CN101235166A - Resorcin phenolic resin modified rubber composition - Google Patents
Resorcin phenolic resin modified rubber composition Download PDFInfo
- Publication number
- CN101235166A CN101235166A CNA2008100322739A CN200810032273A CN101235166A CN 101235166 A CN101235166 A CN 101235166A CN A2008100322739 A CNA2008100322739 A CN A2008100322739A CN 200810032273 A CN200810032273 A CN 200810032273A CN 101235166 A CN101235166 A CN 101235166A
- Authority
- CN
- China
- Prior art keywords
- acid
- resorcinol
- rubber
- aldehyde
- phosphite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a modified cured rubber compound which comprises (i) the rubber components of natural rubber or synthetic rubber, (ii) methano donator, (iii) aralkyl substituted phenol resin as the methano acceptor, wherein the aralkyl substituted phenol (resorcin) methano donator resin can be prepared by reacting the substituted or non-substituted phenol compound, vinyl aromatic compound and aldehyde and/or ketone in the presence of organic metal phosphate or phosphite ester catalyst. The inventive methano acceptor has lower smoke degree than R-80 (resorcin-80). And in the tension strength and dynamic mechanical property test, the aralkyl substituted resorcin phenol resin has better performance than R-80 and resorcin-formaldehyde (RF) resin.
Description
Technical field
The present invention relates to the preparation of the resol of aralkyl replacement, and they are as the application of rubber compounding resin in preparation pneumatic tyre, penstock and belt.
Background technology
In the production of reinforcing rubber goods such as tire and flexible pipe, various supporting materials have been used for increasing the intensity of rubber item.Usually, these supporting materials are made by regenerated fiber, nylon, polyester, steel wire and glass fibre.The steel wire that is used for these purposes is at first wanted brass-plating or zinc.The basic demand of accomplishing effective reinforcement is that these supporting materials will be adhered on the rubber tightly.Maximum when bonding when producing between rubber and the strong material, rubber or rubber compound just can reach maximum reinforcement.Owing to continued deflection when rubber item uses and be exposed in the hot environment, such as in doughnut, just being difficult to reach good bonding.Rubber and steel wire form favorable mechanical and engage the initial viscosity that can obtain excellence in sulfidation, but because the use of aging and rubber item, bond properties weakens or completely dissolve through regular meeting, and causes bonding premature failure.For fear of this situation, add adhesion promotor usually and keep good bonding between rubber or rubber compound and the metal.
Promotion between rubber and brass-plating or the galvanized steel wire is bonding, and traditional method is to adopt two-pack binding system, i.e. methylene receptor and methylene radical donor system.In the past, Resorcinol was as methylene receptor, and vulkacit H (Hexa) and HMMM (HMMM) be as methylene radical donor compound, promoted bonding between steel wire or cord and rubber or the rubber combination.But how long Hexa does not use in actual applications, can corrode steel wire and influence bonding quality because Hexa decomposes the ammonia that produces.In sulfuration process, methylene radical donor compound produces formaldehyde, and formaldehyde and resorcin reaction original position form a kind of Resorcinol-formaldehyde (RF) network structure.The formation of this RF network structure has improved physicals, mechanical property and the bond properties of vulcanized rubber in the sulfidation.
It's a pity, add Resorcinol in the rubber compounding and have some potential unfavorable factors.When Resorcinol was unmodified, its volatility and smokiness were very serious.In order to reduce being fuming of Resorcinol, once researched and developed resorcinol derivatives, Resorcinol-formaldehyde (RF), alkyl-resorcinol-formaldehyde resin, aralkyl-resorcinol-formaldehyde resin, and be applied to rubber compounding, such as tire production.The resorcinol derivatives of these modifications and resin make the mechanical property of vulcanized rubber or rubber combination, bond properties aging and unaged rubber be improved.Improve although carried out these, the content that dihydroxy-benzene is sowed discord in the resorcinol-formaldehyde resin middle reaches is still very high.Therefore, be starved of a kind of low resorcinol resin of not being fuming or being fuming that can be used as methylene receptor of invention, strengthen sulfuration, machinery and the bond properties of vulcanizate compositions.
Main purpose of the present invention provide a kind of volatility methylene receptor material low or that be fuming low be used for rubber compounding strengthen the sulfuration and mechanical property.Use the few resin of free monomer content that the problem of being fuming in the rubber compounding application is minimized or elimination fully.Like this, the resorcinol resin of not being fuming by use in tire and the non-tyre industry can reduce the detrimentally affect to environment and health of human body greatly.
These rubber combinations can be used for the production of pneumatic tyre, flexible pipe and belt.
Summary of the invention
According to the present invention, the aralkyl resin modified phenol resin that comprises following chemical structure is reacted generation in the presence of organo-metallic phosphite or phosphorous acid esters catalyzer:
In above-mentioned chemical structure, R
1And R
2Group can be a hydrogen independently, hydroxyl, amino, chlorine, ethanoyl, benzoyl, alkyl such as methyl, ethyl, propyl group, butyl, hexyl, octyl group, nonyl, decyl, dodecyl and pentadecyl, aralkyl such as phenyl, perhaps alkaryl such as alkyl phenyl; In the following formula, R
3And R
4Group can be hydrogen, alkyl and the alkaryl with 1～9 carbon atom independently.
According to the present invention, this aralkyl resin modified phenol resin can prepare by following method: the phenolic compound of following general formula (a) expression reacts with the vinyl aromatic compounds that (1) is selected from vinylbenzene, alpha-methyl styrene, p-methylstyrene, Vinylstyrene, vinyl naphthalene and Vinyl toluene
In the formula, R
1And R
2Can be hydrogen, hydroxyl, amino, chlorine, ethanoyl, benzoyl independently, alkyl such as methyl, ethyl, propyl group, butyl, hexyl, octyl group, nonyl, decyl, dodecyl and pentadecyl, aralkyl such as benzyl, perhaps alkaryl such as alkyl phenyl;
Then with (2) one or more aldehyde and/or ketone compound, it is selected from: formalin, Paraformaldehyde 96, trioxane, acetaldehyde, paraldehyde, butyraldehyde, isobutyric aldehyde, hexanal, octanal, aldehyde C-9, crotonic aldehyde, phenylacrolein, phenyl aldehyde, furfural, acetone and methylethylketone, react and make under the organo-metallic phosphite of expression or phosphite catalysts or their the mixture existence condition in following structural formula (b) or (c)
In the formula, R represents to have the alkyl or the haloalkyl of 1～20 carbon atom independently, has the aryl or the halogenated aryl of 6～12 carbon atoms, perhaps has the aralkyl or the halo aralkyl of 7～20 carbon atoms.
Can be used for preparing the present invention and can be selected from alkyl phosphite or aryl phosphite as the phosphite catalysts of the resol of methylene radical donor.
The aryl phosphite ester catalyst that the present invention uses is the phosphorous acid ester that contains following group: two fragrant organic ester groups and a hydrogen atom, three aromatic ester groups, or two aromatic ester groups and an alkyl.
Concrete phosphite catalysts comprises tricresyl phosphite phenylester, tricresyl phosphite n-butyl, tricresyl phosphite ethyl ester, tricresyl phosphite methyl ester, tricresyl phosphite (nonyl phenyl) ester, tricresyl phosphite (2-ethylhexyl) ester, three stearyl phosphorous acid esters, phenylbenzene one decyl phosphorous acid ester, phosphorous acid diphenyl, phosphorous acid dimethyl esters, phosphorous acid di-n-butyl ester etc., and their mixture.
The phosphite catalysts that comprises among the present invention can make together with other catalyzer and be used for changing vulcanization rate, as known to those skilled in the art.The common catalyzer that can use together with phosphorous acid ester can be acid and other potential acid catalysts.The acid catalyst that is fit to comprises mineral acid such as phosphoric acid, sulfuric acid or hydrochloric acid, organic acid such as oxalic acid, toxilic acid, perhaps any in acid anhydrides such as the maleic anhydride.Strong acid such as sulfuric acid, hydrochloric acid, phosphoric acid, phosphorous acid, Phenylsulfonic acid, sulfocarbolic acid, toluenesulphonic acids, methylsulfonic acid, three halogenated acetic acids or dihalo acetate can use separately also and can use together with potential acid.For example, the phosphorous acid diphenyl can be earlier in advance with 1～3% 70% Phenylsulfonic acid, methylsulphonic acid or sulfocarbolic acid solution reaction, and as catalyzer.
The usage quantity of phosphite catalysts can be 0.2～10%, in the weight of phenol.
The phenolic compound that can be used for preparing resol among the present invention does not have particular determination, preferably include at least a phenol that is selected from down group: phenol, ortho-cresol, meta-cresol, p-cresol, xylenol, p-tert-butylphenol, to tert-octyl phenol, p-phenyl phenol, bisphenol-A, bisphenol-f, Resorcinol, Phloroglucinol, cashew shell liquid (CNSL) and Metha Amino Phenon.Most preferred phenolic compound is a Resorcinol.
In the preparation process of resol of the present invention, can use various vinyl aromatic compounds.These compounds can be selected from down group: vinylbenzene, alpha-methyl styrene, Beta-methyl vinylbenzene, p-methylstyrene, Vinylstyrene, a di isopropenylbenzene or to di isopropenylbenzene and vinyl naphthalene.Most preferred vinyl aromatic compounds is a vinylbenzene.
In the preparation process of resol of the present invention, the phenolic compound of general formula (a) expression can be at first and vinyl aromatic compounds generation aralkyl glycosylation reaction, then separately or with other phenolic compound with aldehyde and/or reactive ketone.Perhaps, at first prepare resol, vinyl aromatic compounds is reacted on the resol.Except these methods, also can be that part or all of phenolic compound carries out the aralkyl glycosylation reaction when reacting with aldehydes or ketones.But preferred option be phenolic compound at first with vinyl aromatic compounds generation aralkyl glycosylation reaction, react with aldehydes or ketones then.The first-selected formaldehyde of aldehyde cpd.
Prepare preferred phenol of this resol and vinylbenzene mol ratio and can be 1: 0.05～1: 1.5.Similarly, the mol ratio of phenol and aldehyde and/or ketone can be 1: 0.05～1: 0.7.The mol ratio of phenol, vinyl aromatic compounds, aldehyde component is preferably 1: 0.05: 0.2 to 1: 1.5: 0.8, specifically is 1: 0.2: 0.3 to 1: 1.5: 0.7.Three kinds of first-selected Resorcinols of component, formaldehyde and vinylbenzene.
The resorcin phenolic resin that comprises chemical structure (a) can be used as methylene receptor at the rubber combination that is used for producing pneumatic tyre, flexible pipe and belt.Therefore, this invention provides a kind of vulcanizate compositions of modification, and it comprises that (i) is selected from natural rubber or elastomeric rubber components, (ii) methylene radical donor and (iii) as the aralkyl-Resorcinol-air aldehyde resin of methylene receptor.
Rubber components of the present invention can be a cis-1, multipolymer, vinylbenzene and the divinyl of multipolymer, vinyl cyanide and the isoprene of multipolymer, vinyl cyanide and the divinyl of 4-polyisoprene (natural or synthetic), polyhutadiene, sovprene, isoprene and divinyl and the multipolymer of isoprene, isobutene rubber (butyl) and the rare rubber of ethene-third (EPDM), vinylbenzene and the multipolymer of divinyl and their blend.
Compositions of vulcanize rubbers can comprise one or more methylene radical donors among the present invention.The meaning of term " methylene radical donor " is the compound that can produce formaldehyde after the heating, and the formaldehyde of generation can react with aralkyl-Resorcinol-urea formaldehyde, generates crosslinked reticulated structure in rubber compound.The methylene radical donor that the present invention is suitable for comprises: vulkacit H, six ethoxyl methyl trimeric cyanamides, HMMM, 2-nitro-2-methyl isophthalic acid-propyl alcohol (NMP), trioxane and yuban such as Paraformaldehyde 96.
The methylene radical donor among the present invention in the rubber combination and the weight ratio of methylene radical donor can change.But usually, the scope of weight ratio is between about 1: 10～10: 1.The scope of weight ratio is preferably in 1: 5～between 5: 1.
Methylene receptor of the present invention is aralkyl-Resorcinol-urea formaldehyde.These methylene receptor can be reacted in the presence of phosphite catalysts or acid catalyst or their mixture by aralkyl Resorcinol and aldehyde and/or ketone and be made.Resorcinol and vinyl aromatic compounds react in the presence of phosphite catalysts or acid catalyst can generate the aralkyl Resorcinol.The vinyl aromatic compounds that is suitable in the aralkyl glycosylation reaction of the present invention comprises: vinylbenzene, alpha-methyl styrene, Vinylstyrene, vinyl naphthalene, a di isopropenylbenzene or to di isopropenylbenzene and Vinyl toluene.
Except phosphorous acid ester, acid also can be as the common catalyzer of Resorcinol and vinyl aromatic compounds generation aralkyl glycosylation reaction.The acid catalyst that the aralkyl glycosylation reaction is suitable for is selected from down group: mineral acid example hydrochloric acid, sulfuric acid, phosphoric acid, phosphorous acid, sulfonic acid such as benzene monosulfonic acid, benzene disulfonic acid, benzene trisulfonic acid, tosic acid (PTSA) are to Witco 1298 Soft Acid, alkylsulphonic acid, oxalic acid.The amount of the common catalyzer that uses in the aralkyl glycosylation reaction is 0.01～10 part/100 parts Resorcinols.The temperature of reaction that the aralkyl glycosylation reaction adopts is preferably 50 ℃～180 ℃.
Behind Resorcinol and vinylbenzene or vinyl aromatic compounds generation aralkyl glycosylation reaction, can add aldehydes or ketones or aldehyde ketone mixed solution.The aldehyde that is suitable for and the example of ketone comprise: the aldehyde aqueous solution (37%), Paraformaldehyde 96, the solution that contains formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, isobutyric aldehyde, hexanal, octanal, aldehyde C-9, crotonic aldehyde, phenyl aldehyde, furfural, acetone and methylethylketone.The usage quantity of aldehyde and/or ketone can be 0.05～0.8 mole/1 a mole Resorcinol.
Vulcanizate compositions of the present invention can also add additive, as carbon black, cobalt salt, stearic acid, silicon-dioxide, sulphur, zinc oxide, filler, antioxidant and softening oil.Particulate filler such as silicon-dioxide, carbon black, clay, talcum powder, lime carbonate, silicate are generally used in the rubber improving the physical and mechanical property of rubber such as modulus, tensile strength, resistance to abrasion, tear resistance and dynamic property as supporting material.
The sulfuration of normal conditions rubber combination will be carried out in the presence of sulfur vulcanizing agent.The example of the sulfur vulcanizing agent that is suitable for comprises: elementary sulfur (free sulphur) or sulfur donor vulcanizing agent such as curing amine, polymerization polysulfide or sulphur olefin adducts.The first-selected elementary sulfur of sulfur vulcanizing agent.As is known to the person skilled in the art, the consumption of sulfur vulcanizing agent is in the scope of 0.5～10phr.
Promotor normally is used for controlling required time of vulcanization reaction and/or temperature to improve curability.The promotor kind that is suitable for comprises amine, disulphide, guanidine, thiocarbamide, thiazole, thiuram, sulfinyl amine, dithiocar-bamate and xanthogenate.The first-selected sulfinyl amine of first promotor.If use second promotor, second promotor is preferably selected guanidine, dithiocar-bamate or thiuram compound for use.
Additive of the present invention can add in the rubber combination according to the addition means of traditional rubber compounding additive, and described additive is such as HMMM (HMMM).The blending means that rubber combination is commonly used is to mix with the Banbury Banbury mixer.A kind of typical method is that the additive that does not at first participate in reacting mixes with rubber in being warmed up to about 150 ℃ Banbury mixer.Vulcanizing agent, promotor and adhesion promotor add in temperature is about 90 ℃～150 ℃ mixed step of the second and the 3rd step.
The invention still further relates to a kind of compositions of vulcanize rubbers, its physical and mechanical property such as tensile modulus, hardness, anti-incipient scorch, curing time dynamic modulus (G ') and Tan δ (magnetic hysteresis) are improved.
But vulcanisable rubber mixtures of the present invention can be prepared, process and vulcanize according to the method for knowing.They are highly suitable for the production of industrial rubber articles, especially have steel wire cord or fibercord to make the goods of reinforcement support.The rubber combination that contains aralkyl-resorcinol-formaldehyde resin product can be used for composite prod, comprise tire, transmission belt, conveying belt, print roller, rubber boots with and the cleaning shoe of sole, rubber dish-cloth wringers, automobile car pad, truck, ball mill liner, pipeline material, fan belt etc.Vulcanization of rubber product is particularly useful for the production that steel wire covers the body cord or the rubber cover of glue, tire.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.
Embodiment
Embodiment 1
In the 500ml round-bottom reaction flask that agitator, thermometer, reflux exchanger and dropping funnel are housed, add 165.1g (1.5 moles) Resorcinol and 10.71g tricresyl phosphite phenylester catalyzer (TPP), and heated mixt is to fusing.In the Resorcinol of fusing, dripped 78,1g (0.93 mole) formalin at about 90～120 minutes lentamente in the clock time then.After formaldehyde dripped and finishes, the reactant dehydration steamed interior all volatile matters of flask and is raised to about 150 ℃～160 ℃ up to temperature.In the Resorcinol-formaldehyde reaction liquid of fusing, adding 72.6g (0.705 mole) vinylbenzene under the intensification condition then, about 60～120 minutes of the dropping time of control.After vinylbenzene drips and finishes, add the 5.6gNaOH aqueous solution and come the neutralizing acid catalyzer.Vacuumizing dehydration at last, to obtain softening temperature be 108.2 ℃ brown resin.HPLC analyzes and shows that it is 5.4% that the content of dihydroxy-benzene is sowed discord in the resin middle reaches.
Embodiment 2
In the 500ml round-bottom reaction flask that agitator, thermometer, reflux exchanger and dropping funnel are housed, add 165.1g (1.5 moles) Resorcinol and 10.71g tricresyl phosphite phenylester catalyzer (TPP), and heated mixt is to fusing.Then, dropwise add 71.25g (0.675 mole) vinylbenzene in the Resorcinol of fusing, the control dropping time is 120 minutes.In the Resorcinol-vinylbenzene reaction solution of fusing, added 77.5g (0.93 mole) formalin at about 90～120 minutes lentamente in the clock time then.After formaldehyde dripped and finishes, the reactant dehydration steamed interior all volatile matters of flask and is raised to about 150 ℃～160 ℃ up to temperature.Then, under the condition that heats up gradually, in Resorcinol-vinylbenzene-formaldehyde reaction liquid, add 16.5g (1.15 moles) vinylbenzene with about 60～120 minutes clock times.After dripping end, add the 5.5gNaOH aqueous solution and come the neutralizing acid catalyzer.Vacuumizing dehydration at last, to obtain softening temperature be 107 ℃ brown resin.HPLC analyzes and shows that it is 3.4% that the content of dihydroxy-benzene is sowed discord in the resin middle reaches.
Embodiment 3
In the 500ml round-bottom reaction flask that agitator, thermometer, reflux exchanger and dropping funnel are housed, add 165.1g (1.5 moles) Resorcinol and 10.71g triphenyl phosphite catalysts (TPP), and heated mixt is to fusing.Then, dropwise add 109.41g (1.05 moles) vinylbenzene in the Resorcinol of fusing, the control dropping time is 120 minutes.In the Resorcinol-vinylbenzene reaction solution of fusing, added 78.75g (0.945 mole) formalin at about 90～120 minutes lentamente in the clock time then.After all formaldehyde drip and finish, add the 5.5g NaOH aqueous solution and come the neutralizing acid catalyzer.Vacuumizing dehydration at last, to obtain softening temperature be 105 ℃ crimson chromoresin.HPLC analyzes and shows that it is 0.96% that the content of dihydroxy-benzene is sowed discord in the resin middle reaches.
The content that dihydroxy-benzene is sowed discord in the resin middle reaches that obtain thinks that less than 1% it is the extremely low resorcinol resin of a kind of volatility, can be used in many application.
Embodiment 4
In the 500ml round-bottom reaction flask that agitator, thermometer, reflux exchanger and dropping funnel are housed, add 165.1g (1.5 moles) Resorcinol and 10.71g triphenyl phosphite catalysts (TPP), and heated mixt is to fusing.Then, dropwise add 234g (2.25 moles) vinylbenzene in the Resorcinol of fusing, the control dropping time is 180 minutes.In the Resorcinol-vinylbenzene reaction solution of fusing, added 81.88g (0.975 mole) formalin at about 120～150 minutes lentamente in the clock time then.After all formaldehyde drip and finish, add the 5.5g NaOH aqueous solution and come the neutralizing acid catalyzer.Vacuumizing dehydration at last, to obtain softening temperature be 99 ℃ orange-yellow resin.HPLC analyzes and shows that it is zero that the content of dihydroxy-benzene is sowed discord in the resin middle reaches.
Analytical results has clearly illustrated that this resin does not contain free or unreacted Resorcinol.It is applied to rubber combination can make the problem of being fuming reduce to minimum even elimination fully.In tire and non-tyre industry, use the resorcinol resin of not being fuming that makes among this embodiment can improve the influence that environment and health of human body are caused greatly.
Embodiment 5
In the 500ml round-bottom reaction flask that agitator, thermometer, reflux exchanger and dropping funnel are housed, add 165.1g (1.5 moles) Resorcinol and 10.71g triphenyl phosphite catalysts (TPP), and heated mixt is to fusing.Then, dropwise add 31.2g (0.3 mole) vinylbenzene in the Resorcinol of fusing, the control dropping time is 30～60 minutes.In the Resorcinol-vinylbenzene reaction solution of fusing, added 82.2g (1.0 moles) formalin at about 90～120 minutes lentamente in the clock time then.After all formaldehyde drip and finish, add the 5.5g NaOH aqueous solution and come the neutralizing acid catalyzer.Vacuumizing dehydration at last, to obtain softening temperature be 132 ℃ russet resin.HPLC analyzes and shows that it is 6.1% that the content of dihydroxy-benzene is sowed discord in the resin middle reaches.
Embodiment 6
In the 500ml round-bottom reaction flask that agitator, thermometer, reflux exchanger and dropping funnel are housed, add 110.1g (1.0 moles) Resorcinol and 7.2g triphenyl phosphite catalysts (TPP), and heated mixt is to fusing.Then, dropwise add 83.32g (0.8 mole) vinylbenzene in the Resorcinol of fusing, the control dropping time is 120～150 minutes.In the Resorcinol-vinylbenzene reaction solution of fusing, added 30.2g (0.37 mole) formalin at about 90～120 minutes lentamente in the clock time then.After all formaldehyde drip and finish, add the 3.7g NaOH aqueous solution and come the neutralizing acid catalyzer.Vacuumizing dehydration at last, to obtain softening temperature be 74 ℃ russet resin.HPLC analyzes and shows that it is 3.4% that the content of dihydroxy-benzene is sowed discord in the resin middle reaches.
Embodiment 7
In the 500ml round-bottom reaction flask that agitator, thermometer, reflux exchanger and dropping funnel are housed, add 165.1g (1.5 moles) Resorcinol and 3.7g triphenyl phosphite catalysts (TPP), and heated mixt is to fusing.In the Resorcinol of fusing, added 107.3g (0.975 mole) formalin (40% concentration) at about 90～120 minutes lentamente in the clock time then.After all formaldehyde droppings and reaction finish, add the 1.1g NaOH aqueous solution and come the neutralizing acid catalyzer.Vacuumize dehydration at last and obtain crimson chromoresin, softening temperature is 78 ℃.
Embodiment 8
In the 500ml round-bottom reaction flask that agitator, thermometer, reflux exchanger and dropping funnel are housed, add 165.1g (1.5 moles) Resorcinol and 3.7g triphenyl phosphite catalysts (TPP), and heated mixt is to fusing.Then, in the Resorcinol of fusing, add 21.75g (0.375 mole) anhydrous propanone and make it to react completely lentamente.In about 90～120 minutes clock times, under reflux state, in Resorcinol-acetone is anti-, answer liquid to add 50.4g (0.6 mole) formalin (37% concentration) lentamente then.After all formaldehyde droppings and reaction finish, add the 1.0g NaOH aqueous solution and come the neutralizing acid catalyzer.Vacuumize dehydration at last and obtain orange-yellow resin, softening temperature is 76 ℃.
Embodiment 9
In the 500ml round-bottom reaction flask that agitator, thermometer, reflux exchanger and dropping funnel are housed, add 165.1g (1.5 moles) Resorcinol and 3.7g triphenyl phosphite catalysts (TPP), and heated mixt is to fusing.In about 90～120 minutes clock times, under reflux state, in the Resorcinol of fusing, add 78.1g (0.93 mole) formalin (37% concentration) lentamente then.After all formaldehyde droppings and reaction finish, add the 1.0g NaOH aqueous solution and come the neutralizing acid catalyzer.Vacuumizing dehydration at last, to obtain softening temperature be 110 ℃ orange resin.It is 18.9% that HPLC analyzes the content that shows free Resorcinol.
Embodiment 10
In the 500ml round-bottom reaction flask that agitator, thermometer, reflux exchanger and dropping funnel are housed, add 165.1g (1.5 moles) Resorcinol and 3.7g triphenyl phosphite catalysts (TPP), and heated mixt is to fusing.In about 90～120 minutes clock times, under reflux state, in the Resorcinol of fusing, add 78.1g (0.93 mole) formalin (37% concentration) lentamente then.After all formaldehyde droppings and reaction finished, reaction mixture refluxed 60 minutes again.This refluxing stage has steamed water and the volatile matter in the reaction flask under normal atmosphere and soaking condition.In Resorcinol-formaldehyde (RF) resin of fusing, add 59 gram distilled water then, obtain the resin aqueous solution of crimson look.The water-content of resin solution is 29.5% after tested.Utilization is used always
13The C-NMR analytical procedure records that 4,4 ' in this RF resin-with 2,4 '-methylene bridge distribution proportion is 80: 20.
Embodiment 11
In the 500ml round-bottom reaction flask that agitator, thermometer, reflux exchanger and dropping funnel are housed, add 165.1g (1.5 moles) Resorcinol and 8.6g tributyl phosphite catalysts (TBP), and heated mixt is to fusing.Then, dropwise add 78.2g (0.75 mole) vinylbenzene in the Resorcinol of fusing, the control dropping time is 120～150 minutes.In the Resorcinol-vinylbenzene reaction solution of fusing, added 63g (0.75 mole) formalin at about 90～120 minutes lentamente in the clock time then.After all formaldehyde drip and finish, add the 2.8g NaOH aqueous solution and come the neutralizing acid catalyzer.Vacuumizing dehydration at last, to obtain softening temperature be 97 ℃ sorrel resin.HPLC analyzes and shows that it is 9.4% that the content of dihydroxy-benzene is sowed discord in the resin middle reaches.
Embodiment 12
In the 500ml round-bottom reaction flask that agitator, thermometer, reflux exchanger and dropping funnel are housed, add 165.1g (1.5 moles) Resorcinol and 8.6g phenylbenzene phosphite catalysts, and heated mixt is to fusing.Then, dropwise add 78.2g (0.75 mole) vinylbenzene in the Resorcinol of fusing, the control dropping time is 120～150 minutes.In the Resorcinol-vinylbenzene reaction solution of fusing, added 63g (0.75 mole) formalin at about 90～120 minutes lentamente in the clock time then.After all formaldehyde drip and finish, add the 2.8g NaOH aqueous solution and come the neutralizing acid catalyzer.Vacuumizing dehydration at last, to obtain softening temperature be 89 ℃ sorrel resin.HPLC analyzes and shows that it is 5.6% that the content of dihydroxy-benzene is sowed discord in the resin middle reaches.
Embodiment 13
In the 500ml round-bottom reaction flask that agitator, thermometer, reflux exchanger and dropping funnel are housed, add 165.1g (1.5 moles) Resorcinol and 8.6g triethyl phosphorite catalyzer, and heated mixt is to fusing.Then, dropwise add 78.2g (0.75 mole) vinylbenzene in the Resorcinol of fusing, the control dropping time is 120～150 minutes.In the Resorcinol-vinylbenzene reaction solution of fusing, added 63g (0.75 mole) formalin at about 90～120 minutes lentamente in the clock time then.After all formaldehyde drip and finish, add the 2.8g NaOH aqueous solution and come the neutralizing acid catalyzer.Vacuumizing dehydration at last, to obtain softening temperature be 97 ℃ sorrel resin.
Embodiment 14
In the 500ml round-bottom reaction flask that agitator, thermometer, reflux exchanger and dropping funnel are housed, add 165.1g (1.5 moles) Resorcinol, 66g water and 4.35g oxalic acid, and heated mixt.When temperature is raised to about 95 ℃, added 78.1g (0.93 mole) formalin in the clock time lentamente at about 30 minutes, mixeding liquid temperature is controlled at 90～105 ℃.After formaldehyde drips and finishes, continue again to stir 30 minutes.And then carry out normal atmosphere and vacuum distilling dehydration and be raised to 120～125 ℃ up to reacting liquid temperature.Under 120～130 ℃, slowly add 72.6g (0.705 mole) vinylbenzene then, the dropping time was controlled at 60 minutes.After all vinylbenzene drip and finish, add the 5.6g NaOH aqueous solution and come the neutralizing acid catalyzer.Vacuumizing dehydration at last, to obtain softening temperature be 111 ℃ sorrel resin.The content that HPLC analyzes the free Resorcinol that shows this resin is 4.4%.
Embodiment 15
In the 500ml round-bottom reaction flask that agitator, thermometer, reflux exchanger and dropping funnel are housed, add 110.1g (1.0 moles) Resorcinol, 0.8g tosic acid (PTSA) and 2g triphenyl phosphorous acid ester (TPP), and heated mixt is to fusing.Then, dropwise add 31.2g (0.3 mole) vinylbenzene in the Resorcinol of fusing, the control dropping time is 30 minutes.In the Resorcinol-vinylbenzene reaction solution of fusing, added 50.5g (0.62 mole) formalin at about 90～120 minutes lentamente in the clock time then.After all formaldehyde drip and finish, add the NaOH aqueous solution and come the neutralizing acid catalyzer.Vacuumizing dehydration at last, to obtain softening temperature be 121 ℃ sorrel resin.The content that HPLC analyzes the free Resorcinol that shows this resin is 4.3%.
Embodiment 16 (the catalytic resorcinol-formaldehyde resin of control resin-oxalic acid)
In the 500ml round-bottom reaction flask that agitator, thermometer, reflux exchanger and dropping funnel are housed, add 165.1g (1.5 moles) Resorcinol and 1.5g oxalic acid catalyzer, and heated mixt is to fusing.Under reflux state, add 78.1g (0.93 mole) formalin (37% concentration) lentamente in the Resorcinol of fusing then, the dropping time was controlled at 90～120 minutes.After all formaldehyde droppings and reaction finish, add the NaOH aqueous solution and come the neutralizing acid catalyzer.Vacuumizing dehydration at last, to obtain softening temperature be 112.5 ℃ orange-yellow resin.The content that HPLC analyzes the free Resorcinol that shows this resin is 17.3%.
Embodiment 17
When being used for rubber compounding, in the mixed process of rubber combination, can be observed the Resorcinol phenomenon of being fuming when Resorcino with based on the derivative of Resorcino.This is because the volatility and the Resorcinol of Resorcinol are the cause that exists with unreacted monomer in derivative and resin.In order to measure the volatility of material, available hot gravimetry (TGA).Table 1 has provided the hot gravimetric analysis data of the aralkyl-resorcinol-formaldehyde resin that makes among the R-80 that records and the embodiment 2 under nitrogen environment.
| Table 1 | |||||
| Thermogravimetric analysis (TGA) data | |||||
| R-80 and Resorcino-vinylbenzene-formaldehyde resin (embodiment 2) | |||||
| Compound | Weight loss (%) | ||||
| 125℃ | 150℃ | 175℃ | 200℃ | 225℃ | |
| R-80 * | 0.39 | 1.52 | 5.77 | 17.45 | 48.31 |
| R-Sty-F | 0.6 | 1.7 | 3 | 4.5 | 7 |
| *Commercially available 80% pre-dispersed Resorcinol and 20%EPDM blend | |||||
| R-Sty-F resin: Resorcino-vinylbenzene-formaldehyde resin | |||||
| Analysis condition: nitrogen environment, heating rate: 10 ℃/minute | |||||
Find out from the result of table 1 with may be obvious that, the resin that the present invention makes R-80 product more commercially available when high temperature than safe letter company (China), volatility will reduce greatly.This R-80 is the 80% pre-dispersed Resorcinol and the blend of 20%EPDM rubber.
Embodiment 18
The natural rubber composition of test usefulness made by three steps.Table 2 has provided basic rubber compounding.
| Table 2 | |
| The rubber combination of test usefulness | |
| Masterbatch | Weight part |
| Natural rubber | 100 |
| Carbon black (N326) | 42 |
| Silicon-dioxide | 10 |
| Zinc oxide | 8 |
| Sulphur (80%) (OT20) | 5 |
| Cobalt salt (CN 20.5%) | 1.2 |
| Sulfinyl amine (DCBS) | 1.2 |
| Polymeric 1,2-dihydro-2,2,4-trimethylquinoline (TMQ) | 0.5 |
| N-(1, the 2-dimethylbutyl)-N '-phenyl-right-phenylenediamine { 6PPD (4020) } | 1.5 |
| The resin of R-80 or embodiment 2 or embodiment 16 | 1.8 |
| HMMM(65％) | 4.34 |
The RF resin that makes among the resin that makes among the embodiment 2 and the embodiment 16 and commercially available R-80 product are made comparisons, estimate its performance in the natural rubber compound.Commercially available R-80 is 80% pre-dispersed Resorcinol and the 20%EPDM blend that middle Cathay letter is produced.
The first step, in the Banbury Banbury mixer, rubber master batches is mixed under about 150 ℃.In second step, will under the about 145 ℃ of conditions of temperature, sneak in an amount of masterbatch of Banbury Banbury mixer according to the methylene receptor (having added cobalt salt) of embodiment 2 methods preparation.In the 3rd step, the insoluble sulfur shown in the table 2, promotor and an amount of HMMM are added and mix at about 90～100 ℃.This test compounds is placed under the environment of about 23 ℃ of constant room temperatures and 50% relative humidity and is spent the night.Measure its sulphur down at 150 ℃ then and become instrument sulfuration, shape and optimum cure degree, to estimate its mechanical property.
Curability is to become instrument with Alpha Technologies MDR sulphur,, measures under 1 ° of radian and the 1.67 hertz of conditions at 150 ℃ according to ASTM D 5289 and ISO6502 testing method.
Become in the instrument at vibration disk sulphur, the sizing material sample is subjected to the oscillatory shear power effect of uniform amplitude.Measure the moment of torsion that curing temperature embeds the vibration disk in the test glue sample down.Because the change of rubber or glue sample prescription is easy to measure, be very visual and accurate so this sulfuration test obtains data.An advantage clearly can finding out it from following table is that vulcanization rate is fast.
Provided test data in the table 3:
| Table 3 | |||
| Properties of rubber | |||
| Methylene receptor | R-80 | Embodiment 2 | Embodiment 16 |
| Contrast | The present invention | Contrast | |
| Methylene receptor (umber) | 1.88 | 1.88 | 1.88 |
| Methylene radical donor { HMMM (65%) } | 4.84 | 4.84 | 4.84 |
| Sulphur becomes instrument sulfuration (under 150 ℃, 30 minutes) | |||
| ML | 0.89 | 0.92 | 0.74 |
| MH | 30.66 | 27.46 | 27.83 |
| TS1 | 1.3 | 1.4 | 1.41 |
| TS2 | 2.3 | 3.33 | 3.24 |
| T10 | 3.12 | 4.3 | 4.13 |
| T50 | 7.11 | 9.43 | 8.36 |
| T90 | 15.1 | 17.55 | 16.25 |
| Tensile property | |||
| 50% modulus (N/mm 2) | 2.9 | 2.9 | 2.8 |
| 100% modulus (N/mm 2) | 4.6 | 4.6 | 4.4 |
| 300% modulus (N/mm 2) | 15.4 | 15.5 | 15 |
| Tensile strength (N/mm 2) | 21.7 | 24.2 | 16.8 |
| Elongation at break | 405.7 | 444.3 | 332.7 |
| Shore A hardness | 81 | 81 | 80 |
| Steel wire cord bonding (newton) before aging (steel wire: 3+9+15 * 0.22+1) | 1830 | 1615 | 1574 |
| Annotate: R-80 is commercially available 80% Resorcinol and the blend of 20%EPDM | |||
Can know from the data of table 3 and to find out that compare with the R-80 blend of middle Cathay letter, aralkyl-resorcinol-formaldehyde resin that the inventive method makes has improvement in tensile strength.
Embodiment 19
In this embodiment, use rubber machining analyzer (RPA) 2000 to measure dynamic mechanical properties.
RPA2000 can high repeat and highly reproduce before the ground test sulfuration and the rubber after the sulfuration.The sulphur that available test and son are tested under frequency sweeping, steady temperature and the frequency that comprises under steady temperature and the strain becomes the temperature scanning under the strain sweep under steady temperature and the frequency, constant strain and the frequency.The pinpoint accuracy of this instrument can repeated test glue sample performance change.
To be cross-linked rubber samples carry out strain sweep and frequency sweeping records at 60 ℃ for storage modulus, G ' and Tan δ data.Test data is listed in the table 4.
| Table 4 | |||
| The dynamic mechanical properties of glue sample | |||
| (temperature=60 ℃) | |||
| Methylene receptor | R-80 | Embodiment 2 | Embodiment 16 |
| Contrast | The present invention | Contrast | |
| Dynamic property (RPA-2000) | |||
| The strain sweep data | |||
| Storage modulus (G ', kPa) | |||
| 3.5% strain | 1983 | 2040 | 1912 |
| 9.33% strain | 1544 | 1598 | 1495 |
| 15.17% strain | 1382 | 1432 | 1344 |
| 21% strain | 1317 | 1376 | 1295 |
| Tanδ | |||
| 3.5% strain | 0.222 | 0.203 | 0.211 |
| 9.33% strain | 0.212 | 0.202 | 0.207 |
| 15.17% strain | 0.195 | 0.185 | 0.187 |
| 21% strain | 0.171 | 0.161 | 0.164 |
| The frequency sweeping data | |||
| Storage modulus (G ', kPa) | |||
| 0.167Hz | 1246 | 1334 | 1250 |
| 1.22Hz | 1285 | 1354 | 1271 |
| 2.28Hz | 1308 | 1363 | 1280 |
| 3.3Hz | 1316 | 1369 | 1288 |
| Tanδ | |||
| 0.167Hz | 0.138 | 0.13 | 0.131 |
| 1.22Hz | 0.164 | 0.153 | 0.155 |
| 2.28Hz | 0.173 | 0.162 | 0.165 |
| 3.3Hz | 0.174 | 0.163 | 0.165 |
| Annotate: R-80 is commercially available 80% Resorcinol and the blend of 20%EPDM | |||
Above-mentioned data have clearly illustrated that the vulcanized rubber that adds resin of the present invention has shown good dynamic characteristics and lower magnetic hysteresis, keep the bond properties suitable with the R-80 resin with the RF resin simultaneously.
Though as above-mentioned the specific embodiment of the present invention is described for illustrative purposes, under the prerequisite that does not depart from the scope of the invention, those skilled in the art obviously can do various modifications to the present invention.
Claims (10)
1. the vulcanizate compositions of a modification, it comprises:
(i) be selected from natural rubber or elastomeric rubber components;
(ii) methylene radical donor; With
The (iii) phenolic resinoid that replaces as the aralkyl of methylene receptor, it comprises following chemical structure:
In the formula, R
1And R
2Group is hydrogen independently, hydroxyl, amino, chlorine, ethanoyl, benzoyl, alkyl such as methyl, ethyl, propyl group, butyl, hexyl, octyl group, nonyl, decyl, dodecyl and pentadecyl, aralkyl such as benzyl, perhaps alkaryl such as alkyl phenyl; R
3And R
4Group is hydrogen, alkyl and the alkaryl with 1～9 carbon atom independently; It is by being selected from down replacement or the unsubstituted phenolic compound of group: phenol, ortho-cresol, meta-cresol, p-cresol, xylenol, p-tert-butylphenol, to tert-octyl phenol, p-phenyl phenol, bisphenol-A, bisphenol-f, Resorcinol, Phloroglucinol, cashew shell liquid and Metha Amino Phenon, with be selected from vinylbenzene, alpha-methyl styrene, p-methylstyrene, Vinylstyrene, vinyl naphthalene, between di isopropenylbenzene or to di isopropenylbenzene, and the reaction of the vinyl aromatic compounds of Vinyl toluene, then at the organo-metallic phosphite, phosphorous acid ester, perhaps the existence of the mixture of phosphorous acid ester and an acidic catalyst down and aldehyde and/or reactive ketone make.
2. composition as claimed in claim 1 is characterized in that, described organo-metallic phosphite or phosphite catalysts have following structure (b), (c) or their mixture:
In the formula, R represents to have the alkyl or the haloalkyl of 1～20 carbon atom independently, has the aryl or the halogenated aryl of 6～12 carbon atoms, perhaps has the aralkyl or the halo aralkyl of 7～20 carbon atoms.
3. composition as claimed in claim 2 is characterized in that, the described phosphite catalysts that is used to prepare methylene receptor resol is selected from: alkyl phosphite or aryl phosphite; Described phosphite catalysts comprises: tricresyl phosphite phenylester, tricresyl phosphite n-butyl, tricresyl phosphite ethyl ester, tricresyl phosphite methyl ester, tricresyl phosphite (nonyl phenyl) ester, tricresyl phosphite (2-ethylhexyl) ester, three stearyl phosphorous acid esters, phenylbenzene one decyl phosphorous acid ester, phosphorous acid diphenyl, phosphorous acid dimethyl esters, phosphorous acid di-n-butyl ester or their mixture.
4. composition as claimed in claim 1, it is characterized in that, aralkyl-the Resorcinol of described modification-aldehyde methylene receptor resin makes by following method, this method comprises: make Resorcinol and (1) be selected from vinylbenzene, alpha-methyl styrene, p-methylstyrene, Vinylstyrene, vinyl naphthalene, between di isopropenylbenzene or to di isopropenylbenzene, and the vinyl aromatic compounds of Vinyl toluene, and (2) formaldehyde reaction, wherein, Resorcinol: vinyl aromatic compounds: the mol ratio of aldehyde is about 1: 0.05: 0.1 to 1: 1.5: 0.8.
5. composition as claimed in claim 1, it is characterized in that described aldehyde and/or ketone compound are selected from down group: formalin, Paraformaldehyde 96, trioxane, acetaldehyde, paraldehyde, propionic aldehyde, butyraldehyde, isobutyric aldehyde, hexanal, octanal, aldehyde C-9, crotonic aldehyde, phenylacrolein, phenyl aldehyde, furfural, acetone and methylethylketone.
6. composition as claimed in claim 1 is characterized in that, the aralkyl-Resorcinol of described modification-aldehyde methylene receptor resin phosphite catalysts with another kind of as common catalyzer acid and potential catalyst in the presence of make; Described common catalyzer is selected from down group: mineral acid example hydrochloric acid, sulfuric acid, phosphoric acid, phosphorous acid, sulfonic acid such as benzene monosulfonic acid, benzene disulfonic acid, benzene trisulfonic acid, tosic acid, to Witco 1298 Soft Acid, alkylsulphonic acid and oxalic acid; Being used for the catalyzer of resins and the weight ratio of common catalyzer is 0.01: 1 to 1: 0.01.
7. composition as claimed in claim 1, it is characterized in that, described rubber components is natural or synthetic cis-1, the multipolymer of the multipolymer of the multipolymer of the multipolymer of 4-polyisoprene, polyhutadiene, sovprene, isoprene and divinyl, vinyl cyanide and divinyl, vinyl cyanide and isoprene, vinylbenzene and divinyl and isoprene, isobutene rubber (butyl) and the rare rubber of ethene-third, vinylbenzene and the multipolymer of divinyl and their blend.
8. composition as claimed in claim 1, it is characterized in that described methylene radical donor comprises: vulkacit H, six ethoxyl methyl trimeric cyanamides, HMMM, 2-nitro-2-methyl isophthalic acid-propyl alcohol, trioxane, yuban such as Paraformaldehyde 96.
9. composition as claimed in claim 1 is characterized in that the vulcanizate compositions of preparation also comprises additive, as sulphur, promotor, carbon black, cobalt salt, stearic acid, silicon-dioxide, zinc oxide, filler, antioxidant and softening oil.
10. composition as claimed in claim 1, it is characterized in that, described rubber combination is used for the production of composite products, comprise tire, transmission belt, conveying belt, print roller, rubber boots are followed and sole, rubber dish-cloth wringers, car mat, truck splash pan, ball mill liner, pipeline, fan belt and analogous products.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810032273 CN101235166B (en) | 2008-01-04 | 2008-01-04 | Resorcin phenolic resin modified rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810032273 CN101235166B (en) | 2008-01-04 | 2008-01-04 | Resorcin phenolic resin modified rubber composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101235166A true CN101235166A (en) | 2008-08-06 |
| CN101235166B CN101235166B (en) | 2013-06-19 |
Family
ID=39919091
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200810032273 Active CN101235166B (en) | 2008-01-04 | 2008-01-04 | Resorcin phenolic resin modified rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101235166B (en) |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030935A (en) * | 2010-11-09 | 2011-04-27 | 中国海洋石油总公司 | Method for modifying frozen gelatine powder |
| CN102372859A (en) * | 2010-08-09 | 2012-03-14 | 韩国轮胎株式会社 | Rubber composition for tire and tire manufactured by using the same |
| CN101649079B (en) * | 2008-08-12 | 2012-06-06 | 华奇（张家港）化工有限公司 | Application of blend of resorcinol and m-aminophenol derivatives in rubber composition |
| CN102702585A (en) * | 2012-06-21 | 2012-10-03 | 三角轮胎股份有限公司 | Radial tire carcass ply compound and rubber composition containing environment-friendly resin and preparation method thereof |
| CN102702586A (en) * | 2012-06-21 | 2012-10-03 | 三角轮胎股份有限公司 | All-steel radial tire belt compound rubber composition and production method thereof |
| CN102875754A (en) * | 2012-09-28 | 2013-01-16 | 北京彤程创展科技有限公司 | Modified resorcinol phenolic resin and preparation method thereof and rubber compound |
| CN102911622A (en) * | 2012-09-28 | 2013-02-06 | 青岛科技大学 | Adhesive mixture, rubber composition applying adhesive mixture and preparation method of rubber composition |
| CN103897333A (en) * | 2012-12-26 | 2014-07-02 | 华奇（张家港）化工有限公司 | Rubber bonding promoter and its preparation method and use |
| WO2015192033A1 (en) * | 2014-06-14 | 2015-12-17 | Compagnie Generale Des Etablissements Michelin | High rigidity rubber composition |
| CN105254934A (en) * | 2015-08-19 | 2016-01-20 | 苏州国泰科技发展有限公司 | Rubber hose material for vehicle and preparation method thereof |
| CN106496709A (en) * | 2016-12-21 | 2017-03-15 | 上海翎宝传动科技有限公司 | High modulus rubber composition and high load capacity Timing Belt |
| CN106700000A (en) * | 2016-12-13 | 2017-05-24 | 沈阳化工大学 | Heat-resistant phenolic resin containing 4-dimethyl amino cinnamyl aldehyde and preparation method thereof |
| CN107459614A (en) * | 2017-08-28 | 2017-12-12 | 上海超程化工科技有限公司 | A kind of environment-friendly type adhesion promotor and preparation method thereof, application |
| WO2018160750A1 (en) * | 2017-02-28 | 2018-09-07 | SUMITOMO CHEMICAL ADVANCED TECHNOLOGIES LLC, d.b.a. SUMIKA ELECTRONIC MATERIALS | Novolac resins and use in rubber compositions |
| CN109160986A (en) * | 2018-08-22 | 2019-01-08 | 江苏麒祥高新材料有限公司 | A kind of modified metacresol-phenol-formaldehyde resin, preparation method and its rubber composition |
| CN109337028A (en) * | 2018-09-04 | 2019-02-15 | 华奇（中国）化工有限公司 | A kind of polyphenol phenol-formaldehyde resin modified and its preparation method and application |
| 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 |
| CN109516924A (en) * | 2018-11-14 | 2019-03-26 | 南京工业大学 | A method of catalysis resorcinol prepares m-aminophenol |
| CN110753725A (en) * | 2017-06-14 | 2020-02-04 | 株式会社普利司通 | Rubber composition, belt coating rubber, and tire |
| CN113087866A (en) * | 2021-04-01 | 2021-07-09 | 卡德莱化工(珠海)有限公司 | Preparation method and application of cashew phenolic resin |
| CN114945628A (en) * | 2020-01-09 | 2022-08-26 | 住友化学先进技术有限责任公司即住化电子材料公司 | Phloroglucinol resin, preparation method and application in rubber composition |
| CN115286753A (en) * | 2022-08-04 | 2022-11-04 | 南京师范大学 | Styrene modified phenolic resin and preparation method thereof |
| CN116396541A (en) * | 2023-03-06 | 2023-07-07 | 江苏国立化工科技有限公司 | Synthesis method and device of resorcinol rubber adhesive |
| CN116410712A (en) * | 2021-12-30 | 2023-07-11 | 中国石油天然气股份有限公司 | Temperature-sensitive plugging agent and preparation method and application thereof |
-
2008
- 2008-01-04 CN CN 200810032273 patent/CN101235166B/en active Active
Cited By (39)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101649079B (en) * | 2008-08-12 | 2012-06-06 | 华奇（张家港）化工有限公司 | Application of blend of resorcinol and m-aminophenol derivatives in rubber composition |
| CN102372859A (en) * | 2010-08-09 | 2012-03-14 | 韩国轮胎株式会社 | Rubber composition for tire and tire manufactured by using the same |
| CN102372859B (en) * | 2010-08-09 | 2013-05-15 | 韩国轮胎株式会社 | Rubber composition for tire and tire manufactured by using the same |
| CN102030935A (en) * | 2010-11-09 | 2011-04-27 | 中国海洋石油总公司 | Method for modifying frozen gelatine powder |
| CN102702585A (en) * | 2012-06-21 | 2012-10-03 | 三角轮胎股份有限公司 | Radial tire carcass ply compound and rubber composition containing environment-friendly resin and preparation method thereof |
| CN102702586A (en) * | 2012-06-21 | 2012-10-03 | 三角轮胎股份有限公司 | All-steel radial tire belt compound rubber composition and production method thereof |
| CN102875754A (en) * | 2012-09-28 | 2013-01-16 | 北京彤程创展科技有限公司 | Modified resorcinol phenolic resin and preparation method thereof and rubber compound |
| CN102911622A (en) * | 2012-09-28 | 2013-02-06 | 青岛科技大学 | Adhesive mixture, rubber composition applying adhesive mixture and preparation method of rubber composition |
| CN102911622B (en) * | 2012-09-28 | 2015-01-07 | 青岛科技大学 | Adhesive mixture, rubber composition applying adhesive mixture and preparation method of rubber composition |
| CN102875754B (en) * | 2012-09-28 | 2015-05-27 | 北京彤程创展科技有限公司 | Modified resorcinol phenolic resin and preparation method thereof and rubber compound |
| CN103897333B (en) * | 2012-12-26 | 2016-03-16 | 华奇（张家港）化工有限公司 | A kind of rubber adhesion accelerating agent and its preparation method and application |
| CN103897333A (en) * | 2012-12-26 | 2014-07-02 | 华奇（张家港）化工有限公司 | Rubber bonding promoter and its preparation method and use |
| US10106673B2 (en) | 2014-06-14 | 2018-10-23 | Compagnie Generale Des Etablissements Michelin | High rigidity rubber composition |
| WO2015192033A1 (en) * | 2014-06-14 | 2015-12-17 | Compagnie Generale Des Etablissements Michelin | High rigidity rubber composition |
| CN105254934A (en) * | 2015-08-19 | 2016-01-20 | 苏州国泰科技发展有限公司 | Rubber hose material for vehicle and preparation method thereof |
| CN106700000A (en) * | 2016-12-13 | 2017-05-24 | 沈阳化工大学 | Heat-resistant phenolic resin containing 4-dimethyl amino cinnamyl aldehyde and preparation method thereof |
| CN106496709A (en) * | 2016-12-21 | 2017-03-15 | 上海翎宝传动科技有限公司 | High modulus rubber composition and high load capacity Timing Belt |
| US11236190B2 (en) | 2017-02-28 | 2022-02-01 | Sumitomo Chemical Company, Limited | Novolac resins and use in rubber compositions |
| WO2018160750A1 (en) * | 2017-02-28 | 2018-09-07 | SUMITOMO CHEMICAL ADVANCED TECHNOLOGIES LLC, d.b.a. SUMIKA ELECTRONIC MATERIALS | Novolac resins and use in rubber compositions |
| KR102568275B1 (en) | 2017-02-28 | 2023-08-17 | 수미토모 케미칼 컴퍼니 리미티드 | Novolac resins and their use in rubber compositions |
| JP7267203B2 (en) | 2017-02-28 | 2023-05-01 | スミトモ ケミカル アドバンスト テクノロジーズ エルエルシー ディー・ビー・エー スミカ エレクトロニック マテリアルズ | Use in novolak resins and rubber compositions |
| JP2020509138A (en) * | 2017-02-28 | 2020-03-26 | スミトモ ケミカル アドバンスト テクノロジーズ エルエルシー ディー・ビー・エー スミカ エレクトロニック マテリアルズ | Use in novolak resins and rubber compositions |
| KR20190117731A (en) * | 2017-02-28 | 2019-10-16 | 수미토모 케미칼 컴퍼니 리미티드 | Its use in novolak resins and rubber compositions |
| CN110536912A (en) * | 2017-02-28 | 2019-12-03 | 住友化学先进技术有限责任公司即住化电子材料公司 | Novolac resin and the application in rubber composition |
| CN110753725A (en) * | 2017-06-14 | 2020-02-04 | 株式会社普利司通 | Rubber composition, belt coating rubber, and tire |
| CN107459614A (en) * | 2017-08-28 | 2017-12-12 | 上海超程化工科技有限公司 | A kind of environment-friendly type adhesion promotor and preparation method thereof, application |
| CN109160986A (en) * | 2018-08-22 | 2019-01-08 | 江苏麒祥高新材料有限公司 | A kind of modified metacresol-phenol-formaldehyde resin, preparation method and its rubber composition |
| CN109160986B (en) * | 2018-08-22 | 2021-08-17 | 江苏麒祥高新材料有限公司 | Modified m-cresol-phenol-formaldehyde resin, preparation method and rubber composition thereof |
| CN109337028A (en) * | 2018-09-04 | 2019-02-15 | 华奇（中国）化工有限公司 | A kind of polyphenol phenol-formaldehyde resin modified and its preparation method and application |
| 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 |
| CN109516924A (en) * | 2018-11-14 | 2019-03-26 | 南京工业大学 | A method of catalysis resorcinol prepares m-aminophenol |
| CN114945628A (en) * | 2020-01-09 | 2022-08-26 | 住友化学先进技术有限责任公司即住化电子材料公司 | Phloroglucinol resin, preparation method and application in rubber composition |
| CN113087866A (en) * | 2021-04-01 | 2021-07-09 | 卡德莱化工(珠海)有限公司 | Preparation method and application of cashew phenolic resin |
| CN113087866B (en) * | 2021-04-01 | 2022-07-26 | 卡德莱化工(珠海)有限公司 | Preparation method and application of cashew phenolic resin |
| CN116410712A (en) * | 2021-12-30 | 2023-07-11 | 中国石油天然气股份有限公司 | Temperature-sensitive plugging agent and preparation method and application thereof |
| CN116410712B (en) * | 2021-12-30 | 2024-05-24 | 中国石油天然气股份有限公司 | Temperature-sensitive plugging agent and preparation method and application thereof |
| CN115286753A (en) * | 2022-08-04 | 2022-11-04 | 南京师范大学 | Styrene modified phenolic resin and preparation method thereof |
| CN116396541A (en) * | 2023-03-06 | 2023-07-07 | 江苏国立化工科技有限公司 | Synthesis method and device of resorcinol rubber adhesive |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101235166B (en) | 2013-06-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101235166B (en) | Resorcin phenolic resin modified rubber composition | |
| CA2036483C (en) | Rubber compounding resin | |
| KR101009328B1 (en) | Phenolic modified resorcinolic resins for rubber compounding | |
| US8759471B2 (en) | Adhesion-promoting system for rubber goods | |
| CN1882625B (en) | Novolak resins and rubber compositions comprising the same | |
| KR101092931B1 (en) | Modified resorcinol resins and applications thereof | |
| CN101235165B (en) | M-aminophenol modified aralkylresorcinol-aldehydes compound resin used for rubber formulation and application | |
| TW201444898A (en) | Cocondensate and method for producing same, and rubber composition containing cocondensate | |
| CN109160986B (en) | Modified m-cresol-phenol-formaldehyde resin, preparation method and rubber composition thereof | |
| KR20170008782A (en) | Modified phenolic resins and methods of making and using the same as reinforcing resins | |
| CN109476799B (en) | Phenol-aldehyde cocondensate for compounding rubber and method for producing the cocondensate | |
| JP6675137B2 (en) | Resin composition, method for producing the same, and rubber composition containing resin composition | |
| CN109369866A (en) | A kind of resorcinol air aldehyde resin and its preparation method and application | |
| WO2010017673A1 (en) | Resorcinol and m-aminophenol derivatives blends in rubber compounding applications | |
| JPS59204635A (en) | Rubber composition for bead filler | |
| CN107857848B (en) | Melamine modified resorcinol resin and synthesis method and application thereof | |
| CN101649079B (en) | Application of blend of resorcinol and m-aminophenol derivatives in rubber composition | |
| JPS63247102A (en) | Tire | |
| CN104231198B (en) | Aralkyl resorcinol aldehydes compound resin that m-phenylene diamine (MPD) is modified and preparation thereof and application | |
| JP2014105225A (en) | Co-condensed material and rubber composition containing the same | |
| WO2023222427A1 (en) | Adhesion-promoting system for a rubber composition | |
| CN116802219A (en) | Self-polymerizable phenolic resins |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: SINO LEGEND (CHINA) CHEMICAL CO., LTD. Free format text: FORMER NAME: SINA (ZHANGJIEGANG) CHEMICALS CO., LTD. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 215635 No. 99, Pa Pa Road, Yang Zijiang International Chemical Industrial Park, Zhangjiagang, Jiangsu, Jiangsu Patentee after: SINO LEGEND (ZHANGJIAGANG) CHEMICAL CO., LTD. Address before: 215635 No. 99, Pa Pa Road, Yang Zijiang International Chemical Industrial Park, Zhangjiagang, Jiangsu, Jiangsu Patentee before: Sino Legend Zhangjiagang Chemi |