CN1059733A - Epoxy resin toughened preparation method - Google Patents
Epoxy resin toughened preparation method Download PDFInfo
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- CN1059733A CN1059733A CN 91108090 CN91108090A CN1059733A CN 1059733 A CN1059733 A CN 1059733A CN 91108090 CN91108090 CN 91108090 CN 91108090 A CN91108090 A CN 91108090A CN 1059733 A CN1059733 A CN 1059733A
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- unsaturated polyester
- epoxy
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- epoxy resin
- vinyl monomer
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a kind of epoxy resin toughened preparation method who contains the snappiness microgel.Unsaturated polyester and vinyl monomer directly carry out in situ polymerization in Resins, epoxy, make the dispersion of stable microgel in Resins, epoxy.
Description
The invention belongs to the multiphase polymer material field.
Engineering adhesive must have good Joint strength and toughness, but also must have the processing performance that is suitable for constructing.For example in the fabrication line of automobile, tackiness agent is carried with mechanical pump usually, therefore, requires tackiness agent to have lower viscosity.Splicing face is on the position perpendicular to ground under many situations, does not allow the tackiness agent trickling during curing.This just requires tackiness agent not only when mobile lower viscosity to be arranged, and can not trickle when static.
The tough epoxy tackiness agent that the invention provides a kind of single component, does not trickle, be characterized in having very high strength and toughness, have the viscosity that to carry with mechanical pump, and on surface, park for a long time at normal temperatures perpendicular to ground, when perhaps being heating and curing, do not trickle.This tackiness agent is made up of Resins, epoxy, snappiness microgel, reactive thinner, solidifying agent, curing catalyst, mineral filler, silane coupling agent etc.It is that the snappiness microgel combines with the suitable of mineral filler that the present invention is different from existing technical characterictic, tackiness agent is not only had satisfy bonding required bonding strength of engineering and toughness, and do not trickle when solidifying.
Because Resins, epoxy has highly cross-linked structure, though not toughness reinforcing epoxy adhesive has higher shearing resistance, toughness is good inadequately.The toughness of tackiness agent is normally weighed with stripping strength.In order to improve the toughness of epoxy adhesive, can in resin, introduce the rubber disperse phase.
The preparation rubber-toughened epoxy resin use fluid rubber usually, for example, with liquid nbr carboxyl terminal as toughner.In solidification process, be separated, form the rubber disperse phase.Fluid rubber exists as toughner and is separated not exclusively and problem such as the rubber phase crosslinking structure is imperfect.Present inventors etc. are in the paper of publishing [Chin.J, Polym.Sci., 1987,5(1), 76-80 and Angew.Makromol.Chem., 1989,171,65-77] the middle shortcoming that can overcome fluid rubber toughner with the snappiness microgel as the toughner of Resins, epoxy that proves.
The snappiness microgel is the rubber microballoon with crosslinking structure, and its second-order transition temperature is lower than-30 ℃.In Resins, epoxy, add the snappiness microgel, can improve the energy that material is absorbed greatly in destructive process, promptly improved the toughness of material widely.In addition, this crosslinked microballoon has very big specific surface area, and the interaction of the interaction between them and they and inorganic filler surface makes system have special rheological property.
For tackiness agent is not trickled, in system, must form the reversible physical structure.This texture ratio a little less than, under the effect of shearing force, take apart easily.Forming this physical structure method commonly used is to add solid packing in the tackiness agent of liquid state.The surface properties of solid packing and particle size distribution are for the decisive influence that is formed with of reversible physical structure.Japanese Patent [openly specially permit clear 63(1988)-156,817] has used the white carbon black handled through hydrophobic and silica powder as filler, and preparation has good thixotropic epoxy adhesive.
The present invention is different from the prior art part and is to adopt the snappiness microgel to combine with mineral filler, the character that system is had when static, do not trickle, and mineral filler needn't be passed through special surface treatment.
The Resins, epoxy that epoxy adhesive of the present invention adopted is the resin that has two above epoxy group(ing) in the molecule, comprises bisphenol A type epoxy resin, novolac epoxy, polyprotonic acid glycidyl ester type epoxy resin.This based epoxy resin can use separately, also can several mixed with resin use, so that obtain required performance.
The snappiness microgel that epoxy adhesive of the present invention adopted is the multipolymer of unsaturated polyester and vinyl monomer, and its particle diameter is in 50 millimicrons to 2000 millimicrons scopes.Second-order transition temperature is in-30 ℃ to-70 ℃ scopes.The umber of contained snappiness microgel can change in 5 parts to 50 parts scopes in per 100 parts (weight, down with) Resins, epoxy, and the over-all properties of tackiness agent is better in 10 parts to 30 parts scopes.
The dispersion of preparation snappiness microgel in Resins, epoxy, can be according to the method that is adopted among aforementioned paper of having published of present inventor or the Chinese patent publication number CN1033062A, be about to unsaturated polyester and vinyl monomer and carry out emulsion copolymerization, then resulting microgel is separated, make solution, mix with Resins, epoxy again through behind the purifying, remove at last and desolvate.
The invention provides a kind of more easy method for preparing the dispersion of snappiness microgel in Resins, epoxy, i.e. in situ polymerization method.The in situ polymerization method is unsaturated polyester and directly polymerization in Resins, epoxy of vinyl monomer, the preparation dispersion system.Compare with emulsion polymerisation process, can save microgel is separated from emulsion, make solution, mix and remove the step of complexity such as desolvating again with Resins, epoxy.
The technology for preparing the two-phase Polymer Systems by in situ polymerization is known, and for example United States Patent (USP) 4,708,996 and the method that proposed of European patent 137,634.In order to make disperse phase is the elastomerics microballoon with crosslinking structure, adds the polyfunctional group vinyl monomer usually, as Vinylstyrene or glycol methacrylate as linking agent.The control ratio of in situ polymerization is difficult in the presence of linking agent, and the gelation of whole polymkeric substance takes place easily.
Different with existing technology, dispersion, the disperse phase of microgel of the present invention in Resins, epoxy is the multipolymer of unsaturated polyester and vinyl monomer.Here unsaturated polyester is the linking agent of snappiness microgel, and it plays the effect of dispersion stabilizer simultaneously again.So, the very easy control of unsaturated polyester of the present invention and the vinyl monomer in situ polymerization in Resins, epoxy, and resulting dispersion is very stable.
The microgel of making by unsaturated polyester and vinyl monomer in situ polymerization, with add multitube by vinyl monomer and can roll into a ball the resulting microgel of alkene class linking agent copolymerization and compare, other has tangible characteristics, only some participates in copolymerization to two keys when in situ polymerization in the unsaturated polyester ester molecule, do not participate in that part of pair of key of polymeric when epoxy resin cure can with the amido generation addition reaction in the solidifying agent, therefore increased chemical bond combination firm in the two-phase interface.
By the prepared dispersion system of microgel in Resins, epoxy of in situ polymerization method of the present invention, except that being used for tackiness agent, can also be used for coating, matrix material and cast material etc.
Vinyl monomer in the snappiness microgel that epoxy adhesive of the present invention adopted, their polymkeric substance are insoluble in the Resins, epoxy, and second-order transition temperature is lower than-30 ℃.The monomer that can adopt comprises: divinyl, isoprene, chloroprene, butyl acrylate, 2-EHA etc.These monomers can use separately, also can carry out copolymerization with other vinyl monomers.
Unsaturated polyester in the snappiness microgel that epoxy adhesive of the present invention adopted is obtained by unsaturated dibasic acid or acid anhydrides and dibasic alcohol polycondensation.Diprotic acid that can adopt or acid anhydrides comprise maleic acid, MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE, propylenedicarboxylic acid etc., and they can use separately, also can several unsaturated acid or acid anhydrides mixing use.Also can introduce saturated diprotic acid or acid anhydrides, carry out copolycondensation as hexanodioic acid, Succinic Acid, Tetra hydro Phthalic anhydride etc.The dibasic alcohol that is adopted can represent with general formula HO-R-OH, wherein-and R-is the bivalent hydrocarbon radical that contains 2 to 12 carbon atoms, preferably uses the dibasic alcohol that contains 3 to 10 carbon atoms.The number-average molecular weight of unsaturated polyester is in 500 to 5000 scopes, and is better in 1000 to 3000 scopes.Has a carboxyl at least in the molecule of average each unsaturated polyester.
The unsaturated polyester in the snappiness microgel that epoxy adhesive of the present invention adopted and the weight ratio of vinyl monomer were selected in the scope as required at 3: 100 to 50: 100.Both ratios are lower than at 3: 100 o'clock, because the unsaturated polyester ester content is too low, and the dispersion instability of resulting microgel in Resins, epoxy.Both ratios were greater than 50: 100 o'clock, because vinyl monomer content is too low, microgel reduces the toughening effect of Resins, epoxy.
The in situ polymerization of the dispersion of snappiness microgel in Resins, epoxy that is adopted among preparation the present invention is the radical-type polymerization reaction.In order to make unsaturated polyester play stabilization, adding before the vinyl monomer, earlier unsaturated polyester is dissolved in the Resins, epoxy and heating, make carboxyl in the unsaturated polyester and the epoxy reaction in the Resins, epoxy.Heated one hour down at 170 ℃, can finish this esterification.This kind in situ polymerization can be adopted the free radical type initiator, and they comprise azo isobutyronitrile, benzoyl peroxide, t-butylperoxyl benzoate, two 2,4 dichlorobenzoyl peroxide, two cumyl superoxide etc.The temperature of in situ polymerization should be controlled in 50 ℃ to the 160 ℃ scopes, preferably is controlled in 70 ℃ to the 120 ℃ scopes.
Epoxy adhesive of the present invention adopts Dicyanodiamide as solidifying agent, and the tackiness agent that is mixed with is long storage at normal temperatures.In per 100 parts of Resins, epoxy, the consumption of Dicyanodiamide can change in 6 parts to 12 parts scopes, preferably 8 parts to 10 parts.Can add promotor in order to improve curing speed.The promotor that can adopt comprises: glyoxal ethyline, 2-ethyl-4-methylimidazole, imidazoles-cobalt chloride complex compound, imidazoles-cupric chloride complex compound, 1-rubigan-3,3-dimethyl urea, tolylene diisocyanate-dimethylamine affixture, toluene di-iso-cyanide ester-diethylamine affixture.
The mineral filler that epoxy adhesive of the present invention adopted comprises that white carbon black and a kind of median size are less than 10 microns mineral filler.In per 100 parts of Resins, epoxy, the consumption of white carbon black can change in 1 part to 10 parts scope.The mineral filler that can adopt comprises wollastonite powder, silica powder, Paris white, aluminum oxide powder, kaolin powder etc.The consumption of mineral filler can change in 25 parts to 200 parts scopes as required.
In order to regulate the viscosity of tackiness agent, tackiness agent of the present invention can the additive reactive thinner.This class thinner is the low-viscosity (mobile) liquid that contains epoxy group(ing) in a kind of molecule, comprising butylglycidyl ether, phenyl glycidyl ether, octyl glycidyl ether, butyleneglycol glycidyl ether, glycerine glycidyl ether etc.In per 100 parts of Resins, epoxy, the consumption of reactive thinner can change in 5 parts to 30 parts scopes as required.
The adoptable coupling agent of epoxy adhesive of the present invention has silane KH550 and KH560, and their consumption can change in 0.1 part to 3 parts scope as required.
To further specify characteristics of the present invention by embodiment below.
Embodiment one
With MALEIC ANHYDRIDE 216 grams and 1,2-propylene glycol 152 grams place in the reactor, carry out polycondensation under the protection of argon gas.The fs of reaction kept three hours in 100 ℃ to 130 ℃ scopes; The subordinate phase of reaction kept five hours at 150 ℃.Obtain product 330 grams, be called the UP-1 unsaturated polyester.
E51 Resins, epoxy 1000 grams, UP-1 unsaturated polyester 40 grams are placed in the reactor.Under argon shield, stir and be heated to 170 ℃.Under this temperature, keep one hour postcooling to room temperature.Add 2-EHA 160 grams, azo isobutyronitrile 1 gram.Under argon shield, stir and make reactants dissolved become clear solution, be heated to 100 ℃ and under this temperature, kept six hours.Under 20 mmhg vacuum, be warming up to 160 ℃, remove unreacted monomer.Obtain milky product 1180 grams, be called M
1Toughened resin.Record M by the distribution of particle sizes instrument
1The mean diameter of microgel is 0.45 micron in the toughened resin.
Press following composition preparating mixture:
M
1Toughened resin 120 grams
Octyl glycidyl ether 20 grams
Dicyanodiamide 10 grams
2-ethyl-4-methylimidazole 0.5 gram
Wollastonite powder (crossing 1250 mesh sieves) 100 grams
No. 2 white carbon blacks (chemical plant, Shenyang) 5 grams
KH560 coupling agent 1 gram
Said mixture promptly becomes tackiness agent after triple-roller mill grinds.The tackiness agent that will be of a size of 1 * 10 * 100 millimeters places on the steel plate, and steel plate was placed 30 minutes perpendicular to ground, and does not move the position of adhesive tape.The above-mentioned steel plate that has adhesive tape perpendicular in the baking oven, is warming up to 180 ℃ and kept 30 minutes under this temperature, adhesive tape has cured, but profile and position all do not change.With the test piece of above-mentioned tackiness agent bonded steel, heating made adhesive solidification in 30 minutes under 180 ℃, and recording shearing resistance by standard GB 7124-86 is 31 megapascal (MPa)s, and recording T type stripping strength by standard GB 2791-81 is 2.5 thousand Newton/meter.
Embodiment two
MALEIC ANHYDRIDE 228 grams and 1,6 one hexylene glycol, 236 grams are placed reactor, under argon shield, carry out polycondensation.The fs of reaction kept three hours in 100 ℃ to 130 ℃ scopes; The subordinate phase of reaction kept five hours down at 155 ℃.Obtain product 330 grams, be called the UP-2 unsaturated polyester.
E51 Resins, epoxy 1000 gram and UP-2 unsaturated polyester 60 grams are placed in the reactor stirring and be heated to 170 ℃ under argon shield.Under this temperature, keep one hour postcooling to room temperature.Add 2-EHA 240 grams, azo isobutyronitrile 1 gram.Under argon shield, stir and make reactants dissolved become clear solution, be heated to 100 ℃ and under this temperature, kept six hours.Under 20 mmhg vacuum, be warming up to 160 ℃, remove unreacted monomer.Obtain milky product 1280 grams, be called M
2Toughened resin.Record M by the distribution of particle sizes instrument
2The mean diameter of microgel is 0.86 micron in the toughened resin.
Press following composition preparating mixture:
M
2Toughened resin 130 grams
Octyl glycidyl ether 15 grams
Dicyanodiamide 10 grams
2-ethyl-4-methylimidazole 0.5 gram
Wollastonite powder (crossing 1250 mesh sieves) 50 grams
No. 2 white carbon blacks (chemical plant, Shenyang) 5 grams
KH560 coupling agent 1 gram
Said mixture promptly becomes tackiness agent after triple-roller mill grinds.The test of tackiness agent and standard and embodiment are together.The shearing resistance that records is 33 megapascal (MPa)s, and T type stripping strength is 3.2 thousand Newton/meter.
Reference examples
Press following composition preparating mixture:
E51 Resins, epoxy 100 grams
Octyl glycidyl ether 15 grams
Dicyanodiamide 10 grams
2-ethyl-4-methylimidazole 0.5 gram
Wollastonite powder (crossing 1250 mesh sieves) 50 grams
No. 2 white carbon blacks (chemical plant, Shenyang) 5 grams
KH560 coupling agent 1 gram
Said mixture promptly becomes tackiness agent after triple-roller mill grinds.The test of tackiness agent and standard and embodiment are together.The shearing resistance that records is 27 megapascal (MPa)s, and T type stripping strength is 0.9 thousand Newton/meter.
Claims (6)
1, a kind ofly prepares epoxy resin toughened method, it is characterized in that vinyl monomer and unsaturated polyester directly carry out the original place copolymerization in Resins, epoxy, obtain the stabilising dispersions of microgel in Resins, epoxy.
2, according to the epoxy resin toughened method of the described preparation of claim 1, it is characterized in that the polymkeric substance of the vinyl monomer that adopted can not be dissolved in the Resins, epoxy, their second-order transition temperature is-30 ℃～-70 ℃.
3, according to the epoxy resin toughened method of the described preparation of claim 1, it is characterized in that the unsaturated polyester that is adopted is the polycondensate of unsaturated dibasic acid or its acid anhydrides and dibasic alcohol, in the dibasic alcohol molecule, contain 2-12 carbon atom, preferably use the dibasic alcohol that contains 3-10 carbon atom, the number-average molecular weight of unsaturated polyester is 500-5000, have a carboxyl at least in average each unsaturated polyester ester molecule, the weight ratio of unsaturated polyester and vinyl monomer is 3: 100 to 50: 100.
4,, it is characterized in that the optimum number average molecular weight of unsaturated polyester is 1000-3000 according to the number-average molecular weight of the described unsaturated polyester of claim 3.
5, according to the epoxy resin toughened method of the described preparation of claim 1, employed radical initiator is azo isobutyronitrile, benzoyl peroxide, t-butylperoxyl benzoate, two 2 when it is characterized in that unsaturated polyester and vinyl monomer carry out in situ polymerization, 4-dichloro-benzoyl superoxide, two cumene peroxide, polymeric reaction temperature are 50 ℃-160 ℃.
6,, it is characterized in that best polymeric reaction temperature is 70 ℃-120 ℃ according to the described polymeric reaction temperature of claim 5.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90103787 CN1016698B (en) | 1990-05-28 | 1990-05-28 | Single component, the tough epoxy tackiness agent that does not trickle |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90103787 Division CN1016698B (en) | 1990-05-28 | 1990-05-28 | Single component, the tough epoxy tackiness agent that does not trickle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1059733A true CN1059733A (en) | 1992-03-25 |
| CN1020618C CN1020618C (en) | 1993-05-12 |
Family
ID=4878245
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90103787 Expired CN1016698B (en) | 1990-05-28 | 1990-05-28 | Single component, the tough epoxy tackiness agent that does not trickle |
| CN 91108090 Expired - Lifetime CN1020618C (en) | 1990-05-28 | 1991-11-02 | Method for preparation of toughened epoxy resin |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90103787 Expired CN1016698B (en) | 1990-05-28 | 1990-05-28 | Single component, the tough epoxy tackiness agent that does not trickle |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN1016698B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103642021A (en) * | 2013-12-07 | 2014-03-19 | 哈尔滨理工大学 | Nitrogen-containing epoxy resin flexibilizer and preparation method thereof |
| CN107586376A (en) * | 2017-07-31 | 2018-01-16 | 中国林业科学研究院林业新技术研究所 | A kind of preparation method of the polynary amine epoxy curing agent of flame retardant type myrcenyl |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1056402C (en) * | 1996-01-31 | 2000-09-13 | 中国科学院化学研究所 | Anti-flow pasty epoxy adhesive |
| CN101157836B (en) * | 2007-11-08 | 2010-05-19 | 武汉市科达云石护理材料有限公司 | Red-green dry-pasting glue and preparation technique thereof |
| CN101608105B (en) * | 2008-06-17 | 2012-08-22 | 上海得荣电子材料有限公司 | Adhesive for packaging smart card module |
| CN101538397B (en) * | 2009-03-09 | 2013-02-13 | 珠海全宝电子科技有限公司 | Epoxy resin composition, glue film made of same and preparation method |
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| CN102618201B (en) * | 2012-01-13 | 2013-09-18 | 十堰福波新材料有限公司 | Enhanced vibration-proof adhesive with following property and preparation method thereof |
| CN102660875B (en) * | 2012-05-22 | 2016-06-15 | 厦门市豪尔新材料股份有限公司 | A kind of carbon fiber processing polymeric membrane |
| CN102827565A (en) * | 2012-09-19 | 2012-12-19 | 三友（天津）高分子技术有限公司 | One-component epoxy adhesive for automobiles and preparation method thereof |
| CN106753124A (en) * | 2016-12-07 | 2017-05-31 | 安徽艾蒂贝生物有限公司 | A kind of stone material special epoxy resin adhesive |
| CN107142054B (en) * | 2017-06-29 | 2018-12-07 | 杭州之江新材料有限公司 | A kind of Impact-resistant epoxy adhesive adhesive composition and preparation method thereof |
-
1990
- 1990-05-28 CN CN 90103787 patent/CN1016698B/en not_active Expired
-
1991
- 1991-11-02 CN CN 91108090 patent/CN1020618C/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103642021A (en) * | 2013-12-07 | 2014-03-19 | 哈尔滨理工大学 | Nitrogen-containing epoxy resin flexibilizer and preparation method thereof |
| CN103642021B (en) * | 2013-12-07 | 2016-04-27 | 哈尔滨理工大学 | Nitrogen-containing epoxy thermoset toughner and preparation method thereof |
| CN107586376A (en) * | 2017-07-31 | 2018-01-16 | 中国林业科学研究院林业新技术研究所 | A kind of preparation method of the polynary amine epoxy curing agent of flame retardant type myrcenyl |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1046546A (en) | 1990-10-31 |
| CN1020618C (en) | 1993-05-12 |
| CN1016698B (en) | 1992-05-20 |
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