CN1376737A - Epoxy resin toughened by composite rubber/clay toughening agent and its preparing process - Google Patents
Epoxy resin toughened by composite rubber/clay toughening agent and its preparing process Download PDFInfo
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- CN1376737A CN1376737A CN 01110031 CN01110031A CN1376737A CN 1376737 A CN1376737 A CN 1376737A CN 01110031 CN01110031 CN 01110031 CN 01110031 A CN01110031 A CN 01110031A CN 1376737 A CN1376737 A CN 1376737A
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Abstract
A toughened epoxy resin is prepared from epoxy resin as basic material, composite rubber elastomer/clay material as toughening agent, solidifying agent and promoter.
Description
The invention belongs to the chemical industry technology, relate to a kind of increase flexible Resins, epoxy and preparation method thereof.
Resins, epoxy has that bonding force is strong, processibility good and excellent properties such as shrinking percentage is little, be to use one of maximum thermosetting resin at present, but Resins, epoxy is because of the cross-linking density height, and fragility is very big, and its fatigue strength and impelling strength are difficult to satisfy the demand for development of modern industrial technology.Four during the last ten years, and the Research on Toughening of Resins, epoxy is the content that domestic and international industry member and scientific research field are extremely paid close attention to always.The most commonly used and effective so far epoxy resin roughening method still is that rubber elastomer is toughness reinforcing, toughness improves a lot after adding rubber phase in the Resins, epoxy, but because intensity, rigidity and the resistance toheat of rubber self are lower, it is rubber toughened when epoxy toughness is increased substantially, make intensity, modulus and the resistance toheat of material that very big loss be arranged, so this method have its weak point.
PLS (Polymer Layered Silicate, polyalcohol intercalation layered silicate) is a kind of novel method for preparing organic-inorganic nanocomposite that occurred in recent years.With clay and elastomer polymer blend and when being scattered in the elastomerics with the sheet form of nanometer thickness, the intensity of elastomer polymer and modulus can obtain the raising of several times even tens times, elastomerics still can keep higher tension set and impact resistance simultaneously, rubber elastomer after clay strengthens in other words, strength and stiffness improve, and its toughness and toughened ability are not subjected to tangible negative impact.
The objective of the invention is, the elastomeric technology of clay Reinforced Rubber is combined with the technology of rubber-toughened epoxy resin, a kind of over-all properties better toughness epoxide resin material and its preparation method are provided.
Technical scheme of the present invention is: a kind of by rubber/toughness reinforcing Resins, epoxy of clay composite toughing agent, with Resins, epoxy is base-material, with the compound material of rubber elastomer/clay is toughner, and add solidifying agent and promotor and constitute, it is characterized in that, rubber/clay composite toughing agent is combined by chemical bond with rubber by organized clay and forms, clay dispersion is in rubber external phase, and combine with rubber by chemical bond, the content of its medium clay soil is 5～30Wt% of composite toughing agent, and the weight of the compound material toughner of rubber/clay is 10～30% of Resins, epoxy.
A kind of method for preparing by the toughness reinforcing Resins, epoxy of rubber/clay composite toughing agent is characterized in that,
(1) adopt one of following method preparation rubber/clay composite toughing agent,
A, organic clay and rubber are joined in the reactor that has stirring and heating unit simultaneously, here employed clay is for handling the organophilic clay that obtains by polynite is organised, the preparation method is the industrial method for preparing organic clay that generally adopts, must have the active function groups that can react with rubber on the employed intercalator, comprise epoxy-functional, hydroxyl, carboxyl, amido or cyano group, the granularity of clay is 10～20 μ m, the amount that adds clay is 5～30Wt% of toughner total amount, employed rubber is that polarity is bigger, the rubber elastomer CTBN or the ATBN that have active group and can dissolve each other with Resins, epoxy, temperature of reaction kettle is risen to 100 ℃, mixing under this temperature more than 40 minutes, in reactor, be added dropwise to the tertiary amine or imidazoles or the piperidines catalyzer that account for toughner weight 1～2% then, be warming up to 130～140 ℃ and react again more than 30 minutes, obtain rubber/clay nano composite toughing agent;
B, with the rubber of 5～30 parts organophilic clays and 100 parts under 80～100 ℃ the temperature mixing more than 1 hour on the three-roller open mill, obtain rubber/clay composite toughing agent, employed here organic clay and rubber are with identical described in the top A;
(2) rubber/clay composite toughing agent of 10～30% is joined in the Resins, epoxy, mixed 5～15 minutes, make rubber fully dissolving in Resins, epoxy, the epoxy hardener that adds amine, acid anhydrides or other type then, when using acid anhydride type curing agent, also need add the tertiary amines promotor that accounts for weight epoxy 1～2%, mix, pour into mould behind the vacuumize degassing bubble, condition according to the rules is cured, and obtains by rubber/toughness reinforcing Resins, epoxy of clay composite toughing agent.
Advantage of the present invention is: the present invention proposes a kind of new thought, existing two kinds of technology are combined, improve on original composite system basis, obtain the better tough epoxy resin of new generation of performance.Because the cost of clay own is low, the raw materials cost of material does not increase; After adding a small amount of clay in the elastomerics, rheological property and processing characteristics change little, therefore can use original processing technology, do not increase difficulty of processing and cost.Separately carry out with the preparation of the compound material of rubber/clay with to the toughness reinforcing of epoxy, can make things convenient for final user's use.
Description of drawings.
Fig. 1 is the structure iron of rubber-toughened epoxy resin.External phase is Resins, epoxy among the figure, and disperse phase is a rubber.
Fig. 2 is rubber/epoxy resin toughened structure iron of clay composite toughing agent.External phase is epoxy among the figure, and the dispersive ball is a rubber, and the white line that is scattered in the rubber is the cross section of clay gall.
The below is described in further details the present invention. Tough epoxy resin material of the present invention is take epoxy resin as base-material, take rubber elastomer/clay compound material as flexibilizer, and adds curing agent and promoter consists of.
Clay in the composite rubber/clay toughening agent is by imvite being carried out the organoclay that organic-treating obtains, the method of organising is the industrial method for preparing organic clay that generally adopts, just to select special intercalator, thereby between argillic horizon, introduce can with the active group of rubber reaction, the such organoclay not only compatibility with rubber molecule is good, can be dispersed in the rubber, but also be fixed in the rubber by forming chemical bond with rubber. The content of composite rubber/clay toughening agent medium clay soil is 5～30Wt% of flexibilizer total amount. Spendable rubber has CTBN, and the ATBN isopolarity is large, with active group and the rubber elastomer that can dissolve each other with epoxy resin. When epoxy resin toughened, the addition of composite rubber/clay toughening agent is 10～30% of weight epoxy. Employed curing agent is all kinds of curing agent that are applicable to epoxy, and such as acid anhydrides, amine, tertiary amine, boride and latent curing agent etc., promoter can be used tertiary amines, imidazoles.
Use the epoxy resin toughened method of composite rubber/clay toughening agent to be, with organoclay and at a certain temperature blend of rubber, the purpose that improves temperature is to reduce rubber viscosity, makes clay be easy to disperse. In mixed process, the affinity interaction on rubber and the clay between organic intercalation agent impels rubber molecule to be inserted between argillic horizon, obtains rubber/clay intercalation mixture. Group reacts in active group under the effect of heat or tertiary amine catalyst in the initiation clay and the rubber, rubber further is inserted between argillic horizon in this process, final clay is scattered in the rubber with the form of nanoscale twins, and and between rubber with chemical bonds, Here it is the nano combined material of needed rubber/clay. This compound material is joined in the epoxy resin, stirring makes rubber fully dissolving in epoxy resin, then adds curing agent and promoter, pours into mould behind the vacuumize degassing bubble, under certain condition of cure, solidify, obtain by the toughness reinforcing epoxy resin of rubber/clay compound material.
Because rubber and epoxy two are separated in solidification process, rubber-toughened epoxy resin is generally the rubber microballoon and is scattered in two-phase sea-island structure in the epoxy continuous phase, as shown in Figure 1. With the rubber/clay compound material to the material structure that epoxy carries out obtaining after toughness reinforcing be: clay dispersion is in rubber, and the rubber of parcel clay is scattered in the epoxy resin, with microspheroidal again as shown in Figure 2. The strength and modulus that exists because of clay in the rubber phase improves a lot, thereby corrected the too low shortcoming of simple rubbery intensity and rigidity, remedy to a certain extent the simple deficiency that causes when rubber toughened the epoxy resin strength and stiffness to descend, obtained all good epoxy-resin systems of toughness and intensity.
Embodiment.
Table 1 has been listed the mechanical property of using the toughness reinforcing Resins, epoxy of CTBN/ clay composite toughing agent, and with compare without the toughness reinforcing Resins, epoxy of toughness reinforcing and simple rubber CTBN.
Employed rubber is liquid nbr carboxyl terminal in the prescription, and its molecular weight is 3700, and the content of acrylonitrile unit is 17%.Employed organophilic clay granularity is 10-20 μ m, have can with the epoxide group of the end carboxyl reaction of rubber.
The preparation technology of material is among the embodiment 1: the clay of 30g is joined in the 150g rubber, mixed 1 hour at 100 ℃, the dimethyl benzylamine that adds 0.2g then is warming up to 130 ℃, remix reaction 1 hour, the mixture that obtains joins in the 1000g Resins, epoxy, add solidifying agent and promotor simultaneously, mix, vacuumize except that behind the bubble, pour into mould, solidified 4 hours down at 160 ℃.
The preparation technology of material is among the embodiment 2: the clay of 50g is joined in the 150g rubber, 100 ℃ were descended mixing 1 hour on three-roller open mill, the mixture that obtains is joined in the 1000g Resins, epoxy, add solidifying agent and promotor simultaneously, mix, vacuumize except that behind the bubble and pour into mould, solidified 4 hours down at 160 ℃.
Table 1 is without mechanical property toughness reinforcing, simple rubber toughened and that use the toughness reinforcing Resins, epoxy of rubber/clay composite toughing agent.
| Not toughness reinforcing | Rubber toughened merely | Embodiment 1 | Embodiment 2 | ||
| Prescription | Epoxy 618 | ????100 | ????100 | ????100 | ????100 |
| Rubber CTBN | ????0 | ????15 | ????15 | ????15 | |
| Organic clay | ????0 | ????0 | ????3 | ????5 | |
| Methyl tetrahydrochysene acid anhydrides | ????80 | ????80 | ????80 | ????80 | |
| Dimethyl benzylamine | ????2 | ????2 | ????2 | ????2 | |
| Performance | Flexural strength (MPa) | ????139.9 | ????126.8 | ????136.9 | ????138.6 |
| Modulus in flexure (GPa) | ????2.71 | ?????2.59 | ????2.81 | ????3.01 | |
| Shock strength (KJ/m 2) | ????8.69 | ????14.13 | ????13.57 | ????12.48 | |
Result from table finds out that when toughness reinforcing, although resistance to impact shock improves, intensity and modulus all decrease with gum, but common when toughness reinforcing with the compound material of rubber/clay, when resistance to impact shock improved, the intensity reduction was less, and modulus also has a little raising.As seen, using the compound material of rubber/clay toughness reinforcing is to remedy rubbery intensity and the low shortcoming of rigidity, obtains the effective ways of the good epoxy-resin systems of over-all properties.
Claims (2)
1, a kind of by rubber/toughness reinforcing Resins, epoxy of clay composite toughing agent, with Resins, epoxy is base-material, with the compound material of rubber elastomer/clay is toughner, and add solidifying agent and promotor and constitute, it is characterized in that, rubber/clay composite toughing agent is combined by chemical bond with rubber by organized clay and forms, clay dispersion is in rubber external phase, and combine with rubber by chemical bond, the content of its medium clay soil is 5～30Wt% of composite toughing agent, and the weight of the compound material toughner of rubber/clay is 10～30% of Resins, epoxy.
2, a kind of preparation be is characterized in that by the method for the toughness reinforcing Resins, epoxy of rubber/clay composite toughing agent,
(1) adopt one of following method preparation rubber/clay composite toughing agent,
A, organic clay and rubber are joined in the reactor that has stirring and heating unit simultaneously, here employed clay is for handling the organophilic clay that obtains by polynite is organised, the preparation method is the industrial method for preparing organic clay that generally adopts, must have the active function groups that can react with rubber on the employed intercalator, comprise epoxy-functional, hydroxyl, carboxyl, amido or cyano group, the granularity of clay is 10～20 μ m, the amount that adds clay is 5～30Wt% of toughner total amount, employed rubber is that polarity is bigger, the rubber elastomer CTBN or the ATBN that have active group and can dissolve each other with Resins, epoxy, temperature of reaction kettle is risen to 100 ℃, mixing under this temperature more than 40 minutes, in reactor, be added dropwise to the tertiary amine or imidazoles or the piperidines catalyzer that account for toughner weight 1～2% then, be warming up to 130～140 ℃ and react again more than 30 minutes, obtain rubber/clay nano composite toughing agent;
B, with the rubber of 5～30 parts organophilic clays and 100 parts under 80～100 ℃ the temperature mixing more than 1 hour on the three-roller open mill, obtain rubber/clay composite toughing agent, employed here organic clay and rubber are with identical described in the top A;
(2) rubber/clay composite toughing agent of 10～30% is joined in the Resins, epoxy, mixed 5～15 minutes, make rubber fully dissolving in Resins, epoxy, the epoxy hardener that adds amine, acid anhydrides or other type then, when using acid anhydride type curing agent, also need add the tertiary amines promotor that accounts for weight epoxy 1～2%, mix, pour into mould behind the vacuumize degassing bubble, condition according to the rules is cured, and obtains by rubber/toughness reinforcing Resins, epoxy of clay composite toughing agent.
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| CN 01110031 CN1132879C (en) | 2001-03-27 | 2001-03-27 | Epoxy resin toughened by composite rubber/clay toughening agent and its preparing process |
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| CN 01110031 CN1132879C (en) | 2001-03-27 | 2001-03-27 | Epoxy resin toughened by composite rubber/clay toughening agent and its preparing process |
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| CN1376737A true CN1376737A (en) | 2002-10-30 |
| CN1132879C CN1132879C (en) | 2003-12-31 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106118569A (en) * | 2016-07-14 | 2016-11-16 | 中国船舶工业系统工程研究院 | The epoxy adhesive that a kind of end tertiary amine groups polybutadiene rubber is toughness reinforcing |
| CN109096971A (en) * | 2018-07-10 | 2018-12-28 | 西安贝克电子材料科技有限公司 | A kind of high cohesive force composition epoxy resin |
| CN109749131A (en) * | 2017-11-01 | 2019-05-14 | 中国石油化工股份有限公司 | Modified halloysite nanotubes and preparation method thereof and epoxy resin nano composites and its application |
| CN112679908A (en) * | 2019-10-17 | 2021-04-20 | 中国石油化工股份有限公司 | Prepreg toughening material, high-toughness prepreg and preparation method thereof |
-
2001
- 2001-03-27 CN CN 01110031 patent/CN1132879C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106118569A (en) * | 2016-07-14 | 2016-11-16 | 中国船舶工业系统工程研究院 | The epoxy adhesive that a kind of end tertiary amine groups polybutadiene rubber is toughness reinforcing |
| CN106118569B (en) * | 2016-07-14 | 2019-02-19 | 中国船舶工业系统工程研究院 | A kind of epoxy adhesive of end tertiary amine groups polybutadiene rubber toughening |
| CN109749131A (en) * | 2017-11-01 | 2019-05-14 | 中国石油化工股份有限公司 | Modified halloysite nanotubes and preparation method thereof and epoxy resin nano composites and its application |
| CN109749131B (en) * | 2017-11-01 | 2020-12-18 | 中国石油化工股份有限公司 | Modified halloysite nanotube and preparation method thereof, and epoxy resin nanocomposite and application thereof |
| CN109096971A (en) * | 2018-07-10 | 2018-12-28 | 西安贝克电子材料科技有限公司 | A kind of high cohesive force composition epoxy resin |
| CN109096971B (en) * | 2018-07-10 | 2021-03-19 | 西安贝克电子材料科技有限公司 | High-adhesion epoxy resin composition |
| CN112679908A (en) * | 2019-10-17 | 2021-04-20 | 中国石油化工股份有限公司 | Prepreg toughening material, high-toughness prepreg and preparation method thereof |
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| CN1132879C (en) | 2003-12-31 |
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Owner name: BEIJING INSTITUTE OF AERONAUTICAL MATERIALS, CHINA Free format text: FORMER NAME: BEIJING AVIATION MATERIAL INST., CHINA AVIATION INDUSTRY NO.1 GROUP CORP. Owner name: BEIJING AVIATION MATERIAL INST., CHINA AVIATION IN Free format text: FORMER NAME: BEIJING AVIATION MATERIAL INST. |
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Address after: 100095 mailbox 81, Beijing City Patentee after: AVIC BEIJING INSTITUTE OF AERONAUTICAL MATERIALS Address before: 100095 mailbox 81, Beijing City Patentee before: Beijing Institute of aeronautical materials, China aviation industry first Group Corporation Address after: 100095 mailbox 81, Beijing City Patentee after: Beijing Institute of aeronautical materials, China aviation industry first Group Corporation Address before: 100095 mailbox 81, Beijing City Patentee before: Beijing Institute of Aeronautical Materials |
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Assignee: GUODIAN UNITED POWER TECHNOLOGY (CHIFENG) Co.,Ltd. Assignor: AVIC BEIJING INSTITUTE OF AERONAUTICAL MATERIALS Contract record no.: 2011990000126 Denomination of invention: Epoxy resin toughened by composite rubber/clay toughening agent and its preparing process Granted publication date: 20031231 License type: Exclusive License Open date: 20021030 Record date: 20110307 |
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