preparation method thereof |
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Application publication date: 20110824 |