CN102875754B - Modified resorcinol phenolic resin and preparation method thereof and rubber compound - Google Patents
Modified resorcinol phenolic resin and preparation method thereof and rubber compound Download PDFInfo
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- CN102875754B CN102875754B CN201210366295.5A CN201210366295A CN102875754B CN 102875754 B CN102875754 B CN 102875754B CN 201210366295 A CN201210366295 A CN 201210366295A CN 102875754 B CN102875754 B CN 102875754B
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Abstract
The invention relates to modified resorcinol phenolic resin and a preparation method thereof. Reactivity of resorcinol phenolic resin is maintained by using phenolic materials with reactivity to modify the resorcinol phenolic resin. The invention further discloses a rubber compound material which is composed of (i) rubber constituents selected from natural rubber or synthetic rubber; (ii) methylene donors; and (iii) the modified resorcinol phenolic resin serving as a methylene acceptor.
Description
Technical field
The present invention relates to a kind of modification resorcin phenolic resin and preparation method thereof, and comprise the rubber combination of this modification resorcin phenolic resin, this modification resorcin phenolic resin is particularly useful for the matrix material that rubber and steel wire need close adhesion.
Background technology
In the production of elastomeric material, the material of various rigidity is often as effective strongthener, and particularly typically use steel wire as framework material, this has been general way at tyre industry.Owing to there is huge nature difference between rubber and this bi-material of steel wire, the final performance of combination between the two to material has tremendous influence.In order to improve the combination between steel wire and rubber, chemical process is widely used among current tire production.
Chemical process refers to and methylene radical donor and methylene receptor is joined among rubber simultaneously, and in sulfidation, both react formation cross-linked network, improve the physicals of rubber, mechanical property; Simultaneously and generation effect between rubber and steel wire, the interaction between rubber and steel wire is improved and bonding force both finally improving.
Methylene radical donor is comparatively ripe, and two kinds of common methylene radical donors are vulkacit H (HMT) and HMMM (HMMM).And as methylene receptor, higher reactive behavior must be had, the methylene radical that could discharge with methylene radical donor rapidly reacts, and forms cross-linked network in rubbery parent substance, thus the bonding force between raising rubber and steel wire.It is multiple that methylene receptor common at present comprises Resorcinol, resorcin phenolic resin, meta-cresol resol, phenol formaldehyde resin, alkylphenol-resorcinol formaldehyde resin etc.Wherein the reactive behavior of Resorcinol and methylene radical donor is the highest, uses Resorcinol to have unusual effect as jointing material for the bonding force improved between rubber and steel wire.But Resorcinol is a kind of small molecules of easy distillation, namely can produce distillation phenomenon at 105 DEG C, in rubber mixing process, easily produces environmental pollution and cause the health risk of workman.
For this reason, develop the treatment process of many Resorcinols or resorcin phenolic resin, reduce volatile object in use procedure to reach.Such as, Chinese patent CN200910039469.5 application discloses that one by Resorcinol load on rubber carrier, thus the method that minimizing Resorcinol in use volatilizees.
But the method for this physical load only improve only the dispersion of Resorcinol, do not solve the problem of Resorcinol content, volatility reduction is also not obvious.Other method uses small-molecule substance and resorcin reaction, reduces the content that dihydroxy-benzene is sowed discord in resin middle reaches, thus fundamentally reduce Resorcinol content, avoid the volatilization in use procedure.
Such as, US5021522 discloses the method using phenylethene modified resorcinol resin, obtains the resin of low-free phenol content; US7074861 further employs the method that Resorcinol, unsaturated olefin (vinylbenzene), formaldehyde and alkyl aldehydes prepare resin under an acidic catalyst effect.
Chinese patent CN200510046538.7 discloses and uses Resorcinol, formaldehyde, vinylbenzene, oxalic acid, NaOH to prepare the method for resin through alkylation, hydroxylation reaction.
Although aforesaid method solves the problem that Resorcinol volatilization of being heated in use causes environmental pollution, but the modification of unsaturated olefin, alkylphenol all decreases the reactive behavior site of Resorcinol, make resin as the function of methylene receptor by impact to a certain extent.
Summary of the invention
In order to overcome above-mentioned defect of the prior art, present inventor conducts in-depth research.
One object of the present invention is to provide a kind of modification resorcin phenolic resin, the aldehydes matter with reactive behavior is used to carry out modification to resorcin phenolic resin, reduce the reactive behavior keeping resin and methylene radical donor while dihydroxy-benzene content is sowed discord in resorcin phenolic resin middle reaches, thus obtain the resorcin phenolic resin of excellent performance.
Another object of the present invention is the preparation method providing a kind of modification resorcin phenolic resin.
Another object of the present invention is to provide a kind of rubber combination comprising above-mentioned modification resorcin phenolic resin.
Specifically, the invention provides following technical scheme to realize above-mentioned purpose.
The invention provides a kind of modification resorcin phenolic resin, prepared by the raw material reaction comprising at least one properties-correcting agent, Resorcinol and at least one aldehyde.Described properties-correcting agent comprises the phenolic compound (a) containing double bond structure shown at least one formula (1):
Wherein R
1be independently the alkyl containing double bond, R
1be preferably propenyl, pseudoallyl; R
2independently be selected from hydrogen, hydroxyl, alkyl or OR
3group, wherein R
3for alkyl, R
3be preferably methyl, ethyl.
Preferably, the phenolic compound (a) containing double bond structure be selected from 2-chavicol, 4-chavicol, 4-isopropenyl phenol, Eugenol, 2-allyl group Resorcinol, 4-allyl group Resorcinol one or more.
According to a kind of modification resorcin phenolic resin of the present invention, the properties-correcting agent that the present invention uses can further include at least one unsaturated olefin properties-correcting agent (b).That is, the phenolic compound (a) containing double bond structure can be used alone, and also can use with other unsaturated olefin properties-correcting agent (b) simultaneously.
Preferably, described unsaturated olefin properties-correcting agent (b) is selected from Styrene and its derivatives, alpha-methyl styrene and derivative thereof.The example of described unsaturated olefin properties-correcting agent (b) preferably but be not limited in vinylbenzene, vinyl toluene, ethyl styrene, alpha-methyl styrene one or more.
Described aldehyde is selected from RCHO, trioxymethylene, paraformaldehyde, one or more in paraldehyde, furfural, phenyl aldehyde and acetaldol, and the R wherein in RCHO is hydrogen or the alkyl with 1-8 carbon atom.Preferably, described aldehyde is selected from one or more of formaldehyde, acetaldehyde, butyraldehyde-n, valeraldehyde, n-hexyl aldehyde and enanthaldehyde.
Preferably, also catalyzer is contained in described raw material.In described reaction of the present invention, can there is aralkyl glycosylation reaction in the unsaturated double-bond in described properties-correcting agent and Resorcinol.Preferably, the catalyzer being applicable to aralkyl glycosylation reaction of the present invention is selected from Friedel-Crafts catalyzer, an acidic catalyst or their mixture.
Preferably, described an acidic catalyst is selected from one or more the mixture in oxalic acid, sulfuric acid, hydrochloric acid, phosphoric acid, xylene monosulfonic acid, Phenylsulfonic acid, benzene disulfonic acid, C1-C15 alkyl benzene sulphonate (ABS), naphthene sulfonic acid, acidic ion exchange resin.
Preferably, described Friedel-Crafts catalyzer is selected from one or more the mixture in Aluminum chloride anhydrous, zinc chloride, iron trichloride, boron trifluoride.
According to a kind of modification resorcin phenolic resin of the present invention, the reaction sequence of described raw material is not particularly limited,
Can be: after aralkyl glycosylation reaction first occurs for Resorcinol and described properties-correcting agent, then with aldehyde reaction.
Also can be: after Resorcinol and aldehyde first react and prepares resol, then with properties-correcting agent generation aralkyl glycosylation reaction.
Can also be: part or all of Resorcinol be with aldehyde reaction while with properties-correcting agent carry out aralkyl glycosylation reaction.
Several reaction sequence can be used alone or as a mixture above.After preferred Resorcinol first carries out aralkyl glycosylation reaction with properties-correcting agent, then react with aldehyde.
According to a kind of modification resorcin phenolic resin of the present invention, preferably, the ratio of quality and the number of copies of Resorcinol and described properties-correcting agent (a) can be 100: 5 ~ 100: 100.Preferred, the ratio of quality and the number of copies of Resorcinol and described properties-correcting agent (a) can be 100: 10 ~ 100: 60.
According to a kind of modification resorcin phenolic resin of the present invention, preferably, the ratio of quality and the number of copies of Resorcinol and described aldehyde is 100: 20 ~ 100: 100.
According to a kind of modification resorcin phenolic resin of the present invention, preferably, when phenolic compound (a) containing double bond structure and unsaturated olefin properties-correcting agent (b) use simultaneously, the ratio of quality and the number of copies of the two can be 1: 0.1 ~ 1: 10.Further preferably, the ratio of quality and the number of copies of the two is 1: 0.5 ~ 1: 8.
When phenolic compound (a) containing double bond structure and unsaturated olefin properties-correcting agent (b) use simultaneously, both addition sequence is also not particularly limited.
According to a kind of modification resorcin phenolic resin of the present invention, preferably, the ratio of quality and the number of copies of Resorcinol, described properties-correcting agent (a) and properties-correcting agent (b) sum and aldehyde is 100: 10: 25 to 100: 100: 90.
The present invention also provides a kind of preparation method of described modification resorcin phenolic resin, prepared by the raw material reaction making to comprise aldehyde described in properties-correcting agent described at least one, Resorcinol and at least one.
According to the preparation method of a kind of modification resorcin phenolic resin of the present invention, the reaction sequence of described raw material is not particularly limited,
Can be: after aralkyl glycosylation reaction first occurs for Resorcinol and described properties-correcting agent, then with aldehyde reaction.
Also can be: after Resorcinol and aldehyde first react and prepares resol, then with properties-correcting agent generation aralkyl glycosylation reaction.
Can also be: part or all of Resorcinol be with aldehyde reaction while with properties-correcting agent carry out aralkyl glycosylation reaction.
Several reaction sequence can be used alone or as a mixture above.After preferred Resorcinol first carries out aralkyl glycosylation reaction with properties-correcting agent, then react with aldehyde.
Present invention also offers described modification resorcin phenolic resin in rubber combination as the purposes of methylene receptor.Described rubber combination is preferred for producing tire, sebific duct and adhesive tape.
The present invention also provides a kind of rubber combination, comprises following component:
I () is selected from natural rubber or elastomeric rubber components;
(ii) methylene radical donor;
(iii) methylene receptor of described modification resorcin phenolic resin is comprised.
According to rubber combination of the present invention, rubber components can be natural rubber (NR), the rubber synthesized or its composition, synthetic rubber include but not limited in the multipolymer of the multipolymer of the multipolymer of the multipolymer of cis-Isosorbide-5-Nitrae-polyisoprene (BR), polyhutadiene, sovprene, isoprene and divinyl, vinyl cyanide and divinyl, vinyl cyanide and isoprene, the multipolymer of vinylbenzene and divinyl and isoprene, butyl rubber, EPDM, vinylbenzene and divinyl one or more.
One or more methylene radical donors are included in rubber combination of the present invention.Term " methylene radical donor " refers to can produce formaldehydogenic compound under heating condition, and the formaldehyde produced can react with Resorcinol, resorcinol-formaldehyde resin, modification resorcin phenolic resin and form cross-linked network.The methylene radical donor that the present invention uses includes but not limited to that vulkacit H (HMT), HMMM (HMMM), six ethoxyl methyl trimeric cyanamides, trioxymethylene and yuban are as one or more in paraformaldehyde.
The part by weight of rubber combination methylene donor of the present invention and modification resorcin phenolic resin can change.Normally, the weight ratio of use is 1: 10 ~ 10: 1.Best suitable for weight ratio is between 1: 5 ~ 5: 1.
The various additives used in elastomeric material can also be comprised, as components such as carbon black, vulcanizing agent, promotor, stearic acid, zinc oxide, oxidation inhibitor, softening oil, cobalt salts in rubber combination of the present invention.Wherein sulphur Chang Zuowei vulcanizing agent occurs, consumption is well known to those skilled in the art, and adds the sulphur of 0.5 ~ 10 weight part in every 100 parts by weight of rubber.
According to rubber combination of the present invention, described modification resorcin phenolic resin can be mixed in rubber combination in the same way with similar methylene receptor product.
Present invention also offers the preparation method of described rubber combination, comprising: the first step, the binder component beyond rubber and sulphur removal agent, promotor and adhesion promotor is mixed to form mixture; Second step, is mixed in the mixture of the first step formation by described modification resorcinol resin; 3rd step, is mixed in the mixture of second step formation by methylene radical donor; Wherein vulcanizing agent, promotor and adhesion promotor independently add separately in second step and/or the 3rd step.
According to the preparation method of rubber combination of the present invention, Banbury mixer used in combination, such as Banbury Banbury mixer; Preferably, the first step mixing temperature is 150 ~ 155 DEG C; Preferably, the temperature of second step and the 3rd step is 90 ~ 150 DEG C
Preferably, the rubber combination formed can further be shaped and sulfuration.
Present invention also offers the purposes of described rubber combination, described rubber combination is used for the production of matrix material, be especially applied to tire, sebific duct, adhesive tape these need the matrix material that carries out with steel wire or filamentary material combining closely.
Embodiment
In the present invention, the softening temperature testing tool of resin is Mettler Toledo FP90 calorimetry system+FP83HT, and manufacturer is MettlerToledo.
In the present invention, the free phenol content test of resin uses Waters2695 high performance liquid chromatography 2996PPA to carry out (solvent: acetonitrile+water+methyl alcohol; Flow velocity: 1.0ml/min; Temperature: 30 DEG C; Chromatographic column: Waters Sunfire C18,250mm × 4.6mm).
Be further described the present invention referring to the following example, these embodiments only should not be construed restrictive for illustration of the present invention.
Embodiment 1
To in the reaction flask that mechanical stirrer, thermometer, reflux exchanger and dropping funnel are housed, add the Resorcinol of 100 mass fractions, be warming up to 120 DEG C of fusings, add tosic acid monohydrate (Beijing chemical reagents corporation, the purity > 98%) mixing of 0.32 mass fraction.Drip 2-chavicol (AlfaAesar (Tianjin) Chemical Co., Ltd. of 30 mass fractions, purity > 98%), control temperature of reaction between 120-135 DEG C, drip in 30 minutes and terminate, react 1 hour at 130 DEG C of temperature.Then, the formaldehyde (37 % by weight aqueous solution) slowly dripping 48 mass fractions in 1 hour reacts.After formaldehyde drips and terminates, add the NaOH aqueous solution (the 25 % by weight concentration) neutralization of 0.3 mass fraction, then air distillation is carried out to 150-160 DEG C to remove water in reaction system and other volatile matter, obtain the red resin that softening temperature is 120.2 DEG C, free Resorcinol content 16.3 % by weight.
Embodiment 2
To in the reaction flask that mechanical stirrer, thermometer, reflux exchanger and dropping funnel are housed, add the Resorcinol of 100 mass fractions, be warming up to 120 DEG C of fusings, add tosic acid monohydrate (Beijing chemical reagents corporation, the purity > 98%) mixing of 0.32 mass fraction.Drip 2-chavicol (AlfaAesar (Tianjin) Chemical Co., Ltd. of 35 mass fractions, purity > 98%), control temperature of reaction between 120-135 DEG C, drip in 30 minutes and terminate, react 1 hour at 130 DEG C of temperature.Then, the formaldehyde (37 % by weight aqueous solution) slowly dripping 44 mass fractions in 1 hour reacts.After formaldehyde drips and terminates, add the NaOH aqueous solution (the 25 % by weight concentration) neutralization of 0.3 mass fraction, then air distillation is carried out to 150-160 DEG C to remove water in reaction system and other volatile matter, obtain the red resin that softening temperature is 103.5 DEG C, free Resorcinol content 11 % by weight.
Embodiment 3
To in the reaction flask that mechanical stirrer, thermometer, reflux exchanger and dropping funnel are housed, add the Resorcinol of 100 mass fractions, be warming up to 120 DEG C of fusings, add tosic acid monohydrate (Beijing chemical reagents corporation, the purity > 98%) mixing of 0.32 mass fraction.Drip 2-chavicol (AlfaAesar (Tianjin) Chemical Co., Ltd. of 40 mass fractions, purity > 98%), control temperature of reaction between 120-135 DEG C, drip in 30 minutes and terminate, react 1 hour at 130 DEG C of temperature.Then, the formaldehyde (37 % by weight aqueous solution) slowly dripping 44 mass fractions in 1 hour reacts.After formaldehyde drips and terminates, add the NaOH aqueous solution (the 25 % by weight concentration) neutralization of 0.3 mass fraction, then air distillation is carried out to 150-160 DEG C to remove water in reaction system and other volatile matter, obtain the red resin that softening temperature is 98.4 DEG C, free Resorcinol content 13.66 % by weight.
Embodiment 4
To in the reaction flask that mechanical stirrer, thermometer, reflux exchanger and dropping funnel are housed, add the Resorcinol of 100 mass fractions, be warming up to 120 DEG C of fusings, add tosic acid monohydrate (Beijing chemical reagents corporation, the purity > 98%) mixing of 0.32 mass fraction.Drip 2-chavicol (AlfaAesar (Tianjin) Chemical Co., Ltd. of 50 mass fractions, purity > 98%), control temperature of reaction between 120-135 DEG C, drip in 30 minutes and terminate, react 1 hour at 130 DEG C of temperature.Then, the formaldehyde (37 % by weight aqueous solution) slowly dripping 44 mass fractions in 1 hour reacts.After formaldehyde drips and terminates, add the NaOH aqueous solution (the 25 % by weight concentration) neutralization of 0.3 mass fraction, then air distillation is carried out to 150-160 DEG C to remove water in reaction system and other volatile matter, obtain the red resin that softening temperature is 96.4 DEG C, free Resorcinol content 8.7 % by weight.
Embodiment 5
To in the reaction flask that mechanical stirrer, thermometer, reflux exchanger and dropping funnel are housed, add the Resorcinol of 100 mass fractions, be warming up to 120 DEG C of fusings, add tosic acid monohydrate (Beijing chemical reagents corporation, the purity > 98%) mixing of 0.32 mass fraction.Drip 2-chavicol (AlfaAesar (Tianjin) Chemical Co., Ltd. of 60 mass fractions, purity > 98%), control temperature of reaction between 120-135 DEG C, drip in 30 minutes and terminate, react 1 hour at 130 DEG C of temperature.Then, the formaldehyde (37 % by weight aqueous solution) slowly dripping 46 mass fractions in 1 hour reacts.After formaldehyde drips and terminates, add the NaOH aqueous solution (the 25 % by weight concentration) neutralization of 0.3 mass fraction, then air distillation is carried out to 150-160 DEG C to remove water in reaction system and other volatile matter, obtain the red resin that softening temperature is 88.2 DEG C, free Resorcinol content 5.8 % by weight.
Embodiment 6
To in the reaction flask that mechanical stirrer, thermometer, reflux exchanger and dropping funnel are housed, add the Resorcinol of 100 mass fractions, be warming up to 120 DEG C of fusings, add tosic acid monohydrate (Beijing chemical reagents corporation, the purity > 98%) mixing of 0.32 mass fraction.Drip 2-chavicol (AlfaAesar (Tianjin) Chemical Co., Ltd. of 10 mass fractions, purity > 98%), control temperature of reaction between 120-135 DEG C, drip in 15 minutes and terminate, react 30 minutes at 130 DEG C of temperature.Then, in reaction system, drip 55 mass fraction vinylbenzene (Beijing chemical reagents corporation, purity > 99%) in 30 minutes, continue to react 30 minutes at 130 DEG C of temperature, be warming up to 150 ~ 155 DEG C and keep 10 minutes.The formaldehyde (37 % by weight aqueous solution) slowly dripping 42 mass fractions in 1 hour reacts.Formaldehyde reacts 30 minutes after dripping and terminating.Add the NaOH aqueous solution (the 25 % by weight concentration) neutralization of 0.3 mass fraction, then carry out air distillation to 170 ~ 180 DEG C to remove water in reaction system and other volatile matter, slow unlatching vacuum is to maximum vacuum (2.5 kPas) and keep 5 minutes to remove volatile matter, obtain the red resin that softening temperature is 110.5 DEG C, free Resorcinol content 0.6 % by weight.
Embodiment 7
To in the reaction flask that mechanical stirrer, thermometer, reflux exchanger and dropping funnel are housed, add the Resorcinol of 100 mass fractions, be warming up to 120 DEG C of fusings, add tosic acid monohydrate (Beijing chemical reagents corporation, the purity > 98%) mixing of 0.32 mass fraction.Drip the Eugenol (Coryophyllic acid of 30 mass fractions, AlfaAesar (Tianjin) Chemical Co., Ltd., purity > 98%), control temperature of reaction between 120-135 DEG C, drip in 30 minutes and terminate, react 1 hour at 130 DEG C of temperature.Then, the formaldehyde (37 % by weight aqueous solution) slowly dripping 44 mass fractions in 1 hour reacts.After formaldehyde drips and terminates, add the NaOH aqueous solution (the 25 % by weight concentration) neutralization of 0.3 mass fraction, then air distillation is carried out to 170-180 DEG C to remove water in reaction system and other volatile matter, obtaining softening temperature is 105.6 DEG C of red resins, free Resorcinol content 9.8 % by weight.
Embodiment 8
To in the reaction flask that mechanical stirrer, thermometer, reflux exchanger and dropping funnel are housed, add the Resorcinol of 100 mass fractions, be warming up to 120 DEG C of fusings, add tosic acid monohydrate (Beijing chemical reagents corporation, the purity > 98%) mixing of 0.32 mass fraction.Drip the Eugenol (Coryophyllic acid of 40 mass fractions, AlfaAesar (Tianjin) Chemical Co., Ltd., purity > 98%), control temperature of reaction between 120-135 DEG C, drip in 30 minutes and terminate, react 1 hour at 130 DEG C of temperature.Then, the formaldehyde (37 % by weight aqueous solution) slowly dripping 42 mass fractions in 1 hour reacts.After formaldehyde drips and terminates, add the NaOH aqueous solution (the 25 % by weight concentration) neutralization of 0.3 mass fraction, then air distillation is carried out to 150-160 DEG C to remove water in reaction system and other volatile matter, obtain the red resin that softening temperature is 94.6 DEG C, free Resorcinol content 12.3 % by weight.
Embodiment 9
In rubber compounding, carry out testing authentication by according to the resorcinol resin prepared by embodiment 2 and 3, and with the commercially available resorcinol resin with similar free phenol content
resin B-19-s contrasts, and its softening temperature is 107.8 DEG C, and free Resorcinol content is 11.49 quality %.Wherein the formula of rubber is refined according to the formula shown in table one, and wherein the use level of each component is using the rubber of every 100 mass fractions as benchmark (phr).
The mixing process of sizing material is as follows: the first step, the components such as rubber, carbon black, zinc oxide, stearic acid is about in temperature in the Banbury Banbury mixer of 150 ~ 155 DEG C and mixes.The resorcinol resin prepared according to embodiment 2,3 or B-19-s resin, cobalt salt and antioxidant 4020 are be mixed among rubber components in the Banbury Banbury mixer of 140 ~ 145 DEG C in temperature by second step.3rd step, is mixed into the sulphur in table two, sulphenamide accelerators (DZ) and methylene radical donor HMMM (65 % by weight purity) among rubber composite at 90-100 DEG C.This rubber composite is placed and is spent the night in the environment of 23 DEG C of constant room temperature and 50% constant humidity.Then at 150 DEG C, test its curability, and test its mechanical property after carrying out sulfuration, and steel wire bond properties.
Note: B-19-s is from INDESPEC Chemical Corporation, and Pittsburgh, PA obtain
resin B-19-s.
It is suitable with commercially available prod B-19-s that data from table two can observe the physicals showed in sizing material according to the resin prepared by embodiment 2,3, be improved to some extent with the bounding force of steel wire simultaneously, comprise aging before and aging after steel wire cord bounding force.
Embodiment 10
In rubber compounding, carry out testing authentication by according to the resorcinol resin prepared by embodiment 6, and with the commercially available resorcinol resin with similar free phenol content
resin B-20-s contrasts, and its softening temperature is 105 DEG C, and free Resorcinol content is 1.74 quality %.Wherein the formula of rubber is refined according to the formula shown in table one, and wherein the use level of each component is using the rubber of every 100 mass fractions as benchmark (phr).
The mixing process of sizing material is as follows: the first step, the components such as rubber, carbon black, zinc oxide, stearic acid is about in temperature in the Banbury Banbury mixer of 150 ~ 155 DEG C and mixes.Second step, is mixed into the resorcinol resin prepared according to embodiment 6 or B-20-s resin, cobalt salt and antioxidant 4020 among rubber components in the Banbury Banbury mixer of temperature about 140 ~ 145 DEG C.3rd step, is mixed into the sulphur in table two, sulphenamide accelerators (DZ) and methylene radical donor HMMM (65% purity) among rubber composite at 90-100 DEG C.This rubber composite is placed and is spent the night in the environment of 23 DEG C of constant room temperature and 50% constant humidity.Then at 150 DEG C, test its curability, and test its mechanical property after carrying out sulfuration, and steel wire bond properties.
Note: B-20-s is from INDESPEC Chemical Corporation, and Pittsburgh, PA obtain
resin B-20-s.
Can observe from the data of table four, according to the data prepared by embodiment 6, there is the performance similar with commercially available prod B-20-s, there is lower free Resorcinol content simultaneously.Above-mentioned data have absolutely proved that use method of the present invention can be prepared and has the even more high performance resorcin phenolic resin of equal performance with commercially available prod.
Although for illustrative purposes as above-mentioned specific embodiments of the invention are described, under the prerequisite not departing from the scope of the invention, those skilled in the art obviously can carry out various amendment to the present invention.
Claims (17)
1. a modification resorcin phenolic resin, is characterized in that: prepared by the raw material reaction comprising Resorcinol, at least one properties-correcting agent and at least one aldehyde; Described properties-correcting agent comprises the phenolic compound (a) containing double bond structure shown at least one formula (1):
Wherein R
1be independently the alkyl containing double bond, R
2independently be selected from hydrogen, hydroxyl, alkyl or OR
3group, R
3for alkyl;
Unsaturated double-bond in described properties-correcting agent and Resorcinol generation aralkyl glycosylation reaction.
2. modification resorcin phenolic resin as claimed in claim 1, is characterized in that: R
1be selected from propenyl or pseudoallyl; R
3be selected from methyl or ethyl.
3. modification resorcin phenolic resin as claimed in claim 1, it is characterized in that: the phenolic compound (a) containing double bond structure be selected from 2-chavicol, 4-chavicol, 4-isopropenyl phenol, Eugenol, 2-allyl group Resorcinol, 4-allyl group Resorcinol one or more, the mass ratio of Resorcinol and described properties-correcting agent is 100: 5 ~ 100: 100.
4. modification resorcin phenolic resin as claimed in claim 1, is characterized in that: described properties-correcting agent also comprises at least one unsaturated olefin properties-correcting agent (b) further; Described unsaturated olefin properties-correcting agent (b) be selected from vinylbenzene, vinyl toluene, ethyl styrene, alpha-methyl styrene one or more, the mass ratio of described properties-correcting agent and phenolic compound properties-correcting agent (a) is 1: 0.1 ~ 1: 10.
5. modification resorcin phenolic resin as claimed in claim 1, it is characterized in that: described aldehyde is selected from RCHO, trioxymethylene, paraformaldehyde, one or more in paraldehyde, furfural, phenyl aldehyde and acetaldol, R wherein in RCHO is hydrogen or the alkyl with 1-8 carbon atom, and the mass ratio of Resorcinol and described aldehyde is 100: 20 ~ 100: 100.
6. the modification resorcin phenolic resin as described in one of claim 4, is characterized in that: the ratio of quality and the number of copies of Resorcinol, described properties-correcting agent (a) and properties-correcting agent (b) sum and aldehyde is 100: 10: 25 to 100: 100: 90.
7. modification resorcin phenolic resin as claimed in claim 1, is characterized in that: also containing catalyzer in described raw material, described catalyzer is selected from Friedel-Crafts catalyzer, an acidic catalyst or their mixture; Described Friedel-Crafts catalyzer is selected from one or more the mixture in Aluminum chloride anhydrous, zinc chloride, iron trichloride, boron trifluoride; Described an acidic catalyst is selected from one or more the mixture in oxalic acid, sulfuric acid, hydrochloric acid, phosphoric acid, xylene monosulfonic acid, Phenylsulfonic acid, benzene disulfonic acid, C1-C15 alkyl benzene sulphonate (ABS), naphthene sulfonic acid, acidic ion exchange resin.
8. a preparation method for the modification resorcin phenolic resin as described in any one of claim 1-7, is characterized in that:
(1) Resorcinol first with described properties-correcting agent generation aralkyl glycosylation reaction after, then with aldehyde reaction;
Or: after (2) Resorcinol first prepares resol with aldehyde reaction, then with properties-correcting agent generation aralkyl glycosylation reaction;
Or: (3) part or all of Resorcinol with aldehyde reaction while carry out aralkyl glycosylation reaction with described properties-correcting agent.
9. the preparation method of modification resorcin phenolic resin as claimed in claim 8, is characterized in that: after Resorcinol first carries out aralkyl glycosylation reaction with properties-correcting agent, then react with aldehyde.
10. the modification resorcin phenolic resin as described in any one of claim 1-7, is characterized in that: for the methylene receptor of rubber combination.
11. 1 kinds of rubber combinations, is characterized in that: comprise following component:
I () is selected from natural rubber and elastomeric rubber components;
(ii) methylene radical donor;
(iii) methylene receptor of the modification resorcin phenolic resin be selected from described in any one of claim 1-7 is comprised.
12. rubber combinations as claimed in claim 11, it is characterized in that: rubber components is selected from natural rubber, synthetic rubber or its combination, described synthetic rubber be selected from the multipolymer of the multipolymer of the multipolymer of the multipolymer of cis-Isosorbide-5-Nitrae-polyisoprene, polyhutadiene, sovprene, isoprene and divinyl, vinyl cyanide and divinyl, vinyl cyanide and isoprene, the multipolymer of vinylbenzene and divinyl and isoprene, butyl rubber, terpolymer EP rubber, vinylbenzene and divinyl one or more.
13. rubber combinations as claimed in claim 11, is characterized in that: described methylene radical donor be selected from vulkacit H, HMMM, six ethoxyl methyl trimeric cyanamides, trioxymethylene and paraformaldehyde one or more.
14. rubber combinations as claimed in claim 11, is characterized in that: the part by weight of described methylene radical donor and described modification resorcin phenolic resin is between 1: 5 ~ 5: 1.
15. rubber combinations as claimed in claim 11, it is characterized in that: in described rubber combination, also comprise additive, described additive be selected from carbon black, vulcanizing agent, promotor, stearic acid, zinc oxide, oxidation inhibitor, softening oil, cobalt salt one or more.
The purposes of 16. rubber combinations as described in any one of claim 11-15, is characterized in that, for the production of matrix material.
The purposes of 17. rubber combinations as claimed in claim 16, is characterized in that, carries out the matrix material of combining closely for tire, sebific duct, these needs of adhesive tape and steel wire or filamentary material.
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| FR3017070B1 (en) * | 2014-02-06 | 2017-08-25 | Michelin & Cie | STEEL REINFORCING ELEMENT COATED BY AN ADHESIVE COMPOSITION BASED ON AROMATIC ALDEHYDE AND POLYPHENOL |
| FR3017133B1 (en) * | 2014-02-06 | 2016-03-11 | Michelin & Cie | RUBBER COMPOSITE REINFORCED WITH AT LEAST ONE STEEL REINFORCING ELEMENT ADHESIVED BY AN ADHESIVE COMPOSITION BASED ON AROMATIC ALDEHYDE AND POLYPHENOL |
| CN104231198B (en) * | 2014-09-12 | 2016-09-07 | 华奇（中国）化工有限公司 | Aralkyl resorcinol aldehydes compound resin that m-phenylene diamine (MPD) is modified and preparation thereof and application |
| CN104276928B (en) * | 2014-10-08 | 2016-04-13 | 苏州市吴赣药业有限公司 | The preparation method of two [1-(4-hydroxy phenyl)-1-the methylethyl]-Resorcinol of a kind of 4,6- |
| CN105085849B (en) * | 2015-08-01 | 2017-03-29 | 江苏麒祥高新材料有限公司 | A kind of modified resorcinol formaldehyde resin adhesion promotor and preparation method thereof |
| CN109422857A (en) * | 2017-08-30 | 2019-03-05 | 北京彤程创展科技有限公司 | A kind of modified bisphenol phenolic resin, preparation method and application |
| CN107629181B (en) * | 2017-10-30 | 2019-07-26 | 湖南金泰检测检验有限公司 | Phenol-formaldehyde resin modified, modified phenolic resin grease article and its preparation method and application |
| CN107857848B (en) * | 2017-11-16 | 2020-06-12 | 彤程化学（中国）有限公司 | Melamine modified resorcinol resin and synthesis method and application thereof |
| CN109369866A (en) * | 2018-09-28 | 2019-02-22 | 华奇（中国）化工有限公司 | A kind of resorcinol air aldehyde resin and its preparation method and application |
| CN114671741B (en) * | 2020-12-24 | 2024-04-02 | 彤程新材料集团股份有限公司 | Resorcinol oligomer derivative for rubber tyre and its mother colloidal particle preparation and application |
| CN116396541B (en) * | 2023-03-06 | 2023-12-22 | 江苏国立化工科技有限公司 | Synthesis method and device of resorcinol rubber adhesive |
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| CN101235166A (en) * | 2008-01-04 | 2008-08-06 | 华奇（张家港）化工有限公司 | Resorcin phenolic resin modified rubber composition |
| CN102391552A (en) * | 2011-09-22 | 2012-03-28 | 华南理工大学 | Rubber material containing phenolic tackifying resin |
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