CN109438926A - A kind of polysulfide-rubber-modified epoxy and preparation method thereof - Google Patents
A kind of polysulfide-rubber-modified epoxy and preparation method thereof Download PDFInfo
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- CN109438926A CN109438926A CN201811382221.4A CN201811382221A CN109438926A CN 109438926 A CN109438926 A CN 109438926A CN 201811382221 A CN201811382221 A CN 201811382221A CN 109438926 A CN109438926 A CN 109438926A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
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Abstract
The present invention relates to a kind of polysulfide-rubber-modified epoxy, the component including following parts by weight: 100 parts of epoxy resin；20~100 parts of liquid polysulphide rubber；4.8~12 parts of DMP30.In the modified gained epoxy resin toughened curing system of liquid polysulfide rubber of the present invention, curing agent of the DMP30 as epoxy resin and polysulfide rubber mixed system, the network structure that the network structure that polysulfide rubber is formed with epoxy resin is formed with DMP30 is interted mutually, form interpenetrating networks, due to the presence of polysulfide rubber soft segment, so that the toughness of curing system greatly improves.
Description
Technical field
The present invention relates to Epoxy Resin Technology technical field of modification, and in particular to a kind of polysulfide-rubber-modified epoxy and
Preparation method.
Background technique
Epoxy resin is because its solidfied material has excellent adhesion, heat resistance, chemical resistance and mechanical property are good
It the features such as good and excellent electrical properties, is widely used in fields such as coating, adhesive, composite materials.But due to its molecule knot
The defects of the reason of structure, epoxy resin cured product internal stress is big, has matter crisp, impact resistance difference and easy cracking.In order to gram
These defects for taking epoxy resin, give full play to its excellent performance, domestic and foreign scholars use a variety of methods to epoxy resin into
Row toughening modifying research: rubber elastomer toughening modifying；Toughened With High Performance Thermoplastics are modified；Dissaving polymer toughening modifying；Core
Shell structure polymer toughening is modified；Nano-particle toughening modification etc..All in all, tough by the modified epoxy resin of these methods
Property greatly improves, but toughing ways and process slightly show cumbersome.
It is usually necessary to use curing agent and curing accelerator for the solidification of epoxy resin.DMP30 can be used as epoxy resin
Curing agent promotor can also be used directly as curing agent, when it is as curing accelerator, only play urging for curing reaction
Change effect, mainly causes the ring-opening polymerization of molecular resin epoxy group, so that it is cross-linked into the high polymer of three-dimensional-structure, this
Body does not participate in cross-linked network, and dosage is generally 1% to the 2% of system gross mass.When its as curing agent in use,
General dosage is the 10% of epoxy resin, itself can participate in curing reaction, and DMP30 is used alone as epoxy curing agent
Obtained cured product crosslink density is high, but brittleness is bigger, so that its purposes is limited.
Summary of the invention
It is epoxy resin toughened and preparation method thereof the purpose of the present invention is to provide a kind of liquid polysulfide rubber, preparation process
Simply, toughening effect is obvious.
The present invention solves scheme used by above-mentioned technical problem:
A kind of polysulfide-rubber-modified epoxy, the component including following parts by weight:
100 parts of epoxy resin；
20~100 parts of liquid polysulphide rubber；
4.8~12 parts of DMP30 (2,4,6-three (dimethylamino methyl) phenol).
Preferably, the epoxy resin includes bisphenol A epoxide resin, bisphenol F epoxy resin, novolac epoxy resin, shrink
The mixture of any one or more of glycerol ester type epoxy resin.
Preferably, the liquid polysulphide rubber includes JLY-121, G-21, JLY-124, LP-23, JLY-1225, JLY-
155, the mixture of any one or more of JLY-115, JLY-215, LP-3, G-4, LP-2.
Preferably, the weight ratio of the epoxy resin and liquid polysulphide rubber is 10:2.
Preferably, the weight ratio of the DMP30 and epoxy resin is 8:100.
The present invention also provides the preparation methods of above-mentioned polysulfide-rubber-modified epoxy, include the following steps:
(1) liquid polysulfide rubber, epoxy resin, altax P30 are sufficiently stirred in a reservoir until body with glass bar
System is uniformly mixed；
(2) mixture is stirred to 0.5-1.5h with the bubble in removing system under vacuum conditions at room temperature, handled
Bi Hou is cast in Teflon mould, and heating solidifies system sufficiently, and demoulding obtains polysulfide-rubber-modified epoxy
Cured product.
Preferably, the step of elevated cure includes: and mold is put into baking oven to be warming up to 25-50 DEG C, keeps the temperature 12-24h
After be warming up to 50-90 DEG C, keep the temperature 4-10h.
Compared with prior art the present invention has the advantage that
1, DMP30 uses directly as curing agent, and the amine curing agent for having volatility and toxicity, solidfied material is not used in system
Preparation process is environmentally protective；
2, the epoxy resin toughened preparation method of fluid present invention polysulfide rubber is simple, is suitable for industrial applications；
3, the present invention is modified in the gained epoxy resin toughened curing system of liquid polysulfide rubber, and DMP30 is as epoxy resin
With the curing agent of polysulfide rubber mixed system, the network of network structure and DMP30 formation that polysulfide rubber and epoxy resin are formed
Structure is interted mutually, interpenetrating networks is formed, due to the presence of polysulfide rubber soft segment, so that the toughness of curing system substantially mentions
It is high.
Detailed description of the invention
Fig. 1 is the infrared test figure of 1 gained cured product of raw material polysulfide rubber of the present invention, epoxy resin and embodiment；
Fig. 2 is the dynamic mechanical analysis figure of 1~6 products obtained therefrom of the embodiment of the present invention；
Fig. 3 is the tensile strength and elongation at break variation diagram of 1~6 products obtained therefrom of the embodiment of the present invention；
Fig. 4 is the shear strength of 1~6 products obtained therefrom of the embodiment of the present invention；
Fig. 5 is the shore D hardness of 1~6 products obtained therefrom of the embodiment of the present invention；
Fig. 6 is the impact strength of 1~6 products obtained therefrom of the embodiment of the present invention.
Specific embodiment
For a better understanding of the present invention, the following examples are to further explanation of the invention, but the contents of the present invention
It is not limited solely to the following examples.
Embodiment 1
It is poly- that 100g is added in 100g epoxy resin (Yue Hua Organic Chemical Plant, Yueyang general petrochemical works, the trade mark: CYD-128)
Sulphur rubber (Jinxi Research Institute of Chemical Industry Co., Ltd., the trade mark: JLY-1225), 8gDMP30.By liquid polysulfide rubber, epoxy resin,
DMP30 etc. is sufficiently stirred in a reservoir with glass bar until system is uniformly mixed, at room temperature under vacuum conditions by mixture
1h is stirred with the bubble in removing system, after being disposed, is cast in Teflon mould, is put into baking oven and is warming up to 30
DEG C, 60 DEG C are warming up to after keeping the temperature 20h, keeps the temperature 8h, system sufficiently solidifies, and demoulding obtains the solidification of polysulfide-rubber-modified epoxy
Product is denoted as EL3-1.
Raw material polysulfide rubber, epoxy resin and 1 gained cured product of embodiment are subjected to infrared test, test result
As shown in Figure 1.Figure middle line 1 is the infrared spectrum of liquid polysulfide rubber, and the feature stretching vibration for occurring S-H at 2553cm-1 absorbs
Peak；Line 2 is the infared spectrum of epoxy resin, the characteristic peak of epoxy group occurs in 910cm-1；Line 3 is the infrared figure of cured product
Spectrum.Box A selectes the absorption peak that the corresponding absorption peak in 3 region of line is secondary hydroxyl and amino in cured product, illustrates that DMP30 is participated in
Curing reaction, in addition compared with the corresponding epoxy resin of line 2 absorption peak here, the absorption peak of secondary hydroxyl obviously broadens
Height, because the two is herein it includes the absorption peak of secondary hydroxyl in the secondary hydroxyl generated after epoxy ring-opening and original epoxy resin
Region superposition；Characteristic absorption peak 1600cm-1,1580cm-1,1500cm-1 and 1450cm-1 in box B selected 2 and 3 are benzene
The characteristic absorption peak band of ring shows to contain phenyl ring in sample and epoxy resin after solidifying.
Embodiment 2~6
Preparation method is same as Example 1, the difference is that the dosage of polysulfide rubber be respectively 80g, 60g, 40g,
20g, 0g, products therefrom are denoted as respectively: EL3-2, EL3-3, EL3-4, EL3-5, EL3-6.
Dynamic is carried out to product EL3-1, EL3-2, EL3-3, EL3-4, EL3-5, EL3-6 using dynamic thermomechanical analysis apparatus
Mechanical analysis, mode determination are chosen to be stretch mode, test frequency 1Hz, 5 DEG C/min of heating rate, temperature scanning range -30
℃—150℃.Test results are shown in figure 2.In figure, occur two in the dynamic mechanical map of EL3-1, EL3-2, EL3-3
Fissipation factor peak corresponds to polysulfide rubber and reacts the block copolymer generated and epoxy resin with epoxy resin in curing accelerator
The solidfied material that the lower anion autohemagglutination of DMP30 or so is formed, the two is incompatible, and there are phenomenon of phase separation, in the correspondence of low-temperature region
It reacts for polysulfide rubber and epoxy resin and generates the fissipation factor peak of block polymer, polysulfide rubber in block polymer
Content is more, and this fissipation factor peak the mobile to low temperature；Another fissipation factor peak of 120 DEG C or so appearance corresponds to epoxy
The resin cured product that anion autohemagglutination is formed under altax P30 effect.On the corresponding fissipation factor figure of EL3-4, EL3-5
Start the spike for a list only occur, shows that epoxy resin block polymer is consolidated with what epoxy resin anion autohemagglutination was formed at this time
Both compounds compatibility is preferable.The corresponding fissipation factor of EL3-5 spike is 0.62, is the highest loss factor values in cured product
Show that the compatibility of both the corresponding proportion polysulfide rubber block copolymer of EL3-5 and epoxy resin anion autopolymer is best,
Both polysulfide rubber block copolymer and epoxy resin anion autopolymer have been likely to form " sea-sea " structure.EL3-6 is corresponding
Fissipation factor figure only occur one it is unimodal, be epoxy resin anion autohemagglutination product fissipation factor peak, the corresponding temperature in this peak
Spending lower than the peak of tri- kinds of cured products of EL3-1, EL3-2, EL3-3 may be because epoxy resin is being sent out under the action of DMP30
Coagulating when epoxy resin anion autohemagglutination when gel fraction when raw anion autohemagglutination is not so good as to occur there are polysulfide rubber concerted reaction
Glue rate plays internal plasticization to system there are the more epoxy resin that ring-opening reaction does not occur in EL3-6 solidfied material,
Keep the fissipation factor peak of its fissipation factor peak ratio EL3-1, EL3-2, EL3-3 system low.
Stretching, bending, shearing, hardness, letter are carried out respectively to EL3-1, EL3-2, EL3-3, EL3-4, EL3-5, EL3-6
The Mechanics Performance Testings such as strutbeam impact strength comparison, result is as shown in Fig. 3~6 and table 1.
Fig. 3 can be seen that the polysulfide rubber component as soft segment is more, and the elongation at break of cured product is bigger, but
The tensile strength of solidfied material is lower at the same time, the block copolymer and epoxy resin anion that epoxy resin is formed in EL3-5
Both autopolymers compatibility is preferable, can be capable of forming " sea-sea " network structure of interpenetrating, its tensile strength is made to reach close
70Mpa。
Fig. 4 can be seen that the cured product shear strength highest of EL3-2, and close to 12Mpa, and EL3-5 shear strength is lower.
It can be seen that gradually reducing with polysulfide rubber dosage in Fig. 5, in cured product, polysulfide segment flexible is not
Disconnected to reduce, rigid epoxy resin ingredient gradually increases, and shore D hardness is continuously increased.
In Fig. 6 it can be seen that through the cured polysulfide rubber epoxy-resin systems of DMP30 with very excellent toughness, and with
The continuous reduction of polysulfide rubber dosage in cured product, the impact strength of cured product constantly reduce.
Number is that EL3-6 group is divided into DMP30 and directly solidifies the product that E51 epoxy resin obtains, and impact strength is small, and
Bending modulus and shore hardness are all higher, show apparent Brittleness.
As can be seen from Table 1 with the continuous reduction of polysulfide rubber component flexible in cured product system, rigid epoxy
When resin segment increases, the bending strength and modulus of system are continuously increased, and at the same time, bending strain then constantly reduces.EL3-5
Bending strength is 2 times of EL3-6, and bending modulus is higher by 500Mpa, and bending strain is approximately its 4 times, it is seen that polysulfide rubber is to ring
Clearly, this is equally due to the block copolymer that epoxy resin is formed in EL3-5 cured product to the toughening effect of oxygen resin
It is preferable with both epoxy resin anion autopolymers compatibility, " sea-sea " network structure of interpenetrating can be capable of forming.
Bending strength, bending modulus and the bending strain of 1 different component cured product of table.
Embodiment 7
50g polysulfide rubber LP-3,10gDMP30 are added in 100g epoxy resin E51.It is obtained according to method described in embodiment 1
To the cured product of polysulfide-rubber-modified epoxy, it is denoted as EL-0.
Embodiment 8
100g polysulfide rubber LP-3,8gDMP30 are added in 100g epoxy resin E51.It is obtained according to method described in embodiment 1
To the cured product of polysulfide-rubber-modified epoxy, it is denoted as EL-1.
Embodiment 9
100g polysulfide rubber LP-3,5gDMP30 are added in 100g epoxy resin E51.It is obtained according to method described in embodiment 1
To the cured product of polysulfide-rubber-modified epoxy, it is denoted as EL-2.
Embodiment 10
10gDMP30 in 100g epoxy resin E51.Polysulfide rubber modified epoxy tree is obtained according to method described in embodiment 1
The cured product of rouge, is denoted as EL-3.
The gelation time and reacting phenomenon of curing reaction in embodiment 7~10 are recorded, the results are shown in Table 3.
The dynamics presentation of 3 embodiment of table, 7~10 curing system
As can be seen from Table 3, when it is 10% that DMP30 dosage, which is greater than content of epoxy resin, system curing rate is too fast, acute
Strong heat release, obtained solidified sample picture are burnt, and when dosage is 5%, system curing rate is slower, and dosage is selected as 8%, instead
Answer process more steady.
The above is a preferred embodiment of the present invention, cannot limit the right model of the present invention with this certainly
It encloses, it is noted that for those skilled in the art, without departing from the principle of the present invention, may be used also
To make several improvement and variation, these, which improve and change, is also considered as protection scope of the present invention.
Claims (7)
1. a kind of polysulfide-rubber-modified epoxy, which is characterized in that the component including following parts by weight:
100 parts of epoxy resin；
20~100 parts of liquid polysulphide rubber；
4.8~12 parts of DMP30 (2,4,6-three (dimethylamino methyl) phenol).
2. polysulfide-rubber-modified epoxy according to claim 1, which is characterized in that the epoxy resin includes bis-phenol
Any one or more of A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, glycidyl ester type epoxy resin mix
Close object.
3. polysulfide-rubber-modified epoxy according to claim 1, which is characterized in that the liquid polysulphide rubber includes
In JLY-121, G-21, JLY-124, LP-23, JLY-1225, JLY-155, JLY-115, JLY-215, LP-3, G-4, LP-2
Any one or several mixtures.
4. polysulfide-rubber-modified epoxy according to claim 1, which is characterized in that the epoxy resin and liquid are poly-
The weight ratio of sulphur rubber is 10:2.
5. polysulfide-rubber-modified epoxy according to claim 1, which is characterized in that the DMP30 and epoxy resin
Weight ratio be 8:100.
6. the preparation method of described in any item polysulfide-rubber-modified epoxies according to claim 1~5, which is characterized in that
Include the following steps:
(1) liquid polysulfide rubber, epoxy resin, altax P30 are sufficiently stirred in a reservoir until system is mixed with glass bar
It closes uniform；
(2) mixture is stirred to 0.5-1.5h under vacuum conditions at room temperature with the bubble in removing system, after being disposed,
It is cast in Teflon mould, heating solidifies system sufficiently, and demoulding obtains the solidification of polysulfide-rubber-modified epoxy
Product.
7. preparation method according to claim 6, which is characterized in that the step of elevated cure includes: to put mold
Enter baking oven and be warming up to 25-50 DEG C, is warming up to 50-90 DEG C after keeping the temperature 12-24h, keeps the temperature 4-10h.
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| CN201811382221.4A CN109438926A (en) | 2018-11-20 | 2018-11-20 | A kind of polysulfide-rubber-modified epoxy and preparation method thereof |
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| CN201811382221.4A CN109438926A (en) | 2018-11-20 | 2018-11-20 | A kind of polysulfide-rubber-modified epoxy and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113072721A (en) * | 2021-04-09 | 2021-07-06 | 中国人民解放军海军工程大学 | Low-water-absorption anticorrosive coating epoxy resin matrix and preparation method thereof |
| CN113897031A (en) * | 2020-07-06 | 2022-01-07 | 合肥杰事杰新材料股份有限公司 | Thermosetting epoxy resin and preparation method thereof |
| CN118325290A (en) * | 2024-06-12 | 2024-07-12 | 太原理工大学 | Aviation-grade high-strength high-toughness epoxy composite material and preparation method thereof |
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| EP0547905A1 (en) * | 1991-12-19 | 1993-06-23 | Morton International Limited | Polysulfide-modified epoxy resins |
| CN1651542A (en) * | 2005-01-07 | 2005-08-10 | 武汉理工大学 | Epoxy resin binding agent for sand paper and its preparation method |
| CN106810999A (en) * | 2017-01-06 | 2017-06-09 | 南京安透可智能系统有限公司 | Two component fast dry type epoxide resin material |
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2018
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0547905A1 (en) * | 1991-12-19 | 1993-06-23 | Morton International Limited | Polysulfide-modified epoxy resins |
| CN1651542A (en) * | 2005-01-07 | 2005-08-10 | 武汉理工大学 | Epoxy resin binding agent for sand paper and its preparation method |
| CN106810999A (en) * | 2017-01-06 | 2017-06-09 | 南京安透可智能系统有限公司 | Two component fast dry type epoxide resin material |
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| MAJID A: "The Effect of Epoxy-Polysulfide Copolymer Curing Methods on Mechanical-Dynamical and Morphological Properties", 《IRAN. J. CHEM. CHEM. ENG.》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113897031A (en) * | 2020-07-06 | 2022-01-07 | 合肥杰事杰新材料股份有限公司 | Thermosetting epoxy resin and preparation method thereof |
| CN113897031B (en) * | 2020-07-06 | 2023-09-29 | 合肥杰事杰新材料股份有限公司 | Thermosetting epoxy resin and preparation method thereof |
| CN113072721A (en) * | 2021-04-09 | 2021-07-06 | 中国人民解放军海军工程大学 | Low-water-absorption anticorrosive coating epoxy resin matrix and preparation method thereof |
| CN118325290A (en) * | 2024-06-12 | 2024-07-12 | 太原理工大学 | Aviation-grade high-strength high-toughness epoxy composite material and preparation method thereof |
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