CN101012301A - Epoxy acrylic resin and preparing method thereof - Google Patents
Epoxy acrylic resin and preparing method thereof Download PDFInfo
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- CN101012301A CN101012301A CN 200610157635 CN200610157635A CN101012301A CN 101012301 A CN101012301 A CN 101012301A CN 200610157635 CN200610157635 CN 200610157635 CN 200610157635 A CN200610157635 A CN 200610157635A CN 101012301 A CN101012301 A CN 101012301A
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Abstract
The invention discloses an epoxy acrylic acid resin and making method modified by multi-carbon straight-chain saturated fat diacid, which comprises the following parts: 50-75% epoxy resin, 10-30% straight-chain saturated fat diacid with main chain carbon number between 6 and 10, 10-30% acrylic acid, 0.3-0.5% catalyst, wherein the materials proceed ring-opening chain-extending reaction and esterifying reaction to produce the product.
Description
Technical field
The invention belongs to the coating adhesive area, relate in particular to a kind of epoxy acrylic resin.
Background technology
Epoxy acrylate is to be got by unsaturated monoprotic acid esterification such as Resins, epoxy and acrylic or methacrylic acid, is a class photocuring oligopolymer of present domestic photocuring industry internal consumption amount maximum.Its important feature is: when any a kind makes up in the various piece in to its general formula, and the propylene oxide acids vinyl ester resin that can derive and make new advances.Epoxy acrylic resin has the characteristics of two kinds of thermosetting resins concurrently, it is similar to unsaturated polyester resin on the one hand, under the initiator effect, pass through free radical reaction, form one and insolublely do not melt, have the very big polymkeric substance of space reticulated structure, relative molecular mass, have unsaturated group on the end group and make it have unsaturated polyester fast setting, the performance of processing easily; Its photocuring reaction speed is very fast on the other hand, and the product performance after it solidifies can reach the performance such as the favorable mechanical performance of Resins, epoxy, some performance even surpass Resins, epoxy such as resistance toheat, chemical resistance and toughness etc.But existing epoxy acrylic resin also has the following disadvantages: since exist on the molecular backbone chain account in the whole molecule quite a high proportion of, be the inflexible phenyl ring and the molecular backbone chain chain length is shorter, therefore cause cured film flexible not enough, the fragility height; Behind the photocuring in the rete remaining acrylate group more, polyreaction is than just " being freezed " by firm cross-linked structure under the low-conversion, residual unreacted group is unfavorable to performances such as ageing-resistant, anti-xanthochromias, and the small-molecule substance that has neither part nor lot in reaction influences the performance of material.
Summary of the invention
The object of the present invention is to provide a kind of epoxy acrylic resin, big, the shortcomings such as unit elongation is low, fragility height of rigidity when using as the coating glue stick to overcome existing epoxy acrylic resin through the modification of many carbon straight chain saturated fatty diprotic acid.
Another object of the present invention also is to provide a kind of method of utilizing many carbon straight chain saturated fatty diprotic acid to prepare epoxy acrylic resin.
The present invention is achieved by the following technical solutions:
A kind of epoxy acrylic resin with following general structure:
M represents the integer between 4～8, and wherein R is:
Wherein n is any number of 0～4, or R is:
0＜K≤5 wherein.
The preferred structure formula of described epoxy acrylic resin is:
Wherein n is 1 or 2.
The present invention at first utilizes many carbon straight chain saturated fatty diprotic acid that excessive Resins, epoxy is carried out ring-opening reaction, thereby in molecular backbone chain, introduced the long-chain fat monounsaturated dicarboxylic acid, molecular chain length is increased, and then increase the kindliness of polymkeric substance, cause the raising of polymkeric substance elongation.The epoxide group of participating in reaction again with vinylformic acid generation esterification.Acid anhydrides enters the prepolymer molecular backbone chain, thereby improves the light reaction of oligopolymer, reduces cure shrinkage, also helps to improve the heat-drawn wire of solidifying product, makes the resin after the modification aspect flexible significant improvement be arranged also.
The present invention prepares by following technology and step:
By weight, with 50～75 parts of Resins, epoxy, the saturated fatty of carbon straight chain more than 10～30 parts diprotic acid, 10～30 parts of vinylformic acid, 0.3～5.0 part of stopper and 0.05～3.0 part of catalyzer is raw material, at first use described binary acid to the Resins, epoxy chain extension, increase relative molecular weight, concrete operations are as follows: drop into a certain amount of Resins, epoxy in the reactor that agitator, thermometer, dropping funnel are housed, add described binary acid when slowly being heated to 60 ℃ with oil bath, be controlled in 10～30 minutes and dropwise, add 0.05～2.0 part of catalyzer after adding again.Warming while stirring is arrived, and stops heating in the time of 80 ℃, treats that temperature of charge begins cooling when being raised to 100 ℃, can lower the temperature in advance if be warmed up to 100 ℃ of time weak points, but temperature of reaction remains between 80 ℃～115 ℃ reaction 1.5h～3h.
Carry out on the basis of the above and acrylic acid esterification then, make acid anhydrides enter the prepolymer molecular backbone chain.Promptly detect earlier the acid number of step 1 resulting polymers or observe its color, when its acid number is lower than 5 or thin outly add vinylformic acid when yellow, is controlled in 10～30 minutes and dropwises, add stopper and remaining catalyzer again.At 115 ℃～120 ℃ following sampling detecting acid numbers behind reaction 1～3h,, promptly get the epoxy acrylic resin through the modification of saturated fatty diprotic acid of the present invention when acid number cools to 90 ℃ with bottom discharge less than 3 the time.Wherein acid number is measured by GB2895-82 " mensuration of unsaturated polyester resin acid esters ".
The speed control that the present invention drips binary acid dripped off at 10～30 minutes, if drip overlong time, may produce the epoxy addition autohemagglutination; The dropping time is too short, is unfavorable for the control reaction, may cause high temperature polymerization.Temperature of reaction of the present invention is controlled at below 120 ℃.Temperature is too high, and Resins, epoxy may ring-opening polymerization, causes the gel of reaction product to become solid simultaneously; Temperature is low excessively, and reaction is carried out slowly, causes the production cycle to prolong, and speed of reaction is low simultaneously, also can cause the gained resin viscosity to become big, and color and luster is deepened.
The used Resins, epoxy of the present invention is that oxirane value height, viscosity are low, the bisphenol A epoxide resin of lighter color or sylvan formaldehyde epoxy resin, preferred bisphenol A type epoxy resin, more preferably E-51 (618), be epoxy equivalent (weight) between the gram of (0.48～0.54)/100, organic chlorine number between between the gram of (0～0.02)/100, inorganic chlorine number between between the gram of (0～0.001)/100, viscosity is not more than 2.5PaS, volatile content and is not higher than 2% bisphenol A type epoxy resin, the more preferably Epon828 bisphenol A type epoxy resin of shell also.The backbone c atoms of the used straight chain saturated fatty of the present invention diprotic acid its role is to the Resins, epoxy chain extension between 6～10, and the long molecular chain of flexibility is introduced Resins, epoxy, increases the kindliness of system.But be not that the carbon atom number on the main chain is The more the better in the described diprotic acid, carbon atom number too conference causes the molecular resin amount to increase, thereby viscosity is increased, the flow leveling variation, and it is higher that carbonatoms surpasses the temperature of solidification of 10 saturated fatty diprotic acid, almost exceeds experimental temperature of the present invention, the difficult control of processing performance, and the viscosity of the epoxy acrylic resin after its modification is too high, and therefore preferred backbone c atoms number is 10 sebacic acid.In order to prevent the polymerization of heat-processed vinylformic acid (ester), need to add a certain amount of stopper, the stopper that the present invention adopts is Resorcinol, p methoxy phenol, 2, a kind of in 5-dimethyl Resorcinol, 1,4-naphthalenediol and 1, the 4-naphthalene diquinone, wherein the reaction of diphenol stopper is very fast, easily form coloured product, influence product colourity.Described catalyzer should not be used strong acid, highly basic, to avoid meaningless side reaction, suitable catalyzer of the present invention can be one or more in tertiary amine, pyridine derivate, quaternary ammonium salt, the Lewis acid, as triethylamine, N, one or more in N-dimethyl Bian amine, 2-picoline, tetra-n-butyl ammonium bromide, benzyl trimethyl ammonium chloride, triphenylphosphine, antimony triphenyl, triphenylarsine, chromium acetylacetonate (III) organic complex.Activity of such catalysts has nothing in common with each other, and is different to the influence of indexs such as reaction times, terminal point equilibrium value, product viscosity, colourity, product stability in storage.Triethylamine is cheap and easy to get, and catalytic activity is relatively low, and the product stickiness is higher, and the stably stored time is not long.The quaternary ammonium salt catalytic activity is strong slightly, and the product viscosity is a little less than the tertiary amine catalytic result, and cost is higher.The antimony triphenyl activity is higher, and the product viscosity is low, and terminal point balance acid number is low, and esterification is comparatively complete, and the storage stability of product is excellent.Organic chromium complex catalysis activity is very high, acid number can be reduced to very lowly in the short period of time, but terminal point balance acid number is slightly high, and the product viscosity is very low, but such catalyst themselves color is darker, influences esterification products colourity.Since use the back esterification thoroughly, viscosity is low, even and do not add phenolic inhibitor, product is stably stored for a long time still, therefore the preferred mixture of antimony triphenyl and Phenylphosphine.
The present invention with preferred structure formula is to be raw material with shell Epon828 bisphenol A type epoxy resin, sebacic acid, vinylformic acid, with antimony triphenyl and triphenylphosphine mixture is catalyzer, with 1, the 4-naphthalenediol is that stopper makes according to aforementioned preparation method and step.
Among the present invention, Resins, epoxy should keep a part of epoxide group and carry out acroleic acid esterification behind the acid anhydrides chain extension.Therefore Resins, epoxy is excessive relatively, excessive Resins, epoxy impels acroleic acid esterification to react completely, suppress polyreaction than just " being freezed " under the low-conversion, thereby improve the light-cured performance of resin, improve ageing-resistant, yellowing resistance energy by firm cross-linked structure.
The present invention has following beneficial effect:
Raw material sources of the present invention are extensive, all have commercially availablely, conveniently carry out scale operation; Small molecules product content such as vinylformic acid is very low in the product, suppressed under than the low reaction rate polyreaction with regard to frozen phenomenon, so light reaction is higher, and cure shrinkage is lower, and the heat-drawn wire of solidifying product is improved; With respect to other anhydride modified epoxy acrylic resins, owing to introduced long chain alkyl group in the molecular backbone chain, the flexibility of polymkeric substance significantly improves; Simultaneously owing to have a large amount of hydrophilic radicals in the molecule, the wettability of pigment, filler also is improved; With respect to the epoxy acrylic resin of amine modification, have advantages such as low viscosity, low smell, these advantages have been expanded Application Areas of the present invention.
Description of drawings
Fig. 1 is an epoxy acrylic resin preferred construction formula of the present invention.
Embodiment
The preparation of the epoxy acrylic resin of embodiment 1 hexanodioic acid modification
In the reactor that agitator, thermometer, dropping funnel are housed, add 70 parts of Resins, epoxy E-51 (618), add 12 parts of hexanodioic acids with dropping funnel when slowly being heated to 60 ℃ with oil bath, be controlled in 20 minutes and drip off, add 0.5 part of antimony triphenyl after adding again.Stop heating during warming while stirring to 80 ℃, treat that system temperature begins cooling when being raised to 100 ℃, keep system temperature between 80 ℃～115 ℃, to react 1.5h.Adopt GB2895-82 to measure the acid number of system,, add 1.8 parts of p methoxy phenols and 0.7 part of antimony triphenyl after adding again when acid number adds 15 parts of vinylformic acid less than 5 the time.At 115 ℃～120 ℃ following sampling detecting acid numbers behind the reaction 2h, when acid number is cooled to 90 ℃ with bottom discharge less than 3 the time.
The preparation of the epoxy acrylic resin of embodiment 2 pimelic acid modifications
In the reactor that agitator, thermometer, dropping funnel are housed, add 57 parts of epoxy resin E-44s (601), add 21 parts of pimelic acid with dropping funnel when slowly being heated to 60 ℃ with oil bath, be controlled in 30 minutes and drip off, add 11.5 parts of N after adding again, the mixture of N-dimethyl benzylamine and triphenylarsine.Stop heating during warming while stirring to 80 ℃, treat that system temperature begins cooling when being raised to 100 ℃, keep system temperature between 80 ℃～115 ℃, to react 2h.Adopt GB2895-82 to measure the acid number of system,, add 2.5 parts of Resorcinol and 1.0 parts of N after adding again, the mixture of N-dimethyl benzylamine and triphenylarsine when acid number adds 17 parts of vinylformic acid less than 5 the time.At 115 ℃～120 ℃ following sampling detecting acid numbers behind the reaction 2.5h, when acid number is cooled to 90 ℃ with bottom discharge less than 3 the time.
The preparation of the epoxy acrylic resin of embodiment 3 nonane diacid modifications
In the reactor that agitator, thermometer, dropping funnel are housed, add 64 parts of Resins, epoxy E-51 (618), add 16 parts of nonane diacids with dropping funnel when slowly being heated to 60 ℃ with oil bath, be controlled in 15 minutes and drip off, add the mixture of 0.3 part of tetra-n-butyl ammonium bromide and antimony triphenyl after adding again.Stop heating during warming while stirring to 80 ℃, treat that system temperature begins cooling when being raised to 100 ℃, keep system temperature between 80 ℃～115 ℃, to react 2.5h.Adopt GB2895-82 to measure the acid number of system,, add 1.0 part 1 after adding again, the mixture of 4-naphthalenediol and 0.7 part of tetra-n-butyl ammonium bromide and antimony triphenyl when acid number adds 18 parts of vinylformic acid less than 5 the time.At 115 ℃～120 ℃ following sampling detecting acid numbers behind the reaction 2.0h, when acid number is cooled to 90 ℃ with bottom discharge less than 3 the time.
The preparation of the epoxy acrylic resin of embodiment 4 sebacic acid modifications
In the reactor that agitator, thermometer, dropping funnel are housed, add 54 parts of shell Epon828 bisphenol A type epoxy resins, add 20 parts of sebacic acid with dropping funnel when slowly being heated to 60 ℃ with oil bath, be controlled in 25 minutes and drip off, add the mixture of 0.9 part of antimony triphenyl and triphenylphosphine after adding again.Stop heating during warming while stirring to 80 ℃, treat that system temperature begins cooling when being raised to 100 ℃, keep system temperature between 80 ℃～115 ℃, to react 3h.Adopt GB2895-82 to measure the acid number of system,, add 3.0 part 1 after adding again, the mixture of 4-naphthalenediol and 1.1 parts of antimony triphenyls and triphenylphosphine when acid number adds 21 parts of vinylformic acid less than 5 the time.At 115 ℃～120 ℃ following sampling detecting acid numbers behind the reaction 3h, when acid number is cooled to 90 ℃ with bottom discharge less than 3 the time.
The preparation of the epoxy acrylic resin of embodiment 5 suberic acid modifications
In the reactor that agitator, thermometer, dropping funnel are housed, add 60 parts of sylvan formaldehyde epoxy resin F-46, add 22 parts of suberic acids with dropping funnel when slowly being heated to 60 ℃ with oil bath, be controlled in 25 minutes and drip off, add 1.3 parts of triethylamines after adding again.Stop heating during warming while stirring to 80 ℃, treat that system temperature begins cooling when being raised to 100 ℃, keep system temperature between 80 ℃～115 ℃, to react 2h.Adopt GB2895-82 to measure the acid number of system,, add 1.0 part 2 after adding again, 5-dimethyl Resorcinol and 0.7 part of triethylamine when acid number adds 15 parts of vinylformic acid less than 5 the time.At 115 ℃～120 ℃ following sampling detecting acid numbers behind the reaction 3h, when acid number is cooled to 90 ℃ with bottom discharge less than 3 the time.
The epoxy acrylic resin after sebacic acid or hexanodioic acid or nonane diacid modification and the performance of maleic anhydride modified resin are relatively
| Properties-correcting agent | Hexanodioic acid | Nonane diacid | Maleic anhydride | Sebacic acid | ||
| Prescription | Resins, epoxy (E-51) | 70 | 70 | 70 | 70 | |
| Properties-correcting agent | 20 | 20 | 20 | 20 | ||
| Other reagent | 10 | 10 | 10 | 10 | ||
| The resin solidification performance | Heat-drawn wire | 56 | 39 | 75 | 34 | |
| Tensile strength Mpa | 41.19 | 35.30 | 55.9 | 32.36 | ||
| Modulus in tension Mpa | 858 | 837 | 703 | 288 | ||
| Extension at break % | 6.5 | 4.9 | 4.5 | 116.6 | ||
| Shore hardness | 80 | 75 | 72 | 60 | ||
| Dielectric loss tg δ % | 25℃ | 2.0 | 3.2 | 2.2 | 1.2 | |
| 171℃ | 26.4 | 22.4 | 17.3 | 16.8 | ||
| Voltage breakdown KV/mm | 10.3 | 10.5 | 11.2 | 11.7 | ||
Illustrate:
1, the epoxy equivalent (weight) of used Resins, epoxy E-51 between (0.48～0.54)/100 grams, organic chlorine number between between the gram of (0～0.02)/100, inorganic chlorine number between between the gram of (0～0.001)/100, viscosity is not more than 2.5PaS (40 ℃), volatile content is not higher than 2%.
2, other reagent are vinylformic acid, the antimony triphenyl that plays katalysis and the mixture of triphenylphosphine, and the p methoxy phenol of using as stopper, and the content of vinylformic acid, catalyzer and stopper all equates in each prescription.
3, use TF-2030 thermal distortion vicat temperature determinator to test heat-drawn wire, use XLL-50 type tension testing machine, use K3120-SHORE Shore hardness machine to test Shore hardness, use GYZS-2 dielectric loss tester according to loss of GB1409-78 tested media and voltage breakdown according to GB-531-82 according to GB/T1040 tested for tensile strength, modulus in tension and elongation at break according to GB/1634.
Can see that by last table along with the increase of saturated fatty diprotic acid backbone c atoms number, the heat-drawn wire of resulting polymers of the present invention descends gradually, and all be lower than heat-drawn wire through maleic anhydride modified epoxy acrylic resin; The tensile strength of polymkeric substance, elongation at break also reduce gradually, and all are higher than the tensile strength of maleic anhydride modified epoxy acrylic resin.Every performance the best of the epoxy acrylic resin of sebacic acid modification wherein all is better than the performance of maleic anhydride modified epoxy acrylic resin.
The viscosity ratio of epoxy acrylic resin after the sebacic acid modification and amine modified resin
| Properties-correcting agent | Primary amine | Secondary amine | Tertiary amine | Sebacic acid | |
| Prescription | Resins, epoxy (E-51) | 70 | 70 | 70 | 70 |
| Properties-correcting agent | 20 | 20 | 20 | 20 | |
| Other reagent | 10 | 10 | 10 | 10 | |
| Performance | Reactive behavior | High | High | Low | High |
| Oxirane value equivalent/100g | 220-240 | 230-270 | 350-400 | 270-320 | |
| Viscosity mpa.s (25 ℃) | 9000-13000 | 9000-13000 | 9000-13000 | 3500-4500 | |
Illustrate:
1, the epoxy equivalent (weight) of used Resins, epoxy E-51 between (0.48～0.54)/100 grams, organic chlorine number between between the gram of (0～0.02)/100, inorganic chlorine number between (0～0.001)/100 gram ask, viscosity is not more than 2.5PaS (40 ℃), volatile content is not higher than 2%.
2, other reagent are vinylformic acid, the antimony triphenyl that plays katalysis and the mixture of triphenylphosphine, and the p methoxy phenol of using as stopper, and the content of vinylformic acid, catalyzer and stopper all equates in each prescription.
3, use DNJ type rotational viscosimeter according to the GB/T7193.1-1987 tested viscosity.
Claims (10)
1, a kind of epoxy acrylic resin, structural formula is
M represents the integer between 4～8, and wherein R is
Wherein n is any number of 0～4, or R is
0＜K≤5 wherein.
2, the preparation method of epoxy acrylic resin as claimed in claim 1, it is characterized in that: by weight, be to be raw material, may further comprise the steps with 50～75 parts of Resins, epoxy, the saturated fatty of carbon straight chain more than 10～30 parts diprotic acid, 10～30 parts of vinylformic acid, 0.3～5.0 part of stopper and 0.05～3.0 part of catalyzer:
Step 1: in the reactor that agitator, thermometer, dropping funnel are housed, drop into Resins, epoxy, add binary acid when slowly being heated to 50～60 ℃, be controlled in 10～30 minutes and dropwise, and then add 0.05 part～2.0 parts catalyzer, stop heating during warming while stirring to 80 ℃, treat that temperature of charge begins cooling when being raised to 100 ℃, temperature of reaction remains on 80 ℃～115 ℃, reacts about 1.5h～3h;
Step 2: detect the acid number of step 1 resulting polymers or observe its color, when its acid number is lower than 5 or the thin out vinylformic acid that adds when yellow, be controlled in 10～30 minutes and dropwise, and then add remaining catalyzer and stopper, at 115 ℃～120 ℃ following sampling detecting acid numbers behind reaction 1～3h,, acid number gets final product with bottom discharge when cooling to 90 ℃ less than 3 the time.
3, the preparation method of epoxy acrylic resin as claimed in claim 2 is characterized in that: described Resins, epoxy is bisphenol A epoxide resin or sylvan formaldehyde epoxy resin.
4, the preparation method of epoxy acrylic resin as claimed in claim 2 is characterized in that: described many carbon straight chain saturated fatty diprotic acid is the straight chain saturated fatty diprotic acid of backbone c atoms number between 6～10.
5, the preparation method of epoxy acrylic resin as claimed in claim 2 is characterized in that: described stopper is Resorcinol, p methoxy phenol, 2, a kind of in 5-dimethyl Resorcinol, 1,4-naphthalenediol and 1, the 4-naphthalene diquinone.
6, the preparation method of epoxy acrylic resin as claimed in claim 2 is characterized in that: described catalyzer is one or more in tertiary amine, pyridine derivate, quaternary ammonium salt, the Lewis acid.
7, the preparation method of epoxy acrylic resin as claimed in claim 6 is characterized in that: described tertiary amine is preferably triethylamine or N, N-dimethyl Bian amine.
8, the preparation method of epoxy acrylic resin as claimed in claim 6 is characterized in that: described pyridine derivate is preferably the 2-picoline.
9, the preparation method of epoxy acrylic resin as claimed in claim 6 is characterized in that: described quaternary ammonium salt is preferably tetra-n-butyl ammonium bromide or benzyl trimethyl ammonium chloride.
10, the preparation method of epoxy acrylic resin as claimed in claim 6 is characterized in that: described Lewis acid is preferably and is in triphenylphosphine, antimony triphenyl, triphenylarsine, chromium acetylacetonate (III) organic complex one or more.
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