CN101235166B - Resorcin phenolic resin modified rubber composition - Google Patents
Resorcin phenolic resin modified rubber composition Download PDFInfo
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- CN101235166B CN101235166B CN 200810032273 CN200810032273A CN101235166B CN 101235166 B CN101235166 B CN 101235166B CN 200810032273 CN200810032273 CN 200810032273 CN 200810032273 A CN200810032273 A CN 200810032273A CN 101235166 B CN101235166 B CN 101235166B
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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 their application in preparing pneumatic tyre, penstock and belt as the rubber compounding resin.
Background technology
In production at the reinforcing rubber goods 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.At first steel wire for these purposes wants brass-plating or zinc.The basic demand of accomplishing effective reinforcement is that these supporting materials will be adhered on rubber tightly.Maximum when bonding when producing between rubber and strong material, rubber or rubber compound just can reach maximum reinforcement.Continued deflection while using due to rubber item and be exposed in hot environment, such as just be difficult to reach good bonding in doughnut.Rubber and steel wire form good mechanical engagement in sulfidation can obtain excellent initial viscosity, but, due to aging and use rubber item, bond properties often can weaken or completely dissolve, and causes bonding premature failure.For fear of this situation, usually add adhesion promotor to maintain good bonding between rubber or rubber compound and metal.
Promotion between rubber and brass-plating or 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 rubber combination.But how long Hexa does not use in actual applications, because Hexa decomposes the ammonia produced, can corrode steel wire and affect bonding quality.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.In sulfidation, the formation of this RF network structure has improved physicals, mechanical property and the bond properties of vulcanized rubber.
It's a pity, in rubber compounding, add Resorcinol to have some potential unfavorable factors.When Resorcinol is unmodified, its volatility and smokiness are 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.Although carried out these, improve, 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.
It is low or be fuming the methylene receptor material low and strengthen sulfuration and mechanical property for rubber compounding that main purpose of the present invention is to provide a kind of volatility.Use the few resin of free monomer content can make the problem of being fuming in the rubber compounding application minimize or eliminate fully.The resorcinol resin of not being fuming by use in tire and non-tyre industry like this, can reduce the detrimentally affect to environment and health of human body greatly.
These rubber combinations can be for the production of pneumatic tyre, flexible pipe and belt.
Summary of the invention
According to the present invention, the reaction under organo-metallic phosphite or the existence of phosphorous acid esters catalyzer of the resol of the aralkyl modification that comprises following chemical structure generates:
In above-mentioned chemical structure, R
1and R
2group can be hydrogen independently, hydroxyl, and amino, chlorine, ethanoyl, benzoyl, alkyl is as methyl, ethyl, propyl group, butyl, hexyl, octyl group, nonyl, decyl, dodecyl and pentadecyl, and aralkyl is as phenyl, or alkaryl is as alkyl phenyl; In above formula, R
3and R
4group can be hydrogen, alkyl and the alkaryl with 1～9 carbon atom independently.
According to the present invention, can prepare by following method by the resol of this aralkyl modification: the phenolic compound that following general formula (a) means reacts with the vinyl aromatic compounds that (1) is selected from vinylbenzene, alpha-methyl styrene, p-methylstyrene, Vinylstyrene, vinyl naphthalene and Vinyl toluene
In formula, R
1and R
2can be hydrogen, hydroxyl, amino, chlorine, ethanoyl, benzoyl independently, alkyl be as methyl, ethyl, propyl group, butyl, hexyl, octyl group, nonyl, decyl, dodecyl and pentadecyl, and aralkyl is as benzyl, or alkaryl is as alkyl phenyl;
Then with (2) one or more aldehyde and/or ketone compound, it is selected from: formalin, paraformaldehyde, trioxane, acetaldehyde, paraldehyde, butyraldehyde, isobutyric aldehyde, hexanal, octanal, aldehyde C-9, crotonic aldehyde, phenylacrolein, phenyl aldehyde, furfural, acetone and methylethylketone react and make under following structural formula (b) or the organo-metallic phosphite (c) meaned or phosphite catalysts or their mixture existence condition
In formula, R means to have alkyl or the haloalkyl of 1～20 carbon atom independently, has aryl or the halogenated aryl of 6～12 carbon atoms, or has 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 comprised in the present invention can make for changing vulcanization rate, as known to those skilled in the art together with other catalyzer.The co-catalysis agent that can use together with phosphorous acid ester can be acid and other potential acid catalysts.Applicable acid catalyst comprises that mineral acid is as phosphoric acid, sulfuric acid or hydrochloric acid, and organic acid is as oxalic acid, toxilic acid, or acid anhydrides is as any in maleic anhydride.Strong acid can be used with together with potential acid as sulfuric acid, hydrochloric acid, phosphoric acid, phosphorous acid, Phenylsulfonic acid, sulfocarbolic acid, toluenesulphonic acids, methylsulfonic acid, three halogenated acetic acids or dihalo acetic acid can be used separately also.For example, the phosphorous acid diphenyl can be first 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%, with the weighing scale of phenol.
The phenolic compound that can be used for preparing resol in the present invention is not particularly limited, preferably include the phenol that at least one is selected from lower 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 Resorcinol.
In the preparation process of resol of the present invention, can use various vinyl aromatic compounds.These compounds can be selected from lower 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 vinylbenzene.
In the preparation process of resol of the present invention, the phenolic compound that general formula (a) means can be at first and vinyl aromatic compounds generation aralkyl glycosylation reaction, then separately or together with other phenolic compound with aldehyde and/or reactive ketone.Perhaps, at first prepare resol, then make vinyl aromatic compounds be reacted on resol.Except these methods, can be also part or all of phenolic compound with carry out the aralkyl glycosylation reaction when aldehydes or ketones reacts.But preferred option be phenolic compound at first with vinyl aromatic compounds generation aralkyl glycosylation reaction, then with aldehydes or ketones, react.The first-selected formaldehyde of aldehyde cpd.
Preparing the preferred phenol of this resol and vinylbenzene mol ratio 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 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 in the rubber combination for the production of pneumatic tyre, flexible pipe and belt.Therefore, this invention provides a kind of vulcanizate compositions of modification, it comprises that (i) is selected from natural rubber or elastomeric rubber components, (ii) methylene radical donor and (iii) as the aralkyl-Resorcinol of methylene receptor-air aldehyde resin.
Rubber components of the present invention can be cis-Isosorbide-5-Nitrae-polyisoprene (natural or synthetic), polyhutadiene, sovprene, isoprene and multipolymer, vinylbenzene and the divinyl of multipolymer, vinyl cyanide and the isoprene of multipolymer, vinyl cyanide and the divinyl of divinyl and multipolymer, isobutene rubber (butyl) and the rare rubber of ethene-third (EPDM), vinylbenzene and the multipolymer of divinyl and their blend of isoprene.
In the present invention, compositions of vulcanize rubbers can comprise one or more methylene radical donors.The meaning of term " methylene radical donor " is can produce formaldehydogenic compound after heating, and the formaldehyde of generation can react with aralkyl-Resorcinol-urea formaldehyde, generates crosslinked reticulated structure in rubber compound.The applicable methylene radical donor of the present invention comprises: (NMP), trioxane and yuban are as paraformaldehyde for vulkacit H, six ethoxyl methyl trimeric cyanamides, HMMM, 2-nitro-2-methyl isophthalic acid-propyl alcohol.
Methylene radical donor in the present invention in rubber combination and the weight ratio of methylene radical donor can change.But usually, the scope of weight ratio is between approximately 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 and make under the existence of phosphite catalysts or acid catalyst or their mixture with aldehyde and/or ketone by the aralkyl Resorcinol.Resorcinol reacts and can generate the aralkyl Resorcinol under phosphite catalysts or acid catalyst existence with vinyl aromatic compounds.In aralkyl glycosylation reaction of the present invention, applicable vinyl aromatic compounds 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 co-catalysis agent of Resorcinol and vinyl aromatic compounds generation aralkyl glycosylation reaction.The applicable acid catalyst of aralkyl glycosylation reaction is selected from lower group: mineral acid example hydrochloric acid, sulfuric acid, phosphoric acid, phosphorous acid, sulfonic acid is as benzene monosulfonic acid, benzene disulfonic acid, benzene trisulfonic acid, tosic acid (PTSA), to Witco 1298 Soft Acid, alkylsulphonic acid, oxalic acid.The amount of the co-catalysis agent of using 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 ℃.
After Resorcinol and vinylbenzene or vinyl aromatic compounds generation aralkyl glycosylation reaction, can add aldehydes or ketones or aldehyde ketone mixed solution.Applicable aldehyde and the example of ketone comprise: the aldehyde aqueous solution (37%), paraformaldehyde, containing solution, acetaldehyde, propionic aldehyde, butyraldehyde, isobutyric aldehyde, hexanal, octanal, aldehyde C-9, crotonic aldehyde, phenyl aldehyde, furfural, acetone and the methylethylketone of formaldehyde.The usage quantity of aldehyde and/or ketone can be 0.05～0.8 mole/1 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.The physical and mechanical property that particulate filler is generally used for improving rubber as supporting material in rubber as silicon-dioxide, carbon black, clay, talcum powder, calcium carbonate, silicate is as modulus, tensile strength, resistance to abrasion, tear resistance and dynamic property.
The sulfuration of normal conditions rubber combination will be carried out under sulfur vulcanizing agent exists.The example of applicable sulfur vulcanizing agent comprises: elementary sulfur (free sulphur) or sulfur donor vulcanizing agent are 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.Applicable promotor kind comprises amine, disulphide, guanidine, thiocarbamide, thiazole, thiuram, sulfinyl amine, dithiocar-bamate and xanthogenate.The first-selected sulfinyl amine of the first promotor.If use the second promotor, the second promotor is preferably selected guanidine, dithiocar-bamate or thiuram compound.
Additive of the present invention can add in 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 mixed with the Banbury Banbury mixer.A kind of typical method is, the additive that does not at first participate in reaction is mixed with rubber in being warmed up to approximately the Banbury mixer of 150 ℃.Vulcanizing agent, promotor and adhesion promotor add in temperature is about the mixed step of the second and the 3rd step of 90 ℃～150 ℃.
The invention still further relates to a kind of compositions of vulcanize rubbers, its physical and mechanical property is improved as tensile modulus, hardness, anti-incipient scorch, curing time dynamic modulus (G ') and Tan δ (magnetic hysteresis).
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.Can be for composite prod containing the rubber combination of aralkyl-resorcinol-formaldehyde resin product, comprise tire, transmission belt, conveying belt, print roller, rubber boots with and the cleaning shoe of sole, rubber dish-cloth wringers, automobile pad, truck, inner liner of bowl mill, pipeline material, fan belt etc.Vulcanization of rubber product is particularly useful for the production that steel wire covers 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 are not used in and limit the scope of the invention for the present invention is described.
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.Then approximately in 90～120 minutes, dripping 78,1g (0.93 mole) formalin lentamente in the Resorcinol of fusing.After formaldehyde drips and finishes, the reactant dehydration steams the interior all volatile matters of flask until temperature is raised to approximately 150 ℃～160 ℃.Then add 72.6g (0.705 mole) vinylbenzene in the resorcinol-formaldehyde reaction solution of fusing under Elevated Temperature Conditions, control time for adding approximately 60～120 minutes.Vinylbenzene adds the 5.6gNaOH aqueous solution to carry out the neutralizing acid catalyzer after dripping and finishing.Finally vacuumize dehydration and obtain the brown resin that softening temperature is 108.2 ℃.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 in the Resorcinol of fusing, add 71.25g (0.675 mole) vinylbenzene, controlling time for adding is 120 minutes.Then approximately in 90～120 minutes, adding 77.5g (0.93 mole) formalin lentamente in the Resorcinol melted-vinylbenzene reaction solution.After formaldehyde drips and finishes, the reactant dehydration steams the interior all volatile matters of flask until temperature is raised to approximately 150 ℃～160 ℃.Then, under the condition heated up gradually, with about 60～120 minutes, in Resorcinol-vinylbenzene-formaldehyde reaction liquid, add 16.5g (1.15 moles) vinylbenzene.After dripping end, add the 5.5gNaOH aqueous solution to carry out the neutralizing acid catalyzer.Finally vacuumize dehydration and obtain the brown resin that softening temperature is 107 ℃.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 in the Resorcinol of fusing, add 109.41g (1.05 moles) vinylbenzene, controlling time for adding is 120 minutes.Then approximately in 90～120 minutes, adding 78.75g (0.945 mole) formalin lentamente in the Resorcinol melted-vinylbenzene reaction solution.All formaldehyde adds the 5.5g NaOH aqueous solution to carry out the neutralizing acid catalyzer after dripping and finishing.Finally vacuumize dehydration and obtain the crimson chromoresin that softening temperature is 105 ℃.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 is less than 1%, thinks that it is the resorcinol resin that a kind of volatility is extremely low, 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 in the Resorcinol of fusing, add 234g (2.25 moles) vinylbenzene, controlling time for adding is 180 minutes.Then approximately in 120～150 minutes, adding 81.88g (0.975 mole) formalin lentamente in the Resorcinol melted-vinylbenzene reaction solution.All formaldehyde adds the 5.5g NaOH aqueous solution to carry out the neutralizing acid catalyzer after dripping and finishing.Finally vacuumize dehydration and obtain the orange-yellow resin that softening temperature is 99 ℃.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 is not containing free or unreacted Resorcinol.It is applied to rubber combination can make the problem of being fuming be down to minimum elimination even fully.In tire and non-tyre industry, use in this embodiment the resorcinol resin of not being fuming made can greatly improve the impact that environment and health of human body are caused.
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 in the Resorcinol of fusing, add 31.2g (0.3 mole) vinylbenzene, controlling time for adding is 30～60 minutes.Then approximately in 90～120 minutes, adding 82.2g (1.0 moles) formalin lentamente in the Resorcinol melted-vinylbenzene reaction solution.All formaldehyde adds the 5.5g NaOH aqueous solution to carry out the neutralizing acid catalyzer after dripping and finishing.Finally vacuumize dehydration and obtain the russet resin that softening temperature is 132 ℃.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 in the Resorcinol of fusing, add 83.32g (0.8 mole) vinylbenzene, controlling time for adding is 120～150 minutes.Then approximately in 90～120 minutes, adding 30.2g (0.37 mole) formalin lentamente in the Resorcinol melted-vinylbenzene reaction solution.All formaldehyde adds the 3.7g NaOH aqueous solution to carry out the neutralizing acid catalyzer after dripping and finishing.Finally vacuumize dehydration and obtain the russet resin that softening temperature is 74 ℃.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.Then approximately in 90～120 minutes, adding 107.3g (0.975 mole) formalin (40% concentration) lentamente in the Resorcinol of fusing.After all formaldehyde drips and reacts and finish, add the 1.1g NaOH aqueous solution to carry out the neutralizing acid catalyzer.Finally vacuumize dehydration 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, add 21.75g (0.375 mole) anhydrous propanone and make it to react completely in the Resorcinol of fusing lentamente.Then in about 90～120 minutes, under reflux state, answer liquid to add 50.4g (0.6 mole) formalin (37% concentration) in anti-to Resorcinol-acetone lentamente.After all formaldehyde drips and reacts and finish, add the 1.0g NaOH aqueous solution to carry out the neutralizing acid catalyzer.Finally vacuumize dehydration 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.Then in about 90～120 minutes, under reflux state, add 78.1g (0.93 mole) formalin (37% concentration) lentamente in the Resorcinol of fusing.After all formaldehyde drips and reacts and finish, add the 1.0g NaOH aqueous solution to carry out the neutralizing acid catalyzer.Finally vacuumize dehydration and obtain the orange resin that softening temperature is 110 ℃.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.Then in about 90～120 minutes, under reflux state, add 78.1g (0.93 mole) formalin (37% concentration) lentamente in the Resorcinol of fusing.After all formaldehyde drips and reacts and finish, reaction mixture refluxes 60 minutes again.This refluxing stage has steamed water and the volatile matter in the reaction flask under normal atmosphere and soaking condition.Then add 59 gram distilled water in resorcinol-formaldehyde (RF) resin of fusing, obtain the resin aqueous solution of crimson look.The water-content of resin solution is 29.5% after tested.Utilization is commonly used
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 in the Resorcinol of fusing, add 78.2g (0.75 mole) vinylbenzene, controlling time for adding is 120～150 minutes.Then approximately in 90～120 minutes, adding 63g (0.75 mole) formalin lentamente in the Resorcinol melted-vinylbenzene reaction solution.All formaldehyde adds the 2.8g NaOH aqueous solution to carry out the neutralizing acid catalyzer after dripping and finishing.Finally vacuumize dehydration and obtain the sorrel resin that softening temperature is 97 ℃.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 in the Resorcinol of fusing, add 78.2g (0.75 mole) vinylbenzene, controlling time for adding is 120～150 minutes.Then approximately in 90～120 minutes, adding 63g (0.75 mole) formalin lentamente in the Resorcinol melted-vinylbenzene reaction solution.All formaldehyde adds the 2.8g NaOH aqueous solution to carry out the neutralizing acid catalyzer after dripping and finishing.Finally vacuumize dehydration and obtain the sorrel resin that softening temperature is 89 ℃.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 in the Resorcinol of fusing, add 78.2g (0.75 mole) vinylbenzene, controlling time for adding is 120～150 minutes.Then approximately in 90～120 minutes, adding 63g (0.75 mole) formalin lentamente in the Resorcinol melted-vinylbenzene reaction solution.All formaldehyde adds the 2.8g NaOH aqueous solution to carry out the neutralizing acid catalyzer after dripping and finishing.Finally vacuumize dehydration and obtain the sorrel resin that softening temperature is 97 ℃.
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 approximately 95 ℃, approximately in 30 minutes, adding lentamente 78.1g (0.93 mole) formalin, mixeding liquid temperature is controlled at 90～105 ℃.After formaldehyde drips and finishes, then continue to stir 30 minutes.And then carry out normal atmosphere and vacuum distilling dehydration until reacting liquid temperature is raised to 120～125 ℃.Then under 120～130 ℃, slowly add 72.6g (0.705 mole) vinylbenzene, time for adding is controlled at 60 minutes.All vinylbenzene adds the 5.6g NaOH aqueous solution to carry out the neutralizing acid catalyzer after dripping and finishing.Finally vacuumize dehydration and obtain the sorrel resin that softening temperature is 111 ℃.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 in the Resorcinol of fusing, add 31.2g (0.3 mole) vinylbenzene, controlling time for adding is 30 minutes.Then approximately in 90～120 minutes, adding 50.5g (0.62 mole) formalin lentamente in the Resorcinol melted-vinylbenzene reaction solution.All formaldehyde adds the NaOH aqueous solution to carry out the neutralizing acid catalyzer after dripping and finishing.Finally vacuumize dehydration and obtain the sorrel resin that softening temperature is 121 ℃.The content that HPLC analyzes the free Resorcinol that shows this resin is 4.3%.
Embodiment 16 (resorcinol-formaldehyde resin of control resin-Catalyzed by 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 the agent of 1.5g Catalyzed by Oxalic Acid, and heated mixt is to fusing.Then under reflux state, in the Resorcinol of fusing, add lentamente 78.1g (0.93 mole) formalin (37% concentration), time for adding is controlled at 90～120 minutes.After all formaldehyde droppings and reaction finish, add the NaOH aqueous solution to carry out the neutralizing acid catalyzer.Finally vacuumize dehydration and obtain the orange-yellow resin that softening temperature is 112.5 ℃.The content that HPLC analyzes the free Resorcinol that shows this resin is 17.3%.
Embodiment 17
When Resorcino and the derivative based on Resorcino during for rubber compounding, in the mixed process of rubber combination, can be observed the Resorcinol phenomenon of being fuming.This is because the volatility of Resorcinol and Resorcinol are the causes existed 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 made in the R-80 that records under nitrogen environment and embodiment 2.
From the result of table 1, can find out apparently, the resin that the present invention makes when high temperature than safe letter company (China) commercially available R-80 product, volatility will reduce greatly.This R-80 is 80% pre-dispersed Resorcinol and the blend of 20%EPDM rubber.
Embodiment 18
The natural rubber composition of test use makes by three steps.Table 2 has provided basic rubber compounding.
The RF resin that makes in the resin that makes in embodiment 2 and 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 approximately being mixed under 150 ℃.Second step, the methylene receptor (having added cobalt salt) that will prepare according to embodiment 2 methods,, sneak in the appropriate masterbatch of Banbury Banbury mixer approximately under 145 ℃ of conditions in temperature.The 3rd step, by the insoluble sulfur shown in table 2, promotor and appropriate HMMM approximately 90～100 ℃ add and mix.This test compounds is placed and is spent the night under the environment of approximately 23 ℃ of constant room temperatures and 50% relative humidity.Then measure its sulphur and become instrument sulfuration, shape and optimum cure degree under 150 ℃, to estimate its mechanical property.
Curability is to become instrument with Alpha Technologies MDR sulphur, according to ASTM D 5289 and ISO6502 testing method, at 150 ℃, under 1 ° of radian and 1.67 hertz of conditions, measures.
In vibration disk sulphur becomes instrument, the sizing material sample is subject to the oscillatory shear power effect of uniform amplitude.Measure the moment of torsion of the vibration disk in Embedded test glue sample under curing temperature.Because the change of rubber or glue sample formula is easy to measure, so this sulfuration test obtains data, be very intuitively accurately.An advantage clearly can finding out it from following table is that vulcanization rate is fast.
Provided test data in table 3:
Can know and find out from the data of table 3, with the R-80 blend that middle Cathay believes, compare, 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 highly repeat to reproduce the rubber after front and sulfuration are vulcanized in the ground test with height.Available test and son test comprise that the sulphur under frequency sweeping, steady temperature and the frequency under steady temperature and strain becomes, the temperature scanning under the strain sweep under steady temperature and frequency, constant strain and 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 table 4.
Above-mentioned data have clearly illustrated that, add the vulcanized rubber of resin of the present invention to show good dynamic property and lower magnetic hysteresis, keep the bond properties of working as with RF resin and R-80 resin-phase simultaneously.
Although 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 (15)
1. the vulcanizate compositions of a modification, it comprises:
(i) be selected from natural rubber or elastomeric rubber components;
(ii) methylene radical donor; With
(iii) phenolic resinoid replaced as the aralkyl of methylene receptor, it comprises following chemical structure:
In formula, R
1and R
2group is hydrogen independently, hydroxyl, and amino, chlorine, ethanoyl, benzoyl, alkyl,
Aralkyl, or alkaryl, R
3and R
4group is hydrogen, alkyl and the alkaryl with 1～9 carbon atom independently, it is by being selected from replacement or the unsubstituted phenolic compound of lower 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 vinyl aromatic compounds of Vinyl toluene reaction, then at the organo-metallic phosphite, phosphorous acid ester, perhaps under the existence of the mixture of phosphorous acid ester and an acidic catalyst, with aldehyde and/or reactive ketone, make,
Described organo-metallic phosphite or phosphite catalysts have following structure (b), (c) or their mixture:
In formula, R means to have alkyl or the haloalkyl of 1～20 carbon atom independently, has aryl or the halogenated aryl of 6～12 carbon atoms, or has aralkyl or the halo aralkyl of 7～20 carbon atoms.
2. composition as claimed in claim 1, is characterized in that, described alkyl is selected from methyl, ethyl, propyl group, butyl, hexyl, octyl group, nonyl, decyl, dodecyl and pentadecyl.
3. composition as claimed in claim 1, is characterized in that, described aralkyl is benzyl.
4. composition as claimed in claim 1, is characterized in that, described alkaryl is alkyl phenyl.
5. composition as claimed in claim 1, is characterized in that, the described phosphite catalysts for the preparation of 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.
6. 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, the method comprises: make Resorcinol and (1) be selected from vinylbenzene, alpha-methyl styrene, p-methylstyrene, Vinylstyrene, vinyl naphthalene, a di isopropenylbenzene or to the vinyl aromatic compounds of di isopropenylbenzene and Vinyl toluene, and (2) formaldehyde reaction, wherein, Resorcinol: vinyl aromatic compounds: the mol ratio of aldehyde is 1:0.05:0.1 to 1:1.5:0.8.
7. composition as claimed in claim 1, it is characterized in that, described aldehyde and/or ketone compound are selected from lower group: formalin, paraformaldehyde, trioxane, acetaldehyde, paraldehyde, propionic aldehyde, butyraldehyde, isobutyric aldehyde, hexanal, octanal, aldehyde C-9, crotonic aldehyde, phenylacrolein, phenyl aldehyde, furfural, acetone and methylethylketone.
8. composition as claimed in claim 1, is characterized in that, the aralkyl-Resorcinol of described modification-aldehyde methylene receptor resin makes under the existence of phosphite catalysts and the another kind of acid as the co-catalysis agent and potential catalyst; Described co-catalysis agent is selected from lower group: mineral acid, sulfonic acid and oxalic acid; The catalyzer standby for resin is 0.01:1 to 1:0.01 with the weight ratio of common catalyzer.
9. composition as claimed in claim 8, is characterized in that, described mineral acid is selected from hydrochloric acid, sulfuric acid, phosphoric acid and phosphorous acid.
10. composition as claimed in claim 8, is characterized in that, described sulfonic acid is selected from benzene monosulfonic acid, benzene disulfonic acid, benzene trisulfonic acid, tosic acid, to Witco 1298 Soft Acid and alkylsulphonic acid.
11. composition as claimed in claim 1, it is characterized in that, described rubber components is multipolymer, vinylbenzene and the divinyl of multipolymer, vinyl cyanide and isoprene of multipolymer, vinyl cyanide and divinyl of natural or synthetic cis-Isosorbide-5-Nitrae-polyisoprene, polyhutadiene, sovprene, isoprene and divinyl and multipolymer, the isobutene rubber (butyl) and the rare rubber of ethene-third, vinylbenzene and the multipolymer of divinyl and their blend of isoprene.
12. 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 or yuban.
13. composition as claimed in claim 12, is characterized in that, described yuban is paraformaldehyde.
14. composition as claimed in claim 1, it is characterized in that, the vulcanizate compositions of preparation also comprises additive, and described additive is selected from sulphur, promotor, carbon black, cobalt salt, stearic acid, silicon-dioxide, zinc oxide, filler, antioxidant and softening oil.
15. composition as claimed in claim 1, it is characterized in that, described rubber combination is for the production of composite products, comprise tire, transmission belt, print roller, rubber boots with and sole, rubber dish-cloth wringers, car mat, truck splash pan, inner liner of bowl mill, pipeline or fan belt.
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